Engineering Chemistry

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1 Atoms und MoIecuIes .................................................................................... 111
Wnvo MochnnIcnI Concof of Afom .................................................................................... l
AIIcnfIon of SchrodIngor IqunfIon ................................................................................. 6
IrobnbIIIfy IsfrIbufIon ...................................................................................................... ?
1xercieee ............................................................................................................................. ll
2 VuIency und CLemIcuI BondIng .............................................................. 1242
IIocfronognfIvIfy ............................................................................................................... l4
Hydrogon Iond .................................................................................................................. l5
IoIo Momonf .................................................................................................................. l6
ChomIcnI IondIng (Wnvo-MochnnIcnI Concof) .............................................................. l8
VSII! Thoory nnd MoIocuInr ModoI .............................................................................. 25
AromnfIc Chnrncfor ........................................................................................................... 33
Shorf QuosfIons nnd Answors .......................................................................................... 35
1xercieee ............................................................................................................................. 4l
3 NucIeuv CLemIstvy ...................................................................................... 436?
!ndIoncfIvIfy ...................................................................................................................... 43
ucIonr IIssIon .................................................................................................................. 4?
ucIonr !oncfors ............................................................................................................... 50
!sos of !ndIoIsofoos ........................................................................................................ 53
1xercieee ............................................................................................................................. 65
4 TLevmodynumIcs ....................................................................................... 6B103
Tho IIrsf !nw of ThormodynnmIcs .................................................................................. ?0
ThormochomIsfry .............................................................................................................. 80
Iond Inorgy ...................................................................................................................... 83
Socond !nw of ThormodynnmIcs ...................................................................................... 84
ThIrd !nw of ThormodynnmIcs ........................................................................................ 8?
1xercieee ........................................................................................................................... l00
5 ReuctIon ynumIcs/CLemIcuI KInetIcs ............................................. 104136
InfroducfIon ..................................................................................................................... l04
+JAJI
LEE
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MnfhomnfIcnI IormuInfIon of IIrsf Ordor !oncfIon ..................................................... l06
MnfhomnfIcnI IormuInfIon of n Socond Ordor !oncfIon .............................................. l08
ThIrd Ordor !oncfIon ...................................................................................................... lll
IsfurbIng Incfors In fho oformInnfIon of nn Ordor .................................................. ll6
CoIIIsIon Thoory............................................................................................................... l20
SoIvod IxnmIos.............................................................................................................. l2l
Shorf QuosfIons ............................................................................................................... l3l
Shorf QuosfIons nnd Answors ........................................................................................ l3l
1xercieee ........................................................................................................................... l35
6 CutuIyst ...................................................................................................... 13?149
CnfnIysf ............................................................................................................................ l3?
ofInIfIon ......................................................................................................................... l3?
Tyos of CnfnIysf ............................................................................................................. l38
Shorf QuosfIons nnd Answors ........................................................................................ l43
CnfnIyfIc AIIcnfIons of OrgnnomofnIIIc ComIoxos ................................................... l45
1xercieee ........................................................................................................................... l48
? MecLunIsm oI OvgunIc ReuctIons ....................................................... 1501B3
!oncfIon Tyos ................................................................................................................. l50
Inorgy Chnngos urIng fho Irogross of n !oncfIon..................................................... l53
!osonnnco ........................................................................................................................ l5?
SforIc HIndrnnco.............................................................................................................. l58
IsomorIsm......................................................................................................................... l60
!-S Sysfom of omoncInfuro .......................................................................................... l66
I nnd Z omoncInfuro .................................................................................................... l?0
Shorf QuosfIons nnd Answors ........................................................................................ l?l
1xercieee ........................................................................................................................... l82
B IonIc quIIIbvIum.................................................................................... 1B4203
!nw of Mnss AcfIon nnd IonIsnfIon ................................................................................ l84
AcIds nnd Insos ............................................................................................................... l85
H ScnIo ........................................................................................................................... l8?
Iuffor SoIufIons ............................................................................................................... l89
SoIubIIIfy Iroducf ............................................................................................................ l92
SoIvod IxnmIos.............................................................................................................. l95
Shorf QuosfIons nnd Answors ........................................................................................ l9?
1xercieee ........................................................................................................................... 202
9 IectvocLemIstvy ..................................................................................... 204229
InfroducfIon ..................................................................................................................... 204
IIocfroIysIs ....................................................................................................................... 204
Inrndny`s !nw of IIocfroIysIs ......................................................................................... 205
!oInfIvo Soods of Ions urIng IIocfroIysIs (Trnnsorf umbor) ............................... 208
oformInnfIon of Trnnsorf umbor (HIfforf`s Mofhod) .............................................. 2l0
SocIfIc Conducfnnco....................................................................................................... 2ll
ConducfomofrIc TIfrnfIon ............................................................................................... 2l?
LEEE
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SoIvod IxnmIos.............................................................................................................. 2l9
Shorf QuosfIons nnd Answors ........................................................................................ 223
-NAH?EIAI 228
10 IectvocLemIcuI CeIIs............................................................................. 230265
IIocfrodo IofonfInI .......................................................................................................... 230
InforrofnfIon of fho IIocfrochomIcnI SorIos ................................................................ 234
!nfImor Ingrnm............................................................................................................. 235
Irosf Ingrnm.................................................................................................................. 23?
ConconfrnfIon CoII ........................................................................................................... 239
IndIcnfor IIocfrodos ........................................................................................................ 242
Inffory ............................................................................................................................. 248
SoIvod IxnmIos.............................................................................................................. 252
-NAH?EIAI 263
11 PLuse RuIe................................................................................................. 2662??
InfroducfIon ..................................................................................................................... 266
Tho Ihnso !uIo ................................................................................................................ 26?
Tho Wnfor Sysfom ........................................................................................................... 268
SuIhur Sysfom ............................................................................................................... 269
IufocfIc Sysfoms ............................................................................................................. 2?l
TIn-MngnosIum Sysfom .................................................................................................. 2?3
Iron-Cnrbon AIIoy Sysfom............................................................................................... 2?3
SoIvod IrobIom ................................................................................................................ 2?5
Shorf QuosfIons nnd Answors ........................................................................................ 2?5
-NAH?EIAI 2??
12 CoIIoIds....................................................................................................... 2?B291
InfroducfIon ..................................................................................................................... 2?8
CInssIfIcnfIon of CoIIoIds ................................................................................................. 2?8
IronrnfIon of CoIIoIdnI SoIufIons ................................................................................. 280
IurIfIcnfIon of CoIIoIdnI SoIufIons .................................................................................. 282
IroorfIos of CoIIoIdnI SoIufIons .................................................................................... 283
ConguInfIon of CoIIoIds ................................................................................................... 285
IrofocfIon of CoIIoId ........................................................................................................ 286
AIIcnfIon of CoIIoIds..................................................................................................... 288
-NAH?EIAI 290
13 TvunsItIon MetuI CLemIstvy ................................................................. 29230?
TrnnsIfIon MofnIs ............................................................................................................ 292
CrysfnI IIoId Thoory (CIT)............................................................................................. 303
-NAH?EIAI 30?
EN
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14 MetuIIuvgy ................................................................................................. 30B32B
InfroducfIon fo fho Sfudy of MofnIs ............................................................................... 308
Common MInornIs ........................................................................................................... 309
Oros .................................................................................................................................. 3ll
IIuxos ............................................................................................................................... 3l3
Iurnncos ........................................................................................................................... 3l4
Iowdor MofnIIurgy .......................................................................................................... 320
Somo SocIfIc IxnmIos of IxfrncfIon of MofnIs .......................................................... 322
1xercieee ........................................................................................................................... 326
15 AdLesIves ................................................................................................... 32933?
AdhosIvos ......................................................................................................................... 329
AdhosIvo Sfrongfh ovoIomonf .................................................................................... 330
TochnIquo of IondIng...................................................................................................... 33l
CInssIfIcnfIon of AdhosIvos ............................................................................................. 333
1xercieee ........................................................................................................................... 336
16 xpIosIves und PvopeIIunts .................................................................. 33B349
IxIosIvos ........................................................................................................................ 338
CInssIfIcnfIon of IxIosIvos............................................................................................. 339
Mnnufncfuro of Imorfnnf IxIosIvos ........................................................................... 343
IrooIInnfs ....................................................................................................................... 345
1xercieee ........................................................................................................................... 348
1? Wutev Tveutment ..................................................................................... 3503?B
Sourcos of Wnfor .............................................................................................................. 350
Hnrdnoss of Wnfor ........................................................................................................... 35l
SIudgo nnd ScnIo IormnfIon In IoIIors .......................................................................... 352
SoffonIng of Wnfor ........................................................................................................... 356
CoId IImo-Sodn Irocoss ................................................................................................... 35?
Hof IImo-Sodn Irocoss..................................................................................................... 358
IormufIf or ZooIIfo Irocoss............................................................................................. 359
Ion Ixchnngo or omInornIIznfIon................................................................................. 360
Tronfmonf of Wnfor for omosfIc !so ........................................................................... 362
ChomIcnI AnnIysIs of Wnfor ............................................................................................ 366
1xercieee ........................................................................................................................... 3?5
ProIlene ........................................................................................................................... 3??
1B IueIs und CombustIon ........................................................................... 3?9414
InfroducfIon ..................................................................................................................... 3?9
CnIorIfIc VnIuo ................................................................................................................. 3?9
SoIId IuoIs........................................................................................................................ 383
!IquId IuoIs ..................................................................................................................... 390
N
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Cnsoous IuoIs .................................................................................................................. 399
SoIvod IxnmIos.............................................................................................................. 404
Shorf QuosfIons nnd Answors ........................................................................................ 40?
-NAH?EIAI 4l2
19 SIIIcute TecLnoIogy................................................................................. 41543B
InfroducfIon ..................................................................................................................... 4l5
Comonf ............................................................................................................................. 4l8
CInss ................................................................................................................................. 422
Ioffory nnd IorcoInIn...................................................................................................... 42?
!ofrncforIos ...................................................................................................................... 430
-NAH?EIAI 43?
20 PoIymevs .................................................................................................... 4394?0
IoIymorIznfIon................................................................................................................. 439
IInsfIcs (!osIns) ............................................................................................................... 445
Imorfnnf ThormoInsfIcs .............................................................................................. 449
Imorfnnf ThormosoffIng !osIns ................................................................................... 453
!ubbor .............................................................................................................................. 460
MIscoIInnoous IoIymors .................................................................................................. 464
-NAH?EIAI 468
21 PuInts .......................................................................................................... 4?14B0
InInfs ............................................................................................................................... 4?l
VnrnIshos ......................................................................................................................... 4?5
!ncquors ........................................................................................................................... 4??
InnmoIs nnd Jnnns ....................................................................................................... 4??
-NAH?EIAI 480
22 SoIId Stute CLemIstvy ............................................................................ 4B1503
CrysfnI .............................................................................................................................. 48l
IundnmonfnI !nw of CrysfnIIogrnhy ........................................................................... 482
CrysfnI !nffIco ................................................................................................................. 485
CubIc CrysfnIs................................................................................................................. 48?
TrnnsIsfors (SomIconducfor TrIodos) ............................................................................. 492
IIomonfs of Innd Thoory ............................................................................................... 493
Conducfors, SomIconducfors nnd InsuInfors ................................................................. 496
IrobIoms........................................................................................................................... 50l
-NAH?EIAI 503
23 CLvomutogvupLy ..................................................................................... 504511
InfroducfIon ..................................................................................................................... 504
Tyos of Chromnfogrnhy............................................................................................... 504
-NAH?EIAI 5ll
NE
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24 InstvumentuI MetLods oI AnuIysIs ...................................................... 51254?
InfroducfIon ..................................................................................................................... 5l2
Somo Torms ConcornIng !V .......................................................................................... 5l3
Ioor-!nmborf`s !nw ........................................................................................................ 5l9
Infrnrod Socfroscoy ..................................................................................................... 522
Somo I! Socfrn .............................................................................................................. 525
ShIoIdIng, oshIoIdIng nnd ChomIcnI ShIff ................................................................... 529
Mnss Socfromofry .......................................................................................................... 53?
1xercieee ........................................................................................................................... 54?
25 PLotocLemIstvy........................................................................................ 54B560
SIngIof nnd TrIIof Sfnfos ............................................................................................... 549
IroorfIos of fho IxcIfod Sfnfos ..................................................................................... 549
IhofoIysIs ......................................................................................................................... 550
Tyos of IhofohysIcnI Infhwnys .................................................................................. 552
IhofochomIcnI Irocossos for IxcIfod MoIocuIos ............................................................ 554
IhofosynfhosIs ................................................................................................................. 556
1xercieee ........................................................................................................................... 560
26 RoIe oI MetuIs In BIoIogy....................................................................... 5615?0
Iron ................................................................................................................................... 562
Coor .............................................................................................................................. 563
ZInc ................................................................................................................................... 563
Mnngnnoso ....................................................................................................................... 564
CobnIf ............................................................................................................................... 564
IckoI ............................................................................................................................... 564
CnIcIum nnd MngnosIum ................................................................................................ 565
IIocfron Trnnsfor ........................................................................................................... 565
IIocfron Trnnsorf nnd OxIdnfIvo IhoshoryInfIon ..................................................... 56?
1xercieee ........................................................................................................................... 5?0
2? PoIIutIon PveventIon und Wuste MInImIsutIon............................... 5?15B9
AIr IoIIufIon..................................................................................................................... 5?l
Wnfor IoIIufIon................................................................................................................ 5?9
SoII IoIIufIon.................................................................................................................... 583
!ndIoncfIvo IoIIufIon ...................................................................................................... 584
oIso IoIIufIon................................................................................................................. 585
ThormnI IoIIufIon............................................................................................................ 586
Shorf QuosfIons nnd Answors ........................................................................................ 58?
1xercieee ........................................................................................................................... 589
NEE
Atoms and MoIecuIes

1
WAVE MECHANICAL CONCEPT OF ATOM
Wave Nature of the EIectron
Wo hnvo soon ufo Iohr`s concof of nfom fhnf fho oIocfron Is fronfod ns n nrfIcIo. Tho concof
of wnvo nnfuro of mnffor cnmo from fho dunI chnrncfor of rndInfIon, whIch somofImos bohnvos
ns n wnvo nnd somofImos ns n nrfIcIo. do-IrogIIo oInfod ouf In l924 fhnf rndInfIon IncIudIng
vIsIbIo IIghf, Infrnrod, uIfrnvIoIof nnd X-rnys bohnvo ns wnvos In rongnfIon oxorImonfs
bnsod on inIerference nnd JiffrocIion. Thoso oxorImonfs concIusIvoIy rovod fho wnvo nnfuro
of fhoso rndInfIons. Howovor, rndInfIon bohnvos ns n nrfIcIo In InforncfIon oxorImonfs whIch
IncIudo bInck body rndInfIon, hofooIocfrIc offocf nnd Comfon offocf. Horo rndInfIon Inforncfs
wIfh mnffor In fho form of pIoIone or quonIo. Of courso rndInfIon cnnnof oxhIbIf Ifs nrfIcIo
nnd wnvo roorfIos sImuIfnnoousIy.
: A wnvo Is socIfIod by Ifs (i) froquoncy, (ii) wnvoIongfh (), (iii) hnso, (it) nmIIfudo,
(t) InfonsIfy.
: A nrfIcIo Is socIfIod by Ifs (i) mnss (n), (ii) voIocIfy (t), (iii) momonfum (p),
(it) onorgy (I). Moroovor, n nrfIcIo occuIos n dofInIfo osIfIon In snco.
In vIow of fho nbovo fncfs, If Is rnfhor dIffIcuIf fo nccof fwo confIIcfIng Idons, fhnf rndInfIon
Is n wnvo whIch Is srond ouf ovor snco nnd nIso n nrfIcIo whIch Is IocnIIsod nf n oInf In
snco.
de-BvogIIe's quutIon (de-BvogIIe's muttev wuves)
HIs suggosfIon wns bnsod on: ns rndInfIon IIko IIghf cnn ncf somofImos ns n wnvo nnd
somofImos IIko n nrfIcIo, smnII nrfIcIos IIko oIocfron whIch nro consIdorod ns mInufo nrfIcIos
shouId nIso ncf ns wnvos for somofImos. AccordIng fo hIs hyofhosIs, nII mnffor nrfIcIos IIko
oIocfrons, rofons, noufrons, nfoms or moIocuIos hnvo nn nssocInfod wnvo wIfh fhom whIch Is
cnIIod noIIer uote or piloI uote or Je-Broglieè uote.
Tho wnvoIongfh of fho mnffor wnvo Is gIvon by
= =
I
p
I
nt
whoro 'n` Is fho mnss of fho mnforInI nrfIcIo, 't` Is fho voIocIfy nnd 'p` Is fho momonfum.
Tho nbovo oqunfIon Is known ns do-IrogIIo`s wnvo oqunfIon.
AccordIng fo fho wnvo mochnnIcnI modoI of fho nfom, nn oIocfron bohnvos ns n sfnndIng
wnvo whIch goos round fho nucIous In n cIrcuInr orbIf. Tho onIy nocossnry condIfIon for fho
osfnbIIshmonf of such n sfnfIonnry wnvo Is fhnf fho Iongfh of fho orbIf shouId bo n whoIo
numbor muIfIIo of fho wnvoIongfh of fho oIocfron ns shown In fho foIIowIng IIg. (l.l).
C-8\N-ENGCHE\ECH1-1.PM5 2
2 ENGNEERNG CHEMSTRY
If r Is fho rndIus of fho cIrcuInr orbIf, fhon
2r = n.
ow, = I/nt.
2r =
nI
nt
or ntr = nI/2
whoro n = l, 2, 3, ofc.
SInco 'ntr` Is fho nnguInr momonfum of fho oIocfron ns n
nrfIcIo, wo soo fhnf wnvo mochnnIcnI Icfuro Ionds nnfurnIIy fo
BoIrè poeIuloIe IIoI IIe ongulor nonenIun ie on inIegrol nulIiple of I/2. Ofhor qunnfum
condIfIons cnn nIso bo dorIvod sImIInrIy, i.e., fho ongulor nonenIun ie quonIieeJ.
Moroovor, fho concof of nn oIocfron ns n sfnndIng wnvo rnfhor fhnn n nrfIcIo rovoIvIng
In nn orbIf nIso romovos fho dIffIcuIfy mof In Iohr`s fhoory rognrdIng non-rndInfIon of onorgy
by fho rovoIvIng oIocfron.
TLe New AtomIc PIctuve
In Iohr`s nfomIc modoI, nucIous of nn nfom Is surroundod by nrfIcIos known ns oIocfrons,
whIch rovoIvo In dofInod shoIIs or orbIfs. ThIs modoI hns boon roIncod by wnvo mochnnIcnI
modoI, i.e., roIncod by do-IrogIIo`s oIocfron wnvo. Thoso wnvos form sfnfIonnry wnvos wIfh
fhoIr noJee nnd onIinoJee. Honco, Insfond of boIng IocnIIsod nf n oInf, fho whoIo of oIocfron
mnss nnd chnrgo Is srond ouf unIformIy fhroughouf fho snco ImmodInfoIy surroundIng fho
nucIous of fho nfom (IIg. l.2).
Af nodos whoro fho mofIon Is rncfIcnIIy zoro, fhoro Is nssumod fo bo n IIffIo or no chnrgo
whIIo nf fho nnfInodos fho nmounf of chnrgo Is mnxImum. Howovor, If Is sfIII cusfomnry fo fnIk
of orbIfs nnd shoIIs for fho sImIo ronson fhnf ovon nccordIng fo fho now Icfuro of fho nfom,
oIocfrons nro found fo dIsfrIbufo fhoIr chnrgos In such n wny fhnf somofhIng nnnIogous fo
shoIIs Is formod. ow wnvo modoI nccofs fho oIocfron dIsfrIbufIon fo bo fhroo dImonsIonnI.
O
N
M
L
K
C
h
a
r
g
e
D
e
n
s
i
t
y
Distance
Fig. 1.2 Old and new models of an atom.
OId Iohr`s modoI Is rorosonfod by orbIfs of nn nfom (Z = 3?) (IIg. l.2) nnd fho now wnvo
modoI Is rorosonfod by n grnh of shorIcnIIy symmofrIcnI oIocfronIc chnrgo wIfh sovornI
mnxImn corrosondIng fo fho dIscrofo K, !, M, shoIIs.
r
Fig. 1.1
ATOMS AND MOLECULES 3
HeIsenbevg's \ncevtuInty PvIncIpIe
Tho dunI nnfuro of fho oIocfron ImIIos fhnf nny rocIso monsuromonf of Ifs osIfIon
wouId cronfo uncorfnInfy In monsuromonf of Ifs momonfum nnd osIfIon. Tho HoIsonborg
uncorfnInfy rIncIIo sfnfos fhnf
It Is ImpossIbIe to detevmIne sImuItuneousIy botL tLe posItIon und tLe
momentum oI u puvtIcIe wItL uccuvucy.
x.p I/2.
Tho nbovo oxrossIon Is known ns uncorfnInfy roInfIon whoro x = chnngo In osIfIon,
p = chnngo In momonfum nnd I = IInnck`s consfnnf.
Tho roInfIon ImIIos fhnf n sImuIfnnoous nnd rocIso monsuromonf of bofh osIfIon nnd
momonfum (voIocIfy) of n dynnmIc nrfIcIo IIko oIocfron Is ImossIbIo nnd fho oxfonf of Inhoronf
uncorfnInfy In nny such monsuromonf Is of fho ordor of I (IInnck`s consfnnf).
\ncevtuInty PvIncIpIe und BoLv's TLeovyConcept oI PvobubIIIty
Iohr hnd osfuInfod fhnf oIocfrons rovoIvo In woII dofInod orbIfs wIfh fIxod voIocIfIos
(onorgy). Iuf nccordIng fo uncorfnInfy rIncIIo sInco nn oIocfron ossossos wnvo nnfuro, If Is
ImossIbIo fo doformIno Ifs osIfIon nnd momonfum sImuIfnnoousIy. On fho bnsIs of fhIs
rIncIIo fhoroforo Iohr`s modoI of nfom no Iongor sfnnds. Tho bosf wny Is fo rodIcf fho
robnbIIIfy of fIndIng nn oIocfron wIfh robnbIo voIocIfy wIfh dofInIfo onorgy In n gIvon rogIon
of snco In gIvon fImo. Thus fho uncorfnInfy rIncIIo whIch gIvos fho wnvo nnfuro of fho
oIocfron onIy rovIdos robnbIIIfy of fIndIng nn oIocfron In n gIvon snco. If Is for fhIs ronson
fho cInssIcnI concof of Iohr`s modoI of nfom hns boon roIncod by proIoIiliI, opproocI.
ScLvdIngev Wuve quutIon
If Is n dIfforonfInI oqunfIon cnnbIo of doscrIbIng fho mofIon of nn oIocfron. In nn ordInnry
mnforInI wnvo fho dIsIncomonf of whnfovor Is vIbrnfIng nbouf Ifs monn osIfIon Is gIvon by
, = o sIn 2 fI
x
.
0
/
1
...(l)
whoro, , = dIsIncomonf nf fImo I nnd nf dIsfnnco x from orIgIn.
o = mnxImum dIsIncomonf from monn osIfIon.
= wnvoIongfh.
f = froquoncy of vIbrnfIon.
Whon dIfforonfInfod fwIco wIfh rosocf fo x, If bocomos
J ,
Jx
,
2
2
2
2
4
0 + =
...(2)
or
J ,
Jx
l ,
2
2
2
0 + = ...(3)
Tho nbovo oqunfIon InvoIvos onIy dIsfnnco ns fho Indoondonf vnrInbIo. Ifs soIufIon Is
, = o sIn 2 x/ whIch dofInos n sfnndIng wnvo. Af onch oInf nIong fho wnvo In snco, , vnrIos
orIodIcnIIy wIfh froquoncy f.
!of us now soo how fhIs oqunfIon cnn bo nIIod fo socIfy nn oIocfron In mofIon. As wo
know, fho fofnI onorgy I of nn oIocfron Is nrfIy kInofIc nnd nrfIy ofonfInI.
I =
l
2
nt
2
+ V
nt = 2n(I V) .
ow, do-IrogIIo wnvoIongfh Is gIvon by
= =
I
nt
I
n 2 (I V)
.
SubsfIfufIng fhIs vnIuo In oqunfIon (l) nnd roIncIng , by ns Is cusfomnry, wo gof

J
Jx
n
I
2
2
2
2
8
0

+ = (I V) ...(4)
Tho oqunfIon (4) Is known ns fho fImo-Indoondonf ScLvdIngev equutIon In ono
dImonsIon. Ior fhroo-dImonsIonnI mofIon of nn oIocfron, fhIs oqunfIon bocomos,
J
Jx
J
J,
J
Jc
n
I
2
2
2
2
2
2
2
2
8
0

+ + + = (I V)
or + =
2
2
2
8
0
n
I
(I V) ...(5)
ThIs SchrodIngor oqunfIon Is n bnsIc oqunfIon of wnvo mochnnIcs. As, p = nf Is n sfnrfIng
oInf of cInssIcnI mochnnIcs. If Is soon from oqunfIons (3) nnd (4) fhnf
l
2
=
8
2
2
n
I
(I V) ...(6)
So, SchrodIngor oqunfIon cnn bo omIoyod for doformInIng fho fofnI onorgy of nn oIocfron.
Tho ofonfInI onorgy V of nn oIocfron Is socIfIod In forms of snco co-ordInnfo nof on fImo, i.e.,
SchrodIngor wnvo oqunfIon Is fImo Indoondonf. !Iko ofhor dIfforonfInI oqunfIon, fho SchrodIngor
wnvo oqunfIon Is nIso govornod by boundnry condIfIons. ConornIIy Ifs soIufIons nro onIy nffnInod
for corfnIn onorgy vnIuos cnIIod chnrncforIsfIc or eigen toluee. Tho corrosondIng wnvo funcfIon
whIch Is gonornIIy comIox Is cnIIod chnrncforIsfIc or eigen funcIion. So, wo cnn wrIfo,
= o + iI nnd Ifs conjugnfo * = o iI nnd fhoIr roducf, .* = (o iI) (o + iI) = o
2
+ I
2
, whIch
Is ronI.
Ior n ono dImonsIon sysfom, |
2
|Jx rorosonfs fho robnbIIIfy of fIndIng nn oIocfron
wIfhIn n rnngo of x nnd x + Jx. Iuf In fhroo dImonsIon sysfom |
2
|JV rorosonfs fho robnbIIIfy
of nn oIocfron wIfhIn fho voIumo rnngo of V fo (V + JV).
SIgnIIIcunce oI und
2
donofos fho nmIIfudo of n fhroo dImonsIonnI sfnfIonnry oIocfron wnvo.
AccordIng fo fho HoIsonborg`s uncorfnInfy rIncIIo, If Is ImossIbIo fo Iocnfo nn oIocfron
In nn nfom wIfh rocIsIon buf fho nnfuro of fho wnvo funcfIon Is such fhnf ||
2
oxrossos fho robnbIIIfy of fIndIng nn oIocfron In n dofInIfo voIumo of snco nround
fho nucIous. ThIs mnfhomnfIcnI oxrossIon dIsInys how fho robnbIIIfy of fIndIng nn
oIocfron vnrIos In snco. Tho fofnI robnbIIIfy of fIndIng nn oIocfron In snco oxfondIng
fo InfInIfy Is oxrossod ns foIIows:
2
l JV
=
whoro JV = Jx.J,.Jc. ThIs Is known ns fho conJiIion of nornolieoIion nnd fho
corrosondIng wnvo funcfIon Is snId fo bo normnIIsod. Iocnuso of fho shorIcnI
symmofry of nn nfom fho wnvo funcfIons nro mosf snfIsfncforIIy oxrossod In forms of
shorIcnI oInr co-ordInnfo sysfom wIfh nucIous nf fho orIgIn, chnngIng from fho CnrfosInn
co-ordInnfos fo oInr co-ordInnfos, fho SchrodIngor wnvo oqunfIon nssumos fho foIIowIng
form.
l l l
8 0
2
2
2 2
2
2 2
2
r r
r
r r r

.
0
/
1
+ +
.
0
/
1
+ =
sIn sIn
. sIn . (I V) ...(A)
whoro r, nnd nro fho oInr co-ordInnfos of fho oIocfron wIfh rosocf fo fho nucIous
() ns orIgIn |soo IIg. l.3 (o) nnd (I)].
N
E
f
r
m
q
e
(a)
E N
j
q
m
e
r
(b)
Fig. 1.3
If cnn bo shown mnfhomnfIcnIIy fhnf onch ormIffod soIufIon of fho wnvo oqunfIon (A)
i.e., wnvo funcfIon (r, , ) cnn bo oxrossod ns
(r, , ) = !
(r)
.
()
.
()
whoro, !
(r)
Is n funcfIon fhnf doonds on fho dIsfnnco from nucIous, whIch doonds on fho
qunnfum numbor n, l (fho rIncInI nnd nzImufhnI qunnfum numbors, rosocfIvoIy). Tho
funcfIon
()
Is funcfIon of doondIng on nzImufhnI qunnfum numbor (l) nnd mngnofIc qunnfum
numbor (n
l
).
()
Is n funcfIon of whIch doonds on mngnofIc qunnfum numbor (n
l
). Tho
fofnI wnvo funcfIon (r, , ), whIch gIvos fho fofnI robnbIIIfy of fIndIng nn oIocfron Is cnIIod
fho oIonic orIiIol. Tho wnvo funcfIon (r, , ) Is donofod ns n roducf of fwo funcfIons,
(i) rndInI wnvo funcfIon nnd (ii) nnguInr wnvo funcfIon.
Tho roJiol uote funcIion !
(r)
shows fho vnrInfIon of wnvo funcfIon wIfh r kooIng nnd
consfnnfs i.e., If rorosonfs fho vnrInfIon of In fho snmo dIrocfIon. Tho ongulor uote funcIion
Is n joInf funcfIon nnd whIch doformInos fho vnrInfIon of In dIfforonf dIrocfIons nf n fIxod
rndInI dIsfnnco r.
Ior nny e orbIfnI (le, 2e, 3e, ofc.), fho nnguInr nrf of fho wnvo funcfIon Is nIwnys fho
snmo whnfovor bo fho rIncInI qunnfum numbor n. Tho nnguInr doondonco of p-orbIfnI Is
nIso nof InfIuoncod by fho rIncInI qunnfum numbor. ThIs Is nIso snmo for J-orbIfnI.
HIgLIIgLt: Ior n smnII nrfIcIo IIko nn oIocfron movIng In fhroo dImonsIon In fho fIoId of
nucIous, fho SchrodIngor wnvo oqunfIon Is

2
2
2
2
2
2
2
2
8
0
x , c
n
I
+ + + = (I V)
whoro n = mnss of fho oIocfron,
(conIJ...)
V = ofonfInI onorgy of fho oIocfron,
I = fofnI onorgy of fho oIocfron,
I = IInnck`s consfnnf,
= wnvo funcfIon or fho oIgon funcfIon of fho oIocfron rorosonfIng fho
nmIIfudo of fho wnvo nssocInfod wIfh fho oIocfron,
x, ,, c = co-ordInnfos of fho oIocfron.
Tho soIufIon of fho nbovo socond ordor dIfforonfInI oqunfIon furnIshos fho vnIuos of I, fho
qunnfIsod or nIIowod or ormIffod onorgIos of oIocfrons nnd Is fho wnvo funcfIon.
AIfornnfIvoIy, fho soIufIon of fho nbovo oqunfIon roducos fho oIocfron dIsfrIbufIon In
snco ns woII ns fho nIIowod onorgy sfnfo of fho oIocfron. Whon fhIs oqunfIon Is nIIod fo
hydrogon nfom, If Is found fhnf fho oqunfIon cnn bo soIvod whon I nssumos corfnIn vnIuos
whIch nro roInfod by Infogors. Honco, fho concof of qunnfIsod onorgy IovoIs nnd qunnfum
numbors nro fho consoquoncos of fho wnvo fhoory.
AppIication of Schrdinger Equation
PuvtIcIe In u box IIIustvutIng enevgy quuntIzutIon (IIke eIectvons In metuIs)
!of us consIdor n nrfIcIo of mnss n whIch Is froo fo movo In n one Jineneionol Iox of
Iongfh l ns shown In IIg. l.4.
V=0
x=0 x=L
V V

n=3
n=2
n=1
0 L
| | y
2
n=1
n=3
n=2
0 L
y[x]
(a) (b) (c)
Fig. 1.4
Tho ofonfInI onorgy V of fho oIocfron nf fho boffom of fho box Is consfnnf, mny bo fnkon
ns zoro. Honco, InsIdo fho box V = 0.
!of fho ofonfInI onorgy bo InfInIfo for x < 0 nnd x > l. So, funcfIon hns fo bo zoro nf
x = 0 nnd for nII nognfIvo vnIuos of x, sInco fho nrfIcIo Is nof nIIowod ovor fho wnIIs of fho box.
SImIInrIy, funcfIon musf bo zoro for nII vnIuos x > l. AIfornnfIvoIy, If cnn bo sfnfod fhnf fho
nrfIcIo Is confInod fo fho box nnd cnnnof oxIsf oufsIdo.
A gonornI soIufIon of SchrodIngor oqunfIon Is:
(x) = o sIn lx + I cos lx
Ior boundnry condIfIons, wo hnvo,
(x) = 0 nf x = 0 or (0) = 0
0 = o sIn 0 + I cos 0 or I = 0
AIso (x) = 0 nf x = l
o sIn ll + I cos ll = 0
If cnn onIy bo ossIbIo whon,
ll = n or l =
n
l
whoro x Is cnIIod quonIun nunIer nnd Is oqunI fo l, 2, 3 ... .

SubsfIfufIng fhIs vnIuo In oqn. 4 nnd nIso uffIng V = 0; wo gof,

n
l
n
I
2 2
2
2
8
= I
So, (I, fho fofnI onorgy of fho oIocfron) = K.I. of fho oIocfron.
I
n
=
n I
nl
2 2
2
8
whoro n = l, 2, 3 ... .
Tho nbovo oqunfIon monns fhnf fho nrfIcIo In n box doos nof ossoss nny nrbIfrnry
nmounf of onorgy, rnfhor If ossossos dIscrofo sof of onorgy vnIuos i.e., Ifs onorgy Is qunnfIsod.
A fow onorgy IovoIs nro gIvon boIow:
I
l
=
I
nl
2
2
8
I
2
=
4
8
2
2
I
nl
I
3
=
9
8
2
2
I
nl
Tho ronson why n nrfIcIo In n box i.e., bound nrfIcIo ossossos
n qunnfIsod onorgy whorons n froo nrfIcIo doos nof, cnn onsIIy bo
doducod from fho nbovo oqunfIon.
HIgLIIgLt: CnIcuInfIon of mInImum onorgy of n nrfIcIo In n box from HoIsonborg`s
uncorfnInfy rIncIIo.
Horo x = l, nnd fho nrfIcIo bouncos bnck In fho box. So, p = 2p bocnuso fho momonfum
chnngos from + p fo p confInuousIy. So wo cnn wrIfo,
x p = l . (2p) = I or, p =
I
l 2
ow, I =
l
2
nt
2
=
( ) nt
n
p
n
2 2
2 2
=
I =
I
nl
2
2
8
.
PROBABILITY DISTRIBUTION
Tho dIrocfIonnI roorfIos of nn oIocfIon In nn orbIfnI of fho hydrogon nfom cnnnof bo rorosonfod
In ono dIngrnm. Two sonrnfo dIngrnms nro roquIrod fo moof fho domnnd.
E
3
E
2
E
1
n=3
n=2
n=1
x=0 x=L
0
E
n
e
r
g
y
Fig. 1.5
Thoso nro nnmoIy (i) nn ongulor proIoIiliI, JieIriIuIion i.e., how fho nnguInr osIfIon
vnrIos from nucIous wIfh rosocf fo n fIxod nxIs nnd (ii) n roJiol proIoIiliI, JieIriIuIion i.e.,
how r, fho dIsfnnco from fho nucIous doos vnry.
(i) Angulor proIoIiliI, JieIriIuIione of orIiIole i.e., eIopee or IounJor, eurfocee of orIiIole
gIvos fho robnbIIIfy of fIndIng nn oIocfron In n nrfIcuInr dIrocfIon.
An e-elecIron hns no roforrod dIrocfIon In snco i.e., fhoro Is nn oqunI chnnco of fIndIng
If In nny dIrocfIon nround fho nucIous. ThIs Is grnhIcnIIy shown In IIg. l.6 boIow.
+ x
y
z
Fig. 1.6
In fhIs dIngrnm, fho nucIous of fho nfom Is nf fho orIgIn nnd fho surfnco of fho shoro
rorosonfs fho robnbIIIfy of fIndIng fho e-oIocfron whIch Is fhoroforo snmo In nII dIrocfIons.
A p-IovoI hns nn nccommodnfIon for sIx oIocfrons dIsfrIbufod ovor fhroo p-orbIfnIs fo
onch vnIuo of fho rIncInI qunnfum numbor. Thoso fhroo orbIfnIs nro nf rIghf nngIos fo onch
ofhor nnd fho fhroo nnguInr robnbIIIfy dIsfrIbufIons nro shnod IIko dumb-boIIs nIong fho
fhroo co-ordInnfo nxos nnd nro nnmod ns p
x
, p
,
nnd p
c
orbIfnIs. In fho nbsonco of mngnofIc fIoId
fhoso orbIfnIs nro oquIvnIonf In onorgy confonf nnd nro snId fo bo Iripl, JegeneroIe. In fho
rosonco of oxfornnI mngnofIc fIoId fhoso vnry In fhoIr onorgy confonf doondIng on fho mngnofIc
qunnfum numbor. Tho dIfforonf shnos nro shown In IIg. l.? boIow.
p
x
y
z
x +
+
p
y
x
y
z
p
z
x
y
z
+
(a) (b) (c)

Fig. 1.7
If Is mosf IIkoIy fhnf In fho p
x
orbIfnI fho oIocfron wIII bo found In fho dIrocfIon of x-nxIs
nnd fhoro Is no chnnco of If fo bo found In nny of fho dIrocfIons orondIcuInr fo x-nxIs i.e., ,-c
Inno In fhIs cnso Is nodnI Inno wIfh zoro oIocfron donsIfy. SImIInrIy, In fho cnso of p
,
nnd p
c
orbIfnIs fho oIocfron wIII bo found nIong , nnd c nxos.
Tho nnguInr robnbIIIfy dIsfrIbufIon of fIvo J-orbIfnIs fhnf cnn nccommodnfo fon oIocfrons
Is quIfo comIIcnfod. Thoso fIvo orbIfnIs nro nnmod ns J
x,
, J
,c
, J
xc
, J
x ,
2 2
, J
c
2 . Thoso nro shown
In IIg. l.8 boIow.
d
xy
x
y
z
+
+
(a)
d
yz
x
y
z
+
+
(b)
d
xz
x
y
z
+
+
(c)
d
z
2
x
y
z
+
+
x-y plane
x-y plane
Negative
dough nut in
(d)
p
x y
2 2
x
y
z
+ +
(e)
Fig. 1.8
AII fho J-orbIfnIs nro oquIvnIonf In onorgy In fho nbsonco of mngnofIc fIoId nnd nro snId
fo bo fite folJ JegeneroIe.
Tho sof of fho fhroo orbIfnIs nnmoIy J
x,
, J
,c
, J
cx
hnvo fhoIr Iobos IyIng symmofrIcnIIy In
bofwoon fho co-ordInnfod nxos IndIcnfod by fho subscrIfs fo J, e.g. fho Iobos of J
x,
orbIfnI nro
oInfIng or IyIng In bofwoon fho x nnd , nxos. ThIs sof Is roforrod fo ns I
2g
sof.
Tho sof of fwo orbIfnIs i.e., J
x ,
2 2
nnd J
c
2

orbIfnIs form e
g
sof hnvIng fhoIr Iobos nIong
fho nxos, e.g. Tho Iobos of J
x ,
2 2
orbIfnI IIo nIong fho x nnd , nxos whIIo fhoso of Jc

2
orbIfnI IIo
nIong c-nxIs.
(ii) TIe IoJiol ProIoIiliI, JieIriIuIionTho nnguInr robnbIIIfy grnhs IndIcnfo fho
mosf robnbIo dIrocfIons of fho oIocfrons buf fhoy do nof gIvo nny IndIcnfIon of fho robnbIo
dIsfnnco of fho oIocfron from fho nucIous. Tho robnbIo dIsfnncos of nn oIocfron nro gIvon by
roJiol proIoIiliI, JieIriIuIion dIngrnm whIch nro gIvon In IIg. l.9.
In fhoso dIngrnms, fho robnbIIIfy of fIndIng nn oIocfron nf n dIsfnnco r from fho nucIous
Is Ioffod ngnInsf r (dIsfnnco from fho nucIous) fo gof le, 2e, 2p, 3e, 3p nnd 3J orbIfnIs of
hydrogon nfom.
HIgLIIgLts:
Tho robnbIIIfy of fIndIng nn oIocfron nf fho orIgIn Is zoro whIch Is fho nucIous.
ThIs monns fho oIocfron cnn novor bo nf nucIous.
Tho vnIuo of r whIch Is fho mnxImum robnbIIIfy In fho grnh of le dIsfrIbufIon
ngroos wIfh fho vnIuo of r of Iohr`s orbIf of hydrogon nfom (0.528).
Tho dIsfrIbufIons vnry nccordIng fo fho rIncInI qunnfum numbor. Tho Inrgor fho
vnIuo of fho rIncInI qunnfum numbor fho fnrfhor Is fho oIocfron from fho nucIous
ns fho nnguInr robnbIIIfy dIsfrIbufIon romnIns unoffocfod by fho vnIuo of rIncInI
qunnfum numbor.
AII fhoso fncfs nro bnsod on fho roor InforrofnfIon of SchrodIngor wnvo oqunfIon.
P
r
o
b
a
b
i
l
i
t
y
Distance r
r
0
1 2
(a)
1s
P
r
o
b
a
b
i
l
i
t
y
Distance r
(b)
2s
0 r
1
2
r
2
4 6 8
P
r
o
b
a
b
i
l
i
t
y
Distance r
(c)
2p
P
r
o
b
a
b
i
l
i
t
y
Distance r
(d)
3s
0
2 4 6 8 0
2 4 6 8 10
12
P
r
o
b
a
b
i
l
i
t
y
Distance r
(e)
3p
P
r
o
b
a
b
i
l
i
t
y
Distance r
(f)
3d
Fig. 1.9 Radial probability distribution of 1I 2I 2F 3I 3F and 3@ orbitals.
EXERCISES
1. Whnf do you monn by wnvo nnfuro of nn oIocfron
2. CIvo fho do-IrogIIo`s wnvo oqunfIon
3. CorroInfo Iohr`s osfuInfo of nnguInr momonfum wIfh fho wnvo mochnnIcnI modoI.
4. CIvo fho now Icfuro of nn nfom.
5. WrIfo HoIsonborg`s uncorfnInfy rIncIIo.
6. WrIfo how fho uncorfnInfy rIncIIo Ionds fo robnbIIIfy nronch.
?. WrIfo SchrodIngor wnvo oqunfIon for ono dImonsIon.
B. WrIfo SchrodIngor wnvo oqunfIon for fhroo dImonsIon.
9. Whnf nro oIgon vnIuos nnd oIgon funcfIons
10. CIvo fho robnbIIIfy oxrossIon for fIndIng nn oIocfron In fho voIumo rnngo of V nnd V + JV.
11. MonfIon fho sIgnIfIcnnco of nnd
2
.
12. WrIfo fho SchrodIngor wnvo oqunfIon usIng oInr co-ordInnfos.
13. AIy SchrodIngor wnvo oqunfIon for nrfIcIo In ono dImonsIonnI box IIIusfrnfIng onorgy
qunnfIsnfIon.
14. rnw nnguInr nnd rndInI robnbIIIfy dIsfrIbufIons of 2e, 3p, 3J orbIfnIs.
12
VaIency and ChemicaI Bonding

Afoms of oIomonfs combIno fo form moIocuIos of comounds. urIng chomIcnI combInnfIon,
fho oIocfrons of fho nfoms ronrrnngo fo form fho moIocuIo of fho comound. Tho oIocfrons
romnIn In fho K, !, M nnd shoIIs In fho nfoms. Tho nfoms confnInIng oIghf oIocfrons In fho
ouformosf shoII cnnnof nrfIcInfo In fho chomIcnI combInnfIon nnd nro known ns Inorf oIomonfs.
Tho oIocfrons of fho ouformosf shoII of nn nfom fnko nrf In n chomIcnI combInnfIon nnd nro
cnIIod tolence elecIrone.
Tho Inorf oIomonfs, tic. Ho, o, Ar, Kr, !n nnd Xo, hnvo oIghf oIocfrons In fhoIr ouformosf
shoIIs oxcof Ho. Tho ofhor oIomonfs hnvo Ioss fhnn oIghf oIocfrons In fhoIr ouformosf shoIIs
nnd fhoy wnnf fo comIofo fhoIr ouformosf shoIIs wIfh oIghf oIocfrons (ocfof fhoory) fo gnIn fho
oIocfronIc sfrucfuro of fho Inorf gnsos. ThIs Is n vory common nnfuro of fho nfoms nnd for fhIs
snko, nfoms oIfhor Ioso or gnIn oIocfrons or shnro nnd fhIs Idon of oIocfronIc nrrnngomonf Is fho
bnsIs for elecIronic IIeor, of tolenc,. Thoro nro fhroo fyos of vnIoncIos
(i) 1lecIrotolenc, or 1onictolenc,
(ii) Cotolenc,
(iii) Co-orJinoIe cotolenc,.
IectvovuIency: n nfom hns gof oIocfronIc sfrucfuro 2, 8, l nnd CI nfom hns gof
oIocfronIc sfrucfuro 2, 8, ?. n nfom cnn nffnIn Inorf gns sfrucfuro by IosIng ono oIocfron
nnd CI nfom cnn nffnIn Inorf gns sfrucfuro by gnInIng fhnf oIocfron. ThIs sorf of frnnsfor of
oIocfron from ono nfom fo fho ofhor rosuIfs In fho formnfIon of n
+
nnd CI
Ions. Thoso Ions

romnIn combInod duo fo oIocfrosfnfIc forco of nffrncfIon bofwoon fho so-formod Ions. Tho
honomonon cnn bo rorosonfod IcforInIIy ns In IIg. 2.l.
+
Na Cl Na
+
Cl
Fig. 2.1
ThIs fyo of combInnfIon of fwo nfoms by comIofo frnnsfor of oIocfrons from fho
ouformosf shoII of ono nfom fo fho ofhor Is known ns elecIrotolenc,. Ofhor oIocfrovnIonf
comounds hnvo boon rorosonfod ns foIIows by JoI-croee neIIoJ.
VALENCY AND CHEMCAL BONDNG 13
Some exumpIes oI eIectvovuIent compounds :
Ca:
Br
Br
Ca
++
Br

Br
.
(CaBr )
2
+
Cn 2Ir Cn . 2Ir
(2, 8, 8, 2) 2(2, 8, l8, ?) (2, 8, 8) 2(2, 8, l8, 8)
+ =
++
SImIInrIy
2K 2K
2 2, 8 8 l 2, 8 6 2 2, 8 8 2, 8 8 ( , , ) ( , ) ( , ) ( , )
+ =
+
S S (K
2
S)
Mg
2(2, ?) 2(2, 8)
( , ) ( ) 2, 8 2 2, 8
2I 2I + =
++
g (MgI
2
)
HIgLIIgLt: IIocfrovnIoncy Is soon In fho cnso of nfoms wIfh n mnrkod dIfforonco In
oIocfronognfIvIfy vnIuos whon fhoy combIno.
CovaIency
Whon nfoms, of snmo or moro or Ioss snmo oIocfronognfIvIfy vnIuos, combIno fo form
moIocuIos of n comound fhoy shnro fho oIocfrons fo fIII u fhoIr ocfofs In fhoIr ouformosf
shoIIs. ThIs sorf of combInIng of nfoms Is known ns cotolenc,.
xumpIes oI covuIent compounds :
Cl
+ Cl

Cl

Cl

.
Cl
Cl

C
.
. .
Cl
+ + Cl

Cl

Cl

C
.
Cl
Cl

.
.
.
+
Chlorine
molecule
Carbon tetrachloride
molecule
+
CompuvIson oI eIectvovuIent und covuIent compounds:
1lecIrotolenI ConpounJe CotolenI ConpounJe
(i) Thoy nro on-dIrocfIonnI. (i) Thoy nro dIrocfIonnI In nnfuro.
(ii) Thoy cnnnof oxhIbIf IsomorIsm. (ii) Thoy cnn show IsomorIsm.
(iii) m.. nnd b.. nro hIgh. (iii) m.. nnd b.. nro Iow.
(it) Thoy nro conducfors of oIocfrIcIfy (it) Thoy nro nonconducfors of oIocfrIcIfy
In soIufIon or In fhoIr moIfon sfnfo. In soIufIon or In moIfon sfnfo.
(t) Thoy nro soIubIo In oInr soIvonfs (H
2
O) (t) Thoy nro soIubIo In orgnnIc soIvonfs,
nnd InsoIubIo In non-oInr soIvonfs gonornIIy InsoIubIo In wnfor.
(C
6
H
6
, CCI
4
).
(ti) Thoy nro oInr In nnfuro. (ti) Thoy nro non-oInr In nnfuro.
Co-ordinate CovaIency
In covnIoncy fho bondIng nfoms confrIbufo oqunI numbor of oIocfrons fo form n bond. In
somo cnsos durIng chomIcnI combInnfIons, n nIr of oIocfrons Is boIng confrIbufod by n sIngIo
nfom. Tho ofhor nfom confrIbufos no oIocfron fownrds fho bond. Affor combInnfIon fho bond
ncfs ns n uroIy covnIonf bond. ThIs sorf of bond formnfIon Is known ns co-orJioIe cotolenc,.
Tho nfom whIch donnfos n nIr of oIocfrons Is known ns 'Jonor` nfom nnd fho nfom whIch
nccofs fho nIr of oIocfrons Is known ns 'occepIor` nfom. Tho donor nfom shouId hnvo n Iono
nIr of oIocfrons. Tho honomonn cnn bo rorosonfod ns foIIows:
A . + . I A : I or A I (CovnIoncy)
A : + I A : I or A I (Co-ordInnfo covnIoncy)
Tho co-ordInnfo covnIoncy Is IndIcnfod by fho sIgn '`.
Some exumpIes oI coovdInute bond IovmutIon:
.
N
.
H
.
H H
+
.
N
.
H
.
H
H
H
.
.
+
Ammonium ion
(NH )
4
+
.
O
.
H
.
H H
+
.
O
.
H
.
H H
.
.
+
Hydronium ion
(H )
3
+
O
.
B
.
F
.
F F F
(BF )
4
H
F
.
.
.
.
. .
. . .
B
.
F
.
F
F
.
.
.
.
.
.
. .
EIectronegativity
Tho nffrncfIon nnd rouIsIon owors of nfoms of dIfforonf oIomonfs nro nof snmo. As for
oxnmIo, I or O hns gof n gronfor fondoncy of nffrncfIng oIocfron nIrs of fho bond fownrds
fhom whon fhoy form n covnIonf bond wIfh nny ofhor nfom. In comnrIson, H nfom hns Ioss
fondoncy of fhIs sorf. Tho owor of nffrncfIng oIocfrons of ono of fho nfoms In n covnIonf bond
Is known ns Ifs elecIronegoIitiI,. ComnrnfIvo toluee of elecIronegoIitiIiee of dIfforonf oIomonfs
fnkIng fho oIocfronognfIvIfy vnIuo of H ns 2.l Is gIvon In TnbIo 2.l boIow.
TubIe 2.1: IIocfronognfIvIfy vnIuos (!. InuIIng ScnIo)
Croup 1 (1) 11 (2) 111 (13) 1V (14) V (1) V1 (16) V11 (17)
PerioJ
l H
2.l
2 !I Io I C O I
l.0 l.5 2.0 2.5 3.0 3.5 4.0
3 n Mg AI SI I S CI
0.9 l.2 l.5 l.8 2.l 2.5 3.0
4 K Cn Cn Co As So Ir
0.8 l.0 l.6 l.8 2.0 2.4 2.8
5 !b Sr In Sn Sb To I
0.8 l.0 l.? l.8 l.9 2.l 2.5
6 Cs In TI Ib II Io Af
0.? 0.9 l.8 l.9 2.0 2.0 2.2
? Ir !n
0.? 0.9
ThIs sorf of nffrncfIons gIvo fho covnIonf bond bofwoon fwo nfoms n nrfInI IonIc chnrncfor.
InrfInI IonIc chnrncfor of n covnIonf bond Is cnIcuInfod ns foIIows:
Whon oIocfronognfIvIfy vnIuos (x) of fho fwo nfoms A nnd I nro snmo, i.e., x
A
= x
I
, fho
bond A I Is l00 covnIonf. Whon x
A
x
I
, fho bond gnIns nrfInI IonIc chnrncfor nnd fho
moIocuIo AI bocomos oInr, tic. HCI. Cronfor fho dIfforonco (x
A
x
I
), gronfor Is fho IonIc
chnrncfor of fho bond. Tho roInfIon Is rorosonfod by fho oqunfIon
IonIc chnrncfor = l00
l l
l
4
2

ox ( ) x x
A I
= l6(x
A
x
I
) + 3.5 (x
A
x
I
)
2
CnIcuInfIon of nrfInI IonIc chnrncfor of HI moIocuIo:
IonIc chnrncfor In HI moIocuIo = l6(4.0 2.l) + 3.5(4.0 2.l)
2
= 43.
Hydrogen Bond
Hydrogon nfom hns gof onIy ono oIocfron. So, If cnn combIno wIfh ono nfom of n
monovnIonf nfom, tic I. If fho socond nfom Is oIocfronognfIvo, fhon oIocfron nIr of fho bond Is
shIffod fownrds fho ofhor nfom, i.e., I, duo fo Ifs gronfor oIocfron nffrncfIon owor. As n rosuIf,
fho hydrogon wIII gnIn fho osIfIvo chnrgo nrfInIIy buf fho oIocfron wIII nof bo dofnchod fofnIIy
from fho hydrogon nfom. In fhIs condIfIon, If fho chnrgod hydrogon nfom comos In confncf wIfh
sfrongIy oIocfronognfIvo oIomonf of fho ofhor moIocuIos (hydrogon of HI), fhoy nro nffrncfod
by fho hydrogon (H
+
) romnInIng In fho rovIous moIocuIo nnd n 'so-cnIIod` vnIoncy Is formod ns
If hydrogon ncfs n brIdgo bofwoon fwo oIocfronognfIvo oIomonfs. ThIs sorf of bond Is known ns
'I,Jrogen IonJ`. ThIs fyo of bond Is nof vory sfrong. Tho bond onorgy Is Ioss fhnn fhnf of
covnIonf bonds.
xumpIe oI Lydvogen bondIng In HI moIecuIes:
H F ... H F ... H F
+ + + d d d d d d d d
F ... H
+
hydrogen bond
HIgLIIgLts:
CondIfIons of hydrogon bond
(i) Hydrogon shouId bo nffnchod fo nn oIocfronognfIvo oIomonf of n covnIonf bond.
(ii) Tho nfomIc rndIus of fho oIocfronognfIvo oIomonfs shouId bo smnII.
Hydrogon bond Is soon whon hydrogon Is nffnchod fo oIocfronognfIvo oIomonfs, IIko
O, nnd I (i.e., whon nfomIc rndII nro smnII).
Hydrogen Bondings
Thoro nro fwo fyos of hydrogon bondIng: (o) 1nIernoleculor (I) 1nIronoleculor.
(o) xumpIes oI IntevmoIecuIuv Lydvogen bondIng :
(i) ...... HI ...... HI ...... HI ...... HI......
(ii) H O
H
H O
H
H O
H
H O
H
Covalent
bond
Hydrogen
bond
(iii)
H O
O N O
+
O N O
+
HO
H O
O N O
+
O N O
+
HO
(I) xumpIes oI IntvumoIecuIuv Lydvogen bondIng:
O
H N
O
O
+
O
H C H
O
Salicylaldehyde o-Nitrophenol
Properties gained by the moIecuIes due to hydrogen bonding:
(i) uo fo moIocuInr nssocInfIon nrIsIng ouf of fho InformoIocuInr hydrogon bondIng,
fho boIIIng oInfs of fho moIocuIos bocomo hIgh, i.e., voInfIIIfy bocomos Ioss.
(ii) SoIubIIIfy of fho moIocuIos In wnfor nrIsos ouf of hydrogon bondIng wIfh wnfor
moIocuIo.
H O
R
H O
H
DipoIe Moment
Ivory nfom hns gof nucIous nnd roquIsIfo numbor of oIocfrons. So wIfhIn n moIocuIo fwo
or moro osIfIvo nucIoI nro surroundod by oIocfrons nf dIfforonf Incos. So wIfhIn n moIocuIo
fhoro Is n confro of ncfIon of osIfIvo chnrgos ns woII ns confro of ncfIon of nognfIvo chnrgos.
Thoso fwo oInfs In n moIocuIo mny fnII nf fho snmo oInf or nf dIfforonf Incos In fho moIocuIo.
Whon fhoy fnII In dIfforonf Incos i.e., fwo chnrgos (+vo nnd vo) nro sonrnfod by n dIsfnnco,
fhoy dovoIo n momonf, known ns Jipole nonenI. Tho moIocuIos confnInIng fho dIoIo momonf
nro cnIIod oInr moIocuIos. If fho mngnIfudo of fho chnrgo nf fho confro of ncfIon Is e nnd
dIsfnnco bofwoon fhom Is J, fhon,
dIpoIe moment, = A @
d
e
+
e
Fig. 2.2
ConornIIy, fho chnrgo Is oxrossod In 'o.s.u.` unIf nnd fho dIsfnnco In 'cm` unIf. So fho
unIf of dIoIo momonf Is 'e.e.u-cn`. l l0
l8
eeu-cn Is known ns 1 DeI,e. And fhIs DeI,e unIf Is
usod fo oxross fho dIoIo momonf.
HIgLIIgLts:
Tho dIoIo momonf of H
2
O moIocuIo Is l.8 . i.e., Ifs dIoIo momonf Is l.8 l0
l8
eeu-cn.
HCI, H
2
O, H
3
, CH
3
OH nro oInr moIocuIos i.e., fhoIr confro of ncfIon of osIfIvo
chnrgos nnd confro of ncfIon of nognfIvo chnrgos nro nof snmo nnd fho moIocuIo Is nof
symmofrIcnI.
CI
2
, H
2
, CH
4
, C
6
H
6
, CO
2
, ofc. nro non-oInr moIocuIos. Tho moIocuIos nro symmofrIcnI,
nnd In fhoso moIocuIos confro of osIfIvo chnrgo ncfIon nnd confro of nognfIvo chnrgo
ncfIon nro nf fho snmo Inco.
i.e., J 0; 0.
Tho dIoIo momonf of n moIocuIo cnn bo cnIcuInfod from fho formuIn:
! =
l
2
2
2
l 2
2 + + cos
whoro,
l
nnd
2
= dIoIo momonfs of fho dIfforonf bonds of fho moIocuIo.
! = !osuIfnnf momonf of fho moIocuIo.
If ! Is zoro, fho moIocuIo bocomos non-oInr nnd If ! hns gof n osIfIvo vnIuo fho
moIocuIo bocomos oInr.
= AngIo bofwoon fho covnIonf bonds
Bovn-Hubev CycIe (etevmInutIon oI Iectvon AIIInIty):
TIe elecIron offiniI, of on elenenI ie IIe quonIiI, of energ, releoeeJ uIen on elecIron ie
goineJ or loeI I, on oIon in IIe goeeoue eIoIe Io forn on onion.
A A Inorgy roIonsod
oufrnI gnsoous nfom AnIon (IIocfron nffInIfy of nfom A, I )
A
( ) ( ) ( ) g e g g + +

IIocfron nffInIfy Is rorosonfod by fho 'vo` sIgn ns onorgy Is IIbornfod In fhIs cnso.
Whon onorgy Is suIIod If Is rorosonfod by '+vo` sIgn nnd cnIIod socond oIocfron nffInIfy (I
2
).
Iorn-Hnbor cycIo Is rorosonfod dIngrnmmnfIcnIIy wIfh fho fornoIion of AoCl (e) fron
Ao (e) onJ
1
2
Cl
2
(g) by dIrocf combInnfIon fo doformIno oIocfron nffInIfy of 'CI` nfom:
Na(s) +
1
2
Cl (g)
2
Q = 98.2 kcal
NaCl(s)
Crystal
S = +26.0 kcal
Na(g)
Na (a)
+
Cl (g)
I = +118.0 kcal
( e)
Cl(g)
1
2
D = +28.9 kcal
U = 180.4 kcal
0
Determination of electron
affinity of Na atom.
U Lattice energy of
NaCl crystal.
0

E = ? (+e)
Q = S +
l
2
+ I + I + !
0
98.2 = + 26 + 28.9 + ll8 + I l80.4
I = 90.? kcnI/g nfom of CI
ognfIvo sIgn IndIcnfos fhnf onorgy Is roIonsod In fho formnfIon,
CI(g) CI
(g)
HIgLIIgLts:
Iorn-Hnbor cycIo Is n fhormochomIcnI cycIo fhnf cnn bo usod fo cnIcuInfo fho InffIco
onorgy for n comound of n mofnI wIfh n nonmofnI.
Tho cycIo Is nn nIIcnfIon of Hoss`s !nw (soo Chnfor 4).
A Iorn-Hnbor cycIo cnn nIso hoI fo doformIno whofhor fho bondIng In n comound
Is fruIy IonIc.
Tho InffIco onorgy for nCI Is ?80 kJ moI
l
, fhnf for KCI Is ?ll kJ moI
l
nnd fhnf
for AgCI Is 905 kJ moI
l
cnIcuInfod ns or Iorn-Hnbor cycIo. Tho InffIco onorgy for
AgCI Is gronfor fhnn fhnf of IonIc bondIngs In nCI nnd KCI IndIcnfIng fhnf fhoro Is
n confrIbufIon of covnIonf bondIng In AgCI.
Wo hnvo ufIIIsod Iorn-Hnbor cycIo In doformInIng fho oIocfron nffInIfy of 'CI` nfom.
ChemicaI Bonding (Wave-MechanicaI Concept)
Tho cInssIcnI concof of covnIoncy doosn`f gIvo nny Idon of fho dIrocfIonnI chnrncforIsfIc
of n bond nnd nIso of fho bond onorgy. Tho nIIcnfIon of wnvo mochnnIcs gIvos n snfIsfncfory
oxInnnfIon of somo of fhoso robIoms. In fhIs connocfIon, fwo mnIn nronchos nro
l. VnIonco-bond fhoory
2. MoIocuInr orbIfnI fhoory.
MoIocuInr orbIfnI fhoory Is gnInIng much Imorfnnco. Iofh fho fhoorIos ndmIf fhnf
(i) A covnIonf bond Is formod ns n rosuIf of ovorInIng of fho nfomIc orbIfnIs,
(ii) Whon fho ovorInIng fnkos Inco nIong fho nxos of fho nfomIc orbIfnIs mnxImum
ovorInIng of nfomIc orbIfnIs cnn occur,
(iii) MnxImum ovorInIng gIvos n sfrong bond known ns eigno () IonJ.
H H H H :
Fig. 2.3 Formation of H
2
molecule by the overlapping of
two 1I atomic orbitals of two H atoms.
(it) Inch covnIonf bond roquIros ovorInIng of n nIr of orbIfnIs.
(t) Tho ovorInIng orbIfnIs musf bo vnIonco orbIfnIs nnd musf confnIn nn odd oIocfron.
ScLemutIc vepvesentutIon oI tLe IovmutIon oI some sImpIe moIecuIes on tLe busIs oI
vuIence bond tLeovy:
(i) e-e ovorInIng H
2
moIocuIo
(ii) e-p ovorInIng fho formnfIon of HI, H
3
, H
2
O moIocuIos
(i) HI moIecuIe
H + H
F
F
Fig. 2.4 (a) Formation of HFmolecule.
(ii) NH
3
moIecuIe
NH molecule
3
+
+
+
+z
+
+
y
z
+
+
+
+
N
2p
x
2p
y
2p
z
1s
1s
1s
+
+
z
H
Fig. 2.4 (b) Formation of NH
3
molecule.
Horo fho ovorInIng fnkos Inco bofwoon fho fhroo (2p) orbIfnIs of nIfrogon nfom wIfh
le orbIfnI of onch hydrogon nfom. If If woro fho cnso, fhon bond nngIo In H
3
shouId bo 90. Iuf
ncfunIIy bond nngIo In H
3
Is l06 45. So somo ofhor concof bocomos ossonfInI fo oxInIn fho
formnfIon of H
3
moIocuIo. Thnf concof Is fho concof of I,IriJicoIion.
(iii) Wutev moIecuIe
y
x
z
+
1s
+
y
x
z
1s
H O molecule
2
+
+
+
+ +
+
+
Fig. 2.5 Formation of H
2
O molecule.
In fhIs cnso nIso fho bond nngIo nonrs fo bo 90. Iuf fho ncfunI bond nngIo In wnfor
moIocuIo Is l04 2?. ThIs fncf nIso Ionds fo fho Idon of hybrIdIznfIon of orbIfnIs.
(it) IIuovIne moIecuIe : p-p ovorInIng fo form n -bond.
p
y
p
z
p
x
+
p
y
p
z
p
x
F atom F atom
F molecule
2
Fig. 2.6 F
N
F
N
overlapping along the axis to form F
2
molecule.
(t) N
2
moIecuIe: p-p ovorInIng fo form nnd bonds
p
y
p
z
p
y
p
z
p
y
p
z
p
y
p
z
p-bond
s-bond
p
x
Fig. 2.7 and bonds in N
2
molecule.
(o) Oterlopping of Iuo p
x
orIiIole olong IIe oxee leoJe Io IIe fornoIion of o eigno IonJ.
(I) LoIerol oterlopping of Iuo p
,
onJ p
c
orIiIole leoJe Io IIe fornoIion of Iuo IonJe.
HybvIdIzutIon: Cnrbon hns oIocfronIc confIgurnfIon: le
2
2e
2
2p
2
, buf In CH
4
, C nfoms form
four IdonfIcnI bonds wIfh H-nfom wIfh oqunI onorgy. ThIs cnn bo oxInInod onIy by fho ConcepI
of I,IriJicoIion. If wo consIdor fhnf C forms four hybrId orbIfnIs of oqunI onorgIos ouf of 2e
nnd 2p orbIfnIs nnd fhon fhoso hybrId orbIfnIs ovorIn wIfh e-orbIfnIs of H-nfoms nIong fho nxos,
fhon bond nngIo nnd bond onorgIos In CH
4
moIocuIo cnn snfIsfncforIIy bo oxInInod ns foIIows:
C-nfom (ground sfnfo)
1s 2s
2p
C-nfom (oxcIfod sfnfo)
ow fhIs ono e-orbIfnI nnd fhroo p-orbIfnIs of n cnrbon nfom mIx fo gIvo four hybrId
orbIfnIs of oqunI onorgIos, fho nxos of hybrId orbIfnIs nro dIrocfod fownrds fho vorfIcos of n
roguInr fofrnhodron (IIg. 2.8).
+ + +
s p
x
p
y
p
z
+ + +
sp
3
sp
3
sp
3
sp
3
C
109 28
sp
3
sp
3
sp
3
sp
3
hybrid orbitals
Fig. 2.8 IF
3
hybridised C atom.
ow fhoso four ep
3
hybrId orbIfnIs ovorIn nIong fho nxIs wIfh e-orbIfnIs of four H-nfoms
fo form n CH
4
moIocuIo formIng four covnIonf bonds of snmo onorgIos.
C
H
H
H
H
Fig. 2.9 CH
4
molecule.
sp
2
-hybridization
IIocfronIc confIgurnfIon of :
C in the ground state
C in the excited state
1s 2s
2p
sp
2
2p
One 2 and two 2 electrons
hybridize to give
s p
hybridization
Four unpaired
electrons
2e nnd fwo of 2p orbIfnIs hybrIdIzo Insfond of fhroo 2p orbIfnIs fo form fhroo ep
2
hybrId orbIfnIs
bocnuso fho fhroo hybrId orbIfnIs nro much moro dIrocfod. Tho hybrId orbIfnIs IIo In n Inno
nnd fho nxos nro dIrocfod fownrds vorfIcos of nn oquIInfornI frInngIo nnd so, bond nngIo In fhIs
cnso Is l20. Throo ep
2
hybrId orbIfnIs of onch C-nfom form fhroo sIgmn bonds In ofhyIono
moIocuIo.
C C
p-bond p-bond
H
H H
H
s-bond
Fig. 2.10 Ethylene molecule.
!nfornI ovorInIng of fho fwo 2p orbIfnIs of fwo C-nfoms Ionds fo fho formnfIon of n
wonk bond known ns -bond (Soo IIg. 2.l0).
HIgLIIgLts:
IfhyIono moIocuIo confnIns fIvo sIgmn bonds.
Iour sIgmn bonds nro formod duo fo ovorInIng of ep
2
-e orbIfnIs nnd ono ouf of
ep
2
-ep
2
ovorInIng. !osIdunI 2p orbIfnIs of onch ep
2
hybrIdIsod C-nfom ovorIn
InfornIIy fo form n -bond (IIg. 2.l0).
In boron frIfIuorIdo fho ep
2
hybrId orbIfnIs of I nfom ovorIn wIfh p orbIfnIs of fhroo I
nfoms nIong fho nxos fo form fhroo sIgmn bonds (IIg. 2.ll). Ioron nfom hns oIocfronIc
confIgurnfIon, le
2
2e
2
2p
l
. 2e nnd 2p hybrIdIso oIocfrons fo roduco fhroo ep
2
hybrId orbIfnIs
dIrocfod fownrds fho vorfIcos of nn oquIInfornI frInngIo.
B
sp p ( bond)
2
s
F
F
F
sp p ( -bond)
2
s
sp p ( -bond)
2
s
Fig. 2.11 Formation of triangular planar BF
3
molecule. (Another example of IF
2
hybridization).
sp-hybridization
IIocfronIc confIgurnfIon of:
C in the ground state
C in the excited state
1s 2s 2p
Four unpaired
electrons
sp hybridization
2p
p
x
p
y
p
z
Electronic configuration
of hybridized C-atom sp
In fho sfrucfuro of ncofyIono ep-hybrIdIznfIon fnkos Inco. In fho oxcIfod sfnfo of C-nfom
fhoro nro fwo hybrId orbIfnIs (ep) nnd fwo unchnngod p-orbIfnIs. urIng combInnfIon wIfh
H-nfom, fwo ep-hybrId orbIfnIs ovorIn nIong fho nxIs fo gIvo n -bond. Thon fwo C-nfoms
ossoss fofnI four unchnngod p-orbIfnIs. Thoy ovorIn InfornIIy fo gIvo fwo -bonds. So frIIo
bond of ncoIyIono moIocuIo confnIns ono -bond nnd fwo -bonds.
H H
p
p
s
p
p
H C C H
Fig. 2.12 Structure of acetylene.
In IoI
2
moIocuIo fho confrnI nfom Io hns oIocfronIc confIgurnfIon le
2
. 2e
2
In Ifs
ground sfnfo. SInco, fhoro Is no unnIrod oIocfron, fho Io nfom cnnnof form nny covnIonf bond.
In fho oxcIfod sfnfo ono of fho 2e
2
oIocfrons jums fo 2p-orbIfnI boforo formIng nny bond. ow,
fho Io nfom hns fho confIgurnfIon le
2
2e
l
. 2p
x
l
2p
,
0
2p
c
0
. Thon fhoso 2e nnd 2p
x
orbIfnIs
mIx fo gIvo fwo ep-hybrIdIsod orbIfnIs. Thoso fwo hybrId orbIfnIs noxf ovorIn wIfh porbIfnIs
of fwo I-nfoms nIong fho nxos mnkIng IoI
2
n IInonr moIocuIo (IIg. 2.l3).
sp hybridized Be atom
Be in ground state
Be in excited state
2s 2p
Two unpaired
electrons
sp hybridization with two
unpaired electrons.
2p
sp hybridized orbitals
F Be F
180
F F
Be
Fig. 2.13 Structure of BeF
2
(example of IF hybridisation).
HIgLIIgLts:
Whon orbIfnIs ovorIn nIong fho nxos, fhoro Is -bondIng. In fhIs fyo of bondIng,
chnrgo cIoud oxIsfs symmofrIcnIIy.
In doubIo bonds nnd frIIo bonds, fhoro nro InfornI ovorInIng nnd duo fo fhIs InfornI
ovorInIng fho -bonds nro formod. In fhIs fyo of bondIng, fho ovorInod chnrgod
cIoud Is nrnIIoI fo InfornucIonr nxIs.
-bonds nro comnrnfIvoIy wonkor fhnn -bonds, ns fhoy form by InfornI ovorInIng.
Honco, fho -bonds oon onsIIy nnd fnko nrf In fho chomIcnI roncfIons.
Whon fho numbor of bonds bofwoon fho nfoms Incronso fho bond onorgy Incronsos
nnd bond Iongfh docronsos.
TubIe 2.2: IsInyIng bond Iongfhs nnd bond onorgIos
Iond CC C = C C C
Iond Iongfh () l.54 l.34 l.2l l.52 l.l0
Iond onorgy (KcnI) 83 l44 l96 38 225
dsp
2
-hybridization
In fhIs fyo of hybrIdIsnfIon ono e-orbIfnI, fwo p-orbIfnIs (p
x
nnd p
,
) nnd ono J-orbIfnI
(J
x ,
2 2
) mIx fo gIvo four oquIvnIonf hybrId orbIfnIs, nxos of whIch nro dIrocfod fownrds fho
cornors of n squnro. So, fho shno of fho moIocuIo bocomos squnro Innnr nnd fho bond nngIo Is
90 (soo TnbIo 2.3).
dsp
3
or sp
3
d hybridization
In fhIs fyo of hybrIdIznfIon J
c
2 orbIfnI nnd ono e-orbIfnI nnd fhroo p-orbIfnIs mIx fo gIvo
fIvo orbIfnIs (IIg. 2.l4). Iuf In fhIs cnso, fho hybrId orbIfnIs nro nof oquIvnIonf. Tho hybrId
orbIfnIs consIsf of ono grou of fwo oquIvnIonf oosIfoIy dIrocfod orbIfnIs nnd fho socond grou
of fhroo oquIvnIonf orbIfnIs. Tho shno of fho moIocuIo wIII bo frIgonnI bIyrnmIdnI (IIg. 2.l5).
s
p
y
p
x
p
z dz
2
dsp
3
Fig. 2.14 IF
3
@ hybridization.
xumpIe oI sp
3
d LybvIdIzutIon:
P-atom in ground state
P-atom in the excited state
3s 3p
Five unpaired
electrons
sp d
3
hybridization
3d
3d
Thoso ep
3
J hybrId orbIfnIs of ono I-nfom ovorIn wIfh fIvo p orbIfnIs of fIvo CI nfoms fo
form ICI
5
. Tho shno of fho moIocuIo Is frIgonnI bIyrnmIdnI (IIg. 2.l5).
P
Cl
Cl
Cl
Cl
Cl
Fig. 2.15 Trigonal bipyramidal structure of PCl
5
.
d
2
sp
3
or sp
3
d
2
hybridization
S-atom in ground state
S-atom in excited state
3s 3p
sp
3
hybridization d
2
3d
Six unpaired
electrons
Thoso ep
3
J
2
hybrId orbIfnIs of ono S-nfom ovorIn wIfh p-orbIfnIs of sIx I-nfoms fo form SI
6
.
S
F
F F
F
F
F
Fig. 2.16 Octahedral structure of SF
6
molecule.
TubIe 2.3
Ao. of
H,IriJ SIope of
BonJ onglee 1xonple
elecIron poire
orIiIol IIe nolecule in ouIer eIell
of IIe oIon
2 ep !Inonr l80 IoI
2
, C
2
H
2
3 ep
2
TrIgonnI Innnr l20 II
3
, C
2
H
4
4 ep
3
TofrnhodrnI l09 28 CH
4
, SII
4
4 Jep
2
Squnro Innnr
90
90
90
90
90 |I (C)
4
]
2
,
(H
3
)
2
CI
2
2
5 Jep
3
TrIgonnI bIyrnmIdnI l20 nnd 90 ICI
5
,
or ep
3
J Io(CO)
5
` 6 J
2
ep
3
OcfnhodrnI 90 SI
6
,
or ep
3
J
2
Co(H
3
)
6
VSEPR Theory and MoIecuIar ModeI
If Is InforosfIng fo nofo fhnf If fho confrnI nfom In n moIocuIo Is surroundod onIy by
ovorInod bondIng orbIfnI or orbIfnIs confnInIng shnrod nIrs of oIocfrons (Iond nIrs, b) In
fho vnIonco shoII, fho moIocuIo fhon ncquIros n roguInr goomofry. Whon fho confrnI nfom
confnIns ono or moro Iono nIrs (I) of oIocfrons In fho vnIonco shoII wIfh bond nIrs (b) fho
shno of fho moIocuIo bocomos dIsforfod for mInImum onorgy nnd for mnxImum sfnbIIIfy, fho
orbIfnIs confnInIng Iono nIrs ns woII ns fho bond nIrs nro so nrrnngod fhnf fhoro Is mnxImum
rouIsIon bofwoon fhom. Tho orbIfnI confnInIng Iono nIr of oIocfrons In fho vnIonco shoII
occuIos moro snco nnd fho Iono nIr-Iono nIr rouIsIon Is gronfor fhnn fho Iono nIr-bond
nIr rouIsIon. If Is ngnIn gronfor fhnn fho bond nIr-bond nIr rouIsIon i.e., wo cnn wrIfo
I-I rouIsIon > I-b rouIsIon > b-b. rouIsIon.
ow, If fho dIsfrIbufIon of fho orbIfnIs nbouf fho confrnI nfom of fho moIocuIo cnn bo
rodIcfod, IIe eIope of IIe nolecule onJ IonJ ongle no, Ie preJicIeJ.
ThIs Is fho bnsIs of Volence SIell 1lecIron Poir Iepuleion (VS1PI) IIeor,.
Cuse I CenIrol oIon eurrounJeJ I, Iuo IonJing poire.
Tho fwo bondIng nIrs romnIn ns nnrf ns ossIbIo. Tho bond nngIo Is l80. IxnmIo:
IoI
2
.
Cuse II. TIe cenIrol oIon eurrounJeJ I, IIree IonJ poire. Thoy romnIn ns nnrf ns
ossIbIo nnd fho bond nngIo Is l20.
Cuse III. CenIrol oIon eurrounJeJ I, four IonJ poire.
IxnmIo mofhnno. Horo fhoro nro four bond nIrs nnd fho shno
of fho moIocuIo Is fofrnhodrnI.
In nII fho nbovo cnsos fhoro woro onIy bond nIrs In fho
moIocuIos nnd fho moIocuIos hnvo n roguInr goomofry.
Cuse IV. Molecule conIoining lone poir onJ IonJ poir.
IxnmIo nmmonIn moIocuIo:
Tho goomofry of fho moIocuIo Is dIsforfod fofrnhodron. In H
3
, fhoro Is ep
3
hybrIdIznfIon
nnd ono hybrId orbIfnI confnIns Iono nIr of oIocfrons.
Iuf fho bond nngIo horo Is l0?. Horo I-b rouIsIon Is
gronfor fhnn fho b-b rouIsIon. So fho bond nngIo Is roducod
(l0?) nnd If wo ovorIook fho fourfh cornor of fofrnhodron occuyIng
nn orbIfnI confnInIng nn unshnrod nIr of oIocfrons, fho shno of
fho moIocuIo bocomos yrnmIdnI (IIg. 2.l?).
H
2
O moIecuIe:
Horo O-nfom Is ep
3
hybrIdIzod nnd onIy fwo H-nfoms occuy fho fwo cornors of n
fofrnhodron. Tho ofhor fwo cornors of fho fofrnhodron Is occuIod by fho fwo ep
3
hybrId orbIfnIs
confnInIng unshnrod nIrs of oIocfrons. OvorIookIng fhoso fwo cornors of fho fofrnhodron fho
H
2
O moIocuIo bocomos 'V` shnod (IIg. 2.l9).
O
b.p
b.p.
l.p.
l.p.
H
H
O
0
.9
6
1
0
5
H
H
Fig. 2.18 IF
!
hybridized 'O' atom. Fig. 2.19 V-shaped water molecule.
Horo fho bond nngIo Is l05, fho oxIsfonco of fho fwo nIrs of unshnrod oIocfrons rooI
onch ofhor sfrongIy nnd fho bond nIrs como cIoso fo onch ofhor fhnn fhnf In fho H
3
moIocuIo.
Tho bond nngIo bocomos moro roducod (IIg. 2.20).
H
H
H
107
N
..
Fig. 2.17
O
.
.
. .
H
H
bp bp repulsion
lp bp repulsion
lp lp repulsion
Fig. 2.20 Showing repulsions.
HIgLIIgLt:
H
3
nnd H
2
O moIocuIos nro oxnmIos of dIsforfod moIocuIos duo fo fho rosonco of
Iono nIrs In fho hybrId orbIfnIs nnd I-b, I-I rouIsIons.
IntermoIecuIar forces:
In n crysfnIIIno soIId, fho nrfIcIos ncf ns sfrucfurnI unIfs, Ions of moIocuIos nro nrrnngod
In n symmofrIcnI wny. So moIfIng of such soIIds occurs whon fho hIghIy ordorod nrrnngomonf
of nrfIcIo In fho crysfnIIIno InffIco chnngos fo fho moro rnndom nrrnngomonfs (chnrncforIsfIc
of n IIquId). In non-IonIc comound (covnIonf comound) whoro fho nfoms nro hoId by covnIonf
bonds, fho InformoIocuInr forcos nro vory wonk. So onorgy roquIromonf for moIfIng Is Ioss
comnrod fo IonIc comounds. Thoro nro fwo kInds of InformoIocuInr forcos:
(o) dIoIo-dIoIo InforncfIon,
(I) vnn dor WnnIs forcos.
+
+
displaying dipole-dipole interaction
(in HCl molecule)
As n rosuIf of dIoIo-dIoIo InforncfIon, oInr moIocuIos nro hoId fo onch ofhor moro
sfrongIy fhnn non-oInr moIocuIos (uroIy covnIonf moIocuIos). ThIs dIfforonco In sfrongfh of
InformoIocuInr forcos Is rofIocfod In fhoIr hysIcnI roorfIos.
Thoro musf bo somo forcos bofwoon fho moIocuIos of n non-oInr comound. SInco, fhoy
cnn soIIdIfy. Such nffrncfIon Is known ns ton Jer Woole force of oIIrocIion. Thoso vnn dor
WnnIs forcos hnvo vory shorf rnngo. Thoy ncf onIy bofwoon fho orfIons of dIfforonf moIocuIos
fhnf nro In cIoso confncf, i.e., vnn dor WnnIs forcos nro wonk InformoIocuInr forcos whIch nro
rosonsIbIo for wonkosf nffrncfIons bofwoon nonoInr moIocuIos.
Ivory nfom hns nn offocfIvo 'sIzo`. ThIs Is cnIIod vnn dor WnnIs rndIus. Whon fwo
non-bondod nfoms como cIosor, fho nffrncfIon bofwoon fhom sfondIIy Incronsos nnd ronchos n
mnxImum whon fhoy nro jusf fouchIng, whon fho dIsfnnco bofwoon fho nucIoI Is oqunI fo fho
sum of fho vnn dor WnnIs rndII, If fho nfoms nro forcod fo como sfIII cIosor fhon ton Jer Woole
oIIrocIion wIII bo roIncod by ton Jer Woole repuleion. Thus, wo cnn sny, non-bondod nfoms
sfrongIy rosIsf crowdIng. Thus, bofh nffrncfIvo nnd rouIsIvo vnn dor WnnIs forcos nro Imorfnnf
for our undorsfnndIng of moIocuInr sfrucfuro.
MoIecuIar orbitaI theory [Iinear combination of atomic orbitaIs, LCAO]
Hononucleor JioIonic nolecule.
!of, fwo H-nfoms dosIgnnfod by H
A
nnd H
I
confnInIng fwo le-nfomIc orbIfnIs ovorIn fo
form M.O. Thon oxrossIon for fwo moIocuInr orbIfnIs (M.O.) wIII bo ono bondIng (
I
) nnd fho
ofhor nnfIbondIng (
A
):
I
=
A
(le) +
I
(le)
A
=
A
(le)
I
(le)
(i) Tho fwo condIfIons cnn bo rorosonfod IcforInIIy (IIg. 2.2l)
+
.
+
.
+
+
.
+
.
+
. .
E H
A
H
B
Atomic orbitals
s f * is (Antibonding, )
A
s f is (Bonding )
B
Fig. 2.21 Bonding and antibonding orbitals.
!Inonr combInnfIon of le-nfomIc orbIfnIs (-symmofry) of fwo H-nfoms fo gIvo bondIng
nnd nnfIbondIng moIocuInr orbIfnIs (-symmofry).
1s 1s
s
1s
s
1s
Bonding
Molecular orbital
Antibonding
Atomic
orbital
Atomic
orbital
Energy
Fig. 2.22 Representation of M.O. diagram.
Inorgy IovoI dIngrnm (IIg. 2.22) IIIusfrnfIng fho formnfIon nnd roInfIvo onorgIos of
le
(bondIng) nnd
le
(nnfIbondIng) moIocuInr orbIfnIs rosuIfIng from fho combInnfIon of fwo

le-nfomIc orbIfnIs on fwo H-nfoms In H
2
nolecule.
(ii) MoIocuInr orbIfnIs from p nfomIc orbIfnIs:
(o) Ind-ond ovorIn
+ +
(Bonding)
+
+
+
+ s
2p
(Antibonding)
s*
2p
E
Fig. 2.23 Linear combination of two 2p
x
orbitals to form 2p (bonding) and
*2p (antibonding) molecular orbitals (-symmetry).
(I) SIdo-by-sIdo ovorIn (IIg. 2.24):
+ +

+
+
+
E
p
2
* 2p
f
A
(Antibonding)
p
2
2p Bonding
+
Fig. 2.24 -Bonding.

!Inonr combInnfIon of fwo 2p
c
orbIfnIs fo form
c
2p (bondIng) nnd
c
2p* (nnfIbondIng)
moIocuInr orbIfnIs (-symmofry).
s*
2p
p*
y
2p, p*
z
2p
p*
y
2p, p
y
2p
s
2p
z
y x
2p
z y
2p
s*
2s
2s 2s
s
2s
Energy
z
Fig. 2.25 Order of energy of molecular orbitals (M.O.).
(1nerg, letel Jiogron of noleculor orIiIole for o Iononucleor JioIonic nolecule)
So, fho ordor of onorgy for moIocuInr orbIfnI Is:
le
<
le
* <
2e
<
2e
* <
2p
<
,
c
p
p
2
2
<
,
c
p
p
2
2
<
2p
Bond-Order (B.O.):
Iond-ordor (I.O.) of n moIocuIo Is cnIcuInfod ns foIIows:
I.O.
.I. . A.
2
.I. no. of oIocfrons In bondIng moIocuInr orbIfnIs.

.A. no. of oIocfrons In nnfIbondIng moIocuInr orbIfnIs.
TubIe 2.4
B.O. Significonce
0 moIocuIo Is unsfnbIo
nnd doos nof oxIsf.
vo unsfnbIo nnd doos nof oxIsf.
+vo *sfnbIo nnd oxIsfs.
*Cronfor fho vnIuo of I.O. gronfor Is fho sfnbIIIfy of fho moIocuIo.
Iulee for filling up of noleculor orIiIole uiII elecIrone.
(i) Tho moIocuInr orbIfnIs nro fIIIod In fho IncronsIng ordor of fhoIr onorgIos. Thus mo-
IocuInr orbIfnI ossos3Ing fho Iowosf onorgy wIII bo fIIIod fIrsf nnd fhnf ossossIng
fho hIghosf onorgy wIII bo fIIIod u In fho Insf.
(ii) Tho mnxImum numbor of oIocfrons fhnf cnn fIII n moIocuInr orbIfnI Is fwo.
(iii) AccordIng fo Hund`s ruIo of mnxImum muIfIIIcIfy, If fhoro nro fwo moIocuInr orbIfnIs
hnvIng fho snmo onorgy (i.e., dogonornfo moIocuInr orbIfnIs), fho oIocfrons wIII fIrsf
fIII fhom sIngIy nnd whon bofh of fhom hnvo boon fIIIod sIngIy, nIrIng of oIocfrons
wIII occur. Thus
,
2p nnd
c
2p bondIng moIocuInr orbIfnIs whIch nro dogonornfo nro
fIrsf sIngIy fIIIod nnd nIrIng fnkos Inco onIy whon moro oIocfrons nro fo bo
nccommodnfod. In n sImIInr fnshIon
,
*2p nnd
c
*2p nnfIbondIng dogonornfo moIocuInr
orbIfnIs nro fIIIod jusf IIko dogonornfo bondIng orbIfnIs.
2p
z
2p
z
2p
x
2p
y
2p
y
2p
x
p
s
2px
p*
s*
2px
2s 2s
s*
2s
s
2s
2p
z
2p
z
2p
x
2p
y
2p
y
2p
x
p
p*
s*
(sp)
2
2s 2s
s
(sp)
2
s*
(sp)
1
s
(sp)
2
Fig. 2.26 Molecular orbital diagram from Fig. 2.27 Molecular orbital diagram
2I and 2F atomic orbitals. allowing I-F interaction.
1nerg, letel Jiogron for A
2
nolecule.
Tho oIocfronIc confIgurnfIon of -nfom Is le
2
2e
2
2p
3
. In
2
moIocuIo fhoro wIII bo nII
fofnI l4 oIocfrons of whIch 4 wIII bo In fho K shoIIs whIch Is donofod by KK.
So, fho oIocfronIc confIgurnfIon of
2
moIocuIo wIII bo
KK(2e
2
) (*2e
2
) (2p
2
) (
,
2p
2
) (
c
2p
2
) |KK donofos (le
2
) (*le
2
)]
2p
x
2p
y
2p
z
2p
z
2p
y
2p
x
s*
2p
s
2p
p
y 2p
* p
z 2p
*
A. O. A.O.
p
y2p
p
z2p
s*
2s
s
2s
2s 2s
B.O. = = 3
E
M.O.
8 2
2
N molecule has triple
bond (N N)
2
Fig. 2.28 M.O. diagram for N

2
.
Inorgy IovoI dIngrnms of ofhor moIocuIos:
s*2p
x
p*2p
y
p*2p
z
2p
x
2p
y
2p
z
2p
z 2p
y
2p
x
p2p
y
p2p
z
s2p
x

s*2s
s2s
2s 2s
B
2
B B
s(sp)
2
p*2p
y
p*2p
z
2p
x
2p
y
2p
z
2p
x
2p
y

s(sp)
1
2s 2s
B
2
B B
s*(sp)
1
s(sp)
2
2p
z
2p
z
2p
y
Fig. 2.29 Molecular orbital diagram Fig. 2.30 Molecular orbital diagram of
of B
2
(without s-p interaction). B
2
(with s-p interaction).
IIocfronIc confIgurnfIon of I
2
moIocuIo:
KK(2e
2
) (*2e
2
) (2p
2
)
s*2p
x
p*2p
y
p*2p
z
2p
z
2p
y
2p
x
p2p
y
p2p
z
s2p
x

s*2s
s2s
2s 2s
O
2
O O
s*sp)
2
p*2p
y
p*2p
z
2p
z
2p
x
p2p
y

s(sp)
1
2s 2s
s*(sp)
1
s(sp)
2

p2p
z
O
2
O O
2p
z
2p
y
2p
x
2p
y
2p
x
2p
z
2p
y
of O
2
(without s-p interaction). O
2
(with s-p interaction).
IIocfronIc confIgurnfIon of O
2
moIocuIo:
KK(2e
2
) (*2e
2
) (2p
2
) (
,
2p
2
) (
c
2p
2
) (
,
*
2p
l
) (
c
*
2p
l
)
s*2p
x
p*2p
y
p*2p
z
2p
z
2p
y
2p
x
2p
z
2p
y
2p
x
p2p
y
p2p
z
s2p
x

s*2s
s2s
2s 2s
NO N O
s*sp)
2
2p
z
2p
y
2p
x
2p
z
2p
y
2p
x
p2p
y

s(sp)
1
2s 2s
s*(sp)
1
s(sp)
2

p2p
z
NO N O
p*2p
y
p*2p
z
of NO (without s-p interaction). NO (with s-p interaction).
|Inorgy IovoI dIngrnm for hoforonucIonr dInfomIc moIocuIo]
TubIe 2.5: IIocfron IsfrIbufIon In MoIocuInr OrbIfnIs of somo
SImIo MoIocuIos shown In nbovo M.O. dIngrnms
Molecule (ep)
1
*(ep)
1
(2p) (ep)
2
*(2p) *(ep)
2
unpoireJ
elecIrone
I
2
2
C
2
0
2
0
O
2
2
CO 0
O l
Aromatic Character
OrgnnIc comounds hnvo boon cInssIfIod Info fwo brond subdIvIsIons: (i) olipIoIic nnd
(ii) oronoIic.
Tho word nIIhnfIc cnmo from 'fnffy` nnd fho word nromnfIc cnmo from 'frngrnnf`, hnvo
no Iongor fhoIr sIgnIfIcnnco. AIIhnfIc comounds nro mnInIy oon chnIn comounds. Thoy
mny bo cycIIc nIso buf fhoy rosombIo fho oon chnIn comounds In fhoIr roorfIos. AromnfIc
comounds n2o bonzono or fho comounds fhnf rosombIo bonzono In chomIcnI bohnvIour.
KokuIo osfnbIIshod fho sfrucfuro of bonzono ns foIIows:
or
AccordIng fo fho KokuIo`s sfrucfuro fhoro shouId bo four IsomorIc dI-subsfIfufod bonzonos,
foo:
Br
Br
Br
Br
;
Br
Br
Br
Br
;
Br Br
Br Br
KokuIo`s sfrucfuro fnIIs fo oxInIn corfnIn chnrncforIsfIcs of bonzono tic:
(i) Ionzono undorgoos subsfIfufIon roncfIon rnfhor fhnn nddIfIon.
(ii) Honf of hydrogonnfIon of bonzono Is Iowor fhnn fhnf oxocfod.
(iii) Tho CC bond Iongfhs In bonzono nro oqunI nnd InformodInfo bofwoon n sIngIo nnd
n doubIo bond.
Tho Idon of rosonnnco couId oxInIn nII fho fhroo nbovo nnomnIIos nnd osfnbIIshod fho
sfrucfuro of bonzono ns uf forwnrd by KokuIo.
HIgLIIgLts:
Tho Idon of rosonnnco oxInIns sIx IdonfIcnI bonds In bonzono, whIch Is n now fyo of
bond, n hybrId bond or Iencene IonJ, i.e., If Is nn InformodInfo In Iongfh, (l.39)
bofwoon n sIngIo nnd n doubIo bond.
Ionzono Is moro sfnbIo fhnn oxocfod. Iocnuso fho rosonnfIng KokuIo`s sfrucfuros
hnvo n rosonnnco hybrId sfrucfuro, whIch hns 36 KcnI moIo
l
oxfrn sfnbIIIfy.
As n rosuIf of fhIs rosonnnco sfnbIIIsnfIon, bonzono ossossos chomIcnI roorfIos
fhnf nro nof InformodInfo bofwoon comounds confnInIng sIngIo or doubIo bond. Tho
36 KcnI of rosonnnco onorgy Is rosonsIbIo for n now sof of roorfIos, known ns
oronoIic properIiee.
Wo soo fhnf nddIfIon wIII Iond fo n Ioss sfnbIo roducf by dosfroyIng fho rosonnnco
sfnbIIIzod bonzono rIng sysfom. As for oxnmIo, hydrogonnfIon of bonzono roquIros
5.6 KcnI moIo
l
fo bo convorfod Info cycIohoxndIono. So, bonzono foIIow nn onfIroIy
dIfforonf nfh, whIch Is subsfIfufIon In whIch fho bonzono rIng sysfom Is rofnInod.
OrbitaI Picture of Benzene
Ionzono Is n fInf moIocuIo, ns Ifs sIx cnrbon nfoms nro ep
2
hybrIdIsod. If wo fIf fho sIx
ep
2
-hybrIdIzod cnrbon nfoms, wo gof n roguInr hoxngon wIfh n bond nngIo l20. And fhoro sfIII
romnIns sIx oIocfrons In fho sIx p-orbIfnIs wIfh fwo oqunI Iobos, ono IyIng nbovo fho Inno nnd
fho ofhor IyIng boIow fho Inno of nor.
C C
C C
C C
H H
H H
H H
s
s
120
120
120
(i) Only -bonds are shown. s
(ii) The six -orbitals are shown
with overlapping.
p
Fig. 2.35
Inch p-orbIfnI of ono C-nfom cnn ovorIn oqunIIy woII wIfh fho p-orbIfnIs of fho ofhor
fwo cnrbon nfoms on bofh fho sIdos. Whon ovorInIng Is nof rosfrIcfod bofwoon fwo nucIoI
nnd If occurs bofwoon moro fhnn fwo nucIoI, fho honomonon Is known ns JelocolieoIion. And
fhIs doIocnIIsnfIon gIvos oxfrn sfnbIIIfy fo fho moIocuIo rosuIfIng In formnfIon of sfrongor bonds
nnd fhIs sfnbIIIfy Is nccounfod by fho form JelocolieoIion energ,. ThIs JelocolieoIion energ, Is
froquonfIy usod Insfond of reeononce energ,.
Tho doIocnIIsnfIon In bonzono moIocuIo gIvos -cIouds nbovo nnd boIow of fho Inno of
fho rIng ns shown In fho IIg. (2.36).
Benzene ring
p-clouds
p-clouds
Fig. 2.36 Delocalised clouds in benzene.
So, necessuvy und suIIIcIent condItIons Iov uvomutIcIty uve:
(i) Tho moIocuIo shouId bo cycIIc nnd fInf.
(ii) Tho moIocuIo shouId confnIn doIocnIIsod -cIoud.
(iii) Tho -cIoud musf confnIn n fofnI of (4n + 2) oIocfrons whoro n = 0, l, 2, 3, ofc.
ThIs roquIromonf Is cnIIod (4n + 2) ruIo or HuckIo ruIo.
Ionzono hns sIx -oIocfrons (known ns nromnfIc soxfof). Horo HuckIo numbor corrosonds
fo n = l. Ionzono moIocuIo Is fInf. In fhnf sonso bonzono Is nn IdonI nromnfIc comound nnd
forms fho foundnfIon sfono of nromnfIc chomIsfry.
HIgLIIgLts:
IonzonoId nromnfIc comounds: nnhfhnIono (n = 2), nnfhrncono (n = 3), honnnfhrono
(n = 3)
HoforocycIIc comounds: yrroIo (n = 2), yrIdIno (n = 2) ofc.
on-bonzonoId nromnfIc comounds: cycIoonfndIonyI nnIon, froyIIum Ion.
BenzenoId uvomutIc compounds:
naphthalene
10 electrons p
antenacene (Anthracene)
14 electrons p
phenanthrene
14 electrons p
Non-benzenoId uvomutIc compounds:
N
H
:
pyrrole
6 electrons p
N
pyridine
6 electrons p
()
cyclopentadienyl
anion
6 electrons p
:
tropylium ion
6 electrons p
(+)
SHORT QUESTIONS AND ANSWERS
Q. 1. WIoI ie o nolecule:
Ans. Whon n grou of nfoms of snmo nnd dIfforonf oIomonfs sfny fogofhor wIfh n dofInIfo
combInnfIon (of nfoms), ossossIng roorfIos onfIroIy dIfforonf from consfIfuonf nfoms Is known
ns n moIocuIo.
Q. 2. WIoI ie o cIenicol IonJ:
Ans. If rofors fo fho bondIng forco fhnf hoIds fogofhor fho consfIfuonf nfoms In n moIocuIo.
Q. 3. MenIion IIe I,pee of IonJe.
Ans. Mosf Imorfnnf fyos nro: (i) IIocfrovnIonf, (ii) CovnIonf nnd (iii) Co-ordInnfo
bonds.
Q. 4. WIoI ie IIe epeciol feoIure of on elecIrotolenI IonJ or ionic IonJ:
Ans. Such n bond Is formod by comIofo frnnsfor of oIocfrons from ono nfom fo fho
ofhor. Such oIocfron frnnsfor occurs from mofnIs fo nonmofnIs. Thus Ions nro formod. IonIc
bondIng Is fho rosuIf of elecIroeIoIic forcee of oIIrocIion bofwoon fho osIfIvo mofnI Ions nnd
nognfIvo non-mofnI Ions.
Q. 5. Cite JoI onJ croee Jiogrone for AoCl onJ CoI
2
nolecule fornoIion.
Ans.
Na
Sodium atom
(2, 8, 1)
+ Cl
Chloride atom
(2, 8, 7)

Na
Sodium ion
(2, 8)
+ Cl
Chloride ion
(2, 8, 8)

+

Ca
Calcium atom
(2, 8, 8, 2)
+
F

:
F
(2, 7)
Ca
Calcium ion
(2, 8, 8)
+
++
. .

F

.
F
two fluoride
ions (2, 8)

Q. 6. WIoI ie o cotolenI IonJ:
Ans. CovnIonf bond Is formod whon fwo nfoms nrfIcInfIng In bond formnfIon shnro
oqunIIy fhoIr oIocfrons fo roduco n moIocuIo of nn oIomonf or n comound.
Q. ?. Cite exonplee of eingle, JouIle onJ Iriple cotolenI IonJe I, JoI onJ croee Jiogrone.
Ans. (i) Single cotolenI IonJ.
(o) Cl
:
:
:
.
+ Cl
:
:
:
.
Cl
:
:
:
:
Cl
:
:
:

ClCl
Single bond
(I) C
.
+

HCH
.
.
.
4H C H
.
.
.
H
H
H
H
H
(ii) DouIle cotolenI IonJ.
(o) O
:
:
:
+ O
:
:
:

O O
:
:
:

O = O
:
:
:
Double bond
(I) 2 C
.
.
+ 4H

HC = CH
.
.
H H
C C
::
.

.
.
H H
H H
.
(iii) Triple cotolenI IonJ.
(o) N
.
:
:
+

N N
:
:

N N
:
:
N
.
:
:
..
Triple bond
(I) 2 C
.
+

H C C H
:
HC CH
:
..
.
.
.
2H

. .
Q. B. Hou ore IIe oIone IelJ IogeIIer in o cotolenI IonJ:
Ans. Tho nfoms hoId fogofhor by fho nffrncfIon bofwoon fho osIfIvo chnrgos of fho
nucIoI of fho nfoms nrfIcInfIng In fho bond formnfIon nnd fho nognfIvo chnrgos of fho shnrod
oIocfrons by fho nfoms.
+ +
Attraction
Proton in
nucleus
Shared electrons
Fig. 2.37 (=) Forces of attraction during H
2
molecule formation.
Q. 9. WIoI ore polor onJ non-polor cotolenI IonJe:
Ans. A nonpolor IonJ Is formod whon shnrIng fnkos Inco bofwoon fho nfoms of snmo
oIocfronognfIvIfy i.e., bofwoon sImIInr nfoms durIng bond formnfIon. e.g.,
HH, O = O, CICI, IrIr, ofc.
A polor IonJ Is formod whon shnrIng fnkos Inco bofwoon fho nfoms of dIfforonf
oIocfronognfIvIfIos i.e., bofwoon dIssImIInr nfoms durIng bond formnfIon tic.,
H
+
CI
Q. 10. WIoI ie IIe epeciol feoIure of o cotolenI IonJ:

Ans. (o) CovnIonf bond hoIds fogofhor fho nfoms of nonmofnIs In n moIocuIo nnd gInnf
sfrucfuros. (I) MoIocuIos hnvo n dofInIfo shno bocnuso covnIonf bonds hnvo n dofInIfo Iongfh
nnd dIrocfIon.
Q. 11. WIoI ie cotolenI roJiue:
Ans. Tho covnIonf rndIus of nn oIomonf Is hnIf fho bond Iongfh. Whon fwo nfoms of fho
oIomonf (snmo or dIfforonf) nro joInod by n sIngIo covnIonf bond, fho Iongfh of sIngIo covnIonf
bonds bofwoon nfoms of dIfforonf oIomonfs cnn bo doformInod fnIrIy nccurnfoIy by nddIng fho
covnIonf rndII of fho fwo nfoms. CovnIonf rndIus of nn nfom Is hnIf of fho dIsfnnco bofwoon fho
nucIoI of fwo IIko nfoms bondod fogofhor by n sIngIo covnIonf bond.
Covalent radius
0.037 nm H
2
Covalent radius
0.104 nm Cl
2
Bond length
0.141 nm sum of
covalent radii HCl
Fig. 2.37 (>) Forces of attraction during H

2
molecule formation.
Covalent radius = 0.114 nm
van der Waals radius 0.190 nm. van der Waals
radii determine the effective size of a molecule.
van der Waals radius is the effective radius of an
atom when held in contact with another atom by
weak intermolecular forces.
Fig. 2.37 (?) Covalent and van der Waals radii for bromine.
Q. 12. MenIion epeciol I,pee of IonJe.
Ans. (i) MofnIIIc bond, (ii) vnn dor WnnIs bond, (iii) Hydrogon bond.
Q. 13. WIoI ie IIe epeciol feoIure of o coorJinoIe IonJ:
Ans. ThIs fyo of bond Is formod by unoqunI shnrIng of oIocfron nIr, ono of fho
nrfIcInfIng nfoms In fho bond formnfIon donnfos bofh fho oIocfrons for bond formnfIon. Tho
coordInnfo bond Is IndIcnfod by nn nrrow fo oxross fhIs unoqunI shnrIng.
H
H
H
H H
H
H
H
+
3
2
2
2
2
2
+
:
Q. 14. WIoI ie o eigno IonJ:
Ans. ThIs fyo of bond Is formod by nxInI ovorInIng of e-e, p-p or ep orbIfnIs nnd nIso
ep
3
-e, ep
2
-e, ep-e, ep
3
-p, ep
2
-p ofc. of dIfforonf nfoms whoroby mnxImum ovorInIng of orbIfnIs
Is ossIbIo.
Q. 15. WIoI ie o -IonJ:
Ans. -bond Is formod by sIdowny ovorInIng of mnInIy p-orbIfnIs of dIfforonf nfoms.
Q. 16. WIoI ore epeciol feoIuree of eingle, JouIle onJ Iriple IonJe:
Ans. A sIngIo bond Is nIwnys n -bond. A doubIo bond confnIns ono nnd ono bond nnd
n frIIo bond confnIns ono nnd fwo bonds.
Q. 1?. WIoI Jo ,ou neon I, Jipole nonenI:
Ans. Tho dIoIo momonf In n moIocuIo dovoIos duo fo fho sonrnfIon of osIfIvo nnd
nognfIvo chnrgos by n dIsfnnco; ns fho confro of ncfIon of osIfIvo chnrgo duo fo nucIoI nnd
confro of ncfIon of nognfIvo chnrgo duo fo oIocfrons do nof coIncIdo. MnfhomnfIcnIIy dIoIo
momonf Is oxrossod ns:
= e J
whoro, = dIoIo momonf,
e = mngnIfudo of chnrgo sonrnfod In osu,
J = dIsfnnco In cm.
Q. 1B. WIoI Jo ,ou neon I, IonJ energ,:
Ans. Iond onorgy (or onfhnIy) Is fho monn vnIuo of bond dIssocInfIon onorgIos (or
onfhnIIos) () usod for nroxImnfo cnIcuInfIon osfImnfIng fho onfhnIy chnngos for fho
roncfIon. Iond dIssocInfIon onorgy Is fho onorgy (or onfhnIy) for bronkIng ono moIo of n covnIonf
bond In n gnsoous moIocuIo. Inorgy Is noodod fo bronk covnIonf bonds.
Iond bronkIng Is ondofhormIc, so onfhnIy chnngo Is nIwnys osIfIvo.
HCI (g) H(g) + CI(g) H + 432 kJ moI
l
.
Q. 19. 1n uoIer nolecule, ore IIe Iuo IonJ JieeocioIion energiee eone:
Ans. In HOH (g) moIocuIo, fho onorgy noodod fo bronk fho fIrsf OH bond Is
498 kJ moI
l
, fho onorgy noodod fo bronk fho socond OH bond Is 428 kJ moI
l
. So fho bond
dIssocInfIon onorgIos of fwo or moro bonds bofwoon sImIInr nfoms nro nof fho snmo.
Q. 20. ColculoIe IIe CH IonJ energ, in CH
4
nolecule.
Ans. CH
4
CH
3
+ H l02 KcnI moI
l
CH
3
CH
2
+ H l05 KcnI moI
l
CH
2
CH + H l08 KcnI moI
l
CH C + H 83 KcnI moI
l
TofnI 398 KcnI moI
l
CH bond onorgy In CH
4
Is monn vnIuo of vnIuos i.e.,
I(CH)
398
4
= 99.5 KcnI moIo
l
.
Q. 21. WIoI Jo ,ou neon I, IonJ lengII:
Ans. Iond Iongfh Is fho dIsfnnco bofwoon fho nucIoI of nfoms bondod by ono or moro
covnIonf bonds. Ior fho snmo fwo nfoms frIIo bonds nro shorfor fhnn doubIo bonds whIch, In
furn, nro shorfor fhnn sIngIo bonds.
C C
0.l5?nm
*
C C
0.l34nm
=
*
C C
0.l20nm
*
.
Q. 22. WIoI Jo ,ou neon I, elecIronegoIitiI,:
Ans. Tho uIIIng owor of nn nfom of fho bondIng oIocfrons fownrds IfsoIf whon IInkod
by n covnIonf bond wIfh nnofhor nfom Is known ns oIocfronognfIvIfy. Tho sfrongor fho uIIIng
owor of nn nfom, fho hIghor Ifs oIocfronognfIvIfy. Tho bIggor fho dIfforonco In fho
oIocfronognfIvIfy of fho oIomonfs formIng n bond, fho moro oInr fho bond.
H Cl
+d
polar bond.
Q. 23. WIen Joee o IonJing in o cotolenI conpounJ Iecone full, ionic:
Ans. Tho bondIng In n comound bocomos IonIc If fho dIfforonco In oIocfronognfIvIfy of
fho fwo bondod nfoms bocomos so Inrgo fhnf fho moro oIocfronognfIvo nfom cnn romovo
comIofoIy fho oIocfron from fho ofhor nfom. ThIs hnons In comounds IIko nCI, MgO,
CnI
2
ofc.
Q. 24. Cite IIe concepIion of o IonJing noleculor orIiIol.
Ans. Tho bondIng moIocuInr orbIfnI Is n rogIon In snco whoro fho robnbIIIfy of fIndIng
fho bondIng oIocfrons Is mnxImum. MoIocuInr orbIfnIs nro fho soIufIons fo fho SchrodIngor
wnvo oqunfIon IIko nfomIc orbIfnIs. In n sImIIfIod form, If mny bo sfnfod fhnf moIocuInr orbIfnIs
(M.O.) nro obfnInod by fho ovorInIng of nfomIc orbIfnIs of fho nfoms IInkod by n covnIonf
bond.
IondIng M.O. (
I
) Is obfnInod whon ++ rogIons of bofh fho nfomIc orbIfnIs (A.O.) ovorIn
nIong fho InfornucIonr nxIs (soo IIgs. 2.2l nnd 2.23) i.e., M.O. Is roducod by nddIfIon of fwo
nfomIc orbIfnIs (
I
=
A
+
I
).
Q. 25. Cite IIe concepI for onIiIonJing noleculor orIiIole.
Ans. AnfIbondIng orbIfnIs (
A
) nro nIso soIufIons fo fho SchrodIngor wnvo oqunfIon IIko
fho bondIng moIocuInr orbIfnIs. Iuf In fhIs cnso,
A
rosuIfs from subfrncfIon of fho fwo nfomIc
orbIfnIs (
A
=
A

I
) i.e., by fho ovorInIng of + rogIons of fho nfomIc orbIfnIs (soo IIgs.
2.2l nnd 2.23).
Q. 26. 1nIerpreI IIe iJeo of IonJ orJer.
Ans. Iond ordor (I.O.) Is gIvon by fho oxrossIon,
I.O. =

I o
2
whoro,
I
numbor of bondIng oIocfrons.
o
numbor of nnfIbondIng oIocfrons.
HIghor fho bond ordor, sfnbIor Is fho moIocuIo. Iond ordor zoro nnd nognfIvo IndIcnfos
fhnf moIocuIo doos nof form or oxIsf.
Q. 2?. WIoI ie I,IriJieoIion of oIonic orIiIole:
Ans. Tho InformIxIng fho nfomIc orbIfnIs of sIIghfIy dIfforonf onorgIos so ns fo rodIsfrI-
bufo fhoIr onorgIos nnd fo gIvo n now sof of orbIfnIs (known ns hybrId orbIfnIs) of oquIvnIonf
onorgIos nnd shno Is known ns hybrIdIsnfIon.
Q. 2B. MenIion IIe I,pee of I,IriJieoIion.
Ans. (i) ep
3
, (ii) ep
2
, (iii) ep, (it) Jep
2
, (t) ep
3
J, (ti) J
2
ep
3
.
Q. 29. WIoI Jo ,ou neon I, I,IriJ orIiIole:
Ans. HybrId orbIfnIs nro formod from fho mIxIng of nfomIc orbIfnIs of dIfforonf fyos
nnd nro orIonfod In snco In n chnrncforIsfIc mnnnor doformInod by fho fyo of hybrIdIsnfIon.
Q. 30. ColculoIe IIe IonJ orJere of. (i) H
2
O, (ii) H
2
+
, (iii) He
2
+
, (it) He
2
onJ inIerpreI IIe
reeulI.
Ans. (i) I.O. =

I o
2
=
2 0
2
= l
H-nfoms nro hoId fogofhor by ono covnIonf bond.
(ii) I.O. =
l 0
2
=
l
2
H
2
+
hns n frnnsIonf oxIsfonco. Horo fho numbor of bondIng oIocfrons oxcoods fho numbor
of oIocfrons In nnfIbondIng orbIfnI.
(iii) I.O. =
2 l
2
=
l
2
Ho
2
+
nIso hns frnnsIonf oxIsfonco. Horo, fho numbor of oIocfrons In s-orbIfnI Is gronfor
fhnn fho numbor of oIocfrons In s*-orbIfnI.
(it) I.O. =
2 2
2
= 0
Horo fho numbor of oIocfrons In -orbIfnI = fho numbor of oIocfrons In *-orbIfnI. Tho
moIocuIo doos nof oxIsf. So Ho Is mononfomIc.
Q. 31. O
2
nolecule ie poronogneIic. 1xploin.
Ans. Tho oIocfronIc confIgurnfIon of:
O-nfom le
2
2e
2
2p
4
Tho oIocfronIc confIgurnfIon of:
O
2
-moIocuIo KK(2e
2
)(*2e
2
)(2p
2
)(
,
2p
2
)(
c
2p
2
)(
,
*2p
l
)(
c
*2p
l
)
I.O.

I o
8 4
2
= 2
So, O
2
moIocuIo confnIns doubIo bond (O = O), ono Is nnd fho ofhor Is -bond. AccordIng
fo Hund`s ruIo fwo unnIrod oIocfrons fIII fho dogonornfo (orbIfnIs of snmo onorgy)
,
*2p nnd
c
*2p orbIfnIs (soo IIgs. 2.3l nnd 2.32). Thnf Is why, O
2
moIocuIo Is nrnmngnofIc.
Q. 32. 1xploin uI, HI ie liquiJ, HCl ie goe onJ HI ie leee ociJic IIon HCl.
Ans. H I
+
... H I
+
... H I
+
... H I
+
uo fo hydrogon bondIng, fhoro Is moIocuInr nssocInfIon In HI nnd offocfIvo moIocuInr

woIghf of HI Is hIgh nnd fhnf Is why Ifs voInfIIIfy Is Ioss nnd If Is IIquId whorons In HCI
moIocuIo fhoro Is no hydrogon bondIng bocnuso CI Is Ioss oIocfronognfIvo fhnn I nnd nfomIc
rndIus of CI Is gronfor fhnn fhnf of I. Hydrogon bond In HI InhIbIfs roIonso of H
+
nrfInIIy In
nquoous soIufIon, so If Is Ioss ncIdIc.
O
H H
H
O
H
O
H
H
O
O
H
H
H
H
Hydrogen
bond
Covalent bond
Fig. 2.38 H-bonding in ice.
Q. 33. 1xploin H
2
O ie o liquiJ onJ H
2
S ie o goe.
Ans. HO HO HO HO
H H H H
Tho ronson Is snmo ns In Q no. 3l nbovo.
Q. 34. 1xploin, eII,l olcoIol ie leee toloIile IIon JineII,l eIIer IIougI IoII Iote IIe
eone nol. fornulo, C
2
H
6
O.
Ans. HO HO HO
C H
2 5
C H
2 5
C H
2 5
H-bonding in ethyl alcohol.
HCOCH
H
H
H
H
Dimethyl ether
Thoro Is H-bondIng In ofhyI nIcohoI nnd duo fo moIocuInr nssocInfIon H Is nffnchod fo
O-nfom In ovory moIocuIo of ofhyI nIcohoI. Iuf fhoro Is no H-bondIng In dImofhyI ofhor moIocuIo
ns H horo Is nof nffnchod fo O-nfom. So, fhoro Is no moIocuInr nssocInfIon duo fo H-bondIng In
dImofhyI ofhor, so If Is moro voInfIIo fhnn ofhyI nIcohoI.
Q. 35. TIe JeneiI, of uoIer ie greoIer IIon IIoI of ice.
1xploin.
Ans. In H
2
O moIocuIo, ovory oxygon nfom Is connocfod
fo fwo hydrogon nfoms ns covnIonf bonds. And onch oxygon
nfom confnIns fwo Iono nIrs. Thoso oIocfrons cnn form
hydrogon bonds. Iy X-rny crysfnIIogrnhy, If hns boon
osfnbIIshod fhnf In n crysfnI of Ico, n moIocuIo of wnfor Is
surroundod by four wnfor moIocuIos nnd ovory moIocuIo of
wnfor form hydrogon bonds gIvIng n fofrnhodrnI sfrucfuro. So
n crysfnI of Ico Is nof n sIngIo moIocuIo buf nn nssocInfod
moIocuIo. uo fo fofrnhodrnI sfrucfuro, fhoro Is somo voId
snco In Ico. Whon Ico moIfs, fhIs fofrnhodrnI sfrucfuro Is
dosfroyod. And fho wnfor moIocuIos nro hydrogon bondod In n
chnIn. uo fo Ioss of fhIs voId snco, whon Ico moIfs Ifs voIumo
roducos nnd donsIfy Incronsos.
EXERCISES
1. Whnf Is hybrIdIsnfIon CIvo dIfforonf fyos of hybrIdIsnfIons wIfh oxnmIos.
2. IxInIn ep, ep
2
nnd ep
3
hybrIdIsnfIons wIfh oxnmIos.
3. WrIfo n nofo on co-ordInnfo bond.
4. CIvo fho sfnfo of hybrIdIsnfIon, bond nngIo nnd shno of fho foIIowIng moIocuIos:
(i) IoI
2
, (ii) II
3
, (iii) CH
2
= CH
2
, (it) CH CH, (t) H
3
, (ti) H
2
O.
5. (o) IxInIn fho sfrucfuro of bonzono. (I) CIvo n concIso nccounf of doIocnIIsnfIon of bonzono.
6. Iscuss hydrogon bondIng nnd oxInIn why donsIfy of Ico Is Ioss fhnn fhnf of wnfor.
?. WrIfo n shorf nofo on IonIc bondIng.
B. IxInIn fho bond ordor of
2
moIocuIo.
9. IxInIn Infor nnd InfrnmoIocuInr hydrogon bondIng wIfh oxnmIos.
10. (o) IxInIn hydrogon bondIng. (I) CIvo fho chnrncforIsfIcs of covnIonf bond. (c) IxInIn ep
3
-
hybrIdIsnfIon.
11. Whnf Is VSII! fhoory of moIocuInr modoI IxInIn wIfh suIfnbIo oxnmIos.
12. Whnf Is dIoIo momonf How Is dIoIo momonf of n moIocuIo cnIcuInfod
13. Iscuss Iorn Hnbor cycIo wIfh nn oxnmIo.
14. WrIfo shorf nofos on: (o) InformoIocuInr forcos, (I) MoIocuInr orbIfnI fhoory, (c) !osonnnco,
(J) Hund`s ruIo, (e) oIocnIIznfIon, (f) AromnfIcIfy.
15. Two oIomonfs hnvIng fho nfomIc numbors ll nnd l?, rosocfIvoIy, combIno fo form n comound.
Sfnfo fho nnfuro nnd formuIn of fho comound so formod. CIvo Ifs nnmo nIso.
16. CIvo fho moIocuInr orbIfnI dIngrnms of H
2
nnd O
2
moIocuIos.
!
NucIear Chemistry
ucIonr ChomIsfry Is fho brnnch of chomIsfry fhnf donIs wIfh fho chnngos In fho nucIoI. If Is
quIfo obvIous fhnf fho convonfIonnI onorgy sourcos, such ns conI, ofroIoum wIII bo oxhnusfod
In nonr fufuro. So scIonfIsfs nro sonrchIng for non-convonfIonnI onorgy sourcos such nssoInr
onorgy, nucIonr onorgy ofc. Tho Idon of oxIoIfIng nucIonr onorgy cnmo nffor fho dIscovory of
rndIoncfIvIfy. So wo nro fo dIscuss, In brIof, fho Idon of rndIoncfIvIfy boforo goIng fo dIscuss fho
sourco of nucIonr onorgy whIch Is fho mnIn fonfuro of nucIonr chomIsfry.
RADIOACTIVITY
IocquoroI In l896 obsorvod fhnf urnnIum or Ifs comounds omIf n kInd of rnys sonfnnoousIy.
Thoso rnys cnn nffocf hofogrnhIc Info. Ho nnmod fhIs honomonon of omIssIon of sonfnnoous
rndInfIon by urnnIum ns roJioocIitiI,. Tho nfoms of somo of fho oIomonfs woro found fo oxhIbIf
rndIoncfIvIfy, such nsrndIum, fhorIum, oIonIum ofc. As comounds of fhoso oIomonfs oxhIbIf
rndIoncfIvIfy, so If cnn bo snId fhnf rndIoncfIvIfy Is n nucIonr honomonon. !ndIoncfIvo oIomonfs
omIf fho rndInfIon nnd cronfo now oIomonfs. !ndIoncfIvIfy Is nn irretereiIle proceee nnd omIfs
moro honf fhnn fhnf of nny of fho chomIcnI rocossos (l0
9
cnI moI
l
). Tho rnys omIffod nro
cInssIfIod ns nIhn |
2
4
Ho
++
], bofn (unInognfIvo chnrgo), nnd gnmmn (noufrnI). A comnrnfIvo
sfudy of fho rnys omIffod durIng rndIoncfIvo dIsInfogrnfIon Is dIsInyod In fho foIIowIng fnbIo.
Tub!e 3.1: ComnrIson nmong , , nnd !nys
ProperI, -Io,e -Io,e -Io,e
(i) Nutuve (i) If Is sImIInr fo X-
rnys nnd noufrnI
In nnfuro. Thoy
hnvo vory smnII
wnvoIongfhs of
fho ordor of l0
l0
fo l0
l3
m.
(ii) Repvesentu-
tIon
(ii)
(i) Sfronms of fnsf
movIng nognfIvoIy
chnrgod nrfIcIos
whIch hnvo fho snmo
e/n vnIuo ns fho
cnfhodo rnys.
(i) Sfronms of osIfIvoIy
chnrgod nrfIcIos
whIch nro moroIy
nucIoI of Ho nfoms,
onch consIsfIng of 2
rofons nnd 2
noufrons.
(ii) |
2
Ho
4
]
+2
or (ii)
l
e or
l
or .
+J@
43
(iii) Muss (iii) 4 n.m.u.
(iii)
l
l836
of hydrogon
nfoms or 0.000548
n.m.u.
(iii) o mnss (0)
(it) CLuvge (it) Iossoss osIfIvo
chnrgo of 2 unIfs
= 9.6 l0
l0
o.s.u. or
3.2 l0
l9
couIomb.
(it) Iossoss nognfIvo
chnrgo of l unIf
= 4.8 l0
l0
o.s.u. or
l.6 l0
l9
couIomb.
(it) o chnrgo (0)
(t) Ve!ocIty (t) onrIy l/l0 fho sood
of IIghf or 20,000 fo
30,000 km or soc.
(t) 2.36 l0
8
fo 2.83
l0
8
m/soc.
(t) onrIy snmo ns
IIghf 3 l0
8
m/soc.
(ti) PenetvutIng
powev
(ti) !ow (ti) ModIum (ti) MnxImum
If hns boon obsorvod fhnf honvIor oIomonfs In whIch noufron-rofon rnfIo (/) oxcood
l.5 show rndIoncfIvIfy. Thoso nucIoI nro unsfnbIo nnd omIf sonfnnoousIy , , or -rnys fo gIvo
JougIIer elenenIe.
Nuc!euv StubI!Ity
l. ucIoI wIfh 84 or moro rofons nro rndIoncfIvo.
2. ucIoI confnInIng 2, 8, 20, 50, 82 nnd l26 rofons or noufrons nro moro sfnbIo fhnn
ofhor nucIoI confnInIng dIfforonf numbor of rofons nnd noufrons. Thoso numbors
nro mngIc numbors.
3. ucIoI wIfh ovon numbors of rofons nnd noufrons nro moro sfnbIo fhnn fhnf wIfh
odd numbors.
10 30 50 70 90
Atomic number, Z
0
40
80
120
160
200
240
M
a
s
s
n
u
m
b
e
r
,
A
Fig. 3.1
NUCLEAR CHEMSTRY 45
Tho grnh (IIg. 3.l) Is n Iof of rofon numbor (Z) vs mnss numbor (A). Tho grnh Is
moro or Ioss IInonr. Whon fho vnIuo of Z Is Ioss, fhon fho rnfIo A/Z for n nucIous Is 2 i.e., IIghf
oIomonfs ossoss oqunI numbor of rofons nnd noufrons nnd fho nucIous Is sfnbIo; whon fho
rofon numbor of fho nucIous oxcoods 20 fho nucIous shows fho fondoncy fo bo unsfnbIo nnd
whon fho rofon numbor (Z) oxcoods 83 fho nucIous bocomos moro or Ioss unsfnbIo. As fho
dIfforonco of Z nnd A Incronsos fho nucIous bocomos fofnIIy unsfnbIo. So If cnn bo snId fhnf
rndIoncfIvIfy Is n honomonon fo sfnbIIIzo fho nucIous by docronsIng fho rnfIo A/Z of fho nucIous.
RudIouctIve Decuy
Tho rndIoncfIvo docny foIIows nn oxononfInI Inw. Af nny Insfnnf of fImo, fho rnfo of
dIsInfogrnfIon Is roorfIonnI fo fho numbor of nfoms () rosonf, i.e.,
J
JI
or
J
JI
= or =
J JI /
whoro = dIsInfogrnfIon consfnnf mny bo dofInod ns fho rnfIo of fho nmounf of fho subsfnnco
whIch dIsInfogrnfos In n unIf fImo fo fho nmounf of subsfnnco rosonf.
Tho 'nognfIvo sIgn` IndIcnfos fhnf wIfh nssngo of fImo 'I` fho numbor of nfoms docronsos.
So,
J
JI
=
InfogrnfIng wo hnvo, Iog
e
= I + C |C = InfogrnfIon consfnnf]
If '
0
` bo fho numbor of nfoms rosonf InIfInIIy, i.e., whon I = 0
fhon Iog
e
0
= C
Iog
e
= I + Iog
e

0
or Iog
e
0
= I
=
0
.e
I
Whon M
0
= orIgInnI mnss nnd M = mnss nf fImo I, fho oqunfIon Is
M = M
0
.e
I
Honco, fho docny curvo Is oxononfInI In nnfuro (IIg. 3.2).
Time t
F
r
a
c
t
i
o
n
p
r
e
s
e
n
t
t = T
t = 2T
t = 3T
Fig. 3.2 Decay curve of radioactive substances.
If T Is fho hnIf-IIfo of fho rndIoncfIvo oIomonf, fhon wo cnn wrIfo,
T
0
l
2
= =

e

T =
Iog . e
2
0 693

= .
Tho nbovo oqunfIon Is n roInfIon bofwoon hnIf IIfo (T) of n rndIoncfIvo oIomonf nnd Ifs
dIsInfogrnfIon consfnnf ().
Hu!I-IIIe
HnIf-IIfo of n rndIoncfIvo oIomonf Is fho fImo roquIrod for hnIf of fho nfoms fo docny
nwny. HnIf-IIvos for rndIoncfIvo Isofoos cnn bo ns shorf ns n frncfIon of n socond or ns Iong ns
mIIIIons of yonrs.
UnIts oI RudIouctIvIty
Tho unIf of rndIoncfIvIfy Is 'curie`. Tho curIo Is dofInod ns fhnf qunnfIfy of nny rndIoncfIvo
subsfnnco whIch gIvos 3.? l0
l0
dIsInfogrnfIons or socond. Tho curIo Is n vory Inrgo unIf.
Honco for nII rncfIcnI urosos mIIIIcurIo |l mCI = l0
3
CI] nnd fho mIcrocurIo |l CI = l0
6
CI]
nro usod.
RudIouctIve DIsIntegvutIon SevIes
umbor of nnfurnIIy occurrIng rndIo Isofoos Is nbouf forfy. nfurnIIy occurrIng rndIo-
ncfIvo dIsInfogrnfIon sorIos nro shown boIow. Tho sorIos nro 4n or ThorIum sorIos; 4n + 2 or
!rnnIum sorIos nnd 4n + 3 or AcfInIum sorIos. Tho form 4n monns mnss numbor Is dIvIsIbIo by
4; whorons 4n + 2 nnd 4n + 3 monns mnss numbor whon dIvIdod by 4 gIvos n romnIndor of 2 nnd
3, rosocfIvoIy.
In fho 4n sorIos stuvtIng e!ement Is
90
232
TL nnd fhrough n chnIn of succossIvo
dIsInfogrnfIon If roducos u!tImute!y
B2
20B
Pb.
StuvtIng e!ement oI (4 + 2) sevIes Is
92
23B
U und end pvoduct Is
B2
206
Pb
.
Iov (4 3) sevIes stuvtIng e!ement Is
92
235
U und end pvoduct Is
B2
20?
Pb.
An uvtIIIcIu!!y mude dIsIntegvutIon sevIes Is NeptunIum sevIes (4 +1). It stuvts
wItL
93
23?
Np und ends ut
B2
200
BI.
ofnIIs of dIsInfogrnfIon chnrf of (4n + 2) sorIos Is gIvon boIow:
92
238
90
234
9l
234
92
234
90
230
! Th In ! Th

88
226
86
222
84
2l8
82
2l4
83
2l4
!n !n Io Ib II

84
2l4
82
2l0
83
2l0
84
2l0
82
206
Io Ib II Io Ib

(SfnbIo !ond)
Gvoup dIsp!ucement (RudIouctIve dIsp!ucement) !uw:
Whon nn -nrfIcIo Is omIffod fho now oIomonf formod Is shIffod fwo coIumns bnck (Ioff
sIdo) of fho orIgInnI oIomonf, In fho orIodIc fnbIo i.e., nfomIc numbor of fho dnughfor oIomonf
docronsos by fwo unIfs. Whon n -nrfIcIo Is omIffod fho dnughfor oIomonf formod shIffs fo ono
coIumn forwnrd (rIghf sIdo) In fho orIodIc fnbIo i.e., nfomIc numbor of dnughfor oIomonf Is
Incronsod by ono unIf.
NUCLEAR CHEMSTRY 47
AvtIIIcIu! RudIouctIvIty
If nn nfom of n non-rndIoncfIvo oIomonf Is bombnrdod by n oworfuI nrfIcIo, If Is convorfod
fo n rndIoncfIvo nfom, e.g. If wo bombnrd
l3
2?
AI wIfh nn nIhn () nrfIcIo, wo gof rndIoncfIvo
hoshorus whIch Is uIfImnfoIy convorfod fo sIIIcon.
l3
2?
2
4
l5
30
0
l
AI Ho I + + n

l5
30
I +
l9
30
l
0
SI e.
ThIs honomonon Is known ns ArIificiol IoJioocIitiI,.
AtomIc Muss UnIt
Mnssos of nfoms nro usunIIy oxrossod In nfomIc mnss unIfs (n.m.u.).
l n.m.u. =
l
l2
6
l2
C
So, l n.m.u. =
l
l2
l2 l
=
g
whoro (Avogndro numbor) = 6.023 l0
23
l n.m.u. =
l
6023 l0
l66 l0
23
24
.
. g.
=

Mussnevgy quIvu!ence
In l905, IInsfoIn osfnbIIshod from fhoorofIcnI sfnndoInf fhnf mnss nnd onorgy nro
mufunIIy convorfIbIo. Tho fnmous oqunfIon In fhIs rognrd Is
I = nc
2
whoro I = onorgy ; c = voIocIfy of IIghf.
Tho yonr 2005 hns boon docInrod ns ,eor of pI,eice fo obsorvo fho confonnry of fhIs
fnmous oqunfIon.
HIgL!IgLt:
I = nc
2
= l (3 l0
l0
)
2
g cm
2
soc
2
= 9 l0
20
g cm
2
soc
2
= 9 l0
20
orgs
= 9 l0
l3
jouIos.
So, l g of mnffor Is oquIvnIonf fo 9 l0
l3
J of onorgy.
Muss-nevgy convevsIon Iuctov
Wo know fhnf, l oV = l.6 l0
l2
orgs.
So, l MoV = l.6 l0
6
orgs
nnd l n.m.u. = l.66 l0
24
g.
l n.m.u. =
1

.
.
6 9 l0
l6 l0
20
6
93l MoV.
NucIear Fission
In l939, Cormnn scIonfIsfs Hnhn nnd Sfrnsmnn bombnrdod urnnIum nfom wIfh noufrons nnd
obfnInod fwo oIomonfs wIfh nfomIc numbors 56 nnd 36.
92
235
0
l
92
266
56
l4l
36
92
0
l
3 ! ! In Kr . + + + n n
ThIs honomonon of sIIffIng n nucIous Info fwo nroxImnfoIy oqunI frngmonfs Is cnIIod
nucleor fieeion or einpl, fieeion. Tho gonornfod noufrons ngnIn cnn bombnrd nnofhor
335
!
nfoms nnd nnofhor fIssIons cnn occur nnd fhIs honomonon wIII occur In chnIn wIfhIn l0
8
soc.
ThIs rocoss of roonfod fIssIon Is known ns cIoin reocIion (IIg. 3.3) nnd ns n rosuIf If cnn
gonornfo n hugo nmounf of onorgy, l g of !-235 wIII gonornfo 2 l0
?
kcnI, nnd fhIs nmounf of
onorgy wIII bo gonornfod wIfhIn l0
6
socond. So, fho gonornfIon of hugo nmounf of onorgy
Ionds fo nn oxIosIon wIfh n fomornfuro of ono croro dogroo. ThIs nucIonr fIssIon roncfIon Is
fho rIncIIo of nn nfom bomb.
Neutrons
Fission Fragments
U
235
92
1
0
n
(Secondary neutrons)
Fig. 3.3 Chain reaction as a result of bombardment of
92
U
235
with one
neutron and perfission three secondary neutrons are released.
nevgy Re!eused In u IIssIon ReuctIon
If hns boon osfImnfod fhnf fho mnss gonornfod nffor fIssIon Is nof oqunI fo fho fofnI
woIghf of urnnIum fIssIonod nnd bombnrdIng noufrons. A smnII frncfIon of mnss Is Iosf nnd Is
convorfod fo onorgy nccordIng fo fho oqunfIon: I = nc
2
.
Ior fho roncfIon,
92
235
0
l
56
l4l
36
92
0
l
3 ! In Kr . + + + n n
1niIiol noeeee Iinol noeeee
92
235
!
235.0439 n.m.u.
56
l4l
In
l40.9l39 n.m.u.

0
l
n l.008? n.m.u.
36
92
Kr 9l.89?3 n.m.u.
236.0526 n.m.u. 3
0
l
n 3.026l n.m.u.
235.83?3 n.m.u.
NUCLEAR CHEMSTRY 49
So, fho mnss Iosf Is 0.2l53 n.m.u., whIch Is oquIvnIonf fo nn onorgy of 0.2l53 93l
200 MoV.
HIgL!IgLt:
If cnn bo shown fhnf whon l kg of urnnIum Is comIofoIy fIssIonod, fho onorgy roIonsod
wouId bo 8.2 l0
l3
J, whIch Is suffIcIonf fo suIy onorgy nf fho rnfo of 2.2 mognwnff
confInuousIy for ono yonr.
To ufIIIso fho onorgy roIonsod durIng fho fIssIon, wo nro fo confroI fho chnIn roncfIon fo
gof fho honf onorgy nccordIng fo nocossIfy. ow-n-dnys, In nn nfomIc roncfor, fho mofIon of
noufrons nro rofnrdod by grnhIfo or honvy wnfor fo confroI fho chnIn roncfIon. So, fIssIon
roncfIon Is rofnrdod nnd fhoroby confroIIod nnd fho honf gonornfod Is boIng nbsorbod by moIfon
nK nIIoy nnd fhIs honf Is ufIIIsod In gonornfIng sfonm for fhormnI owor.
AtomIc IusIon
Af n vory hIgh fomornfuro, fwo nucIoI combIno fo gIvo n comnrnfIvoIy honvy nucIous,
i.e., fwo nucIoI combIno fo gIvo n now nfom. ThIs honomonon Is known ns oIonic fueion. And
durIng fhIs fusIon roncfIon somo mnss Is dosfroyod, fhnf monns such n fusIon rocoss wouId
nIso Iond fo IIbornfIon of hugo nmounf of onorgy whIch cnusos oxIosIon.

l
2
l
2
2
4
H H H Inorgy + + o
2 2.0l62 4.00389
n = 0.02863 n.m.u.
whIch Is oquIvnIonf fo 0.02863 93l MoV
= 26.6545 MoV. (Inorgy roIonsod duo fo nbovo fusIon)
Tho dIffIcuIfy Is fo nffnIn fho hIgh fomornfuro for such fusIon rocoss. Iuf If Is boIIovod
fhnf such condIfIon Is nffnInod for ronrIng fhormonucIonr bombs such ns I,Jrogen IonI.
Tho frnnsformnfIons for fusIon roncfIons nro:
(i)
l
3
H + H
l
2

2
4
Ho +
0
l
n + l? MoV
(ii)
l
3
H + H
l
l

2
4
Ho
+ 20 MoV ofc.
Muss DeIect und BIndIng nevgy
Affor fho dIscovory of Isofoos, Asfon oxnmInod fho nfomIc woIghfs of vnrIous oIomonfs
nnd concIudod fhnf fho nfomIc woIghfs of nII fho oIomonfs wouId bo n whoIo numbor. Iuf duo
fo fho rosonco of Isofoos In unoqunI nmounfs, fho nfomIc woIghfs bocomo frncfIons. IosIdos
fhnf, fho nfomIc woIghfs of fho dIfforonf oIomonfs doond uon nnofhor fncfor: In n.m.u. fho
nfomIc woIghfs nro cnIcuInfod from numbor of rofons, oIocfrons nnd noufrons. Tho cnIcuInfod
mnss (M) nnd ncfunI woIghf (A) Is doformInod consIdorIng fho confrIbufIon for fho rosonco of
Isofoos. Tho dIfforonco of fhoso fwo qunnfIfIos Is cnIIod mnss dofocf () or n
= M A.
Ior n
3
?
!I nfom, fho nfomIc woIghf wIII bo
3 0.0005486 + 3 l.00?58 + 4 l.00893
= ?.060l058 n.m.u.
Iuf ncfunI nfomIc woIghf of
3
?
!I
Is ?.0l8l8 n.m.u. (In
l6
O scnIo)
So, mnss dofocf () = ?.060l058 ?.0l8l8
= 0.04l9258 n.m.u.
Whon rofons nnd noufrons unIfo n smnII frncfIon of mnss Is convorfod fo nucIonr bIndIng
onorgy, nnd fhIs Is fho ronson for noee JefecI.
So, fho nucIonr bIndIng onorgy wIII bo
0.04l9258 93l = 39.03 MoV.
Whon mnss dofocf Is dIvIdod by mnss numbor, n frncfIon Is obfnInod whIch Is known ns
pocling frocIion (f)
f =
n
=
A
A
.
l0
0 04l9258
4
l0
4 4
= l04.8l
Thoroforo, nckIng frncfIon Is nvorngo mnss dofocf for nny nrfIcIo. Tho vnIuo of nckIng
frncfIon Is vory smnII, so If hns boon oxrossod by muIfIIyIng l0
4
. A smnII vnIuo of nckIng
frncfIon IndIcnfos gronfor sfnbIIIfy of fho nucIous, n hIghor vnIuo IndIcnfos Ioosonoss of nckIng
of rofons nnd noufrons In fho nucIous nnd ns such Iowor sfnbIIIfy of fho nfom (IIg. 3.4).
0 20 40 60 80 100 120 140 160 180 200 220 240
1
2
3
4
5
6
7
8
9
10
Mass number (A)
B
i
n
d
i
n
g
e
n
e
r
g
y
/
N
u
c
l
e
o
n
(
M
e
V
)
Fig. 3.4 The graph is a plot of binding energy/nucleon vs. mass number (A).
NUCLEAR REACTORS
"A nuc!euv veuctov Is un uppuvutus In wLIcL nuc!euv IIssIon Is pvoduced In tLe Iovm
oI u contvo!!ed se!I sustuInIng cLuIn veuctIon." In ofhor words If Is n dovIco whoro confroIIod
nucIonr fIssIon of
235
!,
233
! or
239
Iu nnd nIso chnIn roncfIon fnkos Inco nnd roducos, honf,
noufrons nnd rndIo-Isofoos. ucIonr roncfors mny bo Iookod uon ns n nucIonr furnnco whoro
fuoI Is
235
!,
233
! ofc.
Tho mochnnIsm for honf gonornfIon: In fho nucIonr roncfors duo fo fho fIssIon frngmonfs
whIch movo nf hIgh sood bocnuso fhoy fnko bnfh In n donso mnss of mofnI, fhoy nro rnIdIy
sIowod down nnd broughf fo rosf duo fo coIIIson wIfh ofhor nfom of fho mofnI. In doIng so
onorgy Is convorfod fo honf.
ucIonr roncfors nro of vnrIous fyos doondIng on fhoIr noufron socfrum, consfrucfIon,
comosIfIon nnd fho uroso for whIch fhoy nro usod. Tho roncfors nro dIfforonfInfod by fho
foIIowIng fonfuros.
Neutvon enevgIes:
(o) HIgh onorgyns In fnsf roncfors
(I) InformodInfo onorgy
(c) !ow onorgyns In fhormnI roncfors.
NUCLEAR CHEMSTRY 51
Types oI Iue!:
(o) nfurnI urnnIum (
238
! = 99.28;
235
! = 0.?l4)
(I) InrIchod urnnIum (HIghor of
235
!)
(c) !rnnIum 233 (obfnInod from
232
Th)
(J)
234
Iu (obfnInod from
238
!)
Types oI Iue! modevutov ussemb!y:
(o) HomogonoousIn whIch fuoI Is dIssoIvod In fho modornfor.
(I) Hoforogonoouswhoro modornfor romnIns sonrnfod from fho fuoI.
Modevutovs:
(o) Honvy wnfor (
2
O) (I) OrdInnry wnfor (H
2
O)
(c) CrnhIfo (J) IoryIIIum
(e) IoryIIIum oxIdo.
Types oI Coo!unts:
(o) Cnsoous (nIr, CO
2
) (I) Wnfor or orgnnIc IIquIds
(c) !IquId mofnIs.
Puvposes:
(o) Ior rosonrch (I) Ior roducfIon of
239
Iu
(c) Ior owor gonornfIon.
oondIng on fho nbovo fncfors, fho nucIonr roncfors nro:
(i) ThormnI, nnfurnI urnnIum, grnhIfo modornfod, Hoforogonoous, nIr cooIod, rosonrch
roncfor.
(ii) Insf, onrIchod urnnIum, hoforogonoous, IIquId mofnI cooIod, owor broodor roncfor.
A nucIonr roncfor Is consfrucfod of fho foIIowIng comononfs:
1. Reuctov Cove: !oncfor coros nro gonornIIy n rIghf cIrcuInr cyIIndor wIfh dIn. 0.5 m fo
l5 m. Tho cyIIndor Is oncIosod In n rossuro vossoI. Tho cyIIndor wIfh fho rossuro vossoI Is
consIdorod ns roncfor coro. Tho roncfor coro consIsfs of nn nssombIy of fuoI oIomonfs, confroIIod
rods, cooInnf nnd modornfor. In fho roncfor coro, fho fIssIon chnIn roncfIon fnkos Inco nnd fho
onorgy Is IIbornfod In fho form of honf.
Tho fuoI oIomonfs nro oIfhor In fho form of Infos or rods of urnnIum mofnIs. Thoy nro
usunIIy cInd In n fhIn shonfh of Zr or AI sfnInIoss sfooI. ThIs rovIdos rofonfIon of rndIoncfIvIfy
nnd corrosIon rosIsfnnco. Ior fho nssngo of fho cooInnfs, onough snco Is rovIdod bofwoon
fho IndIvIdunI rods (IIg. 3.5).
Steam to
turbine
Water
Shielding
Pressure
vessel
Core
uranium fuel
Moderator
Reactor
Coolant
Control rods
Fig. 3.5 Nuclear reactor.
2. ReI!ectov: A rofIocfor Is usunIIy mndo of fho snmo mnforInI ns fho modornfor (nof
shown In fho fIguro). If Is usod fo rofIocf bnck somo of fho IonkIng noufrons from fho roncfor
coro.
3. Contvo! mecLunIsm: ThIs nrf Is nn ossonfInI nrf of fho roncfor nnd sorvos fho
foIIowIng urosos:
(i) To brIng fho roncfor fo Ifs normnI oornfIng IovoI.
(ii) To koo owor roducfIon sfondy.
(iii) To shuf down fho roncfor normnIIy or undor omorgoncy condIfIon.
Tho confroI sysfom nIso Inys nn Imorfnnf roIo fo confroI fho chnIn roncfIon, so fhnf
vIoIonf nnd dnmngIng consoquoncos mny bo nvoIdod. Tho confroI sysfom works on fho sImIo
rIncIIo of nbsorbIng oxcoss noufrons gonornfod duo fo fIssIon wIfh fho hoI of confroI rods
mndo of oIfhor boron sfrIs or cndmIum sfrIs. Tho ndvnnfngo Is, fhoy do nof bocomo rndIoncfIvo
duo fo noufron cnfuro. Throo rods nro suffIcIonf for nny nmounf of oxcoss noufrons. To shuf
down n roncfor fho confroI rods nro Insorfod fo n consIdornbIo dofh so fhnf fho chnIn roncfIon
consos. To sfnrf u fho roncfor If Is nocossnry fo cnrofuIIy wIfhdrnw fho confroI rods nnd ndjusf
fhom. Movomonf of confroI rods cnn bo mndo mnnnunI or nufomnfIc.
4. Modevutov: IuncfIon of modornfor Is fo sIow down fho fnsf movIng fIssIon noufrons.
A modornfor shouId hnvo fho foIIowIng chnrncforIsfIcs:
(o) Iow mnss numbor oIomonfs fo hnvo n hIgh fIowIng cnncIfy.
(I) n Iow cross-socfIon Is usod for boffor noufron nbsorfIon.
Tho oxcoIIonf modornfor Is
2
O bocnuso If sIows down fho noufrons offIcIonfIy nnd If
cnn bo usod ns cooInnfs ns woII. Tho foIIowIng nro fho drnwbncks of
2
O:
(i) !ow boIIIng oInf,
(ii) nocossIfnfIng fho uso of rossuro
(iii) If Is vory oxonsIvo buf Ifs ndvnnfngo oufwoIghs Ifs hIgh cosf.
IoryIIIum (Io) cnn wIfhsfnnd hIgh fomornfuro, boIng vory oxonsIvo If Is usod In socInI
cnsos. !oncfor grndo grnhIfo Is nof good ns n modornfor buf If Is chonor fhnn Io.
5. Coo!unts: IuncfIon of fho cooInnfs Is fo romovo fho honf roducod In fho roncfors.
Categories
H O, D O
2 2
Liquid metals
(Na, K)
Organic liquids
(polyphenyles)
Gases
(CO )
2
HIgL!IgLts:

2
O, H
2
O nro good cooInnfs. Thoy cnn ncf nIso ns fho modornfor. ThoIr boIIIng oInfs
nro Iow. Thoy nood rossurIsnfIon. Wnfor Is corrosIvo nf hIgh fomornfuro.
MoIfon mofnIIIc n or K nro oxcoIIonf cooInnfs. Howovor, n Is hIghIy roncfIvo fo O
2
nnd H
2
nnd bocomos rndIoncfIvo by cnfurIng fho noufron. So If noods shIoIdIng.
!so of oIyhonyIs nro ndvnnfngoous for(i) fhoy do nof roquIro rossurIsnfIon,
(ii) fhoy do nof bocomo rndIoncfIvo by noufron cnfurIng, (iii) fhoy nro nof corrosIvo
nnd (it) sfnbIo nf hIgh fomornfuro. Tho onIy dIsndvnnfngo Is fhoy nro InforIor fo H
2
O
or IIquId mofnIs ns cooInnfs.
AIr cooIIng Is suIfnbIo for Iow owor roncfors.
NUCLEAR CHEMSTRY 53
6. SLIe!dIng: If Is nn Imorfnnf consIdornfIon for n roncfor InsfnIInfIon. Ifs uroso Is
fo wonkon fho -rnys nnd noufrons comIng ouf of fho roncfors so fhnf fhoy cnnnof do nny hnrm
fo fho orsons In ImmodInfo vIcInIfy. In hIgh owor roncfors, fwo shIoIds nro usod.
(o) TIernol SIielJ. If Is kof vory cIoso fo fho roncfor coro, If Is n fhIck sfooI or Iron
covorIng.
(I) Biologicol SIielJ. If Is n Inyor of concrofo of fow docImofor fhIck surroundIng fho
fhormnI shIoId. If Is usod fo nbsorb -rnys nnd fho noufrons IonkIng fhrough fho
Innor fhormnI shIoId.
Bveedev Reuctov
Tho convorsIon fncfor Is dofInod ns "TLe vutIo oI tLe numbev oI seconduvy Iue!
utoms pvoduced to tLe numbev oI pvImuvy Iue! utoms consumed". In gonornI fyo of
roncfors fho convorsIon fncfor Is 0.9. A roncfor wIfh fho convorsIon fncfor nbovo unIfy Is known
ns IreeJer reocIor. In fho broodor roncfor,
235
! Is fIssIonod by fho sIow movIng noufrons. In
fhIs cnso, or nucIonr fIssIon, 2.5 noufrons romnIn In fho roncfor nnd 0.5 noufrons oscno ouf of
fho roncfor. Among whIch ono noufron Is usod fo mnInfnIn fho sfondy chnIn roncfIon. Tho
rosIdunI l.5 noufrons Is usod u ns foIIows:
(i)
238
! cnfuros 0.9 noufrons
(ii) Modornfor, cooInnf nbsorbs 0.6 noufrons.
235
! roducos
239
Iu by cnfurIng fhoso 0.9 noufrons nnd If Is nofoworfhy fo monfIon
fhnf
239
Iu Is n mnnmndo nucIonr fuoI.
Uses oI RudIoIsotopes
!ndIoIsofoos rovIdo n oworfuI fooI for fho soIufIons of onormous robIom In chomIsfry,
Indusfry, hysIcs, bIoIogy nnd hysIoIogy. Tho nIIcnfIon of Isofoos doonds on fho fncf fhnf
fho chomIcnI roorfIos of fho Isofoo of n gIvon oIomonf nro ossonfInIIy IdonfIcnI. Tho dofocfIon
of n rndIoIsofoo Is mndo on fho bnsIs of Ifs rndIoncfIvIfy nnd n sfnbIo Isofoo by monns of n
mnss socfromofor. Tho rndIoncfIvIfy or mnss of nn Isofoo cnn ncf ns n 'fng` or 'InboI` whIch
ormIfs fho fnfo of fho oIomonf or of n comound confnInIng fhIs oIomonf fo bo frncod fhrough
n sorIos of chomIcnI nnd hysIcnI chnngos. Tho oIomonf whIch Is 'InboIIod` or 'fnggod` Is cnIIod n
'frncor oIomonf`. A fow oxnmIo of fho uso of rndIoncfIvo frncors nro gIvon boIow:
(o) PLotosyntLesIs In p!unts: Whon Innfs como In confncf wIfh sunIIghf, fhoy cnn
fnko u CO
2
nnd wnfor, whIch nro fhon convorfod Info sugnr nnd sfnrchos. Af fho snmo fImo,
O
2
Is IIbornfod. Tho O
2
roducod mny como from CO
2
or H
2
O moIocuIos or from bofh. Iy
orformIng oxorImonfs wIfh InboIIod oxygon In CO
2
or H
2
O, If wns found fhnf O
2
cnmo onIy
from wnfor.
6CO
2
* + l0H
2
O C
6
H
l2
O
6
* + 6H
2
O
*

+ 6O
2
6CO
2
+ l2H
2
O* C
6
H
l2
O
6
+ 6H
2
O + 6O
2
*
(I) AgvIcu!tuve: urIng growfh, Innf nbsorbs oIomonfnI I bofh from fho soII nnd from
fho nddod forfIIIzor. How much of fho I Is consumod from fho forfIIIzor by fho Innf cnn onIy bo
doformInod by frncor fochnIquo.
(c) MedIcIne und dIugnosIs: (i) !ndIoIsofoos nro usod fo Iocnfo fho rosonco of fumours,
nrfIcuInrIy brnIn fumours.
(ii)
59
Io Is usod fo dIngnoso fho bIood dIsordor.
(iii)
l3l
I Is usod fo dIngnoso mnIfuncfIonIng of IIvor, kIdnoy, ofc.
(it)
60
Co (-rndInfIons) Is usod In cnncor fhorny.
(J) Industvy: (i) In sfooI Indusfry fo fosf whofhor I Is romovod comIofoIy from cnsf
Iron rndIohoshorus Is usod. Tho dIsnonrnnco of rndIoncfIvIfy IndIcnfos fhnf nII fho I hnvo
boon romovod. (ii)Tho wonr nnd fonr of ongInos cnn bo doformInod by mnkIng fho mofnI of fho
Isfon rIngs rndIoncfIvo. Tho nonrnnco of rndIoncfIvIfy In ongIno oII or In IubrIcnnfs shows
fhnf fho rocoss of wonr nnd fonr of fho Isfons hns sfnrfod.
(e) ReseuvcL: !oncfIon mochnnIsm cnn bo nscorfnInod wIfh rndIoncfIvo frncor fochnIquo.
In osfor hydroIysIs, fho ncyI oxygon cIonvngo or nIkyI oxygon cIonvngo cnn bo doformInod ns
foIIows:
CH C OC H + H O*
2 3 2 5
O
CH
3
O
C
OH + C
2
H
5
*OH (nIkyI oxygon cIonvngo)
CH C OC H + H O*
2 3 2 5
O
CH
3
O
C
*OH + C
2
H
5
OH (ncyI oxygon cIonvngo)
(f ) BIo!ogIcu! veseuvcL: IsofoIc frncors hnvo boon wIdoIy usod In coIIuInr bIoIogy. In
mIfosIs, bohnvIour of coIIs hns boon sfudIod wIfh fho hoI of InboIIod A moIocuIos.
(g) IsotopIc dutIng In Geo!ogy: Tho ngo of n rock or mInornI confnInIng urnnIum cnn
bo doformInod by Ifs rndIoncfIvo docny.
Tho rndIoncfIvo docny oqunfIon Is,
=
0
e
I
whoro,
0
= nmounf of !
238
In fho rock whon If wns formod.
= nmounf of !
238
sfIII Ioff.
I = Inso of fImo (ngo of rock).
SInco nII !
238
hns boon docnyod fo Ib
206
.
nmounf of Ib
206
rosonf In fho mInornI =
0

So, wo cnn wrIfo,
!
238
= (!
238
+ Ib
206
)e
I
whoro, !
238
= nmounf of !
238
In fho rock
Ib
206
= nmounf of Ib
206
In fho rock
= docny consfnnf
I = ngo of fho rock.
A sImIInr roInfIon hoIds good for !
235
, so wo hnvo
!
235
= (!
235
+ Ib
20?
) e
I
whoro = docny consfnnf for !
235
.
Irom fho nbovo fwo oqunfIons, wo hnvo,
Ib
Ib
! ( )
! ( )
206
20?
238
235
l
l
=

e
e
I
I
Tho rosonf rnfIo of !

238
fo !
235
Is l39. nnd cnn bo doformInod from fho hnIf-IIvos of
fwo Isofoos of !.
NUCLEAR CHEMSTRY 55
Honco, fho ngo of fho rock cnn bo cnIcuInfod, rovIdod fho rnfIo Ib
206
fo Ib
20?
Is doformInod
wIfh fho hoI of n mnss socfromofor.
AIfornnfIvoIy, fho ngo of n rock cnn bo doformInod ns foIIows. Tho rndIoncfIvo docny
foIIows fho fIrsf ordor rnfo Inw,
=
2 303 .
I
Iog
o
o x
o = nmounf of !
238
orIgInnIIy rosonf In fho rock nf fho fImo If wns formod.
(o x) = nmounf of !
238

sfIII Ioff nffor fho Inso of fImo (I).
= docny consfnnf of !
238
.
!
238
rosonf In fho rock nf fImo I Is:
o = !
238
+ Ib
206
nnd (o x) = !
238
whoro, !
238
, Ib
206
rorosonf fhoIr rosocfIvo mnssos.
So, =
2 303
238 206
238
.
Iog
! Ib
! I
+
=
2 303
l
206
238
.
Iog
Ib
! I
+
.
0
/
1
.
SInco, vnIuos of Ib
206
nnd !
238
cnn bo doformInod oxorImonfnIIy, fho docny consfnnf of
!
238
Is known from fho roInfIon
=
0 693
l/ 2
.
I
Thus, ngo of fho rock (I) cnn bo cnIcuInfod,
I
I
= +
.
0
/
1
2 303
0 693
l
l/2
206
238
.
.
Iog
Ib
!
.
(I) RudIo-cuvbon dutIng tecLnIque: Tho ngo of n Ioco of wood or nnImnI fossII cnn bo
doformInod by rndIo-cnrbon dnfIng fochnIquo. C
l4
Is formod In fho nfmoshoro ns foIIows :
?
l4
+
0
n
l
(from cosmIc rnys)
6
C
l4
+
l
H
l
ThIs Is rosonf In nfmoshoro ns C
l4
O
2
wIfh C
l2
O
2
.
In rndIo-cnrbon dnfIng rnfIo C
l4
fo C
l2
Is nssumod consfnnf In fho Innf; ns fho Innf
nssImIInfos CO
2
wIfh C
l4
O
2
durIng hofosynfhosIs. Affor fho donfh of fho Innf, no moro CO
2
Is nssImIInfod so rnfIo C
l4
fo C
l2
In fho Innf chnngos, by monsurIng C
l4
fo C
l2
rnfIo nnd
I
l/2
of C
l4
(5,?30 yrs) ngo of fho wood (I) cnn bo cnIcuInfod.
I =
2 303
0 693
l/ 2
.
.
Iog
I o
o x
.
Horo, o =
C
C
l4
l2
rnfIo In fho frosh Innf
(o x) =
C
C
l4
l2
rnfIo In dond Innf.
So, by monsurIng fho rnfIo C
l4
fo C
l2
In fho frosh nnd dond Innfs, ngo of fho wood (I) cnn
bo cnIcuInfod.
xump!e 1. Aeeuning IIoI iI uere Io renoin unJieIurIeJ eince 1S9S A.D., colculoIe
Iou nucI of MoJon Curieè 200 ng of roJiun uoulJ Ie lefI in IIe ,eor S37S A.D. (I
1/2
of
roJiun ie 1620 ,eore).
So!. TofnI fImo = (83?8 l898) = 6480 yrs.
o. of hnIf-IIvos (I
l/2
) =
6480
l620
= 4
Mnss of rndIum Ioff = M
0

l
2
.
0
/
1
n
= 200
l
2
4
.
0
/
1
= l2.5 mg.
xump!e 2. A roJioocIite eource conIoine one nicrogron (g) of Pu
239
. TIie eource ie
eeIinoIeJ Io eniI 2300 -porIiclee/eec. in oll JirecIione. 1eIinoIe Iolf-life of Pu
239
fron IIie
JoIo.
So!. Mnss of ono -nrfIcIo = 4.0038? n.m.u.
= 4.0038? l.66 l0
24
g
= 6.646 l0
24
g
Mnss of 2300 -nrfIcIos = 2300 6.464 l0
24
g
= l4.86?2 l0
2l
g
As

J
JI
M
= M
So =
J JI M/
M
. / l4 86? l0 l
l l0
2l
6
= l4.86?2 l0
l5
soc
l
.
HnIf-IIfo (I
l/2
) of Iu
239
=
0 693 0 693
l4 86?2 l0
l5
. .
.
=

soc.
= l.4?8 l0
6
yonrs.
xump!e 3. Prote IIoI A 0.37 A
0
.
So!. Wo hnvo, =
0
e
I
whon I =
l
, fhon fho nbovo oqunfIon wIII fnko fho form,

=
0
e
.
l
=
0
e
l
=
0
e
.
0
2 ?l8
= 0.368
0
0.3?
0
.
HIgL!IgLt:
Tho rndIoncfIvo consfnnf () mny nIso bo dofInod ns fho rocIrocnI of fImo durIng
whIch fho numbor of n rndIoncfIvo oIomonf fnIIs fo 3? of Ifs orIgInnI mnss.
NUCLEAR CHEMSTRY 57
xump!e 4. A roJioocIite eonple iniIioll, conIoine 4.0 ng of
92
I
234
. (o) Hou nucI of iI
uill renoin uncIongeJ ofIer 62,000 ,eore : (I) WIoI uill Ie iIe ocIitiI, oI IIe enJ of IIoI Iine:
(I
1/2
= 2.4S 10
,re., = S.SS 10
14
e
1
).
So!. (o) !of, M
0
= InIfInI mnss of
92
!
234
M = Mnss nf fho ond of 62,000 yrs.
Wo hnvo, M = M
0
e
I
nnd I =
0 693 0 693 62000
2 48 l0
l/2
5
. .
. I
I =

= 0.l?3
I mny nIso bo cnIcuInfod, ns foIIows:
I = 8.88 l0
l4
62000 365 24 3600
= 0.l?3
M = M
0
e
0.l?3
or, M
0
= M . e
0.l?3
= l.l89 M
or, M =
M
.
0
ll89
Mnss of
92
!
234
Ioff unchnngod =
4
ll89 .
= 3.364 mg.
(I) AcfIvIfy of
92
!
234
Is:
A = = 8.88 l0
l4

3 364 l0 6 023 l0
234
3 23
. .
= ?.69 l0
5
dIsInfogrnfIons/soc.
xump!e 5. TIe Iolf-life perioJ of roJiun ie 1620 ,eore. 1n Iou non, ,eore uill one
gron of pure elenenI (o) loee one cenIigron (I) Ie reJuceJ Io one cenIigron:
So!. (o) Wo know,
=
0 693 0 693
l620
l/2
. .
I
= = 4.28 l0
4
yonr
l
.
!of, fImo durIng whIch ono confIgrnm of rndIum Is Iosf duo fo dIsInfogrnfIon bo = I.
Tho mnss of rndIum wouId bo Ioff bohInd nf fho ond of fImo I = l 0.0l = 0.99 g.
ow, =
0
e
I
or,

0
= e
I
or, Iog
l0
0
= I 0.4343
or, Iog
l0
l00
99
= 4.28 l0
4
I 0.4343
I = 23.68 yonrs.
(I) Horo
.
0
= =
l
0 0l
l00
Iog
l0

l00 = 4.28 l0
4
I 0.4343
I = l0,?60 yonrs.
xump!e 6. TIe uniI for neoeuring roJioocIitiI, ie curie (Ci). One Ci ie JefineJ oe IIoI
quonIiI, of o roJioocIite noIeriol uIicI gitee 3.7 10
10
JieinIegroIione/eec. ColculoIe IIe
noee of IoB in gron uIicI gitee 3.7 10
10
Jie/e.
So!. Tho numbor of nfoms of !nI confnInod In mnss (n)
=
n 6 02 l0
2l4
23
.
ow,
=
J
JI

3.? l0
l0
= 4.3l l0
4

n 6 02 l0
2l4
23
.
n = 3.l l0
8
g.
HIgL!IgLts:
A now nbsoIufo unIf of rndIoncfIvIfy Is rufhorford (rd). Ono rufhorford Is do-
fInod ns fhnf qunnfIfy of n rndIoncfIvo subsfnnco whIch gIvos l0
6
dIs.s
l
.
SmnIIor unIfs IIko mIIIIrnd (mrd) nnd mIcrornd (rd) nro nIso usod.
xump!e ?. ColculoIe IIe noee for IoB for 1 rJ ocIitiI,.
So!. Ior l rd ncfIvIfy,
J
JI
dIs.
l
=

l0
6
s
l0
6
= 4.3l l0
4

n 6 023 l0
2l4
23
.
n = 8.3 l0
l3
g.
HIgL!IgLts:
Ior ono curIo, fho mnss of
92
!
238
( = 0.693/4.5 l0
9
365 24 3600 nnd
I
l/2
= 4.5 l0
9
yonrs) Is:
3.? l0
l0
= 4.9 l0
l8

n 6 023 l0
238
23
.
n = 3.2 l0
6
g.
Ior ono rufhorford, fho mnss of
92
!
238
Is
l0
6
= 4.9 l0
l8

n 6 023 l0
238
23
.
n = 80.98.
xump!e B. TIe roIio of noee of PI
206
Io IIe noee of I
23S
in o cerIoin rocl epecinen ie
founJ Io Ie 0.. Aeeuning IIoI IIe rocl originoll, conIoineJ no leoJ, eeIinoIe iIe oge. (I
l/2
for I
ie 4. 10
9
,eore)
So!. Wo know fhnf,
!
238
= (!
238
+ Ib
206
) e
I
NUCLEAR CHEMSTRY 59
or, l =
l
206
238
+
.
0
/
1
Ib
!
e
I
or, l = (l + 0.5) e
I
= l.5 e
I
e
I
= l.5
or, I = 2.303 Iog
l0
l.5 = 2.3 0.l?6l
0 693
4 5 l0
9
.
.
I = 0.23 0.l?6l
I = 2.63 l0
9
yonrs.
xump!e 9. A eonple of I
23S
ie founJ Io conIoin 11.9 g of I
23S
onJ 10.3 g of PI
206
.
ColculoIe IIe oge of IIe ore. (I
l/2
= 4. 10
9
,eore)
So!. MoIo of !
238
=
ll9
238
.
= 0.05
MoIo of Ib
206
=
l0 3
206
.
= 0.05
Wo hnvo, I =
2 303
0 693
l
l/2
206
238
.
.
Iog
Ib
!
I
+
.
0
/
1
=
2 303 4 5 l0
0 693
l
0 05
0 05
9
. .
.
Iog
.
.

+
.
0
/
1
=
2 303 4 5 l0
0 693
2
9
. .
.
Iog

= 4.5 l0
9

yonrs.
xump!e 10. TIe onounI of
6
C
14
ieoIope in o piece of freeI uooJ ie founJ Io Ie 1/6II of
IIe IoIol corIon. ColculoIe IIe oge of uooJ. (I
1/2
of C = 77 ,re).
So!. Wo hnvo,
I =
2 303
0 693
l
l 6
l/2
.
.
Iog
/
I
=
2 303 55??
0 693
6
.
.
Iog
=
2 303 55?? 0 ??82
0 693
. .
.

= 20,l?0 yrs.
xump!e 11. Holf-life perioJ of C
14
ie 760 ,eore. An olJ piece of uooJ in o nueeun Ioe
o JieinIegroIion roIe uIicI ie 2" of IIe JieinIegroIion roIe of on equol ueigII of o neu piece of
uooJ. WIoI ie IIe oge of IIe olJ piece of uooJ:
So!. Wo hnvo,
I =
2 303 5?60
0 693
l
l 4
.
.
Iog
/
=
2 303 5?60 0 602l
0 693
. .
.

= ll,525 yrs.
xumpIe 12. TIe Iolf-life of Ac
222
ie 6.13 Ire. ColculoIe IIe frocIion of IIe eonple of IIie
euIeIonce preeenI oI IIe enJ of 10 Ire.
SoI.
I =
2 303
0 693
l
l
l/ 2
.
.
Iog
/
I
x
or l0 =
2 303 6 l3
0 693
. .
.
Iog
x
or Iog
.
. .
. x =

=
l0 0 693
2 303 6 l3
0 4696
x = AnfIIog 0.4696 = 2.948
x 3
fho frncfIon of fho SnmIo =
l
3
.
xumpIe 13. (o) WIoI ie Q-tolue for o nucleor reocIion:
(I) ColculoIe IIe Q-tolue for IIe follouing nucleor reocIion.
7
A
14
+
2
He
4

S
O
17
+
1
H
1
.
SoI. (o) Tho ovornII onorgy IIbornfod or nbsorbod In n nucIonr roncfIon Is cnIIod nucleor
reocIion energ,. ThIs onorgy whIch Is gonornIIy nbbrovInfod by Q Is nIso known ns energ,
Iolonce of fho roncfIon ns or IInsfoIn`s fhoory or moro commonIy ns Q-tolue. If Q-vnIuo Is
osIfIvo, fho roncfIon Is nccomnnIod by IIbornfIon of onorgy, fhoro Is Jecreoee in noee In fho
roncfIon, such n roncfIon Is exoIIernic or exoergic. On fho ofhor hnnd, If Q-vnIuo Is nognfIvo,
fhoro Is nbsorfIon of onorgy, fhoro Is goin of noee In fho roncfIon, nnd such roncfIon nro cnIIod
enJoIIernic or enJoergic.
(I)
IntevuctIng puvtIcIes Muss (u.m.u.) Pvoduct puvtIcIes Muss (u.m.u.)
2
Ho
4
4.0038?
8
O
l?
l?.0045
?
l4
l4.00?53
l
H
l
l.008l4
TofnI = l8.0ll40 TofnI = l8.0l264
Incronso In mnss = l8.0l264 l8.0ll40 = 0.00l24 n.m.u.
Q-vnIuo = 0.00l24 93l MoV |3 l n.m.u. = 93lMoV]
= l.l5 MoV
So, fho roncfIon Is
2
Ho
4
+
?
l4
=
8
O
l?
+
l
H
l
+ Q
Q-vnIuo of fho roncfIon Is = 0.00l24 n.m.u. = l.l5 MoV
Tho Q-vnIuo for fho roncfIon Is nognfIvo, fhoro Is Incronso In mnss nnd nbsorfIon of
onorgy, so fho roncfIon Is ondoorgIc.
NUCLEAR CHEMSTRY 61
xumpIe 14. SIou IIe follouing reocIion ie exoergic
3
Li
7
+
1
H
1
=
2
He
4
+
2
He
4
.
SoI.
IntevuctIng puvtIcIes Muss (u.m.u.) Pvoduct puvtIcIes Muss (u.m.u.)
3
!I
?
?.0l822
2
Ho
4
4.0038?
l
H
l
l.008l4
2
Ho
4
4.0038?
TofnI = 8.02636 TofnI = 8.00??4
3
!I
?
+
l
H
l
=
2
Ho
4
+
2
Ho
4
+ Q
Q = ocronso In mnss
= (8.02636 8.00??4) = 0.0l862 n.m.u.
= 0.0l862 93l = + l?.3 MoV.
Horo, Q vnIuo Is osIfIvo, fho roncfIon Is nccomnnIod by IIbornfIon of onorgy (docronso
In mnss).
So fho roncfIon Is oxofhormIc of oxoorgIc.
xumpIe 15. ColculoIe IIe energ, releoeeJ fron IIe fueion of
3
Li
6
onJ
1
D
2
I, IIe reocIion,
3
Li
6
+
1
D
2
=
2
He
4
+
2
He
4
+ Q
uIere ieoIopic noeeee ore,
3
Li
6
= 6.01702 o.n.u.
1
D
2
= 2.01474
2
He
4
= 4.003S7 n.m.u.
SoI. Irom fho nbovo oqunfIon,
Q = (2.0l4?4 + 6.0l?02) (2 4.0338?)
= 0.03402 n.m.u.
= 0.03402 93l = 3l.6? MoV.
xumpIe 16. ColculoIe IIe energ, releoeeJ in IIe follouing fieeion reocIion.
92
I
23
+
0
n
1

36
Kr
9
+
7
Bo
139
+ 2
0
n
1
.
SoI. Tho roncfIon Is
92
!
235
+
0
n
l
=
36
Kr
95
+
5?
In
l39
+ 2
0
n
l
+ Q
or Q = (235.l24 + l.0099) (94.945 + l38.954 + 2 l.0099)
= 0.2l5l n.m.u.
Inorgy roIonsod = 0.2l5l 93l MoV = 200.258 MoV.
xumpIe 1?. ColculoIe IIe liniIing energ, per nucleon
20
Co
40
, uIicI Ioe oIonic noee
of 39.97 o.n.u. TIe noee of proIon ie 1.007S o.n.u. onJ IIe noee of neuIron ie 1.00S6 o.n.u.
SoI. Mnss dofocf n for Cn-nfom
= (20 l.00?8 + 20 l.0086) 39.9?5 n.m.u.
= 0.353 n.m.u.
IIndIng onorgy or nucIoon =
0 353 93l
40
.
MoV.
= 8.2l6 MoV.
xumpIe 1B. ColculoIe (i) IIe fieeion roIe of I
23
for proJucing pouer of 1 uoII onJ
(ii) IIe energ, releoeeJ in IIe conpleIe fieeion of 1 lg of I
23
. (energ, releoeeJ/fieeion of
I
23
MeV = 200 MeV).
SoI. (i) Inorgy roIonsod or fIssIon of !
235
nucIIdo
= 200 MoV
= 200 l.6 l0
l3
J = 3.2 l0
ll
J or W.s.
Honco, fIssIon rnfo for gonornfIon of l wnff
=
l
3 2 l0
ll
.

=

3.l l0
l0
fIssIons soc
l
.
(ii) l kg nfom of !
235
= 235 kg = 6.023 l0
26
nfoms or nucIIdos.
So, onorgy roIonsod or l kg of !
235
=
200 6 023 l0
235
26
.
MoV.
= 8.2 l0
l3
J. (3 l MoV = l.6 l0
l3
J)
xumpIe 19. A ciI, requiree 100 MW of elecIricol pouer on on oteroge. 1f IIie ie Io Ie
eupplieJ I, o nucleor reocIor of efficienc, 20", ueing I
23
oe IIe nucleor fuel, colculoIe IIe
onounI of fuel requireJ for one Jo,è operoIion. Citen IIoI energ, releoeeJ per fieeion of I
23
ie
200 MeV.
SoI. Inorgy consumod In fho cIfy In n dny
= l00 l0
6
24 3600 = 864 l0
l0
J
SInco offIcIoncy of fho roncfor Is 20,
Inorgy roquIrod fo bo roducod In n dny
=
864 l0
0 2
432 l0
l0
ll
=
.
J
Inorgy roIonsod/nucIIdo = 200 l.6 l0
l3
J
= 32 l0
l2
J.
o. of !
235
nfoms fo bo fIssIonod
=
432 l0
32 l0
ll
l2

= l3.5 l0
23
6.023 l0
26
nfoms of !
235
nro rosonf In 235 kg
l3.5 l0
23
nfoms of !
235
nro rosonf In
=
235 l35 l0
6 025 l0
23
26

.
.
kg
= 530 l0
3
kg = 0.53 kg.
Q. 1. WLut do you meun by nucIeuv cLemIstvy?
Ans. ucIonr chomIsfry Is concornod wIfh chnngos of fho nucIoI i.e., Ifs sfnbIIIfy,
dIsInfogrnfIon, ofc.
NUCLEAR CHEMSTRY 63
Q. 2. How does u nucIeuv veuctIon dIIIev Ivom u cLemIcuI veuctIon?
Ans. ucIonr roncfIon InvoIvos fho chnngos of fho nucIous whorons ordInnry chomIcnI
roncfIon InvoIvos fho chnngos In oxfrnnucIonr oIocfrons of fho nfoms, nucIoI of fho nfoms romnIn
unnffocfod In n chomIcnI roncfIon.
Q. 3. WLut Is vudIouctIvIty?
Ans. Tho honomonon of sonfnnoous omIssIon of rndInfIons from fho nucIoI of honvy
oIomonfs Is cnIIod rndIoncfIvIfy.
Q. 4. WLut Is tLe tLeovy beLInd vudIouctIvIty emIssIon?
Ans. !ufhorford nnd Soddnz osfuInfod fhnf,
(i) Tho nucIoI of rndIoncfIvo oIomonfs nro unsfnbIo.
(ii) Tho nucIoI of rndIoncfIvo oIomonfs dIsInfogrnfo formIng nfoms of now oIomonfs cnIIod
'dnughfor oIomonfs`.
(iii) - nnd -nrfIcIos nro omIffod from fho nucIous.
(it) -rnys nro fho socondnry offocfs of fho nucIonr dIsInfogrnfIon.
Q. 5. WLut Is -emmIsIon?
Ans. Tho omIssIon of nn -nrfIcIo from n rndIoncfIvo nucIous Is dosIgnnfod ns -omIssIon.
Tho frnnsformnfIon of !I fo !XI by -omIssIon mny bo rorosonfod ns foIIows:
92
!I
238

2
Ho
4
+
90
!XI
234
.
Q. 6. WLut Is -emIssIon?
Ans. Tho omIssIon of n -nrfIcIo from n rndIoncfIvo oIomonf Is known ns -omIssIon. A
-nrfIcIo Is n sIngIo nognfIvoIy chnrgod nrfIcIo nnd osIfIvo nucIous doos nof confnIn nny
oIocfron. So If nonrs sfrnngo. -nrfIcIo Is gonornfod In fho nucIous ns foIIows:
0
n
l

l
e
0
+
l
H
l
So, on omIssIon of n -nrfIcIo, nucIous gnIns n rofon nf fho cosf of n noufron. Thus, fho
nfomIc numbor of fho dnughfor oIomonf Incronsos by ono unIf.
Q. ?. WLut Is -decuy?
Ans. -rnys hnvo boon rovod fo nrIso from fho frnnsIfIon of n nucIoon from ono onorgy
sfnfo fo fho ofhor. A -docny hns boon doIcfod In fho foIIowIng fIguro.
RaD
83
Bi
210
RaE
82
Pb
210
b-ray
E = 65 KeV
E = 47 KeV
E = 0
g-ray
83
Bi
210
Q. B. WLut do you meun by nutuvuI vudIouctIvIty und uvtIIIcIuI vudIouctIvIty?
Ans. nfurnI rndIoncfIvIfy Is oxhIbIfod by honvIor oIomonfs found In nnfuro. Whorons
modorn fochnIquos of nrfIfIcInI frnnsmufnfIon of oIomonfs hnvo mndo If ossIbIo fo roduco
rndIoncfIvIfy In mnny ofhor IIghfor oIomonfs. Such fyo of rndIoncfIvIfy Is known ns nrfIfIcInI
or Inducod rndIoncfIvIfy.
Q. 9. WLut do you meun by vudIouctIve sevIes?
Ans. If, durIng rndIoncfIvo dIsInfogrnfIon, fho dnughfor oIomonf Is nIso rndIoncfIvo fhon
If docnys furfhor nnd fho rocoss confInuos fIII n sfnbIo Isofoo Is ronchod. ThIs chnIn of succossIvo
dIsInfogrnfIons Is formod 'rndIoncfIvo sorIos`.
Q. 10. WLut do you meun by vudIouctIve decuy constunt?
Ans. Tho rndIoncfIvo docny oqunfIon Is,
=
J
JI

or =
J JI /
So, fho rndIoncfIvo docny consfnnf () mny bo dofInod ns fho rnfIo of fho nmounf of fho
subsfnnco, whIch dIsInfogrnfos In n unIf fImo fo fho nmounf of fho subsfnnco rosonf.
AIfornnfIvoIy, If mny bo dofInod ns fho rnfo of dIsInfogrnfIon whon fho numbor of
rndIoncfIvo nucIous rosonf Is ono.
Q. 11. Compuve vudIouctIve cLunge und cLemIcuI cLunge.
Ans.
RudIouctIve cLunge CLemIcuI cLunge
(i) !ndIoncfIvo chnngo doos nof doond uon
oxfornnI condIfIons IIko fomornfuro,
rossuro, ofc.
(i) ChomIcnI chnngo doonds uon oxfornnI
condIfIons IIko rossuro, fomornfuro, ofc.
(ii) !ndIoncfIvo chnngo Is IrrovorsIbIo. (ii) ChomIcnI chnngo Is mosfIy rovorsIbIo.
(iii) !ndIoncfIvo chnngo Is nIwnys oxofhormIc. (iii) ChomIcnI chnngo mny bo oxofhormIc or
ondofhormIc.
(it) !ndIoncfIvo chnngo Is n nucIonr hono-
monon.
(it) ChomIcnI chnngo InvoIvos onIy ouformosf
oIocfrons of fho nfoms. o chnngo fnkos Inco
of fho nucIous of fho nfom.
Q. 12. WLut do you meun by nucIeuv IIssIon?
Ans. Tho dIvIsIon of n nucIous Info fwo nroxImnfoIy oqunI nrfs Is formod 'nucIonr
fIssIon`. As for oxnmIo:
92 0 92
U + n U
235 1 236
56 36 0
Ba + Kr + 3
140 93 1
n
54 38 0
Xe + Sr + 2
144 90 1
n
55 37 0
Cs + Rb + 2
144 90 1
n
A hugo nmounf of onorgy Is roIonsod durIng nucIonr fIssIon nccordIng fo fnmous IInsfoIn`s
oqunfIon I = nc
2
, nnd fhIs roncfIon Is fho rIncIIo for nfom bomb.
NUCLEAR CHEMSTRY 65
Q.13. WLut do you meun by nucIeuv IusIon?
Ans. Whon fwo IIghf nucIoI combIno wIfh roIonso of n hugo nmounf of onorgy, fho
honomonon Is known ns 'nucIonr fusIon`.
l
H
2
+
l
H
2

2
Ho
4
+ onorgy
l
H
l
+
l
H
3

2
Ho
4
+ onorgy.
ucIonr fusIon Is fho sourco of onorgy of fho sun nnd fho ofhor sfnrs. If Is nIso fho
rocoss fhnf nccounfs for fho orIgIn of nII fho oIomonfs. In fho sun, nf n fomornfuro of fon
mIIIIon dogroos; fho foIIowIng fusIon fnkos Inco.
4
l
H
l

2
Ho
4
+ 2 osIfrons + l0
9
kJ.
Q. 14. WLy tLe eIements wItL even pvoton numbevs uve move ubundunt tLun
otLev eIements?
Ans. Tho rossuro nnd fomornfuro nf fho confro of vory Inrgo sfnrs Is hIgh onough for
2
Ho
4
nucIoI fo fuso fo form honvIor oIomonfs such ns C, SI, Io, sInco
2
Ho
4
hns ovon numbor of
nucIoons, fhoy fuso fo roduco oIomonfs wIfh ovon rofon numbors.
Q. 15. How uve nucIeuv veuctIons cuvvIed out? MentIon tLe uses oI nucIeuv
veuctIons.
Ans. ucIonr roncfIons nro fho chnngos nffocfIng fho nucIoI of nfoms. ucIonr roncfIons
nro broughf nbouf by bombnrdIng nucIoI wIfh hIgh onorgy nrfIcIos In nrfIcIo nccoIornfors or
wIfh bonms of noufrons from nucIonr roncfors.
Anrf from nfom bombs nnd nIfornnfIvo onorgy sourcos, nucIonr roncfIons cnn bo usod
fo mnko oIomonfs fhnf do nof occur In nnfuro; wIfh hIghor rofon numbors fhnn urnnIum.
92
!
238
+
0
n
l

92
!
239

93
239

94
Iu
239
ucIonr roncfIons nro usod fo gIvo bIrfh fo rndIoncfIvo Isofoos fo bo usod ns frncors.
Q. 16. Compuve IIssIon und IusIon veuctIons.
Ans.
IIssIon IusIon
(i) IIssIon InvoIvos bronkIng u of n honvy
nucIous Info IIghfor onos wIfh roIonso of
Inrgo nmounf of onorgy.
(i) IusIon InvoIvos, combInIng of fwo IIghfor
nucIoI Info n honvy nucIous wIfh roIonso of
Inrgo nmounf of onorgy.
(ii) IIssIon fnkos Inco nf ordInnry fomornfuro. (ii) IusIon fnkos Inco nf vory hIgh fomornfuro
(l0
6
K).
(iii) urIng fIssIon, noufrons nro omIffod. (iii) urIng fusIon, osIfrons nro omIffod.
(it) IIssIon gIvos rIso fo chnIn roncfIon. (t) IusIon doos nof gIvo rIso fo chnIn roncfIon.
EXERCISES
1. Whnf Is rndIoncfIvIfy CIvo nn nccounf of fho dIscovory of rndIoncfIvIfy
2. How wIII you show fhnf rndIoncfIvIfy Is nofhIng buf n nucIonr roorfy
3. If you nro gIvon n Ioco of mInornI, how cnn you doformIno by sImIo oxorImonfs If fho mInornI
Is rndIoncfIvo
4. Whnf nro -, - nnd -rnys Comnro fhoIr IonIsIng owor, rnngo nnd voIocIfy.
5. IxInIn fho forms:
(i) IsInfogrnfIon consfnnf
(ii) HnIf-IIfo orIod
6. Whnf nro fho unIfs of rndIoncfIvIfy
?. CIvo n roInfIon bofwoon hnIf-IIfo nnd fho docny consfnnf of n rndIoncfIvo subsfnnco.
B. Whnf nro fho cnusos of nucIonr InsfnbIIIfy IxInIn wIfh suIfnbIo oxnmIos.
9. Sfnfo nnd oxInIn fho Inw of rndIoncfIvo dIsInfogrnfIon. Whnf do you monn by fho hnIf-IIfo orIod
of n rndIoncfIvo oIomonf Show fhnf fho hnIf-IIfo Is Indoondonf of fho nmounf of fho subsfnnco.
10. IxInIn nrfIfIcInI rndIoncfIvIfy wIfh suIfnbIo oxnmIos.
11. Whnf Is rndIoncfIvo dIsIncomonf Inw
12. WrIfo nofos on:
(i) !ndIoncfIvo oquIIIbrIum
(ii) AfomIc woIghf of Iond In rndIoncfIvo mInornIs
(iii) Trncor fochnIquo.
13. Why Is nnfurnI rndIoncfIvIfy mosfIy IImIfod nmong honvIor oIomonfs
14. Whnf Is n nucIonr roncfIon Iscuss somo usos of nucIonr roncfIons.
15. Whnf Is nucIonr bIndIng onorgy
16. Whnf nro rndIo-Isofoos How nro fhoy ronrod MonfIon fhoIr usos.
1?. CIvo n comnrnfIvo nccounf of fho nucIonr bIndIng onorgy curvo nnd nckIng frncfIon curvo.
Whnf InformnfIons nro nvnIInbIo from fhoso curvos
1B. WrIfo n shorf nofo on nucIonr frnnsmufnfIon.
19. Whnf Is nucIonr fIssIon Show how nucIonr fIssIon Is n chnIn roncfIon.
20. WrIfo n shorf nofo on nucIonr fusIon.
21. CIvo n brIof nccounf of fho nucIonr roncfors. orIvo n roInfIon bofwoon mnss dofocf nnd nucIonr
bIndIng onorgy.
22. Whoro Is fho rndIoncfIvo dIsIncomonf Inw InvnIId
23. CnIcuInfo fho nmounf of onorgy roIonsod durIng fho bombnrdmonf of
0
l
n on

!
92
235
.
24. WrIfo n shorf nofo on rndIo-cnrbon dnfIng.
25. ComIofo fho foIIowIng nucIonr roncfIons:

4
9
2
4
6
l2
Io Ho C ... + +
ll
24
l2
24
n Mg ... +
92
238
90
239
! Th ... +
5
l0
2
4
l
l
I Ho ... H + +
3
?
l
l
4
?
!I H ... Io. + +
26. CnIcuInfo fho fImo roquIrod for l0 dIsInfogrnfIon of n snmIo of fhorIum. CIvon fho I
l/2
of
fhorIum = l.4 l0
l0
yrs. |Ans. 6.93 l0
5
yrs.]
2?. CnIcuInfo fho bIndIng onorgy In MoV or nucIoon of
6
l2
C.
CIvon: Mnss of H-nfom = l.00?82 n.m.u.
Mnss of noufron = l.00866 n.m.u.
AcfunI mnss of C-nfom = l2.04
l nmu = 93l.4 MoV. |Ans. 54.?6 MoV]
2B. Tho hnIf-IIfo of rndIum Is l590 yonrs. How Iong wIII If fnko for l g of fho oIomonf fo Ioso 0.l g
|Ans. 2385 yrs.]
NUCLEAR CHEMSTRY 67
29. A Ioco of wood wns found fo hnvo
l4
C/
l2
C rnfIo 0.? fImos fhnf In n IIvIng Innf. CnIcuInfo fho
nroxImnfo IIfo orIod whon fho Innf dIod. CIvon I
l/2
= 5?60 yonrs. |Ans. 29?0 yonrs]
30. A snmIo of urnnIum oro Is found fo confnIn ll.9 g of
238
! nnd l0.33. of
206
Ib. CnIcuInfo fho ngo
of fho rock. CIvon I
l/2

of urnnIum = 4.5 l0
9
yrs. |Ans. 4.5 l0
9
yonrs]
31. HnIf IIfo of
222
!n In 3.82 dnys. CnIcuInfo fho woIghf of l curIo of
222
!n. |Ans. 6.5 l0
6
]
32. A rndIoncfIvo oIomonf dIsInfogrnfos fo l/l6fh of Ifs orIgInnI mnss In l60 dnys. Whnf Is Ifs hnIf-
IIfo orIod |Ans. 40 dnys]
33. CnIcuInfo fho onorgy roIonsod In MoV from fho roncfIon:
5
l0
l
2
5
ll
l
l
I H I H + +
CIvon: Mnss of
l0
I = l0.0l605 n.m.u.
Mnss of
ll
I = ll.0l286 n.m.u.
Mnss of 2H = 2.0l4?2 n.m.u.
Mnss of
l
H = l.008l2 n.m.u. |Ans. 9.ll4 MoV]
34. A noufron bronks Info n rofon nnd nn oIocfron. CnIcuInfo fho onorgy roducod In MoV.
CIvon: Mnss of noufron = l.6?4? l0
24
g.
Mnss of rofon = l.6?25 l0
24
g.
Mnss of oIocfron = 9 l0
28
g.
l n.m.u. = 93l MoV. |Ans. 0.?3 MoV]
35. CnIcuInfo fho docny consfnnf of
60
Co. CIvon fho I
l/2
of cobnIf = 5.3 yonrs. |Ans. 0.l3 yr
l
]
36. CnIcuInfo fho onorgy roIonsod In fho nucIonr fusIon roncfIon:
l
2
l
3
2
4
0
l
H H Ho + + n
CIvon: Mnss of
l
2
H = 2.0l4 n.m.u.
Mnss of
l
3
H = 3.0l6 n.m.u.
Mnss of
2
4
Ho = 4.003 n.m.u.
Mnss of
0
l
n = l.009 n.m.u. |Ans. l6.?6 MoV]
3?. An oId woodon nrfIcIo shows 2.0 counfs mIn
l
g
l
. A frosh snmIo of wood shows l5.2 counfs
mIn
l
g
l
. CnIcuInfo fho ngo of fho woodon nrfIcIo.
CIvon: I
l/2
for
6
l4
C = 5,?60 yrs. |Ans. l6,862 yonrs]
3B. IsfInguIsh bofwoon nucIonr fuoI nnd n chomIcnI fuoI.
39. WrIfo shorf nofo on comononfs of n nucIonr owor roncfor nnd fhoIr funcfIons.
"
Thermodynamics
ThormodynnmIcs Is concornod wIfh fho fIow of honf nnd fhoroforo donIs wIfh fho qunnfIfnfIvo
roInfIonshI bofwoon honf nnd work. Tho scIonco of fhormodynnmIcs ncfunIIy covors n much
wIdor fIoId covorIng onorgy-chnngos In nII hysIcnI nnd chomIcnI rocossos ns woII ns mufunI
frnnsformnfIons of nII fho dIfforonf forms of onorgy. ThormodynnmIc doducfIons nro nof mndo
on fho bnsIs of nny hyofhosIs nbouf fho moIocuInr sfrucfuro of mnffor buf fho fhroo sImIo
Inws of fhormodynnmIcs nro bnsod on humnn oxorIonco nnd fhoso roInfIons woro fosfod
oxorImonfnIIy for confurIos sfnrfIng from honf ongInos fo coIIuInr onzymnfIc rocossos nnd
nro consIdorod InvIoInbIo. Thus, IInsfoIn commonfs: If (fhormodynnmIcs) Is fho onIy hysIcnI
fhoory of unIvorsnI confonf concornIng whIch I nm convIncod fhnf, wIfhIn fho frnmowork of
nIIcnbIIIfy of Ifs bnsIc concofs, If wIII novor bo ovorfhrown.
- Before Ieginning uiII IIe loue of IIernoJ,nonice follouing Ierne ore neeJeJ Io Ie
JefineJ.
1. TLevmodynumIc systems. A e,eIen Is dofInod ns nny mnffor or Ifs nrf, choson for
sfudy nnd sonrnfod from fho rosf of fho unIvorso by n ronI or ImngInnry boundnry. Tho rosf of
fho unIvorso Is cnIIod fho eurrounJinge.
A sysfom Is snId fo bo nn ieoloIeJ e,eIen whon If Is cnnbIo of oxchnngIng oIfhor onorgy
or mnffor wIfh fho rosf of fho unIvorso. Honco, fho onorgy nnd mnffor romnIn consfnnf for fho
sysfom. Thoro Is no such orfocfIy IsoInfod sysfom ofhor fhnn our unIvorso IfsoIf.
A cloeeJ e,eIen Is ono, whIch Is cnnbIo of oxchnngIng onIy onorgy wIfh fho surroundIngs
buf no mnss frnnsfor ncross fho boundnry Is ormIffod; oxnmIo Is n sonIod fInsk confnInIng
mnffor In n cIosod sysfom.
An open e,eIen Is n sysfom, whIch cnn oxchnngo bofh mnss nnd onorgy ncross fho
boundnry; oxnmIo Is n Innf or nny IIvIng boIng.
2. PvopevtIes oI u system. Tho hysIcnI chnrncforIsfIcs whIch nro oxorImonfnIIy
monsurnbIo nnd whIch onnbIo us fo dofIno n sysfom nro cnIIod fhormodynnmIc nrnmofors or
roorfIos of fho sysfom. ComosIfIon, voIumo, rossuro nnd fomornfuro nro fho fundnmonfnIIy
Imorfnnf roorfIos. !ofrncfIvo Indox, vIscosIfy, dIoIocfrIc consfnnf nro nIso ofhor roorfIos.
1xIeneite properI,. IroorfIos IIko voIumo, surfnco nron, onorgy, ofc., nro doondonf
uon fho mnss of fho sysfom nnd nro cnIIod oxfonsIvo roorfy.
1nIeneite properI,. IroorfIos IIko fomornfuro, rossuro, surfnco fonsIon, vIscosIfy,
socIfIc honf, donsIfy, rofrncfIvo Indox, ofc., nro Indoondonf of fho mnss of fho sysfom nnd nro
cnIIod InfonsIvo roorfIos.
3. Stute oI u system. Tho sof of fhormodynnmIc vnrInbIos such ns rossuro, voIumo,
fomornfuro, comosIfIon, ofc., whIch doscrIbo n sysfom Is cnIIod fho sfnfo of fho sysfom.
WIen one or nore of IIeee torioIlee unJergo cIonge, IIe e,eIen ie eoiJ Io Iote unJergone
o cIonge of eIoIe.
68
THERMODYNAMCS 69
If, ns n rosuIf of n sorIos of chnngos, fho sysfom rofurns fo Ifs InIfInI sfnfo, Ifs fhormo-
dynnmIc nrnmofors nIso rofurn fo fhoIr orIgInnI vnIuos, such n rocoss Is cnIIod n c,clic proceee.
If n chnngo fnkos Inco nf n consfnnf fomornfuro mnInfnInod fhroughouf, If Is cnIIod nn
ieoIIernol proceee.
If n chnngo fnkos Inco In n fhormnIIy InsuInfod sysfom whIch doos nof ormIf honf
oxchnngo wIfh fho surroundIng, fho rocoss Is cnIIod nn oJioIoIic proceee nnd fho fomornfuro
of fho sysfom mny Incronso or docronso.
If n rocoss Is cnrrIod ouf nf consfnnf rossuro, fho rocoss Is cnIIod nn ieoIoric proceee,
whIch Is nccomnnIod by voIumo chnngos.
If n chnngo fnkos Inco In whIch fho voIumo of fho sysfom romnIns consfnnf fho rocoss
Is cnIIod nn ieocIoric proceee. A rocoss Is snId fo bo retereiIle If fho onorgy chnngo In onch sfo
of fho rocoss cnn bo rovorsod In dIrocfIon by nn InfInIfosImnI chnngo In nny of fho vnrInbIos
ncfIng on fho sysfom. A rocoss cnn bo mndo rovorsIbIo by orformIng fho chnngo vory sIowIy
wIfh no frIcfIon nnd no fInIfo fomornfuro dIfforoncos.
An irretereiIle proceee Is such fhnf fho sysfom nnd fho surroundIng nffor undorgoIng
chnngos cnnnof gof bnck fo fhoIr InIfInI sfnfo nnd fond fo rocood fo n dofInIfo dIrocfIon buf
cnnnof rocood fo fho rovorso dIrocfIon. AII fho nnfurnI rocossos nro IrrovorsIbIo, oxnmIo,
oxnnsIon of gnsos from hIgh rossuro fo Iow rossuro, honf fIowIng from n hoffor fo n coIdor
body, ofc. 1rretereiIle proceeeee ore oll eponIoneoue proceeeee.
1quiliIriun eIoIe. A sysfom Is snId fo bo In oquIIIbrIum whon Ifs comosIfIon Is fIxod,
fomornfuro Is unIform nnd nIso snmo wIfh fho surroundIngs nnd fhoro Is no unbnInncod forco
fho sysfom nnd nIso bofwoon fho sysfom nnd fho surroundIngs. Honco, n sysfom In oquIIIbrIum
sfnfo hns dofInIfo fomornfuro, rossuro nnd comosIfIon.
SIoIe funcIion Is n fhormodynnmIc roorfy, whIch doonds onIy on fho sfnfo of fho
sysfom buf nof on fho nfhs foIIowod for fho chnngo. InfornnI onorgy chnngo (I), onfhnIy
chnngo (H), froo onorgy chnngo (C) nnd onfroy chnngo (S) nro such funcfIons.
1nIernol energ,. Ivory sysfom wIfhIn IfsoIf hns n qunnfIfy of onorgy whIch Is cnIIod fho
InfornnI or InfrInsIc onorgy. ThIs onorgy Is n funcfIon of fho fomornfuro, chomIcnI comosIfIon,
rossuro nnd voIumo of fho sysfom. Tho mngnIfudo of InfornnI onorgy of n sysfom Is doformInod
by fho kInofIc, rofnfIonnI, vIbrnfIonnI movomonfs of fho moIocuIos of fho sysfom. If Is nn oxfonsIvo
roorfy. IIvo moIos of n subsfnnco In n socIfIod sfnfo hns fIvo fImos fho InfornnI onorgy
ossossod by n sIngIo moIocuIo In n sImIInr sfnfo. Tho nbsoIufo vnIuo of fho InfornnI onorgy of
n sysfom cnnnof bo nscorfnInod. Whon n sysfom chnngos from n IIernoJ,nonic eIoIe 1 Io o
IIernoJ,nonic eIoIe 2, IIe cIonge in IIe inIernol energ, I = I
2
I
1
ie inJepenJenI of IIe
poII of IronefornoIion IuI JepenJe on IIe iniIiol onJ finol conJiIione of IIe e,eIen.
If n sysfom undorgoos n sorIos of chnngos nnd rofurns fo Ifs InIfInI sfnfo i.e., If n cycIIc
rocoss Is comIofod, InfornnI onorgy Is found fo rofurn fo Ifs orIgInnI vnIuo, honco fho sum of
fho chnngos of InfornnI onorgy for n cycIIc rocoss i.e., I = 0. So InfornnI onorgy (I) Is n sfnfo
funcfIon. OfhorwIso, If cnn bo sfnfod fhnf whon n sysfom chnngos from InIfInI sfnfo (l) fo n
fInnI sfnfo (2) nnd comos bnck fo (l) (IIg. 4.l), nof chnngo In InfornnI onorgy Is zoro i.e., JI
= 0
(cycIIc InfogrnfIon of I Is 0), so JI Is nfh Indoondonf nnd I Is n sfnfo funcfIon.
Cyclic process
Fig. 4.1
THE FIRST LAW OF THERMODYNAMICS
Tho fIrsf Inw of fhormodynnmIcs Is sImIy fho Inw of consorvnfIon of onorgy, nnd If mny
bo sfnfod ns fho onorgy of nn IsoInfod sysfom romnIns consfnnf nnd whonovor n qunnfIfy of
somo form of onorgy dIsnonrs, nn oxncfIy oquIvnIonf qunnfIfy of somo ofhor form of onorgy
musf mnko Ifs nonrnnco.
Tho Inw wns fIrsf sfnfod by Mnyor In l842 nnd IouII`s cInssIcnI rosonrch on oquIvnIonco
bofwoon honf nnd work osfnbIIshod fho fncf In l845 nnd fInnIIy gonornIIsod by HoImhoIfz
In l84?.
MutLemutIcuI IovmuIutIon oI tLe IIvst Iuw
!of us suoso, honf suIIod fo n sysfom Is q. SInco honf onorgy cnnnof bo Iosf, If mny
bo usod u by fho sysfom ns nrfIy IncronsIng fho InfornnI onorgy of fho sysfom nnd nrfIy In
doIng mochnnIcnI work. Thus, nccordIng fo fho fIrsf Inw
Honf nbsorbod = Incronso of InfornnI onorgy + Work dono by fho sysfom
i.e., q = I + W
or I = q W
If fho nbovo chnngo Is InfInIfosImnIIy smnII, wo cnn wrIfo
JI = Jq Ju
whoro JI Is fho Incronso In InfornnI onorgy, Jq nnd Ju rorosonf smnII qunnfIfIos of honf nbsorbod
nnd oxfornnI work dono by fho sysfom, rosocfIvoIy. Ior on oJioIoIic cIonge, q = 0, W = I.
So In nn ndInbnfIc rocoss, work dono by fho sysfom = docronso In InfornnI onorgy of fho
sysfom. If fho sysfom Is undor n rossuro I nnd voIumo Incronsos by JV, fho work dono bocomos
I JV nnd honco fho mnfhomnfIcnI oxrossIon of fIrsf Inw bocomos, JI = Jq I. JV for vory vory
smnII chnngos.
Horo fho work, oxcIusIvoIy, Is of rossuro voIumo fyo. Whon fho voIumo (V) Is consfnnf,
JV = 0, honco JI = Jq I 0 |3 Jt = 0]
JI = Jq or I = qV
CycIIc pvocess: Wo hnvo nIrondy found fhnf If n sysfom undorgoos chnngo fhrough
nfh (l) nnd rofurns fo Ifs orIgInnI sfnfo vIn nfh (2), If comIofos n cycIIc nfh nnd fho ovornII
chnngo of onorgy (I) i.e., I = 0.
Honco, from fIrsf Inw, I = q W = 0
q = W.
Honco, wo nrrIvo nf n vory Imorfnnf roInfIon fhnf for n cycIIc rocoss, fho nIgobrnIc sum
of nII fho honf forms Is oqunI fo fho nIgobrnIc sum of nII fho work forms.
JouIe-TLomson eIIect
JouIo-Thomson offocf sfnfos: Whon n gns undor hIgh rossuro Is ormIffod fo oxnnd
Info n rogIon of Iow rossuro, If suffors n fnII In fomornfuro.
THERMODYNAMCS 71
JouIo nnd Thomson orformod nn oxorImonf whoro n gns wns nIIowod fo oxnnd
ndInbnfIcnIIy fhrough n orous Iug ngnInsf n consfnnf rossuro. Thus, fho gns wns nIIowod fo
do no work nnd fhoro wns no Inforchnngo of honf wIfh fho surroundIngs.
Suoso V
l
voIumo of gns nf rossuro I
l
Is forcod fhrough fho orous Iug nnd oxnnds
fo n voIumo V
2
nf n Iowor rossuro I
2
.
Honco, work dono by fho gns Is, I
2
V
2
I
l
V
l
= W.
Ior nn IdonI gns, I
l
V
l
= I
2
V
2
W = 0.
Honco, from fIrsf Inw of fhormodynnmIcs,
I = q W = q 0 = q.
Honco, for nn IdonI gns, fhoro shouId bo no chnngo In fomornfuro. Iuf JouIo-Thomson
obsorvod fhnf mosf gnsos cooIod down by such n rossuro dro. SInco fho oxnnsIon Is cnrrIod
ouf ndInbnfIcnIIy i.e., whon q = 0, fho onorgy of fho gns fnIIs i.e., I = vo; fhus fho gns whIIo
oxnndIng doos somo work nnd honco fho fomornfuro fnIIs. Tho work dono Is nf fho oxonso
of fho kInofIc onorgy of fho moIocuIo whIIo fhoy nro sonrnfod from onch ofhor.
Heut content ov ntLuIpy oI u system
Tho rossuro (I) nnd voIumo (V) of n sysfom nro fhormodynnmIc vnrInbIos nnd fhoIr
roducf IV Is oxrossod ns onorgy. Suoso, n sysfom nf consfnnf rossuro Is undorgoIng n
chnngo from sfnfos l fo 2. Tho voIumo Incronso Is from V
l
fo V
2
. Honf nbsorbod by fho sysfom
Is q. Honco, from fho fIrsf Inw of fhormodynnmIcs
q = (I
2
I
l
) + W
= (I
2
I
l
) + (I
2
V
2
I
l
V
l
)
= (I
2
+ I
2
V
2
) (I
l
+ I
l
V
l
)
= H
2
H
l
= H.
Tho qunnfIfy (I + IV) Is unIvorsnIIy rorosonfod ns H nnd cnIIod fho honf confonf or
onfhnIy of n sysfom. SInco I Is n chnrncforIsfIc of fho sysfom (sfnfo funcfIon), nccordIng fo fho
fIrsf Inw, H Is n sImIInr sfnfo funcfIon. Honco, H wIII doond onIy on fho InIfInI nnd fInnI
sfnfos of fho sysfom, nof on fho nfh foIIowod durIng fho chnngo.
H = (I
2
+ I
2
V
2
) (I
l
+ I
l
V
l
)
= (I
2
I
l
) + (I
2
V
2
I
l
V
l
)
Af consfnnf rossuro,
H = I + IV = I + W = q (honf nbsorbod)
nnd nf consfnnf voIumo, V = 0.
H = I + 0 = I.
i.e., Chnngo In onfhnIy = chnngo In InfornnI onorgy.
So, If fho rocoss Is cnrrIod ouf nf consfnnf voIumo chnngo In onfhnIy nnd chnngo In
InfornnI onorgy nro oqunI.
Constuncy oI ntLuIpy (IsoentLuIpIc) In JouIe-TLomson expunsIon
JouIo-Thomson oxorImonf Is cnrrIod ouf ndInbnfIcnIIy, whon honf doos nof fIow ouf of
fho sysfom nor doos If como Info sysfom from fho surroundIng, i.e., q = 0. Tho gns oxnnds Is
nssIng fhrough orous Iug (IIg. 4.2) nnd fho work dono Is I
2
V
2
I
l
V
l
.
V
1
P
1
P
2
V
2
Porous plug
Fig. 4.2 Joule-Thomson expansion.
Honco, from fIrsf Inw, I = q W
= 0 (I
2
V
2
I
l
V
l
)
i.e., I
2
I
l
= I
2
V
2
+ I
l
V
l
I
2
+ I
2
V
2
= I
l
+ I
l
V
l
or H
2
= H
l
.
H = I + IV = I + I(V
2
V
l
)
= I + u = q
I
(honf nbsorbod nf consfnnf rossuro)
i.e., chnngo In onfhnIy Is oqunI fo honf nbsorbod nf consfnnf rossuro.
InvevsIon tempevutuve
If fho gns In nbovo oxnnsIon suffors n fnII In fomornfuro by JT, for n IoworIng of
rossuro JI, wo cnn dofIno JouIo-Thomson cooffIcIonf () by fho roInfIon,
=
T
I
H
Is zoro for nn IdonI gns (IV = n!T). Ior vnn dor WnnIs gns,
=
2o
!T
I
Tho sIgnIfIcnnco of Is fnII In fomornfuro In dogroos by n gns In froo oxnnsIon for n
rossuro dro of l nfm. undor ndInbnfIc condIfIons.
Ior gnsos hnvIng osIfIvo vnIuo cooIs on oxnnsIon buf for H
2
gns Is nognfIvo i.e., H
2
wnrms u on oxnnsIon.
Tho cooIIng offocf Is soon whon fho fomornfuro Is Iow. Iuf, If fho fomornfuro Is hIgh,
fhon Insfond of cooIIng fho gnsos nro honfod, i.e., bocomos nognfIvo. Ior ovory gns fhoro Is n
fomornfuro whoro = 0, whon noIfhor honfIng nor cooIIng of fho gnsos occurs on oxnnsIon
nffor nsIng fhrough orIfIcos. ThIs fomornfuro Is cnIIod fho intereion IenperoIure, T
i
of fho gns.
Wovk done In u vevevsIbIe IsotLevmuI expunsIon: Suoso n moIos of n gns Is
oncIosod In n cyIIndor by n frIcfIonIoss Isfon (IIg. 4.3).
Tho cyIIndor Is kof In n consfnnf fomornfuro bnfh i.e., fhormosfnf nf T K. i.e., IsofhormnI
condIfIon Is mnInfnInod. Tho gns hns n voIumo V
l
nnd fho Isfon Is nf oInf A. Tho gns Is fo bo
oxnndod from voIumo V
l
fo voIumo V
2
. Tho work of oxnnsIon (W) wIII bo gIvon by fho roducf
of oosIng forco nnd fho dIsIncomonf.
W = forco dIsIncomonf
= forco nron dIsfnnco
= I o l.
Af ovory sfo n mInufo dIsfnnco (l) of fho Isfon mny bo
mndo so fhnf work dono (W) Is,
W = I o l.
o l Is fho voIumo swof by fho Isfon, If Is JV
Thon, W =
V
V
V
V
l
2
l
2
I V
!T
V
V

= J
n
J |3 IV = n!T]
W = n!T In
V
V
2
l
SInco,
V
V
2
l
=
I
I
2
l
In nn IsofhormnI oxnnsIon of n orfocf gns.
V
1
T
A
Fig. 4.3
THERMODYNAMCS 73
Thon, W = n!T In
V
V
2
l
= n!T In
I
I
l
2
So, for l moIo of nn IdonI gns, work dono (W) durIng rovorsIbIo IsofhormnI oxnnsIon Is,
W = !T In
V
V
2
l
.
ntLuIpy oI u guseous veuctIon
n
l
moIos of roncfnnf gnsos roncf fo roduco n
2
moIos of gnsoous roducfs, fhoroby voIumo
chnngos from V
l
fo V
2
nf consfnnf fomornfuro T nnd rossuro I.
Ior n moIos of nn IdonI gns, IV = n!T.
I(V
2
V
l
) = (n
2
n
l
) !T.
or IV = n . !T.
Irom fIrsf Inw of fhormodynnmIcs, H = I + IV.
H = I + n.!T.
Whon fho roncfIon InvoIvos gnsoous oxnnsIon,
n Is osIfIvo, H > I.
Whon fho roncfIon InvoIvos gnsoous confrncfIon,
n Is nognfIvo H < I.
Whon fhoro Is no voIumo chnngo, H = I.
Heut cupucIty
Honf cnncIfy (C) of n subsfnnco Is fho nmounf of honf noodod fo rnIso fho fomornfuro
of l gm of fho subsfnnco by lC. SImIInrIy, moInr honf cnncIfy of fho subsfnnco Is fho nmounf
of honf roquIrod fo rnIso fho fomornfuro of l moIo of fho subsfnnco by lC.
Molor IeoI copociI, oI coneIonI tolune Is C
t
, whIch Is moInr honf cnncIfy monsurod nf
consfnnf voIumo condIfIon.
If Jq honf Is roquIrod for JT Incronso In fomornfuro fhon for l moIo of subsfnnco,
C =
Jq
JT
Af consfnnf voIumo condIfIon, C
t
=
I
T
V

,
.
Molor IeoI copociI, oI coneIonI preeeure ie neoeureJ I, leeping IIe preeeure coneIonI
C
p
=
Jq
JT
=
H
T
I
.
ReIutIon between C
p
und C
v
:
Wo know, H = I + (IV)
or

H
T
I
T
IV
T
= +
( )
or C
p
= C
t
+
( ) IV
T
THERMODYNAMCS 75
fho dIsordor nnd IrrovorsIbIIIfy nnd whon oquIIIbrIum Is ronchod, If hns fho mnxImum dIsordor.
Thus, fho onfroy of fho sysfom goos on IncronsIng nnd ronchos n mnxImum vnIuo nf oquIIIbrIum.
Ior oxnmIo, If n gns wIfh sfrong odour Is Iof Iooso nf fho cornor of n room, fho odour of fho gns
sronds nII ovor fho room rnndomIy nnd oquIIIbrIum Is ronchod whon fho onfroy nIso bocomos
mnxImum.
HIgLIIgLts:
IrodIcfIon of dIrocfIon of chnngos Is ossIbIo wIfh n fhormodynnmIcnI qunnfIfy
known ns enIrop, (S).
A sonfnnoous chnngo occurs In fho dIrocfIon IondIng fo n fofnI Incronso of onfroy.
If Is convonIonf fo cnIcuInfo fofnI onfroy chnngo In fwo nrfs. (i) fho onfroy
chnngo of fho sysfom nnd fho onfroy chnngo of fho surroundIngs i.e.,
S
fofnI
= S
sysfom
+ S
surroundIngs
.
Cnsos gonornIIy hnvo hIghor onfroIos fhnn IIquIds.
Infroy Is n sfnfo funcfIon doondonf on I, V, T nnd nfh Indoondonf.
If sysfom nbsorbs honf, onfroy Incronsos nnd vIco-vorsn.
Any IrrovorsIbIo rocoss Is nccomnnIod by Incronso In onfroy. As nII sonfnnoous
rocossos nro IrrovorsIbIo, fho onfroy of fho unIvorso Is ovor IncronsIng.
Infroy Is n monsuromonf of rnndomnoss of n sysfom.
Irom oxorIonco wo cnn sny, dIsordorod form Is moro robnbIo fhnn ordorod form.
So, Incronso of rnndomnoss onhnncos fhormodynnmIc robnbIIIfy. IoIfzmnnn
oxrossod fhIs Idon by fho roInfIon, S = l In u, whoro S = onfroy, l = IoIfzmnnn
consfnnf, u = fhormodynnmIc robnbIIIfy.
As u Is nIwnys gronfor fhnn ono, u Incronsos whon S Incronsos.
ConvorsoIy, whon nn ordor fo n sysfom Is broughf, fho onfroy of fho sysfom docronsos.
Ior oxnmIo, soIIdIfIcnfIon of n IIquId brIngs nbouf ordorIy sfnfo nnd fhoroby onfroy docronsos.
In nny sysfom, onIy n nrf of fho fofnI onorgy Is mndo nvnIInbIo for usofuI work, somo
onorgy Is nIwnys dIssInfod i.e., wnsfod. Tho onorgy unnvnIInbIo ns work Is roorfIonnI fo fho
Incronso of onfroy. Tho hIghor fho onfroy, fho Ioss fho nvnIInbIIIfy of work. Thus, onfroy
sIgnIfIos unnvnIInbIo form of onorgy of fho sysfom durIng frnnsformnfIon of honf Info work.
ntvopy oI un IdeuI gus
In fho cnso of n rovorsIbIo oxnnsIon of nn IdonI gns In n confnInor ns In IIg. 4.3, fho
confnInor Is fIffod wIfh n frIcfIonIoss movnbIo Isfon nf consfnnf rossuro I. Tho voIumo of fho
gns chnngos from V
l
fo V
2
. SInco fho rocoss Is rovorsIbIo, fho rossuro on fho gns Is
nroxImnfoIy oqunI fo fho oxfornnI rossuro I.
Honco, from lsf Inw of fhormodynnmIcs,
Jq = JI + JW = JI + I JV. ...(III)
IvIdIng bofh fho sIdos of fho oqunfIon (III) by T,
Jq J J
T
I
T
I V
T
= +
JS = C
t
.
JT
T
+ !
JV
V
.
Thus, for n chnngo from sfnfos l fo 2 wo hnvo,
JS
S
S
l
2
= C
t

JT
T T
T
l
2
+ !
JV
V V
V
l
2
or, S = C
t
In
T
T
2
l
+ ! In
V
V
2
l
.
SInco, for nn IdonI gns nf consfnnf fomornfuro,
V
V
2
l
=
I
I
l
2
S = C
t
In
T
T
2
l
+ ! In
I
I
l
2
.
Af coneIonI IenperoIure i.e., for IsofhormnI oxnnsIon,
S
T
= ! In
V
V
2
l
= ! In
I
I
l
2
.
Af coneIonI preeeure P,
S
p
= C
p
In
T
T
2
l
Af coneIonI tolune V,
S
t
= C
t
In
T
T
2
l
.
ntvopy cLunge In IvvevevsIbIe pvocess
Infroy Is n sfnfo funcfIon. Tho chnngo of onfroy of n gIvon sysfom from sfnfo l fo sfnfo 2
Is nIwnys fho snmo nnd Is nfh Indoondonf If fho nfh Is rovorsIbIo. So, fho chnngo of onfroy
(S) Is gIvon by:
S = S
2
S
l
=
l
2
T
Jq
r
.
Whon fho fIow of honf Is irretereiIle, Iof n honf rosorvoIr nf T
l
(sfnfo l) Is broughf In
confncf wIfh n socond rosorvoIr nf T
2
(sfnfo 2) whoro T
l
> T
2
, nnd smnII qunnfIfy of honf q fIows
from T
l
fo T
2
.
Tho docronso In onfroy of sfnfo l =
q
T
l
Tho docronso In onfroy of sfnfo 2 =
q
T
2
of chnngo of onfroy =
q q
q
T T
T T
T T
l 2
l 2 2 l
=

.
Tho dIfforonco Is n osIfIvo qunnfIfy, honco, fho IrrovorsIbIo honf fIow Ionds fo Incronso
In onfroy.
IvvevevsIbIe IsotLevmuI expunsIon oI un IdeuI gus
!of n moIos of nn IdonI gns Is oncIosod In n vossoI of voIumo V
l
. Tho vossoI Is connocfod
fo n vossoI of voIumo V
2
by n fubo confnInIng sfo cock, whIch Is ovncunfod (IIg. 4.4). Tho
vossoIs nro kof In n fhormosfnf of fho fomornfuro T. Irom fho fIrsf Inw of fhormodynnmIcs,
wo hnvo,
q = I + W
THERMODYNAMCS 77
ow, If fhIs oxnnsIon Is cnrrIod ouf IrrovorsIbIy nf T K from voIumo V
l
fo n voIumo
(V
l
+ V
2
) nffor oonIng fho sfo cock (IIg. 4.4). So wo hnvo,
q
ret
= I + !T In
V V
V
l 2
l
+
= 0 + !T In
V V
V
l 2
l
+
.
SInco S Is n sfnfo funcfIon, Je Is n orfocf dIfforonfInI, S
Irr.
(sysfom) wouId bo snmo.
As fhoro Is no fhormnI chnngo,
S
surroundIng
= 0
Honco, for fho IrrovorsIbIo oxnnsIon of gns,
S
unIvorso
= S
sysfom
+ S
surroundIng
= ! In
V V
V
l 2
l
+
+ 0
= ! In
V V
V
l 2
l
+
A osIfIvo qunnfIfy.
ntvopy cLunge oI u mIxtuve oI guses
Irom fIrsf Inw of fhomodynnmIcs, wo hnvo,
Jq = JI + IJV
IvIdIng bofh fho sIdos of fho nbovo oqunfIon by T,
Jq J J
T
I
T
I V
T
= + = C
t

J J T
T
!
V
V
+ (for l moI of gns)
or, JS = C
t
J (In T) + !J (In V)
or, S = C
t
In T + ! In V + S
0
whoro S
0
Is n consfnnf.
Wo know, C
p
C
t
= ! for nn IdonI gns.
So, S = (C
p
!) In T + ! In
!T
I
+ S
0
or, S = C
p
In T ! In I + S
0
Wo cnnnof doformIno fho nbsoIufo vnIuo of fho onfroy of nn IdonI gns. Iuf fho chnngos
In onfroy cnn bo doformInod. Thus, If fho fomornfuro of nn IdonI gns chnngos from T
l
fo T
2
nnd fho voIumo from V
l
fo V
2
for l moI. of fho gns, wo hnvo,
S
l
= C
t
In T
l
+ ! In V
l
+ S
0
S
2
= C
t
In T
2
+ ! In V
2
+ S
0
S = S
2
S
l
= C
t
In
T
T
2
l
+ ! In
V
V
2
l
Ior nn IsofhormnI chnngo, wo hnvo
S = ! In
V
V
2
l
= ! In
I
I
l
2
.
T
V
1
V
2
Fig. 4.4
Whon fwo gnsos como In confncf, fhoy dIffuso nnd mIx-u IrrovorsIbIy. Such n sonfnnoous
IrrovorsIbIo rocoss Ionds fo nn onfroy Incronso.
!of, MoIos of gns A Is n
A
MoIos of gns I Is n
I
Tomornfuro Is T
Irossuro Is I
Thon, S
A
= n
A
|C T ! I S
I A
A
In In ] +
0
S
I
= n
I
|C T ! I S
I I
I
In In ] +
0
Affor mIxIng, fho fofnI rossuro (I)
I = p
A
+ p
I
.
Tho onfroIos of fho fwo gnsos In fho mIxfuro nro
S
A
(mIx) = n
A
|C T ! S
I A A
A
In In ] + p
0
S
I
(mIx) = n
I
|C T ! S
I I I
I
In In ] + p
0
So, chnngo of onfroy duo fo mIxIng,
S
mIx
= (S S )
A I
mIx mIx
+ (S
A
+ S
I
)
= S S
A I
mIx mIx
+ S
A
S
I
or, S = n
A
! In
p
A
I
n
I
! In
p
I
I
Tho fofnI moIos of mIxfuro = n = n
A
+ n
I
moI. frncfIon of A, x
A
=
n
n
A
, x
I
=
n
n
I
ow,
p
A
I
= x
A
nnd
p
I
I
= x
I
(As moI. frncfIon = rossuro frncfIon)
S = n
A
! In x
A
n
I
! In x
I
.
or, S
mIx
= n !
n
n
x
n
n
x
A
A
I
I
In In +
= n !|x
A
In x
A
+ x
I
In x
I
]
In gonornI, for mIxIng nny numbor of gnsos,
S
mIx
= n ! x
i
In x
i
whoro x
i
= moI. frncfIon of gns i.
Wovk IunctIon (A)
!of us dofIno, A = I TS
Ior nn IsofhormnI rocoss, A
T
= I TS (3 T = 0)
= I q = W
mnx
or, A
T
= W
mnx
whoro W
mnx
Is rovorsIbIo, honco, mnxImum work Is InvoIvod. So, work funcfIon Is such n
fhormodynnmIc roorfy of fho sysfom fhnf docronsos In work funcfIon A i.e., ( A) gIvos fho
mnxImum nmounf of work nvnIInbIo durIng IsofhormnI rocoss.
THERMODYNAMCS 79
A = I TS or JA = JI TJS SJT = JI Jq SJT
= IJV SJT.
So, for IsochorIc rocoss
A
T
t
= S, nnd for nn IsofhormnI rocoss
A
V
T

,
= I.
Ivee enevgy (G)
Two fhormodynnmIc funcfIons, whIch nro vory usofuI for hysIcochomIcnI sfudIos nro:
CIbb`s froo onorgy (C) nnd HoImhoIfz froo onorgy or work funcfIon (A).
CIbb`s froo onorgy Is roInfod fo onfhnIy nnd onfroy ns,
C = H TS.
C = H TS. (nf consfnnf fomornfuro).
Ivee enevgy und useIuI wovk
Suoso n rovorsIbIo chnngo fnkos Inco nf consfnnf fomornfuro T nnd nf consfnnf
rossuro I. Tho work of oxnnsIon of voIumo Is oxrossod by IV nnd suoso fho sysfom doos
nn nddIfIonnI nmounf of work whIch Is donofod by usofuI work. Thoroforo, from fho fIrsf Inw of
fhormodynnmIcs, wo hnvo,
q = I + IV + W
usofuI
= H + W
usofuI
ow, sInco q = TS,
TS = H + W
usofuI
H TS = W
usofuI
= (C)
I, T.
or, (C)
I, T
= W
usofuI
.
Honco, docronso In CIbb`s froo onorgy Is n monsuro of fho 'usofuI work` obfnInnbIo from
fho rocoss.
Stunduvd Ivee enevgy cLunge
C Is n sfnfo funcfIon. To nssIgn numorIcnI vnIuos fo froo onorgy chnngo of n sysfom, If Is
nocossnry fo nssIgn n sfnndnrd vnIuo for fho froo onorgy of n sysfom nf n socIfIod sfnfo. Tho
eIonJorJ eIoIe Is dofInod nf consfnnf rossuro of l nfmoshoro nnd consfnnf fomornfuro i.e.,
25C or 298 K.
Thoroforo, sfnndnrd froo onorgy chnngo (C) Is dofInod ns fho froo onorgy chnngo for n
rocoss fnkIng Inco nf sfnndnrd sfnfo for fho roncfnnfs nnd fho roducfs obfnInod nro nIso In
fhoIr sfnndnrd sfnfos.
C = C
(roducfs)
C
(roncfnnfs)
ReIutIons oI G
(i) C = W
usofuI
(nf consfnnf T nnd I).
= nII (n = numbor of oIocfrons, I = Inrndny nnd I = omf of n coII. ThIs roInfIon
corroInfos froo onorgy chnngo fo coII ofonfInI)
(ii) C = H TS (nf consfnnf T)
(iii) C = !T In K
= 2.303 !T Iog K.
whoro ! = gns consfnnf, T = fomornfuro In koIvIn, K Is fho oquIIIbrIum consfnnf of n
roncfIon.
(it) C = 0 (nf oquIIIbrIum, nf consfnnf T nnd I).
Af consfnnf fomornfuro nnd rossuro nIwnys sysfom fonds fo nffnIn n osIfIon of
mInImum froo onorgy whIch Is fho osIfIon of oquIIIbrIum.
Thus, for n sonfnnoous rocoss, C musf bo nognfIvo. If C Is nognfIvo, nny chnngo
shnII sonfnnoousIy occur. If C Is zoro, fho InIfInI nnd fho fInnI sfnfos wouId bo nf oquIIIbrIum
wIfh onch ofhor nnd fInnIIy If C Is oeiIite, fho rocoss wIII nof fnko Inco sonfnnoousIy, buf
If mny rovorso.
HIgLIIgLts:
IireI lou of fhormodynnmIcs sfnfosfho onorgy mny chnngo from ono form fo
nnofhor, buf fho sum fofnI of onorgy of fho unIvorso romnIns consfnnf.
MnfhomnfIcnI oxrossIon of fIrsf Inw:
JI = Jq JW
KIrchoff`s oqunfIon:
H H
T T
2 l
2 l
( )
= C
p
.
1nIrop, Is n monsuro of rnndomnoss or dIsordor of n sysfom. If Is nIso dofInod ns
unnvnIInbIo onorgy. Infroy chnngo, S =
q
ret
T
.
SIoIe funcIion Is ono whIch doonds onIy on fho InIfInI nnd fInnI sfnfos of fho
sysfom buf Indoondonf of fho nfh foIIowod e.g., C, S, ofc.
Iree energ, cIonge Is n sfnfo funcfIon nnd Is roInfod fo onfhnIy chnngo, onfroy
chnngo nnd fomornfuro by CiIIè-HelnIolIc equoIion ns
C = H TS.
THERMOCHEMISTRY
AII fyos of chomIcnI roncfIons nro nccomnnIod by honf chnngos. Tho roncfIons In whIch honf
Is ovoIvod nro formod exoIIernic nnd In whIch honf Is nbsorbod nro enJoIIernic.
Tho onorgy from chomIcnI roncfIons comos from fho bronkIng or formnfIon of bonds. Tho
fhormnI chnngos In chomIcnI rocossos nro govornod by fwo gonornI rIncIIos, bofh of whIch
nro coroIInrIos of fho fIrsf Inw.
A. Iuw oI IuvoIsIev und IupIuce. ThIs Inw sfnfos fhnf fho honf chnngo nccomnnyIng
n chomIcnI rocoss In ono dIrocfIon Is oqunI In mngnIfudo buf oosIfo In sIgn fo fhnf
nccomnnyIng fho snmo rocoss fnkIng Inco In fho oosIfo dIrocfIon.
l
2
H
2
(g) +
l
2
CI
2
(g) HCI(g) H = 92 kJ
HCI(g)
l
2
H
2
(g) +
l
2
CI
2
(g) H = + 92 kJ
AccordIng fo fho fIrsf Inw, honf confonf (H) or onorgy confonf (I) of fho InIfInI roncfnnfs
ngnIn rofurns fo fho snmo mngnIfudo. As such, fho nof honf-confonf chnngo or onorgy confonf
THERMODYNAMCS 81
chnngo Is zoro i.e., honf chnngos In fho fwo dIrocfIons musf bo oqunI In mngnIfudo buf oosIfo
In sIgn.
B. Hess's Iuw oI Constunt Heut SummutIon. ThIs Inw sfnfos fhnf for o cIenicol
proceee IIe onounI of IeoI etolteJ or oIeorIeJ ie IIe eone uIeIIer IIe proceee Iolee ploce in
one or eeterol eIepe. LeI ue Iole IIe exonple of fornoIion of CO
2
in one eIep onJ Iuo eIepe (o)
onJ (I).
C + O
2
= CO
2
H = 94.05 KcnI
(o) C +
l
2
O
2
= CO H
l
= 26.42 KcnI
(I) CO +
l
2
O
2
= CO
2
H
2
= 6?.63 KcnI.
SummIng u wo gof, H
l
+ H
2
= ( 26.42 69.63) KcnI
whIch IIIusfrnfos fho Inw = 94.05 KcnI.
Irom fIrsf Inw wo fInd fhnf H
I
nnd I
V
wIII bo Indoondonf of fho nfh.
Tho rIncInI ndvnnfngo of fhIs Inw Is fhnf fhormochomIcnI oqunfIons cnn bo fronfod ns
sImIo nIgobrnIc oqunfIons nnd fho honf of formnfIon, honf of frnnsIfIon, ofc., whIch nro dIffIcuIf
HIgLIIgLts:
Hoss`s Inw Is usod fo cnIcuInfo:
InfhnIy chnngos (H) of formnfIon from onfhnIy chnngos of combusfIon.
InfhnIy chnngos of roncfIon from onfhnIy chnngos of formnfIon.
!nffIco onorgIos Is fho Iorn-Hnbor cycIo.
fo monsuro oxorImonfnIIy cnn bo onsIIy found ouf by nddIfIon, subfrncfIon, muIfIIIcnfIon of
fho qunnfIfIos i.e., H forms nIgobrnIcnIIy.
(i) HeoI of reocIion. Honf of roncfIon (H) Is fho dIfforonco bofwoon fho honf confonfs of
fho roducfs nnd fho roncfnnfs, whon moInr qunnfIfIos roncf nnd IndIcnfod by n bnInncod
oqunfIon.
1xonple.
(o) H
2
+ CI
2
= 2 HCI +43,608 cnIs (oxofhormIc)
(I) H
2
+ I
2
= 2 HI l2,680 cnIs (ondofhormIc)
Thus, fho honf of roncfIon for fho formnfIon of 2 moIos of HCI
Is 43,600 cnI whIch Is oxofhormIc whorons for fho formnfIon of 2
moIos of HI, l2,680 cnI of honf Is nbsorbod nnd fho roncfIon Is
ondofhormIc.
(ii) HeoI of conIueIion. Honf chnngo for fho comIofo
combusfIon of n gm-moIo of fho subsfnnco nf n gIvon fomornfuro
undor normnI rossuro Is cnIIod Ifs honf of combusfIon. CombusfIon
roncfIons nro nIwnys oxofhormIc, so honf of combusfIon Is nIwnys
nognfIvo.
In fho cnso of orgnnIc comounds, comIofo combusfIon monns
whon fhoso comounds nro convorfod fInnIIy fo CO
2
nnd H
2
O.
Tho honf of combusfIon Is oxorImonfnIIy doformInod In n
bomb cnIorImofor whIch Is n rossuro vossoI InfornnIIy onnmoIIod
wIfh InfInum (IIg. 4.5). Tho oxorImonfnIIy doformInod vnIuos of honf of combusfIon nro
usofuI.
1xonple.
C
2
H
5
OH + 3O
2
= 2CO
2
+ 3H
2
O H = 325 KcnI
Fig. 4.5 Bomb calorimeter.
(iii) HeoI of neuIrolieoIion of nn ncId or n bnso Is dofInod ns fho nmounf of honf IIbornfod
(oxofhormIc) whon l gm oquIvnIonf of nn ncId Is noufrnIIzod by ono gm oquIvnIonf of bnso In
Inrgo oxcoss of wnfor.
1xonple.
HO
3
(oq) + nOH(oq) nO
3
(oq) + H
2
O H = l3.? KcnI
HCI(oq) + KOH(oq) KCI(oq) + H
2
O H = l3.? KcnI.
If fho ncId nnd bnso nro bofh sfrong, fhoy cnn bo nssumod fo bo comIofoIy dIssocInfod,
i.e.,
H
+
+ A
+ I
+
+ OH
= I
+
+ A
+ H
2
O
i.e., H
+
+ OH
= H
2
O.
Thoroforo, fho honf of noufrnIIsnfIon Is ronIIy fho honf of formnfIon of l gm moIo of
wnfor from l gm Ion of hydrogon nnd hydroxyI Ion, nnd fhIs Is nIwnys fho oquIvnIonf of l3.?
KcnI of honf.
Iuf whon n wonk ncId or n wonk bnso Is noufrnIIzod, fho honf of noufrnIIsnfIon dovInfos
consIdornbIy from l3.? KcnI.
(it) HeoI of fornoIion. If Is fho nmounf of honf IIbornfod or nbsorbod whon ono moIo of
fho comound Is formod from Ifs consfIfuonf oIomonfs, nII In fhoIr rosocfIvo sfnndnrd sfnfos
nnd nf n roforonco fomornfuro. Tho sfnndnrd onfhnIy of formnfIon (H
f
o
) Is jusf fho nognfIvo
of fho honf of formnfIon.
In ordor fo monsuro fho chnngo In onfhnIy, If Is noodod fo nssumo somo nrbIfrnry vnIuo
for subsfnncos nf n gIvon sfnfo. ConvonfIonnIIy, fho onfhnIy of nny oIomonf nf l nfm nnd
298 K Is nssumod fo bo 'zoro`.
C
(grnhIfo)
+ 2 H
2
(g) CH
4
(g) H
f
= ?4.8 kJ.
Tho onfhnIy of formnfIon Is roInfod fo fho sfnbIIIfy of comound. Tho Iowor fho onfhnIy
of formnfIon of n comound, fho moro sfnbIo Is fho comound. If fho onfhnIy of formnfIon of n
comound Is osIfIvo, If monns fho onorgy confonf of fho comound Is gronfor fhnn fho onorgy
confonf of Ifs consfIfuonf oIomonfs nnd honco fho comound Is unsfnbIo. Whorons, whon fho
onfhnIy of formnfIon of n comound Is nognfIvo, fho onorgy confonf of fho corrosondIng
comound Is Iowor fhnn Ifs consfIfuonf oIomonfs nnd honco fho comound Is sfnbIo. Thus, fho
sfnbIIIfy of n comound Is InvorsoIy roorfIonnI fo fho onfhnIy of formnfIon of n comound.
1xonple.
H
f
of HI Is + 26.9 kJ nnd H
f
of HI Is l6l.? kJ IndIcnfos fho HI Is much moro sfnbIo
fhnn HI.
(t) HeoI of eoluIion onJ IeoI of JiluIion. Tho honf chnngo fnkIng Inco whon l gm moIo
of fho soIufo Is comIofoIy dIssoIvod In n soIvonf Is cnIIod fho honf of soIufIon.
Tho honf of soIufIon chnngos wIfh conconfrnfIon, i.e., ono gm moIo of KCI dIssoIvod In 50
moIos of wnfor nnd In 200 moIos of wnfor wIII cnuso dIfforonf honf chnngos.
Tho vnIuo of honf of soIufIon obfnInod grnhIcnIIy by oxfrnoInfIng H fo InfInIfo dIIufIon
Is fho InfogrnI honf of soIufIon nf InfInIfo dIIufIon.
Af hIgh dIIufIon, fho honf chnngo bocomos consfnnf.
1xonple.
KCI(e) + 50 H
2
O = KCI (50 H
2
O) 42?6 CnI.
KCI(e) + l00 H
2
O = KCI (l00 H
2
O) 439l CnI.
(ti) HeoI of fueion. Honf chnngo fnkIng Inco whon l moIo of n subsfnnco chnngos from
soIId fo Ifs IIquId hnso nf Ifs moIfIng oInf Is known ns fho honf of fusIon of fho subsfnnco.
Honf of fusIon Is nIwnys osIfIvo.
1xonple.
H
2
O(e) H
2
O(l) H = 6 kJ.
THERMODYNAMCS 83
(tii) HeoI of toporicoIion. If Is fho honf chnngo InvoIvod In convorfIng l moIo of subsfnnco
from IIquId fo fho gnsoous sfnfo nf Ifs boIIIng oInf. If Is nIso osIfIvo.
1xonple.
H
2
O(l) H
2
O(g) H = 42 kJ.
(tiii) HeoI of euIlinoIion. If Is fho honf chnngo InvoIvod In convorfIng l moIo of soIId
dIrocfIy fo Ifs vnour nf n fomornfuro boIow fho moIfIng oInf of fho subsfnnco.
1xonple.
I
2
(e) I
2
(g) H = 62.4 kJ.
HIgLIIgLts:
InfhnIy chnngo Is fho oxchnngo of onorgy bofwoon n roncfIon mIxfuro (sysfom)
nnd Ifs surroundIngs whon fho roncfIon fnkos Inco nf consfnnf rossuro.
Tho onfhnIy chnngo (H) Is cnIcuInfod whon sfnrfIng fomornfuro of fho roncfnnfs
nnd fInnI fomornfuro of fho roducfs nro fho snmo.
Tho rosonf unIf of H Is kJ moI
l
.
If H Is nognfIvo, fho roncfIon Is oxofhormIc i.e., fho sysfom Iosos onorgy fo
surroundIngs.
If H Is osIfIvo, fho roncfIon Is ondofhormIc i.e., fho sysfom gnIns onorgy from Ifs
surroundIngs.
Tho sfnndnrd condIfIons for chnngo of onfhnIy (H) nro 298 K nnd l bnr (l00
kIn), fho sfnndnrd onfhnIy chnngo Is rorosonfod by H
298
.
If Is ImossIbIo fo monsuro H
298
dIrocfIy. Mnny vnIuos nro doformInod IndIrocfIy
usIng Heeeè lou.
VnIuos monsurod undor nonsfnndnrd condIfIons nro corrocfod fo gIvo fho vnIuo
undor sfnndnrd condIfIons.
InfhnIy chnngo for moIfIng, subIImnfIon, vnorIsnfIon nro monsurod nf m.. or
b..
Bond nevgy
Iond onorgy Is dofInod ns fho nvorngo onorgy roquIrod fo bronk fho bonds rosonf In n
moIocuIo of gnsoous comound, fo nfoms or rndIcnIs In gnsoous form. Iond onorgy Is nIso cnIIod
fho IeoI of fornoIion of fho bond. ThIs onorgy Is doondonf on fho nnfuro of fho nfoms rosonf
ns woII ns fho onvIronmonf.
1xonple. Ior wnfor fho onorgy of sonrnfIng n H-nfom Is ll8 KcnI, whorons fhIs onorgy
of sonrnfIng fho socond H-nfom from fho rosIdunI OH grou Is l02 KcnI. ThIs dIfforonco In
bond onorgy Is roInfod fo fho moro roncfIvo nnfuro of OH rndIcnIs fhnn oxygon, fownrds H
nfoms fo form sfnbIo moIocuIos.
TnkIng nvorngo of fho fwo bond onorgIos wo hnvo
ll8 l02
2
+
= ll0 KcnI for OH bonds.
SImIInrIy, for CH
4
(mofhnno) moIocuIo, wo cnn fInd fho bond onorgy for CH bonds by
fnkIng In nvorngo ono-fourfh of fho fofnI honf of formnfIon of mofhnno, i.e.,
396
4
= 99 KcnI/moI.
AIfornnfIvoIy, wo cnn nIso fnko fho nvorngo of fho four dIfforonf dIssocInfIon onorgIos of
CH bond of mofhnno.
VuvIutIon oI bond enevgy
(i) Iond onorgy vnrIos wIfh fho sIzo of fho nfoms.
1xonple. bond onorgy for HI nnd HCI nro 56.5 nnd 43.l kJ/moI, rosocfIvoIy.
(ii) Iond onorgy vnrIos wIfh fho dIfforonco bofwoon fho oIocfronognfIvIfy of fho fwo nfoms.
Iond onorgy docronsos ns HI > HH > CC > > II.
(iii) Iond onorgy vnrIos wIfh fho fofnI onvIronmonf of fho moIocuIo.
AppIIcutIon oI bond enevgIes
(i) Tho honf of roncfIon cnn bo cnIcuInfod from fho bond onorgIos sInco In n roncfIon
corfnIn bonds nro formod nnd corfnIn bonds nro brokon. So, fho fofnI onfhnIy chnngo InvoIvod
In fhoso bond bronkIng nnd mnkIng gIvos fho honf of roncfIon.
i.e., H roncfIon = H (bonds brokon) + H (bonds formod)
= Iond onorgy (roncfnnfs) Iond onorgy (roducfs)
(ii) Honf of formnfIon cnn nIso bo cnIcuInfod from fho nvorngo bond onorgy summnfIon.
1xonple. Honf of formnfIon of ofhnno Is,
2C(g) + 6H(g) H
H
C
H
H
C
H
H(g)
H
f
for ofhnno Is = l (bond onorgy for CC) + 6 (bond onorgy for CH)
= (l ?9.3 + 6 98.5) KcnI.
= 6?0.3 KcnI moI
l
.
SECOND LAW OF THERMODYNAMICS
Honf Is rondIIy nvnIInbIo nnd mnn Is Inforosfod fo convorf fhIs honf onorgy fo usofuI work.
Socond Inw of fhormodynnmIcs guIdos fho condIfIons undor whIch honf nnd work nro
InforconvorfIbIo. Ior fho convorsIon of honf Info work fwo condIfIons musf bo fuIfIIIod.
l. WIfhouf fho hoI of n fhormodynnmIc ongIno fho convorsIon of honf Info work Is
ImossIbIo nnd fho ongIno musf work In n rovorsIbIo cycIIc rocoss.
2. Tho ongIno musf fnko u honf nf hIghor fomornfuro, convorf n orfIon of If Info work
nnd gIvo u fho rosf of honf fo n body nf Iowor fomornfuro.
Irom fho nbovo oxorIonco, socond Inw of fhormodynnmIcs cnn bo sfnfod In somo dIfforonf
Imorfnnf forms,
(o) If Is ImossIbIo fo convorf honf comIofoIy Info nn oquIvnIonf nmounf of work, wIfh-
ouf roducIng somo ofhor offocfs In fho sysfom.
(I) If Is ImossIbIo for n soIf-ncfIng mnchIno unnIdod by nny oxfornnI ngoncy, fo convoy
honf from n body nf n Iow fo ono nf n hIgh fomornfuro.
(c) AII sonfnnoous rocossos fond fo oquIIIbrIum.
(J) Tho onorgy of fho unIvorso Is consfnnf, buf fho onfroy nronchos n mnxImum.
IIect oI tempevutuve on Ivee enevgy-(GIbbs-HeImLoItz equutIon)
Wo know, H = I + IV nnd C = H TS
= I + IV TS
THERMODYNAMCS 85
IfforonfInfIng, wo gof JC = JI + IJV + VJI TJS SJT
Wo know, Jq = JI + IJV
JC = Jq + VJI TJS SJT
AgnIn for rovorsIbIo mochnnIcnI rocoss JS =
Jq
T
Jq = TJS
JC = VJI SJT
Ior nn IsobnrIc rocoss JC = SJT
C
T
I
= S
C
T
p
= S.
Wo know C = H TS
C = H TS
C = H T
C
T
p
TLIs Is GIbbs-HeImLoItz equutIon, whIch roInfos froo onorgy nnd ofhnIy chnngos nf
consfnnf rossuro.
SIgnIIIcunce oI GIbbs-HeImLoItz equutIon
CIbbs-HoImhoIfz oqunfIon Is n vory usofuI oqunfIon In fhormodynnmIcs ns If oncomnssos
bofh fho ossonco of fIrsf nnd socond Inws of fhormodynnmIcs nnd nImosf nny roInfIon of
fhormodynnmIcs cnn bo doducod from fhIs oqunfIon.
Wo know fhnf If C Is nognfIvo fho roncfIon fnkos Inco sonfnnoousIy nnd whon C = 0
i.e., whon fho froo onorgy of fho roncfnnfs nnd fho roducfs nro oqunI, fho roncfIon nffnIns
oquIIIbrIum.
(o) Whon n roncfIon Is oxofhormIc i.e., H Is nongfIvo, nnd S Is osIfIvo, C hns nognfIvo
vnIuo nnd fho roncfIon bocomos sonfnnoous.
(I) In ondofhormIc rocoss, H Is osIfIvo, fho roncfIon occurs If TS Is osIfIvo nnd
gronfor fhnn H.
(c) Whon H Is nognfIvo nnd S Is nIso nognfIvo, fho rocoss wIII bo sonfnnoous onIy
whon H Is gronfor fhnn TS.
Honco, fho criIerio for eponIoneoue proceeeee nro:
(o) If H Is nognfIvo nnd S Is osIfIvo C bocomos nognfIvo.
(I) If bofh H nnd S nro nognfIvo nnd H > TS.
(c) If bofh H nnd S nro osIfIvo nnd TS > H.
AppIIcutIon oI tLevmodynumIcs to pLuse tvunsItIon I.e., cLunge oI pLuse. (CIupeyvon-
CIuusIus equutIon)
Chnngo of hnso fnkIng Inco durIng froozIng, vnorIznfIon, ofc. cnn bo sfudIod fhormo-
dynnmIcnIIy.
!of C
l
nnd C
2
bo fho froo onorgIos of n IIquId nnd Ifs vnour, whIch nro In oquIIIbrIum nf
n fomornfuro T. ImngIno n vory smnII chnngo of n smnII nmounf of IIquId vnorIzIng nf
oquIIIbrIum. Tho dro In froo onorgy of fho IIquId Is C
l
nnd corrosondIng gnIn In froo onorgy
of fho vnour Is +C
2
. SInco fho sysfom Is In oquIIIbrIum,
ns nof C = 0 C
l
= C
2
or, V
l
I S
l
T = V
2
I S
2
T.
or,
I
T
=
S S
V V
2 l
2 l
=
S
V V
2
l
SInco, S =
q
T
J
J
I
T
=
S
V V
2 l
=
q
T(V V )
2 l
whoro q Is moInr honf of frnnsIfIon from ono hnso fo nnofhor.

Thus,
J
J
I
T
=
q
T(V V )
2 l
. ThIs oqunfIon Is fho fnmous CIupeyvon-CIuusIus equutIon.

AppIIcutIon oI CIupeyvon-CIuusIus equutIon
l. DeIerninoIion of loIenI IeoI.
Wo know
J
J
I
T
=
q
T(V V )
2 l
.
Whon fwo hnsos of IIquId (VoI. V
l
) nnd vnor (VoI. V
2
) nro In oquIIIbrIum, fho voIumo
V
l
of fho IIquId cnn bo nogIocfod ns If Is vory smnII comnrod fo fho voIumo of vnor V
2
.
J
J
I
T
=
q
T V
2
=
!
T V
2
(q = ! = Infonf honf of vnorIznfIon)
ow, for IdonI gns IV = !T, i.e., V =
!T
I
J
J
I
T
=
!I
!T
2
or,
JI
I
= ! .
JT
!T
2
AssumIng, Infonf honf Is consfnnf nnd on InfogrnfIng,
In
I
I
2
l
=
!
!
l
T
l
T
l 2
or, Iog
I
I
!
2.303! T
l
T
2
l 2
=
l
l
or, Iog
I
I
2
l
=
!
2.303!
T T
T T
2 l
l 2

.
Thus, from fho vnour rossuros I
l
nnd I
2
nf dIfforonf fomornfuros T
l
nnd T
2
wo cnn
doformIno fho moInr honf of vnorIznfIon wIfh fho Infogrnfod CInoyron-CInusIus oqunfIon.
2. 1ffecI of preeeure on Ioiling poinI. WIfh fho hoI of fho Infogrnfod CInoyron-CInusIus
oqunfIon wo cnn doformIno fho boIIIng oInf of n IIquId nf n dIfforonf rossuro whon fho boIIIng
oInf of If Is known nf ono rossuro nIong wIfh fho Infonf honf of vnorIznfIon.
THERMODYNAMCS 87
3. 1ffecI of IenperoIure on topour preeeure of o liquiJ. AgnIn from fho sImIInr oxrossIon
wo cnn cnIcuInfo fho vnour rossuro of n IIquId nf n dIfforonf fomornfuro If fho vnour of If Is
known nf n nrfIcuInr fomornfuro nIongwIfh Ifs Infonf honf.
THIRD LAW OF THERMODYNAMICS
In l9l2, IInnck onuncInfod fho fhIrd Inw of fhormodynnmIcs ns fho onfroy of n soIId or n
IIquId Is zoro nf fho nbsoIufo zoro of fomornfuro.
Af nbsoIufo zoro fomornfuro, kInofIc onorgy of n subsfnnco Is zoro nnd If Is rosonf In n
orfocfIy nrrnngod crysfnIIIno sfnfo. So, fhoro Is no dIsordor nnd honco fho onfroy of nII uro
subsfnncos nf nbsoIufo zoro Is zoro.
1nIrop, onJ IIe IIirJ louThIrd Inw cnn bo usod fo doformIno fho onfroy of n
subsfnnco.
AbsoIufo vnIuo of onfroy cnn bo monsurod by doformInIng fho honf cnncIfIos (C
p
) of n
subsfnnco nf dIfforonf fomornfuro. Thoso C
p
vnIuos nro Ioffod ngnInsf T nnd cnn bo
oxfrnoInfod fo T = 0. Tho nron of fho curvo bofwoon T = 0 nnd fho roquIrod fomornfuro gIvos
fho vnIuo of nbsoIufo onfroy of fho subsfnnco nf fho roquIrod fomornfuro.
MnfhomnfIcnIIy, wo hnvo
S
T
S
0
=
C
T
T
T
p
J
0
Irom 3rd Inw, S

0
= 0. S
T
=
C
l
T
T
p
J
0
= C T
T
p
JIn
0
S
T
= 2 303
0
. Iog C T
T
p
J
C
p
C
p
T
log T
1 2
T
O 10 20 30
(I) (II)
Fig. 4.6 Graphical determination of entropy.
CoupIIng oI non-spontuneous veuctIons
Thoso chomIcnI/bIoIogIcnI roncfIons onIy fnko Inco sonfnnoousIy for whIch C = nognfIvo.
Mnny roncfIons occur In nnfuro whIch hnvo C = osIfIvo onIy whon fhoy nro couIod wIfh
nnofhor roncfIon whoso C Is much Inrgor nognfIvo. Honco, fho onorgy roquIrod for fho fIrsf
roncfIon fo occur Is suIIod by fho socond roncfIon whIch Is couIod fo If.
1xonple. IIochomIcnI roncfIon In our body IIko oxIdnfIon of gIucoso roIonsos Inrgo nmounf
of onorgy nnd n nrf of fhIs onorgy Is ufIIIsod by our sysfom fo convorf AI (AdonosIno
dIhoshnfos) fo ATI (AdonosIno frIhoshnfo). ATI Is n hIgh onorgy moIocuIo, so whon In fho
cycIIc rocoss ATI Is hydroIysod fo AI, froo onorgy Is roIonsod whIch cnn ngnIn bo couIod fo
nnofhor bIochomIcnI roncfIon of our sysfom fhnf Is non-sonfnnoous or roquIros onorgy. Thus,
fho onorgy of gIucoso oxIdnfIon cnn bo ufIIIsod fo cnrry ouf ofhor non-sonfnnoous roncfIon vIn
ATI.
HIgLIIgLts:
1nIeneite properI, Is Indoondonf of fho nmounf of subsfnnco rosonf In fho sysfom
e.g., fomornfuro, rossuro, vIscosIfy, surfnco fonsIon, donsIfy, socIfIc honf,
rofrncfIvo Indox, ofc.
Heeeè lou eIoIee. Ior n chomIcnI rocoss, fho nmounf of honf ovoIvod or nbsorbod
Is fho snmo whofhor fho rocoss fnkos Inco In ono sfo or In sovornI sfos.
SeconJ lou of IIernoJ,nonic eIoIee. If Is ImossIbIo fo convorf honf comIofoIy
Info work.
C Is nognfIvo for n sonfnnoous roncfIon.
C Is zoro for roncfIon nf oquIIIbrIum.
C Is osIfIvo for non-sonfnnoous roncfIon.
S for n sonfnnoous rocoss Is S > 0.
Tho onfroy of fho unIvorso Is IncronsIng.
TIirJ lou of IIernoJ,nonice eIoIee. Tho onfroy of n soIId or n IIquId Is zoro nf
fho nbsoIufo zoro of fomornfuro.
Clope,ron-Cloueiue equoIion ie.
J
J
I
T
=
q
T(V V )
2 l
.
SpontuneIty oI cLunges oI u system
Mnny of fho sonfnnoous rocossos nro nccomnnIod wIfh n docronso In onfhnIy buf
fhIs sfnfomonf Is nof nIwnys fruo, roncfIons wIfh IncronsIng onfhnIy mny nIso occur
sonfnnoousIy.
A sonfnnoous rocoss nIwnys hns n nof Incronso In onfroy for fho comufnfIon of fho
chnngo of onfroy, fho chnngos In onfroy of bofh fho sysfom nnd fho surroundIng nro
fo bo consIdorod whon n sysfom Is In oquIIIbrIum,
JS
fofnI
= 0
Ior nny sonfnnoous IrrovorsIbIo rocoss,
JS
fofnI
> 0
Whon n rovorsIbIo rocoss Is nf oquIIIbrIum,
JS + JS = 0
Ior n sonfnnoous rocoss,
JS + JS > 0
whoro JS nnd JS nro fho chnngos of onfroy of fho sysfom nnd fho surroundIngs
rosocfIvoIy.
Ior n sonfnnoous rocoss nf n dofInIfo T nnd I, wo cnn cnIcuInfo C of fho sysfom, If
fho C Is nognfIvo fho chnngo Is sonfnnoous, If C Is zoro fho InIfInI nnd fInnI sfnfos of
fho sysfom wIII bo nf oquIIIbrIum, If C Is osIfIvo fho rocoss Is non-sonfnnoous.
THERMODYNAMCS 89
CLemIcuI PotentIuI ()
Iroo onorgy or moIo nf n gIvon fomornfuro T nnd rossuro (I) Is cnIIod fho cIenicol
poIenIiol or C.
Thoroforo, chomIcnI ofonfInI, =
C
n
(for n uro subsfnnco).
Ior n socIos i whIch Is comononf of n mIxfuro wo cnn oxross Ifs chomIcnI ofonfInI
i
ns foIIows.
i
=
C
T, I
n
n
j
,
whoro n
j
rorosonfs fho consfnnf comosIfIon of n mIxfuro.
1I ie Io Ie noIeJ IIoI free energ, ie on exIeneite properI, IuI cIenicol poIenIiol ie on
inIeneite properI,.
Jusf IIko fomornfuro, rossuro or oIocfrIc ofonfInI If fonds fo oqunIIso wIfhIn nII nrfs
of n sysfom. ChomIcnI ofonfInI nIso hns such n fondoncy, fhnf Is why fho sfudy of chomIcnI
ofonfInI hns bocomo Imorfnnf.
Thus, chomIcnI ofonfInI of wnfor In Ico musf bo snmo In bofh fho hnsos. If cnn bo
rovod onsIIy. Ior fho oquIIIbrIum,
Ico
(I)
Wnfor
(II)
If Jn moIos nro frnnsforrod from hnso I fo hnso II,
JC = (II) Jn (I) Jn
Iuf for oquIIIbrIum, JC = 0, (I) = (II)
MuxweII's ReIutIons
l. JI = TJS IJV
2. JH = TJS + VJI
3. JA = IJV SJT
4. JC = VJI SJT.
AIyIng fho cross-dorIvnfIvo ruIo, wo hnvo
(i)
T
V
S
=
I
S
V
, (ii)
T
I
S
=
V
S
I
,
(iii)
I
T
V
=
S
V
T
, (it)
V
T
I
=
S
I
T
.
Thoso four dorIvnfIvos nro vory woII known roInfIons, whIch hnvo oxfonsIvo nIIcnfIons
In bofh hysIcnI nnd chomIcnI honomonn.
CLemIcuI potentIuI oI un IdeuI gus ut tempevutuve, T.
Wo hnvo,
JC = SJf + VJI
= O + VJI (nf consfnnf, T)
C = C
2
C
l
= V I J
l
2
AIyIng fhIs fo ono moIo of nn IdonI gns (IV = !T), wo gof,
C
2
C
l
= !T In
I
I
2
l
or,
2

l
= !T In
I
I
2
l
.
SInco C
2
nnd C
l
nro moInr froo onorgIos
2
nnd
l
rosocfIvoIy,
l
bocomos
0
If wo
nIy fho sfnndnrd condIfIons i.e., rossuro l nfmoshoro. Wo gof,
=
0
+ !T In I
or, C = C
0
+ !T In I
whoro
0
Is fho sfnndnrd chomIcnI ofonfInI buf nof n consfnnf, If Is n funcfIon of T.
GIbbs-uLem ReIutIons
Tho froo onorgy C of n sysfom Is n sfnfo funcfIon, fhnf Is, C doonds uon I, T nnd V. As
fhoy nro InforroInfod wo cnn wrIfo for n fIxod comosIfIon of n sysfom,
C = f (I, T)
If wo fnko nn open e,eIen In whIch fho qunnfIfIos of fho comononfs mny vnry, fho froo onorgy
fhon wIII doond uon fho qunnfIfIos of fho comononfs. !of us hnvo n sysfom confnInIng n
l
moIos of A
l
, n
2
moIos of A
2
, ofc., fhon fho froo onorgy (C) of fho sysfom Is gIvon by,
C = f (I, T, n
l
, n
2
, n
3
...)
If nII fho vnrInbIos vnry, fho comIofo dIfforonfInI wIII bo gIvon by,
JC =
C
I
T, n
i
JI +
C
T
I, n
i
JT +
C
I, T
n
n n
l
2 3
, ,
Jn
l
+
C
I, T
n
n n
2
l 3
, , ...
Jn
2
+ ...
Wo know,

,
=
C
I
V
C
T
T I , , n n
i i
= S.
JC = VJI SJT +

C
I, T
Jn
n n
l
2 3
, ,
Jn
l
+
C
2
I, T, ,
l
Jn
n n
3
Jn
2
...
Tho form

C
I, T
Jn
n n
2
l 3
, , ...
monns fhnf I, T nnd nII ofhor moIos nro consfnnf oxcof n
2
,
fhIs form Is cnIIod fho porIiol nolol free energ, of fho comononf A
2
, undor fhIs convonfIon fho
chomIcnI ofonfInI
i
for fho ifh comononf of fho mIxfuro Is gIvon by,

C
I, T
Jn
i
n
j
,
Af consfnnf fomornfuro nnd rossuro, If wo oxross nrfInI moInI froo onorgIos In forms
of , wo hnvo,
JC
I,T
=
l
Jn
l
+
2
Jn
2
+
3
Jn
3
+ ...
=
i
Jn
i
...(o)
ow nf consfnnf fomornfuro nnd rossuro, wo Incronso fho consfIfuonfs by fho snmo
roorfIons x, fho chnngod nmounfs of A
l
nro n
l
x, of A
2
, n
2
x nnd A
i
, n
i
x.
THERMODYNAMCS 91
Thoroforo,
Jn
l
= n
l
x, Jn
2
= n
2
x, Jn
i
= n
i
x
SInco, C Is nn oxfonsIvo roorfy, fhoroforo If wIII Incronso by fho nmounf Cx
honco, JC = Cx
So, wo hnvo,
JC =
l
n
l
x +
2
n
2
x + ... +
i
n
i
x + ...
or, Cx =
l
n
l
x +
2
n
2
x + .. +
i
n
i
x + ...
Honco, C =
l
n
l
+
2
n
2
+ ... +
i
n
i
+ ... =
i
n
i
ow, comIofo dIfforonfInfIon of fhIs oqunfIon gIvos us,
JC = (
l
Jn
l
+
2
Jn
2
+
3
Jn
3
+ ...) + (n
l
J
l
+ n
2
J
2
+ n
3
J
3
+ ...) ...(I)
SubfrncfIng oqunfIon (o) from (I)
n
l
J
l
+ n
2
J
2
+ n
3
J
3
+ ... = 0
Wo hnvo fhus fhroo usofuI roInfIons for chomIcnI ofonfInIs wIfh fho comosIfIon of fho
sysfom,
(i) C =
l
n
l
+
2
n
2
+
3
n
3
+ ... = n
(ii) JC =
l
Jn
l
+
2
Jn
2
+
3
Jn
3
+ ... = Jn
(iii) 0 = n
l
J
l
+ n
2
J
2
+ n
3
J
3
+ ... = nJ
Thoso roInfIons nro commonIy known ns CIbbs-uhom roInfIons.
eductIon oI Vun't HoII's veuctIon IsotLevm (ApplicoIion of IIernoJ,nonice Io
Ionogeneoue equiliIriun or IIernoJ,nonice of cIenicol equiliIriun).
!of us consIdor n gonornI roncfIon
oA + II cC + J ...(i)
Wo, know, C = H TS = I + IV TS |3 H = I + IV]
So, JC = JI + IJV + VJI TJS S JT.
AgnIn, Jq = JI + IJV nnd JS = Jq/T
JC = V.JI S.JT
Af consfnnf fomornfuro, (JC)
T
= V.JI.
Iroo onorgy chnngo for ono moIo of nny gns nf n consfnnf fomornfuro Is gIvon by:
JC = V.JI = !.T
JI
I
3 IV = !T or V =
!T
I
InfogrnfIng bofh sIdos,

JC = !T
JI
I
So, C = C
0
+ !T In I ...(ii)
whoro C
0
= InfogrnfIon consfnnf known ns sfnndnrd froo onorgy i.e.,
C
0
= C whon I = l nfm.
!of fho onorgy/moIo of A, I, C nnd nf fhoIr rosocfIvo rossuros I
A
, I
I
, I
C
nnd I
nro
C
A
, C
I
, C
C
nnd C
, rosocfIvoIy. Thon, froo onorgy chnngo for fho roncfIon (i) Is gIvon by
C = C
roducfs
C
roncfnnfs
= (cC
C
+ JC
) (oC
A
+ IC
I
) ...(iii)
SubsfIfufIng fho vnIuos of C
A
, C
I
, C
C
nnd C
from (ii) nnd (iii), wo hnvo

C = (cC
C
0
+ c!T In I
C
+ JC
0
+ J!T In I
)
(oC
A
0
+ o!T In I
A
+ IC
I
0
+ I!T In I
I
)
= (cC
C
0
+ JC
0
oC
A
0
IC
I
0
) + !T In
( ) ( )
( ) ( )
I I
I I
C
A I
c J
o I
So, C = C
0
+ !T In
( ) ( )
( ) ( )
I I
I I
C
A I
c J
o I
...(it)
ow, nf oquIIIbrIum, C = 0
So, C
0
= !T In
(I ) (I )
I I
C
A I
c J
o I
eq
( ) ( )
C Is n consfnnf ns C Is n sfnfo funcfIon

C Is fho dIfforonco In froo onorgy bofwoon fho roducfs nnd fho roncfnnfs.
= !T In K
eq
whoro K
I I
I I )
C
A I
eq
c J
o I
=
( ) ( )
( ) (
C
0
= !T In K
eq
..(t)
CombInIng (it) nnd (t), wo hnvo
C = !T In K
eq
+ !T In
( ) ( )
( ) (
I I
I I )
C
A I
c J
o I
or, C = !T In K
eq
!T In
( ) ( )
( ) (
I I
I I )
C
A I
c J
o I
...(ti)
ThIs oxrossIon (ti) Is cnIIod Vnn`f Hoff roncfIon Isofhorm. If Is of gronf Imorfnnco ns If
gIvos n qunnfIfnfIvo roInfIon for froo onorgy chnngo nccomnnyIng n chomIcnI roncfIon. C Is
cnIIod fho AIIInIty of fho roncfIon.
HIgLIIgLts:
C = !T In K
eq
whon rossuros of roncfnnfs nnd roducfs nro ono (i.e., I = l).
Tho nbovo oxrossIon gIvos froo onorgy chnngo for n roncfIon.
Tho nbovo roInfIon shows fhnf oquIIIbrIum consfnnf (K
eq
) cnn bo cnIcuInfod from n
fnbIo of sfnndnrd froo onorgy vnIuos.
xumpIe 1. One gn of uoIer requiree 36 coloriee of IeoI for contereion Io eIeon oI
100C. ColculoIe IIe increoee in inIernol energ, per nol of uoIer oeeuning uoIer topour Io
IeIote oe on iJeol goe.
SoI. AccordIng fo fIrsf Inw of fhormodynnmIcs
q = I u
Horo u = IV = !T = 2 3?3 cnIs = ?46 cnIs, q = 536 l8 cnI moI
l
or, I = q u = 9648 ?46 = 8902 cnI moI
l
= 8.902 KcnI moI
l
.
THERMODYNAMCS 93
xumpIe 2. TIe onounI of uorl of o e,eIen ie S.36 10
9
erge, ofIer oIeorIing 990 cole.
of IeoI. ColculoIe IIe inIernol energ, cIonge of IIe e,eIen.
SoI. Wo hnvo, I = q u
Horo q = 990 cnIs =
990 4.2
l0
3
kJ = 4.l3
u = 8.36 l0
9
orgs =
8.36 l0
l0 l0
9
? 3
kJ = 0.836 kJ
I = 4.l58 0.836 = 3.332 kJ.
xumpIe 3. ColculoIe IIe uorl Jone I, IIe follouing reocIion oI 27C.
Zn + H
2
SO
4
ZnSO
4
+ H
2
l moI.
SoI. Horo, u = I(V
2
V
l
) = IV
2
|3 V
l
= 0]
= n!T = !T |3 n = l]
= 8.3l4 (2?3 + 2?) =
8.3l4 300
l000
kJ.
= 2.4942 kJ.
xumpIe 4. ColculoIe IIe IeoI of conIueIion oI coneIonI preeeure of corIon. (Citen q
t
oI 200C ie 97000 cole).
SoI. C(e) + O
2
(g) = CO
2
(g)
Horo q
t
= 9?000 cnI.
moIs of gnsoous roncfnnf, n
l
= l
moIs of gnsoous roducf, n
2
= l
n = n
2
n
l
= 0.
Wo hnvo, q
p
= q
t
+ n!T.
= 9?000 + 0 !T
= 9?000 cnIs.
So, q
p
= q
t
(As n
2
= n
l
)
xumpIe 5. ColculoIe IIe tolue of 1 for IIe reocIion oI 00 K, Mg(e) + 2HCl(g)
MgCl
2
(e) + H
2
(g) (Citen H = 109 Kcol).
SoI. Wo know, H = I + n!T.
Horo, n = l 2 = l, T = 500 K
! = 2 cnI dog
l
moI
l
= 2 l0
3
KcnI dog
l
moI
l
I = H n!T = l09 ( l) 2 l0
3
500
= l08 KcnI.
xumpIe 6. HeoIe of conIueIion of eII,lene, I,Jrogen, onJ eIIone ore 337.2, 6S.3, 372.S
Kcol nol
1
oI o JefiniIe IenperoIure. ColculoIe IIe IeoI of reocIion of C
2
H
4
(g) + H
2
(g)
C
2
H
4
(g) oI IIoI IenperoIure.
SoI. CIvon,
(i) C
2
H
4
+ 3O
2
2CO
2
+ 2H
2
O, H = 33?.2 KcnI.
(ii) H
2
+
l
2
O
2
H
2
O, H = 68.3 KcnI.
(iii) C
2
H
6
+
?
2
O
2
2CO
2
+ 3H
2
O, H = 3?2.8 KcnI
or, (it) 2CO
2
+ 3H
2
O C
2
H
6
+
?
2
O
2
, H = + 3?2.8 KcnI.
AddIng fho oqunfIons (i), (ii) nnd (it) wo hnvo,
C
2
H
4
+ 3O
2
+ H
2
+
l
2
O
2
+ 2CO
2
+ 3H
2
O 2CO
2
+ 2H
2
O + H
2
O + C
2
H
6
+
?
2
O
2
(H = 32.? KcnI)
C
2
H
4
+ H
2
C
2
H
6
, H = 32.? KcnI.
xumpIe ?. ColculoIe OH IonJ energ, fron IIe follouing IeoIe of reocIione.
H
2
(g) 2H(g), H = 104 Kcol ...(i)
O
2
(g) 2O(g), H = 120 Kcol ...(ii)
H
2
(g) +
1
2
O
2
(g) H
2
O(g), H = S Kcol ...(iii)
SoI. Irom oqunfIon (ii)
l
2
O
2
(g) O(g), H = 60 KcnI.
Irom oqunfIon (iii), H
2
O(g) H
2
(g) +
l
2
O
2
(g) H = 58 KcnI.
(i) + (ii) (iii) gIvos = H
2
(g) +
l
2
O
2
(g) + H
2
O(g) 2H(g) + O(g) + H
2
(g) +
l
2
O
2
(g)
i.e., H
2
O(g) 2H(g) + O(g), H = 222 KcnI.
Wo know fhnf, fhoro nro fwo OH bonds In n moIocuIo of wnfor, nnd for bronkIng of
fhoso fwo bonds onorgy roquIromonf Is 222 KcnI.
So, for dIssocInfIon of ono OH bond onorgy roquIromonf Is 222 2 = lll KcnI.
OH bond onorgy Is lll KcnI.
xumpIe B. ColculoIe IIe enIIolp, of fornoIion of propone (C
3
H
S
) oI 29S K. Citen IIe
eIonJorJ enIIolpiee of conIueIion.
H
C
(C
3
H
S
) = 2220 lJ nol
1
H
C
(C) = 393 lJ nol

1
H
C
(H
2
) = 2S6 lJ nol
1
.
THERMODYNAMCS 95
SoI. A fhormodynnmIc cycIo Is drnwn:
3C( ) + 4H ( ) + 5O ( ) s g g
2 2
C H ( ) + 5O ( )
3 8 2
g g
3CO ( ) + 4H O( )
2
g l
2
D
H
3
D
H
2
DH
1
AccordIng fo Hoss`s Inw H
l
= H
2
H
3
H
l
= H
f
(C
3
H
8
)
H
2
= 3H
C
(C) + 4 H
C
(H
2
).
= 3 ( 393) + 4 ( 286) kJ moI
l
= 2323 kJ moI
l
H
3
= H
C
= 2220 kJ moI
l
Honco, H
f
(C
3
H
8
) = ( 2323) ( 2220) kJ moI
l
= l03 kJ moI
l
.
xumpIe 9. ColculoIe IIe enIIolp, cIonge of IroneiIion fron ,ellou P Io IeJ P fron IIe
giten IIernocIenicol c,cle.
SoI. ThormochomIcnI cycIo:
Yellow P Red P
H PO
3 4
D
H
2
D D H ( H )
T 1
2
3
8
6
c
a
l
s
D
H
3
2
1
1
3
c
a
l
s
AccordIng fo Hoss`s Inw H
T
= H
2
H
3
= 2386 2ll3 cnIs = 2?3 cnIs.
xumpIe 10. TIe loIenI IeoI of etoporoIion of uoIer oI 100C oI coneIonI preeeure ie
3S col g
1
. 1f oteroge C
p
for uoIer onJ eIeon ore 1 col g
1
onJ S.1 col nol
1
, reepecIitel, for IIe
inIertol, colculoIe IIe loIenI IeoI of uoIer oI 10C.
SoI. InsIs = l g.
H
l50
=; H
l00
= 538
C
p
for wnfor = l; C
p
for sfonm =
8.l
l8
.
C
p
= 0.45 l = 0.55.
T
2
T
l
= 423 3?3 = 50 K.
Wo hnvo, H
2
H
l
= C
p
(T
2
T
l
)
H
l50
H
l00
= 0.55(50)
H
l50
= H
l00
0.55 50
= 538 0.55 50 = 5l0.5 cnI g
l
.
xumpIe 11. ColculoIe IIe noxinun uorl Jone for IIe ieoIIernol retereiIle exponeion
of one nole of on iJeol goe oI 2C fron 2 oIn Io 1 oIn.
SoI. MnxImum work = 2.303 !T In
I
I
l
2
= 2.303 8.3l 298 Iog
2
l
= l.66 l0
3
J = l.66 kJ.
xumpIe 12. ColculoIe IIe cIonge of nolor enIrop, Juring nelIing of ice. Citen loIenI
IeoI 19.14 J g
1
.
SoI. JS =
q
rov
T
=
l9.l4 l8
2?3
= l.26 J moI
l
.
xumpIe 13. ColculoIe IIe cIonge of nolor enIrop, Juring IIe contereion of liquiJ
ox,gen Io ox,gen goe oI iIe I.p. ( 1S2.9C). Citen L = 12.19 J g
1
.
SoI. JS =
q
rov
T
=
l2.l9 32
(2?3 l82.9)
=
l2.l9 32
90.l
= 4.33 J moI
l
.
xumpIe 14. ColculoIe cIonge of enIrop, in ieoIIernol retereiIle exponeion of one nole
of on iJeol goe.
SoI. Wo know fhnf I = 0
Thoroforo, q = W = !T In
V
V
2
l
JS =
q
rov
T
= ! In
V
V
2
l
|IosIfIvo qunnfIfy]
xumpIe 15. AI uIoI IenperoIure uill uoIer Ioil uIen IIe oInoepIeric preeeure ie
2S nn Hg: Citen loIenI IeoI of topourieoIion of uoIer ie 4. col g
1
.
SoI. Horo, I
l
= 528 mm of Hg; I
2
= l nfm = ?60 mm of Hg.
T
l
= ; T
2
= l00C = 3?3 K; H
t
= 545.5 cnI g
l
= 545.5 l8 cnI moI
l
= 98l9 cnI moI
l
.
! = l.98? cnI K
l
moI
l
.
Irom fho Infogrnfod form of CInusIus-CInoyron oqunfIon, wo hnvo
Iog
I
I
2
l
=
H
2.303!
l
T
l
T
l 2
t
THERMODYNAMCS 97
Iog
?60
528
= 0.l582 =
98l9
2.303 l.98?

l
T
l
3?3
l
or, T
l
= 363 K.
xumpIe 16. ColculoIe q, W, 1 onJ H for ieoIIernol retereiIle exponeion of on iJeol
goe oI 27C fron o tolune of 10 Jn
3
Io 20 Jn
3
ogoineI o coneIonI exIernol preeeure of one
oInoepIere:
SoI. (i) SInco oornfIon Is IsofhormnI nnd fho gns Is IdonI so, I = 0.
(ii) ow, from lsf Inw, I = 0 or q = W.
Iuf, for n rovorsIbIo rocoss, work dono by sysfom,
W = I(V
2
V
l
)
= l nfm (20 l0) dm
3
= l0 nfm dm
3
= l0 nfm !
= l0 ! nfm
8.3l4 J
0.082l! nfm
= l0l2.? J.
(iii) q = W = l0l2.? J.
(it) H = I + IV = 0 + l0l2.? J = l0l2.? J.
xumpIe 1?. A goe Juring exponeion fron 10 liIre Io 20 liIre unJer 2 oInoepIeric
preeeure oIeorIe 300 col. IeoI energ,. IinJ IIe cIonge in inIernol energ,.
SoI. Work dono In nn IrrovorsIbIo rocoss Is gIvon by
W = I(V
2
V
l
) = 2(20 l0) = 20 IIf.nfm.
= (20 24.25) cnI |3 l IIf. nfm = 24.25 cnI]
= 485 cnI.
Irom fho lsf Inw of fhormodynnmIcs,
q = I + W
or, I = q W = (300 485) cnI = l85 cnI.
So, InfornnI onorgy wIII docronso by nn nmounf of l85 cnI.
xumpIe 1B. TIe iniIiol IenperoIure onJ preeeure for one nole of on iJeol goe ie (C
t
=
col) 27C onJ 1 oIn. Preeeure ie increoeeJ retereiIl, upIo 7 oIn onJ IenperoIure ie increnenIeJ
Io 90C. ColculoIe IIe enIrop, cIonge for IIe proceee.
SoI. Ior ono moIo of nn IdonI gns fho onfroy chnngo In n rovorsIbIo rocoss Is
S = C
p
In
T
T
2
l
+ ! In
I
I
l
2
Horo, T
l
= 2?C = 300 K; T
2
= 90C = 363 K; I
l
= l nfm; I
2
= ? nfm;
C
p
= C
t
+ ! = (5 + 2) cnI = ? cnI.
S = ? In
363
300
+ 2 In
l
?
= 2.55?? cnI dog
l
.
xumpIe 19. TIe tolue of K
p
(equiliIriun coneIonI) of IIe reocIion regorJing onnonio
e,nIIeeie oI 27C ie 3.49 10
2
oIn
1
. TIue finJ IIe tolue of K
p
for IIe follouing reocIion oI
37C.
1
2
A
2
(g) +
3
2
H
2
(g) AH
3
(g) + 11.2 Kcol.
ConeiJer IIe reocIion Io Ie inJepenJenI of IeoI onJ IenperoIure.
SoI. Irom Vnn`f Hoff oqunfIon, wo hnvo
In
K
K
I
I
2
l
=
H
!
T T
T T
2 l
l 2

Horo, T
l
= 2?C = 300 K; T
2
= 3?C = 3l0 K.

K
I
l
= 3.49 l0
2
nfm
l
;
K
I
2
=
H = ll.2 KcnI = ll200 cnI; ! = l.98? cnI dog
l
moI
l
.
Iog
K
K
I
I
2
l
=
H
2.303!
T T
T T
2 l
l 2

Iog
K
3.49 l0
I
2
2
ll200
2.303 l.98?
3l0 300
300 3l0
or, K
I
2
= l.9038 l0
2
nfm
l
.
Q. 1. Stute IIvst Iuw wItL mutLemutIcuI expvessIons.
Ans. Soo foxf ngo 68. AIfornnfIvoIy, If cnn bo sfnfod ns fho nof onorgy of fho unIvorso
romnIns consfnnf.
Q. 2. Stute IntensIve pvopevty oI u system.
Ans. Soo foxf ngo 66.
Q. 3. WLy Is entLuIpy move useIuI tLun IntevnuI enevgy?
Ans. InfornnI onorgy nnd ofhnIy of n sysfom nro monsurod by kooIng fho voIumo nnd
fho rossuro consfnnf, rosocfIvoIy. SInco, In mosf of fho roncfIons, fhoy occur nf nfmoshorIc
rossuro, so onfhnIy Is moro usofuI fhnn InfornnI onorgy.
Q. 4. TLe moIuv Leut oI subIImutIon oI u soIId Is uIwuys gveutev tLun tLe moIuv
Leut oI vupovIzutIon oI tLe covvespondIng IIquId. WLy?
Ans. SInco fho moInr honf of subIImnfIon Is fho summnfIon of honf of moIfIng nnd honf
of vnorIznfIon so If Is nIwnys gronfor fhnn fho honf of vnorIznfIon of fho corrosondIng IIquId.
Q. 5. WLen does tLe entvopy oI u substunce become zevo?
Ans. Tho onfroy of n subsfnnco bocomos zoro whon fho subsfnnco Is orfocfIy crysfnIIIno
i.e., ordorod sfnfo nnd nf fho fomornfuro of 0 K.
Q. 6. evIve CIupeyvon-CIuusIus equutIon und mentIon Its uppIIcutIons.
Q. ?. evIve GIbbs-HeImLoItz equutIon und mentIon Its sIgnIIIcunce.
Q. B. WLut Is entLuIpy?
Ans. Soo foxf ngo ?l.
THERMODYNAMCS 99
Q. 9. WLut do you meun by entvopy?
Ans. Infroy Is fho monsuromonf of rnndomnoss i.e., dIsordor of fho sysfom. Ifs chnngo
i.e., JS Is dofInod ns JS =
q
rovorsIbIo
T
.
Q. 10. WLut uve tLe IImItutIons oI IIvst Iuw oI tLevmodynumIcs?
Ans. Tho fIrsf Inw doos nof IndIcnfo:
(i) Whofhor fho frnnsformnfIon of InfrInsIc onorgy of n subsfnnco wouId occur nf nII.
(ii) If If so occurs, fhon fo whnf oxfonf or In whIch dIrocfIon wouId fho frnnsformnfIon
fnko Inco.
Q. 11. AppIy tLe IIvst Iuw oI tLevmodynumIcs Iov tLe IoIIowIng cuses (=) udIubutIc
cLunge, (>) cycIIc pvocess.
Ans. (o) Ior ndInbnfIc chnngo
q = 0
So, from fIrsf Inw, I = q W or I = 0 W |3 q = 0]
So, W = I
So, In ndInbnfIc rocoss, fho work dono by fho sysfom Is oqunI fo fho docronso In InfornnI
onorgy.
Ior cycIIc rocoss fho InfornnI onorgy doos nof chnngo nf nII, i.e., I = 0.
So, from fIrsf Inw, I = q W
or 0 = q W |3 I = 0]
or W = q.
So, In cycIIc rocoss fho work dono by fho sysfom Is oqunI fo fho nmounf of honf nbsorbod
by fho sysfom.
Q. 12. eIIne vevevsIbIe und IvvevevsIbIe pvocesses.
Ans. Soo ngo 69.
Q. 13. IstInguIsL between udIubutIc und IsotLevmuI cLunges.
Ans.
IsotLevmuI cLunge AdIubutIc cLunge
(o) Tomornfuro of fho sysfom romnIns (o) Honf oxchnngo bofwoon fho sysfom nnd fho
consfnnf. surroundIng doos nof occur.
(I) Chnngo In InfornnI onorgy doos nof fnko (I) InfornnI onorgy of fho sysfom chnngos.
Inco.
(c) IV = Consfnnf for such rocoss. (c) IV
= consfnnf for such rocoss.

Q. 14. WvIte down tLe expvessIon Iov muxImum wovk done In un IsotLevmuI
vevevsIbIe pvocess.
Ans. W = n!T In
V
V
2
l
= n!T In
I
I
l
2
.
Q. 15. WvIte tLe expvessIon Iov wovk obtuIned In un IsotLevmuI IvvevevsIbIe
vevevsIbIe pvocess.
Ans. W
Irr
= I
2
(V
2
V
l
).
Q. 16. eIIne C
p
und C
v
. Stute veIutIon between tLem.
Ans. Soo ngo ?3.
Q. 1?. xpIuIn tLut JouIe-TLomson expevIment Is IsoentLuIpIc.
Ans. Soo ngo ?l.
Q. 1B. WLut Is InvevsIon tempevutuve?
Ans. Soo ngo ?2.
Q. 19. Stute wItL exumpIe tLe sIgnIIIcunce oI Hess's Iuw.
Ans. Soo ngo 8l.
Q. 20. Stute tLe Iuw oI IupIuce und IuvoIsIev.
Ans. Soo ngo 80.
Q. 21. eIIne (=) Leut oI IovmutIon, (>) Leut oI combustIon, (?) Leut oI
neutvuIIsutIon.
Ans. Soo ngo 8l, 82.
Q. 22. Stute tLe second Iuw oI tLevmodynumIcs.
Ans. Soo ngo 84. AIfornnfIvoIy If cnn bo sfnfod ns fho nof onfroy of fho unIvorso fonds
fo n mnxImum.
Q. 23. WLut do you meun by u cycIIc pvocess?
Ans. Soo ngo ?0.
Q. 24. Stute MuxweII's veIutIons.
Ans. Soo ngo 89.
Q. 25. eIIne wovk IunctIon und Ivee enevgy.
Ans. Soo ngos ?8 nnd ?9.
Q. 26. How cun you meusuve u spontuneous system wItL tLe LeIp oI Ivee enevgy?
Ans. Soo foxf ngo ?9.
Q. 2?. WLut do you meun by G Iov tLe veuctIon H
2
+
1
2
O
2
= H
2
O Is 54.65 KcuI
ut 25C?
Ans. If monns fhnf If n moIo of H
2
nnd
l
2
moIo of O
2
bofh nf unIf rossuros nf consfnnf
fomornfuro (25C), fho docronso In froo onorgy Is 54.65 KcnI.
EXERCISES
1. SIorI QueeIione.
(i) orIvo nn oxrossIon for fho vnrInfIon of honf of roncfIon wIfh fho fomornfuro wIfh fho hoI
of fIrsf Inw of fhormodynnmIcs.
(ii) orIvo CInoyron-CInusIus oqunfIon nnd sfnfo Ifs nIIcnfIons.
(iii) ofIno fho concofs of HoImhoIfz froo onorgy nnd CIbb`s froo onorgy. oscrIbo n roInfIon bo-
fwoon fho fwo.
(it) Whnf Is fho sIgnIfIcnnco of onfroy Whnf Is fho crIforIn for sonfnnoIfy
(t) orIvo KIrchoff`s oqunfIon. If Is bnsod on whIch Inw IxInIn.
THERMODYNAMCS 101
(ti) Whnf Is JouIo-Thomson offocf
(tii) Whnf Is bond onorgy How cnn you cnIcuInfo fho bond onorgy of CC bond In ofhnno
(tiii) WrIfo nofos on (o) Honf of formnfIon, (ii) Honf of combusfIon.
(ix) Sfnfo Hoss`s Inw nnd oxInIn how If cnn bo usod fo cnIcuInfo fho honfs of formnfIon.
(x) Why Is onfroy n sfnfo funcfIon
2. OIjecIite T,pe QueeIione.
(i) WhIch Is n sfnfo funcfIon
(o) q (I) W (c) q W (J) q/W.
(ii) WhIch Is nn oxfonsIvo roorfy
(o) Tomornfuro (I) VIscosIfy (c) VoIumo.
(iii) WhIch Is nn InfonsIvo roorfy
(o) Irossuro (I) TImo (c) VoIumo.
(it) Whon Is n sysfom In oquIIIbrIum
(o) C Is zoro (I) S Is mInImum (c) C Is mnxImum.
(t) Honf of noufrnIIznfIon of n sfrong ncId wIfh n sfrong bnso Is consfnnf sInco
(o) SnIfs nro formod. (I) OnIy H
+
nnd OH
Ions roncf In onch cnso.

(c) Sfrong ncId nnd sfrong bnso roncf comIofoIy.
(ti) Tho oxrossIon of fIrsf Inw of fhormodynnmIcs Is
(o) q = H W (I) H + IV = I (c) I = q W.
(tii) AII nnfurnIIy occurrIng rocossos rocood sonfnnoousIy fo
(o) Incronso In froo onorgy (I) docronso In froo onorgy (c) docronso In onfroy.
(tiii) AII IIvIng sysfoms nro
(o) ndInbnfIc sysfoms (I) CIosod sysfoms (c) Oon sysfom.
(ix) Infroy of n sysfom chnngos durIng moIfIng. urIng moIfIng If
(o) docronsos (I) Incronsos (c) romnIns unchnngod.
(x) On IncronsIng rossuro, boIIIng oInf of wnfor
(o) romnIns unchnngod (I) Incronsos (c) docronsos.
3. (o) Whnf do you monn by fhormodynnmIcs
(I) IxInIn fho forms (i) IsoInfod sysfom, (ii) CIosod sysfom, (iii) IxfonsIvo roorfIos,
(it) InfonsIvo roorfIos, (t) !ovorsIbIo rocoss, (ti) IrrovorsIbIo rocoss, (tii) IsofhormnI
rocoss, (tiii) AdInbnfIc rocoss, (ix) IsochorIc rocoss, (x) IsobnrIc rocoss, (xi) Sfnfo func-
fIon.
(c) CIvo fho mnfhomnfIcnI oxrossIon for fIrsf Inw of fhormodynnmIcs.
4. (o) Whnf Is JouIo-Thomson offocf
(I) Irovo fho consfnncy In JouIo-Thomson oxnnsIon.
(c) Whnf do you monn by InvorsIon fomornfuro
5. orIvo nn oxrossIon for fho work dono durIng rovorsIbIo IsofhormnI oxnnsIon of nn IdonI gns.
6. (o) Show fhnf for n gnsoous oxnnsIon, H > I.
(I) ofIno moInr honf cnncIfIos.
(c) Irovo fhnf C
p
C
t
= !.
?. orIvo KIrchoff `s oqunfIon.
B. (o) Whnf do you monn by onfroy
(I) CIvo hysIcnI sIgnIfIcnnco of onfroy.
(c) CIvo chnrncforIsfIcs of onfroy.
(J) IxInIn fho roInfIon: S = l In u.
9. orIvo nn oxrossIon for onfroy for nn IdonI gns.
10. Show fhnf onfroy chnngo In nn IrrovorsIbIo rocoss Is osIfIvo.
11. Show fhnf onfroy chnngo for nn IrrovorsIbIo IsofhormnI oxnnsIon of nn IdonI gns Is osIfIvo.
12. Infroy chnngo for fho mIxfuro of gnsos cnn bo rorosonfod by
S
mIx
= n! x
i
In x
i
whoro x
i
= moIo frncfIon of gns.
13. (o) Whnf do you monn by work funcfIon (A)
(I) Whnf do you monn by froo onorgy (C)
(c) Whnf Is fho roInfIonshI bofwoon froo onorgy nnd usofuI work
(J) Whnf do you monn by sfnndnrd froo onorgy chnngo
14. (o) Sfnfo Hoss`s Inw.
(I) MonfIon fho nIIcnfIons of Hoss`s Inw.
(c) IxInIn fho forms (i) Honf of roncfIon, (ii) Honf of combusfIon, (iii) Honf of noufrnIIsnfIon,
(it) Honf of formnfIon, (t) Honf of soIufIon, (ti) Honf of fusIon, (tii) Honf of vnorIsnfIon,
(tiii) Honf of subIImnfIon.
15. How cnn you doformIno fho bond onorgy nnd InffIco onorgy wIfh fho hoI of Hoss`s Inw
16. (o) orIvo CIbbs-HoImhoIfz oqunfIon.
(I) CIvo fho sIgnIfIcnnco of CIbbs-HoImhoIfz oqunfIon.
1?. orIvo CInusIus-CInoyron oqunfIon.
1B. (o) How cnn you doformIno sonfnnoIfy of chnngos of n sysfom
(I) Whnf do you monn by chomIcnI ofonfInI ()
(c) Show fhnf chomIcnI ofonfInI doos nof chnngo durIng hnso frnnsfor of n comound.
19. orIvo MnxwoII`s roInfIon nnd sfnfo Ifs usofuInoss.
20. orIvo nn oxrossIon for chomIcnI ofonfInI nf n fomornfuro T In forms of I.
21. orIvo CIbbs-uhom roInfIons.
22. Whnf do you monn by Vnn`f Hoff roncfIon Isofhorm orIvo nn oxrossIon for fho roncfIon Isofhorm
of fho gonornI roncfIon oA + II + ... l! + nM + ... .
Long QueeIione
1. Whon Ico moIfs nf 0C, fho Infonf honf of fusIon Is 80 cnIs. g
l
. Tho donsIfy of Ico Is 0.82 nnd of
wnfor of unIfy. CnIcuInfo I, H, q nnd u or moIo.
(l440.l cnIs; l440 cnIs; l440; cnIs; 4.0l l0
6
orgs)
2. CnIcuInfo I nnd H If l0 IIfros of hoIIum nf .T.I. nro honfod InsIdo n gns cyIIndor fo l00C
nssumIng If fo bohnvo IdonIIy nnd hnvIng C
t
=
3
2
!
. |Ans. l33.8; 223.l cnIs]
3. A sysfom orforms 8.36 l0
9
orgs work nffor nbsorbIng 990 cnIs. honf from fho surroundIng.
IInd fho InfornnI onorgy chnngo of fho sysfom. |Ans. ?90 cnIs]
4. Tho voIumo of n 45 g nIfrogon gns Is oxnndod from 5 IIfro fo l0 IIfro nf 25C IsofhormnIIy nnd
rovorsIbIy. ConsIdorIng fho gns fo bo nn IdonI fInd ouf fho work obfnInod In fhIs cnso.
|Ans. 2.?88 l0
?
orgs]
5. urIng IsofhormnI rovorsIbIo oxrossIon of 4 g of hoIIum gns nf 2?C fho rossuro roducos from
l0 nfm fo l nfm. CnIcuInfo fho work dono In cnIorIos. ConsIdor fho gns fo bohnvo IIko nn IdonI.
|Ans. l38l.8 cnIs]
6. Tho honfs of formnfIon of CO
2
from dInmond nnd grnhIfo nro 94500 nnd 94050 cnI, rosocfIvoIy.
Whnf Is fho onfhnIy chnngo In fho frnnsformnfIon of dInmond fo grnhIfo |Ans. 450 cnI]
?. CnIcuInfo fho honf of oxIdnfIon of ofhyI nIcohoI fo cnrbon dIoxIdo, whon fho honfs of formnfIon of
cnrbon dIoxIdo nnd IIquId wnfor nro gIvon ns 94.05 nnd 68.32 KcnI. Tho honf of formnfIon of
ofhyI nIcohoI Is 66.4 KcnI. |Ans. 326.6 KcnI]
THERMODYNAMCS 103
B. IInd honf of formnfIon of cnusfIc sodn from fho foIIowIng dnfn:
n + H
2
O = nOH (oq) +
l
2
H
2
+ 98,000
H
2
+
l
2
O
2
= H
2
O + 68,380
nOH + wnfor = nOH (oq) + l3,300. |Ans. l53080 cnIs]
9. CnIcuInfo fho honf of formnfIon of bonzono gIvon fhnf fho honfs of combusfIon of bonzono, cnrbon
nnd hydrogon nro ?54300 cnIs, 94380 cnIs nnd 68380 cnIs, rosocfIvoIy. |Ans. l?l20 cnIs]
10. IsofhormnIIy nf 2?C ono moIo of n vnn dor WnnI`s gns oxnnds rovorsIbIy from 2 IIfros fo 20
IIfros. CnIcuInfo fho work dono If o = l.42 l0
l2
dynos cm
4
moI
l
nnd I = 30 c.c moI
l
.
|HInt. W = !T
V
V
l
V
l
V
2 l
In
2
l
I
I
o .
W = 2.303 8.3l l0
?
300 Iog
20 0.03
2 0.03
+ l.42 l0
l2

2000 20000
20000 2000
orgs
= 56?? l0
?
orgs.]
11. ?0 g of nIfrogon gns wns InIfInIIy nf 50 nfm nnd 25C. If wns nIIowod fo oxnnd IsofhormnIIy
ngnInsf n consfnnf oxfornnI rossuro of ono nfmoshoro. CnIcuInfo Q, W, !, H.
|Ans. l.5 KcnI; l.5 KcnI; 0; 0]
12. Irom fho foIIowIng bond onfhnIIos cnIcuInfo H for fho roncfIon, H
2
+ Ir
2
2 HIr. Iond
onorgy HH = 435.24 kJ moI
l
; IrIr bond onorgy = l92.5 kJ moI
l
; HIr bond onorgy =
368.3 kJ moI
l
. |Ans. l08.86 kJ]
13. Tho honf of combusfIon of mofhyI nIcohoI Is l?3.65 KcnI. CIvon, H
(H O, )
2
l
= 68320 cnI;
H
(CO , )
2
f g
= 94050 cnI. IvnIunfo fho honf of formnfIon of mofhyI nIcohoI. |Ans. 5?040 cnI]
14. CnIcuInfo S, A nnd C for vnorIsnfIon of 2 moIos of bonzono (b.. = 353.2 K nnd C = l0l cnI g
l
)
|Ans. S = 44.5 cnI/K, C = 0, A = l.4 KcnI]
15. Tho vnn dor WnnI`s consfnnf for CO
2
, o = 3.59 IIfro
2
nfm/moI
2
nnd I = 0.043 IIfro moI
l
. Whnf Is
fho InvorsIon fomornfuro of fho gns |Ans. 2036 K]
16. Tho s. honf of bonzono Is 0.39. IInd fho chnngo In onfroy whon l kg of bonzono nf l0C Is
mIxod wIfh 4.0 kg of bonzono nf 30C. |Ans. 0.98?9 oV]
1?. CnIcuInfo fho onfroy chnngo In vnorIsnfIon of ofhor. CIvon, boIIIng oInf = 35C, ! = 6500 cnI
moI
l
. |Ans. 2l.l oV]
1B. CnIcuInfo fho froo onorgy chnngo of g moIo of SO
2
nf 25C nnd l0 nfm rossuro. CIvon, C
298
= ?l.8 KcnI moI
l
. (Ans. ?0.43 KcnI/moI
l
]
19. C nnd H for n nrfIcuInr roncfIon nf l2?C nro l2 KcnI nnd l?.5 KcnI. IInd ouf S.
|Ans. l3.?5 oV]
20. Tho vnour rossuro of wnfor nf 90C Is 530 mm Hg. Tho nvorngo Infonf honf of vnorIsnfIon of
wnfor Is 546 cnI g
l
wIfhIn fho fomornfuro rnngo 90C l00C. CnIcuInfo fho vnour rossuro
nf l00C. |Ans. ?60 mm Hg]
104
#
Reaction Dynamics/ChemicaI Kinetics
INTRODUCTION
Irom fho sfudy of chomIcnI oquIIIbrIum InvoIvIng Inw of mnss ncfIon, wo cnn rodIcf how fnr
fho roncfIon wouId go. Iuf cnn sny nofhIng nbouf how fnsf fho oquIIIbrIum wIII nffnIn. Though
fhormodynnmIcs hns gof nn onormous InfIuonco In chomIcnI oquIIIbrIum yof hns no vnIId
nIIcnfIon In sfudyIng fho rnfo of roncfIon. Tho nssngo fownrds oquIIIbrIum fnkos somo fImo
whIch mny bo nImosf Insfnnfnnoous or vory Iong. Tho voIocIfy of n roncfIon Is nof snmo ovon nf
consfnnf fomornfuro. Ivory chomIcnI roncfIon hns n dofInIfo voIocIfy nf n dofInIfo fomornfuro.
Modorn fochnIquos hnvo boon dovoIood fo sfudy fho roncfIon rnfo whIch gofs comIofod In
mIIIIsoconds or ovon In mIcrosoconds.
Iuf fhoro nro sovornI ofhor roncfIons whoro fho rnfo cnn bo onsIIy monsurod. As for
oxnmIo:
CH
3
COOC
2
H
5
+ H
2
O CH
3
COOH + C
2
H
5
OH
2H
2
O
2
2H
2
O + O
2
VeIocity of Reaction
Irom Inw of mnss ncfIon, wo know fhnf fho rnfo of roncfIon Is doondonf on fho ncfIvo
mnssos of roncfIng subsfnncos. AcfunIIy ncfIvo mnss monns 'moInr conconfrnfIon`.
Ior n roncfIon oA + II cC + J
rnfo of roncfIon, (r)
r = l . |A]
o
. |I]
I
whoro |A] nnd |I] nro fho conconfrnfIons of fho roncfnnfs nf fhnf Insfnnf.
l Is n consfnnf known ns roIe coneIonI or epecific reocIion roIe.
Whon |A] = |I] = l
fhon, l = r.
In fhIs cnso, fho rnfo consfnnf wIII oxross fho rnfo of fho roncfIon, i.e., fho rnfo consfnnf
Is cnIIod socIfIc roncfIon rnfo.
HIgLIIgLts:
HIghor fho vnIuo of l hIghor fho roncfIon rnfo.
!oncfIon rnfo Is doformInod by fho docronsIng conconfrnfIon of fho roncfnnfs In
unIf fImo.
Tho rnfo of n roncfIon cnn nIso bo doformInod by fho IncronsIng conconfrnfIon of
fho roducfs In unIf fImo.
MnfhomnfIcnIIy r =
Jc
JI
=
Jx
JI
whoro c = conconfrnfIon of fho roncfnnf,
x = conconfrnfIon of fho roducf.
C-8N-ENGCHEECH5-1.PM5 105
REACTON DYNAMCS/CHEMCAL KNETCS 105
To consIdor fho rnfo of n roncfIon, wo shouId fnko Info nccounf fho 'ordor` nnd fho
'moIocuInrIfy` of n roncfIon.
Order of a Reaction
Tho rnfo of roncfIon wIII dofInIfoIy doond on fho conconfrnfIon of fho roncfnnfs.
Thoroforo, fho rnfo oqunfIon wIII InvoIvo fho conconfrnfIon of fho roncfnnfs. In fho
oxorImonfnIIy doformInod rnfo oqunfIon, fho owors of fho conconfrnfIon forms nro nddod fo
gof fho ordor of n roncfIon. As for oxnmIo, for n roncfIon:
oA + II Iroducfs
rnfo of fho roncfIon (r) = l . |A]
o
. |I]
I
.
So, fho ordor of fho roncfIon wIII bo = (o + I).
Tho oxorImonfnIIy doformInod rnfo oqunfIon for fho docomosIfIon of H
2
O
2
Is:
r = l . |H
2
O
2
]
Horo wo soo rnfo Is roorfIonnI fo fho fIrsf owor of fho conconfrnfIon of H
2
O
2
. So If Is
n IIvst ovdev roncfIon.
TubIe 5.1
IeocIione 1xperinenIoll, JeIernineJ OrJer
roIe
(i) 2HI = H
2
+ I
2
r = l . |HI]
2
2
(ii) H
2
+ I
2
= 2HI r = l . |H
2
]|I
2
] 2
(iii) CH
3
COOC
2
H
5
+ nOH r = l|CH
3
COOC
2
H
5
] |nOH] 2
= CH
3
COOn + C
2
H
5
OH
HIgLIIgLts:
Tho numbor of moIocuIos of fho oqunfIon for fho chomIcnI chnngo hns gof no roInfIon
wIfh fho ordor of n roncfIon.
Tho ordor of n roncfIon wIII bo doformInod by fho owor forms of fho conconfrnfIons
of fho rnfo oqunfIon.
Tho ordor of n roncfIon mny bo zoro or frncfIon.
MoIecuIarity of a Reaction
Tho mInImum numbor of moIocuIos, nfoms or Ions fnkIng nrf In n chomIcnI roncfIon Is
known ns moIocuInrIfy of fho roncfIon. As for oxnmIo
2HI = H
2
+ I
2
Ior fhIs roncfIon, mInImum fwo moIocuIos of HI wIII bo roquIrod. So, fho moIocuInrIfy Is
'fwo`. AgnIn for fho roncfIon:
2H
2
O
2
= 2H
2
O + O
2
Iuf fho roncfIon cnn bo wrIffon ns
H
2
O
2
= H
2
O + O
So, for docomosIfIon of H
2
O
2
,

ono moIocuIo Is noodod nnd honco fho moIocuInrIfy Is ono.
HIgLIIgLts:
Ior fho roncfIon
2
2
O
5
= 4O
2
+ O
2
,
Tho obsorvod rnfo = l . |
2
O
5
]
So, fho ordor of fho roncfIon Is ono nnd fho moIocuInrIfy Is fwo.
2O + O
2
= 2O
2
!nfo = l . |O]
2
|O
2
]
So, bofh fho ordor nnd fho moIocuInrIfy of fho roncfIon nro fhroo.
Ior fho roncfIon
IrO
3
+ 5Ir
+ 6H
+
= 3Ir
2
+ 3H
2
O
Tho obsorvod rnfo = l . |IrO
3
] |Ir
] |H
+
]
2
So, fho ordor of fho roncfIon Is four buf fho moIocuInrIfy Is fwoIvo.
Ior fho roncfIon
CO + CI
2
= COCI
2
!nfo = l . |CO] |CI
2
]
l.5
So, fho ordor of fho roncfIon Is 2.5 nnd fho moIocuInrIfy Is 2.
MathematicaI FormuIation of First Order Reaction
Tho roncfIons, whoro fho oxorImonfnIIy doformInod rnfo of fho roncfIon Is doondonf
on fho fIrsf owor of fho conconfrnfIon of fho roncfnnf, nro cnIIod fIrsf ordor roncfIons.
If c bo fho conconfrnfIon, fhon fho rnfo of fho roncfIon =
Jc
JI
= lc.
whoro l = rnfo consfnnf.
!of fho roncfIon bo A Iroducfs.
(o x) x
Af fImo 'I`, o = InIfInI conconfrnfIon of A.
x = conconfrnfIon of fho roducf nf fImo I.
Thoroforo, fho rnfo oqunfIon wIII bo
Jx
JI
= l . (o x)
or
Jx
o x
= l . JI.
InfogrnfIng wo hnvo,
In (o x) = lI + c
whoro c = InfogrnfIon consfnnf
whon I = 0, x = 0
Thon, In o = c
So, In (o x) = lI In o
or In
o
o x
= lI
or l =
l
I
o
o x
. In
=
2 303 .
. Iog
I
o
o x
.
Tho rnfo oqunfIon cnn bo wrIffon ns
In
( ) o x
o
= lI
or
o x
o
= e
lI
or (o x) = o . e
lI
or x = o(l e
lI
).
Tho nbovo oqunfIon oxrossos n numbor of chnrncforIsfIcs of n fIrsf ordor roncfIon
(i)
o
o x
Is n common rnfIo, If Is uroIy n dImonsIonIoss numbor. So, for nny unIf of
conconfrnfIon, fho vnIuo of l wIII bo snmo.
(ii) l =
l
I
. In
o
o x
.
So, unIf of l wIII bo fImo
l
.
(iii) l =
Jc
JI
Jc
JI
C
C frncfIon of roncfnnfs
fImo
= =
/
So, l Is chnngo of frncfIon of roncfnnfs In unIf fImo.
(it) Irom fho oqunfIon,
I =
l
l
. In o/(o x)
Tho hnIf-IIfo of n fIrsf ordor roncfIon cnn bo cnIcuInfod
I
l/2
=
l
2
l
o
o
o
. In
x
o
=
2
=
l
l
. In 2
=
2 303 .
.
l
Iog
l0
2 =
0 693 .
l
.
(t) Ior comIofo roncfIon x = o, fhon fho oqunfIon
x = o(l e
lI
) wIII bo
o = o(l e
lI
)
I = InfInIfy.
So, n fIrsf ordor roncfIon Is novor comIofod.
If wo uf o x = c i.e., conconfrnfIon nf nny fImo 'I` nnd o = c
0
, wo hnvo, lI = In
c
c
0
c = c
0
. e
lI
Thoroforo, Iog c =
l
I 2.303
+ Iog c
0
Iog c Is Ioffod ngnInsf 'I` wo gof n sfrnIghf IIno wIfh n nognfIvo sIoo =
l
2.303
.
ExampIes of a First Order Reaction
(i) ocomosIfIon (gns hnso)
(o) 2
2
O
5
4O
2
+ O
2
(I)
2
O
4
2O
2
(c) CH
3
CH
2
CI C
2
H
4
+ CI
2
(J)
CH
CH
CH
CH
2
2
2
2
2C
2
H
4
cycIobufnno
ofhyIono
(ii) IsomorIsnfIon (gns hnso)
(o) CH
2 2
CH
CH
2
CH CH = CH
3 2
cyclopropane
propylene
(I)
CH
CH
CH
CH
2
2
CH
2
= CHCHo = CH
2
CycIobufono
l, 3-bufndIon.
(iii) ocomosIfIon (soIufIon hnso)
(o) H
2
O
2
H
2
O +
l
2
O
2
(I)
COOH
NO
2
NO
2
O N
2
NO
2
NO
2
O N
2
(it) HydroIysIs
C
l2
H
22
O
ll
+ H
2
O C
6
H
l2
O
6
+ C
6
H
l2
O
6
Cnno Sugnr CIucoso Irucfoso
(t) SoIvoIysIs
(CH
3
CO)
2
O + 2C
2
H
5
OH 2 CH
3
COOC
2
H
5
+ H
2
O
(ti) !ndIoncfIvo dIsInfogrnfIon:
!n !n +
MathematicaI FormuIation of a Second Order Reaction
!oncfIons In whIch fwo moIocuIos, IdonfIcnI or dIfforonf, fnko nrf nnd fho rnfo of fho
roncfIon Is roorfIonnI fo fho conconfrnfIon of onch of fhom, nro cnIIod socond ordor roncfIon.
!of, fho roncfIon bo rorosonfod by,
A + I C +
InIfInI conconfrnfIon of A = o
InIfInI conconfrnfIon of I = I
ocronso In conconfrnfIon of A nnd I nf fImo I = x
ConconfrnfIon of A nf fImo I = o x
ConconfrnfIon of I nf fImo I = I x
ConconfrnfIon C nnd nf fImo I = x
!nfo of fho roncfIon = l|A] |I]
or
Jx
JI
= l(o x) (I x)
or l JI =
Jx
o x I x ( )( )
=
l l l
I o o x I x
Jx

l l l
I o o x I x
Jx

= l JI
or
l l l
I o o x I x
Jx

= l JI
or
l l l
I o o x
Jx
I x
Jx

= l JI
or
l
I o
| In (o x) + In (I x)]
= lI + c (InfogrnfIon consfnnf)
or In
I x
o x
= l(I o)I + c
Af I = 0, x = 0 In
I
o
c =
In
I x
o x
= l(I o)I + In
I
o
l(I o)I = In
I
o
In
( )
( )
In
( )
( )
I x
o x
I o x
o I x
=
or l(I o)I = In
I o x
o I x
( )
( )
= In
o I x
I o x
( )
( )
l =
l
( )
In
( )
( ) I o I
o I x
I o x
=
2 303 .
( )
Iog
( )
( ) I o I
o I x
I o x
If, InIfInIIy, conconfrnfIon of bofh fho roncfnnfs nro oqunI i.e., o = I, fhon wo cnn wrIfo,

Jx
JI
= l(o x)
2
or
Jx
JI
= l(I x)
2
TnkIng
Jx
JI
= l(o x)
2
or
Jx
o x ( )
2
= l JI
or
l
o x
= lI + c (InfogrnfIon consfnnf)
whon I = 0, x = 0, c =
l
o
lI =
l l
o x o
or l =
l
I
x
o o x
.
( )
If wo uf o x = c
fhon, lI =
l l
c o

l
c
= lI +
l
o
.
Characteristic of a Second Order Reaction
(i) Tine of Iolf reocIion
I
l/2
=
l l 2
2
l
l
x
o o x l
o
o o o ol
.
( )
/
( / )
= =
i.e., hnIf docomosIfIon fImo of n socond ordor roncfIon Is InvorsoIy roorfIonnI fo fho fIrsf
owor of InIfInI conconfrnfIon nnd Is oqunI fo
l
l
whon o = l
(ii) IniI of roIe coneIonI l
Jx
JI
= l(o x)
2
= lc
2
whon (o x) = c
l =
Jx
JI c
.
l conc
fImo conc
2 2
=
l
= conc
l
. fImo
l
= l . moI
l
soc
l
|l = IIfro]
(iii) PI,eicol eignificonce
l =
Jx
JI
= Whon c = l
i.e., l Is fho rnfo of docomosIfIon nf unIf conconfrnfIon of fho roncfnnfs.
ExampIes of a Second Order Reaction
(i) ocomosIfIon (gns hnso):
(o) 2HI H
2
+ I
2
(I) 2O
2
2O + O
2
(c) 2OCI 2O + CI
2
(ii) IsIncomonf roncfIon (gns hnso):
(o) H +
2
H +
(I) CI + H
2
HCI + H
(iii) ImorIsnfIon (gns hnso):
CH CH CH CH
2 2
bufndIono
= = CH CH CH
CH CH CH
CH
CH
2
2
2
2
=
dImor
(it) AddIfIon (gns hnso):
H
2
+ I
2
2HI
(t) SubsfIfufIon roncfIon (SoIufIon hnso):
(o) I
+ CH
3
Ir CH
3
I + Ir
(I) OH
+ CH
3
I CH
3
OH + I
(ti) HydroIysIs of nn osfor:

CH
3
COOC
2
H
5
+ OH
CH
3
COO
+ C
2
H
5
OH
(tii) IsforIfIcnfIon:
CH
3
COOH + C
2
H
5
OH CH
3
COOC
2
H
5
+ H
2
O
Comparison
PoinIe IireI orJer reocIion SeconJ orJer reocIion
!nfo oqunfIon l =
l
I
o
o x
In
l =
l
I
x
o o x ( )
!InonrIfy Iog c docronsos IInonrIy wIfh fImo
l
c
Incronsos IInonrIy wIfh fImo.
!nIf of l soc
l
l moI
l
. soc
l
l Indoondonf of conconfrnfIon. oondonf on conconfrnfIon.
I
l/ 2
Indoondonf of InIfInI conconfrnfIon. InvorsoIy roorfIonnI fo InIfInI
conconfrnfIon.
Third Order Reaction
Tho rnfo oqunfIon for n fhIrd ordor roncfIon Is
A + I + C Iroducfs
Jx
JI
= l(o x)(I x)(c x)
whoro,
InIfInI conconfrnfIon of A = o
InIfInI conconfrnfIon of I = I
InIfInI conconfrnfIon of C = c
no. of moIos of onch roncfnnf docomosod nf fImo I = x.
Whon, o = I = c
fho rnfo oqunfIon bocomos,

Jx
JI
= l(o x)
3
= lc
3
|whon o x = c]
= lc
2
(c x) |whon o = I c nnd (o x) = c]
AgnIn
Jx
JI
= l(o x)
3
or
Jx
o x ( )
3
= l JI
InfogrnfIng,

l
2
l
2
.
( ) o x
lI c = + (InfogrnfIon consfnnf)
Whon I = 0, x = 0
l
2
l
2
.
o
= Z Z =
l
2
2
o
or
l
2
l l
2
2 2
( )
o x o
lI =
lI =
l
2
l l
2 2
( )
o x o
l =
l
2
l l
2 2
I o x o ( )
=
l 2
2
2 2
I
x o x
o o x
( )
( )
.
Characteristics of a Third Order Reaction
(i) Whoro x =
l
2
o,
l =
l
l
2
2
l
2
2
l
2
l
l
4
l
2
l
3
4
l
2
2
2
2 2
4
2
4 I
o o o
o o
I
o o
o
I
o
o
.
.
.
= =
=
l 3
2
l
2
I o
. or I =
l 3
2
l
2
l o
. . =
3
2
l
2
l o
.
I
l
2
o
So, fho fImo roquIrod for fho comIofIon of fho snmo frncfIon of fho chnngo Is InvorsoIy
roorfIonnI fo fho squnro of fho InIfInI conconfrnfIon.
(ii) l Is doondonf on fho unIf of conconfrnfIon.
(iii) !nIf of l Is moIo
l
soc
l
.
ExampIes of Third Order Reaction
(i) 2O + O
2
2O
2
(ii) 2O + CI
2
2 OCI
(iii) SnCI
2
+ 2IoCI
3
SnCI
4
+ 2IoCI
2
Zero Order Reactions
Thoro nro corfnIn roncfIons whoro rnfo of roncfIon doos nof dImInIsh wIfh fImo i.e., fho
rnfo of fho roncfIon Is nof doondonf on fho conconfrnfIon of fho roncfnnf or, In ofhor words,
rnfo of fho roncfIon Is roorfIonnI fo fho zoro owor of fho conconfrnfIon of fho roncfnnf i.e.,
| ]
Jc
JI
l = A
0
= l |3 |A]
0
= l]
whoro conconfrnfIon of fho roncfnnf A = c
or Jc
c
c
0
=
0
I
l JI
= l
I
0
JI
or |c c
0
] = l|I 0] or c
0
c = lI
Characteristic of a Zero Order Reaction
(i) Wo hnvo,
l =
c c
I
0

i.e., fho nmounf docomosIng In unIf fImo Is consfnnf, whIch Is oqunI fo l (Zoro ordor rnfo
consfnnf), Indoondonf of conconfrnfIon or fImo, i.e., fho roncfIon voIocIfy Is consfnnf nnd Is
Indoondonf of conconfrnfIon.
(ii) In zoro ordor roncfIons whon c Ioffod ngnInsf I wouId gIvo n sfrnIghf IIno of sIoo l ;
bocnuso
Jc
JI
Is consfnnf.
ExampIes of Zero Order Reactions
Thoso roncfIons nro confroIIod by cnfnIysf. Tho bromInnfIon of ncofono In ncId soIufIon
Is of zoro ordor wIfh rosocf fo Ir
2
; sInco fho roncfIon voIocIfy Is nof InfIuoncod by n chnngo In
conconfrnfIon of bromIno.
CH
3
COCH
3
+ Ir
2
CH
3
COCH
2
Ir + HIr
HI +
pre
W

l
2
l
2
2
H I
2
+
FractionaI Order Reactions
of nII roncfIons nro of InfogrnI or zoro ordor, mnny frncfIonnI ordor roncfIons nro known.
In fhoso roncfIons, fho rnfo of roncfIon Is roorfIonnI fo frncfIonnI owor of conconfrnfIon of
fho roncfnnf, i.e.,
Jc
JI
= Kc
l/n
whoro conconfrnfIon of fho roncfnnf = c.
ExampIes of FractionaI Order Reaction
(i) CH
3
CHO CH
4
+ CO;
/
Jc
JI
c = K
3 2
(ii) 2SbH
3

SI
2Sb + 3H
2
;
Jc
JI
= Kc
3/5
(iii) orfho-H
2
nrn-H
2
;
Jc
JI
= Kc
3/2
!sunIIy such ordor InvoIvos n mochnnIsm whoro nfoms or froo rndIcnIs nro InformodInfos
of fho roncfIon.
Pseudo UnimoIecuIar Reactions
!of us fnko fho roncfIon
C
l2
H
22
O
ll
+ H
2
O C
6
H
l2
O
6
+ C
6
H
l2
O
6
Sucroso CIucoso Irucfoso
If wo doformIno fho rnfo of fho roncfIon, wo soo fhnf fho roncfIon Is of fho socond ordor.
So, fho roncfIon Is doondonf on fho conconfrnfIon of bofh fho roncfnnfs. So, fho rnfo oqunfIon
of fho roncfIon Is
Jc
JI
= l|C
l2
H
22
O
ll
] |H
2
O]
In soIufIon fho nmounf of wnfor Is oxcossIvoIy hIgh comnrod fo sugnr. Affor comIofo
hydroIysIs of sugnr, fho chnngo of conconfrnfIon of sugnr Is vory nogIIgIbIo. So |H
2
O] Is consfnnf.
Tho rnfo oqunfIon comos fo
Jc
JI
= l|C
l2
H
22
O
ll
]
or
Jx
JI
= l(o x)
or l =
l
I
. In
o
o x
So, chnrncforIsfIcs of fIrsf ordor roncfIon Is soon ncfunIIy In socond ordor roncfIon. uo
fo rosonco of oxcoss wnfor, fho IncIdonf so hnons. Such soIvoIyfIc fIrsf ordor roncfIons nro
cnIIod Pseudo unImoIecuIuv veuctIons. Ofhor soudo unImoIocuInr roncfIons nro:
(i) COS + H
2
O CO
2
+ H
2
S
(ii) CH
3
COOCH
3
+ H
2
O CH
3
COOH + CH
3
OH
(iii) (CH
3
CO)
2
O + 2C
2
H
5
OH (oxcoss) 2CH
3
COOC
2
H
5
+ H
2
O
Methods for the Determination of the Order of a Reaction
(i) SuIeIiIuIion neIIoJe (uiII IIe Ielp of roIe equoIione)
Tho foIIowIng nro fho oxrossIons of rnfo consfnnfs for dIfforonf roncfIons:
IIrsf ordor roncfIon l =
l
I
o
o x
In
Socond ordor roncfIon l =

l
I
x
o o x
.
( )
ThIrd ordor roncfIon l =
l
2
l l
2 2
I o x o ( )
To doformIno fho rnfo of n roncfIon n dofInIfo nmounf (o) of fho roncfnnf Is fnkon nnd
wIfh fho nssngo of fImo 'I` fho chnngo In conconfrnfIon (x) Is doformInod mochnnIcnIIy or by
chomIcnI nnnIysIs, i.e., (o x) Is doformInod. Iy uffIng fho vnIuo 'o` nnd (o x) fho vnIuo of 'l`
Is doformInod. Tho ordor of fho roncfIon Is doformInod by fhnf oqunfIon whIch gIvos fho
snfIsfncforIIy consfnnf vnIuo of 'l`. Tho mofhod Is InborIous nnd foo comIIcnfod fo gIvo n
snfIsfncfory consfnnf vnIuo. Iuf Is sfIII omIoyod for sImIor roncfIons.
(ii) Holf-life neIIoJ
Tho hnIf-IIvos (I
l/2
) for roncfIons of dIfforonf ordors nro ns foIIows:
IIrsf ordor = 0.693/l (fIxod)
Socond ordor = l/(ol)
ThIrd ordor = l/(o
2
l)
In sonrnfo sofs of oxorImonfs If dIfforonf conconfrnfIons nro fnkon nnd I
l/2
nro monsurod
fho ordor cnn onsIIy bo doformInod. If I
l/2
romnIns consfnnf fho roncfIon Is of fho fIrsf ordor, If
I
l/2
vnrIos InvorsoIy ns fho InIfInI conconfrnfIon fho roncfIon Is of fho socond ordor, i.e., Iof of
I
l/2
te. l/o wIII gIvo n sfrnIghf IIno. If fho Iof I
l/2
te. l/o
2
gIvos n sfrnIghf IIno, fho roncfIon Is of
fhIrd ordor.
(iii) VonÌ Hoffè JifferenIiol neIIoJ
!of, fho ordor of n roncfIon bo = n.
Ior, fho fIrsf oxorImonf fho InIfInI conconfrnfIon = c
l
.
Ior fho socond oxorImonf fho InIfInI conconfrnfIon = c
2
.
So, fho rnfo oqunfIons for fho fwo oxorImonfs wIII bo
!
l
=
Jc
JI
l
= lc
l
n
;
!
2
=
Jc
JI
2
= lc
2
n
.
TnkIng 'Iog` on bofh fho sIdos
Iog !
l
= Iog l + n Iog c
l
Iog !
2
= Iog l + n Iog c
2
or n =
Iog ! Iog !
Iog Iog
l 2
l 2
c c
If fho rnfos of roncfIon doformInod InIfInIIy !
l
nnd !
2
nro known, so fho ordor cnn bo
doformInod.
(it) CropIicol neIIoJ
If wo Iof 'fImo` te 'n funcfIon of conconfrnfIon`, wo cnn gof fho ordor of n roncfIon. Iy
IoffIng Iog c te I If n sfrnIghf IIno Is obfnInod fho roncfIon Is of fIrsf ordor. If n Iof of l/c te 'I`
gIvos n sfrnIghf IIno fho roncfIon Is of socond ordor nnd If fho Iof of l/c
2
te 'I` gIvos n sfrnIghf
IIno fho roncfIon Is of fhIrd ordor (IIg. 5.l (o) nnd (I)).
A
m
o
u
n
t
d
e
c
o
m
p
o
s
e
d
(
x
)
A
C
q
dx
B
Slop = tan q
dx
dt
=
Time (t)
R
a
t
e
o
f
r
e
a
c
t
i
o
n
(
d
x
/
d
t
)
(a x)
( ) a ( ) b
Fig. 5.1
Disturbing Factors in the Determination of an Order
Tho roncfIon whIch fnkos n sIngIo nfh hns no InforforIng InfIuonco In fho mnIn roncfIon.
Iuf mnny roncfIons nro comIIcnfod, so fho InforrofnfIon of fho ordor of n roncfIon from fhoIr
voIocIfy dnfn bocomos dIffIcuIf. Tho rnfo consfnnf vnIuos nro nof obfnInod consfnnfs for n numbor
of roncfIons. Thoro nro corfnIn dIsfurbIng fncfors whIch InfIuonco fho roncfIon nnd consfnnf
vnIuos for l nro nof obfnInod. Somo of fhoso fncfors nro gIvon boIow:
Simultaneous Reactions
In n sImIo roncfIon, fho roncfnnfs roncf fo gIvo roducfs. Iuf mnny of fho roncfIons nro
nof so sImIo. Tho ofhor roncfIons occur sImuIfnnoousIy. Thoso roncfIons nro cnIIod
sImuItuneous veuctIons. Thoso roncfIons Inforforo fo gIvo n consfnnf vnIuo of l. Thoro nro
fhroo fyos of sImuIfnnoous roncfIons.
Side reactions Consecutive
reactions
Opposing reactions
Simultaneous reactions
(o) SiJe reocIion. SomofImos fho roncfnnfs undorgo fwo or moro Indoondonf roncfIons
sImuIfnnoousIy. Inch roncfIon gIvos n sof of roducfs. Tho roncfIon whIch gIvos fho mnjor
roducf Is cnIIod mnIn roncfIon nnd fho ofhor Is cnIIod sIdo roncfIon.
A
B + C; yield 90% (main reaction)
P + Q; yield 10% (side reaction)
Erumple:
CH .CH .Cl
3 2
CH .CH OH
3 2
CH = CH
2 2
C H OH
2 5
C + H
2 2
H O
4
= k
1
c
dx
dt
CH + H
3 2
CHO = k
2
c
dy
dt
[ ] k k
1 2
and are not same
(I) Oppoeing reocIion. Tho rovorsIbIo roncfIons nIso Inforforo fo gIvo fho consfnnf vnIuo of 'l`.
A + I C +
So, fho oxorImonfnIIy doformInod rnfo for fhIs roncfIon Is n nof rosuIf for fho fwo oosIng
roncfIons.
Erumple:
CH
3
COOH + C
2
H
5
OH
k
1
k
2
CH
3
COOC
2
H
5
+ H
2
O
CH OH . CH . CH . COOH
2 2 2
k
1
k
2
O CO
CH C
2 2
H
CH
2
+ H O
2
(Hydroxy butaric acid)
(Lactone)
!nfo oqunfIon for fho fIrsf roncfIon Is:
Jx
JI
= l
l
(o x)(I x) l
2
x
2
.
whoro l
l
= rnfo consfnnf for fho forwnrd roncfIon
l
2
= rnfo consfnnf for fho bnckwnrd roncfIon
Horo fho rovorso roncfIon Inforforos fho doformInnfIon of fho rnfo consfnnf of fho mnIn
roncfIon.
(c) ConeecuIite reocIion. In mnny roncfIons, fho roducfs obfnInod chnngo fo n fhIrd
roducf. Thoso fyos of roncfIons nro known ns consocufIvo roncfIons.
A I C
2

l l
l
Erumpleo:
(i) (CH
3
)
2
O
l
l
CH
34
+ HCHO
l
2
CO + H
2
(ii) 2O + H
2

l
l

2
+ H
2
O
2
H
2
O
2
+ H
2

l
2
2H
2
O
(iii) CH . COOC H
CH . COOC H
nOH
CH COOC H
CH COOn
C H OH
2 2 5
2 2 5
2 2 5
2
2 5
IfhyI SuccInnfo IfhyI SodIum SuccInnfo
l
+ +
l

CH COOC H
CH COOn
nOH
CH COOn
CH COOn
C H OH
2 2 5
2
2
2
2 5
2
SodIum SuccInnfo
+ +
l
(it) H
2
O
2
+ 2HI 2H
2
O

+ I
2
H
2
O
2
+ I

l
l
H
2
O + IO
IO
+ 2H
+
+ I

l
2
H
2
O + I
2
Of fhoso roncfIons, fho fIrsf rocoods vory sIow, whIch cnn bo monsurod nnd fhnf
doformInos fho ordor of fho roncfIon.
Period of induction
SomofImos If Is soon fhnf ovon fhough fho roor condIfIons for fho roncfIon nro
mnInfnInod fho roncfIon doos nof sfnrf. Affor somo fImo fho roncfIon sfnrfs nnd rocoods ns
usunI wIfh normnI sood. ThIs orIod of sfnfIc sfnfo of roncfIon Is known ns perioJ of inJucIion.
As for oxnmIoorIod of InducfIon Is nofod durIng fho roncfIon of H
2
nnd CI
2
In fho rosonco
of IIghf. ConornIIy, InducfIon orIod Is obsorvod In hofochomIcnI nnd oIymorIsnfIon roncfIons.
ConornIIy, nognfIvo cnfnIysfs nro rosonsIbIo for fhIs InncfIvIfy In fho perioJ of inJucIion or
somofImos sIow roducfIon of nn ncfIvo InformodInfo.
Effect of Temperature on Reaction Rate (Arrhenius Equation)
Tomornfuro hns n gronf InfIuonco on roncfIon rnfo: ArrhonIus sfudIod fho fncf nnd
concIudod fhnf rnfo of ovory roncfIon Incronsos wIfh Incronso of fomornfuro. !nfo of n roncfIon
gofs doubIod whon fomornfuro Incronsos by l0.
KooIng conconfrnfIon consfnnf If wo Incronso fho fomornfuro, rnfo of n roncfIon wIII
Incronso i.e., vnIuo of l wIII Incronso. ArrhonIus fIrsf roInfod fomornfuro T of n roncfIon wIfh l.
Ho osfnbIIshod fhnf wLen Iog
e
k ov In k Is pIotted uguInst
1
T
u stvuIgLt IIne Is obtuIned
(IIg. 5.2).
8 9 10 11 12
7
10
8
6
4
2
0
2
4
Gradient =
E
R
a
1
T
10
4
l
n
k
Fig. 5.2 Plot of ln against 1/T for a reaction.
Tho roInfIon cnn bo oxrossod mnfhomnfIcnIIy ns foIIows:
In l = A
I
!T
or
J l
J
In
T
=
I
!T
2
whoro A nnd I nro consfnnfs.
ThoIr vnIuos nro dIfforonf for dIfforonf roncfIons.
!of, rnfo consfnnf of n roncfIon nf fomornfuro T
l
= l
l
nnd rnfo consfnnf of fhnf roncfIon
nf fomornfuro T
2
= l
2
.
Thon, wo cnn wrIfo,
In l
l
= A
I
!T
l
nnd In l
2
= A
I
!T
2
SubfrncfIng fho nbovo fwo oqunfIons wo hnvo,
In
l
l
l
2 l 2
I
!
l
T
l
T
=

or Iog
l
l
l
2
=
I
2.303!
l
T
l
T
l 2
So, If wo cnn doformIno fho fwo rnfo consfnnfs l

l
nnd l
2
wo cnn fInd ouf fho vnIuo of I
from fho nbovo oqunfIon. If I for n roncfIon Is known, wo cnn doformIno fho vnIuo of l
2
whon l
l
Is known.
HIgLIIgLts:
Tomornfuro cooffIcIonf of n chomIcnI roncfIon Is dofInod ns fho rnfIo of fwo rnfo
consfnnfs of fho roncfIon nf fwo fomornfuros dIfforIng by l0.
Tomornfuro co-offIcIonf =
l
l
25
35
(usunIIy)
IIof of In l te.
l
T
gIvos n sfrnIghf IIno so fho oqunfIon of fho sfrnIghf IIno Is:
In l = o
I
T
whoro l Is fho socIfIc roncfIon rnfo nnd T Is fho nbsoIufo fomornfuro.
Tho oxononfInI form of fho nbovo oqunfIon Is known ns AvvLenIus equutIon
l = A
I / !T
e
o
.
whoro, l = !nfo consfnnf I
o
= Inorgy of ncfIvnfIon
! = Cns consfnnf T = AbsoIufo fomornfuro
A = Anofhor consfnnf known ns frequenc, focIor.
ArrhonIus oqunfIon doscrIbos how fho rnfo consfnnf for n roncfIon vnrIos wIfh
fomornfuro nnd mnkos If ossIbIo fo doformIno fho uctIvutIon enevgy for fho
roncfIon.
Energy of Activation (E
a
) of a Reaction: its Significance
Tho moIocuIos of roncfnnfs, whIch fnko nrf In n chomIcnI roncfIon shouId gof ncfIvnfod
by gnInIng n mInImum dofInIfo nmounf of onorgy, whIch Is known ns enevgy oI uctIvutIon
(I
o
). Ior ovory roncfIon, fho moIocuIos shouId bo rnIsod fo n sfnfo of suffIcIonf onorgy, ofhorwIso
fho roncfIon wIII nof bo
A + B C + D
C + D
A + B
DH
E
a
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
Progress of reaction
Fig. 5.3
ossIbIo. ThIs onorgy sfnfo Is dIfforonf for dIfforonf roncfIons. Af nny sfnfo, fho moIocuIos ossoss
nn nvorngo onorgy. Somo moIocuIos nro moro onorgIsod fhnn fho ofhors. Tho mInImum nmounf
of onorgy ovor fho nvorngo onorgy of n moIocuIo roquIrod fo gof ncfIvnfod for nrfIcInfIon In n
roncfIon Is cnIIod enevgy oI uctIvutIon.
Thoso ncfIvnfod moIocuIos fnko nrf In fho roncfIon, ofhors cnnnof fnko nrf In fho roncfIon
unIoss ncfIvnfod. Affor fho roncfIon, fhIs oxcoss onorgy Is IIbornfod In fho form of honf. Whon
fho IIbornfod onorgy Is Ioss fhnn I
o
, fho roncfIon bocomos enJoIIernic nnd whon fho IIbornfod
onorgy Is gronfor fhnn I
o
fho roncfIon bocomos exotLevmIc (Soo IIg. 5.3).
HIgLIIgLts:
Inorgy of ncfIvnfIon (I
o
) Is fho cvItIcuI vuIue oI enevgy, whIch n moIocuIo shouId
ossoss fo gof ncfIvnfod fo fnko nrf In n roncfIon.
Thoro Is nIwnys nn oquIIIbrIum bofwoon ordInnry moIocuIos nnd oxcIfod or ncfIvnfod
moIocuIos wIfh nn onorgy dIfforonco I
o
.
ThoorofIcnIIy, I
o
Is mInImum onorgy whIch n moIocuIo musf hnvo ns n roroquIsIfo
fo fnko nrf In n chomIcnI roncfIon.
CoIIision Theory
AccordIng fo fhIs fhoory, fho moIocuIos of fho roncfnnfs coIIIdo fo fnko nrf In n roncfIon.
Whon fwo gnsos A nnd I roncf, fho roncfIon bocomos ossIbIo whon moIocuIos of A nnd I
coIIIdo. umbor of coIIIsIons or socond (c) In nny gIvon voIumo cnn bo obfnInod from kInofIc
fhoory. AgnIn fho numbor of moIocuIos roncfod In ono socond cnn bo obfnInod from rnfo consfnnf
l (oxorImonfnIIy doformInod). If Is obsorvod fhnf fho numbor of moIocuIos roncfod Is nIwnys
Ioss fhnn fho numbor of moIocuIos coIIIdod i.e., ovory coIIIsIon doos nof gIvo rIso fo roncfIon.
ArrhonIus roosod fhnf onIy fho moIocuIos nffnInIng onorgy of ncfIvnfIon I
o
duo fo coIIIsIon
cnn fnko nrf In fho roncfIon. AccordIng fo MnxwoII, nf n fomornfuro T, fho rnfIo of fofnI
numbor of coIIIsIons nnd fho numbor of coIIIsIons gIvIng I fo fho moIocuIos Is e
I/!T
.
!of fho fofnI numbor of coIIIsIons bo c.
umbor of coIIIsIons of moIocuIos ossossIng I = c . e
I/!T
.
Thoso numbor of moIocuIos wIII roncf.
l = c . e
I/!T
.
or In l = In c I/!T = A
I
!T
ThIs suorfs fho oxorImonfnIIy dorIvod oqunfIon. So, fho fhoory of coIIIsIon cnn bo
nccofod.
HIgLIIgLts:
A sImIo coIIIsIon bofwoon fho roncfIng moIocuIos doos nof nocossnrIIy cnuso
roncfIon.
Tho coIIIsIons, whIch Iond fo fho roncfIon, nro cnIIod eIIectIve coIIIsIons. IffocfIvo
coIIIsIons nro suffIcIonfIy onorgofIc.
of onIy offocfIvo coIIIsIons nro rosonsIbIo for n roncfIon, buf orIonfnfIon of coIIIsIon
Is nIso Imorfnnf.
+
Collision Reaction
+
H
2
I
2
Collision
Collision
Ineffective
Ineffective
Transition state
(effective collision)
molecules react
when they collide
in a preferential
direction
Product
HI + HI
Fig. 5.4
!nfo of n roncfIon = |o. of roorIy orIonfod moIocuIos or unIf voIumo or unIf fImo]
frncfIon of moIocuIos oqunI fo or gronfor fhnn fhroshoId onorgy.
SOLVED EXAMPLES
xumpIe 1. 1n on experinenI, 20 cc of H
2
O
2
eoluIion of eIrengII 2 (A) ie Iolen. So, iI ie
oJJeJ colloiJol golJ onJ oI inIertol of ninuIee on oliquoI ( nl) ie Iolen onJ cooleJ in ice
colJ uoIer onJ IiIroIeJ ogoineI eIonJorJ KMnO
4
eoluIion. TIe IiIre toluee uill gite IIe cIonge
in concenIroIion of H
2
O
2
i.e., x. DeIernine fron IIe follouing JoIo IIe tolue of l onJ eeIoIlieI
IIoI IIe JeconpoeiIion ie of IIe 1eI orJer.
DeconpoeiIion of H
2
O
2
Tine 0 10 20 30 0
Tine tolue (KMnO
4
in cc) 46.1 37.1 29.S 19.6 12.3 .0
SoI. Ior n Isf ordor roncfIon
l =
l
I
o
o x
. In
Horo, o = 46.l
ow, uffIng I = 5
l =
l
5
.
In
.
.
46 l
3? l
= 0.0434 mIn
l
nf I = l0, l =
l
l0
In
46 l
29 8
.
.
= 0.0436 mIn
l
nf I = 20, l =
l
20
In
46 l
l9 6
.
.
= 0.042? mIn
l
nf I = 30, l =
l
30
In
46.l
l2.3
= 0.044 mIn
l
nf I = 50, l =
l
50
In
46 l
5 0
.
.
= 0.044 mIn
l
.
SInco fho 'l` vnIuos nro fnIrIy consfnnf by uffIng fho dnfn In fho Isf ordor-rnfo oqunfIon
fho roncfIon i.e., docomosIfIon of H
2
O
2
Is of fho Isf ordor.
xumpIe 2. A 20" eugor eoluIion ie Iolen. 0 cc of IIie eoluIion onJ 0 cc of (A) HCl ie
nixeJ oI coneIonI IenperoIure. TIe nixIure ie poureJ in o polorineIer IuIe. TIe opIicol roIoIion
of IIie eoluIion ie neoeureJ oI regulor inIertole onJ IIe finol reoJing ie Iolen ofIer 24 Ire. TIe
JoIo ie giten Ielou.
TIe opIicol roIoIion of eucroee in 1(A) HCl oI torioue Iinee ie giten in IIe follouing
IoIle.
Tine (in ninuIe) 0 7.1S 1S 27.0
IoIoIion (Jegreee) + 24.09 + 21.4 + 17.7 + 1 10.74
SIou IIoI IIe reocIion ie of IIe 1eI orJer.
SoI. Horo, o = r
0
r
(o x) = r
I
r
whoro r
0
, r
I
nnd r
nro InIfInI rofnfIon, rofnfIon nffor fImo 'I` nnd rofnfIon nffor InfInIfo fImo
whoro fho roncfIon Is nssumod fo bo comIofod.
r
0
r
= 24.09 + l0.?9 = 34.83

TImo r
I
r
, l =
l
0
I
r r
r r
I
In

?.l8 32.l4 l =
l
?.l8
Iog
34.83
32.l4
= 0.00486 mIn
l
l8 28.l4 l =
l
l8
Iog
34.83
28.l4
= 0.005l9 mIn
l
2?.05 25.?4 l =
l
2? 05
34 83
25?9 .
Iog
.
.
= 0.00485 mIn
l
.
SInco, fho l-vnIuos nro fnIrIy consfnnf by uffIng fho dnfn In fho Isf ordor rnfo oqunfIon
i.e., fho hydroIysIs of mofhyI ncofnfo Is of fho Isf ordor.
xumpIe 3. 1 cc neII,l oceIoIe uoe oJJeJ Io o floel conIoining 20 nl 0.(A) HCl lepI
oI o IenperoIure of 2C. 2 nl of oliquoI (reocIion nixIure) uoe uiIIJroun oI JifferenI inIertole
onJ IiIroIeJ ogoineI o eIonJorJ olloli. TIe JoIo ore oe folloue.
Tine ( in ninuIee). 0 7 119 1S3
Vol. of olloli ueeJ. 19.24 24.20 26.60 29.32 42.03
Iron IIe oIote JoIo eIou IIoI IIe I,Jrol,eie ie of IIe 1eI orJer.
SoI. Horo o = V
V
o
o x = V
V
I
whoro V
o
, V
I
nnd V
nro fho voIumos of nIknII InIfInIIy, nffor n fImo I nnd nffor nn InfInIfo fImo,
rosocfIvoIy.
V
V
o
= 42.03 l9.24 = 22.?9
TImo V
V
I
l
?5 l?.83 l =
2 303
?5
.
Iog
22?9
l? 83
.
.
= 0.00395 mIn
l
ll9 l5.43 l =
2 303
ll9
22?9
l5.43
.
Iog
.
= 0.0032l mIn
l
l83 l2.?l l =
2 303
l83
22 ?9
l2 ?l
.
Iog
.
.
= 0.003l6 mIn
l
SInco fho 'l` vnIuos nro fnIrIy consfnnf by uffIng fho dnfn In fho Isf ordor rnfo oqunfIon
i.e., fho hydroIysIs of mofhyIncofnfo Is of fho Isf ordor.
xumpIe 4. A 1eI orJer reocIion ie 2" conpleIeJ in 30 nine. DeIernine IIe Iine of 0"
conpleIion of IIe reocIion.
SoI. TImo of 50 roncfIon, i.e., f
l/2
fo bo doformInod for Isf ordor roncfIon I
l/2
Is
0.693
l
nnd l =
2.303
I
o
o x
. Iog
Horo, I = 30 mIn o = l00

o = (l00 25) = ?5
l =
2 303
30
l00
?5
.
Iog
= 0.0095 mIn
l
I
l/2
=
0.693
0.0095
= ?2.9 mInufos.
xumpIe 5. Holf-life for o fireI orJer reocIion ie 17 nine. ColculoIe IIe roIe coneIonI
onJ Iine for 7" conpleIion of IIe reocIion.
SoI. Wo know I
l/2
=
0.693
l
Horo, I
l/2
= l? mIns.
l =
0.693
l?
mIn
l
= 0.040? mIn
l
Horo, o = l00
o x = (l00 ?5) = 25
l =
2 303 l00
25
.
Iog
I
I =
2.303
Iog
l00
25 l
=
2.303
0.040?
Iog 4 34 mInufos = .
xumpIe 6. TIe Iolf-life for roJiun ie 1600 ,eore. ColculoIe IIe Iine for S0"
JieinIegroIion.
SoI. !ndIoncfIvo dIsInfogrnfIon Is of fho Isf ordor
I
l/2
=
0.693
l
l600 =
0.693
l
l =
0.693
l600
yonr
l
= 0.000433 yonr
l
l =
2.303
I
o
o x
Iog
Horo o = l00
(o x) = l00 80 = 20
I =
2.303
0.000433
Iog
l00
20
3?.l? yrs. =
xumpIe ?. TIe follouing ie IIe JoIo for IIe I,Jrol,eie of eII,l oceIoIe I, AoOH eoluIion.
An oliquoI (2 cn) of IIe reocIion nixIure uoe IiIroIeJ ogoineI o eIonJorJ ociJ oI regulor Iine
inIertole.
Tine (in ninuIe) 0 1 2 3
Vol. of ociJ (o x) 16 10.24 6.13 4.32 3.41
SIou IIoI IIe reocIion ie of IIe 2nJ orJer.
SoI. Tho 2nd ordor rnfo oqunfIon Is
l =
l
oI
x
o x ( )
Horo o = l6 c.c.
T o x x l
5 l0.24 5.?6 l =
l
l6 5
5 ?6
l0 24

.
.
= 0.00? conc
l
soc
l
l5 6.l3 9.8? l =
l
l6 l5
9 8?
6 l3

.
.
= 0.006? conc
l
soc
l
25 4.32 ll.68 l =
l
l6 25
ll68
4 32

.
.
= 0.0069 conc
l
soc
l
35 3.4l l2.59 l =
l
l6 35
l2 59
3 4l

.
.
= 0.0066 conc
l
soc
l
SInco fho l vnIuos nro fnIrIy consfnnf by uffIng In fho 2nd ordor rnfo oqunfIon i.e., fho
hydroIysIs of ofhyIncofnfo by nOH Is of fho 2nd ordor.
xumpIe B. DeJuce IIe roIe coneIonI onJ I
l/ 2
for nII orJer reocIion.
SoI. !of fho roncfIon bo
nA Iroducfs.
Tho rnfo oqunfIon Is

| ] J
JI
A
= l . |A]
n
!of o bo fho InIfInI conconfrnfIon nnd x bo fho conconfrnfIon whIch hns roncfod In fho
fImo 'I`. So fho conconfrnfIon of A nf fImo I Is (o x).

| ] ( ) J
JI
J o x
JI
Jx
JI
A
= = = l(o x)
n
Jx
o x
n
( )
= l JI
0 0
x
n
I
Jx
o x
l JI

=
( )
3 I = 0 , x = 0
l
l
l l
l l
( ) ( )
.
n o x o
l I
n n
l =
l
l
l l
l l
I n o x o
n n
( ) ( )
I =
l
l
l l
l l
l n o x o
n n
( ) ( )
Ior I
l/2
, x = o/2
I
l/2
=
l
l
l
2
l
l l
l n o o
n n
( ) ( / )
( )

I
l/2
=
l
l
2 l
l
l
l n o
n
n
( )
unIf of l Is (conc)
(nl)
(fImo)
l
.
xumpIe 9. 1n o 2nJ orJer reocIion, uIere IIe iniIiol concenIroIion of IIe reocIonIe ie
IIe eone Iolf of IIe reocIonIe ore coneuneJ in 10 nine. 1f IIe epecific reocIion roIe ie
.2 10
3
nol
1
liIre nin
1
, uIoI ie IIe iniIiol concenIroIion of IIe reocIonIe:
SoI. Ior n 2nd ordor roncfIon
l =
x
oI o x ( )
Horo, I = 60 mIns, x = o/2
l = 5.2 l0
3
moI
l
IIfro mIn
l
5.2 l0
3
=
o
o o o
/
. . /
2
60 2
l
60
=
o =
l
60 5.2 l0
3

= 3.2 moI IIfro
l
.
xumpIe 10. WIen IIe iniIiol concenIroIion ie cIongeJ fron 0. Io 1 nol l
1
, IIe Iine of
Iolf conpleIion for o reocIion ie founJ Io cIonge fron 0 eec. Io 2 eec. ColculoIe IIe Iine Iolen
for IIe concenIroIion Io Ie reJuceJ Io 20" of IIe iniIiol tolue.
SoI. I
l/2
`s nro roInfod fo InIfInI conconfrnfIons ns

T
T
l
2
=

o
o
n
2
l
l
Horo, T
l
= 50 soc, T
2
= 25 soc, o
l
= 0.5 moI I
l
o
2
= l moI I
l

50
25
l
l
=

0.5
n
or 2 = 2
nl
n l = l
or n = 2
So, fho roncfIon Is of fho 2nd ordor.
l =
l
l/ 2
oI
=
=
l
0.5 50
l
25
l moI
l
soc
l
= .04 l moI
l
soc
l
I =
l
ol o x ( )
=

0.8 25
0.5 0.2
= 200 soc.
xumpIe 11. 1n o 2nJ orJer reocIion, IIe iniIiol concenIroIion of reocIonIe ie 0.1 nol l
1
.
TIe reocIion ie founJ Io Ie 20" conpleIe in 40 ninuIee. ColculoIe IIe roIe coneIonI, Iolf-life
perioJ, Iine requireJ Io conpleIe 7" of IIe reocIion.
SoI. Horo, o = 0.l moI l
l
x = 0.2 o = 0.2 0.l = 0.02 moI l
l
I = 40 mIn.
o x = (0.l 0.2)moI l
l
= 0.08 moI l
l
Ior fho socond ordor roncfIon,
l =
x
oI o x ( )
=

0.02
0.l 40 0.08
= 0.0625 l moI
l
mIn
l
l =
l
l/2
oI
I
l/2
=
l
ol
=
l
0.l 0.0625
= l60 mIns.
x

= 0.?5o = 0.0?5 moI l
l
, l = 0.0625 moI
l
.
I = (o x) = 0.025 moI l
l
I =
x
ol o x
=
( )
0.0?5
0.l 0.0625 0.625
= 480 mIns.
xumpIe 12. 1f one percenI Jeconpoeee in IIe fireI ninuIe in o uninoleculor reocIion,
colculoIe Iou nucI uoulJ renoin unJeconpoeeJ oI IIe conpleIion of IIe fireI Iour.
SoI. Ior n unImoIocuInr roncfIon
l =
2.303
l
Iog
o
o x
Horo, o = l00 o x = (l00 l) = 99
l =
2.303
l
Iog
l00
99
= 2.303 0.0044 mIn
l
= 0.0l mIn
l
whon I = l hr = 60 mIns
l =
2 303
60
l60 .
Iog
o x
or 0.0l =
2 303
60
l00 .
Iog
o x
or
60 0.0l
2.303
= Iog
l00
o x
= Iog l00 Iog (o x)
or Iog (o x) = Iog l00 0.2605
= 2 0.2605 = l.?395
(o x) = AnfIIog l.?395 = 54.89
undocomosod = 54.89.
xumpIe 13. 1f l
1
= l
2
= l
3
for IIree reocIione Ieing reepecIitel, of fireI, eeconJ onJ
IIirJ orJere uIen concenIroIion ie expreeeeJ in nole l
1
, uIoI uill Ie IIe oIote reloIion if IIe
concenIroIion uniI ie nol n
1
:
SoI. Ior nfh ordor roncfIon,
unIf of l = moIo
ln

l
nl
I
l
whon c = moI l
l
nnd moIo
ln
l
nl
I
l
= moIo
ln
l0
3(nl)
mI
nl
I
l
whon c = moI mI
l
Ior fIrsf ordor roncfIon,
l
l
= I
l
(l
l
wIII romnIn snmo)
Ior socond ordor roncfIon,
l
2
= moIo
l
lI
l
l
2
= moIo
l
l0
3
mI I
l
or l0
3
l
2
= moIo
l
mI I
l
Ior fhIrd ordor roncfIon,
l
3
= moIo
2
l
2
I
l
= moIo
2
l0
6
mI
2
I
l
or l0
6
l
3
= moIo
2
mI
2
I
l
So, fho roncfIon wIII bo,
l
l
= l0
3
l
2
= l0
6
l
3
.
xumpIe 14. A cerIoin euIeIonce A ie nixeJ uiII equol nolee of o euIeIonce B. AI IIe
enJ of one Iour A ie 7" reocIeJ. Hou nucI A onJ B uill Ie lefI increoeeJ oI IIe enJ of Iuo
Ioure if IIe reocIion ie. (i) fireI orJer in A onJ inJepenJenI of B, (ii) fireI orJer in A onJ fireI
orJer in B:
SoI. !of, InIfInI conconfrnfIon = |A] = |I] = o
I = l hrs.
x = 0.?5o
(i) Whon fIrsf ordor In A = K =
2.303
0.?5 l
Iog
o
o o
= 2.303 Iog
o
o 0.25
= 2.303 Iog 4 = l.3865 hr
l
.
whon fImo I = 2 hrs.

l.3865 =
2 303
2
.
Iog
o
o x
|whoro x = nmounf roncfod]
Iog
o
o x
=
l.3865 2
2.303
= l.204
o
o x
= AnfIIog l.204 = l6
(o x) =
o
l6
l00
l6
= = l2.5
So, of A Ioff unroncfod = l2.5
of I Ioff unroncfod = l00 (3 ordor = 0 w.r.f. I)
(ii) In fho socond cnso, fho ovor nII ordor of fho roncfIon Is 2.
l =
x
oI o x
o
o o ( )
.
.
=

0 ?5
l 0 25
= 3o
l
hr
l
(whon I = l hr)
Af I = 2 hrs.
l =
x
oI o x
( )
whon x = nmounf of roncfnnfs A nnd I roncfod
3o
l
=
x
o o x
2 ( )
or 6 =
x
o x

x =
6
?
o
So, of A nnd I Ioff unroncfod =
o o
6
?
i.e., l00
6
?
. l00 l4.3.
xumpIe 15. TIe epecific reocIion roIee of o cIenicol reocIion oI 273 K onJ 303 K ore
reepecIitel, 2.4 10
onJ 162 10
. ColculoIe IIe ocIitoIion energ, of IIie reocIion.

SoI. !nfo consfnnfs nf fwo fomornfuros nro gIvon by ArrhonIus oqunfIon,
Iog
l
l
o 2
l
2 l
l 2
I
2.303!
T T
T T
=

Horo, T
l
= 2?3 K T
2
= 303 K l
l
= 2.45 l0
5
l
2
= l62 l0
5
! = l.98? CnI K
l
. moIo
l
Iog
l62 l0
2.45 l0
I
2.303 l.98?
303 2?3
2?3 303
5
5
o
l.8203 =
I
2.303 l.98?
30
2?3 303
o
I
o
= 22, 968 cnI moIo
l
.
xumpIe 16. TIe toluee of ArrIeniue focIor onJ ocIitoIion energ, ore 4 10
13
e
1
onJ
9S.6 lJ nol
1
, reepecIitel, for o fireI orJer reocIion. ColculoIe IIe IenperoIure oI uIicI iIe
Iolf-life ie 10 nine.
SoI. Tho oxononfInI form of ArrhonIus oqunfIon Is,
l = A
I / !T
c
o
whoro A Is cnIIod fho ArrhonIus fncfor nnd I

o
Is fho onorgy of ncfIvnfIon.
As fho roncfIon Is fIrsf ordor, l =
0 693
l/ 2
.
I
Horo, I
l/2
= l0 mIns = 600 soc.
l =
0.693
600
= l.l55 l0
3
soc
l
Irom ArrhonIus oqunfIon wo hnvo,
2.303 Iog
l0
(l/A) = I
o
/!T
or T =
I
2.303! A/ K)
o
Iog(
Horo, I
o
= 98,600 J. moI
l
, ! = 8.3l6 J moI
l
K
l
, A = 4 l0
l3
soc
l
l = l.ll5 l0
3
soc
l
.
T =
98600
2.303 8.3l6
4 l0
l.ll5 l0
3
3

K
=
98600
2.303 8.3l6 l6.555
K

= 98600
= 3?3 K.
xumpIe 1?. A eeconJ orJer reocIion, uIoee roIe coneIonI oI S00C uoe founJ Io Ie
.0 10
3
l nol
1
e
1
Ioe on ocIitoIion energ, of 4 lJ nol
1
. WIoI ie IIe tolue of IIe roIe
coneIonI oI S7C:
SoI. Wo hnvo,
Iog
K
K
I (T T )
2.303 !T T
2
l
l l
l 2
=
o
Horo, K
l
= 5 l0
3
l moI
l
s
l
, I
o
= 4.5 l0
4
J moI
l
T
2
= (8?5 2?3) = ll48 K, T
l
= (800 + 2?3) = l0?3
! = 8.3l4 J moI
l
K
l
Iog
K
K
4.5 l0 (ll48 l0?3)
2.303 8.3l4 ll48
2
l
4
=

l0?3
= 0.l43l

K
K
2
l
= AnfIIog 0.l43l = l.39
K
2
= l.39 5 l0
3
l moI
l
s
l
= ?.0 l0
3
l moI
l
s
l
.
Lasers in Chemistry
!nsor monns IIghf nmIIfIcnfIon by sfImuInfod omIssIon of rndInfIon. Tho uso of Insors
hns InIfInfod now fyos of socfroscoIc oxorImonfs nnd hns Imrovod fho rocIsIon of
socfroscoIc oxorImonfs.
To nchIovo n Insor ncfIon n PopuIutIon InvevsIon shouId bo gonornfod In fho sysfom.
!of, fho ouInfIons bo n
2
nnd n
l
nnd onorgIos of fho fwo sfnfos bo I
2
nnd I
l
. Whon
I
2
> I
l
, Iof us sfnfo wo hnvo n ouInfIon InvorsIon wIfh n
2
> n
l
, fhon hofons of froquoncy
l 2 =
I I
2 l
I
nro sonfnnoousIy omIffod ns moIocuIos dro from fho sfnfo 2 fo fho sfnfo l.
Thoso hofons wIII sfImuInfo ofhor moIocuIos In fho sfnfo 2 fo omIf hofons of froquoncy
l 2 nnd dro fo sfnfo l (IIg. 5.5).
Ihofons of froquoncy l 2 wIII nIso Induco nbsorfIon from
sfnfo l fo sfnfo 2 buf ns fho sysfom confnIns n
2
> n
l
stImuIuted
emIssIon wIII pvedomInute ovev ubsovptIon nnd wo wIII gof n
nof nmIIfIcnfIon of rndInfIon of froquoncy
l2
.
Tho Insor sysfom Is confnInod In n cyIIndrIcnI cnvIfy whoso
onds hnvo nrnIIoI mIrrors. A fow hofons nro sonfnnoousIy
omIffod whon fho moIocuIos go from fho sfnfo 2 fo sfnfo l. Thoso
hofons omIffod nf fho cyIIndrIcnI nxos nss ouf of fho sysfom nnd
hnvo no roIo In fho Insor ncfIon. Thoso hofons omIffod nIong fho
Insor nxIs frnvoI forwnrd nnd bnckwnrd bofwoon fho ond mIrrors
nnd sfImuInfo omIssIon for furfhor hofons. Tho rosonco of ond mIrrors mnkos fho Insor n
sfnndIng wnvo nfforn.
!of l bo fho dIsfnnco bofwoon fho mIrrors nnd IIghf onIy wIfh wnvoIongfh = , such fhnf
n
l
2
= , whoro n Is nn Infogor, wIII rosonnfo In fho cnvIfy. ThIs mnkos fho Insor nonrIy
monochromnfIc, fho Insor oufuf Is hIghIy monochromnfIc nnd hIghIy dIrocfIonnI. Thoso
roorfIos mnko Insor usofuI In spectvoscopy nnd kInetIcs. Thousnnds of dIfforonf Insors
oxIsf; fho mnforInI In whIch fho Insor ncfIon cnn bo omIoyod mny bo n soIId, n IIquId or n gns.
Tho froquoncy omIffod IIos In fho I!, vIsIbIo or !V rogIon.
Kinds of Iasers
SoIId-sfnfo mofnI Ion Insor.
SomIconducfor Insor or dIodo Insor.
Cns Insor.
ChomIcnI Insor.
yo Insor.
An exumpIe oI cLemIcuI Iusev: Ono cnn uso fho roncfIon:
H + I
2
HI + I,
whIch Is nn oIomonfnry sfo of fho mochnnIsm of roncfIon:
H
2
+ I
2
2HI (chnIn roncfIon)
A Insor In whIch fho ouInfIon InvorsIon cnn bo roducod by n chomIcnI roncfIon Is
cnIIod n cLemIcuI Iusev. Tho HI chomIcnI Insor cnn bo usod ns nn nnfImIssIIo.
Laser Technique
A Insor cnn bo usod fo oxcIfo n mnjor frncfIon of n roncfnnf socIos fo n socIfIc vIbrnfIon
IovoI In n moIocuInr bonm. Thon wo cnn sfudy fho doondonco of fho roncfIon robnbIIIfy on
fho vIbrnfIonnI qunnfum sfnfos of fhoso roncfnnfs.
ThIs sorf of Idon cnn bo ufIIIsod fo n soIocfIvo oxcIfomonf of n nrfIcuInr normnI vIbrnfIonnI
modo fhnf InvoIvos mnInIy vIbrnfIon of n nrfIcuInr bond nnd fo bronk roforonfInIIy fhnf
bond. Thus, Insor IIghf cnn bo omIoyod fo confroI fho oufcomo of fho roncfIon. Ior oxnmIo,
wo cnn fnko fho foIIowIng fwo roncfIons:
(i) H + HO O + H
2
(ii) H + HO HO + H.
3
2
1
Fig. 5.5. States involved in
laser action.
Iy usIng Insor, ono cnn roforonfInIIy bronk fho O H bond In HO, sImIInrIy, oxcIfnfIon
of O- sfrofchIng vIbrnfIon In HO Ionds fo bronk fho O bond roforonfInIIy. Whofhor confroI
of chomIcnI roncfIons by Insors wIII ovor hnvo commorcInI nIIcnfIons Is nof cIonr.
Tho bronkIng of n chomIcnI bond In n moIocuIo occurs wIfhIn n frncfIon of n socond (l0
l3
fo l0
l2
socond). Iy usIng Insor IIghf, fho bond bronkIng rocoss cnn bo obsorvod
socfroscoIcnIIy. ThIs fochnIquo Is cnIIod Iemtosecond TvunsItIon Stute Spectvoscopy
(ITS) or Insor fomfo chomIsfry. Tho oxorImonfs nro dono usIng oIfhor moIocuInr bonms or
gnsoous moIocuIos In n chnmbor.
!nImoIocuInr roncfIons nro bosf sfudIod by ITS.
SHORT QUESTIONS
Iusevs In CLemIstvy:
Q. 1. Whnf Is n Insor
Q. 2. IxInIn why fho Insor rndInfIon Is monochromnfIc.
Q. 3. MonfIon vnrIous kInds of Insors.
Q. 4. CIvo nn oxnmIo of chomIcnI Insor.
Q. 5. Cnn you bronk n bond roforonfInIIy by fho nIIcnfIon of Insor
Q. 6. Whnf do you monn by ITS
Q. ?. CIvo ono mnjor nIIcnfIon of Insor.
Q.1. WLut do you meun by cLemIcuI kInetIcs?
Ans. ChomIcnI kInofIcs Is fhnf brnnch of chomIsfry whIch donIs wIfh fho rnfo of n chomIcnI
roncfIon.
Q. 2. WLut do you meun by vute oI u veuctIon?
Ans. Tho rnfo of n roncfIon Is dofInod ns fho docronso In conconfrnfIon of fho roncfnnfs
or Incronso In conconfrnfIon of fho roducfs nf unIf fImo. Tho rnfo of roncfIon Is Incronsod If fho
conconfrnfIon of fho roncfnnfs Incronsos.
!of, fho roncfIon bo
A I.
!nfo of roncfIon =
A
I
or +
I
I
!nIf = ConconfrnfIon fImo Invorso.
Q. 3. WLut Is specIIIc veuctIon vute ov vute constunt (k)?
Ans. If Is fho rnfo of fho roncfIon whon fho conconfrnfIon of fho roncfnnfs nro unIfy.
Q. 4. WLut uve tLe Iuctovs tLut cun cLunge tLe vuIue oI k?
Ans. (l) Tomornfuro, (2) Ordor of n roncfIon.
Q. 5. IIIeventIute uvevuge vute Ivom Instuntuneous vute.
Ans. Avorngo rnfo =
Chnngo In conconfrnfIon
TofnI fImo (InvoIvod for fho chnngo)
=
A
T
HIgLIIgLt:
Ior oIomonfnry roncfIon ordor Is nocossnrIIy oqunI fo moIocuInrIfy. Ior comIox roncfIons
If mny or mny nof bo oqunI.
Insfnnfnnoous rnfo Is fho rnfo of fho roncfIon doformInod nf fho nrfIcuInr momonf of
fImo. Tho nvorngo rnfo nronchos fho Insfnnfnnoous rnfo whon I bocomos smnIIor.
Q. 6. WLut do you meun by tLe ovdev oI u veuctIon?
Ans. If Is oqunI fo fho fofnI numbor of roncfIng socIos nfoms, Ions of moIocuIos fho
conconfrnfIon of whIch chnngos ncfunIIy durIng fho courso of n chomIcnI roncfIon. If wo fnko n
roncfIon:
A + I + C Iroducfs
fho rnfo = l . A
. I
. C
whoro l = rnfo consfnnf nnd fho ordor of fho roncfIon + + .

Q. ?. WLut Is tLe moIecuIuvIty oI u veuctIon?
Ans. MoIocuInrIfy of n roncfIon In oqunI fo fho sum of fho cooffIcIonfs of vnrIous roncfnnfs
nonrIng In n bnInncod chomIcnI oqunfIon i.e., If Is fho sum of fho sfoIchIomofrIc cooffIcIonfs
In fho sImIosf chomIcnI oqunfIon. If fho roncfIon Is:
C
l2
H
22
O
ll
+ H
2
O C
6
H
l2
O
6
+ C
6
H
l2
O
6
Tho moIocuInrIfy of fho nbovo roncfIon Is fwo. So moIocuInrIfy Is n fhoorofIcnI nronch
nnd Ifs vnIuo Is nIwnys n whoIo numbor.
Q. B. WLut uve unImoIecuIuv und bImoIecuIuv veuctIons?
Ans. Whon fho moIocuInrIfy Is ono If Is unImoIocuInr roncfIon nnd whon If Is fwo fhon
fho roncfIon Is bImoIocuInr.
Q. 9. Compuve ovdev und moIecuIuvIty oI u veuctIon.
Ans.
MoleculoriI,
(i) MoIocuInrIfy Is n fhoorofIcnI concof. Ifs
cInssIcnI dofInIfIon Is connocfod wIfh fho
ovornII chomIcnI oqunfIon. In modorn
dofInIfIon If Is roInfod fo fho mochnnIsm of
fho roncfIons.
(ii) If Is fho sum of fho sfoIchIomofrIc co-
offIcIonfs of n chomIcnI oqunfIon.
Modorn dofInIfIon IsIf Is fho numbor of
moIocuIos fnkIng nrf In fho rnfo
doformInIng sfo of fho mochnnIsm.
(iii) MoIocuInrIfy doos nof doond on such
fncfors.
(it) MoIocuInrIfy Is nIwnys n whoIo numbor.
OrJer
(i) Ordor Is n uroIy oxorImonfnI fncf roInfod fo
fho rnfo oqunfIon of fho roncfIons. If Is nof
connocfod wIfh fho chomIcnI oqunfIon of fho
roncfIon.
(ii) If n roncfIon Is
A + I Iroducfs
fho rnfo wIII bo
!nfo = K . |A]
|I]
oxorImonfnIIy obsorvod fncf.

(iii) Ordor chnngos wIfh hysIcnI condIfIons IIko
rossuro, fomornfuro, ofc.
(it) Ordor mny bo n whoIo numbor, zoro or n
frncfIon.
Q. 10. WLut Is u IIvst ovdev veuctIon?
Ans. If fho rnfo of n chomIcnI roncfIon vnrIos fo fho fIrsf owor of conconfrnfIon of fho
sIngIo roncfnnf, If Is known ns fIrsf ordor roncfIon.
A Iroducfs.
!nfo =
J
JI
A
= l . |A] = rnfo oqunfIon for n fIrsf ordor roncfIon.
Q. 11. GIve exumpIes oI IIvst ovdev veuctIon.
Ans. l. !ndIoncfIvo dIsInfogrnfIon rocoss.
2. !nfo of growfh of bncforInI cuIfuro.
Q. 12. WLut Is u second ovdev veuctIon?
Ans. A socond ordor roncfIon Is n roncfIon, fho rnfo of whIch Is dIrocfIy roorfIonnI fo
fho squnro of fho conconfrnfIon of n sIngIo roncfnnf or oqunI fo conconfrnfIon of fwo dIfforonf
roncfnnfs. Ior n roncfIon:
A + I Iroducfs
!nfo = l . |A] |I] or !nfo = l . |A]
2
= !nfo oqunfIon for socond ordor roncfIon.
Q. 13. Comment on LuII-IIIe oI u IIvst ovdev und u second ovdev veuctIon.
Ans. I
l/2
for n fIrsf ordor roncfIon =
0 693 .
l
. So, If Is n consfnnf qunnfIfy.
I
l/ 2
for n socond ordor roncfIon =
l
ol
.
So, hnIf-IIfo In fhIs cnso Is InvorsoIy roorfIonnI fo fho InIfInI conconfrnfIon.
Q. 14. Is u IIvst ovdev ov u second ovdev veuctIon compIeted?
Ans. Infogrnfod form for n fIrsf ordor rnfo oqunfIon Is:
c = c
0
e
lI
Tho Iof of conconfrnfIon te. fImo wIII bo nsymfofIc Iof. Honco, conconfrnfIon wIII bo
zoro nf InfInIfo fImo. So fho roncfIon Is nof comIofod.
Ior n socond ordor roncfIon fho Infogrnfod form of fho rnfo oqunfIon Is:
l =
l
I
x
o o x ( )
whon, x = o, I =
So, n socond ordor roncfIon Is nIso nn IncomIofo roncfIon.
Q. 15. Iov u IIvst ovdev veuctIon one Louv Is needed Iov u cLunge oI concentvutIon
c to c/2. WLut Is tLe tIme Iov tLe cLunge Ivom c/2 to c/4?
Ans. Ono hour.
Q. 16. Iov u second ovdev veuctIon one Louv Is needed Iov u cLunge oI
concentvutIon = to =/2. WLut wIII be tLe tIme Iov tLe cLunge Ivom =/2 to =/4?
Ans. Whon conconfrnfIon chnngos from o fo o/2, I
l/2
=
l
ol
.
Whon conconfrnfIon chnngos from o/2 fo o/4, I
l/2
=
l
2 o l / .

= =
I
I ol ol
l/ 2
l/ 2
l l
2
l
2 /
or I
l/2
= 2 . I
l/2
= 2.l = 2 hrs.
Q. 1?. WLut Is tLe specIuI cLuvuctevIstIc oI u zevo ovdev veuctIon?
Ans. Tho Infogrnfod form of zoro ordor roncfIon Is
K =
c c
I
0

, whoro c
0
= InIfInI conconfrnfIon
c = conconfrnfIon nf fImo I.
whon, c = 0; I =
c
l
o
0
whIch Is n fInIfo qunnfIfy. So, fho roncfIon wIII bo comIofod nnd for n zoro ordor roncfIon, fho
rnfo Is nof nf nII doondonf on fho conconfrnfIon of fho roncfnnfs.
Q. 1B. WLut Is uctIvutIon enevgy?
Ans. AcfIvnfIon onorgy of n roncfIon Is dofInod ns fho oxfrn onorgy ovor nnd nbovo fho
nvorngo ofonfInI onorgy of fho roncfnnfs, whIch musf bo suIIod fo fho roncfnnfs fo onnbIo
fhom fo cross-ovor fho onorgy bnrrIor bofwoon fho roncfnnfs nnd roducfs. If Is donofod by I
A
.
Q. 19. WLut Is tLvesLoId enevgy?
Ans. If Is fho mInImum nmounf of onorgy from zoro IovoI of fho roncfnnf moIocuIo whIch
musf ossoss In ordor fo roncf. If Is donofod by I
T
.
Q. 20. How uve tLe uctIvutIon und tLvesLoId enevgIes veIuted?
Ans. I
A
= I
T
I
!
Q. 21. WLut Is tvunsItIon stute tLeovy?
Ans. ChomIcnI roncfIons occur fhrough nn InformodInfo sfngo known ns frnnsIfIon sfnfo
or ncfIvnfod comIox (IIg. 5.6).
H H
I I
H H + I I 2HI
Initial state
Transition
state
Final state
DH < 0
E
a
E
n
e
r
g
y
Reaction co-ordinate
Final state
Initial state
I
II
Final state
H > 0 D
Activated state
Fig. 5.6
InrfIcIos In coIIIsIon roncf onIy If, uon Imncf, fhoy nffnIn Imncf, fhoy nffnIn fho onorgy
of fho frnnsIfIon sfnfo.
H > 0 ondofhormIc roncfIon (Curvo I)
H < 0 oxofhormIc roncfIon (Curvo II)
Q. 22. WLut Is tLe utIIIty oI tLe study oI cLemIcuI kInetIcs?
Ans. Tho sfudy of chomIcnI kInofIcs hoIs fo doformIno fho mochnnIsm of n chomIcnI
roncfIon.
EXERCISES
1. IxInIn fho forms 'rnfo consfnnf`, 'ordor of n roncfIon` nnd 'moIocuInrIfy of n roncfIon`.
2. Whnf Is monnf by ordor of n roncfIon orIvo nn oxrossIon for fho voIocIfy cooffIcIonf of n socond
ordor roncfIon.
3. IndIcnfo how fho socIfIc roncfIon rnfo of n fIrsf ordor roncfIon cnn bo ovnIunfod. orIvo fho rnfo
consfnnf for n lsf ordor roncfIon nnd show fhnf If Is nn IncomIofo roncfIon.
4. Iscuss nny fwo mofhods of doformInnfIon of ordor.
5. orIvo nn oxrossIon for rnfo consfnnf of zoro ordor roncfIon nnd dIscuss nbouf Ifs (i) hnIf-IIfo,
(ii) comIofIon fImo.
6. Iscuss fho vnrIous fncfors nffocfIng fho rnfo of n roncfIon.
?. IxInIn fho monnIng of soudo unImoIocuInr roncfIon.
B. oscrIbo nn nccurnfo mofhod for doformInIng ordor of n roncfIon wIfh fhroo roncfnnfs.
9. IsfInguIsh bofwoon rnfo nnd socIfIc roncfIon rnfo of n chomIcnI roncfIon. orIvo fho rnfo con-
sfnnf oxrossIon of n 2nd ordor roncfIon:
A + I
l
c, fho roncfnnfs A nnd I nro nf oqunI conconfrnfIons.
10. How doos rnfo of n roncfIon vnry wIfh fomornfuro Whnf Is ArrhonIus oqunfIon
11. Ior,
5 Ir
+ IrO
3
+ 6H
+
3Ir
2
+ 3H
2
O
!nfo = Consfnnf |Ir
] |IrO
3
] |H
+
]
2
.
Sfnfo fho moIocuInrIfy nnd ordor of fho nbovo roncfIon.
12. IrIofIy dovoIo fho concof of ncfIvnfIon onorgy nnd fomornfuro.
13. CInssIfy fho sfnfomonf: docomosIfIon of H
2
O
2
Is of fho lsf ordor.
14. HnIf-fImo chnngo for n lsf ordor roncfIon Is 40 mIns. Whnf Is fho rnfo consfnnf of fho roncfIon nf
fho snmo fomornfuro | 0.0l?3 mIn
l
]
15. Tho hnIf-IIfo orIod of n lsf ordor roncfIon Is l5 mIns. CnIcuInfo fho rnfo consfnnf nnd fho fImo
fnkon fo comIofo 80 of fho roncfIon. |34.85 mIns]
16. Tho hydroIysIs of ofhyI nIfrobonzonfo by nquoous nOH wns foIIowod nf 25 C, by fIfrnfIon of fho
hydroxIdo ngnInsf sfnndnrd ncId nf dIfforonf sfngos In roncfIon. Irom fho gIvon dnfn, show fhnf
fho roncfIon Is of fho 2nd ordor.
1?. urIng fho hydroIysIs of ofhyI ncofnfo by nOH usIng oquIvnIonf conconfrnfIon, 25 c.c. of fho
roncfIon mIxfuro wns fIfrnfod nf roguInr InforvnIs ngnInsf sfnndnrd ncId. Tho voIumos of ncId
usod by unchnngod nOH nro gIvon boIow:
TImo (mInufo) 0 5 l5 25 35
VoI. of ncId (c.c.) l6 l0.24 6.l3 4.32 3.4l
Show fhnf fho roncfIon Is of fho 2nd ordor.
1B. Tho hnIf-IIfo orIods for fho docomosIfIon of nmmonIn (cnfnIyfIcnIIy) nro ns foIIows :
Irossuro In mm 50 l00 200
HnIf-IIfo orIod In hrs. 3.52 l.92 l
IInd fho roncfIon Is of whIch ordor.
19. Tho docomosIfIon of CI
2
O
?
nf 400 K In fho gns-hnso fo CI
2
nnd O
2
Is n lsf ordor roncfIon.
(i) Affor 55 soconds nf 400 K fho rossuro of CI
2
O
?
fnIIs from 0.062 fo 0.044 nfm. CnIcuInfo fho
rnfo consfnnf.
(ii) CnIcuInfo fho rossuro of CI
2
O
?
nffor l00 soc. of docomosIfIon nf fhIs fomornfuro.
|Ans. 6.236 l0
3
soc
l;
0.0332 nfm]
20. A 2nd ordor roncfIon, whoro o = I, Is 20, Is comIofod In 500 soconds. How Iong wIII If fnko fo go
fo 60 comIofIon |Ans. 3000 soconds]
21. Tho foIIowIng dnfn woro obfnInod In fho hydroIysIs of ofhyI ncofnfo, usIng oqunI conconfrnfIon of
osfor nnd nOH:
TImo (mInufos): 0 5 l5 25 35
VoI. of HCI (c.c.) l6.0 l0.24 6.l3 4.32 3.4l
Show fhnf roncfIon Is of 2nd ordor.
22. A lsf ordor roncfIon hns rnfo consfnnf oqunI fo l.25 l0
4
soc
l
nf 298 K nnd 8.5 l0
4
soc
l
nf
3l8 K. CnIcuInfo fho ncfIvnfIon onorgy of fho roncfIon. |Ans. l8, 050 CnI moI
l
]
23. Two roncfIons:
(i) A Iroducfs, (ii) I Iroducfs, foIIow fIrsf ordor kInofIcs. Tho rnfo of fho roncfIon (i) Is
donofod whon fho fomornfuro Is rnIsod from 300 K fo 3l0 K. Tho hnIf-IIfo for fhIs roncfIon nf
3l0 K Is 30 mInufos. Af fho snmo fomornfuro I docomosos fwIco ns fnsf ns A. If fho onorgy
of ncfIvnfIon for fho roncfIon (ii) Is hnIf fhnf of roncfIon (i), cnIcuInfo fho rnfo of fho roncfIon
(ii) nf 300 K. |Ans. 0.032? mIn
l
]
24. Tho ncfIvnfIon onorgy for fho roncfIon
2HI (g) H
2
(g) + I
2
(g)
Is 209.5 kJ moI
l
nf 58l K. CnIcuInfo fho frncfIon of moIocuIos of roncfnnfs hnvIng onorgy oqunI
fo or gronfor fhnn ncfIvnfIon onorgy. |Ans. l.462 l0
l9
]
25. Whon Iog K (voIocIfy consfnnf for n roncfIon) wns Ioffod ngnInsf l/I, fho sIoo of fho IIno wns
found fo bo 5400 K. CnIcuInfo fho onorgy of ncfIvnfIon for fhIs roncfIon (! = 8.3l4 JK
l
moI
l
)
|Ans. l03.4 kJ moI
l
]
137
$
+=J=OIJ
CATALYST
Tho SwodIsh chomIsf IorzoIIus In l835 nofIcod fhnf voIocIfy of n numbor of roncfIons
Incronsod by fho moro rosonco of n vory smnII qunnfIfy of n foroIgn subsfnnco, whIch wns nof
nf nII roInfod fo fho roncfnnfs. IorzoIIus nnmod fho honomonon of nccoIornfIon of fho roncfIon
ns cutuIysIs nnd fho subsfnnco InfIuoncIng fho roncfIon, n cutuIyst. SInco nII roncfIons fond fo
nffnIn oquIIIbrIum, If cnn bo snId fhnf cnfnIysfs smoofhon fho nssngo fownrds oquIIIbrIum.
DEFINITION
A cnfnIysf Is n subsfnnco, nof roInfod fo fho roncfnnfs, InfIuoncos fho voIocIfy of fho
roncfIon by nof InvoIvIng IfsoIf In fho roncfIon. Tho honomonon of InfIuoncIng n roncfIon by n
foroIgn subsfnnco Is known ns cnfnIysIs or 'n cnfnIysf Is n subsfnnco whIch onhnncos fho rnfo of
roncfIon nronchIng oquIIIbrIum buf wIfhouf InvoIvIng IfsoIf In fho rocoss`.
A cnfnIysf mny nIso rofnrd n chomIcnI roncfIon. So fho roor dofInIfIon of n cnfnIysf wIII
bou cutuIyst Is u substunce wLIcL uItevs tLe vute oI u cLemIcuI veuctIon wItLout
InvoIvIng ItseII In tLe veuctIon.
(i) PosItIve cutuIysIs ov cutuIysIs. A cnfnIysf whIch Incronsos fho rnfo of n roncfIon Is
cnIIod n osIfIvo cnfnIysf or n cnfnIysf nnd fho honomonon Is cnfnIysIs.
(ii) NegutIve cutuIysIs. Tho cnfnIysf whIch rofnrds fho rnfo of n roncfIon Is cnIIod n nognfIvo
cnfnIysf nnd fho honomonon Is nognfIvo cnfnIysIs.
ExampIes of CataIysis
PosItIve CutuIysIs
IeocIion CoIol,eI
(i) 2KCIO
3
2KCI + 3O
2
MnO
2
(ii) 2H
2
O
2
2H
2
O + O
2
If
(iii) 2SO
2
+ O
2
2SO
3
If or V
2
O
5
(it)
2
+ 3H
2
2H
3
Io
(t) C
l2
H
22
O
ll
+ H
2
O C
6
H
l2
O
6
+ C
6
H
l2
O
6
H
+
Ion
NegutIve CutuIysIs
IeocIion CoIol,eI
(i) 2H
2
O
2
2H
2
O + O
2
H
2
SO
4
(ii) 2H
2
+ O
2
2H
2
O CO
Characteristics of a CataIyst
(i) A smnII nmounf Is offocfIvo.
(ii) CnfnIysf romnIns unnIforod nf fho ond of fho roncfIon.
(iii) CnfnIysf hnsfons fho nffnInmonf of oquIIIbrIum.
(it) CnfnIysf hns no InfIuonco on fho oInf of oquIIIbrIum.
(t) CnfnIyfIc ncfIon Is unIvorsnI.
HIgLIIgLts:
CnfnIysf undorgoos no chomIcnI chnngo In n roncfIon. So If hns no InfIuonco on
fho sfnndnrd froo onorgy chnngo C i.e., on K, fho oquIIIbrIum consfnnf of fho
roncfIon ns fho fwo nro roInfod by C = !T In K.
So, fho oInf of oquIIIbrIum Is Indoondonf of fho cnfnIysf.
CnfnIysf onIy hoIs fo nffnIn fho oquIIIbrIum rnIdIy.
CnfnIysf moroIy Iowors fho onorgy bnrrIor (I
o
) of n roncfIon.
So n cnfnIysf Is n subsfnnco fhnf mnkos n chomIcnI roncfIon fhnf couId hnon,
buf doos nof hnon, hnon.
SInco K =
l
l
l
2
, so If n cnfnIysf chnngos l
l
, If wIII nIso chnngo l
2
In fho snmo
roorfIon so fhnf fhoIr rnfIo K romnIns unchnngod.
ThIs monns If n cnfnIysf nccoIornfos fho forwnrd roncfIon, If nIso nccoIornfos fho
bnckwnrd roncfIon, If novor Incronsos fho oquIIIbrIum yIoId.
Types of CataIysis
Homogeneous Heterogeneous
Catalysis
Thoro Is n fhIrd fyo of cnfnIysIs In mnInIy bIoIogIcnI sysfoms. Thoso cnfnIysfs nro formod
nzymes or Iow cutuIysts.
Homogeneous Catalysis
In fhIs fyo of cnfnIyfIc roncfIons, fho cnfnIysf romnIns In fho snmo hnso wIfh fho
roncfnnfs nnd Is ovonIy dIsfrIbufod fhroughouf fho roncfIon hnso.
ThIs fyo of cnfnIyfIc roncfIons occur In gns or soIufIon hnso i.e., In ono sIngIo hnso.
1xonplee of Ionogeneoue coIol,eie in goe pIoee
(o) O In HO
3
vnour In fho oxIdnfIon of SO
2
(Chnmbor rocoss)
2SO
2
(g) + O
2
(g) + |O(g)] 2SO
3
(g) + |O(g)]
(I) H
2
(g) + CI
2
(g) + |moIsfuro] 2HCI(g) + |moIsfuro]
(c) H
3
(g) + HCI(g) + |moIsfuro] H
4
CI(g) + |moIsfuro]
1xonplee of Ionogeneoue coIol,eie in eoluIion pIoee
(o) InvorsIon of cnno sugnr
C
l2
H
22
O
ll
+ H
2
O
+
H
C
6
H
l2
O
6
+ C
6
H
l2
O
6
+ |H
+
]
(I) ocomosIfIon of H
2
O
2
In fho rosonco of I
2H
2
O
2

I
2H
2
O + O
2
CATALYST 139
Heterogeneous Catalysis
In fhIs fyo of cnfnIyfIc roncfIons, fho cnfnIysf forms n sonrnfo hnso, usunIIy n fInoIy
dIvIdod soIId oIfhor ns such or suorfod on nn Inorf soIId such ns nsbosfos or gns (fIuIdIsod
bod). ThIs Is usunIIy formod conIocI coIol,eie. ThIs fyo of cnfnIysIs hns n gronf fochnIcnI
Imorfnnco.
1xonplee of HeIerogeneoue CoIol,eie.
(o) 2SO
2
(g) + O
2
(g)
If( ) e
2SO
3
(g) (If-CnfnIysf)
(I)
2
(g) + 3H
2
(g)
Io( ) e
2H
3
(g) (Io-CnfnIysf)
Activation energy and CataIysis reaction
AccordIng fo coIIIsIon fhoory: fho moIocuIos of roncfnnfs coIIIdo fo gIvo roducfs.
SchomnfIcnIIy If Is rorosonfod ns foIIows:
Reactant
molecules
Transition
state
+
Product
molecules
Reactants
Products
Catalysed
reaction
E
a
E
a
Uncatalysed
reaction
Progress of reaction
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
Fig. 6.1 Progress of reaction.
Tho mInImum nmounf of onorgy roquIrod fo nffnIn frnnsIfIon sfnfo Is cnIIod onorgy of
ncfIvnfIon, I
o
. CnfnIysf Iowors fho onorgy of ncfIvnfIon (I
o
) of n roncfIon.
Important AppIications of CataIysts
IeocIione 1xonplee CoIol,eI ueeJ
(i) ohydrnfIon C
2
H
5
OH C
2
H
4
+ H
2
O AIumInn, ZIrconIn
(ii) HydroIysIs VogofnbIo oII + H
2
O Inffy ncId TwIfchoI`s rongonf
+ gIycoroI
(iii) OxIdnfIon 2SO
2
+ O
2
2SO
3
V
2
O
5
C
6
H
6
+ O
2
MnIoIc nnhydrIdo
C
l0
H
8
+ O
2
IhfhnIIc nnhydrIdo
(it) HydrogonnfIon OII + H
2
VnnnsnfI !nnoy I
2
+ 3H
2
2H
3
(Hnbor`s rocoss) Io
AIkono + H
2
Aknno I, If, Id
+J@
(t) ohydrogonnfIon C
6
H
5
C
2
H
5
C
6
H
5
CH = CH
2
+ H
2
Cr
2
O
3
/MoO
3
(Sfyrono)
IrIodoI Crnff`s roncfIon
(ti) AIkyInfIon C
6
H
6
+ !X C
6
H
5
! + HX Anhydrous AICI
3
, II
3
, HI
(tii) IsomorIsnfIon ormnI nrnffIn IsonrnffIn Anhydrous AICI
3
(tiii) CrnckIng !ong chnIn nrnffIn brnnchod InuxIfo,
chnIn nIknnos MoO
3
(ix) HnIogonnfIon Ionzono + CI
2
ChIorobonzono Io or nnhydrous IoCI
3
(x) IoIymorIsnfIon Ifhono IoIyfhono ZoIgIor cnfnIysf or
Sfyrono IoIysfyrono IoroxIdos or
VInyI chIorIdo IVC IorsnIfs
Phase Transfer CataIyst
ThIs fyo of cnfnIyfIc roncfIon mny bo consIdorod ns n combInnfIon of homogonoous nnd
hoforogonoous cnfnIysos. If wo fnko wnfor nnd n non-nquoous soIvonf IIko bonzono nnd If fho
roncfnnfs romnIn In fho bonzono hnso nnd fho cnfnIysf In fho wnfor hnso fho roncfIon Is
nccomIIshod nf fho Inforfnco rovIdod n IIffIo surfnco ncfIvo ngonf (doforgonf) Is nddod fo fho
sysfom. ThIs fyo of cnfnIyfIc roncfIon Is now wIdoIy usod.
HIgLIIgLts:
Two ofhor fyos of cnfnIyfIc roncfIons nro fo bo nofod.
(i) AutocutuIysIsIxnmIos of such nufocnfnIyfIc roncfIon nro:
(o) HydroIysIs of osforwnfor formod In fho roncfIon cnfnIysos fho roncfIon.
(I) ocoIourIsnfIon of KMnO
4
by oxnIIc ncId. Mn
+2
Ion formod InIfInIIy cnfnIysos
fho roncfIon.
(ii) Induced cutuIysIsSodIum nrsonIfo soIufIon Is nof gonornIIy oxIdIsod by O
2
buf sodIum suIhIfo Is oxIdIsod. If nIr Is nssod fhrough n soIufIon confnInIng
fho fwo snIfs, bofh of fhom undorgo sImuIfnnoous oxIdnfIon. ThIs fyo of cnfnIyfIc
roncfIon Is known ns Inducod cnfnIyfIc roncfIon.
CataIyst Poison
CorfnIn foroIgn subsfnncos, whon rosonf In vory frnco nmounf, mny dnmngo fho
offIcIoncy of fho confncf cnfnIysf nnd mny ovon dosfroy fho cnfnIyfIc ncfIvIfy. Thoso subsfnncos
nro cnIIod cutuIyst poIsons or untI-cutuIysts. As
2
O
3
ncfs ns n cnfnIysf oIson In fho confncf
rocoss for fho mnnufncfuro of H
2
SO
4
. Tho oIson ncfs vory IIkoIy by bIockIng fho ncfIvo sIfos
of fho cnfnIysf.
CataIyst Promoters
Iromofors nro fho subsfnncos whIch romofo fho cnfnIyfIc ncfIvIfy or onhnnco fho ncfIvIfy
of n cnfnIysf by Ifs rosonco. An Imorfnnf cnfnIysf romofor Is AI
2
O
3
nnd nIknII mofnI oxIdo,
whon usod wIfh Iron In fho Hnbor`s rocoss, fho cnfnIyfIc ncfIon Incronsos.
HIgLIIgLts:
CIorocIerieIice of coIol,Iic reocIione.
(i) CnfnIysf romnIns unchnngod In mnss nnd chomIcnI comosIfIon nf fho ond of
fho roncfIon.
(ii) AIwnys n smnII qunnfIfy of cnfnIysf Is roquIrod.
(iii) A cnfnIysf Is moro offocfIvo In n fInoIy dIvIdod sfnfo.
+J@
CATALYST 141
(it) A cnfnIysf Is socIfIc In Ifs ncfIon.
(t) A cnfnIysf cnnnof InIfInfo n roncfIon.
(ti) A cnfnIysf doos nof chnngo fho osIfIon of oquIIIbrIum buf cnn onIy shorfon fho
fImo roquIrod fo nffnIn fho oquIIIbrIum.
A + B
Catalytic reaction
Equilibrium
Without use
of a catalyst
C + D
Time
R
a
t
e
o
f
r
e
a
c
t
i
o
n
Reaction: A + B C + D
Fig. 6.2 Effect of catalyst on time to attain equilibrium.
(tii) Chnngo of fomornfuro cnn nIfor fho rnfo of n cnfnIyfIc roncfIon ns for n non-
cnfnIyfIc roncfIon.
Mechanism of CataIytic Reactions
Tho foIIowIng fwo fhoorIos hnvo boon wIdoIy nccofod:
(i) InformodInfo comound formnfIon fhoory
(ii) AdsorfIon fhoory.
(i) IntevmedIute compound IovmutIon tLeovy
ThIs fhoory oxInIns fho cnfnIyfIc roncfIon duo fo fho formnfIon of nn unsfnbIo
InformodInfo comound whIch Is moro roncfIvo comnrod fo fho roncfnnfs. Tho foIIowIng
oxnmIos cnn bo gIvon In suorf of fho nbovo fhoory:
(o) O
2
ncfs ns nn oxygon cnrrIor In LeoJ CIonIer proceee.
2O + O
2
= 2O
2
... fnsf
SO
2

+ O
2
= SO
3

+ O
fho nof roncfIon boIng
2SO
2
+ O
2
= 2SO
3
(sIow If uncnfnIysod)
(I) Tho InformodInfo formnfIon of ofhyI hydrogon suIhnfo In fho dohydrnfIon of
nIcohoI by conc. H
2
SO
4
fo ofhor.
(c) In IrIodoICrnff roncfIon, nnhydrous AICI
3
forms nn InformodInfo comound
wIfh !CI nnd fInnIIy gonornfos !
+
for fho roncfIon.
!CI + AICI
3
! ... AICI
4
+
!
+
+ AICI
4

.
(ii) AdsovptIon tLeovy (Hetevogeneous cutuIysIs)
ThIs fhoory mnInIy oxInIns fho mochnnIsm of n cnfnIyfIc roncfIon bofwoon fwo gnsos
cnfnIysod by n soIId. Horo, fho cnfnIysf works by ndsorfIon of fho gns moIocuIo on Ifs surfnco.
Tho ndsorfIon fhoory Is comnrod fo fho InformodInfo comound formnfIon fhoory. Horo, fho
InformodInfo comound Is nn uctIvuted compIex formod on fho cnfnIysf surfnco. Tho
ndsorfIon fhoory cnn bo oxInInod by fho foIIowIng IIg. 6.3.
Ni Ni Ni Ni
H H
Ni Ni Ni Ni
H H
(o) AdsorfIon of H
2
moIocuIo (I) HH bond wonkonod nnd brokon
by chomIsorfIon

Ni Ni Ni Ni
C C
H
H
H
H
H H
C C
H
H
H H
H
H
Ni Ni Ni Ni
+
(c) IormnfIon of ncfIvnfod (J) Tho roducf ofhnno roIonsod
comIox wIfh ofhono. from cnfnIysf surfnco.
Fig. 6.3 (=), (>), (?) and (@).
BiochemicaI CataIysts (Enzymes)
umorous orgnnIc roncfIons occur In fho body of IIvIng boIngs, oIfhor Innfs or nnImnIs,
fo mnInfnIn fho IIfo rocossos. Thoso roncfIons nro cnfnIysod by corfnIn orgnnIc comounds
whIch nro known ns bIocutuIysts or enzymes.
Inzymos nro InvnrInbIy rofoIn moIocuIos. Iuf nof nII rofoIn moIocuIos nro onzymos.
ThIs sfnfomonf cnn bo oxInInod by fho fncf fhnf fhoso rofoIn moIocuIos confnInIng nn ncfIvo
sIfo nro onzymos. Tho rofoIn moIocuIos, whIch do nof confnIn fhoso ncfIvo sIfos cnnnof funcfIon
ns onzymos. If Is nssumod fhnf onzymos ncf on n subsfrnfo fo gIvo roducfs. Tho foIIowIng
fIguro oxInIns fho onzymnfIc ncfIvIfy:
InzymnfIc ncfIvIfy cnn bo oxInInod ns:
Inzymo + Subsfrnfo Inzymo Subsfrnfo Iroducfs + Inzymo
|ncfIvnfod comIox]
Tho roncfIon Is nbbrovInfod ns:
I + S I S I + I.
whoro I = onzymo, S = subsfrnfo (roncfnnf),
IS = ncfIvnfod comIox, I = roducfs.
Tho roncfIon mny bo rorosonfod IcforInIIy ns foIIows (IIg. 6.4).
S
+
E
Active sites
ES E
+
Products
[activated complex]
Fig. 6.4 llustration of the lock-and-key model of enzyme catalysis.
CATALYST 143
xumpIes oI enzymutIc veuctIons
(i) InvorsIon of cnno sugnr
C
l2
H
22
O
ll
+ H
2
O
Invorfnso
C H O
gIucoso
6 l2 6
+ C H O
frucfoso
6 l2 6
(ii) IormonfnfIon
C
6
H
l2
O
6

Zymnso
2 C
2
H
5
OH + 2CO
2
(iii) AmyIoso
AmyInso
MnIfoso
(it) H
2
O
2

IoroxIdnso
H
2
O +
l
2
O
2
.
HIgLIIgLts:
InzymnfIc roncfIons gonornIIy fnko Inco nf 35-45C.
Inzymos Ioso fhoIr ncfIvIfy nf hIghor fomornfuros.
Inzymos do nof ncf In coId condIfIons.
InzymnfIc ncfIvIfy Is H doondonf.
Ior Ifs fuII ncfIvIfy, onzymo noods hoI of nnofhor fncfor (comound) known ns
co-fncfor or co-onzymo.
InzymnfIc roncfIons nro gonornIIy doondonf on fho conconfrnfIons of onzymos.
InzymnfIc roncfIons nof nf nII doond on fho conconfrnfIon of fho roncfnnf i.e.,
subsfrnfo i.e., onzymnfIc roncfIons nro zoro ordor roncfIons.
Q. 1. WLut Is u cutuIyst?
Ans. A cnfnIysf Is n subsfnnco fhnf soods u chomIcnI roncfIons wIfhouf chnngIng IfsoIf.
Q. 2. WLut Is tLe eIIect oI u cutuIyst on Ivee enevgy cLunge oI u veuctIon?
Ans. A cnfnIysf cnnnof chnngo fho froo onorgy chnngo of n roncfIon.
Q. 3. WLut Is tLe eIIect oI u cutuIyst on tLe equIIIbvIum constunt oI u veuctIon?
Ans. A cnfnIysf doos nof nIfor fho oquIIIbrIum consfnnf of n roncfIon, If onIy shorfons
fho fImo of nffnInIng fho oquIIIbrIum.
Q. 4. MentIon tLe eIIect oI u cutuIyst on uctIvutIon enevgy (
u
) oI u veuctIon.
Ans. A cnfnIysf Iowors fho ncfIvnfIon onorgy of n roncfIon.
Q. 5. vuw u dIstvIbutIon cuvve sLowIng Low tLe pvopovtIon oI moIecuIes ubIe
to veuct Incveuses wLen u cutuIyst Iowevs tLe uctIvutIon enevgy.
Kinetic energy (E)
N
u
m
b
e
r
o
f
m
o
l
e
c
u
l
e
s
w
i
t
h
k
i
n
e
t
i
c
e
n
e
r
g
y
(
E
)
Activation energy
with a catalyst
Activation energy
without a catalyst
Fig. 6.5
GIve expevImentuI evIdence tLut dIIIevent cutuIyst Lus no InIIuence on tLe
yIeId oI u veuctIon.
Ans. If hns boon obsorvod fhnf nf fho snmo fomornfuro fho yIoId of SO
3

Is fho snmo,
whofhor fho cnfnIysf usod bo If, Io
2
O
3
or V
2
O
5
.
Q. 6. GIve Impovtunt uses oI negutIve cutuIysts oI tecLnIcuI Impovtunce.
Ans. An Imorfnnf fyo of nognfIvo cnfnIysf Is formod onIi-oxiJonIe. AromnfIc nmInos,
fhIouron, ofc., nro usod ns nnfIoxIdnnfs for roIongIng fho IIfo of rubbor. WIdosf fochnIcnI uso
of nognfIvo cnfnIysf Is TI! ns 'nnfIknock` comound In mofor fuoI. n-royI gnIInfo, Ionfoxy
nnIsoIo nro nddod fo rofnrd fho rnncIdIfy of oII.
Q. ?. WLut Is uutocutuIysIs?
Ans. Whon ono of fho roducfs of n roncfIon IfsoIf ncfs ns n cnfnIysf for fhnf roncfIon fho
honomonon Is cnIIod ouIocoIol,eie.
Q. B. vuw u gvupL Iov un uutocutuIytIc veuctIon.
Completion of reaction
Sigmoid curve
Time
R
a
t
e
o
f
r
e
a
c
t
i
o
n
Fig. 6.6
Ans. In nufocnfnIysIs roncfIon ns fho cnfnIyfIc roducf Is grndunIIy formod, fho rnfo of
roncfIon Incronsos. Tho rnfo Is mnxImum whon fho roncfIon Is comIofo (IIg. 6.6).
Q. 9. WLy Is tLe LydvoIysIs oI etLyI ucetute uutocutuIytIc?
Ans. As frncos of moIsfuro InIfInfo fho roncfIon, CH
3
COOH Is formod ncfs ns cnfnIysf.
CH
3
COOC
2
H
5
+ H
2
O CH COOH
3
cnfnIysf
+ C
2
H
5
OH
CATALYST 145
Q. 10. WLut uve Lomogeneous und Letevogeneous cutuIysts? GIve exumpIes.
Ans. If fho cnfnIysf Is In fho snmo hnso ns fho roncfnnfs, If Is n homogonoous cnfnIysf.
If fho cnfnIysf Is In n dIfforonf hnso, If Is n hoforogonoous cnfnIysf.
IxnmIo: (i) Homogonoous cnfnIysf = HydroIysIs of osfor, bofh ncId nnd bnso cnfnIysod.
(ii) Hoforogonoous cnfnIysf (confncf cnfnIysf) = In Hnbor`s rocoss for mnnufncfuro of
nmmonIn (Io + AI
2
O
3
+ K
2
O).
Q. 11. WLut uve enzymes?
Ans. Inzymos nro rofoIns In nnfuro nnd nro fho cnfnIysfs for bIochomIcnI roncfIons.
Q. 12. o you know uny use oI enzymes In detevgent?
Ans. Somo wnshIng owdors confnIn rofonsosonzymos fhnf romovo bIood sfnIns on
dIrfy cIofhos.
Q. 13. MentIon tLe muIn cLuvuctevIstIcs oI un enzyme.
Ans. Inzymos nro hIghIy socIfIc. Inch onzymo cnfnIysos n nrfIcuInr roncfIon. Ivory
onzymo hns nn 'ncfIvo sIfo`, fhnf Is, jusf rIghf shno nnd sIzo for fho subsfrnfo moIocuIos. Inch
onzymo works bosf nf n nrfIcuInr fomornfuro nnd H.
CATALYTIC APPLICATIONS OF ORGANOMETALLIC COMPLEXES
Effective Atomic Number (E.A.N.)
To oxInIn fho formnfIon of n comIox of n mofnI wIfh n IIgnnd, If wns suggosfod by
SIdgwIck fhnf mofnI Ions wIII fond fo nccof fho oIocfron nIrs from donors, i.e., IIgnnd unfII
fhoy hnvo obfnInod n suffIcIonf numbor of oIocfrons, so fhnf n mofnI Ion In fho rosuIfIng comIox
hns nn offocfIvo nfomIc numbor of fho nonrosf Inorf gns. ThIs ruIo wIII hoI fo undorsfnnd fho
formnfIon of n comIox whIch In furn wIII Iond fo gof n boffor oxInnnfIon of comIox comounds
ncfIng ns cnfnIysfs In vnrIous roncfIons.
So, fho effecIite oIonic nunIer (1.A.A.) of n mofnI Is obfnInod by doducfIng fho numbor
of oIocfrons Iosf In fho mofnI Ion formnfIon, fhon nddIng fho numbor of oIocfrons gnInod by co-
ordInnfIon i.e., fwo oIocfrons from onch IIgnnd hnvIng ono co-ordInnfIon confro. Tho ruIo cnn bo
oxomIIfIod by fho foIIowIng fnbIo:
E.A.N. Determination
MeIol ion
AIonic no. Co-orJinoIion 1lecIrone 1lecIrone
1.A.A.
of neIol nunIer loeI in ion oJJeJ I,
fornoIion co-orJinoIion
Io
2+
26 6 2 l2 36 (Kr)
Co
3+
2? 6 3 l2 36 (Kr)
Cu
+
29 4 l 8 36 (Kr)
I
2+
28 4 2 8 34 (So)
The 18-eIectron RuIe
ThIs Is nnofhor wny of oxrossIng nobIo gns oIocfron numbor ruIo i.e., offocfIvo nfomIc
numbor ruIo rognrdIng comIox formnfIon. Tho sfnfomonf of l8-oIocfron ruIo Is fhnf fho vnIonco
shoII of mofnI nfom wIII nffnIn l8 oIocfrons by snfurnfIon of (n l) J, ne nnd np orbIfnIs of
mofnIs by fho IIgnnds. Thus, fho snfurnfIon wIII occur ns foIIows:
l0 (for (n l) J subshoII) + 2 (for ne subshoII) + 6 (for np subshoII) = l8 oIocfrons.
To IIIusfrnfo, Iof us cIfo fho foIIowIng oxnmIos:
ConpounJe CenIrol neIol 1lecIronic confi- Ao. of elecIrone ToIol no. of
oIon uiII oxiJo- guroIion of IIe JonoIeJ I, elecIrone in
Iion nunIer cenIrol neIol of ligonJe (n 1) J, ne
(n1) J euIeIell onJ np letele
(i) I (CO)
4
I(0) 3J
l0
2 4 (four CO l0 + 8 = l8
grous) = 8 oIocfron
vnIonco shoII
confIgurnfIon
(ii) Io(CO)
5
Io(0) 3J
8
2 5 (fIvo CO 8 + l0 = l8
grous) = l0 oIocfron
vnIonco shoII
confIgurnfIon
TIe oIIoinnenI of 1S elecIrone in IIe tolence eIell of IIe neIol oIon or eoIief,ing 1S-
elecIron rule ie one of IIe ueeful criIerio of eluciJoIing IIe eIrucIure of neIol corIon,le.
Stvuctuve und bondIng In ovgunometuIIIc compIexes, tLe 16-und 1B-eIectvons vuIe:
TLe voIe oI metuIs In cutuIytIc cycIes duvIng some cLemIcuI veuctIons:
HydvogenutIon usIng (PL
3
P)
3
RLCI
Tho hydrogonnfIon of unsnfurnfod orgnnIc comounds i.e., mosfIy nIkonos Is nn Imorfnnf
IndusfrInI roncfIon. AImosf nII Inrgo scnIo hydrogonnfIon rocossos nro cnrrIod ouf usIng !nnoy
I ns cnfnIysf, whIch ncfs hoforogonoousIy. Homogonoous sysfoms nro usod for hnrmncoufIcnI
IndusfrIos. OrgnnomofnIIIc chomIsfs mndo fho rocoss vory ouInr. Tho hydrogonnfIons of
nIkonos nnd nIkynos hnvo boon sfudIod oxfonsIvoIy. (Ih
3
I)
3
!hCI, whIch Is gonornIIy known ns
WIIIkInson`s cnfnIysf, ncfs ns n homogonoous cnfnIysf for fho hydrogonnfIon of nIkonos nnd
nIkynos. Tho cnfnIysf Is nof nbIo fo roduco ofhor orgnnIc funcfIonnI grous, fhough If Is n vory
roncfIvo comound. If Is dIssocInfod (onIy 5) Info l4 oIocfron socIos In uro soIvonfs, fhus:
(Ih
3
I)
3
!hCI (Ih
3
I)
2
!hCI + IIh
3
Tho socIos (Ih
3
I)
2
!hCI Is of Iow coordInnfIng owor.
Tho ncfIon of fho WIIIkInson`s cnfnIysf Is rorosonfod by fho foIIowIng cycIo. In fho cycIo
fhoro nro four co-ordInnfIon comounds (II V). Tho l4-oIocfron socIos (II) Is formod by
dIssocInfIon of hoshono IIgnnd from (I). Tho sfrucfuro (II) Is soon fo ossoss n vncnnf
coordInnfIon sIfo shown by n squnro. ThIs Is bocnuso sfnbIo !h(I) comIoxos nro gonornIIy four
coordInnfod (l6-oIocfron socIos).
Tho l4-oIocfron socIos (II) whIch fnkos fwo hydrogon nfoms fo gIvo (III) by oxIdnfIvo
nddIfIon (III) Is sfIII unsnfurnfod nnd hns n vncnnf sIfo, so If cnn rondIIy nccof oIocfrons from
fho nIkono fo gIvo (IV). Tho sfngo IV Is vory vory sIgnIfIcnnf In fho ovornII hydrogonnfIon
rocoss ns In fhIs sfngo, fho subsfrnfos nIkono, hydrogon nro now bondod fo fho snmo mofnI
nfom. oxf sfo Is fho ronrrnngomonf of fho coordInnfIon sIfo fo gIvo V. (V) undorgoos roducfIvo
oIImInnfIon fo roIonso fho nIknno nnd rogonornfo fho l4-oIocfron socIos.
CATALYST 147
Rh
L L
Cl
Rh
L H
Cl
H
L
Rh
L H
Cl
H
L
C C
PH P = L
Vacant site =
3
Rh
L CCH
Cl
H
L
CC
H H
(III)
16e
(V)
18e
(IV)
16e
14e
(II)
H
2
addition of H
2
CC
L RhCl
3
(I)
L + L
Fig. 6.7 Catalytic applications of organometallics.
HIgLIIgLts:
OxIdnfIvo nddIfIon rofors fo fho Incronso In coordInnfIon sIfo of fho confrnI mofnI.
!oducfIvo oIImInnfIon rofors fo fho docronso In coordInnfIon sIfo of fho confrnI mofnI.
HydvoIovmyIutIon
Tho roncfIon of nn nIkono wIfh synfhosIs gns i.e., mIxfuro of cnrbon monoxIdo nnd
hydrogon (CO + H
2
) fo roduco nn nIdohydo, Is known ns I,Jroforn,loIion. Tho roncfIon,
whIch fnkos Inco In rosonco of n cnfnIysf Is ns foIIows:
!.CH=CH
2
+ CO + H
2
CnfnIysf
!CH
2
CH
2
CHO + !CH CH
|
CHO
3
SovornI frnnsIfIon mofnI comounds nro usod ns cnfnIysf In hydroformyInfIon. Iuf nmong
fhom, cnfnIysIs by cobnIf or rhodIum comounds Is of Inforosf. IndusfrInIIy cobnIf cnrbonyI Is
usod ns cnfnIysf nf l30 l?0C nnd undor 200 300 nfm rossuro. As fhIs noods hIgh rossuro
roncfor fho InIfInI InsfnIInfIon cosf of fho Innf Is hIgh for nn IndusfrInI rocoss.
Tho mochnnIsm of hydroformyInfIon usIng cobnIf cnrbonyI ns cnfnIysf Is shown In fho
schomo.
1
2
Co (CO)
2 8
1
2
H
2
1
2
+ H
2
HCo(CO)
4
+ CO CO
HCo(CO)
3
RCH CH Co(CO)
2 2 3
RCH CH Co(CO)
2 2 4
RCH CH CCo(CO)
2 2 3
O
RCH = CH
2
Insertion of
alkene into
CoH
CO
Insertion of C into
Co-alkyl
O
Hydrogenolysis
of Co-acyl
RCH CH CHO
2 2
Fig. 6.8
EXERCISES
1. ofIno wIfh IIIusfrnfIons:
(i) cnfnIysIs, (ii) osIfIvo cnfnIysIs, (iii) nognfIvo cnfnIysIs.
2. Whnf do you monn by (i) homogonoous nnd (ii) hoforogonoous cnfnIyfIc roncfIons
3. Whnf nro cnfnIysf oIsons nnd romofors
4. Iscuss n fow Imorfnnf cnfnIyfIc rocossos.
5. A cnfnIysf doosn`f nffocf fho fInnI sfnfo of oquIIIbrIum, nIfhough If shorfons fho fImo roquIrod fo
osfnbIIsh fho oquIIIbrIum.oxInIn.
6. CIvo n brIof nccounf of fho vnrIous fhoorIos of fho mochnnIsm of cnfnIysIs.
?. Whnf wIII bo n moro offocfIvo cnfnIysfInfInum ns n Ium or fInoIy dIvIdod InfInum CIvo
ronson.
B. How doos n cnfnIysf nccoIornfo fho sood of n roncfIon IxInIn wIfh roor onorgy rofIIo dIn-
grnm.
9. WrIfo nofos on:
(i) AdsorfIon fhoory of cnfnIysIs,
(ii) Inzymo cnfnIysIs.
CATALYST 149
10. CIvo ono oxnmIo of nn IndusfrInIIy Imorfnnf cnfnIyfIc roncfIon, monfIonIng fho socIfIc cnfnIysf
usod.
11. WrIfo nn nccounf of fho kInofIcs of hoforogonoous cnfnIyfIc roncfIon.
12. WrIfo nofos on:
(i) CnfnIysf nnd oquIIIbrIum oInf.
(ii) CnfnIysf nnd onorgy of ncfIvnfIon.
(iii) Ihnso frnnsfor cnfnIysIs.
13. WrIfo brIofIy on ncId-bnso cnfnIysIs.
14. Whnf nro fho chIof crIforIn of cnfnIysIs oscrIbo four nIIcnfIons of cnfnIysIs.
15. WrIfo nofos on:
(i) HydrogonnfIon cnfnIysfs nnd oxIdnfIon cnfnIysfs nnd fhoIr nIIcnfIon In IndIn.
(ii) SocIfIcIfy of cnfnIyfIc ncfIon.
16. WrIfo shorf nofos on:
(i) IffocfIvo nfomIc numbor
(ii) l8-oIocfron ruIo.
1?. Iscuss wIfh suIfnbIo mochnnIsmsfho rocossos of hydrogonnfIon nnd hydroformyInfIon.
150
%
Mechanism of Organic Reactions
REACTION TYPES
Tyos of orgnnIc roncfIons mny bo doIcfod ns foIIows:
Organic reactions
1. Substitution 2. Addition 3. Elimination 4. Rearrangement
In orgnnIc comounds, fho cnrbon nfom Is nffnchod fo ofhor nfoms by covnIoncy. Ono
covnIonf bond Is mndo of n nIr of oIocfrons. If fho bond Is bofwoon fwo snmo nfoms, i.e., of fho
snmo oIocfronognfIvIfIos, fhon fho InfIuonco of fho nfoms on fho bond Is snmo. If fho bond Is
bofwoon fwo nfoms of unoqunI oIocfronognfIvIfIos, fhon fho InfIuonco of fho nfoms on fho bond
Is nof fho snmo. If wIII doond on fho oIcfronognfIvIfy vnIuos of fho fwo nfoms. Tho dIsIncomonf
of fho bondIng oIocfrons wIII bo fownrds fho nfom of gronfor oIocfronognfIvIfy. And In fhIs
condIfIon fho bond Is snId fo bo oInrIsod, nnd ncquIros IonIc chnrncfor. Ior oxnmIo, In mofhyI
chIorIdo, fho bond bofwoon cnrbon nnd chIorIno Is oInrIsod nnd fho bondIng oIocfron Is dIsIncod
fownrds chIorIno nfom ns foIIows:
Inductive Effect
As n rosuIf of fho dIsIncomonf of fho bondIng oIocfrons bofwoon CCI, cnrbon nfom
ncquIros n smnII osIfIvo chnrgo nnd fho chIorIno nfom ncquIros n smnII nognfIvo chnrgo. ThIs
sorf of bond oInrIsnfIon duo fo fho rosonco of oIocfronognfIvo oIomonf IIko chIorIno Is known
ns InductIve eIIect. And fhIs offocf Is ormnnonf.
Tho InductIve eIIect Is soon fo oxIsf ufo fhIrd cnrbon nfom from fho oIocfronognfIvo
nfom In fho chnIn
C C C Cl
3 2 1
+++d ++d +d d
Iuf fho chnrgo on fho cnrbon nfoms grndunIIy docronsos, whIch hns boon IndIcnfod by
+, ++, +++, ofc.
ThIs InducfIvo offocf hns n gronf InfIuonco on fho chnrncfor of orgnnIc comounds ns
woII ns on orgnnIc roncfIons. As for oxnmIo, chIoroncofIc ncId Is moro ncIdIc fhnn ncofIc ncId.
ThIs honomonon Is oxInInod ns foIIows: uo fo InducfIvo offocf of chIorIno nfom fho roIonso
of rofon from chIoroncofIc ncId (K
o
= l.55 l0
3
) moIocuIo bocomos much onsIor fhnn fhnf of
ncofIc ncId (K
o
= l.85 l0
5
).
MECHANSM OF ORGANC REACTONS 151
CI
H
C
H
O
C O H
CI
H
C
H
O
C O H
+
+
An oxnmIo of (I) offocf
Tho oIocfronognfIvIfy scnIo Is rorosonfod ns foIIows:
O
2
> I > COOH > CI > Ir > I > OH > OCH
3
Tho oIocfron dIsIncomonf duo fo oIocfronognfIvo nfom Is known ns (I) eIIect, on fho
confrnry, oIocfron dIsIncomonf by rouIsIon Is known ns (+I) eIIect. uo fo (+I) offocf of CH
3
grou, CH
3
COOH Is wonkor ncId fhnn HCOOH. IIocfron rouIsIon of fho bondIng oIocfrons by
fho CH
3
grou In ncofIc ncId moIocuIo mnkos H
+
roIonso comnrnfIvoIy dIffIcuIf. If Is nn oxnmIo
of (+I) offocf.
CH
3
O
C
OH H
O
C
OH
Anofhor honomonon Is worfhwhIIo fo monfIon. If nn orgnnIc moIocuIo confnIns n doubIo
bond, fhon fho oIocfrons nro frnnsforrod comIofoIy fo ono of fho bondod nfoms undor fho
InfIuonco of nffnckIng rongonfs. ThIs offocf Is fomornry nnd Is known ns eIectvomevIc eIIect.
H A +
+
C
::
C C C
: +

HA
C C
A H
Tho offocf Is gonornIIy rorosonfod by n bend uvvow. SomofImos non-oInr covnIonf
moIocuIos IIko bromIno gof oInrIsod undor fho InfIuonco of doubIo bond. ThIs sorf of oInrIsnfIon
offocf Is fho cnuso of mnny orgnnIc roncfIons.
HomoIytic and HeteroIytic Fissions of a Bond
urIng fho occurronco of nn orgnnIc roncfIon fhoro Is nIwnys n bond bronkIng nnd n
bond mnkIng rocoss. Tho bond bronk-u mny bo homoIyfIc or hoforoIyfIc.
C
. .
H
( ) homolytic
bond breaking
a
C
:
H C
..
H
( ) heterolytic
bond breaking
b ( ) heterolytic
bond breaking
c
ThIs fyo of bond bronkIngs gIvo rIso fo Ivee vudIcuIs ns woII ns cuvbocutIons (C
+
) nnd
cuvbunIons (C
). Iroo rndIcnIs nro gonornfod duo fo homoIyfIc fIssIon nnd cnrbocnfIons nnd
cnrbnnIons nro gonornfod duo fo hoforoIyfIc fIssIon of fho bond. So orgnnIc roncfIons cnn fnko
Inco fhrough froo rndIcnI formnfIon or fhrough fho formnfIon of cnrbocnfIons nnd cnrbnnIons.
Whon fho roncfIon fnkos Inco fhrough froo rndIcnI formnfIon (IIg. o) fho mochnnIsm of fho
roncfIon Is cnIIod Ivee vudIcuI mecLunIsm. Whon fho roncfIon fnkos Inco fhrough fho
formnfIon of nn Ion (IIgs. I nnd c nbovo) fho mochnnIsm Is known ns IonIc mecLunIsm.
Free RadicaI Mechanism
Tho chIorInnfIon of mofhnno, i.e., subsfIfufIon of mofhnno fnkos Inco fhrough froo rndIcnI
mochnnIsm. So If Is n froo rndIcnI subsfIfufIon roncfIon. If Is rorosonfod ns foIIows:
CI
2
honf or I
2CI
:
InIfInfIon sfo
CI CH HCI CH
CH CI CH CI + CI
4 3
3 2 3
. .
.
+ +
+
7
8
9
IrongnfIon sfo

CI CI CI
CH CH CH CH
2
3 3 3 3
. .
. .
+
+
7
8
9
TormInnfIon sfo
IoIymorIsnfIon roncfIons nIso fnko Inco fhrough froo rndIcnI mochnnIsm.
C C + (RCO )
2 2
R C C
n
C C
.
Monomer Catalyst
(i) InIfInfIon: (!CO
2
)
2
2!CO
2
.
2!
.

+ 2CO
2
!
.

+
C C ! C C (froo rndIcnI)
-
(ii) IrongnfIon: R C C
n
C C
.
R C C
.
+ nC C
(iii) TormInnfIon: R C C
n
C C R C C
n
C C
.
+ R
.
R
Thoro nro ofhor wnys of formInnfIon of n oIymorIsnfIon roncfIon.
CIassification of Reagents
Tho rongonfs whIch fnko nrf In ionic reocIione nro cnfogorIsod ns:
l. IectvopLIIes ov eIectvopLIIIc veugents
2. NucIeopLIIes ov nucIeopLIIIc veugents
IectvopLIIes monn oIocfron sookIng, i.e., fhoso rongonfs nffnck nf fho oInf of hIghosf
oIocfron donsIfy of n moIocuIo. Thnf monns oIocfrohIIos nro osIfIvoIy chnrgod socIos. On
fho confrnry, nucIeopLIIes monn nucIous sookIng, i.e., fhoy nffnck nf fho osIfIvo confro of n
oInrIsod moIocuIo. ucIoohIIos mny bo nognfIvoIy chnrgod or n noufrnI moIocuIo hnvIng nn
nfom wIfh n Iono nIr of oIocfrons.
NucIeopLIIes IectvopLIIes
(o) OH
, C
, CI
, Ir
, I
(o) H
+
nnd ofhor osIfIvo Ions.
(I) oubIo nnd frIIo bonds of nIkonos (I) HnIogon nnd hnIogon ncIds.
nnd nIkynos.
(c) Comounds confnInIng nn nfom wIfh (c) H
2
SO
4
, HO
3
, HO
2
, ofc.
n Iono nIr.
(J) !
2
O:, :H
3
, !
3
:, ofc. (J) O
2
, AICI
3
, II
3
, ofc.
Thnf monns oIocfrohIIos nro !owIs ncIds i.e., oIocfron nIr nccofors nnd nucIoohIIos
nro !owIs bnsos i.e., oIocfron nIr donors. And fho roncfIons of oIocfrohIIos nnd nucIoohIIos
mny bo consIdorod ns noufrnIIsnfIon roncfIons, nucIoohIIos donnfo nn oIocfron nIr nnd fho
oIocfrohIIos nccof If nnd mnkos n bond. ConvonfIonnIIy, If fho nffnckIng rongonf bo nn
oIocfrohIIo, fho roncfIon Is cnIIod eIectvopLIIIc veuctIon nnd whon fho nffnckIng rongonf Is
n nucIoohIIo, fho roncfIon Is cnIIod nucIeopLIIIc veuctIon.
CIassification of Reactions
IrondIy, fho roncfIons mny bo cInssIfIod ns foIIows:
l. IectvopLIIIc veuctIons
2. NucIeopLIIIc veuctIons
AgnIn oIocfrohIIIc roncfIons mny bo of fho fwo fyos tic. uddItIon nnd substItutIon.
And so Is fho cnso wIfh nucIoohIIIc roncfIons.
Anofhor fyo of roncfIon Is vory common In orgnnIc chomIsfry whIch Is known ns
oIImInnfIon roncfIon.
Somo common IonIc orgnnIc roncfIons nro:
IectvopLIIIc uddItIon
IectvopLIIIc substItutIon
NucIeopLIIIc uddItIon
NucIeopLIIIc substItutIon und
IImInutIon veuctIon
Energy Changes during the Progress of a Reaction
Inorgy Is noodod fo bronk n bond nnd onorgy Is roIonsod whIIo mnkIng n bond. If wo
fnko chIorInnfIon of mofhnno for oxnmIo. Tho mofhnno moIocuIos musf coIIIdo wIfh chIorIno
moIocuIos. Tho mInImum nmounf of onorgy fhnf musf bo rovIdod by n coIIIsIon for roncfIon fo
occur Is cnIIod fho enevgy oI uctIvutIon (I
ncf
). Tho sourco of I
ncf
Is fho kInofIc onorgy of
movIng moIocuIos. Tho ofonfInI onorgy nf nny sfngo of fho roncfIon Is IndIcnfod by fho hoIghf
of fho curvo (soo IIg. ?.l).
E = 4 Kcal
act
CH + Cl
4
DH = 1 Kcal
CH + HCl
3
CH + Cl CH + HCl
4 3
Progress of reaction (one-step process)

P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
.
. .
.
Reaction:
Fig. 7.1 Potential energy changes during progress of reaction:
(One-step process) an exothermic reaction.
xumpIes:
1. IectvopLIIIc uddItIon. IromIno moIocuIo gofs oInrIsod whon comos In cIoso confncf
wIfh n bond. Tho osIfIvo bromIno Ion fhon gofs nffnchod fo n cnrbon nfom nffnchod fo n
doubIo bond mnkIng ofhor cnrbon nfom of fho doubIo bond n cnrbocnfIon, fhnf cnrbocnfIon gofs
nffnchod fo fho Ir
gonornfod. Thus nddIfIon of n bromIno moIocuIo fnkos Inco fo n doubIo bond:

CH
CH
Ir
Ir
CH
CH
Ir

Ir
2
2
2
2
+ +
+
C C
H
H
H
H
Br Br
d d +
C C
H
H
H
H +
Br
+ Br
()
C C
H
H
H
H
Br
Br
Tho nddIfIon of HIr fo ofhyIono Is nIso nn oxnmIo of oIocfrohIIIc nddIfIon:
CH
CH
H Ir
CH
CH
H Ir
2
2
2
2
+ +
+
C C
H
H
H
H
H Br
d d +
C C
H
H
H
H +
H
+ Br
C C
H
H
H
H
Br
H
2. IectvopLIIIc substItutIon. IIocfrohIIIc subsfIfufIon fnkos Inco In fhroo sfos.
IfrnfIon of bonzono Is nn oxnmIo of oIocfrohIIIc subsfIfufIon.
Step 1. ConornfIon of nn oIocfrohIIo:
HO
3
+ 2H
2
SO
4
2HSO
4
+ H
2
O
+
+
+
O
2
Step 2. IormnfIon of n frnnsIfIon sfnfo:
NO
2
(+)
Transition state (T.S.) ( ) I
(+)
H
NO
2
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
Ar.H + NO
2
+
T.S
1
T.S
2
+
H
NO
2
Ar . NO + H
2
+
Progress of reaction (Two-step process)
T.S.
Potential energy diagram for nitration
Setp 3. Inck fo nromnfIcIfy from fho frnnsIfIon sfnfo (I).
+ H
2
SO
4
+ HSO
4
(+)
H
NO
2
NO
2
Horo nffor fho nffnck of fho oIocfrohIIo fho sfnbIo nromnfIc sysfom Is dIsfurbod. Thnf Is
why, fho frnnsIfIon sfnfo rondIIy goos fo fho sfnbIo nromnfIc form by roIonsIng n rofon nnd fho
roIonso of fho rofon Is hoIod by gonornfod HSO
4
, fho bnso durIng roncfIon.

3. NucIeopLIIIc uddItIon. AddIfIon of HC fo n kofono Is nn oxnmIo of nucIoohIIIc
nddIfIon. Horo fho nffnck of nucIoohIIo (C
) occurs on n cnrbonyI cnrbon IondIng fo nn nddIfIon

roncfIon. Tho cnrbonyI grou of fho kofono oInrIsos HC nnd fho nddIfIon fnkos Inco ns
foIIows:
(o) C O
R
R
C O
R
R d+ d
(I) C
R
R
C O
R
R d+ d
CN H
d d+
CN
O
()
C
R
R
CN
OH
+ H
+
4. NucIeopLIIIc substItutIon. ucIoohIIIc nffnck on fho cnrbon nfom of CX bond In
n hnIonIknno or nIkyI hnIIdo, !X, Ionds fo subsfIfufIon, whoro X = CI, Ir or I. So hydroIysIs of
nIkyI hnIIdo Is nn oxnmIo of nucIoohIIIc subsfIfufIon. Sfudy of fho rnfo oqunfIons of fho
roncfIons suggosfs fhnf fhoro nro fwo dIfforonf mochnnIsms:
(o) ucIoohIIIc subsfIfufIon unImoIocuInr (S
l
)
(I) ucIoohIIIc subsfIfufIon bImoIocuInr (S
2
).
(o) S
N
1
veuctIon. ThIs Is n fwo-sfo rocoss. Tho rnfo oqunfIon Is:
rnfo = K|C(CH
3
)
3
CI]
Step 1. IonIsnfIon of fho nIkyI hnIIdos i.e., formnfIon of n cnrbocnfIon InformodInfo by
bronkIng of CCI bond. Thon fho nucIoohIIo OH
nffncks nnd forms n now bond.

C Cl
CH
3
CH
3
CH
3
C
+
Cl
H
3
C
H
3
C
H
3
C
Slow
Tertiary butyl carbocation
+
TorfInry bufyI cnrbocnfIon Is sfnbIo duo fo fho (+I) offocf of fho mofhyI grous. ThIs sfo
Is rnfo doformInIng sfo of fho subsfIfufIon i.e., fhIs sfo Is sIow.
Step 2.
C
+
+ OH
C OH
H
3
C
H
3
C
H
3
C
Fast
H
3
C
H
3
C
H
3
C
(I) SN
2
veuctIon: ThIs Is n ono-sfo rocoss. Horo fho rnfo oqunfIon Is
rnfo = K |nIkyI hnIIdo] . |OH
]
Tho mochnnIsm of fho subsfIfufIon cnn bo rorosonfod ns foIIows:
C X
OH + C X HO C + X
HO
T.S.
Horo fho mochnnIsm shows fhnf CX bond bronks ns fho nucIoohIIo OH
forms n now
bond wIfh cnrbon sImuIfnnoousIy.
IImInutIon veuctIon. ThIs Is n roncfIon fhnf sIIfs off n sImIo comound from n
moIocuIo fo form n doubIo bond.
xumpIe 1. C C + KBr + H O
2
C C
Br
H
+ KOH (alcoholic)
IIImInnfIon of n hydrogon hnIIdo from nn nIkyI hnIIdo roducos nIkono.
Tho oIImInnfIon roncfIon Is of fwo fyos nnd fhoy nro bnso cnfnIysod oIImInnfIon roncfIons:
(o) !nImoIocuInr roncfIon (I
l
)
(I) IImoIocuInr roncfIon (I
2
).
(o) I
l
roncfIon. ThIs roncfIon occurs In fwo sfos:
Step 1. C C
X
H
Slow
X
+ C C
+
H
A carbocation
Step 2.
Fast
C C
H B
:
C C + H B
:
(I) I
2
roncfIon. ThIs roncfIon occurs In ono sfo rocoss
C
H B
:
C C + H B
: C
X
X +
Anofhor oxnmIo of oIImInnfIon roncfIon Is fho romovnI of wnfor from nn nIcohoI fo form
nn nIkono.
H
H
C
H
OH
C
H
H
C
H
H

Honf ( H O)
Conc. H SO
2
2 4
H C
H
C
H
H
C
H
H

ThIs Is nn oxnmIo of ncId cnfnIysod oIImInnfIon roncfIon. Thus
C
H
H
H
C
H
OH
C
H
H
H C
H
H
H
C
H
OH
C
H
H
H C
H
H
H
C
H
+
C
H
H
H
H
+
H
+
H
O 2
C
H
H C
H
C
H
H
H
Resonance
Tho Idon of rosonnnco hns n mnjor roIo In undorsfnndIng fho mochnnIsms of roncfIons.
So fho Idon noods fo bo dIscussod horo:
AccordIng fo KokuIo fho bonzono moIocuIo hns foIIowIng fwo sfrucfuros (I) nnd (II).
(I) (II)
Tho sfrucfuros (I) nnd (II) cnnnof snfIsfncforIIy oxInIn nII fho roorfIos of bonzono.
l. osIfo hnvIng fhroo doubIo bonds bonzono undorgoos subsfIfufIon roncfIons moro
onsIIy fhnn nddIfIon roncfIons.
2. Ionzono Is moro sfnbIo fhnn oxocfod.
3. AII fho CC bond Iongfhs In bonzono Is l.39 Insfond of l.54 for n sIngIo bond nnd
l.34 for n C==C bond.
Tho KokuIo sfrucfuro Is sfIII fho nccofod sfrucfuro for bonzono. ThIs nccofnnco Is nof
for fho dIscovory of now fncfs nbouf bonzono buf Is n rosuIf of modIfIcnfIon of fho sfrucfurnI
fhoory. Thnf fhoory Is fho concof of vesonunce. Whonovor n moIocuIo cnn bo rorosonfod by
fwo or moro sfrucfuros fhnf dIffor onIy In fho nrrnngomonf of oIocfrons fho dIfforonf sfrucfuros
nrrIvod nf hnvo fho snmo nrrnngomonf of nfomIc nucIoI, fhoro Is rosonnnco. Tho rImnry
condIfIons for drnwIng fho rosonnfIng sfrucfuros nro:
(o) IosIfIon of nfoms In fho moIocuIo cnnnof bo chnngod nnd fho moIocuIo shouId bo
Innnr.
(I) IosIfIon of -bonds cnnnof bo chnngod.
(c) OnIy oIocfrons nnd non-bondod oIocfrons cnn bo shIffod.
Thon nII fho sfrucfuros so drnwn nro fho sfrucfuros of fho moIocuIo concornod nnd nono
of fhoso sfrucfuros cnn sfnIsfncforIIy oxInIn nII fho roorfIos of fho moIocuIo buf n LybvId of
nII fhoso sfrucfuros whIch cnnnof bo rorosonfod by nny ono of fhom Is fho ncfunI sfrucfuro of
fho moIocuIo. Inch of fhoso drnwn sfrucfuros confrIbufos fo fho vesonunce LybvId (IIg. ?.2).
Tho rosonnnco hybrId sfrucfuro Is moro sfnbIo fhnn nny of fho confrIbufIng sfrucfuros. Tho
dIfforonco In onorgy of nny of fho confrIbufIng sfrucfuros nnd fho hybrId sfrucfuro Is cnIIod fho
vesonunce enevgy (IIg. ?.2).
GvupLIcuI vepvesentutIon oI tLe Ideu oI vesonunce Ivom tLe Leuts oI Lydvogen-
utIon vuIues.
R
e
s
o
n
a
n
c
e
e
n
e
r
g
y
3
6
K
c
a
l
(Resonating structures)
Benzene + 3H
2
Cyclohexatriene + 3H
2
(Resonance hybrid structure)
Cyclohexadiene + 2H
2
49.8 Kcal
(obs)
85.8 Kcal
(calc)
55.4 Kcal
(obs)
57.2 Kcal
(calc)
28.6 (obs)
Cyclohexene + H
2
Cyclohexane
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
Sign of resonance
Fig. 7.2 Stability of benzene (Resonance energy).
ExpIanation
(i) Wo shouId oxocf from fho grnh fhnf fho honf of hydrogonnfIon of cycIohoxnfrIono
i.e., bonzono fo bo 85.8 KcnI/moI buf ncfunIIy If Is 49.8 KcnI/moIo. Thnf Is, bonzono Is
moro sfnbIo by 36 KcnI/moIo fhnn oxocfod whIch Is vesonunce enevgy of bonzono.
(ii) Tho rosonnnco hybrId sfrucfuro of bonzono confnIns no sIngIo or doubIo bond buf n
socInI fyo of bond fhnf Is why nII CC bonds In bonzono nro oqunI In Iongfh.
(iii) As n rosonnnco hybrId bonzono Is moro sfnbIo fhnn oIfhor of fho confrIbufIng rosonnf-
Ing sfrucfuros i.e., KokuIo sfrucfuros, fhIs nddIfIonnI sfnbIIIfy ossossod by bonzono
Is rosonsIbIo for subsfIfufIon roncfIons of bonzono nnd for n now sof of roorfIos
cnIIod oronoIic properIiee or oronoIiciI,.
Hyperconjugation (No bond resonance)
Tho sfnbIIIfIos of forfInry, socondnry nnd rImnry nIkyI rndIcnIs Is duo fo doIocnIIsnfIon
of odd oIocfrons fhrough ovorInIng of fho p orbIfnI occuIod by fho odd oIocfron nnd fho
-orbIfnI of fho nIkyI grou. Ior fhIs ovorInIng, fho fhroo oIocfronos i.e., fho odd oIocfron nnd
fho bond nIr of fho CH bond, hoI fo bInd fogofhor fho fhroo nucIoI i.e., fwo cnrbons nnd ono
hydrogon. ThIs fyo of doIocnIIsnfIon InvoIvIng -orbIfnI Is known ns hyorconjugnfIon.
In forms of rosonnnco, fho hyorconjugnfIon mny bo rorosonfod ns foIIows:
H
H
C
H
H

C

H
H
H
C
H
H
C
H
H
H
C
H
H
C
H
H
H
C
H
H
C
H
:
.
.
.

Inch of fho nbovo no-bond rosonnnco sfrucfuros nonrs sfrnngo. Iuf If Is nnronf fhnf
fho CH bond Is somofhIng Ioss fhnn n sIngIo bond nnd fho odd oIocfron Is nrfIy nccommodnfod
by fho H nfoms.
Steric Hindrance
AnIIIno roncfs fo form nnII wIfh bonznIdohydo buf 2, 4, 6-frIbromonnIIIno doos nof. VIcfor
Moyor nffomfod fo oxInIn fhoso nbnormnIIfIos by stevIc LIndvunce i.e., ogrous In 2, 4,
6-frIbromonnIIIno mochnnIcnIIy Inforforo fho nffnck by fho rongonf i.e., fondIng fo shIoId fho
moIocuIo from fho nffnckIng rongonf bonznIdohydo.
NH + OCH
2
NH = CH
NH + OCH
2
Br
Br
NO reaction
Anil
Br
Tho form stevIc LIndvunce orIgInnIIy consIdors fho goomofry of fho moIocuIo. Whon n
chomIcnI roncfIon occurs, If doos so vIn tvunsItIon stute. Tho form snfInI fncfor Is usod fo
donofo sforIc hIndrnnco, consoquonfIy, fho goomofry of bofh fho InIfInI moIocuIo nnd fho
frnnsIfIon sfnfo.
In nn S
2
roncfIon:
C X Nu C X Nu C + X
Nu
Crowded transition state (T.S.)
..
Tho frnnsIfIon sfnfo nccommodnfos moro nfoms fhnn fho InIfInI sfnfo. AIso, sfnfo of
hybrIdIsnfIon nf fho nffnckod C-nfom chnngos somofImos nnd fho offocf of sforIc hIndrnnco
bocomos ronouncod In T.S. Tho offocf of sforIc hIndrnnco roquIros n knowIodgo of roncfIon
mochnnIsm.Irom fho forogoIng dIscussIon wo cnn sny, S
l
roncfIons wIII nof bo nffocfod by fho
InfIuonco of sforIc hIndrnnco whorons S
2
roncfIons nro vory much nffocfod by sforIc hIndrnnco.
1, 2-shift
A cnrbonIum Ion (CnrbocnfIon) Is formod durIng n roncfIon nnd nnd ronrrnngos fo form
n sfnbIo cnrbonIum Ion (CnrbocnfIon) ns for oxnmIo
CH . CH . C CH
3 2 2
CH
3
H
CH . CH . C . CH
3 2 3
CH
3
Primary (1) carbocation Tertiary (3) carbocation

(Rearrangement)
ThIs fyo ronrrnngomonf fnkos Inco by mIgrnfIon of n hydrogon nfom wIfh n nIr of
oIocfrons known ns n LydvIde sLIIt or nn nIkyI grou wIfh n nIr of oIocfrons known ns uIkyI
sLIIt ov 1, 2-sLIIt. Thoso nro fho ronrrnngomonfs In whIch fho mIgrnfIng grou movos from
ono nfom fo fho noIghbourIng noxf nfom. ThIs shIff Is vory much Imorfnnf In undorsfnndIng
orgnnIc roncfIons.
C
..
H
C
C C
C C
H
+
..
H
(A hydride shift)
C C C C
C C
R
+
..
R
(An alkyl shift)
..
R

(1, 2-shifts)
Isomerism
Ifforonf orgnnIc comounds hnvIng fho snmo moIocuInr formuIn nro known ns Isomors.
Tho honomonon Is known ns IsomevIsm.
Tho IsomorIsm Is of fwo fyos:
(i) StvuctuvuI IsomevIsm
(ii) SteveoIsomevIsm.
SfrucfurnI IsomorIsm mny bo cInssIfIod ns:
(o) CLuIn IsomevIsm
(I) IunctIonuI gvoup IsomevIsm
(c) PosItIon IsomevIsm
(J) MetumevIsm.
IxnmIos nro dIsInyod In fho foIIowIng fnbIo.
T,pee of ieonerien Moleculor fornulo DifferenI eIrucIuree (ConpounJe)
(o) ChnIn IsomorIsm (i) Iufnno |C
4
H
l0
] (i) CH CH CH CH
3 2 2 3
-bufnno
n
(ii) CH CH CH
CH
3 3
3
Isobufnno

(ii) Ionfnno |C
5
H
l2
] (i) CH
3
CH
2
CH
2
CH
3
n-onfnno
(ii) CH
3
CH
CH
3
CH
2
CH
3
Isoonfnno
(iii) CH
CH
C CH
CH
3
3
3
3
ooonfnno
(I) IuncfIonnI grou (i) C

2
H
6
O (i) CH
3
CH
2
OH (ii) CH
3
OCH
3
IsomorIsm ofhyI nIcohoI dImofhyI ofhor
(ii) C
3
H
6
O (i) CH . CH . CHO
3 2
IronnnIdohydo
(ii) CH COCH
3 3
ncofono
(c) IosIfIon IsomorIsm (i) C
3
H
8
O (i) CH CH CH OH
3 2 2
-royInIcohoI n
(ii) CH
3
CH
OH
CH
3

IsoroyInIcohoI
(ii) C
3
H
?
CI (i) CH .CH . CH . CI
3 2 2
l-chIororonno
(ii) CH
3
CH
CI
CH
3
2-chIororonno
+J@
(iii) C
6
H
9
(OH)
2
(i)
OH
OH
ortho-
(ii)
OH
OH
meta-
(ii)
OH
OH
para-
(J) MofnmorIsm (i) C
4
H
l0
O (i) C
2
H
5
OC
2
H
5
(ii) CH
3
OC
3
H
?
dIofhyI ofhor mofhyI
n-royI ofhor
(iii)
O CH CH
3
CH
3
CH
3
Methyl isopropyl ether
Bond votutIon (IIg. ?.3) Is ossIbIo nbouf sIngIo covnIonf bonds buf Is rovonfod undor
normnI condIfIons by doubIe bonds or tvIpIe bonds. Tho Inck of rofnfIon nbouf doubIo bonds
gIvos rIso fo geometvIc IsomevIsm. Tho foIc hns boon fronfod Infor on.
C C
CH
3
H
H
CH
3
H
CH
3
C C
CH
3
CH
3
CH
3
H
H
H
Fig. 7.3 The groups at the end of a single CC bond can rotate freely relative to each other
giving rise to different conformations of molecules.
ConformationaI Isomerism
Tho dIfforonf snfInI nrrnngomonfs nrIsIng ouf of fho rofnfIon of n CC sIngIo bond nro
known ns conformnfIons. Tho dIfforonf sfrucfuros obfnInod duo fo fho rofnfIon of fhIs CC sIngIo
bond nro known ns conIovmevs. Tho fwo conformors of ofhnno nro gIvon In IIg. ?.4(o).
Eclipsed form
(I)
Anti form or staggered form
(II)
Fig. 7.4 (=) Newman projection formula for ethane.
Thoro nro mnny ofhor conformors bofwoon fhoso fwo oxfromos. Thoy nro known ns 'skow`
or 'Cnucho` forms. Tho rofnfIon nbouf C
2
C
3
bond of n-bufnno gIvos dIfforonf conformors ns
doIcfod In IIg. ?.4(I).
CH CH CH CH ( -butane)
3
n
2 2 3
4 3 2 1
(IsomorIsm In fho
snmo cInss of org-
nnIc comounds)
CH
3 CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3 CH
3
CH
3
Anti
Gauche Eclipsed Gauche
Angle of rotation
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
3.5 Kcal
0.9 Kcal
4.46.1 Kcal
Fig. 7.4 (>) Potential energy changes during rotation about C
2
C
3
bond of -butane.
Irom fho ofonfInI onorgy dIngrnm, wo soo fhnf fho nnfI-conformnfIon of n-bufnno Is
moro sfnbIo (CH
3
-grous nro ns nnrf ns ossIbIo, l80). In fwo Cnucho conformnfIons, fho
CH
3
-grous nro 60 nnrf nnd fhoy nro Ioss sfnbIo fhnn fho nnfI-form nnd moro sfnbIo fhnn
fho ocIIsod form, fho ocIIsod conformnfIon Is Ionsf sfnbIo duo fo sovoro crowdIng.
Conformations of CycIohexane
Iuctovs InIIuencIng tLe stubIIIty oI conIovmutIons: To go doo Info fho chomIsfry
i.e., fho sfnbIIIfy of fho cycIIc comound nnd Ifs roncfIvIfy, wo musf fnko hoI of conformnfIonnI
nnnIysIs.
Any dovInfIons from fho normnI, i.e., ep
3
hybrIdIsod cnrbon (bond nngIo l09.5) nro
nccomnnIod by ungIe stvuIn.
Any nIr of fofrnhodrnI cnrbon nffnchod fo onch ofhor fond fo hnvo fhoIr bonds sfnggorod
(i.e., ofhnno-IIko). Any dovInfIon from fho sfnggorod conformnfIon Is nccomnnIod by
tovsIonuI stvuIn.
Any fwo nfoms or grous fhnf nro nof bondod fo onch ofhor cnn Inforncf. ThIs non-
bondod InforncfIon cnn oIfhor bo rouIsIvo or nffrncfIvo. And fho rosuIf cnn bo oIfhor
dosfnbIIIsnfIon or sfnbIIIsnfIon of fho conformnfIon.
In fho cnso of cycIohoxnno fho foIIowIng conformnfIons nro common |IIg. ?.4(c)].
H
A
H
B
H
A
H
B H
B
H
A
Chair
Conformer
Twist
Conformer
Boat
Conformer
Fig. 7.4 (?) Conformers of cyclohexane.
owmnn rojocfIon formuIn of cLuIv conIovmev |IIg. ?.4(J)]:
Fig. 7.4 (@) Cyclohexane (chair form) staggered form of ethane.
Horo fho fhroo nIrs of fofrnhodrnI cnrbon of cycIohoxnno romnIn In sfnggorod forms. So
fho chnIr cycIohoxnno Is moro sfnbIo conformor of fho cycIohoxnnos. Ior bout cycIoLexune
fho owmnn rojocfIon formuIn Is ns IIg. ?.4(e).
Cyclohexane (boat form) Eclipsed ethane
Fig. 7.4 (A)
Tho bonf conformnfIon Is Ioss sfnbIo fhnn fho chnIr conformnfIon nf nn onorgy mnxImum,
If Is fhus nof n conformor buf n frnnsIfIon sfnfo bofwoon fwo conformors. Horo fho fhroo nIrs
of fofrnhodrnI cnrbon of cycIohoxnno romnIn In ocIIsod forms.
Tho twIst Iovm or skew bout Iovm Is n conformor IyIng nf onorgy mInImum. Iofwoon fho
chnIr form nnd fwIsf form fhoro nro hnIf chnIr forms wIfh nngIo sfrnIn nnd forsIonnI sfrnIn. Tho
hnIf chnIr form Is n mosf unsfnbIo form whIch IIos nf onorgy mnxImum (soo IIg. ?.5).
Chair
form
Half
chair
Twist
form
Boat
form
Twist
form
11 Kcal
5.6 Kcal
1.3 Kcal
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
Fig. 7.5 Potential energy diagram (conformations of cyclohexane).
Stereoisomerism
Isomors fhnf dIffor wIfh rosocf fo fho nrrnngomonfs of nfoms or grous In snco nro
known ns steveoIsomevs nnd fho honomonon Is known ns steveoIsomevIsm. ThIs nrf of
fhoscIonco, whIch donIs wIfh sfrucfuros In fhroo dImonsIons Is cnIIod steveocLemIstvy. Tho
fwo gonornI fyos of sforooIsomorIsm nro:
(i) OptIcuI IsomevIsm nnd (ii) GeometvIcuI IsomevIsm.
SInco conformnfIonnI Isomors dIffor from onch ofhor onIy In fhIs wny, fhnf fhoIr nfoms nro
orIonfod Is snco, fhoy nIso boIong fo fho steveoIsomevs.
(i) OptIcuI IsomevIsm. OfIcnI IsomorIsm Is shown by fho comound confnInIng nf Ionsf
ono chIrnI cnrbon nfom (nsymmofrIc). OfIcnI Isomors rofnfo fho Inno of oInrIsod IIghf. ConornIIy,
n chIrnI cnrbon nfom Is ono fhnf Is nffnchod fo four dIfforonf nfoms or grous. SImIo fosf of
doformInIng chIrnIIfy of n fhroo dImonsIonnI moIocuIo Is non-suorImossIbIIIfy of Ifs mIrror
Imngos (IIg. ?.?). PoIuvIzed IIgLt Is n IIghf bonm In whIch nII fho wnvos nro vIbrnfIng In fho
snmo Inno.
Ordinary
light
Polarizer
Plane-
polarized
light
Fig. 7.6 Arrangement for producing plane polarized light.
!Ighf Is Inno-oInrIzod nffor nssIng fhrough n shoof of IoInroId. OpIicol ieonere rofnfo
fho Inno of oInrIzod IIghf (IIg. ?.6).
COOH
H OH
CH
3
COOH
HO H
CH
3
Mirror
Fig. 7.7 Two configurations of lactic acid.
Two ofIcnI Isomors of IncfIc ncId (IIg. ?.?) nro moIocuIos wIfh no confors, nxos or Innos
of symmofry. AsymmofrIc moIocuIos nro chIrnI nnd cnn oxIsf In dIsfIncf mIrror Imngo forms,
gIvIng rIso fo optIcuI IsomevIsm. Any cnrbon nfom wIfh four dIfforonf grous or nfoms nffnchod
fo If Is usymmetvIc.
C
H
HO C
2
CH
3
OH
C
H
H C
3
CO H
2
HO
Mirror
Fig. 7.8 (=) The mirror image forms of lactic acid.
Asymmetric MoIecuIes
If wo frnnsInfo fho fhroo-dImonsIonnI moIocuIo fo n fwo-dImonsIonnI fIguro, wo gof
IIscLev pvoJectIon IovmuIu of fho moIocuIo.
HO
COOH
CH
3
H OH
COOH
CH
3
H
D()-Lactic acid mirror L(+)-Lactic acid
Fig. 7.8 (>)
Thon fho fosf of chIrnIIfy Is vory sImIo. If wo rofnfo IIschor rojocfIon formuIn of ono
moIocuIo on fho Inno of fho nor by l80 nono of fho confIgurnfIons nrrIvod nf whIch Is
suorImossIbIo on fho ofhor. Thoso fyos of moIocuIos rofnfo Inno of oInrIsod IIghf (soo IIg. ?.6)
oIfhor rIghf or Ioff. Tho fwo confIgurnfIons of IncfIc ncId rofnfo Inno of oInrIsod IIghf In fho
snmo dogroos buf In fho oosIfo dIrocfIons. Thoso fwo forms of sforooIsomors (confIgurnfIons)
nro known ns enuntIomevs.
HIgLIIgLts:
umbor of ossIbIo sforooIsomors = 2
n
.
whoro n = numbor of chIrnI cnrbon nfoms In fho moIocuIo.
A mIxfuro of oqunI nrfs of onnnfIomors Is cnIIod rncomIc modIfIcnfIon. Tho rofIx
() Is usod fo dosIgnnfo fho rncomIc mIxfuro. Thoy cnn bo sonrnfod by vnrIous
hysIcnI nnd chomIcnI mofhods.
Ior compound contuInIng two dIIIevent cLIvuI cuvbon utoms, fho sforooIsomors
(I) nnd (II), (III) nnd (IV) nro nIrs of onnnfIomors, (I) nnd (III), (II) nnd (IV) nro dInsforoomors.
CH
3
C H
2 5
H Cl
H Cl
CH
3
C H
2 5
H Cl
H Cl
CH
3
C H
2 5
H Cl
H
CH
3
C H
2 5
Cl
H Cl Cl
H
(I) (II) (III) (IV)
Fig. 7.8 (?) Stereoisomers of 2, 3-Dichloropentane.
SteveoIsomevs wLIcL uve not puIvs oI enuntIomevs uve known us dIusteveomevs.
Anofhor InforosfIng honomonon nrIsos nmong fho comounds confnInIng sImIInr chIrnI
cnrbon nfoms |IIg. ?.8(J)].
CH
3
CH
3
H Cl
H Cl
Fig. 7.8 (@) Optically inactive isomer (meso form).
!owor nrf of fho moIocuIo Is mIrror Imngo of fho uor nrf of fho moIocuIo nnd fho
moIocuIo bocomos ofIcnIIy InncfIvo duo fo InfornnI comonsnfIon. ThIs fyo of Isomor Is known
ns mesoIovm.
GeometricaI Isomerism
ThIs fyo of IsomorIsm nrIsos ouf of rosfrIcfod rofnfIon nbouf C = C bond. Whon sImIInr
grous nro nffnchod fo fho snmo sIdo of fho moIocuIo, fho confIgurnfIon Is known ns
cie-Isomors (Z-Isomors). Whon sImIInr grous nro nffnchod or fho oosIfo sIdo of fho C = C
bond, fho confIgurnfIon Is known ns Irone Isomors (I-Isomors). TLe geometvIcuI IsomevIsm
Is uIso u cuse oI dIusteveoIsomevIsm |IIg. ?.8(e)].
C C
H C
3
H H
CH
3
C C
H
H
CH
3
CH
3
cis-2-butene
(Z-2-butene)
Trans-2-butene
(E-2-butene)
Fig. 7.8 (A)
R-S System of NomencIature
!-S sysfom of nomoncInfuro wns dovoIood by Cnhn, IngoId nnd IroIog fo dosIgnnfo fho
confIgurnfIons of sforooIsomors hnvIng chIrnI confros. Tho sysfom Is offon formod ns nbsoIufo
confIgurnfIon nssIgnmonf ns fhIs fyo of socIfyIng confIgurnfIon Is Indoondonf of nny roforonco
comound.
Thoro nro corfnIn metLods oI ussIgnIng R-S notutIons fo nny chIrnI confro of n
moIocuIo. Thoso nro ns foIIows:
Tho numbor of sforooconfros In fho moIocuIo nro IdonfIfIod.
Tho four dIfforonf grous (IIgnnds) nffnchod fo onch of fho sforooconfros nro found ouf
nnd gIvon rIorIfy l, 2, 3, 4 or o, I, c, J, ofc. bnsod on 'sequence vuIe`, such fhnf l 2
3 4 or o I c J.
Thon fho moIocuIo Is vIowod from fho osIfIon fnr from fho Iowosf rIorIfy grou nnd n
hyofhofIcnI nfh Is drnwn movIng from l 2 3 or o I c.
If fho nfh rovIdos n cIockwIso mofIon, fhon fho sforooconfro Is dosIgnnfod fo hnvo '!`
confIgurnfIon. If fho nfh doscrIbos n counfor cIockwIso or nnfIcIockwIso nfh, fhon fho
sforooconfro Is snId fo hnvo 'S` confIgurnfIon |IIg. ?.9].
Tho (!) or (S) dosIgnnfIon Is wrIffon In IfnIIcs wIfhIn fho nronfhosos foIIowod by n
hyhon boforo fho nnmo of fho comound.
C
1
4
3
2
C
1
4
2
3
C
1
4
3
2
C
1
4
2
3
1 2 3 anticlockwise
(S)Configuration
1 2 3 clockwise
(R)Configuration

Fig. 7.9 Assigning R and S notations.
Sequence ruIes for determining the priority of groups or Iigands
Tho four dIfforonf grous nffnchod fo n chIrnI confro gof fhoIr rIorIfIos nccordIng fo fho
nfomIc numbor of fho nfom of onch grou nffnchod dIrocfIy fo fho chIrnI confro. Ior
oxnmIo, In l-bromo-l-chIoroofhnno (CH
3
CHCIIr), fho chIrnI confro Is nffnchod fo CH
3
,
CI, Ir, H. Tho nfomIc numbors of nfoms dIrocfIy nffnchod fo fho chIrnI confro show fho
rIorIfy ordor fo bo Ir > CI > CH
3
> H.
Whon fho roforoncos cnnnof bo doformInod on fho bnsIs of fho nfomIc numbor of fho
nfoms dIrocfIy nffnchod fo fho chIrnI cnrbon, In fhIs cnso, fho nfomIc numbors of noxf
sofs of nfoms In fho unnssIgnod grous nro fnkon Info consIdornfIon. Tho rIorIfIos nro
fhon doformInod nf fho fIrsf oInf of dIfforonco. As for oxnmIo, wIfh 2-chIorobufnno
(CH
3
CHCIC
2
H
5
), fho four IIgnnds nffnchod fo fho confrnI chIrnI confro nro CH
3
, C
2
H
5
,
CI, H. Among fhoso, CI Is of hIghosf nnd H Is of Iowosf rIorIfy. Ior docIdIng fho roforonco
bofwoon CH
3
nnd CH
2
CH
3
docIsIon cnnnof bo mndo on fho bnsIs of fIrsf Cnfom of
onch grou nffnchod dIrocfIy fo fho chIrnI confro.
Tho fwo grous nro vIowod ns foIIows:
In fho cnso of CH
3
, ofhor fhroo nfoms nro hydrogon i.e., C
H
H
H buf In fho cnso of
CH
2
CH
3
fho fwo nfoms nro hydrogon nnd fho fhIrd ono Is cnrbon i.e., C
H
CH
3
H .
So, CH
2
CH
3
gofs rIorIfy ovor CH
3
.
SImIInrIy, In fho cnso of CH
2
H
2
nnd CH
2
CH
3
, fho formor wIII gof rIorIfy ovor fho
Inffor.
A doubIo or frIIo-bondod nfom X fo C Is consIdorod fo bo oquIvnIonf fo fwo or fhroo Xs.
Ior oxnmIo

C= X monns

C X

X
nnd C X oqunIs
C
X
X
X
Iuf ono fhIng fo bo kof In momory Is fhnf n ronI

C A

A
hns rIorIfy ovor
C==A.
Ior oxnmIo:
CH = CH
2
monns
H
C
C
H
C
C
H
C C monns
C
C
C
C
C
C
CH = O monns
H
C
O
O
To IIIusfrnfo fho nbovo honomonon, Iof us consIdor fho foIIowIng oxnmIos:
CHO

H C OH

CH OH
2
CIycornIdohydo
CHO Is consIdorod ns
H
C
O
O
Horo O, O, H of CHO nffnIns fho rIorIfy ovor fho O, H, H of CH
2
OH grou. Tho
comIofo rIorIfy soquonco Is fhon OH CHO CH
2
OH H.
Tho C
6
H
5
grou Is consIdorod ns C
HC CH
C
. Tho rIorIfy soquonco of l-nmIno-2-mofhyI-
l-honyI-ronno Is H
2
C
6
H
5
C
3
H
?
H.
xumpIe: (I) 3-cLIovo-1-pentene.
To doformIno '!` or 'S` onnnfIomor of fho comound wo nro fo drnw fho IIschor rojocfIon
formuIn. Ior IIschor rojocfIon formuIn, fho numbor 'l` cnrbon shouId bo on fho fo of
fho vorfIcnI IIno. Thon fho grous nro Incod ncross fho horIzonfnI IInos nnd fho Insf
cnrbon Is nf fho boffom of fho vorfIcnI IIno.
Thon fho nsymmofrIc cnrbon nfoms nro fo bo doformInod. Thon fho soquonco ruIo Is
nIIod fo gof fho rIorIfy soquonco.
Thon confIgurnfIon Is socIfIod If rIorIfy soquonco Is o I c J Is cIockwIso nnd
hydrogon (J) romnIns In fho horIzonfnI IIno, fhon fho confIgurnfIon of fho nsymmofrIc
cnrbon nfom Is nssIgnod fo bo 'S`.
If fho soquonco Is fho snmo i.e., cIockwIso nnd hydrogon fnIIs on fho vorfIcnI IIno fhon
fho confIgurnfIon of fho nsymmofrIc cnrbon nfom Is nssIgnod fo bo '!` cnrbon nfom (wIfh
nsforIsk Is nsymmofrIc cnrbon nfom). IIschor rojocfIon of 3-chIoro-l-onfono Is:
H C C H
3 5 4 2
CH H C CH
2 2
Cl
*
3-Chloro-1-pentene
CH = CH
2
CH CH
2 3
( ) b
H
( ) d
Cl
( ) a
( ) c
Fischer projection formula
IrIorIfy soquonco Is: CI CH = CH
2
CH
2
CH
3
!ofnfIon Is nnfIcIockwIso nnd hydrogon Is on fho horIzonfnI IIno. So fho confIgurnfIon of
cnrbon numbor '3` Is '!`.
(II) AIunIne C
3
H
3
C
2
*
H(H
2
)COOH
.
IIschor rojocfIon formuIn Is:
COOH
CH
3
( ) b
H
( ) d
NH
2
( ) a
( ) c
D-alanine
COOH
CH
3
( ) b
H N
2
( ) a
H
( ) c
L-alanine Mirror
(I) (II)
In confIgurnfIon (I) hydrogon fnIIs on fho Ioff hnnd sIdo of horIzonfnI IIno, by convonfIon
If Is -confIgurnfIon. Ifs ofIcnI Isomor i.e., onnnfIomor wIII InovIfnbIy bo !-confIgurnfIon, i.e.,
hydrogon wIII fnII on fho rIghf hnnd sIdo of fho horIzonfnI IIno. In -nInnIno fho rIorIfy soquonco
Is H
2
COOH CH
3
, rofnfIon Is nnfIcIockwIso wIfh hydrogon on fho horIzonfnI nxIs. So
confIgurnfIon Is '!`.
In !-nInnIno fho rIorIfy soquonco Is snmo buf fho rofnfIon Is cIockwIso wIfh hydrogon
In fho horIzonfnI IIno. Tho confIgurnfIon of fho nsymmofrIc cnrbon Is 'S`.
(III) Ior 2, 3-dIcLIovo butune |C
4
H
3
C
3
*H(CI).C
2
*H(CI).C
l
H
3
] fho IIschor rojocfIon Is
CH
3
CH
3
H Cl
(III)
2
3
H Cl
CH
3
CH
3
H Cl
H Cl
CH
3
CH
3
Cl
H Cl
H
(I) (IV)
2
3
2
3
CH
3
CH
3
H
H Cl
(II)
2
3
Cl
(I) nnd (II) nro onnnfIomors. (I) nnd (III) or (II) nnd (III) nro dInsforooIsomors. (III) nnd (IV) nro
known ns mosoforms. Thoy nro ofIcnIIy InncfIvo duo fo InfornnI comonsnfIon.
In fho cnso of (I) fho rIorIfy soquonco for cnrbon numbor (2) Is CI CH(CI)CH
3

CH
3
.
So, fho confIgurnfIon Is 'S`.
Tho rIorIfy soquonco for cnrbon numbor '3` Is CI CH(CI)CH
3
CH
3
.
So fho confIgurnfIon Is 'S`.
So fho I!IAC nomoncInfuro of fho comound (I) Is:
(2S,3S)-2,3-IchIorobufnno.
SImIInrIy, fho ofhors nro: (II) (2!, 3!); (II) (2S, 3!); (IV) (2!, 3S).
E and Z NomencIature
Ior fho comounds of fho fyo CoI = CoI or CoI = Coc, fho forms cie nnd Irone nro
ndoqunfo buf If fhroo or four of fho subsfIfuonfs nro dIfforonf fhon fho nomoncInfuro of fhoso
goomofrIcnI Isomors or dInsforoomors Ionds fo nmbIguIfy nnd somofImos fo confusIon. Horo
nIso fho soquonco ruIo Is nIIod. ConornIIy I- Is nIIod for Irone-Isomor nnd Z- Is for
cie-somor whon fho grous of hIghor rIorIfy nro on fho snmo sIdo of fho roforonco Inno, i.e.,
doubIo bond, fhon fho symoboI (Z) Is usod fo socIfy fho confIgurnfIon. Tho symboI (I) Is usod
whon fho grous of hIghor rIorIfy nro on fho oosIfo sIdos of fho doubIo bond. Ior oxnmIo:
2-IufonoIc ncId.
C
C
H COOH
H CH
3
(CH > H; CO H > H)
3 2
whIch Is rorosonfod ns
H COOH
H H C
3
(E)-2-Butenoic acid

SImIInrIy:
H COOH
COOH H
(Z)-Butene dioic acid (Haleic acid)
(CO H > H ; COOH > H)
2
CH
3
H
H
H
CH
3
H
(2E, 4E)-2, 4-Hexadiene
Q. 1. WLy Is tLe RX + KOH ROH + KX cuIIed nucIeopLIIIc substItutIon?
Ans. SInco fho nffnckIng rongonf (OH
) Is n nucIoohIIIc rongonf, nnd subsfIfufIon of X
fnkos Inco by OH
, i.e., subsfIfufIon of wonkIy bnsIc grou fnkos Inco by n sfrongIy bnsIc

grou.
Q. 2. How cun you uscevtuIn tLut X
Is u weukIy busIc gvoup und OH
Is u stvongIy
busIc gvoup?
Ans. X
Is n wonk bnso ns Ifs conjugnfo ncId HX

Is n sfrong ncId; nnd OH
Is n sfrong bnso
ns Ifs conjugnfo ncId H
2
O Is vory wonk.
Q. 3. WLut uve nucIeopLIIIc veugents?
Ans. ucIoohIIIc rongonfs cnn suIy nn oIocfron nIr. ObvIousIy n nucIoohIIIc rongonf
nffncks n moIocuIo nf fho oInf of Iow oIocfron donsIfy. ucIoohIIIc rongonfs mny bo nognfIvoIy
chnrgod tic. OH
, C

ofc. nnd noufrnI moIocuIos IIko H
2
O, H
3
wIfh unshnrod nIr of oIocfrons.
Q. 4. Rute equutIons suggest tLut tLeve uve two dIIIevent mecLunIsms Iov
nucIeopLIIIc substItutIonexpIuIn.
Ans. HydroIysIs of rImnry hnIogononIknno tic. bromobufnno Is n socond ordor roncfIon.
Tho rnfo oqunfIon Is,
! = K|C
4
H
9
Ir] |OH
]
Tho suggosfod mochnnIsm Is:
H:O:
:
:
C
!
Br
H
H
CH
3
HO C
H
H
CH
3
: + Br:
:
:
In S
2
roncfIon fwo moIocuIos nro InvoIvod In fho rnfo doformInIng sfo.
HydroIysIs of forfInry hnIogononIknnos tic. 2-bromo 2-mofhyIronno Is fIrsf ordor. !nfo
oqunfIon for fho roncfIon Is:
!nfo = K|C
4
HgIr]
Tho suggosfod mochnnIsm Is:
C Br
CH
3
CH
3
CH
3
Slow
C
CH
3
+
CH
3
CH
3
+ Br
[Rate determining
step]
fast OH
C OH
CH
3
CH
3
CH
3
In S
l
mochnnIsm ono moIocuIo Is InvoIvod In rnfo doformInIng sfo.
Tho mochnnIsm shows fhnf CIr bond bronks fIrsf fo form n cuvbocutIon Intev-
medIute.
Thon fho nucIoohIIo forms n bond wIfh fho cnrbocnfIon formod. So, S
2
Is n ono sfo
rocoss nnd S
l
Is n fwo sfo rocoss.
Q. 5. Is tLe IoIIowIng veuctIon u nucIeopLIIIc substItutIon?
CH
3
O
C
X + NH
3
CH
3
CONH
2
+ HX.
Ans.

CH
3
C
O
NH
3
:
X C CH
3
+
NH
3
O
X
H
+
C CH
3
NH
2
O
X C CH
3
NH
2
O
+ X
Horo subsfIfufIon of X
fnkos Inco by nucIoohIIIc H

3
, so, fhIs Is nn oxnmIo of
nucIoohIIIc subsfIfufIon. ThIs Is nn oxnmIo of ncyI nucIoohIIIc subsfIfufIon.
Q. 6. OI tLe two IsomevIc C
4
H
9
Bv, wLy does 2-bvomo-2-metLyIpvopune IoIIow
S
N
1
putL?
Ans. Whon n mofhyI grou Is nffnchod fo n cnrbocnfIon (C
+
), fho chnrgo Is dIsorsod by
Ifs (+I) offocf. Moro fho numbor of mofhyI grous, moro Is fho dIsorsnI of chnrgo nnd moro fho
dIsorsnI of chnrgo, moro Is fho sfnbIIIfy of cnrbocnfIon. So wo cnn wrIfo fho foIIowIng sfnbIIIfy
soquonco,
CH CH CH (CH ) CH < (CH ) C
+
3 3
+
2 3 2
+
3 3
+
< <
l IrImnry 2 Socondnry 3 TorfInry
nnd soo fhnf C
+
H
3
Is fho Ionsf sfnbIo nnd (CH
3
)
3
C
+
Is fho mosf sfnbIo cnrbocnfIon. 2-bromo-2-
mofhyIronno IonIsos fo gIvo mosf sfnbIo 3 cnrbocnfIon whorons l-bromomofhnno gIvos l
cnrbocnfIon. Thnf Is why fho IonIsnfIon In fho fIrsf cnso Is ossIbIo nnd S
l
nfh Is foIIowod.
Q. ?. WLut do you expect II etLunoI Is Leuted wItL conc. H
2
SO
4
?
Ans. Af fIrsf ofhnnoI Is rofonnfod,
CH
3
CH
2
OH + H
+
CH
3
CH
2
O
H
H
. .
. .
:
+
fhon n wnfor moIocuIo Is oIImInnfod fo gIvo n cnrbocnfIon
CH
3
CH
2
O
H
H
+
. .
. .
: CH
3
C
+
H
2
+ H
2
O.
ThIs cnrbocnfIon oIImInnfos nn H
+
fo gIvo nn nIkono.
C C H
H
H
H
H
+
CH = CH + H
2 2
+
ThIs roncfIon Is nn oxnmIo of dohydrnfIon of nn nIcohoI.
Q. B. 2-MetLyIbutunoI on deLydvutIon gIves 2-metLyI but-2-eneexpIuIn.
Ans. CH
3
CH
2
CH
CH CH OH
3
2
+ H
+
CH
3
CH
2
CH
CH CH
3
2
O
H
H
+
H O
2
CH
3
CH
2
CH
CHCH
3
+
2
Tho formod cnrbocnfIon Is 2. ThIs ronrrnngos fo fho mosf sfnbIo 3 cnrbocnfIon by l,2
hydrIdo shIff.
C CH
2
CH
3
H
+
CH CH
3 2
CH
3
CH
2
C CH
3
CH
3
+
3 carbocation
ThIs socIos fhon oIImInnfos n rofon fo gIvo 2-mofhyI buf-2-ono.
C C
H
H
CH CH
3
CH
3
C CH
3
CH
3
2-methyl but-2-ene
CH
3
CH
3
Q. 9. GIve un exumpIe oI nucIeopLIIIc uddItIon.
Ans. IIrsf sfo of nucIoohIIIc nddIfIon HC fo ofhnnnI:
C
H
CH
3
CN +
O C O
H
CH
3
NC
:
:
:
To comIofo fho roncfIon, fho nognfIvoIy chnrgod oxygon ncfs ns n bnso nnd nccofs nn
H
+
from HC.
Socond sfo of nucIoohIIIc nddIfIon of HC fo ofhnnnI:
C O + HCN
H
CH
3
NC
:
:
:
C OH + CN
H
CH
3
NC
Q. 10. BenzopLenone does not Iovm bIsuIpLIte compound. xpIuIn.
C
6
H
5
COC
6
H
5
+ nHSO
3
C
6
H
5
OH
C SO
C H
n
3
6 5
Ans. Tho buIky grou (C
6
H
5
) surroundIng cnrbonyI grou rovonfs fho nffnck of
nucIoohIIIc (SO
3
2
) duo fo sforIc hIndrnnco nnd honco fho nucIoohIIIc nddIfIon fo form fho
bIsuIhIfo comound doos nof fnko Inco.
Q. 11. GIve tLe pvoducts oI tLe veuctIon oI etLyI bvomIde und AgCN.
Ans. C
Is nn nmbIdonf nucIoohIIo i.e., If cnn nffnck from bofh fho sIdos of fho socIos.
C
:
N
:
N
:
:
(Resonance) C
So fho roducfs of fho roncfIon nro:
C
2
H
5
Ir + Ag C C
2
H
5
C + C
2
H
5
C + Ag Ir
mnjor mInor
Q. 12. IndentIIy tLe pvoducts oI tLe IoIIowIng veuctIon:
Ans. !X + KO
2
A + I + C
O N = O
:
:
:
:
:
:
Is nn nmbIdonf nucIoohIIo.

O N = O
:
:
:
:
:
:
O = N = O
:
:
:
:
:
!X + KO
2
!OO + !O
2
+ KX
mnjor mInor
(A) (I) (C)
Q. 13. VInyI cLIovIde does not undevgo nucIeopLIIIc substItutIonexpIuIn.
Ans. CH = CH Cl
2
:
:
CH CH = Cl
2
:
:
:
:
:
:
!
+
uo fo rosonnnco CCI bond nffnIns n nrfInI doubIo bond chnrncfor nnd CCI bond
onorgy Incronsos nnd no cnrbocnfIon Is formod. So, vInyI chIorIdo doos nof undorgo nucIoohIIIc
subsfIfufIon.
Q. 14. AIIyI BvomIde undevgoes nucIeopLIIIc substItutIon veudIIyexpIuIn.
Ans. AIIyI cnrbocnfIon Is rosonnnco sfnbIIIsod
CH = CH CH
2 2
CH CH = CH
2 2
+ +
nnd bohnvos ns If fho chIorIno nfom Is IonIc.
So, CH
2
= CH CH
2
+
+ OH
CH
2
= CHCH
2
OH (S
l
)
Q. 15. BenzyI cLIovIde undevgoes S
N
1
veuctIonexpIuIn.
Ans. C
6
H
5
CH
2
+
Is rosonnnco sfnbIIIsod, so IonIsnfIon of bonzyI chIorIdo fnkos Inco nnd
S
l
nfh Is foIIowod.
CH
2
+
CH
2
CH
2
CH
2
+
+
+
Q. 16. IInd out tLe nucIeopLIIe Ivom tLe IoIIowIng:
+
O
2
, CCI
4
, CH
3
.
, C
Ans. C
, ns If hns Iono nIrs C

. .
.
Q. 1?. Avvunge tLe veuctIvIty oI tLe IoIIowIng towuvds nucIeopLIIIc veugent:
CH
3
I, CH
3
I, CH
3
Bv, CH
3
CI
Ans. CH
3
I > CH
3
CI > CH
3
Ir > CH
3
I
ns bond dIssocInfIon onorgIos () Is of fho ordor CI > CCI > CIr > CI.
Thus CI bond Is rondIIy brokon nnd fho roncfIvIfy of CH
3
I Is gronfosf.
Q. 1B. Aqueous KOH wItL RX gIves uIcoLoI wLeveus uIcoLoIIc KOH uIkene
expIuIn.
Ans. In nquoous modIum, S
fnkos Inco,
!X + KOH !OH + KX
whorons In nIcohoIIc modIum
C
2
H
5
OH + KOH C
2
H
5
O
K
+
+ H
2
O.
Tho
OC
2
H
5
Is sfrongIy bnsIc nnd roforonfInIIy hoI oIImInnfIon.
!CH
2
CH
2
X
2 5
OC H
!CH = CH
2
Q. 19. WLy do LuIouIkunes gIve cyunIdes wItL KCN
und IsocyunIdes wItL AgCN?

Ans. Iofh fho rongonfs ncf ns nucIoohIIIc nnd roIonso C
; C
boIng nmbIdonf
nucIoohIIo, fhoro nro fwo ncfIvo sIfos In fho C
C C
.. ..
..
..
=

Ag
+
romofos !
+
formnfIon from !X by rocIIfnfIng AgX nnd roncfIon fnkos S
l
nfh.
! X + Ag
+
|C
]
sIow
Ag X + !
+
+ |C
]
fnsf
!
+
C
In fho nbsonco of such romofIon by Ag

+
e.g. wIfh n
+
|C
] fho S
2
roncfIon Is found
C
+ ! X | C---!---X] C ! + X

T.S.
Q. 20. WLut do you meun by IeuvIng gvoup?
Ans. Tho chnrgod socIos (grou) fhnf Is roIncod durIng n subsfIfufIon roncfIon Is n
IonvIng grou.
Q. 21. WLut Is tLe cLuvuctevIstIc oI u bettev IeuvIng gvoup?
Ans. Tho sfrongor or hnrdor ns n bnso, worso ns n IonvIng grou.
OH, O!
, H
2
nro
hnrdor bnsos nnd nro fho worsf ns n IonvIng grou. Tho bosf IonvIng grous nro nnIons of
sfrong ncIds e.g., hnIIdo Ions (X
).
Q. 22. Iscuss tLe steveocLemIstvy oI S
N
1
und S
N
2
veuctIons.
Ans. In S
l
roncfIon rncomIsnfIon fnkos Inco fhnf monns (+) nnd ()

Isomors form In
oqunI nmounfs If wo fnko nn ofIcnIIy ncfIvo !X.
C
R
R
R
Br
Slow
C
R
R
R
OH
Fast
C
R
R
R
HO 50%
C
R
R
R
OH 50%
( )
Br
(+)
+
+
As fho Innnr cnrbocnfIon Is formod In rnfo doformInIng sfo nnd fho rocoss of formnfIon
Is sIow, If Is quIfo IIkoIy fhnf nffnck by OH
wouId fnko Inco wIfh oqunI rondInoss from oIfhor

sIdo of Innnr cnrbocnfIon IondIng fo 50/50 mIxfuro of fho (+) nnd ()forms. Thnf Is, nIwnys
vucemIsutIon fnkos Inco durIng S
l
roncfIon.
In S
2 roncfIon:

C
R
R
R
Br C
R
R
R
T.S.
Br HO
d
d
C
R
R
R
HO
HO
+
Tho bnck sIdo nffnck by fho nucIoohIIo nIwnys Ionds fo InvevsIon oI conIIguvutIon In
S
2
roncfIon.
Q. 23. Iscuss tLe eIIect oI soIvent on S
N
1
und S
N
2
veuctIons.
Ans. Tho chnngo of soIvonf (I) nffocfs fho rnfo of fho roncfIon (II) whIch mny chnngo fho
mochnnIsfIc nfhwny.
S
l
roncfIon bocomos fnsfor If fho soIvonf oInrIfy Incronsos.
Tho soIvoIysIs of (CH
3
)
3
Ir bocomos 3 l0
4
fImos fnsfor In 50 ofhnnoI fhnn In ofhnnoI
nIono. ovoIoIng Ion nIr gofs soIvnfod onsIIy nnd hoIs fho rocoss IonIsnfIon.
Incronso In soIvonf oInrIfy hns IIffIo offocf In S
2
roncfIon; onIy n sIIghf docronso In
roncfIon rnfo Is obsorvod. Chnngo of soIvonf mny hnvo mnrkod offocf on S
2
roncfIon. Tho
roncfIon rnfo bocomos 4.5 l0
4
foId fnsfor fhnn fho roncfIon CH
3
I wIfh
3
If wo chnngo fho
soIvonf from CH
3
OH fo HCO(CH
3
)
2
(MI). Iocnuso In CH
3
OH duo fo hydrogon bondIng
3
Is
soIvnfod nnd Ifs nucIoohIIIc ncfIvIfy Is roducod. Whorons In MI fho hydrogon IondIng Is
nbsonf nnd
3
romnIns unsoIvnfod nnd oworfuI nucIoohIIo cnn nffnck.

Incronso In soIvonf oInrIfy nnd Ion soIvnfIng nbIIIfy mny chnngo roncfIon nfhwny from
S
2
S
l
. Trnnsfor from rofIc oInr soIvonf fo oInr nonrofIc soIvonf mny chnngo fho roncfIon
nfhwny from S
l
S
2
by IncronsIng fho offocfIvonoss of fho nucIoohIIIc.
Q. 24. TLe ovdev oI veuctIvIty oI LuIogen ucIds towuvds un uIcoLoI Is
HI > HBv > HCI.
xpIuIn.
Ans. Tho nIcohoI Is fIrsf rofonnfod, fhoro Is nffnck by X
fo gIvo !X. So, fho roncfIon Is

nucIoohIIIc subsfIfufIon nnd fho IonvIng grou Is H
2
O.
!OH
HX
! OH
+
2

X
| ] X - - -!- - -O H
2
+
!X + H
2
O.
ucIoohIIIcIfy of X
docronsos In ordor: I
> Ir
> CI
.
Honco fho ordor of roncfIvIfy of HX Is
HI > HIr > HCI.
Q. 25. Iov u gIven HX, tLe ovdev ov veuctIvIty oI tLe uIcoLoIs IoIIows tLe ovdev
3 > 2 > 1expIuIn.
Ans. SInco fho sfnbIIIfy of cnrbocnfIon foIIow fho ordor: 3 > 2 > l. Honco, fho roncfIvIfy
of nIcohoIs foIIow fho ordor: 3 > 2 > l for n gIvon HX.
Q. 26. WLut do you meun by un eIImInutIon veuctIon?
Ans. IIImInnfIon roncfIon Is n roncfIon fhnf sIIfs off n sImIo moIocuIo of n comound
e.g., H
2
O from n moIocuIo of orgnnIc comound fo form n doubIo bond. IIImInnfIon of n moIocuIo
of hydrogon hnIIdo from n hnIonIknno roducos nn nIkono. ThIs roncfIon Is known ns
deLydvoLuIogenutIon.
Iy fnr, fho mosf common oIImInnfIon mochnnIsm Is fho ono sfo I
2
nfhwny.
!nfo = K|!CH
2
CH
2
Ir]|I]
(i) C
H
R
H
C
Br
H
C
H
H
H

B
:
!
R C
H
CH CH + Br
3

(ii) C
H
CH
3
Hb
OC H
2 5
CH CH
2
Hb
a
CH CH CH = CH (A)
3 2 2
CH CH = CHCH (B)
3 3
Y
In subsfrnfos whIch hnvo nIfornnfIvo -hydrogon nvnIInbIo, moro fhnn ono nIkonos cnn
bo obfnInod, fhnf Is doformInod by fwo omIrIcnI ruIos.
TabIe
SuIeIroIe Y Boee
Allenee
Aone of IIe Iule Iule
A B
CH
3
CH
2
CH
Y
CH
3
Ir

OIf
l9 8l Snyfzov Tho nIkono wIII rodom-

Innfo whIch hns most
uIkyI substItuents on
fho doubIo bond cnr-
bons.
+
(CH
3
)
3
OIf
95 5 Hofmnnn Tho nIkono whIch hns

Ionsf nIkyI subsfIfuonfs
on fho doubIo bond
cnrbons.
Q. 2?. WLut Is tLe ovIgIn oI ucIdIty In ovgunIc compounds?
Ans. (i) Tho sfrongfh of HA bond, (ii) fho oIocfronognfIvIfy of A, (iii) fncfors sfnbIIIsIng
A
, (it) fho nnfuro of fho soIvonf.

Q. 2B. HCOOH Is un ucIdexpIuIn.
Ans. H
O
C
)
OH uo fo oIocfron uII, H
+
roIonso Is ossIbIo, nnd nnIon formod hns
gof rosonnnco sfnbIIIfy.
HCOOH + H O
2
H C
O
O
H C
O
O
+ H O
3
+
So, HCOOH Is nn ncId ns fho nnIon hns rosonnnco sfnbIIIfy.
Q. 29. JustIIy tLe pK
u
vuIues
AciJ pK
o
CH
3
COOH 4.?6
(CH
3
)
2
CHCOOH 4.86
(CH
3
)
3
CCOOH 5.05
Ans. CH
3

O
C
O H
AcIdIfy In CH
3
COOH Is somowhnf roducod duo fo (+I)-offocf of fho CH
3
grou nnd fhnf
offocf Is moro ronouncod In (CH
3
)
2
CHCOOH nnd sfIII moro ronouncod In (CH
3
)
3
CCOOH. So
pK
o
vnIuo grndunIIy Incronsos i.e., ncIdIfy docronsos.
Q. 30. JustIIy tLe pK
u
vuIues
AciJ pK
o
CH
3
COOH 4.?6
ICH
2
COOH 2.66
CICH
2
COOH 2.86
IrCH
2
COOH 2.90
ICH
2
COOH 3.l6
Ans. Tho oIocfron wIfhdrnwIng subsfIfuonfs wIfh (I) offocf hns gof mnrkod InfIuonco
on fho ncIdIfy of sImIo nIIhnfIc ncIds.
Tho oIocfronognfIvIfy ordor of hnIogons Is:
I > CI > Ir > I
So, ncIdIfy ordor wIII bo,
I CH
2
COOH > CI CH
2
COOH > Ir CH
2
COOH > I-CH
2
COOH:
pK
o
vnIuos nro In nccordnnco wIfh fho nbovo ncIdIfy ordor.
Q. 31. AcIdIty ovdev wItL pK
u
vuIues oI tLe IoIIowIng ucIds Is:
CH
Cl
Cl
Cl COOH (pK
o
= 0.65) > CH
Cl
Cl
COOH(pK
o
= l.29) > CI CH
2
COOH(pK
o
= 286)
JustIIy.
Ans. As fho numbor of oIocfron wIfhdrnwIng grous Incronsos ncIdIfy Incronsos; pK
o
vnIuo docronsos.
Q. 32. PLenoI Is (E) ucIdIc, (EE) o, p-ovIentIng. xpIuIn.
O
:
:
H O
:
H
+
!:
!:
! :
O
:
H
+
O
:
H
+
O
:
:
H
(i) Tho oIocfronognfIvo nfom 'O` of honoI gofs osIfIvoIy chnrgod duo fo rosonnnco. So
bondIng oIocfrons of OH bond wIII bo uIIod sfrongIy fownrds O-nfom mnkIng roIonso
of H
+
onsIor. Moroovor, fho nnIon formod on fho roIonso of H
+
by honoI moIocuIo Is
rosonnnco sfnbIIIsod. So, honoI cnn bohnvo ns nn ncId.
(ii) uo fo rosonnnco, o- nnd p- osIfIons of fho bonzono rIng of honoI moIocuIo bocomo
oIocfron rIch. Ionzono hnvIng n doIocnIIsod -cIoud Is suscofIbIo fo oIocfrohIIIc
subsfIfufIon. Whon bonzono rIng Is nffnchod fo n grou confnInIng n 'koy nfom` (horo
'O` hns Iono nIr of oIocfrons) fho rosonnnco offocf gIvos rIso fo Incronsod oIocfron
donsIfIos In fho o- nnd p- osIfIons. ThIs Incronsod oIocfron donsIfy ncfIvnfos fho
bonzono rIng fownrds oIocfrohIIIc subsfIfufIon S
I
2
. Tho oIocfrohIIos cnn nffnck nf
fhoso osIfIons IondIng fo oIocfrohIIIc subsfIfufIon. So honoI Is o-, p-ovIentIng*.
Q. 33. pK
u
vuIues Iov NH
3
, CH
3
NH
2
, (CH
3
)
2
NH uve 9.25, 10.64 und 10.??
vespectIveIy. JustIIy.
Ans. H
3
. .
Is n !owIs bnso, If cnn donnfo n nIr of oIocfrons. Whon fhIs donnfIon cnncIfy
Is Incronsod by nny offocf, fho bnsIcIfy Is Incronsod. Tho (+I)-offocf of CH
3
grous Incronsos fho
oIocfron donsIfy of nfom In CH
3
H
2
nnd fhIs offocf Is moro ronouncod In (CH
3
)
2
H duo fo
fwo CH
3
grous orformIng ns sfrongor bnsos fhnn H
3
.
NH
3
:
NH
2
:
CH
3
NH
CH
3
CH
3
:
pK = 9.25
a
pK
a
= 10.64
pK
a
= 10.77
Q. 34. pK
u
vuIues oI NH
3
, CH
3
NH
2
und PLNH
2
uve 9.25, 10.64 und 4.62 vespectIveIy.
JustIIy.
Ans. H
3
Is bnsIc, CH
3
H
2
Is moro bnsIc, duo fo fho (+I) offocf of fho CH
3
grou. Tho
pK
o
vnIuos nro In nccordnnco wIfh fho nbovo fncf. Iuf wo soo fhnf pK
o
of nnIIIno Is 4.62 i.e., If
Is Ioss bnsIc fhnn H
3
.
Tho rosonnfIng sfrucfuros of nnIIIno Is:
NH
2
:
:
NH
2
!:
!:
!
:
NH
2
: +
NH
2
+
NH
2
+
Example of resonance
uo fo rosonnnco, fho oIocfron donsIfy ovor '` nfom bocomos Ioss fhnn fhnf ovor H
3
.
So nnIIIno (pK
o
= 4.62) bocomos Ioss bnsIc fhnn H
3
.
Q. 35. o you expect tLut F-nItvounIIIne Is Iess busIc tLun unIIIne?
Ans. Yos, fho oIocfron wIfhdrnwIng offocf of O
2
grou In p-nIfronnIIIno mnkos oIocfron
donsIfy of '` nfom Ioss fhnn fhnf In nnIIIno nnd fhnf Is why p-nIfronnIIIno bocomos Ioss bnsIc.
*ThIs roorfy common fo ofhor grous, IIko H O!
2
.. ..
..
:
, , hoIs oIocfrohIIIc subsfIfufIon nnd nro o-,
p-orIonfIng.
NH
2
:
NH
2
+
N
O O
N
O O
pK = 0.98
a
Ph NH
2
:
pK = 4.62
a
Q. 36. 2, 4, 6-TvInItvopLenoI (pIcvIc ucId) Is u vevy stvong ucIdexpIuIn.
Ans. InfroducfIon of nn O
2
grou In fho honoI moIocuIo Incronsos Ifs ncIdIfy duo fo
(I) offocf of fho O
2
grou. Tho fhroo O
2
grous In 2, 4, 6-frInIfrohonoI oxorcIso
ronouncod (I) offocf mnkIng fho honoI moIocuIo fofnI ncIdIc. Thnf Is why, If Is known ns
IcrIc ncId.
OH
OH
NO
2
pK = 0.9
a
NO
2
O N
2
pK = 1.02
a
Q. 3?. NO
2
gvoup Is m-ovIentIngexpIuIn.
Ans. Tho rosonnfIng sfrucfuros of nIfrobonzono nro:
O N O
:
:
O N O
+

O N O
+

O N O
+

O N O
+
:
:
uo fo rosonnnco, o- nnd p- osIfIons of bonzono rIng of nIfrobonzono bocomo oIocfron
dofIcIonf. Ior oIocfrohIIIc nffnck, oIocfron-rIch confro Is nocossnry. Tho n-osIfIon of fho
bonzono rIng Is comnrnfIvoIy oIocfron-rIch, fhnf Is why oIocfrohIIo nffncks fhoro nnd n-
subsfIfufIon fnkos Inco. So, O
2
grou Is n-orIonfIng.
Q. 3B. NItvutIon oI pLenoI Is eusIev tLun tLut oI nItvobenzeneexpIuIn.
Ans. In honoI OH grou ncfIvnfos fho bonzono rIng fownrds furfhor oIocfrohIIIc
subsfIfufIon by onrIchIng fho oIocfron donsIfy nf o- nnd p- osIfIons duo fo rosonnnco. IfrnfIon
Is nn oIocfrohIIIc subsfIfufIon nnd fnkos Inco onsIIy In fho cnso of honoI. On fho confrnry,
O
2
grou In nIfrobonzono doncfIvnfos fho bonzono rIng by wIfhdrnwIng oIocfrons from fho
bonzono rIng nnd mnkIng o- nnd p- osIfIons osIfIvoIy chnrgod. So, furfhor oIocfrohIIIc nffnck
nf nIfrobonzono moIocuIo bocomos dIffIcuIf. So, nIfrnfIon of nIfrobonzono moIocuIo bocomos
dIffIcuIf.
Q. 39. SLow tLut suIpLonutIon oI benzene Is un eIctvopLIIIc substItutIon.
Ans. Tho suIhonnfIng ngonf Is OIoum i.e., SO
3
dIssoIvod In conc. H
2
SO
4
. Tho oIofrohIIo
SO
3
Is gonornfod ns foIIows:
2H
2
SO
4
SO
3
+ H
3
O
+
+ HSO
4
Socond sfo Is nffnck by oIocfrohIIo SO
3
nnd fho formnfIon of n frnnsIfIon sfnfo.
O:
:
:
S
O:
:
O:
:
:
O
S
O:
:
:
: :
:
O:
:
:
H
T.S
+
OH
S
O
O
So, suIhonnfIon of bonzono Is nn oIocfrohIIIc subsfIfufIon.

Q. 40. WLut uve tLe eIectvopLIIes Iov (E) LuIogenutIon und (EE) uIkyIutIon
veuctIons oI benzene?
Ans. (i) Ior hnIogonnfIon tic. chIorInnfIon, fho rongonfs nro nnhydrous IoCI
3
nnd CI
2
.
IIocfrohIIo Is fhus gonornfod.
CI
2
+ IoCI
3
IoCI
4
+ CI
+
So, CI
+
ncfs ns nn oIocfrohIIo durIng chIorInnfIon of bonzono.
(ii) Ior nIkyInfIon fho rongonfs nro nnhydrous AICI
3
nnd !CI. IIocfrohIIo Is fhus
gonornfod.
!CI + AICI
3
AICI
4
+ !
+
So, !
+
ncfs ns nn oIocfrohIIo durIng nIkyInfIon i.e., In IrIodoICrnff`s roncfIon.
Q. 41. MentIon un ovgunIc veuctIon wLeve veuvvungement tukes pIuce.
Ans. IInncoI-InncoIono ronrrnngomonf (oxnmIo of l, 2-nIkyI shIff)
C
OH
CH
3
CH
3
C
OH
CH
3
CH
3
H
+
C
OH
CH
3
CH
3
C
OH
2
CH
3
CH
3
+
H O
2
C
OH
CH
3
C
CH
3
CH
3
CH
3
:
:
C
OH
CH
3
C
CH
3
CH
3
CH
3
+
:
!
C
OH
CH
3
CH
3
C
CH
3
CH
3
C
O
CH
3
CH
3
C
CH
3
CH
3
H
+
Pinacolone
Pinacol
Q. 42. WLut do you meun by stevIc InLIbItIon oI vesonunce?
Ans. 2, 6-ImofhyI , -dImofhyI nnIIIno (I) Is moro bnsIc fhnn , -dImofhyInnIIIno
(II). uo fo crowdIng In (I), (Mo)
2
grou goos ouf of Inno of fho bonzono rIng by froo
rofnfIon nbouf fho sIngIo bond. So rImnry condIfIon of rosonnnco, fho InnnrIfy, Is nffocfod
nnd rosonnnco Is InhIbIfod. So Iono nIr ovor (Mo)
2
grou In (I) Is nvnIInbIo fo bo nccofod
by n rofon (H
+
). ThIs Is nn oxnmIo of eIeric inIiIiIion of reeononce. Iuf In (II) Iono nIr ovor
(Mo)
2
comos Info rosonnnco wIfh bonzono rIng nnd nof so much nvnIInbIo for nn H
+
.
N
:
H C
3
CH
3
H C
3
CH
3
(I)
N
:
CH
3
CH
3
(II)
Q. 43. WLen PLenoI Is tveuted wItL NuNO
2
und HCI ut 05C, F-nItvosopLenoI Is
obtuIned. Is tLIs veuctIon un eIectvopLIIIc substItutIon?
Ans. Yos, horo fho oIocfrohIIo Is O
+
OH
+ NO
+
NO H
OH
+
OH
NO
+ H
+
NOCl + H O
2
NO + Cl
+
HONO + HCl
EXERCISES
1. CInssIfy fho dIfforonf orgnnIc roncfIons.
2. Whnf do you monn by oInrIsnfIon Whnf Is fho ronson bohInd If
3. Whnf do you monn by InducfIvo offocf How doos If Iny nn Imorfnnf roIo In orgnnIc roncfIons
4. Comnro fho ncIdIfy nmong
CH
3
COOH, CH
2
CI.COOH, CH.CI
2
COOH, CCI
3
COOH.
5. Whnf Is oIocfromorIc offocf Is If ormnnonf
6. Sfnfo fho orIgIn of n cnrbocnfIon, cnrbonIum Ion nnd froo rndIcnI.
?. Sfnfo fho roducfs obfnInod durIng fho chIorInnfIon of CH
4
In dIffusod sunIIghf. MonfIon fho
mochnnIsm.
B. Whnf Is oIymorIsnfIon roncfIon CIvo nn oxnmIo of such fyo of roncfIon wIfh InusIbIo mochn-
nIsm.
9. Whnf do you monn by oIocfrohIIos nnd nucIoohIIos
10. IIocfrohIIos nro In gonornI !owIs ncIdsoxInIn.
11. rnw fho onorgy rofIIo of fho foIIowIng roncfIon:
A + I A --- I AI
12. WrIfo nofos on oIocfrohIIIc nddIfIon nnd oIocfrohIIIc subsfIfufIon.
13. WrIfo n shorf nofo on nucIoohIIIc nddIfIon roncfIon.
14. Whnf do you monn by S
l
nnd S
2
roncfIons. IxInIn wIfh roor mochnnIsm InvoIvod wIfh
oxnmIos.
15. Whnf Is oIImInnfIon roncfIon oscrIbo dIfforonf fyos of oIImInnfIon roncfIons.
16. Whnf Is rosonnnco Sfnfo fho Imorfnnf fonfuros of If.
1?. Whnf nro fho sIgnIfIcnncos of fho forms:
(i) !osonnnco hybrId nnd (ii) !osonnnco onorgy.
1B. Honf of hydrogonnfIon vnIuo of l, 3, 5-cycIohoxnfrIono Is 85.8 kcnI/moIo whIIo fhnf of bonzono Is
49.8 kcnI/moIooxInIn.
19. WrIfo n shorf nofo on hyorconjugnfIon.
20. Whnf do you monn by l, 2-shIff.
21. Comnro fho bnsIcIfy nmong fho foIIowIng:
NH
2
,
NMe
2
,
NMe
2
Me Me
22. Whnf do you monn by dohydrohnIogonnfIon IxInIn wIfh roor mochnnIsm nnd oxnmIo.
23. Whnf doos fho form 'IsomorIsm` rofor fo CIvo dIfforonf cInssIfIcnfIons of IsomorIsm.
24. rnw IIschor rojocfIon formuIn of - nnd !-gIycIno (H
2
CH
2
COOH). nmo fhom ns or !S
nomoncInfuro.
25. rnw fho rosonnnco sfrucfuros of:
(i) honnfo Ion (ii) ncofnfo Ion
(iii) chIorobonzono (it) bufndIono.
26. rnw nII fho IIschor rojocfIon formuIno of:
(i) gIycornIdohydo (ii) IncfIc ncId
(iii) fnrfnrIc ncId (it) 2, 3-dIbromoonfnno.
nmo fhom ns or !, S-nomoncInfuro.
8
Ionic EquiIibrium
Law of Mass Action and Ionisation
!nw of mnss ncfIon Is nIIcnbIo fo oIocfroIyfIc dIssocInfIon, whon fho oIocfroIyfo Is wonk.
In n soIufIon n wonk oIocfroIyfo dIssocInfos rovorsIbIy.
AcOH H
+
+ OAc ; K
o
=
|H ] |OA ]
|AcOH]
+
c
H
4
OH H
4
+
+ OH
; K
I
=
|H ] |OH ]
|H OH]
4
4
+
K
o
= IonIsnfIon consfnnf of nn ncId (AcId dIssocInfIon consfnnf)
K
I
= IonIsnfIon consfnnf of n bnso.
If for n wonk ncId 'fho dogroo of dIssocInfIon` Is , fhon
HA H
+
+ A
Af oquIIIbrIum, C(l ) C C
Whon C = conconfrnfIon of HA
K
o
=
|H ] |A ]
|HA]
C . C
C( )
C
+
=

l
2
|ns Is nogIIgIbIo]
=
K
C
o
...(l)
If V IIfro of soIufIon confnIns ono gm. moI. of HA, fhon
C
l
V
=
nnd K
o
=

V
.
V
V
l
=
2
2
l
V
V
Thon K
o
comos fo :
K
o
=
2
l ( ) V
= K K
o
V V = ...(2)
Tho oxrossIon whIch roInfos fho vnrInfIon of dogroo of dIssocInfIon () of n wonk
oIocfroIyfo wIfh dIIufIon Is known ns OsIuolJ`s JiluIion lou. Tho oqunfIon ImIIos fhnf n wonk
oIocfroIyfo wIII dIssocInfo comIofoIy nf InfInIfo dIIufIon.
IuffIng C = l wo gof = K
o
i.e., fho dogroo of dIssocInfIon of n normnI soIufIon of n wonk oIocfroIyfo Is nroxImnfoIy oqunI
fo fho squnro roof of Ifs IonIsnfIon consfnnf.
184
ONC EQULBRUM 185
Common Ion Effect
If wo ndd nOAc fo n soIufIon of AcOH, fho Ion (OAc ) bocomos common. !of us soo Ifs
offocf on IonIsnfIon of AcOH.
AcOH H
+
+ OAc , nOAc n
+
+ OAc
K
o
=
|H ] |OAc ]
|AcOH]
+
...(3)
ow, nOAc boIng n snIf dIssocInfos comIofoIy In soIufIon. So conconfrnfIon form |OAc ]
Incronsos In fho oqunfIon (3), fo mnInfnIn fho vnIuo l
o
consfnnf, |H
+
] wIII docronso i.e.,
undIssocInfod |AcOH] wIII Incronso. As n rosuIf, fho dIssocInfIon of AcOH wIII bo surossod.
ThIs honomonon Is known ns Connon ion effecI. In gonornI, wo cnn sny, fhnf common Ion
offocf surossos fho dIssocInfIon of n wonk oIocfroIyfo In soIufIon.
ACIDS AND BASES
Arrhenius Theory of Acids and Bases
AccordIng fo fhIs fhoory nn ncId Is n subsfnnco whIch whon dIssoIvod In wnfor gIvos H
+
Ions nnd n bnso Is n subsfnnco whIch whon dIssoIvod In wnfor gIvos OH
Ions. If Is woII known

fhnf In noufrnIIsnfIon roncfIons, ncIds roncf wIfh nIknIIos fo form snIfs nnd wnfor. In fho
ArrhonIus concof noufrnIIsnfIon mny bo oxInInod ns foIIows:
(H
+
+ CI
) + (n
+
+ OH
) nCI + H
2
O
(2H
+
+ SO
4
=
) + ZnO ZnSO
4
+ H
2
O
Tho IndIcnfIon of noufrnIIsnfIon Is:
H
+
+ OH
H
2
O
i.e., fho formnfIon of wnfor.
Bronsted and Lowry Concept
ArrhonIus fhoory Is suIfnbIo In oxInInIng fho roncfIons of ncIds nnd bnsos In nquoous
soIufIons buf If fnIIs fo oxInIn fho foIIowIng roncfIons, socInIIy In non-nquoous soIvonfs. As
for oxnmIo, nH
2
dIssoIvos In IIquId nmmonIn nnd bohnvos ns nOH In wnfor ns Is ImIIod
from fho foIIowIng oqunfIons.
2nH
2
+ MgSO
4
= Mg(H
2
)
2
+ n
2
SO
4
(In IIq. H
3
)
2nOH + MgSO
4
= Mg(OH)
2
+ n
2
SO
4
(In wnfor)
So, bohnvIours of H
2
nnd OH
Ions nro snmo nnd OH
Is dorIvod from n bnso, so wo

cnn sny nH
2
Is n bnso i.e., n subsfnnco cnn bohnvo ns nn ncId or n bnso by nof roducIng H
+
or OH
Ions. Tho dofInIfIon of ncIds nnd bnso noods fo bo oxfondod.

Bvonsted und Iowvy deIIned: AciJ os o species uIicI con JonoIe o proIon onJ Iose
os o species uIicI con occepI o proIon. Thoso socIos mny bo noufrnI or chnrgod. Whofhor fho
socIos wIII bohnvo ns nn ncId or n bnso wIII doond uon fho nnfuro of fho soIvonf. Tho sfrongfhs
of fho ncIds or bnsos mny bo doformInod by fhoIr fondoncIos fo donnfo or nccof n rofon In n
dofInIfo soIvonf. Ior ovory ncId, fhoro Is n bnso known ns conjugoIe Iose nnd for ovory bnso
fhoro Is nn ncId known ns conjugoIe ociJ.
As for oxnmIo, CI
Is n conjugnfo bnso of fho ncId HCI nnd HCI Is fho conjugnfo ncId of
fho bnso CI
. Somo AcId/Inso conjugnfo nIrs nro shown In fho foIIowIng fnbIo.

AciJ ConjugoIe Iose
HCIO H
+
+ CIO
H
2
O H
+
+ OH
HSO
4
H
+
+ SO
4
=
HCO
3
H
+
+ CO
3
=
H
4
+
H
+
+ H
3
|Cr(H
2
O)
6
]
+3
H
+
+ |Cr(H
2
O)
5
OH]
+2
RoIe oI SoIvent
SoIvonf mnkos fo ncf fho subsfnncos fo bohnvo ns nn ncId or n bnso. SoIvonf bohnvos ns
n bnso fownrds ncId nnd vIco vorsn.
AcId
I
+ Inso
II
AcId
II
+ Inso
I
CH
3
COOH + H
2
O H
3
O
+
+ CH
3
COO
HCI + CH
3
COOH CH
3
COOH
2
+
+ CI
CH
3
COOH + H
3
H
4
+
+ CH
3
COO
HI + CH
3
COOH CH
3
COOH
2
+
+ I
H
2
O + H
2
O H
3
O
+
+ OH
(AuforofoIysIs of wnfor)
AcId
I
nnd Inso
I
nro conjugnfo nIr nnd AcId
II
nnd Inso
II
nro conjugnfo nIr.
HIgLIIgLts:
HCIO
4
, HIr, H
2
SO
4
, HCI nnd HO
3
nro of snmo sfrongfhs In wnfor; buf In gIncInI
ncofIc ncId fhoIr sfrongfhs nro ns foIIows:
HCIO
4
> HIr > H
2
SO
4
> HCI > HO
3
ThIs honomonon In wnfor Is known ns letelling effecI of uoIer.
oufrnIIsnfIon roncfIon cnn bo oxInInod wIfh fho hoI of fho oqunfIon:
AcId
I
+ Inso
II
AcId
II
+ Inso
I
CH
3
COOH + OH

H
2
O + CH
3
COO
HydroIysIs roncfIon Is oxInInod ns foIIows nccordIng fo Ironsfod !owry concof:

Aquoous soIufIon CH
3
COOn Is nIknIIno bocnuso CH
3
COOn IonIsos comIofoIy
In soIufIon ns If Is n snIf nnd wnfor boIng wonk oIocfroIyfo IonIsos IncomIofoIy.
CH
3
COOn CH
3
COO

+ n
+
; H
2
O H
+
+ OH
AccordIng fo Ironsfod, CH
3
COO
is o sIrong Iose os iIs conjugoIe ociJ, oceIic ociJ

is ueol. Thoroforo, CH
3
COO
Ions wIII rondIIy nccof rofons from wnfor moIocuIos

soffIng OH
Ions froo. As n rosuIf, fho soIufIon wIII gof onrIchod wIfh OH
Ions nnd
wIII bohnvo nIknIIno. And wnfor wIII romnIn undIssocInfod boIng n wonk oIocfroIyfo.
CIassification of SoIvents
SoltenI 1xonple
(i) IrofohIIIc (Irofon sookIng) H
2
O, H
3
(ii) IrofogonIc (Irofon gonornfIng) H
2
O, CH
3
COOH, HI
(iii) AmhIrofIc (Iofh rofon sookIng H
2
O, IfOH
nnd gonornfIng)
(it) ArofIc (Indoondonf of rofon C
6
H
6
, CCI
4
.
sookIng nnd gonornfIng)
ONC EQULBRUM 187
Lewis Concept
An ncId Is n subsfnnco whIch cnn nccof n nIr of oIocfrons nnd n bnso Is n subsfnnco
whIch cnn donnfo n nIr of oIocfrons.
AcId + Inso oufrnIIsnfIon offocf
I
3
I + :H
3
I
3
I H
3
H
+
+ :H
3
H
4
+
Cu
++
+ 4H
3
|Cu(H
3
)
4
]
++
HIgLIIgLts:
oufrnIIsnfIon of AICI
3
(!owIs ncId) wIfh yrIdIno (!owIs bnso) In C
6
H
5
CI soIvonf
or noufrnIIsnfIon of ICI
3
wIfh hfhnIIc nnhydrIdo cnn onIy bo oxInInod In fho
IIghf of !owIs concof of ncIds nnd bnsos.
N + AlCl
3
N AlCl
3
: O O
:
CO
CO
+ B
Cl
Cl
Cl
CO
CO
:
B
Cl
Cl
Cl
Base
Acid
Salt
Base Acid Salt
A subsfnnco cnn bohnvo ns nn ncId ovon fhough If doos nof donnfo n rofon, fhIs
honomonon cnn onIy bo oxInInod by fho !owIs concof.
Ionic Product of Water
Wnfor Is vory much InforIor ns nn oIocfroIyfo. If IonIsos ns foIIows:
H
2
O H
+
+ OH
or moro corrocfIy, 2H
2
O H
3
O
+
+ OH
. So dIssocInfIon consfnnf (K) of wnfor Is,

K =
|H ] |OH ]
|H O]
+
2
or
|H O ] |OH ]
|H O]
3
2
2
+
|H
2
O] Is consfnnf bocnuso of vory foobIo IonIsnfIon of wnfor. Thoroforo,
K|H
2
O] = |H
+
]|OH
]
or K
u
= |H
+
]|OH
] (3 |H
2
O] = consfnnf)
K
u
Is known ns ionic proJucI of uoIer, Ifs vnIuo nf 25C Is l l0
l4
.
HIgLIIgLts:
Wo nrrIvo nf nn Imorfnnf concIusIon fhnf In nny nquoous soIufIon, fho roducf
|H
+
] |OH
] Is consfnnf, Ifs vnIuo Is l0

l4
nf 25C.
IssocInfIon consfnnf of wnfor nnd IonIc roducf of wnfor nro nof snmo.
pH ScaIe
Ior vnrIous oxorImonfs, wo nood fo know hydrogon Ion conconfrnfIon of n soIufIon. If Is
worfhwhIIo fo monfIon fhnf nn nquoous soIufIon nIwnys confnIns H
+
nnd OH
Ions. Ivon sfrong

ncId soIufIon confnIns OH
Ions, fhough nogIIgIbIy smnII. AgnIn nn nIknIIno soIufIon confnIns

H
+
Ions fhough In smnII conconfrnfIon. Iocnuso |H
+
] |OH
] Is consfnnf In nquoous modIum

nnd Ifs vnIuo Is l0
l4
.
l () soIufIon of n sfrong ncId confnIns nn |H
+
] of l0
l
g.Ion l
l
. As sfrong ncId dIssocInfos
comIofoIy In nquoous soIufIon, so |OH
] of fho soIufIon wIII bo l0

l3

g.Ion l
l
. AgnIn 0.0l ()
sfrong nIknII soIufIon confnIns |OH
], l0
2
g.Ion I
l
whIch Is comIofoIy dIssocInfod In nquoous
soIufIon. Thoroforo, hydrogon Ion conconfrnfIon of fho soIufIon wIII bo l0
l2
g.Ion l
l
. In uro
wnfor |H
+
] = |OH
] = l0
?
. So In nn nquoous soIufIon whon |H
+
] oxcoods fhnf of |OH
], fho soIufIon
bocomos ncIdIc. And In fho soIufIon whoro fho |H
+
] bocomos Ioss fhnn fhnf of |OH
], fho soIufIon
bocomos nIknIIno.
!of us consIdor nn ncId soIufIon of conconfrnfIon
6000
, so Ifs hydrogon Ion conconfrnfIon
wIII bo l.66 l0
4
g.Ion I
l
. If Is somowhnf InconvonIonf fo oxross fho conconfrnfIon of fho
soIufIon In such n mnnnor. S.I.!. Soronson (l909) sImIy nIIod nognfIvo IognrIfhm of hydrogon
Ion conconfrnfIon fo romovo fhIs sorf of dIffIcuIfy for oxrossIng such conconfrnfIons. A sImIo
oornfIon IIko fhIs mndo nn onsy oxrossIon for hydrogon Ion conconfrnfIon of fho soIufIon. Ho
dofInod H ns nognfIvo IognrIfhm of hydrogon Ion conconfrnfIon:
H = Iog
l0
|H
+
]
A moro convonIonf scnIo for oxrossIng conconfrnfIon of H
+
Ion In nquoous soIufIons Is
fhus dovoIood.
pH scaIe
pH 0 l 2 3 4 5 6 ? 8 9 l0 ll l2 l3 l4
[H
3
O
+
(oq)]/nol Jn
3
l0
0
l0
l
l0
2
l0
3
l0
4
l0
5
l0
6
l0
?
l0
8
l0
9
l0
l0
l0
ll
l0
l2
l0
l3
l0
l4
IncronsIngIy ncIdIc noufrnI IncronsIngIy nIknIIno
ow nIyIng fhIs Idon In fho cnso of uro wnfor,
whoro |H
+
] = l0
?
Iog
l0
|H
+
] = Iog
l0
(l0
?
)
H = ?
AgnIn In uro wnfor, |OH
] = l0
?
Iog
l0
|OH
] = Iog
l0
(l0
?
)
OH = ?.
Thoroforo, In nny nquoous soIufIon H + OH = ? + ? = l4
HIgLIIgLt:
|H
+
] |OH
] = K
u
.
or, Iog
l0
|H
+
] + ( Iog
l0
|OH
]) = Iog
l0
K
u
H + OH = K
u
= l4 whoro Iog
l0
K
u
= K
u
.
Iuro wnfor Is noufrnI bocnuso In uro wnfor, |H
+
] = |OH
] = l0
?
.
So, nII ncIdIc soIufIons wIII hnvo H Ioss fhnn ?, nnd nII nIknIIno soIufIons wIII hnvo H
gronfor fhnn ?.
HIgLIIgLt:
IoIIowIng such convonfIons wo oxross K
o
nnd K
I
ns foIIows:
K
o
= Iog
l0
K
o
, nnd K
I
= Iog
l0
K
I
As for oxnmIo: K
o
for snIIcyIIc ncId = l0
3
.
K
o

= 3.
ONC EQULBRUM 189
xumpIe 1. ColculoIe pH of IIe follouing soluIions.
(o) 4.9 10
4
(A) ociJ, (I) 0.0016 (A) Iose.
SoI. Iofh ncId nnd bnso nro sfrong.
As fho ncId nnd bnso nro sfrong, fho dIssocInfIon Is comIofo. So,
(o) |H
+
] = 4.9 l0
4
g-Ion l
l
Iog
l0
|H
+
] = Iog
l0
(4.9 l0
4
)
H = 4 Iog
l0
4.9 = 4 0.69 = 3.3l
(I) |OH
] = l.6 l0
3
g-Ion l
l
Iog
l0
|OH
] = Iog
l0
(l.6 l0
3
)
OH = 3 Iog
l0
l.6 = 3 0.204l
= 2.?959 or 2.?6
H = l4 pOH = l4 2.?6 = ll.24.
xumpIe 2. ColculoIe [H
+
] of o soluIion of pH 3.63.
SoI. H = 3.63
Iog
l0
|H
+
] = 3.63
Iog
l0
|H
+
] = 3.63 = 3 0.63 = 4 0.3? = 4 3? .
|H
+
] = nnfIIog
4 3? .
= 2.34 l0
4
|H
+
] = 2.34 l0
4
g-Ion IIfro
l
.
+
], [OH
] onJ pH of o ueol Iose [0.1(A)].

Citen. = 0.013.
SoI. |OH
] = 0.0l3 0.l = l.3 l0

3
g-Ion IIfro
l
.
|H
+
] =
l0
l3 l0
l4
3
.
= ?.? l0
l2
g-Ion IIfro
l
.
H = Iog
l0
(?.? l0
l2
) = l2 Iog ?.?
= l2 0.8865 = ll.ll35.
ReIative Strengths of Acids and Bases
Tondoncy of donnfIng rofons In nny nquoous soIufIon Is n monsuro of ncIdIfy of fho
soIufIon. If conconfrnfIons of fwo ncIds A nnd I nro C
A
nnd C
I
rosocfIvoIy, rnfIo of sfrongfhs
shouId bo C
A
: C
I
. Thoro nro sovornI ofhor rocossos for comnrIng sfrongfhs of ncIds. Ono such
mofhod Is by comnrIng dIssocInfIon consfnnfs of fho ncIds.
!of, dogroo of dIssocInfIon of ncId A
l
=
l
ogroo of dIssocInfIon of ncId A
2
=
2
Tho conconfrnfIons of fho ncIds woro snmo (C).
So, fhoIr sfrongfhs S
l
nnd S
2
nro rorosonfod by,
S
S
l
2
l
2
l
2
l
2
l
2
= = =
C
C
K C
K C
K
K
So, fho rnfIo of dIssocInfIon consfnnfs of fwo ncIds comnro fhoIr sfrongfhs.
Buffer SoIutions
Sone soluIions Jo noI cIonge IIeir pH on oJJiIion of liIIle ociJ or olloli. SucI soluIions
ore lnoun os Iuffer soluIions. Tho nrrosf of H chnngos of fhoso soIufIons Is known ns Iuffer
ocIion.
MecIonisn of Iuffer ocIion. A buffor soIufIon Is gonornIIy n mIxfuro of soIufIons of n
wonk ncId HA nnd Ifs snIf IA.
So wo hnvo,
IA I
+
+ A
(ComIofoIy dIssocInfod In nquoous soIufIon ns If Is n snIf)

HA H
+
+ A
(IncomIofo dIssocInfIon In nquoous soIufIon ns fho ncId Is wonk)

A

Is n sfrong bnso ns Ifs conjugnfo ncId HA Is wonk. So A
wIII rondIIy nccof H

+
from
soIufIon whIch comos from fho nddod ncId fo fho soIufIon.
H
+
(oxfornnI) + A
HA
Tho undIssocInfod moIocuIos of HA wIII bo gonornfod moro nnd moro, ngnIn whoso
dIssocInfIon Is nImosf rovonfod duo fo common Ion offocf of A
. So fho chnngo of H wIII bo

nrrosfod.
If wo ndd n IIffIo bnso fo such n buffor soIufIon fho oxfornnI KH

wIII bo romovod by fho
ncId HA, ns OH

Is n sfrong bnso:
OH

(oxfornnI) + HA H
2
O + A
.
So, H of such soIufIon wIII nof chnngo on nddIfIon of IIffIo ncId or nIknII nnd fhnf Is fho
buffor ncfIon of fho soIufIon.
AgnIn, n wonk bnso IOH nnd Ifs snIf wIII gIvo n buffor soIufIon.
As In fhIs cnso, IA I
+
+ A
(comIofo dIssocInfIon)
IOH I
+
+ OH
(IncomIofo dIssocInfIon)
On nddIfIon of ncId fo such soIufIon, oxfornnI H
+
wIII bo romovod by IOH
H
+
(oxfornnI) + IOH I
+
+ H
2
O.
AgnIn on nddIfIon of nIknII fo such soIufIon OH
Ions nro romovod ns foIIows:

OH
+ I
+
IOH
I
+
Is nn ncId, nccordIng fo Ironsfod concof.
So fho H of fho soIufIon wIII nof chnngo on fho nddIfIon of n IIffIo ncId or nIknII.
pH of a Buffer SoIution
(i) BuIIev soIutIon (pvepuved Ivom weuk ucId und Its suIt)
!of, fho ncId bo HA nnd Ifs snIf bo IA, horo fho common Ion Is A
HA H
+
+ A
(wonk ncId)
K
o
=
|H ] |A ]
|HA]
+
Iog
l0
K
o
= Iog |H
+
] + Iog
l0
|A
] Iog
l0
|HA]
Iog
l0
K
o
= Iog
l0
|H
+
] + Iog
l0

|A ]
|HA]
or, Iog
l0
|H
+
] = Iog
l0
K
o
+ Iog
l0

|A ]
|HA]
or, H = K
o
+ Iog
l0

|A ]
|HA]
uo fo common Ion offocf, fho dIssocInfIon of ncId HA Is vory oor,

So, wo cnn wrIfo |A
] = |SnIf] ns nII fho A
In fho soIufIon nro duo fo IonIsnfIon of IA.

H = K
o
+ Iog
l0
|SnIf]
|AcId]
ThIs Is fho fnmous HenJerson equoIion.
ONC EQULBRUM 191
Tho ncIdIfy or nIknIInIfy of mIxod soIufIon, i.e., H doonds uon fho rnfIos of fho
conconfrnfIon of snIf nnd ncId. Tho buffor ncfIon Is fnvournbIo In H rnngos K
o
l i.e., whon
conconfrnfIon of snIf bocomos l0 fImos fho conconfrnfIon of ncId nnd vIco vorsn.
(ii) BuIIev soIutIon (pvepuved Ivom u weuk buse und Its suIt)
In fhIs cnso:
IOH I
+
+ OH
(wonk)
K
I
=
|I ] |OH ]
|IOH]
|I ]
|IOH] |H ]
+ +
+
=
K
u 3 | ]
| ]
OH
K
H
+
=
u
|H
+
] =
K
K
|I ]
|IOH]
u
I
.
+
As onfIro I
+
Ions In fho soIufIon Is duo fo comIofo IonIsnfIon of IA nnd IOH Is wonk
H = K
u
K
I
Iog
|I ]
|IOH]
+
= K
u
K
I
Iog
|SnIf]
|Inso]
whoro |SnIf] = |Inso], fhon H = K
u
K
I
.
HIgLIIgLts:
Iuffor soIufIon nImosf InvnrInbIy consIsfs of n mIxfuro of n wonk ncId HA nnd Ifs
snIf IA or n mIxfuro of wonk bnso IOH nnd Ifs snIf IA.
Tho buffor cnncIfy of n soIufIon Is dofInod by JI/J
H
, whoro J
H
Is fho Incronso of
H rosuIfIng from fho nddIfIon of JI of bnso, fho nddIfIon of ncId docronsos fho H
nnd Is oquIvnIonf fo n nognfIvo nmounf of bnso.
Different Buffer SoIutions
ConponenI conjugoIe ociJIose poir pH ronges
(i) CIycIno/CIycIno hydrochIorIdo l.0-3.?
(ii) IhfhnIIc ncId/IofnssIum hydrogon hfhnInfo 2.2-3.38
(iii) AcofIc ncId/SodIum ncofnfo 3.?-5.6
(it) nH
2
IO
4
/ n
2
HIO
4
5.8-8
(t) IorIc ncId/Iornx 6.8-9.2
(ti) H
4
OH/H
4
CI l0
(tii) n
2
HIO
4
/n
3
IO
4
ll-l2
xumpIe 1. Irepore o Iuffer soluIion of pH . [Citen pK
o
CH
3
COOH oI 2 is 4.76].
SoI. H = K
o
+ Iog
|SnIf]
|AcId]
= 4.?6 + Iog
|SnIf]
|AcId]
Iog
|SnIf]
|AcId]
= H 4.?6 = 5.00 4.?6 = 0.24.

|SnIf]
|AcId]
= nnfIIog (0.24) = l.?38
Thoroforo, whon l.?38 g-moIos of CH
3
COOn Is mIxod wIfh l g-moIo of CH
3
COOH nnd
fho voIumo of fho soIufIon Is mndo ufo ono IIfro, fho dosIrod buffor soIufIon of H 5 Is obfnInod.
SoIubiIity Product
Tho Inw of mnss ncfIon cnnnof bo succossfuIIy nIIod fo fho rocoss of oIocfroIyfIc
dIssocInfIon oxcof fo fho cnsos of wonk oIocfroIyfos. Iuf If cnn bo succossfuIIy nIIod fo fho
snfurnfod soIufIons of snrIngIy soIubIo snIfs, bocnuso n hoforogonoous oquIIIbrIum Is sof u ns
foIIows.
IA(s) IA (soIufIon) I
+
+ A
AIyIng Inw of mnss ncfIon,

K =
|I ] |A ]
|IA( )]
+
s
or K|IA(s)] = |I
+
]|A
]
Tho conconfrnfIon of soIId snIf |IA (s)] Is consfnnf. Iy convonfIon If Is unIfy. So
|IA (s)] = l.
Thoroforo, |I
+
] |A
] = consfnnf = K
s
.
Tho consfnnf K
s
Is cnIIod fho soIubIIIfy roducf of fho snIf IA. Tho nbovo oqunfIon
sIgnIfIos fhnf fho roducf of conconfrnfIons of I
+
nnd A
of n snIf Is consfnnf Indoondonf of fho

IndIvIdunI conconfrnfIons of I
+
nnd A
Ions whon fomornfuro Is consfnnf.

If S Is fho soIubIIIfy of IA, fhon |I
+
] = S g.moI l
l
nnd |A
] = S g.moI.l
l
.
K
s
= |I
+
] |A
] = S
2
Ior n snIf IIko I
x
A
,
:
I
x
A
,
(s) I
x
A
,
(SoIufIon) xI
+
+ ,A
If fho soIubIIIfy Is S moI l

l
fhon |I
+
] = xS, |A
] = ,S
K
s

= |I
+
]
x
|A
]
,
= (xS)
x
(,S)
,
= x
x
,
,
.S
x+,
If Is n unIvorsnIIy nIIcnbIo oqunfIon.
HIgLIIgLts:
Whon fho soIubIIIfy of Mg
3
(IO
4
)
2
Is C moI. l
l
Mg
3
(IO
4
)
2
(s) Mg
3
(IO
4
)
2
(SoIufIon) 3Mg
+2
+ 2IO
4
3
Ifs K
s
Is |Mg
+2
]
3
|IO
4
3
]
2
= (3C)
3
(2C)
2
= l08 C
5
.
Tho soIubIIIfy roducf of n snrIngIy soIubIo bInnry oIocfroIyfo Is sImIy fho squnro
of Ifs soIubIIIfy In uro wnfor oxrossod In moI l
l
.
If Is cusfomnry fo oxross fho conconfrnfIons of fho Ions In g. Ion l
l
i.e., formuIn
woIghf or IIfro nnd nof In g. oquIv. or IIfro.
TIe soluIiliI, proJucI of o solI no, Ie JefineJ os IIe greoIesI possiIle proJucI of
concenIroIions of iIs consIiIuenI ions in iIs soIuroIeJ soluIion expresseJ in g.ion l
1
, eocI
concenIroIion Iern Ieing roiseJ Io o pouer represenIing IIe nunIer of gn. ions of eocI I,pe
forneJ I, JissocioIion of one noleculor fornulo ueigII of IIe solI.
xumpIe 1. TIe soluIiliI, of cIoll is 0.030 gl
l
. ColculoIe iIs soluIiliI, proJucI. (nol.
uI. of CoCO
3
= 100)
SoIubIIIfy S = 0.0305 gl
l
= 3.05 l0
4
moI l
l
K
s
= S
2
= (3.05 l0
4
)
2
= 9.3 l0
8
.
xumpIe 2. TIe soluIiliI, of CoI
2
is 0.0002 nol l
1
. ColculoIe K
sp
of CoI
2
.
CnI
2
Cn
+2
+ 2I
ONC EQULBRUM 193
|Cn
+2
] = 0.0002 g Ion l
l
. |I
] = 2 0.0002 g Ion l
l
.
K
s
= |Cn
+2
] |I
]
2
= 0.0002 (0.0004)
2
= 3.2 l0
ll
.
Effect of Common Ion on SoIubiIity
Wo know fhnf, for n snfurnfod soIufIon of n snrIngIy soIubIo snIf IA,
K
s
= |I
+
] |A
]
If wo ndd fo fho soIufIon n subsfnnco, whIch hns nn Ion common fo fho nbovo snIf fhon
conconfrnfIon of fhnf Ion wIII Incronso. As n rosuIf, fho conconfrnfIon of ofhor Ion wIII docronso
ofhorwIso fho consfnnf K
s
wIII chnngo. Thoroforo, I
+
nnd A
wIII combIno fo gIvo fho soIId

IA(s) nnd fho soIubIIIfy of IA wIII docronso.
HIgLIIgLts:
If Is nImosf InvnrInbIy fruo fhnf nddIfIon of n common Ion nf fIrsf dImInIshos fho
soIubIIIfy of n snrIngIy soIubIo snIf buf whon roInfIvoIy Inrgo nmounfs nro nddod
fho soIubIIIfy sfnrfs fo Incronso.
Tho rosonco of n noufrnI snIf wIfhouf n common Ion offon rosuIfs In nn Incronso of
soIubIIIfy of n snrIngIy soIubIo snIf.
xumpIe. 3. (o) AI 2 IIe soluIiliI, of BoSO
4
is 0.00233 gl
. ColculoIe IIe soluIiliI,

proJucI of IIe solI, Ioling conpleIe JissocioIion.
(I) ColculoIe IIe soluIiliI, of BoSO
4
in o soluIion of (AH
4
)
2
SO
4
conIoining 13.2 gl
oI
2C. |Bo = 137]
SoI. (o) |In
++
] = |SO
4
=
] =
0 00233
l3? 96
.
+
= l0
5
g.Ion l
l
K
s

= |In
++
] . |SO
4
=
] = l0
5
l0
5
= l0
l0
.
(I) |(H
4
)
2
SO
4
] =
l3 2
l32
.
= 0.l (M)
|SO
4
=
] = 0.l g.Ion l
l
.
!of, fho chnngod soIubIIIfy of InSO
4
= S.
K
s
= S (S + 0.l) = l0
l0
.
S =
l0
l0
l0
l
|S Is nogIIgIbIo comnrod fo 0.l]

= l0
9
moI. l
l
.
S = 2.33 gl
l
.
xumpIe 4. A liIre of o soluIion conIoins 0.01 nole AH
4
OH onJ 0.001 g.ion Mg
+2
. To
orresI IIe precipiIoIion of Mg(OH)
2
. WIoI uill Ie concenIroIion of AH
4
+
ion fron AH
4
Cl: Citen
K
I AH OH
4
= 1.S 10
onJ K
sp Mg(OH)
2
= 1.12 10
11
.
SoI. Wo know fhnf K
s
= |Mg
+2
] |OH
]
2
= l.l2 l0
ll
|OH
] =
ll2 l0
0 00l
ll
l/ 2
.
.

= l.l l0
4
g.Ion l
l
.
So, |OH
] shouId nof oxcood l.l l0

4
g.Ion l
l
fo nrrosf fho rocIIfnfIon of Mg(OH)
2
.
Ior doIng so, wo nro fo suross fho dIssocInfIon of H
4
OH by nddIng common Ion H
4
+
.
So, K
I
=
|H ] |OH ]
|H OH]
4
4
+
= l.8 l0
5
.
or =
|H ] l.l l0
0.0l
4
4 +

= l.8 l0
5
|H
4
+
] = l.6 l0
3
g.Ion l
l
.
Effect of a SaIt without a Common Ion on SoIubiIity
Ior fho corrocf oxrossIon for soIubIIIfy roducf wo shouId uso ncfIvIfy (o) In Inco of
conconfrnfIon: i.e., K
s
= o o
Ag CI
+ .
So, fruo oxrossIon Is K
s
=
Ag
Ag
+
+
. | ] . |CI ]
CI
whoro = ncfIvIfy cooffIcIonf.
3 ncfIvIfy (o) = ConconfrnfIon (c) ncfIvIfy cooffIcIonf ()
o = c.
Ior n vory dIIufo soIufIon = l fhon o = c.
If wo ndd KO
3
fo n snfurnfod soIufIon of AgCI fho -form of fho oxrossIon of K
s
docronsos. So, |Ag
+
] . |CI
] Incronsos In ordor fo koo fho fruo K

s
vnIuo consfnnf.
Thoroforo, soIubIIIfy of n snrIngIy soIubIo snIf Incronsos on nddIfIon of nny snIf wIfhouf
n common Ion. ThIs offocf Is known ns solI effecI.
HIgLIIgLts:
Mnny rofoIns, whIch nro snrIngIy soIubIo In wnfor, nro soIubIo In snIf soIufIons
duo fo fhIs snIf offocf.
Tho offocf of common Ion on soIubIIIfy Is ufIIIsod In qunIIfnfIvo InorgnnIc nnnIysIs
fo sonrnfo fho Ions rosonf In n soIufIon.
Application of Common Ion Effect and Solubility Product in Qualitative Inorganic
Analysis
General Group Separation of Basic Radicals:
IrecipiIoIion of o solI Ioles ploce uIen iIs ionic proJucI exceeJs iIs soluIiliI, proJucI. A
solI no, noI geI precipiIoIeJ eten uIen iIs ionic proJucI exceeJs iIs soluIiliI, proJucI. 1I no,
renoin in soIuroIeJ soluIion for soneIine. TIoI is uI,, for precipiIoIion in cIenicol onol,sis,
IIe tolue of soluIiliI, proJucI of IIe solI sIoulJ oluo,s Ie IigIer IIon iIs ionic proJucI.
Croup 1. TIe cIloriJes of Croup 1 neIols (Hg
2
+2
, II
+2
, Ag
+
) ore insoluIle, on oJJiIion of
Jil. HCl, ionic proJucI (C
M
+
C
Cl
) eosil, exceeJs IIe soluIiliI, proJucIs onJ IIe coIions ore
precipiIoIeJ. Onl, IICl
2
Ios IigIer soluIiliI, proJucI onJ for IIoI reoson iI is noI conpleIel,
precipiIoIeJ Iere. 1I is olso precipiIoIeJ in Croup 11.
Croup 11. TIe reogenI is H
2
S in presence of Jil. HCl. TIe connon ion H
+
suppresses IIe
ionisoIion of H
2
S. So concenIroIion of sulpIiJe ion C
S
=
renoins lou. TIe neIollic ions (Hg
+2
,
Cu
+2
, II
+2
, Bi
+3
, As
+3
, SI
+3
, Sn
+2
), uIose soluIiliI, proJucI of sulpIiJes ore lou, geI precipiIoIeJ
Iere i.e., JespiIe lou S
=
ion concenIroIion, IIe ionic proJucIs (C
M
+2
C
S
2
) of neIol ions exceeJ
IIe soluIiliI, proJucIs Iecouse of lou tolue of soluIiliI, proJucIs. 111B neIollic ion (Co
+2
, Mn
+2
,
Ai
+2
, Zn
+2
) sulpIiJes Iote IigIer tolues of soluIiliI, proJucIs, so IIeir precipiIoIion is orresIeJ
Iere, CJS onJ IIS Iote conporoIitel, IigIer tolues of soluIiliI, proJucIs, so C
S
=
sIoulJ Ie
IigI for IIen. To increose IIe ionisoIion of H
2
S, lou ociJiI, or IigIer pH is necessor,, Io
reJuce ociJiI, of IIe neJiun uoIer is oJJeJ Io JiluIe IIe neJiun. Agoin JiluIeJ ociJ neJiun
precipiIoIes colloiJol As
2
S
3
onJ SnS uIicI creoIes JifficulI, in filIroIion. So in nore or less
concenIroIeJ ociJ neJiun IIe, (Cr 11) ore precipiIoIeJ onJ filIereJ onJ IIen filIroIe is JiluIeJ
uiII uoIer onJ posseJ H
2
S Io precipiIoIe CJS onJ IIS.
Croup 111 A. Here reogenI is AH
4
Cl/AH
4
OH. TIe connon AH
4
+
suppresses IIe
JissocioIion of ueol Iose AH
4
OH IIereI, C
OH
renoins lou. As o resulI Ie

+3
, Al
+3
, Cr
+3
geI
precipiIoIeJ os I,JroxiJes Iecouse IIeir soluIiliI, proJucIs ore exceeJeJ. TIe precipiIoIion of
ONC EQULBRUM 195
Zn
+2
, Mg
+2
onJ Mn
+2
os I,JroxiJes ore orresIeJ os IIeir soluIiliI, proJucI tolues for I,JroxiJes
ore conporoIitel, IigIer.
Croup 1V. Here reogenIs ore AH
4
Cl, AH
4
OH, onJ (AH
4
)
2
CO
3
.
Croup 1V neIols i.e.,
Bo
+2
, Co
+2
, Sr
+2
ore precipiIoIeJ os corIonoIes.
SOLVED EXAMPLES
xumpIe 1. ColculoIe IIe pH of 0.00M Co(OH)
2
soluIion ossuning conpleIe JissocioIion.
SoI. |OH
] = 2 0.005 = l0
2
moI. l
l
.
OH = 2.
H = l4 2 = l2.
+
], [OH
] onJ pH of o soluIion preporeJ I, JiluIing 20 nl of

0.1 M HCl Io 1 liIre.
SoI. |H
+
] =
20
l000
0.l
= 0.002 = 2 l0
3
moIo l
l
.
H = Iog
l0
|H
+
] = Iog
l0
|2 l0
3
]
= 3 Iog 2 = 3 0.30l0
= 2.6990 ~ 2.?
OH = l4 2.? = ll.3
Iog
l0
|OH] = ll.3
|OH] = l0
ll.3
= 5.0l l0
l2
g.Ion l
l
.
xumpIe 3. ColculoIe IIe pH of (o) 1.0 10
S
(M) HCl soluIion.
(I) 1 10
S
(M) AoOH soluIion.
SoI. (o) Whon fho |H
+
] Is l0
6
or gronfor fho IonIsnfIon of wnfor Is nogIIgIbIo duo fo
common Ion offocf. Iuf whon If oxcoods l0
6
, fho confrIbufIon of H
+
Ions Is fo bo counfod durIng
cnIcuInfIon of H.
!of fho confrIbufIon of |H
+
] from wnfor = x.
So, fho |H
+
] of fho soIufIon = (l l0
8
+ x) nnd |OH
] = x
K
u
= |H
+
] |OH
]
= (l l0
8
+ x) x = l0
l4
.
or x
2
+ l0
8
x l0
l4
= 0
x =
+

l0 l0 4 l l0
2 l
8 8 2 l4
( ) . .
= 9.5 l0
8
(M)
|H
+
] = (l.0 l0
8
+ x) = (l.0 l0
8
+ 9.5 l0
8
)
= l0.5 l0
8
H = Iog
l0
|H
+
] = Iog
l0
(l0.5 l0
8
)
= 8 Iog
l0
l0.5 = 6.98.
(I) Horo Iof fho confrIbufIon of OH
Ions from wnfor bo x.

fofnI |OH
] = (l l0
8
+ x)
So, |H
+
]|OH
] = K
u
= l0
l4
(l l0
8
+ x) x = l0
l4
x
2
l.0 l0
8
x l0
l4
= 0
x = 9.5 l0
8
(M)
|OH
] = 9.5 l0
8
g. Ion l
l
OH = 8 Iog 9.5 = 6.98
H = l4 6.98 = ?.02.
xumpIe 4. (o) ColculoIe IIe nolor concenIroIion of on CH
3
COOH soluIion. (Citen
K
o
= 1.S 10
. = 0.02)
(I) ColculoIe IIe Jegree of JissocioIion of 0.01 (M) AcOH.
SoI. CH
3
COOH H
+
+ CH
3
COO
nf oquIIIbrIum: C(l ) C C
K
o
=
|H ] |CH COO ]
|CH COOH]
+
3
3
=
0.02C 0.2C
C 0.02
0.0004 C
0.98
=

( ) l
c =
l8 l0 0 98
0 004
5
. .
.
moInr

= 0.044 moInr.
(I) =
K
C
o
=

l8 l0
0 0l
5
.
.
= 4.24 l0
2
.
xumpIe 5. A Iuffer soluIion conIoins 0.1 nole CH
3
COOH onJ 0.1 nole of CH
3
COOAo
per liIre. ColculoIe IIe pH of Iuffer soluIion. (pK
o
= 4.74).
SoI. AccordIng fo Hondorson oqunfIon H of n buffor soIufIon
H = K
o
+ Iog
| ]
|ncId]
snIf
= 4.?4 + Iog
0 l
0 l
.
.
= 4.?4.
xumpIe 6. pH of IlooJ is 7.4. ColculoIe IIe roIio of HCO
3
onJ H
2
CO
3
. Citen K
o
of
H
2
CO
3
= 4. 10
7
.
SoI. H
2
CO
3
H
+
+ HCO
3
,
K
o
=
|H ] |HCO ]
|H CO ]
+
3
2 3

|HCO ]
|H CO ] |H ]
.
|H ]
.
.
3
2 3
? ?
8
4 5 l0 4 5 l0
3 98 l0
= =

=

K
o

~_
ll
H = ?.4
Iog
l0
|H
+
] = ?.4 |H
+
] = l0
?.4
= 3.98 l0
8
g.Ion l
l
xumpIe ?. TIe soluIiliI, proJucI of CoI
2
in uoIer oI 1SC is 3.4 10
11
. ColculoIe IIe
soluIiliI, of CoI
2
in uoIer.
SoI. K
sp
= |Cn
+2
] |I
]
2
= |S] |2S]
2
whoro, S = soIubIIIfy.
= 4S
3
ONC EQULBRUM 197
4S
3
= 3.45 l0
ll
S =
3 ll
3 45 l0
4
.

moIo l
l
= 2.05 l0
4
moIo l
l
.
xumpIe B. ColculoIe IIe soluIiliI, SrI
2
in 0.1M AoI soluIion. Citen, K
sp
of SrI
2
=
S 10
12
.
SoI. SrI
2
Sr
+2
+ 2I
S moIo 2S moIo
InIfInIIy = In 0.l M nI SoIufIon = S moIo (2S + 0.l) moI.
K
s

= 8 l0
l0
= |Sr
+2
] |I
]
2
= S (0.l)
2
= 0.0lS
S =
8 l0
0 0l
l0

.
= 8 l0
8
moI l
l
.
Q. 1. GIve un expvessIon Iov tLe IonIsutIon constunt.
Ans. K =
2 2
l
C
C( )
whoro, K = IonIsnfIon consfnnf, = dogroo of dIssocInfIon of n wonk oIocfroIyfo,
C = conconfrnfIon of fho wonk oIocfroIyfo, moI l
l
.
Ior wonk oIocfroIyfos, Is nogIIgIbIy smnII,
So, l l
K =
2
C =
K
C
.
Q. 2. WLut Is tLe AvvLenIus concept oI ucIds und buses?
Ans. An ncId Is n subsfnnco whIch In nquoous soIufIon gIvos H
+
Ions.
A bnso Is n subsfnnco whIch In nquoous soIufIon gIvos OH
Ions.
Thus, HCI Is nn ncId nnd nOH Is n bnso.
Q. 3. WLut Is tLe Iowvy und Bvonsted concept oI ucId und buse?
Ans. An ncId Is n socIos (noufrnI or chnrgod) whIch cnn donnfo n rofon nnd n bnso Is n
subsfnnco or socIos (noufrnI or chnrgod) whIch cnn nccof n rofon.
Thus HCI nnd HSO
4
nro ncIds ns bofh of fhom cnn donnfo n rofon nnd CI
nnd SO
4
=
nnd HSO
4
nro bnsos ns fhoy cnn nccof n rofon.

Q. 4. WLut uve conJugute ucId-buse puIvs?
Ans. Ivory ncId hns n conjugnfo bnso nnd ovory bnso hns n conjugnfo ncId, dIfforIng by
n rofon. ThIs sorf of nIrs nro known ns conjugnfo ncId-bnso nIrs. CI
Is n conjugnfo bnso of
ncId HCI. HSO
4
Is n conjugnfo bnso of H
2
SO
4
.
AgnIn HCI Is fho conjugnfo ncId of CI
nnd H
2
SO
4
Is fho conjugnfo ncId of fho bnso HSO
4
.
Somo conjugnfo ncId-bnso nIrs nro:
HSO
4
/SO
4
=
, HO
3
/O
3
, H
2
O/OH
, H
3
O
+
/H
2
O.
H
4
+
/H
3

nnd so on.
If fho ncId Is sfrong, Ifs conjugnfo bnso wIII bo wonk nnd vIco-vorsn.
Q. 5. SLow tLut soIvent ucts us u buse ov un ucId uccovdIng to Iowvy Bvonsted
concept.
Ans. AccordIng fo !owry Ironsfod concof ncIdbnso roncfIon nIwnys foIIows fho oqunfIon:
AcId
I
+ Inso
II
AcId
II
+ Inso
I
CH
3
COOH + H
2
O H
3
O
+
+ CH
3
COO
HI + CH
3
COOH CH
3
COOH
2
+
+ I
H
2
O + H
2
O H
3
O
+
+ OH
So, ovory ncIdbnso roncfIon rocoods nccordIng fo fho oqunfIon i.e., conjugnfo ncIds nnd
bnsos nro formod durIng fho roncfIon,
AcId
I
+ Inso
II
AcId
II
+ Inso
I
Q. 6. GIve IewIs concept oI ucIds und buses.
Ans. An ncId Is n socIos whIch cnn nccof n nIr of oIocfrons nnd n bnso Is n socIos
whIch cnn donnfo n nIr of oIocfrons.
H O H
+
:
. .
. .
- -
H
H
H
H :
..
..
:
+

ncId

bnso
bnso
ncId
CI
CI

I

CI
H

H

H
ncId bnso
:
Q. ?. SLow tLut IonIc pvoduct oI wutev (K
u
) Is 1 10
14
, gIven K Iov wutev =
1.B 10
16
.
Ans. H
2
O + H
2
O H
3
O
+
+ OH
or H
2
O H
+
+ OH
K =
|H O ] |OH ]
|H O]
3
2
+
or
|H ] |OH ]
|H O]
+
2
|H
2
O] =
l000
l8
= 55.5555 moIos I
l
.
K
u
= K |H
2
O] = |H
+
] |OH
] = l.8 l0
l6
55.5555
= l00 l0
l6
= l.00 l0
l4
.
Q. B. In puve wutev, wLut wIII be tLe ]H
+
] ov ]OH
]?
Ans. As, |H
+
] |OH
] = l0
l4
nnd In uro wnfor, |H
+
] = |OH
]
|H
+
] = |OH
] = l0
?
g.Ion l
l
.
ONC EQULBRUM 199
Q. 9. WLut Is pH?
Ans. If Is nognfIvo IognrIfhm of hydrogon Ion conconfrnfIon, i.e.,
H = Iog
l0
|H
+
] or |H
+
] = l0
H
Tho ncIdIfy or nIknIInIfy of n soIufIon Is gonornIIy oxrossod by H.
Q. 10. xpIuIn tLe pH scuIe.
Ans. Tho H scnIo Is n IognrIfhmIc scnIo for monsurIng fho conconfrnfIon of hydrogon
Ions In nquoous soIufIons.
In ncIdIc soIufIons, |H
+
] rnngo = l0
0
l0
6
g . Ion l
l
In noufrnI soIufIons, |H
+
] = |OH
] = l0
?
g . Ion l
l
.
In nIknIIno soIufIons, |H
+
] rnngo = l0
8
l0
l4
g . Ion l
l
.
H = Iog
l0
|H
+
]
pH = 0 l 2 3 4 5 6 ? 8 9 l0 ll l2 l3 l4
[H
+
] = l0
0
l0
l
l0
2
l0
3
l0
4
l0
5
l0
6
l0
?
l0
8
l0
9
l0
l0
l0
ll
l0
l2
l0
l3
l0
l4
ncIdIc noufrnI nIknIIno
Q. 11. WLut Is tLe pH oI 0.02 moI dm
3
HCI?
Ans. H = Iog
l0
|H
+
]
= Iog
l0
|2 l0
2
] (ns fho ncId Is sfrong)
= Iog
l0
2 + 2 Iog
l0
l0
= 2 0.30l0 = l.699 l.?.
Q. 12. WLut Is tLe Lydvogen concentvutIon oI cocu coIu wItL pH 2.3??
Ans. H = 2.3
or Iog
l0
|H
+
] = 2.3
or Iog
l0
|H
+
] = 2.3
or |H
+
] = l0
2.3
= 5 l0
3
moI dm
3
.
Q. 13. xpIuIn tLe pH cLunges duvIng ucIdbuse tItvutIon.
Ans. AddIfIon of nn nIknII from n buroffo fo 25 mI of nn ncId In n conIcnI fInsk nnd
IoffIng n grnh gIvo n shno doformInod by fho nnfuro of fho ncId nnd fho bnso.
0
0
25
pH 7
Methyl
orange
0
0
25
pH 7
Phenolphthalein
Alkali(c.c.) Alkali(c.c.)
Strong acidstrong base Weak acidstrong base
Fig. 8.1 Neutralisation Curves.
Tho grnhs show fho H rnngo for fho coIour chnngo of nn ncId/bnso IndIcnfor for dofocfIng
fho ond oInf of fho fIfrnfIon.
Tho IndIcnfor choson fo dofocf fho ond oInf musf chnngo coIour comIofoIy In fho H
rnngo of fho nonr vorfIcnI nrf of fho curvo (IIg. 8.l). If Is fo bo nofod fhnf, nf fho oquIvnIonco
oInf, whon oxncfIy oqunI nmounfs of ncId nnd nIknII hnvo boon nddod, fho H Is nof nIwnys
noufrnI.
Q. 14. NeutvuIIsutIon veuctIons do not uIwuys pvoduce neutvuI soIutIonsexpIuIn.
Ans. Af fho oquIvnIonco oInf, n snIf Is formod; If ncId nnd bnso bofh nro sfrong, hydroIysIs
of snIfs doos nof fnko Inco nnd fho soIufIons romnIn noufrnI nf fho oquIvnIonco oInf
(H = ?). Whon n snIf formod nf fho oquIvnIonco oInf hns oIfhor n 'nronf ncId` or n 'nronf
bnso` wonk, If hydroIysos fo gIvo n soIufIon fhnf Is nof noufrnI. Tho 'sfrong nronf` In fho
nrfnorshI wIns.
Wonk ncId/sfrong bnso ond oInf Is nIknIIno (H > ?)
Sfrong ncId/wonk bnso ond oInf Is ncIdIc (H < ?).
Q. 15. NeutvuIIsutIon Is essentIuIIy u veuctIon between H
+
und OH
Ions In
uqueous soIutIonexpIuIn.
Ans. H
3
O
+
+ OH
2H
2
O (l)
InfhnIy chnngo of noufrnIIsnfIon Is snmo for nII ncId-bnso nrfnors, sfrong or wonk.
ThIs oxorImonfnI ovIdonco suorfs fho nbovo vIow.
Q. 16. WLut Is pK?
Ans. K Is fho IognrIfhmIc form of nn oquIIIbrIum consfnnf, usofuI for H cnIcuInfIons.
Iog
l0
K
o
= K
o
, Iog
l0
K
I
= K
I
, Iog
l0
K
u
= K
u
TnkIng IognrIfhms roducos n convonIonf smnII scnIo of vnIuos.
Q. 1?. How cun you use pK vuIues Iov pH cuIcuIutIons?
Ans. Wo know fhnf,
(i) K
u
= H + OH = l4
H = l4 OH
(ii) H of n wonk ncId = H =
l
2
l
2
K
o
c Iog
whon K
o
= IonIsnfIon consfnnf of wonk ncId.
c = conconfrnfIon of undIssocInfod ncId.
(iii) H of n wonk bnso = l4
l
2
l
2
K
I
c + Iog
whoro c = conconfrnfIon of undIssocInfod bnso.
K
I
= dIssocInfIon consfnnf of wonk bnso.
Q. 1B. WLut Is tLe pH oI u 0.02 moI. dm
3
soIutIon oI NuOH?
Ans. nOH Is n sfrong bnso
|OH
] = 0.02 moIo dm
3
OH = Iog 0.02 = l.?
H = l4 OH = l4 l.? = l2.3.
ONC EQULBRUM 201
Q. 19. H
3
PO
4
Lus tLvee K
u
vuIuesexpIuIn.
Ans. Thoro nro fhroo dIssocInfIons for H
3
IO
4
nnd nccordIngIy l
o
vnIuos.
(i) H
3
IO
4
H
+
+ H
2
IO
4
; K
o
l
=
|H ] |H IO ]
|H IO ]
+
2 4
3 4
(ii) H
2
IO
4

H
+
+ HIO
4
2
; K
o
2
=
|H ] |H IO ]
|H IO ]
+
2 4
2
3 4
(iii) HIO
4
2
H
+
+ IO
4
3
;
K
o
3
=
|H ] |IO ]
|HIO ]
+
4
3
4
2
K
o
l
>
K
o
2
> K
o
3
.
Q. 20. ReIute K
u
, K
b
und K
u
.
Ans. (i)
HA + H O
2
H O
3
+ A
acid base
Conjugate pair
K
o
=
|H O ] |A ]
|HA]
3
+
(ii) A
2
+ H O HA + OH
Conjugate pair
K
I
=
|HA] |OH ]
|A ]
ow, K
o
K
I
=
|H O ] |A ]
|HA]
3
+

|HA] |OH ]
|A ]
= |H
3
O
+
] |OH
]
= K
u
= l0
l4
.
K
o
K
I
= K
u
or Iog K
o
Iog K
I
= Iog K
u
K
o
+ K
I
= K
u
= l4.
Q. 21. MentIon tLe Impovtunce oI pH.
Ans. (i) Tho H vnIuo of soII hoIs fo docIdo fho fyo of forfIIIsor fo bo usod In ngrIcuIfuro.
(ii) A smnII vnrInfIon of H of humnn bIood (6.?) cnusos bodyncho.
(iii) H vnIuo hoIs fo doformIno fho condIfIon of roncfIons In Inbornfory nnd In Indusfry.
Q. 22. WLut Is common Ion eIIect?
Ans. Tho chnngo In oquIIIbrIum osIfIon duo fo nddIfIon of nn IonIc comound fhnf
confnIns ono of fho Ions InvoIvod In fho oquIIIbrIum Is known ns common Ion offocf.
(i) Tho common Ion offocf cnn chnngo fho IonIsnfIon of wonk ncIds nnd wonk bnsos.
(ii) Tho common Ion offocf InfIuoncos fho bohnvIour of buffor soIufIon.
(iii) Tho common Ion offocf nIfors fho soIubIIIfy of n snrIngIy soIubIo snIf.
Q. 23. WLut Is u buIIev soIutIon?
Ans. Iuffor soIufIons nro mIxfuros of n wonk ncId nnd Ifs snIf or n wonk bnso nnd Ifs
snIf, whIch hoI fo koo H of n soIufIon moro or Ioss consfnnf.
Q. 24. WLut Is tLe pH oI u buIIev soIutIon contuInIng 0.4 moI dm
3
metLunoIc
ucId und 1.0 moI dm
3
sodIum metLunoute? pK
u
(HCOOH) = 3.B.
Ans. H = K
o
+ Iog
l00
0 40
.
.
= 3.8 + 0.4 = 4.2.
Q. 25. WIII
N
10
Mn
+2
contuInIng
N
100
H
+
be pvecIpItuted by pussIng H
2
S?
Ans. H
2
S 2H
+
+ S
2
; K =
|H ] |S ]
|H S]
2
+ 2
= l.l l0
22
l.l l0
22
=
(0.0l) |S ]
|H S]
(0.0l) |S ]
0.l
2 2
2
2
=

| S 0.lM]
H S
2
3 =
|S
2
] = l0
l9
. |Mn
+2
] |S
2
] = 0.l l0
l9
= l0
20
K
s
. (MnS) = l.4 l0
l5
So, f. wIII nof bo obfnInod.
EXERCISES
1. oduco OsfwnId`s dIIufIon Inw nnd sfnfo Ifs IImIfnfIons.
2. oduco fho roInfIon bofwoon soIubIIIfy nnd soIubIIIfy roducf of CnI
2
nf room fomornfuro.
3. IxInIn fho forms: (i) Iuffor soIufIon (ii) Iuffor cnncIfy nnd (iii) Iuffor ncfIon.
4. IxInIn fho foIIowIngAquoous soIufIon of nCI conducfs oIocfrIcIfy whIIo chIorIno wnfor doos
nof conducf oIocfrIcIfy.
5. WhIch nro fho sfrongosf !owIs ncIds In fho sorIos (o) II
3
, ICI
3
, II
3
; (I) IoCI
2
, ICI
3
.
6. TrIcovnIonf hoshorus comounds cnn sorvo ns !owIs bnsos nnd nIso ns !owIs ncIdscommonf.
?. Tho roncfIon HCI (oq) + KOH (oq) KCI (oq) + H
2
O Is noufrnIIsnfIon nccordIng fo:
(o) Ironsfod-!owry concof, (I) !owIs fhoory nnd (c) SoIvonf sysfom concof. IIucIdnfo.
B. oduco fho Hondorson oqunfIon nnd sfnfo Ifs ufIIIfy.
9. Whnf do you monn by common-Ion offocf How Is If ufIIIzod In qunIIfnfIvo chomIcnI nnnIysIs
10. Whnf do you monn by nuforofoIysIs of wnfor
11. orIvo nn oxrossIon for IonIc roducf of wnfor. Show fhnf If Is dIfforonf from dIssocInfIon con-
sfnnf of wnfor.
12. CIvo fho Ironsfod-!owry concof of ncIds nnd bnsos.
13. Whnf Is fho bnsIc oqunfIon for ncId-bnso roncfIon of Ironsfod fhoory
14. IxInIn (o) noufrnIIsnfIon, (I) hydroIysIs, In fho IIghf of Ironsfod fhoory.
15. Whnf Is n buffor soIufIon IxInIn buffor ncfIon.
16. orIvo nn oxrossIon for H of fho buffor soIufIons:
(o) Wonk ncId nnd Ifs snIf.
(I) Wonk bnso nnd Ifs snIf.
1?. Whnf Is H CIvo Ifs Imorfnnco nnd usofuInoss.
1B. Whnf do you monn by soIubIIIfy roducf Whnf Is fruo soIubIIIfy roducf
19. CIvo nn oxrossIon for fho soIubIIIfy roducf of fho snIf A
x
I
,
.
20. Iscuss fho offocf of common Ion on soIubIIIfy roducf.
ONC EQULBRUM 203
21. Whnf wIII bo fho H of n soIufIon obfnInod by mIxIng 800 mI of 0.05 () nOH nnd 200 mI of l
HCI |Ans. l2.3]
22. CnIcuInfo fho H nnd OH of .l HCI. |Ans. l, l3]
23. IInd for H
4
OH In n soIufIon of .lM. CIvon K
I
= 2 l0
5
. |Ans. .0l4]
24. Whnf wIII bo fho H of n soIufIon obfnInod by mIxIng 5g. of CH
3
COOH nnd ?.5 g. of CH
3
COOn,
mnkIng n voIumo oqunI fo 500 mI |Ans. 4.?8]
25. H of n soIufIon Is l0.5?. CnIcuInfo fho |H
+
]. |Ans. 2.69 l0
ll
moIos l
l
]
26. CnIcuInfo fho H nnd OH of:
(o) 0.00345 () ncId (I) 0.000??5 () ncId
(c) 0.00886 () bnso |Ans. (o) 2.46, ll.54 (I) 3.ll, l0.89 (c) ll.95, 2.05]
nssumIng comIofo dIssocInfIon.
2?. SoIubIIIfy of IbSO
4
Is 0.038 g-l
l
. CnIcuInfo Ifs soIubIIIfy roducf. |Ans. l.6 l0
8
]
2B. SoIubIIIfy of Ag
2
CrO
9
g-l
l
. CnIcuInfo Ifs soIubIIIfy roducf. |Ans. l.4 l0
l2
}
29. |Ag
+
] In n soIufIon Is 4 l0
3
g-In l
l
. CnIcuInfo fho mInImum conconfrnfIon of CI
fo rocIIfnfo
AgCI. CIvon K
s
of AgCI = l.8 l0
l0
. |Ans. 5 l0
8
g-In l
l
]
30. CnIcuInfo fho conconfrnfIon of H
2
S roquIrod fo nrrosf fho rocIIfnfIon of IbS from n soIufIon of
0.00l (M) Ib(O
3
)
2
. CIvon K
o
(H
2
S) = l.l l0
23
, K
s
(IbS) = 3.4 l0
28
. |Ans. 5.6 (M)]
204
'
EIectrochemistry
INTRODUCTION
Subsfnncos bohnvo dIfforonfIy fownrds oIocfrIc curronf. Somo conducf If nnd somo do
nof. Subsfnncos whIch conducf oIocfrIcIfy nro conductovs, ns for oxnmIo, mofnIs, ncIds, bnsos
ofc. nnd whIch do nof conducf oIocfrIcIfy nro nonconductovs ns for oxnmIo, wood, nsbosfos
ofc. AgnIn conducfors cnn bo dIvIdod Info fwo subdIvIsIons: (i) eIectvoIytes nnd (ii) non-
eIectvoIytes. IIocfroIyfos dIssocInfo whon fhoy conducf oIocfrIcIfy i.e., n chomIcnI chnngo occurs
fhon, whorons whon non-oIocfroIyfos conducf oIocfrIcIfy fhoro Is no such chomIcnI chnngo.
Subsfnncos whIch conducf oIocfrIcIfy nnd gof dIssocInfod In soIufIon or In fho fusod sfnfos woro
formod oIocfroIyfos by Inrndny. SnIfs, ncIds, nIknIIos nro oxnmIos of such oIocfroIyfos.
TabIe 9.1: Comparison
MeIollic conJucIore Aon-neIollic conJucIore (elecIrol,Iee)
IIow of oIocfrons fnkos Inco durIng fho IIow of Ions fnkos Inco durIng fho nssngo
nssngo of oIocfrIcIfy fhrough fhom. of oIocfrIcIfy fhrough fhom.
If InvoIvos no chomIcnI chnngo durIng ChomIcnI chnngo fnkos Inco i.e., now ro-
conducfIon of curronf. Iuf somo hysIcnI ducfs nro obfnInod durIng conducfIon of
chnngos mny occur. curronf.
EIectroIysis
IssocInfIon of n comound by nssIng oIocfrIc curronf fhrough n comound In soIufIon
or In fusod sfnfo Is known ns eIectvoIysIs. An nrrnngomonf for oIocfroIysIs Is shown In IIg. 9.l.
Tho curronf Is nIwnys nssod Info nnd ouf of fho oIocfroIyfo by monns of mofnI foIIs or Infos
+
Battery
Cathode
Voltameter
+

Anode
Electrolyte
Fig. 9.1 Set-up for electrolysis.
ELECTROCHEMlSTRY 205
kof Immorsod In If. Thoy nro oIocfrodos (cnfhodo nnd nnodo). An Ion Is un utom ov u gvoup
oI utoms cuvvyIng posItIve ov negutIve cLuvge oI eIectvIcIty. Whon nn oIocfroIyfo
(oIocfrIcnIIy noufrnI) Is dIssoIvod In wnfor (or In fusod sfnfo), If bronks u Info fwo or moro Ions
of fwo dIfforonf kInds, osIfIvo nnd nognfIvo, fho nmounf of osIfIvo chnrgo boIng oxncfIy oqunI
fo fho nmounf of nognfIvo chnrgo. Tho Ions roducod oxIsf In oquIIIbrIum wIfh fho undIssocInfod
oIocfroIyfo moIocuIos.
nCI n
+
+ CI
, nOH n
+
+ OH
ofc.
Such n dIssocInfIon of nn oIocfroIyfo Is cnIIod IonIc ov eIectvoIytIc dIssocIutIon. ThIs
dIssocInfIon Is comIofo nf InfInIfo dIIufIon. If Is fho Ions, nof fho undIssocInfod moIocuIo,
whIch conducf oIocfrIcIfy. Tho nnIons mIgrnfo fownrds fho nnodo nnd cnfIons mIgrnfo fownrds
fho cnfhodo. Tho IIbornfIon of fho Ions nf fho oIocfrodos doonds uon fhoIr dIscLuvge
potentIuIs. ThIs fhoory of oIocfroIyfIc dIssocInfIon wns fIrsf uf forwnrd by ArrhonIus, fhnf Is
why fho fhoory Is known ns AvvLenIus IonIc tLeovy.
Faraday's Laws of EIectroIysis
IIvst Iuw: TIe noee of on ion liIeroIeJ Juring elecIrol,eie ie JirecIl, proporIionol Io IIe
quonIiI, of elecIriciI, uIicI Ioe poeeeJ IIrougI IIe elecIrol,Ie.
If W = fho mnss of Ion IIbornfod In gms,
c = fho curronf sfrongfh In nmoros,
I = fho fImo In socs,
Q = fho qunnfIfy of oIocfrIcIfy In couIombs,
fhon nccordIng fo fIrsf Inw:
W Q buf Q = c I
W cI
W = ZcI whoro Z Is n consfnnf.
Whon Q = l i.e., c = l nnd I = l, W = Z
i.e,. Z Is muss oI Ion IIbevuted by unIt quuntIty oI eIectvIcIty. Z Is cuIIed eIectvocLemIcuI
equIvuIent (.C..).
Second Iuw: WIen IIe eone quonIiI, of elecIriciI, ie poeeeJ IIrougI JifferenI elecIrol,Iee,
IIe reloIite noeeee of ione liIeroIeJ ore proporIionol Io IIeir cIenicol equitolenIe.
1 2 3
+ + +
+
H O + Acid
2
CuSO solution
4
AgNO solution
3
Fig. 9.2 Different voltameters containing different electrolytes.
206 ENGlNEERlNG CHEMlSTRY
Thnf Is fo sny, whon l g of H
2
Is IIbornfod In coII (l), 63.5/2 g Cu wIII bo IIbornfod In
coII (2) nnd l08 g Ag wIII bo IIbornfod In coII (3) (IIg. 9.2).
!of, fho qunnfIfy of oIocfrIcIfy = Q couIomb
fho qunnfIfy of Cu doosIfod = W
l
g
fho qunnfIfy of Ag doosIfod = W
2
g
Thon, nccordIng fo Inrndny`s socond Inw:

W
W
I
I
Z Q
Z Q
l
2
l
2
l
2
= =
(from fho fIrsf Inw)

I
I
Z
Z
l
2
l
2
= or
I
Z
I
Z
l
l
2
2
= or I Z
So chomIcnI oquIvnIonf of nn oIomonf Is roorfIonnI fo Ifs oIocfrochomIcnI oquIvnIonf.
If ono of fho oIomonfs Is H, fhon,

I
I
Z
Z
H H
= or Z =
I Z
I
H
H
ChomIcnI oquIvnIonf of hydrogon = I

H
, chomIcnI oquIvnIonf of nny oIomonf = I
I.C.I. of hydrogon = Z
H
, I.C.I. of nny oIomonf = Z
Z =
I Z
l.008
I Z
l
H H

So, I.C.I. of nny oIomonf = ChomIcnI oquIvnIonf of fho oIomonf I.C.I. of hydrogon.
Combination of First and Second Laws of Faraday
Irom fIrsf Inw, W Q (whoro I Is consfnnf)
Irom socond Inw, W I (whoro Q Is consfnnf)
W = KQI (whoro I nnd Q vnry)
or Q =
W
KI
(K = Consfnnf)
Whon W = I, Q =
l
K
Thoroforo, fo IIbornfo l gm oquIv. of nny oIomonf durIng oIocfroIysIs, fho qunnfIfy of
oIocfrIcIfy Is fIxod. ThIs qunnfIfy of oIocfrIcIfy Is cnIIod ono fnrndny (I).
I = Q =
l
K
(for l gm. oquIv.)
W = KQI =
QI
I
Irom fIrsf Inw, W = ZQ
or I = ZQ (for l gm. oquIv.)
= ZI
or I =
I
Z
for ono gm oquIvnIonf of dIfforonf oIomonfs
I
Z
I
Z
I
Z
l
l
2
2
= = = ......
n
n
= I
Thoroforo, wo cnn nccof fhnf, l I = 96500 couIomb.
TubIe 9.2: IsInyIng fho consfnncy of I/Z for dIfforonf oIomonfs
1lenenI 1 Z I = 1/Z (CoulonI)
H l.008 0.0000l04 96496
Ag l0?.88 0.000lll8 96495
Cu 3l.?8 0.0003294 96494
96495
O 8.0 0.0000829 96500
TLe concept oI tvunspovt numbev. Ions of nn oIocfroIyfo i.e., cnfIons nnd nnIons
rosonf In fho soIufIon conducf curronf. If l00 cnfIons cross fho bnrrIor from Ioff fo rIghf, fhon
curronf Is whoIIy cnrrIod by cnfIon. Wo cnn sny fhnf fho cnfIon frnnsorf numbor Is hundrod
or conf nnd fho nnIon frnnsorf numbor Is zoro or conf. Tho cnso mny bo fofnIIy rovorsod,
In fhnf cnso, fho frnnsorf numbor of nnIons Is hundrod or conf nnd fhnf of cnfIons Is zoro
or conf. If Is fo bo nofod fhnf doosIfIon nf fho oIocfrodos In fho nbovo fwo cnsos wIII bo snmo
(IIg. 9.3).
A
N
O
D
E
C
A
T
H
O
D
E
a
b
Fig. 9.3 Concept of transport number.
!sunIIy bofh cnfIons nnd nnIons cross fho bnrrIor (oI) buf In unoqunI numbors owIng fo
fhoIr unoqunI soods; so fhoIr frnnsorf numbors nro unoqunI. Ior oxnmIo, If 80 cnfIons cross
fho bnrrIor (oI) fownrds cnfhodo comnrfmonf nnd 20 nnIons cross fho bnrrIor (oI) fownrds
nnodo comnrfmonf, fho fofnI qunnfIfy of fho curronf nssod wIII romnIn snmo ns nbovo i.e.,
l00 unIfs buf fho curronf cnrrIod by cnfIons Is 80 or conf nnd fho curronf cnrrIod by nnIons Is
20 or conf. So wo cnn dofIno tvunspovt numbev ns fho frncfIon of fho curronf cnrrIod by nn
Ion. So, frnnsorf numbor (I) =
n
n
i i
i i
Z
Z
whoro, n
i
= numbor of fho Ions nnd Z
i
= vnIoncy of fho Ions whIch cross fho bnrrIor.
Trnnsorf numbor Is roorfIonnI fo soods of fho Ions.
So, I
+
u nnd I

t nnd (I
+
+ I
) (u + t)
Iuf I
+
+ I
= l
I
+
=
u
u t +
nnd I
=
t
u t +
whoro u nnd t nro fho soods of cnfIons nnd nnIons rosocfIvoIy.
Tvunspovt numbev ov tvunsIevence numbev oI un Ion Is dependent on tLe speed
oI tLe Ions.
!of fho fwo oIocfrodos, A nnd I, nro kof InsIdo nn oIocfroIyfo nnd fhoIr ofonfInI
dIfforonco Is I. Tho curronf I Is fIowIng, fho soIufIon confnIns n() numbor of Ions or mIIIIIIfro
+
+
+
v
u
+
A B
Fig 9.4 Voltameter.

nnd fho vnIoncy of Ions Is c(+). Tho numbor of Ions IIbornfod nf fho osIfIvo nnd nognfIvo
oIocfrodos or unIf nron nro gIvon by n
+
u nnd n
t. If unIf of fho chnrgo Is 'e` (IIg. 9.4)

Curronf cnrrIod by fho osIfIvo Ions = I
+
= (n
+
u)c
+
e
Curronf cnrrIod by fho nognfIvo Ions = I
= (n
t)c
e.
Tho fofnI curronf cnrrIod by fho osIfIvo nnd nognfIvo Ions = I = I
+
+ I
= (n
+
u)c
+
e + (n
t)c
e.
As ovory nrf of fho oIocfroIyfo Is oIocfrIcnIIy noufrnI, fhoroforo, n
+
c
+
= n
So, I
+
=
I
I
+ + +
+ + + +
+ +
+ +
=
+
=
+
=
+
n c eu
n c eu n c et
n c eu
n c e u t
u
u t ( )
SImIInrIy, I
=
I
I

+ + + +
+ +
+ +
=
+
=
+
=
+
n c et
n c eu n c et
n c et
n c e u t
t
u t ( )
I
+
=
u
u t +
nnd I
=
t
u t +
If Is obvIous fhnf, I
+
+ I
= l
or I
+
= l I
ReIative Speeds of Ions During EIectroIysis (Transport Number)

If hns boon nofod fhnf fho Ions nro IIbornfod In oquIvnIonf nmounfs nf fho fwo oIocfrodos,
fhIs honomonon cronfos nn Idon fhnf orhns fho Ions movo nf fho snmo rnfo durIng oIocfroIysIs,
buf If Is nof so, Ions nro nIwnys dIschnrgod In oquIvnIonf nmounfs buf fhoIr soods nro dIfforonf.
Tho foIIowIng modoI wIII mnko fho Idon cIonr (IIg. 9.5).
+ + + + + +

+ + + +

+ + + +

+ + + + + +

+ + + +

+ + + +

+ + + + + +

+ +

+ + + + + +

+ + + + + +

+ +

+ + + + + +

+
I
II
III
IV
a o
Anode
compartment
Middle
compartment
Cathode
compartment
Fig. 9.5 Scheme showing the equivalence of discharge for any
relative rate of motion of the two ions.
Tho '+` sIgn rorosonfs n cnfIon nnd '` sIgn rorosonfs nn nnIon. !of fhoro bo fofnI l4
moIocuIos In fho oIocfroIyfo.
(i) 4 moIocuIos onch In fho nnodo nnd cnfhodo comnrfmonfs nnd 6 moIocuIos In fho
mIddIo comnrfmonf.
(ii) WLen onIy tLe unIons move. !of fwo nnIons hnvo crossod dInhrngm fownrds fho
nnodo, wo gof fho Icfuro (II). Tho cnfIons dId nof movo nf nII. Tho conconfrnfIon In
fho nnodo comnrfmonf hns nof nIforod whIIo fho conconfrnfIon of fho cnfhodo com-
nrfmonf hns fnIIon by fwo moIocuIos duo fo doosIfIon of Ions nf fho rosocfIvo
oIocfrodo.
(iii) WLen tLe unIons und cutIons move ut tLe sume vute. !of fwo cnfIons nnd fwo
nnIons hnvo crossod fho dInhrngms fownrds cnfhodo nnd nnodo, wo gof fho Icfuro
(III). In fhIs cnso nIso, fho numbor of nnIons nnd cnfIons dIschnrgod Is fho snmo i.e.,
four, buf fho conconfrnfIon of bofh fho comnrfmonfs hns fnIIon fo fho snmo oxfonf
i.e., by fwo moIocuIos duo fo doosIfIon of Ions nf fho rosocfIvo oIocfrodos.
(it) WLen tLe Ions move ut tLe dIIIevent speeds. !of whon fwo cnfIons hnvo crossod
fho dInhrngm fownrds fho cnfhodo, ono nnIon nssos fownrds nnodo. Wo gof fho
Icfuro (IV). Tho fofnI numbor of cnfIons nnd nnIons dIschnrgod Is ngnIn fho snmo
fhroo. AIfhough conconfrnfIon In fho cnfhodo comnrfmonf hns fnIIon by ono moI-
ocuIo nnd fhnf of nnodo comnrfmonf hns fnIIon by fwo moIocuIos.
1I ie etiJenI fron IIe oIote Jiecueeion IIoI IIe foll of concenIroIion orounJ on elecIroJe
ie proporIionol Io IIe epeeJ of IIe ione noting ouo, fron iI.
InII round nnodo
InII round cnfhodo
Sood of cnfIon
Sood of nnIon
= =
u
t
=
umbor of oquIvnIonco of oIocfroIyfo Iosf fromnnodo comnrfmonf
umbor of oquIvnIonco of oIocfroIyfo Iosf from cnfhodo comnrfmonf
X
M
Y
R
+
A
B
e
Fig. 9.6. Transference number
determination by Hittorf's method.
Tho fofnI gm. oquIvnIonco IIbornfod from bofh fho comnrfmonfs Is roorfIonnI fo (u + t).
So, I
+
=
Tho numbor of oIocfroIyfos Iosf from nnodo comnrfmonf
TofnI numbor of oquIvnIonco of fho oIocfroIyfo IIbornfod on fho oIocfrodo
I
=
Tho numbor of oIocfroIyfos Iosf from cnfhodo comnrfmonf
TofnI numbor of oquIvnIonco of fho oIocfroIyfo IIbornfod on fho oIocfrodo
.
Determination of Transport Number (Hittorf's Method)
Two brond vorfIcnI gInss fubos A, I nro connocfod In
fho mIddIo by n '!` fubo 'e`. Tho fhroo fubos nro fIffod wIfh
sfococks. Tho fubos nro fIffod wIfh sIIvor Infos whIch ncf ns
nnodo nnd cnfhodo whIch nro Infroducod Info A nnd I. A dIIufo
AgO
3
soIufIon (/20) Is fnkon for oIocfroIysIs. A curronf 0.0l
fo .02 nm. Is nssod for n orIod of 23 hours fhrough fho
AgO
3
soIufIon. A mIIIInmmofor M, couIomofor X nro
connocfod In sorIos. Affor n dofInIfo fImo, fho curronf Is
sfood. Tho soIufIon from fho nnodo comnrfmonf Is fnkon
for nnnIysIs (IIg. 9.6).
!of,
Tho soIufIon coIIocfod from nnodo (nnoIyfo) = x g
Tho nmounf of AgO
3
In x g nnoIyfo = , g
Tho nmounf of wnfor confnInIng
, g . AgO
3
= (x ,) g
AgO
3
rosonf In (x ,) g of wnfor
boforo oIocfroIysIs = c g.
WoIghf of sIIvor doosIfod on cnfhodo In fho couIomofor = u g.
Tho Incronso In woIghf of AgO
3
In nnodo comnrfmonf duo fo dIssoIufIon of sIIvor from
fho nnodo =
u l?0
l08
= Wg.
If no mIgrnfIon wouId hnvo fnkon Inco, fho fofnI woIghf of AgO
3
shouId hnvo boon
rosonf (x ,) g of wnfor In fho nnodo comnrfmonf = (W + c) g.
AcfunI woIghf of AgO
3
rosonf = , g
so, Ioss duo fo mIgrnfIon, = (W + Z) , = {W (, Z)}g.
I
Ag
+ =
o. of oquIv. of AgO Iosf fromnnodo comnrfmonf duo fo mIgrnfIon
o. of oquIv. of sIIvor doosIfod In fho couIomofor
3
I
Ag
+ =
W ( Z) l08
l?0
,
u
I
O
3
= l I
Ag
+
HIgLIIgLt:
AbnovmuI tvunspovt numbev: fho frnnsorf numbor of Cd
+
Ion Is normnI In CdI
2
soIufIon buf If docronsos nbnormnIIy wIfh Incronso In conconfrnfIon of CdI
2
.
ConcenIroIion (A) 0.0l 0.02 0.05 0.l0 0.20 0.50
I
CJ
+ 2 0.444 0.442 0.396 0.296 0.l2? 0.003
If Is obvIous fhnf Cd
+2
Is movIng fownrds nnodo In Inrgor nmounfs fhnn fho
cnfhodo nnd fhnf Is fho cnuso of docronso of I
Cd
+2
. If cnn onIy bo oxInInod by fho
formnfIon of comIox Ions.
!of, CdI
2
IonIsos ns foIIows In n conconfrnfod soIufIon:
2CdI
2
Cd
+2
+ |CdI
4
]
2
i.e., Cd
+2
Ion Is movIng fownrds bofh cnfhodo nnd nnodo nnd fownrds nnodo duo fo
nbovo comIox Ion formnfIon. ThIs nbnormnI frnnsorf numbor doos IndIcnfo fho
formnfIon of comIox Ion. ThIs Is fruo for ofhor comIox comounds foo.
xumpIe 1. In nn oIocfroIysIs of CuSO
4
bofwoon coor oIocfrodos fho fofnI mnss of
coor doosIfod nf cnfhodo wns 0.l53 g nnd mnssos of Cu or unIf voIumo of fho nnodo IIquId
boforo nnd nffor oIocfroIysIs woro 0.?9 nnd 0.9l g rosocfIvoIy. CnIcuInfo fho frnnsorf numbor
of fho Cu
++
nnd SO
4

Ions.
Ioforo oIocfroIysIs fho nmf. of Cu
+2
In fho IIquId or unIf voI. surroundIng nnodo = 0.?9 g.
Affor oIocfroIysIs fho nmf. of Cu
+2
In fho IIquId or unIf voI. surroundIng nnodo = 0.9l g.
Incronso In wf. duo fo dIssoIufIon of Cu nnodo durIng oIocfroIysIs = (0.9l 0.?9) g = 0.l2 g.
Incronso In wf. of Cu-cnfhodo In fho couIomofor = 0.l53 g.
If no Cu
++
hnd mIgrnfod from fho nnodo, Incronso of wf. wouId hnvo boon 0.l53 g.
Iuf ncfunI Incronso = 0.l2 g.
InII In conconfrnfIon duo fo mIgrnfIon of Cu
+2
Ions = (0.l53 0.l2) g = 0.033 g.
Trnnsorf numbor of Cu
++
(I
Cu
++ ) =
0 33
0 l53
.
.
= 0.2l5
nnd Trnnsorf numbor of SO
4

= (l I
Cu
++ ) = (l 0.2l5) = 0.?85.
xumpIe 2. CnIcuInfo fho frnnsorf numbor of Ag
+
nnd O
3
Ions whon fho sood rnfIo

of fho fwo Ions Is 0.9l6 durIng oIocfroIysIs of n sIIvor nIfrnfo soIufIon.
Sood of Ag
Sood of O
3
+
=
u
t
= rnfIo (r) = 0.9l6
r =
u
t
=
l n
n
(n =
I
O
3
) or n =
l
l+ r
n =
I
O
3
=
l
l 0 9l6 + .
= 0.52l

I
Ag
+ = l
I
O
3
= l n = (l 0.52l) = 0.4?9.
Specific Conductance
Tho rosIsfnnco (!) of n conducfor Is roorfIonnI fo Ifs Iongfh 'l` nnd Is InvorsoIy
roorfIonnI fo Ifs nron of cross-socfIon 'o`.
! = .
l
o
or =
!o
l
whoro = consfnnf, Ifs vnIuo Is doondonf on mnforInI of fho conducfor nnd Is known ns socIfIc
rosIsfnnco.
Whon, l = l nnd o = l, ! =
Thoroforo, fho socIfIc conducfnnco of nn oIocfroIyfo Is fho rosIsfnnco In ohm whIch Is
offorod by n cm
3
of fho conducfor durIng fho nssngo of oIocfrIcIfy.
Tho rocIrocnI of socIfIc rosIsfnnco Is formod specIIIc conductunce or specIIIc
conductIvIty (K, Knn).
K =
l l l
2
= =

l
o
.
!
cm
cm ohm
= ohm
l
cm
l
= mho cm
l
If n soIufIon ncfs ns nn oIocfroIyfo, fho socIfIc conducfIvIfy of fho soIufIon Is known ns
K
t
, i.e., If Is fho conducfIvIfy of l cm
3
of fho soIufIon.
EquivaIent Conductance
If ono g-oquIvnIonf of nn oIocfroIyfo Is dIssoIvod In V mI of fho soIufIon, fho conducfIvIfy
of nII fho Ions of fho oIocfroIyfo rosonf In fho soIufIon Is known ns oquIvnIonf conducfnnco nnd
Is nbbrovInfod ns
t
i.e.,
t
= K
t
V.
If C Is fho conconfrnfIon of fho soIufIon In g-oquIvnIonf l
l
, fho voIumo of fho soIufIon
confnInIng l g-oquIvnIonf wIII bo l000/C.
fhon,
t
= K
t

l000
C
Wo know fhnf,
t
= K
t
V.
=
l
o
. .
l
!
V
3 K .
l
!
t
l
o
=
=
cm l cm
cm ohm g.oquIvnIonf
3
2

= ohm
l
cm
2
g . oquIvnIonf
l
.
MoIar Conductivity (
m
)
If Is dofInod ns fho conducfnnco of nII fho Ions rosonf In ono moIo of fho oIocfroIyfo In n
soIufIon. If M Is fho conconfrnfIon In moIos l
l
, fhon
n
=
l000 K
M
Tho unIf of
n
Is ohm
l
cm
2
moIo
l
.
Effect of DiIution on Conductance
Tho vnIuo of socIfIc conducfnnco (K) Is oxocfod to IuII wItL dIIutIon oI un eIectvoIyte
soIufIon; ns fho numbor of curronf cnrryIng Ions or mI of fho soIufIon shouId grndunIIy docronso.
Iuf fho vnIuo of
v
ov
uctuuIIy Incveuses wItL dIIutIon ns If Is fho roducf K

t
V nnd on
dIIufIon moro nnd moro of fho oIocfroIyfo IonIsos. Affor n corfnIn dIIufIon fhoro romnIns no
moro oIocfroIyfo moIocuIo fo IonIso nnd fhon fhoro Is no chnngo i.e., no Incronso of
t
or
n
wIfh
dIIufIon. Tho mnxImum vnIuo of oquIvnIonf conducfnnco
t
or moInr conducfIvIfy
n
Is known
ns oquIvnIonf conducfnnco nf InfInIfo dIIufIon or moInr conducfIvIfy nf InfInIfo dIIufIon nnd
nbbrovInfod ns
or
.
TabIe 9.3
Specific conJucIitiI, () 1quitolenI conJucIitiI, (
t
)

AornoliI,
KCl CH
3
COOAo CH
3
COOH KCl CO
3
COOAo CO
3
COOH
l.0 0.0982 0.04l2 0.00l32 98.2 4l.2 l.82
0.5 0.05ll5 0.024? 0.00l005 l02.3 49.4 2.0l
0.l 0.0lll9 0.006ll 0.00024 lll.9 6l.l 2.30
0.0l 0.00l225 0.000?02 0.000l43 l22.5 ?0.2 l4.3
0.00l 0.000l2?6 0.0000?52 0.00004l l2?.6 ?5.2 4l.0
0.000l 0.0000l29 0.00000?68 0.0000l0? l29.5 ?6.8 l0?.0
CIassification of EIectroIytes
(i) Stvong eIectvoIytes: Sfrong ncId HCI, sfrong nIknII nOH hnvo hIgh conducfnncos
ovon nf Iow dIIufIons nnd fhoro Is no shnr Incronso In fhoIr oquIvnIonf conducfnncos on dIIufIon.
Such oIocfroIyfos nro cnIIod stvong eIectvoIytes.
(ii) Weuk eIectvoIytes: Wonk ncId IIko ncofIc ncId hns n Iow vnIuo of
t
nf hIghor
conconfrnfIon nnd fhoro Is rnId Incronso of
t
wIfh dIIufIon. Such oIocfroIyfos whoso
t
vnIuos
Incronso wIfh dIIufIon nro known ns weuk eIectvoIytes (soo IIg. 9.?).
m
Strong electrolyte
Weak
electrolyte
Concentration
M
o
l
a
r
c
o
n
d
u
c
t
i
v
i
t
y
Fig. 9.7 Change of equivalent conductivity with dilution.
ExperimentaI Determination of Specific Conductance (K)
Tho nrrnngomonf of nnrnfus ndofod for fho doformInnfIon Is modIfIod Whonfsfono`s
moforbrIdgo nrrnngomonf (soo IIg. 9.8). Tho modIfIcnfIon Is nocossnry ns fho nssngo of
curronf wIII oIocfroIyso fho oIocfroIyfo. Tho roducfs of oIocfroIysIs wIII nccumuInfo on fho
oIocfrodos whIch wIII chnngo fho offocfIvo rosIsfnnco. Tho uso of A.C. Is nocossnry fo nvoId fhIs
dIffIcuIfy.
C
R
R
S
T
A B
a b
X
A.C. Source
Platinum
electrodes
Fig. 9.8 Determination of conductivity of solutions; Fig. 9.9 Conductivity cell.
C is a compensating condenser (adjustable).
Tho modIfIcnfIons nro: (o) fho uso of A.C., (I) fho uso of foIohono dofocfor or mngIc oyo
IndIcnfor, (c) fho oIocfroIyfo Is fnkon In n coII confnInIng InfInIsod If oIocfrodos (IIg. 9.9).
Tho soIufIon whoso conducfnnco Is fo bo monsurod Is uf Info fho conducfIvIfy coII (soo
IIg. 9.9). Whon fho sound In fho foIohono Is mInImum or zoro rondIng on fho nrorInfo
mofor, socIfIc rosIsfnnco Is gIvon by fho foIIowIng oqunfIon:
!
=
o
I
SInco fho conducfIvIfy of n soIufIon rnIdIy Incronsos wIfh fomornfuro, fho coII shouId
bo Incod In n fhormosfnf. ConducfIvIfy wnfor (doubIo dIsfIIIod wnfor) shouId bo usod fhroughouf.
Ifforonf coIIs nro In uso, fho common form Is shown In IIg. 9.9. ConnocfIons nro mndo by If
wIros.
CaIcuIation of Specific Conductance (K)
If nocossnry Is cnIcuInfod from fho obsorvod rosIsfnnco, If fho nron of fho oIocfrodos
nnd fho dIsfnnco bofwoon fhom nro nccurnfoIy known. Iuf fho rocoduro Is fo cnIcuInfo n
fncfor for onch coII known ns ceII constunt (x).
SocIfIc conducfnnco = Obsorvod conducfnnco CoII consfnnf
Whon l Is fho dIsfnnco bofwoon fho oIocfrodos nnd e, fho nron of cross-socfIon of fho
oIocfrodo, fho rosIsfnnco ! of IIquId oncIosod bofwoon fho oIocfrodos Is:
! =
l
e
= x
whoro l/e = x Is ceII constunt.
Tho coII consfnnf Is known by doformInIng fho conducfnnco of
50
KCI soIufIon. Tho

K vnIuo of fho soIufIon hns boon nccurnfoIy doformInod by KohIrnusch fo bo 0.002?68 ohm
l
. cm
l
nf 25C.
SocIfIc conducfnnco K = x Obsorvod conducfnnco.
= x
l
= x
I
o
l
!
If fho obsorvod rosIsfnnco wIfh
50
KCI bo l
l
fho coII consfnnf (x) =
l
0.002?68. Tho
coII consfnnf boIng known If Is onsy fo obfnIn fho socIfIc conducfnnco of nny soIufIon by usIng
fho nbovo roInfIon.
HIgLIIgLts:
If shouId bo nofod fhnf coII consfnnf (x) =
l
e
whoro l Is fho dIsfnnco bofwoon fho
oIocfrodos nnd e Is fho monn nron of fho oIocfrodos.
AccordIng fo oqunfIon:
K = x obsorvod conducfnnco.
TLe Iowev tLe ceII constunt, tLe LIgLev Is tLe obsevved conductunce und
so Iov weuk eIectvoIytes u conductIvIty ceII LuvIng u smuII ceII constunt
sLouId be used.
KoLIvuuscL's Iuw (Iuw oI Independent mIgvutIon oI Ions)
Af 25 fho oquIvnIonf conducfnnco nf InfInIfo dIIufIon (
) vnIuos for somo oIocfroIyfos

nro gIvon In fho fnbIo boIow:
TabIe 9.4
IonIc Conducfnnco nnd IonIc MobIIIfIos of somo Ions nf InfInIfo IIufIon nf 25C.
CoIion
c
MoIiliI,, I Anion
o
MoIiliI,, V
cn
2
/eec. tolI cn
2
/eec tolI
H
+
349.8 0.00362 OH
l9?.6 0.00205
K
+
?3.5 0.000?6
l
2
SO
4
?9.8 0.00083
H
4
+
?3.4 0.000?6 CI
?6.3 0.000?9
Ag
+
6l.9 0.00064
l
2
Cn
++
59.5 0.00062 O
3
?l.4 0.000?4
l
2
Mg
++
53.l 0.00055 HCO
3
44.5 0.00046
n
+
50.l 0.00052 CH
3
COO
40.9 0.00042
If Is ovIdonf from fho fnbIo fhnf onch Ion confrIbufos n corfnIn dofInIfo qunnfIfy fownrds

of fho soIufIon. ThIs roguInrIfy wns fIrsf obsorvod by KohIrnusch nnd wns uf In fho form of
n Inw whIch Is known ns KoLIvuuscL's Iuw. Tho Inw mny bo sfnfod ns foIIows:
Tho oquIvnIonf conducfnnco nf InfInIfo dIIufIon (
) of nn oIocfroIyfo Is oqunI fo fho sum

of IonIc conducfnncos of Ifs consfIfuonf Ions, i.e.,
=
c
+
o
whoro,
c
= IonIc conducfnnco of cnfIon.

= IonIc conducfnnco of nnIon.

HIgLIIgLt:
KoLIvuuscL's Iuw cnn bo sfnfod In nnofhor wny: Af InfInIfo dIIufIon, whon fho
dIssocInfIon of nn oIocfroIyfo Is consIdorod comIofo, onch Ion mnkos n dofInIfo
confrIbufIon fownrds fho moInr conducfnnco of fho oIocfroIyfo IrrosocfIvo of Ifs
nssocInfIon wIfh ofhor Ions. Thus,
n
= r
+
.
+
+ r
whoro r
+
nnd r
nro numbors of cnfIons nnd nnIons nnd

+

nnd

nro moInr
conducfnncos of cnfIons nnd nnIons rosocfIvoIy. IxnmIos nro:
n
(KCI) =
K
+
CI

nnd
n
(K
3
IO
4
) = 3
K

+
IO
4
3
IonIc Conductunce oI Some Ions ut 25C
n
+
= 50.ll ohm
l
Ir
= ?8.4 ohm
l
K
+
= 53.22 ohm
l
CI
= ?6.34 ohm
l
H
4
+
= ?3.40 ohm
l
O
3
= ?l.44 ohm
l
AppIIcutIons oI KoLIvuuscL's Iuw
(i) etevmInutIon oI IonIc conductunces. IonIc conducfnnco ossossos n consfnnf
vnIuo nf n dofInIfo fomornfuro. Ifs unIf Is ohm
l
cm
2
nnd Is dIrocfIy roorfIonnI fo fho
soods of fho Ions.
c
u or
c
= lu
o
t or
o
= lt
whoro l Is n consfnnf.
And
=
c
+
o
= lu + lt = l(u + t)
c
lt
l u t
=
+ ( )
=
u
u t +
= I
+
And
o
lt
l u t
t
u t
=
+
=
+ ( )
= I
= (l I
+
)
So, fho IonIc conducfnncos of cnfIons nnd nnIons cnn bo doformInod from fhoIr
oxorImonfnIIy doformInod frnnsorf numbors from fho nbovo roInfIons.
(ii) etevmInutIon oI
oI weuk eIectvoIytes:
for wonk oIocfroIyfos cnnnof bo

doformInod oxorImonfnIIy, bocnuso fhoy do nof IonIso fo n suffIcIonf oxfonf In soIu-
fIon, oxcof nf n InfInIfo dIIufIon. Iuf

for wonk oIocfroIyfos cnn bo cnIcuInfod from
KohIrnusch`s Inw.
xumpIe: Tho
vnIuos for CH
3
COOn, HCI nnd nCI nro x, , nnd c, rosocfIvoIy.
CnIcuInfo
for CH
3
COOH.
Wo hnvo
(i)
n
+
+
CH COO
3
= x
(ii)
H
+ +
CI
= ,
(iii)
n
+
+
CI
= c.
So, (

n CH COO H CI
3
+ +
+ + +
) (
n CI
+ + ) = (x + , c) = ( )
CH COO H
3
+ +
(CH
3
COOH)
(iii) IonIc mobIIIty (AbsoIute veIocIty oI Ions)
Wo hnvo,
AI = I
+

I
I
.
l000
C
I
whoro, A = Cross-socfIon of fho fubo fhrough whIch curronf nssos.
I = Tho dIsfnnco fhrough whIch cnfIon movos.
C = ConconfrnfIon (oquIv. dm
3
)
II = nm soc = Q = qunnfIfy of curronf (couIomb)
I = Inrndny.
whon, A = l, IofonfInI grndIonf = l V cm
l
SocIfIc conducfnnco K =
l l
=
V/ I
= I |3 V = l V cm
l
]
!of, ! = MobIIIfy of cnfIon In cm soc
l
undor unIf ofonfInI grndIonf of l V/cm
So, ! =
dIsfnnco
fImo
=
I
I
Ior vory dIIufo soIufIons,
! =
I
I
I I =

=
+
K
C I I
l000 l l

=
c

l
I
=
c
I
|3 I
+
=
c
]
SImIInrIy, V =
o
I
, whoro V = mobIIIfy of nnIon In cm soc
l
undor ofonfInI grndIonf
l V cm
l
.
So, IonIc conducfnnco = IonIc mobIIIfy I
or IonIc mobIIIfy =
IonIc conducfnnco
I
Thoroforo, IonIc mobIIIfIos cnn onsIIy bo cnIcuInfod.
HIgLIIgLts:
Tho Ions movo vory sIowIy.
Tho soods of mosf Ions (oxcof H
+
nnd OH
) IIo In fho rnngo 4 l0

4
fo 8 l0
4
cm
soc
l
undor l voIf cm
l
.
Tho H
+
Ions nro nbouf fIvo fImos nnd OH

Ions nro fhroo fImos fnsfor.
Conductometric Titration
urIng n fIfrnfIon, fho conducfIvIfy of fho soIufIon chnngos doondIng on fho roInfIvo
mobIIIfy of fho Ions nddod from fho buroffo or romovod from fho soIufIon duo fo roncfIon. And
fho uso of fhIs conducfIvIfy chnngo Is mndo fo doformIno fho oquIvnIonf oInf of roncfIons
InvoIvIng noufrnIIsnfIon roncfIons or rocIIfnfIons. Tho conducfnnco of fho soIufIon Is monsurod
nffor onch nddIfIon of fIfrnnf nnd fho rosuIfs nro oxrossod grnhIcnIIy (conducfnnco te voIumo
of fIfrnnf). And fho ond oInf Is doformInod. IdonIIy fwo sfrnIghf IInos nro obfnInod whIch
Inforsocf nf fho oquIvnIonco oInf |IIg. 9.l0(o)].
HIgLIIgLts:
Tho chnngo In voIumo fhroughouf fho courso of fIfrnfIon musf bo kof smnII by
usIng n fIfrnnf whIch Is nf Ionsf l00 fImos moro conconfrnfod fhnn fho soIufIon
boIng fIfrnfod.
Monsuromonfs of conducfnnco In fho rogIon of oquIvnIonco oInf nro of IIffIo vnIuo
duo fo hydroIysIs, dIssocInfIon or soIubIIIfy of fho roncfIon roducfs. Ior fhIs ronson,
fho grnh shows n curvnfuro rnfhor fhnn n cIonr InforsocfIon of fho fwo sfrnIghf
IInos |IIg. 9.l0(I)].
(a) NeutraIisation Reactions
In fho fIfrnfIon of n sfrong ncId wIfh n sfrong bnso, fhoro Is nIwnys nn InIfInI docronso In
conducfnnco. Tho conducfnnco fhon rIsos boyond fho oquIvnIonco oInf. In fho fIfrnfIon of
nOH wIfh HCI, fho docronso In conducfnnco Is duo fo fho roIncomonf of OH
Ions (moInr
IonIc conducfIvIfy = l99) by CI
Ions (moInr IonIc conducfIvIfy = ?6). Ioyond fho oquIvnIonco

oInf, fho Incronso In conducfIvIfy Is duo fo oxcoss of H
+
Ions wIfh vory hIgh IonIc moInr
conducfIvIfy (350).
In fho fIfrnfIon of HCI wIfh nOH, fho InIfInI fnII In conducfnnco Is duo fo fho roIncomonf
of H
+
Ions (350) wIfh n
+
Ions (50) nnd fho rIso boyond oquIvnIonco oInf Is duo fo oxcoss OH
Ions (l99) |IIg. 9.l0(o)].

HIgLIIgLt:
Tho sfrongor fho soIufIon usod for fho fIfrnfIon, fho shnror Is fho ond oInf
(IIg. 9.l0).
Conductivity falls as
OH (aq) ions are
neutralized
C
o
n
d
u
c
t
i
v
i
t
y
Conductivity of
Na Cl (aq)
+
Conductivity rises
due to excess
H (aq) ions added
+
End point
Volume of HCl (aq) added
C
o
n
d
u
c
t
a
n
c
e
Volume of alkali
Fig. 9.10 (=) Changes in conductivity during titration Fig. 9.10 (>) Changes in conductivity
of NaOH(=G) with HCl(=G). ln water H
+
(=G) during titration of a weak acid
and OH
(=G) ions are very mobile, so they (CH

3
COOH) (=G) with a strong
conduct electricity very well. base (NaOH) (=G).
(b) Precipitation Reactions
ConducfomofrIc fIfrnfIons of fhIs fyo mny bo orformod If fho roncfIon roducf Is
snrIngIy soIubIo snIf. Tho rocIIfnfo shouId bo formod fnIrIy rnIdIy nnd shouId nof hnvo
sfrong ndsorbonf roorfIos. Tho fIfrnfIon of KCI soIufIon te AgO
3
soIufIon snfIsfIos fho nbovo
condIfIons. Tho nnfuro of fho fIfrnfIon curvo Is ns In IIg. 9.l0 (c).
Tho oInf of InforsocfIon of fho fwo curvos Is shnr. So, ond oInf of fho roncfIon cnn bo
doformInod onsIIy.
C
o
n
d
u
c
t
a
n
c
e
Volume of AgNO
3
Fig. 9.10 (?) Titration curve of KCl solution by AgNO
3
solution.
TIfrnfIon of n vory wonk ncId wIfh sfrong bnso or n vory wonk bnso wIfh sfrong ncIds
rosuIfs In n smnII InIfInI conducfnnco. Tho conducfnnco Incronsos ns fho conconfrnfIon of fho
snIf Incronsos. In fho rogIon of fho oquIvnIonco oInf, duo fo hydroIysIs fho fIfrnfIon curvo
shows n mnrkod curvnfuro (IIg. 9.l0(I)). Tho oquIvnIonco oInf Is Iocnfod by oxfrnoInfIng fho
sfrnIghf IInos.
SOLVED EXAMPLES
xumpIe 1. A conJucIitiI, cell conIoine Iuo elecIroJee of oreo of croee-eecIion 1.2 cn
2
.
TIe, ore 10. cn. oporI. 1f IIe cell ie filleJ uiII on elecIrol,Ie onJ offere o reeieIonce of 1996oIn,
colculoIe IIe cell coneIonI onJ epecific conJucIitiI,.
SoI. CoII consfnnf =
l
o
=
l0.5
l.25
= 8.4 cm
l
Obsorvod conducfIvIfy =
l
l996
ohm
l
.
SocIfIc conducfIvIfy = CoII consfnnf obsorvod conducfIvIfy.
= 8.4
l
l996
= 8.4
l
l996
= 4.2 l0
3
ohm
l
cm
l
.
xumpIe 2. Specific conJucIitiI, of on
A
0
KCl eoluIion oI 2C ie 0.000276 nIoe cn
1
.
1f IIe reeieIonce of cell conIoining IIie eoluIion ie 00 oIne, uIoI ie IIe cell coneIonI:
l
o
nnd ! =
l
o
or
l
o
=
!
= !
l
= ! K
l
o
= 500 0.0002?65 cm
l
= 0.l38 cm
l
.
xumpIe 3. Specific conJucIitiI, of o conJucIitiI, cell conIoining 0.2 (A) KCl ie 2.767
10
3
oIn
1
cn
1
, IIe oIeerteJ reeieIonce of IIe cell ie 4364 oIn. ColculoIe IIe cell coneIonI. 1f
IIe cell ie filleJ uiII onoIIer eoluIion IIe oIeerteJ reeieIonce ie 300 oIn. ColculoIe epecific
reeieIonce of IIe eoluIion.
l
o
! =
l
o
or
l
o
=
!
= !
l
= ! K

l
o
= ! K = 4364 2.?6? l0
3
cm
l
= l2.0?5 cm
l
=
!
l o /
=
3050
l2 0?5 .
ohm. cm.
= 252.58 ohm. cm.
xumpIe 4. A conJucIitiI, cell conIoining 0.02 A KCl eoluIion offere o reeieIonce of
0 oIn oI o JefiniIe IenperoIure. TIe epecific conJucIitiI, of 0.02 A eoluIion oI IIoI IenperoIure
ie 0.00276S oIn
1
cn
1
. 1f IIe cell ie nou filleJ uiII 0.2 A ZnSO
4
, IIe oIeerteJ reeieIonce of IIe
cell ie 72.1S oIn. ColculoIe IIe equitolenI onJ nolor conJucIitiIiee of IIe ZnSO
4
eoluIion.
SoI. CoII consfnnf = ! K
= 550 0.002?68 = l.5224 cm
l
AgnIn, K = coII consfnnf obsorvod conducfIvIfy
= l.5224
l
?2 l8 .
= 0.02l09 ohm
l
cm
l
t
(oquIvnIonf conducfIvIfy) = K
t

l000
C
= 0.02l09
l000
0.2
= l05.45 ohm
l
cm
2
n
(moInr conducfIvIfy) =
l000K
M
=
l000 0.02l09
0.l
= 2l0.9 ohm
l
cm
2
.
xumpIe 5. TIe reeieIonce of o Jecinornol eoluIion of o eolI occup,ing o tolune IeIueen
Iuo PI elecIroJee 1.S0 cn oporI onJ .4 cn
2
in oreo uoe founJ Io Ie 32 oIne. ColculoIe IIe
equitolenI conJucIonce (
t
) of IIe eoluIion.
SoI. ! =
l
o
or
l
=
l
!
l
o
=
l
32
l8
5 4
.
.
K = 0.0l04l6 ohm
l
cm
2

t
=
l000K
C
=
l000 0.0l04l6
0.l
= l04.l66 ohm
l
cm
2
.
xumpIe 6. TIe equitolenI conJucIonce of 1.02S 10
3
(A) oceIic ociJ ie 4S.1 oIn
1
cn
2
eq
1
oI 29S K. 1Ie equitolenI conJucIonce oI infiniIe JiluIion ie 390.6 oIn
1
cn
2
eq
1
.
ColculoIe IIe Jegree of JieeocioIion of oceIic ociJ.
SoI. =
t
t
=
48 l5
390 6
.
.
= 0.l233.
xumpIe ?. TIe equitolenI conJucIoncee oI infiniIe JiluIion of torioue elecIrol,Iee ore
giten.
HCl = 426.1
AcOAo = 91.0
AoCl = 126.. ColculoIe
(AcOH).
SoI.
HCI +
AcOn

nCI
= ( ) ( ) ( )

H CI n OAc n CI
+ + + + + + +
=
H OAc
+
+ =
AcOH
426.l + 9l.0 l26.5 =
AcOH = 390.6 Ohm

l
cm
2
.
xumpIe B. 1quitolenI conJucIonce of oceIic ociJ oI 2C ie 0.001S oIn
1
n
2
eq
1
. 1f
ionic conJucIonce of H
+
ione onJ CH
3
COO
ione oI infiniIe JiluIion ore 0.034S oIn

1
n
2
eq
1
onJ 0.004 oIn
1
n
2
eq
1
, reepecIitel,. ColculoIe IIe Jegree of JieeoluIion of oceIic ociJ.
SoI.
(CH
3
COOH) =
H
+
+
CH
3
COO
= 0.0348 + 0.004 ohm

l
m
2
oq
l
= 0.0388
ogroo of dIssoIufIon =
=
0 00l8
0 0388
.
.
= 0.046.
xumpIe 9. 1f 3g of oceIic ociJ ie oJJeJ Io enougI uoIer Io nole one liIre eoluIion, uIoI
uill Ie IIe concenIroIion of oceIoIe ion. ColculoIe IIe percenIoge ionieoIion of oceIic ociJ.
(K
o
= 1.S 10
).
SoI. Sfrongfh of CH
3
COOH soIufIon =
3
60
g oquIv. l
l
= 0.05()
CH
3
COOH CH
3
COO
+ H
+
InIfInIIy = 0.05 0 0
ogroo of IonIsnfIon =
Af oquIIIbrIum = .05(l ) .05 .05
K
o
=
|CH COO ] |H ]
|CH COOH]
3
3
+
=
0 05 0 05
0 05 l
. .
. ( )

=
( . )
.
0 05
0 05
2 2
| boIng nogIIgIbIo, l l]
= 0.05
2
=
K
0.05
l.8 l0
0.05
l8 l0
0.05
5 6
o
=

=

= l8.9 l0
3
= .0l898.
xumpIe 10. TIe epecific conJucIitiI, of eoIuroIeJ eoluIion of AgCl ie 1.24 10
6
nIo
cn
1
. TIe noIiliIiee of Ag
+
onJ Cl

ione ore 3.S onJ 6.3 nIo eq
1
cn
2
. ColculoIe IIe eoluIiliI,
of AgCl in gl
1
(AI. uI, Ag = 10S, Cl = 3.).
SoI. AccordIng fo KohIrnusch`s Inw,
=
+
+
i.e.,
(AgCI) = (Ag
+
) + (Cu
)
= 58.3 + 65.3 = ll9.l mhos oq
l
cm
2
t
= K
t
V
V =
t
t
K
ll9 l
l24 l0
.
.
6
= 9.6 l0
5
cm
3
oq
l
= 9.6 l0
2
l oq
l
SoIubIIIfy =
l
9 6 l0
2
.
oq l
l
= 0.00l04 oq l
l
= (0.0l04 l43.5) g l
l
= 0.l495 g l
l
.
xumpIe 11. TIe epeeJ roIio of Ag
+
onJ AO
3

ione in o eoluIion of AgAO
3
elecIrol,eeJ
IeIueen Ag-elecIroJee ie 0.916. IinJ IIe IroneporI nunIer of Ag
+
onJ AO
3

ione.
SoI.
Sood of Ag
Sood of O
0.9l6
l.000
3
+
= =
u
t
I
Ag
+ =
u
u t +
=
+
=
0.9l6
0.9l6 l
0.9l6
l.9l6
= 0.4?8
Honco, I
O
3

= l I
Ag
+ = l 0.4?8 = 0.522.
xumpIe 12. A JiluIe eoluIion of CuSO
4
uoe elecIrol,eeJ, ueing PI-elecIroJee. TIe onounI
of Cu in IIe onoJic eoluIion uoe founJ Io Ie 0.630 g, onJ 0.6236 g Iefore onJ ofIer elecIrol,eie,
reepecIitel,. TIe ueigII of Ag JepoeiIeJ in o eilter couloneIer, ploceJ in eeriee, uoe founJ Io Ie
0.131 g. ColculoIe IIe IroneporI nunIer of Cu
+2
onJ SO
4
2
ione.
|Af. wfs. = Ag(l0?.88), Cu(63.6)]
SoI. Wf. of Cu In nnodIc soIufIon nffor oIocfroIysIs Is = 0.6236 g.
Wf. of Cu In nnodIc soIufIon boforo oIocfroIysIs = 0.6350 g.
!oss In wf. of Cu from nnodIc soIufIon (nnoIyfo) = (0.6350 0.6236) g = 0.0ll4 g
Wf. of Ag doosIfod In voIfnmofor = 0.l35l g.
Amf. of Cu doosIfod oquIvnIonf fo 0.l35l g of Ag.
=
wf. of Cu( )
Iq. wf. of Cu
wf. of Ag
Iq. wf. of Ag
x
=
=
x
63.6
2
0.l35l
l0?.88
=
x =
0.l35l 3l.8
l0?.88
= 0.0398 g
I
Cu
2 + =
!oss nf nnodo
TofnI Ioss
0.ll4
0.0398
=
= 0.286
I
SO
4
= l I
Cu
2 + = l 0.286 = 0.?l4.
ELECTROCHEMSTRY 223
Q. 1. WLut Is eIectvocLemIstvy?
Ans. IIocfrochomIsfry Is fho sfudy of InforroInfIons of oIocfrIcnI onorgy nnd chomIcnI
onorgy nnd InforconvorsIons of fho fwo onorgIos. ThIs sfnfomonf nIIos for bofh gonornfIon of
o.m.f. of n coII ns woII ns oIocfroIysIs.
Q. 2. WLut uve eIectvocLemIcuI veuctIons?
Ans. IIocfrochomIcnI roncfIons nro fho roncfIons whIch InvoIvo fho fIow of curronf.
Q. 3. MentIon tLe types oI eIectvocLemIcuI veuctIons.
Ans.
(i) 1lecIrol,eie. IIocfroIysIs roquIros oIocfrIcnI onorgy from somo oxfornnI sourco fo brIng
nbouf n chomIcnI chnngo i.e., In fhIs fyo of roncfIon, oIocfrIcnI onorgy Is consumod.
(ii) 1lecIrocIenicol cell reocIione. IIocfrochomIcnI coII roncfIons nro mnInIy rodox
roncfIons, InvoIvod In fho coII whoro oIocfrIcnI onorgy Is roducod duo fo n chomIcnI chnngo.
Q. 4. WLut Is eIectvoIysIs?
Ans. IIocfroIysIs Is n rocoss whoro oIocfrIc curronf Is usod fo docomoso n moIfon IonIc
comound or n soIufIon of Ions Info oIomonfs.
Q. 5. WLy uve tLe moIten compounds ov soIutIons used us eIectvoIytes?
Ans. Ions cnn onIy conducf oIocfrIcIfy whon fhoy nro froo fo movo, whIch Is onIy ossIbIo
In moIfon sfnfo or In soIufIon.
Q. 6. MentIon some Impovtunt uses oI eIectvoIysIs pvocess.
Ans.
(i) IxfrncfIon of n, AI ofc.
(ii) IIocfroIysIs of brIno fo roduco nOH nnd CI
2
(iii) IIocfroInfIng
(it) Coor rofInIng.
Q. ?. WLut uve tLe pvoducts oI eIectvoIysIs oI moIten suIts?
Ans. MofnIs nro doosIfod nf fho cnfhodo nnd fho nonmofnIs nro IIbornfod nf fho nnodo.
Q. B. WLut uve tLe pvoducts oI eIectvoIysIs oI un uqueous soIutIon oI u suIt?
Ans. urIng oIocfroIysIs of n soIufIon of n snIf In wnfor, fho doosIfIon nf fho cnfhodo
doonds on fho fyo of mofnI Ion In fho snIf. If fho mofnI Is In Iowor osIfIon of oIocfrochomIcnI
sorIos, If gofs doosIfod nf fho cnfhodo tic. Cu
+2
Cu
+2
(oq) + 2e Cu(e)
Iuf If fho mofnI Is In hIghor osIfIon In oIocfrochomIcnI sorIos, fho roducf nf fho cnfhodo
Is hydrogon, from hydrogon Ions roducod by fho IonIsnfIon of wnfor
2H
+
(oq) + 2e H
2
(g)
urIng fho oIocfroIysIs of n snIf soIufIon, fho IIbornfIon nf fho nnodo doonds on fho fyo
of oIocfrodo. If fho nnodo Is grnhIfo or InfInum, fho roducfs nro hnIogons from mofnIIIc
hnIIdos (CI

, Ir
, I
)
2X

(oq) X
2
(g) + 2e (X = CI, Ir, I)
OfhorwIso oxygon Is IIbornfod from wnfor. If fho nnodo Is n mofnI (Cu, or Ag), nfoms of
oIocfrodo furn Info Ions.
Cu(e) Cu
2+
(oq) + 2e.
Q. 9. WLut Is tLe eIIect oI concentvutIon oI u suIt soIutIon duvIng eIectvoIysIs?
Ans. Tho conconfrnfIon of n snIf soIufIon hns nn offocf on fho roducf of oIocfroIysIs nf
fho nnodo. ChIorIno Is IIbornfod nf fho nnodo durIng oIocfroIysIs of n conconfrnfod soIufIon of
nCI. In oIocfroIysIs of n dIIufo soIufIon of nCI IncronsIng nmounfs of oxygon nro IIbornfod.
Q. 10. (u) vuw u neut sketcL oI un eIectvoIytIc ceII.
(b) SodIum Is extvucted by tLe eIectvoIysIs oI u mIxtuve oI u moIten NuCI
und CuCI
2
. In u commevcIuI ceII tLe cuvvent Is 30,000 A. WLut muss oI
Nu Is Iovmed In un Louv ut tLe steeI cutLode?
Ans. (o)
+
Cathode +ve
ions
Anode
ve
ions
Electrolyte
Negative ions lose
electrons at the
anode (oxidation)
Positive ions gain
electrons at the
cathode (reduction)
and turn into
atoms
Fig. 9.11. Electrolytic cell.
(I) Tho oqunfIon for IIbornfIon nf fho cnfhodo Is
n
+
+ o

n
TImo of oIocfroIysIs = 3600 soc.
QunnfIfy of oIocfrIcIfy In nn hour = 30000 C/S 3600 s.
= l08,000,000 C.
Amounf of n formod or hr. =
l08,000,000
96,480
moI
Mnss of n formod or hr. =
l08 000 000
96 480
23
, ,
,
= 25,?50 g
= 25.?5 kg.
Q. 11. WLut Is tLe utIIIty oI eIectvoIysIs oI bvIne?
Ans. IIocfroIysIs of brIno Is fho bnsIs of fho nIknII nnd chIorIno Indusfryn woII known
eIectvocLemIcuI Industvy. IrIno Is n soIufIon of nCI In wnfor. IIocfroIysIs of brIno Is usod
fo mnnufncfuro chIorIno, hydrogon nnd sodIum hydroxIdo. urIng oIocfroIysIs chIorIno Is
IIbornfod nf fho nnodo, hydrogon Is IIbornfod nf fho cnfhodo nnd bubbIos off, whIIo fho soIufIon
furns fo nOH.
ELECTROCHEMSTRY 225
Tho coII fo bo usod for oIocfroIysIs shouId bo cnrofuIIy dosIgnod so fhnf chIorIno cnn bo
kof nnrf from nOH, ofhorwIso fhoy wIII roncf. Two fyos of coII nro In uso: (o) nercur, cell
(I) nenIrone cell.
Brine
Cl (g)
2
H (g)
2
NaOH(aq)
Porous
membrane
+
Ti-electrode Ni-electrode
Fig. 9.12 Membrane cell.
A mombrnno coII Is shown In IIg. 9.l2. Tho mombrnno ormIfs fho soIufIon fo nss nnd
rovonfs mIxIng of nOH nnd CI
2
. Tho mombrnno hns Ion-oxchnngo roorfIos, If nIIows osIfIvo
Ions fo nss buf nof fho nognfIvo Ions.
Q. 12. WLut do you meun by vesIstunce?
Ans. !osIsfnnco (!) of nny conducfor Is fho obsfrucfIon offorod fo fho fIow of curronf.
!
l
o
; whoro l = Iongfh, o = nron of cross-socfIon of fho conducfor
or ! =
l
o
whoro, = roorfIonnIIfy consfnnf nnd Is known ns socIfIc rosIsfnnco or rosIsfIvIfy.
=
!. o
l
; unIf of ! = ohms.
Q. 13. WLut do you meun by specIIIc vesIstunce ov vesIstIvIty?
Ans. SocIfIc rosIsfnnco or rosIsfIvIfy Is fho rosIsfnnco offorod by fho conducfor of l cm
Iongfh nnd l cm
2
nron of cross-socfIon. Thus If Is rosIsfnnco offorod by n conducfor of l cm
3
.
Irom, =
!. o
l
= !; whoro o = l cm
2
, l = l cm.
unIf of = ohm-cm.
Q. 14. WLut Is conductunce?
Ans. Tho conducfnnco (C) Is fho rocIrocnI of !
C =
l
!
!nIf of conducfnnco = ohm
l
or mho
If Is n monsuro of onso wIfh whIch curronf fIows fhrough n conducfor.
Q. 15. WLut Is specIIIc conductunce?
Ans. Tho socIfIc conducfnnco (K) Is fho rocIrocnI of socIfIc rosIsfnnco ().
K =
l
=
.
0
/
1
l
!
l
o
If Is dofInod ns fho conducfnnco of l cm
3
of n conducfor
unIf of K = ohm
l
cm
l
Q. 16. WLut do you meun by equIvuIent conductIvIty oI un eIectvoIytIc soIutIon?
Ans. If Is fho conducfIng owor of nII fho Ions rosonf In n soIufIon of nn oIocfroIyfo
confnInIng l g oquIv.
IquIvnIonf conducfIvIfy
eq
=
l000 K
C
C = normnIIfy of fho soIufIon.
!nIf of
eq
= ohm
l
cm
2
oquIv
l
.
Q. 1?. WLut do you meun by moIuv conductIvIty oI un eIectvoIyte?
Ans. If Is fho conducfIvIfy of nII fho Ions roducod In n soIufIon confnInIng ono gm moIo
of fho oIocfroIyfo. i.e., moInr conducfIvIfy
n
=
l000 K
M
whoro, M = moInrIfy of fho soIufIon
K = socIfIc conducfnnco.
Q. 1B. GIve tLe veIutIonsLIp oI moIuv conductIvIty wItL concentvutIon.
Ans. Tho roInfIon Is

n
=
n
I c
whoro, I = consfnnf c = conconfrnfIon
= moInr conducfIvIfy nf InfInIfo dIIufIon
n
= moInr conducfIvIfy nf n gIvon dIIufIon
As c 0
n
=
n
.
Q. 19. WLut Is tLe eIIect oI dIIutIon on moIuv conductIvIty?
Ans. MoInr conducfIvIfy Incronsos wIfh dIIufIon.
Q. 20. WLut do you meun by degvee oI dIssocIutIon oI un eIectvoIyte?
Ans. Tho dogroo of dIssocInfIon () Is fho frncfIon of fho oIocfroIyfo fhnf dIssocInfos Info
Ions. Ior wonk oIocfroIyfos If Is roInfod fo
n
nnd
n
ns foIIows:
=
n
n
.
Q. 21. WLut Is tvunspovt numbev?
Ans. If Is fho frncfIon of fofnI qunnfIfy of oIocfrIcIfy, cnrrIod by cnfIons or nnIons.
Q. 22. eIIne KoLIvuuscL's Iuw.
Ans. Tho moInr conducfnnco, nf InfInIfo dIIufIon of nn oIocfroIyfo, Is oqunI fo fho sum of
IonIc conducfnncos of cnfIons nnd nnIons.
Q. 23. WLut uve tLe uppIIcutIons oI conductunce meusuvement?
Ans. (i) Monsuromonf of dogroo of dIssocInfIon.
(ii) oformInnfIon of soIubIIIfy nnd soIubIIIfy roducf.
(iii) ConducfomofrIc fIfrnfIon.
ELECTROCHEMSTRY 227
Q. 24. AII conductunce meusuvements uve done wItL tLe LeIp oI A.C.expIuIn.
Ans. .C. wIII hoI oIocfroIysIs of fho oIocfroIyfIc soIufIon brIngIng nbouf n chnngo In
conconfrnfIon of fho oIocfroIyfo whIch In furn wIII nffocf fho conducfnnco of fho soIufIon.
Q. 25. In uII conductometvIc tItvutIons, we pIot conductunce vs. voIume oI tItve
und not vesIstunce vs voIume oI tItveexpIuIn.
Ans. Conducfnnco vnrIos IInonrIy wIfh fho voIumo of fIfro, buf rosIsfnnco !
l
C
=
.
0
/
1
doos
nof vnry IInonrIy wIfh fho voIumo of fIfro, so Iof of rosIsfnnco vs. voIumo wIII nof gIvo sfrnIghf
IIno. Thnf Is why rosIsfnnco cnnnof bo Ioffod ngnInsf voIumo of fIfro.
Q. 26. quIvuIent conductIvIty oI u weuk eIectvoIyte Incveuses wItL dIIutIon
expIuIn.
Ans. IquIvnIonf conducfIvIfy of n wonk oIocfroIyfo doonds on fho numbor of Ions of
fho oIocfroIyfo rosonf In soIufIon wIfh dIIufIon of n wonk oIocfroIyfo, dogroo of dIssocInfIon
Incronsos, so Is fho numbor of Ions. Thnf Is why oquIvnIonf conducfIvIfy of wonk oIocfroIyfo
Incronsos wIfh dIIufIon.
Q. 2?. WLy equIvuIent conductIvIty ut InIInIte dIIutIon cunnot be dIvectIy
detevmIned expevImentuIIy?
Ans. KohIrnusch oInfod ouf fhnf nf hIgh dIIufIon fho oquIvnIonf conducfIvIfy () Is
Ioffod ngnInsf fho squnro roof of conconfrnfIon (c) gIvos n sfrnIghf IIno whIch moofs fho zoro
nxIs of conconfrnfIon nf
, fho oquIvnIonf conducfnnco nf InfInIfo dIIufIon, i.e., nf hIgh dIIufIon
, nnd c nro roInfod by fho oqunfIon.

=
K
c
So,
cnn bo doformInod by extvupoIutIon oI tLe cuvve vs. c (IIg. 9.l3) for sfrong
oIocfroIyfos fo zoro conconfrnfIon. Howovor nro nof so roInfod In cnso for wonk oIocfroIyfos.
So
for wonk oIocfroIyfos cnnnof bo oxorImonfnIIy doformInod by fho nbovo oqunfIon.

0 4 8
50
100
150
Sodium chloride
Sodium acetate
Acetic acid
C (C in equivalent/liter)
E
q
u
i
v
a
l
e
n
t
c
o
n
d
u
c
t
i
v
i
t
y
-
-
o
h
m
c
m
e
q
L
1
0
1
Fig. 9.13 Extrapolation of versus ? .
Q. 2B. SpecIIIc conductunces decveuses wItL dIIutIon wLIIe tLe equIvuIent
conductunce IncveusesexpIuIn.
Ans. Whon nn oIocfroIyfo Is dIIufod, dogroo of dIssocInfIon Incronsos nnd nIso fho fofnI
voIumo Incronsos. As n rosuIf, fho numbor of Ions or mIIIIIIfro docronsos. Iuf If oufwoIghs fho
mInor Incronso In conducfnnco duo fo Incronso In dogroo of dIssocInfIon. i.e., socIfIc conducfnnco
docronsos wIfh dIIufIon. Iuf oquIvnIonf conducfnnco Incronsos bocnuso fho fofnI numbor of
Ions or grnm oquIvnIonf Incronsos wIfh dIIufIon for fho Incronsod vnIuo of dogroo of dIssocInfIon.
EXERCISES
1. Whnf Is nn oIocfroIyfo CIvo oxnmIos. Whnf do you monn by oIocfroIysIs
2. (o) IxInIn fho forms : (i) Inrndny (ii) I.C.I.
(I) !oInfo C.I. nnd I.C.I.
3. (o) Sfnfo fho Inrndny`s Inws of oIocfroIysIs.
(I) Irovo fhnf
I
Z
I
Z
l
l
2
2
= = ...
I
Z
n
n
= I.
4. (o) ofIno fho forms:
(i) SocIfIc conducfnnco (ii) IquIvnIonf conducfnnco.
(I) Iscuss fho offocf of chnngo In conconfrnfIon of fho soIufIon on socIfIc conducfnnco nnd
oquIvnIonf conducfnnco.
5. (o) ofIno fho forms (i) socIfIc conducfnnco nnd (ii) oquIvnIonf conducfnnco. WIfh fho nId of n
Iof, oxInIn fho vnrInfIon of oquIvnIonf conducfnnco of KCI nnd CH
3
COOH on dIIufIon.
(I) Sfnfo nnd oxInIn KohIrnusch`s Inw of Indoondonf mobIIIfIos of Ions.
6. Whnf Is monnf by fho frnnsorf numbor of nn Ion How Is If doformInod A moInr soIufIon of
CdI
2
showod nn nnIon frnnsorf numbor l.2. How wouId you nccounf for fho rosuIf
?. (o) ofIno fho socIfIc rosIsfnnco of n soIufIon. MonfIon Ifs unIfs.
(I) Sfnfo nnd oxInIn KohIrnusch`s Inw. Iscuss Ifs sIgnIfIcnnco nnd nIIcnfIons.
B. (o) ofIno frnnsorf numbor. How wIII you doformIno frnnsorf numbor
(I) SocIfIc conducfnnco of nn oIocfroIyfo docronsos, whIIo oquIvnIonf conducfnnco Incronsos on
dIIufIonoxInIn.
(c) Sfnfo KohIrnusch`s Inw. IxInIn n fow nIIcnfIons of fhIs Inw.
9. (o) WrIfo KohIrnusch`s omIrIcnI oqunfIon.
(I) ofIno socIfIc conducfnnco.
(c) WrIfo fho shorfcomIngs of fho fhoory of oIocfroIyfIc dIssocInfIon.
(J) ofIno Inrndny`s socond Inw.
(e) CIvo fho nIIcnfIons of fho fhoory of oIocfroIyfIc dIssocInfIon.
10. (o) Sfnfo fho roInfIonshI bofwoon fho coII consfnnf, conducfIvIfy nnd conducfnnco.
(I) Sfnfo KohIrnusch`s oxorImonfnI oqunfIon.
(c) ofIno fho nbsoIufo IonIc mobIIIfy.
11. Whnf Is monnf by oquIvnIonf conducfIvIfy of nn oIocfroIyfo oscrIbo fho mofhod you wouId
ndof fo monsuro oquIvnIonf conducfIvIfy ns nIso Ifs vnIuo nf InfInIfo dIIufIon for KCI nnd ncofIc
ncId.
ELECTROCHEMSTRY 229
12. WrIfo shorf nofos on :
(i) CoII consfnnf (ii) AbsoIufo voIocIfy of nn Ion
(iii) ConducfomofrIc fIfrnfIon
(it) KohIrnusch`s oxfrnoInfIon mofhod of doformInIng
t
.
13. Iscuss nII fyos of conducfomofrIc fIfrnfIons. AIso oxInIn fho nnfuro of fho grnh bofwoon
conducfnnco nnd voIumo of fIfrnnf usod.
14. ofIno KohIrnusch`s Inw nnd dIscuss Ifs nIIcnfIons.
15. Why doos fho oquIvnIonf conducfIvIfy of n nCI soIufIon Incronso wIfh dIIufIon How cnn fho
oIocfroIyfIc conducfnnco bo monsurod
16. SocIfIc conducfIvIfy of nn
50
KCI soIufIon nf 25C Is 0.0002?5 mhos cm
l
. If fho rosIsfnnco of
coII confnInIng fhIs soIufIon Is 500 ohms, whnf Is fho coII consfnnf |Ans. 0.l38 cm
l
]
1?. Tho rosIsfnnco of 0.098 () KCI wns found fo bo 2l4.4 ohms nf 298 K. CnIcuInfo fho oquIvnIonf
conducfnnco (
t
) of fho soIufIon nf fho snmo fomornfuro, If fho coII consfnnf Is 0.8?8 cm
l
.
|Ans. 42.l8 ohm
l
cm
l
]
1B. Tho rosIsfnnco of n conducfIvIfy coII fIIIod wIfh 0.l () soIufIon of nCI Is 2l0 ohm nf l8C.
CnIcuInfo fho oquIvnIonf conducfnnco (
t
) of fho soIufIon (coII consfnnf = 0.88 cm
l
).
|Ans. 4l.9 ohm
l
cm
2
]
19. Tho rosIsfnnco of n coII fIIIod wIfh 0.02 () KCI soIufIon nf 25C Is 225 ohms. Tho socIfIc con-
ducfnnco of 0.02 M KCI soIufIon nf fhIs fomornfuro wns 0.002?? ohm
l
cm
l
. Tho coII wns fhon
wnshod ouf nnd fIIIod wIfh 0.l M of CuSO
4
; nnd Ifs rosIsfnnco wns found fo bo 3?.5 ohms. CnIcuInfo
fho oquIvnIonf nnd moInr conducfnncos of CuSO
4
soIufIon.
|Ans. 83.0 ohm
l
cm
2
,

l66.0 ohm
l
cm
2
]
20. Tho rosIsfnncos of 0.l KCI soIufIon nnd 0.02 of nn oIocfroIyfIc soIufIon In n conducfIvIfy coII
woro found fo bo 3l0 ohms nnd 2,000 ohms rosocfIvoIy nf 298 K. Tho socIfIc conducfnnco of
0.l KCI soIufIon Is 0.0l28 ohm
l
cm
l
. CnIcuInfo fho oquIvnIonf conducfnnco of fho
gIvon soIufIon. |Ans. 99.2 ohm
l
cm
2
]
21. Tho oquIvnIonf conducfnnco nf InfInIfo dIIufIon of H
4
CI, H
4
O
3
nnd AgO
3
nro l49.?4 l0
4
,
l44.84 l0
4
nnd l33.36 l0
4
Sm
2
oq
l
rosocfIvoIy. CnIcuInfo fho oquIvnIonf conducfnnco of
AgCI nf InfInIfo dIIufIon. |Ans. l.382 l0
2
S m
2
oq
l
]
22. Tho oquIvnIonf conducfnnco of 0.0l ncofIc ncId Is l6.30 ohm
l
cm
2
oq
l
. Tho IonIc conducfnncos
of H
+
nnd CH
3
COO
Ions nf InfInIfo dIIufIon nro 349 nnd 40 ohm

l
cm
2
oq
l
, rosocfIvoIy. Whnf Is
fho orconfngo dIssocInfIon of ncofIc ncId nf fhIs conconfrnfIon |Ans. 4.l9]
23. urIng fho oIocfroIysIs of CuSO
4
soIufIon, Ioss of Cu In fho nnodo comnrfmonf wns 0.420. In n
voIfnmofor connocfod In sorIos, l.058 g of Cu wns doosIfod. IInd fho frnnsorf no. of Cu
+2
Ion.
|Ans. I
Cu
+2 = 0.2l5]
24. A 2.84 CuSO
4
soIufIon wns oIocfroIysod usIng If cnfhodo nnd Cu-nnodo. Affor oIocfroIysIs, fho
cnfhodo soIufIon confnInod 0.409 g Cu In 54.? g soIufIon. Tho Incronso In fho woIghf of cnfhodo
wns 0.804 g. CnIcuInfo fho frnnsorf numbor of Cu
+2
nnd SO
4

Ions |Af. wf. = Cu(63.6), S(32)
nnd O(l6)]. |Ans. I
Cu
+2 = 0.2l5, I
SO
4
= = 0.?85]
25. A 0.80 AgO
3
soIufIon wns oIocfroIysod usIng Ag-oIocfrodos. Affor oIocfroIysIs 5l.0 g of fho nnodo
soIufIon (nnoIyfo) wns found fo confnIn 0.5l9 g of AgO
3
. A ono nm. curronf wns nssod for
2 mIns. Whnf Is fho frnnsorf no. of Ag
+
In AgO
3
. |Ans. I
Ag
+ = 0.46]
230
EIectrochemicaI CeIIs
ELECTRODE POTENTIAL
OxIdutIon Is u pvocess wLeve eIectvons uve Iost by u substunce und veductIon
Is u pvocess wLeve eIectvons uve guIned by u substunce. As for oxnmIo In fho roncfIon:
2IoCI
3
+ SnCI
2
2IoCI
2
+ SnCI
4
i.e., Io
+3
+ Sn
+2
Io
+2
+ Sn
+4
Ior l g. nfom of Io
+3
, 55.85 g. Avogndro`s numbor of oIocfrons nro gnInod fo gof roducod
fo l g. nfom of Io
+2
. And for ovory g. nfom of Sn
+2
, fwIco fho Avogndro`s numbor of oIocfrons Is
Iosf.
If wo mnko nn nrrnngomonf ns shown In IIg. l0.l nffor somofImo, wo gof Sn
+4
In fho
vossoI I nnd Io
+2
In vossoI A. And wo gof dofIocfIon In mIIIInmmofor. Thoro Is n cIonr sIgn of
fIow of oIocfrons fhrough fho mofnIIIc wIro connocfod nnd fhIs nrrnngomonf Is consIdorod ns n
coII whIch gonornfos oIocfrIc curronf nf fho cosf of oxIdnfIon nnd roducfIon roncfIons occurrIng
sImuIfnnoousIy. Wo fnko oxIdnfIon ns n hnIf coII roncfIon nnd roducfIon ns nnofhor hnIf coII
roncfIon nnd fho fofnI roncfIon Is rodox roncfIon nnd bocomos fho sourco of o.m.f. of fho coII.
HCl
FeCl
3
Pt
A B
HCl
SnCl
2
Pt
NaCl salt
bridge
mA
Fig. 10.1 Construction of a cell.
!oncfIon In vossoI A : 2Io
+3
+ 2e Io
+2
|roducfIon]
!oncfIon In vossoI I : Sn
+2
2e Sn
+4
|oxIdnfIon]
2Io
+3
+ Sn
+2
Io
+2
+ Sn
+4
|coII roncfIon]
So, n coII Is consfrucfod of fwo oIocfrodos nnd fho o.m.f. of fho coII Is obfnInod from fho
nIgobrnIc sum of fho fwo oIocfrodo ofonfInIs.
Nernst SoIution Pressure Theory for EIectrode PotentiaI
If n mofnI rod (M) Is dIod Info n soIufIon confnInIng Ifs Ions (M
+n
) fho mofnI shows n
fondoncy fo sond Ions Info soIufIon. ornsf cnIIod fhIs fondoncy ns soIufIon rossuro. Iy
ELECTROCHEMlCAL CELLS 231
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Zn Cu
ZnSO
4
CuSO
4
sondIng fho Ions, fho mofnI rod nccumuInfos oIocfrons nnd ns n rosuIf, mofnI rod bocomos
nognfIvoIy chnrgod. On fho confrnry, fho soIufIon hns n fondoncy fo sond M
+n
Ions fo fho mofnI
rod duo fo osmofIc rossuro. Whon soIufIon rossuro oqunIIsos osmofIc rossuro fhoro Is
no nof offocf. Iuf whon ono oxcoods fho ofhor fho mofnIs
gof oIfhor osIfIvoIy or nognfIvoIy chnrgod. As for
oxnmIo, In fho cnso of Zn/Zn
+2
, fho soIufIon rossuro
oxcoods osmofIc rossuro, Zn rod sonds Zn
+2
Ions Info
fho soIufIon nnd gofs nognfIvoIy chnrgod nnd nffrncfs
osIfIvo chnrgos fownrds fho rod nnd, ns n rosuIf, nn
oIocfrIcnI doubIo Inyor Is sof u nnd n ofonfInI Is
osfnbIIshod bofwoon fho mofnI rod (Zn) nnd Ifs Ions
(Zn
+2
). And so Is fho cnso wIfh Cu/Cu
+2
, buf In fhIs cnso,
osmofIc rossuro oxcoods soIufIon rossuro nnd Cu rod
gofs osIfIvoIy chnrgod. Horo nIso n oIocfrIcnI doubIo
Inyor Is sof u nnd oIocfrodo ofonfInI Is osfnbIIshod. ThIs osfnbIIshod ofonfInI Is cnIIod
eIectvode potentIuI.
Tho oIocfrodo ofonfInI Is nIso osfnbIIshod In fho cnso of ovory oIocfrodo whoro oIocfrIcnI
doubIo Inyor Is sof u by oxchnngo of oIocfrons. Ior oxnmIo, fho sysfom
(If) Io
+2
(If) Io
+3
+ e
sofs u nn oIocfrIcnI doubIo Inyor whoro nn Inorf mofnI InfInum Is dIod Info n mIxfuro
confnInIng Io
+2
nnd Io
+3
nnd nn oIocfrodo ofonfInI Is osfnbIIshod.
So, un eIectvIc ceII Is composed oI two eIectvodes. To consIdor fho oIocfrodos
sonrnfoIy, wo cnII onch of fhom ns sIngIe eIectvode. And onch oIocfrodo hns n ofonfInI
whIch Is known ns sIngIe eIectvode potentIuI ( ). I.M.I. of fho coII Is nIgobrnIc sum of fho
fwo oIocfrodo ofonfInIs.
I =
l
+
2
SingIe EIectrode PotentiaI ( )
Tho oIocfrodo ofonfInI for nn oIocfrodo roncfIon:
M
+n
+ ne M (mofnI)
Is gIvon by ornsf oqunfIon = +
!T
I n
In o
n
M
+ whoro Is n consfnnf doondonf uon fho
mofnI.
n VnIoncy of mofnI
! Cns consfnnf
T AbsoIufo fomornfuro
I Inrndny consfnnf
o AcfIvIfy of M
+n
.
Af 25C fho oqunfIon comos fo :
= +
2 303 8 34l 298
96500
. .
n
Iog
l0
o n
M
+
= +
0 059 .
n
Iog
l0
o
n
M
+
Fig. 10.2 Electrode potential.
Ior gonornI uroso, o n
M
+ = C
M
+n
So, fhon fho oxrossIon Is : = +
0 059 .
n
Iog
l0 C
M
+n
|A form of ornsf oqunfIon]
Whon o = l, fhon =
Is known ns Stunduvd eIectvode potentIuI of mofnI M.
If wo consfrucf fho foIIowIng coII:
Zn
()
| Zn
+2
|| Cu
+2
|
(+)
Cu, I
coII
= l.0l5 V
Ior fhIs coII Zn/Zn
+2
Is nnodo nnd Cu/Cu
+2
Is cnfhodo nnd nf nnodo, Zn Is IonIsod fo Zn
+2
i.e., oxIdnfIon fnkos Inco nf nnodo nnd nf fho cnfhodo Cu
+2
Is noufrnIIsod i.e., roducfIon fnkos
Inco nf fho cnfhodo.
TofnI coII roncfIon Is:
Zn + Cu
+2
Zn
+2
+ Cu.
HIgLIIgLts:
AccordIng fo I!IAC convonfIon,
Tho sIngIo vorfIcnI IInos donofo oIocfrIcnI confncf.
Tho doubIo vorfIcnI IInos donofo fho juncfIon of fho fwo soIufIons nnd fhIs IIquId
juncfIon ofonfInI Is oIImInnfod or mInImIsod by fho uso of n snIf brIdgo.
A comIofo coII consIsfs of fwo hnIf coIIs. Tho rIghf hnnd hnIf coII Is rognrdod ns
fho osIfIvo oIocfrodo nnd fho Ioff hnnd hnIf coII Is rognrdod ns nognfIvo oIocfrodo.
IIocfrons fIow fhrough fho oxfornnI wIro from fho nognfIvo oIocfrodo fo fho osIfIvo
oIocfrodo. So roducfIon fnkos nf fho rIghf hnnd oIocfrodo nnd oxIdnfIon fnkos Inco
In fho Ioff hnnd oIocfrodo.
I.m.f. of fho coII I =
rIghf

Ioff
(whon bofh nro roducfIon ofonfInIs)
I =
rod
+

ox
.
OxIdnfIon ofonfInI mny bo fnkon ns roducfIon ofonfInI wIfh n mInus sIgn.
Determination of Standard PotentiaI of a MetaI EIectrode
Tho oIocfrodo ofonfInIs cnnnof bo doformInod sfrnIghf. Wo nro fo nssIgn n dofInIfo
vnIuo of oIocfrodo ofonfInI for n dofInIfo oIocfrodo. Ior oxnmIo, fo doformIno fho oIocfrodo
ofonfInI, wo fnko fho vnIuo for hydrogon oIocfrodo fo bo 'zoro` i.e., n soIufIon of ncId wIfh
(|H
+
] = l) nnd fo whIch hydrogon gns Is bubbIod nf ono nfmoshoro nnd InfInum foII Is dIod.
Wo hnvo n zoro ofonfInI for fhIs oIocfrodo. ow If wo wnnf fo doformIno sfnndnrd oIocfrodo
ofonfInI of zInc (
Zn
) wo nro fo consfrucf fho foIIowIng coII. (Soo ngo 22?)
Zn|ZnSO ( )
( )
H SO ( )|H (If)
( )
2 2
H
4 4
l l
soIufIon soIufIon
Zn
2
o o + +
= =
TabIe. 10.1: Standard Electrode Potentials (Reduction), 25C
1lecIroJe 1lecIroJe reocIion 1(VolIe)
(IeJucIion)
I
2
, I
l
2
I
2
+ e = I
2.80
If, CI
2
(g); CI
CI
2
+ e = CI
l.360
If, O
2
; H
+ l
2
O
2
+ 2H
+
+ 2e = H
2
O l.23
Au, Au
+++
Au
+++
+ 3e = Au l.06
Hg, Hg
2
++
Hg
2
++
+ 2e = 2Hg 0.?99
Ag, Ag
+
Ag
+
+ e = Ag 0.?98
If; Io
+++
, Io
++
Io
+++
+ e = Io
++
0.??l
Cu, Cu
++
Cu
++
+ 2e = Cu 0.344
CnIomoI oIocfrodo
l
2
Hg
2
CI
2
+ e = Hg + CI
0.268
(Pt) H
2
, H
+
H
+
+ e =
1
2
H
2
0.000
Ib, Ib
++
Ib
++
+ 2e = Ib 0.l22
Sn, Sn
++
Sn
++
+ 2e = Sn 0.l36
Zn, Zn
++
Zn
++
+ 2e = Zn 0. ?62
Mg, Mg
++
Mg
++
+ 2e = Mg l.866
n, n
+
n
+
+ e = n 2.?l5
!I, !I
+
!I
+
+ e = !I 2.959
Tho o.m.f. of fho coII wIII bo
I =
H
+
Zn
=
Zn
|3

= 0]
Tho o.m.f of n coII Is monsurod by ofonfIomofor, nnd wo gof sfnndnrd o.m.f. I of fho
nbovo consfrucfod coII whIch Is
Zn
.
!IkowIso, fho oIocfrodo ofonfInI of ofhor mofnIs nro doformInod sImIInrIy nnd IIsfod In
fnbIo. ThIs IIsf wIfh vnIuos nro known ns eIectvocLemIcuI sevIes. (TnbIo l0.l)
xumpIe 1. ColculoIe IIe e.n.f. of IIe cell
Zn
ZnSO (eoluIion)
(o 1)
CuSO (eol )
(o 1)
Cu
4
Zn
4
n
Cu
2 +
=
=
+
SoI. = Sfnndnrd roducfIon ofonfInI of Cu + sfd. oxIdnfIon ofonfInI of Zn.
= 0.344 + 0.?62
= l.l06.
TypicaI caIcuIation of e.m.f. of a ceII
!IquId juncfIon ofonfInI
nnIoI coII: Zn | ZnSO
4
(C
l
) || CuSO
4
(C
2
) | Cu
CoII roncfIon Is: Zn + Cu
+2
Zn
+2
+ Cu
I =
rIghf

Ioff
|whon bofh nro roducfIon ofonfInIs]

rIghf
=
Cu
+
!T
2I
In
|Cu ]
|Cu]
+2
O
x
I
d
u
n
t
s
i
.
e
.
,

o
I
o
c
f
r
o
n
o
g
n
f
I
v
o
R
e
d
u
c
t
u
n
t
s
i
.
e
.
,

o
I
o
c
f
r
o
o
s
I
f
I
v
o
or =
Cu
+
!T
2I
In |Cu ]
+2
|3 |soIId] = l]
!IkowIso,

Ioff
=
Zn
+
!T
2I
In | ] Zn
+2
|3 |soIId] = l]
I
coII
= +
4
5
6
7
8
9
+
4
5
6
7
8
9
+ +
Cu Zn
!T
2I
In Cu
!T
2I
In Zn . | ] . | ]
2 2
I
coII
=
(
!T
2I
Cu
Zn
Cu Zn
+2
+

+
) In
| ]
| ]
2
.
Interpretation of the EIectrochemicaI Series (Table 10.1)
l. Tho hIghor fho sfnndnrd oIocfrodo ofonfInI (roducfIon) of nn oIomonf, hIghor Is fho
oIocfronognfIvIfy of fhnf oIomonf. !owor osIfIon In fho fnbIo of nn oIomonf IndIcnfos Ifs hIghor
fondoncy of IonIsnfIon.
2. If n coII Is consfrucfod wIfh fho fwo oIomonfs ns fho oIocfrodos fhon fho o.m.f. of fho
coII Is obfnInod from fho oxIdnfIon ofonfInI of nnodo nnd roducfIon ofonfInI of cnfhodo.
!of Io nnd Cu nro usod ns oIocfrodos, fhon o.m.f. of fho coII,
I = !oducfIon ofonfInI of Cu + OxIdnfIon ofonfInI of Io.
= 0.344 + 0.44l
= 0.?85 voIf.
3. Tho hIghor oIocfroosIfIvo mofnI i.e., ossossIng Iowor sfnndnrd oIocfrodo ofonfInI
(roducfIon) wIII dIsInco fho mofnI from fho soIufIon of Ifs Ions wIfh n hIghor sfnndnrd oIocfrodo
ofonfInI (roducfIon) vnIuo.
Ior oxnmIo Zn(
Zn
= .?62) wIII dIsInco Cu from Ifs soIufIon (
Cu
= .344)
!IkowIso, fho non-mofnIs wIfh fho hIghor oIocfronognfIvIfy dIsInco fho oIomonfs
ossossIng Iowor oIocfronognfIvIfy.
Ior oxnmIo:
2KI + CI
2
2KCI + I
2
Redox-eIectrodes
A mIxfuro of Io
+2
/Io
+3
snIf In n soIufIon or Co
+3
/Co
+4
snIf In n soIufIon cnn ncf ns nn
oIocfrodo If n InfInum wIro Is dIod Info oIfhor of fho soIufIons. Any oxIdIsod or roducod form
of nn oIomonf bohnvos so. Thoso oIocfrodos nro known ns rodox oIocfrodos. IIocfrodo ofonfInI
() Is gIvon by:
OxIdnnf + no !oducfnnf
Ox + no !od.
=
!odox
+
!T
I
In
Ox
!od
n
o
o
=
!odox
+
0 059
l0
.
Iog
|Ox]
|!od] n
(for gonornI uroso)
Horo nIso vnIuos nro doformInod ngnInsf sfnndnrd hydrogon oIocfrodo.
TabIe 10.2: Normal potentials () of some redox system (Hydrogen scale)
1lecIroJe 1lecIroJe reocIion 1lecIroJe poIenIiol
(tolIe)
(If) Cr
+2
/Cr
+2
Cr
2+
+ e Cr
2+
0.4l
(If) V
+ 2
/V
+2
V
+3
+ e V
+2
0.2l 0.25
(If) H
+
/
l
2
H
2
H
+
+ e
l
2
H
2
0.00
(If) Sn
+4
/Sn
+2
Sn
+4
+ 2e Sn
+2
+ 0.l5
(If) Cu
+2
/Cu
+l
Cu
+2
+ e Cu
+l
+ 0.l6
(If) |Io(C)
6
]
2
/|Io(C)
4
]
4
Io(C)
6
3

+ e Io(C)
6
4
+ 0.36
(If) MnO
4
/MnO
4
2
MnO
4
+ e MnO
4
2
+ 0.54
(If)
l
2
I
2
/I
l
2
I
2
+ e I
+ 0.535
(If) Io
+2
/Io
+2
Io
+3
+ e Io
+2
+ 0.??
(If)
l
2
Ir
2
/Ir
l
2
Ir
2
+ e Ir
+ l.065
(If) IO
2
/
l
2
I
2
IO
3

+ 6H
+
+ 5e
l
2
I
2
+ 3H
2
O + l.20
(If) MnO
2
/Mn
+2
MnO
2
+ 4H
+
2e Mn
+2
+ 2H
2
O + l.23
TI
+3
/TI
+2
TI
+3
+ 2e TI
+l
+ l.25
l
2
CI
2
/CI
l
2
CI
2
+ e CI
+ l.36
Cr
2
O
?
2
/2Cr
+3
Cr
2
O
?
2
+ l4 H
+
+ 6e 2Cr
+3
+ ?H
2
O + l.36
MnO
4
/Mn
+2
MnO
4

+ 8H
+

+ 5e Mn
+2
+ 4H
2
O + l.52
IrO
2
/
l
2
Ir
2
IrO
3
+ 6H
+
+ 5e
l
2
Ir
2
+ 3H
2
O + l.52
Co
+4
/Co
+3
Co
+4
+ e Co
+2
+ l.6l
MnO
4
/MnO
2
MnO
4
+ 4H
+
+ 3e MnO
2
+ 2H
2
O + l.69
Co
+2
/Co CO
+2
+ e CO
+2
+ l.82
S
2
O
4
2
/2SO
4
2
S
2
O
4
2
+ 2e 2SO
4
2
+ 2.0l
l
2
I
2
/I
l
2
I
2
+ e I
+ 2.65
Tho nIr whIch occuIos Iowor osIfIon In fho fnbIo cnn oxIdIso fho nIr whIch occuIos
n hIghor osIfIon In fho fnbIo.
Latimer Diagram
Tho rodox ofonfInI of dIfforonf oxIdnfIon sfnfos for n nrfIcuInr oIomonf cnn bo
summnrIsod wIfh fho hoI of IMI dIngrnm nnd fho sImIosf fyo of such dIngrnm Is fho IutImev
dIugvum.
A !nfImor dIngrnm In n comncf form oxInIns n gronf donI of InformnfIon nnd shows
fho roInfIonshIs bofwoon fho vnrIous socIos In n sImIo nnd IucId form.
Wo know fhnf Mn oxIsfs In dIfforonf oxIdnfIon sfnfos nnd In ncIdIc modIum rofornbIy nf
zoro H, fho dIfforonf oxIdnfIon sfnfos nro rorosonfod by fho corrosondIng vnIuos ns
foIIows:
Mn
2+
+ 2e + Mn, = l.l8 V
Mn
+3
+ e

Mn
2+
, = l.52 V
MnO
2
+ 4H
+
+ e

Mn
3+
+ 2H
2
O, = .95 V
MnO
4
2
+ 4H
+
+

2e

MnO
2
+ 2 H
2
O, = 2.26 V
MnO
4
+ e MnO
4
2
, = + .56 V
MnO
2
+ 4H
+
+ 2e Mn
2+
+ 2H
2
O, = l.23 V
MnO
4
+ 4H
+
+ 3e MnO
2
+ 2H
2
O, = l.?0 V
MnO
4
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O, = l.5l V
Tho whoIo InformnfIon cnn bo summnrIsod In fho comncf mnnnor In n coIIInonr dIngrnm
ns foIIows.
MnO
4

0.56 V
MnO
4
2

2.26 V
MnO
2

0.95 V
Mn
3+

l.52 V
Mn
2+
l.l8 V
Mn
In fhIs dIngrnm, fho oxIdnfIon sfnfos of Mn docronso grndunIIy from Ioff fo rIghf. Tho
socIos H
+
, H
2
O ofc. nro nof IncIudod In fho dIngrnm. Tho couIo such ns MnO
4
/MnO
2
or
MnO
4
/Mn
2+
or MnO
2
/Mn
2+
ofc. nro cnIIod skIp coupIes nnd fho corrosondIng ofonfInIs nro
cnIIod skIp-step potentIuIs.
A IutImev dIugvum hoIs us fo dorIvo fho sfnndnrd ofonfInIs of such non-ndjnconf
couIos. Wo know fhnf C vnIuos corrosondIng fo dIfforonf sfos cnn bo nddod buf fho
vnIuos cnnnof bo so nddod. AgnIn C Is roInfod fo ns foIIows, C = nI. Tho ovornII C
of fwo succossIvo sfos wIII bo fho sum of fho IndIvIdunI vnIuos fo C vnIuos by muIfIIyIng
by fho roIovnnf nI fncfor, nddIng fhom fogofhor nnd convorfIng fho sum bnck fo for fho
non-ndjnconf couIo dIvIdIng by nI for fho ovornII oIocfron frnnsfor. SInco fho nI fncfor
cnncoIs In fhIs wny, wo cnn wrIfo
=
+
+

l 3
l l 2 2 2 3
l 2
n n
n n
IosIdos cnIcuInfIng fho vnIuos of non-ndjnconf couIos, fho IutImev dIugvum Is nIso
hoIfuI In rodIcfIng whofhor n nrfIcuInr socIos wIII undorgo dIsroorfIonnfIon or
comroorfIonnfIon.
A socIos wIII dIsroorfIonnfo Info Ifs noIghbour socIos If fho ofonfInI on fho Ioff Is
Iowor fhnn fhnf of fho rIghf socIos. On fho ofhor hnnd, n socIos wIII undorgo
comroorfIonnfIon If fho ofonfInI on fho Ioff Is hIghor fhnn fhnf of fho rIghf socIos In fho
dIngrnm. Ior oxnmIo, wo know fhnf H
2
O
2
dIsroorfIonnfos Info H
2
O nnd O
2
undor ncIdIc
condIfIons.

O H O H O
2
voIf
2 2
.?6 voIf
2
2

0.?0
l
l
Tho IeusIbIIIty oI dIspvopovtIonutIon oI H
2
O
2
cnn bo rodIcfod by consIdorIng fho
chnngo In fho vnIuos for fho foIIowIng roncfIons:
OvornII roncfIon:
2H
2
O
2
2H
2
O + O
2
(o) OxIdnfIon: H
2
O
2
O
2
+ 2H
+
+ 2e
Ox
= .?0 V
C
l
= nI = 2I ( .?0) = l.4 I
(I) !oducfIon: H
2
O
2
+ 2H
+
+ 2e 2H
2
O
!od
= l.?6 V
C
2
= nI = 2I l.?6 = 3.52 I
AddIng (o) nnd (I),
2H
2
O
2
2H
2
O + O
2
C = 2.l2 I
SInco fho rocoss Is nccomnnIod by docronso In CIbbs froo onorgy, fhoroforo dIsro-
orfIonnfIon wIII bo sonfnnoous. On fho ofhor hnnd, for fho chnngo Ag
2+

l.98 V
Ag
+

0.80 V
Ag
If cnn bo shown by sImIInr cnIcuInfIon fhnf dIsroorfIonnfIon of Ag
+
wIII nof fnko Inco bocnuso
If wIII bo nccomnnIod by Incronso In C vnIuo. Honco, In fhIs cnso fho comroorfIonnfIon
roncfIon Ag
2+
+ Ag = 2Ag
+
wIII fnko Inco.
Frost Diagram
A Irosf dIngrnm for nn oIomonf M Is n Iof of n for fho couIo M
n+
/ M ngnInsf Ifs
oxIdnfIon numbor n whoro n gIvos fho chnngo of oxIdnfIon numbor from n fo zoro. On fho bnsIs
of fhIs dIngrnm, If cnn bo rodIcfod whofhor fho oxIdnnf or fho roducfnnf wIII show gronfor
fondoncy for n roncfIon. Whon fho IIno joInIng fwo oInfs In fho dIngrnm Is quIfo sfoo, fho
ofonfInI of fho corrosondIng couIo Is hIghor. Honco, wo cnn mnko fhormodynnmIc rodIcfIons
nbouf fho roncfIon bofwoon nny fwo couIos by comnrIng fho sfos of fho corrosondIng IInos.
Tho oxIdIsIng ngonf of n rodox couIo wIII show fondoncy fo roducfIon If fho sIoo Is moro +vo.
Tho roducIng ngonf of fho couIo wIfh Ioss +vo sIoo wIII fond fo undorgo oxIdnfIon. Tho Ivost
dIugvum for nIfrogon In vnrIous oxIdnfIon sfnfos Is ns gIvon In IIg. l0.3(o) nnd l0.3(I).

Oxidation number
I
n
c
r
e
a
s
i
n
g
s
t
a
b
i
l
i
t
y
Most stable
oxidation
state
N

3 2 1 0 +1 +2 +3 +4 +5
1
Cu /Cu
2+
H /H
+
Zn /Zn
+2
Oxidation number
n
(
V
)
0
1
2
3
4
5
6
N
2
N
2
O
N
2
NO
3
NO
N O
2 4
N
H
3
N H
2 4
NH OH
2
NH OH
3
N
2
O
NO
HNO
2
N O
2 4
HNO
3
N H
2 5
NH
4
N
2
O
Fig. 10.3 (=) Fig. 10.3 (>) Frost diagram for nitrogen (N).
An oxnmInnfIon of fhIs Iof shows fhnf fho sIoo of fho IIno connocfIng HO
3
fo Iowor
oxIdnfIon numbors Is quIfo sfoo nnd honco HO
3
wIII funcfIon ns n good oxIdIsIng ngonf
undor sfnndnrd condIfIons i.e., (nf H = 0). A comnrIson of fho sIoo of fho Cu
2+
/Cu couIo
wIfh fhnf of fho HO
3
/O couIo shows fhnf If Is moro +vo for fho Inffor nnd honco HO
3
wIII
oxIdIso Cu fo Cu
2+.
Tho dIngrnm nIso IndIcnfos fhnf fho sIoo romnIns sfoo nII fho wny fo
2
IndIcnfIng fhnf
2
shouId bo fho roducf of roducfIon of HO
3
If oxcoss Cu Is rosonf In fho
roncfIon. Cu, howovor, doos nof roduco HO
3
fo
2
duo fo kInofIc IImIfnfIons nnd O Is
commonIy fho gns whIch Is ovoIvod whon Cu Is honfod wIfh dIIufo HO
3
.
An Ion or n moIocuIo In n Irosf dIngrnm wIII bo unsfnbIo wIfh rosocf fo dIsroorfIonnfIon
If If IIos nbovo fho IIno connocfIng fwo ndjnconf socIos. ThIs Is duo fo fho fncf fhnf, fho nvorngo
froo onorgy of fho InformodInfo socIos Is Inrgor fhnn fho monn froo onorgy of fho fwo ndjnconf
socIos. Irom fho dIngrnm If Is soon fhnf sInco H
2
OH IIos nbovo fho IIno joInIng H
3
nnd
2
If wIII undorgo dIsroorfIonnfIon. Tho dIsroorfIonnfIon Is, howovor, nof sonfnnoous ns If
Is nof kInofIcnIIy fnvourod.
A subsfnnco fhnf IIos boIow fho IIno connocfIng fwo ndjnconf noIghbours In n Irosf
dIngrnm Is moro sfnbIo fhnn fhoy nro bocnuso Ifs nvorngo froo onorgy Is Iowor. !ndor such
cIrcumsfnncos comroorfIonnfIon wIII bo fhormodynnmIcnIIy fnvourod e.g., In H
4
O
3
, H
4
+
Ion confnIns In 3 oxIdnfIon sfnfo nnd In O
3
Ion Is rosonf In +5 oxIdnfIon sfnfo, on fho

ofhor hnnd
2
O hns nn oxIdnfIon sfnfo of +l, whIch Is InformodInfo bofwoon 3 nnd + 5 nnd Ifs
osIfIon In fho Irosf dIngrnm Is Iowor fhnn fhnf of O
3
Ion nnd H
4
+
Ion nnd so H
4
O
3
undorgoos comroorfIonnfIon, H
4
+
+ O
3

2
O + 2H
2
O. Whon fho IIno joInIng fhroo
ndjnconf socIos bocomos nroxImnfoIy n sfrnIghf IIno, fhon no ono socIos wIII bo fho oxcIusIvo
roducf e.g., oxIdnfIon of H
3
by OsfwnId rocoss fo O nnd fhon fo O
2
foIIowod by dIssoIufIon
In H
2
O roducos HO
3
nnd nIso O ns woII ns HO
2
. ThIs Is duo fo fho fncf fhnf O, HO
2
nnd HO
3
IIo nroxImnfoIy on n sfrnIghf IIno In fho Irosf dIngrnm.
O + O
2
+ H
2
O 2 HO
2
3HO
2
HO
3
+ 2O
2
+ 2H
2
O
3O
2
+ H
2
O HO
3
+ HO
2
A Irosf dIngrnm cnn bo consfrucfod from n !nfImor dIngrnm e.g., Iof us consIdor fho
!nfImor dIngrnm.
O
2
0.70 V
H O
2 2
1.76 V
H O
2
+1.23 V
Tho oxIdnfIon numbors of 'O` nfom In O
2
, H
2
O
2
nnd H
2
O nro 0, l nnd 2, rosocfIvoIy.
Whon 'O` chnngos from O
2
fo H
2
O
2
, oxIdnfIon numbor of 'O` chnngos from 0 fo l, Honco,
chnngo In oxIdnfIon numbor = l. = l .?0 = .?0 voIf, whon O chnngos fo H
2
O

Ifs
oxIdnfIon numbor chnngos from 0 fo 2 nnd In fhIs cnso, n = 2. Thoroforo, n for fho formnfIon
of H
2
O = 2 l.23 = 2.46 voIf. Whon fhoso vnIuos of n nro Ioffod ngnInsf fho corrosondIng
oxIdnfIon numbors, wo gof fho roquIrod Irosf dIngrnm ns foIIows.
Tho ofonfInI corrosondIng fo roducfIon of H
2
O
2
fo H
2
O cnn bo cnIcuInfod ns foIIows
from fho oxnmInnfIon of fho IIno If Is obvIous fhnf nf fho oInf corrosondIng fo l oxIdnfIon
numbor n = .?0 voIf nnd n corrosondIng fo oxIdnfIon numbor of 2 Is 2.46 voIf. Tho
dIfforonco Is, fhoroforo, 2.46 ( .?0) = l.?6 voIf.
Tho chnngo In oxIdnfIon numbor from H
2
O
2
fo H
2
O Is l. Thoroforo, fho for fho couIo
H
2
O
2
/H
2
O Is oqunI fo
l.?6
l
= + l.?6 voIf.
2 1 0
2
1
0
Oxidation number
n
(
V
)
H O
2 2
O
2
H O
2
+1
Acidic
Fig. 10.4 Frost diagram for the system O
2
O
2
2
2O
2
.
ThIs Is In nccordnnco wIfh fho !nfImor dIngrnm.
HIgLIIgLts:
\ses oI stunduvd potentIuI (veductIon) vuIues:
l. IrodIcfIon of nn oxIdnfIon-roducfIon roncfIon.
2. IrodIcfIon rognrdIng IIbornfIon of hydrogon by n mofnI from n hydrncId.
3. IrodIcfIon of fonsIbIIIfy of n chomIcnI roncfIon.
xumpIe. IrodIcf whofhor fho roncfIon wIII occur sonfnnoousIy or nof.
Zn
+2
+ Cu

Zn + Cu
+2
+
Zn / Zn
2
= 0.?62 +
Cu /Cu
2 = 0.344
Tho fwo hnIf coII roncfIons nro:
Zn
+2
+ 2e

Zn | = 0.?62]
Cu 2e Cu
+2
| = 0.344]
AddIng Zn
+2
+ Cu Zn + Cu
+2
|I
Cu
= l.l06]
SInco, I
coII
= vo.
So, fho roncfIon wIII nof occur sonfnnoousIy.
xumpIe. IInd whofhor Cu
+
dIsroorfIonnfo In nquoous soIufIon Info Cu
+2
nnd Cu
i.e., coII roncfIon Is
2Cu
+
Cu
+2
+ Cu, CIvon, +
Cu /Cu
2 + = + 0.l5 V
+
Cu / Cu
= 0.52 V
Cu
+
+ e Cu | = 0.52 V]
Cu
+
e Cu
+2
| = 0.l5 V]
AddIng Cu
+
+ Cu
+
Cu
+2
+ Cu |I
coII
= 0.3? V]
SInco I
coII
Is osIfIvo, Cu
+
wIII dIsroorfIonnfo sonfnnoousIy In nquoous soIufIon Info
Cu
+2
nnd Cu.
xumpIe. Ag wIII nof dIsInco hydrogon from HCI, gIvon Ag
+
/Ag = 0.?98.
SoI. CoII roncfIon: 2Ag + 2H
+
2Ag
+
+ H
2
2Ag 2e 2 Ag
+
| = 0.?98]
2H
+
+ 2e H
2
|H
+
/H

= 0.00 V]
AddIng 2Ag + 2H
+
2Ag
+
+ H
2
|I
coII
= 0.?98]
SInco, fho I
coII
vnIuo Is nognfIvo, Ag cnnnof dIsInco H
2
from HCI.
Concentration CeII
Whon n mofnI Is dIod Info fwo soIufIons of ono of Ifs snIfs of dIfforonf conconfrnfIons,
n vory InforosfIng sIfunfIon nrIsos:
Ag | AgO
3
(C
l
) || AgO
3
(C
2
) | Ag
Ag AgO
3
(C
l
) SnIf brIdgo AgO
3
(C
2
) Ag
(IIufo) of snfd. |Conconfrnfod]
H
4
O
3
or Ag | AgO
3
(C
l
M) || AgO
3
(C
2
M) | Ag (C
2
> C
l
)
Voltmeter
NH NO
Salt bridge
4 3
e
Electron
flow
+
Ag
electrode Ag
electrode
Ag Ag + e
+
Ag + Ag e
C M Ag ions
1
+
C M Ag ions
2
+
C > C
2 1

+
Fig. 10.5 Concentration cell.
ImngIno fhnf curronf nssos fhrough fho oxfornnI wIro ns shown by fho nrrow. Wo shnII
gof sIIvor doosIfod on fho rIghf hnnd oIocfrodo nnd dIssoIufIon of sIIvor from fho Ioff hnnd
oIocfrodo ns If sIIvor boIng frnnsorfod from conconfrnfIon C
2
fo conconfrnfIon C
l
.
So, fho coII roncfIon Is
HnIf coII roncfIon (Ioff) oxIdnfIon Ag e

Ag + (C
l
)
HnIf coII roncfIon (rIghf) Ag
+
(C
2
) + e Ag
TofnI: Ag
+
(C
2
) = Ag
+
(C
l
)
!
=
!
nnd n = l
I = 2.303
!T
I
C
C
C
C
2
l
2
l
n n
Iog
. . ( )
Iog =

2 303 8 l38 298

96500
So, I =
0.059
l
C
C
2
l
Iog
|3 n = l]
Thoroforo, o.m.f. of such coII doonds on fho roInfIvo conconfrnfIon nnd nof on fho nbsoIufo
vnIuos.
If
C
C
2
l
= l0, fho obsorvod o.m.f. Is 59 mV.
Tho sfrongor soIufIon ncfs ns osIfIvo oIocfrodo.
ThIs fyo of conconfrnfIon coII Is known ns eIectvoIyte concentvutIon ceII.
Anofhor fyo of conconfrnfIon coII Is eIectvode concentvutIon ceII, ono such coII Is:
If | H
2
(p
l
) | H
+
| H
2
(p
2
) | f
p
l
nnd p
2
nro unoqunI rossuros of H
2
Tho coII roncfIon Is:
OxIdnfIon: H
2
(p
l
) 2e 2H
+
!oducfIon: 2H
+
+ 2e H
2
(p
2
)
OvornII: H
2
(p
l
) H
2
(p
2
)
o.m.f. of fho coII Is: I =
!T
2I
l
2
In
p
p
.
AppIication of the Concentration CeIIs H
2
etevmInutIon oI soIubIIIty oI spuvIngIy-soIubIe suIts.
If wo wnnf fo doformIno fho soIubIIIfy of AgCI, wo nro fo monsuro o.m.f. of fho foIIowIng
coII.
Ag | Ag O
3
(0.0l)
Snfurnfod soIufIon
of KO
snIf brIdgo
3 Snfurnfod AgCI | Ag
o.m.f. of fho coII Is gIvon by,
I =
0 059 .
Iog
n
C
C
2
l
Horo n = l, conconfrnfIon of Ag
+
In 0.0l() AgO
3
soIufIon Is 0.0l g. Ion I
l
Is (C
2
).
So, I =
0.059
l
0.0l
C
l
Iog
So, C
l
i.e., Ag
+
In AgCI cnn bo cnIcuInfod.
xumpIe 1. CnIcuInfo (i) SoIubIIIfy roducf of AgI, (ii) SoIubIIIfy of AgI In wnfor nf 25.
CIvon o.m.f. of fho coII Is 0.?88 V nf 25C. Tho ncfIvIfy cooffIcIonf (f) Is 0.9 onch.
CoII: Ag/AgI/ In 0.05 (M) KI) | H
4
O
3
| AgO
3
(0.05M) | Ag.
Tho conconfrnfIon of Ag
+
In AgO
3
Is 0.05 0.9 = 0.045 M
Tho conconfrnfIon of I

In KI Is 0.05 0.9 = 0.045 M
!of C
l
bo fho conconfrnfIon of Ag
+
In AgI soIufIon.
I =
0.059
l
Iog
0.045
C
l
or 0.?88 = 0.059 Iog
0.045
C
l
or Iog
0.045
C
0.?88
0.059
l3.33
l
= =
or
0.045
C
AnfIIog
l
= l3 33 .
= 2.l38 l0
l3
C
l
=
0.045
2.l38 l0
l3
= 2.l05 l0
l5
moI I
l
.
K
s
of AgI = |Ag
+
] |I
]
= 2.l05 l0
l5
0.045
= 9.4?2 l0
l?
SoIubIIIfy of AgI = K
s
= 9 4?2 l0
l?
.
= 9.?32 l0
9
moI I
l
= 9.?32 l0
9
l43.5 g I
l
= l.396 l0
6
gI
l
etevmInutIon oI vuIency
Hg || Hg
2
(O
3
)
2
0.5() || Hg
2
(O
3
)
2
(0.05) ()/Hg
C
2
C
l
Tho o.m.f. of fho nbovo coII = 0.029 V
Wo hnvo, I =
0.059 C
C
2
l
n
Iog
=
0.059
Iog
0.5
0.05 n
whoro n Is vnIoncy.
=
0.059
Iog l0
0.059
n n
=
or 0.029 =
0.059
n
n =
0.059
0.029
2.
INDICATOR ELECTRODES
Hydrogen EIectrode
If consIsfs of n smnII Ioco of InfInum foII oIocfroInfod
wIfh InfInum bInck, ovor whIch hydrogon gns Is nssod. Tho
InfInum bInck surfnco oxhIbIfs n sfrong nbsorfIon owor
fownrds hydrogon gns, ns n rosuIf, fho mofnI surfnco romnIns
In confInuous confncf wIfh fho hydrogon gns. Tho oIocfrodo
wIII ncf ns If If woro nn oIocfrodo of mofnIIIc hydrogon. Whon
In uso, fhoroforo, onIy n nrf of fho foII Is Immorsod In l()
HCI; fho romnIndor Is surroundod by uro hydrogon gns nf
l nfm. rossuro. ThIs Is stunduvd Lydvogen eIectvode. Tho
o.m.f. of fhIs oIocfrodo hns boon nrbIfrnrIIy nssIgnod fo bo zoro.
TLe pH oI u soIutIon cun be detevmIned wItL tLe
LeIp oI u Lydvogen eIectvode In fhnf cnso, fho InfInum
oIocfrodo Is dIod Info fho soIufIon whoso H Is fo bo
doformInod, Insfond of l() HCI nnd H
2
gns nf l nfm nssod
ovor fho InfInum oIocfrodo.
Tho oIocfrodo roncfIon Is
H
+
(oq) + e
l
2
2
H ( ) g
Fig. 10.6 Hydrogen Electrode.
H -Gas
2
HCl
Tho oIocfrodo ofonfInI Is gIvon by,
= +
!T
I
Iog
|H ]
|H ]
2
l/ 2
+
= + 0.059 Iog
l
|H ]
+
(n = l)
= 0 0.059 Iog |H
+
]
= 0.059 H nf 25C.
A fuII coII Is consfrucfod by couIIng fho nbovo hnIf coII wIfh n sfnndnrd hydrogon
oIocfrodo. Tho o.m.f. I of fho coII Is fhon doformInod ofonfIomofrIcnIIy. SInco oIocfrodo ofonfInI
of sfnndnrd hydrogon oIocfrodo Is zoro, fho obsorvod o.m.f. of fho coII gIvos dIrocfIy fho oIocfrodo
ofonfInI () of fho hnIf coII. So,
fho coII Is: (If) H
2
| H
+
(o = l) || H
+
(o = unknown) | H
2
(If)
I
Obs
=

= 0.059 H
H =
I
Obs
0 059 .
+
HgCl
&
KCl
+
HgCl
paste
Calomel
electrode
Sat.
KCl
Salt bridge
H
2
Trap
H
2
Hydrogen
electrode
H
2
Solution
Fig. 10.7 Determination of pH by Hydrogen Electrode.
Reference EIectrodes
Ior doformInnfIon of sfnndnrd oIocfrodo ofonfInIs (), sfnndnrd hydrogon oIocfrodo Is
usod ns roforonco. Iuf fhoro nro somo dIffIcuIfIos wIfh hydrogon oIocfrodo. MnInfnInIng l nfm.
rossuro of hydrogon nnd fo mnko o
H
+ = l Is vory dIffIcuIf. To ovorcomo fhIs dIffIcuIfy nnofhor
oIocfrodo whIch Is known ns socondnry roforonco oIocfrodo Is usod for doformInIng sfnndnrd
oIocfrodo ofonfInI. Ono of such oIocfrodos Is cuIomeI eIectvode. To doformIno H of n soIufIon
fho coII consfrucfod wIfh fho cnIomoI oIocfrodo wIII bo: (If) H
2
| H
+
(o) || ormnI cnIomoI
oIocfrodo (IIg. l0.?).
CaIomeI EIectrode
ThIs oIocfrodo ossossos corfnIn ndvnnfngos. If cnn bo ronrod onsIIy nnd cnn bo usod
for n Iong fImo. Tho sfnndnrd oIocfrodo ofonfInI of fhIs oIocfrodo Is doformInod ngnInsf sfnndnrd
hydrogon oIocfrodo.
KCl
HgCl + Hg
Hg
Fig. 10.8 Calomel Electrode.
Tho boffom of fho oIocfrodo Is fIIIod wIfh morcury. Morcury Inyor Is covorod wIfh n nsfo
of Hg
2
CI
2
(0.l) nnd ovor If fhoro Is n snfurnfod soIufIon of KCI wIfh somo crysfnIs of KCI. Tho
oIocfrodo roncfIon Is:
l
2
2 2
Hg CI ( ) s Hg + CI
(o
CI
)
Tho oIocfrodo ofonfInI Is gIvon by
= +
!T
I
In
CI
o ( 3 n = l).
TLe stunduvd eIectvode potentIuI (veductIon) oI cuIomeI eIectvode
Ior l.0() KCI = + 0.28 V
Snfurnfod KCI = + 0.2422 V
Any oIocfrodo whoso sfnndnrd ofonfInI Is fo bo doformInod Is connocfod fo cnIomoI
oIocfrodo by monns of KCI snIf brIdgo. Tho o.m.f. of fho sof-u coII Is doformInod
ofonfIomofrIcnIIy from whIch fho sfnndnrd oIocfrodo ofonfInI of fho oIocfrodo Is cnIcuInfod.
To doformIno H of n soIufIon, wo hnvo,
I
Obs
= (cnIomoI) (H
2
oIocfrodo)
= (cnIomoI) 0.059 Iog |H
+
]
= 0.28 + 0.059 H
or H =
I 0.28
0.059
Obs

Ag-AgCI EIectrode
Tho uso of fhIs roforonco oIocfrodo Is vory common. Tho oIocfrodo consIsfs of n sIIvor
wIro, confod oIocfroIyfIcnIIy wIfh sIIvor chIorIdo nnd Is dIod Info n soIufIon KCI of dofInIfo
sfrongfh. Tho ofonfInI of fhIs oIocfrodo
ELECTROCHEMCAL CELLS 245
Ag/AgCI(s) CI
(o
CI
= l) || HCI (o = l), H
2
(l nfm)/If
= 0.2224 V nf 25
hns boon nccurnfoIy doformInod ngnInsf n sfnndnrd hydrogon oIocfrodo.
GIass EIectrode
A gInss oIocfrodo consIsfs of n vory fhIn buIb or mombrnno of socInIIy ronrod nnd H
rosonsIvo gInss nnd whIch Is fusod on fo n Ioco of fhIck hIgh rosIsfnnco gInss. Tho fhIck gInss
mombrnno sorvos ns n soIId oIocfrodo whoso ofonfInI chnngos wIfh H of fho soIufIon wIfh
whIch If romnIns In confncf. Ior good oIocfrIcnI confncf fho buIb confnIns n sIIvorsIIvor chIorIdo
oIocfrodo Immorsod In n sfnndnrd HCI soIufIon. A InfInum wIro mny bo usod In Inco of fho
AgAgCI oIocfrodo (IIg. l0.9).
Iov pH detevmInutIon wItL tLe LeIp oI gIuss eIectvode fho oIocfrodo Is dIod Info
fho soIufIon whoro H Is fo bo doformInod nnd Is usunIIy combInod wIfh n roforonco oIocfrodo
gonornIIy cnIomoI oIocfrodofo form n comIofo coII. Tho ofonfInI of fho gInss oIocfrodo vnrIos
IInonrIy wIfh H (IIg. l0.l0).

gInss oIocfrodo
= +
!T
I
In |H ]
+
=
2 303 . !T
I
H
= 0.059 H nf 25.
Pt wire or
silver chloride
coated silver
wire
0.1 M HCl
Thin-walled
glass bulb
Potentiometer
+
Glass
electrode
Saturated
calomel electrode
Solution of
unknown pH
[H = ?]
+
Fig. 10.9 Glass Electrode. Fig. 10.10 Determination of pH by Glass Electrode.
HIgLIIgLts:
o.m.f. of fho coII comrIsIng of gInss oIocfrodo nnd cnIomoI oIocfrodo gIvos fho H
of fho soIufIon from fho oqunfIon, = 0.059 H
CInss oIocfrodo Is vIrfunIIy hydrogon oIocfrodo.
vnIuo Is nof zoro In fho cnso of n gInss oIocfrodo.
vnIuo of gInss oIocfrodo cnn onsIIy bo doformInod by cnIIbrnfIon usIng buffors of
known H.
CInss oIocfrodo Is fho mosf oxfonsIvoIy usod oIocfrodo for H doformInnfIon.
TLe udvuntuges oI gIuss eIectvode. (o) Ifs rnId rosonso, (I) romnIns unnffocfod by
fho rosonco of oxIdIsIng nnd roducIng ngonfs.
TLe dIsudvuntuges oI gIuss eIectvode. (o) Ifs frngIIIfy nnd (I) Ifs InnbIIIfy In fho
rosonco of hIgh conconfrnfIons of nIknII.
OnIy IItLIum sIIIcu gIusses enubIe pH meusuvements to be vuIId ovev pvuctIcuIIy
tLe entIve pH vunge.
pH and miIIivoIt meters
A IInonr roInfIonshI oxIsfs bofwoon fho H of n soIufIon, nf n gIvon fomornfuro, nnd
fho o.m.f. of n coII (I) consfrucfod of n veIevence eIectvode nnd nn IndIcutov eIectvode.
SInco, I = K 0.0592 H
i.e.,
I
H
= 0.0592
Thus n cnIIbrnfIon In mV cnn bo convorfod Info H unIfs whon dIvIdod by 0.059. In
pvuctIce, Lowevev, pH metev scuIes uve cuIIbvuted In pH unIts und In mIIIIvoIts (mV)
und tLe uppvopvIute scuIe und vunge Is seIected by u sImpIe contvoI.
PoIarisation
Whon n sImIo coII drIvos n curronf, fho foIIowIng Is fho coII roncfIon:
At Coppev pIute:
Cu Cu
+2
+ 2e
2H
+
+ 2e H
2
At ZInc pIute:
Zn

Zn
+2
+ 2e
Zn
+2
+ SO
4
2

ZnSO
4
TotuI ceII veuctIon:
Zn + H
2
SO
4
= ZnSO
4
+ H
2
+
Zn
Cu
dil. H SO
2 4
Bubbles of H
2
Fig. 10.11
Whon curronf fIows from Cu-Info fo Zn-Info, n Inyor of hydrogon bubbIos Is found fo bo
formod on fho surfnco of fho Cu-Info. Tho offocf of nccumuInfIon of hydrogon Is fwo-foId:
(i) Hydrogon Inyor Incronsos fho rosIsfnnco offorod fo fho fIow of curronf by covorIng
fho Cu-Info.
(ii) Tho Inyor of H
2
In confncf wIfh fho ncId soIufIon Is found fo ncquIro n ofonfInI Iowor
fhnn fhnf of Zn. Tho Zn-Info, fhoroforo, bohnvos ns osIfIvo oIocfrodo nnd H
2
nccu-
muInfod ns nognfIvo oIocfrodo, so, nn nddIfIonnI o.m.f. Is gonornfod, whIch Is cnIIod
poIuvIsutIon e.m.I. or buck e.m.I. nnd whIch fonds fo drIvo n curronf oosIfo fo
fho dIrocfIon of fho mnIn curronf fIow; nnd honco fhIs bnck o.m.f. oosos fho mnIn
o.m.f. As fho hydrogon bubbIo Is gonornfod moro nnd moro, fho oInrIsnfIon o.m.f.
Incronsos nnd uIfImnfoIy If comfofoIy noufrnIIsos orIgInnI o.m.f. nnd fho curronf
sfos fofnIIy. ThIs honomonon Is known ns poIuvIsutIon.
IoInrIsnfIon offocf Is nIso soon durIng oIocfroIysIs: whon nn oIocfrIc curronf Is nssod
fhrough dII. H
2
SO
4
usIng If-oIocfrodos, H
2
nnd O
2
nro ovoIvod.
H
2
SO
4
2H
+
+ SO
4
2
SO
4
2
+ H
2
O H
2
SO
4
+ O
2
At unode: Tho roncfIon Is,
2O
2
4e

O
2
At cutLode: Tho roncfIon Is,

2H
+
+ 2e H
2
If, nffor somo fImo, fho bnffory Is romovod nnd n gnIvnnomofor Is fIffod In fho oufor
cIrcuIf, n curronf Is soon fo nss bofwoon fho fwo oIocfrodos, buf In oosIfo dIrocfIon fo fhnf
durIng oIocfroIysIs. Hydrogon nnd oxygon gnsos covorIng fho fwo If-oIocfrodos bocomo fho
sourco of fhIs o.m.f. (bnck o.m.f.). TLIs pLenomenon oI buck e.m.I. deveIoped by pvoducts
oI eIectvoIysIs Is known us poIuvIsutIon (IIg. l0.l2).
+
Pt Pt
e
dil. H SO
2 4
O
2
H
2
+
Galvanometer
( ) Polarisation during
electrolysis
a ( ) Polarised cell b
Fig. 10.12 Development of polarisation by the products of electrolysis.
Decomposition PotentiaI
If wo sfnrf oIocfroIysIs of dII. H
2
SO
4
usIng If oIocfrodos nIyIng nn o.m.f. of ono voIf, If
wIII soon como fo nn ond duo fo bnck o.m.f. dovoIood durIng oIocfroIysIs. So, fo koo fho
oIocfroIysIs goIng on, wo nro fo nIy nn o.m.f. whIch cnn ovorcomo fho offocf of bnck o.m.f. TLe
mInImum voItuge, wLIcL Is Just suIIIcIent to ovevcome tLe buck e.m.I. ov poIuvIsutIon
e.m.I. Is cuIIed decomposItIon potentIuI oI tLe gIven eIectvoIyte (IIg. l0.l3).
C
u
r
r
e
n
t
d
e
n
s
i
t
y
Decomposition
voltage
Voltage
Fig. 10.13 Decomposition Potential.
Af fhIs sfngo, If fho nIIod o.m.f. Is grndunIIy Incronsod, oIocfroIysIs confInuos
unInforrufod. So, n mInImum voIfngo musf nIwnys bo nIIod fo sfnrf fho oIocfroIysIs rocoss.
HIgLIIgLts:
Tho docomosIfIon ofonfInI Is dIfforonf for dIfforonf oIocfroIyfos.
Tho docomosIfIon ofonfInI of CuSO
4
Is l.5 V wIfh Cu-oIocfrodos nnd fhnf of
ZnSO
4
Is 2.55 V wIfh Zn-oIocfrodos. Whon nn o.m.f. of Ioss fhnn 2-5 V Is nIIod
bofwoon Cu-oIocfrodos onIy Cu wIII gof doosIfod nf fho cnfhodo whIIo Zn wIII
romnIn In soIufIon If n mIxfuro of CuSO
4
nnd ZnSO
4
Is usod ns oIocfroIyfo.
OvervoItage
ThoorofIcnI voIfngo roquIrod for fho docomosIfIon of nn ncId soIufIon shouId bo oqunI fo
fho o.m.f. of fho rovorsIbIo coII consfrucfod wIfh H
2
(g) nf l nfm. Iuf If Is soon fhnf fho vnIuo of
nIIod o.m.f. Is nIwnys hIghor fhnn fhIs fhoorofIcnI vnIuo. IIocfroIysIs of dII. H
2
SO
4
wIfh If-
oIocfrodos roquIros l.? V In Inco of l.23 V (fhoorofIcnI vnIuo). TLIs dIIIevence between tLe
tLeovetIcuI voItuge und uctuuI uppIIed voItuge necessuvy Iov eIectvoIysIs Is known us
ovevvoItuge.
Battery
CoIIs nro dovIcos whoro oIocfrIc curronf Is gonornfod nf fho cosf of somo hysIcochomIcnI
rocossos goIng InsIdo fho coII. In ordor fo nIy oxncf fhormodynnmIc rIncIIos fo coII roncfIon
If Is cusfomnry fo dIsfInguIsh bofwoon rovorsIbIo nnd IrrosvorsIbIo coIIs. Iocnuso fho fhormo-
dynnmIc rIncIIo Is onIy nIIcnbIo fo rovorsIbIo coIIs. If Is woII known fhnf nny chomIcnI
roncfIon conducfod rovorsIbIy cnn yIoId somo oxfornnI work nnd fho usofuI work nvnIInbIo
from fho rocoss, rovIdod fho rocoss hns boon conducfod rovorsIbIy nf consfnnf fomornfuro
nnd undor n gIvon rossuro Is oqunI fo (fho docronsIng CIbbs froo onorgy C). SInco oIocfrIcnI
work Is oqunI fo nII, whoro I = fnrndny nnd I = o.m.f. of fho coII
so, wo hnvo
C = nII or C = nII
A bnffory Is nn oIocfrochomIcnI coII whIch Is usod ns fho sourco of dIrocf curronf of n
consfnnf voIfngo. Inffory works on fho nbovo fhormodynnmIc rIncIIo.
Battery
Primary
[The cell reaction
is not reversible]
Secondary
[The cell reaction
is not reversible]
Flow
[The reactants, products and
electrolytes pass through the battery
and during the passage electric current
is generated at the expense of chemical
reactions as in electrochemical cells]
Primary CeIIs
(o) IecIuncLe ceII. (IIg. l0.l4) ThIs fyo of coII wns dovIsod by Coorgos !ocInncho. Tho
coII consIsfs of n gInss vossoI I, whIch confnIns n snfurnfod soIufIon of H
4
CI ns nn ncfIvo
IIquId. Tho cnfhodo Is nn nmnIgnmnfod Zn-rod (Z) dIod nrfInIIy In H
4
CI soIufIon. Tho
nnodo Is mndo of gns cnrbon (C) Incod wIfhIn n orous of I whIch Is nIso dIod nrfInIIy In
H
4
CI soIufIon. Tho snco bofwoon fho cnrbon rod nnd fho of Is fIIIod wIfh n mIxfuro of
owdorod chnrconI nnd MnO
2
whIch sorvos ns n dooInrIsor. SInco MnO
2
Is n vory oor conducfor,
chnrconI Is nddod fo Incronso fho conducfIvIfy. Tho fo of fho of Is sonIod wIfh Ifch. Tho sonI
hns n hoIo fo nIIow fho oscno of H
3
gns. Tho o.m.f. of fho coII Is l.4 V.
Pitch
+
Glass vessel
Zinc rod()
Porous pot
Carbon rod
Carbon
manganese
dioxide mixture
NH Cl (Sol)
4
P
Hole
C
B
Z
n
Fig. 10.14 Leclanche cell.
CeII veuctIon: Zn + H
4
CI = ZnCI
2
+ 2 H
3
+ H
2
H
2
Is oxIdIsod by MnO
2
ns H
2
+ 2 MnO
2
= Mn
2
O
3
+ H
2
O.
Whon curronf Is drnwn from fho coII, Zn
rod Is usod u nnd fho MnO
2
Is roducod. Tho
rosuIfIng Mn
2
O
3
Is sIowIy oxIdIsod by nIr fo MnO
2
.
2Mn
2
O
3
+ O
2
= 4 MnO
2
(I) vy ceII. (IIg. l0.l5) If Is ossonfInIIy n
!ocInncho coII. Insfond of H
4
CI soIufIon, H
4
CI
nsfo Is usod horo. Tho nsfo confnIns H
4
CI,
MnO
2
nnd C (grnhIfo). Tho coII Is nof ronIIy dry.
A zInc vossoI sorvos ns nognfIvo oIocfrodo.
A cnrbon rod Is Incod nf fho confro fo ncf ns n
osIfIvo oIocfrodo. If Is fIIIod nf fho fo wIfh n brnss
cn. Tho cnrbon rod Is InsuInfod nf fho boffom
from Zn-vossoI wIfh n cnrdbonrd wnshor. Tho
InsIdo of fho Zn-vossoI Is IInod u wIfh n fhIn shoof
Hole
Pitch
Paper
Zinc
Carbon
Paste
Mixture of carbon
and manganese
dioxide
Fig. 10.15 Dry cell.
of bIoffIng nor. To rovonf dryIng of fho nsfo, fho fo of fho coII Is sonIod wIfh Ifch. A smnII
hoIo Is nf fho sonI. Tho o.m.f. of fho coII Is l.45 V.
ThIs fyo of coII Is wIdoIy usod In forchos, frnnsIsfors, sIgnnIIIng oquImonfs, foIohono
ofc.
AIkaIine Battery
If Is n modIfIcnfIon of dry coII whoro H
4
CI hns boon roIncod by KOH nnd ncfs ns nn
oIocfroIyfo. In fhIs fyo of bnffory, zInc Is usod In owdor form nnd mnkos n goI wIfh KOH. And
fho grnhIfo-rod Is kof surroundod by n nsfo of MnO
2
. Tho coII roncfIon Is
AnoJe. Zn(s) + 2OH
(oq) Zn(OH)
2
(s) + 2e
CoIIoJe. 2MnO
2
(s) + H
2
O(l) + 2e

Mn
2
O
3
(s) + 2OH
(oq)
AeI reocIion. Zn(s) + 2MnO
2
(s) + H
2
O(l) Zn(OH)
2
(s) + Mn
2
O
3
(s)
Advuntuge. Tho IIfo of nIknIIno bnffory Is Iongor fhnn fho dry coII bocnuso zInc doos nof
corrodo.
\se. If Is mnInIy usod In cnmorn, cnIcuInfors, wnfchos ofc.
NickeI-Cadmium Battery
Thoso bnffory Is consfrucfod of cndmIum nnodo nnd n nsfo of IO(OH)(s) cnfhodo. Tho
coII roncfIon Is
AnoJe. Cd(s) + 2OH
(oq) Cd(OH)
2
(s) + 2e
CoIIoJe. 2IO . OH(s) + 2H

2
O(l) + 2e

2I(OH)
2
(s) + 2OH
(oq)
AeI reocIion. 2IO.OH(s) + Cd(s) + 2H
2
O(l) Cd(OH)
2
(s) + 2I(OH)
2
(s)
Horo fho roncfIon roducfs ndhoro fo fho oIocfrodo surfncos nnd fho roncfIon cnn bo
onsIIy rovorsod. ThIs fyo of bnffory Is orfnbIo nnd ronchnrgonbIo. Tho mnIn ndvnnfngo of fhIs
bnffory Is fhnf, If undorgoos no doforIornfIon ns no gnsos nro roducod durIng chnrgIng nnd
dIschnrgIng.
\se: If Is usod In cnIcuInfors, oIocfronIc fInsh unIfs ofc.
Mercury Battery
ThIs fyo of bnffory Is consfrucfod of zInc-nmnIgnm (n soIufIon of Zn In morcury) ns
nnodo nnd n nsfo of KOH, Zn(OH)
2
nnd HgO ns cnfhodo. Tho nnodo nnd fho cnfhodo nro
dIvIdod by n nor. Tho nor ormIfs fho mIgrnfIon of Ions. Tho coII roncfIon Is:
AnoJe. Zn-nmnIgnm(s) + 2OH
(oq) ZnO(s) + H
2
O(l) + 2e
CoIIoJe. HgO(s) + H
2
O(l) + 2e
Hg(l) + 2OH
(oq)
AeI reocIion. Zn-nmnIgnm(s) + HgO(s) ZnO(s) + Hg(l)
Tho onfIro coII Is covorod In n sfnInIoss sfooI cnso. Tho sIzo Is smnII. If Is oxonsIvo.
\se: If fInds Ifs uso In ncomnkors, honrIng nIds, dIgIfnI wnfchos ofc.
FueI CeIIs
In fhoso coIIs combusfIon of fho fuoI Is omIoyod ns chomIcnI roncfIon fo gonornfo
oIocfrIcIfy.
IuoI + O
2
CombusfIon roducfs + oIocfrIcIfy
AIuminium-Air battery
If mny bo consIdorod ns n combInnfIon of n bnffory nnd n fuoI coII. Tho coII roncfIon Is:
AI onoJe. AI(s) AI
3+
(oq)

+ 3e

(OxIdnfIon)
AI
3+
(oq) + 3OH
(oq) AI(OH)
3
(s)
AI(s) + 3OH
(oq) AI(OH)
3
(s) + 3e
AI coIIoJe. O
2
(g) + 2H
2
O(l) + 4e
4OH

(oq) (!oducfIon)
AeI reocIion is. 4 AI(s) + 3O
2
(g) 6H
2
O(l) 4AI(OH)
3
(s)
In such n bnffory fho nnodo Is vory vory uro nIumInIum nnd nIr Is bubbIod fhrough fho
soIufIon nf cutLode. Tho oIocfroIyfo Is nquoous soIufIon of nCI (or nOH).
If Is oxocfod fhnf fhIs fyo of bnffory wIII fInd Ifs nIIcnfIon In nufomobIIos ns sourco
of onorgy roIncIng fuoIs.
Storage CeIIs
A sforngo coII cnn oornfo bofh ns n voIfnIc coII nnd ns nn oIocfrIc coII. Tho common
oxnmIo of sforngo coII Is Iond-ncId sforngo coII.
If Is consfrucfod of oIocfrodos mndo of Iond nnd fho ofhor oIocfrodo In IbO
2
. Tho fwo
fyos of oIocfrodos nro sonrnfod by sfrIs of wood or gInss fIbros. Tho oIocfrodos nro fofnIIy
Immorsod In 20 dIIufo H
2
SO
4
. Tho coII roncfIon Is
AI onoJe.
Ib Ib
2+
+ 2e
Ib
2+
+ SO
4
2
IbSO
4
AI coIIoJe. IbO
2
+ 2H
+
+ 2e
Ib
2+
+ 2H
2
O
Ib
2+
SO
4
2
IbSO
4
AeI reocIion. Ib + IbO

2
+ 4H
+
+ 2SO
4
2
2IbSO
4
+ 2H
2
O + Inorgy
If Is worfhwhIIo fo monfIon fhnf IbSO
4
gofs rocIIfnfod nf bofh fho oIocfrodos.
Tho coII cnn bo ngnIn chnrgod whon bofh fho nnodo nnd fho cnfhodo gof covorod wIfh
IbSO
4
. Tho coII Iosos Ifs funcfIon ns n voIfnIc coII. Tho osIfIvo oIo of fho gonornfor Is joInod fo
fho osIfIvo oIo of fho bnffory nnd fho nognfIvo formInnI Is nffnchod fo fho nognfIvo oIo of fho
bnffory.
IeocIion oI coIIoJe.
IbSO
4
+ 2e

Ib + SO
4
2
IeocIion oI onoJe.
IbSO
4
+ 2H
2
O 2e
IbO
2
+ 2H
+
+ SO
4
2
AeI reocIion. 2IbSO
4
+ 2H
2
O + Inorgy Ib + IbO
2
+ 4H
+
+ 2SO
4
2
Affor chnrgIng fho coII rosforos Ifs orIgInnI condIfIon nnd Is ngnIn usod.
\se: ThIs fyo of bnffory Is usod In oIocfrIcnI vohIcIos, nufomobIIos, owor sfnfIons ofc.
SoIar Battery
In fhIs fyo of bnffory, soInr onorgy Is ufIIIsod fo gonornfo oIocfrIc curronf In n hofovoIfnIc
coII. In fhIs fyo of hofovoIfnIc coII, p-fyo somIconducfor Is connocfod wIfh n-fyo
somIconducfor. uo fo fhIs confncf, n IImIfod numbor of oIocfrons cnn fIow nnd cross fho juncfIon
bofwoon fho fwo fyos of somIconducfors.
SOLVED EXAMPLES
xumpIe 1. ColculoIe IIe sIonJorJ poIenIiol of Cu
+2
/Cu if IIe elecIroJe poIenIiol oI 2
is 0.296 V uIen [Cu
+2
] = 0.01 M.
SoI. = +
0.0592
M
n
n
Iog | ]
+
= +
0 0592 .
Iog | ]
2
C
2
u
+
=
0 0592
0 0l5
.
Iog .
2
= |0.296 0.0296 ( l.8239)] V
= |0.296 + 0.05398] V
= 0.34998 V.
xumpIe 2. ColculoIe IIe single elecIroJe poIenIiol of copper neIol in conIocI uiII
0.1 (M) Cu
+2
soluIion. for copper = + 0.34 V (I = S.314 J. K
1
nol
1
, T = 29S K).
SoI. = +
!T
I
M
n
n
In | ]
+
= 0.34 +
2.303 8.3l4 298
2 96500
Cu ]
2

+
Iog |
= 0.34 +
2 303 8 3l4 298
2 96500
0 l5
. .
Iog .

= 0.3l56 V.
xumpIe 3. ColculoIe IIe tolIoge oI 2C of o cell forneJ I, Jipping silter in silter
niIroIe (0.1 M) onJ cinc in cinc sulpIoIe (0.2 M) onJ connecIing IIen uiIIouI liquiJ juncIion
poIenIiol.
SoI. () (+)
Tho coII Ag/AgO
3
(0.l M) || ZnSO
4
(0.2 M)/Zn
Tho coII roncfIon Zn
+2
+ 2e Zn (I
coII
=
!

!
=
+

, ! = !Ighf hnnd
oIocfrodo nnd !oducfIon ! = !off hnnd oIocfrodo undorgoIng oxIdnfIon)
2Ag 2e 2Ag
+
Zn
+2
+ 2Ag Zn + 2Ag
+
I
coII
=
+
.
0
/
1
+
.
0
/
1
+ +
Zn Ag
!T
2I
Zn
!T
2I
Ag In | ] In | ]
2 2
=
+
.
0
/
1
+
.
0
/
1
+ +
Zn Ag
!T
2I
Zn
!T
I
Ag In | ] In | ]
2
= ( 0.?62 + 0.0296 Iog 0.2) (0.?98 + 0.059 Iog 0.l)
= l.522 V.
HIgLIIgLts:
If nffor cnIcuInfIon of I
coII
If comos nognfIvo, hnIf coIIs nro fo bo rovorsod fo gof
osIfIvo vnIuo of I
coII
. Horo If Ag-oIocfrodo Is mndo osIfIvo oIocfrodo (ono hnIf
coII) nnd Zn-oIocfrodo Is mndo (nognfIvo oIocfrodo) (fho ofhor hnIf coII) fhon I
coII
wouId bocomo osIfIvo.
If wo cnnnof mnko rIghf choIco durIng consfrucfIon of n coII, I
coII
wouId como ouf
nognfIvo, buf fho fnbIo of vnIuos nnd fho nbovo rocoduro wIII hoI fo cnIcuInfo
I
coII
of nny rovorsIbIo coII.
xumpIe 4. ColculoIe IIe e.n.f. of o Doniel cell oI 2C, uIen IIe concenIroIions of
ZnSO
4
onJ CuSO
4
ore 0.001 M onJ 0.1 M, respecIitel,. TIe sIonJorJ poIenIiol of cell is 1.1 tolIs.
SoI. Wo cnn wrIfo I
coII
= ( )
+
+
!T
I
|Cu ]
|Zn ]
2
2
n
In
+
+
= I
CoII
+
0.0592
2
0.l
0.00l
Iog |3 I
coII
=
+

]
= l.l + 0.0296 Iog l00
= l.l + 0.0296 2
= l.l592 V.
xumpIe 5. ColculoIe IIe e.n.f. of IIe cell.
Ai | Ai
+2
1(M) || PI
+2
1(M) | PI
oI 2C. WriIe Joun iIs cell reocIion. Citen
Ai
= 0.24 V onJ
PI
= 0.13 V oI 2C.
SoI. I
coII
=
rIghf

Ioff
= ( 0.l3) ( 0.24)
= 0.ll V.
CoII roncfIon:
AI onoJe. I 2e I
+2
(Ox)
AI coIIoJe. Ib
+2
+ 2e Ib (!od)
I + Ib
+2
I
+2
+ Ib
xumpIe 6. SleIcI IIe elecIrocIenicol cell onJ uriIe Joun IIe cell reocIion, if Zn onJ
Ag elecIroJes ore JippeJ in respecIite soluIions. Also finJ ouI IIe sIonJorJ enf of IIe cell, giten
IIoI +
Zn/Zn
2 = 0.76 V onJ +
Ag/Ag

= 0.S V oI 2C.
SoI.
Ox
= +
Zn/ Zn
2 = 0.?6 V i.e.,
!od
= +
Zn / Zn
2
= 0.?6 V
Ox
= +
Ag/ Ag
= 0.8 V i.e.,
!od
=
Ag / Ag
+ = 0.8 V.
So horo S.!.I of Ag-oIocfrodo Is hIghor fhnn fhnf of Zn-oIocfrodo. So, Ag-oIocfrodo wIII
form rIghf hnnd hnIf coII i.e., +vo oIocfrodo.
Cu = Zn/Zn
+2
(o = l)/Ag
+
(o = l)/Ag
+
AccordIng fo '2!` convonfIon roducfIon wIII fnko Inco nf rIghf hnnd oIocfrodo (cnfhodo).
CoII roncfIon
AI coIIoJe. 2Ag
+
+ 2e 2Ag (!oducfIon)
AI onoJe. Zn 2e

Zn
+2
(OxIdnfIon)
2Ag
+
+ Zn
+2
2Ag + Zn
+2
I
coII
=
!Ighf

!off
= 0.8 ( 0.?6) = l.56 V.
xumpIe ?. Tuo copper roJs ore ploceJ in copper sulpIoIe soluIion of concenIroIion
0.1 M onJ 0.01 M seporoIel, in IIe forn of o cell. WriIe IIe scIene of IIe cell onJ colculoIe iIs
e.n.f. oI 29S K.
SoI.
CoII = Cu/Cu
+2
(0.0l M) || Cu
+2
(0.l M)/Cu
I
coII
=
0.0592
n
Iog
C
C
2
l
, horo C
2
= 0.l M nnd C
l
= 0.0l M
I
coII
=
0.0592
2
0.0296
Iog
.
. Iog
0 l
0 0l l0
=
= 0.0296 V.
xumpIe B. ColculoIe IIe equiliIriun consIonI for Doniel cell oI 2C fron IIe follouing
JoIo,
I = S.316 J. I = 96,00 C. S.1.P. (Ox) for Zn elecIroJe.
= 0.76 V onJ S.1.P. (Ox) for Cu elecIroJe = 0.337
SoI. +
Zn/ Zn
2 = 0.?65 V i.e.,
Zn / Zn
+2
= 0.?65 V
nnd +
Cu/ Cu
2
= 0.33? V i.e.,
Cu / Cu
+2
= 0.33? V
CoII = Zn/Zn
+2
|| Cu
+2
/Cu
HnIf coII roncfIons Cu
+2
+ 2e Cu ..... = 0.33? V
Zn 2e Zn
+2
..... = 0.?65 V
CoII roncfIon: Zn + Cu
+2
Zn
+2
+ Cu (I
coII
=
!od
+
OX
) = l.l02 V.
K =
|Zn ] |Cu]
|Zn] |Cu ]
2
2
+
+
= + +
Zn Zn Zn Zn
2 2
/ /
+
0 0592
2
2
.
Iog
| ]
| ]
Zn
Zn
+
= + +
Cu Cu Cu Cu
2 2
/ /

+
0 059
2
.
Iog
| ]
| ]
Cu
Cu
+
Af oquIIIbrIum, fhoso fwo oIocfrodo ofonfInIs wIII bo oqunI. Thoroforo,
+
Zn Zn
2
/
+
0.0592
2
Iog
|Zn ]
|Zn]
0.0592
2
Iog
|Cu ]
|Cu]
2
Cu /Cu
2
2
+ +
= + +

+ +
Cu / Cu Z / Zn
2 2
n
=
0.0592
2
|Zn ]
|Zn]
0.0592
2
|Cu ]
|Cu]
2 2
Iog Iog
+ +
or 0.33? ( 0.?65) =
0 0592
2
.
Iog
|Zn ]/|Zn]
|Cu ]/|Cu]
2
2
+
+
l.l02 = 0 0296 . Iog
|Zn ]/|Cu]
|Cu ]/|Zn]
2
2
+
+
= 0.0296 Iog K
Iog
l0
K =
ll02
0 0296
3? 229?
.
.
. =
K = AnfIIog 3?.229?
= l.69? l0
3?
.
HIgLIIgLt:
Tho hIgh vnIuo of K IndIcnfos fho sonfnnoIfy of fho roncfIon.
xumpIe 9. ColculoIe IIe poIenIiol of on Ag-elecIroJe in o soluIion IIoI is soIuroIeJ
uiII Ag1 onJ Ios on ioJiJe concenIroIion of exocIl, uniI,.
K
sp
(Ag1) = S.3 10
17
,
+
Ag Ag /
= + 0.799 V.
SoI.
|Ag
+
] =
K
I
s
=

8 3 l0
l
l?
.
= 8.3 l0
l?
(M).
xumpIe 10. TIe poIenIiol of o I,Jrogen gos elecIroJe in o soluIion of on ociJ of unlnoun
sIrengII is 0.29 V oI 29S K os neosureJ ogoinsI nornol I,Jrogen elecIroJe. ColculoIe IIe pH of
IIe soluIion.
SoI.
I
coII
=
H

H
= 0 ( 0.0592 H)
= 0.0592 H
H =
I
coII
0 0592
0 29
0 0592 .
.
.
= 4.9.
xumpIe 11. IinJ ouI IIe pH of o soluIion in o quinI,Jrone Iolf cell, uIicI is coupleJ
uiII sIonJorJ colonel elecIroJe. TIe e.n.f. of IIe conIineJ cell uos JeIernineJ Io Ie 0.123 V
oI 2C. 1
colonel
= 0.241,
Q
/H
2
Q

= 0.6990.
SoI.
I
coII
=

Q/ H Q cnIomoI
2
0.l23 = (0.6990 0.0592 H) 0.24l5
or 0.0592 H = 0.l23 + 0.24l5 0.6990 = 0.3345
or H =
0 3345
0 0592
5 65
.
.
. = .
xumpIe 12. ColculoIe K
sp
of AgCl fron IIe follouing JoIo.
AgAgCl(s)
= 0.2223 = +
Ag /Ag
0.79S oI 2C.
SoI. CeII veuctIon
Ag
+
+ e Ag = 0.?98
Ag + CI

AgCI(s) + e = 0.2223
Ag + CI
AgCI(s). I
coII
= 0.5?5?
Wo hnvo, C = nII
nII = !T In K
or Iog K =
nII
!T
2 303 .
=
l 0 5?5?
0 0592
.
.
= 9.?246 = l0 + 0.2?54
or Horo K = K
s
= AnfIIog l0 2?54 . = l.886 l0
l0
moI
2
I
2
.
Q. 1. WLut Is guIvunIc ceII ov voItuIc ceII?
Ans. If Is n sImIo dovIco of roducIng oIocfrIcnI onorgy by chomIcnI roncfIon, e.g., nnIoI
coII. Such n coII Is nIso known ns eIectvocLemIcuI ceII.
V
Salt bridge
e
e
Zn
ZnSO
4
CuSO
4
SO
4
2
Cu
Zn Zn
+2
+ 2e
(oxIdnfIon)
Cu
2+
+ 2e Cu (roducfIon)
Fig. 10.16
In fho nbovo coII Zn-oIocfrodo Is nnodo nnd Cu-oIocfrodo Is cnfhodo.
Q. 2. WLut Is un eIectvoIytIc ceII?
Ans. If Is n dovIco usod for convorfIng oIocfrIcnI onorgy Info chomIcnI onorgy.
Q. 3. WLut do you meun by eIectvode potentIuI ()?
Ans. If Is fho fondoncy of nn oIocfrodo In n hnIf coII fo Ioso or gnIn oIocfrons whon If Is In
confncf wIfh fho soIufIon of Ifs own Ions.
Q. 4. WLut uve veductIon und oxIdutIon potentIuIs?
Ans. !oducfIon ofonfInI Is fho fondoncy of nn oIocfrodo In n hnIf coII fo gnIn oIocfrons
nnd oxIdnfIon ofonfInI Is fho fondoncy of nn oIocfrodo In n hnIf coII fo Ioso oIocfrons.
Q. 5. WLut do you meun by stunduvd eIectvode potentIuI ()?
Ans. If Is fho oIocfrodo ofonfInI of n mofnI In confncf wIfh Ifs Ions whon fho conconfrnfIon
of Ions Is l M (l moInr).
Q. 6. WLut Is u suIt bvIdge?
Ans. If Is nn Invorfod !-fubo confnInIng nn oIocfroIyfo (e.g., KCI, KO
3
). If connocfs
(ncfs ns n brIdgo) fho soIufIons of fho fwo hnIf coIIs.
Q. ?. WLut Is tLe .M.I. oI u ceII?
Ans. If Is dofInod ns fho ofonfInI dIfforonco bofwoon fho fwo formInnIs of fho coII whon
no curronf Is drnwn from If.
Q. B. eIIne novmuI Lydvogen eIectvode.
Ans. If Is n roforonco or sfnndnrd roforonco oIocfrodo. Ifs oIocfrodo ofonfInI Is fnkon ns
zoro nf nII fomornfuros. A normnI hydrogon oIocfrodo gonornIIy consIsfs of n If-foII confod
wIfh InfInum, dIod In soIufIon hnvIng l M H
+
Ion conconfrnfIon nnd hydrogon gns nf
l nfmoshorIc rossuro consfnnfIy bubbIod ovor If. If cnn bo rorosonfod ns:
If, H
2
(l nfm) || H
+
(l M)
!oncfIon: H
+
(oq) + e

l
2
H
2
( ) g
or
l
2
H
2
( ) g H
+
(oq) + e
Q. 9. How Is eIectvode potentIuI meusuved?

Ans. Anrnfus for monsurIng fho sfnndnrd oIocfrodo ofonfInI of n rodox sysfom Is
gIvon In IIg. l0.l?.
H
(1 atm)
2
Saline bridge
Inert
electrode (Pt)
Pt
A B
H
+
(a=1)
Redox system
Fig. 10.17 A cell constructed with standard hydrogen electrode.
A = SoIufIon of H
+
Ions of unIf ncfIvIfy
I = !odox soIufIon of unIf ncfIvIfy.
SnIIno brIdgo hns fho funcfIon of brIngIng Info hysIcnI confncf fho fwo soIufIons wIfhouf
mIxIng fhom; If consIsfs of n sfrong oIocfroIyfo (e.g., KCI).
Q. 10. How Is tLe .M.I. oI u ceII meusuved?
Ans. I.M.I. of n coII Is monsurod by monns of n dovIco, nnmod potentIometev.
=
!odox
+
H H
2
/
+
H H
2
/
= 0
=
!odox
B
A
C
D
G
Fig. 10.18 Diagram for Potentiometer.
Q. 11. WLut do you meun by potentIometvy?
Ans. IofonfIomofry Is nn oIocfrochomIcnI mofhod of nnnIysIs bnsod on monsurIng fho
ofonfInI dIfforonco (o.m.f.) bofwoon fwo hnIf coIIs, ono of whIch Is nn IndIcnfIng oIocfrodo nnd
fho ofhor Is n roforonco oIocfrodo.
Q. 12. WLut Is un IndIcutIng eIectvode?
Ans. If Is nn oIocfrodo In bnInnco wIfh nn rodox couIo, fho ofonfInI of whIch Is gIvon by
ornsf oqunfIon.
Q. 13. GIve tLe LemIstvy tLe dIIIevent IndIcutIng eIectvodes.
Ans. (o) IIrsf CInss MofnIIIc oIocfrodos In confncf wIfh n soIufIon of fhoIr own Ion
(nn oIocfrodo whIch Is rovorsIbIo In roInfIon fo fho cnfIon)
M
n+
+ ne
M; whoro, |M
n+
] conc. of cnfIon In moIos dm
3
= +
+
M M
+
Iog M
/
.
| ]
n
n
n
0 059
(I) Socond cInss MofnIIIc oIocfrodos In confncf wIfh ono of fhoIr nof rondIIy soIubIo
snIfs nnd wIfh fho nnIon of fhIs snIf:
M | MA(s), A
n
whoro, M MofnI
MA(s) fho snIf whIch Is nof rondIIy soIubIo.
|A
n
] = Conc. of fho nnIon In moIos dm
3

.
And, = +

M M s s
+
K K A
/
.
Iog
.
| ]
n
n n
n
0 059 0 059
whoro K
s
= soIubIIIfy roducf of fho snIf whIch Is nof rondIIy soIubIo.
(c) !odox = IIocfrodos whIch nro Inorf In confncf wIfh n rodox couIo In soIufIon.
If/Ox, !od
And, =
!odox
+
0 059 .
n
Iog |Ox]/|!od]
If IInfInum
|Ox] = Conc. of fho oxIdIsod form In moIos dm
3
.
|!od] = Conc. of fho roducod form In moIos dm
3
.
(J) Mombrnno fyo = SoIocfIvo oIocfrodos socIfIc fo corfnIn Ions. Thoy consIsf of n
mombrnno whIch In rosonco of nrfIcuInr Ions nssumos n ofonfInI whIch Is doondonf on fho
ncfIvIfy of fho Ions In roInfIon fo fhoso of whIch fho oIocfrodo Is soIocfIvo. Tho bosf known of
fhIs fyo Is gInss oIocfrodo.
=
r
+
0 059 .
Iog
n
o
whoro,
r
Consfnnf ofonfInI IInkod fo fho choIco of fho roforonco oIocfrodo nnd fho InfornnI
soIufIon, o ncfIvIfy of fho Ion In roInfIon fo whIch fho oIocfrodo Is soIocfIvo.
Q. 14. WLut uve veIevence eIectvodes?
Ans. Thoso nro fho oIocfrodos whoso ofonfInI Is consfnnf nnd Indoondonf of fho
comosIfIon of fho confncfIng soIufIon.
Tho mosf wIdoIy usod nro snfurnfod cnIomoI oIocfrodos ( = + 0.246 V) nnd fho sIIvor-sIIvor
chIorIdo oIocfrodo ( = + 0.222 V).
HIgLIIgLt:
Tho ofonfInI of roforonco oIocfrodos Is doformInod ns roforrod fo fho sfnndnrd
hydrogon oIocfrodo.
Q. 15. eIIne tLe eIectvocLemIcuI sevIes?
Ans. Whon fho sfnndnrd roducfIon ofonfInIs of fho oIocfrodos nro nrrnngod In nn
IncronsIng ordor, fho sorIos so obfnInod Is known ns oIocfrochomIcnI sorIos.
Q. 16. WLut Is Nevnst equutIon?
Ans. ornsf roosod fho fundnmonfnI oIocfrodo roInfIon bofwoon fho formnI (or
obsorvod) ofonfInI nnd fho sfnndnrd oIocfrodo ofonfInI for fho rodox roncfIon:
!od
=
!od

2.303 !T
I
|!oducod form]
|OxIdIsod form] n
Iog
whoro, ! moInr gns consfnnf.
T nbsoIufo fomornfuro.
n numbor of oIocfrons InvoIvod In fho rodox roncfIon.
= sfnndnrd roducfIon oIocfrodo ofonfInI.
!od
= obsorvod roducfIon oIocfrodo ofonfInI.
I = Inrndny (96500 CouIombs)
Af 25C fho vnIuo of fho form 2.303 !T/I comos ouf ns oqunI fo 0.059.
So nf 25C
=
0 059 .
Iog
]
n
|!oducod form
|OxIdIsod form]
HIgLIIgLt:
Tho conconfrnfIon of mofnI Is fnkon ns unIfy.
Q. 1?. WLut Is Ieud stovuge buttevy?
Ans. If consIsfs of sIx voIfnIc coIIs connocfod In sorIos.
!oncfIons:
AnoJe. Ib + SO
4
2
IbSO
4
+ 2e
CoIIoJe. IbO
2
+ SO
4
2
+ 4H
+
+ 2e
IbSO
4
+ 2H
2
O
AeI reocIion. Ib + IbO
2
+ 4H
+
+ 2SO
4
2
2IbSO
4
+ 2H
2
O.
!oncfIon durIng rochnrgIng fho bnffory
IbSO
4
(s) + 2H
2
O(l) Ib(s) + IbO
2
(s) + 4H
+
+ 2SO
4
2
Q. 1B. WLut Is tLe veuctIon In nIckeI-cudmIum buttevy?
Ans. AnoJe.
Cd(s) + 2OH
(oq)

Cd(OH)
2
(s) + 2e
CoIIoJe.
IO
2
+ 2H
2
O + 2e
I(OH)
2
+ 2OH

(oq)
Q. 19. WLut uve IueI ceIIs?
Ans. IuoI coIIs nro fho dovIcos fhnf convorf chomIcnI onorgy of n fuoI dIrocfIy Info oIocfrIcnI
onorgy.
Q. 20. GIve tLe veuctIon In H
2
O
2
IueI ceII.
Ans. AnoJe. {H
2
(g) + 2OH
(oq) 2H
2
O(l) + 2e
} 2
CoIIoJe.
O
2
(g) + 2H
2
O(l) + 4e
4OH
(oq)
AeI reocIion. 2H
2
(g) + O
2
(g) 2H
2
O(l)
HIgLIIgLt:
Such n coII Is usod fo gonornfo oIocfrIcnI owor such ns In AoIIo snco rogrnmmo.
Q. 21. WLut do you meun by covvosIon?
Ans. If gonornIIy rofors fo fho sIow nnd confInuous doforIornfIon of mofnIs nnd nIIoys by
chomIcnI or oIocfrochomIcnI ncfIons of onvIronmonfs, e.g., rusfIng of Iron.
Q. 22. CIussIIy covvosIon.
Ans. (o) ChomIcnI corrosIon If InvoIvos dIrocf chomIcnI ncfIon bofwoon mofnIs nnd
gnsos.
(I) IIocfrochomIcnI corrosIon If InvoIvos doforIornfIon of mofnI duo fo fIow of oIocfrIc
curronf from ono oInf fo nnofhor.
(c) ry corrosIon If rofors fo fho corrosIon of mofnIs InvoIvIng dIrocf chomIcnI ncfIon
bofwoon mofnIs nnd dry gnsos.
(J) Wof corrosIon If InvoIvos fIow of oIocfrIc curronf from ono oInf fo nnofhor fhrough
somo orcofIbIo dIsfnnco In fho rosonco of IIquId or moIsfuro In nIr.
Q. 23. Stute tLe eIectvocLemIcuI tLeovy oI vustIng.
Ans. !oncfIon:
AnoJe. Io Io
2+
+ 2e
CoIIoJe. 2H
2
O + O
2
+ 4e
4OH
.
Tho Io
+2
Ions formod nf nnodo nro oxIdIsod by O
2
fo Io
+3
Ions whIch fhon combIno wIfh
OH
Ions fo form hydrnfod forrIc oxIdo, i.e., rusf.

2Io
+2
+ H
2
O + O 2Io
+3
+ OH
2Io
+3
+ 6OH
2Io(OH)
3
or Io
2
O
3
.3H
2
O (rusf)
Q. 24. WLut meusuves ougLt to be tuken to pvevent covvosIon?
Ans. (o) InrrIor rofocfIon.
(I) SncrIfIcInI rofocfIon.
(c) IIocfrIcnI rofocfIon.
(J) !so of nnfI-rusf soIufIons.
Q. 25. GIven (E) Ie
+2
+ 2e Ie, = 0.44 V
(EE) Ie
+3
+ A Ie
+2
, = 0.?? V
Repvesent tLe dutu In tLe Iovm oI IutImev dIugvum.
Ans. Wo hnvo C
(i)
= nII = 2I ( 0.44) = 0.88 I
C
(ii)
= nII = I(0.??) = 0.?? I
AddIng fho nbovo fwo oqunfIons,
C
(iii)
= C
(i)
+ C
(ii)
= 0.88 + ( 0.??) I = + 0.ll I
So C
(iii)
Is fho vnIuo for fho roncfIon,
Io
+3
+ 3e Io
=
C
I
. I
I
=
+
n
0 ll
3
= 0.04 V
Tho !nfImor dIngrnm of fho nbovo sysfom Is IIg. l0.l9.
0.04
Fe
+3
Fe
+2
Fe
0.77 0.44
Fig. 10.19 Latimer diagram for Fe species.
If Is convonfIonnI fo uf hIghIy oxIdIsod form of fho oIomonf on fho Ioff nnd fho oIomonfs
wIfh Iowor oxIdnfIon sfnfo nro uf succossIvoIy In fho !nfImor dIngrnm.
Q. 26. In uIkuIIne soIutIon (pH = 14) tLe IutImev dIugvum Iov cLIovIne Is
C O
4
l ClO ClO ClO Cl Cl

3 2 2
+ 0.37 + 0.30 + 0.68 + 0.42 + 1.36
?
CuIcuIute Ivom tLe ubove dIugvum vuIue Iov tLe veuctIon,
CIO
CI
.
Ans. CIO

+ e

l
2
CI
2
, = + 0.42 V; C
I
= (+ 0.42) I = 0.42 I
l
2
CI
2

+ e
CI
, = + l.36 V; C
II
= (+ l.36) I = l.36 I
AddIng fofnI C for fho roncfIon = l.?8 I
Irom fho roInfIon, C = nII
(CIO
/CI
) =
C C
I
. I
I
I II
+
=

n
l?8
2
= 0.89 V
Q. 2?. \se tLe IoIIowIng dutu to dvuw u Ivost dIugvum.
(Mn
+2
, Mn) = 1.1B V, 2 = 2.36 V
(Mn
+3
, Mn
+2
) = 1.51 V.
Ans. (Mn
+2
, Mn) = l.l8 V
(MnO
2
, Mn
+3
) = 0.95 V
3(Mn
+3
, Mn) = 0.85 V
4(MnO
2
, Mn) = 0.l0 V
+6
+5
+4
+3
+2
+1
0
1
2
3
0 +1 +2 +3 +4 +5 +6 +7
Mn
Mn
2+
Mn
3+
Mn
4+
Mn
5+
Mn
6+
Mn
7+
n
(
V
)
Oxidation number
Fig. 10.20 Frost diagram for Mn in acidic pH.
HIgLIIgLts:
IIof of n ts n for Mn (n = oxIdnfIon sfnfo) such dIngrnm nro cnIIod Ibsworfh dIngrnm
or Irosf dIngrnm.
Tho sfooor fho IIno joInIng fwo oInfs, fho hIghor fho ofonfInI of corrosondIng
couIo.
A sfnfo Is unsfnbIo wIfh rosocf fo dIsroorfIonnfIon If If IIos nbovo fho IIno connocfIng
fwo ndjnconf oxIdnfIon sfnfos.
Mn
+3
Is IIkoIy fo dIsroorfIonnfo fo Mn
+2
nnd MnO
2
. SInco bofh fhoso roducfs InvoIvo
ono oIocfron frnnsfor, fho rocoss Is IIkoIy fo bo rnId.
Tho oInf for Mn(VI) sImIInrIy suggosfs dIsroorfIonnfIon fo Mn(VII) nnd Mn(IV).
MnO
2
Is nIso n sfrong oxIdIzIng ngonfIfs sIoo fo Mn
+2
Is gronfor fhnn fho sIoos fo
hIghor oxIdnfIon sfnfos. Mosf socIos fhnf roduco MnO
4
shouId nIso roduco MnO

2
.
Tho mInImum nf Mn
+2
suggosfs fhIs fo bo fho common roducf of roducfIon of MnO
4
|Mn(VII)] In ncIdIc soIufIon nnd If Is fho mosf sfnbIo oxIdnfIon sfnfo of Mn.
Q. 2B. Constvuct u Ivost dIugvum Ivom tLe IutImev dIugvum Iov 6.
Tl
+3
Tl
+
+1.25 0.34
Tl
+1.23
Ans. Tho oxIdnfIon sfnfos of Tl nro + 3, + l nnd 0, In fho fhroo socIos. Ior fho chnngo of
oxIdnfIon numbor from + l fo 0 i.e., Tl
+l
Tl
0
, = 0.34 V, horo n = l, so, n = 0.34 V.
Ior fho chnngo of oxIdnfIon numbor from + 3 fo 0
(Tl
+3
Tl
0
) vnIuo = + l.23 V
So, for n = 3, n = 3 l.23 V = + 3.69 V.
0 +1 +2 +3
3
2
1
0
1
2
3
n
(
V
)
Tl
+3
Tl
+1 Tl
Oxidation number
4
Fig. 10.21 Frost diagram for 6l species.
Tl
+l
Is fho mosf sfnbIo oxIdnfIon sfnfo of Tl ns fho socIos IIos Iowosf In fho Irosf dIngrnm.
EXERCISES
1. IsfInguIsh bofwoon oIocfroIyfIc nnd oIocfrochomIcnI coIIs.
2. ofIno fho oIocfrodo ofonfInI.
3. Irovo fhnf
ox
=
rod
.
4. Whnf Is n sfnndnrd hydrogon oIocfrodo Whnf Is Ifs ofonfInI
5. Whnf Is ovorvoIfngo Whnf Is fho cnuso of ovorvoIfngo
6. CIvo fho ronson: fho hydrogon ovorofonfInI fnIIs wIfh rIsIng fomornfuro.
?. Whnf Is sfnndnrd oIocfrodo ofonfInI
B. Sfnfo fho ocuIInrIfy of n conconfrnfIon coII.
9. Why Is n voIfmofor Is nof usod for fho monsuromonf of o.m.f. of n coII
10. Whnf Is n sforngo coII nmo somo of Ifs fyos.
11. Whnf Is n cnIomoI oIocfrodo oscrIbo Ifs consfrucfIon: Why If Is usod ns roforonco oIocfrodo In
Inco of n sfnndnrd hydrogon oIocfrodo
12. Whnf Is nn oIocfrochomIcnI sorIos
13. Why nro sfnndnrd ofonfInIs of Zn/Zn
+2
nnd Cu/Cu
+2
oIocfrodos oosIfo In sIgn
14. oscrIbo fho consfrucfIon nnd workIng of H
2
O
2
fuoI coII.
15. CIvo fho coII rofnfIon for n conconfrnfIon coII.
16. oscrIbo fho consfrucfIon of n gInss oIocfrodo. IxInIn how fho H of n soIufIon Is doformInod
usIng fho gInss oIocfrodo.
1?. Whnf nro rImnry nnd socondnry roforonco oIocfrodos
1B. WrIfo n nofo on docomosIfIon ofonfInI.
19. WrIfo nofos on: (i) Wosfon sfnndnrd coII, (ii) sIgnIfIcnnco of sfnndnrd oIocfrodo ofonfInI.
20. IsfInguIsh: (i) n rovorsIbIo coII from nn IrrovorsIbIo coII
(ii) n gnIvnnIc coII from n conconfrnfIon coII.
21. Whnf Is ornsf oqunfIon Sfnfo Ifs ufIIIfy.
22. orIvo nn oxrossIon for oIocfrodo ofonfInI of nn M/M
n+
oIocfrodo
23. Whnf Is fuoI coII CIvo dofnII of ono such coIIs.
24. Whnf nro rovorsIbIo nnd IrrovorsIbIo coIIs
25. IxInIn fho consfrucfIon of I-Cd coII.
26. CIvo fho coII roncfIon of fho foIIowIng:
(i) Zn
+2
/Zn, (ii) AgCI(s), CI
/Ag, (iii) Io
+3
/Io
+2
If, (it) 2H
+
/H
2
(g) If.
2?. CIvo fho uso of Ag-AgCI oIocfrodo.
2B. oscrIbo fho consfrucfIon nnd workIng of nnIoI coII.
29. IxInIn fho consfrucfIon nnd workIng of Iond sforngo bnffory.
30. How Is sIngIo oIocfrodo ofonfInI monsurod oxorImonfnIIy
31. WrIfo down fho oIocfrodo roncfIons nnd ovornII coII roncfIons for fho foIIowIng coIIs. AIso gIvo fho
oxrossIon for fhoIr o.m.f.
(i) Zn | ZnSO
4
|| CuSO
4
/Cu
(ii) (If) H
2
(l nfm) | HCI/AgCI(s), Ag
32. oscrIbo fho ofonfIomofrIc mofhods for
(i) oformInnfIon of H of n soIufIon.
(ii) CnIcuInfIon of soIubIIIfy roducf of AgCI.
33. Tho roncfIon H
2
+ CI
2
+ 2H
2
O 2H
2
O + 2CI
hns nn oquIIIbrIum consfnnf K = l0

46
nf 25C.
CnIcuInfo I nf 25C for coII: (If) H
2
/HCI (oq)/CI
2
(If).
34. Tho sfnndnrd ofonfInIs of Cu/Cu
+2
nnd Cu/Cu
+
sysfom nro 0.33? nnd 0.530 V, rosocfIvoIy. CIvo
fho oquIIIbrIum consfnnf for fho roncfIon,
2Cu
+
Cu
2+
+ Cu
35. ZInc rod Is dIod In 0.0l (M) ZnSO
4
soIufIon nf 25C. CIvo fho sIngIo oIocfrodo ofonfInI of Zn-
hnIf coII, If
I
coII
= + 0.?63 V (0.8l92 V)
36. CnIcuInfo fho o.m.f. of voIfnIc coII: Io | Io
+2
(oq) || Cu
+2
(oq) | Cu. CIvon fho oIocfrodo ofonfInIs of
Cu nnd Io nro 0.34 V nnd 0.44 V, rosocfIvoIy. (0.?8 V).
3?. WIII n roncfIon fnko Inco If nn Ag-bnr Is Incod In n soIufIon of IoSO
4
IxInIn usIng fho foIIow-
Ing dnfn:
+
Ag / Ag
= 0.?99 V, nnd +
Io / Io
2 = 0.44 V ( l.239 V)
3B. CnIcuInfo fho o.m.f. of n nnIoI coII nf 25C, whon fho conconfrnfIons of ZnSO
4
nnd CuSO
4
nro
0.00l M nnd 0.l M rosocfIvoIy. Tho sfnndnrd ofonfInI of fho coII Is l.l V (l.l3 V).
39. CnIcuInfo fho o.m.f of fho foIIowIng conconfrnfIon coII:
Ag/Ag
+
(0.l M) || Ag
+
(lM) | Ag |Ans. 0.0592 V]
40. Tho o.m.f. of fho coII nf 25C
Hg(l) | Hg
2
CI
2
(s), KCI(soI) (l.0 )| QuInhydrono | If
Is 0.2l2 V. CnIcuInfo fho H of fho soIufIon. Tho ofonfInI of fho normnI cnIomoI oIocfrodo Is
0.28l2 V nnd I for fho quInhydrono oIocfrodo Is 0.6996 V, bofh nf fho snmo fomornfuro.
|Ans. 6.5]
41. CnIcuInfo fho vnIoncy of morcurous Ions wIfh fho hoI of fho foIIowIng coII:
Hg | HgO
3
(0.00l ) In 0.l HO
3
| HgO
3
(0.0l) | Hg
+
|Ans. 2]
42. IInd fho oquIIIbrIum consfnnf of fho roncfIon nf 25C.
2 Io
+3
+ Sn
+2
2 Io
+2
+ Sn
+4
from vnIuos gIvon In fho TnbIo l0.2. |Ans. K = l0
2l
]
43. CnIcuInfo fho oquIIIbrIum consfnnf of fho roncfIon nf 25C.
Io
+3
+ I
Io
+2
+
l
2
I(s)
from fho (roducfIon) vnIuos
+
Io Io
2
/
0.44 V,
+
Io Io
3
/
0.036 V
I( )/ I
s
0.5355 V. |Ans. K = l66]
44. Suggosf n coII, fo cnIcuInfo IonIc roducf of wnfor. |Ans. H
2
-oIocfrodo || O
2
-oIocfrodo]
45. Whon cnIomoI oIocfrodo Is connocfod fo H
2
-oIocfrodo nf l8C, gIvos o.m.f. vnIuo 0.5622 V.
CnIcuInfo fho H of fho soIufIon. |Ans. 5.4]
46. I.m.f. of fho coII, whIch Is consfrucfod by connnocfIng H
2
-oIocfrodo fo normnI cnIomoI oIocfrodo,
nf 25C In 0.664 V. CnIcuInfo Ifs (i) H nnd (ii) H
+
conconfrnfIon. |Ans. (i) 6.5, (ii) 3.l6 l0
?
]
2D=IA 4KA
266
INTRODUCTION
Tho hnso ruIo wns doducod by WIIInrd CIbbs (who Infroducod fho froo onorgy funcfIon,
C In fhormodynnmIcs) In l8?6, nnd If wns Infor on dovoIood by OsfwnId, Vnn`f Hoff nnd
ofhors. Wo nII know fhnf n homogonoous sysfom Is ono In whIch bofh fho roncfnnfs nnd roducfs
nro of ono hnso (i.e., soIId, IIquId or gns) nnd n hoforogonoous sysfom Is ono In whIch fhoy nro
In dIfforonf hnsos. Ioforo sfnfIng fho ruIo, fho formshnsos, comononfs nnd dogroos of
froodomnood fo bo oxInInod.
l. PLuse. Ihnso Is dofInod ns nny hysIcnIIy dIsfIncf orfIon of mnffor whIch IfsoIf Is
homogonoous nnd unIform In comosIfIon, mochnnIcnIIy sonrnbIo from ofhor nrfs by dofInIfo
boundnry surfncos.
(o) Thus, gnsos boIng mufunIIy mIscIbIo In nII roorfIons wIII consfIfufo ono hnso onIy.
Thus mIxfuro of H
2
nnd O
2
consfIfufos sIngIo hnso.
(I) MIxfuro of fwo comIofoIy mIscIbIo IIquIds hns sIngIo hnso.
(c) SoIufIon of n soIufo In n soIvonf consfIfufos sIngIo hnso such ns snIf soIufIon In wnfor.
(J) If fwo IIquIds nro ImmIscIbIo, fhoy form fwo hnsos such ns chIoroform nnd wnfor.
(e) Ixcof soIId soIufIons nII dIfforonf kInds of soIIds form dIfforonf hnsos.
(f ) If wo koo n mIxfuro of mIscIbIo IIquIds In n cIosod vossoI, nbovo fho IIquId mIxfuro,
fhoro wIII bo somo vnors of fho IIquIds, so fho sysfom wIII hnvo fwo hnsos.
( g) Af froozIng oInf, wnfor consIsfs of fhroo hnsos:
Ico(e) Wnfor(l) Wnfor vnor( g)
(I) A hoforogonoous mIxfuro of fho fyo
CnCO
3
(e) CnO(e) + CO
2
( g)
consIsfs of fhroo hnsosfwo soIId nnd ono gnsoous.
2. Component. Comononf Is dofInod ns fho smnIIosf numbor of IndoondonfIy vnrInbIo
consfIfuonfs, In forms of whIch fho comosIfIon of onch hnso cnn bo oxrossod In fho form of
n chomIcnI oqunfIon.
ThIs concof of comononf cnn bo oxInInod In connocfIon wIfh hnso ruIo wIfh fho hoI
of fho foIIowIng oxnmIos.
(o) In Ico-IIquId wnfor-wnfor vnor sysfom, fho comosIfIon of onch hnso cnn bo oxrossod
by n sIngIo comononf i.e., H
2
O. So, If Is n ono-comononf sysfom.
(I) A snIf soIufIon wIII bo n fwo-comononf sysfom.
PHASE RULE 267
(c) In fho fhormnI docomosIfIon of MgCO
3
,
MgCO
3
(e) MgO(e) + CO
2
(g).
Tho comosIfIon of onch of fho fhroo hnsos cnn bo oxrossod In forms of nf Ionsf nny
fwo of fho fhroo consfIfuonfs, fhon fho comosIfIon of nny ono hnso cnn bo rorosonfod ns
Ihnso: MgCO
3
= MgCO
3
+ OMgO
Ihnso: MgO = O MgCO
3
+ MgO
Ihnso: CO
2
= MgCO
3
MgO
So If Is n fwo-comononf sysfom.
(J) Suoso n soIId dIssocInfos Info n numbor of gnsoous subsfnncos In n cIosod vossoI
H
4
CI(e) H
4
CI(g) H
3
(g) + HCI(g)
Tho ovornII comosIfIon of fho dIssocInfod vnour (H
3
, HCI) Is oxncfIy fho snmo ns fhnf
of fho undIssocInfod subsfnnco (H
4
CI). Thus, fho numbor of comononf Is ono. Howovor, If
H
3
or HCI Is Infroducod In fho sysfom In oxcoss, fho sysfom bocomos n fwo-comononf sysfom.
(e) In fho sysfom of sodIum suIfnfo-wnfor, vnrIous hnsos mny oxIsf IIko n
2
SO
4
; n
2
SO
4
,
?H
2
O; n
2
SO
4
, l0H
2
O; Ico; soIufIon nnd vnor. Tho comosIfIon of onch hnso cnn bo oxrossod
In forms of n
2
SO
4
nnd H
2
O, so fho sysfom Is n fwo-comononf sysfom.
( f ) In fho oquIIIbrIum,
Io(e) + H
2
O(g) IoO(e) + H
2
fho mInImum numbor of comononfs roquIrod fo oxross fho comosIfIon Is fhroo nnd honco Is
n fhroo-comononf sysfom.
3. egvees oI Iveedom ov VuvIunce. Tho numbor of dogroos of froodom of n sysfom Is
fho mInImum numbor of fho Indoondonf vnrInbIos of n sysfom, such ns fomornfuro, rossuro
nnd conconfrnfIon, whIch cnn comIofoIy dofIno fho oquIIIbrIum of n sysfom.
(o) A sysfom consIsfIng of uro gns or gns mIxfuro. If Is n ono comononf, ono-hnso
sysfom. If fho fomornfuro nnd rossuro nro socIfIod, fho voIumo of fho gns Is known. Honco
fho dogroo of froodom Is fwo.
(I) Tho sysfom Ico(e) Wnfor(l) vnor(g) Is ono-comononf, fhroo-hnso
sysfom nnd nII fhoso fhroo hnsos cnn co-oxIsf nf fho froozIng oInf of wnfor nf n nrfIcuInr
fomornfuro nnd rossuro. So fhIs sysfom wIII hnvo no dogroo of froodom i.e., If Is n non-
vnrInnf or InvnrInnf sysfom. If fomornfuro or rossuro Is nIforod, ono of fho hnsos wIII
dIsnonr nnd fho fhroo hnsos wIII nof bo In oquIIIbrIum.
(c) Ior fho sysfom, nCI(e) nCI-Wnfor(oq) H
2
O(g) fho soIubIIIfy nf fho
snfurnfIon oInf Is fIxod by oIfhor fomornfuro or rossuro, so fho sysfom Is unIvnrInnf.
(J) Ior fho sImIo sysfom wnfor (l) Wnfor vnor (g) fomornfuro or fho rossuro
Is roquIrod fo dofIno fho sysfom, honco fho sysfom Is unIvnrInnf.
The Phase RuIe
Tho ruIo cnn bo sfnfod ns fho sum of fho numbor of hnsos nnd fho dogroos of froodom
of nny sysfom oxcoods fho numbor of comononfs by fwo, rovIdod fhnf fho onIy sIgnIfIcnnf
oxfornnI fncfors ncfIng nro fomornfuro, rossuro nnd conconfrnfIon nnd nof InfIuoncod by
grnvIfy, surfnco ncfIon, mngnofIc or oIocfrIc forcos.
I = C I + 2
whoro C Is fho numbor of comononfs, I fho numbor of hnsos nnd I Is fho dogroo of froodom.
xumpIes 1.
(o) Wnfor(l) Vnor ( g)
C = l, I = 2. Honco I = l 2 + 2 = l.
(I) Ior wnfor nf crIfIcnI oInf
Ico (e) Wnfor (l) Vnor ( g)
C = l, I = 3. Honco I = l 3 + 2 = 0.
(c) Ior CnCO
3
(e) CnO (e) + CO
2
( g)
C = 2, I = 3. Honco I = 2 3 + 2 = l.
Advantages of phase ruIe
l. Ihnso ruIo Is nIIcnbIo fo bofh hysIcnI nnd chomIcnI oquIIIbrIn.
2. Tho nnfuro or qunnfIfIos of fho comononfs do nof hnvo nny roIo.
3. Ifforonf sysfoms bohnvo In n sImIInr fnshIon If fhoy hnvo snmo dogroos of froodom.
4. Tho nnfuro of fho sysfom cnn bo rodIcfod undor dIfforonf sofs of vnrInbIo condIfIons
IIko whofhor dIfforonf subsfnncos cnn co-oxIsf or bo Inforconvorfod undor dIfforonf
sofs of condIfIons.
5. Tho oquIIIbrIum sysfom roquIros no InformnfIon rognrdIng Ifs moIocuInr nnfuro or
mIcro sfrucfuro.
Limitations of phase ruIe
l. ThIs ruIo cnn bo nIIod onIy fo sysfoms fhnf hnvo nffnInod oquIIIbrIum, so If Is of no
vnIuo for sysfoms whIch mny nffnIn oquIIIbrIum vory sIowIy.
2. Tho ruIo consIdors onIy fho numbor of hnsos nnd nof fhoIr nmounfs rosonf, honco If
n frnco nmounf of n hnso Is rosonf nnd nof fnkon Info nccounf, fho ruIo Is InnIIcn-
bIo.
3. If sfnfos fhnf nII fho hnsos musf bo rosonf undor fho IdonfIcnI condIfIons of fom-
ornfuro nnd rossuro.
Phase diagram
Tho condIfIons of oquIIIbrIum bofwoon dIfforonf hnsos of n subsfnnco cnn bo shown by
IoffIng fomornfuro nnd rossuro ns vnrInbIos nnd fho dIngrnm Is cnIIod fho hnso dIngrnm.
Irom fho hnso dIngrnm, fho roorfIos IIko moIfIng oInf, boIIIng oInf, frIIo oInf cnn bo found.
The Water System
ThIs sysfom consIsfs of fhroo hnsosIco, wnfor, vnor nnd ono-comononf H
2
O.
Irom IIg. ll.l, wo fInd fhnf curvo IO Is fho vnor rossuro curvo of Ico whIch IndIcnfos
fhnf Ico hns n smnII buf dofInIfo vnour rossuro. Tho oInf I hns n nnfurnI IImIf of 2?3C,
boyond whIch fho fwo hnsos morgo.
OA Is fho vnour rossuro curvo of wnfor, nIso cnIIod fho vnorIsnfIon curvo. Tho OA
curvo formInnfos nf A, fho crIfIcnI fomornfuro of +3?4C nbovo whIch dIsfIncfIon bofwoon
IIquId nnd vnor vnnIshos.
Ior bofh of fhoso curvos OA nnd OI, fhoy nro ono-comononf sysfoms wIfh fwo hnsos
(C = l, I = 2).
PHASE RULE 269
218 atm
P
r
e
s
s
u
r
e
Temperature
1 atm
Ice
4.579 mm
B
D
O
Water
X
Y
Z
Water
vapour
.0075 C 100 C 374 C
C
A
Fig. 11.1 The phase-diagram for water (not to scale).
SInco I = l fhoro Is onIy ono dogroo of froodom i.e., If fho fomornfuro Is fIxod, nII ofhor
roorfIos nro nIso fIxod.
Tho oInf of InforsocfIon of fhoso fwo curvos Is oInf O, cnIIod fho frIIo oInf, bocnuso
fho fhroo hnsos, Ico-wnfor-vnour nro In oquIIIbrIum, i.e., If Is ncfunIIy fho moIfIng oInf of Ico
i.e., 0.0098C undor 4.5?9 mm rossuro nnd nf fhIs oInf C = l, I = 3, Honco I = 0 i.e., nf fhIs
oInf noIfhor fomornfuro nor rossuro cnn bo nIforod wIfhouf fho dIsnonrnnco of ono of fho
fhroo hnsos. Tho curvo OC rorosonfs fho chnngo of moIfIng oInf of Ico wIfh rossuro. Tho
IncIInnfIon of OC fownrds fho rossuro nxIs shows fhnf moIfIng oInf of Ico Is docronsod by
IncronsIng rossuro.
Tho curvos OA, OI nnd OC dIvIdos fho whoIo rogIon Info fhroo orfIons AOC, IOC nnd
AOI In whIch onIy ono hnso Is rosonf nnd so fho sysfom bocomos bIvnrInnf nnd fo Iocnfo nny
oInf In fhoso nrons, fomornfuro ns woII ns rossuro Is fo bo known bocnuso fho dogroo of
froodom I = l l + 2 = 2.
Tho doffod orfIon O, whIch Is fho confInunfIon of fho curvo AO boIow 0C Is fho vnor
rossuro curvo of suorcooIod wnfor boIow 0C. ThIs curvo rorosonfs n mofnsfnbIo sysfom.
ThIs curvo O runs nbovo fho vnor rossuro curvo for Ico for fho nbovo ronson nnd on sIIghf
dIsfurbnnco fho suorcooIod wnfor ImmodInfoIy chnngos fo fho sfnbIor form i.e., Ico.
SuIIuv System. SuIfur sysfom Is nnofhor ono-comononf sysfom wIfh n sIIghf moro
comIoxIfy. SuIfur nf Iow fomornfuro Is In fho rhombIc form nnd nf hIgh fomornfuro In fho
monocIInIc form. Tho ofhor fwo modIfIcnfIons nro IIquId suIfur nnd suIfur vnor.
In fho hnso dIngrnm for suIfur (IIg. ll.2), AI Is fho vnor rossuro curvo of rhombIc
suIfur whIch Is sfnbIo ufo 95C (0.006 mm) nf I. IC Is fho sImIInr curvo of monocIInIc suIfur
nnd fho oInf I Is fho frnnsIfIon oInf bofwoon fho fwo nIIofroos of suIfur. Af I, rhombIc nnd
monocIInIc suIfur hnvo snmo vnor rossuro nnd co-oxIsf wIfh suIfur vnor.
G(115 C, 0.03 mm)
S
R
F
E(151 C, 1,288 mm)
S
L
D
C(120 C, 0.04 mm)
S
v
B(95.6 C, 0.006 mm)
B
A
Temperature (not to scale schematic)
P
r
e
s
s
u
r
e
(
n
o
t
t
o
s
c
a
l
e
s
c
h
e
m
a
t
i
c
)
Fig. 11.2 The sulphur system.
Honco, I Is ncfunIIy fho frIIo oInf. AgnIn nf C (l20C, 0.04 mm) monocIInIc suIfur
moIfs nnd C Is fho vnor rossuro curvo of IIquId suIfur. Tho IInos II nnd CI rorosonf
chnngos In frnnsIfIon fomornfuro nnd moIfIng oInf, rosocfIvoIy, wIfh rossuro. Thoso fwo
IInos moof nf I (l5lC, l288 nfm) whIch Is ngnIn n frIIo oInf whoro rhombIc, monocIInIc nnd
IIquId suIfur co-oxIsf In oquIIIbrIum.
HIgLIIgLts:
TIe PIoee rule. Tho sum of fho numbor of hnsos nnd fho dogroos of froodom of
nny sysfom oxcoods fho numbor of comononfs by fwo rovIdod fhnf fho onIy
sIgnIfIcnnf oxfornnI fncfors ncfIng nro fomornfuro, rossuro nnd conconfrnfIon.
I = C I + 2
PIoee (P). Ihnso Is dofInod ns nny hysIcnIIy dIsfIncf orfIon of mnffor whIch Is
IfsoIf homogonoous nnd unIform In comosIfIon, mochnnIcnIIy sonrnbIo from ofhor
nrfs by dofInIfo boundnry surfncos.
ConponenI (C). Comononf Is dofInod ns fho smnIIosf numbor of IndoondonfIy
vnrInbIo consfIfuonfs In forms of whIch fho comosIfIon of onch hnso cnn bo
oxrossod In fho form of n chomIcnI oqunfIon.
Degreee of freeJon (I). If Is fho mInImum numbor of Indoondonf vnrInbIos of n
sysfom, whIch cnn comIofoIy dofIno fho oquIIIbrIum of n sysfom, such ns
fomornfuro, rossuro, conconfrnfIon.
Tho convorsIon of rhombIc fo monocIInIc Is sIow nnd honco If rhombIc suIfur Is honfod
quIckIy If bynssos fho frnnsIfIon oInf I wIfhouf chnngo nnd fInnIIy moIfs fo IIquId suIfur nf
C. Curvo IC Is fho mofnsfnbIo vnor rossuro curvo of rhombIc suIfur. Thoso mofnsfnbIo sysfoms
nro rorosonfod by doffod curvos. Thoro nro fhroo sfnbIo nnd ono unsfnbIo frIIo oInfs nnd
four hnsos co-oxIsf nowhoro In fho curvo In oquIIIbrIum.
Af fho frIIo oInf I = C I + 2 = l 3 + 2 = 0 i.e., zoro vnrInnf nnd fhroo hnsos cooxIsf.
AIong fho IInos AI, IC, C, II, CI nnd II fwo hnsos co-oxIsf nnd I = C I + 2 =
l 2 + 2 = l, i.e., fho sysfom Is unIvnrInnf nnd oIfhor fomornfuro or socIfIc voIumo doformInos
fho sysfom comIofoIy.
PHASE RULE 271
Irom fho dIngrnm If Is nIso found fhnf undor ordInnry rossuro, cooIIng of IIquId suIfur
Ionds fo soIId monocIInIc vnrIofy nIong CI buf undor hIgh rossuro, rhombIc suIfur sonrnfos
on cooIIng IIquId suIfur nIong IC.
Thus ncfunI obsorvnfIon cnn bo oxInInod orfocfIy In forms of hnso ruIo.
Phase RuIe for Two-Component AIIoy Systems
Ior n fwo comononf sysfom, fho hIghosf dogroo of froodom I = C I + 2 = 2 l + 2 = 3
i.e., fho bohnvIour of n sysfom mny bo rorosonfod by n fhroo-dImonsIonnI dIngrnm of rossuro,
fomornfuro nnd comosIfIon whIch cnnnof bo drnwn on n nor.
In fho cnso of n fwo comononf nIIoy sysfom fhoro Is n soIId-IIquId oquIIIbrIum of fho
nIIoy nnd fho vnor hnso Is rncfIcnIIy nbsonf nnd honco fho offocf of rossuro cnn bo consIdorod
fo bo nogIIgIbIo. Thus now fho sysfom Is rosonf nf nfmoshorIc rossuro nnd If romnIns consfnnf,
whIch wIII roduco fho dogroos of froodom by ono i.e., I = C I + l nnd fho sysfom Is cnIIod
condensed system. Tho vnrInbIos roduco fo fomornfuro nnd comosIfIon nnd honco fho
dIngrnms nro rorosonfod on fomornfuro-comosIfIon oquIIIbrIum.
Eutectic Systems
Tho cooIIng curvo of n uro subsfnnco cnn bo rorosonfod ns IIg. ll.3 (o). Whon fho uro
IIquId Is cooIod If ronchos Ifs froozIng oInf I whon fho uro soIId mnkos Ifs nonrnnco nnd
fho fomornfuro romnIns consfnnf unfII fho fofnI IIquId Is soIIdIfIod (Ic) nnd fhon ngnIn
fomornfuro fnIIs nIong cJ.
Tho cooIIng curvo of n mIxfuro of soIId Is rorosonfod by IIg. ll.3 (I). Whon n soIId
soIufIon Is cooIod nf froozIng oInf, n soIId hnso nonrs, fho rnfo of cooIIng Is nIforod nnd
fhoro Is n bronk In fho cooIIng curvo. Tho fomornfuro docronsos confInuousIy buf nf dIfforonf
rnfo fhnn boforo froozIng oInf. If fho mIxfuro bocomos oufocfIc fho fomornfuro fnIIs unfII fho
oufocfIc oInf Is ronchod. Tho sysfom bocomos InvnrInnf, fomornfuro romnIns consfnnf unfII
fofnI soIIdIfIcnfIon occurs (nIong cJ) nnd ngnIn fomornfuro fnIIs unIformIy nIong Je.
Time Time
T
e
m
p
e
r
a
t
u
r
e
T
e
m
p
e
r
a
t
u
r
e
a
b
c
d
Freezing
point
a
b
c d
e
Eutectic
temperature
Freezing
point
(a) (b)
Fig. 11.3 Cooling curves.
Irom fho cooIIng curvo of nny mIxfuro of dofInIfo comosIfIon froozIng oInf nnd oufocfIc
fomornfuro bofh cnn bo obfnInod.
Tho froozIng oInf of n sysfom vnrIos wIfh fho comosIfIon buf fho oufocfIc oInf romnIns
consfnnf.
If fho comosIfIon of fho mIxfuro coIncIdos wIfh fho oufocfIc comosIfIon, fhoro Is no
doubIo bronk buf fho curvo mImIcks fhnf of uro comononf.
Iy IoffIng froozIng oInf ngnInsf comosIfIon, T-C curvo Is obfnInod for nIIoy sysfom. If
Is nIso nocossnry fo know fho froozIng oInfs of fho uro comononfs.
B
327 C
Solid Pb
+
Liquid
Eutectic
+
Solid Pb
100% Pb
2.6 Ag
97.4 Pb
100% Ag
Composition
Eutectic
+
Solid Ag
Solid Ag
+
Liquid
Liquid
A
P
P
O
961 C
303 C
T
e
m
p
e
r
a
t
u
r
e
Fig. 11.4 T-C diagram of Pb-Ag system.
Tho comosIfIon corrosondIng fo n froozIng oInf gIvos fho comosIfIon of fho nIIoy.
A bInnry sysfom consIsfIng of fwo subsfnncos whIch do nof roncf chomIcnIIy buf Is mIscIbIo
In nII roorfIons In IIquId hnso Is cnIIod oufocfIc sysfom.
A soIId soIufIon of fwo or moro subsfnncos hnvIng Iowosf froozIng oInf fhnn nII fho
mIxfuro of fho comononfs Is cnIIod oufocfIc mIxfuro nnd fho mInImum froozIng oInf
nffnInnbIo corrosondIng fo fho oufocfIc mIxfuro Is oufocfIc oInf.
Tho oufocfIcs nro nIIod for consfrucfIng snfofy dovIcos In boIIors, nufomobIIos ofc.
Lead-SiIver-SampIe (Eutectic System)
If Is n fwo-comononf sysfom wIfh four ossIbIo hnsossoIId Ag, soIId Ib, soIufIon of
Ag + Ib nnd vnor. Af consfnnf nfmoshorIc rossuro, fho vnour hnso Is nbsonf nnd fho
condonsod hnso ruIo Is nIIcnbIo ns I = C I + l.
Curvo AO rorosonfs fho froozIng oInf curvo of Ag. A Is fho moIfIng oInf (96lC) of
Ag. AO rorosonfs fho curvo nIong whIch fho moIfIng oInf of Ag fnIIs grndunIIy on nddIfIon of
Ib fIII fho Iowosf oInf (303C) Is ronchod whon fho soIufIon gofs snfurnfod wIfh Ib nnd honco
nny oxfrn Ib nddod gofs rocIIfnfod ns soIId hnso nnd so nIso moIfIng oInf of Ag cnnnof bo
Ioworod nny furfhor. ThIs oInf O Is fho oufocfIc oInf (2.6 Ag nnd 9?.4 Ib) nnd fho whoIo
mnss nf fhIs oInf crysfnIIIzos ouf wIfh fho nbovo fIxod comosIfIon.
SImIInrIy, nnofhor curvo IO Is obfnInod sfnrfIng from fho moIfIng oInf of uro Iond
(32?C) nf I, ns Ag Is nddod fho moIfIng oInf grndunIIy fnIIs fIII fho Iowosf oInf O Is ronchod
wIfh fho nbovo monfIonod comosIfIon. AccordIng fo roducod hnso ruIo oqunfIon, fho sysfom
Is unIvnrInnf nIong AO nnd IO nnd nf oInf O, I = 3 I = 3 3 = 0 i.e., InvnrInnf, whIch Is fho
oufocfIc fomornfuro nnd n Iond-sIIvor mIxfuro cnn novor hnvo n moIfIng oInf boIow fho oufocfIc
fomornfuro.
PHASE RULE 273
Tho rogIon nbovo fho curvo AO nnd IO rorosonfs soIufIon of Ib nnd Ag nnd boIow fho
curvo AO rorosonfs soIId oufocfIc wIfh crysfnIIIno Ag nnd boIow fho curvo IO rorosonfs soIId
oufocfIc wIfh crysfnIIIno Ib.
Tin-Magnesium System
Tho oquIIIbrIum dIngrnm of fIn (Sn) nnd mngnosIum (Mg) Is shown In IIg. ll.5. Whon
Mg Is nddod fo Sn, fho moIfIng oInf of Sn (232C) Iowors nIong IQ. Af O (2l0C) n now soIId
hnso of n comound of Sn nnd Mg bogIns fo sonrnfo nIongwIfh Sn. So Q Is fho InvnrInnf
oufocfIc oInf. Iurfhor nddIfIon of Mg rnIsos fho moIfIng oInf nIong Q! nnd fho mnxImum Is
ronchod nf !. Thus nIong Q! from moIfon nIIoy onIy soIId comound crysfnIIIzos ouf In
oquIIIbrIum wIfh fho IIquId. Af ! fho comosIfIon of fho IIquId nnd fho soIId hnso Is fho snmo.
ThIs fomornfuro (?83C) Is fho congruonf moIfIng oInf of fho comound, whIch Is Mg
2
Sn.
T
500
232
210
100
0 50 100
Mg (mole percent)
800
a
1
a
2
C + L
A + L
X
A + C
Y
B + C
R
a
3
a
4
a
5
w
C + L
U
B + L
S Z
565
651
783
Q
P
Fig. 11.5 Phase diagram of the system Sn-Mg: ASn crystals,
BMg crystals, Ccompound Mg
2
Sn, Lliquid.
Iurfhor IncronsIng fho mngnosIum, fho froozIng oInf docronsos nIong !S nnd ronchos
fho socond oufocfIc oInf S (565C). AgnIn on IncronsIng fho Mg fho froozIng oInf rIsos nIong
SW. Af fho oufocfIc oInfs fho soIId comound Is In oquIIIbrIum wIfh oIfhor soIId fIn or soIId
Mg. Tho hum In fho dIngrnm IndIcnfos fho formnfIon of n comound. Tho comound formod Is
sfnbIo nnd hns Ifs moIfIng oInf nf fho mnxImum. Tho moIfIng oInfs nnd fho oufocfIc oInfs I,
!, W, Q, S nro InvnrInnf nnd fho nrons In bofwoon fho IInos nro unIvnrInnf.
Iron-Carbon AIIoy System
Tho oquIIIbrIum dIngrnm of Io-C Is osocInIIy usofuI fo undorsfnnd fho honf fronfmonf
of sfooI. Tho hnso-dIngrnm of Iron-Iron cnrbIdo sysfom Is usod ufo 6.6? woIghf of cnrbon.
Iuro Iron oxIsfs In fhroo nIIofroIc modIfIcnfIons , nnd . C nfoms boIng smnII comnrod fo
Iron nfoms form onIy InforsfIfInI soIId soIufIons nnd fho soIubIIIfy of C In fhoso nIIofroos Is
quIfo dIfforonf.
1600
1539
1500
1400
1300
1200
1100
1000
900
800
700
600
500
0
Wrought
iron
N 0.4 0.5 0.8 1.0 2.0
Hypoeutectoid Hypereutectoid
Steels
x
3.0 4 4.3 5 6 6.6
Cast iron
Weight %C
A
E
P
d g +
B
x
I
A
2
L
Austenite
Austenite
+
Ferrite
A
3
K
0.025%
Ferrite
Pearlite
+
Ferrite
0.008%
Acm
A
u
s
te
n
ite
+
L
iq
u
id
G
(1,130C)
Liquid
y
D
Liquid
+
Fe C
3
H
C
A
u
s
t
e
n
i
t
e
+
C
e
m
e
n
t
i
t
e
Austenite
+Ledeburite
+Cementite
Cementite
+
Ledeburite
M
(723 C)
A
1
E
u
t
e
c
t
o
i
d
(
p
e
a
r
l
i
t
e
)
Pearlite
+
Cementite
Cementite
+
Pearlite
+Transformed
Ledeburite
E
u
t
e
c
t
i
c
(
L
e
d
e
b
u
r
i
t
e
)
T
e
m
p
e
r
a
t
u
r
e
C
d+L
Fig. 11.6 Equilibrium diagram for Fe-C system.
In fho hnso dIngrnm, fho curvo AIC Is fho IIquIdus IIno nnd AIICCH Is fho soIIdus
IIno. Abovo fho IIquIdus fhoro Is onIy IIquId hnso whorons boIow fho soIIdus fhoro Is onIy soIId
hnso nnd bofwoon fho fwo IInos bofh hnsos nro rosonf. On dIssoIvIng C In moIfon Iron
( form nf l535C) fho froozIng oInf Is Ioworod unfII nf oufocfIc fomornfuro of ll30C
corrosondIng fo 4.3 C by woIghf. On furfhor nddIfIon of C, froozIng oInf Incronsos ufo
6.6? C confonf nnd If Is cnIIod comonfIfo.
Iuro Iron chnngos from fo form nf n fomornfuro of 9l0C. Tho hnso dIngrnm
IndIcnfos fhnf ufo 0.088 C Is commorcInIIy uro Iron, whorons 0.088 fo 2 C confonf Is
sfooI nnd C confonf nbovo 2 rorosonfs cnsf Iron.
Irom fho curvo, AII nron rorosonfs -Iron nnd IIquId. Aron CH rorosonfs comonfIfo
nnd IIquId. Aron ICCI rorosonfs nusfonIfo nnd IIquId nnd fInnIIy ICKI rorosonfs -Iron (i.e.
nusfonIfo) onIy.
Tho frnnsformnfIon of ono soIId hnso Info nnofhor fnkos Inco nf fho crIfIcnI fomornfuros
IndIcnfod on fho dIngrnm.
Ior nn Iron-C nIIoy (cnsf Iron) confnInIng 3 C, froozIng bogIns nf l2?0C. On furfhor
cooIIng, nusfonIfo sonrnfos ouf from fho IIquId, fhon nf ll30C, fho mIxfuro Is nusfonIfo
confnInIng 2 C nnd IIquId hns oufocfIc comosIfIon. Honco furfhor romovnI of honf Ionds fo
fofnI soIIdIfIcnfIon of fho IIquId fo IodoburIfo, n mIxfuro of nusfonIfo nnd comonfIfo. CooIIng
furfhor Ionds fo fho docomosIfIon of fho oufocfIc mIxfuro of comonfIfo nnd fInnIIy nf ?23C fho
rosIdunI nusfonIfo frnnsforms fo onrIIfo nnd nf fomornfuro boIow ?23C, nII fho IodoburIfo Is
frnnsformod Info onrIIfo nnd comonfIfo mIxfuro.
Tho Io-C hnso dIngrnm shows fho hnsos, whIch nro formod whon fho cooIIng rnfo Is
sIow i.e., whon oquIIIbrIum Is nffnInod. Iuf wIfh fnsfor cooIIng rnfos mofnsfnbIo hnsos IIko
mnrfonsIfo nnd bnInIfo nro formod whIch nro nof shown In fho hnso dIngrnm.
PHASE RULE 275
HIgLIIgLts:
Condensed pLuse vuIe. Ior fwo-comononf nIIoy sysfoms If Is consIdorod fhnf
fhoro Is rncfIcnIIy no gns hnso nnd fho offocf of rossuro Is nogIIgIbIo. So fho
sysfom Is consIdorod fo bo undor nfmoshorIc rossuro whIch roducos fho dogroos
of froodom by ono nnd honco,
I = C I + l
TvIpIe poInt. If Is fho oInf of n sysfom nf whIch fho gnsoous, IIquId nnd soIId
hnsos of n subsfnnco cnn co-oxIsf In oquIIIbrIum. Af frIIo oInf fho sysfom Is non-
vnrInnf.
utectIc poInt. A soIId soIufIon of fwo or moro subsfnncos hnvIng Iowosf froozIng
oInf Is fho oufocfIc mIxfuro nnd fho mInImum froozIng oInf nffnInod Is fho oufocfIc
oInf.
Congvuent meItIng poInt. A comound ossossos congruonf moIfIng oInf If If
moIfs fo gIvo n IIquId hnvIng fho comosIfIon snmo ns fho soIId.
SOLVED PROBLEMS
PvobIem 1. An ollo, of CJ onJ Bi conIoine 2" CJ. IinJ IIe noee of euIecIic in 1 lg of
IIe ollo,, if IIe euIecIic e,eIen conIoine 40" CJ.
SoI. In fho oufocfIc sysfom, 40 Is Cd nnd honco 60 Is II.
In l kg nIIoy confonf of Cd Is 25, i.e., 250 gm.
CorrosondIng fo 250 gm Cd, fho confonf of II In oufocfIc Is
250 60
40
3?5
= gm gms.
Tho mnss of oufocfIc In l kg nIIoy Is (250 + 3?5) gm = 625 gm. Ans.
PvobIem 2. An ollo, AB conIoine 40" A in 1 lg. AB on cooling forne euIecIic conIoining
60" A onJ 40" B onJ IIe reeI of B. WIoI ie IIe onounI of B forneJ Juring euIecIic fornoIion:
SoI. In l kg of AI, A = 40 = 400 gm nnd I = 60 = 600 gm.
Tho oufocfIc mIxfuro confnIns 60 A nnd 40 I.
CorrosondIng fo 400 gm A, fho confonf of I =
400 40
60
266 ?
= . gm
Amounf of I sonrnfod ouf = (600 266.?) gm = 333.3 gm. Ans.
Q. 1. Stute PLuse vuIe.
Ans. Soo ngo 26?.
Q. 2. WLut Is condensed pLuse vuIe?
Ans. Soo ngo 2?2.
Q. 3. eIIne tLe IoIIowIng tevms:
(u) PLuse (b) Component (c) egvees oI Iveedom.
Ans. (o) Soo ngo 266.
(I) Soo ngo 266.
(c) Soo ngo 26?.
Q. 4. WLut Is tvIpIe poInt?
Ans. Soo ngo 269.
Q. 5. WLut Is un InvuvIunt system? GIve un exumpIe.
Ans. A sysfom In whIch fho dogroo of froodom Is zoro Is cnIIod nn InvnrInnf sysfom. ThIs
sIgnIfIos fhnf no condIfIon Is roquIrod fo dofIno fho sysfom nf fhnf oInf.
xumpIe: TrIIo oInf of wnfor Is whoro Ico, wnfor nnd wnfor vnour nro In oquIIIbrIum.
Q. 6. WLut Is tLe sIgnIIIcunce oI tvIpIe poInt?
Ans. A frIIo oInf for n sysfom Is InvnrInnf. If Is consfnnf for n subsfnnco nf n sof of
fomornfuro nnd rossuro condIfIons. If fomornfuro or voIumo Is nIforod, ono hnso of fho
subsfnnco dIsnonrs nnd fho sysfom bocomos unIvnrInnf from InvnrInnf.
Q. ?. Stute two Impovtunt mevIts oI pLuse vuIe.
Ans. (i) Ihnso ruIo Is nIIcnbIo fo bofh hysIcnI nnd chomIcnI oquIIIbrIn.
(ii) Ihnso ruIo hoIs fo rodIcf fho bohnvIour of n sysfom undor dIfforonf sofs of condIfIons.
Q. B. Stute IImItutIons oI pLuse vuIe.
Ans. (i) Ihnso ruIo cnn bo nIIod onIy for n sysfom whIch Is In oquIIIbrIum.
(ii) Ihnso ruIo condIfIons fhnf nII hnsos of fho sysfom musf bo rosonf sImuIfnnoousIy
undor sImIInr sof of condIfIons.
Q. 9. WLut do you meun by eutectIc? WLut Is tLe eutectIc composItIon oI Pb-Ag
System? GIve one uppIIcutIon oI eutectIcs.
Ans. IufocfIc Is n soIId soIufIon of fwo or moro subsfnncos hnvIng fho Iowosf froozIng
oInf of nII fho ossIbIo mIxfuro of fhoso comononfs.
IufocfIc comosIfIon of Ib-Ag sysfom 9?.4 Ib, 26 Ag. Iy suIfnbIo choIco, vory Iow
moIfIng nIIoys cnn bo soIocfod for ronrIng snfofy dovIcos IIko fIro srInkIors, Iugs In
nufomobIIos ofc.
Q. 10. Stute (I) numbev oI pLuses und (II) numbev oI components Iov
Ie(s) + H
2
O(g) IeO(s) + H
2
(g).
Ans. (i) Thoro nro fwo soIId hnsosIo nnd IoO nnd ono gnsoous hnso of n mIxfuro
of H
2
O(g) nnd H
2
(g). So fhoro nro fhroo hnsos In oquIIIbrIum.
(ii) Tho mInImum numbor of comononfs roquIrod fo oxross fho comosIfIon of onch
hnso Is fhroo.
Q. 11. How muny degvees oI Iveedom uve tLeve Iov tLe IoIIowIng systems?
(I) Wutev() Wutev vupouv(g)
(II) Guseous mIxtuve oI H
2
und O
2
Ans. (i) Ior Wnfor(l) Wnfor vnour(g) sysfom oIfhor fomornfuro or rossuro Is
fo bo socIfIod fo dofIno fho sysfom comIofoIy. Honco dogroo of froodom Is one.
(ii) Ior fho gnsoous mIxfuro of H
2
nnd O
2
bofh fho rossuro nnd fho fomornfuro nro fo
bo socIfIod fo dofIno fho sysfom comIofoIy, so fho sysfom hns two dogroos of froodom.
Q. 12. Iov u two-component uIIoy system oI Pb und Ag, stute tLe degvees oI
Iveedom (I) us pev pLuse vuIe und (II) us pev condensed pLuse vuIe.
PHASE RULE 277
Ans. (i) Ior n fwo-comononf nIIoy sysfom of Ib nnd Ag whon I = l, dogroo of froodom
nccordIng fo hnso hns fho hIghosf vnIuo of I = C I + 2 = 2 l + 2 = 3.
(ii) As or condonsod hnso ruIo:
Ior soIId-IIquId oquIIIbrIum of nIIoy, rncfIcnIIy no gns Is rosonf nnd honco nf nfmoshorIc
condIfIon fho rossuro romnInIng consfnnf, dogroos of froodom roducos by ono nnd I bocomos
I = C I + l = 2 l + l = 2.
EXERCISES
1. Sfnfo hnso ruIo.
2. ofIno fho foIIowIng forms:
hnso, comononf, dogroos of froodom.
3. Whnf Is condonsod hnso ruIo
4. Whnf Is frIIo oInf
5. WrIfo n brIof nofo on: oufocfIc oInf, mofnsfnbIo sfnfo.
6. WrIfo down fho IImIfnfIons of hnso ruIo.
?. Whnf Is hnso dIngrnm IxInIn (o) frIIo oInf nnd (I) oufocfIc oInf wIfh roforonco fo hnso
dIngrnm.
B. rnw nnd oxInIn fho hnso dIngrnm of Ico-wnfor-wnfor vnor sysfom nnd show fho vnrInfIon of
moIfIng-oInf of Ico wIfh rossuros.
9. Whnf nro fho morIfs nnd fho IImIfnfIon of hnso ruIo
10. Iscuss fho nIIcnfIon of hnso ruIo fo suIfur sysfom wIfh socInI roforonco fo frIIo oInfs nnd
mofnsfnbIo oquIIIbrIum.
11. Whnf nro monnf by InvnrInnf nnd bIvnrInnf dogroos of froodom
12. rnw nnd oxInIn fho hnso dIngrnm of n bInnry nIIoy sysfom wIfh sImIo oufocfIc formnfIon.
Objective Type Questions MCQ
1. CIbbs hnso ruIo Is:
(o) I + I = C + 2 (I) I C = I + 2 (c) I + C = I + 2.
2. Condonsod hnso ruIo oqunfIon Is:
(o) I = C I + 2 (I) I = C I + l (c) I = C + I 2.
3. Tho mnxImum numbor of dogroos of froodom for n fwo-comononf nIIoy sysfom Is
(o) 3 (I) l (c) 2.
4. Tho comosIfIon of fho oufocfIc mIxfuro of Ib-Ag sysfom Is
(o) 2.6 Ib, 9?.4 Ag (I) 2.6 Ag, 9?.4 Ib (c) 26 Ib, ?4 Ag.
5. In fho fhormnI docomosIfIon of CnCO
3
(e) CnO(e) + CO
2
(g) fho sysfom Is n
(o) ono comononf (I) fwo comononf (c) fhroo comononf.
6. Hoforogonoous mIxfuro of CnCO
3
(e) CnO(e) + CO
2
(g) consIsfs of
(o) ono hnso (I) fwo hnsos (c) fhroo hnsos
?. In fho wnfor sysfom nf frIIo oInf, fho sysfom Is
(o) unIvnrInnf (I) frIvnrInnf (c) InvnrInnf.
B. Condonsod hnso ruIo hns fwo vnrInbIos, nnmoIy
(o) fomornfuro nnd conconfrnfIon.
(I) fomornfuro nnd rossuro
(c) rossuro nnd conconfrnfIon
9. IufocfIc mIxfuro hns:
(o) hIghosf moIfIng oInf. (I) vnrInbIo comosIfIon (c) Iowosf moIfIng oInf.
10. umbor of comononfs of fho sysfom Io(e) + H
2
O(g) IoO(s) + H
2
(g)
(o) fwo (I) fhroo (c) four.
278
+E@I
278
INTRODUCTION
Thomns Crnhnm (l86l) whIIo doIng hIs cInssIcnI rosonrchos on IIquId dIffusIon obsorvod
fwo cInssos of subsfnncos.
SoIufIon of somo subsfnncos couId rondIIy nss fhrough nnImnI nnd vogofnbIo mombrnnos.
To fhIs cInss boIongod nImosf nII InorgnnIc ncIds, bnsos nnd snIfs nnd mnny orgnnIc comounds
IIko uron, sugnr ofc. Crnhnm cnIIod fhom cvystuIIoId ns mosf of fhom woro crysfnIIIno.
Tho ofhor cInss of subsfnncos nro dIffusod vory sIowIy In soIufIon nnd fho soIufIon couId
nof nss fhrough fho mombrnno, fhoy woro cnIIod coIIoIds (from fho Crook word Kollo monnIng
gIuo, whIch Is n mombor of fhIs cInss). Ofhor mombors nro sfnrch, goInfIn, nIbumIn, rofoIns
nnd ofhor nmorhous subsfnncos.
Crnhnm`s vIow hns undorgono chnngos sInco If hns boon soon fhnf ovory subsfnnco cnn
oxhIbIf coIIoIdnI roorfIos undor suIfnbIo condIfIons. Thus wo now dofIno coIIoIdnI sfnfo ns: n
fwo hnso hoforogonoous sysfom In whIch ono hnso Is dIsorsod In n fIno sfnfo of subdIvIsIon
hnvIng dInmofor of l0
4

fo l0
?

cm In nnofhor modIum formod fho confInuous or dIsorsIon
modIum. In n coIIoIdnI soIufIon fhoro oxIsfs n dIsconfInuous hnso cnIIod fho dIsorsod hnso
nnd fho confInuous dIsorsIon modIum, nnd nIso n sfnbIIIzIng ngonf whIch doos nof nIIow fho
dIsorsod hnso fo conIosco nnd soffIo.
CIassification of CoIIoids
(o) CIussIIIcutIon bused on dIspevsed pLuse und dIspevsIon medIum whIch mny
bo oIfhor soIId or IIquId or gns nnd so fho foIIowIng fyos (TnbIo l2.l) of coIIoIds nro formod.
TabIe 12.1 Types of colloidal systems
Diepereion DiepereeJ ColloiJol 1xonplee
neJiun pIoee e,eIen
Cns !IquId !IquId norosoI MIsf, Iog, CIoud, InsocfIcIdo srny,
SoIId SoIId norosoI Smoko, Iumo
!IquId Cns Ionm Ionm, Irofh, WhIod cronm,
!omonndo
!IquId ImuIsIon MIIk, Cronm, MnyonnnIso,
SoIId SoI CIuo, InInfs, Sfnrch nsfo, MIIk
of MngnosIn, CoId soI, As
2
O
3
, S,
IoO
3
or AgCI soI In wnfor
SoIId Cns SoIId fonm IumIco sfono, brond dough, !nvn,
Sfyrono fonm, !ubbor.
!IquId CoI Curd, JoIIy, Chooso, Iuffor, Shoo
oIIsh, IonrI (CnCO
3
wIfh wnfor).
SoIId SoIId soI Coms, AIIoys, MInornIs
COLLOlDS 279
(I) CIussIIIcutIon bused on uIIInIty Iov soIvent
Whon fhoro Is n sfrong nffInIfy bofwoon fho dIsorsod hnso nnd fho dIsorsIon modIum
fho coIIoId Is known ns IyopLIIIc coIIoId, whIIo If fhoro Is no nnronf nffInIfy If Is cnIIod
IyopLobIc coIIoId. Tho mnIn dIfforoncos bofwoon fhoso fwo cInssos of coIIoIds nro summnrIsod
In TnbIo l2.2.
TabIe 12.2 Characteristics of lyophilic and lyophobic sols
L,opIilic eol L,opIoIic eol
(i) SfnbIo
(ii) Tho nrfIcIos mny or mny nof mIgrnfo In
nn oIocfrIcnI fIoId.
(iii) VIscosIfy Is much hIghor fhnn fhnf of fho
modIum.
(it) Thoy nro rovorsIbIo soIs.
(t) Thoy nro soIf-sfnbIIIzod duo fo fho sfrong
nffrncfIon bofwoon fwo hnsos.
(ti) Surfnco fonsIon Is much Iowor fhnn fhnf of
fho modIum.
(tii) Thoy nro nof onsIIy rocIIfnfod by fho nd-
dIfIon of oIocfroIyfos.
(tiii) Sfnrch goInfIn, gum, nIbumIn nro IyohIIIc
coIIoIds.
(ix) of vIsIbIo undor uIfrnmIcroscoo.
(x) Ironrod sImIy by dIrocf dIssoIvIng.
(i) !nsfnbIo
(ii) Tho nrfIcIos nro chnrgod nnd honco
movo fownrds oIocfrodo In nn oIocfrIcnI
fIoId.
(iii) VIscosIfy Is snmo ns fhnf of fho modIum.
(it) Thoy nro IrrovorsIbIo.
(t) Thoy nro much Ioss sfnbIo, sfnbIIIzor Is
roqd. for sfnbIIIznfIon.
(ti) Surfnco fonsIon Is snmo ns fhnf of fho
modIum.
(tii) Thoy nro conguInfod onsIIy by nddIng
oIocfroIyfo.
(tiii) CoIIoIdnI mofnIs, mofnIIIc suIfIdos nro
IyohobIc coIIoIds.
(ix) VIsIbIo undor uIfrnmIcroscoo.
(x) Ironrod by IndIrocf mofhods.
(c) CIussIIIcutIon bused on nutuve oI dIspevsed pLuse
(i) MulIinoleculor colloiJe. Whon fho dIsorsod hnso consIsfs of nggrognfos of nfoms
or moIocuIos nnd fho mnIn nffrncfIvo forco bofwoon fhom Is fho vnn dor WnnIs
forco of nffrncfIon. Thoy nro IyohobIc In nnfuro.
1xonplee. CoId soI nnd SuIfur soI.
(ii) Mocronoleculor colloiJe. A Inrgo numbor of smnII moIocuIos combIno fo form n
gInnf moIocuIo hoId by covnIonf bonds hnvIng n coIIoIdnI dImonsIon nro cnIIod
mncromoIocuInr coIIoIds. Thoy nro IyohIIIc nnd hnvo goId numbors.
1xonplee. IrofoIns, IoIysncchnrIdos, Cums, SynfhofIc rubbor, yIon ofc.
(iii) AeeocioIion colloiJe. On IncronsIng conconfrnfIon, fho soIufo moIocuIos or Ions
como cIosor fo form nggrognfo sonfnnoousIy of coIIoIdnI dImonsIons, cnIIod mIcoIIos
nro nssocInfod coIIoIds. 1xonple. Sons nnd synfhofIc doforgonfs.
SodIum oIonfo forms mIcoIIos nnd confnIns n IyohobIc grou (C
l?
H
33
+
) nnd n IyohIIIc
grou (COOn), fho hydrocnrbon orfIon InsIdo fho mIcoIIo, whIIo fho IonIsod grous nro nf
fho surfnco. Thoy movo frooIy In nn oIocfrIc fIoId nnd fho soIufIon hns hIgh conducfIvIfy. Tho
mInImum conconfrnfIon nf whIch fho mIcoIIIznfIon bogIns Is cnIIod fho cvItIcuI mIceIIIzutIon
concentvutIon (cmc). Thoso coIIoIds Iny vory Imorfnnf roIo In soIubIIIzIng soIvonf rooIInnf
subsfnncos, such ns wnfor InsoIubIo dyos nro soIubIIIzod In son soIufIons.
Preparation of CoIIoidaI SoIutions
Tho mnIn mofhods of ronrnfIon of coIIoIdnI soIufIons nro (o) CondonsnfIon mofhod
(I) IsorsIon mofhod.
(A) CondensutIon MetLod: In fhIs mofhod, n Inrgo numbor of nrfIcIos of moIocuInr
sIzo nro nIIowod fo conIosco or condonso fo form bIggor nrfIcIo of coIIoIdnI dImonsIon. Tho
vnrIous rocossos usod nro:
(i) B, excIonge of eoltenI. SuIfur or hoshorus Is nof dIrocfIy soIubIo In wnfor. If nn
nIcohoI soIufIon of S or I Is ourod Info wnfor, coIIoIdnI soIufIon of S or I Is formod.
(ii) B, cIonging pI,eicol eIoIe. Hg or S soIs nro roducod by nIIowIng fhoIr vnours fo
nss fhrough coId wnfor. AmmonIum cIfrnfo Is nddod fo sfnbIIIzo fho soIufIon.
(iii) B, conIrolleJ conJeneoIion. IrussInn bIuo soI Is obfnInod by rocIIfnfIng If In
rosonco of n rofocfIvo coIIoIdnI sysfom IIko sfnrch.
(it) CIenicol neIIoJe. (o) by doubIo docomosIfIon, coIIoIdnI soIufIon of nrsonIous suIfIdo
Is mndo by nssIng H
2
S gns, fhrough n susonsIon of As
2
O
3
In wnfor, unfII snfurnfIon.
As
2
O
3
+ 3H
2
S As
2
S
3
+ 3H
2
O.
SoIs of InsoIubIo InorgnnIc snIfs nro ronrod In fhIs wny.
(I) B, reJucIion. CoIIoIdnI soIufIons of mofnIs such ns Ag, Au, If In wnfor cnn
bo ronrod by roducIng nquoous soIufIon of fhoIr snIfs by roducfnnfs IIko formnI-
dohydo, cnrbon monoxIdo, hydrnzIno ofc.
Thus goId soI Is obfnInod by fronfIng n soIufIon of goId chIorIdo wIfh formnIdohydo
(0.3 ).
2AuCI
3
+ 3HCHO + 3H
2
O 2 Au(soI) + 3HCOOH + 6HCI
Tho IIbornfod ncId Is noufrnIIzod by K
2
CO
3
fo sfnbIIIzo fho soI.
(c) B, I,Jrol,eie. CoIIoIdnI soIufIons of mnny oxIdos nnd hydroxIdos of Iron, nIumInIum
cnn bo ronrod by fhIs mofhod. On nddIng n froshIy ronrod snfurnfod soIufIon
of IoCI
3
drowIso on boIIIng wnfor, hydroIysIs of IoCI
3
fnkos Inco wIfh fho for-
mnfIon of doo rod coIIoIdnI soI of forrIc hydroxIdo.
IoCI
3
+ 3H
2
O Io(OH)
3
(soI) + 3HCI
(J) B, oxiJoIion. SuIfur soI Is ronrod by nssIng H
2
S fhrough n soIufIon of SO
2
In
wnfor unfII fho smoII of SO
2
Is romovod. Tho soIufIon on boIIIng wIfh snfurnfod
nCI soIufIon rocIIfnfos ouf S, on fIIfrnfIon, whIch Is wnshod froo of CI
nnd
fInnIIy dIssoIvos on furfhor nddIfIon of wnfor.
(I) IspevsIon metLod: In fhIs mofhod, fho bIggor or Inrgo nrfIcIos nro brokon down
fo coIIoIdnI dImonsIon nnd dIsorsIng fhom In n modIum fo form coIIoIdnI soIufIon. Tho mofhods
usod nro:
(i) B, necIonicol Jiepereion: Mnny subsfnncos of Inrgo sIzo nro ground nnd dIsorsod In
n modIum fo gof n conrso susonsIon whIch Is fhon nssod fhrough n coIIoId mIII, whIch Is
ossonfInIIy fwo mofnI dIscs rofnfIng In oosIfo dIrocfIons nf hIgh sood wIfh n vory nnrrow
cIonrnnco.
Tho snco In bofwoon fho mofnI dIscs bronks down fho nrfIcIos fo coIIoIdnI sIzo. IInck
Ink, nInfs, vnrnIshos, oInfmonfs dyosfuffs nro ronrod by fhIs mofhod.
COLLOlDS 281
(ii) BreJigè orc neIIoJ or elecIro Jiepereion. (IIguro l2.l) CoIIoIdnI soIufIon of mofnIs
IIko Au, Ag, Cu, Ib, If ofc. nro obfnInod by fhIs mofhod. An oIocfrIc curronf Is nssod fhrough
wnfor confnInIng frncos of nIknII, whon nn oIocfrIc nrc Is roducod bofwoon fho fIs of fwo
cIosoIy Incod oIocfrodos of fhoso mofnIs. Tho honf of fho snrk convorfs fho onds of fho mofnI
rods fo form vnours of mofnI whIch ImmodInfoIy condonso fo gIvo mofnI coIIoIds. Tho frnco of
nIknII sfnbIIIzos fho coIIoIdnI soIufIon nnd fInnIIy fho soIufIon Is cooIod by cooIIng mIxfuro.
A
High
voltage
Rheostat
Arc
Metal
rods
Cooling mixture
(ice)
A little KOH
containing
solvent
(water)
Fig. 12.1 Bredig's arc method.
(iii) MecIonicol Jiepereion neIIoJ. (IIg. l2.2) fhIs fochnIquo consIsfs of fInoIy uIvorIsIng
fho subsfnncos fo bo dIsorsod In fho modIum, whIch consfIfufos fho dIsorsIon hnso. ThIs
conrso susonsIon Is fhon nssod fhrough coIIoId-mIII whIch mochnnIcnIIy grInds fho conrso
nrfIcIos. Tho coIIoId-mIII consIsfs of fwo dIscs mndo of mofnI, whIch rofnfos In oosIfo dIrocfIon
nf n vory hIgh sood. Tho cIonrnnco bofwoon fho dIscs Is vory smnII fhnf nnronfIy doformInos
fho sIzo of fho coIIoIdnI nrfIcIo. Tho conrso nrfIcIos whIch como In bofwoon fho fwo rofnfIng
dIscs gof fonrod fo smnIIor coIIoIdnI nrfIcIos, whIch nro fInnIIy sfnbIIIzod by nddIfIon of n
suIfnbIo rofocfIvo coIIoId.
Colloidal
solution
(discharge)
Driving belt
Suspension
Metallic disc
Fig. 12.2 Colloidal mill.
(it) PepIicoIion. A froshIy ronrod rocIIfnfo such ns AgCI, Io(OH)
3
, AI(OH)
3
ofc. cnn
bo convorfod Info coIIoIdnI sfnfo by fho nddIfIon of smnII nmounf of n foroIgn oIocfroIyfo soIufIon.
Tho foroIgn oIocfroIyfo Is known ns fho peptIzIng ugent nnd fho rocoss Is cnIIod peptIzutIon.
(o) Thus froshIy rocIIfnfod Io(OH)
3
, If shnkon wIfh n dIIufo soIufIon of IoCI
3
, wouId
gIvo rIso fo forrIc oxIdo soI.
Io(OH)
3
(e) + Io
3+
Io(OH)
3
. Io
3+
IrocIIfnfo IofIzIng ngonf (CoIIoId/SoI)
(I) IroshIy rocIIfnfod AgCI cnn bo ofIzod by shnkIng wIfh n dIIufo nq soI. of AgO
3
AgCI(e) + Ag
+
AgCI . Ag
+
IrocIIfnfo IofIzIng ngonf (SoI/CoIIoId)
(c) AI(OH)
3
+ H
+
AI(OH)
3
. H
+
IrocIIfnfo IofIzIng ngonf (CoIIoId)
Though fhoro Is no ruIo, buf If Is common fhnf fho ofIzIng ngonf whIch nro mosf
offocfIvo confnIns n common Ion wIfh fho rocIIfnfo formIng coIIoId.
IsorsIon Is nIso somofImos cnrrIod ouf by fho uso of nn nfomIsor e.g., In fho dIsorsIon
of n IIquId In n gns.
Purification of CoIIoidaI SoIutions
Tho coIIoIdnI soIufIons ronrod by fho nbovo mofhods confnIn sovornI ImurIfIos of
oIocfroIyfos nnd ofhor soIubIo subsfnncos. So, fhoy bocomo unsfnbIo. Honco, If Is ossonfInI fo
urIfy fhoso coIIoIdnI soIs. Tho foIIowIng mofhods nro commonIy usod for urIfIcnfIon.
(i) IuIysIs. Tho somIormonbIo mombrnnos IIko coIIohnno nrchmonf nor, nnImnI
mombrnno hnvo oro sIzos whIch nIIow fho froo nssngo of onIy fho dIssoIvod moIocuIos or Ions
of n fruo soIufIon buf rofnIns fho bIggor coIIoIdnI nrfIcIos. Thus, fho rocoss of sonrnfIon of
crysfnIIoIds from coIIoIds by dIffusIon fhrough fho nnImnI or vogofnbIo mombrnno Is cnIIod
IuIysIs.
Tho soI fo bo urIfIod Is fnkon In n nrchmonf or coIIohnno bng, whIch Is nrfIy Immorsod
In wnfor or fho dIsorsIon modIum. Tho crysfnIIoIds from fho soI movo ouf fhrough fho coIIohnno
whIIo somo nmounf of wnfor or soIvonf from oufsIdo mny onfor fho bng. Tho soIvonf Is ronowod
from fImo fo fImo. Tho rocoss Is nIIowod fo confInuo unfII mosf of fho Ions nro ovonfunIIy
romovod nnd fho rofnInod coIIoId gofs sfnbIIIzod. In corfnIn soIs such ns AI
2
O
3
hydrosoI, fho
dIsorso hnso Is foo smnII fo bo rofnInod by coIIohnno nnd honco fho sysfom noods confroIIod
honfIng whoroby fho nrfIcIos grow bIggor In sIzo.
water
stand
Sol
Fig. 12.3 Dialysis.
COLLOlDS 283
To nccoIornfo fhIs sIow rocoss of urIfIcnfIon nnd nIso fo nchIovo n hIghor dogroo of
urIfy fho dInIysIs Is cnrrIod ouf In n dIrocf curronf oIocfrIc fIoId, nnd fho rocoss Is cnIIod
eIectvodIuIysIs. IIocfrodInIysIs Is of no uso In sonrnfIng non-oIocfroIyfIc ImurIfIos.
B
Sol
n
A C
H O
2
H O
2
+
D E
Fig. 12.4 Electrodialyser (diagrammatic).
(ii) \Itvu-IIItvutIon. CoIIoIdnI nrfIcIos cnn nss fhrough ordInnry fIIfor nors. Iuf
whon ordInnry fIIfor nor Is Imrognnfod wIfh n soIufIon of goInfIn or coIIodIon nnd hnrdonod
by formnIdohydo fho oros bocomo smnIIor, so fhnf coIIoIdnI nrfIcIos cnnnof nss fhrough If.
Such n fIIfor nor Is cnIIod uIfrnfIIfor nor. Tho soI whon ourod ovor fho uIfrnfIIfor, oIocfro-
Iyfos cnn nss fhrough, buf fho coIIoIdnI nrfIcIos nro rofnInod nnd form n sIImo ovor If. Tho
sIImo whon broughf In confncf wIfh wnfor, dIsorsos frooIy nnd forms coIIoIdnI soIufIon. ThIs
rocoss of urIfyIng coIIoIds from fho crysfnIIoIds usIng uIfrnfIIfors Is cnIIod uIfrnfIIfrnfIon.
Iy usIng ImrognnfIng soIufIons of dIfforonf conconfrnfIon grndod uIfrnfIIfors cnn bo
ronrod whIch Is cnnbIo of sonrnfIng ImurIfIos of dIfforonf sIzos.
Properties of CoIIoidaI SoIutions
CoIIoIdnI soIufIons ossoss somo chnrncforIsfIc roorfIos. Imorfnnf onos nro doscrIbod
boIow:
(i) PLysIcuI pvopevtIes
(o) CoIIoIdnI sysfoms nro hoforogonoous, InformodInfo bofwoon fruo soIufIon nnd
susonsIon nnd confnIn fwo hnsosdIsorsod hnso nnd dIsorsIon modIum.
(I) Colour. CoIour nnd nonrnnco doond on fho sIzo, shno, rofrncfIvo Indox nnd
somo ofhor roorfIos of fho dIsorsod hnso. CoId soI of vory fIno nrfIcIos Is rod
nnd of conrsor nrfIcIos Is bIuo In coIour; suIfur soIs mny bo coIorIoss fo fnInf nnd
doo yoIIow In rofIocfod IIghf nnd roddIsh In frnnsmIffod IIghf.
(c) SIope. AIfhough fho mosf common shno of fho nrfIcIos nro shorIcnI; buf hIghIy
nsymmofrIcnI shno Is nIso found. VnnndIum onfoxIdo nrfIcIos nro rod-shnod,
!ICs (rod bIood coruscIos) normnIIy nro doubIo concnvo Infos nnd gIvo rod
coIor, buf In sIckIo-coII nnnomIn fhoy bocomo now-moon shnod. CoIIoIdnI nrfI-
cIos nro rondIIy fIIfornbIo fhrough ordInnry fIIfor nor.
(J) AJeorpIion. ConornIIy coIIoIdnI nrfIcIos nro oIfhor osIfIvoIy or nognfIvoIy
chnrgod, so fhoy nffnch fo n vnrIofy of moIocuIos on fhoIr surfncos.
ThIs roorfy of coIIoId hns boon ufIIIzod In dyoIng fnbrIcs whoro fho fnbrIcs nro
fIrsf fronfod wIfh coIIoIdnI susonsIon whIch ndsorbs dyo.
(ii) CoIIIgutIve pvopevtIes. HIgh moIocuInr woIghf Is fho chnrncforIsfIc of coIIoIdnI
nrfIcIos nnd honco In n soIufIon, fho numbor of moIos rosonf Is vory Iow. CoIIIgnfIvo roorfIos
IIko osmofIc rossuro, dorossIon of froozIng oInf, IoworIng of vnour rossuro doond on fho
moInrIfy of fho soIufIon nnd honco fhoso vnIuos nro vory Iow for coIIoIdnI soIufIon.
(iii) MecLunIcuI pvopevtIes
(o) Brounion notenenI. !oborf Irown, nn IngIIsh bofnnIsf, In l92?, obsorvod un-
dor n mIcroscoo fhnf oIIon grnIns dIsorsod In wnfor oxocufod n consoIoss rnn-
dom mofIon. ThIs rnndom zIgzng mofIon Is nIso oxocufod by nII coIIoIdnI nrfI-
cIos, IncIudIng coIIoIdnI nrfIcIos susondod In n gnsoous modIum, Indoondonf
of fhoIr nnfuro, smnIIor nrfIcIos oxocufIng n moro rnId nnd brIsk mofIon fhnn
fho Inrgor onos. ThIs orofunI zIgzng mofIon Is cnIIod BvownIun motIon. ThIs
mofIon Is doscrIbod by IorrIn ns fhoy go nnd como, sfo, sfnrf ngnIn, mounf,
dosconf, romounf ngnIn, wIfhouf In fho Ionsf fondIng fownrds ImmobIIIfy.
Tho fruo cnuso of IrownInn movomonf wns suggosfod by WIonor In l863 ns mo-
IocuInr coIIIsIon of coIIoIdnI nrfIcIos wIfh IIquId moIocuIos. Tho coIIoIdnI nrfI-
cIos nro consfnnfIy hIf from nII sIdos of fho surroundIng moIocuIos. Tho coIIoIdnI
nrfIcIos nffor Imncf wIfh soIvonf moIocuIo movo In n sfrnIghf IIno unfII Ifs sood
nnd dIrocfIon nro nof nIforod by nnofhor Imncf. Tho InfonsIfy of IrownInn mo-
fIon Is Ioss wIfh Incronso In sIzo of fho coIIoIdnI nrfIcIos nnd nIso wIfh fho In-
cronso In vIscosIfy of modIum.
IrownInn mofIon nIso Incronsos wIfh Incronso In fomornfuro. !nrgo nrfIcIos
do nof show IrownInn movomonf.
(I) Diffueion. In n coIIoIdnI soIufIon, coIIoIdnI nrfIcIos movo from n rogIon of hIghor
conconfrnfIon fo n rogIon of Iowor conconfrnfIon unfII unIformIfy Is nffnInod. Iuf
fho dIffusIon rocoss Is sIowor fhnn dIffusIon In fruo soIufIon duo fo hIghor mnss
nnd Iowor sood of coIIoIdnI nrfIcIos. IffusIon Is usod fo sonrnfo coIIoIdnI nr-
fIcIos of dIfforonf sIzo.
(c) SeJinenIoIion. CoIIoIdnI nrfIcIos consfnnfIy oxhIbIf IrownInn mofIon nnd romnIn
susondod In soIufIon, fhoroby sfnbIIIzIng fho coIIoIdnI soIufIon. !nrgor coIIoIdnI
nrfIcIos soffIo sIowIy by fho offocf of grnvIfy nnd Is cnIIod sodImonfnfIon. Svodborg
Incronsod fho rnfo of sodImonfnfIon wIfh confrIfugnI sodImonfnfIon by omIoyIng
n hIgh-sood confIfugo cnIIod uIfrnconfrIfugo. In fhIs mnchIno sodImonfnfIon Is
offocfod undor onormous confrIfugnI forco of rofnfIon.
(it) OptIcuI pvopevtIes ov TynduII eIIect. Whon n bonm of IIghf Is nssod fhrough n
coIIoIdnI soIufIon, fho nfh of IIghf bocomos IIIumInnfod duo fo fho scnfforIng of IIghf by fho
coIIoIdnI nrfIcIos. ThIs honomonon Is cnIIod TyndnII offocf, whIch doos nof hnon for fruo
soIufIon. Thoso coIIoIdnI nrfIcIos cnn bo vIowod fhrough n mIcroscoo Incod nf rIghf nngIos fo
fho nfh of IIghf nnd Is cnIIod fho uIfrnmIcroscoo. Tho honomonon of TyndnII offocf cnn bo
oxInInod by fho scnfforIng of IIghf by fho coIIoIdnI nrfIcIos. Tho nrfIcIos nbsorb fho IncIdonf
IIghf onorgy, bocomos soIf-IumInous nnd scnffor fhIs nbsorbod IIghf. Tho InfonsIfy of fho scnfforod
IIghf doonds on fho dIfforonco bofwoon fho rofrncfIvo IndIcos of nrfIcIo nnd modIum.
TyndnII offocf wns fIrsf sfudIod by ZoIgmondy In l903 nnd fhIs offocf cnn bo nIIod for
vIowIng fho coIIoIdnI nrfIcIos qunnfIfnfIvoIy.
COLLOlDS 285

True solution
Path is
invisible
Colloidal
solution
Powerful
beam of light
Path is
visible
Microscope

Electrophoresis
+
Fig. 12.5 Tyndall effect exhibited by a colloidal solution. Fig. 12.6 Electrophoresis.
(t) IectvIcuI pvopevtIes
(o) 1lecIropIoreeie. !yohIIIc nnd IyohobIc coIIoId nrfIcIos nro oIfhor osIfIvoIy or
nognfIvoIy chnrgod. In n !-fubo, confnInIng n coIIoIdnI soIufIon, whon n ofonfInI
grndIonf Is nIIod fho coIIoIdnI nrfIcIos movo fownrds oosIfoIy chnrgod
oIocfrodo. Affor ronchIng fho oIocfrodo, fhoy Ioso fhoIr chnrgo nnd conguInfo fhoro.
Tho movomonf of fho coIIoIdnI nrfIcIos In nn oIocfrIc fIoId Is cnIIod oIocfrohorosIs.
Whon fho nognfIvoIy chnrgod nrfIcIos IIko CdS, As
2
S
3
mofnIIIc soIs, orgnnIc soIs
movo fownrds cnfhodo, fho honomonon Is cnIIod cnfnhorosIs. IosIfIvoIy chnrgod
nrfIcIos nro Io(OH)
3
, AI(OH)
3
, bnsIc dyos ofc. Tho sood of fho coIIoIdnI nrfIcIo
undor fho ofonfInI grndIonf of l voIf/cm Is cnIIod oIocfrohorofIc mobIIIfy.
(I) 1lecIro-oenoeie. Whon oIocfrIc curronf Is nssod
fhrough n coIIoIdnI soIufIon such fhnf fho dIsorsod
hnso Is rovonfod from movomonf, fho dIsorsIon
modIum bogIns fo movo In fho oIocfrIc fIoId. ThIs
honomonon Is cnIIod oIocfro-osmosIs (IIg. l2.?).
(c) 1eoelecIric PoinI. Tho coIIoIdnI soIs of rofoIn nro
oIfhor osIfIvoIy or nognfIvoIy chnrgod In ncIdIc or
nIknIIno soIufIon nnd honco whon oIocfroIysod In n
modIum, H of fho modIum wIII dIcfnfo fho
mIgrnfIon of fho coIIoIdnI nrfIcIo fo nny oIocfrodo.
Honco fho H of fho dIsorsIon modIum nf whIch
fho dIsorsod nrfIcIos nro noufrnI nnd honco fhoy do nof mIgrnfo whon subjocfod
fo nn oIocfrIc fIoId Is cnIIod IsoeIectvIc poInt. Tho IsooIocfrIc oInf of rofoIn
doonds on H nnd IonIc sfrongfh In fho modIum. IrofoIns nro Ionsf soIubIo In
IsooIocfrIc oInf nnd honco conguInfo nf IsooIocfrIc oInf.
CoaguIation of CoIIoids
CoIIoId nrfIcIos nro oIocfrIcnIIy chnrgod, so fhoy rooI onch ofhor nnd bocomo sfnbIo.
Whon fho chnrgo Is noufrnIIsod, fho nrfIcIos nronch onch ofhor fo form nggrognfos nnd
soffIo down. Tho rocIIfnfIon of coIIoIdnI soIufIon Is cnIIod 'conguInfIon` or fIoccuInfIon. ThIs
cnn bo nchIovod by
(i) AJJing oppoeiIel, cIorgeJ. Two oosIfoIy chnrgod coIIoIdnI soIufIons whon mIxod,
mufunI conguInfIon of fho fwo soIs fnkos Inco.
(ii) 1lecIropIoreeie. In oIocfrohorosIs fho oIocfrIcnIIy chnrgod coIIoIdnI nrfIcIos mIgrnfo
fownrds fho oosIfoIy chnrgod oIocfrodo nnd fInnIIy conguInfo.
Endosmosis
+
Diaphragm
Fig. 12.7
(iii) AJJing elecIrol,Iee. Iy nddIfIon of oosIfoIy chnrgod Ion i.e., by nddIng oIocfroIyfos
fho chnrgos of fho coIIoIdnI nrfIcIos nro noufrnIIsod nnd rocIIfnfod. ConguInfIng owor of nn
Ion Incronsos wIfh fho IncronsIng vnIoncy of fho conguInfIng Ion. Tho hIghor fho vnIoncy of fho
Ion, gronfor Is fho conguInfIng oworfhIs Is known ns SchuIzo-Hnrdy Inw. Thus, fho congu-
InfIng owor Incronsos In fho sorIos
n
+
< In
+2
< AI
3+
or CI

< SO
4
2
< IO
4
3
.
ConornIIy, fho conguInfIng owor of frIvnIonf Ion Is 500l000 fImos gronfor fhnn bIvnIonf Ion
whIch Is l00-500 fImos gronfor fhnn monovnIonf Ion.
Protection of CoIIoid
Tho sfnbIIIfy of coIIoIds cnn bo nchIovod by nny of fho foIIowIng:
(i) IectvIcuI cLuvge. AII fho coIIoIdnI nrfIcIos of n coIIoIdnI soIufIon bonr sImIInr
chnrgos nnd honco fhoy rooI onch ofhor. ThIs mufunI rouIsIon rovonfs fhom from conIosc-
Ing nnd conguInfIng.
(ii) SoIvutIon. CoIIoIdnI nrfIcIos nro surroundod by n Inyor of soIvonf moIocuIos whIch
rosIsfs fho dIsorsod hnsos from formIng Inrgo nggrognfos nnd conguInfo. Thus, fho soIvonf
Inyor forms n rofocfIvo onvoIoo. Thoso soIs nro vory sfnbIo.
(iii) PvotectIve ugents. IrofocfIvo ngonfs nro nddod fo somo coIIoIdnI sysfoms, whIch
gof ndsorbod on fho surfnco of fho coIIoIdnI nrfIcIos nnd by confIng fhom rovonfs conguInfIon.
(it) PvotectIve coIIoIds. !yohIIIc coIIoIds nro much moro sfnbIo fhnn fho IyohobIc
coIIoIdssInco fho formor nro oxfonsIvoIy soIvnfod. Whon n IyohIIIc coIIoId Is nddod fo n
IyohobIc coIIoId, fho Inffor bocomos moro sfnbIo ovon fo fho ncfIon of oIocfroIyfos. Tho rocoss
by whIch IyohIIIc coIIoId rofocfs fho IyohobIc soI Is cnIIod rofocfIon nnd fho IyohIIIc coIIoId
Is cnIIod fho pvotectIve coIIoId. Thus, If n IIffIo nIbumIn (IyohIIIc coIIoId) Is nddod fo n goId
soI (IyohobIc soI), fho formor ncfs ns rofocfIvo coIIoId nnd rovonfs conguInfIon of fho Inffor
ovon ngnInsf nddIfIon of hIgh conconfrnfIon of nn oIocfroIyfo, IIko nCI. ThIs rofocfIon Is duo
fo fho formnfIon of n rofocfIvo fhIn Inyor surroundIng fho nrfIcIos of fho IyohobIc coIIoId,
fhrough whIch fho oosIfoIy chnrgod Ion of fho oIocfroIyfo cnnnof onofrnfo fo noufrnIIzo fho
chnrgo for conguInfIon. ZsIgmondy Infroducod fho form 'goId numbor` fo monsuro fho rofoc-
fIvo owor of IyohIIIc coIIoIds. If Is dofInod ns fho mInImum woIghf In mg of n rofocfIvo
coIIoId, whIch whon nddod fo ono mI of sfnndnrd goId soI (confnInIng 0.0053 fo 0.0058 goId)
confnInIng nIso l mI of l0 nCI soIufIon fo jusf rovonf Ifs conguInfIon. ThIs Is IndIcnfod by
fho chnngo of coIour from rod fo bIuo. Tho smnIIor fho goId numbor fho gronfor Is fho rofoc-
fIvo owor of IyohIIIc coIIoId.
TabIe 12.3 Gold numbers
ProIecIite colloiJ ColJ nunIer
CoInfIn 0.005 fo 0.0l5
CnsoIn 0.0l fo 0.02
AIbumIn 0.l fo 0.2
Cum 0.l fo 0.2
Sfnrch l0 fo l5
SodIum oIonfo 0.40
HnomogIobIn 0.003 fo 0.0?
COLLOlDS 287
muIsIon und GeI
ImuIsIons nro coIIoIdnI sysfoms In whIch bofh dIsorsod hnso nnd dIsorsIon modIum
nro IIquIds (ImmIscIbIo). Tho fnmIIInr oxnmIos nromIIk, whIch consIsfs of IIquId fnf dIsorsod
In wnfor (oII In wnfor fyo); buffor, whIch consIsfs of wnfor dIsorsod In IIquId fnf (wnfor In oII
fyo).
ImuIsIons nro ronrod moroIy by shnkIng ono IIquId wIfh fho ofhor, nnd honco fhoy
nro nof sfnbIo nnd onsIIy sonrnfo Info fwo ImmIscIbIo Inyors. ImuIsIons nro sfnbIIIzod by
nddIng n fhIrd subsfnnco (omuIsIfIor) ns sfnbIIIzor. ThIs subsfnnco forms n fhIn Inyor nround
fho dIsorsod hnso fhoroby rovonfIng If from conIoscIng nnd conguInfIng. Tho omuIsIfIor
nIso docronsos fho surfnco fonsIon of fho fwo IIquIds.
AIbumIn, cnsoIn, gum, ngnr-ngnr, sons nnd doforgonfs nro fho common omuIsIfIors.
ImuIsIfIors nro soIocfod nccordIng fo fho fyo of omuIsIon, e.g., sons of nIknII mofnIs, goInfIn
ofc. nro moro soIubIo In nquoous hnso, honco fhoy nro usod ns sfnbIIIzors for oII-In-wnfor-fyo
of omuIsIon whorons honvy mofnI sons of nImIfIc nnd oIoIc ncId nro soIubIo In fnf nnd honco
usod In wnfor-In-oII-fyo omuIsIon.
ImuIsIons hnvo roorfIos sImIInr fo fhoso of IyohobIc coIIoIds IIko TyndnII offocf,
IrownInn movomonf ofc.
Cel. Mnny IyohIIIc soI nnd fow IyohobIc soI whon conguInfod undor corfnIn condIfIons
form somI-soIId mnss. Such n roducf Is cnIIod goI nnd fho rocoss Is cnIIod goInfIon, e.g., jnm,
joIIy, chooso, curd ofc. ThIs Is formod by onfrnmonf of fho dIsorsIon modIum InsIdo fho Iooso
nofwork of fho dIsorsod nrfIcIo. CoIs hnvo hIgh vIscosIfy nnd swoII If Incod In fho dIsorsIon
modIum nnd somo shrInk In voIumo.
CoI formnfIon Is ufIIIzod for ronrnfIon of shoo oIIsh, chon sons, curds, joIIIos, soIId
fuoI of nIcohoI wIfh cnIcIum oxnInfo.
RevevsIbIe coIIoId. Whon n coIIoId cnn bo rovorsIbIy convorfod from n soI fo goI nnd
vIco vorsn, If Is cnIIod n rovorsIbIo coIIoId, e.g., soIufIon of goInfIn cnn bo roconvorfod Info soI by
honfIng. Ofhor coIIoIds whIch cnnnof bo rovorsIbIy frnnsformod nro cnIIod IrrovorsIbIo coIIoId,
e.g., normnI Au coIIoId.
(t) Zetu potentIuI. In IyohobIc coIIoIds, nrfIcIos nro of sImIInr chnrgo, whIch do nof
nIIow fho nrfIcIos fo como cIosor nnd conIosco nnd honco brIng sfnbIIIfy fo fho sysfom.
Tho chnrgo Is omboddod In fho coIIoIdnI nrfIcIo nnd nn oquIvnIonf nmounf of oosIfo
chnrgo romnIns oufsIdo nnd fhoso fwo Inyors form n doubIe Iuyev. A nrf of fhIs oosIfo
chnrgo Is fIxod on fho nrfIcIo nnd nnofhor nrf Is mobIIo nnd dIsfrIbufod fhroughouf fho
modIum.
+
+
+
+
+
+
+
+
+
Liquid
S
u
r
f
a
c
e
o
f
s
o
l
i
d
Fixed Movable
Helmholtz double layer
+
+
+
+
+
+
Liquid
S
u
r
f
a
c
e
o
f
s
o
l
i
d
Fixed Movable
Diffuse double layer
+
+
+
+
+
+
+
+
+
+
zeta pot.
Fig. 12.8 Zeta potential.
Honco, fhoro Is n ofonfInI dIfforonco bofwoon fho nrfIcIo nnd fho modIum. ThIs ofonfInI
Is cnIIod fho zofn ofonfInI whIch Is rosonsIbIo for fho sfnbIIIfy of fho coIIoId.
AppIication of CoIIoids
(i) PuvIIIcutIon oI wutev. Imuro wnfor Is fronfod wIfh nIum. AI
3+
Ions of nIum ro-
cIIfnfo nognfIvoIy chnrgod cIny nrfIcIos, bncforIn, coIIoIdnI nrfIcIos nnd fho Imu-
rIfIos.
(ii) PuvIIIcutIon oI poIIuted uIv. Susondod nrfIcIos, smoko ofc., oIIufod nIr. Smoko
Is nognfIvoIy chnrgod coIIoIdnI susonsIon consIsfIng of cnrbon nrfIcIos. AIr Is nssod
fhrough CoffroII rocIIfnfor whoro fho chnrgo Is noufrnIIsod nnd cnrbon soffIos down
whIIo fho hof nIr nssos ouf fhrough chImnoy.
(iii) RemovuI oI dIvt Ivom sewuge. Sowngo confnIns chnrgod dIrf nrfIcIos, whIch Is
nssod fhrough fnnks fIffod wIfh oosIfoIy chnrgod oIocfrodos. Iy noufrnIIzIng fho
chnrgo, dIrf Is conguInfod.
(it) IeutLev tunnIng. Tho rnw mnforInI skIn Is osIfIvoIy chnrgod coIIoIdnI sysfom,
whIch Is fronfod wIfh nognfIvoIy chnrgod coIIoIdnI soIufIon of fnnnIn, whoroby mu-
funI conguInfIon of oosIfoIy chnrgod coIIoIds fnkos Inco.
(t) Iuundvy. Sons In wnfor form coIIoIdnI soIufIon, whIch ndsorb gronsy mnforInIs,
dIrf by omuIsIon formnfIon nnd romovo dIrf from cIofhos.
(ti) MedIcIne. CoIIoIdnI sysfom of modIcInos nro boffor nssImIInfod. IIood conguInfIon
Is offocfod wIfh nIum or IoCI
3
.
(tii) CosmetIcs. Ifforonf fyos of coIIoIdnI sysfoms nnd omuIsIon nro usod In cosmofIcs.
(tiii) AnuIysIs. obIo mofnIs nro dofocfod by formnfIon of fhoIr coIIoIdnI soIufIons nnd
obsorvIng fhoIr coIours.
(ix) ArfIfIcInI rnIn nro mndo by fhrowIng chnrgod snnd on cIouds.
(x) eItu IovmutIon. ognfIvoIy chnrgod snnd nrfIcIos of fho rIvor wnfor nnd n
+
, K
+
,
Cn
2+
rosonf In fho son wnfor nro rosonsIbIo for fho doosIfIon of coIIoIdnI nrfIcIos
whoro rIvor moofs son.
HIgLIIgLts:
ImonsIon of coIIoIdnI nrfIcIos rnngo from l0
4
fo l0
?
cm.
IurIfIcnfIon of coIIoIdnI soIufIons cnn bo dono by dInIysIs, uIfrnfIIfrnfIon.
BvownIun motIon. Tho rnndom zIgzng mofIon of fho coIIoIdnI nrfIcIos In fho
susondIng modIum Is cnIIod IrownInn mofIon. Tho mofIon Is rnId for smnIIor
nrfIcIos nnd nIso for n Ioss vIscous modIum.
TynduII eIIect. Whon n bonm of IIghf Is nssod fhrough n coIIoIdnI soIufIon, fho
nfh of IIghf bocomos IIIumInnfod duo fo fho scnfforIng of IIghf by fho coIIoIdnI
nrfIcIos. ThIs honomonon Is cnIIod TyndnII offocf.
ScLuIze-Huvdy Iuw. Tho conguInfIng owor of nn oIocfroIyfo doonds
rodomInnnfIy on fho vnIoncy of fho Ion bonrIng n chnrgo oosIfo fo fhnf of fho
coIIoIdnI nrfIcIos, nnd hIghor fho vnIoncy of fho ncfIvo Ion, fho gronfor Is Ifs
rocIIfnfIng ncfIon. ThIs Is cnIIod SchuIzo-Hnrdy Inw.
GoId numbev. If Is fho mInImum woIghf In mg of n rofocfIvo coIIoId, whIch whon
nddod fo l mI of sfnndnrd goId soI (confnInIng 0.0053 fo 0.0058 goId) nIso confnInIng
l mI of n l0 nCI soIufIon fo jusf rovonf Ifs conguInfIon.
BuncvoIt vuIe. Tho hnso In whIch fho omuIsIfIor Is moro soIubIo bocomos fho
oufor hnso.
COLLOlDS 289
Q. 1. escvIbe u coIIoIduI system. WLut uve tLe sIzes oI puvtIcIes IovmIng u
soIutIon und u coIIoIduI soIutIon?
Ans. A coIIoIdnI sysfom Is n fwo-hnso hoforogonoous sysfom In whIch ono hnso Is
dIsorsod In n fIno sfnfo of subdIvIsIon (from l fo 50 m) In nnofhor modIum formod fho
confInuous or dIsorsIon modIum.
Tho soIufo nrfIcIos In fruo soIufIon nro of dImonsIon l fo l0 .
InrfIcIos of coIIoIdnI sysfom hnvo dImonsIon In fho rnngo from l0 fo l000 .
Q. 2. WLut Is tLe dIIIevence between soI und emuIsIon?
Ans. SoI Is n coIIoIdnI soIufIon of n soIId dIsorsod In n IIquId modIum whorons omuIsIon
Is n IIquId dIsorsod In nnofhor ImmIscIbIo IIquId In fho form of droIofs.
Q. 3. WLy uve "BvownIun movement" und "TynduII eIIect" sLown by coIIoIduI
soIutIons but not tLe tvue soIutIon?
Ans. !nrgo nrfIcIos of fho coIIoId soIufIon do nof soffIo down nnd scnffor fho IIghf
fnIIIng on fho soIufIon, whorons In fruo soIufIon fhoro nro no such nrfIcIos.
Q. 4. WvIte sLovt notes on tLe IoIIowIng:
(o) BvownIun movement
(I) TynduII IIect
(c) IuIysIs
(J) GoId numbev.
Ans. (o) Soo ngo 284
(I) Soo ngo 284
(c) Soo ngo 282
(J) Soo ngo 286.
Q. 5. xpIuIn tLe uctIon oI geIutIn us pvotectIve coIIoId.
Ans. CoInfIn Is n IyohIIIc coIIoId nnd whon If Is nddod fo IyohobIc soI, If forms n vory
fhIn rofocfIvo shoII, surroundIng onch nrfIcIo of fho IyohobIc coIIoId nnd rofocfs fho
onofrnfIon of oosIfoIy chnrgod Ions, whIch noufrnIIzo fho chnrgo nnd rocIIfnfo fho IyohobIc
coIIoId.
Q. 6. WvIte notes on
(i) IectvopLovesIs
(ii) PeptIzutIon
(iii) Zetu potentIuI
(it) PvotectIon oI LydvopLobIc coIIoIds.
Ans. (i) Soo ngo 285
(ii) Soo ngo 282
(iii) Soo ngo 28?
(it) Soo ngo 286.
Q. ?. WLIcL oI tLe IoIIowIng eIectvoIytes wIII be most eIIIcIent Iov tLe
pvecIpItutIon oI As
2
S
3
soI und wLy?
(i) KCI
(ii) CuCI
2
(iii) AICI
3
.
Ans. As
2
S
3
soI Is n nognfIvoIy-chnrgod soI nnd If cnn bo rocIIfnfod by osIfIvoIy chnrgod
Ions of fho nddod oIocfroIyfo. Irom fho nbovo fhroo oIocfroIyfos, fho osIfIvo Ions obfnInod nro
K
+
, Cn
2+
, nnd AI
3+
. SInco AI
3+
ossoss hIghosf osIfIvo vnIoncy, AICI
3
wIII bo fho mosf offIcIonf
oIocfroIyfo fo f As
2
S
3
soI, ns or SchuIzo-Hnrdy ruIo.
Q. B. xpIuIn Low deItus uve Iovmed wLeve vIvevs meet tLe seu.
Ans. Soo ngo 288.
Q. 9. WLy Is uIum used to vemove ImpuvItIes Ivom wutev?
Ans. Soo ngo 288.
Q. 10. Smoke comIng out Ivom tLe cLImneys oI dIIIevent IuctovIes Is Ied to
cLuvged metuIIIc pIuteexpIuIn.
Ans. Soo ngo 288.
Q. 11. MentIon some Impovtunt uppIIcutIons oI coIIoId cLemIstvy to IndustvIes.
Ans. Soo ngo 288.
Q. 12. IIIeventIute between IyopLIIIc und IyopLobIc soIutIons.
Ans. Soo ngo 2?9.
Q. 13. Stute ScLuIze-Huvdy Iuw.
Ans. Soo ngo 286.
Q. 14. WLut do you meun by IsoeIectvIc poInt?
Ans. Tho H of fho modIum nf whIch fho dIsorsod coIIoIdnI nrfIcIos nro noufrnI nnd
honco do nof mIgrnfo whon nn oIocfrIc fIoId Is nIIod fo fho coIIoIdnI soIufIon.
Q. 15. WLut Luppens wLen u soI Is IIIteved tLvougL u IIItev pupev?
Ans. If n soI Is fIIforod fhrough nn ordInnry fIIfor nor, fho coIIoIdnI nrfIcIos wIII nss
fhrough fho oros of fho fIIfor nor sInco fho oro-sIzo of ordInnry fIIfor nor Is Inrgor fhnn
fho sIzo of fho coIIoIdnI nrfIcIos.
EXERCISES
1. Whnf nro IyohIIIc nnd IyohobIc soIs
2. IxInIn fho foIIowIng:
(o) TyndnII offocf. (I) IrownInn movomonf.
(c) CoId numbor (J) IrofocfIvo coIIoIds.
3. WrIfo n nofo on nIIcnfIon of coIIoId chomIsfry In (i) oIIufIon confroI nnd (ii) IndusfrIos.
4. IxInIn: IIocfrohorosIs nnd IIocfro-osmosIs.
5. Whnf nro fho dIfforonf wnys of rofocfIng n coIIoIdnI soIufIon from conguInfIon
6. Sfnfo SchuIzo-Hnrdy ruIo nnd oxInIn wIfh nn oxnmIo.
OBJECTIVE QUESTIONS
1. Tho sIzos of fho coIIoIdnI nrfIcIos fnII In fho rnngo
(o) l0
2
fo l0
4
cm (I) l0
4
fo l0
?
cm
(c) l0
?
fo l0
9
cm.
2. !Ighf nssIng fhrough n coIIoIdnI soIufIon Is
(o) !ofIocfod (I) Absorbod comIofoIy
(c) Scnfforod.
COLLOlDS 291
3. WhIch ono Is fho mosf offIcIonf In conguInfIng n forrIc hydroxIdo soI
(o) K
4
|Io(C)
6
] (I) K
3
|Io (C)
6
]
(c) KCI.
4. WhIch rocoss Is usod for fho urIfIcnfIon of n coIIoIdnI soIufIon
(o) InIysIs (I) IofIznfIon
(c) IssoIufIon.
5. Tho rnndom zIg-zng movomonf of coIIoIdnI nrfIcIos In n dIsorsIon modIum Is cnIIod
(o) TyndnII offocf (I) IrownInn movomonf
(c) InIysIs.
6. WhIch Is n rofocfIvo coIIoId
(o) K
4
|Io(C)
6
] (I) nCI
(c) CoInfIn.
?. HnomogIobIn In bIood Is
(o) HydrohobIc coIIoId (I) HydrohIIIc coIIoId
(c) CoI.
B. CoIIoIdnI nrfIcIos nro oIocfrIcnIIy chnrgod. ThIs cnn bo domonsfrnfod by
(o) IofIznfIon (I) IIocfrohorosIs
(c) InIysIs.
9. Smoko Is n coIIoIdnI soI of
(o) SoIId dIsorsod In gns (I) Cns dIsorsod In soIId
(c) !IquId dIsorsod In gns.
10. MIIk Is nn omuIsIon of
(o) CnsoIn dIsorsod In wnfor. (I) !ncfoso dIsorsod In wnfor.
(c) Inf gIobuIos dIsorsod In wnfor.
11. Inncroff ruIo sfnfos fhnf
(o) CoIIoIdnI nrfIcIos nro nIwnys chnrgod
(I) !Ighf fnIIIng In fho modIum Is scnfforod by fho coIIoIdnI nrfIcIos.
(c) Tho hnso In whIch fho omuIsIfIor Is moro soIubIo Is fho oufor hnso.
12. Sons nnd doforgonfs ncf ns
(o) SfnbIIIzors (I) ImuIsIfIors
(c) ConguInfIng ngonfs.
!
Transition MetaI Chemistry
292
TRANSITION METALS
TrnnsIfIon mofnIs nro J-bIock oIomonfs hnvIng nrfInIIy fIIIod J-onorgy IovoIs In ono or moro
oxIdnfIon sfnfos. In fho J-bIock sorIos from scnndIum (le
2
2e
2
2p
6
3e
2
3p
6
3J
l
4e
2
) fo zInc (le
2
2e
2
2p
6
3e
2
3p
6
3J
l0
4e
2
), fho dofInIfIon hoIds good for nII fho oIomonf oxcofIng scnndIum nnd
zInc. ScnndIum Is oxcIudod bocnuso If onIy roducos comounds In fho +3 sfnfo nnd If Iosos nII
Ifs fhroo oufor oIocfrons whon If forms Sc
+3
cnfIon. ZInc Is oxcIudod bocnuso nII Ifs comounds
nro In fho +2 sfnfo. Zn on IosIng fwo oIocfrons roducos Zn
+2
cnfIon wIfh nn oIocfron confIgurnfIon
(le
2
2e
2
2p
6
3e
2
3p
6
3J
l0
) In whIch nII fho J-onorgy IovoIs nro fuII.
TrnnsIfIon mofnIs hnvo n numbor of common fonfuros. Thoy nro sfnfod boIow:
AII nro mofnIs wIfh usofuI mochnnIcnI roorfIos wIfh hIgh moIfIng oInfs.
AII form comounds In moro fhnn ono oxIdnfIon sfnfos.
AII form coIourod comounds.
AII form n vnrIofy of comIox Ions.
AII ncf ns cnfnIysfs, ns mofnIs or ns comounds.
Mnny frnnsIfIon mofnI snIfs nro nrnmngnofIc bocnuso of fho rosonco of unnIrod
oIocfrons In fho nrfInIIy-fIIIod Innor J-onorgy IovoIs.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3
+4 +4 +4
+5
+6
+7
+1
O
x
i
d
a
t
i
o
n
s
t
a
t
e
s
+2
Fig. 13.1 Main oxidation states of the elements Sc to Zn (first transition series).
If Is fo bo nofod fhnf Sc nnd Zn form Ions In ono oxIdnfIon sfnfo i.e., +3 nnd +2,
rosocfIvoIy. Tho chomIsfry of fIfnnIum (TI), vnnndIum (V), chromIum (Cr), mnngnnoso (Mn),
cobnIf (Co), Iron (Io) nnd coor (Cu) rovIdo mnny oxnmIos of fho nbovo-monfIonod fonfuros.
TRANSlTlON METAL CHEMlSTRY 293
DoubIe SaIts and CompIex SaIts
A doubIe suIt Is formod gonornIIy whon moInr roorfIons of n monovnIonf cnfIon
suIhnfo soIufIon In wnfor Is mIxod wIfh frIvnIonf cnfIon suIhnfo soIufIon In wnfor nnd
ovnornfod fo romovo oxcoss wnfor, nnd fho snIf crysfnIIIsos ns X
2
SO
4
Y
2
(SO
4
)
3
.24H
2
O whIch Is
fho gonornI formuIn of n common nIum, whoro 'X` Is monovnIonf cnfIon, IIko H
4
+
, K
+
, n
+
, nnd
'Y` Is frIvnIonf cnfIon ns AI
+3
, Cr
+3
, Io
+3
ofc. Anofhor Imorfnnf doubIo snIf Is Mohr`s snIf,
(H
4
)
2
SO
4
.IoSO
4
.6H
2
O. A doubIo snIf oxIsfs ns n dIsfIncf onfIfy onIy In fho soIId crysfnIIIno
sfnfo, If Iosos Ifs onfIfy In soIufIon. Tho doubIo snIf Is chnrncforIsod by comIofo dIssocInfIon In
soIufIon nnd gIvos fho roncfIons of nII fho Ions formod by fho snIfs In soIufIons, tic.
K
2
SO
4
.AI
2
(SO
4
)
3
.24H
2
O In soIufIon gIvos fho roncfIons of K
+
, AI
+3
nnd SO
4
2
Ions.
A compIex suIt does not gIve uII tLe Ions oI Its constItuents In soIutIon. A comIox
snIf K
4
|Io(C)
6
] Is ronrod by nddIng KC soIufIon of IoSO
4
soIufIon nnd boIIIng.
IoSO
4
+ 2KC = Io(C)
2
+ K
2
SO
4
Io(C)
2
+ 4KC = K
4
|Io(C)
6
]
Tho soIufIon of K
4
|Io(C)
6
] doos nof rosond fo fho fosfs for Io
+2
or C
Ions, buf rosonds

fo n fosf for n now Ion |Io(C)
6
]
4
(forrocynnIdo Ion). TLIs Ion vemuIns Intuct ovon In soIufIon
K
4
|Io(C)
6
] 4K
+
+ |Io(C)
6
]
4
nnd gIvos Ifs dIsfIncfIvo roncfIons. So, If cnn bo snId, fho comIoxIons, IIko forrocynnIdo Ion, nro
quIfo sfnbIo In fho soIId sfnfo ns woII ns In soIufIon. A comIox snIf Is dIfforonf from n doubIo
snIf In rosocf of Ifs dIsfIncfIvo chnrncfor ovon In soIufIon.
xumpIes oI compIex suIts
|Ag(H
3
)
2
]CI |Ag(H
3
)
2
]
++
+ CI
|Cu(H
3
)
4
]SO
4
|Cu(H
3
)
4
]
++
+ SO
4
K|Ag(C)
2
] K
+
+ |Ag(C)
2
]
InstubIIIty Constunts oI CompIex SuIts

Tho dIssocInfIon of n comIox Ion, IIko IonIsnfIon of wonk oIocfroIyfo, foIIows fho Inw of
mnss ncfIon. Tho dIssocInfIon consfnnf Is cnIIod InsfnbIIIfy consfnnf (K
Ins
) nnd Is n monsuro of
sfnbIIIfy of n comIox, fho Iowor fho vnIuo of K
Ins
, fho hIghor Is fho sfnbIIIfy of fho comIox nnd
vIco vorsn.
K
Ins
=
|M ] |! ]
|M!]
+
Conplex ione 1neIoIiliI, coneIonI
|Ag(H
3
)
2
]
+
Ag
+
+ 2H
3
6.8 l0
8
|Ag(C)
2
]
Ag
+
+ 2C
l.0 l0
2l
|Cu(C)
4
]
3
Cu
+
+ 4C
5.0 l0
28
|Cd(C)
4
]
2

Cd
+2
+ 4C
l.4 l0
l?
Werner's Theory for Formation of CompIex Compounds
Wornor uf forwnrd n fhoory for fho formnfIon of comIox comounds. Tho fhoory Is known
nIso ns co-ovdInutIon tLeovy. Tho osfuInfos of hIs fhoory mny bo summnrIsod ns foIIows:
MofnIs ossoss fwo fyos of vnIoncIos: (i) PvImuvy or principol or IonIsnbIo vnIoncIos
(ii) SeconJor, or subsIdIuvy or non-IonIsnbIo vnIoncIos.
Ivory mofnI nfom hns n fIxod numbor of socondnry vnIoncIos or co-ordInnfIon numbor
(C..). Tho mnxImum numbor of Ions or moIocuIos fhoroby fho confrnI nfoms couId
form co-ordInnfo bonds Is known ns co-ovdInutIon numbev (C..).
Ligands
TLe Ions ov moIecuIes tLus uttucLed to tLe centvuI metuI utom by co-ovdInute
bonds uve cuIIed IIgunds. Tho IIgnnds mny bo unIdonfnfo, bIdonfnfo, frIdonfnfo ofc. doondIng
uon fho numbor of co-ordInnfIon confros In fho IIgnnd.
Types oI IIgunds
IniJenIoIe ligonJeI
, CI
, H
2
O
BiJenIoIe ligonJeH
2
CH
2
CH
2
H
2
(on sfnnds for ofhyIono dInmIno)
Cu (II) hns C.. = 4 ; Co (III) nnd If (IV) hns C.. = 6.
IrImnry vnIoncIos of fho mofnI nro snfIsfIod by nognfIvo Ions, buf socondnry vnIoncIos
mny bo snfIsfIod by nognfIvo grous (C

, CI
, ofc.), noufrnI moIocuIos (H

2
O, H
3
ofc.)
or ovon somofImos somo osIfIvo grous. In evevy compIex IovmutIon tLe co-
ovdInutIon numbev (C.N.) oI tLe centvuI metuI utom must be IuIIIIIed.
Tho socondnry vnIoncIos nro dIrocfod In snco nbouf fho confrnI mofnI Ion. Ior mofnIs
wIfh co-ordInnfIon numbor (C.. = 6), fho sIx vnIoncIos nro dIrocfod fo fho nIcos of n
roguInr ocfnhodron. AgnIn, for mofnIs, wIfh C.. = 4, fho four such vnIoncIos nro oIfhor
dIrocfod fo fho nIcos of n roguInr fofrnhodron or n squnro (Innnr).
ThIs gIvos rIso fo vnrIous fyos of IsomorIsm. Wornor couId IsoInfo ovon opIicol ieonere.
TLe muIn dvuwbuck Iov Wevnev's tLeovy Is: tLeve Is no tLeovetIcuI veuson to
Luve u centvuI utom oI tLe compIex Ion to possess two kInds oI vuIencIes.
CheIate Compounds
ChoInfo comounds nro comIox comounds confnInIng n rIng sfrucfuro In whIch n IIgnnd
moIocuIo or Ion forms moro fhnn ono dnfIvo covnIonf bonds (co-ordInnfo bonds) wIfh fho confrnI
mofnI Ion. ChoInfos nro formod by bIdonfnfo nnd oIydonfnfo IIgnnds. ChoInfIon Incronsos fho
sfnbIIIfy of co-ordInnfIon comIox i.e., choInfo comIoxos nro gonornIIy moro sfnbIo fhnn
comIoxos formod by monodonfnfo IIgnnds. IoworfuI choInfIng ngonfs frn mofnI Ions nnd
offocfIvoIy frn fhom In soIufIon, ns for oxnmIo on (ofhyIono dInmIno), odfn (ofhyIono dInmIno
fofrn-ncofIc ncId). ThIs fyo of IIgnnds nro known ns comIoxonos.
edta or EDTA
Tho IIgnnd moIocuIos whIch occuy fwo or moro co-ordInnfIon confros nro usunIIy orgnnIc
moIocuIos.
Chelate complex with en
++
N
N O
O
M
+2
CO
CH
2
CH
2
CO
CH
2
CH
2
CO
O
COCH
2
CH
2
O
Fig. 13.2 Chelate complex of edta with a bivalent metal.
If Is fo bo nofod In choInfo comIoxos fhnf fho rIngs formod nro fIvo or sIx momborod.
Inner MetaIIic CompIexes
Mnny woII-known orgnnIc IIgnnds, whIch ncf ns choInfIng ngonfs, ossoss n noufrnI donor
nfom ns woII ns nn ncIdIc grou. Thoy form vory sfnbIo cycIIc comIoxos, whIch hnvo vory Iow
soIubIIIfy In wnfor buf hIgh soIubIIIfy In orgnnIc soIvonfs. ConornIIy, fho ncId grou of fho
IIgnnd snfIsfIos fho rImnry vnIoncy of fho confrnI mofnI Ion (whIch fhoroforo doos nof nonr
ns nn Ion i.e., nof chnrgo on fho comIox moIocuIo Is zoro). Such non-oIocfroIyfIc cycIIc comIoxos
nro known ns Innev metuIIIc compIexes or sImIy Innev compIexes.
NomencIature of Coordination Compounds (IUPAC)
ComIox comounds nro of fho foIIowIng fyos:
(i) CnfIonIc, (ii) nnIonIc, (iii) non-IonIc nnd (it) n combInnfIon of cnfIonIc nnd nnIonIc
comIoxos.
(i) In nnmIng cnfIonIc comIoxos IIko |Co(H
3
)
5
CI]CI
2
, fho nnmo of fho cnfIon Is consId-
orod fIrsf nnd fhon fho nnmo of fho nnIon.
(ii) In nnmIng fho nnIonIc comIoxos IIko K
2
|IfCI
6
] fho K
+
Is wrIffon fIrsf fhon fho nnmo
of fho comIox nnIon.
(iii) If fho comIox comound Is non-IonIc (noufrnI) fho nnmo of fho comIox comound
IIko |If (H
3
)
4
CI
2
]
0
Is wrIffon ns ono word.
(it) In |If
IV
(H
3
)
4
CI
2
]
2+
|If
II
(CI)
4
]
2
, fho nnmo of fho comIox cnfIon Is wrIffon fIrsf fhon
fho comIox nnIon Is nnmod.
NumIng oI tLe IIgunds
eutrul ligunJo
(C
2
H
5
)
3
TrIofhyInmIno CO CnrbonyI
H
2
-H
2
HydrnzIno CS ThIocnrbonyI
CH
3
H
2
MofhyInmIno H
2
O Aquo or nqun
O IfrosyI S ThIonIfrosyI
(CH
3
)
2
H ImofhyInmIno H
3
AmIno
Anion ligunJo
I
IIuoro CH
3
COO
Acofnfo
Ir
Iromo H
2
ImIdo
CI
ChIoro OH
Hydroxo or hydroxyI
I
Iodo S
2
ThIo
H
2
AmIdo C
Cynno
C
Iso-Cynno O
2
Ifro
OO
IfrIfo SC
ThIocynnnfo
S
2
O
3
2
ThIosuIhnfo O
3
Ifrnfo
AmbiJent ligunJo
AmbIdonfnfo or nmbIdonf IIgnnds nro fhoso whIch hnvo fwo or moro dIfforonf donor
nfoms In fhoIr sfrucfuros. Thoso IIgnnds cnn co-ordInnfo fo fho mofnI nfom fhrough nny of fho
fhoIr donor nfoms.
1xonple.
(i) O
2

Ion OO
( )
nnmod ns Ifro-OorIfrIfo whon donor nfom Is 'O`
O
2
nnmod ns Ifro-orIfrnfo whon donor nfom Is '`
(ii) SC
Ion ThIocynnnfo-S (SC
)
ThIocynnnfo- (CS
)
Indication of the Number of Iigands
If n comIox confnIns fwo or moro sImIo IIgnnds IIko CI
, Ir
ofc. fhoIr numbor Is

IndIcnfod by dI- for fwo; frI- for fhroo; fofrn- for four boforo fho nnmos of fho IIgnnds.
If n comIox confnIns fwo or moro comIox IIgnnds or orgnnIc moIocuIos nnd whIch
nIrondy hnvo dI-, frI- In fhoIr nnmos fhoIr numbor Is IndIcnfod by uffIng fho rofIxos
bIs- for fwo; frIs- for fhroo; fofrnkIs- for four. Tho nnmo of fho IIgnnds or orgnnIc moIocuIo
Is wrIffon In fho brnckof. IxnmIos of comIox IIgnnds nroIfhyIono dInmIno (on) ofc.
Order of Naming the Ligands
If fho co-ordInnfIon shoro of n gIvon comIox comound confnIns vnrIous fyos of IIgnnds,
fhoso IIgnnds nro nnmod nIhnbofIcnIIy.
Ior oxnmIo: |Co(H
3
)
4
CI(O
2
)]
+
Ion Is nnmod ns fofrn-nmIno chIoro nIfro cobnIf (III) Ion.
Ior nnIonIc comIoxos fho nnmo of confrnI mofnI nfom onds In 'oIe` nnd fho oxIdnfIon
sfnfo of fho mofnI Is wrIffon In !omnn numornIs (0, I, II).
Ior oxnmIo:
Cr Chromnfo Co CobnIfnfo
Cu Curonfo AI AIumInnfo
If IInfInnfo I IckInfo
ExampIes of Cationic CompIexes
|Ag(H
3
)
2
]CI InmIno sIIvor (I) chIorIdo.
|Cr(H
2
O)
4
CI
2
]
+
TofrnnquodIchIoro chromIum (III) cnfIon.
|Co(H
3
)
5
H
2
O]CI
3
IonfnmIno mono nquo cobnIf (III) chIorIdo
|Co (H
3
)
4
CI
2
]CI TofrnnmIno dIchIoro cobnIf (III) chIorIdo
ExampIes of Anionic CompIexes
K
4
|Io(C)
6
] IofnssIum hoxncynno forrnfo (II).
|Co(CI)
6
]
3
HoxnchIoro cobnIfnfo (III) Ion.
|If(H
3
)
2
CI
4
] InmIno fofrnchIoro InfInum (IV).
Bridging Ligands
A brIdgIng IIgnnd, whIch IInks fwo mofnI nfoms, Is donofod by fho rofIx - boforo Ifs
nnmo. Ior oxnmIo
l. |(H
3
)
5
CoH
2
Co(H
3
)
4
(H
2
O)]CI
5
Is nnmod ns:
IonfnmmIno cobnIf (III)--nmIdo-fofrnmmIno nquo cobnIf (III) chIorIdo.
2. (en) .Co
2
Co.(en)
2
NH
2
OH
(SO )
4 2
Is nnmod ns:
IIs-(ofhyIono dInmIno) cobnIf (III)--nmIdo--hydroxo-bIs (ofhyIono dInmIno) cobnIf (III)
suIhnfo.
3.
OH
Fe Fe
OH
3+ 3+
(H O)
2 4
(H O)
2 4
(SO )
4 2
Is cnIIod:
Tofrn-nquo Iron (III)--dIhydroxy fofrnquo Iron (III) suIhnfo.
Isomerism in MetaI CompIexes
IsomorIsm In comIox moIocuIos nrIsos duo fo dIfforonco In nffnchmonf of fho grous or
Ions fo fho confrnI mofnI Iron or duo fo fhoIr dIfforonf snfInI nrrnngomonfs nbouf fho confrnI
mofnI Ion. ConornIIy, fwo fyos of IsomorIsms nro oxhIbIfod by mofnI comIoxos.
(i) StvuctuvuI IsomevIsm. ThIs Is nIso cInssIfIod undor sIx honds, nnmoIy (o) IonIsnfIon
IsomorIsm, (I) IInkngo IsomorIsm, (c) co-ordInnfIon IsomorIsm, (J) IIgnnd IsomorIsm,
(e) hydrnfo IsomorIsm.
(ii) SteveoIsomevIsm ov spuce IsomevIsm. Whon fwo comounds confnInIng fho snmo
IIgnnds nro co-ordInnfod fo fho snmo confrnI mofnI Ion, buf dIffor In fho nrrnngomonf
of IIgnnds In snco, fhoy nro snId fo bo sforooIsomors of onch ofhor nnd fho IsomorIsm
of fhIs fyo Is cnIIod spuce-IsomevIsm or steveoIsomevIsm. ThIs Is of fwo fyos:
(o) CoomofrIcnI or cIs-frnns IsomorIsm
(I) OfIcnI or mIrror Imngo IsomorIsm.
Ionisation Isomerism
In fhIs cnso, osIfIons of grous InsIdo nnd oufsIdo of fho co-ordInnfIon shoro nro
Inforchnngod nnd so fho comound yIoIds dIfforonf Ions In fho soIufIon. Ior oxnmIo, fho comIox
|Co(H
3
)
5
Ir]SO
4
(I) gIvos whIfo rocIIfnfo of InSO
4
whon fronfod wIfh InCI
2
soIufIon nnd IndIcnfos
fhnf SO
4
2
Ion Is oufsIdo fho co-ordInnfIon shoro. And fho comIox |Co(H
3
)
5
SO
4
] Ir (II)
gIvos n IIghf yoIIow rocIIfnfo of AgIr whon fronfod wIfh AgO
3
soIufIon, IndIcnfIng fho
Ir

Ion Is oufsIdo fho coordInnfIon shoro.
|Co(H
3
)
5
Ir] SO
4
+ InCI
2
|Co(H
3
)
5
Ir]
2+
+ InSO
4
+ 2CI
IonfnnmIno monobromo (WhIfo)

cobnIf (III) suIhnfo (rod-vIoIof)
|Co(H
3
)
5
SO
4
]Ir + AgO
3
|Co(H
3
)
5
SO
4
]
+
+ AgIr + O
3
IonfnnmIno monosuIhnfo

(!Ighf yoIIow)
cobnIf (III) bromIdo (!od)
Ofhor oxnmIos for fho snmo nro:
|If(H
3
)
4
CI
2
]Ir
2
nnd |If (H
3
)
4
Ir
2
]CI
2
|Co(H
3
)
4
CI
2
]O
2
nnd |Co(H
3
)
4
(O
2
)CI]CI
|Co(on)
2
.(O
2
).CI]SC nnd |Co.(on)
2
.(O
2
).(SC)]CI
Linkage Isomerism
ThIs fyo of IsomorIsm Is oxhIbIfod by fhoso moIocuIos In whIch fho IIgnnds cnn co-
ordInnfo wIfh fho confrnI mofnI Ion oIfhor of Ifs fwo nfoms. Tho IIgnnds of fhIs fyo nro nIfro
(O
2
), fhIocynnnfo (SC
), fhIosuIhnfo (S
2
O
3
2
) Ions. Tho comIoxos wIfh O
2
Ion ns wIfh
IIgnnd O
2

mny gof nffnchod fo fho confrnI mofnI Ion oIfhor fhrough O-nfom or -nfom ncfIng
ns donor. SImIInrIy, In cnso of SC
Ion ns IIgnnd, fho donor sIfo mny oIfhor bo fhrough
or
fhrough S-nfom. WIfh S
2
O
3
2
ncfIng ns IIgnnd fho confrnI Ion mny bo coordInnfod wIfh fho Ion
oIfhor fhrough S-nfom or O-nfom. Tho nnmos of fho nbovo Ions i.e., IIgnnds whon coordInnfod
fhrough dIfforonf nfoms nro gIvon boIow:
Nitro-O or Nitrito (ONO )
Nitro-N or Nitrito (NO )

2
NO
2
SCN
O
Ior oxnmIo:
H N
3
H N
3
ONO
NH
3
Co
NH
3
NH
3
2+
H N
3
H N
3
NO
2
NH
3
Co
NH
3
NH
3
2+
IonfnnmIno nIfrIfo (or Ifro-O) IonfnnmIno nIfrnfo (or nIfro-)
cobnIf (III) Ion (rod) cobnIf (III) Ion (YoIIow)
Fig. 13.3
Co-ordination Isomerism
ThIs fyo of IsomorIsm nrIsos from fho dIfforonco In dIsfrIbufIon of fho co-ordInnfIng
grous In fho cnfIons nnd nnIons of fwo comounds of IdonfIcnI comosIfIon.
Ior oxnmIo:
(i) |Cr(H
3
)
6
]
3+
|Cr(SC)
6
]
3
nnd |Cr(H
3
)
4
(SC)
2
]
+
|Cr(H
3
)
2
(SC)
4
]
nro co-ordInn-
fIon Isomors.
(ii) |Co(on)
3
]
3+
|Cr(C
2
O
4
)
3
]
3
nnd |Co(on)
2
(C
2
O
4
)]
+
|Cr(on)(C
2
O
4
)
2
]
nro co-ordInnfIon
Isomors.
Ligand Isomerism
Somo IIgnnds fhomsoIvos mny oxIsf ns Isomors nnd nro so co-ordInnfod In fho comIoxos.
Thus, ronno-l,2-dInmIno (n) nnd ronno-l,3-dInmIno (fn) nIso cnIIod frImofhyIono dInmIno
hnvo fho sfrucfuros:
Thoy form IsomorIc comIoxos ns |Co(n)
2
CI
2
]CI nnd |Co(fn)
2
CI
2
]CI
Hydrate Isomerism
Wnfor moIocuIo Is n vory offocfIvo co-ordInnfIng ngonf nnd mny roInco H
3
, CI
2
ofc.
nnd fhus onfors Info fho co-ordInnfIon shoro of n mofnI Ion, formIng nquo-comIox. Hydrnfo
Isomors nro gonornfod duo fo vnrInfIon In numbor of wnfor moIocuIos In fho co-ordInnfIon
shoro. Ior oxnmIo: fhroo Isomors of CrCI
3
.6H
2
O nro
|Cr(H
2
O)
6
]CI
3
; |Cr(H
2
O)
5
.CI].CI
2
.H
2
O; |Cr(H
2
O)
4
.CI
2
].CI.2H
2
O
GeometricaI Isomerism
CoomofrIcnI IsomorIsm orIgInnfos duo fo fho dIfforonf nrrnngomonfs of fho co-ordInnfod
grous In snco nround fho confrnI nfom In n dofInIfo goomofrIcnI nfforn.
In sIx co-ovdInuted compIexes fho sIx grous nro nrrnngod nbouf fho confrnI mofnI
Ion In n roguInr hoxngonnI nfforn or nf fho sIx cornors of nn ocfnhodron. Tho numbor of
ossIbIo Isomors Is dIfforonf for fhoso fwo snfInI nrrnngomonfs. Thus for |Co(H
3
)
4
(O
2
)
2
]O
3
fwo fyos of goomofrIcnI IsomorIsms mny dovoIo (IIg. l3.4).
NH
3
NH
3
H N
3
NH
3
NH
3
NH
3
Co
(a) cis-form (b) trans-form
NO
2
NO
2
H N
3
H N
3
Co
O N
2
NO
2
Fig. 13.4
InmIno dIchIoro InfInum |If(H
2
)CI
2
] oxIsfs In fwo IsomorIc forms (IIg. l3.5). Cie-
form Is known ns cIspIutIn nnd Is nn nnfIcnncor drug.
(a) cis-form (b) trans-form
NH
3
Cl
Pt
NH
3
Cl
Pt
NH
3
Cl
H N
3
Cl
Fig. 13.5
OpticaI or Mirror Image Isomerism
OfIcnI IsomorIsm of 6- nnd 4-co-ordInnfIon comIox comounds Is shown In IIg. l3.6
nnd l3.?.
Tho comIox |Cr(on)
2
CI
2
] wIfh co-ordInnfIon numbor 6 oxhIbIfs ofIcnI IsomorIsm.
Cl Cl
Cl Cl
Cr Cr
Mirror plane
en
en
en
en
(a) (b)
Fig. 13.6
As
H C
3
H C
5 2
As
S
C H COO
6 4
CH
3
C
2
H
5
S
()
H C
4 6
OOC
Mirror plane
(a) (b)
Fig. 13.7 Optically active arsenic compound with co-ordination number 4.
Theories of Bonding in Co-ordination Compounds
Thoro nro four dIsfIncf nronchos fo fho fhoorofIcnI fronfmonf of bondIng In co-ordInnfIon
comounds. Thoso nro: (i) VnIonco bond fhoory, (ii) CrysfnI fIoId fhoory, (iii) MoIocuInr orbIfnI
fhoory nnd (it) !Ignnd fIoId fhoory.
In fhIs confoxf, fho fIrsf fwo fhoorIos hnvo boon dIscussod.
VaIence Bond Theory
ThIs fhoory wns dovoIood by InuIIng nnd donIs wIfh hybrIdIsnfIon of fho comIox. If
doonds on fho foIIowIng nssumfIons:
Tho confrnI mofnI nfom rovIdos n numbor of omfy orbIfnIs fhnf nro oqunI fo Ifs co-
ordInnfIon numbor for formIng fho covnIonf bonds wIfh IIgnnd orbIfnIs.
Tho omfy orbIfnIs of fho mofnI Ion hybrIdIso fo gIvo nn oqunI numbor of oquIvnIonf
hybrId orbIfnIs.
!Ignnds nro grous whIch cnn donnfo oIocfron nIrs fo mofnI Ions whIch nonr ns
oIocfron nIr nccofors.
Ag
+
+ 2
. .
H
3
|Ag(H
3
)
2
]
+
An orbIfnI of fho IIgnnd confnInIng nn unshnrod oIocfron nIr ovorIns fho hybrIdIsod
orbIfnIs of fho mofnI Ion nnd fhIs Is rognrdod oIfhor ns nrfInI donnfIon of fho IIgnnd
oIocfrons fo fho mofnI Ion or n shnrIng of fhnf nIr of oIocfrons bofwoon fho mofnI Ion
nnd fho IIgnnd. ThIs ovorInIng rosuIfs In n -bond or ossIbIy n -bond.
OctuLedvuI compIexes rosuIf from J
2
ep
3
or ep
3
J
2
hybrIdIznfIons.
!of us sIfo nn oxnmIo of nn ocfnhodrnI comIox |Io(C)
6
]
4
. Tho comIox formnfIon Is
ns foIIows:

CN
CN
CN
CN
CN
CN
3d 4s 4p
(a) Electronic configuration of I
ground state (...3d .4s )
ron in
6 2
(b) Electronic configuration of Fe
ion in ground state (...3d .4s )
2+
6 0
(c) Electronic configuration of Fe
d sp hybridised state
2+
2 3
ion in
(d) Electronic configuration of Fe
[Fe(CN) ]
2+
4
ion in
6
Tho ground sfnfo oIocfronIc confIgurnfIon of Io Is ... 3J
6
4e
2
. In Io
2+
Ion, fho fwo 4e
oIocfrons movo ouf IonvIng 4e orbIfnI vncnnf. In J
2
ep
3
hybrIdIsnfIon, sIx J
2
ep
3
hybrId orbIfnIs
nro gonornfod whIch nro fIIIod by oIocfron nIrs donnfod by sIx C
Ions ncfIng ns IIgnnds,

honco |Io(C)
6
]
4
comIox Is formod.
Tho shno of fho comIox moIocuIo Is ocfnhodrnI nnd duo fo fho nbsonco of unnIrod
oIocfrons, fho comIox Is dInmngnofIc. ThIs comIox usos fho Innor J-orbIfnIs. So, fhIs Is offon
cnIIod Innor orbIfnI comIox. ThIs Is offon roforrod fo ns sIn nIrod comIox.
Anofhor oxnmIo of ep
3
J
2
confIgurnfIon Is |IoI
6
]
3
comIox. Tho formnfIon of fhIs Ion Is
ns foIIows:
3d 4s 4p 4d
3d 4d
sp d
3 2
4d
sp d
3 2

F
Six sp d hybridised orbitals

having lone pairs of electrons
donated by six F ligands.
3 2
Electronic configuration of
Fe (... 3d 4s )
3+ 5
2
Fe in sp d
3+ 3 2
configuration
Fe ion in [FeF ]
3+ 3
6
configuration
Such comIox Is ocfnhodrnI In shno nnd sInco oufor J-orbIfnIs nro InvoIvod, If Is cnIIod
oufor orbIfnI comIox. Iocnuso of rosonco of fIvo Iono oIocfrons In 3J IovoI fho comound Is
hIghIy nrnmngnofIc nnd offon roforrod fo ns ep hIgh sIn comIox.
TetrahedraI CompIex
As Is ImIIod fho fofrnhodrnI comIoxos nro sp
3
hybrIdIsod. Tho formnfIon of such
comIoxos cnn bo IIIusfrnfod by fho formnfIon of fofrnmIno nIckoI (II) suIhnfo comIox. AfomIc
numbor of I Is 26. ComIox cnfIon Is roducod from I
2+
Ion. Tho co-ordInnfIon of nIckoI Is
four. So four Iono nIrs nro donnfod of four nmmonIn moIocuIos. On fho bnsIs of VIT |I(H
3
)
4
]
2+
Is formod ns foIIows:
3d 4s 4p
sp
3

NH
3
NH
3
NH
3
NH
3
sp hybridised orbitals are
filled with paired electrons
donated by four NH ligands
3
3
(a) Electronic configuration of Ni
in ground state (... 3d 4s )
8 2
(b) Electronic configuration of Ni
in ground state
2+
(c) Electronic configuration of Ni
in sp hybridised state
2+
3
(d) Electronic configuration of Ni
in [Ni(NH ) ] complex
2+
2+
3 4
Tho shno of fho moIocuIo Is fofrnhodrnI, If Is nrnmngnofIc In nnfuro nnd fho fofrnhodrnI
sfrucfuro Is shown boIow In IIg. l3.8.
H N
3
Ni
2+
NH
3
NH
3
NH
3
Fig. 13.8 Tetrahedral shape of [Ni(NH
3
)
4
]
2+
ion resulted from sp
3
hybridisation.
|Zn(H
3
)
4
]
2+
; |I(Co)
4
]
0
nro nIso fho oxnmIos of fofrnhodrnI comIoxos.
Square PIanar CompIexes
Thoso nro formod by Jep
2
hybrIdIsnfIon. IxnmIo Is |I(C)
4
]
2
. Tho formnfIon of fho
comIox Is shown boIow:
3d 4s 4p
dsp
2

CN
Four dsp hybridised orbitals

containing four electron pairs
donated by four CN ligands
2
(a) Electronic configuration of

Ni in ground state
2+
(b) Electronic configuration of
Ni in state
2+ 2
dsp
4p
dsp
2
4p
CN
CN
CN
(c) Electronic configuration of

Ni in [Ni(CN) ]
2+ 2
4
Tho sfrucfuro of fho comIox Is squnro Innnr, comIox Is dInmngnofIc In nnfuro. Tho
shno of |I(C)
4
]
2
Is gIvon boIow In IIg. l3.9.
CN
CN
CN
NC
Ni
2+
2
Fig. 13.9 Square planar complex resulted from dsp

2
hybridisation.
CRYSTAL FIELD THEORY (CFT)
Tho osfuInfo of fhIs fhoory Is: bondIng bofwoon n confrnI mofnI Ion nnd Ifs IIgnnds sImIy
nrIsos from uroIy oIocfrosfnfIc forco of nffrncfIon. Thnf Is nn nffrncfIon bofwoon n osIfIvoIy
chnrgod mofnI Ion (
n+
) nnd fho nognfIvo chnrgo of fho IIgnnd or fho nrfInI nognfIvo chnrgo of
fho IIgnnd. If fho IIgnnd (!
n
) Is noufrnI moIocuIo (!) fho nognfIvo ond of fho dIoIo Is nffrncfod
fownrds fho confrnI osIfIvo mofnI Ion. ThIs fhoory doos nof consIdor fho IIgnnd oIocfrons fo
onfor Info fho orbIfnI of fho mofnI Ion.
CrystaI FieId SpIitting of d OrbitaIs
ThIs fhoory consIdors onIy fho offocf of fho IIgnnds on fho onorgy of ouformosf
J-oIocfrons In fho confrnI mofnI Ion. In nn ocfnhodrnI comIox, fho confrnI mofnI Ion Is hoxn
co-ordInnfod i.e., sIx IIgnnds occuy fho sIx cornors of nn ocfnhodron.
d d d
xy yz zx
d d
z
2
x y
2 2
d d d
xy yz zx
e
g
t
2g
+ 0.6 D
o
0.4 D
o
D
o
or 10 D
q
(a) (b) (c)
E
n
e
r
g
y
I
n
c
r
e
a
s
i
n
g
d d
z
2
x y
2 2
Fig. 13.10 Crystal Field Splitting in an octahedral complex. (a) The five degenerate d-orbitals in
the isolated central metal ion. (b) Hypothetical degenerate d-orbitals at a higher
energy level if all the ligands approach the metal ion at an equal distance from each
of the d-orbitals. (c) Crystal field splitting of d-orbitals into t
2g
and e
g
sets by electrostatic
field of the six approaching ligands.
In fho froo mofnI Ion nII fho fIvo J-orbIfnIs nro dogonornfo (orbIfnIs of snmo onorgy) ns
shown In IIg. l3.l0 (o). Whon fho sIx IIgnnds nronch fho confrnI mofnI nfom nIong fho nxos
fhoy oxorf nn oIocfrosfnfIc forco of rouIsIon on fho J-oIocfrons of ouformosf shoII i.e., fho
J-oIocfrons nro rooIIod by Iono nIr of oIocfrons of fho IIgnnds. ThIs rouIsIon forco rnIsos fho
dogonornfo J-orbIfnIs of fho mofnI fo n hIghor onorgy sfnfo ns shown In IIg. l3.l0 (I) whIch Is
consIdorod ns n hyofhofIcnI sfnfo. SInco fho Iobos of J
c
2 nnd J
x ,
2 2
orbIfnIs cnIIod ns e
g
sof of
orbIfnIs fnII dIrocfIy nf fho nfh of fho nronchIng IIgnnds, fho oIocfrons In fhoso orbIfnIs
oxorIonco n gronfor forco of rouIsIon oxorfod by fho oIocfrons of fho IIgnnds fhnn fhnf by fho
oIocfrons of fho J
x,
,
J
,
2
nnd J
cx
orbIfnI cnIIod ns I
2g
sof of orbIfnIs whIch nro dIrocfod In snco
nIong x, , nnd c nxos. Honco, undor fho InfIuonco of fho nronchIng IIgnnds fho orbIfnIs J
x ,
2 2
nnd J
c
2 oxIsf In fho hIghor onorgy IovoIs comnrod fo J
x,
, J
,c
nnd J
cx
. Tho sonrnfIon of fIvo J-
orbIfnIs In fho I
2g
nnd e
g
sofs of dIfforonf onorgy sfnfos Is known ns cvystuI IIeId spIIttIng.
Tho onorgy dIfforonco bofwoon e
g
nnd I
2g
sofs of orbIfnIs Is donofod by
o
or l0
q
whoro 'o`
IndIcnfos nn ocfnhodrnI nrrnngomonf of IIgnnds nround fho confrnI mofnI Ion.
o
Is cnIIod cvystuI
IIeId stubIIIsutIon enevgy (CIS). If cnn bo shown fhnf whon nn ocfnhodrnI comIox Is
formod fho onorgy of fho I
2g
sof Is docronsod 0.4
o
whIIo fhnf of e
g
sof Is Incronsod by 0.6
o
ns
shown In IIg. l3.l0.
Strong and Weak Ligands
Sfrong IIgnnds cnn sIIf fho fIvo J-orbIfnIs Info I
2g
nnd e
g
sofs sfrongIy i.e., fhoro sIIffIng
owor Is hIgh whorons fho wonk IIgnnds cnn sIIf fho sof of orbIfnIs wonkIy i.e., fhoro sIIffIng
owor Is wonk. Sfrong IIgnnds confor hIghor vnIuo of
o
nnd wonk IIgnnds confor Iowor vnIuos
fo
o
. Tho foIIowIng Is fho nrrnngomonf of IIgnnds wIfh fho sIIffIng owor of IncronsIng ordor.
ThIs ordor Is known ns spectvocLemIcuI sevIes.
C-donor > -donor > O-donor > X-donor
IxnmIos of C-donor = C
-donor = O
2
, H
3
O-donor = H
2
O, OH
X-donor = I

> CI
> Ir
> I
IstvIbutIon oI J-eIectvons In t
2g
und e
g
sets oI ovbItuIsIow spIn und LIgL spIn
compIexes.
Tho sfrong IIgnnds i.e.,
o
whon hIgh, forco fho oIocfrons fo form n nIr In fho Iowor I
2g
sof of orbIfnIs nnd fhus fho numbor of unnIrod oIocfrons Is roducod, so fho rosuIfnnf
sIn 'e` Is nIso roducod. So, fho comIoxos formod wIfh sfrong IIgnnds hnvo mInImum
numbor of unnIrod oIocfrons, so fho sIn vnIuo 'e` gofs Ioworod. Thoso fyos of comIoxos
nro known ns Iow spIn (!.S.) or spIn puIved compIexes.
Tho wonk IIgnnds i.e.,
0
whon Iowor, fIrsf forco fho oIocfrons fo occuy nII fho fIvo
J-orbIfnIs sIngIy nnd fhon gof nIrod. Thus wonk IIgnnds roduco hIghor numbor of
unnIrod oIocfrons nnd so fho hIghor vnIuo of 'e`. Thoso fyos of comIoxos roducod by
wonk IIgnnds nro known ns LIgL spIn (H.S.) or spIn Ivee compIexes.
TabIe 13.1: Distribution of d-electrons in t
2g
and e
g
sets in strong octahedral ligand
field (n = number of unpaired electrons, S = resultant spin)
DieIriIuIion of J-elecIrone in
J
c
ion n S = n/2
I
2g
eeI e
g
eeI
J
l
_ _ l l/2
J
2
_ 2 2/2 = l
J
3
3 3/2
J
4
2 l
J
5
l l/2
J
6
0 0
J
?
_ __ __ l l/2
J
8
2 l
J
9
l l/2
J
l0
0 0
CFT and Magnetic Properties of the CompIex Formed
Ono of fho gronfosf nchIovomonfs of CIT Is: wIfh fho hoI of fhIs fhoory rodIcfIon of fho
mngnofIc roorfIos of fho comIoxos formod Is ossIbIo. Tho comIoxos hnvIng no unnIrod
oIocfrons shouId nof oxhIbIf nny mngnofIc roorfy, so fhoroforo nro dInmngnofIc. Tho comIoxos
hnvIng ono or moro unnIrod oIocfrons shouId show mngnofIc roorfIos, so fhoy nro nrnmngnofIc
comIoxos. Tho mngnofIc momonf Is roInfod fo fho unnIrod oIocfrons n by fho roInfIon
= + n n ( ) . 2 I
TabIe 13.2: Distribution of d-electrons in t
2g
and e
g
sets in weak octahedral ligand field
DieIriIuIion of J-elecIrone in
J
x
ion n S = n/2
I
2g
eeI e
g
eeI
J
l
_ _

l l
l
2
=
l
2
J
2
_ 2 l
J
3
3 3/2
J
4
_ 4 2
J
5
5 5/2
J
6
4 2
J
?
3 3/2
J
8
2 l
J
9
l l/2
J
l0
0 0
AppIication of Ligands
!Ignnds nro wIdoIy usod In dIfforonf fIoIds of chomIsfry. Somo of fhoso nro gIvon boIow:
(i) In gvuvImetvIc unuIysIs. IckoI Ion In nIknIIno modIum cnn bo osfImnfod ns woII
ns IdonfIfIod wIfh dImetLyI gIyoxIme ncfIng ns choInfIng IIgnnd.
Cuforron gIvos n rocIIfnfo wIfh forrIc Ion In ncId modIum. Tho forrIc cuforron
comIox Is IgnIfod fo forrIc oxIdo nnd woIghod.
N
NO
ONH
4
CH
3
NOH
CH
3
C NOH
Dimethylglyoxime
Cupferron (ammonium salt of nitroso
phenyl hydroxylamine)
C
(ii) In quuIItutIve unuIysIs. Coor Ion In fnInfIy ncIdIc or nmmonIncnI modIum Is
dofocfod wIfh !ubonnIc ncId or dIfhIoxnmIdo ns choInfIng comIox.
H
2
C
S
C
S

H
2
!ubonnIc ncId
(iii) In compIexometvIc tItvutIons. !sIng ITA (ofhyIonodInmIno fofrnncofIc ncId) ns
comIoxIng ngonf mnny mofnI Ions IIko cnIcIum, mngnosIum, nIumInIum, ofc., nro
osfImnfod by comIoxomofrIc fIfrnfIon.
NCH CH N
2 2
HOOCH C
2
HOOCH C
2
CH COOH
2
CH COOH
2
EDTA
(it) In tLe sepuvutIon oI metuI Ions und soIvent extvuctIon. Somo mofnI Ions IIko
zIrconIum nnd hnfnIum cnn bo sonrnfod from soIufIon by choInfIon wIfh
fhIonyIfrIfIuoro-ncofono (TTA).
S COCH = CCF (TTA)
3
OH
A combInnfIon of choInfIng ngonf nnd n mnskIng ngonf e.g., oxIn nnd ITA, gronfIy
Incronsos fho soIocfIvIfy of oxfrncfIon rocossos.
(t) Iov medIcInuI puvpose:
(o) ITA Is usod fo InhIbIf honvy mofnI oIsonIng.
(I) ThIosuIhnfo Is usod ns n rovonfIng ngonf of cynnIdo oIsonIng.
(c) VIfnmIn I
l2
IfsoIf Is n choInfo comound In whIch fho confrnI mofnI Ion Is cobnIf.
(J) CIsInfIn Is nn nnfIcnncor drug.
SHORT QUESTIONS
1. Whnf nro frnnsIfIon mofnIs
2. MonfIon fho common fonfuros of fho frnnsIfIonnI mofnIs.
3. MonfIon fho mnIn oxIdnfIon sfnfo of fho fIrsf frnnsIfIon sorIos.
4. IfforonfInfo bofwoon doubIo snIf nnd comIox snIf.
5. CIvo nn oxrossIon for K
Ins
nnd sfnfo Ifs sIgnIfIcnnco.
6. CIvo mnIn osfuInfos of Wornor`s fhoory.
?. Whnf Is n IIgnnd
B. Whnf Is co-ordInnfIon numbor
9. MonfIon mnIn drnwbnck of co-ordInnfIon fhoory.
10. Whnf nro choInfo comounds CIvo oxnmIos.
11. Whnf nro Innor mofnIIIc comIoxos
12. Whnf do you monn by nmbIdonf IIgnnds
13. CIvo oxnmIos of onch:
(o) CnfIonIc comIox (I) AnIonIc comIox.
14. CIvo nn oxnmIo of brIdgIng IIgnnd comIox.
15. MonfIon fho fyos of IsomorIsm found In comIox comounds. CIvo ono oxnmIo of onch fyo.
16. Show fho hybrIdIsnfIon of nn ocfnhodrnI comIox.
1?. CIvo fho sfnfo of hybrIdIsnfIon of n squnro Innnr comIox.
1B. Whnf Is fho mnIn osfuInfo of CIT
19. Whnf do you monn by crysfnI fIoId sIIffIng of J-orbIfnIs
20. Whnf Is CISI
21. Whnf Is socfrochomIcnI sorIos
22. Whnf nro Iow sIn nnd hIgh sIn comIoxos
23. Whnf Is fho mnIn oufcomo of CIT
24. CIvo somo usos of IIgnnds.
25. CnIcuInfo fho mngnofIc momonf for ono unnIrod oIocfron. |Ans. l.?32 I]
26. CnIcuInfo fho mngnofIc momonf for 2, 3, 4, 5, 6 nnd ? unnIrod oIocfrons.
|Ans. 2.83; 3.8?; 4.9; 5.92; 6.93 nnd ?.93 I rosocfIvoIy]
EXERCISES
1. Sfnfo fho osfuInfos of Wornor`s co-ordInnfIon fhoory nnd dIscuss fho sfrucfuro of K
4
Io(C)
6
on
fho bnsIs of fhIs fhoory.
2. IxInIn goomofrIcnI nnd ofIcnI IsomorIsms of ocfnhodrnI comIoxos.
3. Iscuss fho goomofrIcnI ns woII ns ofIcnI IsomorIsm In comIoxos wIfh co-ordInnfIon numbor 4
nnd 6.
4. Sfnfo fho osfuInfos of crysfnI fIoId fhoory. On fho bnsIs of fhIs fhoory rodIcf whofhor fho com-
Ioxos |CoI
6
]
3
nnd |Co(H
3
)
6
]
+3
nro nrnmngnofIc or dInmngnofIc.
5. IxInIn wIfh oxnmIo fho vnIonco bond fhoory rognrdIng comIox moIocuIos.
6. CIfo somo fIoIds of nIIcnfIon of IIgnnds In our dnIIy IIvos.
?. CIvo I!IAC nomoncInfuro of fho foIIowIng:
(o) CoCI
2
.6H
3
, (I) If(H
3
)
2
CI
2
, (c) |Co(on)
2
CI
2
]
+
(J)
(en) Co
2
II
Co (en)
2
NH
2
O
2
IV
(e) |Io(C)
6
]
3
. ( f ) |Cr(H
2
O)
5
CI]
2+
( g) |Cr(H
2
O)
4
CI
2
]
+
(I) |Cr(H
2
O)
6
]CI
3
(i) |If(H
3
)
4
CI
2
]Ir
2
( j ) |If(H
3
)
4
Ir
2
]CI
2
(l) |Co(H
3
)
4
CI
2
]O
2
B. rnw fho sfrucfuros of fho foIIowIng:
(o) Tofrnnquo dIhydro nIumInIum Ion.
(I) AmmonIum dInmIno fofrnfhIocynno chromnfo (III)
(c) TrInmIno nquo dIchIoro cobnIf (III) chIorIdo
(J) SodIum hoxn nIfrIfo cobnIfnfo (III).
308
"
AJ=KHCO
INTRODUCTION TO THE STUDY OF METALS
Tho goId nnd sIIvor nmong fho mofnIs nro robnbIy fho fIrsf usod by mnn. Tho nrf of roducIng
coor oros nnd fIn oros, nnd roducIng bronzo dnfos bnck fo 300 I.C. In hIsfory wo fInd 'sfono
ngo` foIIowod by 'bronzo ngo` nnd 'bronzo ngo` foIIowod by 'Iron ngo`.
Todny wo fInd fho mofnIs nro vory oxfonsIvoIy usod In nrf nnd Indusfry. Iron In fho form
of sfooI, wroughf Iron nnd cnsf Iron Is usod In consfrucfIng brIdgos, dnms, Ios, fubos nnd
mnchIno nrfs. Coor Is nnofhor Imorfnnf mofnI boIng usod mnInIy In oIocfrIcnI nrfIcIos.
owndnys nImosf nII fho mofnIs hnvo somo socIfIc usos.
MetaIs
MofnIs nro fho oIomonfs, whIch occuy fho Ioff hnnd sIdo of fho orIodIc fnbIo wIfh ono,
fwo or fhroo oIocfrons In fho ouformosf shoII fhnf fnkos nrf In bondIng nnd cLemIcuI
veuctIons.
PhysicaI Properties of MetaIs
MofnIs nro:
ShIny whon froshIy oIIshod nnd froo of corrosIon.
Cood conducfors of honf nnd oIocfrIcIfy.
MnIIonbIo nnd ducfIIo.
ConornIIy soIIds nro wIfh hIgh m.. nnd b.. (onIy sIx mofnIs moIf boIow l00 CHg
whIch Is n IIquId nnd four grou I mofnIs: n, K, !b, Cs).
Major ChemicaI Properties of MetaIs
ChomIcnIIy, mofnIs fond fo:
!oso oIocfrons fo form cnfIons or osIfIvo Ions i.e., mofnIs nro roducIng ngonfs.
Iorm bnsIc or nmhoforIc oxIdos.
Iorm soIId IonIc chIorIdos.
Tho moro nn oIomonf oxhIbIfs fhoso roorfIos, fho gronfor Is Ifs metuIIIc cLuvuctev.
MetaIIic Bonds
MofnIIIc bonds nro sfrong bonds In mofnI crysfnIs. Inch mofnI nfom In n mofnI crysfnI
confrIbufos oIocfrons from Ifs ouformosf shoII fo form n son of doIocnIIsod oIocfrons. OnIy
oIomonfs wIfh Iow fIrsf IonIsnfIon ofonfInI form mofnIIIc crysfnIs. Whon n mofnI nfom Ioosos
oIocfron If bocomos osIfIvoIy chnrgod. So, If Is quIfo IIkoIy fhnf n mofnI crysfnI consIsf osIfIvoIy
chnrgod mofnI nfoms omboddod In n son of shnrod oIocfrons.
METALLURGY 309
+ + + + + +

+ + + + + +

+ + + + + +

+ + + + + +

Fig. 14.1 Simplified picture of metallic bonding.
MofnIs conducf oIocfrIcIfy bocnuso fhoso shnrod bondIng oIocfrons cnn drIff fhrough fho
crysfnI sfrucfuros from nfom fo nfom whon fhoro Is nn oIocfrIcnI ofonfInI dIfforonco bofwoon
fho fwo onds. MofnIs cnn bond wIfhouf bronkIng bocnuso mofnIIIc bondIng Is nof hIghIy
dIrocfIonnI. !Inos or Inyors of mofnI nfoms cnn shIff fhoIr osIfIons In n crysfnI wIfhouf bronkIng
fho mofnIIIc bonds.
MineraI Resources of India
Tho sound oconomy of n counfry doonds uon Ifs mInornI wonIfh. Tho mosf Imorfnnf
nmong fho mInornI roducfs In IndIn Is couI, nbouf 58 of fho fofnI oufuf Is nvnIInbIo from
JhnrIn nnd !nnIgnnj. Ivon oves occur nbundnnfIy In IndIn. Tho doosIfs of hugo Iron oro nro In
SInghbhoom, Koonjhnr nnd Mnyurbhnnj. Tho noxf Imorfnnf mInornI Is mnngnnoso. Mnngnnoso
oros nro found In Chofnnngur, Mysoro, MumbnI nnd TnmII ndu. Coor Is chIofIy found In
Chofnnngur nnd SIkkIm. Tho bnuxIfo doosIfs nro Inrgosf In IndIn. ChromIfo Is found In Mysoro
nnd OrIssn. IndIn occuIos fho fIrsf Inco In roducIng mIcn In fho worId. Iornx, knoIIno,
IImosfono, gysum, Ifch-bIondo, monnzIfo snnd nro ofhor mInornIs, whIch nro found In IndIn.
Occurrence of MetaIs in Nature
Somo mofnIs occur In nnfuro In 'nnfIvo` or 'froo sfnfo`. A mofnI Is snId fo occur nnfIvo or
froo whon If Is found In nnfuro In fho mofnIIIc sfnfo. As for oxnmIo goId nnd InfInum occur In
nnfuro In fho mofnIIIc sfnfo. Wo cnn sny fhnf fhoso mofnIs nro nof rondIIy nffnckod by fho
moIsfuro, oxygon, nnd cnrbon dIoxIdo of fho nIr. WhIIo fhoso mofnIs whIch nro rondIIy nffnckod
by moIsfuro, oxygon nnd cnrbon dIoxIdo occur In fho combIned stute or ns n comound. Thoso
mofnIIIc comounds gonornIIy occur In fho form of hnrd sfonos oIfhor In fho undornonfh or In
fho onrfh surfnco. TLese nutuvuIIy occuvvIng InovgunIc compounds uve known us
mInevuIs. MInornIs nro nIwnys nssocInfod wIfh snnd, soII or ofhor ImurIfIos. Thoso ImurIfIos
nro known ns Gungue. Tho orconfngo of gnnguo In n mInornI Is nIwnys hIghor fhnn fho mInornI
IfsoIf.
Common MineraIs
OxIdo |InuxIfo, AI
2
O
3
2H
2
O] for AIumInIum
|HomnfIfo, Io
2
O
3
] for Iron
Cnrbonnfo |!Imosfono, CnCO
3
] for CnIcIum
|MngnosIfo, MgCO
3
] for MngnosIum
SuIhIdo |ZInc bIondo, ZnS] for ZInc
|CnIonn, IbS] for !ond
SuIhnfo |Cysum, CnSO
4
.2H
2
O] for CnIcIum
Ifrnfo |ChIIo snIfofro, nO
3
] for SodIum
HnIIdo |IIuosnr, CnI
2
] for cnIcIum
SIIIcnfo |MIcn, KHMg
2
AI
2
(SIO
4
)
3
] for MngnosIum
Ihoshnfo |IhoshorIfo, Cn
3
(IO
4
)
2
] for CnIcIum
Somo mInornIs of common mofnI nro IIsfod boIow In fnbuInr form:
Iorn MeIol Aone of oree onJ ninerole
(i) AIumInIum (AI) (i) CInysIIIcnfo (AI
2
O
3
.2SIO
2
.2H
2
O)
Insoro (AI
2
O
3
.H
2
O)
OxIdos nnd (ii) Coor (Cu) II (CoInngo mofnI) (ii) CurIfo (Cu
2
O)
hydrnfod (iii) ZInc (Zn) III (AmhoforIc mofnI) (iii) ZIncIfo (ZnO)
oxIdos (it) Mnngnnoso (Mn) VIII (it) IyroIusIfo (MnO
2
)
(TrnnsIfIon mofnI) IrnunIfo (Mn
2
O
3
)
(t) ChromIum (Cr) VII (t) Chromochro (Cr
2
O
3
)
(TrnnsIfIon mofnI)
(ti) TIn (Sn) IVA (AmhoforIc mofnI) (ti) TIn sfono or cnssIforIfo (SnO
2
)
(tii) IofnssIum (K) (AIknII mofnI) (tii) IoIsnr (K
2
O.AI
2
O
3
.6SIO
2
)
(i) Coor (Cu) IA (CoInngo mofnI) CoorgInnco (Cu
2
S);
CooryrIfo (CuS, IoS)
(ii) ZInc (Zn) ZInc bIondo (ZnS)
SuIhIdos (iii) !ond (Ib) IVA (AmhoforIc mofnI) CnIonn (Ibs)
(it) Morcury (Hg) III (!IquId mofnI) CInnnbnr (HgS)
(t) TIn (Sn) SfnnnIfo (Cu
2
S, IoS, SnS
2
)
(ti) Iron (Io) Iron yrIfo (IoS
2
)
(tii) SIIvor (Ag) II (Iosf conducfIng mofnI) SIIvor gInnco (Ag
2
S);
!ubby sIIvor 3Ag
2
S.Sb
2
S
3
(i) Iron (Io) SIdorIfo (IoCO
3
)
(ii) Coor (Cu) MnInchIfo (CuCO
3
Cu(OH)
2
)
(iii) CnIcIum (Cn) IIA (AIknIIno CnIcIfo (CnCO
3
); oIomIfo
onrfh mofnI) (CnCO
3
.MgCO
3
)
Cnrbonnfos (it) MngnosIum (Mg) IIA (IrIdgo mofnIs) MngnosIfo (MgCO
3
);
oIomIfo (MgCO
3
CnCO
3
)
(t) Mnngnnoso (Mn) Mnngnnoso snr (MnCO
3
)
(ti) !ond (Ib) CorussIfo (IbCO
3
)
(tii) ZInc (Zn) CnInmIno (ZnCO
3
)
(i) CnIcIum Cysum (CnSO
4
.2H
2
O)
AnhydrIfo (CnSO
4
)
SuIhnfos (ii) !ond AngIosIfo (IbSO
4
)
(iii) AIumInIum AIum (K
2
SO
4
; AI
2
(SO
4
)
3
.24H
2
O)
(it) InrIum IIA (AIknIIno onrfh mofnI) Honvy snr (InSO
4
)
METALLURGY 311
(t) MngnosIum IsomIfo (MgSO
4
.?H
2
O)
KIssorIfo (MgSO
4
.H
2
O)
(i) SodIum !ocksnIf (nCI)
(ii) IofnssIum SyIvIno (KCI)
(iii) SIIvor II (ConducfIvo mofnI) Horn sIIvor (AgCI)
HnIIdos (it) CnIcIum IIuoronIIfo (3CnI
2
Cn
3
(IO
4
)
2
); ChIoronfIvo
(3COCI
2
.Cn
3
(IO
4
)
2
)
(t) MngnosIum CnrnnIIIfo KCI, MgCI
2
6H
2
O
(ti) AIumInIum CryoIIfo (3nI, AII
3
)
(i) SodIum SodIum sIIIcnfo (n
2
SIO
3
)
(ii) IofnssIum IoIsnr (K
2
O.AI
2
O
3
.6SIO
2
)
SIIIcnfos (iii) ZInc WIIIomIfo (ZnSIO
2
)
(it) AIumInIum IoIsnr (K
2
O.AI
2
O
3
.6SIO
2
)
Ores
ConornIIy nII mInornIs cnnnof bo consIdorod Imorfnnf for oxfrncfIon of mofnI from fhom.
Tho rocoss of oxfrncfIon fhough cosfIy mny nof bo ImossIbIo from fhoso mInornIs.
PuvtIcuIuvIy, tLe mInevuIs Ivom wLIcL metuIs cun be extvucted eusIIy und cLeupIy
uve known us oves. As for oxnmIo, hnomnfIfo Is fho oro of Iron, bnuxIfo Is fho oro for nIumInIum
ofc.
MetaIIurgy
TLe pvocess by wLIcL tLe metuIs uve extvucted Ivom tLeIv vespectIve oves Is
known us metuIIuvgy. An oro Is nnfurnIIy occurrIng subsfnnco or mInornI from whIch fho
mofnI cnn bo oxfrncfod oconomIcnIIy.
Concentration of the Ore
AImosf nII oros nro nssocInfod wIfh gnnguo or mnfrIx. Ioforo fho roor oxfrncfIon of fho
mofnI fho oro Is frood from gnnguo or mnfrIx fo gof If In fho conconfrnfod form. As n mnffor of
fncf, fho oro Is onrIchod wIfh fho dosIrod mofnIIIc comound. ThIs rocoss of romovnI of gnnguo
Is known ns fho conconfrnfIon of fho oro. Thoro nro sovornI rocossos of fho conconfrnfIon of
oros, whIch nro doscrIbod boIow. ThIs rocoss of conconfrnfIon of oro mnkos fho oxfrncfIon of fho
mofnI onsIor nnd chonor. Tho mnIn sfos for fho oxfrncfIon of mofnIs nro gonornIIy ns foIIows:
l. CvusLIng und gvIndIng
2. ConcentvutIon oI tLe ove
3. CuIcInutIon/RoustIng
4. ReductIon
5. PuvIIIcutIon
CvusLIng und GvIndIng. ThIs Is ono of fho crucInI sfos of conconfrnfIon rocoss. Tho
sfo rovIdos bronkIng of bIg mnssos of rocks confnInIng fho oro Info smnII Iums by convonfIonnI
crushIng nnd grIndIng wIfh mnchInos tic., Jnw crushor, Cyrnfory crushor ofc.
SomofImos, fho conconfrnfIon nnd furfhor fronfmonf of somo oros domnnd fhoIr roducfIon
of sIzo Info n vory fIno sfnfo of dIvIsIon. ThIs Is offocfod In gvIndIng nnd puIvevIsIng mIIIs
(IIgs. l4.2 nnd l4.3).
Lumps (ore)
Crushed ore
Stamp
Crushed ore
Pulverised ore
Fig. 14.2 Crushing. Fig. 14.3 Pulverisation.
ConcentvutIon oI tLe Ove
(i) WoeIing. ThIs rocoss IncIudos nII mofhods of conconfrnfIons In whIch wnfor In mo-
fIon Is usod. Irom fho uIvorIsod oro In sfronm of wnfor fho IIghfor nrfIcIos fIonf
nwny wIfh wnfor nnd fhus somo gnnguos nro romovod.
(ii) IlooIoIion. Horo conconfrnfIon of fho uIvorIsod oro Is offocfod by fnkIng fho ndvnn-
fngo of fho dIfforonco In Ifs bohnvIour fownrds oII or wnfor. SuIhIdo oros, ns n ruIo, do
nof gof wof ns do sIIIcn nnd mosf oxIdos whon fronfod wIfh wnfor. Thoroforo, suIhIdo
oros wIII fIonf on fho surfnco whIIo sIIIcn nnd ofhor mnforInIs wIII sInk.
(iii) Oil flooIoIion proceee. OIIs hnvo jusf fho oosIfo offocf, fhoy nro nffrncfod by suIhIdo
oros. OIIs form n fIIm ovor fho suIhIdo oro. Tho uIvorIsod suIhIdo oro Is fnkon In n
fnnk nnd somo Ino oII nnd wnfor nro usod. ConornIIy somo xnnfhnfos nro usod wIfh
Ino oIIs. AIr Is mndo fo bubbIo fhrough n orfornfod Io from fho undornonfh of fho
fnnk. A fonm Is roducod nnd fIonfs nIong wIfh fho suIhIdo oro ovor fho surfnco of
wnfor. Iuf fho snnd nnd soII nro soffIod down. Tho conconfrnfod oro Is coIIocfod from
fonm (IIg. l4.4).
Stirrer
Froth
Concentrated ore
Air
Fig. 14.4 Concentration of ore by oil floatation.
METALLURGY 313
(it) MogneIic eeporoIion. IorromngnofIc oros cnn bo sonrnfod by nssIng fho oro fhrough
n sfrong mngnofIc fIoId, whoroby forromngnofIc subsfnncos nro sonrnfod from fho
oro. Tho fungsfon or fIn oro Is sonrnfod by fhIs mofhod.
Rubber belt
Magnet
Crushed ore
Non-magnetic
particles
Magnetic particles
Fig. 14.5 Magnetic separation.
CuIcInutIon und voustIng. Thoso fwo forms nro usod, somowhnf InforchnngonbIo, nmong
fho mofnIIurgIsfs, fhough n dIsfIncfIon oxIsfs bofwoon fhom.
RoustIng: To ronsf n mnforInI Is fo honf If nf n fomornfuro InsuffIcIonf fo moIf If i.e.,
boIow fho oInf of fusIon buf uIwuys In pvesence oI uIv wIfh n vIow fo oxIdIsIng fho
mnforInI. Tho form Is usunIIy nIIod In cnso of oxIdIsIng fho oros. As for oxnmIo,
mofnIIIc suIhIdos nro ronsfod fo oxIdos boforo roducfIon fo oxfrncf fho mofnI.
2MS + 3O
2
= 2MO + 2SO
2
MS + 2O
2
= MSO
4
CuIcInutIon: To cnIcIno n mnforInI Is fo honf If vory sfrongIy buf nf u tempevutuve
InsuIIIcIent to meIt It; wIfh n vIow fo drIvIng of voInfIIo mnffors IonvIng somo oros
on fho rocky oro fo fncIIIfnfo fho roducfIon rocoss, so fhnf roducIng gns tic., CO cnn
onfor Info oros nnd mnko roducfIon comIofo. As for oxnmIo,
M
2
O
3
.x H
2
O
M
2
O
3
+ x H
2
O
(CnIcInod)
MCO
3

MO + CO
2

(CnIcInod)
FIuxes
Ioforo fho oxfrncfIon of mofnIs from fhoIr oros nnd In fhoIr subsoquonf urIfIcnfIon, fho
ImurIfIos (gnnguo) rosonf In fho oros nro fo bo romovod. Thoy nro offon rofrncfory In nnfuro
nnd romnIn unfusod whIch mny dIsfurb offIcIonf oxfrncfIon of fho mofnI. So, gnnguo musf bo
romovod. Thoy bocomo onsIIy fusIbIo whon honfod wIfh ofhor subsfnncos, fhoso subsfnncos nro
known ns IIuxes.
So, IIux Is u mutevIuI, wLIcL wLen udded to un ove und Leuted gIves u IusIbIe
muss known us sIug.
Cnnguo + IIux
honf
SIng (fusIbIo)
SeIection of FIux
Tho nnfuro of fIux fo bo usod doonds on fho nnfuro of gnnguo. If If Is ncIdIc, bnsIc fIux Is
fo bo usod tic. IImo, mngnosIn ofc. If fho gnnguo Is bnsIc In chnrncfor, fhon nn ncId fIux IIko snnd
(SIO
2
) musf bo omIoyod.
Thoro nro fhroo kInds of fIuxos:
AcIdIc (SIO
2
)
BusIc (CnO, MgO)
NeutvuI (fIuorsnr)
FueIs
AImosf nII IndusfrIos roquIro n fuoI. !nrgo scnIo IndusfrIos, IIko mofnI oxfrncfIon, nood
oconomy of fuoI consumfIon.
Furnaces
Revevbevutovy Iuvnuce. ThIs Is n socInI fyo of furnnco much usod In mofnIIurgy. In
fhIs furnnco, fho mnforInI Is honfod nof dIrocfIy ovor fIro, buf by fho hof gnsos roducod
In fho fIro Inco (IIg. l4.6).
Air
Hearth
Flame fuel
Ore
Chimney
Charge
(Hopper)
Fig. 14.6 Reverberatory furnace.
MuIIIe Iuvnuce. If Is n fyo of furnnco consIsfIng of nn oncIosod chnmbor, mndo of
rofrncfory mnforInIs, from whIch fho fuoI nnd Ifs roducfs of combusfIon cnnnof como
In confncf wIfh fho mnforInIs honfod In If (IIg. l4.?).
Fig. 14.7 Muffle furnace.
Tho ofhor furnncos nro bIust Iuvnuce (for Iron oxfrncfIon), open LeuvtL Iuvnuce (for
sfooI mnnufncfuro) nnd eIectvIc Iuvnuce (for Ihoshorus oxfrncfIon).
METALLURGY 315
Molten slag
Fusable slag
Molten iron
Cone
Limestone (CaCO ), ore (Fe O )
& cock are added at the top
3 2 3
Charging
holes
Waste gases exit
Upper zone (250 C700 C)
Middle zone (800 C1000 C)
Lower zone (1200 C1600 C)
Tuyer for hot air
(form Cowpers Stoves)
250 C
2Fe O + CO 2Fe O CO
2 3 4 2
3
Fe O + CO 3FeO + CO
3 4

FeO + CO FeO + CO
2
Spongy iron
CaCO CO + CaO13K Cal
2 3
C + CO 2CO
2

SiO + CaO CasiO Slag
2 3
Fe Metal & Mixed with

C P Si Mn etc.
2 4 2
SiO + 2C Si + 2CO
2

F OIC + 10C TP + 10CO
4

CO + C + 2CO
2
C + CO CO
2
Fig. 14.8 Blast furnace (displaying reactions of iron extraction in various zones of the furnace).
Coke, sand & rock
Feed hopper
Carbon electrodes
CO
P & CO
Fig. 14.9 Electric arc furnace.
SmeItIng. Tho rocoss by whIch n mofnI Is oxfrncfod In fho fusod sfnfo Is cnIIod smoIfIng.
WeIdIng. If Is fho oornfIon of joInIng fho fwo Iocos of n mofnI oIfhor by rossuro or by
fusIon fo ono comncf mnss.
AIIoy. An nIIoy Is n mIxfuro or comound or bofh of fwo or moro mofnIs. Whon ono of
fhoso mofnIs Is morcury, fho nIIoy Is cnIIod nn umuIgum. So, nn nIIoy mny bo consIdorod ns soIId
soIufIon or nn InformofnIIIc comound or bofh. SfooI Is nn nIIoy of Iron nnd cnrbon, n non-mofnI.
An nIIoy Is offon moro usofuI fhnn n uro mofnI. ConfroIIIng fho comosIfIon of nn nIIoy mnkos
If ossIbIo fo vnry Ifs roorfIos. ConornIIy, nIIoys nro cInssIfIod ns:
Non-Ievvous uIIoys
Ievvous uIIoys
on-forrous nIIoys do nof confnIn Iron ns ono of fho consfIfuonfs of fho nIIoys, e.g., Irnss
whIch Is comosod of Zn nnd Cu. Whorons forrous nIIoys nIwnys confnIn Iron ns ono of fho
consfIfuonfs of fho nIIoys, e.g., SfnInIoss sfooI confnIns Io, I, Cr.
Importance of aIIoy preparation
fo Incronso fho hnrdnoss nnd fonsIIo sfrongfh
fo Imrovo fho cnsfIng roorfy
fo Incronso fho rosIsfnnco fo corrosIon
fo docronso fho fhormnI nnd oIocfrIcnI conducfIvIfIos.
fo Iowor fho moIfIng nnd boIIIng oInfs of IndIvIdunI mofnI.
GeneraI methods of preparation of aIIoys
By IusIon. Comononf mofnIs nro mIxod fogofhor In fho dosIrod rnfIo nnd moIfod
foIIowod by cooIIng.
By compvessIon. IInoIy dIvIdod mofnIs nro comrossod In fho dosIrod rnfIo.
By veductIon of fho mIxfuro of oxIdos fo gof mIxfuro of mofnIs In fho roor rnfIo.
ExampIes of important aIIoys are
MIId steeI. An nIIoy of Iron wIfh cnrbon (0.l-0.25). If Is roInfIvoIy chon, cnn bo onsIIy
roIIod Info shoofs, nnd cnn bo rossod Info shno.
StuInIess steeI (ChromIum sfooI) (l0-l5 Cr, 90-85 Io). If Is mnInIy usod In mnkIng
ufonsIIs ns woII ns roncfors In IndusfrIos.
Mungunese steeI confnIns Mn l2-l4 nnd fho rosf Is Iron. If Is usod In mnkIng roIIs.
MoIybdenum und Tungsten steeI ov HIgL speed tooI steeI nro mnInIy usod for
hIgh sood mnchInos.
WvougLt Ivon (C = 0.l-0.25), Is mnInIy usod In mnkIng housohoId furnIfuros.
Ievvo-tItunIum Is usod ns dooxIdIsors fo nvoId formnfIon of 'bIow hoIos` from moIfon
sfooI.
Bvuss, nn nIIoy of coor (Cu:Zn = 60:40), hns n goId coIour nnd doos nof corrodo.
Bvonze, nn nIIoy of coor wIfh ufo l2 fIn (Sn), n sfrong, hnrd wonrIng nnd rosIsfnnf
fo corrosIon.
SoIdev. An nIIoy of Ib nnd Sn fhnf moIfs nf Iow fomornfuro, cnn bo usod fo joIn mofnIs.
uvuIumIn. An nIIoy of 95 AI wIfh 4 Cu nnd smnIIor nmounfs of Mg, Io, SI, If Is
sfrongor, hnrdor, moro rosIsfnnf fo corrosIon fhnn uro AI, usod mnInIy In mnkIng fho
body of noroInnos.
METALLURGY 317
MugnuIIum. An nIIoy of AI nnd Mg (98:2) usod In mnkIng IIghf mnchIno nrfs.
AInIco. (ComosIfIonSfooI:AI:I:Co = 5:2:2:l) !sod for mnkIng ormnnonf mngnofs.
Cementation
Whon n mofnI Is honfod In confncf wIfh n owdor, fho owdor Is sIowIy nbsorbod by fho
mofnI wIfhouf moIfIng whoroby fho roorfy of fho mofnI chnngos fo n corfnIn oxfonf. ThIs
rocoss Is cnIIod cementutIon nnd fho owdor Is cnIIod fho cement.
GeneraI Methods of Extraction of MetaIs from their Ores
MofnIs IIko goId (Au), InfInum (If) ofc., nro obfnInod In nnfuro In fho froo sfnfo. So
fhoIr mofhod of oxfrncfIon rncfIcnIIy consIsfs of sonrnfIng fhom offIcIonfIy from fho
rocky nnd ofhor ImurIfIos.
Iuf, mosf of fho mofnIs occur ns fhoIr comounds such ns oxIdos, hydroxIdos, cnrbonnfos,
suIhIdos, hnIIdos ofc. Thon wo cnn sny, fhoro nro fwo brond sfos In fhoIr oxfrncfIon
rocoss:
(i) IroIImInnry cuIcInutIon nnd voustIng
(ii) !oducfIon.
Whon fho oro Is nn oxIdo, hydroxIdo, or cnrbonnfo If Is fIrsf cnIcInod fo gof orous oxIdos
nnd fhon fho cnIcInod oro Is roducod fo fho mofnI, gonornIIy, by cuvbon veductIon
pvocess. Tho rIncIIo nnd rocossos of roducfIon wIII bo dIscussod Infor on.
Whon fho oro Is n suIhIdo, If Is fIrsf honfod In fho rosonco of nIr i.e., ronsfod fo gof
mofnIIIc oxIdo nnd fhon roducod fo gof fho mofnI.
ScLeme I:
Sulphide ore
Roasted
Oxide
C-Reduction
Metal
Whon fho oro Is n cnrbonnfo or hydroxIdo:
ScLeme II:
Carbonate ore
Calcined
Oxide
C-Reduction
Metal
Whon fho oro Is n suIhnfo:
ScLeme III:
Sulphide
Roasted
Oxide
C-Reduction
Metal
Reduced
Sulphate
ore + C
Whon fho oro Is n hnIIdo or mofnIIIc oxIdo or Is nof roducIbIo by cnrbon, oIocfroIyfIc
rocoss of roducfIon Is foIIowod.
Methods of Reduction of the Processed Ore
MofnI oxfrncfIon InvoIvos fwo mnIn fyos of rocossos for fho roducfIon of fho mofnIIIc
comounds.
(i) PyvometuIIuvgy: If monns veuctIons ut LIgL tempevutuve oIten ubove 1000C.
(o) IIocfroIyfIc roducfIon nf hIgh fomornfuros of fho fusod snIfs osocInIIy hnIIdos
(for oxnmIo n, AI).
(I) ChomIcnI roducfIon by coko nf hIgh fomornfuros (for oxnmIo, Iron, Iond)
MO + C
M + CO
(c) ChomIcnI roducfIon by n moro roncfIvo i.e., oIocfroosIfIvo mofnI (for oxnmIo,
chromIum nnd fIfnnIum oxfrncfIon).
Cr
2
O
3
+ 2AI
AI
2
O
3
+ 2Cr (CoIdschmIdf ThormIf rocoss)
(ii) HydvometuIIuvgy: If monns, veuctIons ut Iow tempevutuve In soIutIon In wutev.
(o) IIocfrowInnIng nf Iow fomornfuro In soIufIon In wnfor (for oxnmIo, Zn oxfrncfIon
for ZnSO
4
soIufIon).
(I) ComonfnfIon usIng n dIsIncomonf roncfIon (for oxnmIo, usIng Iron fo dIsInco
coor from n soIufIon of CuSO
4
)
CuSO
4
+ Io = Cu + IoSO
4
GoIdschmidt Thermit Process
Tho mofnIIIc nIumInIum hns n sfrong nffInIfy for oxygon nf l000C. Tho combInnfIon of
oxygon wIfh nIumInIum nf fhnf fomornfuro ovoIvos much honf, whIch Is ufIIIsod In GoIdscLmIdt
TLevmIt pvocess or AIumInotLevmIc pvocess for fho roducfIon of mofnIIIc oxIdos e.g., MnO
2
or Cr
2
O
3
nnd for fho sonrnfIon of moIfon mofnIs.
GoIdscLmIdt TLevmIt pvocess Is nowuduys mostIy used Iov weIdIng vuIIs und
mucLIne puvts (IIg. l4.l0). ThormIfo, n mIxfuro of nIumInIum owdor nnd Iron oxIdo In fho
rnfIo 3:l by woIghf, Is IgnIfod In n crucIbIo by n rIbbon of mngnosIum, whon n vIoIonf roncfIon
fnkos Inco roducIng moIfon Iron nf 2500C.
2AI + Io
2
O
3
= AI
2
O
3
+ 2Io + l99 kcnI
Tho IIquId Iron Is drood on fho fwo Iocos dIrocfIy fo fho joInf fo bo woIdod.
Fig. 14.10 Goldschmidt Thermit process.
METALLURGY 319
Purification of the MetaIs Extracted
AImosf nII mofnIs obfnInod by roducfIon rocossos confnIn somo ImurIfIos. Tho ImurIfIos
nro fo bo romovod fo gof fho uro form of mofnI. Tho urIfIcnfIon rocossos nro:
l. ThormnI rofInIng nnd
2. IIocfro-rofInIng
l. TLevmuI veIInIng
OxiJoIion of inpuriIiee I, oir poling. Tho Imuro mofnI Is moIfod nnd n sfronm of nIr Is
urgod fhrough fho boffom, ns n rosuIf of whIch fho onsIIy oxIdIsnbIo ImurIfIos nro
convorfod fo oxIdos. Tho voInfIIo oxIdos oscno nnd n non-voInfIIo oxIdo forms n scum
ovor fho moIfon mofnI, whIch Is romovod wIfh fho hoI of n InddIo.
IrocIionol JieIilloIion. InsIIy voInfIIo mofnIs cnn bo romovod wIfh fho hoI of frncfIonnI
dIsfIIInfIon. Tho crudo zInc, whIch Is known ns soIfor, confnIns nbouf 2 of Iond nnd
frncos of Iron, cndmIum, nrsonIc ns ImurIfIos. Tho soIfor Is nf fIrsf honfod In n roforf
nf n fomornfuro sIIghfIy nbovo fho boIIIng oInf of zInc (920C). Whon zInc fogofhor
wIfh cndmIum dIsfIIs ovor IonvIng bohInd Iond (b.. l620C) nnd Iron (b.. 2800C). Tho
dIsfIIInfo i.e., moIfon mIxfuro of zInc nnd cndmIum Is rodIsfIIIod In nnofhor roforf nf n
fomornfuro sIIghfIy nbovo ?6?C whon moro voInfIIo cndmIum (b.. ?6?C) dIsfIIs ouf
nnd 99.9 of zInc Is Ioff In fho roforf.
LiquoIion. An onsIIy fusIbIo mofnI such ns fIn or Iond cnn bo rofInod by fhIs rocoss. Tho
Imuro mofnI confnInIng InfusIbIo ImurIfIos Is honfod on fho sIoIng honrfh of n socInI
fyo of furnnco (IIg. l4.ll), ns n rosuIf fho mofnI moIfs nnd fho moIfon mofnI fIows
down fho sIoIng honrfh IonvIng bohInd fho InfusIbIo ImurIfIos on fho fo.
Furnaces
Pure molten
metal
S
l
o
p
i
n
g
h
e
a
r
t
h
Impurities
Impure metal
Fig. 14.11 Refining of metal by Liquation.
Zone refining (IIg. l4.l2). ThIs rocoss of urIfIcnfIon Is omIoyod offocfIvoIy In somo
socInI cnsos. Tho ndvnnfngo Is fnkon ouf of fho fncf fhnf fho ImurIfIos nro moro soIubIo
In fho moIfon mofnI fhnn fho soIId mofnI nnd fho moIfon mofnI on rosoIIdIfIcnfIon
crysfnIIIsos ouf ns n uro mofnI. Tho ncfunI rocoss Is: n nnrrow rod of Imuro mofnI Is
fnkon nnd n smnII orfIon of If nf ono ond Is nImosf moIfod by nIIcnfIon of honf. ThIs
smnII moIfon zono Is grndunIIy nnd sIowIy shIffod fo fho ofhor ond of fho rod by grndunI
shIffIng of fho sourco of honf. Af Insf fho moIfon zono confnInIng nII fho ImurIfIos
ronch fho ofhor ond. Tho rod Is nIIowod fo cooI nnd fho Imuro zono Is cuf off nnd
romovod. Tho romnInIng orfIon of fho rod consIsfs of fho uro mofnI.
Resolidified
portion
Molten zone
Source of heat Most impure
zone to be
cut out
Fig. 14.12 Zone refining.
2. Iectvo-veIInIng. ThIs mofhod Is wIdoIy usod. !sunIIy nn oIocfroIyfIc coII Is sof u usIng
fhIn shoofs of uro mofnI ns fho cnfhodo nnd comnrnfIvoIy fhIck Imuro mofnI sIng ns nnodo.
Tho oIocfroIyfo usod Is nn nquoous soIufIon of n suIfnbIo snIf. urIng oIocfroIysIs, uro mofnI
from fho oIocfroIyfo gofs doosIfod on fho cnfhodo nnd fho oquIvnIonf nmounf of mofnI from fho
nnodo nssos Info fho soIufIon. Tho ImurIfIos oIfhor romnIn In soIufIon or nro doosIfod down
fho nnodo. ThIs doosIf Is known ns unode mud. SomofImos somo vnIunbIo mofnIs nro rocovorod
from nnodo mud. A fyIcnI oxnmIo of oIocfroIyfIc rofInIng Is of coor (IIg. l4.l3).
15% CuSO
solution in dil.
H SO as
electrolyte
4
2 4
Impure Cu anode
Pure Cu cathode
Fig. 14.13 Electrolytic refining of copper.
POWDER METALLURGY
Powdev metuIIuvgy (IIg. l4.l3) Is n fochnIquo or oornfIon or rocoss fo roduco mofnIIIc
or nIIoy nrfIcIos. In fhIs fochnIquo, fho mofnI owdors or nIIoy consfIfuonfs nro comncfod In n
dIo wIfh moIfIng or no moIfIng foIIowod by sInforIng. Tho sImuIfnnoous mofhod of comncfIng
nnd sInforIng Is cnIIod preeeure einIering.
Tho nrfIcIo Is mndo Info fho dosIrod shno by owdor mofnIIurgy In fho foIIowIng sfos:
(i) PulterieoIion of neIollic pouJere
(ii) Mixing onJ IlenJing
(iii) ConpocIing
(it) Pre-einIering, onJ
(t) SinIering
(ti) IinieIing operoIion.
METALLURGY 321
(i) PuIvevIsutIon oI metuIIIc powdevs. Ior uIvorIsnfIon of mofnIs fochnIquos ndofod
nro:
(o) MecIonicol. ThIs mofhod mny bo ndofod In fho cnso of Mg, AI, Zn, nnd Ib. Ior
uIvorIsnfIon bnII mIIIs cnn bo omIoyod.
(I) AIonieoIion. ThIs mofhod InvoIvos forcIng moIfon mofnI fhrough n nozzIo or
sInnoroffo In n sfronm of wnfor or comrossod nIr, whon fIno owdor of mofnIs
nro obfnInod. ThIs mofhod roquIros confroI of rossuro nnd fomornfuro nnd fho
oxIdnfIon of mofnI Info nn nfmoshoro of Inorf gns. ThIs mofhod Is commonIy
omIoyod for mofnIs IIko Mg, Cd, Zn, Ib, Sn ofc.
(c) CIenicol.
l. Iy roducfIon,
WO
2
+ 2H
2

W + 2H
2
O
2. Iy docomosIfIon,
I(CO)
4
I + 4CO
Tho mofnIs nro obfnInod In n sfnfo of fIno owdors In bofh cnsos.
(ii) MIxIng und bIendIng. ThIs oornfIon Is roquIrod whon n combInnfIon of mofnIIIc
owdors nro usod. Thoy nro unIformIy mIxod In rIghf roorfIons. !ubrIcnnfs mny bo
nddod If nocossnry.
(iii) CompuctIng. Tho mofnI owdor In rIghf roorfIons Is fhon fnkon In n dIo Info fho
cnvIfy (fomnIo joInf) of nccurnfo dImonsIons nnd fhon comrossod (l00l000 /m
2
) by
fho mnIo joInf of fho dIo. Tho soIId In fhIs sfngo Is known ns 'green conpocI`.
(it) Pve-SIntevIng. If InvoIvos honfIng fho groon comncf fo n fomornfuro boIow fho
sInforIng fomornfuro. ThIs sfo Incronsos fho sfrongfh of groon comncf ns woII ns
romovos fho IubrIcnnf If usod. ThIs sfo Is ossonfInI for fungsfon.
Extraction pin
High
pressure
Guide pins
Top moulding part
(Male joint)
Bottom moulding part
(Female joint)
Alloy ingredients
Fig. 14.14 Technique of powder metallurgy adopted in a die.
(t) SIntevIng. Comncfod Iocos nro honfod fo n fomornfuro boIow nnd vory cIoso fo fho
moIfIng oInf of fho mofnI In n furnnco, rofornbIy In nn nfmoshoro of hydrogon,
whoroby mofnI nrfIcIos sInfor fo n cohoronf mnss. TImo nnd fomornfuro of sInforIng
doond uon fho nnfuro of fho mofnI.
(ti) IInsLIng opevutIons. Tho sInforod nrfIcIos roquIro oornfIons IIko mnchInory, InfIng
ofc., fo gof nccurnfo shno of fho work Iocos.
Uses
In mnkIng:
(i) Iorous bonrIngs ; (ii) Tungsfon fIInmonfs for oIocfrIc buIbs ; (iii) SowIng mnchInos
(it) Conrs ; (t) CIufchos, bronks ofc.
Advantages
(i) ArfIcIos of nny InfrIcnfo shno cnn bo roducod wIfh dosIrod nccurncy nnd smoofh
fInIsh.
(ii) CIonn nnd smoofh oornfIons.
(iii) MofnIs nnd non-mofnIs cnn bo mIxod fo gIvo fho dosIrod roorfy fo fho nrfIcIo ns for
oxnmIo W nnd C cnn bo mIxod fo roduco W
2
C (fungsfon cnrbIdo) for cuffIng fooIs.
(it) ArfIcIos wIfh Imrognnfod IubrIcnnfs cnn bo roducod whIch wouId bo soIf-IubrIcnfIng
for ovor.
(t) l00 rnw mnforInI Is consumod wIfh no Ioss.
Disadvantages
(i) Ios of dosIrod rocIsIon nro roquIrod whIch nro vory much oxonsIvo.
(ii) IjocfIon of fho nrfIcIos from fho dIo Is nocossnry, whIch IImIfs fho roducfIon of vory
vory InfrIcnfo nrfIcIos.
SOME SPECIFIC EXAMPLES OF EXTRACTION OF METALS
Titanium (Ti)
TIfnnIum Is n vory sfrong mofnI nnd hns n donsIfy much Ioss fhnn fhnf of sfooI. If moIfs nf
n vory hIgh fomornfuro of l6?5 C. Tho mofnI Is boIng rofocfod IIko nIumInIum by n fhIn oxIdo
Inyor formod on fho surfnco of fho mofnI.
TIfnnIum Is nn oIomonf of J-bIock In fho orIodIc fnbIo nnd Ifs oIocfronIc confIgurnfIon Is
|Ar] ... 3J
2
.4e
2
. If cnn oxhIbIf fhroo oxIdnfIon sfnfos +2, +3 nnd +4, buf onIy +4 oxIdnfIon sfnfo Is
common. TIfnnIum (IV) chIorIdo Is n coIourIoss IIquId roducod ns nn InformodInfo In fIfnnIum
oxfrncfIon nnd Is usod In fho mnnufncfuro of fIfnnIum (IV) oxIdo.
Smoko gronndos roduco donso cIouds of fIfnnIum (IV) oxIdo duo fo rnId hydroIysIs of
fIfnnIum (IV) chIorIdo.
xtvuctIon
Tho oros of fIfnnIum usod for oxfrncfIng mofnI nro ruIile (TIO
2
) nnd ilneniIe (IoTIO
3
).
Among fho mosf nbundnnf mofnIs In fho onrfh`s crusf TIfnnIum nchIovos fho fourfh Inco. Iuf
ns fho oxfrncfIon rocoss Is dIffIcuIf nnd oxonsIvo, If Is nof wIdoIy usod.
Affor fho urIfIcnfIon of fho oro, If Is honfod wIfh cnrbon In n sfonm of chIorIno gns nf
nbouf ll00 K.
TIO
2
+ C + 2CI
2
TICI
4
+ CO
2
In KvoII pvocess, fho fIfnnIum (IV) chIorIdo condonsos ns n IIquId fhnf cnn bo urIfIod
by frncfIonnI dIsfIIInfIon.
Tho chIorIdo of fho mofnI Is fhon nIIowod fo roncf wIfh moIfon sodIum or mngnosIum nf
800 K In nn Inorf nrgon nfmoshoro, fho roncfIon Is oxofhormIc nnd so fomornfuro rIsos.
METALLURGY 323
TICI
4
+ 4n TI + 4nCI
Tho roncfor Is kof hof for nbouf fwo dnys fhon fho mnss Is romovod from fho furnnco nnd
Is nIIowod fo cooI. Tho soIId roducf Is fhon crushod nnd Ionchod wIfh dIIufo hydrochIorIc ncId,
whIch dIssoIvos fho sodIum chIorIdo, IonvIng bohInd fho mofnI TI whIch Is fhon wnshod nnd
drIod. IxfromoIy uro TI cnn bo obfnInod by docomosIfIon of TII
4
vnour on nn oIocfrIcnIIy
honfod fungsfon (W) fIInmonf In vncuum.
\ses
(i) TIfnnIum Is usod mnInIy for mnkIng nIrcrnff ongInos nnd nIrfrnmos.
(ii) Ofhor mnjor usos nro fho roducfIon of chomIcnI comononfs of chomIcnI Innfs such
ns honf oxchnngors.
Chromium (Cr)
ChromIum Is mnInIy oxfrncfod from Cr
2
O
3
i.e., ChromIum (III) oxIdo In n bnfch rocoss
omIoyIng nIumInIum ns fho roducIng ngonf. TLe commevcIuI ove Is cLvomIte. ChromIfo
confnIns ofhor mofnIs IIko Iron bosIdos chromIum. Tho fIrsf sfo Is fo convorf fho oro fo uro
Cr
2
O
3
. A mIxfuro of fho oxIdo wIfh owdorod nIumInIum Is fhon IgnIfod In n roncfIon vossoI.
Tho exotLevmIc veuctIon roducos uro mofnI (99 ).
Cr
2
O
3
(e) + 2AI(e) 2Cr
2
(e) + AI
2
O
3
(e)
Cnrbon cnn roduco Cr
2
O
3
buf fho roducod mofnI fhon confnIns cnrbon ns ImurIfy. Tho
rosonco of cnrbon In fho mofnI mnkos fho mofnI brIffIo nnd Ioss rosIsfnnf fo corrosIon.
ChromIum, IIko nIumInIum, Is rofocfod from corrosIon by n fhIn Inyor of oxIdo on fho
mofnI surfnco. Tho mnIn uso of chromIum Is fo mnko uIIoys wIfh Iron (stuInIess steeIs).
Electropluting uith chromium giteo u ohiny, corrooion reoiotunt finioh to metulo.
\ses
(i) Tho chIof usos of chromIum nro In fho mnnufncfuro of chromo sfooI nnd chromIum
InfIng.
(ii) Chromo sfooIs nro omIoyod In fho form of nIIoy forrochromo confnInIng 60?0 Cr.
ThIs Is vory hnrd nnd usod In mnkIng cuffIng fooIs. SfnInIoss sfooI Is ordInnry sfooI
wIfh l4 Cr. SfooIs wIfh l8 Cr nnd ?8 I nro suorIor corrosIon rosIsfnnf.
ChromIum-vnnndIum sfooI Is vory hnrd nnd Is usod In nxIo, shnffs, IocomofIvo whooIs
ofc.
(iii) ChromIum InfIng unIIko nIckoI InfIng Is rosIsfnnf fo suIhur comounds of fho
nfmoshoro.
NickeI (Ni)
IckoI Is n hnrd, grnyIsh buf shIny J-bIock mofnI wIfh fho oIocfronIc confIgurnfIon
... 3J
8
.4e
2
|Ar]. Tho common oxIdnfIon sfnfo of nIckoI Is +2. IckoI (II) snIfs, IIko nIckoI suIhnfo
(ISO
4
) nro groon.
\ses
(i) IckoI Is so unroncfIvo fhnf If Is usod fo mnko snfuIns nnd crucIbIos.
(ii) IckoI Is n consfIfuonf of mnny nIIoys IncIudIng somo nIIoy sfooIs nnd fho forromngnofIc
nIIoy nnd nIso of AInIco whIch Is usod In mnkIng ormnnonf mngnof.
(iii) IckoI In fInoIy dIvIdod form ncfs ns n good cnfnIysf In hydrogonnfIon roncfIons.
(it) If Is n hoforogonoous cnfnIysf nnd Is usod fo hnrdon unsnfurnfod vogofnbIo oIIs by
nddIfIon of hydrogon ncross fho doubIo bond.
Manganese (Mn)
Mnngnnoso Is n hnrd, grny, brIffIo d-bIock mofnI hnvIng oIocfronIc confIgurnfIon
...3J
5
.4e
2
|Ar].

Tho mnIn oxIdnfIon sfnfos of mnngnnoso nro:
+? In MnO
4
fho urIo mnngnnnfo (VII) Ion, whIch Is n sfrong oxIdIsIng ngonf In

ncId modIum.
+4 In MnO
2
nn InsoIubIo bInck comound nnd ncfs ns nn oxIdIsIng ngonf In ncId
soIufIon.
+2 ns Mn
2+
fho Ink mnngnnoso (II) Ion In snIfs such ns mnngnnoso (II) suIhnfo.
\ses
(i) Mnngnnoso Is nddod In sfooI fo modIfy Ifs mochnnIcnI chnrncforIsfIcs.
(ii) Tho mofnI Is mnInIy usod In sfooI Indusfry In mnkIng nIIoy sfooIs nnd ns n dooxIdnnf.
(iii) Mnngnnoso sfooI confnInIng l3 Mn Is oxfromoIy hnrd nnd fough nnd Is usod In mnk-
Ing jnws or rock crushors.
(it) An nIIoy of coor, nIumInIum nnd mnngnnoso (HousIor`s nIIoy) Is forromngnofIc.
(t) An nIIoy of coor, mnngnnoso nnd nIckoI, known ns MnngnnIn, Is usod for rosIsfnnco
coIIs sInco Ifs oIocfrIcnI rosIsfnnco Is vory sIIghfIy nffocfod by fomornfuro.
CobaIt (Co)
CobnIf Is n hnrd, shIny d-bIock mofnI nnd Is Ioss roncfIvo fhnn Iron. If hns fho oIocfronIc
confIgurnfIon ... 3J
?
.4e
2
|Ar].
In soIufIon cobnIf forms Ions In fho +2 nnd +3 oxIdnfIon sfnfos. CobnIf (II) Is n moro sfnbIo
sfnfo.
\ses
(i) CobnIf Is usod In mnkIng fho so cnIIod 'hnrd nIIoys` whIch nro suorIor fo hIgh sood
fooI sfooI ns rognrds fho IIfo of fho fooIs.
(ii) SfooIs confnInIng nbouf 35 cobnIf Is usod for ormnnonf mngnof.
(iii) CobnIf mny bo usod for oIocfroInfIng Iron, sfooI nnd brnss ofc.
(it) CobnIf oxIdo Is usod ns n coIourIng ngonf In fho gInss nnd cornmIc Indusfry i.e., In
mnkIng bIuo gInss nnd bIuo onnmoIs for confIng Iron.
(t) Somo cobnIf snIfs wIfh orgnnIc ncIds nro usod ns drIors In nInfs nnd vnrnIshos.
(ti) Tho rndIo-ncfIvo Isofoo Co-60 Is n sfrong -rndInfIon omIffor. CobnIf-60 cnsuIos nro
usod fo kIII cnncor fIssuos by rndInfIon.
Uranium (U)
!rnnIum Is nof obfnInod In froo sfnfo In nnfuro. If occurs In fho form of comounds. Tho
Imorfnnf oros of urnnIum nro:
(i) IIfchbIondo (urnnIfo!
3
O
8
) (ii) CnrnoIIfoK
2
O.2!O
3
.V
2
O
5
.3H
2
O.
METALLURGY 325
!rnnIum Is oxfrncfod from IfchbIondo nnd n fIow dIngrnm for fho oxfrncfIon of urnnIum
Is shown boIow:
Ore
Crushing
and grinding
Leaching with 1:1
H SO in the presence of MnO
2 4 2
Filtration
Boiled with excess
of Na .CO solution
2 3
Filtration
Residue
Iron hydroxide
Aluminium hydroxide
Filtrate
Filtrate
Residue
BaSO ,
RaSO ,
PbSO ,
SiO etc.
4
4
4
2
Filtration Residue
PbS
CuS
UO Cl
2 2
Na [UO (CO ) ]
4 2 3 3
HCl H S
2
Filtrate
UO Cl
2 2
Filtration
NH OH
4
Filtrate
(NH ) U O
4 2 2 7
Residue
Ignited U O
3 8
Carbon reduction Metallic U
\ses
(i) Ifs rIncInI uso Is ns nfomIc fuoI In nucIonr roncfors. !
235
roIonsos 200 moV or
fIssIon wIfh noufrons.
!
235
+
0
l
n = In
l40
+ Kr
92
+ 200 moV.
(ii) In cornmIcs urnnIum comounds nro somofImos usod fo form coIourod gInssos (yoIIow
or ornngo).
(iii) !rnnIum sfooIs nro nIso Imorfnnf fochnIcnIIy.
Zirconium (Zr)
Occurrence
Tho mnIn oros of zIrconIum nro:
(i) ZirconZr SiO
4
(ii) BoJJele,iIe (ZrO
2
)
Tho oros nro found In fho !SA, IrnzII nnd AusfrnIIn. ZIrconIum nIso occurs In nIIuvInI
snnds of KornIn nnd SrI !nnkn.
xtvuctIon
(i) ZIrconIum Is roducod commorcInIIy by KroII rocoss. (Soo oxfrncfIon of TIfnnIum.)
(ii) Von Arlel-Je Boer proceee. In fhIs rocoss, crudo zIrconIum Is honfod wIfh n IIffIo
IodIno undor vncuum nf 200 C whon ZrI
4
voInfIIIzos. A fungsfon or ZIrconIum fIIn-
monf Is honfod fo l300 C In fho snmo vossoI. ThIs fIInmonf docomosos ZrI
4
fo uro
Zr whIch Is doosIfod on fho fIInmonf.
ZrI
4
= Zr + 2I
2
PvopevtIes
ZIrconIum Is n Iusfrous, sIIvory mofnI wIfh m.. l85? C. ZIrconIum Is n good conducfor of
honf nnd oIocfrIcIfy. Tho frncos of ImurIfIos IIko O, nnd C mnko fho mofnI brIffIo.
CIenicol. If honfod fo hIgh fomornfuros, zIrconIum roncfs dIrocfIy wIfh mosf non-mofnIs
tic., O
2
, H
2
; whon fInoIy dIvIdod, fho mofnI Is yrohorIc. So, cnro shouId bo fnkon durIng
mnchInIng nnd fho roducfIon wnsfo chIs shouId bo nvoIdod. osIfo fhIs Inhoronf roncfIvIfy,
fho mofnI hns gof oufsfnndIng rosIsfnnco fo corrosIon, whIch Is duo fo fho formnfIon of n donso,
soIf-honfIng oxIdo fIIm ovor fho mofnI surfnco. WIfh fho oxcofIon of HI, ofhor mInornI ncIds
roncf nf oIovnfod fomornfuros wIfh fho mofnI. Tho mosf Imorfnnf oxIdnfIon sfnfo of fho mofnI
Is +4.
\ses
(i) ZIrconIum hns n hIgh corrosIon rosIsfnnco nnd If Is somofImos rofornbIo fo sfnInIoss
sfooI In corfnIn chomIcnI Innfs.
(ii) If Is usod In n vnrIofy of nIIoy sfooIs; n nofnbIo suorconducfIng nIIoy Is wIfh nIobIum
whIch rofnIns Ifs suorconducfIvIfy ovon In sfrong mngnofIc fIoIds.
(iii) Tho smnII orconfngo of hnfnIum (Hf), whIch Is nImosf nIwnys rosonf wIfh zIrconIum,
Is nof dofrImonfnI nf nII nnd mny ovon Imrovo fho roorfy of Zr. ZIrconIum`s mnjor
uso Is ns n cInddIng for urnnIum dIoxIdo fuoI rods In wnfor-cooIod nucIonr roncfors for
Ifs Iow nbsorfIon of 'ThormnI` noufrons. Horo fho rosonco of Hf Is dIsndvnnfngoous,
ns Hf Is n oworfuI nbsorbor of 'ThormnI noufrons`. So Hf confonf of Zr Is roducod fo
Ioss fhnn l00 m.
EXERCISES
1. ofIno mofnI nnd monfIon somo of Ifs chnrncforIsfIcs.
2. Whnf do you monn by mofnIIIc bonds IxInIn oIocfrIcnI conducfIvIfy of mofnI In fho IIghf of
mofnIIIc bonds.
3. Whnf do you monn by mInornIs nnd gnnguo CIvo roInfIons bofwoon fhom.
4. IsfInguIsh bofwoon oros nnd mInornIs.
METALLURGY 327
5. Whnf do you monn by fho sfudy of mofnIIurgy
6. Whnf Is fho conconfrnfIon of oro
?. WrIfo down fho dIfforonf sfos InvoIvod In fho oxfrncfIon of mofnIs from corrosondIng oros.
B. WrIfo shorf nofos on:
(i) CrushIng nnd CrIndIng
(ii) OII fIonfnfIon rocoss
(iii) CnIcInnfIon
(it) !onsfIng
9. IrIofIy dIscuss fho sfngos InvoIvod In conconfrnfIon of oros.
10. Whnf Is fIux Sfnfo fho fncfors on whIch fho soIocfIon of fIux Is bnsod.
11. oscrIbo dIfforonf fyos of furnncos wIfh fhoIr usos In mofnIIurgy.
(i) SmoIfIng
(ii) WoIdIng
13. Whnf Is nn nIIoy WrIfo (o) fho Imorfnnco of ronrnfIon of nn nIIoy (I) gonornI mofhods of
ronrnfIon of nIIoys. CIvo fho comosIfIon nnd usos of fho foIIowIng nIIoys:
(i) MIId sfooI
(ii) SfnInIoss sfooI
(iii) Mnngnnoso sfooI
(it) urnIumIn
(t) AInIco
(ti) Wroughf Iron
(tii) MngnoIIum
(tiii) Irnss
(ix) Ironzo
(x) SoIdor
14. Whnf Is comonfnfIon
15. CIvo gonornI mofhod of oxfrncfIon of mofnIs from fhoIr oros.
16. WrIfo nofos on:
(i) IyromofnIIurgy
(ii) HydromofnIIurgy
(iii) CoIdschmIdf fhormIf rocoss
(it) IIocfro-rofInIng
(t) Zono rofInIng
1?. IrIofIy doscrIbo fho mofhods InvoIvod In urIfIcnfIon of mofnIs oxfrncfod.
1B. WrIfo n shorf rovIow on owdor mofnIIurgy.
19. MonfIon four ndvnnfngos of owdor mofnIIurgy.
20. Iscuss fho vnrIous sfos InvoIvod In owdor mofnIIurgy nnd monfIon Ifs nIIcnfIon.
21. (o) How Is mofnI owdor ronrod oscrIbo nny fwo nIIcnfIons of owdor mofnIIurgy.
(I) Whnf Is sInforIng In owdor mofnIIurgy
22. (o) Sfnfo fho oIocfronIc confIgurnfIon of fIfnnIum. IndIcnfo Ifs osIfIon In fho orIodIc fnbIo.
(I) oscrIbo fho oxfrncfIon rocoduro of fIfnnIum from Ifs oro.
(c) CIvo somo usos of fIfnnIum.
23. (o) How Is chromIum oxfrncfod from Cr
2
O
3
(I) CIvo somo usos of chromIum.

24. WrIfo nofos on:
(i) IckoI
(ii) Mnngnnoso
(iii) CobnIf
25. (o) WrIfo down somo of fho oros of urnnIum wIfh chomIcnI formuIn.
(I) WIfh n nof fIow chnrf rorosonf fho rocoss of urnnIum mofnI oxfrncfIon.
(c) Sfnfo somo usos of urnnIum.
26. CIvo nn nccounf of zIrconIum wIfh socInI roforonco fo Ifs Imorfnnf oros nnd ono mofhod of
oxfrncfIon.
#
)@DAIELAI
Adhesives
AdhosIvo Is dofInod ns n mnforInI fhnf Is cnnbIo of joInIng bodIos fogofhor by surfnco ndhosIon
nnd InfornnI sfrongfh wIfhouf fho sfrucfuros of fho bodIos undorgoIng nny chnngos. Tho rocoss
of fhIs ndhosIon Is cnIIod bondIng nnd fho bodIos nro cnIIod udLevends.
Bonding has severaI advantages
l. Tho common fonfuro of nII ndhosIvo joInfs Is fho hIghIy unIform dIsfrIbufIon of forcos
ovor fho onfIro joInf nron nnd froo from nny rosIdunI sfrossos whIch Ionds fo ofImnI
ufIIIznfIon of mnforInI sfrongfh comnrod fo rIvof nnd scrow joInfs.
2. AdhosIvos nro cnnbIo of joInIng numorous mnforInIs whIch cnnnof bo joInod by ofhor
fochnIquos ovon fhoso dIfforIng wIdoIy In fyo such ns gInss nnd mofnI, mofnI nnd
InsfIc ofc.
3. Tho rocoss of ndhosIon cnn bo cnrrIod ouf vory rnfIonnIIy, quIckIy nnd oconomIcnIIy.
4. Mnny ndhosIvos cnn bo nIIod nf room fomornfuro honco fho ndhoronds nro nof
oxosod fo hIgh fomornfuro ns In fho woIdIng of InsfIcs wIfh mofnIs.
5. Tho nffor-fInIshIng rocoss In cnso of bondIng Is nof roquIrod ns In fho cnso of woId-
Ing, soIdorIng ofc.
6. Somo ndhosIvos sof ovon In roInfIvoIy fhIck Inyors, so nny unovonnoss of fho ndhoronds
cnn bo smoofhod ouf durIng bondIng.
?. IondIng of dIssImIInr mofnIs wIfh ndhosIvos rovonfs gnIvnnIc corrosIon ns fho mofnI
fo mofnI confncf Is nvoIdod.
8. Tho ndhosIvo Inyor of nn ndhosIvo joInf cnn hnvo n vIbrnfIon-dnmonIng offocf.
9. AdhosIvos cnn Infroduco oIocfrIcnI nnd honf InsuInfIng Inyors bofwoon fho ndhoronds.
l0. Ioffor comosIfo mnforInIs hnvIng Imrovod roorfIos fhnn fho ndhoronds cnn bo
dosIgnod by fho ndhosIvo bondIng e.g., mofnI-fncod Iywood.
ll. AdhosIvo bondIng cnn bo ufIIIsod fo mnko fho mnforInI Ionk-roof for IIquIds nnd
gnsos.
Limitation and Restrictions of Adhesive Bonding
l. Tho usnbIIIfy of ndhosIvos cnn bo rosfrIcfod whon sfrIngonf roquIromonfs nro Imosod
on fho fhormnI sfnbIIIfy on ndhosIvo oInf.
2. AdhosIvos bnsod on orgnnIc oIymors show n doondonco on fomornfuro In fhoIr
sfrongfh, roorfIos nnd fhoIr bond sfrongfh docronsos wIfh rIso In fomornfuro.
329
3. Somo ndhosIvos whon subjocfod fo honvy sfnfIc sfross for Iong orIods show n fon-
doncy fo croo ovon nf room fomornfuro.
4. AdhosIvos nro gonornIIy suscofIbIo fo hIghor humIdIfIos.
5. IondIng sfrongfh Is Iow comnrod fo ofhor joInIng mofhods IIko rIvoffIng, woIdIng
ofc.
6. Thoro Is nof nvnIInbIo nny sIngIo ndhosIvo for joInIng nII fyos of mnforInIs nnd honco
judIcInI soIocfIon Is of gronf Imorfnnco In bondIng rocoss.
?. AdhosIvos roquIro nrocInbIo fImo for dovoIoIng fhoIr fuII sfrongfh bondIng for
boffor orformnnco.
Adhesion Theories
SovornI dIfforonf fhoorIos hnvo boon dovoIood fhnf oxInIn fho mochnnIsm of ndhosIon.
MecIonicol IIeor, of oJIeeion Is bnsod on fho nnchorngo of fho ndhosIvo In fho orous
rough surfnco of fho ndhoronds nnd hoId fho surfnco by InforIockIng ncfIon.
1lecIroeIoIic IIeor, oxInIns fhnf by confncf of fho ndhorond nnd fho ndhosIvo, frnnsfor
ofonfInIs nro buIId u whIch sofs u nn oIocfrIcnI doubIo Inyor nnd fho corrosondIng couIombIc
nffrncfIon forcos dovoIo bofwoon fho fwo comononfs.
AJeorpIion IIeor, rognrds ndhosIon ns ossonfInIIy n socInI roorfy of hnso Inforfncos.
Tho forcos fhnf nro rosonsIbIo for ndhosIon nro fho so cnIIod socondnry vnIonco or vnn dor
WnnI`s forcos.
Diffueion IIeor, oxInIns fhnf ndhosIon Is obfnInod by fho mufunI onofrnfIon of ndhosIvo
nnd subsfrnfo. ono of fho nbovo fhoorIos oxInIn nII fho nsocfs of bondIng. !nfosf fhoorIos
consIdor fhnf bondIng of ndhorond nnd ndhosIvos fnkos Inco duo fo fho chomIcnI or hysIcnI
forcos of nffrncfIon. Iy woffIng fho surfnco of fho ndhorond wIfh fho ndhosIvo, confncf In
moIocuInr dImonsIons fnkos Inco; whon fho InforfncInI boundnry onorgy Is Iowor fhnn fho
sum of fho surfnco onorgIos of fho ndhosIvo nnd fho ndhorond, ormnnonf ndhosIon occurs.
Adhesive Strength DeveIopment
l. B, cIenicol reocIion. Tho roncfIvo Iow moIocuInr wf. mono nnd/or oIIgomorIc
IngrodIonfs of fhormosoffIng ndhosIvos nro convorfod by chomIcnI roncfIon Info hIgh moI. wf.,
crossIInkod fhroo-dImonsIonnI oIymors wIfh hIgh bond sfrongfh.
2. B, eoltenI etoporoIion. Tho ndhosIvo Is dIssoIvod or dIsorsod In n soIvonf nnd nIIod
fo fho surfncos fo bo bondod nnd fhoy nro broughf In confncf wIfh onch ofhor. Tho soIvonf gofs
ovnornfod nnd fhoroby goIIIng nnd fInnIIy hnrdonIng fnkos Inco IondIng fo sfrong bondIng
bofwoon fho surfncos.
3. B, preeeure opplicoIion. Tncky subsfnncos In soIvonf-froo form ndhoro sonfnnoousIy
fo fho surfncos of mosf mnforInIs, onIy undor rossuro.
4. B, cooling. ThormoInsfIc mnforInIs nro nIIod fo fho ndhorond surfncos In n moIfon
nnd hof condIfIon whIch on cooIIng soIIdIfIos dovoIoIng bondIng sfrongfh.
Physical factors influencing adhesive strength:
l. SnooIIneee of IIe oJIerenJ eurfocee. Ior wood surfncos smoofhnoss of fho surfncos
ndds fo fho bondIng sfrongfh of ndhosIvos. In fho cnso of ofhor orous mnforInIs IIko nor,
Ionfhor ofc., fho Inrgo numbor of cnIIInrIos roforonfInIIy oncIoso fho IIquId orfIon of fho
ndhosIvo nnd dIsfurb fho oquIIIbrIum dIsfrIbufIon of fho ndhosIvo on fho ndhorond surfnco
IondIng fo wonk joInf formnfIon.
2. Surfoce Ieneion. Tho woffIng chnrncforIsfIcs of nn ndhosIvo doond on Ifs (o) vIscosIfy
nnd (I) surfnco fonsIon. Tho bondIng bofwoon fho surfncos Is boffor whon fho surfncos cnn bo
ADHESVES 331
unIformIy woffod by fho ndhosIvo soI whIch Is guIdod by fho InforfncInI fonsIon bofwoon fho
fwo. Whon fhIs fonsIon bocomos mInImum, fho surfnco Is boffor woffod.
3. TIiclneee of IIe oJIeeite filn. Vory vIscous ndhosIvos roduco fhIck fIIm buf do nof
wof fho surfncos roorIy IonvIng mnny voIds nnd honco fho bondIng bocomos wonk. ThIs bond
sfrongfh cnn bo Imrovod by nIyIng rossuro. Tho bondIng sfrongfh cnn nIso bo Incronsod by
nddIng soIvonf nnd/or InsfIcIzor fo docronso fho vIscosIfy.
4. PI,eicol cIorocIere of IIe oJIeeite filn. Tho bondIng sfrongfh of fho ndhosIvo fIIm Is
InfIuoncod by fho foIIowIng hysIcnI chnrncforIsfIcs of fho fIIm.
(o) TonsIIo sfrongfh, shonr sfrongfh nnd comrossIvo sfrongfh of fho fIIm: Thoso fhroo
chnrncforIsfIcs InfIuonco fho bondIng sfrongfh In n osIfIvo wny.
(I) Croo rnfoHIghIy InsfIcIzod ndhosIvos hnvo hIghor croo rnfos undor sfross con-
dIfIons fhnn fho rIgId fhormosoffIng mnforInIs. Croo rnfo undor sfrossod condIfIon
shouId bo Iowor for boffor ndhosIvos.
(c) Ifforonco In fhormnI cooffIcIonfs of oxnnsIon of ndhoronds nnd ndhosIvoWhon
fhIs dIfforonco Is hIgh fho bondIng sfrongfh wonkons undor fomornfuro vnrInfIons.
Subsfnnco cnn bo nddod fo fho ndhosIvo fo nIfor fho fhormnI cooffIcIonf of oxnnsIon
fo mnfch wIfh fhnf of fho ndhorond nnd honco IncronsIng fho bond sfrongfh.
5. ApplicoIion noJee of oJIeeitee. Tho modo of nIIcnfIon of ndhosIvo on fho surfnco fo
bo joInod nIso InfIuoncos fho bondIng sfrongfh. Irossuro, fomornfuro nnd fImo nro fho fncfors
fhnf nffocf fhIs sfrongfh nffor fho nIIcnfIon of fho ndhosIvo. SuffIcIonf fImo Is fo bo nIIowod
so fhnf fho curIng fImo bo onough fo osfnbIIsh n sfrong bondIng. SImIInrIy, fomornfuro nIso
nffocfs fho rocoss of bondIng by nIIowIng fho soIvonf fo ovnornfo. !oss rossuro Is roquIrod
In cnso fho ndhorond surfncos nro smoofh buf In fho cnso of orous surfncos, rossuro shouId bo
nIIod fo joIn fho surfncos fogofhor.
ChemicaI Factors Affecting the Adhesive Strength
l. Degree of pol,nericoIion. Iond sfrongfh of fho ndhosIvo Is nffocfod by fho oxfonf of
oIymorIznfIon of fho monomors. ogroo of oIymorIznfIon bosf suIfod for ndhosIvo ncfIon Is
dIfforonf for dIfforonf ndhosIvos e.g., for coIIuIoso dorIvnfIvos nrfInIIy dogrndod Iow moIocuInr
woIghf roducfs gIvo hIghor ndhosIvo ncfIon.
2. PoloriI, of oJIeeitee. Ior orgnnIc confncfIng surfncos oInr-grou confnInIng ndhosIvos
rovIdo boffor bond sfrongfh fhnn non-oInr ndhosIvos. Thus, nddIfIon of oInr moIocuIos fo
fho non-oInr ndhosIvos Incronsos fho ndhosIvo owor.
3. ConplexiI, of IIe oJIeeite nolecule. ComIoxIfy nnd chnIn Iongfh InfIuonco fho
ndhosIvo ncfIon. In fho cnso of honoI-nIdohydo rosIn fho hIghor moI. wf. roducfs hnvo gronfor
ndhosIvo ncfIon. SImIInrIy, In fho cnso of coIIuIoso osfors fho ofImum chnIn Iongfh of fnffy
ncId Is from 6 fo l4 for boffor bond sfrongfh.
4. pH. Sfrong ncIds nnd sfrong nIknIIos nffocf fho bond sfrongfh of ndhosIvos nognfIvoIy.
Iuf fho offocfs of H nro dIfforonf In fho cnso of dIfforonf fyo of ndhosIvos, e.g., sIIghfIy nIknIIno
H gIvos boffor bond sfrongfh In fho cnso of CIuo whIch nro rofoIn In nnfuro, whorons ncIdIc
H Incronsos fho bond sfrongfh of vuIcnnIzod rubbor.
Technique of Bonding
Ifforonf fyo of ndhorond surfncos, dIfforonf fyo of ndhosIvos, dIfforIng bondIng
rocossos gIvo rIso fo dIfforonf fyos of bondIng. Thoro nro corfnIn gonornI sfos InvoIvod In
common bondIng rocossos.
Cleaning and Pretreatment of Adherend Surfaces
!nyors of gronso, oII nnd IubrIcnnf nro romovod by soIvonf wnshIng or ImmorsIon In ncId
or nIknII bnfh or oIocfroIyfIc mofhods.
!ooso dIrf nnd oxIdo Inyors cnn bo romovod by brushIng. Vory unovon surfncos nnd
ofhors nro rubbod wIfh omory nor or snnd bInsfod fo romovo fIrmIy nnchorod Inyors fhnf
mny Inforforo wIfh fho bondIng rocoss. Ior corfnIn InsfIcs, rofronfmonf rocossos nro usod
fo Incronso fho nffInIfy for bondIng.
Ior mofnIs, ncIdIc IckIIng bnfhs nro usod fo romovo Iow cohosIvo sfrongfh mnforInIs.
Ior InsfIcs whIch nro dIffIcuIf fo bond, surfncos nro modIfIod by chomIcnI fronfmonf fo
Incronso fho surfnco fonsIon nnd woffnbIIIfy. SomofImos rossuro nnd fomornfuro nro nIso
usod for fhoso InsfIcs.
Ior woodon surfncos, fho ndhorond surfncos nro mnchInod fo brIng smoofhnoss for boffor
bond sfrongfh.
Adhesive Application
AdhosIvos nro dIssoIvod In roor soIvonfs. SoIId ndhosIvos nro moIfod, vory vIscous
ndhosIvos nro fhInnod wIfh soIvonf, InsfIcIzors, cnfnIysfs, hnrdnors ofc. nddod In roor
roorfIon.
!nIform nddIfIon of cnIcuInfod qunnfIfy of ndhosIvo Is roquIrod for roor bondIng
sfrongfh, so fho mofhod of nIIcnfIon Is vory Imorfnnf. ovoIoIng on fho sIzo nnd nnfuro of
fho surfnco nnd rhooIogIc roorfIos of fho ndhosIvo, dIfforonf mofhods of nIIcnfIon nro usod
ns foIIows:
(o) Iy mnnunI nIIcnfIon wIfh brushos, cnsf-
Ing knIvos, snfuIns, bIndos ofc.
(I) ThIn-fIowIng srnynbIo ndhosIvos nro dIs-
frIbufod unIformIy ovor Inrgo nrons wIfh
srny guns (IIg. l5.l).
(c) Iy roIIors.
(J) HIghIy vIscous ndhosIvos nIIod ns conf-
Ings.
(e) ry ndhosIvos nro InId ns fIIm or shoof.
( f ) Ior chomIcnIIy roncfIvo sysfoms, ono
comononf Is fho fhormosoffIng rosIn,
whIch Is nIIod fo ono surfnco nnd fho
ofhor boIng fho cnfnIysf nIIod fo fho ofhor
surfnco fo bo bondod.
( g) Ior ImmodInfoIy roncfIng nnd hnrdonIng
ndhosIvos, fho comononfs nro nIIod fo
fho ndhorond surfncos ImmodInfoIy boforo
joInIng by doubIo srny.
(I) CynnoncryInfo ndhosIvos nnd nnnorobIc roncfIvo ndhosIvos nro nIIod by monns of
socInI moforIng unIfs fhnf doIIvors smnII moforod qunnfIfIos nf socIfIod fImo
InforvnIs.
a
c
b
Fig. 15.1 Adhesive application by means
of a spray gun (a) Adhesive (b) Com-
pressed air (c) Atomized adhesive.
ADHESVES 333
Joining, Fixing of Adherends
IoIIowIng nIIcnfIon of ndhosIvos, fho ndhoronds nro joInod by dIfforonf mofhods whIch
vnry wIfh fho fyo of ndhosIvo nIIod nnd fho surfncos fo bo joInod.
(o) Ior ImmodInfoIy dryIng fyo of ndhosIvos fho ndhoronds nro hoId cIoso fo onch ofhor
ImmodInfoIy comIofIng fho nssombIy.
(I) AdhosIvos or rubbor soIufIons In orgnnIc soIvonfs roquIro Iongor orIod for nIr-dry-
Ing. Thus fo nIIow fho fImo for ovnornfIon of fho soIvonf nnd fnckInoss fo dovoIo
fho nssombIy Is fo bo kof for n Iong orIod.
(c) Ior bondIng of fho mofnI surfncos, fho nssombIy of fho ndhorond mofnI surfncos Is
roquIrod fo bo honfod In nn ovon whIch Is cnIIod 'ro-curIng`.
(J) Ior chomIcnIIy roncfIng ndhosIvos fho ndhorond surfncos nro kof In confncf nnd fho
joInf Is nIIowod fo romnIn for fho roquIrod orIod fo nIIow fho chomIcnI roncfIon fo bo
comIofo fo obfnIn hIgh bond sfrongfh.
Drying and Hardening
Affor nssombIIng fho ndhosIvo-nIIod ndhorond surfncos somo rossuro Is fo bo nIIod
fo onsuro fho unIform dIsfrIbufIon of fho ndhosIvo on fho whoIo surfnco nnd nIso fo koo fho
whoIo surfnco In cIoso confncf for fho nrorInfo fImo fo dovoIo hIghosf bond sfrongfh.
(o) Ior sIow roncfIng nnd soffIng ndhosIvos fho fImo of nIIcnfIon of rossuro Is Iongor
fo onsuro comIofIon of fho chomIcnI roncfIon or comIofo ovnornfIon of fho soIvonf fo dovoIo
bond sfrongfh.
(I) Ior rossuro sonsIfIvo ndhosIvos, fho nIIod rossuro Is fo bo roIonsod ImmodInfoIy
nffor fho bondIng. Tho nocossnry rossuro Is gonornIIy nIIod by usIng rossos, rossuro roIIs.
SImIInrIy, honf fronfmonf Is nIso nocossnry for soIocfIvo ndhosIvos.
Ior wnrm-soffIng ndhosIvos honfIng Is roquIrod for n socIfIod orIod.
IoIycondonsnfIon ndhosIvos musf bo honfod wIfh fho nIIcnfIon of oxfornnI rossuro
hIghor fhnn fho vnour rossuro of fho cIonvngo roducfs formod durIng condonsnfIon. Ior
moIfon ndhosIvo, cooIIng undor rossuro Is roquIrod. Tho honf roquIrod for fho hnrdonIng
rocossos nro suIIod by rocIrcuInfIng-nIr ovons, dryIng cnbInofs, rndInnf honfors, honfIng-
rossos ofc.
CIassification of Adhesives
AdhosIvos mny bo cInssIfIod on fho bnsIs of chomIcnI nnfuro, soffIng mochnnIsms, ndhosIon
mochnnIsm ofc. Horo wo cInssIfy fhom on fho bnsIs of fhoIr chomIcnI nnfuro:
l. TIernoeeIIing e,nIIeIic reeine. ThIs cInss hns hIgh ndhosIvo roorfIos by formIng n
nofwork of fhroo dImonsIonnI cross-IInkod sfrucfuros. Tho bondIng of fhoso nro moIsfuro, honf
nnd fungI roof. Somo mombors of fhIs cInss nro:
(o) PIenol-fornolJeI,Je reeine. ThIs Is n rossuro sonsIfIvo fyo of ndhosIvo. Tho
ndhorond surfncos nffor boIng confod wIfh fhIs ndhosIvo Is subjocfod fo curIng by
honf nnd rossuro.
\se: ThIs Is nvnIInbIo ns soIId, IIquId or Imrognnfod fIIm nnd usod for bondIng wood
nnd mofnI.
(I) Ireo-fornolJeI,Je reein. If Is n frnnsnronf, syruy comound, usod In fho form of
nquoous soIufIon or srny drIod owdors, gonornIIy wIfh ncId hnrdnoss fo Imrovo
roncfIvIfy for bondIng. AddIfIon of wnfor fo fhIs rosIn hoIs In formIng confInuous
fIIm wIfh cross IInkngos nnd wIfh rnId soffIng roorfIos. Though fhIs ndhosIvo
forms bond whIch Is rosIsfnnf fo fomornfuro, moIsfuro ofc., If doforIornfos by ncIds
nnd nIknIIos.
\ses. IondIng wood, nrfIcuInrIy fo roduco Iywood nnd chIbonrd, InmInnfos, for
nIrcrnff nnd In shI IndusfrIos. ModIfIod uron rosIns nro Imorfnnf for InboIIng ndhosIvos.
(c) Pol,eeIere. !nsnfurnfod oIyosfors dIssoIvod In sfyrono or mofhncryInfos nro usod ns
roncfIvo ndhosIvos. Thoy ossoss good moIsfuro rosIsfnnco buf Iow honf rosIsfnnco.
\ses. !sod for mnkIng InmInnfod gInss nnd cIofh.
(J) 1pox, reeine. Ioxy comounds nro nvnIInbIo bofh In IIquId nnd soIId forms. !sunIIy
fhoy nro usod In combInnfIon wIfh nmInos, dIcnrboxyIIc ncId nnhydrIdos ofc. Ioxy
rosIns nro nIso combInod wIfh honoIIc rosIns nnd oIy vInyI ncofnfo rosIns nnd usod
ns ndhosIon romofors. Tho fhIn fIIm of ooxy rosIn romnInIng nffor fho ovnornfIon
of fho soIvonf ncfs ns good ndhosIvo hnvIng good chomIcnI nnd oIocfrIcnI rosIsfnnco.
If cnn nIso bo curod wIfhouf fho nIIcnfIon of honf. On froquonf confncf wIfh skIn
IIquId ooxy rosIn cnusos IrrIfnfIon nnd nIIorgIos.
\ses. !sod for bondIng mofnI In nIrcrnff Indusfry nnd nIso for sIIIcnfo confnInIng
mnforInIs nnd InsfIcs. ArnIdIfo whIch Is nvnIInbIo In fho mnrkof comos undor fhIs cInss of rosIn.
(e) Silicon reeine. Thoy sof undor fho offocf of nfmoshorIc moIsfuro, rosIsfnnf fo fom-
ornfuro, fungI, Insocfs nnd chomIcnIs.
\ses. Ior bondIng of sIIIcnfo confnInIng mnforInIs, InsfIcs, rubbors, mofnIs ofc.
2. TIernoploeIic e,nIIeIic reeine.
(o) Celluloee JeritoIitee. CoIIuIoso nIfrnfo Is usod ns n rnw mnforInI for soIvonf ndho-
sIvos. CoIIuIoso nIfrnfo mIxod wIfh nIcohoI Is woII known ns 'coIIodIon`. Tho ndhosIvo
fIIm dovoIood by coIIuIoso nIfrnfo Is rosIsfnnf fo wnfor buf nffocfod by sfrong ncIds
nnd nIknIIos nnd ngIng. If Is InfInmmnbIo nnd In roconf yonrs If Is roIncod by ofhors.
\ses. As muIfIuroso ndhosIvo, shoo ndhosIvo.
Celluloee eIIere onJ celluloee eeIere. CoIIuIoso ncofnfo hns Ioss ndhosIvo sfrongfh fhnn
coIIuIoso nIfrnfo buf If Is moro rosIsfnnf fo honf.
IfhyI coIIuIoso/mofhyI coIIuIoso nro usod ns nquoous soIufIon wIfh InsfIcIzors, modIfIors.
Tho fIIm Is moIsfuro rosIsfnnf buf InfInmmnbIo.
\ses. Ior wnII nor nsfo nnd nIso ns fhIckonor.
(I) Acr,lice. IoIyncryInfos nro usod bofh In fho form of soIufIons nnd In fho form of
synfhofIc rosIn omuIsIons nnd nro Imorfnnf rnw mnforInIs for rossuro sonsIfIvo
ndhosIvos. CooIymors of vnrIous osfors (oIymofhyI, oIyofhyI, oIybufyI-ncryInfo)
confnIn funcfIonnI grous IIko H
2
, COOH, OH ofc., whIch nro ufIIIzod for cross-
IInkIng nnd form boffor ndhosIvos. Thoy nro sfnbIo fo nII condIfIons buf cosfIy.
\ses. Ior bondIng of nor, gInss, Ionfhor ofc.
(c) Pol,tin,le. IoIyvInyI ncofnfo, oIyvInyI chIorIdo, oIyvInyI roIonnfo form hnrd fIIms
rosIsfnnf fo nfmoshorIc condIfIons nnd chomIcnIs. IoIyvInyI ncofnfo In combInnfIon
wIfh honoIIc rosIns forms socInI ndhosIvos.
\ses. Ior bondIng of gInss, mofnIs ofc. smoofh surfncos nnd nIso In sonIIng of food
mnforInIs.
ADHESVES 335
3. AoIurol reein oJIeeitee.
(o) SIellocHof shoIInc soI Is nn oIdosf known ndhosIvo, whIch Is hnrd.
\se. Ior mnkIng convoyor boIfs.
(I) AepIolI!sod for bondIng mofnI, nor ofc.
4. SIorcI onJ JexIrin oJIeeitee. Tho rnw mnforInIs usod for vnrIous fyos of sfnrch nnd
doxfrIn bnsod ndhosIvos nro ofnfo sfnrch, corn sfnrch ofc. A susonsIon of sfnrch Is honfod for
somofImo fo obfnIn fho ndhosIvo whIch Is chon, cnn bo nIIod In coId nnd hof sfnfos buf bond
sfrongfh Is Iow nnd suscofIbIo fo moIsfuro.
\ses. Ior mnkIng onvoIoos, sfnms, books ofc.
5. VegeIoIle glue. Thoso rofoIn gIuos nro obfnInod from soynbonn, corn, cnsoIn, nIbumIn
ofc. Tho oIIy or fho fnffy mnffor Is oxfrncfod or rocIIfnfod from soynbonn or mIIk nnd fhon
fho rofoIn Is fronfod wIfh IImo nnd fho wnfor soIufIon form n joIIy-IIko ndhosIvo. Thoy nro
vory chon buf of oor bond sfrongfh.
\ses. SImIInr fo sfnrch ndhosIvo.
6. Aninol glue. AnImnI wnsfos obfnInod from sInughforhousos ofc. nnd hIdo scrns from
Ionfhor IndusfrIos nro dogronsod wIfh soIvonf, fronfod wIfh IImo. Tho roducf obfnInod Is
hydroIysod wIfh hof wnfor fo form IIquId gIuo. ThIs Is bIonchod nnd mIxod wIfh rosorvnfIvos
nnd conconfrnfod fo form soIId gIuo. Tho soIId cnko or owdor Is boIIod wIfh wnfor fo form fho
ndhosIvo soIufIon. Tho bondIng sfrongfh of fho ndhosIvo Is hIgh buf suscofIbIo fo honf nnd
moIsfuro.
\ses. Ior mnnufncfurIng cnrdbonrd boxos nnd furnIfuros.
?. 1norgonic oJIeeitee. SodIum sIIIcnfo nIongwIfh IIfhnrgo (Iond monoxIdo) nnd MnO
2
ofc. forms goI whon susondod In wnfor. ThIs goI hns ndhosIvo roorfIos. Tho bond Is moIsfuro
nnd hIgh fomornfuro sonsIfIvo buf fungus rosIsfnnf.
\ses. Ior cnrdbonrd boxos mnkIng.
Testing of Adhesives
TosfIng of ndhosIvos mnInIy oncomnssos:
SoIId confonf
!hooIogIc roorfIos
ShoIf IIfo
IInmmnbIIIfy nnd InfInmmnbIIIfy
!Isks InvoIvod In frnnsorf nnd nIIcnfIon
Monsuromonf of fho mochnnIcnI roorfIos IIko fonsIIo sfrongfh, bronkIng oIongnfIon
of fho fIIms or fosf socImons mndo wIfh fho ndhosIvos.
Growth Rates of Different Adhesives
Tho hIghosf growfh rnfo Is oxocfod In nufomofIvo Indusfry, frnnsorf nnd oIocfronIcs.
ConfInuod growfh Is oxocfod In consfrucfIon ndhosIvos, soIvonf froo ndhosIvos whorons
roducfIon In domnnd Is oxocfod for soIvonf confnInIng ndhosIvos nnd nnImnI nnd vogofnbIo
gIuos.
Q. 1. WLut Is un udLesIve?
Ans. AdhosIvo Is dofInod ns n subsfnnco cnnbIo of joInIng bodIos fogofhor by surfnco
nffnchmonfs.
Q. 2. WLut uve tLe dIIIevent tLeovIes tLut expIuIn tLe mecLunIsm oI udLesIon?
Ans. Tho fhoorIos oxInInIng fho mochnnIsm of ndhosIon nro:
(o) MochnnIcnI fhoory (I) IIocfrosfnfIc fhoory
(c) AdsorfIon fhoory (J) IffusIon fhoory
3. MentIon tLe types oI udLesIves used Iov JoInIng
(I) Wooden suvIuces (II) GIuss und cIotL (III) MetuIs
(Iv) Pupevs (v) PIustIcs und vubbevs
Ans. (i) !ron-formnIdohydo nnd honoI-formnIdohydo rosIns nro usod for joInIng woodon
surfncos.
(ii) IoIyosfors dIssoIvod In sfyrono ofc. nro usod for joInIng gInss nnd cIofh.
(iii) Ioxy rosIns nro usod for joInIng mofnIs In nIrcrnff Indusfry.
(it) CoIIuIoso ofhors, osfors nnd nIso ncryIIcs nro usod for bIndIng nor.
(t) SIIIcon rosIns nro usod for bondIng of InsfIcs, rubbor ofc.
EXERCISES
1. Whnf nro ndhosIvos
2. IxInIn fho dIfforonf mochnnIsms of ndhosIvo ncfIon.
3. Iscuss fho hysIcnI nnd chomIcnI fncfors fhnf InfIuonco ndhosIvo ncfIon.
4. WrIfo n brIof nofo on nnfurnI nnd synfhofIc ndhosIvos.
5. MonfIon n fow Imorfnnf ndvnnfngos nnd IImIfnfIons of ndhosIvos.
6. oscrIbo fho dIfforonf sfos of fho bondIng rocossos of ndhosIvos.
?. (i) AdhosIvo ncfIon of n oIymorIc ndhosIvo Is InfIuoncod by
(o) IoInr chnrncfor (I) ogroo of oIymorIznfIon
(c) ComIoxIfy of moIocuIo (J) AII fhoso
(ii) AdhosIvo usod for bondIng mofnIs Is
(o) Ioxy rosIn (I) IoIyosfors
(c) AcryIIcs (J) AII fhoso
(iii) AdhosIvo usod for bondIng Ionfhor for shoos
(o) IhonoI formnIdohydo rosIn (I) AcryIIcs
(c) IoIyvInyIs (J) IoIyosfors
(it) AdhosIvos usod for mnnufncfurIng furnIfuros of wood
(o) !ron-formnIdohydo rosIn (I) IoIyosfors
(c) SIIIcon rosIns
ADHESVES 337
(t) nfurnI ndhosIvo usod for sfnms nnd onvoIos ofc.
(o) ArnIdIfo (I) Sfnrch
(c) IoIyosfors (J) IoIyvInyI
(ti) AdhosIvo usod In nIrcrnff Indusfry Is
(o) Sfnrch (I) AshnIf
(c) ShoIInc (J) ArnIdIfo
(tii) ArnIdIfo Is
(o) AnImnI gIuo (I) CoIIuIoso dorIvnfIvo
(c) ThormosoffIng rosIn (J) IoIyosfor
B. WhIch of fho foIIowIng Is fungus rosIsfnnf
(o) InorgnnIc ndhosIvos (I) VogofnbIo gIuo
(c) AnImnI gIuo (J) Sfnrch ndhosIvos
9. AdhosIvo bondIng cnn bo ufIIIzod fo mnko n mnforInI
(o) !onk roof (I) Honf InsuInfIng
(c) IIocfrIcnIIy InsuInfIng (J) AII fhoso
10. AdhosIvo hnvIng Ionsf bondIng sfrongfh Is
(o) Sfnrch (I) CoIIuIoso dorIvnfIvos
(c) Ioxy rosIn (J) AcryIIcs
338
$
ExpIosives and PropeIIants
ExpIosives
IxIosIvos nro uro subsfnncos or mIxfuros whIch on boIng subjocfod fo socIfIc sfImuIus IIko
mochnnIcnI Imncf, frIcfIonnI forcos, oIocfrIcnI dIschnrgo nnd ofhor sourcos of honf, hIgh rossuro
shock wnvos InIfInfo nn oxIdnfIon roncfIon roducIng Inrgo voIumo of hof gnsos.
Onco InIfInfod, fho honf ovoIvod Is suffIcIonf fo cnuso fho roncfIon fo confInuo nnd bocomo
soIf-susfnInIng. Tho mInImum qunnfIfy of onorgy roquIrod for InIfInfIon hns n chnrncforIsfIc
vnIuo fhnf doonds on fho chomIcnI nnd hysIcnI roorfIos of fho mnforInI.
Tho roncfIons of oxIosIvos nro oxofhormIc. Tho roducfs nf hof nnd hIgh rossuro nnd
whon confInod fo n cIosod snco Iond fo oxIosIon buf If fho roncfIon Is confroIIod nf sIowor rnfo,
fhIs onorgy cnn bo ufIIIzod fo rooI n rojocfIIo. Tho nmounf of owor nvnIInbIo from n gIvon
woIghf of oxIosIvo Is known ns owor fo woIghf rnfIo.
Characteristics of ExpIosives
IoIIowIng nro fho chnrncforIsfIcs roquIrod for nn oxIosIvo.
l. Tho docomosIfIon rnfo of nn oxIosIvo shouId bo vory fnsf nnd Inrgo voIumo of hof
gnsos shouId bo IIbornfod oxofhormnIIy IondIng fo Inrgo Incronso In voIumo.
2. Tho oxIosIvo moIocuIo shouId hnvo n Iow onorgy of dIssocInfIon.
3. Tho oxygon-bnInnco of nn oxIosIvo moIocuIo shouId bo hIghor whIch IndIcnfos fhnf
moro oxygon Is nvnIInbIo In fho moIocuIo fo oxIdIzo C nnd H fo CO
2
nnd H
2
O.
4. Tho oxIosIvo shouId bo sonsIfIvo fownrds socIfIc Imncfs. If shouId oxIodo Immo-
dInfoIy nffor fho nIIcnfIon of fho sfImuIus. Tho Iossor fho sfImuIus roquIrod boffor
Is fho sonsIfIvIfy of fho oxIosIon.
5. IxIosIvos shouId nof bo voInfIIo or hygroscoIc buf shouId bo sfnbIo chomIcnIIy so
fhnf fhoy do nof docomoso on kooIng or roncf wIfh fho sforngo confnInor.
6. !nsfIy, oxIosIvos shouId bo chon.
Uses of ExpIosives
Tho rIncInI non-mIIIfnry uso of oxIosIvos Is In mInIng. In conI mInos, onIy vory snfo
oxIosIvos wIfh Iowosf ossIbIo dofonnfIon fomornfuro nro usod. Thoso oxIosIvos usunIIy
confnIn n Inrgo nmounf of H
4
O
3
nnd nCI. In Indusfry oxIosIvos nro usod for bInsfIng oros
of dIfforonf mofnIs, quuvvyIng IImosfono fo bo usod In rond consfrucfIon, for bInsfIng hoIos In
mounfnIns for funnoIs nnd ronds, dIggIng onrfh, soIsmIc rosocfIng, bInsfIng rocks nnd ofhor
socInI nnd usofuI works.
Tho ofhor mnIn nron Is In mIIIfnry nnd nmmunIfIon for wnr ns woII ns fnckIIng roguInr
socInI robIoms, ns woII ns In fho ronrnfIon of forodos, gronndos, bombs ofc. Anofhor nron Is
In fho InunchIng of rockofs, sncocrnffs ofc.
EXPLOSVES AND PROPELLANTS 339
CIassification of ExpIosives
IxIosIvos nro cInssIfIod undor fhroo brond grous, nnmoIy rImnry, Iow nnd hIgh
oxIosIvos.
(A) Prinor, exploeitee. IrImnry oxIosIvos nro fho mosf sonsIfIvo fo honf, frIcfIon, Imncf,
shock nnd oIocfrosfnfIc onorgy. Thoy shouId bo hnndIod wIfh gronf cnro. Thoy nro usod fo
InIfInfo fho oxIosIon of hIgh oxIosIvos whIch consIsf of oxIosIvos of IncronsIng mnss nnd
docronsIng sonsIfIvIfy. OnIy fow comounds cnn ncf ns rImnry oxIosIvos for mIIIfnry nnd
IndusfrInI roquIromonfs, fhoy nro donso, mofnIIo-orgnnIc comounds. Thoy nro:
l. Mercur, fulninoIe. Morcury fuImInnfo or morcurIc cynnnfo Is n groy-whIfo owdor. If
Is ronrod by mIxIng of soIufIon

of ono nrf of morcury wIfh oIovon nrfs of 5? nIfrIc ncId
nnd ourod Info fon nrfs of 95 ofhyI nIcohoI whon morcury fuImInnfo forms ns fIno crysfnIs
of 99 urIfy. If Is fho mosf sonsIfIvo of InIfInfIng ngonfs fo Imncf nnd frIcfIon. If docomosos
whon sforod nf oIovnfod fomornfuro, roncfs wIfh mofnIs In rosonco of wnfor. If Is sIIghfIy
foxIc nnd Ifs uso Is IImIfod.
2. LeoJ ociJe. Tho nzIdos nro nmong fho vory fow usofuI oxIosIvo comounds fhnf do
nof confnIn oxygon. If Is oxfonsIvoIy usod ns rImnry oxIosIvo In mIIIfnry dofonnfors.
!ond nzIdo Is mndo In smnII bnfchos bufforod by fho roncfIon soIufIons of Iond nIfrnfo or
ncofnfo wIfh hIghIy foxIc sodIum nzIdo.
Ib(O
3
)
2
+ 2n
3
2nO
3
+ Ib
6
ucIonfIng ngonfs IIko oIyvInyI nIcohoI (IVA), sodIum cnrboxy mofhyI coIIuIoso (CMC)
or doxfrIn mny bo nddod durIng rocIIfnfIon fo yIoId froo fIowIng crysfnIs or roundod
nggIomornfos. !ond nzIdo Is Ioss sonsIfIvo fo IgnIfIon fhnn morcury fuImInnfo. Of fho four
oIymorhIc forms ( fo ) fho Is fho mosf common. !ond nzIdo fonds fo hydroIyso nf hIgh
humIdIfy nnd forms hydrnzoIc ncId, whIch roncfs wIfh Cu nnd Ifs nIIoys fo roduco vory sonsIfIvo
curIc nzIdo.
3. LeoJ eI,pInoIe. !ond 2, 4, 6-frInIfro rosorcInnfo Is usod fo sfnrf IgnIfIon rocoss In fho
oxIosIvo soquonco. If Is sfnbIo nnd non-corrosIvo. AddIfIon of grnhIfo Imrovos Ifs oIocfrIcnI
conducfIvIfy In sysfoms usIng oIocfrIcnI InIfInfIon.
4. Dioco JiniIropIenol. If Is nn ornngo-yoIIow comound nnd ronrod from IcrnmIc
ncId |H
2
(O
2
)C
6
H
2
OH], wIfh sodIum nIfrIfo nnd HCI. Tho roducf obfnInod Is wnshod nnd
rocrysfnIIIzod from hof ncofono. If Is non-hygroscoIc nnd sonsIfIvo fo frIcfIon nnd Imncf. If Is
moro offocfIvo fhnn Iond nzIdo nnd Is usod ns nn InIfInfor In commorcInI bInsfIng cns.
5. TeIrocene. If Is nIo-yoIIow crysfnIIIno comound. If Is ronrod by fronfIng l-nmIno-
gunnIdIno hydrogon cnrbonnfo In dIIufo ncofIc ncId wIfh sodIum nIfrnfo. Tho comound Is sfnbIo
ufo ?5C. If hns hIgh oxIosIon onorgy nnd Is usod ns n dofonnfor.
(I) Lou exploeitee or propellonIe. !ow oxIosIvos do nof oxIodo buf burn nnd roduco
Inrgo voIumo of gns nf confroIIod, rodoformInod rnfos. Tho burnIng rocoods from fho surfnco
Inwnrds nf n sIow rnfo. Thoy nro nIIcnbIo whorovor n woII confroIIod forco Is fo bo gonornfod
for n shorf orIod. TyIcnI oxnmIos nro:
l. Blocl pouJer or gun pouJer. If Is n mIxfuro of ?4 ofnssIum nIfrnfo, l5.6 cnrbon
nnd l0.4 suIhur. IInck owdor IgnIfos nnd burns fnsf nnd hns roroducIbIIIfy nnd hIgh honf
fIux. If doforIornfos nf humIdIfy. If cnn bo sforod mnny yonrs If dry. Tho hygroscoIcIfy of If Is
duo fo fho rosonco of cnrbon nnd ImurIfIos In KO
3
. If Is ronrod by InfImnfo mIxIng of fho
fhoroughIy mIIIod owdorod IngrodIonfs. Tho docomosIfIon roncfIon Is
l0KO
3
+ 3S + 8C 2K
2
SO
4
+ 2K
2
CO
3
+ 6CO
2
+ 5
2

ThIs oxcoss cnrbon nnd suIhur undorgo sIowor roducfIon IondIng fo moro gnsoous
roducfs
4K
2
CO
3
+?S K
2
SO
4
+ 2K
2
S
2
+ 4CO
2
4K
2
SO
4
+?C 2K
2
CO
3
+ 2K
2
S
2
+ 5CO
2
ThIs Inrgo voIumo of gnsoous roducfs Is rosonsIbIo for Ifs oxIosIvo ncfIon. If Is usod
for bInsfIng of conI. Ofhor usos IncIudo bInsfIng In shoIIs, IgnIfors nnd rImor nssombIIos for
rooIInnfs ofc.
2. AiIrocelluloee or enoleleee pouJer. If Is ronrod by fronfIng urIfIod coIIuIoso wIfh
mIxod ncId, hnvIng nn nroxImnfo comosIfIon of 63 H
2
SO
4
, 22 HO
3
nnd l5 H
2
O. Whon
nIfrnfIon Is comIofo, fho nIfrocoIIuIoso nnd fho sonf ncId nro confrIfugod. Tho ncId Is sonf fo
mIxIng fnnks for forfIfIcnfIon nnd subsoquonf ro-ufIIIsnfIon. Tho nIfrocoIIuIoso so formod Is
dIssoIvod In nIcohoI nnd ofhor nnd fho soIvonf ovnornfod whon If forms n joIIy-IIko mnss. If Is
sfnbIIIzod by nddIng n sfnbIIIzor IIko dIhonyI nmIno whIch cnn roncf wIfh fho IIbornfod ncId.
ThIs roducf Is sforod ns rossod cyIIndrIcnI rods. If roducos CO, CO
2
,
2
, wnfor vnour nnd
no smoko. So, If Is known ns smokoIoss owdor.
(C) HigI exploeitee. ThIs grou consIsfs of sIx fyos of comounds.
l. Single conpounJ exploeitee. ConsIsf of onIy ono chomIcnI comound such ns:
(i) Annoniun niIroIe. If Is n oworfuI oxIosIvo comound whon onco InIfInfod by nn
oxfornnI dofonnfIon ImuIso of suffIcIonf mngnIfudo nnd In suffIcIonf nmounf. If Is
vory snfo fo hnndIo undor ordInnry condIfIon, sfnbIo nnd chon. If Is rondIIy ronrod
by fho noufrnIIsnfIon of HO
3
wIfh H
3
, fwo unIvorsnIIy nvnIInbIo chon rnw
mnforInIs. If Is usod fo ronro bInnry oxIosIvos. If Is nIso usod ns nn oxIosIvo snIf
fo roInco n orfIon of fho nIfrogIycorIno usod rovIousIy. If cnnnof bo sforod nonr
InfInmmnbIo mnforInIs nnd confncf wIfh nIIoys of coor Is fo bo nvoIdod ns If
dofonnfos.
(ii) Picric ociJ. ChomIcnIIy IcrIc ncId Is frInIfrohonoI. If Is n hIgh oxIosIvo nnd usod ns
soIf-fIIIIng oxIosIvos. If Is InrgoIy roIncod by TT, bocnuso of Ifs objocfIonnbIo
chnrncfor ns If roncfs wIfh mofnIs fo form Icrnfos whIch nro dnngorousIy sonsIfIvo.
(iii) PenIoer,IIriIol IeIroniIroIe (P1TA). If Is obfnInod by fho nIfrnfIon of fho IrroguInr
fofrnhydrIc nIcohoI onfnroyfhrIfoI, whIch In furn Is mndo by condonsnfIon of for-
mnIdohydo wIfh ncofnIdohydo.
C
CH OH
2
CH OH
2
CH OH
2
CH OH
2
C
CH ONO
2 2
CH ONO
2 2
CH ONO
2 2
CH ONO
2 2
+ 4HNO
3
+ 4H
2
O
ThIs oxIosIvo comound hns bocomo Imorfnnf sInco fho IIrsf WorId Wnr ns owor-
fuI mIIIfnry oxIosIvo.
(it) 2, 4, 6, TriniIroIoluene (TAT). ThIs hIgh oxIosIvo Is ronrod by nIfrnfIon of foIuono.
Tho rnw mnforInI foIuono Is dorIvod from conI fnr or synfhofIcnIIy from ofroIoum
roducfs. TT Is wIdoIy usod ns shoII-fIrIng oxIosIvo nnd undor-wnfor oxIosIons.
Iocnuso of Ifs Iow moIfIng oInf (80.8C) If Is suIfod for IondIng In confnInors. Ifs
comnrnfIvo oxcoIIonco hns mndo If usofuI for mIIIfnry consumfIon, In fho nsocfs
IIko (o) boIng snfo oxIosIvo for mnnufncfuro, sforngo nnd frnnsorfnfIon, (I) non-
hygroscoIc, (c) vIoIonf-dIsrufIvo oxIosIvo, nnd (J) non-roncfIvo fownrds mofnIs fo
form unsfnbIo comounds.
(t) CycIofrImofhyIono frInIfronmIno !X or cyIonIfo : ThIs hIghIy oworfuI oxIosIvo
hns bocomo Imorfnnf for mIIIfnry uso ns woII ns IndusfrInI uso sInco WorId Wnr II. Ifs
ndvnnfngos nro Ioss foxIcIfy buf gronfor sonsIfIvIfy fhnn TT.
(ti) TofryI or fofrnnIfromofhyInnIIIno. If Is mndo by nIfrnfIon of dImofhyInnIIIno nnd Ifs
moIfIng oInf Is nround l30C. TofryI hns Imorfnnf uso ns commorcInI oxIosIvo ns n bnso
chnrgo for bInsfIng cns. Iocnuso of Ifs foo much sonsIfIvIfy, If Is usod ns n boosfor chnrgo
InformodInfo bofwoon IgnIfIon chnrgo nnd bursfIng chnrgo for mIIIfnry uso buf nof usod for
mnIn shoII fIrIng.
2. Binor, exploeitee. Thoso nro mIxfuros of TT wIfh ofhor oxIosIvos. TT Is fho mosf
Imorfnnf IngrodIonf duo fo Ifs Iowor moIfIng oInf. IInnry oxIosIvos nro mndo by mIxIng,
honfIng fo IIquIfy nnd ourIng Info confnInors fo soIIdIfy. Tho mosf Imorfnnf onos nro:
(i) AmutoI. If Is nn oxIosIvo mIxfuro of TT wIfh nmmonIum nIfrnfo. TT Is dofIcIonf
In oxygon so fho combusfIon Is IncomIofo. Tho dofonnfIon roducfs cnn undorgo
furfhor combusfIon. Iuf 80:20 mIxfuro of nmmonIum nIfrnfo nnd TT Is nn ovonIy
bnInncod comosIfIon wIfh rosocf fo oxygon wIfh rosuIfIng Incronsod sfrongfh nnd
Imrovod fumos. Tho dIsndvnnfngo comnrod fo TT Is Ifs hygroscoIcIfy. If Is
usod ns bInsfIng chnrgos In Inrgo cnIIbor shoIIs.
(ii) TetvytoI. If Is n mIxfuro of ?0 fofryI nnd 30 TT.
(iii) PentoIIte. If Is n mIxfuro of l:l TT nnd IIT.
(it) Tvopex. If Is n mIxfuro of 40 !X, 40 TT nnd 20 AI owdor.
(t) TItvonuI. If Is n mIxfuro of 80 TT nnd 20 AI fInkos.
AII fhoso mIxfuros hnvo somo ndvnnfngos ovor TT nIono by hnvIng hIghor onorgy or by
boIng chonor.
3. PloeIic exploeitee. Thoso nro combInnfIons of oxIosIvos hnvIng n InsfIc sfnfo wIfh
mnny dIfforonf shnos fhnf cnn bo roducod wIfhouf rIsk by hnnd mouIdIng or ross IondIng.
Tho combInnfIon IncIudos n hIgh oxIosIvo mIxod wIfh wnx oII (fhnf gIvos fho InsfIc nnfuro)
nnd Iowor sonsIfIvIfy. Thoy cnn bo mndo Info fIoxIbIo shoofs, whIch cnn fInnIIy bo cuf Info
Iocos, fIxod fo n mofnI wIfh ndhosIvos nnd mndo fo socInI shnos. Thoy nro usod for bofh
IndusfrInI nnd mIIIfnry nIIcnfIons.
4. D,noniIee. Tho form dynnmIfo hns boon IImIfod fo fhoso commorcInI oxIosIvos, whIch
confnIn nIfrogIycorIno ns fho rIncInI IngrodIonf. IfrogIycorIno Is nn oIIy IIquId, whIch
dofonnfos by shock or rossuro nbovo 50C. Tho InvonfIon of dynnmIfo dnfos bnck fo l866, by
AIfrod oboI, who concoIvod fho Idon of mIxIng fho nIfrogIycorIno wIfh hIghIy nbsorbonf
mnforInIs. In fhIs wny, ho convorfod n IIquId, whIch Is dnngorous fo hnndIo nnd frnnsorf, fo n
soIId whIch Is roInfIvoIy InsonsIfIvo fo ordInnry shock buf cnnbIo of dofonnfIng by n bInsfIng
cn. Tho nmounf of nbsorbonf nddod vnrIos fho roInfIvo sfrongfh of dynnmIfo.
4C
3
H
5
(O
3
)
3
l0H
2
O + 6H
2
+ l2CO
2
+ O
2
l voI. l0,000 voI. of oxIosIon

Tho vnrIous fyos of dynnmIfos nro:
(i) SIroigII J,noniIee. l5 fo 60 nIfrogIycorIno nro nbsorbod In combusfIbIo mnforInIs
IIko wood uI, sfnrch nnd ofhor Iow-donsIfy fIbros. SodIum nIfrnfo Is nddod ns nn
oxIdIsIng ngonf fhnf ndds on good fumo roorfIos nnd good bInsfIng oxocufIon.
AnfncId mnforInI IIko CnCO
3
fo noufrnIIzo fho ncIdIfy of nIfrogIycorIno Is fo bo nddod
nIso. Imorfnnf usos of fhIs cInss nro bInsfIng of hnrd rocks, conI, mInornIs ofc.
(ii) CeloIin J,noniIee. CoInfIn dynnmIfos nro mndo by nrfIy goInfInIsIng fho nIfrogIycorIno
by nIfrocoffon. Tho sfrongosf known IndusfrInI oxIosIvo Is fho 'bInsfIng goInfIn`,
boIongIng fo fhIs cInss. ComosIfIon Is nrox. 9l.5 nIfrogIycorIn, 8 nIfrocoffon
nnd 0.5 CnCO
3
. IInsfIng goInfIn Is n soIId, oInsfIc mnforInI. !owor rnfIo of nIfrocoffon
In nIfrogIycorIn gIvos vIscous IIquId Insfond of fho soIId mnss. Thoy oxcoII ofhors by
four Imorfnnf roorfIoshIgh buIk donsIfy, hIghosf wnfor rosIsfnnco nmong dy-
nnmIfos, sfIck woII fo hoIos Info whIch fhoy nro Iondod bocnuso of fhoIr InsfIc nnfuro
nnd InsfIy fhoy oxcoII from fho oInf of vIow of fumos. Thoy nro nof sonsIfIvo fo shock
nnd honco nro roforrod for uso undor wof condIfIons. Thoy nro mnInIy usod for
submnrIno bInsfIng, bInsfIng of hnrd rocks, undorground bInsfIng IIko doo-woII shoof-
Ing, funnoI drIvIng ofc. Isndvnnfngo Is fhnf fhoy nro cosfIy comnrod fo ofhors.
(iii) Cun coIIon or celluloee niIroIe. If Is ronrod by sfooIng coffon for 30 mInufos In n
cooIod mIxfuro of conc. H
2
SO
4
nnd conc. HO
3
C
6
H
?
O
2
(OH)
3
+ 3HO
3
C
6
H
?
O
2
(O
3
)
3
+ 3H
2
O
ry gun coffon cnn bo IgnIfod by shock. If oxIodos vory shnrIy If sof on fIro. ry
gun coffon Is usod In forodos, submnrInos, ns n rooIInnf In rIfIos, nrfIIIory shoIIs.
!nfo of oxIosIon of If cnn bo confroIIod by mIxIng ofhor subsfnncos.
(it) Annonio J,noniIee. Thoso nro dynnmIfos In whIch n orfIon of fho nIfrogIycorIn
hns boon roIncod by nmmonIum nIfrnfo. ThoIr sfrongfhs nro oquIvnIonf fo sfrnIghf
dynnmIfo buf of Iowor voIocIfy.
Thoy ossoss somo nffrncfIvo roorfIos for whIch fhoy hnvo wIdo uso. Thoso nro
offocfIvonoss, chonnoss, InsonsIfIvonoss fo shock nnd frIcfIon, non-InfInmmnbIIIfy.
Tho onIy dIsndvnnfngo Is fhoIr Iow wnfor rosIsfnnco, so fhoy nro nof fIf fo bo usod In
wof condIfIon.
(t) CorJiIe. If Is mndo by 65 nrfs of gun coffon, 30 nrfs of nIfrogIycorIno nnd 5 nrfs of
vnsoIIno In ncofono. ThIs nsfo Is roIIod nnd cuf Info Iocos of dIfforonf sIzos VnsoIIno
ncfs ns n sfnbIIIzor nnd cooIIng ngonf on fho owdor. Affor fho ovnornfIon of fho
ncofono, fho horny cordIfo romnIns. Cun coffon confroIs fho oxIosIvo roncfIon of
nIfrogIycorIno nnd If cnn bo snfoIy usod for Inrgo cnIIbor nnvnI guns.
(ti) CeligniIe. ThIs oworfuI oxIosIvo Is n mIxfuro of 65 bInsfIng goInfIno nnd 35
nbsorbIng owdor. If Is usod for undor-wnfor works.
PevmIssIbIe dynumItes. Thoso nro hIgh oxIosIvos socInIIy usod for gnsy conI mInos
ofc. whoro InfInmmnbIo gnsos nro rosonf.
Tho common ormIssIbIo confnIn (o) nbouf 80 nmmonIum nIfrnfo, (I) Iow orconfngo
of nIfrogIycorIno ns sonsIfIzIng ngonf, dynnmIfos, (c) fIbrous combusfIbIo mnforInI fo ufIIIzo
fho oxcoss oxygon of nmmonIum nIfrnfo nnd nbsorbIng nIfrogIycorIno.
Tho goInfInous fyo of ormIssIbIo dynnmIfos confnIns n hIghor orconfngo of
nIfrogIycorIno nnd Iowor confonf of nmmonIum nIfrnfo nIong wIfh n smnII orconfngo of
nIfrocoffon. ThIs Is mnInIy usod for bInsfIng In wof condIfIons.
CommerciaI High ExpIosives Containing No NitrogIycerine
(i) AmmonIum nItvute expIosIves. ThIs fyo of oxIosIvo, cnIIod ofrnmon, Is n snfo
buf hIgh-voIocIfy ngonf. If Is IncnnbIo of dofonnfIng undor fho InfIuonco of bInsfIng
cn buf onco InIfInfod by boosfor chnrgo If cnn rongnfo oxIosIon IndofInIfoIy.
AmmonIum nIfrnfo Is hIghIy doIIquosconf snIf, buf fhIs dIsndvnnfngo cnn bo ovorcomo
by oncIosIng fho mnforInI In n wnforroof mofnIIIc confnInor. Iocnuso If Is nof sonsIfIvo
fo Imncf, frIcfIon nnd shock, If Is fho snfosf hIgh-voIocIfy ngonf.
(ii) CLIovute expIosIve. SodIum or ofnssIum chIornfo mIxod wIfh oxIdIsnbIo mnforInIs
IIko sugnr, chnrconI, suIfur ofc., bocomos hIghIy InfInmmnbIo nnd sonsIfIvo fo Imncf.
!oconfIy, n dosonsIfIzIng mnforInI or IIquId IngrodIonf Is nddod fo fhIs mIxfuro fo
ovorcomo fho nbovo dIsndvnnfngo. Iuf fhough boIng chon, fhoy nro nof ouInr.
(iii) IIquId oxygen expIosIves. Cnrbonncoous nbsorbonf mnforInIs IIko InmbInck or
ofhor cnrbon bInck nro nckod In n orous confnInor nnd fhIs cnrfrIdgo Is dIod Info
IIquId oxygon fo gof snfurnfod. Thoso IIquId oxygon oxIosIvos nro of hIgh sfrongfh
nnd voIocIfy buf fhoy hnvo sovornI dIsndvnnfngos. Thoy nro hIghIy sonsIfIvo fo shock.
Tho sfrongfh doos nof romnIn consfnnf sInco fho IIquId oxygon sfondIIy ovnornfos
nnd honco fhoy cnnnof bo sforod for Iong.
Manufacture of Important ExpIosives
(i) AiIrogl,cerine. Tho rnw mnforInIs nro 99 uro gIycorIno, HO
3
nnd H
2
SO
4
.H
2
SO
4
Is fnkon In sIIghf oxcoss of HO
3
nnd Is nbsoIufoIy froo from wnfor. In n sfooI nIfrnfIng
vossoI, whIch Is cooIod oxfornnIIy by brIno, fho mIxod ncId Is fnkon nnd nIfrogIycorIno
Is nddod nnd nIfrnfIon Is dono nf n vory Iow fomornfuro undor sfIrrIng. Tho rosuIfIng
nIfrogIycorIno nnd sonf ncId, hnvIng n comosIfIon of ?6 H
2
SO
4
, ? HO
3
nnd
l? H
2
O nro run fo n sonrnfor. Affor nbouf 3/4 of nn hour, fhoy form sonrnfo
Inyors, nIfrogIycorIno boIng on fho fo. Tho nIfrogIycorIno Is drnwn off, wnshod wIfh
wnfor, fho ncId Is noufrnIIsod wIfh n wonk soIufIon of n
2
CO
3
undor vIgorous sfIrrIng.
Tho yIoId Is nround 230, cnIcuInfod on fho bnsIs of gIycorIno ns l00.
In roconf yonrs, confInuous rocoss hns boon dovoIood. If Is vory Imorfnnf fhnf fo
nvoId nny nccIdonfnI oxIosIon n cIoso confroI of fho fomornfuro Is fo bo dono durIng
nIfrnfIon. ThIs nIfrogIycorIno Is fhon convorfod fo dynnmIfos by nbsorbIng In dIfforonf
Inorf mnforInIs.
CH OH
CHOH
CH OH
HO
2
2
3
+ 3

Conc. H SO
2 4

CH OO
CH OO H O
CH OO
2 2
2
2 2
3
2
(ii) TriniIroIoluene (TAT). TT Is ronrod by nIfrnfIon of foIuono usIng l:l mIxfuros of
H
2
SO
4
nnd HO
3
In n sfIrrod fnnk roncfor. IIfhor n fwo or n fhroo-sfo rocoss Is
usod, fho formor sonrnfIng ouf fho mono-nIfro comound fIrsf, fhon ronrIng bI
nnd frI comounds In ono sfo.
CH
3
+ 3HNO
3
Conc.
H SO
2 4
CH
3
O N
2
NO
2
NO
2
+ 3H
2
O
SIx Isomors nro ossIbIo for fho frInIfro comound. Tho formnfIon of fhoso Isomors
nnd oxIdnfIon roducfs Ionds fo fho formnfIon of undosIrnbIo ImurIfIos. Tho IIquId
roducf confnInIng TT Is fnkon ouf, wnshod wIfh nmmonIncnI soIufIon of n
2
SO
3
nnd fInnIIy wIfh coId wnfor. TT Is crysfnIIIzod nnd fho urIfIod mnforInI moIfs nf
80.8C, whIch Is fInnIIy drIod nnd sforod.
(iii) IDX. BecInon proceee. (80 yIoId)
HoxnmIno + HO
3
(98) + H
4
O
3
+ (CH
3
CO)
2
O O NN
2
CH NCH
2 2
CH NCH
2 2
N N O
2
NO
2
NO
2
Fuses
Iusos nro of fwo fyos:
(o) SofeI, fuee. Snfofy fuso Is omIoyod whoro oIocfrIcnI fIrIng Is nof usod. If consIsfs of
n smnII-dInmofor coro of bInck owdor oncIosod In n wrnor of wnfor-roof fnbrIc. If hns nn
nroxImnfo burnIng sood of 30 or 40 soc or ff. So whon n fuso Is usod for bInsfIng, n suffIcIonf
Iongfh Is usod so fhnf fho shof-fIrors gof fImo fo ronch fo n oInf of snfofy.
(I) DeIonoIing fuee. ofonnfIng fuso hns n voIocIfy of dofonnfIon ovor 5000 mofros or
soc. If consIsfs of n chnrgo of hIgh voIocIfy oxIosIvo IIko TT In n smnII dInmofor Iond fubo.
Tho IIno of fho fuso (cordonn) Is In confncf wIfh fho chnrgo fhroughouf Ifs Iongfh nnd honco
cnusos Insfnnfnnoous dofonnfIon of fho whoIo chnrgo. A roconf fyo of dofonnfIng fuso confnIns
onfnoryfhrIfoI fofrnnIfrnfo In n non-mofnIIIc wrnIng nnd fho voIocIfy Is ns hIgh ns ?000
mofros or soc. Thoso fusos nro usod for oxIodIng chnrgos of oxIosIvo In doo hoIos.
Squibs
Whon dofIngrnfIng oxIosIvos IIko bInck owdor nro usod, nIIcnfIon of fInmo Is
InsuffIcIonf for fIrIng. SquIbs nro usod for fhIs uroso. SquIbs mny bo In mofnI or cnrdbonrd
fubos nnd mny bo oon or cIosod nf fho fIrIng ond. IrofornbIy, oIocfrIc squIbs nro usod.
BIasting Caps
IInsfIng cns nro smnII cyIIndrIcnI shoIIs of coor or nIumInIum confnInIng n dofonnfIng
chnrgo of oxIosIvos. IInsfIng cns nro usod for InIfInfIng fho oxIosIon of dynnmIfos nnd nro
Insorfod Info fho oxIosIvo nf fho fImo of uso.
Thoro nro fhroo fyos of bInsfIng cns ns shown In IIg. l6.l. In ordInnry fuso cn, n
Iongfh of snfofy fuso Is Insorfod Info fho oon ond nnd fho mofnI wnII Is crImod nbouf fho fuso.
Tho ond of fho fuso whIch Is nwny from fho cn Is IIghfod nnd fho sIf of fInmo from fho fuso In
fho cn fIros fho IgnIfIon chnrgo IondIng fo dofonnfIon.
In oIocfrIc bInsfIng cn, fwo IondIng wIros nro connocfod wIfhIn fho cn by n fIno wIro of
hIgh oIocfrIcnI rosIsfnnco. On nssIng oIocfrIc curronf fhIs brIdgo wIro Is honfod nnd bocomos
Incnndosconf nnd fIros fho IgnIfIon chnrgo.
In fho doIny oIocfrIc bInsfIng cn, fhoro Is n doIny chnrgo of n sIow burnIng comosIfIon,
Insorfod In fho cn fo doIny fho dofonnfIon of fho cn chnrgo.
ThIs fImo InforvnI cnn bo vnrIod from l5 fo 20 soc. by usIng fhoso doInys. Tho comosIfIon
of fho doInys hns boon Imrovod so fhnf no gns Is gIvon off on combusfIon.
Insulated wire
Sulphur seal
Waterproofing
Ignition
powder
Base charge
Regular electric
blasting cap
Shell
Plug
Bridge
wire
Insulated wire
Sulphur seal
Waterproofing
Plug
Ignition
powder
Air
chamber
Delay
tube
Base
charge
Delay electric
blasting cap
Delay
powder
Bridge
wire
Shell
Shell
Capsule
Base
charge
Primary
charge
Ignition
powder
Fuse
Crimp
Ordinary
blasting cap
Fig. 16.1 Three types of blasting caps.
HandIing and Storage of ExpIosives
Thoro nro mnny ruIos fo bo obsorvod In hnndIIng nnd sforIng of oxIosIvos fo nvoId
dIfforonf hnznrds.
(i) IxIosIvos shouId bo fronfod wIfh cnro.
(ii) Thoy shouId bo hnndIod onIy by oxorIoncod nnd roorIy Insfrucfod orsons.
(iii) Thoy shouId bo sforod undor fnvournbIo condIfIons nnd nf osIfIons suffIcIonfIy IsoInfod
from nny workIng furnnco or kIIn.
(it) Tho boundnry of fho oxIosIvo sforo shouId bo rofocfod by foncIng nnd wnfchmnn
wIfh roor 'CnufIon Ionrds`.
(t) SmokIng/fIro shouId bo sfrIcfIy rohIbIfod wIfhIn 50-m rndIus from oxIosIvo sforo.
(ti) Jorks nnd dros of oxIosIvos nro rohIbIfod.
(tii) AII oIocfrIcnI fIffIng of fho sforo shouId bo roorIy InsuInfod nnd onIy forch IIghf
nIIowod InsIdo In cnso of owor fnIIuro.
(tiii) Ifforonf oxIosIvos fo bo sforod sonrnfoIy.
(ix) IfrogIycorIno oxIosIvos shouId nof bo hnndIod In unwrnod condIfIon ns If cnusos
hondncho ofc. on confncf.
(x) Confncf or InhnInfIon of vnors of nromnfIc nIfrocomounds shouId bo nvoIdod duo fo
fhoIr Inhoronf foxIcIfy.
(xi) MngnzInos confnInIng oxIosIvos shouId hnvo IIghfnIng conducfors, nnd fhoy shouId
nof bo hnndIod durIng fhundor sform.
(xii) MngnzInos shouId bo nf snfo dIsfnnco from buIIdIngs, rnII ronds nnd hIghwnys.
PropeIIants
IrooIInnfs nro dofInod ns subsfnncos or mIxfuros of subsfnncos of nn oxIosIvo nnfuro
In n soIId fo IIquId sfnfo fhnf burn oxofhormnIIy wIfhouf confncf wIfh nfmoshorIc oxygon nnd
form n Inrgo voIumo of gns. SInco rooIInnfs burn wIfhouf nfmoshorIc oxygon, fho rooIInnf
sysfom musf confnIn fho oxIdIzor nIong wIfh fho fuoI. Tho fuoI burn nnd fho Inrgo voI. of hof
gnsos oxIf fhrough n smnII oonIng nf n Inrgo voIocIfy (ns or owfon`s fhIrd Inw of mofIon)
whIch cnn bo usod for sovornI urosos IIko chnrgos for guns, rockofs, gns gonornfors, rooIIIng
rockofs, InunchIng mIssIIo. Tho gonornfod gnsos cnn nIso bo usod fo drIvo ums, omfy fnnks,
ncfunfo vnIvos, InfInfo nIr bngs ofc.
Classification of propellants
IrooIInnfs cnn bo cInssIfIod Info soIId nnd IIquId rooIInnfs brondIy.
(A) SoliJ propellonIe. SoIId rooIInnfs mny bo ngnIn cnfogorIzod Info 'homogonoous`
nnd 'comosIfo`.
l. Honogeneoue eoliJ propellonIe nro mIxod homogonoousIy In n coIIoIdnI sfnfoIf Is
homogonoous soIId rooIInnf
(o) Single-Ioee propellonIe. If Is n fyo of homogonoous soIId rooIInnf consIsfIng of
mnInIy InsfIcIzod nIfrocoIIuIoso. Thoy confnIn sfnbIIIzors IIko dIhonyInmIno,
InsfIcIzors IIko dIbufyI hfhnInfo. Thoy cnn bo usod onIy ns gun rooIInnfs or In
buIk owdor fIIIIngs for gns gonornfors.
(I) DouIle-Ioee propellonIe. ConornI comosIfIon Is 5055 nIfrocoIIuIoso nnd 4045
nIfrogIycorIno, 5 dIofhyI fhnInfo ns InsfIcIzor gIvIng n smoofh mnss, l
dIhonyInmIno Is nIso nddod ns sfnbIIIzor. IInmo fomornfuro ronchos nbouf 2?00C
nnd gnsos IIbornfod nf nbouf l500 fImos fho orIgInnI voIumo.
Ofhor comosIfIons nro 65 nIfrocoIIuIoso, 30 nIfrogIycorIno, 5 ofroIoum joIIy, whoro
fho Insf ono funcfIons ns InsfIcIzor.
(c) Triple-Ioee propellonIe. IfrogunnIdIno, hnvIng n Iow fInmo fomornfuro Is usod ns
'coId owdors` for frIIo-bnso rooIInnfs fo roduco fho fInmo fomornfuro. In fhoso
rooIInnfs, nIfrogIycorIno Is roIncod by oxIosIvo InsfIcIzors IIko dIofhyIono gIycoI
dInIfrnfo or bufnnofrIoI frInIfrnfo whIch hnvo Iow honf of oxIosIon. Thoy nro usod ns
gun rooIInnfs nnd rockof rooIInnfs. Ior rockof rooIInnf, Iond or coor snIfs
nro usod ns bnIIIsfIc modIfIors fo roduco rossuro.
2. ConpoeiIe propellonIe. HoforogonoousIy formuInfod soIId rooIInnfs fhnf consIsf of
n oIymorIc bIndor In whIch crysfnIIIno oxIdIzors nro Incorornfod In nmounfs ufo nbouf 90
by woIghf. ComosIfo rooIInnfs nro usod ns gun nnd rockof rooIInnfs. IrooIInnfs for Inrgor
gns gonornfors nro gonornIIy of fho comosIfo fyo. Ior smnII chnrgos, sIngIo nnd doubIo-bnso
rooIInnfs nro usod. ComosIfo fyo hnvo Iow bIndor confonf nnd fho crysfnIIIno fIIIors on
burnIng roducos Ingor nmounf of gnsos nnd nIso fho fInmo fomornfuro Is comnrnfIvoIy Iow.
Cun owdor Is fho oIdosf comosIfo rooIInnf. If gIvos of n fInmo fomornfuro of 800-l500C
nnd fho voIumo of gnsos Is 400 fImos fho voIumo of fho orIgInnI. Ifforonf comosIfo soIId
rooIInnfs confnIn ?5 ofnssIum orchIornfo + 25 nshnIf oII, 80 nmmonIum orchIornfo
+ 20 rosIn bIndor. Tho oxIdIzors nro soIocfod whIch shouId bo sfnbIo, non-hygroscoIc nnd
shouId nof roduco nny corrosIvo or objocfIonnbIo roducf on combusfIon, tic; nmmonIum
orchIornfo roducos HCI on combusfIon whIch Is corrosIvo, AIumInIum owdor In rockof ro-
oIInnf roducos Inrgo nmounf of smoko duo fo AI
2
O
3
formnfIon.
AmmonIum orchIornfo Is roIncod by nmmonIum nIfrnfo fo roduco HCI gonornfIon.
InorgofIc subsfnncos (!X or HMX), oxIosIvo InsfIcIzors (nIfrogIycorIno ofc.) nnd onorgy-
rIch bIndors (CAI) nro usod fo Imrovo fho orformnnco.
(I) LiquiJ propellonIe. !IquId rooIInnfs confnIn fho fuoI nnd oxIdIzor ns n sIngIo
subsfnnco or mIxfuro of subsfnncos (mono) or In fwo sonrnfo hnsos (bIrooIInnfs). Thoy nro
moro ndvnnfngoous for uso fhnn fho soIId rooIInnfs nnd so fhoIr usos nro moro vorsnfIIo.
SoIId rooIInnfs nro Iocnfod In n chnmbor for combusfIon buf fho IIquId rooIInnfs nro Injocfod
Info fho combusfIon chnmbor from n sforngo fnnk by moforIng dovIco nnd honco fho ongInos
usIng IIquId rooIInnfs nro moro doIIcnfo. Tyo of IIquId rooIInnfs nro:
(i) MonopvopeIIunts. MonorooIInnf hns fuoI nnd oxIdIzor ns fho snmo comound or
n soIufIon confnInIng bofh. IxnmIos of monorooIInnfs nro 80-99 H
2
O
2
, hydrnzIno
nnd Ifs dorIvnfIvos, nIfromofhnno, ofhyIono oxIdo, royI nIfrnfo ofc. MonorooIInnf
for guns hnvo comosIfIons IIko 63.2 hydroxyInmmonIum nIfrnfo (HA), 20
frIofhyInmmonIum nIfrnfo (TIA) nnd l6.8 wnfor; mIxfuros of nIfromofhnno nnd
IsoroyI nIfrnfo or mofhnnoI. MonorooIInnfs shouId bo sfnbIo on sforngo nnd
smoofh on burnIng. Iuf unforfunnfoIy H
2
O
2
Is hIghIy roncfIvo nnd docomosIfIon
occurs fhough sfnbIIIzors nro nddod. MofnIIIc sforngo fnnks nro gonornIIy nvoIdod for
H
2
O
2
ns mofnI oxIdo cnfnIyzos Ifs docomosIfIon.
(ii) BIpvopeIIunts. IIrooIInnfs consIsf of nn oxIdIzor nnd n fuoI fhnf nro Injocfod In
fwo sonrnfo hnsos fo fho combusfIon chnmbor. CommonIy usod oxIdIzors nro ozono,
IIquId O
2
, IIquId fIuorIno or n mIxfuro of fIuorIno nnd oxygon (I!OX). Common fuoI
usod nro hydrnzIno, IIquId H
2
, ofhyI nIcohoI, nnIIIno, korosono, nmInos.
ConvonfIonnI rockof rooIInnfs confnIn H
2
O
2
, conc. HO
3
, O
2
or IIquId O
2
ns oxIdIzor
nnd hydrocnrbons, nIcohoIs, nmInos, hydrnzInos nnd nIkyI dorIvnfIvos ns fuoI. !IquId fIuorIno
or I!OX Is usod In norosnco nIIcnfIon wIfh Imrovod orformnnco.
Thoro nro sovornI robIoms wIfh fhoso combInnfIon. Ozono nnd IIquId fIuorIno, fhough
oworfuI oxIdIzors, nro foxIc nnd oxIodo nf hIgh conconfrnfIon. AIso fhoy nro dIffIcuIf fo hnndIo
nnd sforo.
Production
IrooIInnfs nro onorgofIc mnforInIs nnd honco nro fo bo mnnufncfurod nnd frnnsorfod
wIfh gronf cnro. A romofo confroI Is nocossnry wIfh nII rocossos In whIch oxIosIvo mnforInIs
nro InvoIvod nnd oxosod fo fhormnI or mochnnIcnI sfrossos. Tho roducfIon rocossos nro:
(o) SoIvonf rocoss
(I) SoIvonfIoss rocoss!oIo nnd oxfrusIon rocoss
(c) Scrow oxfrusIon rocoss
(J) InII owdor rocoss
(e) CnsfIng rocoss
TestIng for rooIInnf IncIudos
(o) IurnIng bohnvIour (InIIIsfIc Iomb)
(I) IurnIng rnfo (Crnwford Iomb)
(c) Honf of oxIosIon
Tho onvIronmonfnIIy-snfo dIsosnI nnd foxIcoIogIcnI offocfs of rooIInnfs nro nIso of
concorn nnd nro comIng undor sfrIcf roguInfIons.
HIgLIIgLts:
xpIosIve: IxIosIvos nro uro subsfnncos or mIxfuro, whIch whon subjocfod fo
socIfIc sfImuIus InIfInfo nn oxIdnfIon roncfIon roducIng Inrgo voIumo of hof gnsos.
PvImuvy expIosIves: Thoy nro hIghIy sonsIfIvo oxIosIvos, whIch oxIodo on
rocoIvIng n sIIghf shock or fIro.
HIgL expIosIves: HIgh oxIosIvos hnvo hIghor onorgy confonf comnrod fo rImnry
oxIosIvos buf fhoy nro quIfo InsonsIfIvo fo oxfornnI sfImuII.
PvopeIIunts: IrooIInnfs nro uro subsfnncos or mIxfuros In IIquId or soIId sfnfo
fhnf burn oxofhormnIIy uiIIouI conIocI uiII oInoepIeric ox,gen nnd form Inrgo
voIumo of gnsoous roducfs.
Iuses: Iuso Is n fhIn wnfor-roof cnnvns Iongfh of fubo whIch confnIns gun-owdor
fhnf burn nf n gIvon sood for soffIng off chnrgos of oxIosIvos.
ynumItes: IxIosIvos confnInIng nIfrogIycorIno ns fho rIncInI IngrodIonf.
RX: IoworfuI oxIosIvo consIsfIng of cycIofrImofhyIono frInIfronmIno.
Q. 1. WLut uve expIosIves?
Ans. IxIosIvos nro subsfnncos or mIxfuros, whIch whon subjocfod fo mochnnIcnI or
fhormnI shock, Iond fo rnId oxIdnfIon oxofhormnIIy fo roduco Inrgo nmounf of gnsoous roducfs
of gronfIy Incronsod voIumo nnd nIso n Inrgo nmounf of onorgy.
Q. 2. WLut Is u vocket pvopeIIunt?
Ans. !ockof rooIInnf Is oIfhor n hIgh oxygon confnInIng fuoI or n fuoI wIfh nn oxIdnnf
whIch Is burnf undor confroIIod condIfIon wIfh fho ovoIufIon of n Inrgo voIumo of gns.
Q. 3. WLut uve dynumItes?
Ans. ynnmIfos nro hIgh oxIosIvos confnInIng nIfrogIycorIno ns fho rIncInI IngrodIonf.
IfrogIycorIno Is usunIIy mIxod wIfh nn Inorf nbsorbonf IIko wood uI, sfnrch monIs, snw dusf
ofc. wIfh vnryIng nmounf of nIfrogIycorIno fhnf doformInos Ifs roInfIvo sfrongfh.
Q. 4. WLut uve Iuses?
Ans. Iusos nro fhIn wnfor-roof cnnvns Iongfh of fubo confnInIng gun-owdor or TT,
whIch burn nf n gIvon sood for soffIng-off fho chnrgos of oxIosIvo. Iusos nro of fwo fyos:
(i) snfofy fuso, (ii) dofonnfIng fuso.
Q. 5. WLut do you meun by "oxygen-buIunce oI un expIosIve"?
Ans. IosIfIvo oxygon bnInnco Is nn Imorfnnf chnrncforIsfIc of n good oxIosIvo. If
IndIcnfos fho oxygon confnInod In fho moIocuIo, whIch wIII bo ufIIIzod fo oxIdIzo fho C nnd H of
fho moIocuIo fo form CO
2
nnd H
2
O, rosocfIvoIy. If Is oxrossod ns fho dIfforonco bofwoon fho
oxygon confnInod In fho moIocuIo nnd fho oxygon ncfunIIy roquIrod fo oxIdIso fho fofnI C nnd H
confnInod In fho moIocuIo.
EXERCISES
1. Whnf nro oxIosIvos Whnf nro rockof rooIInnfs
2. How nro oxIosIvos cInssIfIod
3. nmo fwo for onch cInss:
(o) IrImnry oxIosIvo (I) Two Iow oxIosIvo
(c) HIgh oxIosIvo (J) MonorooIInnfs nnd bIrooIInnfs
4. Whnf nro fho roquIromonfs of n good oxIosIvo
5. Why nro dofonnfors roquIrod for hIgh oxIosIvo Whnf nro fho usos of oxIosIvos
6. Whnf nro rooIInnfs How nro rooIInnfs cInssIfIod Sfnfo fho roquIromonfs of n good rooIInnf
?. Whnf Is gun-coffon Whnf Is !X Whnf nro fusos
B. IxInIn fho form oxygon-bnInnco of nn oxIosIvo.
9. Whnf nro dynnmIfos Sfnfo fho rocoduro of Ifs mnnufncfuro.
10. WrIfo nofos on fho foIIowIng:
(o) Modorn oxIosIvos (I) IfrogIycorIno
(c) !ockof rooIInnf (J) CordIfo
(e) TT
11. (i) !X Is
(o) TrInIfrofoIuono (I) CycIofrImofhyIono frInIfronmIno
(c) !ond nzIdo (J) IfrocoIIuIoso
(ii) TT Is n comound of
(o) CoIIuIoso (I) CIycoroI
(c) ToIuono (J) IhonoI
(iii) ChnrncforIsfIc of n good oxIosIvo Is
(o) HIgh onorgy of oxIdnfIon (I) SIow nnd confroIIod oxIdnfIon rnfo
(c) IosIfIvo oxygon bnInnco (J) ocomosIfIon rnfo shouId bo sIow
(it) IxnmIo of hIgh oxIosIvo Is
(o) TT (I) Cun owdor (c) !ond nzIdo
(t) IxnmIo of rImnry oxIosIvo Is
(o) AmmonIum nIfrnfo (I) TT (c) !ond nzIdo
(ti) Cum owdor Is
(o) IrImnry oxIosIvo (I) !ow oxIosIvo
(c) HIgh oxIosIvo
(tii) SmokoIoss owdor Is
(o) Tofrncono (I) IfrocoIIuIoso (c) IIcrIc ncId
(tiii) IInnry oxIosIvos nro mIxfuros of ofhor oxIosIvos wIfh
(o) TT (I) ynnmIfo (c) IfrocoIIuIoso
(ix) IurnIng sood of snfofy fuso Is
(o) l m soc
l
(I) l cm soc
l
(c) l00 m soc
l
(x) IInck owdor Is
(o) IfrocoIIuIoso (I) Morcury fuImInnfo (c) Cun owdor
350
%
Water Treatment
Tho nnfuro`s mosf nbundnnf suIy i.e., wnfor Is ossonfInI for fho survIvnI of nII fho IIvIng
boIngs on onrfh i.e., mnn, nnImnIs nnd Innfs. Wnfor Is nof onIy ossonfInI for fho survIvnI of
IIfo, buf If Is nIso usod for fho oornfIon In n Inrgo numbor of IndusfrIos ns cooInnf, soIvonf, for
sfonm gonornfIon, for nIr condIfIonIng, fIro-fIghfIng ofc. Wnfor Is nIso usod for nII domosfIc
urosos IIko bnfhIng, drInkIng, wnshIng, snnIfnry, IrrIgnfIon ofc.
Sources of Water
l. RuInwutev. If Is fho urosf form of nnfurnI wnfor. Iuf unforfunnfoIy If dIssoIvos fho
foxIc gnsos IIko CO
2
, SO
2
, O
2
ofc. nnd ofhor soIIds, whIch oIIufo fho nfmoshoro.
2. Seu wutev. If Is fho mosf Imuro form of wnfor confnInIng nbouf 3.5 dIssoIvod snIfs
of whIch nbouf 2.6 Is sodIum chIorIdo. Ofhor snIfs rosonf IncIudo suIfnfos, bIcnrbonnfos,
bromIdos of sodIum, ofnssIum, mngnosIum ofc. Ofhor ImurIfIos nro cnrrIod fo son fhrough
rIvors.
3. RIvev wutev. Tho sourcos of rIvor wnfor nro fho srIngs nnd fho rnInwnfor. !Ivor
wnfor whIIo fIowIng fhrough fho Innd coIIocfs Iofs of orgnnIc mnffors from fnIIIng froos nnd
nonrby hnbIfnfs nnd nIso ofhor soIubIo nnd susondod mnffors from fho Innds, soIIs ofc. Tho
dIssoIvod mnffors IncIudo fho snIfs IIko suIfnfos, bIcnrbonnfos nnd bromIdos of sodIum, ofnssIum
nnd mngnosIum.
4. Iuke wutev. If Is much uror fhnn rIvor wnfor, dIssoIvod ImurIfIos nro Ioss buf
confnIns Iofs of orgnnIc mnffor.
5. \ndevgvound wutev. Tho rnInwnfor nnd ofhor surfnco wnfor orcoInfo down fhrough
fho soII nnd rocks nnd gof fIIforod nnd fInnIIy coIIocfod on rocky surfnco or ngnIn como ouf ns
srIng. Though If confnIns Ioss susondod mnffor buf fho dIssoIvod mInornI confonf Is quIfo
hIgh nnd Is of hIgh orgnnIc urIfy.
Thus wo cnn sny fhnf fho surfnco wnfor coIIocfs Iofs of susondod mnforInIs, mIcro-
orgnnIsms nnd ofhor oIIufnnfs from fho hnbIfnfs nnd bocomo unsuIfnbIo for dIrocf humnn
consumfIon nnd ofhor usngo.
Effect of Water on Rocks
Wnfor, whIIo orcoInfIon, gofs confnmInnfod by fho foIIowIng rocossos:
(o) IssoIutIon. SodIum chIorIdo, gysum (CnSO
4
.2H
2
O) nnd ofhor soIubIo snIfs gof
dIrocfIy dIssoIvod In fho orcoInfod wnfor.
(I) HydvutIon. WhIIo orcoInfIon, wnfor cnusos hydrnfIon of fho mInornIs IIko nnhydrIfo,
oIIvIno whIch Ionds fo Incronso In voIumo nnd dIsInfogrnfIon of such rocks, tic.
CnSO
4
+ 2H
2
O CnSO
4
.2H
2
O
AnhydrIfo Cysum
WATER TREATMENT 351
Mg
2
SIO
4
+ xH
2
O Mg
2
SIO
4
.xH
2
O
OIIvIno SoronfIno
(c) OxIdutIon. IssoIvod oxygon brIngs nbouf oxIdnfIon nIongwIfh hydrnfIon.
2Io
3
O
4

OxIdnfIon
2Io
2
O
3

HydrnfIon
2Io
2
O
3
.2H
2
O
MngnofIfo HnomnfIfo !ImonIfo
(J) ActIon oI cuvbon dIoxIde. InsoIubIo cnrbonnfos of Cn, Mg nnd Io nIongwIfh sIIIcnfos
of n, K, Cn, nnd Io nro convorfod Info soIubIo bIcnrbonnfos nnd soIubIo cnrbonnfos, tic.
CnCO
3
+ CO
2
+ H
2
O Cn(HCO
3
)
2
(InsoIubIo) (SoIubIo)
K
2
O.AI
2
O
3
.6SIO
2
+ CO
2
+ 2H
2
O AI
2
O
3
.2SIO
2
.2H
2
O + K
2
CO
3
+ 4SIO
2
Hardness of Water
HorJneee of wnfor Is fho chnrncforIsfIc of rovonfIng Infhor formnfIon of wnfor wIfh
son. ConornIIy snIfs IIko chIorIdos, bIcnrbonnfos nnd suIfnfos of Cn
2+
, Mg
2+
nnd Io
2+
mnko
wnfor hnrd. ThIs hnrd wnfor on fronfmonf wIfh son whIch Is sfonrIc or nImIfIc ncId snIfs of
sodIum or ofnssIum cnusos whIfo rocIIfnfo formnfIon of cnIcIum or mngnosIum sfonrnfo or
nImIfnfo.
2C
l?
H
35
COOn + CnCI
2
(C
l?
H
35
COO)
2
Cn + 2nCI
SodIum sfonrnfo CnIcIum sfonrnfo
(son) (InsoIubIo)
Thus fho cnuso of hnrdnoss Is fho rocIIfnfIon of fho son nnd honco rovonfs InfhorIng
nf fIrsf. Whon fho hnrdnoss cnusIng Ions nro romovod ns InsoIubIo sons, wnfor bocomos soff
nnd forms Infhor.
Tho hnrdnoss Is of fwo fyos:
(i) Tenporor, IorJneee Is duo fo fho bIcnrbonnfos of Cn
2+
nnd Mg
2+
nnd cnrbonnfo of
Io
2+
. SInco bIcnrbonnfos rondIIy gof rocIIfnfod on boIIIng fho wnfor, fho fomornry hnrdnoss
cnn bo onsIIy romovod, tic.
Cn(HCO
3
)
2

honf
CnCO
3
+ H
2
O + CO
2
InsoIubIo
(ii) PernonenI IorJneee Is duo fo fho rosonco of chIorIdos nnd suIfnfos of Cn, Mg, Io,
ofc. Iormnnonf hnrdnoss cnnnof bo romovod onsIIy on boIIIng.
Units of Hardness
Iofh fomornry nnd ormnnonf hnrdnossos nro oxrossod In m ns CnCO
3
. Tho choIco
of CnCO
3
Is duo fo fho fncf fhnf Ifs moI. wf. Is l00 nnd oquIvnIonf woIghf Is 50 nnd If Is IIe noeI
ineoluIle eolI In wnfor. IquIvnIonf of CnCO
3
=
(Mnss of hnrdnoss roducIng subsfnnco) (ChomIcnI oquIvnIonf of CnCO )
ChomIcnI oquIvnIonf of hnrdnoss roducIng subsfnnco
3
=
Mnss of hnrdnoss roducIng subsfnnco 50
ChomIcnI oquIvnIonf of hnrdnoss roducIng subsfnnco
Hnrdnoss Is rIncInIIy oxrossod In m unIf. Ofhor IImIfs IncIudo Ironch dogroo of

hnrdnoss, IngIIsh dogroo of hnrdnoss or CInrk, !SA dogroo of hnrdnoss nnd Cormnn dogroo of
hnrdnoss.
l m =
lnrf of hnrdnoss
l0 nrfs of wnfor
6
l Ir. dogroo of hnrdnoss =
lnrf of hnrdnoss
l0 nrfs of wnfor
5
l CInrk =
l grnIn of hnrdnoss
lgnIIon or ?0,000 grnIns
l
? l0
4
=
l !SA dogroo of hnrdnoss =

lgrnIn
l !SA gnIIon
lgrnIn
58,300 grnIns
l
5.83 l0
4
= =
l Cormnn dogroo of hnrdnoss =

lgrnIn
lCormnn grnIn
lgrnIn
56,000 grnIns
l
5.6 l0
4
= =
ReIutIon between vuvIous unIts oI Luvdness

l m = l mg/I = 0.l Ir = 0.0? CI
l mg/I = l m = 0.l Ir = 0.0? CI
l CI = l.43 Ir = l4.3 m = l4.3 mg/I
l Ir = l0 m = l0 mg/I = 0.? CI.
Disadvantages of Hard Water
(o) 1n JoneeIic ueee. Ior uoeIing nnd IoIIing, hnrd wnfor cronfos dIffIcuIfIos, sInco If
doos nof form Infhor frooIy wIfh son. If nIso cronfos sfIcky rocIIfnfos fhnf doosIf on bnfh
fub, body, cIofhos ofc. unfII nII fho Cn/Mg snIfs gof rocIIfnfod. Thus n Iof of son gof wnsfod
nIso.
Ior cooling hnrd wnfor cronfos sImIInr dIffIcuIfIos by roducIng scum on fho boffom of
fho vossoIs. uo fo fho rosonco of hnrdnoss roducIng snIfs In hnrd wnfor, boIIIng oInf gofs
oIovnfod nnd durIng cookIng n Iof of fuoI Is wnsfod. IuIsos ofc. do nof cook In hnrd wnfor. Tnsfo
of fon, coffoo bocomos unIonsnnf. Drinling of hnrd wnfor Is nIso robIomnfIc sInco If nffocfs
fho dIgosfIvo sysfom nnd nf fho snmo fImo fho ossIbIIIfy of doosIfIon of cnIcIum oxnInfo
crysfnIs In fho urInnry frncf Is nInrmIng.
(I) 1n inJueIriol ueee. Ior IexIile inJueIr, nnd J,eing inJueIr,, hnrd wnfor cnusos fho
usunI robIom of doosIfIon of InsoIubIo snIfs fhnf Inforforo wIfh fho roor dyoIng nnd rInfIng
of fho fnbrIcs. Tho sfnIns of Iron snIfs nIso nro undosIrnbIo on fnbrIcs. Hnrd wnfor nIso hnmors
fho oconomy by wnsfngo of son ns If doos nof form good Infhor.
Ior eugor inJueIr,, fho snIfs rosonsIbIo for hnrdnoss cronfo dIffIcuIfIos In sugnr rofInIng
nnd crysfnIIIznfIon of sugnr nnd fho sugnr bocomos doIIquosconf.
CnIcIum nnd mngnosIum snIfs nIso Inforforo wIfh fho smoofh nnd gIossy fInIsh of fho
nors In fho poper inJueIr,. Iron snIfs Inforforo wIfh fho coIour of fho nor.
In lounJr,, hnrd wnfor cnusos wnsfngo of cosfIy son nnd nIso Inforforos wIfh fho
coIornfIon duo fo fho sfnInIng of Iron snIfs.
Tho hydrnfIon of comonf nnd fInnI hnrdonIng of comonf nro nffocfod by uso of hnrd
wnfor In concreIe noling.
Hnrd wnfor Is nof suIfnbIo for ronrIng drug soIufIons In pIornoceuIicol inJueIr,.
Ior eIeon generoIion in Ioilere, hnrd wnfor cronfos mnny robIoms IIko (i) scnIo
formnfIon, (ii) corrosIon, (iii) rImIng nnd fonmIng nnd (it) cnusfIc ombrIffIomonf.
SIudge and ScaIe Formation in BoiIers
Whon hnrd wnfor Is usod for boIIors, on confInuous ovnornfIon, fho snIfs rosonf In fho
hnrd wnfor gofs snfurnfod nnd nro fInnIIy doosIfod In fho nrons whoro fho fIow Is sIow. Whon
WATER TREATMENT 353
fhoso rocIIfnfos nro Iooso nnd sIImy In nnfuro, If Is cnIIod eluJge whorons whon fhoso
rocIIfnfos nro hnrd nnd fhoy ndhoro sfrongIy fo fho Innor surfnco of fho boIIors, fhoy nro
cnIIod ecole.
SluJge cnn bo onsIIy romovod by scrnIng wIfh n brush. SIudgo Is formod by fho rosonco
of MgCO
3
, MgSO
4
, MgCI
2
, CnCI
2
ofc. Thoso snIfs nro moro soIubIo In hof wnfor.
DieoJtonIogee of eluJge formnfIon nro (i) oor honf conducfIon duo fo fho rosonco of
sIudgo on fho surfnco; (ii) dIffIcuIfy In fho oornfIon of fho boIIor; (iii) If sIudgo Is formod nIong
wIfh fho scnIo nnd Is frnod wIfhIn fho scnIo formod nnd so If Is dIffIcuIf fo romovo nnd (it) If
cIogs fho Io IInos nnd ofhor connocfIons fo fho vossoI nonr fho Incos whoro wnfor cIrcuInfIon
rnfo Is sIow.
Ienotol of eluJgee. SIudgo formnfIon cnn bo rovonfod by (i) usIng soff wnfor for boIIor
oornfIon nnd (ii) romovIng fho conconfrnfod snIfy wnfor from fImo fo fImo so fhnf doosIfIon
of sIudgo Is rovonfod.
Scolee nro fho hnrd doosIfs on fho Innor surfnco of fho boIIors whIch nro dIffIcuIf fo
romovo. ThIs scnIo formnfIon fnkos Inco duo fo fho foIIowIng ronsons:
(o) In Iow rossuro boIIors scnIo formnfIon occurs duo fo fho formnfIon of CnCO
3
from
Cn(HCO
3
)
2
.
i.e., Cn(HCO
3
)
2
CnCO
3
+ H
2
O + CO
2
ScnIo
(I) In hIgh rossuro boIIors fhIs CnCO
3
gofs convorfod fo soIubIo Cn(OH)
2
. Iuf horo
CnSO
4
forms fho hnrd scnIo. SInco fho soIubIIIfy of CnSO
4
docronsos wIfh Incronso In
fomornfuro, nnd nf hIgh fomornfuro fho rocIIfnfod CnSO
4
forms hnrd scnIo.
SImIInr hnrd scnIos nro formod whon SIO
2
Is rosonf In fho hnrd wnfor. If doosIfs ns
CnSIO
3
or MgSIO
3
. Thoso cnIcIum or mngnosIum sIIIcnfo scnIos nro vory dIffIcuIf fo romovo.
IssoIvod mngnosIum snIfs nIso rocIIfnfo ns Mg(OH)
2
formIng soff fyo of scnIo.
DieoJtonIogee of ecole fornoIion nro sImIInr fo sIudgo formnfIon buf fho sovorIfy Is
moro, sInco Ifs romovnI Is moro dIffIcuIf.
DieoJtonIogee IncIudo
(i) Poor IeoI Ironefer from boIIor fo wnfor IondIng fo Incronso In fuoI consumfIon. Tho
Incronso In fhIcknoss of fho scnIo from l.25 mm fo l2 mm Ionds fo Incronso In fuoI
consumfIon from ovor 50 fo l50.
(ii) uo fo fho ovorhonfIng of fho boIIor, dIfforonf nrfs of fho boIIor bocomo wonk nnd
dIsforfod nnd so fho oornfIon of fho boIIor bocomos uneofe, nrfIcuInrIy fho hIgh
rossuro boIIors.
Tho fhIck scnIos mny somofImos Iond fo exploeion duo fo suddon dovoIomonf of hIgh
rossuro.
(iii) VnIvos nnd condonsors of fho boIIors nro chockod duo fo scnIo formnfIon nnd Ioiler
efficienc, Jecreoeee.
Ienotol of ecolee cnn bo dono by:
(i) Woodon scrnor or wIro brush, suIfnbIo for romovIng Iooso scnIos.
(ii) IIow down oornfIons for Iooso scnIos. Tho oornfIon ncfunIIy InvoIvos fho ro-
movnI of vory hnrd wnfor from n fn nf fho boffom of fho boIIor nnd roIonIshIng
fho wnfor wIfh soffonod wnfor cnIIod 'mnko u` wnfor.
(iii) CIvIng fhormnI shocks, whIch InvoIvo nIfornnfo honfIng nnd cooIIng fo mnko fho
scnIos brIffIo.
(it) ChomIcnI fronfmonf wIfh 5-l0 HCI for cnrbonnfos nnd ITA fronfmonf for
Cn/Mg snIfs formIng comIoxos.
Thoso nro mofhods for fho romovnI of fho scnIos, whon fhoy nro formod. Thoro nro nIso
somo mofhods for fho pretenIion of ecole formnfIon by inIernol or exIernol fronfmonf.
Internal treatment
InfornnI fronfmonf InvoIvos nddIfIon of chomIcnI fo fho boIIor wnfor oIfhor fo (i) rocIIfnfo
fho scnIo formIng ImurIfIos In fho form of sIudgos, whIch cnn bo onsIIy romovod or (ii) convorf
fho ImurIfIos fo soIubIo comounds, so fhnf scnIo formnfIon cnn bo nvoIdod. Imorfnnf InfornnI
fronfmonfs InvoIvo.
(o) ColloiJol ConJiIioning. OrgnnIc subsfnncos IIko korosono, fnnnIn, ngnr-ngnr nro nddod
fo form goIs nnd form Iooso non-sfIcky doosIfs wIfh scnIo-formIng rocIIfnfos, whIch
cnn bo onsIIy romovod by bIow-down oornfIons In Iow rossuro boIIors.
(I) Ifforonf sodIum hoshnfos IIko nH
2
IO
4
, n
2
HIO
4
nnd n
3
IO
4
nro nddod fo hIgh
rossuro boIIors fo roncf wIfh fho hnrdnoss formIng ImurIfIos fo form soff sIudgo of
cnIcIum nnd mngnosIum hoshnfos nnd fInnIIy fhIs cnn bo romovod by bIow down
oornfIon.
3CnCI
2
+ n
3
IO
4
Cn
3
(IO
4
)
2
+ 6nCI
(c) CorIonoIe conJiIioning. SodIum cnrbonnfo Is nddod fo fho wnfor of Iow rossuro
boIIor whoroby fho scnIo formIng CnSO
4
gofs convorfod fo Iooso sIudgo of CnCO
3
,
whIch cnn bo onsIIy romovod by bIow-down oornfIon.
CnSO
4
+ n
2
CO
3
= CnCO
3
+ n
2
SO
4
.
(J) Colgon conJiIioning. CnIgon i.e., sodIum hoxn mofn hoshnfo whon nddod fo boIIor
wnfor, roncfs wIfh scnIo formIng CnSO
4
nnd forms soIubIo comIox comound.
2CnSO
4
+ |n
4
I
6
O
8
]
2
|Cn
2
I
6
O
l8
]
2
+ 2n
2
SO
4
(e) SoJiun oluninoIe conJiIioning. SodIum nIumInnfo Is hydroIysod yIoIdIng nOH
nnd goInfInous AI(OH)
3
. Tho nOH formod roncfs wIfh mngnosIum snIfs fo rocII-
fnfo Mg(OH)
2
. ThIs Mg(OH)
2
nnd AI(OH)
3
nro fIoccuIonf nnd onfrns fho coIIoIdnI ns
woII ns fho fInoIy dIvIdod ImurIfIos IIko sIIIcn In fho boIIor wnfor nnd fho Iooso
rocIIfnfo Is fInnIIy romovod by bIow down oornfIon.
nAIO
2
+ 2H
2
O nOH + AI(OH)
3
MgCI
2
+ 2nOH Mg(OH)
2
+ 2nCI
( f ) 1lecIricol conJiIioning. !ofnfIng morcury buIbs on honfIng by fho boIIIng wnfor omIf
oIocfrIcnI dIschnrgos fhnf rovonf scnIo formnfIon by fho nrfIcIos.
( g) IoJioocIite conJiIioning. TnbIofs of rndIoncfIvo snIfs Incod InsIdo n boIIor omIf
rndInfIons, whIch rovonf scnIo formnfIon.
Caustic EmbrittIement
ImbrIffIomonf Is fho nnmo fhnf hns boon gIvon fo boIIor fnIIuros duo fo dovoIomonf of
corfnIn fyos of crnck rosuIfIng from oxcossIvo sfross nnd chomIcnI nffnck. In sfonm boIIor
oornfIon, fho chomIcnIs fhnf nro boIIovod fo bo rosonsIbIo nro nOH nnd sIIIcn. urIng
soffonIng rocossos, n
2
CO
3
nro nddod nnd If gIvos rIso fo nOH nf oIovnfod fomornfuro
nccordIng fo fho foIIowIng roncfIon.
n
2
CO
3
+ H
2
O 2nOH + CO
2
Sfonm boIIors nro mndo by rIvoffIng consfrucfIons rnfhor fhnn woIdIng nnd nro
nrfIcuInrIy IInbIo fo dnmngo by cnusfIc nIknII soIufIons. ThIs crnckIng Is nof duo fo corrosIon
nnd fho crncks nonr IIko brIffIo frncfuro nnd honco cnIIod cnusfIc ombrIffIomonf. nOH
nffncks nnd dIssoIvos ouf Iron of boIIor formIng sodIum forronfo. ThIs fInnIIy cnusos fho sfrossod
nrfs IIko bonds, joInfs, rIvofs fo Iond fo fho boIIor fnIIuro.
WATER TREATMENT 355
ConconfrnfIon coII dovoIos bofwoon fho boIIor nnd fho nOH of dIfforonf conconfrnfIons ns
+ Io nf
rIvofs, joInfs
ofc.
Conconfrnfod
nOH
SoIufIon
IIufo
nOH
SoIufIon
Io nf
Inno
Surfncos
Prevention of Caustic EmbrittIement
(i) AddIfIon of sodIum hoshnfo ns soffonIng ngonf Insfond of n
2
CO
3
.
(ii) AddIfIon of sodIum suIfnfo fo onsuro n woIghf rnfIo n
2
SO
4
/nOH > 2.5, whoroby
fho doosIfIon of n
2
SO
4
rovonfs fho onofrnfIon of nOH Info fho crncks nnd sfos
cnusfIc ombrIffIomonf In hIgh rossuro boIIors.
(iii) AddIfIon of orgnnIc ngonfs IIko fnnnIn, IIgnIn, quorbrncho ofc. nIso rovonfs crnckIng
sImIInr fo sodIum suIfnfo In Iow rossuro boIIors.
(it) !so of crnck-rosIsfIng sfooIs: CorfnIn sfooIs confnInIng AI nddod durIng mnnufncfuro
nonr fo bo rosIsfnnf ngnInsf cnusfIc crnckIng.
Corrosion in BoiIers
IoIIor corrosIon occurs by chomIcnI or oIocfrochomIcnI nffnck of fho confonfs of wnfor.
MnIn fyos nro of chomIcnIs:
(o) DieeolteJ ox,gen. Oxygon Is dIssoIvod In wnfor fo fho oxfonf of 8 mI/l nf room fomornfuro
nnd If Is rosonsIbIo for corrosIon In fho boIIor. Cronfor fho rossuro, hIghor fho dIssoIvod O
2
confonf. As fho wnfor Is honfod In fho boIIor fho dIssoIvod oxygon Is IIbornfod nnd Iron Is corrodod.
2Io + 2H
2
O + O
2
2Io(OH)
2

4Io(OH)
2
+ O
2
2|Io
2
O
3
.2H
2
O]
DiooolteJ orygen cun be remoteJ by:
(i) MochnnIcnI donornfIon mofhods usIng dIsfIIInfIon, sfonm scrubbIng, dosorfIon, fInsh-
fyo donornfIon, whIch roduco O
2
conconfrnfIon fo nbouf 0.0l m.
(ii) ChomIcnI fronfmonfoxygon conconfrnfIon Is vIrfunIIy mndo zoro by usIng roducIng
ngonfs IIko hydrnzIno, sodIum suIfIfo ofc.
(iii) Ion oxchnngo fochnIquos nIso roduco oxygon conconfrnfIon fo vory Iow IovoI.
(I) DieeolteJ CO
2
: Wnfor confnIns somo CO
2
nnd fho docomosIfIon roducf of bIcnrbo-
nnfos rosonf In wnfor nIso roducos CO
2
. ThIs CO
2
dIssoIvos In wnfor formIng cnrbonIc ncId
whIch cnusos IocnI corrosIon cnIIod pIttIng.
Io + CO
2
+ H
2
O IoCO
3
+ H
2
4IoCO
3
+ O
2
+ l0H
2
O 4Io(OH)
3
+ 4H
2
O + 4CO
2
4Io(OH)
3
2Io
2
O
3
+ 6H
2
O
Remotul of CO
2
io Jone by:
(i) MochnnIcnI donornfIon.
(ii) AddIng IImo or H
3
.
(iii) HonfIng.
(c) Minerol ociJe. Wnfor from IndusfrInI nrons confnIns ncIdIc wnsfos or InorgnnIc snIfs
whIch on hydroIysIs roduco ncIds. Thoso ncIds cnuso corrosIon In boIIors. Tho ncIds roncf wIfh
Iron In chnIn roncfIons roducIng ncIds ngnIn nnd ngnIn nnd nIso roduco H
2
cnusIng hydrogon
ombrIffIomonf whIch Ionds fo boIIor fnIIuro.
MgCI
2
+ 2H
2
O Mg(OH)
2
+ 2HCI
Io + 2HCI IoCI
2
+ H
2
IoCI
2
+ 2H
2
O Io(OH)
2
+ 2HCI
Priming and Foaming
urIng rnId sfonm roducfIon, somo IIquId wnfor dros nro nIso cnrrIod nIong wIfh fho
sfonm. ThIs wof-sfonm formnfIon Is cnIIod prining.
IrImIng occurs duo fo (i) rosonco of Inrgo nmounf of dIssoIvod soIIds, (ii) hIgh sfonm
voIocIfIos, (iii) suddon boIIIng nnd (it) suddon Incronso In sfonm roducfIon. IrImIng cnn bo
confroIIod by (i) mnInfnInIng Iow wnfor IovoI In boIIor, (ii) nvoIdIng rnId chnngo In sfonm rnfo,
(iii) soffonIng of boIIor wnfor nnd (it) usIng mochnnIcnI dovIco for sfonm urIfIcnfIon.
Iooning Is fho roducfIon of bubbIos nnd fonms whIch do nof bronk onsIIy. IonmIng
occurs duo fo fho rosonco of oII In fho wnfor.
IonmIng cnn bo roducod by (i) romovIng oII from boIIor-food wnfor nnd (ii) nddIng nnfI-
fonmIng ngonfs.
IrImIng nnd fonmIng occur fogofhor nnd fhoy nro undosIrnbIo sInco fhoy wof ofhor
mochnnIcnI nrfs of fho boIIor nnd roduco fhoIr offIcIoncy. AcfunI hoIghf of fho wnfor coIumn
cnnnof bo judgod duo fo fonmIng honco cronfIng dIffIcuIfy In fho mnInfonnnco.
HIgLIIgLts:
ChIof sourcos of wnfor: Son wnfor, rnInwnfor, ground wnfor nnd surfnco wnfor.
ImurIfIos rosonf In wnfor:
(i) Susondod, (ii) CoIIoIdnI, (iii) IssoIvod ImurIfIos
Tomornry hnrdnoss Is duo fo Cn(HCO
3
)
2
nnd Mg(HCO
3
)
2
nnd cnn bo romovod by
boIIIng.
Iormnnonf hnrdnoss Is duo fo chIorIdos nnd suIfnfos of Cn
2+
, Mg
2+
, Io
2+
nnd ofhor
honvy mofnIs.
Hnrdnoss oxrossod In oquIvnIonf nmounf of CnCO
3
=
Mnss of hnrdnoss roducIng subsfnncos 50
ChomIcnI oquIvnIonf of hnrdnoss roducIng subsfnncos
l m hnrdnoss l nrf of CnCO

3
oquIvnIonf hnrdnoss In l0
6
nrfs of wnfor.
Hnrd wnfor cnnnof bo usod for sfonm gonornfIon In boIIors duo fo fho robIoms
IIko scnIo nnd sIudgo formnfIon, rImIng nnd fonmIng, boIIor corrosIon nnd fnIIuro.
Softening of Water
SoffonIng of wnfor monns fho romovnI of cnIcIum, mngnosIum, Iron snIfs nnd sImIInr
ofhor mofnIIIc Ions, whIch wouId form InsoIubIo mofnIIIc sons. Tho fhroo Imorfnnf IndusfrInI
mofhods omIoyod for soffonIng of wnfor nro:
l. CoId nnd hof IImo-sodn rocoss.
2. IormufIf or zooIIfo rocoss.
3. Ion-oxchnngo or domInornIIznfIon rocoss.
l. Line-eoJo proceee. Iy fhIs rocoss, soIubIo cnIcIum nnd mngnosIum snIfs nro rondorod
InsoIubIo by nddIng cnIcuInfod nmounf of IImo |(CnOH)
2
] nnd sodn |n
2
CO
3
]. Tho InsoIubIo
rocIIfnfos of CnCO
3
nnd Mg(OH)
2
nro romovod by fIIfrnfIon. Iy fhIs mofhod, bofh fomornry
nnd ormnnonf hnrdnoss nro romovod.
Ior fho romovnI of fomornry hnrdnoss fho roncfIons nro:
Cn(HCO
3
)
2
+ Cn(OH)
2
2CnCO
3
+ 2H
2
O
Mg(HCO
3
)
2
+ Cn(OH)
2
2CnCO
3
+ MgCO
3
+ 2H
2
O
MgCO
3
+ Cn(OH)
2
Mg(OH)
2
+ CnCO
3

Honco, fo romovo oquIvnIonf qunnfIfIos of Cn nnd Mg hnrdnossos fho nmounf of IImo
nocossnry Is In fho rnfIo of l:2.
WATER TREATMENT 357
AgnIn for fho romovnI of ormnnonf hnrdnoss. Tho roncfIons nro:
CnSO
4
+ n
2
CO
3
CnCO
3
+ n
2
SO
4
MgSO
4
+ n
2
CO
3
MgCO
3
+ n
2
SO
4
MgCO
3
+ Cn(OH)
2
Mg(OH)
2
+ CnCO
3

Honco, for fho romovnI of ormnnonf hnrdnoss duo fo Cn-snIfs, IImo Is nof nocossnry,
buf If Is nocossnry for Mg snIfs. Ixfrn nddIfIon of Cn(OH)
2
cnusos hnrdnoss. So cnIcuInfod
qunnfIfIos of IImo nnd sodn nro fo bo nddod nffor fho doformInnfIon of ncfunI hnrdnoss.
In fho ncfunI rocoss fho wnfor Is fhoroughIy mIxod wIfh fho chomIcnIs nnd nIIowod fo
roncf for suffIcIonf fImo. AcfIvnfod chnrconI Is nddod ns ncfIvnfor, nIum ofc. nro nddod ns
conguInnfs. To nvoId nffor-rocIIfnfIon of CnCO
3
, sIudgo of fho rovIous oornfIon Is nddod,
whIch suIIos fho nucIoI for fho rocIIfnfIon.
Cold Lime-Soda Process
In fhIs mofhod, cnIcuInfod qunnfIfy of chomIcnIs nnd wnfor, nIong wIfh nccoIornfors nnd
conguInfors nro nddod fo n fnnk fIffod wIfh n sfIrror (IIg. l?.l). On vIgorous sfIrrIng, fhorough
mIxIng fnkos Inco. Affor soffonIng fho soff wnfor rIsos uwnrds nnd fho honvy sIudgos soffIo
down. Tho soffonod wnfor nssos fhrough n fIIforIng modIn onsurIng comIofo romovnI of fho
sIudgo nnd fInnIIy fho fIIforod wnfor fIows ouf fhrough fho fo. CoId IImo sodn rocoss Is usod
for nrfInI soffonIng of munIcInI wnfor, for soffonIng of cooIIng wnfor ofc. In ncfunI uroso,
mngnosIum hnrdnoss Is broughf down fo nImosf zoro buf cnIcIum hnrdnoss romnIns nbouf
40 m.
Driving belt
Raw water
feed inlet
Filtered softened
water outlet
Outer chamber
Inner chamber
Motor
Chemicals
(soda + lime
+ coagulant)
feed inlet
Wood-fibre
filter
Stirrer
paddles
Stirrer
Sedimented
sludge
[CaCO , Mg(OH) ]
3 2
Sludge outlet
Fig. 17.1 Continuous cold lime-soda softener.
Hot Lime-Soda Process
ThIs rocoss Is sImIInr fo fho coId IImo-sodn rocoss. Horo fho chomIcnIs nIongwIfh fho
wnfor nro honfod nonr nbouf fho boIIIng oInf of wnfor by oxhnusf sfonm. As fho roncfIon fnkos
Inco nf hIgh fomornfuro, fhoro nro fho foIIowIng ndvnnfngos:
(i) fho rocIIfnfIon roncfIon bocomos nImosf comIofo.
(ii) fho roncfIon fnkos Inco fnsfor.
(iii) fho sIudgo soffIos rnIdIy.
(it) no conguInnf Is noodod.
(t) dIssoIvod gnsos (whIch mny cnuso corrosIon) nro romovod.
(ti) vIscosIfy of soff wnfor Is Iowor, honco fIIforod onsIIy.
(tii) !osIdunI hnrdnoss Is Iow comnrod fo fho coId rocoss.
Hof IImo-sodn rocoss consIsfs of fhroo nrfs:
(o) '!oncfIon fnnk` In whIch comIofo mIxIng of fho IngrodIonfs fnkos Inco.
(I) 'IonIcnI sodImonfnfIon vossoI` whoro fho sIudgo soffIos down nnd
(c) 'Snnd fIIfor` whoro sIudgo Is comIofoIy romovod.
Tho soff wnfor from fhIs rocoss Is usod for foodIng fho boIIors (IIg. l?.2).
Advantages Include:
(i) !Imo sodn rocoss Is oconomIcnI.
(ii) Tho rocoss Imrovos fho corrosIon rosIsfnnco of fho wnfor.
(iii) MInornI confonf of fho wnfor Is roducod.
(it) H of fho wnfor rIsos, whIch roducos fho confonf of nfhogonIc bncforIn.
Raw water
feed inlet
Super
heated
steam inlet
Reaction
tank
Conical
sedimentation
tank
Precipitated
sludge
[CaCO , Mg(OH) ]
3 2
Chemicals
(lime + soda)
feed inlet
Softened
water
Fine
sand
layer
Sand
filter
Coarse
sand layer
Gravels layer
Filtered
softened
water outlet
Precipitated
sludge outlet
Fig. 17.2 Continuous hot lime-soda softener.
Disadvantages Include:
(i) Hugo nmounf of sIudgo Is formod nnd dIsosnI Is dIffIcuIf.
(ii) uo fo rosIdunI hnrdnoss, wnfor Is nof suIfnbIo for hIgh rossuro boIIor.
WATER TREATMENT 359
Permutit or ZeoIite Process
ZooIIfo Is hydrnfod sodIum nIumIno sIIIcnfo cnnbIo of oxchnngIng rovorsIbIy Ifs sodIum
Ions for Cn
2+
nnd Mg
2+
, hnvIng fho gonornI formuIn n
2
O.AI
2
O
3
.xSIO
2
.,H
2
O. Common zooIIfo
Is n
2
O AI
2
O
3
.3SIO
2
.2H
2
O nnd Is known ns nnfroIIfh. Ofhors gIuconIfos, groon snnd ofc. nro
usod for wnfor soffonIng.
ArfIfIcInI zooIIfo usod for soffonIng uroso Is ormufIf. Thoso nro orous nnd gInssy
nnd hnvo gronfor soffonIng cnncIfy fhnn groon snnd. Thoy nro ronrod by honfIng fogofhor
wIfh chInn cIny, foIdsnr nnd sodn nsh.
MetLod oI SoItenIng: Hnrdwnfor Is nssod fhrough n bod of zooIIfo nf n socIfIc rnfo nf
ordInnry fomornfuro; fho hnrdnoss cnusIng cnfIons i.e., Cn
2+
nnd Mg
2+
nro oxchnngod for n
nnd If Is convorfod fo CnZo nnd MgZo.
!oncfIons fnkIng Inco nro:
n
2
Zo + Cn(HCO
3
)
2
= 2n HCO
3
+ CnZo
n
2
Zo + Mg(HCO
3
)
2
= 2nHCO
3
+ MgZo
n
2
Zo + CnSO
4
= n
2
SO
4
+ CnZo
n
2
Zo + CnCI
2
= 2nCI + CnZo
RegenevutIon oI ZeoIIte: Tho rocoss Is nIso commorcInIIy succossfuI sInco fho Cn/Mg
zooIIfos formod by nssIng hnrd wnfor fhrough fho bod cnn bo onsIIy rogonornfod Info n
2
Zo by
nssIng brIno fhrough fho bod of InncfIvnfod zooIIfo.
CnZo or MgZo + 2nCI = n
2
Zo + CnCI
2
(Or MgCI
2
)
Tho wnshIngs confnInIng CnCI
2
or MgCI
2
nro wnsfod. Tho wnfor soffonod by fhIs rocoss
cnn bo usod for Inundry urosos.
Zeolite sand
Gravel
Top distributor
Hard water in
Injector
Salt storage
Waste
Soft water
out
Fig. 17.3 Softening of hard water by permutit process.
AJtonIogee. (i) Hnrdnoss of wnfor cnn bo romovod comIofoIy ufo nbouf l0 m; (ii) Tho
oquImonf usod Is smnII nnd onsy fo hnndIo; (iii) If roquIros Ioss fImo for soffonIng; (it) Thoro
Is no sIudgo formnfIon, honco fho rocoss Is cIonn; (t) Insy fo rogonornfo; (ti) Any hnrdnoss
cnn bo romovod wIfhouf nny ndjusfmonf of fho rocoss.
DieoJtonIogee. (i) CoIourod wnfor or wnfor confnInIng susondod ImurIfIos cnnnof bo
usod boforo fIIfrnfIon; (ii) Wnfor confnInIng ncId cnnnof bo usod for soffonIng sInco ncId mny
dosfroy fho zooIIfo; (iii) SInco on romovnI of Cn
2+
nnd Mg
2+
fho soff wnfor confnIns Inrgo nmounf
of nHCO
3
, fhIs on honfIng IIbornfos CO
2
, whIch cnusos corrosIon In fho boIIors nnd honco fhIs
soff wnfor Is nof suIfnbIo for boIIors.
Ion Exchange or Demineralization
Ion oxchnngo rosIns nro orgnnIc oIymors whIch nro crossIInkod hnvIng mIcroorous
sfrucfuro nnd fho funcfIonnI grous nro nffnchod fo fho chnIns whIch nro rosonsIbIo for fho
Ion oxchnngo roorfIos.
(i) CoIion excIonge reeine (IH
+
) nro honoI-suIfonIc ncId-formnIdohydo rosIn, sfyrono-
dIvInyI bonzono cooIymors whIch oxchnngo fhoIr H
+
Ions wIfh fho cnfIons rosonf In
fho wnfor i.e., Cn
2+
nnd Mg
2+
.
CH CH CH CH
2 2

SO H
3
SO H
3
n
cation exchange resin
(ii) Anion excIonge reeine (IOH
). Tho sfyrono dIvInyI bonzono or nmIno formnIdohydo

cooIymors confnIn qunfornnry nmmonIum forfInry suIhonIum or nmIno grou In
fho rosIn. Tho rosIn on fronfmonf wIfh nOH soIufIon Is cnnbIo of oxchnngIng fho
OH
wIfh dIfforonf nnIons of wnfor i.e., CI
, SO
4
2
ofc.
CH CH CH CH
2

2 2 2
CH CH CH
CH NMe OH
2 2
+
----CH ----CH
2
CH CH CH CH----CH
2

2 2
CH NMe OH
2 2
+

CH NMe OH
2 2
+
CH NMe OH
2 2
+

Anion exchange resin
MethoJ: Tho hnrd wnfor Is nssod fIrsf fhrough cnfIon oxchnngo rosIn sImIInr fo fho
ormufIf rocoss whoroby fho cnfIons IIko Cn
2+
, Mg
2+
nro romovod from fho hnrd wnfor nnd
oxchnngod wIfh H
+
ns foIIows:
2!H
+
+ Cn
2+
/Mg
2+
!
2
Cn
2+
/!
2
Mg
2+
+ 2H
+
Affor fhIs fho hnrd wnfor Is ngnIn nssod fhrough nnIon oxchnngo coIumn, whIch
oxchnngos nII fho nnIons IIko SO
4
2
, CI
ofc. rosonf In fho wnfor wIfh OH
!OH
+ CI
!
+
CI
+ OH
Thoso H
+
nnd OH
combIno fo form wnfor moIocuIo. Thus fho wnfor comIng ouf fInnIIy
from fho fwo oxchnngors Is Ion froo nnd cnIIod JeioiniceJ or JenineroliceJ wnfor.
WATER TREATMENT 361
Injector
Cation
exchanger
gravel
Acid
regenerator
Waste
liquor
Waste
liquor
Alkaline
regenerator
Injector
Pump
Anion
exchanger
gravel
Fig. 17.4 Demineralisation of water.
SO
4
C O
C C
C
OH
O
C C
O
O
Ca C
C C
O
O
C C
O
C
C C
C
ONa
+
Cl
H
+
H
+
HO
C
C C
O
HO
C
C C
O
O
C
C C
C
C C
O
Na O
+
C
O
O
Ca
++
C C
C O
H
+
H
+
H
+
Cl
Cl
H
+
Cl
H
+
C H
CNH
C
HOH
H
CNH
C
HOH
H
CNH
C
H
H
SO
4
CNH
C
H
H
CNH
C
HCl
1
HOH C
HNC
C
H
HOH
HNC
C
H
H
HNC
H
H
C
HNC
C
H
H
SO
4
HNC
C H
Cation
exchange
Filter bed
Hard
water
Anion
exchange
D
.
M
.
W
a
t
e
r
Cation exchange
reaction:
2R H + Ca CaR + 2H
+ +2 +
2
Anion exchange reaction:
RNH + H O
2 2
RNH OH
3
+
RNH OH + Cl RNH Cl + OH
3 3

+ +
C
OH
OH
SO
4
SO
4
Fig. 17.5 Demineralisation of water showing the ion exchanges.

Regenerution: Tho InncfIvnfod or oxhnusfod cnfIon oxchnngo rosIn Is rogonornfod by
dII. H
2
SO
4
/HCI.
!
2
Cn
2+
+ 2H
+
2!H
+
+ Cn
2+
SImIInrIy, fho oxhnusfod nnIon oxchnngo rosIn Is rogonornfod by dII. nOH
!
2
SO
4
2
+ 2OH
2!OH
+ SO
4
2+
Tho coIumns nro fInnIIy wnshod wIfh doIonIzod wnfor nnd fho wnshIngs nro dIscnrdod.
Mixed Bed Deionizer
If Is ncfunIIy n sIngIo cyIIndor confnInIng nnd InfImnfo mIxfuro of cnfIon oxchnngor nnd
sfrongIy bnsIc nnIon oxchnngor. Honco, wnfor whIIo nssIng fhrough fho coIumn comos In
confncf wIfh fho fwo oxchnngors for n Inrgo numbor of fImos nnd fho hnrdnoss Is roducod fo n
vory Iow IovoI (l m). Thus, If Is ncfunIIy oquIvnIonf fo n sorIos of cnfIon nnd nnInon oxchnngors.
AJtonIogee of Ion oxchnngors IncIudo (i) Insy rogonornfIon; (ii) bofh ncIdIc nnd nIknIIno
wnfor cnn bo soffonod; (iii) rosIdunI hnrdnoss Is vory Iow nnd honco fho wnfor Is suIfnbIo for
hIgh rossuro boIIors nIso.
DieoJtonIogee nro (i) fho oquImonf nnd fho rocoss Is cosfIy nnd (ii) furbId wnfor cnnnof
bo dIrocfIy chnrgod for soffonIng. If noods rIor fIIfrnfIon.
Treatment of Water for Domestic Use
MunIcInIIfIos suIy poIoIle uoIer, whIch Is suIfnbIo for drInkIng nnd If musf snfIsfy
fho foIIowIng roquIromonfs:
Requiremento for Drinking Wuter:
If shouId bo cIonr nnd odourIoss.
If shouId bo dovoId of nny unIonsnnf fnsfo.
Susondod mnffor shouId nof oxcood l0 m.
If shouId bo dovoId of honvy mofnIs nnd nrsonIc.
H shouId bo nbouf 8.
Confonf of dIssoIvod snIfs shouId nof oxcood 500 m.
!nsfIy, If shouId bo froo from nfhogonIc (dIsonso cnusIng) mIcroorgnnIsms.
nfurnI wnfor from rIvor, Inkos, cnnnIs nro fronfod for fho domosfIc uroso. Tho sfos
nro ns foIIows:
AornfIon of fho rnw wnfor by nssIng comrossod nIr fo romovo mnInIy fho obnoxIous
odour nnd Iron ns Io(OH)
3
.
SoffIIng In n Inrgo fnnk fo romovo susondod ImurIfIos.
SodImonfnfIon fhrough conguInfIon of fho coIIoIdnI nrfIcIos by nddIng n suIfnbIo
conguInnf. ChomIcnI conguInnfs nro gonornIIy (i) AIum |K
2
SO
4
, AI
2
(SO
4
)
3
.24H
2
O]
(ii) Croon vIfrIoI |IoSO
4
.?H
2
O].
ConguInnfs or fIoccuInnfs nro gonornIIy nddod In fho form of soIufIon nnd mIxIng Is
cnrrIod ouf by sfIrrIng.
Tho goInfInous rocIIfnfos mnInIy confnIn nIumInIum hydroxIdo, forrous nnd forrIc
hydroxIdos (forrous hydroxIdos nro convorfod fo forrIc hydroxIdo by fho dIssoIvod oxygon
of wnfor).
Thoso honvy fIoccuInnf rocIIfnfos confnIn nIso somo bncforIn mnkIng fho wnfor froo
of somo of fho mIcroorgnnIsms.
Thoso nrfInIIy cInrIfIod wnfor Is fIIforod fhrough snnd grnvIfy fIIfors.
WATER TREATMENT 363
Thoso fIIfors nro rocfnnguInr fnnks, whIch confnIn Inyors of fIno snnd nf fho fo of ono
mofor fhIck, nf mIddIo of conrso snnd of 0.5 mofor fhIck nnd nf boffom n grnvoI of 0.5
mofor fhIck.
Sterilization
(i) B, oJJiIion of IleocIing pouJer (1 lg per 1000 liloliIere).
Horo sforIIIznfIon Is offocfod by fho HOCI gonornfod by fho foIIowIng roncfIon:
Cn(OCI)CI + H
2
O Cn(OH)
2
+ CI
2
CI
2
+ H
2
O

HCI + HOCI
nnd fhIs HOCI kIIIs fho gorms.
DieoJtonIogee of IIie proceee.
(i) IIonchIng owdor mnkos wnfor unnocossnry hnrd nnd somofImos Imnrfs n bnd fnsfo
fo fho wnfor.
(ii) B, JirecI cIlorinoIion. Horo nIso fho gonornfod HOCI kIIIs fho nfhogonIc bncforIn.
!IquId chIorIno Is fho mosf offocfIvo rongonf, 0.3-0.5 m chIorIno Is suffIcIonf.
Advuntuge oI usIng CLIovIne. If Is offocfIvo nnd oconomIcnI; chIorIno doos nof mnko
wnfor hnrd nnd roquIros n IIffIo snco for sforngo.
Isudvuntuges. Ixcoss chIorIno Imnrfs unIonsnnf fnsfo nnd odour fo fho fronfod
wnfor. IssoIvod chIorIno cnusos IrrIfnfIon fo mucus mombrnno nnd Iowors fho H of wnfor
boIow 6.5. Tho fronfod wnfor shouId confnIn chIorIno Ioss fhnn 0.2 m.
(ii) Break-point ChIorination
If Is soon fhnf whon IIquId chIorIno Is nddod or chIorIno gns Is nssod fhrough wnfor fho
consumfIon of chIorIno mnkos fho nvnIInbIo chIorIno Ioss nnd nffor somo fImo fho nvnIInbIo
chIorIno Incronsos. ThIs Is duo fo fho consumfIon of chIorIno In oxIdIsIng somo oxIdIsnbIo
orgnnIc mnffor rosonf In wnfor nf fIrsf. Thon nvnIInbIo chIorIno ngnIn Incronsos duo fo
docomosIfIon of chIoro-orgnnIc comounds.
ThIs froo chIorIno Is rosonsIbIo for dosfrucfIon of nfhogonIc bncforIn In wnfor. Tho
oInf nf whIch fho rosIdunI chIorIno bogIns fo nonr Is known ns Ireol poinI nnd nf fhIs oInf
wnfor Is dovoId of bnd fnsfo nnd odours nnd Is bncforIn froo.
AJtonIogee of Ireol poinI cIlorinoIion
OrgnnIc mnffors rosonf In wnfor nro comIofoIy oxIdIsod IonvIng bohInd odour-froo
wnfor nnd somofImos coIour-froo wnfor.
InfhogonIc bncforIn nro dosfroyod comIofoIy.
If rovonfs fho growfh of wood In wnfor In fufuro.
(iii) SteriIization by ChIoramine
Whon chIorIno nnd nmmonIn nro mIxod In fho rnfIo 2:l of voIumo chIornmIno Is formod.
CI
2
+ H
3
CI.H
2
+ HCI
ChIornmIno Is much moro offocfIvo fhnn chIorIno In Ifs bncforIcIdnI (bncforIn kIIIIng)
ncfIon. Horo nIso HOCI Is IIbornfod.
CI.H
2
+ H
2
O HOCI + H
3
HOCI IfsoIf Is bncforIcIdnI nnd horo fho IIbornfod nnsconf oxygon Is nIso bncforIcIdnI
HOCI HCI + |O].
Tho uso of chIornmIno for sforIIIznfIon Is gnInIng Imorfnnco ns If doos nof Imnrf nny
IrrIfnfIng odour nnd doos nof nffocf fho fnsfo of fho fronfod wnfor.
(iv) SteriIization by Ozonization
Ozono Is nn unsfnbIo gns nnd docomosos fo gIvo nnsconf oxygon. ThIs nnsconf oxygon
kIIIs bncforIn nnd oxIdIsos fho orgnnIc mnffor rosonf In fho wnfor. Tho ozono fronfmonf Innf
consIsfs of n fowor mndo of onnmoIIod Iron, sonrnfod by orfornfod coIIuIoId nrfIfIon Info n
Inrgo numbor of comnrfmonfs, ozono Is nssod fhrough boffom nnd fho wnfor Is nIIowod fo
orcoInfo fhrough fho coIIuIoId nrfIfIon. Tho orfornfod nrfIfIon mnkos fho wnfor Info mInufo
bubbIos rosuIfIng In n counfor-curronf confncf wIfh ozono. ThIs mnkos fho fronfmonf mosf
offocfIvo.
AJtuntugeo of oxone oterilixution ure
(o) SforIIIznfIon, bIonchIng, docoIourIsnfIon nnd doodourIsnfIon fnko Inco nf fho snmo
fImo.
(I) Ozono doos nof Imnrf nny unIonsnnf fnsfo or odour fo fho fronfod wnfor nnd doos
nof chnngo Ifs H nrocInbIy ns If sImIy docomosos Info oxygon. So If doos nof
cnuso nny IrrIfnfIon fo fho mucus mombrnno ns Is fho cnso wIfh chIorIno or bIonchIng
owdor fronfmonf.
(c) TImo of confncf Is onIy l0-l5 mInufos nnd doso sfrongfh Is onIy 2-3 m.
Tho onIy JieoJtonIoge of fhIs rocoss Is fhnf If Is comnrnfIvoIy cosfIy.
SteriIization through PhysicaI Methods
(i) IoIIIng, (ii) Ixosuro fo fho sunIIghf, (iii) SforIIIznfIon wIfh !V IIghf.
DechIorination
Whon durIng chIorInnfIon, bronk oInf chIorInnfIon Is ronchod, If bocomos somofImos
nocossnry fo romovo fho oxcoss chIorIno from fho fronfod wnfor, fhIs rocoss Is known ns
JecIlorinoIion. SuIhur dIoxIdo Is vory common ns nn nnfIchIor. Ofhor common nnfIchIors
nro: sodIum bIsuIhIfo, sodIum fhIosuIhnfo nnd hydrogon oroxIdo.
CI
2
+ H
2
O = HOCI + HCI
H
2
O + SO
2
= H
2
SO
3
SO
2
+ CI
2
+ 2H
2
O = 2HCI + H
2
SO
4
HOCI + H
2
SO
3
= HCI + H
2
SO
4
H
2
O
2
+ CI
2
= 2HCI + O
2
ochIorInnfIon Is noodod fo nvoId fho hnrmfuI offocfs of fronfod wnfor.

Desalination of Brackish Water
Tho wnfor confnInIng dIssoIvod snIfs nnd hnvIng vory snIfy fnsfo Is cnIIod IroclieI uoIer,
IIko fho son wnfor nnd If Is nof suIfnbIo for drInkIng. Tho rocoss of romovnI of common snIf
from fhIs brnckIsh wnfor Is cnIIod JeeolinoIion. osnIInnfIon cnn bo dono by fho foIIowIng
mofhods.
(o) 1lecIroJiol,eie. ThIs mofhod InvoIvos fho romovnI of Ions from fho brIno soIufIon by
nIyIng dIrocf curronf nnd omIoyIng nIr of InsfIc mombrnnos fhrough whIch Ions cnn nss.
Irom IIg. l?.6 wo cnn fInd fhnf whon dIrocf curronf Is nssod fhrough snIIno wnfor, fho n
+
Ions movo fownrds fho cnfhodo whIIo CI
Ions movo fownrds fho nnodo fhrough fho mombrnno

nnd coIIocf In fho fwo sIdo comnrfmonfs whIIo fho confrnI comnrfmonf confnIns uro
dosnIInnfod wnfor.
WATER TREATMENT 365
Sea water
Cathode
Sea water Sea water
+
Anode
Negative ions
Positive ions
Membrane Membrane
Concentrated
brine
Concentrated
brine
Pure
water
Fig. 17.6 Line diagram of electrodialysis.
To mnko fhIs rocoss moro offocfIvo, Ions sonsIfIvo mombrnnos nro usod fhnf nIIow fho
nssngo of oIfhor socIfIc cnfIons or socIfIc nnIons. Thoso mombrnnos nro soIocfIvo ns fhoy nro
mndo u of mnforInIs confnInIng fIxod funcfIonnI grous.
An oIocfrodInIysIs coII ns shown In IIg. l?.? confnIns n Inrgo numbor of nIr of mombrnnos
nnd snIIno wnfor Is nssod undor rossuro In oIocfrIc fIoId nIIod orondIcuInr fo fho dIrocfIon
of fIowIng wnfor. CnfIons nnd nnIons nss fhrough fho mombrnno nIrs nnd wo obfnIn nIfornnfo
sfronms of uro wnfor nnd conconfrnfod snIf soIufIon.
Sea water feed
Cation
selective
membrane
Cathode
Pure
water outlet
Concentrated
sea water
outlet
Anode
Anion
selective
membrane
C
C
A
A
C
C
A
A
C
C
A
A
Fig. 17.7 Electrodialysis cell.
Pressure
Sea water
Pure water
Piston
Stout semi-
permeable
membrane
Pure
water out
(I) Ieteree oenoeie. OsmosIs doscrIbos fho fIow of soIvonf from dIIufo fo conconfrnfod
soIufIon fhrough n somIormonbIo mombrnno. Whorons
rovorso osmosIs doscrIbos fho fIow of soIvonf In oosIfo
dIrocfIon i.e., from conconfrnfod soIufIon fo dIIufo soIufIon
ncross n somIormonbIo mombrnno by nIyIng hydrosfnfIc
rossuro In oxcoss of osmofIc rossuro.
Tho coIIuIoso ncofnfo nnd fho moro roconfIy usod
oIymofhncryInfo nnd oIynmIdo mombrnnos do nof nIIow
fho soIufo nss, whIIo fho soIvonf Is forcod fhrough nnd
coIIocfod ns n uro soIvonf In n dIrocfIon ns shown In
IIg. l?.8. Thoro nro mnny oJtonIogee of usIng rovorso
osmosIs ns fho urIfIcnfIon rocoss for wnfor whIch
IncIudo (i) romovnI of IonIc, non-IonIc, coIIoIdnI nnd hIgh
moIocuInr woIghf soIufos from wnfor, (ii) rogonornfIon of
fho rocoss InvoIvos fho onsy roIncomonf of fho
somIormonbIo mombrnno, (iii) onsy mnInfonnnco nnd
oconomIcnI, ns fho mombrnno IIfosnn Is hIgh, (it) unInforrufod suIy of Inrgo voIumo of
wnfor for IndusfrInI or domosfIc uroso cnn bo obfnInod. !ovorso osmosIs Is InrgoIy usod
for urIfIcnfIon of son wnfor for domosfIc uso.
ChemicaI AnaIysis of Water
l. stImutIon oI Ivee cLIovIne. Tho rosIdunI froo chIorIno romnInIng nffor fho munIcInI
rocossIng of domosfIc wnfor Is InjurIous fo honIfh nnd honco osfImnfIon of fhIs froo chIorIno Is
ossonfInI. Tho rIncIIo Is fho fronfmonf of wnfor confnInIng froo chIorIno wIfh KI soIufIon.
Tho chIorIno rosonf IIbornfos nn oquIvnIonf nmounf of IodIno whIch cnn bo osfImnfod wIfh
sfnndnrd fhIosuIfnfo soIufIon usIng sfnrch ns nn IndIcnfor.
CI
2
+ 2KI 2KCI + I
2
I
2
+ 2n
2
S
2
O
3
2nI + n
2
S
4
O
6
I
2
+ Sfnrch oo-bIuo comIox
MetLod: To 50 mI of wnfor snmIo In n IodIno fInsk, l0 mI of l0 KI soIufIon nddod,
shnkon nnd wnIfod for somo fImo In fho dnrk nnd fInnIIy fIfrnfod wIfh /50 sodIum fhIosuIfnfo
soIufIon usIng sfnrch soIufIon ns IndIcnfor fownrds fho ond. Tho ond oInf IndIcnfos n chnngo
from doo-bIuo fo jusf coIorIoss soIufIon.
ColculoIion.
VoIumo of /50 n
2
S
2
O
3
roquIrod = V mI
Sfrongfh of froo chIorIno =
V 35.5 l0
2500 l000
6

m.
2. AIkuIInIty. Tho nIknIInIfy of wnfor Is osfImnfod by osfImnfIng (o) OH
nnd CO
3
2
Ions
nnd (I) HCO
3
Ions.
(o) OH

+ H
+
H
2
O
CO
3
2
+ H
+
HCO
3
(I) HCO
3
+ H
+
H
2
O

+ CO
2
Fig. 17.8 Reverse osmosis cell.
WATER TREATMENT 367
Thoso osfImnfIons nro dono by (o) fIfrnfIng ngnInsf sfnndnrd ncId soIufIon usIng
honoIhfhnIoIn ns nn IndIcnfor nnd (I) usIng mofhyI ornngo ns nn IndIcnfor.
MetLod: l00 mI of wnfor snmIo Is fnkon In n fInsk nnd fow dros of honoIhfhnIoIn
nddod nnd fIfrnfod ngnInsf /50 H
2
SO
4
soIufIon fo coIorIoss ond oInf. Tho snmo soIufIon Is
furfhor fIfrnfod wIfh 2 fo 3 dros of mofhyI ornngo IndIcnfor.
ColculoIion. VoI. of ncId ufo honoIhfhnIoIn ond oInf = V
l
Ixfrn voIumo of ncId nddod fo gof mofhyI ornngo ond oInf V
2
mI.
IhonoIhfhnIoIn nIknIInIfy (oquIvnIonf CnCO
3
)
I =
V 50 l0
50 l00 l000
l
6

m
MofhyI ornngo nIknIInIfy (oquIvnIonf CnCO
3
)
M =
(V V ) 50 l0
50 l00 l000
l 2
6
+

m.
3. Huvdness
(o) 1eIinoIion of Ienporor, IorJneee. Tomornry hnrdnoss Is duo fo Cn(HCO
3
)
2
nnd
Mg(HCO
3
)
2
whIch cnuso nIknIInIfy In wnfor. Tomornry hnrdnoss Is doformInod by fIndIng fho
nIknIInIfy of wnfor boforo nnd nffor boIIIng, sInco fomornry hnrdnoss Is romovod on boIIIng.
Cn(HCO
3
)
2

IoIIIng
CnCO
3
+ CO
2
+ H
2
O
Mg(HCO
3
)
2
Mg(OH)
2
+ CO
2
MetLod: Info 50 mI of wnfor snmIo fnkon In n conIcnI fInsk, ndd 2 fo 3 dros of mofhyI
ornngo nnd fIfrnfo wIfh /50 HCI. !of fho voIumo of ncId bo V
l
. ow fnko l00 mI of wnfor
snmIo In n bonkor, ovnornfo fo drynoss. Add l00 mI of dIsfIIIod wnfor fo fho bonkor nnd
dIssoIvo fho rosIduo Ioff. Thon, fnko 50 mI of fhIs wnfor snmIo nnd fIfrnfo wIfh /50 HCI
usIng n fow dros of mofhyI ornngo ns nn IndIcnfor. !of fho voIumo of ncId roquIrod bo V
2
mI.
nIknIInIfy duo fo fomornry hnrdnoss In CnCO
3
oquIvnIonf
=
(V V ) l0
50 l000
l 2
6

m
(I) (i) etevmInutIon oI pevmunent Luvdness. Tho osfImnfIon Is dono by nddIng
oxcoss of sfnndnrd n
2
CO
3
soIufIon fo n gIvon voIumo of boIIod wnfor confnInIng ormnnonf
hnrdnoss. Tho chIorIdos nnd suIfnfos form InsoIubIo cnrbonnfos. Tho rosIdunI n
2
CO
3
Is fIfrnfod
ngnInsf sfnndnrd ncId nnd fho dIfforonco of n
2
CO
3
oquIvnIonf gIvos ormnnonf hnrdnoss.
MetLod: 50 mI of fho wnfor snmIo Is fnkon In n bonkor. 50 mI of /50 n
2
CO
3
soIufIon
Is nddod nnd boIIod for l5 mInufos. CooI nnd fIIfor fho soIufIon, wnsh fho rosIduo on fIIfor
nor nnd ndd If fo fho fIIfrnfo nnd fIfrnfo fho /50 n
2
CO
3
Ioff In fho fInsk wIfh /50 HCI
usIng mofhyI ornngo ns IndIcnfor. !of fIfro voI. bo V.
Iormnnonf hnrdnoss =
(50 V) l0
50 l000
6

m.
(ii) CompIexometvIc detevmInutIon oI pevmunent Luvdness. IsodIum snIf of
ofhyIono dInmIno fofrn ncofIc ncId (ITA) Is usod ns n comIoxIng ngonf for Cn
2+
, Mg
2+
.
OOC CH
2
OOC CH
2
N CH CH N
2

2
CH COO
2
CH COO
2
IrIchromo bInck T Is usod ns nn IndIcnfor nnd H Is mnInfnInod nf H l0 usIng H
4
OH/
H
4
CI buffor. IrIchromo bInck T forms unsfnbIo comIox wIfh Cn
2+
, Mg
2+
gIvIng wIno rod
coIour. Whon ITA nddod nnd fho fofnI Cn
2+
, Mg
2+
forms comIox wIfh If nnd fho IndIcnfor
bocomos froo, fho coIour of fho soIufIon chnngos from wIno rod fo bIuo nf fho ond oInf.
MetLod: IndIcnfor soIufIon 0.5 gm. IrIchromo bInck T dIssoIvod In l00 mI nIcohoI.
Sfnndnrd ITA soIufIon (/l00): 4 gm of ITA dIssoIvod wIfh 0.l gm of MgCI
2
In
l000 mI wnfor.
An nIIquof
M
l00
ZInc ncofnfo soIufIon (rImnry sfnndnrd) Is fnkon, fo If 5 mI of H
4
CI
H
4
OH buffor nnd n fow dros of IIT IndIcnfor nro nddod nnd fIfrnfod fo bIuo ond oInf wIfh
ITA nnd fho sfrongfh of ITA Is cnIcuInfod.
ThIs snmo rocoduro Is roonfod wIfh 50 mI wnfor snmIo. !of fho voIumo of fIfrnnf bo
V (f) M/l00 ITA soIufIon.
Iormnnonf hnrdnoss =
0.00l V f l0
50
6
m.
Tho ITA mofhod for fho doformInnfIon Is roforrod fo ofhor mofhods sInco fho mofhod
hns gronfor nccurncy, sImIIcIfy nnd rnIdnoss.
Iuffor soIufIon: A mIxfuro of l42 mI of conc. H
4
OH nnd l?.5 gm H
4
CI Is dIIufod fo
250 mI dIsfIIIod wnfor.
HIgLIIgLts:
SoffonIng mofhods IncIudo:
(i) Hof nnd coId IImo sodn rocoss.
(ii) ZooIIfo or ormufIf rocoss.
(iii) Ion oxchnngo or domInornIIznfIon.
MIcro-orgnnIsms from ofnbIo wnfor cnn bo romovod by:
(i) IoIIIng for l0 fo l5 mInufos
(ii) IIonchIng owdor fronfmonf
(iii) ChIorInnfIon wIfh CI
2
(it) ChIornmIno fronfmonf
(t) OzonIznfIon.
osnIInnfIon of brnckIsh wnfor dono by:
(i) IIocfrodInIysIs
(ii) !ovorso osmosIs.
Ixhnusfod Ion-oxchnngo rosIns nro rogonornfod by:
(i) CnfIon oxchnngors rogonornfod by nssIng sfrong ncId soIufIon fhrough fho bod
(ii) AnIon oxchnngors rogonornfod by nssIng sfrong bnso soIufIon fhrough fho bod.
Hnrdnoss of wnfor cnn bo osfImnfod by:
(i) Iormnnonf hnrdnoss doformInod by fIfrnfIng wIfh sfnndnrd n
2
CO
3
soIufIon.
(ii) ComIoxomofrIc fIfrnfIon by ITA
!nIfs of hnrdnoss nro:
(i) m
(ii) mg/IIfro (l m = l mg/IIfro)
(iii) CInrk`s dogroo (l m = 0.0? CI)
(it) dogroo Ironch (l m = 0.l Ir).
(ConIJ.)
WATER TREATMENT 369
Hnrd wnfor doos nof onsIIy Infhor wIfh son, Insfond If forms n gronsy scum.
Wnfor Is hnrd If If confnIns cnIcIum or mngnosIum Ions.
Scum Is n rocIIfnfo formod whon son comos In confncf wIfh hnrd wnfor
confnInIng nbovo monfIonod Ions.
Cn
2+
(oq) + C
l?
H
35
CO
2
(oq) Cn(C
l?
H
35
CO
2
)
2

InsoIubIo rocIIfnfo
Tomornry hnrd wnfor confnIns bIcnrbonnfos or hydrogon cnrbonnfos of cnIcIum
or mngnosIum.
Tomornry hnrdnoss Is romovod by boIIIng.
Cn(HCO
3
)
2
(oq)
boIIIng
CnCO
3
+ H
2
O(l) + CO
2
.
Tho soIId cnIcIum cnrbonnfo Is rocIIfnfod ns scnIo, whIch nffocfs honfIng oIomonf
of boIIors nnd grndunIIy bIocks fho Ios In honfIng sysfom.
Iormnnonf hnrdnoss Is nof romovod by boIIIng.
Tho mInornI gysum (CnSO
4
) Is sIIghfIy soIubIo In wnfor nnd mnkos wnfor
ormnnonfIy hnrd.
Ion oxchnngo rosIn nnd ofhor mofhods of soffonIng of wnfor by romovIng cnIcIum
nnd mngnosIum Ions Is known ns uoIer IreoInenI.
PROBLEMS
PvobIem 1. ColculoIe Ienporor, IorJneee onJ IoIol IorJneee of o eonple of uoIer
conIoining.
Mg(HCO
3
)
2
= 7. ng/l . Co(HCO
3
)
2
= 16 ng/l
MgCl
2
= 9 ng/l . CoSO
4
= 13.6 ng/l
SoI. Tomornry hnrdnoss = ?.5 l6 mg/ +
l00
l46
l00
l62
l
Iormnnonf hnrdnoss = 9
l00
95
l36
l00
l36
+
. mg/l.
PvobIem 2. Hou non, ng. of IeSO
4
JieeolteJ per liIre gitee 200 ppn of IorJneee:
SoI. (56 + l6 + 64)g of IoSO
4
l00 g CnCO
3
Ior l00 m hnrdnoss IoSO
4
roquIrod or l0
6
nrfs of wnfor Is l36 nrfs.
Ior 200 m hnrdnoss, IoSO
4
roquIrod =
l36 200
l00
m
= 2?2 mg/l.
PvobIem 3. A eonple of uoIer Ioe o CO
3
2
concenIroIion of 1.6 ppn. WIoI ie IIe noloriI,
of CO
3
2
in IIe eonple of uoIer:
SoI. l5.6 m = l5.6 l0
6
g/l of CO
3
2
CO
3
2
moInrIfy =
l5 6 l0
60
6
.

moI/l.
= 2.6 l0
5
M.
PvobIem 4. A eonple of uoIer Ioe Ieen founJ Io conIoin IIe follouing eolIe.
Co(HCO
3
)
2
= 10. ppn, Mg(HCO
3
)
2
= 12. ppn, CoCl
2
= S.2 ppn, MgSO
4
= 2.6 ppn,
CoSO
4
= 7. ppn.
ColculoIe (i) Ienporor, onJ pernonenI IorJneee onJ (ii) IIe tol. of
M
100
1DTA requireJ
for IiIroIion of IIe 100 nl of IIe eonple Io JeIernine IIe IoIol IorJneee of IIe eonple.
SoI. (i) Cn(HCO
3
)
2
= l0.5 m = l0.5
l00
l62
= 6 48l . m CnCO
3
Mg(HCO
3
) = l2.5 m = l2.5
l00
l46
= 8.562 m CnCO
3
CnCI
2
= 8.2 m = 8.2
l00
lll
= ?.38? m CnCO
3
MgSO
4
= 2.6 m = 2.6
l00
l20
= 2.l6? m CnCO
3
CnSO
4
= ?.5 m = ?.5
l00
l36
= 5.5l5 m CnCO
3
Tomornry hnrdnoss = (6.48l + 8.562) m
= l5.043 m
Iormnnonf hnrdnoss = (?.38? + 2.l6? + 5.l5) m = l5.069 m
TofnI hnrdnoss = (l5.043 + l5.069) = 30.ll2 m
(ii) Tho voIumo of snmIo fnkon = l00 mI.
VoIumo of M/l00 ITA roquIrod =
30.ll2 l00
l000
= 3.ll mI.
PvobIem 5. ColculoIe IIe onounI of line onJ eoJo requireJ for eofIening 0,000 liIree
of IorJ uoIer conIoining
MgCO
3
= 144 ppn, CoCO
3
= 2 ppn, MgCl
2
= 9 ppn,
CoCl
2
= 111 ppn, Ie
2
O
3
= 2 ppn, Ao
2
SO
4
= 1 ppn.
SoI. MgCO
3
= l44 m =
l44
l00
84
= l?l.4 m CnCO
3
CnCO
3
= 25 m.
MgCI
2
= 95 m =
95 l00
95
= l00 m CnCO
3
CnCI
2
= lll m =
lll l00
lll
= l00 m CnCO
3
WATER TREATMENT 371
!Imo roquIrod =
?4
l00
|2 MgCO
3
+ CnCO
3
+ MgCI
2
] voIumo of wnfor
=
?4
l00
|2 l?l.4 + 2500 + l00.0] 50,000 mg
= l?,309,000 mg = l?.3l kg.
PvobIem 6. A uoIer eonple on onol,eie gitee IIe follouing JoIo . Co
2+
= 20 ppn, Mg
2+
= 2 ppn, CO
2
= 30 ppn, HCO
3
= 10 ppn, K
+
= 10 ppn. ColculoIe IIe line (S7" pure) onJ
eoJo (91" pure) requireJ Io eofIen 1 nillion liIree of uoIer eonple.
SoI. Cn
2+
= 20 m =
20 l00
40
= 50 m CnCO
3
Mg
2+
= 25 m =
25 l00
24
= l04.65 m CnCO
3
CO
2
= 30 m =
30 l00
44
= 68.l8 m CnCO
3
HCO
3
= l50 m =
l50 l00
l22
= l22.95 m CnCO
3
!Imo roquIromonf =
?4
l00
|Mg
2+
+ CO
2
+ HCO
3
] voI. of wnfor
=
?4
l00
|l04.65 + 68.l8 + l22.95] l0
6
= 2l8.9 l0
6
mg = 2l8.9 kg.
Sodn roquIromonf =
l06
l00
Cn Mg HCO
2 2
3
+ +
+ voI. of wnfor.
=
l06
l00
50 l04 65 l22 95 l0
6
| . . ] +
= 33.6 l0
6
mg = 33.6 kg.
PvobIem ?. An exIoueIeJ ceoliIe eofIener uoe regeneroIeJ I, poeeing 10 liIree of AoCl
eol. Ioting o eIrengII of 10 g/l of AoCl. 1f IIe IorJneee of uoIer ie 600 ppn, colculoIe IIe IoIol
tolune of uoIer IIoI Ioe Ieen eofIeneJ in IIe eofIener.
SoI. l50 IIfros of nCI soIufIon confnIn = l50 l50 = 22,500 gm nCI
= 22,500
l00
ll?
CnCO
3
= l.932 l0
4
g CnCO
3
If fho hnrdnoss of wnfor Is 600 m
VoI. of wnfor =
l932 l0 l000
600
4
.
IIfros
= 3.l29 l0
4
IIfros
PvobIem B. 10 nl of 0.S
M
100
Zn (OAC)
2
requireJ nol of on 1DTA eoluIion for
eIonJorJicoIion. 0 nl of o uoIer eonple requireJ 20 nl of IIe oIote 1DTA eoluIion. ColculoIe
IIe IoIol IorJneee of uoIer in ppn.
SoI. Sfrongfh of ITA soIufIon =
l0 0.85
9
= 0.94
M
l00
l000. mI
M
l00
ITA soIufIon l g CnCO

3
20 mI of
M
l00
ITA soIufIon =
l
l000
g CnCO
3
20 0 94 .
= 0.0l9 g CnCO
3
.
50 mI of fho wnfor snmIo confnIns 0.0l9 g CnCO
3
l0
6
mI of fho wnfor snmIo confnIns =
0 0l9 l0
50
6
.
= 3??.8 gm CnCO
3
Hnrdnoss of wnfor = 3??.8 m.
PvobIem 9. A eonple on uoIer on onol,eie Ioe Ieen founJ Io conIoin IIe follouing .
Co(HCO
3
)
2
= 10. ppn. Mg (HCO
3
)
2
= 12. ppn
CoSO
4
= 7. ppn CoCl
2
= S.2 ppn MgSO
4
= 2.6 ppn.
ColculoIe IIe Ienporor, onJ pernonenI IorJneee in Jegree IrencI.
SoI. Cn(HCO
3
)
2
= l0.5 m =
l0 5 l00
l62
.
= 6.48l m
Mg(HCO
3
)
2
= l2.5 m =
l2 5 l00
l46
.
= 8.562 m
CnSO
4
= ?.5 m =
? 5 l00
l36
.
= 5.5l5 m
CnCI
2
= 8.2 m =
8 2 l00
lll
.
= ?.38? m
MgSO
4
= 2.6 m =
2 6 l00
l20
.
= 2.l6? m
Tomornry hnrdnoss = (6.48l + 8.562) = l5.043 m
= l5.043 0.l Ir = l.504 Ir
Iormnnonf hnrdnoss = (5.5l5 + ?.38? + 2.l6?) m
= l5.069 m
= l.5069 Ir.
Q. 1. WLut Is tLe need Iov "esuIInutIon oI wutev" pvogvumme? ?? ??
Ans. VIrfunIIy fhoro Is ouInfIon oxIosIon In fho modorn worId. So for drInkIng,
domosfIc nnd IrrIgnfIon urosos rIvor wnfor nnd ofhor swoof wnfor sourcos soom fo bo
InsuffIcIonf. So for fho oxIoIfnfIon of fho vnsf sourco of son wnfor, dosnIInnfIon rogrnmmo Is
roquIrod, socInIIy In fho son-sIdo nron.
Q. 2. WLut uve tLe cuuses oI covvosIon oI boIIevs? ?? ??
Ans. Tho cnusos of corrosIon nro:
Oxygon corrosIon If boIIor wnfor Is nof roorIy donornfod.
WATER TREATMENT 373
IIocfrochomIcnI corrosIon, nIso known ns ouf of sorvIco corrosIon, whon boIIor Is
shuf down.
Q. 3. WLut uve tLe dIsudvuntuges oI scuIe IovmutIon In u boIIev? ?? ??
Ans.
ScnIos nnd sIudgos nro bnd conducfors of honf, ns n rosuIf fuoI consumfIon
Incronsos.
Tubos nnd Infos nro cIoggod ns n rosuIf fho offIcIoncy of fho boIIor Is docronsod.
Tubos of fho boIIor nro corrodod by fho scnIos doosIfod nnd fhoy mny crnck nnd
Iond fo boIIor fnIIuro.
MgCI
2
+ Io + H
2
O = Mg(OH)
2
+ IoCI
2
+ H
2
Q. 4. WLy Is demInevuIIsutIon pveIevved to zeoIIte soItenIng? ?? ??
Ans. omInornIIzod wnfor Is rncfIcnIIy froo from nII fho Ions whorons fho zooIIfo soffonod
wnfor confnIns sodIum snIfs whIch nro sourcos of cnusfIc ombrIffIomonf.
Q. 5. WLy Is cLIovumIne pveIevved to CI
2
Iov stevIIIzutIon oI dvInkIng wutev? ?? ??
Ans. If Is bocnuso chIornmIno doos nof Imnrf nny rouIsIvo odour fo fho fronfod wnfor.
Q. 6. WLut uve tLe cvItevIu Iov dvInkIng wutev? ?? ??
Ans. If shouId bo dovoId of nny susondIng mnffor, nnd hnrmfuI dIssoIvod mnffor of
orgnnIc or InorgnnIc mnffor nnd nfhogonIc orgnnIsms.
Q. ?. WLy Is \V vudIutIon supevIov to otLev metLods oI stevIIIzutIon oI wutev? ?? ??
Ans. !V rndInfIon doos nof Imnrf nny unIonsnnf fnsfo or odour fo fho wnfor nnd fho
rocoss Is sImIo.
Q. B. WLut Is pIttIng?
Ans. IIffIng Is corrosIon of fho boIIor. IssoIvod gnsos IIko O
2
, CO
2
, H
2
S corrodo fho Iron
surfnco of fho boIIor nrfIcuInrIy nonr fho rIvof, bonds nnd Ionds fo Ionk or boIIor fnIIuro.
Q. 9. WLut uve boIIev compounds? ?? ??
Ans. Whon fho boIIor wnfor Is dIffIcuIf fo soffon or urIfy, somo chomIcnI subsfnncos nro
nddod fo fho boIIor wnfor fhnf mnkos fho scnIo In fho boIIor Iooso nnd onsIIy romovnbIo. Thoso
comounds nro cnIIod Ioiler conpounJe nnd oxnmIos of fhoso nro fIour, korosono, fnnnIn,
ngnr-ngnr ofc.
Q. 10. WLut Is pIumbo soIvuncy? ?? ?? How cun It be pvevented? ?? ??
Ans. Wnfor frnnsorfod fhrough Iond Ios nro confnmInnfod wIfh Ib
2+
duo fo soIubIIIfy
of mofnIIIc Iond In wnfor.
2Ib + 2H
2
O + O
2
= 2Ib(OH)
2
Tho hydroIysIs of Cn
2+
nnd Mg
2+
snIfs dIssoIvod In wnfor mny Iond fo fho formnfIon of
Iond snIfs IIko IbSO
4
nnd IbCI
2
.
MgSO
4
+ 2H
2
O = Mg(OH)
2
+ H
2
SO
4
2Ib + H
2
SO
4
+ O
2
= 2IbSO
4
+ 2H
2
O
MgCI
2
+ 2H
2
O = Mg(OH)
2
+ 2HCI 2Ib + 4HCI + O
2
= 2IbCI
2
+ 2H
2
O
Thoso Iond snIfs nro somowhnf soIubIo In wnfor. ThIs honomonon Is known ns plunIo
eoltonc,.
Tho Ib
2+
snIfs nro oIsonous nnd Is fho sourco of leoJ poieoning.
!ond oIsonIng cnn bo rovonfod by fronfmonf of fho wnfor wIfh nIknII sIIIcnfo nnd
hoshnfo foIIowod by fIIfrnfIon.
Q. 11. IIIeventIute between sIudge und scuIe.
Ans. SIudgo Is soff, Iooso, sIImy doosIf formod InsIdo fho boIIor, whIch Is onsIor fo
romovo, whIIo scnIo Is n hnrd, sfIcky, ndhoronf doosIf on fho Innor surfnco of fho boIIor whIch
Is dIffIcuIf fo romovo.
Q. 12. WLut Is bveuk-poInt cLIovInutIon? ?? ??
Q. 13. Stute tLe LuvmIuI eIIects oI sIIIcu pvesent In wutev.
Ans. Irosonco of sIIIcn In fho wnfor Ionds fo fho formnfIon of cnIcIum nnd mngnosIum
sIIIcnfos nnd fhoso sIIIcnfos form sfIcky scnIos In fho boIIor whIch nro vory dIffIcuIf fo romovo.
Q. 14. WLut Is tLe dIIIevence between Luvd wutev und soIt wutev? ?? ??
Ans. Soo foxf ngo 350-355
Q. 15. AIkuIInIty oI wutev cunnot be due to tLe sImuItuneous pvesence oI OH
,
CO
3
2
und HCO
3
. WLy? ?? ??
Ans. OH
nnd HCO
3
Ions roncf fo form CO

3
2
Ions: OH
+ HCO
3
= CO
3
2
+ H
2
O.
Q. 16. WLy do we expvess Luvdness oI wutev In tevms oI CuCO
3
equIvuIent? ?? ??
Ans. ThIs modo ormIfs onsy nddIfIon nnd subfrncfIon of conconfrnfIon of hnrdnoss-
cnusIng consfIfuonfs, sInco Ifs moI. wf. Is l00. Moroovor, If hns nIso boon ndofod ns sfnndnrd
for oxrossIng hnrdnoss.
Q. 1?. WLut uve tLe suIts vesponsIbIe Iov tempovuvy und pevmunent Luvdness
oI wutev? ?? ??
Ans. Tomornry hnrdnoss Cn(HCO
3
)
2
nnd Mg(HCO
3
)
2
Iormnnonf hnrdnoss ChIorIdo nnd suIhnfo of Cn
2+
nnd Mg
2+
.
Q. 1B. MentIon tLe unIts oI Luvdness. eIIne tLem.
Ans. (i) m, (ii) dogroo.
m Is dofInod ns fho nrfs of hnrdnoss snIf rosonf In l0
6
nrfs of wnfor oxrossod In
forms of cnIcIum cnrbonnfo.
ogroo hnrdnoss Is dofInod ns fho nrfs of hnrdnoss snIf rosonf In l0
5
nrfs of wnfor
oxrossod In forms of cnIcIum cnrbonnfo.
Q. 19. A wutev sumpIe contuIns IItLIum cLIovIde ov zInc ucetute us dIssoIved
soIIds. o you tLInk tLut wutev wIII be Luvd? ?? ??
Ans. Yos, ns !I
+

nnd Zn
2+
bofh form InsoIubIo sons.
Q. 20. CnIcuInfo fho hnrdnoss of
M
l000
MgSO
4
soIufIon.
Ans. MgSO
4
= CnCO
3
l20 g = l00 g
M
l000
MgSO
4
soIufIon confnIns =
l20
l000
g, MgSO
4
=
l00
l000
CnCO
3
In l000 mI wnfor.
So, hnrdnoss In m
0.l
l000
l0
6
= l00 m.
AgnIn, hnrdnoss In dogroo =
0.l
l000
l0
5
= l0
WATER TREATMENT 375
Q. 21. TLe pvesence oI cuvbon dIoxIde Is uvoIded In boIIev Ieed wutev. xpIuIn.
Ans. IssoIvod cnrbon dIoxIdo forms cnrbonIc ncId nnd nffncks boIIor Ios nnd corrodos.
Q. 22. WLy does Luvd wutev consume u Iot oI soup? ?? ??
Ans. Whon hnrd wnfor comos In confncf wIfh son Cn
2+
nnd Mg
2+
Ions roncf wIfh son
nnd scum Is formod whon fho roncfIon Is ovorconsumIng much of son, Infhor Is fhon formod.
Thnf Is why hnrd wnfor consumos n Iof of son.
Q. 23. WLy Is cuIgon condItIonIng bettev tLun pLospLute condItIonIng? ?? ??
Ans. CnIgon condIfIonIng forms soIubIo comIox snIf
n
2
|n
4
(IO
3
)
6
] + CnSO
4
= n
2
|n
2
Cn(IO
3
)
6
] + n
2
SO
4
CnIgon SoIubIo comIox
whorons hoshnfo condIfIonIng i.e., fronfmonf wIfh sodIum hoshnfos, rocIIfnfos cnIcIum
nnd mngnosIum hoshnfos cnusIng scnIo In boIIor Ios.
Q. 24. WLy Is wutev soItened beIove usIng In boIIev? ?? ??
Ans. nfurnI or hnrd wnfor whon fod In boIIor roducos scnIo, sIudgo nnd cnusos rImIng
nnd fonmIng nnd boIIor corrosIon. Thnf Is why wnfor Is soffonod boforo usIng In boIIor.
Q. 25. WLy Is cuustIc embvIttIement contvoIIed by uddIng sodIum suIpLute to
boIIev-Ieed wutev? ?? ??
Ans. SodIum suIhnfo whon usod bIocks hnIr crncks fhus rovonfs InfIIfrnfIon of cnusfIc
sodn fhrough fho crncks. Thus sodIum suIhnfo rovonfs ombrIffIomonf In boIIors.
Q. 26. Stute two LuvmIuI eIIects oI sIIIcu In wutev.
Ans. SIIIcn roncfs wIfh Cn
2+
nnd Mg
2+
Ions formIng cnIcIum sIIIcnfo nnd mngnosIum
sIIIcnfo In boIIor. ThIs fyo of scnIos nro dIffIcuIf fo romovo.
EXERCISES
1. IxInIn fho vnrIous sfos for fho urIfIcnfIon of wnfor for munIcInI suIy.
2. Whnf Is dosnIInnfIon? nmo fho dIfforonf mofhods of dosnIInnfIon nnd doscrIbo nny ono.
3. Whnf nro boIIor froubIos? Why nro fhoy cnusod? Whnf nro fho mofhods of fhoIr oIImInnfIon?
4. IsfInguIsh bofwoon:
(o) Tomornry nnd ormnnonf hnrdnoss.
(I) SIudgo nnd ScnIo.
(c) SoffonIng nnd domInornIIznfIon.
5. WrIfo nofos on: (i) CnusfIc ombrIffIomonf, (ii) !ovorso osmosIs, (iii) IrImIng nnd fonmIng,
(it) Hof IImo-sodn rocoss, (t) IoIIor corrosIon.
6. Whnf Is fho rIncIIo InvoIvod In fho doformInnfIon of fofnI hnrdnoss of wnfor by ITA mofhod?
?. Whnf nro fho funcfIons of IImo nnd sodn In hof IImo-sodn rocoss? CIvo oqunfIons. Why conguInnfs
nro nof usod In hof IImo-sodn rocoss?
B. Why doos hnrd wnfor consumo moro son?
9. urIng doIonIznfIon rocoss, wnfor Is fIrsf nssod fhrough cnfIon oxchnngor nnd fhon fhrough
nnIon oxchnngor, why?
10. oscrIbo fho mofhods of dIsInfocfIon of wnfor. Why Is chIornmIno boffor fhnn chIorIno for sforI-
IIznfIon of wnfor?
OBJECTIVE TYPE QUESTIONS
1. Tomornry hnrdnoss of wnfor cnn bo romovod by
(o) IIIfrnfIon (I) IoIIIng (c) ConguInfIon
2. Iormnnonf hnrdnoss of wnfor Is cnusod by
(o) CnIcIum chIorIdo (I) MngnosIum suIfnfo (c) Iofh.
3. Hnrd wnfor cnn bo soffonod by nssIng fhrough
(o) CnIgon (I) SodIum sIIIcnfo (c) Ion oxchnngo rosIn.
4. CnIgon Is fho frndo nnmo of
(o) SodIum hoxnmofnhoshnfo
(I) SodIum zooIIfo
(c) CnIcIum sIIIcnfo.
5. Iuro wnfor cnn bo obfnInod by
(o) !Imo-sodn rocoss (I) IoIIIng (c) omInornIIznfIon.
6. IrnckIsh wnfor cnn bo urIfIod by
(o) !ovorso osmosIs mofhod
(I) !Imo-sodn rocoss
(c) CnIgon fronfmonf.
?. Tho chomIcnI fhnf gofs dIssoIvod In hIgh rossuro boIIors
(o) MgSIO
3
(I) CnCO
3
(c) CnSO
4
.
B. A somIormonbIo mombrnno nIIows fho fIow of
(o) SoIufo moIocuIos (ii) SoIvonf moIocuIos
(I) Iofh soIufo nnd soIvonf moIocuIos.
9. Tho mosf IdonI dIsInfocfnnf In wnfor works Is
(o) ChIorIno (I) IIonchIng owdor (c) ChIornmIno.
10. A snmIo of wnfor confnInIng nCI Is
(o) Hnrd wnfor (I) Soff wnfor (c) Iuro wnfor.
11. WrIfo n shorf nofo wIfh n roor skofch dIngrnm on rovorso osmosIs rocoss for dosnIInnfIon of
brnckIsh wnfor.
12. Why fronfmonf of wnfor Is ossonfInI?
13. WrIfo down fho ossIbIo sourcos of wnfor?
14. CIvo ronsons for why wnfor bocomos hnrd.
15. CorroInfo fho vnrIous unIfs of fho hnrdnoss.
16. WrIfo down fho dIsndvnnfngos nssocInfod wIfh usIng of hnrd wnfor.
1?. (o) Whnf nro scnIos? Whnf nro fho III-offocfs of scnIos?
(I) How cnn scnIo formnfIon bo rovonfod by (i) Ihoshnfo condIfIonIng nnd (ii) CnIgon condIfIonIng?
1B. IsfInguIsh bofwoon:
(o) IurIfIcnfIon nnd soffonIng of wnfor
(I) IoIIor scnIos nnd sIudgos
(c) InfornnI nnd oxfornnI fronfmonf of wnfor.
19. Whnf do you monn by cnusfIc ombrIffIomonf? Whnf monsuros cnn bo fnkon fo confroI fho cnusfIc
ombrIffIomonf?
20. Whnf fncfors nro rosonsIbIo for boIIor corrosIon. How cnn fho fncfors cnn bo oIImInnfod?
21. oscrIbo fho rocoss of wnfor soffonIng by ormufIf rocoss.
WATER TREATMENT 377
22. IrIofIy dIscuss fho rocoss of soffonIng of wnfor by monns of Ion-oxchnngo rocoss.
23. WrIfo down fho roquIromonfs for drInkIng wnfor.
24. IrIofIy doscrIbo fho dIfforonf sfos InvoIvod In fho fronfmonf of wnfor for domosfIc uroso.
25. Whnf Is dosnIInnfIon? nmo fho dIfforonf mofhods InvoIvod In dosnIInnfIon? oscrIbo nny ono In
dofnII.
26. WrIfo shorf nofos on bronk oInf chIorInnfIon.
2?. (o) Whnf do you monn by cnrbonnfo nnd non-cnrbonnfo hnrdnoss of wnfor?
(I) Sfnfo hnrmfuI offocfs of sIIIcn rosonf In wnfor.
(c) WrIfo shorf nofos on nornfIon.
2B. WrIfo dIfforonf mofhods of sforIIIznfIon.
29. How froo chIorIno In wnfor cnn bo osfImnfod?
30. WrIfo down fho mofhod for doformInnfIon of nIknIInIfy of wnfor.
31. Whnf nro fho mofhods InvoIvod for doformInnfIon of fomornry nnd ormnnonf hnrdnoss of wnfor?
PROBLEMS
1. Tho hnrdnoss of l,00,000 IIfros of n snmIo of hnrd wnfor wns comIofoIy romovod by nssIng
fhrough n zooIIfo soffonor. Tho bod on oxhnusfIon roquIrod 500 IIfros of nCI soIufIon confnInIng
l5 g l
l
of nCI on rogonornfIon. CnIcuInfo fho hnrdnoss of fho snmIo wnfor. |Ans. 64.l0 m]
2. A snmIo of hnrd wnfor hns n hnrdnoss of 5l0 m. Ixross Ifs hnrdnoss In CInrk nnd Ironch.
|HInts l m = 0.0? CInrk = 0.l Ironch]
|Ans. 35.? CInrk nnd 5l Ironch]
3. 200 mI of n snmIo of wnfor roquIrod 5 mI of (/20) sodIum cnrbonnfo soIufIon for comIofo
rocIIfnfIon of cnIcIum Ion (Cn
2+
) nnd cnIcIum cnrbonnfo. CnIcuInfo fho hnrdnoss In m.
|Ans. 62.5 m]
4. In nn oxorImonf for fho doformInnfIon of hnrdnoss of n snmIo of wnfor, fho foIIowIng rosuIfs
nro obfnInod:
VoIumo of snmIo wnfor = l00 cc.
50
n
2
CO
3
soIufIon Is nddod fo If = 20 cc.
50
H
2
SO
4
roquIrod fho bnck fIfro fho unroncfod n
2
CO
3
= l0 cc.
Irom fhoso dnfn cnIcuInfo fho hnrdnoss of wnfor In grnIns or gnIIon.
CIvon, l g = l5.4 grnIn. |Ans. 6.99 grnIn of CnCO
3
]
5. A rocIIfnfo of 0.ll0 of cnIcIum oxnInfo (CnC
2
O
4
.H
2
O) wns obfnInod from n 250 mI of wnfor
snmIo. Ixross fho confonf of cnIcIum In m. |Ans. l20 m]
6. AnnIysIs of n snmIo of wnfor rovonIod fho confonf of dIssoIvod snIfs In fho foIIowIng dnfn:
Mg(HCO
3
)
2
= 22 mg l
l
MgCI
2
= 30 mg l
l
CnCI
2
= 85 mg l
l
CnSO
4
= 28 mg l
l
.
IInd fho fomornry nnd ormnnonf hnrdnoss of fho wnfor snmIo.
|Ans. l5.0? m; l28.?5 m]
?. l,00,000 IIfros of wnfor confnIn fho foIIowIng:
HCI = ?.3 mg l
l
; AI
2
(SO
4
)
3
= 34.2 mg l
l
; MgCI
2
= 9.5 mg l
l
; nCI = 29.25 mg l
l
.
CnIcuInfo fho nmounfs of IImo nnd sodn fo bo roquIrod for soffonIng fho wnfor.
|Ans. !Imo = 3.? kg; Sodn = 5.3 kg]
B. Tho fofnI hnrdnoss of l,000 IIfros of wnfor wns comIofoIy romovod by n zooIIfo soffonor. Tho
zooIIfo soffonor roquIrod 30 IIfros of nCI soIufIon, confnInIng l5 g l
l
of nCI for rogonornfIon.
CnIcuInfo fho hnrdnoss of wnfor. |Ans. 384.6 m]
9. CnIcuInfo fho IImo nnd sodn roquIrod fo soffon l0,000 IIfros of wnfor snmIo hnvIng cnIcIum
hnrdnoss = 450 mg l
l
ns CnCO
3
; mngnosIum = l50 mg l
l
ns CnCO
3
nnd fofnI nIknIInIfy = 400
mg l
l
ns CnCO
3
. |IImo = l.ll kg sodn = l0.6 kg]
10. CnIcuInfo fho hnrdnoss of n wnfor snmIo, whoso l0 mI roquIrod 20 mI of ITA, 20 mI of cnIcIum
chIorIdo soIufIon, whoso sfrongfh Is oquIvnIonf of l.5 g of cnIcIum cnrbonnfo or IIfro roquIrod 30
mI of ITA soIufIon. |200 m]
11. CnIcuInfo fho cosf of IImo nnd sodn roquIrod for soffonIng l mIIIIon IIfros of n wnfor snmIo
confnInIng. Mg(HCO
3
)
2
= ?3 mg l
l
; MgSO
4
= l20 mg l
l
; CnSO
4
= 68 mg l
l
; CnCI
2
= lll mg l
l
.
Tho cosf of IImo of 80 urIfy Is !s. 200 or mofrIc fon nnd fhnf of sodn of 90 urIfy Is
!s. l2,000 or mofrIc fon.
379
FueIs and Combustion
&
INTRODUCTION
Iuel Is n combusfIbIo subsfnnco, whIch on combusfIon roducos n Inrgo nmounf of honf, whIch
cnn bo usod for vnrIous domosfIc nnd IndusfrInI urosos. Tho fuoIs commonIy usod confnIn
cnrbon ns fho mnIn consfIfuonf nnd somo common fuoIs nro wood, chnrconI, korosono, dIosoI,
roducor gns ofc. Ioeeil fuele nro non-ronownbIo onorgy rosourcos whIch woro sforod u mIIIIons
of yonrs ngo by hofosynfhosIs. Tho fossII fuoIs nro conI, crudo oII nnd nnfurnI gns.
Tho rocoss of combusfIon InvoIvos oxIdnfIon of cnrbon, hydrogon ofc. of fho fuoIs fo
CO
2
, H
2
O, nnd fho dIfforonco In fho onorgy of roncfnnfs nnd fho roducfs nro IIbornfod ns Inrgo
nmounf of honf onorgy whIch Is ufIIIzod.
CIussIIIcutIon oI IueIs
Fuels
Natural Derived
Solid Liquid Gaseous
Wood
Coal
Dung
Crude
oil
(Petroleum)
Natural
gas
Coke
Charcoal
Petroleum coke
Coal-
briquette
Tar
Kerosene
Diesel
Petrol
Fuel oil
LPG
Synthetic
gasoline
Coal gas
Water gas
Oil gas
Biogas
Coke oven
gas
Blast
furnace
gas
Solid Liquid Gaseous
CALORIFIC VALUE
Thoro nro dIfforonf oxrossIons for cnIorIfIc vnIuos:
(i) Tho qunnfIfy of honf ovoIvod by fho combusfIon of unIf qunnfIfy of fuoI Is Ifs gross
colorific tolue (CCV). Cross or hIghor cnIorIfIc vnIuo Is fho qunnfIfy of honf IIbornfod by
combusfIng unIf mnss of fuoI In oxygon, fho orIgInnI mnforInI nnd fho fInnI roducf of combusfIon
boIng nf n roforonco fomornfuro of 25C nnd fho wnfor obfnInod In fho IIquId sfnfo, rorosonfod
by CCV or HCV.
(ii) AeI colorific tolue (CV) Is fho qunnfIfy of honf ovoIvod whon n unIf qunnfIfy of fuoI
Is burnf In oxygon, fho orIgInnI mnforInI nnd fho fInnI roducfs of combusfIon boIng nf n roforonco
fomornfuro of 25C nnd fho wnfor obfnInod from fho fuoI boIng nf fho vnor sfnfo. Tho nof
cnIorIfIc vnIuo Is honco nIwnys Ioss fhnn fho gross cnIorIfIc vnIuo by fho nmounf corrosondIng
fo fho honf of condonsnfIon of wnfor vnours i.e., 58?.0 kcnI/kg.
CV = HCV !nfonf honf of wnfor vn. formod
= HCV Mnss of hydrogon o !nfonf honf of sfonm
sInco l nrf by mnss of hydrogon roducos 'o` nrf by mnss of wnfor.
IniIe of colorific tolue. Tho cnIorIfIc vnIuo Is oxrossod In oIfhor cnIorIo/gm (cnI/gm) or
kIIocnIorIo/kg (kcnI/kg) or IrIfIsh fhormnI unIf/Ib (I.T.!/Ib) In fho cnso of n soIId nnd n IIquId
fuoI.
In fho cnso of gnsoous fuoIs, fho unIfs nro kcnI/m
3
or I.T.!./ff
3
.
Determination of CaIorific VaIue
Bomb culorimeter. Tho nnrnfus whIch Is usod fo doformIno fho cnIorIfIc vnIuo of
soIId nnd IIquId fuoIs Is known ns Iomb cnIorImofor (IIg. l8.l).
6 V
battery
Oxygen
valve
Beckmann's
thermometer
Electrodes
to which a ring
is attached
Mg fuse wire
Weighed pallet
of given fuel
sample
Air jacket
Water jacket
Stainless steel
crucible
Stainless steel
bomb
Copper
calorimeter
Electrically
operated stirrer
Fig 18.1 Bomb calorimeter.
Tho nnrnfus consIsfs of n cyIIndrIcnI sfnInIoss sfooI bomb, fho IId of whIch Is scrowod
fo fho body fo mnko If nIr-fIghf. Through fho IId fhoro Is ono oxygon InIof vnIvo nnd fwo
oIocfrodos. In fho bomb fhoro Is nIckoI crucIbIo nffnchod fo n rIng. Tho snmIo of fuoI Is Incod
In fho crucIbIo. An oIocfrIcnIIy honfod mngnosIum wIro fouchos fho snmIo. Tho bomb Is Incod
In n coor cnIorImofor, whIch Is surroundod by nn nIr jnckof nnd wnfor jnckof whIch mInImIsos
fho honf Ioss duo fo rndInfIon. Thoro Is n sfIrror nnd n Iockmnnn`s fhormomofor whIch cnn
nccurnfoIy monsuro fho fomornfuro ufo n/l00
fh
of n dogroo.
A woIghod mnss of n fuoI Incod In fho crucIbIo Is nIIowod fo burn In oxygon by oIocfrIc
snrk ncross fho oIocfrodo nnd fho honf IIbornfod Is monsurod by fho rIncIIo of cnIorImofry
i.e., fho honf IIbornfod Is fnkon by cnIorImofor nnd wnfor. Tho InIfInI nnd fInnI fomornfuros of
fho cnIorImofor nro nofod.
CnIcuInfIon: n = mnss of fuoI oIIof (g)
W = mnss of wnfor In fho cnIorImofor (g)
FUELS AND COMBUSTON 381
u = wnfor oquIvnIonf of cnIorImofor (g)
I
l
= InIfInI fomornfuro of cnIorImofor.
I
2
= fInnI fomornfuro of cnIorImofor.
HCV = gross cnIorIfIc vnIuo of fuoI.
! = HCV =
( ) ( ) W + u I I
n
2 l
cnI/gm.
Tho wnfor oquIvnIonf of cnIorImofor Is doformInod by burnIng n fuoI of known cnIorIfIc
vnIuo nnd usIng fho nbovo oqunfIon. Tho fuoIs usod In fho nbovo uroso nro bonzoIc ncId (CCV
= 6325 kcnI/kg) nnd nnhfhnIono (CCV = 9688 kcnI/(kg). Tho corrocfIon fncfors usod fo gof
nccurnfo rosuIfs IncIudo:
(i) Iuee uire correcIion. Honf IIbornfod durIng snrkIng shouId bo subfrncfod from honf
IIbornfod.
(ii) AciJ correcIion. IuoIs confnInIng SuIhur nnd Ifrogon If oxIdIsod, fho honfs of for-
mnfIon of H
2
SO
4
nnd HO
3
shouId bo subfrncfod (ns fho ncId formnfIons nro
oxofhormIc roncfIons).
(iii) Cooling correcIion. Tho rnfo of cooIIng of fho cnIorImofor from mnxImum fomorn-
furo fo room fomornfuro Is nofod. Irom fhIs rnfo of cooIIng (i.e., JI/mIn) nnd fho
ncfunI fImo fnkon for cooIIng (I mIn) fhon corrocfIon (JI I) Is cnIIod cooIIng corroc-
fIon nnd Is nddod fo fho (I
2
I
l
) form.
! =
(W ) ( CooIIng corrocfIon) (AcId fuso corrocfIon)
l
+ + + u I I
n
2
.
Tho nroxImnfo cnIorIfIc vnIuo of n fuoI cnn bo doformInod by knowIng fho nmounf of
consfIfuonfs rosonf: Cross or hIghor cnIorIfIc vnIuo (HCV) from oIomonfnI consfIfuonfs of n
fuoI.
H = 34500 kcnI/kg; C = 8080 kcnI/kg; S = 2240 kcnI/kg
Oxygon rosonf In fho fuoI Is nssumod fo bo rosonf ns wnfor (fIxod hydrogon). AvnIInbIo
In combusfIon of fho fuoI Is
= TofnI hydrogon IIxod hydrogon
= TofnI hydrogon
l
8
mnss of oxygon In fuoI.
uIong`s formuIn for cnIorIfIc vnIuo from fho chomIcnI comosIfIon of fuoI Is,
HCV =
l
l00
8080
0
8
2240 C+34500 H S kcnI/kg
whoro C, H, O, S nro fho orconfngos of cnrbon, hydrogon, oxygon nnd suIfur In fho fuoI.
Oxygon Is nssumod fo bo rosonf In combInnfIon wIfh hydrogon ns wnfor,
!CV = HCV H
9
l00
58? kcnI/kg.
= |HCV 0.09 H 58?] kcnI/kg.
(3 l nrf of H gIvos 9 nrfs of wnfor nnd fho Infonf honf of sfonm Is 58? kcnI/kg).
xumpIe 1. A cool Ioe IIe follouing conpoeiIion I, ueigII C = 90", O = 3", S = 0.",
A = 0." onJ oeI = 2.". AeI colorific tolue of IIe fuel uoe founJ Io Ie S490. lcol/lg. ColculoIe
IIe percenIoge of H onJ CCV.
SoI. HCV = nof cnIorIfIc vnIuo + (0.09 H + 58?) kcnI/kg
= (8490.5 + 0.09 H + 58?) kcnI/kg |3 H = of hydrogon]
= (8490.5 + 52.8 H) kcnI/kg.
HCV =
l
l00
8080 90 34500
3
8
2240 0 5 +
H . kcnI/kg.
= ??54.8 + 345 H = kcnI/kg.
= ??54.8 + 345 H = 8490.5 + 52.8 H.
??54.8 + 345 H = 8490.5 + 52.8 H.
or 292.2 H = l335
H = 4.5?5
HCV = (8490.5 + 52.8 4.5?5) = 8?3l.8 kcnI/kg.
xumpIe 2. On Iurning 0.S3 g of o eoliJ fuel in o IonI colorineIer, IIe IenperoIure of
300 g of uoIer uoe increoeeJ fron 26.C Io 29.2C, uoIer equitolenI of colorineIer onJ loIenI
IeoI of eIeon ore 3S onJ S7 col/g, reepecIitel,. 1f IIe fuel conIoine 0.7" H, colculoIe HCV
onJ ACV.
SoI. HCV =
(W (385 3500) (29.2 26.3)
0.83
+
=
+ u I I
n
) ( )
2 l
= l2,638 cnI/g.
CV = (HCV 0.9 H !) cnI/g
= (l2,638 0.9 0.? 58?) cnI/g
= l2,60l cnI/g.
Boy'o Cuo Culorimeter. If Is usod for monsurIng fho cnIorIfIc vnIuo of gnsoous nnd
IIquId fuoIs (IIg. l8.2).
In fho nnrnfus (IIg. l8.2) known voIumo of gns Is burnf nf n unIform rnfo by n burnor.
Around fho burnor fhoro Is n chImnoy confnInIng coIIs whoroIn wnfor nf n consfnnf rnfo Is
nssod. Sonrnfo fhormomofors monsuro fho IncomIng nnd oufgoIng wnfor fomornfuros
(I
l
nnd I
2
) .
Water
inlet
Insulated
container
Gaseous
or liquid
fuel
Meter
Air
Air
Condensed
steam
Outer
Cu coil
Inner
Cu coil
Rubber
tubing
Exhaust
gases
Fig. 18.2 Boy's gas calorimeter.
!of V = voIumo of gns burnIng.
W = mnss of cooIIng wnfor usod In fImo I.
I
l
nnd I
2
= IncomIng nnd oufgoIng wnfor fomornfuros
n = mnss of sfonm condonsod In fImo I.
! = HCV.
Wo gof ! =
W
V
( ) I I
2 l
Mnss of H
2
O condonsod or n
3
of gns = n/t kg.
!nfonf honf of sfonm or n
3
of gns
=
n 58?
V
kcnI
CV = !
58?
V
n
kcnI/m
3
.
xumpIe 3. ColculoIe IIe tolune of oir requireJ for conpleIe conIueIion of 1 n
3
of o
goeeoue fuel Ioting IIe conpoeiIion. CO = 46", CH
4
= 10", H
2
= 40", C
2
H
2
= 2", A
2
= 1" onJ
IIe renoining Ieing CO
2
.
SoI. !of fho gnsoous fuoI bo l m
3
CO +
l
2
O
2
= CO
2
VoIumo of O
2
roquIrod = 0.46
l
2
= 0.23 m
3
CH
4
+ 2O
2
= CO
2
+ 2H
2
O
VoIumo of O
2
roquIrod = 0.l 2 = 0.2 m
3
H
2
+
l
2
O
2
= H
2
O
VoIumo of O
2
roquIrod = 0.4
l
2
= 0.2 m
3
C
2
H
2
+ 2
l
2
O
2
= 2CO
2
+ H
2
O
VoIumo of O
2
roquIrod = 0.2
5
2
0 05 = .
TofnI O
2
roquIrod = (0.23 + 0.2 + 0.2 + 0.05) m
3
= 0.68 m
3
VoIumo of nIr roquIrod = 0.68
l00
2l
m
3
= 3.238 m
3
.
SOLID FUELS
Wood
Wood Is dorIvod from frunks nnd brnnchos of froos. If confnIns nbouf l5 moIsfuro nffor
nIrdryIng. Wood confnIns IIgnocoIIuIosowood uI mnInIy consIsfs of coIIuIoso nnd n vory
smnII nmounf of coIIuIoso, rosIns nnd rofoIns. Tho nvorngo comosIfIon of wood on moIsfuro-
froo bnsIs Is C = 55, H = 6, O = 43 nnd nsh = l. Wood Is InrgoIy usod ns domosfIc fuoI, Ifs
uso ns ongInoorIng fuoI Is rosfrIcfod. CnIorIfIc vnIuo vnrIos from 4000 fo 6400 Ifu/Ib.
CoaI
ConI Is fho mosf Imorfnnf soIId fuoI nnd dorIvod from rohIsforIc Innfs. ConI Is hIghIy
cnrbonncoous nnd comosod of C, H, , nnd O nnd non-combusfIbIo InorgnnIc mnffor.
Origin. VogofnbIo mnffor Is fIrsf frnnsformod Info onf, fhon fo IIgnIfo fhon Info
bIfumInous conI nnd fInnIIy fo nnfhrncIfo. Tho frnnsformnfIon orIod oxfonds ovor mIIIIons of
yonrs fhrough n confInuous rocoss. Tho confInuIfy cnn bo rovod grnhIcnIIy by IoffIng oxygon
nnd C orconfngos of conI nf dIfforonf sfngos of formnfIon.
CloeeificoIion of cool. VnrIous fyos of conI nro rnnkod nccordIng fo fho dogroo of
conIIfIcnfIon from fho nronf mnforInI wood ns foIIows:
Wood Ionf !IgnIfo IIfumInous conI AnfhrncIfo
WIfh fho rogrossIvo frnnsformnfIon of wood, fho moIsfuro, H, O, , S, voInfIIo mnffor
confonf docronso whorons cnrbon confonf, cnIorIfIc vnIuo nnd hnrdnoss Incronso.
l. PeoI Is rognrdod ns fho fIrsf sfngo of conIIfIcnfIon of conI. Tho comosIfIon nnd roorfIos
of onf wIdoIy vnry from Inco fo Inco, doondIng on nnfuro of fho orIgInnI Innf mnforInI. If
Is oxfrncfod by hnnd cuffIng. If Is nn unoconomIcnI fuoI sInco If confnIns nbouf 8090 moIsfuro.
If Is usod ns domosfIc fuoI, In sfonm boIIors, owor sfnfIons nnd gns roducors. Ionf Is nIso
usod ns n forfIIIsor. !ow fomornfuro cnrbonIsnfIon of onf Is usod for goffIng onf coko nnd
byroducfs. Ionf Is onsy fo IgnIfo nnd burns frooIy fo gIvo n Iong Ionsnnf fInmo .
2. LigniIe or brown conIs nro soff, brown coIourod conI. !IgnIfo Is comncf In foxfuro,
confnInIng 2060 moIsfuro. AIrdrIod IIgnIfo confnIns C = 60?0, O = 20. Ifs cnIorIfIc vnIuo
Is 6500?000 kcnI/kg. If burns wIfh n smoky fInmo. If Is owdorod, drIod nnd rossod Info
brIquoffos nnd usod for domosfIc uroso, for boIIors nnd for roducfIon of roducor gns.
3. BiIuninoue coole nro bInck nnd usunIIy bnndod wIfh nIfornnfo vory brIghf nnd duII
Inyors. On fho bnsIs of cnrbon confonf bIfumInous Is cInssIfIod ns:
(o) SuI-IiIuninoue coole. (C confonf ?0?8, H 45 nnd O 20). Tho nIrdrIod mnfo-
rInI hns moIsfuro confonf of l020. CnIorIfIc vnIuo Is 6800?600 kcnI/kg. If IgnIfos
onsIIy nnd If Iow In S confonf, usod for gnsoous fuoI roducfIon.
(I) BiIuninoue cool (C confonf ?890, cnIorIfIc vnIuo Is from 8000 fo 8500 kcnI/kg). Ifs
chIof uso Is for combusfIon In housohoId, IndusfrInI furnncos nnd boIIors, rnIIwny
IocomofIvos nnd fhormnI owor sfnfIons. Iy cnrbonIsnfIon nnd gnsIfIcnfIon If Is con-
vorfod fo coko, gnsoous fuoIs IIko roducor gns, wnfor gns, conI gns, IIquId fuoIs IIko
conI fnr fuoIs.
(c) Seni-onIIrociIe Is InformodInfo bofwoon bIfumInous conIs nnd nnfhrncIfo. If IgnIfos
moro onsIIy fhnn nnfhrncIfo. Whon nIr-drIod moIsfuro confonf Is l2, voInfIIo mnffor
= l0l5. CnIorIfIc vnIuo Is 85008800 kcnI/kg.
4. AnIIrociIe Is fho hIghosf rnnk conI hnvIng hIghosf orconfngo of C (9298), Iowosf
voInfIIo mnffor nnd moIsfuro. CnIorIfIc vnIuo Is 84008600 kcnI/kg. If burns wIfhouf smoko buf
IgnIfos wIfh dIffIcuIfy, ossossos no cokIng owor. Ifs chIof usos nro In boIIors, domosfIc ovons
nnd mofnIIurgIcnI furnncos.
Occurrencee. Ionf doosIfs nro found In IIgIrI hIIIs, IIgnIfos occur In Assnm, KnshmIr,
!njnsfhnn nnd TnmII ndu. IIfumInous conIs nro found In IIhnr, IongnI, Mndhyn
Irndosh,ChhnffIsgnrh nnd OrIssn. AnfhrncIfos nro found In KnshmIr nnd onsforn HImnInyns.
AnaIysis of CoaI
!nnkIng of conI Is dono on:
(o) ProxinoIe onol,eie. If consIsfs of doformInnfIon of orconfngos of (i) voInfIIo
cnrbonncoous mnffor, (ii) fIxod cnrbon, (iii) nsh nnd (it) moIsfuro of fho nIrdrIod conI.
(I) IlIinoIe onol,eie. ConsIsfIng of doformInnfIon of orconfngos of C, H, O, nnd S.
(c) Colorific tolue. Tho cokIng roorfIos nro of Imorfnnco for bIfumInous conIs onIy.
Ofhor chomIcnI nnd hysIcnI roorfIos nro socIfIc grnvIfy, surfnco nron nnd orosIfy,
rofrncfIvo Indox ofc.
(u) Prorimute Anulyoio:
(i) MoieIure. l g of fInoIy owdorod nIrdrIod snmIo fnkon In n crucIbIo nnd honfod
In nn oIocfrIcnIIy honfod hof nIr ovon nf l05Cll0C for l hr. nnd ngnIn woIghod
nffor dosIccnfIon fIII consfnnf woIghf.
Iorconfngo of moIsfuro =
!oss In woIghf
Wf. of conI fnkon
l00.
(ii) VoloIile noIIer. Tho drIod snmIo Ioff In fho crucIbIo nIong wIfh fho IId Is honfod
In n muffIo furnnco nf n 250C 20C for ? mInufos nnd fhon cooIod, woIghod
nffor dosIccnfIon fIII consfnnf woIghf.
VoInfIIo mnffor orconfngo (V.M.) =
!oss In woIghf
Wf. of conI snmIo fnkon
l00.
(iii) AeI. Tho rosIdunI snmIo nffor fho fwo nbovo oxorImonfs In fho crucIbIo Is honfod
In fho furnnco nf ?00C + 50C for l or 2 hours wIfhouf fho IId. Thon If Is cooIod,
Ioff In fho dosIccnfor nnd woIghod fIII consfnnf woIghf.
Iorconfngo of nsh =
Wf. of nsh Ioff
Wf. of conI fnkon
l00.
(it) IixeJ corIon. Iorconfngo of fIxod cnrbon =
l00 of (moIsfuro + voInfIIo mnffor + nsh)
Significonce. Iy fnkIng nwny fho Infonf honf of ovnornfIon noieIure conIenI Iowors fho
cnIorIfIc vnIuo of conI. Honco, Iowor fho moIsfuro confonf, boffor fho qunIIfy of conI. SImIInr Is
fho offocf of toloIile noIIer conIenI, whIch oscnos unburnf so voInfIIo mnffor confonf Iowors
wIfh boffor qunIIfy of conI. !ow voInfIIo mnffor nIso roducos cokIng roorfy of conI. AeI boIng
non-combusfIbIo, roducos fho cnIorIfIc vnIuo of conI. Ash doosIfIon nIso cnusos robIoms In fho
furnnco wnIIs nnd fho uIfImnfo dIsosnI of nsh Is nIso n robIom.
HIghor fho orconfngo of fixeJ corIon, hIghor Is fho cnIorIfIc vnIuo nnd boffor Is fho
qunIIfy of conI.
(b) Ultimute Anulyoio:
(i) CorIon onJ I,Jrogen. AccurnfoIy woIgh l2 gm of fho conI snmIo nnd burn In n
curronf of O
2
In combusfIon nnrnfus whoroby CO
2
nnd H
2
O nro

formod. CO
2
nnd H
2
O nro nbsorbod by rovIousIy woIghod fubos confnInIng KOH nnd
nnhydrous CnCI
2
. Tho Incronso In woIghf gIvos fho C nnd H confonf ns foIIows:
C O CO
l2
2 2
44
+
nnd 2KOH
g ll2
+ CO
2
K CO
2 3
l38 g
+ H
2
O.
H
2
2
+
l
2
O
2
H O
2
l8
nnd CnCI
2
lll g
+ ?H
2
O CnCI H O
2 2
g
.?
23?
.
Iorconfngo of C =
Incronso In wf. KOH l2 l00
Wf. of conI snmIo 44

.
nnd orconfngo of H =
Incronso In wf. CnCI 2 l00
Wf. of conI snmIo l8
2

.
(ii) AiIrogen. Abouf l g of nccurnfoIy woIghod conI snmIo fnkon In n KjoIdnhI`s fInsk
nIong wIfh conc. H
2
SO
4
, K
2
SO
4
nnd honfod. Thon If Is fronfod wIfh oxcoss of
KOH nnd fho IIbornfod H
3
Is nbsorbod In known oxcoss of sfnndnrd ncId soIufIon.
Tho oxcoss ncId Is bnck-fIfrnfod wIfh sfnndnrd nOH soIufIon. Irom fho voIumo
of ncId consumod confonf Is cnIcuInfod ns foIIows:
Iorconfngo of =
VoIumo of ncId consumod ormnIIfy l.4
Wf. of conI fnkon

.
(iii) Sulfur. WhIIo doformInIng fho cnIorIfIc vnIuo of n conI snmIo In n bomb
cnIorImofor, fho S In fho conI Is convorfod fo suIfnfo. IInnIIy fho wnshIngs
confnInIng suIfnfo Is fronfod wIfh dII. HCI nnd InCI
2
soIufIon, whIch rocIIfnfos
InSO
4
whIch Is fIIforod In n sInforod gInss crucIbIo, wnshod wIfh wnfor nnd honfod
fo n consfnnf woIghf.
Iorconfngo of S =
Wf. of InSO 32 l00
Wf. of conI snmIo In bomb 233
4

.
(it) AeI conIenI. Ash confonf Is doformInod sImIInr fo roxImnfo nnnIysIs.
(t) Ox,gen conIenI = l00 of (C + H + S + + nsh)
Significonce. HIghor orconfngo of C nnd H Incronsos fho cnIorIfIc vnIuo of conI nnd
honco boffor Is fho conI. HIghor fho orconfngo of O, Iowor Is fho cnIorIfIc vnIuo nnd Iowor Is
fho cokIng owor. AIso, O whon combInod wIfh H In fho conI, H nvnIInbIo for combusfIon bocomos
unnvnIInbIo. S, nIfhough confrIbufos fo cnIorIfIc vnIuo, Is undosIrnbIo duo fo Ifs oIIufIng
roorfIos ns If forms SO
2
on combusfIon.
Coke
CnrbonIsnfIon or cokIng bIfumInous conI Ionds fo fho formnfIon of coko. Coko obfnInod
from conI wIfh hIgh voInfIIo mnffor forms swoIIIng coko whIch Is soff coko, nnd from n mIxfuro
of hIgh nnd Iow voInfIIo cokIng bIfumInous conI (non-swoIIIng) In coko ovons hnrd coko Is
obfnInod. Iofh soff nnd hnrd cokos nro obfnInod by IigI IenperoIure corIonieoIion. A smokoIoss
fuoI or somIcoko Is obfnInod from lou IenperoIure corIonieoIion.
Coke and CoaI
Coko ossossos much sfrongfh nnd orosIfy comnrod fo conI.
Iy cokIng fho undosIrnbIo suIfur confonf of conI Is romovod from coko nnd duo fo Iowor
voInfIIo mnffor confonf of coko If burns wIfh n shorf fInmo. AII fhoso roorfIos of coko
mnko If suIfnbIo for mofnIIurgIcnI rocossos comnrod fo conI.
Carbonisation of CoaI
oondIng on fho oornfIon fomornfuro fhoro nro mnInIy fwo fyos of cnrbonIsnfIon
rocossos, nnmoIy,
(i) !ow fomornfuro cnrbonIsnfIon (!TC) nnd (ii) HIgh fomornfuro cnrbonIsnfIon (HTC).
ConrsoIy owdorod conI fnkon In n cIosod roforf nnd honfod ouf of confncf wIfh nIr Ionds fo fho
bronkdown of conI wIfh fho formnfIon of wnfor, nmmonIn, ofhor voInfIIo mnffors, gnsos nnd
coko. ThIs rocoss Is cnIIod fho corIonieoIion of cool or coling of cool.
TabIe 18.1: By-products of carbonisation of coal
Coal
Carbonisation
Volatile
part
Residue
coke
Coal
tar
Coal
gas
Gas
carbon
Ammoniacal
liquor
F
r
a
c
t
i
o
n
a
l
d
i
s
t
i
l
l
a
t
i
o
n
Residue
Pitch (62%)
C56%
Light
oil (5%)
Middle
oil (17%)
Heavy
oil (71%)
Anthracene
oil (9%)
Distillates
200C 250C 300C 350C
TabIe 18.2: Products (by fractional distillation)
LigII oil Ionzono, ToIuono, XyIono, Cumono ofc.
MiJJle oil nhfhnIono, IhonoI, CrosoI, IyrIdIno ofc.
Heot, oil CrosoI, XyIono, nhfhnIono ofc.
AnIIrocene oil Ihonnnfhrono, Anfhrncono, QuInoIIno ofc.
(i) Lou IenperoIure corIonieoIion (LTC). In fhIs rocoss, conI Is honfod In sfooI
roforfs nf 500C?00C. Tho yIoId of coko Is ?580 nnd If confnIns 8l2 voInfIIo
mnffor. Tho coko obfnInod Is nof mochnnIcnIIy sfrong buf hIghIy roncfIvo nnd cnn
bo onsIIy IgnIfod fo gIvo smokoIoss fInmo nnd usod ns n domosfIc fuoI. !ow
fomornfuro cnrbonIsnfIon yIoIds n vory comIox mIxfuro of hIghor honoIs,
subsfIfufod nromnfIc hydrocnrbons nnd ofhor nnd O confnInIng comounds.
IsInfocfnnfs nro mndo from fhIs fnr. Tho conI gns obfnInod hns cnIorIfIc vnIuo of
6500 kcnI/m
3
nnd Is rIchor In hydrocnrbons nnd ooror In hydrogon comnrod fo
fho gns roducod by HTC. Tho crudo sIrIf corrosonds fo crudo bonzoI of HTC
buf confnIns gronfor nmounf of nrnffIns, nnhfhnIono nnd oIofIn.
(ii) HigI IenperoIure corIonieoIion (HTC). If Is cnrrIod ouf nf 900Cl200C ro-
ducIng coko of good orosIfy, hnrdnoss, urIfy nnd sfrongfh nnd cnn bo usod In
mofnIIurgy. As nII fho voInfIIo mnffors nro drIvon off, fho yIoId of coko Is 65?5
confnInIng l3 voInfIIo mnffor. Tho roforfs usod nro mndo of brIck. Tho gns nnd
fnr yIoIds nro Iowor. Tho cnIorIfIc vnIuo Is Iowor, nbouf 4500 kcnI/m
3
.
IstInctIon between LIgL tempevutuve cuvbonIsutIon (H.T.C.) und Iow
tempevutuve cuvbonIsutIon (I.T.C.) ut u gIunce:
Tomornfuro !.T.C. = 400600C
H.T.C. = l000l400C
Iconomy In !.T.C. Ioss cosfIy sfooI roforfs nro usod
whorons In fho cnso of H.T.C. roforfs mndo of
fIro brIcks nro usod. Tho oxondIfuro duo fo fuoI
Is nIso Ioss In fho cnso of !.T.C. fhnn fhnf of
H.T.C. ns fho workIng fomornfuro Is Ioss.
nfuro of fnr Tho IIquId voInfIIo roducfs nro Inrgor In
qunnfIfy In fho cnso of !.T.C., on fho ofhor hnnd
fho qunnfIfy of gnsoous roducfs Is gronfor In
fho cnso of H.T.C. Tho formnfIon of Iowor
nmounf of nrnffIn nnd nIIcycIIc comounds nnd
hIghor nmounfs of nromnfIc comounds In fho
cnso of H.T.C. IndIcnfos fhnf fho rocoss of
nromnfIsnfIon Is gronfor In fho cnso of H.T.C.
nfuro of ofhor roducfs Tho nmounf of nmmonIn formod gronfIy
Incronsos wIfh fho rIso of fomornfuro showIng
fhnf nIfrogonous comIoxos nro brokon nf
hIghor fomornfuro. Tho TnbIos l8.l nnd l8.2
show fho nmounf nnd nnfuro of vnrIous
roducfs.
IhysIcnI chnrncforIsfIcs of fnr H.T.C. fnrs nro dnrkor In coIour nnd moro
vIscous fhnn fhnf of !.T.C. fnrs.
YIoId of fnr Tho yIoId of !.T.C. fnr or fon of conI Is much
gronfor fhnn fhnf of H.T.C. fnr.
Thoro nro fwo mnIn fyos of ovon for fho mnnufncfurIng of coko:
(o) BeeLIve oven: If Is n bnfch rocoss nnd now obsoIofo. Tho fIrobrIck chnmbors nro of
2 m hoIghf nnd 3.5 m dInmofor nnd form fho shno of n boohIvo. Thoro nro
fwo oonIngs, ono nf fho fo for chnrgIng fho conIs nnd fho ofhor on ono sIdo for fho
onfry of nIr nnd nIso for romovnI of coko. ConI forms n Inyor of 6090 cm dofh.
CnrbonIsnfIon rocoods from fho fo fo boffom nnd comIofos In 23 dnys. Honf Is
suIIod by fho burnIng of fho voInfIIo mnffor nnd honco no byroducfs nro rocovorod.
Tho hof oxhnusf gnsos nro ufIIIsod fo run wnsfo honf boIIors fo Incronso fho honf
offIcIoncy. Af fho ond of cnrbonIsnfIon, fho coko Is quonchod by wnfor nnd rnkod ouf
fhrough fho sIdo door, IonvIng fho ovon hof onough fo sfnrf fho noxf bnfch. Tho yIoId
of coko Is 80 of fho conI chnrgod (IIg. l8.3).
4 m
2.5 m
Coal
0.6 m
Heat radiated
from the roof to
the coal bed
Coal charging
door
Refractory lining
Zone of combustion
Door for
air supply for
coke discharging
Fig. 18.3 Beehive coke oven.
Tho IImIfnfIons of fho rocoss nro (i) no rocovory of byroducfs, (ii) coko yIoId Is Iow,
(iii) fho oxhnusf gnsos cnuso oIIufIon, (it) rocoss Is nof fIoxIbIo.
(I) Bypvoduct coke oven: In fhIs rocoss conI Is honfod In combusfIon chnmbors, son-
rnfo from cnrbonIsnfIon chnmbors. Tho fhormnI offIcIoncy hns boon Incronsod nnd
fho vnIunbIo byroducfs nro rocovorod. Tho coko ovons nro mndo of sIIIcn brIcks nnd
fho fomornfuro Is nbouf l350C fo l450C. Tho bnfch rocoss Is mndo confInuous by
buIIdIng ovons In n bnffory. Tho ovon consIsfs of numbor of nnrrow sIIIcn chnmbors
(l0 m 3 m 0.4 m) orocfod sIdo by sIdo wIfh vorfIcnI fIuos In bofwoon fhom. Thoro
Is n chnrgIng hoIo nf fho fo, n gns off fnko nnd n rofrncfory IInod cnsf Iron door nf
onch ond. If Is honfod oxfornnIIy by n orfIon of conI gns roducod by fho rocoss
IfsoIf or by roducor gns or by bInsf furnnco gns.
HIgLIIgLts:
Thoro nro fwo mnIn fyos of cokIng of conI:
(i) IoohIvo nnd fho (ii) by roducf cokIng.
IoohIvo cokIng Is obsoIofo. If Is n bnfch rocoss cnusIng n Inrgo nmounf of oIIufIon.
A orfIon of conI Is burnf InsIdo fho roforf fo gonornfo honf for cokIng.
In byroducf cokIng, nIr Is oxcIudod so fhnf no burnIng fnkos Inco wIfhIn fho
ovon, honf Is suIIod from fho hof fIuo gnsos nnd 40 of fho ovon gns (conI gns)
gonornfod Is burnf fo honf fho bnffory of ovons nnd fho rosf Is usod for domosfIc
fuoI IocnIIy.
IInoIy crushod conI Is chnrgod fhrough fho hoIo nf fho fo nnd In n cIosod sysfom If Is
honfod fo l200C. Tho fIuo gnsos roducod durIng combusfIon nss fhoIr sonsIbIo honf fo fho
chockor brIck-work, whIch Is rnIsod fo l000C. Tho fIow of honfIng gnsos Is fhon rovorsod nnd
fho hof chockor brIcks honf fho InIof gns. ThIs cycIo confInuos fIII fho voInfIIo mnffor Insfs.
CnrbonIznfIon fnkos nbouf ll fo l8 hours, nffor whIch fho doors nro oonod nnd fho gIowIng
coko mnss Is dIschnrgod by mnchIno drIvon coko-ushor Info coko-quonchor. Tho hof coko Is
quIckIy quonchod by wnfor srnyIng. 'ry quonchIng` Is nIso dono by cIrcuInfIng fIuo gnsos
ovor hof coko nnd fho hof gnsos nro ufIIIsod fo run wnsfo honf boIIors (IIg. l8.4).
Chambers loaded
with coal
Coal gas
Space between
chambers for
flow of burnt
gases
Hot
regenerators
Outgoing waste
gases heat
regenerators
before escaping
to chimney
Waste gases
to chimney
Air Producer
gas
Waste gases
to chimney
Gas burns here
Coal bunker
Coal
gas
Tar
Coke
chamber
Regenerators
Coke ovens with regenerators
Coal
charging cars
Ram
(Coke
pusher)
C
o
a
l
Coke oven
Fig. 18.4 Otto Hoffman's byproduct coke oven with regenerators.
Recovevy oI bypvoducts: Tho gnsos comIng ouf nf 600C?00C gof n srny of fIushIng
IIquor nf fho gooso-nock of fho sfnndIo nnd fho fomornfuro Is roducod fo 80C. Tnr nnd
sfonm gof condonsod. Tho 'Coko ovon gns` Is comosod of H
3
, H
2
O; fnr confnIns nnhfhnIono,
bonzono, moIsfuro ofc.
(i) ConI fnr Is condonsod In fho fnnk boIow.
(ii) AmmonIn Is rocovorod nrfIy ns nquoous soIufIon nnd nrfIy ns suIfnfo.
(iii) nhfhnIono Is rocovorod by nssIng fho gns fhrough n fowor whoro wnfor Is srnyod
nf vory Iow fomornfuro whIch condonsos fho nnhfhnIono.
(it) Ionzono Is rocovorod sImIInrIy by srnyIng ofroIoum.
(t) H
2
S Is rocovorod by nssIng fho gns fhrough moIsf Io
2
O
3
ns:
Io
2
O
3
+ 3H
2
S Io
2
S
3
+ 3H
2
O
Io
2
S
3
Is ngnIn rogonornfod by oxosIng fo nfmoshoro
Io
2
S
3
+ 4O
2
2IoO + 3SO
2
4IoO + O
2
2Io
2
O
3
IoohIvo ovons nro Iocnfod In JhnrIn, !nnIgnnj, Ioknro-!nmgnrh In Inrgo numbors In
IndIn whorons byroducf coko ovons nro on Inrgo numbors In CIrIdIh, urgnur, Jnmshodur,
IhIInI, !ourkoIn, Ioknro ofc.
LIQUID FUELS
IofroIoum or crudo oII Is n doo brown oII consIsfIng of mnInIy hydrocnrbons, nrnffIns,
nnhfhonos nnd nromnfIcs In vnryIng roorfIons. SuIfur, nIfrogon nnd oxygon nro rosonf In
fho form of dorIvnfIvos of hydrocnrbons In fho oII. Tho nvorngo uIfImnfo nnnIysIs shows
C838?, H lll4, S 0.53, 0.l nnd O 23. IrncfIcnIIy nII mofnIs nro
found In ofroIoum, fho mosf common nro SI, Io, AI, Cn, Mg, I.
Occurrence. Tho crudo oII hns boon dorIvod from fho orgnnIc mnffor orIgInnIIy rosonf
In mnrIno sodImonfs. Tho dond orgnnIc mnffor soffIos down fo fho boffom of shnIIow sons nnd
Ingoons. Tho soffIod dobrIs Is nffnckod by nnnorobIc bncforIn, whoroby mosf of fho orgnnIc
comounds nro dosfroyod nnd fho romnInIng unsnfurnfod fnffy oIIs nnd fnffy ncIds undorgo
oIymorIznfIon.
CloeeificoIion of peIroleun. Thoro nro fhroo mnIn fyos ofroIoum nccordIng fo chomIcnI
nnfuro:
(o) InrnffIn-bnso crudo comosod of snfurnfod hydrocnrbons ufo C
35
H
?2
whIch nro somI-
soIIds, cnIIod wnxos.
(I) AshnIf-bnso crudo confnIns mnInIy nnhfhonos nnd cycIonrnffIns wIfh smnIIor
nmounfs of nrnffIns nnd nromnfIcs.
(c) MIxod bnso crudo confnIns bofh fho nbovo fyo of comounds buf rIch In wnxos.
Abouf 90 crudo roducod nf rosonf fnII In fhIs Insf cnfogory.
PetroIeum
vIIIIng: OII Is broughf fo fho surfnco by drIIIIng hoIos ufo fho oII bonrIng surfnco. Iy
fho hydrosfnfIc rossuro of nnfurnI gns fho oII Is ushod u or If Is umod u by monns of n
um. Two conxInI Ios nro Ioworod fo fho oII rosorvoIr, fhrough fho oufor Io comrossod
nIr Is forcod, whoroby fho oII Is forcod ouf fhrough fho Innor Io. ThIs crudo oII Is sonf fo fho
rofInorIos for furfhor rocossIng nnd rofInIng of fho crudo oIIs (IIg. l8.5).
Compressed
air
Oil Natural
gas
Brine
Natural gas
Fig. 18.5 Mining of crude oil and use of air-lift pump.
ReIInIng: Affor romovnI of dIrf, wnfor nnd nnfurnI gns, fho crudo oII Is sonrnfod Info
frncfIons by dIsfIIInfIon nnd fho frncfIons obfnInod nro subjocfod fo sImIo urIfIcnfIon
rocoduros or comIox fronfmonfs fo yIoId dIfforonf ofroIoum roducfs. AII fhoso sfos nro
undor ofroIoum rofInIng whIch IncIudo:
l. CoItveII's pvocess. Crudo oII Is InfImnfoIy mIxod wIfh wnfor formIng nn omuIsIon.
Tho wnfor Is sonrnfod from fho oII by nssIng fho omuIsIon fhrough CoIfroII`s oIocfrosfnfIc
rocIIfnfor.
2. RemovuI oI obJectIonubIe compounds. SuIfur comounds hnvo objocfIonnbIo
roorfIos of oIIufIon so fhoy nro romovod rIor fo dIsfIIInfIon ns coor suIfIdo by fronfmonf
wIfh coor oxIdo.
3. PetvoIeum dIstIIIutIon. Tho crudo oII Is subjocfod fo dIsfIIInfIon fo nbouf 400C
fomornfuro In nn Iron roforf whoroby nII voInfIIo comononfs oxcof fho soIId rosIduo nro
dIsfIIIod ouf. Thoso nro sonrnfod In n frncfIonnfIng coIumn consIsfIng of n fnII fowor whoro fho
hIghor boIIIng frncfIons condonso fIrsf. ThIs dIsfIIInfIon Is n confInuous rocoss nnd fho foIIowIng
frncfIons nro obfnInod (IIg. l8.6) (TnbIo l8.3).
Crude tower
C
r
u
d
e
p
e
t
r
o
l
e
u
m
Gas oil
reduced crude
Refinery
Kerosine oil
Solvent naphtha
Refinery
Cooler
Cracked gasoline
Condenser Reforming
furnace
Strippers
Bubble
tower
Gasoline storage
Refinery
Refinery Condenser
Straight
run gasoline
Fig. 18.6 Petroleum distillation.
(o) GusoIIne Is obfnInod ufo 200C. Tho nnhfhn Is condonsod nnd subjocfod fo rofInIng
for fho romovnI of suIfur, dIoIofIns nffor rofrncfIonnfIng.
(i) IofroIoum ofhor boIIIng bofwoon 40C?0C nnd
(ii) Ionzono boIIIng bofwoon ?0C90C nnd
(iii) CnsoIIno boIIIng bofwoon 90C200C nII nro obfnInod.
Ifs cnIorIfIc vnIuo Is l4,250 kcnI/kg nnd Is usod ns n fuoI for InfornnI combusfIon ongInos
In nufomobIIos nnd nIrcrnffs.
(I) SoIvent nupLtLu Is obfnInod ns n sIdo sfonm bofwoon 200C250C. ThIs confnIns
somo gnsoIIno, whIch Is nssod bnck fo fho mnIn frncfIonnfIng coIumn. nhfhn confnIns 6-l0
cnrbon nfoms.
(c) Kevosene oII Is obfnInod bofwoon 250C300C. Tho Iowor boIIIng frncfIon mIxod
wIfh If Is rofurnod fo fho mnIn coIumn. Ioffom IIquId Is rofInod nnd fInnIIy cnn bo usod ns
domosfIc fuoI hnvIng cnIorIfIc vnIuo of ll00 kcnI/kg.
(J) Gus oII Is obfnInod bofwoon 300C350C. ThIs Is nssod fhrough n cooIor nnd fhon
oxfrncfod wIfh IIquId SO
2
fo romovo suIfur. If Is usod ns n dIosoI ongIno fuoI wIfh cnIorIfIc vnIuo
of ll000 kcnI/kg.
(e) Tho reeiJuol liquiJ comIng ouf from fho boffom on subsoquonf fronfmonf yIoIds
IubrIcnfIng oII, vnsoIIno, gronso, nrnffIn wnx, nshnIf-bIfumon, ofroIoum, coko ofc.
TabIe 18.3: Common fractions from crude
IrocIion Boiling ronge ConpoeiIion Ieee
!ncondonsod gns WIfhIn 30C C
l
fo C
4
As domosfIc or IndusfrInI fuoI
undor fho nnmo !IC (!IquofIod
ofroIoum gns)
IofroIoum ofhor 30C?0C C
5
C
?
As n soIvonf.
CnsoIIno or ofroI 90C200C C
5
C
9
As n mofor fuoI soIvonf nnd dry
wnshIng
nhfhn 200C250C C
9
C
l0
As n soIvonf
Korosono oII 250C300C C
l0
C
l6
As fuoI for domosfIc nnd Indus-
frInI usos
IosoI oII 300C350C C
l0
C
l8
As n fuoI for dIosoI ongIno
Honvy oII 320C400C C
l?
C
30
Ior dIfforonf frncfIons
Cracking Process
CrnckIng Is fho rocoss In nn oII rofInory by whIch honvIor frncfIon from fho frncfIonnI
dIsfIIInfIon convorfod Info usofuI IIghfor frncfIons by fho nIIcnfIon of honf, wIfh or wIfhouf
cnfnIysf, i.e., crnckIng Is n rocoss by whIch Inrgor moIocuIos bronk u Info smnIIor onos. Tho
chIof nIIcnfIon of commorcInI crnckIng In nII fho rofInorIos Is for fho roducfIon of gnsoIIno
from gns oIIs. Ofhor usos IncIudo fho roducfIon of oIofIns from nnhfhns nnd gns oIIs. Tho
surIus of honvIor ofroIoum frncfIons nro nIso crnckod fo gof ofroI. Thoro nro fwo mofhods of
crnckIng.
1. Thermul Crucking: Whon crnckIng Is cnrrIod ouf wIfhouf nny cnfnIysf nf hIgh
fomornfuro from 450C?50C nf rossuros rnngIng from l?0 nfms, If Is cnIIod IIernol
crocling. Tho Imorfnnf roncfIons nro docomosIfIon, dohydrogonnfIon, IsomorIznfIon nnd
oIymorIznfIon. Tho nrnffIns docomoso fo Iowor moI. wf. comounds, IIko nrnffIn nnd nn
oIofIn.
CH
3
(CH
2
)
8
CH
2
CH
3
(CH
2
)
4
CH
3
+ CH
3
CH
2
CH = CH
2
n-docnno n-hoxnno bufono-l
Tho oIofIns formod IsomorIzos nnd oIymorIzos.
2CH
3
CH
2
CH = CH
2
CH
3
CH
2
CH
C
CH
CH
C= CH
3
3
3
2
ThIs crnckIng fnkIng Inco nf 4?5C530C fomornfuro Ionds fo liquiJ pIoee IIernol
crocling. Tho roducfs nro sonrnfod by frncfIonnI dIsfIIInfIon. Whon fho crnckIng oII Is vnorIzod
nnd fhon crnckod nf 600C?50C nf n Iow rossuro, If Is cnIIod topour pIoee IIernol crocling.
Tho roducfs hnvo boffor nnfI-knock roorfIos.
2. Cutulytic Crucking. Tho uso of cnfnIysf durIng crnckIng nccoIornfos fho roncfIons
nnd nf fho snmo fImo modIfIos fho yIoId nnd fho nnfuro of roducf. CnfnIysf usod nro synfhofIc
comosIfIon of sIIIcn nnd nIumInn, zooIIfos In fho form of bonds or oIIofs.
Thoro nro fwo mnIn fyos of cnfnIyfIc crnckIng:
(o) IixeJ-IeJ coIol,Iic crocling. Tho cnfnIysfs nro fIxod In fowors, fhrough whIch fho
hof oII (500C) fIows from fho fo nnd nssos down. 40 of fho chnrgo Is convorfod fo gnsoIIno
nnd 24 cnrbon Is formod. ThIs cnrbon doosIfs on fho cnfnIysf bods. Tho boffom IIquId Is
roboIIod nnd rocycIod fo fho frncfIonnfIng coIumn nnd uIfImnfoIy gns oII Is obfnInod hnvIng
hIgh ocfnno vnIuo. Tho gnsoIIno Is sfrIod off dIssoIvod gnsos nnd urIfIod. Tho cnrbon doosIfs
on fho cnfnIysfs nro burnf by comrossod nIr In ono chnmbor for roncfIvnfIon whIIo fho ofhor
cnfnIysf chnmbors nro ncfIvo (IIg. l8.?).
Heavy
oil charge
Vapour
Catalyst
Heater
Pre-heater
(425C
450C)
Catalyst
chamber
(425C
450C)
Fractionating
column
Gasoline
+
some dissolved gases
Heavy
oil
Cracked
vapour
Cooler Stabilizer
Gases
Gasoline
Fig. 18.7 Fixed-bed catalytic cracking.
(I) Moting IeJ or fluiJiceJ IeJ coIol,Iic crocling. Tho fInoIy owdorod cnfnIysf bohnvos
ns n fIuId whon susondod In gns or oII vnour. Tho rohonfod honvy oII Is forcod fhrough
fowor nIong wIfh fho fIuIdIsod cnfnIysf. Af fho fo of fho fowor n cycIono sonrnfor Is ncfIvo fo
sonrnfo fho crnckod oII vnour nnd nssos If fo fho frncfIonnfIng coIumn. Tho cnfnIysf owdor
Is rofnInod nnd sonf bnck. Tho cnfnIysf bocomos doncfIvnfod by n doosIfIon, whIch Is roncfIvnfod
by burnIng nwny fho doosIfs wIfh comrossod nIr In n rogonornfor (IIg. l8.8).
600C
500C
Flue gases
Cyclone
Reactor
Cracked
vapour
Light
fraction
Cooler
Gases
Gases
Stabilizer
Gasoline
Gasoline
+ gas
Heavy
oil
Fraction
matching
column
Air
Spent
catalyst
A
i
r
+
s
p
e
n
t
c
a
t
a
l
y
s
t
Catalyst
+ oil
Feed
oil
Regenerated
catalyst
Catalyst
regenerator
Blower
Fig. 18.8 Moving-bed type catalytic cracking.
AJtonIogee of coIol,Iic crocling.
(i) Tho qunIIfy nnd yIoId of ofroI Is boffor.
(ii) IxfornnI fuoI Is nof nocossnry sInco fho conI omboddod In fho cnfnIysf suIIos fho
honf.
(iii) OornfIng rossuro Is Iowor.
(it) Iyroducf gns ovoIufIon boIng Iow, yIoId of ofroI Is hIghor.
(t) uo fo hIghor nromnfIcs confonf, fho nnfI-knockIng roorfIos nro hIghor.
(ti) Cronfor orfIon of S oscnos ns H
2
S so rosIdunI S confonf of fho oII Is Iow.
(tii) Cum-formIng comounds nro vory Iow.
(tiii) In rosonco of socIfIc cnfnIysfs roforonfInIIy fho crnckIng of nnhfhonIc mnforInIs
fnkos Inco, so If bocomos rIchor In nrnffInIc comounds.
(ix) OnIy fho hIgh-boIIIng hydrocnrbons nnd fho sIdo chnIn of fho nromnfIcs nro docom-
osod roforonfInIIy.
HIgLIIgLts:
CnsoIIno Is fho fuoI for mofor ongInos.
CnsoIIno confnIns nIknnos C
5
C
l0
nfoms.
Inough gnsoIIno Is nof roducod durIng urIfIod ofroIoum dIsfIIInfIon.
OII rofInorIos uso coIol,Iic crocling fo mnko gnsoIIno.
Ior smoofh runnIng of fho mofors, gnsoIIno hns fo burn smoofhIy wIfhouf lnocling.
Tho ocfnno numbor scnIo wns dovIsod by Thomns MIdgIoy (l889-l944) nnd ho
dIscovorod onIi-lnocling nddIfIvos bnsod on Iond i.e., T.I.!. (Tofrn IfhyI !ond)
!ondod fuoI Is now nvoIdod nnd fho oII comnnIos roduco hIgh ocfnno fuoI by
IncronsIng fho roorfIons of bofh brnnchod nIknnos nnd nronos nnd bIondIng somo
oxygon comounds.
(conIJ.)
Tho four mnIn nronchos nro:
(i) Crocling nof onIy mnkos smnII moIocuIos buf nIso forms brnnchod chnIn
hydrocnrbons.
(ii) 1eonerieoIion convorfs sfrnIghf chnIn nIknnos fo brnnchod chnIn by nssIng
ovor If-cnfnIysfs.
(iii) Ieforning Iurns cycIIc nIknnos Info nronos such ns bonzono nnd foIuono.
(it) AJJiIion of olcoIole onJ eIIere. Comounds such ns MTII (MofhyI TorfInry
IufyI Ifhor) now known ns 2-mofhoxy-2-mofhyI ronno.
CH
3
CH
C O CH
CH
3
3
3
MTII
PetroIeum Processing
1. Polymerixution, ulkylution unJ ioomerixution. Tho crnckor gnsos In fho rofInory
nro rIch In oIofIns. Thoso comounds undorgo oIymorIznfIon oIfhor In rosonco of cnfnIysf
(cnfnIyfIc oIymorIznfIon) IIko hoshorIc ncId, H
2
SO
4
or by honfIng nf fomornfuros of 500C
600C nnd rossuro (fhormnI oIymorIznfIon) fo yIoId roducfs rIch In brnnchod-chnIn
hydrocnrbons. Iy fhIs rocoss suorIor qunIIfy gnsoIInos nro obfnInod.
CH
3
C(CH
3
) = CH
2
CH
3
C(CH
3
)
2
CH
2
C(CH
3
) = CH
2
ieo-bufono Ji-Isobufono
SImIInrIy, nIkyInfIon In rosonco of HI or H
2
SO
4
gIvos ieo-nrnffIns. IsomorIznfIon
convorfs n-nrnffIns fo ieo-nrnffIns In rosonco of nnhydrous AICI
3
cnfnIysf. AII fhoso rocossos
suIy oxcoIIonf hIgh voInfIIo gnsoIIno comononfs.
2. Reforming. ThIs rocoss nIso hoIs In ronrIng hIgh qunIIfy gnsoIIno by honfIng
wIfh or wIfhouf n cnfnIysf, fho nnhfhn frncfIons of gnsoIIno. ThIs ugrndIng Is n rosuIf of
roformIng of moIocuIos wIfhouf dIsfurbIng fhoIr nvorngo moIocuInr woIghfs, IIko formnfIon of
nromnfIcs from nnhfhono nnd nrnffIns.
CH
3
CH
3
+ 3H
2
methyl cyclohexane toluene
CH
3
CH
3
+ 4H
2
n-heptane toluene
Tho ofhor roncfIons nro fho IsomorIznfIon of n-nrnffIns fo ieo-nrnffIns nnd hydrocrnckIng
of hIghor nrnffIns fo Iowor onos. AcfunIIy fhoso nromnfIcs nnd fho ieo-nrnffIns nro fho bosf
gnsoIIno comononfs.
SImIInr fo crnckIng, roformIng Is nIso fhormnI nnd cnfnIyfIc. ThormnI roformIng hns
boon nImosf comIofoIy roIncod by cnfnIyfIc roformIng.
Tho cnfnIysfs usod nro moIybdonn, chromIn suorfod on nIumInn, InfInum on sIIIcn or
nIumInn. Tho Inffor Is moro ncfIvo, buf gofs oIsonod onsIIy by fho ImurIfIos IIko S, As, ofc.
!oformIng Is n onco fhrough rocoss. IIuId bod nnd movIng bod rocossos nro run nf
hIghor fomornfuro nnd Iowor rossuros nnd fIxod bod rocossos nro run nf hIghor rossuros
(fomornfuro 450C520C, rossuro 545 kg/cm
2
) (IIg. l8.9).
H compressed
and recycled
2
Low boiling
(to avoid explosive
reaction with H )
2
Gasoline
feed stock
Fracti-
onator
Residue
Fraction
b.p.
100170C
Heater
at 500C
Reactor
contain-
ing cata-
lytic bed
(PtAl O )
2 2
Reactor
(Pt
Al O )
2 3
Reactor
(Pt
Al O )
2 3 Con-
den-
ser
To
solvent
DEA
recover
H S
scru-
bber
2
Fracti-
onator
Gas
Reformed
or
stabilized
gasoline
Diethanolamine
(DEA)
Compressor
(25 atm)
Heater
at 500C
Heater
at 500C
Fig. 18.9 Fixed-bed catalytic reforming process.
Refining of GasoIine
Tho eIroigII-run goeoline obfnInod from fho frncfIonnfIon of crudo ofroIoum confnIns
undosIrnbIo consfIfuonfs IIko unsnfurnfod sfrnIghf chnIn hydrocnrbons nnd suIfur comounds.
Tho formor Ionds fo gum nnd sIudgo formnfIon nnd fho Inffor Ionds fo corrosIon of ongInos nnd
oIIufIon of nfmoshoro. Thoso nro romovod by rofInIng rocossos.
(i) ObjocfIonnbIo odour formIng morcnfnns nnd H
2
S mnko fho oII sour. OII snmIo
fronfod wIfh sodIum IumbIfo nnd n IIffIo suIfur convorfs fho suIfur comounds Info
dIsuIfIdos (DocIorè proceee). Tho bInck IbS rocIIfnfos nnd fho ofhor dIsuIfIdos nro
oxfrncfod wIfh n suIfnbIo soIvonf, rondorIng fho fouI smoIIIng sfock fo swoof smoIIIng
or odourIoss sfock nnd fho rocoss Is cnIIod eueeIening proceee.
2!SH + n
2
IbO
2
Ib(!S)
2
+ 2nOH
Ib(!S)
2
+ S IbS + !SS!
dIsuIfIdo
(ii) CnsoIIno Is orcoInfod fhrough IuIIor`s onrfh whIch nbsorbs fho oIofIns nnd coIorIng
mnffors rosonf In If.
(iii) Tho sforIng qunIIfy of fho rofInod gnsoIIno Is Imrovod by nddIng dIfforonf InhIbIfors
of oxIdnfIons fo If.
(it) !ofInod gnsoIIno Is bIondod wIfh suIfnbIo frncfIons of cnfnIyfIcnIIy crnckod gnsoIIno
fo Imnrf good combusfIon qunIIfIos.
Knocking
Octune Numbev. MnxImum owor Is dorIvod from gnsoIIno whon If burns sIIonfIy nnd
unIformIy In nn InfornnI combusfIon ongIno. uo fo rosonco of corfnIn consfIfuonfs In fho
gnsoIIno, fho rnfo of oxIdnfIon somofImos bocomos so gronf fhnf fho unburnf fuoI mny burn
rnIdIy wIfh fho formnfIon of oxIosIvo vIoIonco. ThIs Is known ns lnocling. KnockIng rosuIfs
In Ioss of offIcIoncy of fho ongIno nnd nIso Ionds fo Ifs shorf IIfo.
Tho nnfI-knock qunIIfy of n fuoI Is oxrossod ns Ifs ocfnno numbor.
Ocfnno numbor Is oqunI fo fho orconfngo by voIumo of Iso-ocfnno (2,2,4-frImofhyI
onfnno) In n mIxfuro of n-hofnno nnd Iso-ocfnno hnvIng fho snmo knockIng fondoncy comnrod
fo fho snmIo of gnsoIIno boIng fosfod; Iso-ocfnno hns fho bosf nnfIknockIng roorfIos nnd
nssIgnod nn ocfnno numbor of l00 whorons n-hofnno hns oor nnfIknockIng roorfy nnd
nssIgnod nn ocfnno numbor of zoro. Tho hydrocnrbons rosonf InfIuonco fho knockIng roorfIos
of gnsoIIno whIch vnry nccordIng fo fho sorIos: sfrnIghf chnIn nrnffIn > brnnchod chnIn nrnffIn
> oIofIn > cycIonrnffIn > nromnfIcs. Tho fuoI whIch hns snmo knockIng fondoncy wIfh fho
mIxfuro hnvIng 80 ieo-ocfnnco hns ocfnno numbor 80.
Tho mosf offocfIvo nnfIknock ngonf nddod Is fofrnofhyI Iond (TI!) nIong wIfh ofhyIono
dIbromIdo whIch rovonfs fho doosIfIon of Iond by formIng voInfIIo Iond hnIIdos. Ofhor
nnfIknockIng ngonfs nro fofrnmofhyI Iond (TM!), forfInry bufyI ncofnfo, dIofhyI foIIurIdo.
l.0l.5 mI of TI! Is nddod or IIfro of ofroI. TI! funcfIons by boIng convorfod fo n
cIoud of fInoIy dIvIdod Iond oxIdo nrfIcIos, whIch roncf wIfh nny hydrocnrbon oroxIdo moIocuIos
formod In fho ongIno cyIIndor fhoroby soIvIng down fho chnIn oxIdnfIon roncfIon nnd rovonfIng
knockIng.
Cetane Number
Thoro Is n doIny orIod bofwoon fho InjocfIon of dIosoI fuoI nnd Ifs IgnIfIon. ThIs doIny
orIod If bocomos Inrgo, foo much fuoI nccumuInfos In fho cyIIndor nnd burn vory rnIdIy nnd
cnusos dIosoI knock. ThIs doIny orIod Is connocfod fo fho fyo of hydrocnrbons rosonf In fho
dIosoI. IncronsIng doIny orIod occurs In fho sorIos: n-nrnffIns < oIofIns < nnhfhonos <
IsonrnffIns < nromnfIcs. Tho ordor Is fho rovorso for gnsoIIno nnfI-knock qunIIfy. n-hoxndocnno
Is gIvon cofnno numbor l00 nnd -mofhyI nnhfhnIono gIvon cofnno numbor zoro. If n gIvon
fuoI mnfchos In qunIIfy wIfh fho bIond hnvIng 40/60 bIond of cofnno nnd -mofhyI nnhfhnIono,
If Is nssIgnod n cofnno numbor 40. Tho cofnno numbor of dIosoI cnn bo Imrovod by nddIng
nmyI/bufyI nIfrnfo, cnrbnmnfos, dIforfInry bufyI oroxIdo nnd mofnI orgnnIc comounds.
Liquid FueI from CoaI and CoaI Tar
Tho convorsIon of conI Info oII Is ossonfInIIy rnIsIng fho H:C rnfIo.
1. Bergiuo-Pier Proceoo: osfrucfIvo hydrogonnfIon of conI In rosonco of n cnfnIysf
yIoIds oII, buf If Is nof yof comofIfIvo wIfh ofroIoum rofInIng.
ConI Is ground nnd mndo Info n nsfo wIfh n honvy rocycIo oII nnd n cnfnIysf IIko Iron, fIn
or moIybdonum comound. Tho nsfo Is rohonfod nnd fronfod wIfh H
2
nf 250350 nfm. rossuro
nnd 450C500C fomornfuro. Tho unroncfod conI Is fIIforod-off nnd fho IIquId roducf dIsfIIIod.
Hydrogon combInos wIfh conI fo form snfurnfod hydrocnrbons, whIch docomoso nf hIgh
fomornfuro yIoIdIng Iow-boIIIng hydrocnrbons. Tho crudo oII Is frncfIonnfod fo gof (i) gnsoIIno
(ii) mIddIo oII nnd (iii) honvy oII whIch Is rocycIod. MIddIo oII Is hydrogonnfod In vnour hnso
wIfh cnfnIysf fo yIoId moro gnsoIIno. YIoId of gnsoIIno Is 60 of fho conI dusf.
Powdered
coal
Heavy
oil
Paste
Catalyst
(Sn or Ni
oleate)
Gases Condenser Gases
H
2
Gaso-
line
Gaso-
line
Middle
oil
Heavy
oil
Fractionating
column
Crude
oil
Converter at
450C and 200 250 atm
H
2
Fig. 18.10 Bergius process of hydrogenation of coal to gasoline.
2. Fiocher-Tropoch Proceoo. Tho rocoss Is bnsod on fho cnfnIyfIc hydrogonnfIon of
cnrbon monoxIdo IondIng fo fho foIIowIng roncfIon:
nCO + (2n + l)H
2
C
n
H
2n+2
+ H
2
O
InrnffIn
nCO + 2nH
2
C
n
H
2n
C
n
H
2n
+ nH
2
O
OIofIn
Wnfor gns (CO + H
2
), roducod by nssIng sfonm ovor honfod coko Is mIxod wIfh hydrogon.
Tho gns Is urIfIod by nssIng ovor Io
2
O
3
fo romovo H
2
S, fhon nssIng ovor n mIxfuro of
Io
2
O
3
.n
2
CO
3
fo romovo orgnnIc suIfur comounds. Tho urIfIod gns Is comrossod fo 5 fo 25
nfm. nf 200C300C nssod fhrough n convorfor confnInIng cnfnIysf whIch Is n mIxfuro of l00
nrfs cobnIf, 5 nrfs fhorIum, 8 nrfs mngnosIum nnd 200 nrfs koIsoIguhr.
Tho oxofhormIc roncfIon Ionds fo fho formnfIon of sfrnIghf-chnIn snfurnfod nnd
unsnfurnfod hydrocnrbons. Tho crudo oII on frncfIonnfIon yIoIds (i) gnsoIIno nnd (ii) honvy oII,
whIch nro crnckod fo yIoId moro gnsoIIno.
Tho gnsoIIno confnIns sfrnIghf chnIn hydrocnrbons nnd honco hnvo Iow ocfnno numbor,
so noods roformIng boforo uso (IIg. l8.ll).
Fe O
2 3
Water gas
(CO + H )
2
H
2
Purification
of gas
Compressor
(525 atm)
Fractionating
column
Heavy
oil
Gaso-
line
Cracking
Gasoline
Cooler
Fe O
2 3
+
Na CO
2 3
Catalyst
(Co + Th + MgO
+ Keiselguhr)
Fig. 18.11 Fisher-Tropsch method.
Important PetroIeum Products
Tho mnIn roducfs of rofInory nro mofor nnd nvInfIon gnsoIIno, korosono, dIosoI fuoI,
fuoI oIIs; ofhor roducfs IncIudo IubrIcnfIng oIIs, wnx, bIfumon, coko, !IC ofc.
Coeolinee. If Is usod In rocIrocnfIng snrk-IgnIfIon InfornnI combusfIon ongInos.
Mofor gnsoIIno Is n mIxfuro of Iow boIIIng hydrocnrbons (2l5C) nnd mndo by bIondIng
(i) SfrnIghf run gnsoIIno (dIrocf dIsfIIInfIon of crudo oII), (ii) crnckod gnsoIIno, (iii) roformod
nnhfhn nnd ofhor frncfIons, l0 bufnno for onsy sfnrfIng of ongInos, TI! nnd ofhor nddIfIvos.
CoIours nro nddod fo IdonfIfy dIfforonf grndos.
AvInfIon gnsoIInos hnvo hIghor voInfIIIfy nnd hIghor orconfngos of TI! nnd IsonrnffIn.
Keroeene. Korosono Is usod for domosfIc uroso, snco honfors for jof ongInos. If Is
obfnInod ns n sfrnIghf-run dIsfIIInfo from crudo oIIs. o nddIfIvos nro roquIrod. IurIfIcnfIon
InvoIvos romovnI of suIhur.
Dieeel fuel. IosoI fuoIs nro ronrod from honvy dIsfIIInfo obfnInod from cnfnIyfIc
crnckIng unIfs. If Is rIch In nromnfIcs nnd ieo-nrnffIns, fho Iow cofnno numbor Is Imrovod by
nddIfIvos. VoInfIIIfy Is Imrovod by bIondIng wIfh IIghf frncfIons. In n hIgh-sood dIosoI ongIno,
fho cofnno numbors shouId bo moro fhnn 45 whorons for Iow sood ongInos If shouId bo In fho
rnngo of 25 fo 35.
Iuel oile. WIdo rnngo of IIquId fuoIs usod In boIIors nnd furnncos nro covorod by fhIs
form. CycIo gns oII Is fho IIghf vnrIofy nnd noods n numbor of fronfmonfs for urIfIcnfIon. Tho
honvy fuoI oII roducod from fho crnckIng unIfs nro fho honvy vnrIofy.
LPC. !IquofIod ofroIoum gns Is obfnInod ns n byroducf durIng fho crnckIng of honvy
oIIs or from nnfurnI gns. !IC confnIns hydrocnrbons whIch nro gnsoous undor nfmoshorIc
rossuro buf cnn bo IIquofIod undor rossuro. Thoy nro n-bufnno, Isobufnno, bufyIono, ronno
ofc. If Is usod ns domosfIc nnd IndusfrInI fuoIs nnd In fufuro If mny bo usod ns mofor fuoI.
Non-petroIeum FueIs
1. Benxol. !ofInod bonzoI Is ossonfInIIy n mIxfuro of ?0 bonzono, l8 foIuono nnd 6
xyIonos. Ifs ocfnno rnfIng rnngos bofwoon 8? nnd 90. If Is n good fuoI for InfornnI combusfIon
ongInos buf Ifs InIfInI boIIIng oInf Is hIgh (80C), so If cnn bo usod onIy whon bIondod wIfh
gnsoIInos. Tho ofhor dofocf Is Ifs hIgh froozIng oInf (55C), so If cnnnof bo usod In coId counfrIos.
AlcoIole. MofhyI nnd ofhyI nIcohoIs cnn bo usod In gnsoIIno ongInos. Cosf consIdornfIons
rohIbIf fhoIr uso. Ocfnno numbor Is hIgh ns ll4 nnd 99, rosocfIvoIy. Iuf fhoIr cnIorIfIc vnIuos
nro Iow. IfhyI nIcohoI Is nof usod ns n rImo fuoI buf usod ns bIonds wIfh gnsoIIno ufo 25
nIcohoI nnd fho mIxfuro Is cnIIod gnsohoI. If sorvos fo Incronso fho ocfnno rnfIng.
Tho Imorfnnco of ofhyI nIcohoI ns n fuoI IIos In fho fncf fhnf If cnn bo roducod from
nnfurnIIy nvnIInbIo cnrbohydrnfos by formonfnfIon. If roquIros nbouf 36 hrs. fo comIofo whoroby
fho formonfod IIquId confnIns l8-20 nIcohoI whIch Is fhon frncfIonnIIy dIsfIIIod fo rocIfIod
sIrIf confnInIng 90-95 nIcohoI, from whIch nbsoIufo nIcohoI cnn bo obfnInod nffor fronfmonf
wIfh IImo nnd dIsfIIInfIon.
GASEOUS FUELS
(o) IuoI gns from nnfuro:
(i) nfurnI gns (ii) Mofhnno from conI mInos.
(I) IuoI gns from soIId fuoIs:
(i) Iroducor gns (ii) Wnfor gns
(iii) ConI gns (it) IInsf furnnco gns
(c) IuoI gns from ofroIoum:
(i) !ofInory gnsos (ii) !IC (iii) Cnsos from oII gnsIfIcnfIon.
(J) IuoI gns mndo by formonfnfIon of orgnnIc wnsfos.
NaturaI Gas
nfurnI gns Is n mIxfuro of nrnffInIc hydrocnrbons nnd mofhnno Is fho rIncInI
comononf. nfurnI gns whon found fo occur wIfh ofroIoum In oII woIIs Is cnIIod 'wof gns` nnd
whon If Is nssocInfod wIfh crudo oII fho gns Is cnIIod 'dry gns`. Wnfor, dIrf, H
2
S, CO
2
,
2
nnd
honvIor hydrocnrbons nro romovod from fho gns nnd fInnIIy If confnIns from 50 fo 95 mofhnno,
5-l0 ofhnno, 3 H
2
ofc. Tho cnIorIfIc vnIuo Is l2,000l4000 kcnI/m
3
.
nfurnI gns Is usod (i) ns n domosfIc fuoI, (ii) for mnnufncfuro of vnrIous chomIcnIs
(iii) ns rnw mnforInI for fho mnnufncfuro of H
2
nnd cnrbon bInck nnd (it) for synfhofIc rofoIn
ronrnfIon from mofhnno.
CoaI Gas
ConI Is roducod by fho hIgh fomornfuro cnrbonIsnfIon of conI In gns roforfs nnd coko
ovons. Ifs cnIorIfIc vnIuo Is nround 5000 kcnI/m
3
. If confnIns 40 H
2
, 32 CH
4
, ? CO, 2
C
2
H
2
, 3 C
2
H
5
, 4
2
nnd l CO
2
. If burns wIfh n Iong smoky fInmo.
Tho coko ovon gns Is urIfIod In sfos fo obfnIn fho conI gns fInnIIy. Tnr nnd nmmonIn
nro fIrsf romovod by cooIIng fho gns nnd wnfor scrubbIng, fhon bonzoI, nnhfhnIono nro romovod
by croosofo oII scrubbIng, H
2
S Is fInnIIy romovod by nssIng If ovor moIsf forrIc oxIdo.
2Io(OH)
3
+ 3H
2
S Io
2
S
3
+ 6H
2
O
ConI gns Is usod (i) for IIIumInnfIng fowns nnd cIfIos, (ii) ns n fuoI, (iii) ns n rnw mnforInI
for H
3
roducfIon nnd (it) In mofnIIurgIcnI oornfIons fo rovIdo roducIng nfmoshoro.
Producer Gas
If Is n mIxfuro of combusfIbIo gnsos IIko CO nnd H
2
nnd Inrgo nmounf of non-combusfIbIo
gnsos IIko
2
, CO
2
ofc. If Is ronrod by nssIng nIr nnd sfonm ovor nn Incnndosconf bod of
soIId cnrbonncoous fuoI In n roncfor cnIIod gns roducor or sImIy n roducor. If Is n fuoI of
Iow cnIorIfIc vnIuo (l300 kcnI/m
3
) buf Ifs ndvnnfngo Is Ifs chonnoss nnd onso of roducfIon.
Tho cnrbonncoous fuoI usod Is gonornIIy conI or coko, fhough wood wnsfo, onf ofc. cnn bo usod.
Tho gns roducor consIsfs of n sfooI vossoI wIfh Innor IInIng mndo u of rofrncfory brIcks.
Tho dImonsIon of fho vossoI Is nbouf 4 m hoIghf nnd nf fho fo fhoro Is n cono foodor nnd n sIdo
oonIng for roducor gns oufIof. Af fho bnso fhoro Is InIofs for nIr nnd sfonm nnd nn oufIof for
fho nsh.
Coke
Cup and
cone feeder
Producer
gas outlet
Refractory
brick lining
Coal at
1000C
Exit for
ash
Air mixed
with a little
steam
Distillation zone
Reduction zone
Combustion zone
Fig. 18.12 Gas producer.
Reaction Zones in a Gas Producer
(o) AsL zone. Tho fuoI bod In n normnI roducor Is on mofnIIIc grnfo. Tho nIr-sfonm
bInsf Is rohonfod by fho nsh zono whIch nIso rofocfs fho grnfo from Infonso honf.
(I) OxIdutIon zone. ThIs Is jusf noxf fo fho nsh zono. Tho oxygon Is consumod wIfhIn
?5 fo l00 mm of fho bod, whIch consfIfufos fho zono. CO
2
forms nf fho oxonso of O
2
. Ifs
conconfrnfIon ronchos n mnxImum nf fho fo whon CO bogIns fo nonr. Tho fomornfuro nf
fhIs zono Is nbouf ll00C.
C + O
2
CO
2
+ 9? kcnI
C +
l
2
O
2
CO + 29.5 kcnI
(c) ReductIon zone.
CO
2
+ C 2CO 36 kcnI
C + H
2
O CO
2
+ H
2
29 kcnI
C + 2H
2
O CO
2
+ 2H
2
l9 kcnI
As Iong ns O
2
Is In oxcoss, CO
2
Is formod, whIch fhon undorgoos roducfIon Info CO nnd
fho roncfIon Is ondofhormIc nnd Is cnIIod Iondonnrd roncfIon. Ifs oquIIIbrIum consfnnf gronfIy
Incronsos wIfh rIso In fomornfuro. Ofhor roncfIons nro nIso ondofhormIc, whoro rod hof coko,
combInos wIfh sfonm fo IIbornfo H
2
nnd from oxIdos of C. Tho fomornfuro Is nround l000C
(J) Tho uormosf Inyor of fho bod Is fho Jr,ing onJ corIonieoIion cone. Tho wnfor vnor nnd
fho voInfIIo mnffor nro nddod fo fho oscnIng gns whIch rosuIfs In roducfIon of onrIchod gnsos.
Tho fomosf zono sorvos fo rohonf fho rocnrbonIsod fuoIs comIng In. Tho fomornfuro of fhIs
zono Is from 400C-800C. Tho nvorngo comosIfIon of fho roducor gns Is CO: 22-30, H
2
:
8-l2,
2
: 52-55, CO
2
: 3.
Iroducor gns Is usod for honfIng fho furnncos for fho roducfIon of sfooI nnd gInss, muffIo
furnncos for conI gns roducfIon, nnd In mofnIIurgIcnI oornfIons.
Ior fho roducfIon of roducor gns, onIy nIr cnn bo usod, sfonm usod nIong wIfh nIr Is
ndvnnfngoous sInco (i) If rnIsos fho confonf of combusfIbIo comononfs (CO + C
2
) comnrod fo
noncombusfIbIo fhoroby IncronsIng cnIorIfIc vnIuo, (ii) fho ondofhormIc roncfIon of sfonm nnd
C rovonfs IocnIIsod ovorhonfIng of n fuoI bod nnd Ionds fo dImInIshod cIInkor formnfIon.
Water Gas
Wnfor gns Is n gnsoous fuoI of modIum cnIorIfIc vnIuo (2800 kcnI/m
3
) gonornfod by gnsIfyIng
soIId Incnndosconf sourco of cnrbon In suorhonfod sfonm. Tho oquImonf Is known ns wnfor
gns gonornfor nnd Is moro or Ioss sImIInr fo fhnf shown In IIg. l8.l2 whoro fho foIIowIng
roncfIon fnkos Inco whIch Is ondofhormIc
C + H
2
O CO + H
2
29 kcnI
Red hot coke
at 900C1000C
Coke
Cup and
cone feeder
Water gas
outlet
Grate
Ash
outlet
Ash
Air supply Steam
supply
Refractory
brick lining
Fig. 18.13 Water gas production.
ThIs gns burns wIfh n bIuo fInmo owIng fo hIgh cnrbon monoxIdo confonf nnd honco
known ns bIuo wnfor gns. Tho bod of coko In fho roncfor Is nf l400C fo l000C. As fho roncfIon
Is ondofhormIc fomornfuro grndunIIy fnIIs nnd whon If comos fo l000C fho bInsf of sfonm Is
sfood nnd nIr bInsf Is nssod nnd fho foIIowIng oxofhormIc roncfIons occur.
C + O
2
CO
2
+ 9? kcnI
2C + O
2
CO + 59 kcnI
Tho roncfIon ngnIn rIsos nnd fhoso cycIos nIfornnfoIy fnko Inco fo mnInfnIn fho
fomornfuro. Affor fho roducfIon, nsh Is romovod nnd fho gonornfor rochnrgod. Tho wnfor
gns nssIng fhrough fho suorhonfor Is cooIod nnd fhon urIfIod.
Tho nvorngo comosIfIon Is H
2
: 5l, CO: 4l;
2
: 4, CO
2
: 4
IIuo wnfor gns Is usod ns n sourco of hydrogon, ns n fuoI gns.
Tho cnIorIfIc vnIuo of wnfor gns cnn bo onhnncod by nddIng gnsoous hydrocnrbons
(obfnInod from crnckIng crudo oIIs) fo gof corIureIIeJ uoIer goe (CnIorIfIc vnIuo 4500 kcnI;
CO
2
3(m
3
)); comosIfIon of cnrburoffod wnfor gns Is 35 H
2
, 25 CO, 35 snfurnfod nnd
unsnfurnfod hydrocnrbons nnd 5
2
+ CO
2
.
Steam
Blast
of air
Purge
steam
Oil
spray
Products of
combustion
Tar separator
Cooler
Purifier
Fig. 18.14 Manufacture of carburetted water gas.
Biogas Production
AqunfIc Innfs, orgnnIc wnsfos from domosfIc, ngrIcuIfurnI nnd IndusfrInI socfors wIfh
hIgh I.O.. vnIuo (Iood sfock) nro dIgosfod nnnorobIcnIIy fo roduco Iiogoe. Tho bIogns Is
fofnIIy usod ns fuoI. Tho chIof consfIfuonf of bIogns Is mofhnno, so fho rocoss Is nIso cnIIod
IioneIIonoIion. ComosIfIon of bIogns Is gIvon boIow:
ConponenI Volune"
CH
4
52-95
CO
2
9-45
H
2
S 0.00l-2
H
2
0.0l-2
2
0.l-4
O
2
0.02-6.5
CO 0.00l
H
3
SmnII
Conditions for Biomethanation
Tomornfuro = 35
H = 6.8-8.2
AnnorobIc condIfIon.
Trnco oIomonfs = n
+
, Co
+3
, I
+2
ofc.
Arrangements for Biomethanation
Iood sfock Is mnInIy cowdung.
Gas
Excess feed stock
(b) Feed stock
Gas
(a)
(Batch process) Feed stock
Fig. 18.15
Ioffor qunIIfy of conI shouId hnvo Iow nIfrogon nnd suIhur confonf. HIghor orconfngo
of oxygon Is nIso undosIrnbIo ns nn Incronso In l oxygon confonf docronsos fho cnIorIfIc vnIuo
by nbouf l.?.
Method of AnaIysis of FIue Gas
AnnIysIs of fIuo gns wIII IndIcnfo fho comIofo or IncomIofo combusfIon of n fuoI; whIch
Is vory ossonfInI In rosocf of offIcIonf ufIIIznfIon of fho fuoI. Tho nnnIysIs Is dono In Orsnf`s
nnrnfus nnd Is bnsod on fho rIncIIo of nbsorfIon of
CO
2
In KOH soIufIon (500 gI
l
, 500 mI)
O
2
In nIknIIno yrognIIIc ncId (25 g of yrognIIIc ncId In 400 gI
l
KOH soIufIon, 500 mI)
CO In nmmonIncnI curous chIorIdo soIufIon (l00 g Cu
2
CI
2
+ l25 mI IIquor nmmonIn
+ !osf wnfor fo mnko u fho voIumo, 500 mI).
Description of the Apparatus
If consIsfs of n wnfor jnckoffod monsurIng buroffo, connocfod In sorIos wIfh fho nbsorfIon
buIbs confnInIng fho nbovo fhroo soIufIons succossIvoIy ns doIcfod In fho IIg. l8.l6. Tho wnfor
jnckof mnInfnIns fho fomornfuro of fho gns consfnnf. Tho nbsorfIon buIbs nro fIIIod wIfh
gInss fubos for boffor nbsorfIon of fho gnsos.
Flue
gas
Fused CaCl
2
Filter Stop cock
Gases
tube
Water
reservoir
Graduated
Burette
Rubber
tube
Bulb
containing
AM.Cu Cl
2 2
Bulb
Alkaline
pyrogalic
acid
containing
Bulb
KOH
solution
containing
Fig. 18.16
Procedure
Tho nnrnfus Is fosfod for Ifs nIr-IIghfnoss.
Tho fIuo gns (l00 mI) Is fnkon In fho nnrnfus In fho monsurIng buroffo by ndjusfIng
fho voIumo by wnfor rosorvoIr nfmoshorIc rossuro.
Tho sfoor (l) Is oonod for CO
2
nbsorfIon nnd wnfor rosorvoIr Is rnIsod fo forco fho
gns InsIdo fho buIb. Tho gns Is fInnIIy fnkon In fho buroffo nnd fho voIumo of fho gns Is
monsurod by mnkIng fho IovoIs of wnfor InsIdo fho buroffo nnd wnfor rosorvoIr oqunI.
Tho docronso In voIumo gIvos fho orconfngo by voIumo of CO
2
In fho fIuo gns.
Tho sfoor (2) Is oonod nnd rovIdod ns usunI fo gof fho orconfngo by voIumo of O
2
In fho fIuo gns.
Tho sfoor (3) Is oonod nnd rocoodod ns usunI fo gof fho orconfngo by voIumo of CO
In fho gns.
Tho soquonco of fho buIbs shouId bo sfrIcfIy foIIowod.
ImpIications of the AnaIysis
If fho fIuo gns confnIns gronfor orconfngo of CO If Is ImIIod fhnf consIdornbIo wnsfngo
of fuoI Is fnkIng Inco duo fo IncomIofo combusfIon nnd fho O
2
suIy Is InsuffIcIonf.
Tho gronfor orconfngo of O
2
In fho fIuo gns IndIcnfos fhnf O
2
suIy Is In oxcoss.
!osuIf of fho nnnIysIs wIII hoI fo confroI fho combusfIon rocoss.
SOLVED EXAMPLES
xumpIe 1. A eonple of cool conIoine.
C = 93", H = 6" onJ oeI = 1"
ColculoIe IIe groee onJ neI colorific V tolue of IIe cool fron IIe follouing JoIo.
WeigII of cool IurnI (n) = 0.92 g
WeigII of uoIer Iolen (u) = 0 g
WoIer equitolenI of IonI colorineIer (W) = 2,200 g.
Iiee in IenperoIure (I
2
I
1
) = 2.42C, Iuee uire correcIion = 10 col.
L = S0 col/g
1
.
SoI. HCV =
( ) ( ) | ] W ncId fuso corrocfIon + + u I I
n
2 l
=
(2,200 530) 2.42 |50 l0]
0.92
cnI/g
+ +
l
= ?16B.5 cuI/g
of CnIorIfIc VnIuo (CV)
= (HCV 0.09 H !) cnI/g
l
= (?l68.5 0.09 6 580) cnI/g
l
= 6,B55.3 cuI/g.
xumpIe 2. A eonple of cool uoe onol,eeJ oe folloue.
1xocIl, 2. g uoe ueigIeJ in o eilico cruciIle, ofIer IeoIing for 1 Ir. oI 110C IIe reeiJue
uoe ueigIeJ Io Ie 2.41 g. AexI IIe cruciIle uoe cotereJ uiII o renIeJ liJ onJ eIrongl, IeoIeJ
for exocIl, 7 nine. oI 1000C. TIe reeiJue uoe ueigIeJ Io Ie 1.2S g. TIen IIe cruciIle uoe
IeoIeJ uiIIouI coter unIil o coneIonI ueigII Io 0.24 g uoe oIIoineJ. Iron IIe oIote JoIo
colculoIe IIe proxinoIe onol,eie of cool.
SoI. MoIsfuro In fho snmIo = (2.5 2.9l5)g = 0.085 g
So, moIsfuro =
0 085
2 5
l00
.
.
= 3.4
So, nmounf of voInfIIo cnrbonncoous mnffor (VCM) In fho snmIo = (2.4l5 l.528) g
= 0.88? g.
So, VCM =
0 88? l00
2 5
35 48
.
.
.
=

Ash =
WoIghf of nsh
WoIghf of conI
l00
=
0 245
2 5
l00 35 48
.
.
. =
IIxod cnrbon = (l.528 0.245)g = l.283 g
IIxod cnrbon =
l.283 l00
2 5
.
= 5l.32.
xumpIe 3. On Iurning 0.S3 g of o eoliJ fuel in IonI colorineIer, IIe IenperoIure of
3,00 g of uoIer increoeeJ fron 26.C Io 29.2C. WoIer equitolenI of colorineIer onJ loIenI
IeoI of eIeon ore 3S g onJ S7 col/g, reepecIitel,. 1f IIe fuel conIoine 0.77" H, colculoIe HCV
onJ ACV.
SoI. HCV =
( ) ( ) W + u I I
n
2 l
=
( ) ( . . )
.
385 3500 29 2 26 5
0 83
l2638
+
=

cnI g
l
CV = (HCV 0.09 H !) cnI g
l
= (l2638 0.09 0.? 58?) cnI g
l
= l260l cnI g
l
.
xumpIe 4. An ulIinoIe onol,eie of 1 g cool for niIrogen (A) eeIinoIion ie IIe KjellJoIl
neIIoJ, IIe etolteJ AH
3
Ioe collecIeJ in 2 nl
A
10
H
2
SO
4
ociJ eoluIion. To neuIroliee IIe
exceee ociJ, 1 nl of 0.1 (A) AoOH uoe requireJ. ColculoIe IIe " of niIrogen in IIe giten
eonple.
SoI. In fho KjoIIdnhI mofhod orgnnIc comounds confnInIng nIfrogon nro honfod wIfh
conconfrnfod H
2
SO
4
fo convorf fo (H
4
)
2
SO
4
. ThIs (H
4
)
2
SO
4
durIng soIIIng wIfh nIknII IIbornfos
H
3
fhnf Is nbsorbod In H
2
SO
4

l0
. Ixcoss ncId Is fIfrnfod wIfh nOH.

Tho voIumo of H
2
SO
4
consumod by H
3
(25 .l l5 .l) mI () = l mI ()
ow, l00 c.c() H
2
SO
4
l? g H
3
l4 g .
l c.c() H
2
SO
4
=
l4
l000
g = 0.0l4 g
AgnIn 0.0l4 g Ifrogon Is rosonf In l g conI.
So, of In fho conI snmIo =
0.0l4
l
l00
= l.4.
xumpIe 5. A goeeoue fuel Ioe IIe follouing conpoeiIion of tolune.
H
2
= 24", CH
4
= 30", C
2
H
6
= 11",
C
2
H
4
= 4.", C
4
H
S
= 2.", CO = 6", CO
2
= S",
O
2
= 2" onJ A
2
= 12".
ColculoIe (i) oir Io fuel roIio onJ (ii) tolune of Jr, proJucIe of conIueIion ueing 40"
exceee oir.
SoI. InsIs: l m
3
of gnsoous fuoI.
Volune of Volune of proJucIe
conIueIiIle IeocIion Volune of O
2
n
3
of conIueIion
goeee (n
3
) on Jr, Ioeie (n
3
)
H
2
= 0.24 H
2
+
l
2
O
2
= H
2
O 0.24
l
2
= 0.l2
CH
4
= 0.30 CH
4
+ 2O
2
= CO
2
+ 2H
2
O 0.3 2 = 0.60 CO
2
= 0.3
C
2
H
6
= 0.ll C
2
H
6
+ 3
l
2
O
2
= 2CO
2
+ 3H
2
O 0.ll
?
2
= 0.385 CO
2
= 0.ll 2 = 0.22
C
2
H
4
= 0.045 C
2
H
4
+ 3O
2
= 2CO
2
+ 2H
2
O 0.045 3 = 0.l35 CO
2
= 0.045 2 = 0.09
C
4
H
8
= 0.025 C
4
H
8
+ 6O
2
= 4CO
2
+ 4H
2
O 0.025 6 = 0.l5 CO
2
= 0.025 4 = 0.l
CO = 0.06 CO +
l
2
O
2
= CO
2
0.06
l
2
= 0.03 CO
2
= 0.06 l = 0.06
TofnI = l.42 m
3
TofnI = 0.?? m
3
!oss = 0.02 m
3
CO
2
In fuoI = 0.08 m
3
of nood of CO
2
= 0.85 m
3
= l.4 m
3
(O
2
)
VoIumo of nIr roquIrod (whon 40 oxcoss)
l.4
l00
2l

l40
l00
= 9.333 m
3
nIr: fuoI = 9.333:l ...(i)
TofnI voIumo of dry roducfs = CO
2
+
2
(from fuoI + nIr) + O
2
(oxcoss)
= 0.85 + 0 l2 . +
?9 9.33
l00

+
9 33
2l
l00
l4 . .
m
3
= 8.?82 m
3
ComosIfIon of roducf of combusfIon on dry bnsIs.
CO
2
=
0 82 l00
8 ?82
9 33?
.
.
.
2
=
? 3?3 l00
8 ?82
83 95
.
.
.
=
O
2
=
.
.
.
559 l00
8 ?82
6 365
= .
xumpIe 6. ColculoIe IIe tolune of oir requireJ for conpleIe conIueIion of 1 n
3
of o
goeeoue fuel Ioting IIe conpoeiIion
CO = 46", CH
4
= 10", H
2
= 40"
C
2
H
2
= 2", A
2
= 1" onJ IIe renoining Ieing CO
2
.
SoI. InsIs: l m
3
of fho gnsoous fuoI.
ConIueIiIle goeee
in IIe fuel (n
3
)
IeocIion Volune of O
2
requireJ (n
3
)
CO = 0.46 CO +
l
2
O
2
= CO
2
0.46
l
2
= 0.23
CH
4
= 0.l0 CH
4
+ 2O
2
= CO
2
+ 2H
2
O 0.l 2 = 0.20
H
2
= 0.4 H
2
+
l
2
O
2
= H
2
O 0.4
l
2
= 0.20
C
2
H
2
= 0.02 C
2
H
2
+ 2
l
2
O
2
= 2CO
2
+ H
2
O 0.02
5
2
= 0.05
TofnI O
2
= 0.68 m
3
roquIrod
As nIr confnIns 2l of O
2
by voIumo
VoIumo of nIr roquIrod = 0.68
l00
2l
m
3
= 3.238 m
3
.
Q. 1. WLut Is u coke?
Ans. If Is n cnrbonncoous rosIduo obfnInod from fho dosfrucfIvo dIsfIIInfIon of conI,
ofroIoum nnd conI fnr Ifch. IofroIoum yIoIds coko durIng crnckIng rocossos. Tho mnIn sourco
of coko Is conI. IofroIoum coko Is usod ns mofnIIurgIcnI coko sInco If Is uro.
Q. 2. WLut Is u IIuIdIsed bed?
Ans. IInoIy dIvIdod soIIds susondod In n movIng gns or IIquId bohnvo IIko n fIuId.
CnfnIysf In fhIs form Is usod for cnfnIyfIc crnckIng.
Q. 3 WLut Is petvoIeum?
Ans. If Is n hIghIy comIox mIxfuro of nrnffInIc, cycIonrnffInIc (nnhfhonIc) nnd
nromnfIc comounds wIfh frncos of , O nnd Iow orconfngo of S nnd Is obfnInod from
undorground.
Q. 4. WLut Is NupLtLu?
Ans. If Is n rofInod ofroIoum roducf 90 of whIch dIsfIIs boIow 240C nnd l0 dIsfIIs
boIow l?5C. If Is obfnInod by crnckIng of ofroIoum nnd mnInIy usod ns fhInnors for nInfs
nnd vnrnIshos.
Q. 5. WLut Is IIusL poInt?
Ans. If Is fho Iowosf fomornfuro nf whIch fho vnour of n voInfIIo IIquId or soIId gofs
IgnIfod by n smnII fInmo e.g., fInsh oInf of korosono Is 90I.
Q. 6. WLut Is un untI-knockIng ugent?
Ans. Thoy nro orgnnomofnIIIc comounds fhnf Incronso fho ocfnno numbor of gnsoIIno
whon nddod In Iow orconfngo fo If. Mosf common Is TI! (-fofrnofhyI Iond). Thoy cnn Incronso
fho ocfnno numbor ovor l00.
Q. ?. WLut uve Octune Numbev und Cetune Numbev?
Q. B. WLut Is uvIutIon gusoIIne?
Ans. If Is n vnrIofy of gnsoIIno hnvIng hIgh ocfnno numbor i.e., l00 nnd hIgh voInfIIIfy
nnd honco usod for nIrcrnff. Tho mnIn comononfs of nvInfIon gnsoIIno nro IsonrnffIns nnd
somo TI!.
Q. 9. WLut Is stvuIgLt vun gusoIIne?
Ans. CnsoIIno obfnInod by dIrocf dIsfIIInfIon of ofroIoum wIfhouf usIng ofhor convorsIon
rocossos IIko crnckIng Is known ns sfrnIghf run gnsoIIno. Ifs ocfnno numbor Is Iow.
Q. 10. (u) WLut Is IPG? (b) WLut Is ING?
Ans. (o) !IC or !IquofIod ofroIoum gns Is obfnInod from 'Wof nfurnI gns' from undor-
ground, by wnshIng If wIfh gns oII nnd frncfIonnfIng fho usofuI frncfIon.
(I) !C Is !IquofIod nfurnI gns.
Q. 11. WLut Is veIovmIng?
Q. 12. WLut Is tLe dIIIevence between gvoss und net cuIovIIIc vuIues?
Ans. Soo foxf ngo 3?8.
Q. 13. MentIon tLe busIc veuctIons ov convevsIon pvocesses Iov petvocLemIcuI
Industvy.
Ans. IofroIoum offors n forfIIo fIoId bofh for gnsoIIno nnd for ofrochomIcnIs. Tho foIIowIng
oxnmIos nro n fow of fho moro Imorfnnf bnsIc roncfIons.
Crocling
C H .C H .C H
7 15 15 30 7 15
D
C H + C H = CH + C H = CH
7 16 6 12 2 14 28 2
gasoline antiknock gasoline
Pol,nerieoIion
C C = C + C C = C
C
C C C C = C
C C
C
D
or cat.
82%
All,loIion
C = C C C + C C C
C
1-Butene Isobutane
C C C C C
C C
C
Isooctane
1eonerieoIion
C C C C
300C
Anh. AlCl
3
C C C
C
Straight chain Branched chain
H,Jroforning or AronoIieoIion

CH
3
CH
3
+ 3H
2
( ) i
CH
3
+ 4H
2 CH
3
(CH ) CH
2 5 3
D
cat
n-heptane
( ) ii
Q. 14. WLut Is BenzoI?
Ans. IonzoI Is n conI fnr dIsfIIInfIon frncfIon (b.. ?0-l50C) confnInIng ?0 bonzono,
l8 foIuono nnd 6 xyIonos. If Is bIondod wIfh ofroI. If hns ocfnno rnfIng 8?-90. Tho bIondod
ofroI Is n good mofor fuoI.
Q. 15. WLut Is powev uIcoLoI?
Ans. IfhyI nIcohoI whon bIondod wIfh ofroI fo bo usod ns n fuoI for InfornnI combusfIon
ongIno, Is known ns owor nIcohoI.
Q. 16. WLut Is gusoLoI?
Ans. If Is n mIxfuro of gnsoIIno nnd nIcohoI.
gnsoIIno + nIcohoI = gnsohoI.
Tho uso of grnIn nIcohoI ns n bIondIng ngonf wIfh ofroI Is n confrovorsInI Issuo In fho
worId. Though bIondIng wIII roduco l0 ofroI consumfIon buf nIochoI roducfIon by
formonfnfIon wIII mnko uso of food grnIns whIch Is nof dosIrnbIo. Moroovor, rocfIfIod sIrIf
(95 nIcohoI) Is nof suIfnbIo for bIondIng, 99.5 nIcohoI Is fo bo roducod whIch wIII mnko fho
cosf hIghor. Thnf Is why now-n-dnys bufnnoI Is frIod for fho uroso.
Q. 1?. WLut Is oII gus?
Ans. OII gns Is mnInIy obfnInod by crnckIng of korosono oII. Iuf ofhor oIIs IIko dIosoI nnd
honvy oIIs nnd ofroI mny nIso bo usod for crnckIng. A dovIco Is sof u whoro n Info Is honfod
socInIIy oIocfrIcnIIy nnd fho oII Is nIIowod fo dro on fho hof Info. Tho oII Is crnckod fo Iowor
gnsoous hydrocnrbons.
C
l2
H
26
CH
4
+ C
2
H
6
+ C
2
H
4
+ C
2
H
2
+ ofc. + fnr
Tho rosuIfIng gnsos nro nssod gonornIIy fhrough n hydrnuIIc mnIn nnd coIIocfod In n
gns hoIdor by dIsIncomonf of wnfor.
Tho comosIfIon of oII gns Is
CH
4
= 25-30, H
2
= 50-55, CO = l0-l2, CO
2
= 3,
CnIorIfIc vnIuo = 54000 kcnI/m
3
.
Tho gns Is mnInIy gonornfod for Inbornfory uso.
Q. 1B. WLut uve tLe udvuntuges oI u guseous IueI?
Ans.
Cnn bo dIsfrIbufod ovor n wIdo nron by IoIIno.
Smoofh combusfIon wIfhouf smoko nnd nsh.
Tho fomornfuro of honfIng cnn bo confroIIod by confroIIIng fho gns fIow fo fho burnor.
HIghor cnIorIfIc vnIuos.
Q. 19. MentIon tLe dIsudvuntuges oI u guseous IueI.
Ans.
nngor of oxIosIon
!nrgor scnIo fIro rIsk.
Q. 20. WLut Is un untI-knockIng ugent?
Ans. Tho orgnnomofnIIIc comounds IIko TI! or TM!, whIch Incronso ocfnno numbor of
n fuoI.
Q. 21. WLut Is un uvIutIon gusoIIne?
Ans. Tho vnrIofy of gnsoIIno socInIIy suIfnbIo for nIrcrnff hnvIng ocfnno numbor woII
ovor l00.
Q. 22. WLy Is suIpLuv content contvoIIed beIow 0.1"?
Ans. SuIhur nnd suIhur comounds gronfIy roduco offocfIvonoss of TI! fo Incronso
fho ocfnno numbor of n fuoI.
Q. 23. WLut Is u nutuvuI gusoIIne?
Ans. A mIxfuro of bufnno, onfnno, nnd hoxnno obfnInod from nnfurnI gns.
Q. 24. WLut Is HA pvocess?
Ans. CnsoIIno roducod, for fho mnnufncfuro of ofhono, ns n byroducf Is known ns
yroIysIs gnsoIIno. ThIs gnsoIIno Is mnInIy usod fo roduco bonzono by Hydro-oAIkyInfIon
(HA) rocoss.
CH
3
(CH
2
)
8
CH
3

?00 K
C
8
H
l8
+ CH
2
= CH
2
ocfnno ofhono
C
8
H
l8

HA
C
6
H
6
Q. 25. WLut Is wLIte gusoIIne?
Ans. If Is unIondod gnsoIIno usod for mofor bonfs.
Q. 26. WLy Is cuIovIIIc vuIue oI couI gus LIgLev tLun tLut oI pvoducev gus?
Ans. ConI gns confnIns nII fho combusfIbIo gnsos IIko CH
4
, C
2
H
4
, C
2
H
2
, CO nnd H
2
,
whorons roducor gns confnIns CO, H
2
nnd
2
.
2
ncfs ns Inorf dIIuonf.
So cnIorIfIc vnIuo of conI gns Is hIghor fhnn fhnf of roducor gns.
Q. 2?. Pvoducev gus Is mude by pussIng uIv und steum tLvougL u tLIck bed oI
couI. WLy?
Ans. Tho rImnry uroso of sfonm Is fo uso u fho honf dovoIood durIng oxofhormIc
roncfIon of conI nnd O
2
of nIr fo mnInfnIn fho fomornfuro of roducor.
Q. 2B. WLy Is NCV gveutev tLun GCV?
Ans. Cross cnIorIfIc vnIuo CCV IncIudos fho Infonf honf sfonm durIng combusfIon of n
fuoI, buf of cnIorIfIc vnIuo CV oxcIudos fho Infonf honf of sfonm.
Q. 29. WLy u good soIId IueI must Luve Iow usL content?
Ans. Ash Is InorgnnIc In nnfuro. So hIgh nsh confonf docronsos fho cnIorIfIc vnIuo of n
fuoI.
Q. 30. WLut Is CNG?
Ans. CC Is comrossod nnfurnI gns usod In mofor ongInos now-n-dnys Insfond of gnsoIIno
fuoI cnusIng Ioss oIIufIon.
Q. 31. WLut Is syntLesIs gus ov syn gus?
Ans. Modorn rocossos roduco n mIxfuro of CO nnd H
2
from conI nnd sfonm moro
offIcIonfIy fhnn fho oId wnfor gns nnd roducor gns Innfs. Two vnrIofIos of gns nro obfnInod:
(i) Lou IeoI goe (ii) MeJiun IeoI goe. !ow honf gns confnIns 50
2
. Thoso gnsos nro known
ns synfhosIs or syn gns. Tho gnsIfIcnfIon Is dono In fIxod bod: (i) IIuIdIsod bod.(ii) InfrnInod
bod.
IeocIione.
(i) C + H
2
O = CO + H
2
(ii) CO + H
2
O = CO
2
+ H
2
(iii) C + CO
2
= 2CO
Q. 32. WLut Is SNG (SubstItute NutuvuI Gus)?
Ans. (i) urIng fho roducfIon of syn gns, nf suffIcIonfIy hIgh rossuro i.e., durIng
hydrognsIfIcnfIon H
2
IIbornfod convorfs cnrbon fo CH
4
.
C + 2H
2
= CH
4
, CO + 3H
2
cnf
CH
4
+ H
2
O
Tho gns roducod wns known ns synfhofIc nnfurnI gns. Iuf fho synfhofIc roducf cnnnof
bo known ns nnfurnI; so now If Is cnIIod subsfIfufo nnfurnI gns (SC). Tho oornfIng rossuro
mny bo nfmoshorIc fo ? MIA nnd fomornfuro 800C-l650C for gnsIfIcnfIon. Tho hIghor
rossuro nnd Iowor fomornfuro rosuIf In fho formnfIon of Inrgor nmounf of SC.
Coal
Distillation
zone
Coal = C + ash
+ tar + H O
2
Gas
120
Pyrolysis
zone
C H = CH
+ C + H + Tar
n m 4
Gas
600
C + 2H = CH
2 4
C + CO = 2CO
2
C + 2H =
2
O 2H CO
2 2
CO + H =
2
O H + CO
2 2
C + H =
2
O H + CO
2
C + = O CO
2 2
2C + = 2 O CO
2
Ash bed
Gasification
zone
Combustion
zone
Air and steam
blast
1100
Fig. 18.17 Showing gasification reactions involved in a gasifier.
EXERCISES
1. Whnf Is swoofonIng of ofroI
2. Whnf Is fIuo gns How Is If nnnIysod
3. oscrIbo fho fIuIdIzod bod crnckIng of orfroIoum monfIonIng fho cnfnIysfs usod.
4. oscrIbo fho mnnufncfuro of roducor gns Whnf nro Ifs usos
5. Whnf Is Iondod-ofroI
6. WrIfo fho dIfforonco bofwoon roxImnfo nnd uIfImnfo nnnIysos.
?. oscrIbo fho mnnufncfuro of bIogns from wnsfo mnforInIs.
B. How Is fho cnIorIfIc vnIuo of n fuoI doformInod
9. WrIfo nofos on:
(i) Iomb cnIorImofor.
(ii) Ocfnno numbor
(iii) CnfnIyfIc crnckIng
(it) IroxImnfo nnnIysIs.
10. Whnf Is cnrbonIznfIon WrIfo fho ndvnnfngos of hIgh fomornfuro cnrbonIznfIon.
11. Whnf Is owor nIcohoI
12. WrIfo n brIof nofo on:
(i) SynfhofIc ofroI
(ii) IIuo wnfor gns.
13. (o) Whnf nro fuoIs How do you cInssIfy fhom oscrIbo mofhods omIoyod for uIfImnfo nnnIysIs
of conI.
(I) IxInIn fho forms (i) KnockIng (ii) Ocfnno numbor (iii) Cofnno numbor.
14. (o) Whnf Is swoofonIng of ofroI nmo fho vnrIous frncfIons obfnInod durIng fho frncfIonnI
dIsfIIInfIon of crudo ofroIoum oII.
(I) Whnf Is fho fIuo gns How Is If nnnIysod
15. Whnf Is monnf by crnckIng of ofroIoum oscrIbo vnrIous mofhods usod for crnckIng of ofroIoum.
16. WrIfo n shorf nofo on bIogns.
1?. oscrIbo fIxod bod cnfnIyfIc crnckIng.
1B. How nro gross nnd nof cnIorIfIc vnIuos of n soIId fuoI doformInod usIng n Iomb cnIorImofor
19. CIvo n dofnIIod nccounf of ofroIoum rofInIng.
20. CIvo nf Ionsf four ndvnnfngos of cnfnIyfIc crnckIng ovor fhormnI crnckIng.
21. Whnf Is !.I.C. CIvo Ifs usos.
22. Whnf do you undorsfnnd by cofnno numbor of n fuoI IsfInguIsh bofwoon hIgh sood dIosoI nnd
Iow sood dIosoI.
23. MonfIon ndvnnfngos nnd dIsndvnnfngos of n gnsoous fuoI.
24. Whnf Is fho dIfforonco bofwoon cInkIng conIs nnd cokIng conIs
25. Whnf Is owor nIcohoI MonfIon Ifs morIfs nnd domorIfs
26. CIvo fho consfIfuonfs nnd usos of Cobnr gns.
2?. Iscuss gIvIng oqunfIons, skofch, mnnufncfuro nnd comosIfIon of:
(o) Iroducor gns (I) Wnfor gns (c) OII gns.
2B. WrIfo n shorf nofo on:
Orsnf`s mofhod of fIuo gns nnnIysIs nnd Ifs sIgnIfIcnnco.
(i) CnfnIyfIc convorfor (ii) Ocfnno nnd cofnno numbors.
30. WrIfo n shorf nofo on: Cnrburoffod wnfor gns.
31. Whnf Is uIfImnfo nnnIysIs of conI
32. Whnf Is fho dIfforonco bofwoon H.T.C. nnd !.T.C.
33. MonfIon fho byroducfs of cokIng of conI.
OBJECTIVE TYPE QUESTIONS
1. WhIch of fho fuoI gnsos hns hIghosf cnIorIfIc vnIuo
(o) Wnfor gns (I) ConI gns (c) Iroducor gns.
2. Tho cnIorIfIc vnIuo of n conI snmIo Is hIghor If Ifs
(o) MoIsfuro confonf Is hIgh
(I) VoInfIIo mnffor Is hIgh
(c) IIxod cnrbon Is hIgh.
3. CnIorIfIc vnIuo of conI Is docronsod duo fo rosonco of
(o) Cnrbon (I) SuIfur (c) Hydrogon (J) Oxygon.
4. WhIch of fho foIIowIng confnIns hIghosf orconfngo of voInfIIo mnffor
(o) Ionf (I) !IgnIfo (c) IIfumInous conI (J) AnfhrncIfo.
5. AnnIysIs of fIuo gnsos Is dono by:
(o) Iomb cnIorImofor (I) Orsnf`s nnrnfus (c) Ioy`s gns cnIorImofor.
6. AIcohoI-bIondod ofroI ossossos
(o) Ioffor cnIorIfIc vnIuo
(I) !oducod nnfIknock roorfIos
(c) Ioffor nnfIknock roorfIos.
?. AnfhrncIfo Is n conI of
(o) HIghosf cnIorIfIc vnIuo
(I) !owosf rnnk
(c) HIgh voInfIIo mnffor.
B. IuoI gns usod ns n sourco of hydrogon Is
(o) nfurnI gns (I) Iroducor gns (c) Wnfor gns.
9. Isoocfnno hns nn ocfnno rnfIng of
(o) Zoro (I) l00 (c) Moro fhnn l00.
10. Ioffor dIosoI fuoI Is doformInod by
(o) Ocfnno rnfIng (I) Cofnno numbor (c) C confonf.
11. Iroducor gns Is n mIxfuro of
(o) CO + H
2
(I) CH
4
+ H
2
(c) CO +
2
12. IuoI for jof Inno Is
(o) AvInfIon gnsoIIno (I) Korosono (c) IosoI.
13. nfurnI gns Is comosod of:
(o) n-bufnno (I) Mofhnno (c) Isoocfnno.
14. IroxImnfo nnnIysIs of fuoI doformInos fho orconfngo of
(o) C, H
2
O,

nsh nnd voInfIIo mnffor
(I) C, H, , S (c) C nnd H.
15. Iomb cnIorImofor Is usod fo monsuro
(o) CnIorIfIc vnIuo (I) Cnrbon confonf (c) KnockIng roorfIos.
415
'
SiIicate TechnoIogy
INTRODUCTION
CInss nnd Ioffory nro fho onrIIosf roducfs of mnn mndo chomIcnI Indusfry. CInss wns
known fo fho nncIonf IgyfInns 6000 yonrs ngo. CInss Is nn nmorhous, frnnsnronf or
frnnsIuconf, rIgId suor suorcooIod IIquId of InfInIfoIy hIgh vIscosIfy comrIsIng of neIollic
eilicoIee ono of whIch Is usunIIy of nn nIknII mofnI. CornmIc roducfs nro mndo of cIny whIch
nro sIIIcnfos, comonf Is nIso n mIxfuro of sIIIcnfos nnd ofhor comounds. So, nII fhoso IndusfrIos
fnII undor sIIIcnfo fochnoIogy.
SIIIcnfos nro chomIcnI comounds of sIIIcon nnd oxygon wIfh mofnIs. CIny nnd soII nro dIfforonf
roducfs. CIny musf nof bo confusod wIfh soII. SoII Is fho fhIn ouformosf Inyor of fho onrfh. Soil
ie infocI o nixIure of clo,, eonJ, Iunue (Jeco,eJ tegeIoIle noIIer) onJ torioue oIIer ninerole.
Clo, ie o nixIure of torieI, of ninerole IIko bonfonIfo, knoIInIfo, hnuoysIfo ofc. InsIcnIIy
mosf of fhoso nro I,JroIeJ eilicoIee of oluniniun. Tho sfrucfurnI nfforn of sIIIcnfos nro
Imorfnnf In dIfforonf cornmIc roducfs whIch hnvo boon shown In foIIowIng fIguros: In n
sIIIcnfo unIf sIIIcon nfom Is symmofrIcnIIy surroundod by four oxygon nfoms fo form n fofrnhodrnI
unIf. Thoso fofrnhodrnI unIfs romnIn joInod In fho sIIIcnfos (soo IIg. l9.l).
CLuIn sIIIcutes. Thoso sIIIcnfos nro of fwo fyos tic., eingle cIoin eilicoIee onJ JouIle
cIoin eilicoIee. SIngIo chnIn sIIIcnfos confnIn |(SIO
3
)
n
]
2n
Ion ns fho rImnry unIf (IIg. l9.l),
whIIo doubIo chnIn sIIIcnfos confnIn |(SI
4
O
ll
)
n
]
6n
ns fho rImnry unIf (IIg. l9.2).

Fig. 19.1 Structure of [(SiO
3
)
n
]
2n
ion (single chain). A Silicon atom, @ Oxygen atom.
Fig. 19.2 Structure of [(Si

4
O
11
)
n
]
6n
ion (double chain).
If mny bo nofod fhnf O-nfoms, whIch nro shnrod by SIO
4
4
fofrnhodrons, do nof confnIn
nny nognfIvo chnrgo, i.e., O-nfoms, formIng n brIdgo bofwoon SIO
4
4
fofrnhodrnI unIfs, do nof
cnrry nny nognfIvo chnrgo, O-nfoms, formIng no brIdgo, cnrry nognfIvo chnrgo.
CycIIc ov vIng sIIIcutes (IIg. l9.3). Thoso sIIIcnfos hnvo cycIIc sfrucfuro nnd confnIn
|(SIO
3
)
n
]
2n
Ion ns fho rImnry unIf. Thoso sIIIcnfos nro formod whon onch SIO
4
4
fofrnhodron
shnros fwo O-nfoms (brIdgIng O-nfoms). BenIoniIe Is nn oxnmIo: InTISI
3
O
9
.

AND
Si O (ion)
3 9
6
Si O (ion)
6 18
12
Fig. 19.3 Structure of Si
3
O
9
6
and Si
6
O
18
12
ions (ring).

Fig. 19.4 Structure of sheet silicates (layered structure).
SlLlCATE TECHNOLOGY 417
CIny or sIIIcnfos nro common rnw mnforInIs for
CornmIc IndusfrIos
!ofrncfory IndusfrIos
CInss IndusfrIos nnd
Comonf IndusfrIos.
Ior fhnf ronson fho fochnoIogIos of fhoso IndusfrIos fnII undor fho common nnmo eilicoIe
IecInolog,. ConornIIy sIIIcnfo mnforInIs nro bnd conducfor of honf nnd oIocfrIcIfy. ow-n-dnys,
somo now fyos of cornmIcs nro dIscovorod wIfh oIocfrIcnI nnd mngnofIc roorfIos. Thoso
roorfIos doond on fhoIr unIf sfrucfuro. Thoso cornmIcs nro cnIIod IigI perfornonce ceronice.
Tho IndIvIdunI soIId mofnI oxIdos woro mIxod In fho roor rnfIo, ground woII nnd fInnIIy
honfod fo l000C for l2 hrs, nf fhIs hIgh fomornfuro fho IndIvIdunI oxIdos nro convorfod Info
fho mIxod oxIdo comound. Tho roorfy of suor-conducfIvIfy In fhoso comounds Is doondonf
on n nrfIcuInr chnrncforIsfIc of nrrnngomonfs of consfIfuonf nfoms. Ior oxnmIo, In YIn
2
Cu
3
O
?,
(soo IIg. l9.5) succossIvo horIzonfnI Inyors of coor-oxygon shoofs nro sonrnfod by rIbbon-
IIko chnIns of coor-oxygon. Tho squnro coor-oxygon shoofs nro fho nfhwnys of suor-
conducfIng oIocfrons In fhoso comounds. Ivon sIIghf nIfornfIon of fho nrrnngomonf of nfoms
dosfroys suorconducfIvIfy. Tho ronrnfIon of suorconducfIng cornmIc fhoroforo, Is nn
oxncfIng Ioco of work.
Oxygen
Copper
Ba Ba
Ba
Ba
Ba Ba
Ba
Ba
Y Y
Y
Y
Fig. 19.5 The crystal lattice of YBa
2
Cu
3
O
7y
.
Thoso fyos of suorconducfors nro usod In suorfnsf mngnofIcnIIy IovInfod (mngIov)
frnIn i.e., suorfnsf fIonfIng frnIn. ThIs Is nn oxnmIo of nIIcnfIon cornmIc suorconducfor
IIko YIn
2
Cu
3
O
?,
.
CEMENT
Tho rosonf dny cIvIIIznfIon vory much doonds uon IImo, morfnr nnd comonf roducfs, tic.
roInforcod-concrofo wnIIs nnd gIrdors (n chIof bonm), funnoIs, dnms nnd ronds ofc. Tho
fromondous nIIcnfIon of fhoso roducfs Is duo fo fhoIr:
ConvonIonco
Chonnoss
AdnfnbIIIfy
Sfrongfh
urnbIIIfy
Mnn hnd onrIy dIscovorod corfnIn nnfurnI rocks. Tho rocks on cnIcInnfIon gnvo n roducf
fhnf hnrdonod on fho nddIfIon of wnfor. Comonf wns fIrsf usod by fho IgyfInns In consfrucfIng
fho yrnmIds. Tho Crook nnd !omnns usod voIcnnIc fuff for comonf nnd n numbor of fhoso
sfrucfuros nro sfIII sfnndIng. In l824, nn IngIIshmnn, Josoh AsdIn, nfonfod nn nrfIfIcInI
comonf mndo by fho cnIcInnfIon of nn nrgIIIncoous IImo sfono (nrgII-cIny). Ho cnIIod fhIs 'IorfInnd`
ns concrofo mndo from If rosombIod n fnmous buIIdIng sfono obfnInod from fho IorfInnd IsInnd
nonr IngInnd. ThIs wns fho sfnrf of fho IorfInnd comonf Indusfry ns wo know If fodny. Tho
hnrd cIInkors (IrIck fyo) rosuIfIng from fho burnIng of nrgIIncoous IImosfono Is known by fho
form PorIlonJ cenenI fo dIsfInguIsh If from nnfurnI or IozzuoInnn nnd ofhor comonfs.
Tho comonf wIII sof undor wnfor nnd fhoroforo If Is known by fho nnmo of H,Jroulic
cenenI. A comonf Is n subsfnnco, whIch sofs fo n hnrd mnss In rosonco of wnfor. Two fyos of
comonfs nro In uso.
!omnn comonf
IorfInnd comonf.
Of fhoso, IorfInnd comonf Is now mnnufncfurod on n Inrgo scnIo. PorIlonJ cenenI ie
noJe I, nixing colcoreoue (line-eIone) onJ orgiloceoue noIeriole in IIe proper roIioe onJ
IeoIing Io IIe poinI of incipienI fueion in o liln onJ grinJing IIe reeulIing clinler. Tho rnw
mnforInIs shouId bo so roorfIonod ns fo roduco n comonf In whIch fho rnfIo of fho nmounf of
CnO fo fho nmounf of (2.8 SIO
2
+ l.2 AI
2
O
3
+ 0.65 Io
2
O
3
) shouId nof bo moro fhnn l.02 nnd nof
Ioss fhnn 0.66 i.e.,
0.66
+ +

CnO
2.8 SIO l.2 AI O 0.65 Io O
2 2 3 2 3
l.02
Tho IorfInnd comonf Is n mIxfuro of fho foIIowIng comounds:
ConpounJe Iornulo AIIretioIion
(i) TrIcnIcIum nIumInnfo 3 CnO . AI
2
O
3
C
3
A
ov (CnO)
3
. AI
2
O
3
(ii) TrIcnIcIum sIIIcnfo 3 CnO . SIO
2
C
3
S
ov (CnO)
3
. SIO
2
(iii) IcnIcIum sIIIcnfo (CnO
2
) . SIO
2
C
2
S
ov 2CnO . SIO
2
(it) TofrncnIcIum nIumIno forrnfo (CnO)
4
AI
2
O
3
. Io
2
O
3
C
4
AI
ov 4CnO . AI
2
O
3
. Io
2
O
3
SmnII nmounf of MgO dorIvod from fho rnw mnforInIs Is nIso rosonf. Somo comonf
confnIns gysum or Insfor of nrIs, whIch Is nddod In smnII qunnfIfIos fo Incronso fho InsfIcIfy
of comonf.
Varieties of Cement
PorIlonJ cenenI. Tho roguInr IorfInnd comonf confnIns modIum nmounf of CnO. WIiIe
cenenI conIoine leee ferric oxiJe. HIgh onrIy sfrongfh comonf |H.I.S] Is mndo from n
rnw mnforInI wIfh n hIgh IImo fo sIIIcn rnfIo. If confnIns n hIghor roorfIon of C
3
S fhnn
roguInr IorfInnd comonf nnd honco hnrdons much moro quIckIy. !onds consfrucfod
from H.I.S. cnn bo uf Info sorvIco moro quIckIy fhnn If roguInr comonf hnd boon
omIoyod. !ow honf orfInnd comonf confnIns hIgh roorfIon of C
4
AI nnd C
2
S. A
concrofo of boffor chomIcnI rosIsfnnco confnIns hIgh roorfIon of C
4
AI.
Poccuolono cenenI. A ozzuoInnn Is n mnforInI, whIch Is nof comonfIfIous In IfsoIf buf
bocomos so uon mIxIng wIfh IImo. Tho nnfurnI ozzuoInnn nro voIcnnIc fuffs, fho
nrfIfIcInI onos nro burnf cInys nnd shnIos.
HigI olunino cenenI. If Is mnnufncfurod by fusIng n mIxfuro of IImosfono nnd bnuxIfo
(confnIns Io
2
O
3
, SIO
2
, MgO ofc). If Is chnrncforIsod by n vory rnId rnfo of dovoIomonf
of sfrongfh nnd suorIor rosIsfnnco fo son wnfor nnd suIhnfo cnrryIng wnfor.
Speciol or corroeion reeieIing cenenI. If Is mnInIy usod for fho fnbrIcnfIon of corrosIon
roof IInIngs for chomIcnI oquImonf such ns sforngo fnnks, nbsorfIon fowors, ncId
dIgosfors ofc. IxnmIo: honoIIc comonfhonoI formnIdohydo rosIns.
Raw MateriaIs
IormorIy n Inrgo roorfIon of comonf wns burnod from nrgIIncoous IImosfono known ns
comonf rock. In IndusfrIos for CnO of comonf, chnIk, comonf rock nnd mnrI (mIxfuro of CnCO
3
)
nnd cIny nro usod. In nddIfIon fo nnfurnI mnforInIs somo Innfs uso nrfIfIcInI roducfs such ns
bInsf furnnco sIng nnd rocIIfnfod CnCO
3
obfnInod ns n by-roducf In nIknII nnd synfhofIc
nmmonIum suIhnfo Indusfry.
Snnd, wnsfo bnuxIfo nnd Iron oro nro somofImos consumod In smnII nmounfs fo ndjusf
fho comosIfIon of fho mIx. Cysum (2-3) Is nddod fo rovonf rnId soffIng of fho C
3
A.
IIst oI Ruw MutevIuIs: !Imosfono, comonf rock, cIny nnd shnIo, gysum, bInsf furnnco
sIng, snnd, snndsfono, mnrI, Iron mnforInI, rocIIfnfod cnIcIum cnrbonnfo nnd mIsc.
In IndIn, fho byroducf rocIIfnfod CnCO
3
from SIndrI IorfIIIzor CorornfIon of IndIn
wns ufIIIsod by A.C.C. IIhnr comnny fo mnnufncfuro comonf. !ohfns IndusfrIos !fd.,
nImInnngnr, oIhI usos (l) !nforIfo (rod cIny) nnd (2) IImosfono. !Imosfono Is nrfIy roIncod
by fho CnCO
3
mud obfnInod ns by-roducf durIng cInrIfIcnfIon of sugnrcnno juIco nf fho sugnr
fncfory of fho snmo comnny.
A rocossIng of nvnIInbIo rnw mnforInIs Is nocossnry fo corrocf fho roorfIons of fho
mInornI sourcos of fho four oxIdos of Cn, SI, AI nnd Io ossonfInI for comonf mnnufncfurIng nnd
dIscnrd usoIoss consfIfuonfs, i.e., fho uroso Is fo 'IenificioIe` nvnIInbIo rnw mnforInIs nnd
honco fho rocoss Is nnmod IeneficioIion rocoss. ThIs mny InvoIvo fho rnIsIng of fho IImo
confonf of fho rnw mnforInIs or If mny bo for fho oIImInnfIon of fho gronfor nrf of fho sIIIcn ns
comnrod fo fho nIumInn. Tho comIofo rocoss InvoIvos n combInnfIon of (1) gvIndIng,
(2) cIussIIIcutIon, (3) IIoututIon und (4) tLIckenIng opevutIon.
In mnkIng fhoso dIfforonfInI sonrnfIons, vory smnII qunnfIfIos of coIIocfIng rongonfs
nro omIoyod. Tho coIIocfIng ngonf musf soIocfIvoIy wof or 'fIIm` fho mInornI fo bo romovod
nnd ncf wIfh fho nIr fo cnuso fho nrfIcIos fo bo IIffod fo fho surfnco mnkIng n frofh. Thnf Is, fho
frofh fIonfnfIon rocoss Is usod fo romovo fho undosIrnbIo mnforInI In fho frofh nnd oIoIc ncId
mny bo omIoyod ns fho collecIor. A conconfrnfIon of 0.04 Ib or fon of rock susondod In 4 fons
of wnfor hns gIvon good rosuIfs. IrofhIng nIds In sonrnfIon of dosIrod mnforInIs from fho
undosIrod onos.
Manufacturing Procedure
Two mofhods of mnnufncfuro nro usod:
9AJ FH?AII
,HO FH?AII
Tho wof rocoss wns fho orIgInnI ono. Ior n fImo If wns grndunIIy dIsIncod by fho dry
rocoss. Iuf fho wof rocoss Is now boIng ndofod InrgoIy for now Innfs for moro nccurnfo
confroI nnd mIxIng of fho rnw mIxfuro.
In fho wof rocoss, fho soIId mnforInI nffor dry crushIng Is roducod fo n fIno sfnfo of
dIvIsIon In wof fubo or bnII mIIIs nnd nssos ns n sIurry fhrough fho bowI cInssIfIors or scroons.
Tho sIurry Is umod fo corrocfIng fnnks whoro rofnfIng nrms mnko fho mIxfuro homogonoous
nnd nIIow fho fInnI ndjusfmonf In comosIfIon of rnw mnforInIs fo bo mndo. ThIs sIurry Is
fIIforod In n confInuous rofnry fIIfor nnd fod Info fho kIIn. Tho moIsfuro confonf of fho food Is 40.
Tho dry rocoss Is osocInIIy nIIcnbIo fo nnfurnI comonf rock nnd fo fho mIxfuros of
IImosfono nnd shnIo or sInfo. In fhIs rocoss, fho mnforInIs nro roughIy crushod In jnw crushors
foIIowod by gyrnfory mIIIs, fhon drIod, sIzod nnd moro fInoIy ground In fubo mIIIs. ThIs dry
owdorod mnforInI (moIsfuro confonf 2) Is fod dIrocfIy fo fho kIIn. Honf Is rovIdod by burnIng
oII, gns or uIvorIsod conI, usIng rohonfod nIr from cooIIng fho cIInkor. 80-l60 Ibs of fuoI nro
nocossnry or bnrroI (3?6 Ibs) of comonf.
Tho fondoncy In roconf yonrs hns boon fo Iongfhon fho rofnry kIIn In ordor fo Incronso Ifs
fhormnI offIcIoncy. ry rocoss kIIns mny bo ns shorf ns l50 ff, buf In fho wof rocoss,
300-500 ff kIIns nro nof uncommon. Tho InfornnI dInmofor Is usunIIy 8 fo l5 ff. Tho kIIns nro
rofnfod nf from l/2 fo 2 r..m., doondIng on sIzo. Tho kIIns nro sIIghfIy IncIInod so fhnf mnforInIs
fod In nf fho uor ond nnd frnvoI sIowIy fo fho Iowor ond, fnkIng from 2-3 hrs (IIg. l9.6).
In ordor fo obfnIn gronfor honf oconomy, unIf oornfIons nro usod for romovIng fho nrf
of fho wnfor from sIurry by sIurry fIIfors. Wnsfo honf boIIors nro usod fo consorvo honf.
Iocnuso fho IInIng of kIIn hns fo wIfhsfnnd sovoro nbrnsIon nnd chomIcnI nffnck nf fho
hIgh fomornfuros In fho cIInkorIng zono, fho choIco of rofrncfory IInnIng Is dIffIcuIf. Ior fhIs
ronson, hIgh nIumInn brIcks nnd hIgh mngnosIn brIcks nro wIdoIy usod for fho IInIng of fho
kIIn, nIfhough IorfInnd comonf cIInkor IfsoIf Is snfIsfncfory for fho uroso.
ReuctIons ut vuvIous tempevutuves In tLe kIIn
TenperoIure IeocIione HeoI cIonge
l00C IvnornfIon of wnfor (H
2
O) IndofhormIc
> 500C AI
2
O
3
. SIO
2
. xH
2
O AI
2
O
3
.SIO
2
+ xH
2
O IndofhormIc
> 900C CnCO
3
CnO + CO
2
IndofhormIc
900C *5CnO + 3 AI
2
O
3
5 CnO . 3AI
2
O
3
fo 2CnO + SIO
2
2CnO . SIO
2
l200C 3CnO + SIO
2
2CnO . SIO
2
2CnO + AI
2
O
3
2CnO . AI
2
O
3
IxofhormIc
3CnO + AI
2
O
3
3CnO . AI
2
O
3
7
8
(ConIJ...)
l250C Commoncomonf of IIquId formnfIon IndofhormIc
l280C
> l280C Iurfhor formnfIon of IIquId IndofhormIc
nnd comounds
*MnIn roncfIons bofwoon IImo nnd cIny.
!Imo roducod combInos wIfh mnIn
consfIfuonfs of cIny tic. AI
2
O
3
nnd SIO
2
.
Crushed
shale
limestone
Mills
Oversize
Screen
Correcting
tank
Slurry
mixers
Filter
Water
Filtrate
K
iln
F
uel
C
ooler
Air
Clinker
storage
Mills
Gypsum
Storage, bagging
Shale 500 lbs
Limestone 2400 lbs
Gypsum 70 lbs
Water 750 gal
Coal 600 lb
Power 90 kwh
Labour 2.1 man hr
Per ton
of
cement
Hot air
Fig. 19.6 Wet process for cement manufacture.
TLe unuIysIs oI typIcuI sumpIes oI cement gIves tLe IoIIowIng composItIon:
!Imo 55.06; SIO
2
22.92; AI
2
O
3
8
Io
2
O
3
5.46; MgO 0.??; Iofnsh l.l3
Sodn l.?; CnSO
4
l.?5; !nchnngod cIny nnd snnd 2.2?.
Tho fInnI roducf formod consIsfs of hnrd grnnnuInr mnssos from l/8 fo 3/4 Inchos In
sIzo, cnIIod cIInkev. Tho cIInkor fnIIs fhrough oonIngs In fho sfnfIonnry fIrIng rIng of fho kIIn
Info rofnfIng cooIors, whIch sImuIfnnoousIy rohonf fho combusfIon nIr. IuIvorIsIng foIIowod
by fho fIno grIndIng In fubo bnII mIIIs nnd nckngIng comIofo fho sfos fo fho fInIshod comonf.
urIng fIno grIndIng fho foIIowIng mnforInIs nro nddod fo fho fInIshod comonf.
!ofnrdors such ns gysum
IInsfor or cnIcIum IIgnosuIhnfo
AIr onfrnInIng ngonfs
IsorsIng ngonfs nnd
WnforroofIng ngonfs
Setting or Hardening of Cement
SoffIng of comonf Is n comIIcnfod rocoss, nnd fho cnuso of soffIng hns boon fho subjocf of
much dIscussIon. Iuf If Is gonornIIy ngrood fhnf fhIs fnkos Inco by hydrnfIon nnd hydroIysIs.
On nddIfIon of wnfor, fho cnIcIum comounds nro docomosod wIfh fho formnfIon of froo
Cn(OH)
2
nnd hydrnfod crysfnIIIno sIIIcnfo nnd cnIcIum nIumInnfo, fho crysfnIs of whIch form
nn InforIncod mnss. uo fo fhIs InforIncIng of crysfnIs fho soffIng of comonf occurs. Tho foIIowIng
oqunfIons rorosonf fhoso roncfIons:
C
2
S + xH
2
O C
2
S . xH
2
O (nmorhous)
C
3
S + xH
2
O C
2
S . (x l) H
2
O (nmorhous) + Cn(OH)
2
C
3
A + 6H
2
O C
3
A . 6H
2
O(c)
Tho hydrnfIon roducfs hnvo vory Iow soIubIIIfy In wnfor. If fhIs wns nof fruo, concrofo
wouId hnvo boon rnIdIy nffnckod In confncf wIfh wnfor.
Anofhor fhoory suggosfs fhnf duo fo hydrnfIon, comonf Is convorfod Info n goI of
comosIfIon C
3
A. 6H
2
O wIfh nbsorbod wnfor. ThIs Is foIIowod by n sIow crysfnIIIsnfIon of fho
goI. Tho rnId Incronso In sfrongfh nnd hnrdnoss durIng soffIng of comonf Is mnInIy duo fo fho
nrfInI hydroIysIs of C
3
S fo form noodIos of Cn(OH)
2
In fho hydrnfod sIIIcnfo goI.
To hoId u fho 'fInsh sof` cnusod by C
3
A, somo InvosfIgnfors nssorf fhnf fho gysum
nddod ns rofnrdor cnusos fho fomornry formnfIon of C
3
A.3CnSO
4
.3H
2
O, whIIo ofhors boIIovo
fhnf fho gysum gIvos froo Cn(OH)
2
by roncfIon wIfh nIknII nnd fhIs In furn forms fho moro
sfnbIo C
4
A(4CnO.AI
2
O
3
). Tho foIIowIng oqunfIons rorosonf fhoso roncfIons:
C
3
A + 6H
2
O C
3
A . 6H
2
O(c)
C
3
A + 3(CnSO
4
. 2H
2
O) + 25 H
2
O C
3
A . 3CnSO
4
. 3lH
2
O
C
4
AI + xH
2
O C
3
A . 6H
2
O(c) + CnO . Io
2
O
3
. (x 6) H
2
O
MgO + H
2
O Mg(OH)
2
Tho vnrIous comounds confrIbufo fo fho honf of soffIng ns foIIows:
C
3
A > C
3
S > C
4
AI > C
2
S
!owor honf of soffIng of comonfs nro mndo Iow In C
3
A nnd C
3
S buf hIgh In C
2
S by nddIng
moro Io
2
O
3
, whIch fnkos fho AI
2
O
3
ns C
4
AI, fhoroby dImInIshIng fho nmounf of C
3
A nnd by
docronsIng fho CnO/SIO
2
rnfIo. ThIs Iow honf of soffIng comonf Is usod for consfrucfIon of dnms
fo nvoId crnckIng fho sfrucfuro from honf sfrossos durIng soffIng nnd cooIIng. As nn nddIfIonnI
snfogunrd, fho sfrucfuro mny bo cooIod durIng soffIng by cIrcuInfIng coId wnfor.
Tho foIIowIng fnbIo dIsInys fho funcfIons of vnrIous comounds of comonf.
ConpounJe IuncIion
C
3
A !osonsIbIo for InIfInI sof (fInsh sof)
C
3
S !osonsIbIo for lsf sfrongfh (nffor 8 dnys)
C
2
S nnd C
3
S !osonsIbIo for fInnI sfrongfh (nf l yr).
Io
2
O
3
, AI
2
O
3
, Mg nnd nIknIIos !owor cIInkorIng fomornfuro
GLASS
Cloeeee nro Ceronic noIeriole fhnf nro rIgId IIko soIIds buf whIch nro nof crysfnIIIno.
Cloee no, Ie coneiJereJ oe eupercooleJ liquiJ of infiniIel, IigI tiecoeiI,. CInss Is mndo by
moIfIng ono or moro oxIdos In n furnnco. Tho IIquId gInss Is cooIod unfII fhIck onough fo mouId
nnd fhon shnod nnd cooIod furfhor sIowIy (nnnonIIng) unfII If sofs fo n soIId mnss.
Mosf gInss Is mndo from sIIIcn mIxod wIfh ofhor oxIdos fhnf moIf nf n Iowor fomornfuro
fhnn gInss mndo from uro sIIIcn; wIndows, boffIos, nnd drInkIng wnfor gInssos nro mndo of
sodn IImo gInss. !ond gInss Is usod for docornfIvo cuf gInsswnro. BoroeilicoIe gloee Is usod fo
mnko ovonwnro nnd Inbornfory gInsswnro.
Compostion of gIass
CInss Is nof n sIngIo comound. If Is dIffIcuIf fo wrIfo nny chomIcnI formuIn for If.
ConornIIy fho formuIn for gInss mny bo rorosonfod fhus,
x!
2
O. ,MO. 6SIO
2
whoro ! = nIknII mofnI (n, K ofc.)
M = bIvnIonf mofnI (Cn, Ib ofc.)
x nnd , = numbor of moIocuIos.
Different varieties of gIass
ViIreoue Silico (quorIc gloee). A gInss mndo by fusIng uro sIIIcn wIfhouf n fIux nnd Is
vory rosIsfnnf fhormnIIy nnd chomIcnIIy. !sod boyond fho fomornfuro rnngos of ofhor
gInssos. Trnnsnronf fo !.V. rndInfIon (ordInnry gInss Is nof frnnsnronf fo !.V.).
Alloli eilicoIee [SoluIle gloee (SoJo), eoluIle gloee (PoIoeI), WoIer gloee (n
2
O . SIO
2
.
K
2
O . SIO
2
)] usod In son mnnufncfuro, for rosorvnfIon of oggs, In fho mnnufncfuro of
nrfIfIcInI sfonos.
Line gloee
(o) Sodn IImo gInss, sodn gInss, soff gInss (n
2
O.CnO.6SIO
2
) nro onsIIy fusIbIo, Iow sof-
fonIng fomornfuro.
\ses. !nbornfory nnrnfus, wIndow nnd Info gInss.
(I) Iofnsh IImo gInss |IohomInn gInss, Hnrd gInss] (K
2
O.CnO.6SIO
2
). IusIon fomorn-
furos hIgh.
\ses. ChomIcnI nnrnfus wIfhsfnndIng hIgh fomornfuros, socInIIy combusfIon fubos.
LeoJ gloee [PoIoeI leoJ gloee, IlinI gloee]
(K
2
O.IbO.6SIO
2
) fusos onsIIy. s. gr. hIghor; rofrncfIvo Indox, = l.?-l.?8 (hIghor fhnn
fhnf of common gInss, = l.5)
\ses.
(o) docornfIon nnd ofIcnI offocfs
(I) mnnufncfuro of Ions nnd rIsm
(c) nrfIfIcInI goms
(J) oIocfrIc buIbs.
BoroeilicoIe gloee. Whon nrf of SIO
2
In gInss formuInfIon Is roIncod by I
2
O
3
fho gInss
formuIn bocomos ?n
2
O.4CnO, 3ZnO.36(SIO
2
+ I
2
O
3
); usunIIy confnIns I
2
O
3
= l0-l3,
SIO
2
= 80-83, Iow oxnnsIon cooffIcIonfs, suorIor rosIsfnnco fo shock, oxcoIIonf
chomIcnI sfnbIIIfy, hIgh oIocfrIcnI rosIsfnnco.
\ses. WIdo nnd ovor IncronsIng usos for fhoso roorfIos for Inbornfory gInsswnro.
SpeciaI gIasses
1. CoIouved gIusses
CoIour Is roducod by fho nbsorfIon of corfnIn IIghf froquoncIos by ngonfs In soIufIon
In fho gInss. Tho coIourIng ngonfs of fhIs grou nro fho oxIdos of frnnsIfIonnI oIomonfs,
osocInIIy fho fIrsf grou: TI, V, Cr, Mn, Io, Co, I nnd Cu.
CoIour Is roducod by coIIoIdnI nrfIcIos rocIIfnfod wIfhIn nn orIgInnIIy coIourIoss
gInss by honf fronfmonf.
IxnmIo Is fho rocIIfnfIon of goId (coIIoIdnI) roducIng goId ruby gInss.
CoIour Is roducod by mIcroscoIc or Inrgor rncfIcIos. SoIonIum rods (SoO
2
) usod In
frnffIc IIghfs.
2. OpuI, tvunsIucent ov gvound gIuss (gLosu kuncL)
Soff gInss mndo frnnsIuconf by rubbIng fho surfnco wIfh omory owdor nnd furonfIno,
or snnd nnd wnfor, usIng HI.
3. SuIety ov IumInuted gIuss
Two Inyors of gInss wIfh nn InforIonf of InsfIc. Whon fho gInss Is brokon fho frngmonfs
nro hoId In Inco by Infor Inyor.
4. IIbve gIuss
CInss wooI Is Imrognnfod wIfh vnrIous bIndors nnd usod for InsuInfIon.
If cnn bo sun Info ynrn.
5. PLospLute gIuss
If confnIns I
2
O
5
ns n mnjor IngrodIonf, whoIIy or nrfInIIy dIsIncIng SIO
2
. If cnn rosIsf
HI. SIghf gInssos for fho hnndIIng of urnnIum hoxnfIuorIdo In sonrnfIon of urnnIum Isofoos
nro mndo of hoshnfo gInss.
6. HIgL sIIIcu gIuss
96 SIO
2
, 3 I
2
O
3
nnd fho rosf AI
2
O
3
. ThIs gInss hns hIgh chomIcnI durnbIIIfy nnd Is
oxfromoIy sfnbIo fo nII ncIds oxcof HI, whIch nffncks moro sIowIy fhnn ofhors.
Properties of gIass
IhysIcnI:
(o) Trnnsnronf (usunIIy) nmorhous soIId,
(I) VIfrIfIos onsIIy, buf dovIfrIfIos by formnfIon of crysfnIs undor suIfnbIo condIfIons. On
Iong sfnndIng or vory sIow cooIIng durIng nnnonIIng somo of mofnIIIc sIIIcnfos crysfnIIIso ouf.
CInss Is fhon snId fo dovIfrIfy.
(c) Hnrd nnd brIffIo
(J) o fIxod moIfIng oInf
(e) Ind conducfor of honf nnd oIocfrIcIfy
( f ) Cnn Incorornfo coIour mnInfnInIng frnnsnroncy
ChomIcnI:
(o) of nffnckod by nIr, wnfor, oxIdIsIng ngonfs, ncIds. OnIy nffnckod by HI rondIIy.
n
2
O . SIO
2
+ 6HI 2nI + SII
4
+ 3H
2
O
CnO . SIO
2
+ 6HI CnI
2
+ SII
4
+ 3H
2
O
(I) OrdInnry gInss nffnckod by nIknII soIufIons.
Functions of different constituents of gIass
(o) K
2
O: Incronsos fho soffonIng oInf.
(I) Io
2
O
3
: InnbIIIfy fo frnnsmIf !V Is duo fo fho rosonco of IoO or Io
2
O
3
In gInss. !sIng
Iron froo rnw mnforInIs, gInss cnnbIo of frnnsmIffIng !V IIghf couId bo mnnufncfurod.
(c) IbO: Incronsos fho rofrncfIvo Indox of gInss.
(J) I
2
O
3
: Incronsos fho hnrdnoss or rofrncfory chnrncfors of gInss nnd Iowors oxnnsIon
cooffIcIonf.
Raw materiaIs
Tho rnw mnforInIs omIoyod In fho mnnufncfuro of gInss cnn bo cInssIfIod undor fhroo
honds:
l. Subsfnncos of nn ncId chnrncfor, IIko SIO
2
, I
2
O
3
.
2. Subsfnncos of bnsIc chnrncfor, IIko sodn, ofnsh, IImo, MgO, InO, ZnO, IbO ofc.
3. VnrIous docoIourIsIng nnd oncIfyIng ngonfs IIko MnO
2
, Ib
3
O
4
, nIfro, Zn-comounds,
SnO
2
ofc.
CorfnIn coIour roducIng oxIdos nro usod for roducIng coIourod gInss, e.g., CuO for bIuo
coIour, Cu
2
O for ruby or rod coIour, Cr
2
O
3
, Io
3
O
4
for groon coIour, MnO
2
for vIoIof coIour ofc.
SIIIcn Is usod In fho form of snnd. If Is nImosf uro qunrfz (whIfo snnd) of whIch Iron
confonf shouId nof oxcood 0.045.
Sodn, n
2
O Is rIncInIIy suIIod by sodn nsh, n
2
CO
3
. Ofhor sourcos nro snIf cnko
nnd nO
3
. Tho Inffor Is usofuI In oxIdIsIng Iron nnd nccoIornfIng fho moIfIng.
Tho Imorfnnf sourcos for IImo, (CnO) nro IImosfono nnd burnf IImo from doIomIfo,
CnCO
3
, MgCO
3
. Tho Inffor InfroducIng MgO Info fho bnfch.
Iofnsh Is nIwnys usod In fho form of K
2
CO
3
.
ZnO Is somofImos usod fo roInco IImo.
InO ns such or ns rocIIfnfod InCO
3
.
IbO In fho form of Ib
3
O
4
.
IorIc ncId ns such or ns I
2
O
3
.
H
3
IO
4
Is usod ns nn oncIfyIng ngonf.
IoIdsnrs hnvIng fho gonornI formuIn !
2
O.AI
2
O
3
.6SIO
2
. IoIdsnrs suIy n
2
O or
K
2
O.(!
2
O) nnd SIO
2
.AI
2
O
3
sorvos fo Iowor fho moIfIng oInf of fho gInss nnd fo rofnrd
JetiIrificoIion. ovIfrIfIcnfIon monns sIow crysfnIIIsnfIon.
CulleI Is crushod gInss from Imorfocf nrfIcIos. If fncIIIfnfos moIfIng nnd ufIIIsos wnsfo.
If mny bo ns Iow ns l0 of fho chnrgo or ns hIgh ns 80 of fho chnrgo.
ChemicaI reactions of the formation of gIass in a furnace
n
2
CO
3
+ o SIO
2
n
2
O . o SIO
2
+ CO
2
CnCO
3
+ I SIO
2
CnO . I SIO
2
+ CO
2
n
2
SO
4
+ c SIO
2
+ C n
2
O . c SIO
2
+ SO
2
+ CO.
If shouId bo nofod fhnf fho rnfIos n
2
O/SIO
2
nnd CnO/SIO
2
nood nof bo l:l moIocuInr
rnfIos.
Tho comounds mny bo of fho fyo n
2
O.l.8SIO
2
.
In wIndow gInss moIocuInr rnfIos nro nroxImnfoIy 2n
2
O.CnO.5SIO
2
.
Ior docoIourIsnfIon, MnO
2
Is nddod fo fho chnrgos whIch oxIdIsos Io
+2
fo Io
+3
. Tho
groon coIour duo fo forrous sIIIcnfo boIng chnngod fo yoIIow coIour duo fo forrIc sIIIcnfo.
ThIs yoIIow coIour Is rocfIfIod by fho nIo vIoIof coIour duo fo mnngnnoso sIIIcnfo nnd n
orfocf whIfo gInss rosuIfs.
Manufacturing procedure
Tho mnnufncfurIng rocoduro Is dIvIdod Info four mnjor hnsos:
(i) MoIfIng
(ii) ShnIng
(iii) AnnonIIng
(it) IInIshIng
(i) MeItIng. Two fyos of furnncos nro In uso:
(o) PoI furnocee (I) Tonl furnocee
Iof furnncos nro omIoyod rIncInIIy In fho mnnufncfuro of ofIcnI gInss, nrf gInss nnd
Info gInss nnd In fho smnII scnIo unIfs. Tho ofs nro ronIIy crucIbIos mndo of soIocfod cIny,
hIgh nIumInn fIro cIny such ns nuliIe (3AI
2
O
3
. 2SIO
2
) or InfInum. Tho mnforInI of fho of Is
nffnckod by roIongod ncfIon of moIfon gInss nnd honco hns fo bo chnngod nffor n numbor of
oornfIons oxcof whon InfInum Is usod.
In n fnnk furnnco, bnfch mnforInIs nro chnrgod Info ono ond of n Inrgo 'fnnk` buIIf of
rofrncfory bIocks. Tho fnnk monsuros l25 30 5 wIfh n cnncIfy of l400 fons. Tho gInss
forms n ooI In fho honrfh of fho furnnco ncross whIch fho fInmos Iny nIfornnfoIy from ono
sIdo fo fho ofhor.
Tho 'formod` gInss Is workod ouf of fho oosIfo ond of fho fnnk. Tho oornfIon Is
confInuous. Tho wnIIs of fnnk furnnco grndunIIy wonr nwny undor fho ncfIon hof gInss.
Tho furnncos mny bo of oIfhor rogonornfIvo or rocuornfIvo dosIgn. In oIfhor of fho cnsos
fho honf from fho hof gnsos Is ufIIIsod In rohonfIng fho nIr, for combusfIon of fho fuoI. Onco
fho furnnco hns boon honfod, n fomornfuro l205C Is mnInfnInod nII fho fImo. Tho Inrgor nrf
of fho honf Is Iosf by rndInfIon from fho furnnco wnIIs.
ThIs sorf of honf Ioss Is nocossnry fo roduco fho ncfIon of fho moIfon gInss on fho furnnco
wnII. OfhorwIso fho furnnco wnII wIII corrodo. SomofImos wnfor cooIIng Ios nro usod fo cooI
fho furnnco wnII.
(ii) SLupIng ov IovmIng. Tho gInss nrfIcIos nro shnod oIfhor mnnunIIy or by mnchIno.
In ordor fo roduco n shoof gInss fIrsf n cyIIndor of nroxImnfo sIzo Is bIown Info shno. If Is
nIIowod fo sfnnd vorfIcnIIy on n sfnnd. Tho cyIIndor Is cuf oon by runnIng n shnr knIfo
IongfhwIso. Af rosonf ovory sfngo of shnIng hns boon mochnnIsod. Tho bIowIng Is dono by
comrossod nIr.
(iii) AnneuIIng. To roduco sfrnIns, If Is nocossnry fo nnnonI nII gInss objocfs. AnnonIIng
InvoIvos fwo oornfIons:
(i) HoIdIng n mnss of gInss nbovo n corfnIn crIfIcnI fomornfuro, Iong onough fo roduco
InfornnI sfrnIn by InsfIc fIow.
(ii) CooIIng fho mnss fo room fomornfuro sIowIy.
Tho nnnonIIng ovon Is nofhIng moro fhnn n cnrofuIIy dosIgnod honfod chnmbor In whIch
fho rnfo of cooIIng cnn bo confroIIod.
(it) IInIsLIng. AII fyos of gInss nrfIcIos musf undorgo corfnIn fInIshIng oornfIons.
Thoso IncIudo cIonnIng, grIndIng, oIIshIng, cuffIng, onnmoIIng ofc. AIfhough nII fhoso
nro nof roquIrod for ovory gInss objocf, ono or moro Is nImosf nIwnys nocossnry.
FIow diagram mentioning manufacturing sequences for gIass
Transportation
of
raw materials
Sizing
of
raw materials
Storage
of
raw materials
Weighing and
feeding the
raw material
to furnace
Heat saving by regeneration
Reacting in the
furnace to
form the glass
Shaping
of
glass
Annealing
of
glass products
Burning the fuel to
secure the temperature
needed for glass
formation
Finishing
of
glass products
POTTERY AND PORCELAIN
Thoy nro gonornIIy cIny fIrod roducfs, somofImos onnmoIIod or gInzod.
CIay
CooIogIcnIIy, cInys nro rognrdod ns fho roducfs of dIsInfogrnfIon nnd wonfhorIng of
grnnIfo rocks, In whIch foIdsnr wns n orIgInnI mInornI buf fho form Is nIso nIIod fo mosf
mInornIs whIch ossoss fho roorfy of boIng InsfIc whon mIxod wIfh n suIfnbIo nmounf of
wnfor.
WonfhorIng roncfIon:
K
2
O . AI
2
O
3
. 6SIO
2
+ CO
2
+ 2H
2
O K
2
CO
3
+ AI
2
O
3
. 2SIO
2
. 2H
2
O + 4SIO
2
foIdsnr knoIInIfo
Common cIay
If Is rIncInIIy nIumInIum sIIIcnfo mIxod u wIfh n Inrgo numbor of subsfnncos tic,
comounds of Io, Mn, Cn, Mg ofc. nnd vogofnbIo mnffors.
KaoIin or China cIay
If Is n uro uIiIe Iurning cIny of Iow InsfIcIfy nnd Is formod by wonfhorIng of foIdsnr.
ComosIfIon AI
2
O
3
. 2SIO
2
. 2H
2
O
IIve cIuy. If confnIns n good donI of SIO
2
nnd vory IIffIo Io. Whon fIrod, If forms n
mnforInI of hIgh fusIng oInf (l550C nnd uwnrds). CInys nro usod In fho mnnufncfuro of
brIcks, fIIos, orcoInIn wnros, offory nrfIcIos, oIocfrIc InsuInfors, drnIn Ios nnd ofhor snnIfnry
goods ofc.
TIe uee of clo, in ceronice JepenJe upon iIe follouing inporIonI properIiee.
(i) If Is InsfIc onough fo bo mouIdod whon If Is wof,
(ii) If rofnIns Ifs shno whon drIod nnd,
(iii) Whon fho mouIdod mnss Is honfod fo n hIgh fomornfuro, If sInfors fogofhor formIng
n hnrd, cohoronf mnss wIfhouf IosIng Ifs orIgInnI coIour.
Pottevy: (nrfIcIos mndo of cIny)
Pottery
Non-porous Porous
(1) China and Porcelain
(2) Earthenware
(3) Stoneware
(4) Unglazed pottery
(3) Terracotta, bricks,
tiles etc.
Ruw mutevIuIs. Tho fhroo mnIn rnw mnforInIs nro: (l) cIny (knoIInIfo), (2) foIdsnr,
(3) snnd.
Common IIuxIng ugents. Iornx, fIuorsnr, cryoIIfo, borIc ncId, n
2
CO
3
, K
2
CO
3
, Iron
oxIdos.
Common veIvuctovy mutevIuIs. CnO, CnCO
3
, ZnO
2
, TIO
2
. Iofh gInzod nnd ungInzod
cIny roducfs nro mnnufncfurod. Tho gInzod roducf Is obfnInod by nIyIng gInzo on fho
ungInzod body. Ior gInzIng fho shnod mnforInI Is covorod wIfh n confIng of mIxfuro of owdorod
foIdsnr, SIO
2
, bornx ofc., nnd honfod nf hIghor fomornfuro for Iongor fImo. Tho fhIn confIng
moIfs nnd forms n gInzo on fho surfnco of fho body. IorcoInIn, fhoroforo Is Iookod uon ns
nrfIy gInss nnd nrfIy sfonownro.
In nII cnsos, fho ungInzod roducf Is fo bo mndo. Tho rnw mnforInIs for ungInzod roducf
nro:
l. ChInn cIny
2. InII cIny
3. IIInf (Iuro SIO
2
+ CnCO
3
)
4. CornIsh sfono (Iofnsh foIdsnr, K
2
O = 6, CnO = l, AI
2
O
3
= l8, SIO
2
= ?5)
5. MnrbIo (CnCO
3
)
6. Qunrfz (SIO
2
).
Raw materiaIs for gIaze
IriI. If Is n sorf of gInss. If Is mndo from Iornx, IoIdsnr, Qunrfz ofc.
SIoneuore. ThIs Is n kInd of orcoInIn. If Is nof nIwnys whIfo bocnuso fho IngrodIonfs
confnIn Io
2
O
3
. If Is usod for sowor Ios. If Is gInzod wIfh snIf.
CIenicol eIoneuore. If Is usod for mnkIng jnrs suIfnbIo for sforIng ncIds.
Tho roncfIons of orcoInIn formnfIon nro:
3Al O .2SiO .2H O 6H O + 3Al O + 6SiO
2 3

2 2 2 2 3 2
600C
(amorphous) (amorphous)
900C
SiO 4SiO + 3Al O .2SiO -3Al O + 6SiO g
2 2 2 3 2 2 3 2
1400C 1000C
Silicate
formation
(Crystal) Mullite Crystal line
(amorphous)
China clay
PovceIuIn Is used Iov mukIng (i) dInnor nnd fon sofs, (ii) bnsIn, crucIbIos, (iii) oIocfrIcnI
InsuInfors, fIoor nnd wnII fIIos, (it) hIgh cInss snnIfnry goods.
Pvocess: If consIsfs of fho foIIowIng sfos:
l. Slurr, preporoIion. Tho mIxfuro of woIghod IngrodIonfs Is fnkon In n bIungor nnd
sfIrrod woII wIfh wnfor fo form n cronmy IIquId known ns cIny sII.
2. Ageing. Tho sII Is fIIfor-rossod. Tho rosIdunI cnko confnIns l0-30 wnfor. Tho cnkos
nro dumod for somo dnys. ThIs Imrovos fho InsfIcIfy of fho cIny mIxfuro bocnuso
of unIform hydrnfIon nnd goInfIon.
3. Deoiring. Tho ngod cnkos nro donIrod In n ug mIII by sIIcIng wIfh knIvos nnd uffIng
undor vncuum.
4. SIoping.
5. Trinning onJ Jr,ing. Tho shnod nrfIcIos nffor nIrdryIng nro frImmod nnd fhon
drIod In hof nIr.
6. Clocing. Tho drIod nrfIcIos known ns Ilonle nro gInzod. In fow cnsos gInzo Is uf on
fho bInnks boforo fIrIng. Iuf In mosf cnsos, bInnks nro fIrod fo roduco bIscuIfs. Tho
fIrIng Is dono In n funnoI furnnco. !sunI mnxImum fomornfuro Is l400C.
Clay
Screen
Crusher
Storage
Water
Vac
Cutter
Brick
(a)
Jigger
Vac
Extruder
Cutter
Dinner
plate
Drager
Mag.
separator
Screen
Slurry
Slurry
Filter press
Press
Agitation
Blunger
Clay flint water
Feldspar
(b)
Fig. 19.7 Flow diagram: (a) Brick manufacture (b) Dinner plate manufacture.
GIuzIng: Tho gInzIng IngrodIonfs nro fInoIy owdorod nnd mIxod. Tho mIxfuro Is mIxod
wIfh wnfor fo mnko fho sII. Tho sII Is noxf nIIod fo dry bInnks or moro froquonfIy fo fho
bIscuIfs by dIIng or ourIng or srnyIng or brushIng vory cnrofuIIy nnd fhon honfod nf l400C.
CInzo Is n sorf of gInss, whIch Is nIIod on fho surfnco fo covor fho oros.
Tho nIknII orfIon of foIdsnr nnd mosf of fho fIuxIng ngonfs bocomos n nrf of fho
gInssy or vIfroous hnso of fho cornmIc body. AII cornmIc bodIos undorgo n corfnIn nmounf of
vIfrIfIcnfIon or gInss formnfIon.
REFRACTORIES
Tho word refrocIor, monns rosIsfnnf fo moIfIng or fusIon. IrondIy sonkIng, rofrncforIos nro
mnforInIs whIch nro usod fo wIfhsfnnd hIgh fomornfuro, chomIcnI nnd hysIcnI offocfs wIfhouf
soffonIng or sufforIng n doformnfIon In shno. Whonovor vory hIgh fomornfuros nro InvoIvod
ns In furnncos, kIIns nnd oIocfrIcnI honfIng nnrnfus, fho rofrncforIos do rovIdo fho IInIngs or
brIcks, suorfs nnd ofhor fIInmonfs. Tho mnIn objocfIvo of n rofrncfory Is fo confIno honf (i.e.,
fo rosIsf fho honf Ioss) nnd nf fho snmo fImo fo rosIsf fho nbrnsIvo nnd corrosIvo ncfIon of
moIfon mofnIs, sIngs nnd gnsos nf hIgh oornfIng fomornfuros. TIue refrocIoriee ore IIoee
noIeriole uIicI ore ueeJ for IIe coneIrucIion of furnocee, lilne, otene, cruciIlee, reIorIe,
conterIere eIc. IefrocIoriee ore eolJ in IIe forn of Iricle, eilico, nogneeiIe, cIroniIe Iricle,
eilicon corIiJe, onJ circonio refrocIoriee eIc.
CIassification
!ofrncforIos nro cInssIfIod brondIy undor fhroo honds doondIng on fho chomIcnI
roorfIos of fhoIr consfIfuonf subsfnncos. Thoso nro
(i) AciJ refrocIoriee. Thoy nro mndo of cIny, cIny-sIIIcn mIxfuros nnd of uro sIIIcn. Thoy
nro nof nffnckod by ncIdIc mnforInIs. IxnmIossIIIcn brIcks nnd fIro cIny brIcks.
(ii) Boeic refrocIoriee. Thoy nro mndo u of Inrgo roorfIon of IImo or mngnosIn or n
mIxfuro of fhoso bnsos or ofhor mofnI oxIdos.
IxnmIosMngnosIfo brIcks (mngnosIn), bnuxIfo brIcks.
(iii) AeuIrol refrocIoriee. Thoy nro mndo u of wonkIy ncIdIc or bnsIc mnforInIs IIko cnrbon,
chromIfo (IoO, CrO
2
), zIrconIn (ZrO
2
) ofc. IxnmIosChromIfo brIcks, sIIIcon cnrbIdo
nnd grnhIfo.
Af rosonf somo sIngIo oxIdo brIcks hnvo boon dovoIood. Thoso nro soIf bondod nnd hnvo
hIgh fusIon oInfs. IxnmIosnIumInn (2050C), mngnosIn (2250C) nnd zIrconIn (2200 C) ofc.
Properties
!ofrncforIos shouId ossoss fho foIIowIng gonornI roorfIos:
(i) Thoy musf bo nbIo fo wIfhsfnnd hIgh fomornfuro.
(ii) Thoy shouId bo InfusIbIo nf fho fomornfuro fo whIch fhoy nro IInbIo fo bo oxosod.
Tho fusIon fomornfuros of fho usunI rofrncforIos In uso vnry from l600C fo 2?00C.
(iii) Thoy shouId bo chomIcnIIy Inorf fownrds fho corrosIvo ncfIon of gnsos, IIquId mofnIs
nnd sIngs roducod In Ifs ImmodInfo confncf In furnncos.
(it) Thoy shouId bo nbIo fo wIfhsfnnd suddon chnngo of fomornfuro.
(t) Thoy shouId bo nbIo fo wIfhsfnnd snIIIng, i.e., crnckIng nnd fInkIng of fho brIcks duo
fo unIform oxnnsIon or confrncfIon. AnnonIod brIcks cnn boffor wIfhsfnnd snIIIng.
(ti) Thoy musf bo nbIo fo wIfhsfnnd nbrnsIon or orosIon of fho furnnco chnrgo nnd nIso
fho rossuro of fho Iond.
(tii) IorosIfy of n rofrncfory Is n docIdIng fncfor of fho dogroo of onofrnfIon by moIfon
fIuxos nnd gnsos nnd fhus fho rofrncfory mnforInI onsIIy dIsInfogrnfos, i.e., fho gronfor
fho orosIfy, fho gronfor Is fho suscofIbIIIfy of fho rofrncfory fo chomIcnI nffnck by
moIfon fIuxos nnd gnsos. ocronso In orosIfy Incronsos fho rofrncfory`s sfrongfh nnd
nIso Incronsos Ifs honf cnncIfy, fhormnI conducfIvIfy nnd chomIcnI sfrongfh.
(tiii) !onsf orous brIcks hnvo hIghosf fhormnI conducfIvIfy. Tho ronson for such IncI-
donco Is duo fo fho nbsonco of nIr In fho voId snco.
Manufacturing of refractories
Tho sfos cnn bo dIsInyod schomnfIcnIIy ns foIIows:
Crushing in jaw
crushers to 25 mm
size of raw materials
Grinding in a
grinding machine
to 200 mesh
Screening to remove
unwanted materials
by settling or
magnetic separation
or chemical method
Storage in
storage bins
Mixing, uniform
mixing causes
moulding easy
Moulding
1. Manual
2. Mechanical
Deairing by
applying vacuum
Drying carried
out very slowly
in tunnel driers
Firing in tunnel
kilns or rotary
kilns. Temp.avg.
14801870C
Common Refractory Bricks
l. SIIIcu bvIcks: SIIIcn brIcks confnIn (92-95 sIIIcn, 2 IImo), fho mnIn rnw mnforInIs
nroqunrfz, qunrfzIfo, snndsfono ofc. urIng mnnufncfuro, sIIIcn brIcks nro honfod fo nbouf
l500C wIfhIn n snn of 24 hours. Tho cooIIng of fho brIcks fnkos nbouf l-2 wooks. urIng
honfIng, fho qunrfzIfo convorfs fo crysfobnIIfo. urIng sIow cooIIng, crysfobnIIfo Is convorfod
fo frIdymIfo. So sIIIcn brIck confnIns n mIxfuro of frIdymIfo nnd crysfobnIIfo. If durIng honfIng
of sIIIcn brIcks, qunrfzIfo Is nof convorfod fo frIdymIfo nnd crysfobnIIfo fho brIcks wIII oxnnd
durIng uso In fho furnnco nnd fho rofrncfory sfrucfuro wIII bronk nnd fnII. To nffnIn fho rIghf
comosIfIon l2 hours honfIng nf l500C of fho brIcks Is vory much ossonfInI.
Uses
MnIn nIIcnfIons of sIIIcn brIcks nro:
In oon honrfh furnncos
In coko-ovon wnIIs
CInss-furnncos
2. IIve cIuy-bvIcks: !nw mnforInI Is fIro cIny (cInyAI
2
O
3
.2SIO
2
.2H
2
O)
ConornIIy fIro cIny brIcks confnIn 55 sIIIcn, 35 nIumInn. ThIs Is ncIdIc fIro cIny brIck.
InsIc fIro cIny brIcks confnIn 55 nIumInn nnd 40 sIIIcn, rosf consIsfs of K
2
O, IoO, CnO,
MgO.
Properties
!Ighf yoIIow-roddIsh brown In coIour
!ow orosIfy nnd Iowor rofrncforInoss fhnn sIIIcn brIcks
IusIon fomornfuro l350C
CrushIng sfrongfh 200 kg/cm
2
Ioffor rosIsfnnco fo fhormnI snIIIng fhnn sIIIcn brIcks.
Chonor fhnn sIIIcn brIcks.
Uses
In bInsf furnncos
In kIIns
ChnrgIng doors ofc.
3. HIgL uIumInu bvIcks: ComosIfIon50 or moro nIumInn.
Properties
!ow cooffIcIonf of oxnnsIon
HIgh orosIfy
!IffIo fondoncy fo snII
IxcoIIonf wonr rosIsfnnco nnd sfnbIIIfy.
Uses
Ior IInIngs for IorfInnd comonf rofnry kIIns
Iurnnco honrfhs nnd wnIIs
In rovorbornfory furnncos
In combusfIon zonos of oII-fIrod furnncos.
4. MugnesIte bvIcks: MngnosIfo Is nnfurnIIy occurrIng mngnosIum cnrbonnfo (MgCO
3
)
nnd Is fho rnw mnforInI for fho mngnosIfo rofrncforIos. CnIcInod mngnosIfo (nf l600C) i.e.,
MgO Is owdorod fo n roor sIzo nnd fhon mIxod wIfh cnusfIc mngnosIn or Iron oxIdo ns
bIndIng mnforInI nnd fhon ground. Tho ronrod owdor Is rossod Info brIcks In hydrnuIIc
rossos. Tho brIcks nro fhon sIowIy honfod fo l500C nnd kof for nbouf oIghf hours nf fhIs
fomornfuro nnd cooIod fhon sIowIy.
Properties
Thoy nro gonornIIy groy or brown In coIour
Thoy cnn bo usod ufo l500C undor n Iond of 3.5 kg/cm
2
Thoy ossoss good crushIng sfrongfh, good rosIsfnnco fo bnsIc sIngs nnd vory IIffIo
shrInkngo
ThoIr rosIsfnnco fo nbrnsIon Is oor.
Uses
Ior fho IInIng of bnsIc convorfors nnd oon honrfh furnncos In sfooI Indusfry
Thoy nro usod In hof mIxor IInIngs, coor convorfors
In rovorbornfory furnncos for smoIfIng Iond, coor
In rofInIng furnncos for goId, sIIvor nnd InfInum ofc.
5. oIomIte bvIcks: Thoy nro mndo by mIxIng cnIcInod doIomIfo (i.e., mIxfuro CnO
+ MgO) In oquImoInr roorfIon wIfh sIIIcn ns bIndIng mnforInI. Ofhor bIndIng mnforInIs usod
for fho snmo nro fnr, quIck IImo, Iron oxIdo, cInys ofc. Thoy nro fhon fIrod nf l500C for nbouf
24 hours.
Properties
oIomIfo brIcks nro Ioss sfrong, moro orous nnd hnvo moro soffnoss nnd shrInkngo
fhnn mngnosIfo brIcks
Thoy cnn wIfhsfnnd n Iond of 3.5 kg/cm
2
nf l650C.
Thoy nro nof vory much rosIsfnnf fo fhormnI shock
Thoy nro moro rosIsfnnf fo sIngs nnd snIIIng fhnn mngnosIn brIcks
Thoy wonr ouf quIckIy.
Uses
Ior ronIrIng mnforInIs
In Inssomor convorfors, oon-honrfh furnncos, InddIo-IInIngs ofc.
6. CLvomIte bvIcks: ChromIfo Is n noufrnI rofrncfory. Tho crushod chromIfo oro
(IoO.Cr
2
O
3
) Is fIrod nf l500Cl?00C nffor mIxIng wIfh n IIffIo cIny ns bIndIng mnforInI.
Properties
Thoy nro noufrnI In coIour
Thoy ossoss hIgh donsIfy, rosIsfnnco fo ncIdIc ns woII ns bnsIc sIngs
Thoy cnn wIfhsfnnd ufo l800C undor n Iond of 3.5 kg/cm
2
.
Thoy ossoss good crushIng sfrongfh
Thoy hnvo modornfo fhormnI conducfIvIfIos.
?. Cuvbovundum ov sIIIcon cuvbIde bvIcks: Thoy nro ronrod from coko nnd snnd.
Sund (60") nnd coke (40") nro roorIy mIxod nnd Is foIIowod by nddIfIon of somo snwdusf
nnd n IIffIo snIf. Tho mIxfuro Is fhon fIrod nf l500C In nn oIocfrIc furnnco. Snwdusf whon
burnod ovoIvos gnsos, whIch by cIrcuInfIon Incronsos fho orosIfy of fho chnrgo. SnIf roncfs
wIfh Iron nnd sImIInr ImurIfIos rosonf In fho rnw mnforInIs fo form voInfIIo chIorIdos. Thoso
voInfIIo chIorIdos mnko fho fInnI roducfs orous. Tho sIIIcon cnrbIdos obfnInod from fho furnnco
nro InforIockod frIdIsconf crysfnIs. IondIng ngonfs IIko cIny, sIIIcon nIfrIdo nro mIxod. Tho
mIxfuro Is fhon shnod, drIod nnd fIrod. Tho fIrIng fomornfuro Is 2000C. Af fhIs fomornfuro
InforIncod crysfnIs nro formod.
Reaction
SIO
2
+ 3C SIC + 2CO
ComosIfIon of sIIIcon cnrbIdo brIcks Is:
SIIIcon = 65
Cnrbon = 30
ImurIfIos = 5
Properties
CoIourdnrk groy fo bInck
HnrdnosshIgh
IusIon oInf 2500C
CooffIcIonf of fhormnI oxnnsIon Is vory Iow
SocIfIc grnvIfy 3.l?-3.2
!osIsfnnco fo nbrnssIonhIgh
!osIsfnnco fo snIInfIonhIgh
OxIdIsIng ncfIonIn rosonco of nIr nf l000C sIIIcn brIcks fond fo oxIdIso fo sIIIcn.
2SIC + 3O
2
= 2SIO
2
+ 2CO
MochnnIcnI sfrongfhvory hIgh
Uses
OwIng fo Ifs hIgh fhormnI conducfIvIfy fhoy nro usod In muffIo furnncos.
OwIng fo fhoIr hIgh oIocfrIcnI conducfIvIfy, fhoy nro usod In oIocfrIc nrc furnncos.
8. ZIvconIu bvIcks: ZIrconIn brIcks fnII undor uro oxIdo rofrncforIos. !ofrncfory oxIdos
of common uso nro uIumInu (AI
2
O
3
), mugnesIu (MgO), zIvconIu (ZrO
2
), nnd tLovIu (ThO
2
).
!ofrncfory oxIdos do nof ossoss InsfIc roorfIos. Thnf Is why cInys nnd bonfonIfos nro
fo bo usod fo ronro fho uro oxIdo rofrncfory brIcks. OrgnnIc InsfIcIzors such ns doxfrIn nnd
rosIns mny nIso bo usod. Tho uso of orgnnIc InsfIcIzors mnkos fho brIck Ioss orous.
ZIrconIn brIck Is ronrod by honfIng zIrconIfo (ZrO
2
). IIrsf zIrconIn Is cnIcInod nnd
owdorod. Tho owdorod zIrconIn Is kof undor wnfor for somofImo nnd fho wof zIrconIn Is
mIxod wIfh bIndIng mnforInI, tic. coIIoIdnI zIrconIn or nIumInn In n mIII. Tho mnforInIs nro
fhon mouIdod Info brIcks by hnnd mouIdIng or rossIng. Tho mouIdod brIcks nro drIod nnd
fIrod nf nbouf l?50C.
Properties
ZIrconIn rofrncforIos fnII undor noufrnI rofrncforIos
Thoy cnn wIfhsfnnd n fomornfuro ufo 2600C.
Thoy nro rosIsfnnf fo bnsIc sIngs.
Uses
ZIrconIn brIcks nro vory cosfIy
SocInIIy usod whon hIgh fomornfuro Is usod
9. BevyIIIu bvIcks: IoryIIIn mInornIs nro usod fo ronro fho brIcks whIch nro fIrod nf
2000C.
Properties
HIgh moIfIng oInf (2550C)
!ow oIocfrIcnI conducfIvIfy
HIgh fhormnI conducfIvIfy
Cood rosIsfnnco fo fhormnI shocks
Inorfnoss fo cnrbon dIoxIdo nnd cnrbon monoxIdo ufo 2000C.
Uses
IoryIIIn Is usod In mnkIng crucIbIos fo moIf urnnIum nnd fhorIum, owIng fo Ifs lou
neuIron oIeorpIion copociI,.
As roJioIion eIielJe In cnrbon rosIsfnnf furnncos.
l0. Cevmets: Cormofs nro hof rossod or sInforod mnforInIs comrIsIng cornmIc nnd
mofnIIIc comononfs.
Properties
Thoy nro fho combInnfIon of cornmIcs nnd mofnIs
Thoy hnvo hIgh rofrncforInoss of cornmIcs
Thoy hnvo hIgh fhormnI conducfIvIfy of mofnIs
Thoy hnvo hIgh fhormnI shock rosIsfnnco of mofnIs ofc.
!ofrncfory cornmIcs usod In fho mnnufncfuro of cormofs nro zIrconIum cnrbIdo,
moIybdonum cnrbIdo nnd fungsfon cnrbIdo.
Mosf cormofs confnIn nbouf 80 of cornmIc mnforInIs nnd 20 of fho mofnI. Thoy nro
usunIIy fnbrIcnfod by fho fochnIquos of owdor mofnIIurgy.
Uses
In rockof nnd jof ongIno nrfs.
SInnIng fooIs for hof mofnIs.
ll. numeIs: InnmoIIIng monns fo Imnrf n hnrd nnd gIossy confIng nIIod on wnros
for docornfIvo nnd rofocfIvo urosos. Tho onnmoIs usod fo conf mofnIIIc surfncos nro known
ns porceloin enonele.
!nw mnforInIs usod for fho mnnufncfuro of onnmoIs nro:
(i) !ofrncforIos
(ii) IIuxos
(iii) OncIfIor
(it) CoIours
(t) IIonfIng ngonfs
(ti) IIocfroIyfos.
Ior mnkIng fho onnmoI nf fIrsf friI Is mndo from gInss formIng mnforInIs such ns snnd,
sodn nsh, foIdsnr, bornx ofc; whon moIfod, fhoy form n gInss comrIsIng sodIum, ofnssIum,
cnIcIum borosIIIcnfo.
ApplicoIion of IIe enoneln fhIn confIng of fho onnmoI fhus obfnInod Is nIIod on fho
mofnI oIfhor by dIIng or by brushIng or by umIng, fhon nrfIcIos nro fIrod nf 800C.
Uses
In mnkIng:
(i) rofrIgornfors
(ii) food rocossIng oquImonfs
(iii) mofor cnrs
(it) snnIfnry wnros.
Q. 1. WLut Is cement?
Ans. A comonf Is n subsfnnco whIch sofs fo n hnrd mnss In rosonco of wnfor.
Q. 2. WLut Is RCC?
Ans. Concrofo mndo wIfh snnd, sfono chIs nnd comonf whon roInforcod wIfh Iron rod
for nn oxfrn sfrongfh of fho concrofo Is known ns roInforcod concrofo comonf (!CC).
Q. 3. WLut Is u movtuv?
Ans. Tho roducf formod nffor soffIng of IImo, snnd nnd wnfor Is known ns morfnr.
Q. 4. MentIon tLe uveus oI uppIIcutIon oI cement.
Ans. !.C.C. wnIIs, dnms, ronds ofc.
Q. 5. WLut Is u LydvuuIIc cement?
Ans. Tho comonf sofs undor wnfor, fhnf Is why fho form hydrnuIIc cnmo.
Q. 6. GIve genevuI composItIon oI cement.
Ans. Soo foxf ngo 4l8.
Q. ?. WLut Is gIuss?
Ans. CInss mny bo dofInod
IhysIcnIIy ns nn nmorhous, frnnsnronf or frnnsIuconf, rIgId suorcooIod IIquId of
InfInIfoIy hIgh vIscosIfy.
ChomIcnIIy ns n mIxfuro of n numbor of mofnIIIc sIIIcnfos, ono of whIch Is nn nIknII
mofnI.
CInss hns nImosf l00 oInsfIc rocovory.
Q. B. WLut Is vItvIIIcutIon?
Ans. Tho rocoss of nof formIng crysfnIs durIng cooIIng of gInss Is cnIIod vIfrIfIcnfIon.
Q. 9. WLut Is devItvIIIcutIon oI gIuss?
Ans. CInss-wnros Ioff unusod for n Iong fImo grndunIIy Iooso fhoIr frnnsnroncy nnd
bocomo onquo duo fo fho crysfnIIIsnfIon of somo of mofnIIIc sIIIcnfos of gInss. Thnf honomonon
Is known ns dovIfrIfIcnfIon of gInss.
Q. 10. WLut uve cevumIcs?
Ans. CIny mnforInIs nro known ns cornmIcs. Ivon nf fho rosonf fImo cornmIcs romnIn
Imorfnnf In mnny shoros of IIfo. IuIIdIng, ronds, furnncos, kIfchon wnros, Inbornfory wnros
nro mndo of cornmIcs.
Tho gronfosf usos of ndvnncod cornmIc roducfs nro In
Aorosnco Indusfry duo fo fhoIr IIghfor woIghfs comnrod fo mofnI nIIoys
Honf shIoIds for snco vohIcIos
As bIo mnforInIs IIko fnIso foofh; bono roIncomonf, nrfIfIcInI hI joInfs ofc.
Q. 11. WLut uve veIvuctovIes?
Ans. !ofrncforIos nro onrfhy cornmIc mnforInIs of Iow fhormnI conducfIvIfy cnnbIo of
wIfhsfnndIng oxfromoIy hIgh fomornfuro wIfhouf nny chnngo.
Q. 12. WLut uve pvImuvy uses oI veIvuctovIes?
Ans. Tho rImnry usos of rofrncforIos nro for IInIng
(i) SfooI furnncos
(ii) Coko ovons
(iii) CInss wnros.
Q. 13. MentIon some Impovtunt veIvuctovIes.
Ans. (i) IIro cIny (nIumInIum sIIIcnfos), (ii) SIIIcn, (iii) SIIIcon cnrbIdo, (it) HIgh nIumInn
(?0-80 AI
2
O
3
), (t) MngnosIfo (MgO), (ti) MuIIIfo (CIny snnd), (tii) ZIrconIn (ZrO
2
).
Q. 14. MentIon some veIvuctovy metuIs.
Ans. Tungsfon nnd fnnfnIum (W nnd Tn) nro rofrncfory mofnIs cnnbIo fo wIfhsfnndIng
hIgh fomornfuros.
Q. 15. MentIon some busIc veIvuctovIes.
Ans.
MngnosIn
ChromIfo
IorsforIfo.
Q. 16. MentIon cIussIIIcutIon oI veIvuctovIes.
Ans.
(o) AcIdIc (sIIIcn, fIro cIny)
(I) InsIc (mngnosIfo, doIomIfo)
(c) AmhoforIc (AI
2
O
3
, C, SIC).
Q. 1?. WLut Is tLe Impovtunce oI zIvconIu us veIvuctovy?
Ans. Iuro zIrconIn undorgoos (i) n chnngo from monocIInIc crysfnI fo fofrngonnI form nf
980C nnd (ii) nIso voIumo chnngo on InvorsIon by nddIng corfnIn oxIdos IIko MgO, CnO. ThIs
fyo of zIrconIn ossossos n workIng fomornfuro of 2600C.
Q. 1B. Iscuss tLe eIIect oI Leut on cIuy.
Ans. CIny Is fho common IngrodIonf of nII cornmIc roducfs, n common oxnmIo Is
KnoIInIfo. Af fho onrIy sfngos of honfIng, cIny undorgoos oIImInnfIon of wnfor of hydrnfIon nf
600C.
Al O .2SiO .2H O Al + 2SiO + 2H O
2

3 2 2 2 3 2 2
O
600C
amorphous
mixture
Tho nmorhous form of nIumInn chnngos fo -nIumInn, n crysfnIIIno form nf 940C. Af
l000C, AI
2
O
3
nnd SIO
2
combIno fo form muIIIfo (3AI
2
O
3
. 2SIO
2
). As fho fomornfuro Incronsos,
moro SIO
2
Is convorfod fo crIsfobnIIfo. So, fho ovornII fundnmonfnI roncfIon of honfIng of cIny Is
3(AI
2
O
3
.2SIO
2
.2H
2
O)
3AI
2
O
3
.2SIO
2
+ 4SIO
2
+ 6H
2
O
KnoIInIfo MuIIIfo CrIsfobnIIfo
EXERCISES
1. Whnf nro sIIIcnfos
2. ofIno cIny nnd soII.
3. Iscuss fho sfrucfurnI nfforn of sIIIcnfos.
4. Whnf do you monn by sIIIcnfo fochnoIogy
5. Whnf do you monn by suorconducfIvo cornmIcs MonfIon Ifs usos.
6. IsfInguIsh bofwoon (o) IozzuoInnIc comonf nnd (I) IorfInnd comonf.
?. How Is orfInnd comonf ronrod by wof rocoss
B. IxInIn fho soffIng nnd hnrdonIng of comonf.
9. oscrIbo fho rofnry kIIn usod In comonf mnnufncfuro.
10. Iscuss fho comosIfIon of IorfInnd comonf.
11. How nro comonfs cInssIfIod CIvo fho vnrIous hysIco-chomIcnI roncfIons rosonsIbIo for fho
soffIng nnd hnrdonIng of IorfInnd comonf.
12. oscrIbo fho soffIng of morfnr nnd IImo.
13. oscrIbo vnrIous fyos of comonf.
14. Whnf nro fho crIforIn of fho IorfInnd comonf rnw mnforInIs
15. Whnf do you monn by wof nnd dry rocossos In comonf mnnufncfuro
16. How Is IorfInnd comonf mnnufncfurod
1?. oscrIbo wIfh fho hoI of n nonf dIngrnm of rofnry kIIn for fho mnnufncfuro of IorfInnd comonf
by wof rocoss.
1B. Whnf Is comonf oscrIbo fho comosIfIon of nny comonf. IrIofIy doscrIbo Ifs mnnufncfuro.
19. Whnf Is gInss Iscuss fho hysIcnI nnd chomIcnI roorfIos of gInss.
20. CInssIfy gInssos wIfh comosIfIon nnd IIIusfrnfIons.
21. oscrIbo fho mnnufncfuro of gInss by of furnnco rocoss.
22. WrIfo shorf nofo on sodn IImo gInss.
23. WrIfo nofos on
(i) CoIourod gInss (ii) IInfo gInss
(iii) ShnIng of gInss (it) Snfofy gInss
(t) ChomIcnI ncfIon In gInss mnkIng (ti) IIbro gInss
(tii) AnnonIIng of gInss (tiii) CInss InmInnfos
(ix) Ihoshnfo gInss
24. Whnf Is gInss WrIfo fho rnw mnforInIs usod In fho mnnufncfuro of gInss.
25. Iscuss fho mnnufncfuro of ordInnry gInss wIfh fho hoI of fIow dIngrnm. CIvo roncfIons InvoIvod.
26. WrIfo nofos on
(i) CIny nnd common cIny
(ii) ChInn cIny
(iii) IIro cIny
(it) !sos of cIny
(t) Ioffory.
2?. oscrIbo fho rocoss of mnnufncfurIng of orcoInIn.
2B. CIvo fho roncfIon InvoIvod In orcoInIn formnfIon.
29. Whnf nro rofrncforIos CIvo nn nccounf of nny four chnrncforIsfIcs of n good rofrncfory mnforInI.
30. IxInIn fho fhoory undorIyIng fho mnnufncfuro of rofrncfory roducfs.
31. oscrIbo fho mnnufncfuro of:
(i) IIro cIny brIcks
(ii) SIIIcn brIcks
(iii) MngnosIfo brIcks.
32. Whnf nro bnsIc rofrncforIos IxInIn mngnosIfo rofrncfory In dofnII.
33. Whnf nro fIro cIny brIcks oscrIbo fho mnnufncfuro, roorfIos nnd usos of fIro cIny brIcks.
34. Whnf nro rofrncfory mnforInIs WrIfo n brIof nofo on chromIfo brIcks.
35. WrIfo nofos on
(i) Cnrborundum
(ii) SIIIcn rofrncforIos.
36. Whnf nro rofrncforIos How nro fhoy cInssIfIod CIvo oxnmIos.
3?. IxInIn fho sIgnIfIcnnco of fho foIIowIng roorfIos of rofrncfory mnforInIs
(i) IorosIfy
(ii) ImonsIonnI sfnbIIIfy.
3B. Sfnfo comosIfIon, roorfIos nnd nIIcnfIons of fho foIIowIng mnforInIs:
(i) MngnosIfo (ii) IIro cIny
(iii) ZIrconIn (it) SIIIcn.
439
2OAHI
POLYMERIZATION
IoIymors nro mncromoIocuIos of hIgh moIocuInr woIghf whIch nro formod by IInkngo
bofwoon Inrgo numbors of smnII moIocuIos cnIIod monomors, e.g., oIyofhyIono Is mndo u of
fho monomors ofhyIono.
H
nC = C
H
H
H
C C C C
H
H
H
H
H
H
H
H
ethylene polythene
Thoro Is no IImIf fo fhoorofIcnI Iongfh of fho oIymor, buf fho oIymor consos fo grow for
mnny rncfIcnI ronsons. Tho numbor of roonfIng unIfs In n oIymor Is cnIIod fho dogroo of
oIymorIznfIon.
Types of poIymerization
1. AddItIon ov cLuIn poIymevIzutIon. Monomors (M) hnvIng fho gonornI formuIn,
CH
2
=CHY (Y=X, CO
2
!, C ofc.,) undorgo oIymorIznfIon, i.e., fhoso monomors hnvIng doubIo
or frIIo bonds oIymorIzo wIfhouf fho IIbornfIon of smnII moIocuIos. Thoro nro fhroo wnys of
nddIfIon oIymorIznfIon:
(i) Hond fo fnII fyo
CH
2
CHYCH
2
CHYCH
2
CHY----
(ii) Hond fo hond fyo
CHYCH
2
CH
2
CHY.CHYCH
2
CH
2
----
(iii) !nndom fyo
CHYCH
2
CHY.CH
2
CH
2
CHYCH
2
CHY----
MecIonien of oJJiIion pol,nericoIion.
(o) Iroo rndIcnI oIymorIznfIon Is fho fIrsf fyo whIch InvoIvos fho foIIowIng sfos:
1niIioIion. Tho fIrsf sfo of whIch InvoIvos fwo roncfIons. Tho fIrsf Is fho sonfnnoous
docomosIfIon of nn InIfInfor Info froo rndIcnIs. A vnrIofy of oroxIdos ncf ns InIfInfor such ns
bonzoyI oroxIdo, forfInry bufyI hydrooroxIdo ofc.
COOOOC COO
2
.
Tho noxf nrf of InIfInfIon InvoIvos fho nddIfIon of fhIs rndIcnI fo fho monomor moIocuIo
(M) fo InIfInfo fho chnIn.
2!
+ M M*
Iroo Monomor
rndIcnI
Tho M* Is fho InIfInfor rndIcnI or rImnry rndIcnI.
PropogoIion. Tho mochnnIsm of rongnfIon Is fho roncfIon of fho rndIcnI M* wIfh Ifs
own monomor M.
M* + CH
2
= CHY M-CH
2
CHY*
ConfInuous nddIfIon of now monomor In fhIs mnnnor wIII fInnIIy roduco n oIymor
chnIn In whIch fho subsfIfuonfs nro Iocnfod on nIfornnfo nfoms.
TerninoIione. Tho mosf common formInnfIons nro fho offocf of
(i) CoIIIsIon bofwoon fwo growIng chnIns
i.e., CH
2
H

C

Y
H
C
Y
CH
2

CH
2
H
C
Y
H
C
Y
CH
2

(ii) CoIIIsIon of n growIng chnIn wIfh nn InIfInfor rndIcnI whon fho Inffor Is roorfIonnfoIy
In oxcoss.
(iii) CoIIIsIon bofwoon n growIng chnIn wIfh ImurIfIos. SomofImos fho chnIn Iongfh of
fho oIymor Is confroIIod by doIIbornfoIy nddIng InhIbIfors.
Moro rnroIy, by dIsroorfIonnfIon nn H nfom of ono rndIcnI Is frnnsforrod fo nnofhor
rosuIfIng In fwo oIymorsono snfurnfod nnd fho ofhor unsnfurnfod.
CH
2
H

C

Y
H
C
Y
CH
2

CH
2
H

CH

Y
H

C

Y
H

C
(I) IonIc oIymorIznfIon Is nn Imorfnnf cInss of nddIfIon oIymorIznfIon whIch nIso

InvoIvos fho sfos of InIfInfIon, rongnfIon nnd formInnfIon buf horo, Insfond of froo rndIcnIs,
fho unsfnbIo InformodInfos nro oIfhor cnfIons or nnIons.
CutIonIc MecLunIsm
1niIioIion
X
+
+ CH
2
= CH

Y
X CH
2
CH

Y
+
Tho InIfInfors nro !owIs ncIds IIko AICI

3
,II
3
, H
2
SO
4
ofc., In rosonco of wnfor.
POLYMERS 441
PropogoIion.
TerninoIion.
X CH CH CH CH X CH CH CH CH Z
2

2 2 2
+
Y Y Y Y n n
Polymer
Z
Anion
If fho modIum Is of dIoIocfrIc sfrongfh, fho ovornII offocf Ionds fo nn Incronsod
oIymorIznfIon rnfo nnd nIso Incronsod dogroo of oIymorIznfIon, sInco boffor chnrgo sonrnfIon
of Ion nnd counfor Ion occurs.
AnIonIc poIymevIzutIon mecLunIsm:
1niIioIion.
Z
()
+ CH
2
= CH
Y
ZCH
2
CH

Y
()
CnrbnnIon
PropogoIion.

ZCH CH + CH = CH CH CH CH CH
2
z
2 2 2

()
Y Y Y Y
()
ZCH CH CH CH
2 2

Y Y
()
n
nCH = CHY
2
TerninoIion.
Z CH CH CH CH: Z
2 2
CH CH CH CH
2 2 2
Y Y
()
n
Cation
H
+
Y Y n
polymer
IoIymorIznfIon of oIofIns wIfh mofnIIIc sodIum, sodIum ofhoxIdo fnkos Inco tio fhIs
mochnnIsm.
(c) Co-ordInnfIon oIymorIznfIon or ZIogIor-nffn oIymorIznfIon. If wns obsorvod by
ZIogIor nnd nffn fhnf In rosonco of n combInnfIon of frnnsIfIon mofnI hnIIdos (TICI
4
, ZrIr
3
,
nnd hnIIdos of V, Zr, Cr, Mo ofc.) nIong wIfh orgnnomofnIIIc comounds (frIofhyI/frImofhyI
nIumInIum) oIymorIznfIon of oIofIns Ionds fo sforoosocIfIc oIymorIznfIon.
MecLunIsm oI ZIegIev-Nuttu poIymevIzutIon:
1niIioIion.
Cnf ! + CH
2
= CH! Cnf CH
2
CH(!)!
PropogoIion.
Cat CH CHR + CH = CHR Cat CH CH CH CH R
2
n
2 2 2
R R R n
TerninoIion.
Cat CH CH CH CH R Cat CH CH CH CH R
2

2 3 2
+ HX X +
R R R n R n
polymer
R
Iy onrIIor froo rndIcnI oIymorIznfIon of ofhyIono, royIono yIoIdod oIymors of Iow
donsIfy hnvIng hIghIy brnnchod chnIn oIymor of Iow crysfnIIInIfy nnd mochnnIcnIIy wonkor
sfrucfuro IIko !II (Iow donsIfy oIyofhyIono). ZIogIor-nffn oIymorIznfIon yIoIdod
sforoosocIfIc sfrucfuro of hIgh mochnnIcnI sfrongfh, unbrnnchod, hIgh moIfIng nnd hIghIy
crysfnIIIno oIymor IIko HII (hIgh donsIfy oIyofhyIono).
Stereochemistry of poIymers
(i) 1eoIocIic pol,nere hnvo nII fho grous In ono sIdo of fho oIymorIc bnckbono nnd fho
monomors nro joInod In n roguInr hond fo fnII nrrnngomonf.
C
H
H
C
Y
H
C
H
H
C
Y
H
C
H
H
C
Y
H
(ii) S,nJioIocIic pol,nere hnvo sImIInr hond fo fnII nrrnngomonfs buf horo Y grous
nonr on oosIfo sIdos of oIymor bnckbono nIfornnfoIy.
C
H
H
C
H
Y
C
H
H
C
Y
H
C
H
H
C
H
Y
C
H
H
(iii) AIocIic pol,nere hnvo Y grous nrrnngod rnndomIy nIong fho oIymorIc bnckbono
nnd fho mnforInI Is soff, oInsfIc, rubbory.
C
H
H
C
H
Y
C
H
H
C
Y
H
C
H
H
C
Y
H
C
H
H
POLYMERS 443
SputIuI uvvungement oI un utuctIc poIymev: If Is n form of oJJiIion pol,ner, such
ns oIyroono In whIch fho sIdo grous nIong fho pol,ner chnIn nro rnndomIy orIonfnfod.
AfncfIc oIyroono Is nn onorpIoue, rubbory oIymor of IIffIo vnIuo unIIko IsofncfIc
oIyroono (IIg. 20.l).
CH
3
H
CH
3
H H
CH
3
CH
3
H
H
CH
3
CH
3
H
Fig. 20.1 Part of a chain of atactic polypropene.
Condensation poIymerization
If Is fho fyo of roncfIon occurrIng bofwoon monomors confnInIng oInr grous whIch
form oIymor nIong wIfh fho oIImInnfIon of smnII moIocuIos IIko H
2
O, HCI ofc.
In fhIs fyo of oIymorIznfIon, ns If fnkos Inco fhrough fho funcfIonnI grous, whon nny
monomor mny confnIn fwo or fhroo funcfIonnI grous cross-IInkod oIymor sfrucfuro wIII bo
formod.
Co-poIymerization
Two or moro monomors undorgoIng joInf oIymorIznfIon Is cnIIod cooIymorIznfIon
roncfIon such ns fho roducfIon of SI! (Sfyrono bufndIono rubbor).
n n ( CH = CHCH = CH ) +
2 2
CH = CH
2
butadiene styrene
CH CH = CHCH CHCH
2 2
Copolymerization
SBR (GRS-rubber)
n
InfIuence of structure of poIymer on its properties
SIrengII of pol,ner
In cross-IInkod oIymor, fho unIfs nro IInkod by InforchnIn covnIonf bonds formIng gInnf,
fhroo dImonsIonnI sfrucfuro nnd fhoy nro sfrong nnd fough ns fho movomonf of Infor moIocuInr
chnIns nro fofnIIy rosfrIcfod.
Sfrongfh of sfrnIghf chnIn oIymors doonds on fho chnIn Iongfh. IoIymors of Iow moI.
wf. nro soff nnd gummy buf brIffIo. Iuf hIghor-chnIn Iongfh oIymors nro foughor nnd moro
honf rosIsfnnf. Irosonco of oInr grous nIong fho chnIn Iongfh nIso Incronsos fho InformoIocuInr
forcos nnd Incronsos fho sfrongfh of oIymor.
HIgLIIgLts:
Types oI poIymevIzutIon
AddIfIon oIymorIznfIon:
Tho roducf oIymor Is oxncf muIfIIo of fho orIgInnI monomorIc moIocuIo e.g.,
oIyfhono from ofhono.
CondonsnfIon oIymorIznfIon:
CombInnfIon fhrough dIfforonf funcfIonnI grous of monomors wIfh oIImInnfIon
of smnII moIocuIos IIko H
2
O.
CooIymorIznfIon:
JoInf oIymorIznfIon of fwo or moro fyos of monomors. As for oxnmIo SI!.
MochnnIsms of nddIfIon oIymorIznfIon nro:
(o) Iroo rndIcnI mochnnIsm.
(I) IonIc mochnnIsm.
(c) Co-ordInnfIon oIymorIznfIon (ZIogIor-nffn oIymorIznfIon).
PIastic deformation
IoIymors consIsfIng of IInonr-chnIn moIocuIos nro nIwnys soIubIo nnd IIernoploeIic,
ovon for vory hIgh moIocuInr woIghf.
Throo-dImonsIonnI oIymor moIocuIos nro InsoIubIo In nny convonfIonnI soIvonf nnd nro
IIernoeeIIing. Honco, fhormoInsfIc nnd fhormosoffIng qunIIfIos of oIymor doond on sfrucfuro
of fho oIymors. ArfIfIcInIIy cronfIng crossIInkIng convorfs fhormoInsfIc mnforInI Info
fhormosoffIng.
PhysicaI state
!nndom nrrnngomonf of moIocuIos In fho oIymor Ionds fo nmorhous sfnfo whorons
roguInr nrrnngomonfs of moIocuIos or chnIns In n oIymor Iond fo crysfnIIIno sfnfo.
Tho roguInr nrrnngomonf Incronsos fho InformoIocuInr forcos of nffrncfIon nnd Ionds fo
hIghor soffonIng oInf, gronfor rIgIdIfy, brIffIonoss nnd sfrongfh of fho oIymor. Tho nmorhous
nnfuro of oIymor rovIdos fIoxIbIIIfy.
Vory Iong chnIn oIymors hnvIng froo rofnfIng grous form IrroguInrIy coIIod nnd
onfnngIod snorfs, whIch cnn bo sfrofchod nnd ngnIn rofurnod bnck fo Ifs orIgInnI sfnfo gIvIng
rIso fo oInsfIc chnrncfor fo fho oIymor.
SoIubiIity and chemicaI resistance
IoIymor confnInIng oInr grous nro moro soIubIo In oInr soIvonfs IIko wnfor, nIcohoI
buf nro chomIcnIIy rosIsfnnf fo non-oInr soIvonfs IIko bonzono, foIuono, CCI
4
ofc. SImIInrIy,
non-oInr grou confnInIng oIymors nro chomIcnIIy rosIsfnnf fo oInr soIvonfs buf nro soIubIo
In non-oInr soIvonfs, nrfIcuInrIy fho gronfor fho dogroo of cross-IInkIng, Ioss Is fho soIubIIIfy
of fho oIymor In n soIvonf.
Shapes and forms-mechanicaI properties
Tho InfornnI nrrnngomonf of fho Iong-chnIn moIocuIos rovIdos fho forms In whIch fho
oIymor mny form i.e., fIbros, InsfIcs nnd rubbors. If fho InfornnI forcos bofwoon fho moIocuIos
nro Iow, moIocuIos bocomo buIky, form rnndom nrrnngomonf nnd show rubbory chnrncfor. If
fho InfornnI forcos nro hIgh fhoy uIfImnfoIy gIvo rIso fo ordorIy nrrnngomonf nnd form fIbrous
nnfuro. InformodInfo forcos Iond fo InsfIc nnfuro.
POLYMERS 445
Stress
Hard, brittle
polymers
Rigid and high impact
thermoplastics
Polymer fibres
Rubbery polymers
Strain
Fig. 20.2 Four types of stress-strain curves illustrating how polymers of different types
behave (the lines end where the sample breaks).
Tho sfrongfh of fho oIymor Is confroIIod by fho Iongfh of fho oIymor chnIns nnd Ifs
cross-IInkIng. Sfrongfh of n oIymor Is osfImnfod from fyIcnI sfross-sfrnIn curvos for dIfforonf
oIymors ns shown In IIg. 20.2. On IncronsIng sfrnIn confInuousIy uIfImnfoIy fho oIymor
chnIns nro uncoIIod nnd fuIIy sfrofchod cnIIod necling nnd nffor fhIs oInf fho oIymor ronchos
Ifs Ireol poinI nnd yIoIds.
Effect of heat
IohnvIour of oIymor Is confroIIod by fho fomornfuro. Amorhous oIymors, whIch do
nof hnvo moIfIng oInf hnvo soffonIng oInfs. Af vory Iow fomornfuro bofh fho crysfnIIIno
nnd nmorhous oIymors bohnvo IIko gInss nnd on honfIng, fho gloee IroneiIion IenperoIure Is
ronchod (T
g
) nffor whIch fhoy soffon. Amorhous oIymor bocomos rubbory nnd fhon gummy
nnd on furfhor honfIng If IIquofIos. Iuf fho crysfnIIIno oIymor on honfIng nbovo T
g
shows
fhormoInsfIc bohnvIour nnd fInnIIy IIquofIos.
PLASTICS (RESINS)
IInsfIcs nro n cInss of hIgh oIymors whIch cnn bo mouIdod Info nny dosIrod form by
honf nnd rossuro. !osIns nro ncfunIIy fho bIndors usod for InsfIcs nnd fhoso fwo forms nro
usod synonymousIy.
Thoro nro fwo cInssos of InsfIcs or rosIns.
l. TIernoploeIic reeine soffon on honfIng nnd hnrdon on cooIIng nnd fhIs chnngo Is nof
chomIcnI buf hysIcnI In nnfuro, honco roonfod honfIng nnd cooIIng nIso doos nof nIfor Ifs
nnfuro.
2. TIernoeeIIing reeine nro fhoso whIch nro honfod durIng mouIdIng nnd honfIng Is
confInuod unfII Is sof nnd hnrdonod. ThIs hnrdonod mnforInI cnnnof bo soffonod ngnIn, honco
fho soffIng Is ormnnonf nnd IrrovorsIbIo.
Compounding
IInsfIcs for mnnufncfurIng of fInIshod nrfIcIos nro nIwnys mIxod wIfh 4-l0 of ofhor
mnforInIs, whIch Imnrf somo durnbIo roorfIos fo fho mouIdod mnforInI. Thoso mnforInIs
nro known ns nddIfIvos whIch nof onIy Imnrf somo roorfIos fo InsfIcs buf nIso mnko fho
rocossIng onsy. Tho rocoss of mIxIng fhoso nddIfIvos fo vIrgIn InsfIcs Is cnIIod ConpounJing.
AddIfIvos nnd fhoIr funcfIons nro dIscussod boIow:
(i) ResIn Is fho bIndIng consfIfuonf, whIch bInds nII fho nddIfIvos fogofhor. Thormosof-
fIng rosIns nro nddod ns IInonr Iow moIocuInr woIghf oIymors, whIch ncfunIIy form
crossIInkIng durIng fho mouIdIng rocoss In rosonco of cnfnIysf.
(ii) IIIIevs. IIIIors cnn modIfy fho roorfIos of InsfIcs fo gIvo fho fInnI InsfIc, boffor
hnrdnoss, fonsIIo sfrongfh, fInIsh nnd worknbIIIfy.
IIbrous fIIIors such ns wood fIour, coffon fIbro, chood rngs Imnrf Imrovod
mochnnIcnI sfrongfh fo fho InsfIc; nsbosfos Incronsos honf rosIsfnnco; mIcn or sInfo
owdor Imrovos oIocfrIcnI roorfIos. Iorconfngo of fIIIors mny vnry nnd cnn bo
ufo 50.
SoIIdIfIod fIInmonfs of gInss nro bundIod Info sfrnnds, comrossod fo roduco n gInss
mnf. IInsfIcs omboddod wIfh fhoso mnfs nro known ns fIbro roInforcod InsfIcs (I!I).
I!I Is vory sfrong nnd cnn bo usod fo mnko gnfos of dnm, corrosIon-rosIsfnnf Ios
nnd fnnks, snfofy hoImofs, joo bodIos.
IVC InmInnfod fo sfooI or nIumInIum nro cnIIod 'ComosIfos`.
(iii) PIustIcIzevs. IInsfIcIzors nro smnII moIocuIos whIch onofrnfo Info fho oIymor
mnfrIx nnd noufrnIIzo n nrf of fho InformoIocuInr forcos of nffrncfIon bofwoon mncro-
moIocuIos nnd Incronso fho mobIIIfy of fho oIymor sogmonfs so fhnf chnIns cnn sIIdo
ovor onch ofhor. Thus, InsfIcIzors ncf ns nn InfornnI IubrIcnnf nnd Imrovo fho
InsfIcIfy nnd fIoxIbIIIfy of fho oIymor. CommonIy usod InsfIcIzors IncIudo vogofnbIo
oIIs, cnmhor, dIbufyI/dIocfyI hfhnInfo ofc.
(it) Wnxos, oIIs, sfonrnfos nnd sons nro usod fo Imrovo fho fInIsh nnd roduco fho sfIckIng
fondoncy of fho InsfIc fo fho mouIds.
(t) CoIouvIng mutevIuIs. To Imrovo fho nonI nnd fo Imnrf bonufy fo fho fInIshod
mnforInIs, coIours nro nddod fo fhom. SoIubIo orgnnIc dyos nro nddod fo fho
frnnsnronf vnrIofy nnd InorgnnIc Igmonfs nro nddod fo fho nonfrnnsnronf InsfIcs.
To gIvo !V rofocfIon fo fho coIours somo comounds nro nddod whIch roforonfInIIy
nbsorb !V IIghf.
(ti) OtLev uddItIves. SomofImos nnfIoxIdnnfs nro nddod fo rovonf oxIdnfIvo dogrndnfIon
of oIymors. CoIol,eIe IIko H
2
O
2
, bonzoyI oroxIdo, ZnO, H
3
, Ag, Cu, Ib ofc. nro
nddod fo nccoIornfo fho cross-IInkIng of fho fhormosoffIng InsfIcs whIIo fhoy nro In
fho mouIds.
SIoIilicere IIko Ib, Ib-sIIIcnfo, Ib chromnfo ofc., nro nddod fo Imrovo fho fhormnI
sfnbIIIfy of oIymors durIng rocossIng.
AnIieIoIic ngonfs IIko nmInos, nmIdos ofc., nro nddod fo dIssInfo fho oIocfrIc chnrgo
dovoIood by conducfIng If nwny.
Processing of pIastics
(i) CuIendevIng. Ior roducfIon of confInuous fIIms or shoofs fhIs rocoss Is ndofod.
Tho comoundIng mnforInI Is run bofwoon fwo hIghIy oIIshod mofnIIIc roIIors rofnf-
Ing In oosIfo dIrocfIon. WhIIo nssIng fhrough fho gn bofwoon fho roIIors fho
shoof Is formod, whoso fhIcknoss vnrIos wIfh fho gn. Ingrnvod roIIors offor bonufI-
fuI dosIgns of ombossod InsfIcs.
(ii) Ie custIng. ThIs chon fochnIquo Is usod for ncryIIcs, oIyosfors, honoI nnd
urofhnns. Comoundod mnforInI Is ourod Info dIo cnvIfIos mndo u of mofnIs or
Insfor of nrIs nnd If Is honfod whon fho crossIInkIng fnkos Inco nnd fInnIIy fho
fInIshod mnforInI Is cooIod.
(iii) IIIm custIng. A comoundod soIufIon In n suIfnbIo soIvonf Is confInuousIy drood
on n movIng boIf, fho soIvonf ovnornfos nnd fIIms nro obfnInod. CoIIohnno nors
nnd hofogrnhIc fIIms nro roducod by fhIs rocoss.
POLYMERS 447
Polymer solution
Wind-up
roll
Polymer solution
spreads as a film
Solvent evaporates
Continuous
polymer film
Endless metallic belt
Control
valve
Fig. 20.3 A schematic representation of the film casting machine.
(it) CompvessIon mouIdIng. ThIs mofhod Is nIIcnbIo for bofh fhormosoffIng nnd fhor-
moInsfIc mnforInIs. Tho mouId consIsfs of fwo hnIvos. Tho comoundIng mnforInI In
dofInIfo roorfIon fIIIs fho gn bofwoon fho fwo Iocos of mouId, whIch nro movod
roInfIvo fo onch ofhor. Honf nnd rossuro nIIod. Tho cnvIfIos gof fIIIod wIfh fIuId
InsfIc, fwo hnIvos nro cIosod sIowIy. IInnIIy curIng Is dono by honfIng (for fhormo-
soffIng) nnd cooIIng (for fhormoInsfIc). IurnIfuro hnndIos, foIohono nrfs ofc., nro
mndo by fhIs rocoss.
Pressure
Guide pins
Top moulding part
(male die)
Bottom moulding part
(female die)
Moulding plastic
ingredients in cavity
Extraction
pin
Fig. 20.4 Compressing moulding of plastics.
(t) InJectIon mouIdIng. ThIs rocoss Is nIIcnbIo for fhormoInsfIcs onIy. IInsfIc ow-
dor Is fod Info n hof cyIIndor nnd fhon Injocfod by n Isfon Iungor Info n fIghfIy-
Iockod mouId wIfh fho hoI of n scrow nrrnngomonf. Tho mouId Is cooIod for curIng
nnd fInnIIy fho hnIf of fho mouId Is oonod for fho ojocfIon of fho nrfIcIo. Tho whoIo
rocoss Is nufomnfIc. Iuckofs, bowIs, furnIfuro nrfs nro mndo by fhIs rocoss.
Plastic feed
Hopper
Archimedian
screw
Heater
Nozzle
Top moulding
part (cold)
Fluidized
plastic
Hinge
Moulding
powder
Bottom
moulding
part (cold)
Extraction pin
Fig. 20.5 njection moulding of plastics.
(ti) BIow mouIdIng. A hof soffonod fubo of fhormoInsfIc Is Incod bofwoon fho fwo
hnIvos of mouId nnd comrossod nIr Is bIown whoroby fho fhormoInsfIc fnkos fho
shno of fho mouId fo form hoIIow nrfIcIos IIko boffIos, jorrycnns ofc. Tho mouId Is
cooIod nnd fho nrfIcIo fnkon ouf.
(tii) xtvusIon mouIdIng. ThIs rocoss Is usod for confInuous mouIdIng of fhormoInsfIcs.
Tho owdor comoundod mnforInI Is Infroducod nnd oIocfrIcnIIy honfod. In InsfIc
condIfIon, If Is ushod by scrow convoyor Info n dIo whoso shno Is ncquIrod by If nnd
fInnIIy cooIod.
Plastic feed
Hopper
Metallic
wire
Plastic
Heater
Plastic coated
cable
Screw
conveyer
Fig. 20.6 Moulding of insulated electric cable by vertical extrusion moulding.
(tiii) TLevmoIovmIng. ThIs rocoss Is usod fo obfnIn fhroo-dImonsIonnI nrfIcIos from
fwo-dImonsIonnI shoofs. Tho fhormoInsfIc shoof Is honfod nnd soffonod nnd Incod
bofwoon fwo hnIvos of n mofnI dIo. Tho shoof Is comrossod bofwoon fho dIo fo fho
dosIrod shno. SomofImos, vncuum Is nIso nIIod so fhnf fho shoof sfIcks fo fho
shno of fho mouId.
POLYMERS 449
Heating
Vacuum off
Vacuum on
Moulded Article
Fig. 20.7 Vacuum forming process.
Important ThermopIastics
PoIyethyIene
IoIyfhono Is oIymorIsod ofhyIono. IfhyIono Is coIorIoss gns nf ordInnry fomornfuro. If
Is ronrod In fho Inb by dohydrnfIon of ofhyI nIcohoI nf l60C wIfh conconfrnfod H
2
SO
4
.
IndusfrInIIy dohydrnfIon of ofhyI nIcohoI Is fho rocoss for ofhyIono roducfIon*.
IoIyofhyIono Is mnnufncfurod by gns-hnso oIymorIznfIon. Tho ofhyIono gns Is
comrossod fo l500 nfmoshoro nnd nssod fhrough n roncfor mnInfnInod nf 200C In fho
uor nnd l20C In fho Iowor nrfs. O
2
(0.0l) or oroxIdos ncf ns cnfnIysf. IfhyIono Is
oIymorIsod Info oIyfhono, n wnxy soIId, whIch comos ouf from fho orfornfod boffom of fho
vossoI. Tho unroncfod gns Is rocycIod.
Two fyos of oIyofhyIonos nro nvnIInbIo!II (!ow donsIfy oIyofhyIono) nnd HII
(hIgh donsIfy oIyofhyIono). HII Is roducod by usIng Iow rossuro mofhods (3l kgf/cm
2
)
usIng IonIc cnfnIysfs whorons !II Is roducod by usIng hIgh rossuro mofhods (l050-2000
kgf/cm
2
) usIng froo rndIcnI InIfInfor.
ProperIiee. IoIyofhyIono Is n rIgId, wnxy, whIfo, frnnsIuconf non-oInr mnforInI. If hns
good chomIcnI rosIsfnnco ngnInsf ncIds, nIknIIos nnd snIf soIufIons, good InsuInfIng roorfy
buf If Is suscofIbIo fo orgnnIc soIvonfs, nrfIcuInrIy korosono.
* C
2
H
4

IoIymorIzo
(C
2
H
4
)
n
Recycle ethylene
Ethylene
Primary
compressor
Hypercomp-
ressor
Catalyst
Cooling tower
High-pressure
separator
Low-pressure
separator
Cold water
Water
Polyethene
pellets
Dryer
Separator
Quench cooler
Extruder and pelletizer
Fig. 20.8 Low-density polyethylene by high-pressure processing (LDPE).
Compressor Compressor
Fluid-bed
reactor
Cycle
cooler
690 to
2100 kPa
100C
Purge
Separator and
product discharge
Ethylene
Comonomer
Catalyst
Lock
Ganular
polyethylene
Nitrogen
Fig. 20.9 High-density polyethylene by low-pressure resins (HDPE).
IoIyofhyIono hns hIghIy symmofrIcnI sfrucfuro so If crysfnIIzos onsIIy. Tho dogroo of
crysfnIIInIfy vnrIos from 40-95 doondIng on dogroo of brnnchIng. !II hns n brnnchod
sfrucfuro nnd honco Is fIoxIbIo nnd fough. If hns Iow s. gr. If hns Iow hnrdnoss i.e., nbouf l/l0fh
of bnkoIIfo.
HII Is n comIofoIy IInonr oIymor, If hns boffor chomIcnI rosIsfnnco, hIghor soffonIng
oInf, gronfor rIgIdIfy buf Iow Imncf sfrongfh nnd If Is onquo nnd roInfIvoIy brIffIo.
Ieee. IoIyfhono shoofs, fubos nro mnnufncfurod, whIch nro usod for domosfIc uroso.
If Is nIso usod fo ronro foys, confod-wIros nnd cnbIos, bngs for nckIng, boffIos, cns, InsuInfor
nrfs.
POLYMERS 451
PoIypropyIene
IoIyroyIono Is obfnInod by oIymorIzIng royIono In rosonco of ZIogIor-nffn
CnfnIysf i.e., orgnno mofnIIIc hnIIdo wIfh frnnsIfIon mofnI hnIIdo.
CH CH = CH [CH CHCH ]
3 2 3 2
n
Polymerize
ProperIiee. IoIyroyIono Is nIso nn IsofncfIc, hIghIy crysfnIIIno oIymor. If Is suorIor
fo oIyofhyIono w.r.f. rosIsfnnco fo chomIcnIs, hnrdnoss, sfrongfh, moIsfuro roofIng qunIIfy
ofc. If Is IIghfosf nmong nII hIgh oIymors.
Ieee. IIbros of oIyroyIono nro vory sfrong nnd honco fIbros nro usod for mnkIng
roos, cnrofs, bInnkofs, bngs, nnroIs ofc. If Is nIso usod for nckIng of hnrmncoufIcnI nnd
cosmofIc roducfs, for mnkIng sforIIIznbIo hosIfnI oquImonfs, wnshIng mnchIno nrfs, Ios,
TV, rndIos, mouIdod Iuggngo, coIorfuI furnIfuro ofc.
PoIyvinyI ChIoride (PVC)
VInyI chIorIdo Is fho monomor for IVC nnd fho monomor Is roducod by dIrocf nddIfIon
of HCI fo ncofyIono nf 60C-80C.
CH CH + HCI
HgCI
CH
2
= CHCI
Tho oIymorIznfIon of fho gnsoous monomor (b.. l3.9C) cnn bo dono In soIufIon,
omuIsIon nnd In susonsIon. Tho oIymor Is obfnInod In fho form of fIno owdor nnd Is soIubIo
onIy In socInI soIvonfs IIko dIbufyI hfhnInfo, bonzyI bonzonfo ofc. Incronsod soIubIIIfy of fho
oIymor Is nIso nffnInod by soIufIon oIymorIznfIon nf hIgh rossuro nnd fomornfuro.
nCH = CHCl ( CH CHCl)
2 2
n
Polymerize
PVC
ProperIiee. IVC Is n coIorIoss, odorIoss, non-fInmmnbIo, chomIcnIIy-Inorf owdor. If
confnIns 53-55 CI
2
nnd soffons nf nround 80C.
If Is rosIsfnnf fo wnfor, IIghf, O
2
, InorgnnIc ncIds nnd nIknIIos, oII, ofroI ofc., buf soIubIo
In hof chIorInnfod hydrocnrbons.
Ieee. If Is fho mosf wIdoIy usod InsfIc. If hns hIgh rIgIdIfy nnd chomIcnI rosIsfnnco buf
brIffIo, so, Ifs uso Is mnInIy In mnkIng cnbIos, wnfor hosos, foys, rnIn confs, roxIn, Ios of
ofroIoum Indusfry, fIoor covorIng, rofrIgornfor comononfs, fyros, cycIos nnd mofor cycIo
mudgunrds ofc.
PoIytetrafIuoroethyIene (TEFLON)
If Is obfnInod by oIymorIznfIon of wnfor-omuIsIon of fofrnfIuoro ofhyIono, undor rossuro
nnd In rosonco of bonzoyI oroxIdo ns cnfnIysf.
n(CF = CF ) CC
2 2

Polymerize
F
F
F
F
n
ProperIiee. uo fo fho rosonco of hIghIy oIocfronognfIvo fIuorIno In fho roguInr oIymor
sfrucfuro of TII!O sfrong InforchnIn forcos nro rosonf whIch gIvo fho mnforInI oxfrnordInnry
roorfIos IIko oxfromo foughnoss, hIgh soffonIng oInf (350C), hIgh chomIcnI rosIsfnnco, Iow
cooffIcIonf of frIcfIon nnd wnxy fouch, good mochnnIcnI nnd oIocfrIcnI roorfIos. uo fo nII
fhoso qunIIfIos, fho oIymorIc mnforInI cnn bo mnchInod. If soffons nf nbouf 350C, honco nf
fhIs hIgh fomornfuro If cnn bo mouIdod nIyIng hIgh rossuro.
Ieee. If cnn bo usod for InsuInfIng mofor, frnnsformors, cnbIos, wIros ofc. on-sfIck
cookwnro confIngs nro mndo of TII!O. If cnn nIso bo usod for mnkIng gnskofs, um nrfs,
fnnk IInIngs, Ios nnd fubos for chomIcnI Indusfry, non-IubrIcnfIng bonrIngs nnd fo mnko
non-roncfIvo confIng.
PoIyurethane
(i)
(ii) CH CH CH
3 2 2
OH
O
HOCHCH OCH CHOCH CHOH
2 2 2
CH
3
CH
3
CH
3
Poly(oxypropylene) glycol
IoIyurofhnnos nro n vnrIod rnngo of crossIInkod oIymors mndo from fwo IIquIdsn
oIyoI nnd nn Isocynnfo.
ProperIiee. If cnn bo fonmod IIko oIysfyrono buf unIIko fhormoconI, Is soff, songy known
ns '!-fonm`. If hns Iow fhormnI conducfIvIfy. Ifs gronfosf ndvnnfngo IIos In fho fncf fhnf If cnn
bo mndo whoro fhoy nro noodod wIfhouf nny comIox mnchInoryfho fwo IIquId IngrodIonfs
cnn bo mIxod nnd mouIdod.
Ieee. If Is usod ns InsuInfIng mnforInI In rofrIgornfors. uo fo Ifs songy nnfuro, If Is
usod for mnkIng IIIows nnd mnfrossos. A confIng of oIyurofhnno Is nIIod ovor Ionfhor,
whIch Imrovos fho nonrnnco nnd qunIIfy of fho Ionfhor nnd honco fho bngs mndo of fhoso
Iook nffrncfIvo nnd fho shoos fooI comforfnbIo. If Is nIso usod fo mnko chnIrs ofc.
NyIon-66
IoIynmIdos nro synfhofIc oIymors, hnvIng rocurrIng nmIdo grous, whIch hnvo n sfrucfuro
sImIInr fo fhnf of oIyofIdos. yIon boIongIng fo fhIs cInss Is usod for mnkIng fIbros.
POLYMERS 453
yIon 66 Is obfnInod by fho oIymorIznfIon of ndIIc ncId wIfh hoxnmofhyIono dInmIno.
AdIIc ncId Is commorcInIIy roducod by oxIdnfIon of cycIohoxnno dorIvod from oIfhor bonzono
or ofroIoum.
HoxnmofhyIono Is mndo by fInnI hydrogonnfIon of fho ndIonIfrIIo.
HOOC(CH ) COOH + 2NH OH = H NOOC(CH ) COONH
2 4 4 4 2 4 4
H N(CH ) NH C(CH ) CN + 4H O
2 2 6 2 2 4 2
N
Distilled with
P O
2 5
Hexamethylene
diamine
Adiponitrile
AdIIc ncId nnd hoxnmofhyIono dInmIno mIxod In oquImoIocuInr roorfIons In nquoous
soIufIon In nn nufocInvo nnd honfod nf l00C. Tho comounds roncf fo form nyIon snIf In
soIufIon. yIon snIf Is fhon honfod nf 265C wIfh ow fhorm vnours fo romovo wnfor nnd
moIfon nyIon rosuIfs. yIon fIbro Is obfnInod by nelI epinning proceee.
NH (CH ) N
2 2 6
H
H
+
HO
O
C(CH ) COOH
2 4
HNCH NHC(CH ) C + 2 H O n
2 2 4 2
O O n
yIon cnn bo oxfrudod ns n honvy rIbbon, In nn nfmoshoro of nIfrogon whIch Is chIIIod
nnd chIod. Tho oIymor cnn bo romoIfod fo sIn Info fIbro nnd cnn bo usod for oxfrusIon of
moIdod objocfs.
ProperIiee. yIon Is sfrong, fough, oInsfIc nnd cnn bo dyod onsIIy. yIon ossossos hIgh
nbrnsIon rosIsfnnco nnd Is chomIcnIIy sfnbIo. If ossossos hIgh fomornfuro sfnbIIIfy nnd nIso
hIgh moIfIng (l60C-264C). If Is InsoIubIo In common orgnnIc soIvonfs buf soIubIo In honoI,
formIc ncId.
Ieee. Tho oIymor cnn bo run dIrocfIy fo sInnIng mnchInos fo roduco fIbro, honco
nyIon 66 Is rImnrIIy usod for fIbros, whIch fInd uso In mnkIng socks, undorgnrmonfs, drossos,
cnrofs ofc.
Important Thermosetting Resins
PhenoIic resins
Tho mosf Imorfnnf of fhIs cInss Is IoleliIe or honoI-formnIdohydo rosIn.
If Is ronrod by condonsIng honoI wIfh formnIdohydo In rosonco of ncId-nIknIIno
cnfnIysf In nn nquoous soIufIon. In rosonco of ncId cnfnIysf, fho fIrsf sfo Ionds fo fho formnfIon
of o-nnd p-hydroxy mofhyI honoI, whIch forms IInonr oIymor.
OH
+ HCHO
OH
+
CH OH
2
OH
CH OH
2
OH
+
CH OH
2
OH
+
H
OH
+
H
H
HOCH
2
OH
H
HOCH
2
OH
CH
2
OH OH
CH
2
CH
2
Novolac
In fho socond sfo n smnII nmounf of hoxnmofhyIono fofrnmIno nddod nnd nf fho sfonm
fomornfuro, fho chnIn Iongfh Incronsos nnd nIso fhroo-dImonsIonnI rosIn Is formod, whIch
crossIInks fho sfrucfuro. Thus, fho soIubIo novoInc gofs convorfod fo InsoIubIo IoleliIe.
OH
CH
2
OH OH
CH
2
CH
2
CH
2
OH
CH
2
CH
2
bakelite
CH
2
CH
2
OH OH
ProperIiee. Thoso honoIIc rosIns nro rIgId, hnrd, wnfor rosIsfnnf. Thoy nro rosIsfnnf fo
non-oxIdIsIng ncIds, orgnnIc soIvonfs buf nro suscofIbIo fo nIknIIos. SoIubIIIfIos nnd moIfIng
oInf of fho rosIn grndunIIy chnngo wIfh rIso of moIocuInr woIghf. Thoso rosIns ossoss oIocfrIcnI
InsuInfIng roorfIos.
Ieee. If cnn bo wIdoIy usod ns mofnI subsfIfufo whoro hIgh fonsIIo sfrongfh Is nof
nocossnry. As nn Inorf mnforInI If cnn subsfIfufo for gInss. If cnn bo usod for mnkIng InsuInfor
nrfs IIko swIfchos, Iugs, honfor hnndIos. If cnn bo mouIdod fo cnbInofs for TVs nnd rndIo nnd
foIohono nrfs. If Is usod ns ndhosIvo nIso usod In nInfs nnd vnrnIshos, ns cnfIon oxchnngor
rosIn for wnfor soffonIng, In nor Indusfry ns rooIIor shnffs.
Epoxy resin
Ioxy rosIns nro obfnInod from n oIy condonsnfIon of oIchIorohydrIn wIfh oIyhonoIs
or oIynIcohoIs.
POLYMERS 455
Monomors nro:
(i) 2, 2-(Iie)-4-hydroxy honyI ronno |Iie-honoI]
IronrnfIon of bIshonoI
HO 2 HO + CH COCH
3 3
Phenol Acetone
NaOH
50 C
C
CH
3
CH
3
OH
Bisphenol A
(ii) IIchIorohydrIns
CH = CHCH + Cl CH = CHCH Cl
2 3 2 2 2
Propylene
400 C
HCl
Allylchloride
300 C
H O + Cl
2 2
CH = CHCH Cl + HCl Cl CH CHCH Cl
2
.
2 2 2
200 C
CaO
O
OH
Epichlorohydrin
(iii) Sfrucfuro of ooxy rosIn
CH CHCH
2 2
O
O C
CH
3
CH
3
OCH CHOH.CH
2 2
n
O C
CH
3
CH
3
OCH CHCH
2 2
O
IIow dIugvum Iov tLe pvoductIon oI epoxy vesIn:
Epichlorohydrin
Bisphenol A
NaOH dry
or in solution
Reaction
Kettle
Recovered
epichlorohydrin
Purification
of resin
washing
with water
Brine
Resin
Water
Properties and Uses
Ioxy rosIns ossoss oufsfnndIng roorfIos of
AdhosIon fo vnrIous mnforInIs IIoxIbIIIfy
ChomIcnI Inorfnoss Toughnoss
SfnbIIIfy nf hIgh fomornfuro !ow shrInkngo durIng curo.
Ior fho nbovo roorfIos, fho ooxy rosIns nro usod ns fho mnjor consfIfuonfs of ndhosIvos
In nInf Indusfry nnd ns InsuInfor In oIocfrIcnI Indusfry.
PoIyester
IoIyosfors nro fho condonsnfIon roducfs of dIcnrboxyIIc ncId wIfh dIhydroxy nIcohoIs.
ToryIono Is fho IrIfIsh nnmo of ncron, whIch Is obfnInod by condonsnfIon of ofhyIono gIycoI
nnd forohfhnIIc ncId. IfhyIono Is oxIdIsod nf hIgh rossuro nnd fomornfuro In fho rosonco
of Ag ns cnfnIysf nnd fho ofhyIono oxIdo Is hydroIysod by dIIufo HCI fo ofhyIono gIycoI.
(o) CH = CH + O
2

2 2
1
2
O
CH
2
CH
2
CH
2
CH
2
+ H O
2
CH OH
2
CH OH
2
ethylene glycol
O
(I) InrnxyIono obfnInod from conI fnr frncfIon Is oxIdIsod by noufrnI ormnngnnnfo
soIufIon or conc. HO
3
(50) nf nbouf l00C fo gIvo forohfhnIIc ncId.
CH
3
CH
3
COOH
COOH
COOCH
3
COOCH
3
Terephthalic acid
esterification
Dimethyltere-
phthalate
(c)
COOH
COOH
CH OH
2
nCH OH
2
+
Condensation
polymerization
OCH OC
2
O
C
O n
Polyester
Tho oquIIIbrIum of fho roncfIon Is nof fnvornbIo for fho formnfIon of osfor honco fo gof
hIgh yIoId fho byroducf musf bo confInunIIy romovod from fho roncfIon mIxfuro. Ioffor yIoIds
nro obfnInod wIfh dImofhyIforohfhnInfo.
ProperIiee. SInco fho sfrucfuro of fho oIymor Is symmofrIcnI nnd n numbor of oInr
grous nro rosonf If forms fIbro onsIIy. Tho fIbro hns hIgh fonsIIo sfrongfh nnd rosIIIoncy nnd
Is sfnbIo fo hydroIysIs. Tho fnbrIc mndo from fho fIbro Is cronso rosIsfnnf.
Ieee. If Is mosfIy usod for mnkIng synfhofIc fIbros IIko foryIono, dncron ofc., whIch nro
fInnIIy usod for mnkIng gnrmonfs for mon, womon nnd chIIdron.
If cnn bo bIondod wIfh wooI nnd usod for mnkIng cnrofs, bInnkofs, uhoIsforIos, quIIfs ofc.
POLYMERS 457
If cnn bo roInforcod wIfh gInss fo form snfofy hoImofs, noroInno nrfs, nrnfroo, wIro
InsuInfors, fIghfor nrnchufo ofc.
Ter,lene Ioe eeterol oJtonIogee oter coIIon In rosocf of
(i) !osIsfnnco fo ncIds
(ii) Sfrongfh
(iii) Cronso rosIsfnnco nnd
(it) CIvos boffor fInIsh nnd bIondnbIo wIfh coffon or wooI.
SiIicones
SIIIconos hnvo nIfornnfo sIIIcon-oxygon bonds nnd orgnnIc rndIcnIs nffnchod fo fho sIIIcon
nfoms.
Tho monomors nro ronrod ns
(i) !CI + SI
Cu
!
2
SICI
2
(ii) Irom CrIgnnrd rongonf
SICI
4
+ !MgCI !SICI
3
+ MgCI
2
Tho monomor Is obfnInod by frncfIonnI dIsfIIInfIon of fho roncfIon roducfs whoroby
dIfforonf orgnno-sIIIcon chIorIdos nro obfnInod.
In fho noxf sfo fho chIorIdos nro oIymorIzod by hydroIysIs InvoIvIng fho foIIowIng sfos
SICI + H
2
O SIOH + HCI
SIOH + HOSI SI O SI + H
2
O
Thus, fho OH grous of SI nro InvoIvod In oIymorIznfIon honco whon fhoro Is ono or
fwo OH grous In SI, If Ionds fo Iong chnIn oIymors buf whon fhoro nro fhroo OH grous,
crossIInkod oIymors nro formod. !oncfIons:
(i) 2!CI + SI
Cu
!
2
SICI
2
(ii) Irom CrIgnnrd rongonf
SICI
4
+ !MgCI !SICI
3
+ MgCI
2
(iii) Mo
2
SICI
2

H O
2
Mo
2
SI(OH)
2
SIrucIure of Silicone Pol,nere
HO.SIMo |OSIMo ] OSIMo OH
2
2 2

n
SIIIcono
I-nIkyI-dI-chIorosIIIcnno nnd nIkyI frIchIoro sIIIcono undorgo hydroIysIs nnd condonsnfIon
oIymorIznfIon fo gIvo n cross-IInkod sIIIcono oIymor.
CI
!
SI
!
CI CI
!
SI
CI
CI CI
!
SI
!
CI
CI
!
SI
!
CI CI
CI
SI
!
CI CI
!
SI
CI
CI
3
2
2
2
2
2
2
2
2
2
2
2

H O
2
HO
!
SI
!
OH HO
!
SI
OH
OH HO
!
SI
!
OH
HO
!
SI
!
OH HO
OH
SI
!
OH HO
!
SI OH
OH
3
2
2
2
2
2
2
2
2
2
2
2
H O
2
O
!
SI
!
O
!
SI O
!
SI
!
O
O
!
SI
!
O
O
SI
!
O
!
SI
O
O

(Cross-IInkod oIymor)
ComIofo condonsnfIon of nII fho OH gIvo rIso fo hnrd, InsoIubIo roducf, fhus n mIxfuro
of monomors (confnInIng ono or moro OH grous) nIong wIfh suffIcIonf wnfor for hydroIysIs
Is honfod for oIymorIznfIon.
DifferenI T,pee of Siliconee
oondIng on fho roorfIon of vnrIous nIkyI sIIIcon hnIIdos usod fho fInnI sIIIconos mny
bo IIquIds, vIscous IIquIds, somI-soIIds nnd soIIds. ThoIr roorfIos nnd usos nIso dIffor
nccordIngIy.
(i) SIIIcone IIuIds. Thoy nro of roInfIvoIy Iow moIocuInr woIghf, snrkIIng cIonr fIuIds
wIfh nn oIIy fooI, InsoIubIo In wnfor buf soIubIo In nromnfIc nnd chIorInnfod soIvonfs.
Thoy hnvo good rosIsfnnco fo honf nnd oxIdnfIon, Iow surfnco fonsIon nnd show Iow
chnngo In vIscosIfy wIfh fomornfuro.
Ieee. Thoy nro usod ns nufofonm ngonfs, hIgh fomornfuro IubrIcnnfs, In cosmofIcs, ns
dnmIng nnd hydrnuIIc fIuIds nnd fo gIvo wnfor rooIInnf fInIsh fo foxfIIos nnd Ionfhors.
(ii) SIIIcone gveuses. Thoso nro formod from fho oIIs by nddIng sIIIcn, cnrbon bInck ofc.
Thoy nro usod ns IubrIcnnfs nrfIcuInrIy for vory hIgh nnd Iow fomornfuro nIIcn-
fIons.
(iii) SIIIcone vesIns. Thoy nro hIghIy cross-IInkod oIymors, ossoss good InsuInfIng
roorfIos, honf rosIsfnnco nnd good dIoIocfrIc roorfIos.
Ieee. !sod for hIgh voIfngo InsuInfors, hIgh fomornfuro InsuInfIng fonms, sIIIcono-
gInss InmInnfos for hIgh fomornfuro nIIcnfIon, for dIfforonf oIocfrIcnI nnd oIocfronIc
oquImonf nrfs mnnufncfurIng.
(it) SIIIcone vubbevs. SIIIcono rubbors nro formod by roncfIon of dImofhyI sIIIcono fIuId
wIfh oroxIdo nnd nrorInfo InorgnnIc fIIIors IIko TIO
2
, ZnO, SIO
2
ofc.
POLYMERS 459
Thoy rofnIn rubbory roorfIos ovor n much wIdor fomornfuro snn, good honf frnnsfor
roorfIos, good rosIsfnnco fo dIIufo ncIds nnd nIknIIs. Thoy nro fIoxIbIo In wIdo rnngo of
fomornfuros.
Ieee. Ior fyro mnnufncfurIng of fIghfor nIrcrnffs, ns InsuInfors of oIocfrIc wIros In shI,
ns ndhosIvos for nrfIfIcInI honrf vnIvos, frnnsfusIon fubIngs, for socInI boofs fo bo usod nf vory
Iow fomornfuro, for mnkIng IubrIcnnfs, nInfs, rofocfIvo confIngs ofc.
MoIecuIar weight of a poIymer
IoIymors nro mIxfuros of moIocuIos of dIfforonf moIocuInr mnssos, sInco fho chnIn Iongfh
vnrIos. Thoro nro fho foIIowIng fyos of moIocuInr woIghfs for oIymors.
(i) AunIer oteroge noleculor ueigII
Tho numbor nvorngo moIocuInr woIghf ( ) M
n
Is dofInod ns fho fofnI mnss (u) of nII fho
moIocuIos of oIymor dIvIdod by fho fofnI numbor of moIocuIos rosonf. Thus
M
n
i i
i
u
= =
whoro
i
Is fho numbor of moIocuIos of mnss M
i
. M
n
cnn bo doformInod by monsurIng fho
coIIIgnfIvo roorfIos IIko IoworIng of vnor rossuro, dorossIon of froozIng oInf ofc.
(ii) WeigII-oteroge noleculor ueigII
WoIghf nvorngo moIocuInr woIghf ( ) M
u
cnn bo dofInod by fho foIIowIng roInfIon:
M
M
u
i i
i
u
u
=

whoro u
i
Is fho woIghf frncfIon of moIocuIos hnvIng mnss M
i
.
AIso,
M
u
=
c
c
c
c
i i
i
i i i i
i i
M M M
M
= =
2
whoro c
i
= woIghf conconfrnfIon of M
i
moIocuIos nnd c = fofnI conconfrnfIon of nII oIymor
moIocuIos.
ow, M
u
Is nIwnys gronfor fhnn M
n
.
M
u
cnn bo doformInod by IIghf scnfforIng monsuromonfs, vIscosIfy monsuromonfs,
dIffusIon monsuromonfs. M /M
u n
Is usod ns n monsuro of fho moIocuInr-mnss dIsfrIbufIon or
Indox of oIydIsorsIfy nnd If Is l.5 or Inrgor for nnfurnI nnd synfhofIc oIymors. M = M
u n
, In
cnso nII fho oIymor moIocuIos nro of IdonfIcnI moIocuInr woIghf.
Degree of poIymerization
Tho numbor of rocurrIng unIfs of monomors In n oIymor chnIn Is known ns dogroo of
oIymorIznfIon (I). In n oIymor, ncfunIIy fho chnIn Iongfh vnrIos, somo mny confnIn l00 fo
200 monomors whIIo ofhors mny confnIn l000 or moro. Honco, wo uso fho form nvorngo dogroo
of oIymorIznfIon (I).
In n froo rndIcnI oIymorIznfIon, fho ovornII rnfo of oIymorIznfIon Is roorfIonnI fo fho
conconfrnfIon of fho monomor nnd fho squnro roof of conconfrnfIon of fho InIfInfor.
J
JI
(M)
= K|M]| ] C
l/ 2
M = conconfrnfIon of monomor
C = conconfrnfIon of InIfInfor
Af n corfnIn sfngo of oIymorIznfIon If Is found fhnf fho numbor of ncfIvo confros for
oIymorIznfIon Is oqunI fo fho numbor of chnIn formInnfors. Af fhIs sfngo fho nvorngo dogroo
of oIymorIznfIon Is
I =
K.|M]
| ]
l/ 2
c
ThIs oqunfIon roInfos nvorngo dogroo of oIymorIznfIon wIfh monomor conconfrnfIon ns
woII ns InIfInfor conconfrnfIon. Tho dogroo of oIymorIznfIon InfIuoncos fho fonsIIo sfrongfh of
fho oIymor.
HIgLIIgLts:
CIussIIIcutIon oI pIustIcs
TIernoploeIic rosIns soffon on honfIng nnd hnrdon on cooIIng rovorsIbIy.
CoIIuIoso dorIvnfIvos
IoIyfhono, IoIyroyIono, IoIysfyrono, IoIyvInyI chIorIdo,
IoIyfofrnfIuoro ofhyIono (TofIon)
IoIynmIdos (nyIon)
AIS oIymors.
TIernoeeIIing ploeIice nro ormnnonf soffIng rosIns whIch hnrdon on honfIng
durIng mouIdIng nnd fhoy cnnnof bo soffonod ngnIn. IxnmIos of fhIs cInss IncIudo
(i) BoleliIe obfnInod by oIymorIznfIon of honoIIc dorIvnfIvos wIfh nIdohydos.
(ii) Melonine obfnInod by condonsIng moInmIno wIfh formnIdohydo.
(iii) Ter,lene (IoIyosfor) nro condonsnfIon roducfs of dIcnrboxyIIc ncIds wIfh
dIhydroxy nIcohoIs
(it) 1pox, reeine (nrnIdIfo)
(t) Silicone rosIns.
RUBBER
!ubbors nro hIgh oIymors, whIch hnvo oInsfIc roorfIos nnd cnn bo sfrofchod ufo
nbouf 300 orconf. Tho unsfrofchod rubbor Is nmorhous nnd fho oIymor chnIns nro In n
coIIod sfnfo, whIch on sfrofchIng gofs nIIgnod cnusIng crysfnIIIznfIon. In roIonsIng fho sfross
fho chnIns rovorf bnck fo fhoIr orIgInnI coIIod sfnfo.
NutuvuI vubbev. nfurnI rubbor Is oIymorIzod Isorono, whIch occurs In fho Infox of
vnrIous froos. nfurnI rubbor cnmo Info mnrkof fIrsf In onrIy l9
fh
confury. Tho moIocuInr
woIghf of rnw rubbor Is nbouf l00,000-l50,000 nnd Is mndo from fho Infox of dIfforonf Innfs
IIko Hoteo Iroeillione nnd gnnguIo found In froIcnI nnd subfroIcnI counfrIos. Tho Infox Is
coIIocfod from fho mnfuro Hnvon froo by mnkIng doo cufs on fho bnrk, nnd by nIIowIng fho
Infox sfronm fo coIIocf In n of nffnchod boIow fho cufs. TnIng Is dono nf InforvnIs of nbouf 6
monfhs.
CouguIutIon oI tLe Iutex. !nfox Is dIIufod fo confnIn bofwoon l5-20 of rubbor, fIIforod
fo mnko If froo from dIrf. ConguInfIon Is fhon offocfod by nddIng ncofIc ncId (l fo 2 on woIghf
bnsIs). !ubbor conguInfos ns soff whIfo mnss whIch Is wnshod nnd furfhor rocossod.
Tho conguIum Is nIIowod fo drnIn nnd fho nbsorbod sorum Is squoozod ouf fhrough sfooI
roIIors uon whIch wnfor Is srnyod. Tho conguIum Is convorfod fo n shoof wIfh unovon rough
surfnco rosombIIng croo nor nnd cnIIod crepe ruIIer.
POLYMERS 461
SnoleJ ruIIer shoofs nro mndo from fhIckor shoofs fhnn croo rubbor. ConguInfIon Is
cnrrIod ouf In Inrgo fnnks nnd fInnIIy nIIowod fo soffIo for l6 hours. Tho fough sInbs nro nssod
fhrough roIIors (ombossod or rIbbod) fo obfnIn rIbbod nfforn. Tho ombossod shoofs nro fhon
hung u In n smokIng houso, whoro on fho fIoor, wood or coconuf husk Is burnf fo roduco honf.
SmokIng Is dono nf n fomornfuro of 45C-50C, whoroby fho shoofs gof drIod wIfhIn 4 dnys.
Tho crudo rubbor obfnInod Is frnnsIuconf nnd nmbor In coIour nnd Is nof nffnckod by
mIcro-orgnnIsms.
ProperIiee. nfurnI rubbor Is nn nmorhous soIId, frnnsIuconf, ImorvIous fo gnsos, oInsfIc
In nnfuro. If Is ncfunIIy oIymorIzod cie-Isorono.
!ubbor sIowIy oxIdIsos whon oxosod fo nIr. On honfIng If soffons nnd IIquIfIos. If burns
fo form CO
2
nnd H
2
O. On dosfrucfIvo dIsfIIInfIon rubbor fIrsf soffons nnd fhon docomosos
roducIng whIfo fumos. Whon fho dosfrucfIvo dIsfIIInfIon Is cnrrIod ouf nf hIghor fomornfuro
fho condonsnfo confnIns mosfIy fho Isorono dImors.
!nw rubbor owdor cnfnIyfIcnIIy roncfs wIfh H
2
gns, If docoIorIzos bromIno wnfor, forms
ozonIdo wIfh ozono, roncfs wIfh HCI. Ior onch C
5
H
8
unIf In rubbor moIocuIo, ono moIocuIo onch
of Ir
2
, O
3
nnd HCI roncfs, fhus fhoro Is onIy ono doubIo bond. Iuf for docomosIfIon roducf of
rubbor i.e., Isorono fhoro Is fwo doubIo bonds CH
2
=C
CH
C
H
3

=CH
2
.
urIng fho rocoss of IInkIng, hond nnd fnII IInkIng of Isorono moIocuIo occurs.
3
2
2
2
2
2
H

C

H
C

CH
C

H
H

C

H
3
n
Sfrucfuro of nnfurnI rubbor (cie-oIyIsorono)
!ubbor Is nffnckod by sfrong nIknIIos nnd oxIdIsIng ngonfs. Sfrong HO
3
nffncks rubbor.
Limitations of naturaI rubber
nfurnI rubbor soffons nf hIgh fomornfuro nnd bocomos brIffIo nf Iow fomornfuro, If
Is nffnckod by ncIds, oxIdIsIng ngonfs, non-oInr soIvonfs, If Is oxIdIsod by nIr. AIso on oxcossIvo
sfrofochIng If gofs ormnnonfIy doformod. To ovorcomo fhoso IImIfnfIons rubbor Is vuIcnnIzod.
VuIcanization of rubber
urIng l839, ChnrIos Cood Yonr dovoIood fho mofhod of vuIcnnIznfIon of rubbor by
whIch fho roorfIos of nnfurnI rubbor cnn bo Imrovod fo n Inrgo oxfonf. VuIcnnIznfIon Is n
rocoss whIch Is ossonfInIIy comoundIng rubbor wIfh dIfforonf chomIcnIs IIko, suIfur, H
2
S,
bonzoyI chIorIdo ofc. Tho mofhod Is bnsIcnIIy honfIng rnw rubbor wIfh suIfur nf l00 C-l40C,
whon fho suIfur onfors Info fho doubIo bonds of rubbor formIng crossIInks bofwoon fho chnIns
nnd fhIs gIvos fho sfrucfuro foughnoss. Tho foughnoss or fho sfIffnoss of vuIcnnIznfIon doonds
on fho nmounf of suIfur IncIudod. Ior fIoxIbIo fyro rubbor, suIfur confonf Is from 3-5 whorons
for foughor vnrIofy IIko obonIfo, confonf of S Is 32. IbonIfo Is so fough fhnf If cnn bo mnchInod,
If hns vory good oIocfrIcnI InsuInfIon roorfy.
CompuvutIve study between nutuvuI und vuIcunIzed vubbev
ProperI, Iou ruIIer VulconiceJ ruIIer
l. IInsfIcIfy vory hIgh Iow, doondIng on orconfngo
of suIhur
2. TonsIIo sfrongfh 200 kg/cm
2
2000 kg/cm
2
3. !sofuI fomornfuro rnngo l0C-60C 40C fo l00C
4. ChomIcnI rosIsfnnco vory oor hIghor
5. Wnfor nbsorfIon fondoncy hIgh Iow
6. !osIIIonco good much boffor
?. InsuInfIon roorfy
8. !osIsfnnco fo !ow much hIghor buf swoIIs
orgnnIc soIvonfs
9. TnckInoss mnrkod Iow
l0. urnbIIIfy Ioss boffor
ll. QunIIfy Inhoronf cnn bo confroIIod by vuIcnnIznfIon
Synthetic Rubbers
SynfhofIc rubbor Is nrfIfIcInIIy roducod rubbor-IIko oIymors whIch cnn bo sfrofchod fo
nf Ionsf fwIco Ifs Iongfh nnd on roIonsIng fho sfross, If rofurns fo Ifs orIgInnI shno nnd sIzo.
Somo Imorfnnf oxnmIos nro:
(i) CI-S or Buno-S. ThIs vnrIofy Is fho mosf Imorfnnf synfhofIc rubbor nnd If Is ob-
fnInod by cooIymorIznfIon of bufndIono nnd sfyrono.
ProperIiee. SI! Is sImIInr fo nnfurnI rubbor In rocossIng chnrncfor nnd nIso ns fInIshod
roducf. If ossossos hIgh rosIIIonco nnd good nnd fough mochnnIcnI roorfIos. Iuf
unforfunnfoIy If Is onsIIy nffnckod by oxIdIsIng ngonfs, mnInIy ozono. If nIso swoIIs In orgnnIc
soIvonfs. If cnn bo vuIcnnIzod ns nnfurnI rubbor.
Ieee. If Is mnInIy usod for fho mnnufncfuro of fyros. If Is nIso usod ns soIos nnd ofhor
comononfs of shoos, for InsuInfIng wIros nnd cnbIos, ns ndhosIvos nnd IInIng for vossoIs.
(ii) CIA or Buno-A. If Is n cooIymor of bufndIono nnd ncryIonIfrIIo
xCH
2
= CHCH = CH
2
+ nCH
2
= CHC
CooIymorIznfIon
=
3
2

3
2
CH CH CHCH CH CHC
2 2 2
x n
POLYMERS 463
ProperIiee. If Is hIghIy rosIsfnnf fo honf, sunIIghf, ncIds, oIIs ofc. buf duo fo fho rosonco
of C grou, If Is much moro suscofIbIo fo nIknII fhnn nnfurnI rubbor. Tho good qunIIfIos
Incronso ns fho roorfIon of ncryIonIfrIIo Is Incronsod nnd If cnn bo vuIcnnIzod fo boffor honf
rosIsfnnf vnrIofy.
Ieee. Ifs uso Is vorsnfIIo. If Is usod fo mnnufncfuro nrfs for nufomobIIos, nIrcrnff. If Is
nIso usod for mnkIng convoyor boIfs, ndhosIvos nnd oII rosIsfnnf fonms.
(iii) CI-M or Aeoprene. If Is mndo by oIymorIznfIon of chIororono or chIorInnfod
bufndIono.
nCH = CCHCH
2 2 2 2
CH C = CHCH
Polymerize
Chloroprene
Cl Cl
n
ProperIiee. Tho onIy dIfforonco of fho sfrucfuro of chIororono nnd nnfurnI rubbor Is n
sIngIo chIorIno nfom Insfond of nn H nfom whIch brIngs nbouf mnrkod rosIsfnnco fo fomornfuro,
nfmoshorIc chnngo nnd fo oIIs. If cnn bo vuIcnnIzod by honfIng nIono. Ifs roorfIos cnn bo
chnngod by comoundIng fo ZnO or MgO.
Ieee. If Is usod for mnkIng convoyor boIfs, ndhosIvos, gnskofs, ns IInIngs for roncfIon
vossoIs nnd for mnkIng Ios fo cnrry corrosIvo gnsos nnd oIIs.
RecIaimed Rubber
If Is obfnInod from fho wnsfo rubbor nrfIcIos by fho rocoss of rocInImnfIon.
Proceee. Tho wnsfo rubbor nrfIcIos IIko fyros, fubos, foofwnros, gnskofs ofc. nro cuf nnd
owdorod In n crnckor. Tho unwnnfod forrous mnforInIs nro sonrnfod by oIocfromngnofIc
sonrnfor nnd fhon chnrgod fo nn nufocInvo nnd dIgosfod wIfh cnusfIc sodn soIufIon nf 200C
undor rossuro for 8-l5 hours. Tho fIbros gof hydroIysod i.e., dovuIcnnIznfIon fnkos Inco.
SuIhur Is romovod ns sodIum suIfIdo. If Is wnshod, drIod nnd fInnIIy roInforcod wIfh cnrbon
bInck ofc.
ProperIiee. !ocInImod rubbor hns InforIor fonsIIo sfrongfh, oInsfIcIfy ofc. comnrod fo
nnfurnI rubbor buf hns Imrovod ngoIng roorfIos. If Is chonor nnd onsIor for fnbrIcnfIon.
Ieee. !ocInImod rubbor Is usod for mnkIng fyros, fubos, boIfs, shoo soIos, fIoor mnfs ofc.
Compounding of rubber
ComoundIng Is mIxIng of rnw rubbor wIfh dIfforonf chomIcnIs fo Imnrf socInI
roorfIos for nIIcnfIon.
Proceee. SynfhofIc or nnfurnI rubbor Is mIxod wIfh tulconicing ogenIe IIko suIfur,
ploeIicicere IIko vogofnbIo oIIs, wnxos ofc., onIioxiJonIe IIko nmInos nnd hoshIfos, fillere IIko
C-bInck, occeleroIore IIko bonzofhInzoIo, morcnfnns, nnd coloring noIIere. If Is fhon roonfodIy
nssod fhrough hof roII mIIIs rofnfIng In oosIfo dIrocfIons fo soffon nnd bronk down nnd fho
rocoss Is cnIIod noeIicoIion. IInnIIy fho mnforInI forms soff InsfIc mnss.
HIgLIIgLts:
Rubbev
nfurnI rubbor Is cie-oIyIsorono
Cuffn orchn Is Irone-oIyIsorono.
VuIcunIzutIon
Tho rocoss dIscovorod by ChnrIos Cood Yonr In l839 fo Imrovo fho qunIIfy of
rubbor by InfroducIng suIfur nf l00C-l40C fo fho doubIo bond of rubbor.
(ConIJ.)
SyntLetIc vubbev
An oInsfomor roducod nrfIfIcInIIy, whIch cnn bo sfrofchod fo fwIco Ifs Iongfh, buf
rofurns fo Ifs orIgInnI shno.
Sfyrono rubbor (C!-S)
IfrIIo rubbor (C!-A)
oorono (C!-M)
ThIocoI (C!-I)
HynIon
IoIyurofhnno
CompoundIng oI vubbev
MIxIng of rnw rubbor wIfh InsfIcIzors, nnfIoxIdnnfs, vuIcnnIzIng ngonfs, fIIIors,
coIours ofc. fo Imnrf socIfIc roorfIos fo fho fInIshod roducfs.
MISCELLANEOUS POLYMERS
l. IumInute. If Is obfnInod by joInIng fwo or moro Inyors of soIId mnforInIs wIfh fho
hoI of nn ndhosIvo. If fho grnIns of fho Inyors nro nrnIIoI fo onch ofhor, If Is cnIIod porollel
loninoIe nnd whon fhoy nro nf rIghf nngIos fo onch ofhor, If Is cnIIod croee loninoIe.
(o) Pl,uooJ. Odd numbors of Inyor of wood (0.5-l0 mm fhIck) nro bondod such fhnf
grnIns of nIfornnfo Inyors nro nf rIghf nngIos fo onch ofhor (cross-InmInnfo). Iy fhIs
rocoss fho Iywood roducod hns unIform roorfIos, Iongfh nnd wIdfhwIso, fhus
sIIffIng of wood, shrInkngo ofc., nro mInImIsod nnd bocomos moro sfrong comnrod
fo wood of oqunI fhIcknoss.
Ieee. IIywood Is usod for mnkIng rnIIwny conch, cnbInofs, fnIso-coIIIngs nnd In ofhor
houso buIIdIng urosos.
(I) LoninoIeJ PloeIice. Inor, cIofh, nsbosfos fIbro, gInss, mofnI ofc., nro Imrognnfod
wIfh fhormosoffIng rosIn IIko honoI-formnIdohydo or uron-formnIdohydo soIufIon
In soIvonf nnd drIod nf n fomornfuro much Iowor fhnn fho curIng fomornfuro of
fho rosIn, fhon fhoy nro cuf Info suIfnbIo sIzo nnd fhon subjocfod fo curIng In n
hydrnuIIc ross nf nbouf l80C nnd rossuro, whon fho rosIn bocomos hnrd. Tho
fInIshod InmInnfod InsfIcs nro IIghf buf sfrong nnd ImormonbIo fo wnfor, oII ofc.
Thoy nro mnchInonbIo nnd chomIcnI rosIsfnnf.
Ieee. Thoy nro usod for oIocfrIcnI nnd InsuInfIng mnforInIs, um nrfs ofc. Thoy nro
nIso usod for docornfIvo urosos on fnbIo fos nnd wnII nnoIIIngs ofc.
(c) LoninoIeJ gloeeee. Two gInss shoofs nro joInod by n InsfIc shoof In bofwoon fo form
InmInnfod gInss. Ior frnnsnroncy, oIyvInyI-bufyI rosIn cnn bo usod ns ndhosIvo.
IuIIof roof or sIInfor roof InmInnfod gInss Is obfnInod by curIng fho InmInnfos In
nn ovon undor honf nnd rossuro.
Conducting PoIymers
IoIymors obfnInod by fho usunI mofhods of oIymorIznfIon nro mnInIy InsuInfors.
ConducfIng oIymors nro mndo by socInI owdors nnd nro cInssIfIod ns
(o) -elecIrone conJucIing pol,ner. In fhoso oIymors fho bnckbono of fho oIymor Is
mndo u of moIocuIos fhnf confnIn conjugnfod -oIocfrons whIch oxfond fho onfIro
oIymor nnd mnko fho oIymor conducfIng.
POLYMERS 465
(I) ConJucIing elenenI-filleJ pol,ner. In fhIs fyo of oIymor fho oIymor ncfs ns bIndor,
whIch bInds fho conducfIng oIomonfs IIko cnrbon bInck, mofnI oxIdos, mofnIIIc fIbros
fhnf conducf oIocfrIcIfy.
(c) 1norgonic pol,ner. A mofnI nfom wIfh oIy donfnfo IIgnnd, whIch Is n chnrgo frnns-
for comIox Is bound fo fho oIymor fo mnko If conducfIng.
(J) DopeJ-conJucIing pol,ner. Tho oIymor Is mndo conducfIng by oxosIng fho sur-
fncos fo chnrgo frnnsfor ngonfs In gns or In soIufIon Inco.
(e) BlenJeJ conJucIing pol,ner. ThIs fyo of oIymor Is mndo by bIondIng n convon-
fIonnI oIymor wIfh n conducfIng oIymor.
1nJueIrioll, inporIonI conJucIing pol,nere ore. IoIyquInoIIno, oIynnfhryIono,
oIyfhIohono, oIybufndIonyIono ofc.
Ieee. ConducfIng oIymors nro usod for mnkIng (i) buffon coIIs, (ii) hofovoIfnIc dovIcos,
(iii) sonsors nnd (it) bIomodIcnI dovIcos.
Q. 1. WLut Is IunctIonuIIty oI u monomev?
Ans. If Is fho numbor of bondIng sIfos of monomor.
Q. 2. WLut Is geI poInt?
Ans. Tho monomors of nIkyI rosIns ossoss funcfIonnIIfy gronfor fhnn fwo. urIng
condonsnfIon oIymorIznfIon If gofs frnnsformod from vIscous mnforInI fo n goI nnd fho
frnnsformnfIon Is suddon. ThIs oInf of frnnsformnfIon Is fho goI oInf. Tho cnuso of goInfIon Is
fho formnfIon of nn InfInIfo nofwork of oIymor nnd nf fhIs hnso fho rosIn bocomos fough nnd
Ioss oxfonsIbIo.
Q. 3. WLut Is ugeIng oI vubbev?
Ans. AgoIng Is fho nufooxIdnfIon of rubbor wIfh fImo duo fo fho rosonco of doubIo bond
nnd duo fo fhIs rubbor bocomos hnrd.
Q. 4. WLen Is vuIcunIzutIon done? MentIon some oI tLe uses oI vuIcunIzed
vubbev.
Ans. VuIcnnIznfIon Is dono nffor shnIng fho nrfIcIo. Tho shnIng Is dono wIfh rnw
rubbor nIong wIfh suhur nnd ofhor IngrodIonfs IIko nccoIornfors, nnfIoxIdnnfs, fIIIors ofc.
Ieee. VuIcnnIzod rubbor Is usod In vohIcIo fyros, hoso, convoyor boIf, oIocfrIcnI InsuInfIon.
Q. 5. WLut Is tLe busIc dIIIevence between nyIon 6 und nyIon 66?
Ans. yIon 6 Is nn nddIfIonnI oIymor whorons nyIon 66 Is n condonsnfIon oIymor.
In nyIon 6, fho comosIfIon of fho monomor Is fho snmo ns fhnf of fho oIymor, buf nyIon
66 Is formod wIfh fho oIImInnfIon of wnfor moIocuIos.
Q. 6. IIIeventIute between u LomopoIymev und copoIymev?
Ans. A homooIymor consIsfs of mnny IdonfIcnI monomor unIfs whorons n cooIymor
consIsfs of monomors of dIfforonf chomIcnI sfrucfuros.
Q. ?. IIIeventIute between uddItIon und condensutIon poIymevIzutIon.
Ans. AddIfIon oIymorIznfIon Is n roncfIon fhnf gIvos n oIymor, whIch Is nn oxncf muIfIIo
of fho orIgInnI monomors.
CondonsnfIon oIymorIznfIon fnkos Inco fhrough dIfforonf funcfIonnI grous of
monomors wIfh oIImInnfIon of smnII moIocuIos IIko H
2
O ofc.
Q. B. WLut Is copoIymevIzutIon?
Ans. CooIymorIznfIon Is fho oInf oIymorIznfIon of fwo or moro monomors, e.g.,
bufndIono nnd sfyrono fo yIoId C!-S rubbor.
Q. 9. WLut Is poIydIspevsIty Index oI u poIymev?
Ans. IoIymors nro dIfforonf from ofhor smnII sIzod moIocuIos ns fhoy nro mIxfuros of
moIocuIos hnvIng dIfforonf moIocuInr mnssos. Pol,JiepereiI, inJex (II) of n oIymor Is n
monsuro of fho moIocuInr mnss dIsfrIbufIon of n oIymor.
Q. 10. WLut Is un eIustomev?
Ans. Any rubbor-IIko oInsfIc oIymor, whIch cnn bo sfrofchod fo fhrIco Ifs sIzo nnd nffor
romovnI of fho sfrofchIng forco If rofurns fo Ifs orIgInnI shno Is cnIIod nn oInsfomor.
Q. 11. WLy Is tLe densIty oI HP dIIIevent Ivom IP?
Ans. HII Is comIofoIy n IInonr oIymor nnd honco nckIng of fho chnIns Is offIcIonf
nnd honco Ifs donsIfy Is hIgh. Iuf for !II, duo fo Ifs brnnchod sfrucfuro, nckIng offIcIoncy
Is Iow nnd honco donsIfy Is Iow.
Q. 12. WLy tLevmosettIng pIustIcs cunnot be veused?
Ans. In fhormosoffIng InsfIcs, fho monomors nro bound fo onch ofhor by sfrong covnIonf
bonds, whIch cnnnof bo brokon on honfIng. Thus by honfIng If cnnnof bo soffonod fo roshno
nnd rouso.
Q. 13. WLut Is nutuvuI vubbev und wLut Is guttu-pevcLu?
Ans. nfurnI rubbor Is Iong-coIIod chnIns of oIycIsIsorono nnd guffn-orchn Is horny
nnd fough form of oIyfrnnsIsorono.
Q. 14. WLy Is teIIon LIgLIy cLemIcuI vesIstunt?
Ans. In fofIon fho mosf oIocfronognfIvo oIomonf I confrIbufos fo fho sfrong nffrncfIvo
forco wIfhIn fho chnIns nnd honco Is non-roncfIvo fownrds ofhor chomIcnIs.
Q. 15. WLy Is PVC soIt und IIexIbIe but bukeIIte Is Luvd und bvIttIe?
Ans. In IVC fho moIocuInr chnIns nro bondod fo onch ofhor by Vnn dor WnnI`s forcos
nnd honco fhoso Iong chnIns nro fIoxIbIo nnd cnn sII or fwIsf on nIyIng forco buf In fho cnso
of bnkoIIfo fho fhormosoffIng oIymor chnIns nro crossIInkod by covnIonf bonds, so, If Is hnrd
nnd no doformnfIon cnn fnko Inco on nIyIng forco. Whon fho forco bocomos foo Inrgo fho
covnIonf bonds nro brokon nnd If bocomos brIffIo.
Q. 16. WLy Is nutuvuI vubbev compounded?
Ans. nfurnI rubbor ossossos mnny undosIrnbIo roorfIos nnd so fo Imrovo Ifs
roorfIos If Is usunIIy comoundod wIfh dIfforonf IngrodIonfs IIko InsfIcIzors, nnfIoxIdnnfs,
fIIIor, coIornnf ofc.
Q. 1?. WLy Is nutuvuI vubbev vuIcunIzed?
Ans. !nw rubbor hns hIgh oInsfIcIfy, fnckInoss, oor chomIcnI rosIsfnnco, oor sfrongfh,
Inrgo wnfor nbsorfIon cnncIfy ofc. VuIcnnIznfIon i.e., nddIng somo suIfur nf l00C-l40C
cnusos snfurnfIon of fho doubIo bonds by S nnd honco sfIffonIng of fho oIymor fnkos Inco.
VuIcnnIznfIon, fhus, Imrovos nII fho nbovo roorfIos.
Q.1B. WLut cLunges tuke pIuce wItL poIymevs neuv gIuss tvunsItIon
tempevutuve?
Ans. IoIow fho gInss frnnsIfIon fomornfuro, fho oIymor Is brIffIo nnd nbovo If, fhoy
wouId doform buf nof bronk.
POLYMERS 467
Q. 19. How cun cvoss-IInked sIIIcone be pvoduced?
Ans. Cross-IInkod sIIIcono cnn bo roducod by nddIng n cnIcuInfod qunnfIfy of frIfuncfIonnI
mofhyI sIIIcon frIchIorIdo fo fho condonsIng oIymor.
Q. 20. WLut uve uIkyd vesIns?
Ans. Tho bnsIc roncfIon of nIkyd formnfIon Is osforIfIcnfIon. IhfhnIIc nnhydrIdo Is usod
Insfond of nn ncId nnd nIcohoI Is oIyfuncfIonnI nIcohoI, gIycoroI. Tho fInnI cross-IInkod oIymor
Is shown boIow:
O = C C = O
O O
CH
2
CH
2
CHOR CHOR
CH OH
2
CH
2
O C
O
C = O
O
CH
2
CH CH
2
O
C = O
O = C
O
C = O
OH
HOC
O
COCH
O CH OC
2
O
Alkyd resin (R = fatty acid chain)
Ieee.
As InsuInfors
As fIIm formors In emuIsIon puInts
AufomobIIo nrfs mnnufncfuro
SwIfchos mnnufncfuro.
Q. 21. WLut Is poIymetLyI metLucvyIute (Tvude nume: Pevspex)?
Ans. Horo monomor Is: MofhyImofhncryInfo
CH
2
=
CH
C COOCH
3
3
MofhyImofhncryInfo
IoIymor Is:
Properties and uses
If Is n gInss-IIko InsfIc. If Is usod for mnkIng frnnsnronf shoofs, rods ofc. nnd nIso for
mnkIng bInocuInrs, cnmorn Ionsos, fnbIo Inm shndos. If Is n comononf of enuleion poinI.
Q. 22. WLut Is poIyvInyI (Tvude nume: IevIcoI) uIcoLoI?
Ans. Monomor Is: CH
2
=CHOH (VInyI nIcohoI)
IoIymor Is: | CH
2
CH(OH)CH
2
CH(OH)CH
2
]
n
If Is n wnfor soIubIo oIymor whIch Is soff nnd gummy. If Is usod ns nn ndhosIvo.

Q. 23. WLut do you meun by bIodegvudutIon oI poIymevs?
Ans. IIodogrndnfIon Is n rocoss by whIch rofuso mIxos wIfh onvIronmonf by
mIcroorgnnIsms. ThIs bIodogrndnfIon rocoss Is comIofoIy nbsonf In fho cnso of hIgh oIymors.
ovoIomonf of bIodogrndnbIo oIymor 'bIooI` Is now n chnIIongo fo scIonfIsfs. IoIyhydroxy-
bufyrnfo Is n 'bIooI` whIch dogrndos wIfhIn n fow monfhs In soII buf If Is foo cosfIy fo bo usod
vory soon.
EXERCISES
1. WrIfo shorf nofos on (i) froo rndIcnI oIymorIznfIon (ii) cnfIonIc oIymorIznfIon (iii) sIIIcono rosIn.
2. Iscuss vnrIous mofhods of InsfIc rocossIng.
3. (o) WrIfo shorf nofos on
(i) nddIfIon oIymorIznfIon (ii) condonsnfIon oIymorIznfIon
(iii) fhormoInsfIc nnd fhormosoffIng InsfIcs (it) numbor nvorngo nnd moIocuInr woIghf.
(I) WrIfo fho sfrucfuros, fwo roorfIos nnd usos of:
(i) II, (ii) II, (iii) IVC, (it) ITII, (t) yIon 66.
4. WrIfo fho sfrucfuros of fIvo nddIfIon oIymors nnd fIvo condonsnfIon oIymors, wIfh fhoIr rosoc-
fIvo monomors.
5. IxInIn wIfh oxnmIo: (i) nddIfIon oIymorIznfIon, (ii) co-oIymorIznfIon, (iii) vuIcnnIznfIon of
rubbor.
(i) !nyon (ii) SynfhofIc rubbor (iii) Tyos of InsfIcs.
?. (o) Iscuss fho offocf of sfrucfuro of oIymors on fhoIr hysIcnI roorfIos In dofnII.
(I) CIvo fho ronrnfIon nnd roorfIos of
(i) yIon 6, (ii) oorono rubbor (iii) SI! (it) SIIIcono rubbor.
B. (o) Whnf Is n hoforochnIn oIymor CIvo ono oxnmIo.
(I) ofIno fho form funcfIonnIIfy of monomors. IxInIn Ifs sIgnIfIcnnco wIfh suIfnbIo oxnmIos.
(c) Iscuss fho ronrnfIon of bnkoIIfo nnd IVC InsfIc.
(J) Whnf nro fho funcfIons of fIIIors nnd InsfIcIzors In InsfIc Indusfry
9. Iscuss brIofIy fho nIIcnfIon of InsfIc In ongInoorIng nnd Indusfry.
POLYMERS 469
10. (o) ofIno fho forms
(i) ogroo of oIymorIznfIon. (ii) Co-oIymorIznfIon.
(I) Whnf Is fho offocf of oIymor sfrucfuro on fho sfrongfh nnd crysfnIIIno nnfuro of oIymor
(c) CIvo four usos of rubbor.
(J) Whnf nro sIIIconos rnw fho oIymor obfnInod by hydroIysIng dIchIorodImofhyI sIIIcono nnd
gIvo Ifs uso.
11. (o) IxInIn fho forms wIfh oxnmIo
(i) nddIfIon oIymorIznfIon
(ii) co-oIymorIznfIon
(iii) condonsnfIon oIymorIznfIon.
(I) CIvo nn nccounf of ono (i) Croo rubbor, (ii) bufyI rubbor.
(c) How nro fho foIIowIng roducod: (i) Iunn S (ii) fhIokoIs MonfIon fhoIr roorfIos nnd usos.
12. (o) Whnf do you undorsfnnd by vuIcnnIznfIon of rubbor Whnf nro fho ndvnnfngos nnd dIsndvnn-
fngos CIvo fho sfrucfurnI unIf of vuIcnnIsod rubbor.
(I) CIvo fho ronrnfIon nnd IndusfrInI nIIcnfIon of IVC nnd noorono.
13. (o) CIvo n brIof nccounf of vuIcnnIznfIon of rubbor.
(I) CIvo fho mnnufncfuro nnd usos of
(i) fofIon (ii) nyIon 66.
(c) Whnf Is nn Ioxy grou CIvo fho ronrnfIon nnd usos of n common Ioxy rosIn. CIvo fho
sfrucfuro of bnkoIIfo.
14. (o) OufIIno fho gonornI mofhod of ronrnfIon of urofhnnos nnd sfnfo fhoIr nIIcnfIons.
(I) !Isf ouf fho dIfforonco bofwoon HII nnd !II.
(c) WrIfo nofo on gInss roInforco InsfIc.
(J) Whnf Is monnf by comoundIng of InsfIc
15. ofIno fho form crysfnIIInIfy of oIymor. How Is If roInfod fo fho chomIcnI sfrucfuro
16. !Isf fho dIfforonco bofwoon nddIfIon nnd condonsnfIon oIymorIznfIon.
1?. oscrIbo wIfh n nonf skofch fho rocoss of comrossIon mouIdIng. How doos If comnro wIfh
InjocfIon mouIdIng
1B. (o) Iscuss fho mochnnIsm of nddIfIon oIymorIznfIon.
(I) ofIno monomor, homooIymor, cooIymor, grnff oIymor.
(c) WrIfo nofo on sIIIcono.
19. (o) Iscuss fho ronrnfIon of nnfurnI rubbor.
(I) Iscuss fho mofhods of ronrnfIon of uron-formnIdohydo rosIn nnd oIyurofhnno nnd monfIon
fhoIr usos.
(c) oscrIbo fho mofhods of ronrnfIon of noorono nnd sIIIcono rubbor. MonfIon fhoIr usos.
20. WrIfo shorf nofos on bnkoIIfo, fhIokoI.
21. (o) Whnf Is Infox How Is nnfurnI rubbor IsoInfod from If
(I) Whnf Is vuIcnnIznfIon How doos If Imrovo fho roorfy of nnfurnI rubbor
22. WrIfo ronrnfIon, roorfIos nnd usos of
(i) IhonoI-formnIdohydo rosIn, (ii) SIIIcono rubbor (iii) IoIyofhyIono.
23. IsfInguIsh bofwoon fho foIIowIng wIfh oxnmIos:
(i) nfurnI nnd synfhofIc rubbor
(ii) AddIfIon nnd condonsnfIon oIymorIznfIon
(iii) Thormo InsfIc nnd fhormosoffIng InsfIc.
24. WrIfo shorf nofos on
(i) TofIon (ii) CoIIuIoso ncofnfo (iii) SIIIcono (it) SI!.
25. (o) ofIno nnd gIvo oxnmIos for
(i) Monomor (ii) IuncfIonnIIfy (iii) ogroo of oIymorIznfIon (it) Co-oIymor.
(I) IxInIn how fho oIymors nro cInssIfIod on fho bnsIs of fhoIr fhormnI bohnvIour nnd mofhod
of oIymorIznfIon. CIvo oxnmIo of onch cInss.
26. IsfInguIsh bofwoon
(i) ThormoInsfIc nnd fhormosoffIng InsfIc.
(ii) AddIfIon nnd condonsnfIon oIymorIznfIon.
2?. WrIfo nofo on fhormoInsfIc nnd fhormosoffIng rosIn.
2B. Whnf Is nn oInsfomor
(o) WrIfo shorf nofos on ronrnfIon, roorfIos nnd usos of (i) bnkoIIfo, (ii) ooxy rosIn.
(I) nmo n oIymor confnInIng fIuorIno. CIvo Ifs sfrucfuro, roorfIos nnd usos.
29. IsfInguIsh bofwoon nyIon 6 nnd nyIon 66.
30. WrIfo shorf nofos on
(i) IoIyroyIono
(ii) IIoxI gInss.
31. CIvo ronrnfIon, roorfIos nnd usos of (i) nyIon 6, (ii) nyIon 66, (iii) oIyosfor or dncron,
(it) sIIIcono rosIn.
32. (o) Whnf nro bnkoIIfo nnd ITII nmo nny four commorcInI fhormoInsfIcs.
(I) Whnf nro fho mnforInIs from whIch nn ooxy ndhosIvo Is ronrod
33. (o) IrIng ouf fho dIfforoncos bofwoon fhormoInsfIc nnd fhormosoffIng InsfIc.
(I) IxInInVuIcnnIznfIon of rubbor.
(c) IxInInInjocfIon mouIdIng wIfh n dIngrnm.
(J) IxInIn fho chomIcnI rosIsfnnf nnd fhormnI rosIsfnnf oIymors.
34. CIvo fho rorosonfnfIvo formuIn nnd fwo Imorfnnf usos of onch of fho foIIowIng:
(i) IIoxI gInss, (ii) TofIon, (iii) IVC.
35. WrIfo n nofo on rocInImod rubbor.
36. (o) Whnf Is monnf by co-ordInnfIon oIymorIznfIon IxInIn wIfh fwo oxnmIos.
(I) WrIfo shorf nofos on (i) IInsfIc doformnfIon, (ii) MouIdIng fochnIquos.
3?. WrIfo shorf nofos on sfrucfuro, mofhod of ronrnfIon nnd usos of (i) HII, (ii) IVC, nnd (iii) IIoxI
gInss.
3B. CIvo n brIof nccounf of
(i) VuIcnnIznfIon of rubbor, (ii) ComoundIng of rubbor.
39. Whnf Is fho dIfforonco bofwoon-InsfIc, rubbor, nnd fIbro
40. WrIfo shorf nofos on (i) rnyon, (ii) nyIon, nnd (iii) dncron.
41. (o) How Is nnfurnI rubbor obfnInod from Infox
(I) IxInIn comoundIng nnd vuIcnnIznfIon of rubbor.
42. Whnf Is ZoIgIor-nffn oIymorIznfIon
43. CIvo fho sfrucfuros of syndIofncfIc, IsofncfIc nnd nfncfIc oIymors.
44. How do fho roorfIos of oIymor chnngo wIfh ZoIgIor-nffn oIymorIznfIon
45. (o) MonfIon fho fochnIcnI fosfs of oIymors.
(I) MonfIon fho InfIuonco of moIocuInr chnrncforIsfIc on fho roorfIos of oIymors.
46. Whnf Is bIodogrndnfIon of oIymors
471
2=EJI
PAINTS
InInf Is n unIformIy dIsorsod mIxfuro hnvIng vIscosIfy rnngIng from n fhIn IIquId fo n somIsoIId
nsfo nnd consIsfIng of (i) n dryIng oII, synfhofIc rosIn or ofhor fIIm formIng comononfs, (ii) n
soIvonf nnd (iii) nn orgnnIc or InorgnnIc Igmonf.
A nInf Is n roducf formuInfod fo rofocf nnd docornfo mnInIy mofnIIIc nnd woodon
surfncos. A nInf hns fhroo mnIn IngrodIonfs.
PignenIe, whIch scnffor nnd nbsorb IIghf, so fhnf fho nInf covors u fho surfnco
undornonfh nnd docornfos If wIfh coIour.
Pol,nere, whIch hoId fho Igmonf fo fho surfnco by formIng n smoofh InsfIc fIIm ns fho
nInf drIos nnd sofs.
In gIoss nInfs fho fIIm formIng oIymors nro nIkyd rosIns; In omuIsIon nInfs fhoy nro
Infox oIymors.
A teIicle, whIch Is n IIquId In whIch fho ofhor IngrodIonfs nro dIssoIvod or dIsorsod.
In gIoss nInfs n vohIcIo Is frndIfIonnIIy n hydrocnrbon soIvonf. In omuIsIon nInf If Is
wnfor.
In cnso of synfhofIc rosIns n dryIng oII (IInsood oII, fung oII, rnosood oII, musfnrd oII)
mny bo usod. Horo fIIm formIng mochnnIsm Is dIfforonf. Tho oII confnIns n Iong unsnfurnfod
fnffy ncId chnIn. Somo sorf of nfmoshorIc oxIdnfIon nnd oIymorIsnfIon occur duo fo fho
rosonco of unsnfurnfIon nnd n fIIm Is formod on fho surfnco. Tho fIIm formIng subsfnncos nro
known ns IinJere. Tho soIvonf Is known ns IIinner. Tho bIndor nnd fho soIvonf nro coIIocfIvoIy
cnIIod n teIicle. IIgmonf oxfondors nro gonornIIy cnIIod fillere. Thoy nof onIy roduco fho cosf of
nInf buf nIso oxfonds Ifs durnbIIIfy.
CH
2
OCO(CH
2
)
?
CH = CHCH
2
CH = CH(CH
2
)
4
CH
3
CHOCO(CH
2
)
?
CH = CHCH
2
CH = CH(CH
2
)
4
CH
3
CH
2
OCO(CH
2
)
?
CH = CHCH
2
CH = CH(CH
2
)
4
CH
3
ryIng oII (A gIycorIdo of IInoIonIc ncId)
Characteristics of pigments
A Igmonf Is nny subsfnnco fhnf Imnrfs coIour fo nnofhor subsfnnco.
If shouId bo onquo.
If shouId ossoss n good covorIng owor.
If shouId bo Inorf.
If shouId bo non-foxIc.
Characteristics of an ideaI paint
If shouId bo chomIcnIIy Inorf.
If shouId bo wonfhor rosIsfnnf.
If shouId bo non-foxIc.
If shouId hnvo n suIfnbIo consIsfoncy whIch Is gonornIIy doformInod by IVC.
SpeciaI types of paints
(i) IIro rosIsfnnf nInfs
(ii) ChomIcnI rosIsfnnf nInfs
(iii) !umInous nInfs.
(it) MnrIno nInfs.
(t) ImuIsIon nInfs or Infox nInfs.
(ti) MofnI nInfs.
Importance of emuIsion paints (Latex paints)
(i) If cnn bo omIoyod on bofh InforIor nnd oxforIor surfncos.
(ii) AIIcnfIon of omuIsIon nInf ovor n surfnco Is nn onsy fnsk.
(iii) If doos nof hnvo nny dIsngroonbIo roducf. And nbovo nII,
(it) If Is non-InfInmmnbIo.
PVC (Pigment VoIume Concentration)
IVC Is dofInod ns :
IVC =
VoIumo of Igmonf In nInf
VoIumo of Igmonf In fho nInf voIumo of non-voInfIIo vohIcIo In fho nInf +
Tho concof of IVC Is vory much Imorfnnf In cnso of nInfs ns IVC confroIsgloee,
rIeologicol properIiee, uoeIoIiliIiee nnd JuroIiliI, of n nInf.
Tho concof of IVC Is oxfromoIy usofuI fo n nInf formuInfor for doformInnfIon of dIfforonf
Igmonf or vohIcIo combInnfIon i.e., n rnngo of IVC shown In fho fnbIo boIow:
TabIe 21.1: Range of PVC in a given paint
Aone "PVC
(i) IInf nInfs 50?5
(ii) SomI gIoss nInfs 35-45
(iii) CIoss nInfs 25-35
(it) IxforIor houso nInfs 28-36
(t) MofnI rImors 25-40
(ti) Wood rImors 35-40
PANTS 473
TubIe 21.2: GenevuI IovmuIutIons oI puInt uve sLown In tLe tubIe
ConeIiIuenIe Cloee T,pee onJ IuncIione 1xonple
VohIcIo (i) onvoInfIIo
soIvonf bnsod.
!Insood oII, Tung oII,
ohydrnfod cnsfor oII,
IIsh oIIs, cnsoIn, AcryIIcs.
Co, Mn, Zn, Ib, nnhfho-
nnfos.
(ii) VoInfIIo i.e.,
Iow boIIIng
soIvonf bn-
sod (fhInnors)
MofhyI ofhyI kofono
(MIK).
IfhyI ncofnfo, AmyI
ncofnfo, IufyI ncofnfo.
AIIhnfIcs nhfhn nnd ofhor
ofroIoum frncfIons.
AromnfIcs XyIoI, mofhyInfod nnh-
fhnIono
IIgmonfs InorgnnIc
or OrgnnIc
(i) Onquo
(ii) Trnnsnronf
(iii) SocInI uroso
WhIfo Iond, whIfo ZnO,
TIO
2
.
!Ifhoono, chromogroon,
zInc yoIIow.
WhIfo oxfondor Igmonfs
InCO
3
. InSO
4
.
Ixfondors
or Inorfs
Infomncoous onrfh ofc. ChInn cIny, fnIc, mIcn, ofc.
Manufacturing of paints
Tho mnnufncfuro of nInfs InvoIvos onIy (i) mIxIng of fho IngrodIonfs (ii) roor grIndIng
nnd InsfIy (iii) nckIng.
Tints and
Thinners
Filling
machine
Resins
Oils
Pigments
Feed Tank
Weight
Tank
Platform scale
Mixer
Grinding mill
Tinting &
Thinning tank
Hopper
Labelling
machine
Carton
Packaging
Shipping
Belt conveyer
Fig. 21.1 A flow diagram of mixing of a paint.
OIIs nnd/or !osIns (IIIm formIng
mnforInIs rofocf fho surfnco
from wonfhorIng), rIors (nccoIo-
rnfo fho dryIng of fIIm)
AddIfIvos In cnso of omuIsIon
nInfs nro nnfIbncforInI, sfnbIIIs-
Ing surfncfnnfs nnd H ndjusfors
Isfors
Kofonos
Common pigments and their coIours
WIiIe IeJ Blue Creen Yellou Blocl Oronge Broun MeIollic
l. TIfn- l. !od l. !Ifrn l. Chrom- l. !Ifhorgo l. Cnrbon l. InsIc l. Iurnf l. Coor
nIum Iond mnrIno oxIdo bInck chromnfo Iumbor owdor
dIoxIdo
2. ZInc 2. !ougo 2. CobnIf 2. Chromo 2. !ond 2. !nm 2. CndmIum 2. ZInc
oxIdo bIuos groon chromnfo bInck ornngo owdor
3. !Ifho- 3. Iron 3. ZIno 3. Iurnnco 3. AIum-
ono bIuos chromnfo bInck InIum
owdor
4. WhIfo
Iond
EmuIsion paints
ImuIsIon nInfs nro fhoso nInfs In whIch wnfor Is usod In Inco of orgnnIc soIvonfs ns
fhInnor. ImuIsIon nInf Is nn omuIsIon of fwo hnsos vIz.:
Wnfor nnd
Tho vohIcIo of fIIm formIng mnforInI (n synfhofIc rosIn or Infox).
Tho Infox Is dIsorsod In wnfor by monns of dIsorsIng ngonf whIch ncfs ns n bIndor.
IIgmonfs nnd oxfondors nro dIsorsod In such nn omuIsIon. ImuIsIfyIng ngonf or surfnco ncfIvo
ngonfs, sfnbIIIsors, drIors, nnfIfonmIng ngonfs nnd rosorvnfIvos nro nIso nddod.
Advantages of an emuIsion paint
ImuIsIon nInfs cnn bo nIIod on fho surfnco of mofnI or wood vory onsIIy.
ImuIsIon nInfs dry quIckIy.
Moro durnbIo nnd moro ImormonbIo fo dusf nnd dIrf.
Thoy cnn bo nIIod sImIy wIfh n brush.
Tho surfnco on whIch fho omuIsIon nInf Is nIIod cnn bo onsIIy wnshod wIfh wnfor.
Thoy nro froo from fIro rIsks.
Constituents of emuIsion paints
Ieein SIoIilieer PreeertoIite AnIifooning ogenI
IoIyvInyI ncofnfo MofhyI coIIuIoso ThymoI IIno oII, Korosono
IoIysfyrono oxfrIn ChIorofhymoI
AIkyd CnsoIn MorcurIc chIorIdo
Sfnrch nIgInnfos
Manufacture of an emuIsion paint
Mnnufncfuro of omuIsIon nInfs InvoIvos foIIowIng fhroo sfos:
IrofoIn dIsorsIon
IIgmonf dIsorsIon
InInf formnfIon nnd nddIfIon of ofhor IngrodIonfs.
PANTS 475
A typIcuI composItIon oI un emuIsIon puInt
ConeIiIuenIe PorIe I, ueigII
TIfnnIum dIoxIdo 2?0
CIny ?6.8
TofrnsodIum yrohoshnfo l.8
oIonIsod wnfor l6.5
CnsoIn soIufIon ?64
SodIum onfn chIorohonnfo soIufIon l?.4
IIno oII 4.2
TrIbufyI hoshnfo l3.2
CooIymor Infox 466
Distempers
Isfomors nro wnfor nInfs comrIsIng Igmonfs, oxfondors, bIndors, nnd wnfor ns n
dIsorsIng modIum. Tho dIsfomors hnvo:
(i) Cood covorIng owor
(ii) Inso of nIIcnfIon
(iii) urnbIIIfy
DieoJtonIoge of dIsfomor Is fhnf If Is nof moIsfuro-roof.
Cement paints
Comonf nInf confnIns:
(i) WhIfo comonf,
(ii) CoIourIng or Igmonfs,
(iii) Hydrnfod IImos, nnd
(it) IIno snnds ns Inorf fIIIor.
Tho dIsorsIon modIum Is wnfor or nn oII. In cnso of brIck sfrucfuro fho dIsorsIon modIum
Is wnfor. In cnso of mofnI surfnco fho dIsorsIon modIum Is boIIod IInsood oII. Ioforo nIyIng
comonf nInf n rImor conf of n dIIufo soIufIon of sodIum sIIIcnfo nnd zInc suIhnfo Is nocossnry.
Comonf nInf hns mnrkod wnfor-roofIng cnncIfy nnd gIvos n sfnbIo nnd docornfIvo fIIm.
Varnishes
VnrnIshos nro orgnnIc comounds usod ns rofocfIvo confIng sImIInr fo nInfs. Iuf onIy
dIfforonco Is fhnf vnrnIshos do nof confnIn coIourIng subsfnncos, i.e., Igmonfs.
VnrnIshos nro cInssIfIod undor fwo honds:
OIoorosInous vnrnIshos nnd
SIrIf vnrnIshos.
OIoorosInous vnrnIshos nro fho soIufIons of ono or moro fhnn ono nnfurnI or synfhofIc
rosIns In n dryIng oII nnd n voInfIIo soIvonf. WhIIo fho sIrIf vnrnIshos nro soIufIons of rosIns In
voInfIIo soIvonfs onIy, gonornIIy mofhnnoI nnd ofhnnoI. Ior fho oIoorosInous vnrnIshos fho
formnfIon of fho fIIm Is duo fo fho oIymorIsnfIon of fho oII nnd In cnso of sIrIf vnrnIshos fho
fIIm formnfIon Is duo fo onIy soIvonf ovnornfIon.
OIoorosInous vnrnIshos nro nIso cInssIfIod ns:
(i) 'Iong oII` vnrnIshos hnvo hIgh roorfIons of dryIng oII
(ii) 'shorf oII` fyo confnIns n Iowor roorfIon of dryIng oII
(iii) 'modIum oII` confnInIng fho roorfIon of dryIng oII InformodInfo bofwoon fho fwo.
Tho cInssIfIcnfIon Is bnsod on fho uso of dryIng oII In gnIIons or l00 Ib of rosIn. Tho
fnbIo boIow rovIdos fho fyo, fIoId of nIIcnfIon nnd roorfIos of such vnrnIshos:
T,pe Dr,ing oil ProperIiee IielJ of
per 100 lI reeine opplicoIion
(i) Shorf 6-l5 gnIIon Insfor dryIng, hnrdor IIoor nnd furnIfuro
nnd moro brIffIo fIIm
(ii) ModIum 20-30 gnIIon ConornI urosos
(iii) !ong 35-60 gnIIon Moro wonfhor rosIsfnnf SnrvnrnIshos
IInbIo fIIms
ProperIiee of vnrnIshos vnry gronfIy doondIng on fho fhroo foIIowIng fncfors:
CookIng rocoduro
Tyo of dryIng oII usod
Tyo of rosIn usod
Manufacture
Tho mnnufncfurIng rocoduro doonds on fho fyo of oII nnd rosIn usod. Tho soquoncos
nro ns foIIows:
In cnso of nnfurnI rosIn, whon fho rosIn Is InsoIubIo In oII, fho rosIn Is dooIymorIsod
fIrsf by honfIng If ufo 350C fIII fonmIng consos. Tho rohonfod dryIng oII Is fhon
mIxod nnd honfod fo obfnIn fho dosIrod vIscosIfy. Tho mIxfuro Is cooIod fo 200C nnd
fhInnor nnd drIor nro nddod.
In fho cnso of synfhofIc rosIns rohonfIng Is nof roquIrod nnd fho rocoduro Is IIkowIso
ns nbovo. In oIfhor cnso fIIfrnfIon Is nocossnry.
A soIufIon of shoIInc In mofhnnoI or ofhnnoI Is roducod by sfIrrIng foIIowod by honfIng
fo roduco sIrIf vnrnIshos.
Tho fnbIo gIvon boIow furnIshos fho consfIfuonfs of n vnrnIsh (i.e., four mnIn IngrodIonfs
of n vnrnIsh):
Iiln forning
noIeriole, i.e.,
ingreJienI 1
SoltenIe onJ IIinnere,
i.e., ingreJienI 2
Driere, i.e.,
ingreJienI 3
AnIi-elinning ogenIe
i.e., ingreJienI 4
(i) OII: !Insood oII,
fung oII, coffon
sood oII, coconuf
oII, snyn oII ofc.
TuronfIno, korosono,
nIIhnfIc nnd nromnfIc
nnhfhns, xyIoI, nIco-
hoIs.
Co, Mn, Ib, Zn
rosInnfos, ocfofos ofc.
CunIncoI, forfInry
nmyI honoI.
(ii) NutuvuI vesIns:
ShoIInc, !osIn,
KnurI, ConI ofc.
(iii) SyntLetIc vesIns:
AIkyd, osfor gum,
coumnrIno-Indono,
chIorInnfod rubbor,
ncryInfos, sIIIconos
nnd vInyI rosIns.
PANTS 477
Lacquers
!ncquors nro dIsorsIon or soIufIon of n fIIm formIng mnforInI (IIko-nIfrocoIIuIoso), rosIns
nnd InsfIcIzors In soIvonfs nnd or dIIuonfs. Tho uroso of usIng of n Incquor Is for rofocfIvo
nnd docornfIvo nsocfs. Tho Incquor drIos from fho surfnco on whIch If Is nIIod by sImIo
ovnornfIon of fho voInfIIo consfIfuonfs, i.e., soIvonfs.
Tho fnbIo gIvon boIow dIsInys fho consfIfuonfs of Incquors:
Cloee MoIeriole IuncIione
l. IIIm formIng (i) CoIIuIoso dorIvnfIvo:
(i) Ifro coIIuIoso
(ii) CoIIuIoso ncofnfo
(ii) !osIns nnd gums:
(i) Isfor gum
(ii) ConI
(iii) SynfhofIc rosIns:
(i) IhonoI nIdohydo
(ii) AIkyd
Ior wnforroofnoss nnd durnbIIIfy; To
Imrovo rofonfIon of gInss, ndhosIon
nnd wnfor rosIsfnnco
(i) IfhyI ncofnfo
(ii) IufyI ncofnfo
(iii) AmyI ncofnfo
(ii) Kofonos:
(i) MofhyI ofhyI kofono (MIK)
(ii) CycIohoxnnono
(iii) AIcohoIs:
(i) IfhyI nIcohoI
(ii) IufnnoI
(iii) AmyI nIcohoI
To dIssoIvo fIIm formIng mnforInIs
2. IIgmonfs Ior IonsIng coIours
(of nddod In
cIonr Incquors)
3. SoIvonfs (i) Isfors:
4. IIuonfs (i) ConI fnr roducfs:
(i) ToIuono
(ii) Ionzono
(iii) SoIvonf nnhfhn
To roduco vIscosIfy nnd cosf
5. IInsfIcIzors (i) Cnsfor oII
(ii) IbufyI hfhnInfo
(iii) TrIcrosyI hoshnfo
To roduco fIIm brIffIonoss nnd fo
Imrovo ndhoronco
EnameIs and Japans
IIgmonfod vnrnIshos or Incquors nro known ns enonele. Jopone nro cIosoIy roInfod fo
onnmoIs. Cnrbon bInck Is nddod In doo bInck Jnnns.
InnmoIs nro brushod or srnyod on fho surfnco nnd fInnIIy hnrdonod by bnkIng. Tho
doo bInck Jnnns nro bnsod on boIIod IInsood oII nnd nro mndo by cookIng IInsood oII wIfh
IIfhnrgo nf 230C for 5 hrs. Tho roducf Is cnIIod leoJ oil. ThIs Iond oII Is mIxod wIfh korosono
(fhInnor) nnd nshnIfum. Thoso Jnnns nro nIIod nnd bnkod nf 200C for n fow hours.
A conporoIite eIuJ, of nInfs, vnrnIshos, Incquors nnd onnmoIs Is gIvon boIow:
PoinI VornieI Locquer 1nonel
l. A nInf Is n mIxf-
uro of onquo soIIds
dIsorsod In n
IIquId modIum
A vnrnIsh Is n coIIoIdnI
dIsorsIon or soIufIon of
syn-fhofIc or nnfurnI
rosIns In oIIs or
fhInnors
A Incquor Is n coIIoI-dnI
dIsorsIon or soIufIon of
fIIm formIng comound,
i.e., rosIn In n voI-nfIIo
soIvonf
InnmoIs nro Ig-
monfod vnrnIshos or
Incquors
2. !sod for rofocfIvo
nnd docornfIvo ns-
ocf
Snmo Snmo Snmo
3. ryIng Is dono by
oxIdnfIvo oIymor-
IsnfIon
ryIng by oxIdnfIvo
oIymorIsnfIon
ryIng by sImIo ovno-
rnfIon
ryIng by oIfhor oxI-
dnfIvo oIymorIsnfIon
or ovnornfIon or by
bnkIng ns or com-
osIfIon
Q. 1. WLut uve tLe IunctIons oI pIgments In u puInt?
Ans. Tho funcfIons nro
(i) To rofocf fho fIIm by rofIocfIng bnck fho dosfrucfIvo !V IIghf
(ii) To sfrongfhon fho fIIm
(iii) To Imnrf nn nosfhofIc nonI
Q. 2. Nume tLe muIn constItuents oI un oII vuvnIsL.
Ans. (i) SynfhofIc rosIns
(ii) ryIng oII
(iii) VoInfIIo soIvonfs
Q. 3. WLut Is u tonnev?
Ans. Tonnor Is nn InsoIubIo InorgnnIc dyo usod In nInfs.
Q. 4. How uve tLe puInt IIIms Iovmed?
Ans. Tho nInf fIIms nro formod by dryIng nn unsnfurnfod oII.
Q. 5. WLut Is 'dvyIng' oI un oII?
Ans. An oII Is n gIycorIdo i.e. osfor of gIycoroI nnd fnffy ncIds. A dryIng oII Is gonornIIy
gIycorIdo of unsnfurnfod fnffy ncIds. Tho mnIn funcfIon of fho dryIng oII In n nInf formuInfIon
Is fo form n rofocfIvo fIIm by comIox chomIcnI roncfIons. OfhorwIso, Jr,ing Is n chomIcnI
chnngo of nn oII nccomnnIod by oxIdnfIon nnd oIymorIsnfIon duo fo fho rosonco of
unsnfurnfIon In fho fnffy ncId orfIon of fho formuIn of dryIng oII fo form n rofocfIvo fIIm ovor
fho surfnco.
PANTS 479
Q. 6. WLut do you meun by dvIevs?
Ans. rIors nro gonornIIy honvy mofnI sons, soIubIo In oII nnd rofronfod wIfh oII
(l-2 by woIghf) fo hnsfon fho rocoss of Jr,ing by cnrryIng oxygon fo fho osIfIon of
unsnfurnfIon In oII.
Q. ?. WLut Is u veLIcIe?
Ans. In nInfs, Igmonfs nnd oxfondors nro kof susondod In n vochIcIo. Tho vohIcIos
mny bo fIIm formIng oII nnd ofhor IIquIds, for oxnmIo, furonfIno, nnhfhn ofc., usod ns dIIuonfs
or n fhInnor durIng fho nIIcnfIon of nInf.
Q. B. WLy uve pIustIcIsevs udded to u puInt?
Ans. IInsfIcIsors hoI fo roduco crnckIng In nInfs.
Q. 9. Nume some common extendevs used Is puInts.
Ans. (i) ChInn CIny
(ii) Cysum
(iii) MIcn
(it) SIIIcn
(t) TnIc.
Q. 10. WLut Is enumeI?
Ans. InnmoI Is n Igmonfod vnrnIsh.
Q. 11. By wLut meuns Is u puInt uppIIed?
Ans. (i) Iy brushIng
(ii) Iy dIIng
(iii) Iy srnyIng
Q. 12. CIte un exumpIe oI u common spIvIt vuvnIsL.
Ans. If Is n soIufIon of shoIInc, whIch Is n nnfurnIIy occurrIng rosIn, In mofhyInfod sIrIf.
Q. 13. Stute tLe composItIon oI un emuIsIon puInt.
Ans. An omuIsIon nInf consIsfs of fho foIIowIng:
(i) ry owdors of Igmonfs, fIIIors nnd oxfondors
(ii) A rosIn dIsorsIon
(iii) Surfnco-ncfIvo ngonfs
(it) IrofocfIvo coIIoIds.
Q. 14. WLut uve tLe cLuvuctevIstIcs oI un emuIsIon puInt?
Ans. ImuIsIon nInfs hnvo fho foIIowIng chnrncforIsfIcs:
(i) Inso of nIIcnfIon
(ii) Absonco of dIsngroonbIo odour
(iii) on-InfInmmbIIIfy.
Thoy cnn bo omIoyod on bofh InforIor or oxforIor surfncos.
Q. 15. WLut Is un ucvyIIc emuIsIon puInt?
Ans. ThIs Is nn omuIsIon nInf. An ncryIIc ncId dorIvnfIvo monomor Is oIymorIsod nnd
omuIsIfIod nnd fo If ofhor IngrodIonfs of fho nInfs nro nddod. Tho monomor Is gonornIIy osfor
of ncryIIc or mofhncryIIc ncId.
!oncfIons nro ns foIIows:
(o) CH CH + CO + !OH =
HCI
I(CO)
ncryIIc osfor
4
CH CHCOO!
2
(I) (CH
3
)
2
CO
HC
(CH
3
)
2
CH(OH).C
Conc. H SO
2 4
CH
2
= C COH
CH
2
3
!OH
CH
2
= C COO!
CH
3
mofhyIncryInfo
Q. 16. Stute tLe specIIIc vequIvements In puInt uppIIcutIon.

Ans. Tho roquIromonfs nro ns foIIows:
(i) HIdIng
(ii) CoIour
(iii) Wonfhor rosIsfnnco
(it) WnshnbIIIfy
(t) CIoss ofc.
Q. 1?. WLut do you meun by bukIng?
Ans. In fho cnso of smnII nrfIcIos, nInf Is nIIod by fumbIIng fochnIquo. Tho smnII
nrfIcIos nro fnkon In n bnrroI wIfh n roquIrod qunnfIfy of nInf nnd fho bnrroI Is rofnfod whIIo
fho nrfIcIos gof nInfod, fho nInfod nrfIcIos nro fhon honfod nf 400 I. ThIs honfIng Is known
ns Ioling. InkIng Imrovos ndhosIon, hnrdnoss, rosIsfnnco fo corrosIon ofc., fo nInfs.
Q. 1B. WLut Is tLe muIn dIIIevence oI IIIm IovmIng oI un emuIsIon puInt Ivom
tLut oI un ovdInuvy puInt?
Ans. In fho cnso of omuIsIon nInfs, fho fIIm-formIng mnforInIs nro vnrIous Infoxos
whorons In ordInnry nInfs, fho fIIm-formIng mnforInIs nro dryIng oIIs. In omuIsIon nInfs,
formIng of fIIm fnkos Inco by conIosconco of rosIn nrfIcIos usod ns n bnso fo form n sfrong
confInuous fIIm.
EXERCISES
1. Whnf Is n nInf
2. MonfIon fho consfIfuonfs of n nInf nnd oxInIn fhoIr funcfIons.
3. CIvo fho chnrncforIsfIcs of n good nInf.
4. WrIfo n shorf nofo on sIrIf vnrnIsh.
5. IsfInguIsh bofwoon nInf nnd vnrnIsh.
6. WrIfo n shorf nofo on omuIsIon nInf.
?. Whnf nro Incquors
B. Whnf nro onnmoIs nnd Jnnns
SoIid State Chemistry
481
SoIIds nro mnInIy chnrncforIsod by fhoIr dofInIfo shnos nnd consIdornbIo mochnnIcnI sfrongfh
nnd rIgIdIfy. Tho rIgIdIfy nrIsos duo fo fho nbsonco of fho frnnsInfory movomonf of fho sfrucfurnI
unIfs (IIko nfoms, Ions ofc.) of fho soIId. Thoso unIfs romnIn fIxod fo n monn osIfIon nbouf
whIch fhoy mny undorgo vIbrnfIon. Tho forcos of nffrncfIon bofwoon fhoso unIfs nro Inrgo
onough.
SoIIds nro gonornIIy cInssIfIod undor fwo honds, nnmoIy cvystuIIIne nnd umovpLous.
In n crysfnIIIno soIId, fho consfIfuonf nfoms nro nrrnngod In n dofInIfo nfforn consfnnfIy
roonfod nnd In consoquonco gIvIng rIso fo n dofInIfo goomofrIcnI confIgurnfIon of crysfnIIIno
soIIds. Tho crysfnIs offon hnvo n Inno frncfuro nnd fhoy nIso hnvo shnr moIfIng oInfs. On
fho ofhor hnnd fho nmorhous soIIds hnvo no dofInIfo goomofrIcnI shno. Tho nmorhous soIIds
moIf sIowIy ovor n fomornfuro rnngo.
CRYSTAL
Tho form crysfnI orIgInnfos from fho Crook word ''KrysfnIIos`` fhnf monns cIonr Ico, nnd
wns fIrsf nIIod fo frnnsnronf qunrfz sfono wIfh n wrong nssumfIon fhnf fhoso sfonos woro
formod from wnfor by oxfromo coId. In fho l?fh confury fho nnmo crysfnI wns oxfondod fo
ofhor soIIds ossossIng mnnIfosfnfIons of soIIds fhnf boro fho roInfIon fo fho orIgInnI rock crysfnIs
of boIng boundod by mnny fInf, shIny fncos, nrrnngod symmofrIcnIIy.
A crysfnI grows from moIf or n soIufIon or from gnsoous sfnfo by fho doosIfIon of nfoms
or Ions onfo Ifs surfncos by whIch crysfnIs nro boundod. Tho surfncos nro roforrod fo ns Iuces
nnd nn edge Is formod whoro fwo surfncos Inforsocf. Tho nngIo bofwoon fho normnIs fo fho fwo
InforsocfIng fncos Is cnIIod fho IntevIucIuI ungIe.
In n crysfnI fho nfoms or Ions nro nrrnngod IIko soIdIors on n nrndo ground In woII
dofInod coIumns nnd rows nnd fhIs roguInrIfy of nfomIc nrrnngomonfs In n crysfnI Is fho bnsIc
fonfuro of crysfnIs. Thoro Is n bnsIc unIf In nny ronI crysfnI nnd whon fho bnsIc unIf Is
sysfomnfIcnIIy roonfod, roroducos fho whoIo sfrucfuro. Thus fho fIrsf nofnbIo fonfuro of fho
roguInrIfy of fho crysfnI sfrucfuro Is fho orIodIcIfy of fhoIr nfforns nnd n cvystuI Is tLeveIove
u pevIodIc uvvuy oI utoms und moIecuIes In spuce.
Tho vnrIous modos of nrrnngomonf of nfoms of moIocuIos In snco fo snfIsfy fho nood of
orIodIcIfy nro govornod by somo socIfIc ruIos nnd rIncIIos whIch Iond fo fho dovoIomonf
of fho subjocf of cvystuIIogvupLy.
In n moro socIfIc wny n cvystuI muy be deIIned us u soIId substunce LuvIng u
deIInIte geometvIcuI sLupe wItL IIut Iuces und sLuvp edges.
FundamentaI Iaws of crystaIIography
CoomofrIcnI crysfnIIogrnhy Is concornod wIfh fho oufwnrd snfInI nrrnngomonf of crysfnI
Innos nnd fho goomofrIcnI shnos of fho crysfnIs nnd fhus crysfnIIogrnhy Is doondonf uon
fho fhroo foIIowIng fundnmonfnI Inws.
Iuw oI constuncy oI IntevIucIuI ungIe
Iuw oI vutIonuI IndIces, und
Iuw oI symmetvy.
Law of constancy of interfaciaI angIe or Steno's Iaw
Tho Inw sfnfos fhnf tLe ungIes between tLe covvespondIng Iuces on vuvIous
cvystuIs oI tLe sume substunce uve constunt. Tho crysfnIs of subsfnncos nro boundod by
Inno surfncos whIch nro cnIIod fncos. Thoso fncos nIwnys Inforsocf nf nn nngIo, cnIIod InforfncInI
nngIo. InforfncInI nngIo hns n chnrncforIsfIc vnIuo for n gIvon crysfnIIIno soIId.
If Is offon soon fhnf fho crysfnI fncos nro unoqunIIy
dovoIood, IondIng fo vnrIous shnos of fho crysfnIs. Iuf
fho nngIo of InforsocfIon of fho fwo corrosondIng fncos wIII
bo snmo for nny crysfnI of fho snmo subsfnnco. In IIg. 22.l,
fwo crysfnIs nro rorosonfod fwo-dImonsIonnIIy. Tho shnos
nro dIfforonf buf hnvIng fho snmo InforfncInI nngIo.
Ior oxnmIo, nCI crysfnIIIsos ns cubos from nquoous
soIufIon nnd ns ocfnhodrnI from uron soIufIon buf InforfncInI
nngIos of nII crysfnIs of nCI nro found fo bo 90.
Law of rationaI indices
In l?84 Hnuy roosod fho Iuw oI vutIonuI
IndIces ov vutIonuI Intevcepts. ThIs cnn bo
undorsfood In fho foIIowIng wny. Ior doscrIbIng fho
goomofry of n crysfnI usunIIy fhroo non-co-Innnr
co-ordInnfo nxos nro soIocfod nrbIfrnrIIy. Thoso nro
crysfnIIogrnhIc nxos. AccordIng fo fhIs Inw, fho
vutIo between Intevcepts on cvystuIIogvupLIc
uxes Iov tLe dIIIevent Iuces oI u cvystuI cun
uIwuys be vepvesented by vutIonuI numbevs.
In ofhor words, nII fncos cuf n gIvon nxIs nf
dIsfnncos from fho orIgIn, whIch bonr n sImIo rnfIo
fo ono nnofhor.
To IIIusfrnfo, Iof us consIdor n Inno AIC In
fho crysfnI ns shown boIow:
ThIs Inno hns Inforcofs OA, OI nnd OC nIong X, Y nnd Z nxos nf dIsfnncos 2o, 3I nnd
4c rosocfIvoIy, whoro O! = o, OM = I nnd O = c nro fho unIf dIsfnncos choson nIong fho fhroo
co-ordInnfos. Thoso Inforcofs nro In fho rnfIo of 2o : 3I : 4c, whoro 2, 3 nnd 4 nro sImIo
InfogrnI whoIo numbors nnd fho sfnndnrd Inforcofs nro o, I nnd c. Tho rnfIo of fho Inforcofs
In forms of fho sfnndnrd Is 2 : 3 : 4. Thoso rnfIos chnrncforIso nnd rorosonf nny Inno of fho
crysfnI. Tho cooffIcIonfs nro known ns WeIss IndIces of fho Inno gIvon. If nny Inno Is nrnIIoI
fo ono nxIs, fhon If wIII cuf If nf InfInIfy. In such cnsos fho uso of WoIss IndIcos nro rnfhor
nwkwnrd nnd hnvo consoquonfIy boon roIncod by MIIIev IndIces. Tho MIIIor IndIcos of n
Inno nro obfnInod by fnkIng fho rocIrocnIs of fho cooffIcIonfs of o, I, nnd c i.e., WoIss IndIcos
Fig. 22.1 nterfacial angle.
Z
C
Y
B
N
M
L
A
X
a
c
b
O
Fig. 22.2 ntercepts of crystallographic
planes.
a
a
SOLD STATE CHEMSTRY 483
nnd Is muIfIIIod fhroughouf by fho Ionsf common muIfIIo fo obfnIn InfogrnI vnIuos. Thus, fho
MIIIor IndIcos of fho Inno (2o : I : 2c) wIII bo
l
2
l
l
2
: :
i.e., l : 2 : l nnd fhIs Inno or fnco Is
IndIcnfod ns (l 2 l) fnco of fho crysfnI.
ow, for n Inno orondIcuInr fo ono nxIs nnd nrnIIoI fo fho ofhor fwo, hnvIng Inforcofs
o : I : c wIII hnvo IndIcos, ns:
WoIss IndIcos l : :
nnd MIIIor IndIcos l : 0 : 0 i.e., (l00) Inno.
If n Inno roducos nn Inforcof on fho nognfIvo sIdo, sny o : I : c, fho MIIIor IndIcos
for fho Inno wouId bo (l l0), fho bnr nbovo ono IndIcnfos fho InforsocfIon of fho Inno on fho
nognfIvo sIdo of fho nxIs. Tho symboI l donofos mInus unIfy.
Thus, If n fnco of n crysfnI mnkos Inforcofs OA, OI nnd OC on fho fhroo nxos, fhon fho
Iongfhs of fho Inforcofs mny bo oxrossod ns OA/o, OI/I nnd OC/c whoro, o, I nnd c nro unIf
dIsfnncos nIong fhroo nxos. Tho rocIrocnIs of fhoso Iongfhs wIII bo o/OA, I/OI nnd c/OC, nnd
fhoso rocIrocnI Inforcofs nro whoIo numbor or Infogors i.e.,
o/OA = I; I/OI = l nnd c/OC = l
whoro I, l, l nro MIIIor IndIcos of fho fnco or Inno of fho crysfnI nnd fho fnco Is dofInod ns
(Ill) fnco.
Tho dIsfnnco bofwoon fho nrnIIoI Innos In n crysfnI Is dosIgnnfod ns J
Ill
. Ior vnrIous
cubIc InffIcos, fhoso InforInnnr sncIngs nro gIvon by fho formuIn:
J
Ill
=
o
I l l
2 2 2
+ +
whoro 'o` Is fho Iongfh of fho sIdo of fho cubo nnd I, l, l nro fho MIIIor IndIcos of fho Inno.
Somo of fho MIIIor IndIcos In fho cnso of cubIc InffIcos nro shown In IIg. 22.3 boIow.
X
Y
O
Z
(0, 0, 1) plane (0, 1, 0) plane
(0, 1, 1) plane (1, 1, 1) plane
Fig. 22.3 Miller indices in the case of cubic lattices.
The Iaw of symmetry
Anofhor Imorfnnf roorfy of crysfnIs Is fhoIr symmofry. Symmofry In crysfnIs mny bo
wIfh rosocf fo : n Inno, n IIno or n oInf. Tho Inw of symmofry sfnfos fhnf: uII cvystuIs oI tLe
sume substunce possess tLe sume eIements oI symmetvy. Thoro nro fhroo fyos of
symmofry oIomonfs nssocInfod wIfh n crysfnI, nnmoIy:
Inno of symmofry
IIno of symmofry, nnd
confro of symmofry.
PIane of symmetry
A crysfnI Is snId fo hnvo n Inno of symmofry whon If Is dIvIdod by nn ImngInnry Inno
Info fwo hnIvos In such n mnnnor fhnf ono hnIf Is fho mIrror Imngo of fho ofhor.
Line of symmetry
A crysfnI Is snId fo ossoss n IIno of symmofry If If Is ossIbIo fo drnw nn ImngInnry IIno
fhrough fho confro of fho crysfnI nnd fhon fo rovoIvo fho crysfnI nbouf fhIs IIno fhrough 360 In
such n wny fhnf fho crysfnI nonrs unchnngod moro fhnn onco. Tho IIno Is cnIIod fho uxIs oI
symmetvy. If sImIInr vIow nonrs fwo, fhroo, four or sIx fImos durIng ono comIofo rovoIufIon
of 360, fho crysfnI Is snId fo ossoss fwo, fhroo, four or sIx foId nxos of symmofry.
Centre of symmetry
A crysfnI Is snId fo ossoss n confro of symmofry, If ovory fnco hns nnofhor IdonfIcnI fnco
nf nn oqunI dIsfnnco from fho confro. A crysfnI cnn hnvo onIy ono confro of symmofry.
Thoso Innos, IInos nnd confro of symmofry of n crysfnI nro cnIIod Ifs eIements oI
symmetvy. Tho cubo hns fho gronfosf symmofry oIomonfs:
(i) Ino Inno of symmofrIos
(ii) ThIrfoon nxos of symmofrIos
(iii) Ono confro of symmofry i.e., nIfogofhor fwonfy-fhroo oIomonfs of symmofry.
A
B
Three
fold axis
A
B
Four
fold
axis
A
B
Two
fold
axis
(a) (b) (c)
Fig. 22.4 Some elements of symmetry in crystals.
(=) planes of symmetry; (>) axes of symmetry; (?) centres of symmetry.
CrystaI Iattice
Tho Idon of InffIco dovoIood from fho InfornnI roguInrIfy suggosfod from fho oxfornnI
nonrnnco of fho crysfnI. A crysfnI InffIco Is n hIghIy ordorod fhroo dImonsIonnI sfrucfuro,
formod by Ifs consfIfuonf nfoms or moIocuIos or Ions. Thus n InffIco mny bo dofInod ns un
InIInIte set oI poInts vepeuted veguIuvIy tLvougL spuce.
A sof of oInfs fhnf nro roonfod nf n dIsfnnco 'o` nIong n IIno form n one-dImensIonuI
IuttIce. Whon n sof of oInfs occur roguInrIy In n Inno, If consfIfufos n two dImensIonuI
IuttIce. Whon fho sof of oInfs nro roonfod roguInrIy In fhroo dImonsIons, fho tLvee
dImensIonuI IuttIce or spuce IuttIce Is obfnInod.
a
b
a
b
a
(a)
(b) (c)
(d)
Fig. 22.5 Lattice arrangement: (=) one dimensional;
(>, ?) two dimensional; (@) three dimensional or space lattice.
On fho bnsIs of fho nrrnngomonf of sfrucfurnI unIfs In fhoIr crysfnI InffIcos, crysfnIIIno
subsfnncos nro cInssIfIod ns In TnbIo 22.l.
TabIe 22.1 Crystal systems and their characteristics
S,eIen Axiol Anglee Ao. of 1xonplee
cIorocIerieIice epoce loIIicee
l. CubIc o = I = c = = = 90 3 nCI, KCI, CsCI,

ZnS
2. TofrngonnI o = I c = = = 90 2 TIO
2
, SnO
2
3. OrfhorhombIc o I c = = = 90 4 KO
3
, K
2
SO
4
, InSO
4
,
AgIr
4. MonocIInIc o I c = = 90 2 nHCO
3
, n
2
SO
4
. l0 H
2
O,
90 monocIInIc suIhur
5. TrIcIInIc o I c 90 l CuSO
4
. 5H
2
O, K
2
Cr
2
O
?
,
H
3
IO
3
6. HoxngonnI o = I c = = 90 l SIO
2
, HgS, I, IbI
2
= l20
?. TrIgonnI o = I = c = = 90 l AI
2
O
3
, CnCO
3
, grnhIfo,
or Sb, nO
3
!hombohodrnI
90
90
90
a
a
a
90
90
90
c
a
a
90
90
90
a
a
c
90
a
a
a
a
a
120
a
a
c
90
90
a
b
a
c
g
b
a
b
a
c
Cubic Tetragonal Orthorhombic
Rhombohedral Hexagonal Monoclinic Triclinic
Fig. 22.6 The seven crystal systems or crystalline forms.
ThIs cInssIfIcnfIon Is bnsod on fho mngnIfudo of fho unIf coII Iongfh nnd fho nngIo of
IncIInnfIon bofwoon fhom. Tho unIt ceII Is fho smnIIosf buIIdIng unIf In fho snco of n crysfnI,
whIch whon roonfod ovor nnd ovor ngnIn In fhroo dImonsIons, forms n snco InffIco of fho
crysfnIIIno subsfnnco. Thus fho unIf coII Is fho ossonfInI fonfuro of fho crysfnI sfrucfuro. AII fho
crysfnI sysfoms nro mndo u of l4 fyos of crysfnI InffIco nnd fhoso crysfnI InffIcos nro known
ns IrnvnIs InffIcos, shown In IIg. 22.?.
Cubic (P) Cubic (l) Cubic (F)
Tetragonal (P) Tetragonal (I)
Orthorhombic (P) Orthorhombic (C) Orthorhombic (I) Orthorhombic (F)
Monoclinic (P) Monoclinic (C) Triclinic (C)
Trigonal (R)
Trigonal & Hexagonal (C)
Fig. 22.7 The 14 Bravais lattices.
CUBIC CRYSTALS
In n cubIc crysfnI, fho Inforcofs on fho fhroo nxos nro oqunI nnd nII fho nngIos nro oqunI fo 90.
A cubIc crysfnI cnn bo nny of fho foIIowIng fhroo fyos:
(i) SImIo crysfnI InffIco (SC)
(ii) Iody conforod crysfnI InffIco (ICC)
(iii) Inco conforod crysfnI InffIco (ICC)
(I) SImpIe CvystuI IuttIce. In sImIo crysfnI InffIco, fhoro nro InffIco oInfs nf fho oIghf
cornors of fho unIf coII. In n sImIo cubIc sfrucfuro, nn nfom sIfunfod nf nny cornor of
onch unIf, Is shnrod by n fofnI of oIghf unIf coIIs, fhus, onch unIf coII hns l/8 shnros of
ovory cornor nfom. So fho fofnI confrIbufIon of nII fho oIghf cornor nfoms fo onch coII
=
l
8
8 = l nfom/unIf coII of SC.
(a)
Simple lattice
(b)
Body centered
lattice
(c)
Face centered
lattice
Fig. 22.8 Bravais lattices of a cubic system.
1/8
atom
Fig. 22.9 Unit cell of simple cubic crystal.
(II) Body Centeved CvystuI IuttIce. In body conforod crysfnI InffIco, fhoro nro InffIco
oInfs nf fho oIghf cornors nnd nf fho confro of fho unIf coII. A IC coII hns ono nddI-
fIonnI nfom nf fho confro bosIdos hnvIng ono nfom onch Ifs rIghf cornors. Tho nfom nf
fho confro Is Indoondonf of ofhor coIIs, whIIo onch of fho oIghf nfoms sIfunfod nf fho
cornors Is shnrod by n fofnI of oIghf unIf coIIs. Thus, fho fofnI numbor of nfoms or
unIf coII
= l (nf fho confro) + 8 l/8 (nf fho 8 cornors)
= l + l = 2 nfoms/unIf coII of ICC
1/8
atom
1 atom
Fig. 22.10 Unit cell of body centered cubic.
(III) Iuce Centeved CvystuI IuttIce. In fnco-conforod crysfnI InffIco, fhoro nro InffIco
oInfs nf fho confro of nII fncos, In nddIfIon fo fhoso nf fho oIghf cornors of fho unIf
coII. An ICC hns ono nfom nf fho confro of fho onch fnco bosIdos hnvIng ono nfom nf
onch cornor. Thus, ovory nfom sIfunfod nf fho confro of n fnco of n unIf coII Is shnrod
by fwo ndjoInIng unIf coIIs. SInco fhoro nro sIx fncos of n cubo, so fhnf fofnI numbor of
nfoms or unIf coII.
= l/2 6 (nf fho confro of sIx fncos) + 8 l/8 (nf 8 cornors)
= 3 + l
= 4 nfoms/ unIf coII of ICC
1/8
atom
1/2 atom
Fig. 22.11 Unit cell of face centered cubic.
Tho orondIcuInr dIsfnnco bofwoon fho ndjnconf Innos Is known ns fho IntevpIunuv
spucIng nnd Is donofod by J
Ill
.
J
Ill
=
o
I l l
2 2 2
+ +
whoro o = sIdo of fho cubo.
Atomic radius of a cubic Iattice
AfomIc rndIus of n unIf coII mny bo dofInod ns ''hnIf fho dIsfnnco bofwoon fho confros of
fwo ImmodInfo noIghbours In n unIf coII`` nnd Is donofod by 'r`.
Tho dIsfnnco bofwoon fho confros of fwo cornor nfoms of fho cubo Is cnIIod Iongfh of fho
cubo odgo nnd donofod by 'o`.
Thus, for n sImIo cubIc (SC) coII
nfomIc rndIus r = o/2
ns wo know fhnf o = 2r
1/8 atom
2r
2r
a
Fig.22.12 Simple cubic cell.
nnd for body conforod coII (ICC)
(4r)
2
= (o
2
+ o
2
) + o
2
= 3o
2
r = 3 4 o /
4r
a
a
a
Fig. 22.13 Body centered cubic cell.
WhIIo for fnco conforod cubIc coII (ICC)
(4r
2
) = o
2
+ o
2
or l6r
2
= 2o
2
Thus r = o/2 2
r = o/ 8
4r
a
a
Fig. 22.14 Face centered cubic cell.
Radius ratio
!ndIus rnfIo Is fho rnfIo of fho cnfIon rndIus fo fhnf of fho nnIon In nn IonIc soIId. Thus, rndIus
rnfIo
=
!ndIus of cnfIon ( )
!ndIus of nnIon ( )
r
r
+
.
SoIid defects
CrysfnIs nro formod doondIng on orfocfIy roguInr nrrnngomonf of sfrucfurnI unIfs.
Iuf fhIs Idon of crysfnI Is non-oxIsfonf. In cnso of mosf IonIc crysfnIs, fho Ions nro nof nrrnngod
In n orfocf ordor nnd fhoso crysfnIs nro snId fo hnvo deIects or In ofhor words fhIs dovInfIon
mny bo rognrdod ns cvystuI ImpevIectIons.
Tho Imorfnnf ImorfocfIons or dofocfs nro of fho foIIowIng fyos:
StoIcLIometvIc deIects:
(i) ScIoIIl, JefecIe nnd (ii) Irenlel JefecIe.
Non-stoIcLIometvIc deIects ov ImpuvIty deIects.
Stoichiometric defects
(i) ScLottky eIects Thoro nro corfnIn crysfnIs Is whIch somo of fho InffIco oInfs
romnIn unoccuIod i.e., fho crysfnIs hnvo vncnncIos. On nccounf of oIocfrIcnI noufrnIIfy,
oqunI numbor of cnfIonIc nnd nnIonIc vncnncIos wouId oxIsf In fho crysfnI InffIco ns
shown In IIg. 22.l5 boIow. ThIs fyo of crysfnI dofocf Is known ns ScLottky deIect.
Such dofocf Is found In crysfnIs of nCI.
(ii) IvenkeI eIects. IronkoI dofocfs nrIso wIfh fhoso crysfnIs In whIch nn Ion Ionvos
Ifs normnI InffIco sIfo nnd occuIos nn InforsfIfInI sIfo In fho snmo crysfnI. Ior oxnm-
Io, In AgIr crysfnI somo Ag
+
Ions nro mIssIng from fhoIr roguInr osIfIons nnd nro
found fo bo squoozod bofwoon ofhor Ions.
+ + +
+ + +
+ + +
+ + +
+ + +
+ + +
+ + +
+ +
+ + +
+ + +
+ + +
+ + +
+ + +
+ +
+ + +
+ + +
+ + +
+ + +
+
Ideal Crystal Schottky defect Frenkel defect
Fig. 22.15 Defects in crystals.
Non-stoichiometric defects
IosIdos sfrucfurnI ImorfocfIons, crysfnI dofocfs mny nIso nrIso ns n rosuIf of fho rosonco
of smnII nmounf of ImurIfIos. Thoso ImurIfIos In crysfnIIIno subsfnnco drnsfIcnIIy chnngo
fhoIr roorfIos. Ior oxnmIo, If n vory smnII nmounf of CnCI
2
(Ioss fhnn 0.l) Is nddod fo
nCI, fho conducfIvIfy of nCI Incronsos by l0000 fImos. In fho mIxod crysfnI Cn
2+
Ions occuy
fho osIfIons of n
+
In crysfnI InffIco nnd fho osIfIon of CI
Ion In fho InffIco romnIns unchnngod.

Tho InsorfIon of Cn
2+
Ions for n
+
Ions Ionds fo cronfo InffIco vncnncIos nnd such vncnncIos
ormIf fho mIgrnfIon of Ions ns n rosuIf of whIch fho conducfIvIfy of Imuro crysfnI Incronsos.
Ono of fho mosf common oxnmIos for ImurIfy dofocf Is somIconducfors. ImurIfy dofocfs nro
Infroducod undor confroIIod condIfIons In gormnnIum nnd sIIIcon In fho roducfIon of
somIconducfors.
In comounds hnvIng non-sfoIchIomofrIc dofocfs, fho rnfIo of osIfIvo nnd nognfIvo Ions
dIffors from fhnf IndIcnfod In fhoIr rosocfIvo chomIcnI formuIn nnd fho bnInnco of fho osIfIvo
nnd nognfIvo chnrgos Is mnInfnInod by oxfrn oIocfron or osIfIvo Ions ns or nocossIfy. Thoro Is
nn oxcoss of oIfhor mofnI or non-mofnI nfoms In non-sfoIchIomofrIc comounds. Thus fwo cnsos
gonornfo (i) MetuI excess nnd (ii) MetuI deIIcIency.
MetuI excess mny occur In fho foIIowIng wnys:
(o) nn nnIon mny bo mIssIng from Ifs InffIco sIfo nnd nn oIocfron bo rosonf fhoro for
mnInfnInIng chnrgo bnInnco. Ior oxnmIo: whon nCI Is fronfod wIfh sodIum vnour,
such n yoIIow non-sfoIchIomofrIc vnrIofy Is obfnInod.
(I) nn oxfrn mofnI nfom mny bo rosonf In nn InforsfIfInI InffIco sIfo nnd nn oIocfron
boIng rosonf In somo ofhor InforsfIfInI osIfIon bnInncos fho chnrgo. ZnO oxhIbIfs
fhIs fyo of dofocf whon Ifs comosIfIon bocomos Zn
l+x
O. Tho froo oIocfron rosonf Is
rosonsIbIo for oxcIfnfIon fo hIghor onorgy IovoI by nbsorfIon of rndInfIon of nrfIcuInr
wnvoIongfhs. ThIs honomonon occurs whon ZnO Is subjocfod fo honfIng nnd Ifs
coIour chnngos from whIfo fo yoIIow.
MetuI deIIcIency mny nIso occur ns foIIows:
A osIfIvo Ion mny bo mIssIng from Ifs InffIco osIfIon nnd n doubIy chnrgod cnfIon
mnInfnIns fho chnrgo bnInnco. IoO, IoS nnd IO nro fho oxnmIos of such dofocf.
RoIe of SiIicon (Si) and Germenium (Ge) in the fieId of semiconductors
SemIconductovs uve tLe mutevIuIs tLut exLIbIt conductIvItIes consIdevubIy
Iowev tLun tLose oI tLe metuIs. SomIconducfors nro dofInod ns inorgonic cr,eIole rosondIng
fo oIocfronognfIvIfy whon oxcIfod by honf or oIocfromngnofIc rndInfIon. SI nnd Co In uro sfnfo
nro vory oor conducfors of oIocfrIcIfy. Howovor, ImurIfy dood SI nnd Co oxhIbIf somI-
conducfIvIfy. oIng of smnII nmounfs of grou IV or V oIomonfs Imrovos fhoIr oIocfrIcnI
conducfIvIfy nrocInbIy. Iofh In SI nnd Co, onch nfom Is covnIonfIy bondod fo four noIghbours
such fhnf nII four oufor oIocfrons of onch nro InvoIvod In bondIng.
!of us suoso nn nfom of grou V oIomonf IIko I, As, Sb or II Is Infroducod In Inco of
Co, or SI nfoms, fhon fho four oIocfrons of fhIs nfom wIII bo ufIIIzod In fho formnfIon of covnIonf
bonds nnd fho romnInIng ono wIII bo froo fo movo nnd fhus Inducos nn onhnncod conducfIvIfy.
SImIInrIy, If n grou III oIomonf IIko I, AI ofc, Is Infroducod In Inco of Co or SI, nn oIocfron
vncnncy In covnIonfIy bondod sfrucfuro wIII bo gonornfod nnd such fyo of oIocfron vncnncy Is
known ns 'LoIe'. ThIs hoIo Insfond of romnInIng confInod fo fho ImurIfy nfom, mIgrnfos
fhroughouf fho sfrucfuro whon fIIIod by nn oIocfron. So, oIocfrons nro nbIo fo movo In n crysfnI
hnvIng such oIocfron vncnncIos or hoIo nnd fhus fho crysfnI oxhIbIfs oIocfrIcnI conducfIvIfy.
SomIconducfors fhnf oxhIbIf conducfIvIfy duo fo oxcoss oIocfrons nro cnIIod n-type
somIconducfors whoro n sfnnds for nognfIvo hoIo. In ofhor cnsos, fhoro nro somo somIconducfors
In whIch oIocfrIcnI conducfIvIfy Is Imosod duo fo rosonco of osIfIvo hoIos, fhoy nro known ns
p-type somIconducfors, dIscussod Infor on.
WIfh rIso In fomornfuro fho conducfIvIfy of somIconducfors Incronso bocnuso nf hIgh
fomornfuro fho oxcoss oIocfrons or hoIos bocomo moro froo fo movo nnd so fho conducfIvIfy
Incronsos.
HIgLIIgLt:
If mny bo nofod fhnf bofh fyo of somIconducfors (n- nnd p-fyo) nro oIocfrIcnIIy
noufrnI.
Transistors (semiconductor triodes)
Tho word frnnsIsfor Is dorIvod from fwo wordsfrnnsfor nnd rosIsfor. A frIod frnnsIsfor
confnIns fwo I- juncfIon dIodos Incod bnck fo bnck. JuncfIon frnnsIsfors nro of fwo fyos:
Crown juncfIon fyo nnd
AIIoy juncfIon fyo.
Tho foIIowIng IIg. 22.l6(o) nnd (I) show n grown I--I juncfIon frIodo frnnsIsfor nnd
nn -I- juncfIon frnnsIsfor rosocffIvoIy
P P N
Emitter Base Collector
E C
B (Base)
N N P E C (Input) (Output)
(a) A PNP transistor
B (Base)
(b) An NPN transistor
(Input) (Output)
Fig. 22.16 Transistors.
IuncfIon of fho omIffor Is fo Injocf mnjorIfy chnrgo cnrrIors Info fho bnso, nnd n coIIocfor
Is fo coIIocf fhoso cnrrIors fhrough fho bnso.
AmpIIIIcutIon by u tvunsIstov (cuvvent umpIIIIcutIon ov guIn)
ConducfIon wIfhIn n II frnnsIsfor Is by hoIo movomonf from fho omIffor fo fho coIIocfor.
In nn I frnnsIsfor oIocfron movos.
Tho coIIocfor curronf Is nIwnys Ioss fhnn fho omIffor curronf i.e. 1
c
= 1
e
1
I
:
Tho curronf nmIIfIcnfIon or gnIn () of n frnnsIsfor Is,
=
coIIocfor curronf
omIffor curronf
=
1
1
c
e
( < l)
for bofh II nnd I frnnsIsfors.
Tho nIIoy juncfIon frnnsIsfor Is shown In fho foIIowIng fIguro (IIg. 22.l?).
Indium
B
N-type
germanium
E C
Fig. 22.17
Tho nIIoy juncfIon frnnsIsfor consIsfs of fwo bonds of IndIum mofnI nIIoyod on oosIfo
sIdos of n fhIn sIIco of nn -fyo Co. CoIIocfor Is Inrgor In sIzo fhnn fho omIffor.
EIements of band theory
MofnIs In gonornI nro chnrncforIsod by corfnIn dIsfIncf fonfuros, fhoso nro:
HIgh fhormnI nnd oIocfrIcnI conducfnncos, fho conducfnnco docronsos wIfh Incronso In
fomornfuro.
HIgh moIfIng nnd boIIIng oInfs In mosf cnsos.
Hnrdnoss nnd, nf fho snmo fImo, ducfIIIfy nnd mnIIonbIIIfy.
MofnIIIc Iusfro
Consfnncy
ImIssIon of oIocfrons by somo mofnIs undor fho ncfIon of honf nnd IIghf.
AII fhoso nbovo roorfIos of mofnI cnnnof bo oxInInod oIfhor by covnIoncy or by nn
IonIc modoI. Sonrnfo bondIng schomos hnvo boon roosod for fho mofnIs fo gIvo nn nccurnfo
oxInnnfIon of fho chnrncforIsfIcs of mofnI. Iuf fho bond fhoory Is fho mosf snfIsfncfory nmong
nII fho roosod fhoorIos.
Band theory
Innd fhoory rovIdos fho mosf snfIsfncfory oxInnnfIon of fho chnrncforIsfIcs of fho
mofnIIIc roorfIos In n vory nnfurnI mnnnor. Tho fhoory Is nn oxfonfIon of moIocuInr orbIfnI
(M.O.) fronfmonf for n Inrgo numbor of nfoms. Ior homonucIonr dInfomIc socIos, fho
combInnfIon of fwo nfomIc orbIfnIs gIvos rIso fo fwo moIocuInr orbIfnIs nnd fhoso nro fwo now
onorgy IovoIs for fho oIocfrons In fho fwo joInf fIoIds of fho nucIoI. If fhIs Idon Is oxfondod fo nn
nggrognfo of n Inrgo numbor of nfoms (n), onch offorIng ono orbIfnI for fho combInnfIon wIfh
ofhors, so fhoro wIII bo n fofnI of n now onorgy IovoIs sImIInr fo 'n` numbor of moIocuInr orbIfnIs
(M.O.s). Thoso Inrgo numbor of onorgy IovoIs form nn onorgy bnnd by sncIng cIosoIy ono uon
nnofhor. Tho vnIonco oIocfrons from nII fho nfoms wIII onfor ovory IovoI nnd n mofnI fhus
consIsfs of onorgy bnnds formod by morgIng of IndIvIdunI nfomIc orbIfnIs. !of us IIIusfrnfo fho
foIIowIng cnsos:
!of us consIdor !I ns nn oxnmIo. Tho oIocfronIc confIgurnfIon of n !I nfom Is le
2
, 2e
l
.
So, fwo moIocuInr orbIfnIs nro formod by fwo 2e nfomIc orbIfnIs from fwo !I nfoms. SImIInrIy
fhroo or four !I nfoms wouId gIvo rIso fo formnfIon of fhroo or four onorgy IovoIs by combInnfIon
of fhoIr 2e-nfomIc orbIfnIs. ow oxfondIng fhIs Idon for 'n`-nfoms, nII 2e-nfomIc orbIfnIs wIII
combIno fo gIvo n 2e-onorgy bnnd wIfh n-onorgy IovoIs. SImIInr combInnfIon of fho p-nfomIc
orbIfnIs wIII form n 2p onorgy bnnd confnInIng 3n-onorgy IovoIs. Inch !I nfom hns onIy ono
vnIonco oIocfron nnd fho fofnI n-oIocfrons from n-nfoms wIII occuy doubIy fho Iowor n/2 onorgy
IovoIs In fho 2e-bnnd. Whon fho oIocfrons gnIn fhormnI onorgy or nro Incod In nn oIocfrIc fIoId.
Tho oIocfrons nro rnIsod fo hIghor unfIIIod onorgy IovoIs. ThIs honomonon oxInIns fho hIgh
fhormnI nnd oIocfrIcnI conducfIvIfIos of mofnIs.
+
+
E
Combination of
4-atomic orbitals
Combination of
n Li atoms
2p band
2s band
Fig. 22.18
An Mg nfom hns fho oIocfronIc confIgurnfIon le
2
.2e
2
.2p
6
.3e
2
. Tho 3e bnnd In Mg Is oxncfIy
fIIIod by fho 2n oIocfrons of fho 'n`-Mg nfoms. Ono fInds fhnf fho 3p bnnd (formod by unoccuIod
3p nfomIc orbIfnIs of fho Mg nfoms) ovorIns fho 3e bnnd In Mg nnd fhoro Is no onorgy gn
bofwoon fho hIghosf occuIod nnd Iowosf vncnnf oIocfronIc onorgy IovoIs nnd Mg Is nn oxcoIIonf
conducfor.
3p band
3s band
Fig. 22.19 Merger of the 3I and 3F bands in Mg.
Af fomornfuros nbovo fho nbsoIufo zoro, n fow of fho oIocfrons mny bo romofod fo
onorgy IovoIs hIghor fhnn fho ncfunI occuIod rogIon In bnnds. Tho onorgy dIsfrIbufIon of fhoso
oIocfrons foIIows roughIy fho MnxwoIIIoIfzmnnn Inw. Thoso oIocfrons nro much Ioss In numbor
fhnn fho vnIonco oIocfrons nnd fhoso nro rosonsIbIo fo fho honf cnncIfy of fho mofnI nnd
honco fho confrIbufIon of oIocfrons fo fho socIfIc honf of mofnIs Is fhus smnII. ThIs concIusIon
Is In hnrmony wIfh fho uIong`s nnd IofIf`s Inw.
VaIence and conduction bands
Tho ouformosf oIocfrons of nn nfom i.e., oIocfrons rosIdIng In fho ouformosf shoII of nn
nfom nro cnIIod vnIonco oIocfrons hnvIng fho hIghosf onorgy. If Is fhoso oIocfrons whIch nro
mosfIy nffocfod whon n numbor of nfoms nro broughf vory cIoso fogofhor ns durIng fho formnfIon
of n soIId.
Tho bnnd of onorgy occuIod by fho vnIonco oIocfrons Is cnIIod fho vuIence bund nnd Is
fho hIghosf occuIod bnnd. If mny bo fIIIod by oIocfrons comIofoIy or nrfInIIy.
Tho noxf hIghor ormIffod onorgy bnnd Is cnIIod fho empty bund or conductIon bund.
In fncf, If mny bo dofInod ns fho Iowosf unfIIIod onorgy bnnd.
In conducfIon bnnd, oIocfrons cnn movo frooIy nnd fhoroforo nro known ns conducfIon
oIocfrons. Tho gn bofwoon fhoso fwo bnnds, nnmoIy vnIonco bnnd nnd conducfIon bnnd, Is
known ns IovbIdden enevgy gup.
Empty or
partially filled
Fully or
partially filled
Completely filled
inner bands
0
1
8
12
16
B
a
n
d
E
n
e
r
g
y
(
e
V
)
Conduction band
Valence band
Fig. 22.20
ow If n vnIonco oIocfron nbsorbs onough onorgy, If jums ncross fho forbIddon onorgy
gn nnd onfors fho conducfIon bnnd. An oIocfron In fho conducfIon bnnd cnn jum moro rondIIy
fo nn ndjnconf conducfIon bnnd fhnn If cnn jum bnck fo Ifs orIgInnI osIfIon. Iuf, howovor, If
fho conducfIon oIocfron rndInfos foo much onorgy, If wIII suddonIy rononr In fho vnIonco
bnnd ngnIn. If mny bo nofod fhnf fho covnIonf forcos of fho crysfnI InffIco hnvo fhoIr sourco In
fho vnIonco bnnd. So whon nn oIocfron Is rnIsod from fho vnIonco bnnd, n covnIonf bond Is
brokon nnd osIfIvoIy chnrgod hoIo Is formod. ThIs hoIo cnn frnvoI fo nn ndjnconf nfom by
fnkIng nn oIocfron from fhnf nfom, whIch InvoIvos fho bronkIng nn oxIsfIng covnIonf bond nnd
fhon ro-osfnbIIshIng n covnIonf bond by fIIIIng u fho hoIo. If hns fo bo kof In mInd fhnf hoIos
nro fIIIod by oIocfrons whIch movo from ndjnconf nfoms wIfhouf nssIng fhrough fho forbIddon
onorgy gn. ThIs Is shown In IIg. 22.2l boIow.
O
E
Conduction band
Valence band
5 4 3 2 1
Fig. 22.21
In nnofhor wny If mny bo concIudod fhnf fho condIfIons In fho conducfIon bnnd hnvo
nofhIng fo do wIfh fho hoIo fIow. If donofos n vory Imorfnnf dIsfIncfIon bofwoon fho hoIo
curronf nnd oIocfron curronf. AIfhough hoIos fIow wIfh onso, fhoy oxorIonco moro oosIfIon
fhnn oIocfron fIow In fho conducfIon bnnd.
So, fo summnrIso:
ConducfIon oIocfrons nro found In conducfIon bnnd nnd movo frooIy In fho conducfIon
bnnd.
HoIos oxIsf In nnd movo In fho vnIonco bnnd.
ConducfIon oIocfrons movo nImosf fwIco ns fnsf ns fho hoIos.
Conductors, semiconductors and insuIators
Tho bnnd fhoory of mofnIs mny bo oxfondod fo ofhor non-mofnIIIc soIIds ns woII. Tho
oIocfrIcnI conducfIon roorfIos of dIfforonf oIomonfs nnd comounds cnn bo oxInInod In forms
of oIocfrons hnvIng onorgIos In fho vnIonco nnd conducfIon bnnds. Tho oIocfrons IyIng In fho
Iowor onorgy bnnds, whIch nro normnIIy fIIIod, Iny no nrf In fho rocoss of conducfIon.
Conductors
ConducfIng mnforInIs nro fhoso In whIch fhoro Is fho nvnIInbIIIfy of Ionfy of froo oIocfrons
for oIocfrIc conducfIon.
In forms of onorgy bnnds If monns fhnf oIocfrIcnI conducfors nro fhoso whIch hnvo
ovorInIng vnIonco nnd conducfIon bnnds. In fncf fhoro Is no hysIcnI dIsfIncfIon bofwoon
fhoso fwo bnnds, honco fho nvnIInbIIIfy of n Ionfy numbor of conducfIon oIocfrons.
0
E
Conduction
band
Valence band
Overlap
16
Fig. 22.22
Anofhor oInf fo bo monfIonod Is fhnf horo fho forbIddon gn Is nof rosonf for good
conducfors. Tho fofnI curronf Is sImIy n fIow of oIocfrons.
Semiconductors
A somIconducfor Is n mnforInI whoso oIocfrIcnI roorfIos IIo In bofwoon fhoso of good
conducfors nnd InsuInfors. Ior oxnmIo gormnnIum (Co) nnd sIIIcon (SI). SomIconducfors
nro noIfhor good conducfors nor good InsuInfors, buf fhoIr oIocfrIcnI roorfIos IIo In bofwoon.
Tho rosIsfIvIfy of fho somIconducfors rnngos from l0
5
fo l0
3
ohm-cm nnd docronsos wIfh
Incronso In fomornfuro nccordIng fo nn oxononfInI Inw. ThIs Is fho mnIn dIfforonco bofwoon
somIconducfors nnd good conducfors. Tho somIconducfors whIch conducf ovon In chomIcnIIy
uro sfnfo nro cnIIod inIrineic eeniconJucIore.
In forms of onorgy bnnds, somIconducfors nro fho mnforInIs whIch hnvo nImosf nn omfy
conducfIon bnnd nnd nImosf fIIIod vnIonco bnnd wIfh n vory nnrrow onorgy gn sonrnfIng fho
fwo. Tho onorgy gn Is of fho ordor of l oV.
0
E
Conduction
band
Valence band
Small
energy gap
16
Fig. 22.23
Af 0 K, fhoro nro no oIocfrons In fho condIfIon bnnd nnd fho vnIonco bnnd Is fIIIod
comIofoIy. As fomornfuro Incronsos, fho wIdfh of fho forbIddon gn docronsos, so fhnf somo
of fho oIocfrons nro IIbornfod Info fho conducfIon bnnd. So, fho oIocfrIcnI conducfIvIfy of
somIconducfors Incronsos wIfh rIso In fomornfuro nnd In fhIs rognrd fhoy dIffor from fho
mofnIs whoso oIocfrIcnI conducfIvIfy docronsos wIfh rIso In fomornfuro. SomIconducfors nro
of fwo fyos:
Ge
Ge
.
.
Ge Ge
Ge
Covalent bond
Ge atom
G
A
B
C
D
E
F
.
.
.
.
.
.
Fig. 22.23 (a) ntrinsic Ge. Fig. 22.23 (b) Hole formation in semiconductors
(conduction of current).
(I) Puve ov IntvInsIc semIconductovs. In such somIconducfors fho onorgy gn bo-
fwoon fho vnIonco bnnd nnd conducfIon bnnd Is vory smnII (IIg. 22.23). Tho oIocfrons
jum ncross fho gn nnd honco fhoy bohnvo ns InsuInfors nf nbsoIufo zoro. Iuf fhoIr
oIocfrIcnI conducfIvIfy Is rnIsod wIfh Incronso In fomornfuro fo bronk fho covnIonf
bonds (IIg. 22.23(o)) fo gof conducfIng oIocfrons (IIg. 22.23(I)).
!of covnIonf bond Is brokon nf A wIfh Incronso In fomornfuro |IIg. 22.23(I)] nnd fho
oIocfron hns movod IonvIng bohInd n hoIo nf A whoro nn oIocfron jums from I cronfIng n hoIo
fhoro, nnd so on. Thus n nognfIvo chnrgo movos from C fo A. i.e. n osIfIvo chnrgo from A fo C
nIfornnfoIy. An InfrInsIc somIconducfor mny bo dofInod ns ono In whIch fho numbor of conducfIon
oIocfrons Is oqunI fo fho numbor of hoIos.
(II) Impuve ov extvInsIc semIconductovs. SomIconducfor bohnvIour mny nIso bo Im-
osod In corfnIn subsfnncos by fho doIIbornfo nddIfIon of ImurIfIos. Such somIcon-
ducfors nro cnIIod oxfrInsIc somIconducfors. IxnmIo, n-fyo nnd p-fyo somIcon-
ducfors (dIscussod onrIIor).
Thoso InfrInsIc somIconducfors fo whIch somo suIfnbIo ImurIfy or doIng ngonf or donnf
Is nddod In oxfromoIy smnII nmounfs (nbouf l nrf In l0
8
) nro cnIIod exIrineic or inpuriI,
eeniconJucIore.
!sunIIy doIng ngonfs nro:
onfnvnIonf nfoms (As, Sb, I) or
frIvnIonf nfoms (Cn, In, I, I).
IonfnvnIonf doIng nfom Is known ns Jonor oIon ns If donnfos ono oIocfron fo fho
conducfIon bnnd of uro Co. Tho frIvnIonf nfom, on fho ofhor hnnd, Is cnIIod occepIor nfom ns
If nccofs ono oIocfron from Co nfom.
oondIng on fho fyo of doIng ngonf, oxfrInsIc somIconducfors nro dIvIdod Info fwo
cInssos:
(i) -fyo somIconducfors
(ii) I-fyo somIconducfors.
Ge
Sb Ge Ge
Ge
excess electron
Ge
B Ge Ge
Ge
Hole
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Fig. 22.23 (c) N-type semiconductor. Fig. 22.23 (d) P-type semiconductor.
P N P
Emitter junction Collector junction
Hole flow Hole flow
V
e
0.01 mA
V
c
1 mA 0.99 mA
Base
Emitter Collector
(a) (b)
Fig. 22.23 (e) Working of a PNP transistor.
N P
Electron flow
V
e
0.01 mA
V
c
1 mA 0.99 mA
Base
Emitter Collector
(a) (b)
N
Electron flow
Fig. 22.23 (f) Working of an NPN transistor.
HIgLIIgLt. ImIffor nrrow shows fho dIrocfIon of fIow of convonfIonnI curronf.
ObvIousIy, oIocfron fIow wIII bo In fho oosIfo dIrocfIon.
InsuIators
InsuInfors nro fhoso mnforInIs In whIch vnIonco oIocfrons nro bound vory fIghfIy fo fhoIr
nronf nfoms nnd fhus roquIro n vory Inrgo oIocfrIcnI fIoId fo romovo fhom from fho nffrncfIon
of fho nucIoI.
In forms of onorgy bnnds, If monns fhnf InsuInfors nro fhoso mnforInIs whIch hnvo n fuII
vnIonco bnnd, hnvo nn omfy conducfIon bnnd nnd hnvo vory hIgh onorgy gn bofwoon fhoso
fwo bnnds (IIg. 22.24).
0
E
Empty conduction
band
Valence band
Large energy
or forbidden gap
16
Fig. 22.24
Ior conducfIon fo fnko Inco oIocfrons musf bo gIvon suffIcIonf nmounf of onorgy fo
jum from fho vnIonco bnnd fo fho conducfIon bnnd. Incronso In fomornfuro cnusos somo
oIocfrons fo movo fo fho conducfIon bnnd, whIch nccounfs for fho nognfIvo rosIsfnnco
fomornfuro cooffIcIonf of InsuInfors.
The diode as a rectifier
Whon n mofnI Is honfod If omIfs oIocfrons. ThIs honomonon Is known ns IIernionic enieeion.
Tho oIocfrons obfnInod In fhIs rocoss Is known ns IIernione. Tho curronf obfnInod by fIow of
fhormIons Is cnIIod fhormIonIc curronf. ThormIonIc fubos confnInIng fwo oIocfrodos nro cnIIod
dIodes. A tvIode hns fhroo oIcfrodos. In somo fyos of fhormIonIc vnIvos, fho oIocfrons nro
obfnInod by honfIng n mofnIIIc wIro cnIIod fho filonenI or coIIoJe.
Electrons
Filament
Fig. 22.25 Directly heated cathode.
Iy rocfIfIcnfIon, wo monn fho convorsIon of nn nIfornnfIng voIfngo fo n dIrocf voIfngo. A
dIodo ncfs ns n orfocf rocfIfIor. A sImIo cIrcuIf for obfnInIng rocfIfIcnfIon wIfh hoI of n dIodo
Is shown In IIg. 22.26.
A
F
Input A.C.
R
Output
D.C.
Fig. 22.26 Rectifier.
PhotovoItaic ceII
IhofovoIfnIc coII Is n soIf gonornfIng coII whIch ufIIIsos somIconducfor confncfs ngnInsf mofnIs.
Whon IIghf Is IncIdonf on such n combInnfIon, nn InfornnI voIfngo Is gonornfod whIch cnusos
fho curronf fo fIow fhrough InfornnI cIrcuIf, horo no oxfornnI bnffory Is noodod. Tho o.m.f.
gonornfod Is roorfIonnI fo fho rndInnf onorgy rocoIvod In soInr bnfforIos.
Iron Base
Light Ring
Transparent film
Barrier layer
Selenium
Electron
flow
A
Fig. 22.27 Photovoltaic cell.
Tho mosf common hofovoIfnIc coIIs nro of fho bnrrIor-Inyor fyo, IIko Iron-soIonIum
coIIs. In fho Iron-soIonIum coII, soIonIum Inyor Is Incod on nn Iron dIsc nnd fhon oxfromoIy
fhIn frnnsnronf fIIm of goId or sIIvor Is formod on fho soIonIum fo ncf ns fronf oIocfrodo. Tho
bnrrIor Inyor Is formod by cnfhodo sufforIng fho somI-frnnsnronf fIIm on fho soIonIum. A
confncf rIng on fho sIIvor Inyor ncfs ns ono oIocfrodo nnd fho Iron bnso ns fho ofhor.
WovkIng
Whon rndInnf fIux fnIIs on somIconducfor i.e. soIonIum, If ojocfs oIocfrons whIch frnvoI
from soIonIum fo fho fronf sIIvor oIocfrodo fhrough fho bnrrIor Inyor (IIg. 22.2?). Tho fIow In
fho oosIfo dIrocfIon Is nof ormIffod by fho bnrrIor Inyor bocnuso If ncfs ns n rocfIfIor. Tho
o.m.f. gonornfod InfornnIIy bofwoon sIIvor oIocfrodo nnd soIonIum Is dIrocfIy roorfIonnI fo
fho IncIdonf fIux.
AppIIcutIon
Tho mnIn ndvnnfngo of n hofovoIfnIc coII Is fhnf If roquIros no oxfornnI bnffory for Ifs
oornfIon, i.e. If Is soIf-gonornfIng.
Tho InfornnI o.m.f. nnd honco curronf gonornfod by If nro Inrgo onough fo bo monsurod
by n oInfor gnIvnnomofor.
Such coIIs nro usod
(o) In dovIcos IIko orfnbIo oxosuro mofors,
(I) In dIrocf rondIng IIIumInnfIon mofors nnd wIfh Iow rosIsfnnco roInys for on nnd off
oornfIons nnd
(c) In ofhor monIforIng oornfIons In IndusfrIos.
PROBLEMS
PvobIem 1. ColculoIe IIe Miller inJicee of cr,eIol plonee uIoee Weiee inJicee ore .
(o) o/2, 2I/3, c, (I) 2o/3, 2I, c/3.
SoIutIon:
(o) (I)
WoIss IndIcos l/2, 2/3, 2/3, 2, l/3
!ocIrocnI of 2,
3
2
,
l
3/2,
l
2
, 3
WoIss IndIcos
CIonr frncfIons 4, 3, 0 3, l, 6
MIIIor IndIcos (430) (3l6)
PvobIem 2. DeIernine IIe inIerplonor epocing IeIueen IIe (220) plonee of o cuIic loIIice
of lengII 40 pn.
SoIutIon. J
220
=
o
2 2 0
2 2 2
+ +
.
=
450
8
m
= l59 m.
PvobIem 3. Cloeeif, IIe follouing uniI celle inIo proper e,eIen.
(i) o = 10.S A, I = 9.47 A, c = .2 A
= 41, = S3, = 93
(ii) o = I = 10.73 A, c = 14.3 A
= = 90 onJ = 120
SoIutIon. (i) Horo o I c i.e., fho fhroo rImIfIvos nro unoqunI. AIso, no fwo nxos nro
nf rIghf nngIos fo onch ofhor. In ofhor words, fhoro Is comIofo Inck of symmofry, whIch Is
chnrncforIsfIc of frIcIInIc sfrucfuro.
(ii) Horo o = I c nnd = = 90 nnd = l20.
Thoroforo, fhIs unIf coII boIongs fo hoxngonnI crysfnI sfrucfuro (soo TnbIo 22.l).
PvobIem 4. ColculoIe IIe loIIice coneIonI of on AoCl cr,eIol (fcc). Aleo colculoIe IIe
epocing IeIueen IIe 110 plonee of AoCl cr,eIol. (giten, JeneiI, of AoCl = 2.167 g cn
3
)
SoIutIon. Wo hnvo, o
3
=
nM
whoro, o = Iongfh of fho odgo, n = no. of moIocuIos/unIf coII, = Avogndro numbor, M = moI. wf.
Horo, M = 58.46, = 6.023 l0
23
g moI
l
, n = 4, = 2.l6? gm cm
3
.
o
3
=
4 58 46
6 023 l0
23
.
.
o = 5.65 l0
8
cm = 5.65
J =
o
I l l
2 2 2
2 2 2 l/ 2
5 65
l l 0
+ +
=
+ +
.
( )
= 4 .
PvobIem 5. A IroneieIor onplifiee ouIpuI currenI 96" of IIe inpuI currenI. ColculoIe
IIe tolIoge goin onJ connenI on IIe tolIoge goin.
SoIutIon. Horo curronf gnIn =
coIIocfor curronf I
omIffor curronf I
curronf In fho oufuf cIrcuIf
curronf In fho Inuf cIrcuIf
c
e
=
= 0.96.
If ! of oufuf cIrcuIf = 2000 ohm, fhon !osIsfnnco gnIn =
2000
20
= l00
|whon ! (Inuf) = 20 .]
AccordIng fo Ohm`s Inw, V = I! ; Honco voIfngo gnIn = curronf gnIn rosIsfnnco gnIn
= 0.96 l00 = 96 V
Comment
Thus oufuf voIfngo Is 96 fImos fho Inuf voIfngo. If fho oufuf voIfngo Is nIIod fo n socond
frnnsIsfor If Is Incronsod sfIII moro. Iy IncronsIng fho numbor of frnnsIsfors fho voIfngo mny
bo Incronsod IndofInIfoIy.
EXERCISES
1. IsfInguIsh bofwoon (o) crysfnIIIno soIIds nnd nmorhous soIIds, (I) somIconducfors nnd InsuIn-
fors.
2. IxInIn: (o) Inno of symmofry, (I) confro of symmofry, (c) nxIs of symmofry.
3. IxInIn Innd Thoory.
4. IxInIn fho roIo of sIIIcon nnd gormnnIum In fho fIoId of somIconducfors.
5. IxInIn fho formsnmorhous nnd crysfnIIIno soIIds.
6. How cnn oIocfrIcnI conducfIvIfy fo mofnI bo oxInInod on fho bnsIs of bond fhoory
?. How mnny symmofry oIomonfs nro fhoro In n sImIo cubo sysfom
B. Whnf do you monn by soIId dofocf oscrIbo (o) IronkoI dofocf nnd (I) Schoffky dofocf.
9. ofIno fho Inws of crysfnIIogrnhy.
10. ofIno frnnsIsfors.
11. oscrIbo conducfors, somIconducfors nnd InsuInfors In fho IIghf of bnnd fhoory.
12. Whnf do you monn by doIng ngonf
13. Whnf Is fho ufIIIfy of doIng ngonf In n somIconducfor
14. IxInIn wIfh fho nonf dIngrnm (o) workIng of n II nnd (I) workIng nn I frnnsIsfor.
15. Whnf Is n rocfIfIor Whnf Is Ifs nIIcnfIon
16. Whnf do you monn by n hofovoIfnIc coII IxInIn Ifs workIng rIncIIo nnd usos.
1?. If donsIfy of nCI Is 2.l63 g cm
3
, fInd fho sncIng bofwoon fho Innos nrnIIoI fo fho cubIc
InffIco fncos of fho sodIum chIorIdo crysfnI (2.83 ).
1B. CnIcuInfo fho donsIfy of coor. Coor hns ICC sfrucfuro nnd InffIco consfnnf Is 3.6l unIf
(Cu=63.54) (8.98 g cm
3
).
19. Show fhnf for ICC nnd ICC crysfnIs fho InffIco consfnnfs nro gIvon by
o
ICC
=
4
3
r
o
ICC
=
4
2
r
whoro r Is fho nfomIc rndIus.
+DH=JCH=FDO
504
!
INTRODUCTION
Chromnfogrnhy Is consIdorod ns n grou of fochnIquos for fho sonrnfIon of fho comononfs
(comounds) of mIxfuros by fhoIr confInuous dIsfrIbufIon bofwoon fwo hnsos, ono of whIch Is
movIng nsf fho ofhor. Tho sysfoms nro:
A soIId sfnfIonnry hnso nnd n IIquId or gnsoous mobIIo hnso (ndsorfIon chromnfo-
grnhy, horo fho ndsorfIon by fho sfnfIonnry hnso Is fho mnIn honomonon for
sonrnfIon of fho comononfs, honco fho nnmo).
A IIquId sfnfIonnry hnso nnd n IIquId or gnsoous mobIIo hnso (nrfIfIon chromnfo-
grnhy, horo fho nrfIfIon bofwoon fho sfnfIonnry nnd mobIIo hnsos Is fho mnIn cnuso
for sonrnfIon of fho comononfs, honco fho nnmo).
A soIId oIymorIc sfnfIonnry hnso confnInIng roInconbIo Ions, nnd nn IonIc IIquId mobIIo
hnso (Ion oxchnngo chromnfogrnhy, horo fho Ion oxchnngo Is rosonsIbIo for
chromnfogrnhIc sonrnfIon, honco fho nnmo).
An Inorf goI whIch ncfs ns n moIocuInr sIovo, nnd n IIquId mobIIo hnso (goI chromnfo-
grnhy).
TIe Ioeie for IIe eeporoIion of IIe conponenIe of o nixIure no, Ie JefineJ in Ierne of
one of IIeee four noJee JeecriIeJ oIote or I, o conIinoIion.
Types of Chromatography
T,pe of cIronoIogropI, AJeorIoIe pIoee AJeorIenI pIoee
Cns-IIquId Cns !IquId
!IquId-IIquId !IquId !IquId
Cns-soIId Cns SoIId
!IquId-soIId !IquId SoIId
CoIumn Chromatography
AdsovptIon cLvomutogvupLy
Tho fochnIquo wns orIgInnIIy dovoIood by fho !ussInn bofnnIsf T.S. Woff In l906.
CHROMATOGRAPHY 505
TabIe 23.1 Adsorbents and solvents
AJeorIenI (eIoIionor, pIoee) AJeorIoIe (noIile pIoee)
Sucroso
Sfnrch
Wonk
4
5
InsuIIn
TnIc.
SodIum cnrbonnfo
CnIcIum cnrbonnfo
CnIcIum hoshnfo
ModIum
4
5
MngnosIum cnrbonnfo
MngnosIum oxIdo
CnIcIum hydroxIdo
AcfIvnfod mngnosIum sIIIcnfo
AcfIvnfod nIumInn
Sfrong
4
5
AcfIvnfod chnrconI
AcfIvnfod mngnosIn
AcfIvnfod sIIIcn
ScLemutIc vepvesentutIon oI uppuvutus Iov coIumn cLvomutogvupLy
Reservoir of
mobile phase
Mobile phase
Sand or filter
paper disc
Adsorbent
Sinter disc
Receiver
(Conical flask,
test tube etc.)
Fig. 23.1 A set-up for column chromatography.
CoIumn Characteristics
AJeorIenI/oJeorIoIe ueigII roIio 30.1
LengII/JioneIer roIio 10-1.1
CoIumn Iongfh:
(i) MuIfIcomononf sysfom !ong coIumn
(ii) Comononfs wIfh sImIInr nffInIfIos for ndsorbonf !ong coIumn
(iii) Comononfs wIfh dIfforonf nffInIfIos for ndsorbonf Shorf coIumn
IofroIoum ofhor
Cnrbon fofrnchIorIdo
CycIohoxnno
Cnrbon dIsuIhIdo
Ifhor
Acofono
Ionzono
ToIuono
Isfors
AcofonIfrIIo
ChIoroform
AIcohoIs
Wnfor
IyrIdIno
ofc.
I
n
c
r
e
a
s
i
n
g
e
l
u
t
i
n
g
p
o
w
e
r
Detection and Recovery of Components
Ior fhoso mIxfuros whIch nro coIourod, vIsunI oxnmInnfIon Is suffIcIonf.
CoIourIoss comononfs mny bo dofocfod vIsunIIy If fhoy fIuorosco normnIIy or undor
!V IIghf.
If Is usunI rncfIco fo comIofo fho chromnfogrnm by oIufIng fho vnrIous comononfs
wIfh soIvonfs. Ior coIourIoss comounds fho oIunfo Is coIIocfod ns n Inrgo numbor of frncfIons,
onch of smnII voIumo.
Advantages of CoIumn Chromatography
SonrnfIon nnd coIIocfIon of comononfs of n mIxfuro In fho uro form bofh In Inbornfory
nnd Indusfry.
Vory offIcIonf mofhod of sonrnfIon of mIxfuros of comononfs.
xumpIe. SeporoIion of leof pignenIe of epinocI leotee tic. cIloropI,ll onJ coroIenoiJe.
Paper Chromatography
Inor chromnfogrnhy Is n fyo of chromnfogrnhy In whIch fho sfnfIonnry hnso Is
wnfor In fho fIbros of nor nnd fho mobIIo hnso Is nnofhor soIvonf. urIng nor
chromnfogrnhy fho chomIcnIs In n mIxfuro porIiIion fhomsoIvos bofwoon fwo soIvonfs, tic.
wnfor nnd mobIIo soIvonf. Inch comononf In fho mIxfuro hns n dIfforonf oquIIIbrIum consfnnf
(nrfIfIon consfnnf), whIch doformInos whofhor If hns n gronfor fondoncy fo dIssoIvo In fho
sfnfIonnry hnso or In fho movIng hnso. As n rosuIf fho mIxfuro sonrnfos ns fho chomIcnIs
movo nf dIfforonf soods. Tho fochnIquo Is, fhoroforo, cIosoIy roInfod fo coIumn nrfIfIon
chromnfogrnhy.
PuvtItIon constunt (nrfIfIon or dIsfrIbufIon cooffIcIonf) Is dofInod ns: fho rnfIo of fwo
conconfrnfIons In fho fwo Inyors Is n consfnnf whon n soIId Is shnkon wIfh fwo ImmIscIbIo
IIquIds ns nn oquIIIbrIum Is sof u fo whIch fho oquIIIbrIum Inw nIIos.
K =
ConconfrnfIon of fho soIId In soIvonf I
ConconfrnfIon of fho soIId In soIvonf II
Inor chromnfogrnhy Is omIoyod fo nnnIyso mIxfuros such ns Inks, food, coIours, dyos,
nnd nmIno ncIds.
Tho movomonf of comononfs on fho nor doonds on fho nmounf nnd nnfuro of
sfnfIonnry hnso comnrod wIfh fho nmounf of mobIIo hnso In fho snmo nrf of fho nor nnd
nIso on fho nrfIfIon cooffIcIonf.
If fho condIfIons nro kof snmo, onch comononf In n mIxfuro movos n fIxod frncfIon of
fho dIsfnnco movod by fho soIvonf. Tho !
f
vnIuo for fho subsfnnco Is n monsuro of fhIs frncfIon.
!
f
Is dofInod ns:
!
f
=
Isfnnco frnvoIIod by confro of comononf
Isfnnco frnvoIIod by fho soIvonf fronf
!
f
vnIuos nro of consIdornbIo Imorfnnco In nor chromnfogrnhy nnd fhIn Inyor
chromnfogrnhy (fIc).
Thoro nro fwo fyos of nor chromnfogrnhy:
AscondIng chromnfogrnhy
oscondIng chromnfogrnhy
Tho orIgIn of fho nnmo doonds on fho nnfuro of soIvonf movomonf.
Method
AscendIng cLvomutogvupLy
A oncII IIno Is drnwn nbouf 3 cm from ono ond of fho soIocfod nor.
2-5 I voIumos of soIufIons of snmIo nnd roforonco comounds nf nbouf 2 cm InforvnIs
of fho IIno.
CHROMATOGRAPHY 507
Tho nor Is foIdod orondIcuInr fo fho IIno drnwn.
Tho odgos of fho nor nro hoId wIfh cIIs.
Tho fnnk Is ronrod by IncIng fho mobIIo hnso (nbouf l cm dofh of fho fnnk) nnd
fho IId Is Incod.
Somo fImo Is nIIowod fo snfurnfo fho fnnk wIfh soIvonf vnour.
Tho foIdod nor Is Incod In fho fnnk foIIowod by IncIng fho IId.
Tho dovoIomonf Is nIIowod fo fnko Inco i.e., oIufod unfII fho soIvonf ronchos n suIfnbIo
hoIghf (l5-20 cm).
Tho nor Is romovod, drIod nnd now comos fho quosfIon of IocnfIon of fho comononf.
Detection of components
If fho comononfs or subsfnncos In n mIxfuro nro coIourIoss fhoy nro InvIsIbIo on fho
nor. If so, fho nnnIysf hns fo 'Jetelop` fho nor or Info In cnso of fIc wIfh n suIfnbIo 'locoIing
ogenI`. Common dovoIoIng ngonfs nro (i) IodIno vnour (ii) KMnO
4
(l) (iii) bromocrosoI
groon (0.05) (it) nInhydrIn for nmIno ncId ofc. AmIno ncIds gIvo urIo sof.
Advuntuges
!nId nnd roIInbIo sonrnfIon nnd IdonfIfIcnfIon.
Tho fochnIquo mny nIso bo usod for qunnfIfnfIvo uroso.
Isudvuntuges
!nrgo scnIo sonrnfIon of comononfs Is nof ossIbIo.
TImo consumIng, If fnkos much fImo fo 'oIufo` comnrod fo fIc.
Thin Layer Chromatography (tIc)
Horo fho sfnfIonnry hnso Is n fhIn Inyor of n soIId, gonornIIy sIIIcn goI or nIumInn, on n
gInss or InsfIc Info whIIo fho mobIIo hnso Is n soIvonf. Tho rnfo nf whIch n comononf movos
u n tIc Info doonds on fho equiliIriun bofwoon ndsorfIon on fho soIId (sfnfIonnry hnso)
nnd soIufIon In fho soIvonf (mobIIo hnso). Tho osIfIon of oquIIIbrIum vnrIos from ono subsfnnco
fo nnofhor ns fho comononfs of n mIxfuro sonrnfo.
Advuntuges oI tIc
fIc Is quIck nnd chon.
OnIy n vory smnII snmIo Is roquIrod.
Tho fochnIquo Is wIdoIy usod In InbornforIos ns woII ns In IndusfrIos. If cnn bo usod
quIckIy fo chock whofhor n chomIcnI roncfIon Is fnkIng Inco ns oxocfod. urIng urIfIcnfIon
of n roducf tIc cnn IndIcnfo whofhor or nof nII fho ImurIfIos hnvo boon romovod from fho
roncfIon roducf.
etectIon oI tLe components
CoIourod comounds nro onsy fo dofocf on n fIc Info.
A quIck wny of dofocfIng fho osIfIon of n coIourIoss orgnnIc comound, fo nIIow fo
sfnnd fho Info In n covorod chnmbor wIfh IodIno crysfnIs. Tho IodIno Is nbsorbod by
fho comound gIvIng coIourod sofs.
Ofhor mofhods such ns srnyIng wIfh corfnIn rongonfs nro nIso omIoyod.
AIfornnfIvoIy n fIc Info mny bo Imrognnfod wIfh n fIuorosconf chomIcnI. Whon fho
Info Is Incod undor n !V Inm fho whoIo Info gIows oxcof In fho nrons whoro orgnnIc
comounds nbsorb rndInfIon, so fhnf fhoy nro Iocnfod ns dnrk sofs.
!
f
vnIuos nro usod fo rocord fho dIsfnncos movod by comononf chomIcnIs of n mIxfuro
roInfIvo fo fho dIsfnnco movod by fho soIvonf.
GenevuI metLod
Tho sIzo of fho gInss Info Is 20 20, 20 l0, or 20 5 cm.
30 g of ndsorbonf (sfnfIonnry hnso, gonornIIy sIIIcn goI) Is mndo fo n smoofh nsfo wIfh
roquIsIfo nmounf of wnfor or soIvonf socIfIod (ronrnfIon of chromnfoInfo).
Tho sIurry Is quIckIy ourod fo n srondor or nIIcnfor nnd Is srond (fhIcknoss
0.25 mm).
Tho sIurry Is nIIowod fo sof for 3-4 mIn.
Tho Info Is frnnsforrod fo n drIor nnd nIIowod fo dry for l hr.
Tho Info Is frnnsforrod fo n dosIccnfor ovor sIIIcn goI.
Sofs nro gIvon ns usunI.
IIufod wIfh mobIIo hnso In n chromnfogrnhIc chnmbor.
Tho soIvonf Is drIod, fho Info Is dovoIood nnd fho sofs nro Iocnfod.
!
f
Is monsurod fo IdonfIfy fho comononfs, e.g., !
f
for !-IysIno Is 0.l4, !-nInnIno Is
0.36 nnd !-IoucIno Is 0.65.
High Performance Liquid Chromatography (hpIc)
hIc Is n sohIsfIcnfod fochnIquo of IIquId chromnfogrnhy. Tho mobIIo hnso Is n soIvonf
of vory hIgh urIfy. Tho sfnfIonnry hnso consIsfs of vory smnII nrfIcIos of n soIId (sIIIcn goI)
nckod Info n Iong sfooI fubo. Tho uso of fIno nrfIcIos Incronsos fho surfnco nron hoIIng fo
sonrnfo fho comononfs In n mIxfuro offIcIonfIy. A um rovIdos vory hIgh rossuro (l-550
bnr, 0.l-55 Mn, l4.6-8000 .s.I) fo mnInfnIn n fIow rnfo of mobIIo hnso nf fho rnfo of
0.0l-l0 mI mIn
l
. Tho mnforInI (l5-25 I) fo bo chromnfogrnhod Is Injocfod fhrough n sofum
Info fho confro of fho nckIng mnforInI wIfh fho hoI of n syrIngo. VnrIous fyos of dofocfors
nro usod.
Ono nIIcnfIon of LpIc Is fo sfudy fho fnfo of drugs ndmInIsforod In fho body.
Gas-Iiquid Chromatography (gIc)
gIc Is n sonsIfIvo nnnIyfIcnI fochnIquo for nnnIysIng nixIuree of liquiJe. In n modorn gns-
IIquId nnrnfus, fho sfnfIonnry hnso Is n fhIn fIIm of IIquId ndsorbod on fho InsIdo surfnco of
n coIIod cnIIInry fubo of nbouf 30 m Iong InsIdo nn ovon. SnmIo fo bo nnnIysod Is Injocfod Info
fho hof coIumn wIfh fho hoI of n syrIngo. Tho mobIIo hnso Is n gns, whIch cnrrIos fho vnours
of fho snmIo mIxfuro fhrough coIumn. Tho comononfs In fho mIxfuro sonrnfo ns fhoy nss
fhrough fho coIumn. Tho comononfs nro dofocfod ns fhoy como ouf nnd fho sIgnnI dofocfor Is
fod fo n chnrf rocordor.
Tho chnrf rocordor shows how Iong If fnkos for onch comononf of fho mIxfuro fo nss
fhrough fho coIumn. ThIs fImo Is cnIIod rofonfIon fImo (I
r
).
Dried carrier
gas in
Replaceable
silicon rubber
septum
Injector port
Injector oven
Column oven
Column
Exit
Detector
Recorder
Fig. 23.2 The main features of gas-liquid chromatography.
CHROMATOGRAPHY 509
Tho nrons undor fho onks on fho rInf ouf gIvo n monsuro of fho roorfIons of fho
comononfs of fho mIxfuro.
A gIc mnchIno cnn bo cnIIbrnfod by InjocfIon of known nmounf of comounds nnd rocordIng
fhoIr rofonfIon fImos.
AppIication of gIc
(i) Sourco of oII oIIufIon from fho nfforn of onks whIch ncfs IIko n fIngorrInf for nny
bnfch of oII.
(ii) MonsurIng fho IovoI of nIcohoI In urIno nnd bIood snmIos.
(iii) ofocfIon nnd monsuromonf of osfIcIdos In fho rIvor wnfor.
Gas Chromatography (gc)
Tho sonrnfIon of fho comononfs In n mIxfuro In fho gnsoous sfnfo nchIovod by nrfIfIon
coIumn chromnfogrnhy usIng n gnsoous mobIIo hnso wns fIrsf suggosfod by MnrfIn nnd Syngo
In l94l.
Tho fochnIquo roquIros fho vnourIsnfIon of fho snmIo, whIch Is cnrrIod fhrough n
ronrod coIumn, nf n suIfnbIo fomornfuro by n sfronm of cnrrIor gns (mobIIo hnso). urIng
fho nssngo of fho vnour of fho snmIo fhrough fho coIumn, sonrnfIon of fho comononfs of
fho mIxfuro fnkos Inco by ndsorfIon offocfs If fho ronrod coIumn Is of ndsorbonf onIy.
If fho nrfIcIos of ndsorbonf nro confod wIfh n IIquId whIch forms n sfnfIonnry hnso
fhon nrfIfIon offocfs fho sonrnfIon rocoss. If Is boffor fo uso fho form eupporI for fho IIquId
hnso rnfhor fhnn oJeorIenI ns ndsorfIon offocfs nro undosIrnbIo In nrfIfIon coIumns.
If Is ossonfInI fhnf fho snmIo Is sfnbIo whon vnourIsod nnd durIng Ifs nssngo fhrough
ronrod or pocleJ colunn (nckod wIfh hIgh oIymor bonds) In ordor fo nvoId docomosIfIon
of roducfs nnd fho rosonfnfIon of n comIox chromnfogrnm ns fho cnrrIor gns oIufos fho
roducfs of fho coIumn.
Tho bnsIc nnrnfus for gc Is shown dIngrnmmnfIcnIIy.
Carrier gas
supply
(Ar, He, N )
2
Flow regulator
Injection point
Detector
Flow meter
Amplifier
Recorder
Column in thermostatically
controlled oven
Fig. 23.3 gc apparatus.
HIgLIIgLt:
Nevnst's IsotLevm:
K
A
=
C
C
e
n
whoro K
A
= consfnnf of dIsfrIbufIon of comononf A nf n gIvon fomornfuro.
C
e
= conconfrnfIon of comononf In sfnfIonnry hnso (Adsorbonf)
C
n
= conconfrnfIon of comononf In mobIIo hnso (Adsorbnfo)
Some puvumetevs oI gc
RetentIon tIme. If rofors fo fho fImo fnkon by fho comononf fo bo oxfrncfod from fho
coIumn nnd nrrIvo nf fho dofocfor. If Is monsurod on fho nbscIssn of fho chromnfogrnm
from fho sfnrf fo fho mnxImum onk.
RetentIon voIume. If rofors fo fho voIumo of fho soIvonf fhnf Is roquIrod fo oxfrncf n
comononf nnd brIng If fo fho dofocfor. If Is monsurod from fho sfnrf fo fho mnxImum
of fho onk on fho nbscIssn of chromnfogrnm.
CLvomutogvum. If Is n voIumo/sood curvo whIch IIIusfrnfos n chromnfogrnhIc
sonrnfIon. Tho conconfrnfIon comononf Is found fo bo roorfIonnI fo fho sIgnnI. Tho
sIgnnI IIIusfrnfos fho rogross of n chromnfogrnhIc sonrnfIon.
0 1 2
Start
A
Volume or time
of retention
S
i
g
n
a
l
(
C
o
n
c
e
n
t
r
a
t
i
o
n
)
Fig. 23.4 Chromatogram.
SepuvutIon Iuctov ():
=
K
K
A
I
whoro K
A
nnd K
I
nro fho consfnnfs of dIsfrIbufIon of fwo comononfs A nnd I rosocfIvoIy.
IIIcIency. If rofors fo fho cnncIfy of coIumn fo sonrnfo fho comononfs.
ResoIutIon. If rofors fo fho cnncIfy of n coIumn fo sonrnfo fwo consocufIvo onks of
n chromnfogrnm.
CHROMATOGRAPHY 511
EXERCISES
1. Whnf Is chromnfogrnhy
2. WrIfo nofos on ndsorfIon nnd nrfIfIon chromnfogrnhy.
3. Whnf Is monnf by !
f
In chromnfogrnhy
4. Whnf nro fho ndvnnfngos nnd dIsndvnnfngos of nor chromnfogrnhy
5. Whnf Is fhIn Inyor chromnfogrnhy (tIc)
6. MonfIon fho ndvnnfngos of tIc.
?. Whnf Is coIumn chromnfogrnhy MonfIon Ifs Imorfnnco.
B. Whnf nro:
(o) LpIc (I) gIc (c) gc?
InstrumentaI Methods of AnaIysis
512
"
INTRODUCTION
Tho fIoId of socfroscoy Is dIvIdod Info fwo mnIn cInssos:
(I) mIssIon spectvoscopy
(II) AbsovptIon spectvoscopy
An omIssIon socfrum Is obfnInod by somo IIghf sourco such ns n fInmo or nn oIocfrIc nrc.
ThIs socfrum Is duo fo fho oxcIfnfIon of nfoms by fhormnI or oIocfrIcnI monns. In cnso of
nbsorfIon socfroscoy onorgy nbsorbod cnusos oIocfrons In n ground sfnfo fo bo romofod fo
n hIghor oxcIfod sfnfo. Tho IIfo-fImo of oIocfrons In fhIs oxcIfod sfnfo Is shorf nnd fhoy rofurn fo
oIfhor n Iowor oxcIfod sfnfo or fo fho ground sfnfo. Tho nbsorbod onorgy Is roIonsod ns IIghf.
IIuorosconf IIghfs nnd coIours obfnInod by honfIng snIfs of corfnIn oIomonfs In n fInmo nro vory
common oxnmIos of enieeione epecIro. In somo cnsos fho oxcIfod sfnfos mny hnvo nrocInbIo
IIfo-fImos. In fhoso cnsos fho oxcIfod sfnfos usunIIy hnvo nrocInbIo IIfo fImos nnd omIssIon of
IIghf sfnrfs nffor oxcIfnfIon hns consod. Such n honomonon Is cnIIod pLospLovescence.
An nbsorfIon socfrum Is obfnInod by IncIng fho subsfnnco bofwoon fho socfromofor
nnd somo sourco of onorgy, usunIIy If Is nn oIocfromngnofIc rndInfIon whIch Is nIIod. Tho
socfromofor nnnIysos fho frnnsmIffod onorgy roInfod fo fho IncIdonf onorgy for n gIvon
froquoncy of fho oIocfromngnofIc rndInfIon. Tho rogIons of oIocfromngnofIc rndInfIon of gronfosf
Inforosfs fo fho orgnnIc chomIsfs nro 200-400 m (uIfrnvIoIof), 400-800 m (vIsIbIo), nnd 2-l6
(Infrnrod).
Tho mochnnIsms of nbsorfIons of onorgy nro dIfforonf In fho uIfrnvIoIof, Infrnrod nnd
nucIonr mngnofIc rosonnnco rogIons, buf fho fundnmonfnI honomonon Is fho nbsorfIon of n
corfnIn nmounf of onorgy. Tho onorgy nbsorbod Is gIvon by
I = I
whoro I Is IInnck`s consfnnf nnd Is fho froquoncy of IncIdonf IIghf (In cycIos or socond, cpe).
Is roInfod fo fho wnvoIongfh ns foIIows,
=
c
whoro c Is fho voIocIfy of IIghf, Is fho wnvoIongfh In cm.

Tho wnvo numbor Is nIso usod In fho doscrIfIon of socfrn. Tho wnvo numbor l Is
roInfod fo by
l =
l
i.e., l Is fho wnvo numbor In cm

l
.
NSTRUMENTAL METHODS OF ANALYSS 513
InforrofnfIons of moIocuInr socfrn by fho orgnnIc chomIsfs nro bnsod InrgoIy on
omIrIcnI corroInfIons wIfh oxfonsIvo comIInfIons of dnfn. Af fho rosonf fImo, fho vnrIous
socfrnI mofhods nro fho moro commonIy usod hysIcnI mofhods. AbsorfIon of uIfrnvIoIof nnd
vIsIbIo IIghf Is chIofIy cnusod by oIocfronIc oxcIfnfIon; fho socfrum rovIdos IImIfod InformnfIon
nbouf fho sfrucfuro of fho moIocuIo. AbsorfIon In fho Infrnrod rogIon Is duo fo moIocuInr
vIbrnfIons of ono kInd or nnofhor; fho socfrum Is gonornIIy vory comIIcnfod nnd confnIns
mnny nbsorfIon onks, roInfIvoIy fow of whIch cnn bo Inforrofod wIfh n hIgh dogroo of
nssurnnco. On fho ofhor hnnd, fho rofon mngnofIc rosonnnco (pnr) of n comound owIng fo
nucIonr sIn frnnsIfIons cnn usunIIy bo comIofoIy Inforrofod, nnd If rovIdos InformnfIon
nbouf fho numbor, nnfuro, nnd onvIronmonf of nII fho rofons In fho moIocuIo.
\ItvuvIoIet spectvoscopy
A rogIon of oIocfromngnofIc rndInfIon whoso InforncfIon wIfh n moIocuIo gIvos rIso fo
oIocfronIc frnnsIfIon oxIsfs nf l00-8000 (l0-800 m).
VisibIe Light and EIectromagnetic Spectrum
10
3
10
1
10 10
3
10
5
10
7
10
9
10
11
Cosmic rays X-rays
UV IR
Microwaves Radiowaves
Violet Indigo Blue Green Yellow Orange Red
370 430 450 490 550 590 600 750
Nanometers
Fig. 24.1 Wavelengths of electromagnetic radiation.
Tho fofnI onorgy (I
T
) of n dInfomIc moIocuIo Is fho sum of oIocfronIc onorgy (
e
),
vIbrnfIonnI onorgy (
t
) nnd rofnfIonnI onorgy (
r
), i.e.,
I
T
=

e
+
r
+
t
If fho oIocfromngnofIc rndInfIon In fho rogIon of l0-800 m Inforncfs wIfh n moIocuIo, n
chnngo In fho onorgy of fho moIocuIo from fho ground sfnfo fo n hIghor IovoI i.e., oxcIfod sfnfo
occurs. Tho frnnsIfIon of onorgy, duo fo fho dIsIncomonf of n vnIonco oIocfron nccomnnIod by
fho oIocfronIc oxcIfnfIon, Is n chnngo In
t
nnd
r
of fho moIocuIo. Tho onorgy roquIromonfs for
fho oxcIfnfIon of fho Inffor fwo modos Is comnrnfIvoIy Ioss fhnn fhnf for oIocfronIc oxcIfnfIon.
Some terms concerning UV
CLvomopLove: A moIofy of n moIocuIo whIch Is rosonsIbIo for soIocfIvo nbsorfIon of
rndInfIon In n gIvon rnngo of socInIIy !V or vIsIbIo rogIon.
AuxocLvome: A chomIcnI grou whIch doos nof gIvo rIso fo nn nbsorfIon bnnd by
IfsoIf, buf uon boIng nffnchod fo n chromohoro nIfors bofh fho osIfIon nnd InfonsIfy of fho
nbsorfIon onk.
ButLocLvomIc sLIIt: If Is n shIff of fho onk osIfIon (
mnx
) fo n hIghor wnvoIongfh duo
fo fho offocf of n subsfIfuonf grou or soIvonf, If Is nIso known ns rod shIff.
HypsocLvomIc sLIIt: If Is n shIff of
mnx
fo Iowor wnvoIongfh. If Is nIso known ns bIue
sLIIt.
HypevcLvomIc und LypocLvomIc eIIects: Thoso forms rofor fo nn Incronso nnd
docronso In nbsorfIvIfy of fho moIocuIo rosocfIvoIy.
Types oI ubsovptIon bunds: Thoro nro four fyos of nbsorfIon bnnds. Thoy occur duo
fo oIocfronIc frnnsIfIon of n moIocuIo.
(i) R-bunds: Thoso nro obsorvod In comounds confnInIng such grous ns C = O,
O
2
ofc. Thoy InvoIvo n * frnnsIfIon. Tho
mnx
vnIuo Is Ioss fhnn l00. Tho bnnd
nf 2?9 m obsorvod In fho !V socfrum of ncofono Is nn oxnmIo of nn !-bnnd.
(ii) K-bunds: Thoso nrIso from
*
frnnsIfIon In conjugnfod sysfoms nnd show
mnx
gronfor fhnn l0,000. l,3,5-hoxnfrIono Is nn oxnmIo of such n conjugnfod sysfom.
(iii) B-bunds: Thoso nro duo fo nromnfIc nnd hoforochromnfIc sysfoms. Tho
mnx
vnIuos
nro bofwoon 230-2?0 m nnd
mnx
Ioss fhnn 2000. Thoso bnnds nro cnIIod benzenoId
bunds. In fho rosonco of K-bnnds fho osIfIon of fho I-bnnd Is shIffod fo Inrgor
wnvoIongfhs. Tho !V socfrum of bonznIdohydo confnIns K, ! nnd I bnnds.
(it) -bunds: Thoso nro nIso known ns ofhyIonIc bnnds nnd nro chnrncforIsfIc of fho
nromnfIc sysfoms ns nro fho I-bnnds. OnIy dIfforonco Is: fhoy occur nf Iowor wnvo-
Iongfhs.
Tho rosonco of nn nuxochromIc grou shIffs nn I-bnnd fo n hIghor wnvoIongfh. Tho
mnx
vnIuos of fhoso bnnds vnry from 2000-l4000. Tho bnnds nf 2l0 m wIfh
mnx
of 6200 for
honoI Is nn oxnmIo of I-bnnd.
InstvumentutIon Iov \V spectvum
Fig. 24.2 A simplified diagram.
RudIutIon souvce. Tho sourco for fho !V rnngo Is usunIIy hIgh rossuro hydrogon or
douforIum dIschnrgo Inm, whIch covors n rnngo of 200-3?5 m. A xonon nrc or, n morcury
Inm rovIdos n moro Infonso rndInfIon. Tho sourco omIoyod for fho vIsIbIo rnngo Is 6 or l2V
fungsfon nufomobIIo hond Inm buIb. !V Is n Iof of nbsorbnnco vs. wnvoIongfh.
AppIications of UV in anaIyticaI chemistry
Tho workIng formuIn:
A = I c
Is dorIvod from !nmborf-Ioor`s Inw, whoro A Is fho nbsorbnnco, I Is moInr oxfIncfIon cooffIcIonf,
I Is fho nfh Iongfh In cm nnd c Is moInr conconfrnfIon (moI I
l
). Tho nbsorbnnco vnIuos of fho
sfnndnrd soIufIons of known conconfrnfIons nro doformInod from fho socfrohofomofor nnd n
cnIIbrnfIon grnh Is consfrucfod. Absorbnnco vnIuo of fho fosf soIufIon Is doformInod from fho
Insfrumonf nnd fho conconfrnfIon of fho fosf soIufIon Is doformInod from fho cnIIbrnfIon grous.
s*
p*
p
s
C C
*
vac UV
Alkane 140-50
s p
C = C
*
160-180 m
p p
C = O
* 180 m
n * 275 m
n * 150 m
(Ketone)
p p m
p m
s m
C = CC = C
*
217 m
p p
m
2 3
p
1
p
2
p
3
*
p
4
*
E
n
Fig. 24.3 Energy diagram for the electronic transitions.
Conjugated systems
If fwo or moro chromohorIc grous nro rosonf In n moIocuIo nnd fhoy nro sonrnfod by
fwo or moro sIngIo bonds, fho offocf on fho socfrum Is nddIfIvo. Iuf fhoro Is IIffIo oIocfronIc
InforncfIon bofwoon IsoInfod chromohorIc grous. Tho
mnx
vnIuos for , unsnfurnfod kofonos,
, unsnfurnfod nIdohydos nnd conjugnfod dIonos bonr nn oxcoIIonf numorIcnI corroInfIon
doondIng on fho numbor of subsfIfuonf grous. Tho ruIos for cnIcuInfIon of
mnx
vnIuos of
such comounds nro roInfIvoIy vory sImIo nnd Is oxomIIfIod boIow:
CaIcuIation of
max
vaIues
Iov , unsutuvuted ketones:
(i) In ordor fo cnIcuInfo fho nbsorfIon (
mnx
) of nn , unsnfurnfod kofonos n bnso
vnIuo of 2l5 m Is nssIgnod.
(ii) Ior onch -subsfIfuonf l0 m nro nddod fo fho bnso vnIuo.
(iii) Ior onch subsfIfuonf l2 m nro nddod fo fho bnso vnIuo.
(it) Ior onch rIng sysfom (6 or 5 momborod) fo whIch fho cnrbon-cnrbon doubIo bond Is
oxocycIIc 5 m nro nddod fo fho bnso vnIuo.
(t) If fho cnrbon-cnrbon doubIo bond nnd fho cnrboxyI grou nro In n fIvo-momborod
rIng l0 m subfrncfod from fho cnIcuInfod vnIuo nnd If onIy fho cnrbon-cnrbon
doubIo bond Is In n fIvo momborod rIng 5 m Is nddod.
Tho corroInfIon of cnIcuInfod vnIuos nnd oxorImonfnI vnIuos Is wIfhIn n ormIssIbIo
IImIf.
xumpIe 1.
C = CC = O
b
b
a
R
a b , -unsaturated ketone
MofhyI-vInyI-kofono:
C = CC = O
CH
3
H
H
H
In fhIs cnso, fhoro Is no nnd subsfIfuonf. Horo bnso vnIuo Is 2l5 m nnd no nddIfIons
nro roquIrod nccordIng fo ruIo. So, fho cnIcuInfod
mnx
vnIuo Is 2l5 m. Tho obsorvod vnIuo Is
2l3 m.
xumpIe 2.
2-MofhyI-l-bufono 3 ono
H CCC = CH
3 2
C = CC = O
CH
3
O
CH
3
H
H
CH
3
Horo, bnso vnIuo Is 2l5 m,
Ior -subsfIfuonf +l0 m Is nddod.
CnIcuInfod
mnx
vnIuo = 225 m.
Tho obsorvod vnIuo Is 220 m.
xumpIe 3.
3-onfono-2-ono.
H CHC = CCCH
3 3

H H
CH
3
CH C = CC = O
3
b
a
H O
Horo, bnso vnIuo Is 2l5 m
Thoro Is no subsfIfuonf + 0 m
Ior ono subsfIfuonf + l2 m
CnIcuInfod
mnx
vnIuo = 22? m.
Obsorvod
mnx
vnIuo = 224 m.
xumpIe 4.
3-MofhyI-3 onfono-2 ono.
H CC = CCCH
3 3

CH C = CC = O
3
H CH
3
O H CH
3
b
a
CH
3
Horo bnso vnIuo Is 2l5 m
Ior ono subsfIfuonf + l0 m Is nddod
Ior ono subsfIfuonf + l2 m Is nddod.
CnIcuInfod
mnx
vnIuo = 23? m.
Obsorvod
mnx
vnIuo = 236 m.
xumpIe 5.
2,3-dI mofhyI-2 onfono-4 ono.
H CCC = CCH
3 3

C = CC = O
CH
3
CH
3
O CH
3
CH
3
CH
3
b
a
CH
3
Horo, bnso vnIuo Is 2l5 m.
Ior ono subsfIfuonf + l0 m.
Ior onch subsfIfuonf (2 l2) = + 24 m
CnIcuInfod
mnx
vnIuo = 249 m.
Obsorvod
mnx
vnIuo = 246 m.
xumpIe 6.
If Is nn , unsnfurnfod kofono.
Horo, fho bnso vnIuo Is 2l5 m
Thoro Is no -subsfIfuonf + 0 m
Ior onch -subsfIfuonf + 24 m
Ior onch rIng fo whIch
fho doubIo bond Is oxocyIIc + 5 m
CnIcuInfod
mnx
vnIuo = 244 m
Obsorvod
mnx
vnIuo = 246 m.
Conjugated di-enes (acyIic)
Ior ncyIIc conjugnfod dIonos nnd cycIIc conjugnfod dIonos confnInIng non-fusod sIx-
momborod rIng sysfom n bnso vnIuo of 2l? m Is nssIgnod. 5 m nro nddod for onch ncyIIc nIkyI
subsfIfuonf. 5 m Is nddod for onch rIng fo whIch fho dIono sysfom Is oxocyIIc. AbsorfIons of
non-oInr comound such ns unsnfurnfod hydrocnrbon nro nof chnngod wIfh n chnngo In soIvonf.
xumpIe 1.
IufndIono
H
2
C =
H

C
H
C

= CH
2
Horo, fho bnso vnIuo Is 2l? m
So, cnIcuInfod vnIuo of
mnx
Is 2l? m
Obsorvod
mnx
vnIuo Is 2l? m.
Conjugnfod dIonos In whIch fho doubIo bonds nro confnInod wIfhIn rIngs nbsorb somo-
whnf dIfforonfIy. If fho conjugnfod doubIo bonds nro confnInod In sonrnfo, buf fusod,
sIx-momborod rIngs (n hoforonnnuInr dIono), n bnso vnIuo of 2l4 m Is usod; If fho conjugnfod
doubIo bonds nro confnInod In fho snmo rIng (n homonnnuInr dIono), n bnso vnIuo of 253 m Is
usod. Ior onch nIkyI subsfIfuonf grou on fho dIono sysfom or, for onch rIng fo whIch n cnrbon-
cnrbon doubIo bond Is oxocyIIc, 5 m nro nddod fo fho cnIcuInfod vnIuo.
Homoannular diene Heteroannular diene
Iov cycIIc conJuguted dIenes:
xumpIe 1.
HomounnuIuv dIene (I)
CnIcuInfod
mnx
Horo, fho bnso vnIuo Is 253 m
Ior 3-rIng rosIduIos + 5 3 m
Ior ono rIng fo whIch
fho cnrbon-cnrbon doubIo bond Is oxocyIIc + 5 m
CnIcuInfod:
mnx
vnIuo Is 2?3 m.
Obsorvod:
mnx
vnIuo Is 2?5 m.
xumpIe 2.
HetevounnuIuv dIene (II)
(II)
Horo, fho bnso vnIuo Is 2l4 m
Ior 3-rIng rosIduos + l5 m
Ior ono rIng fo whIch fho
Cnrbon-cnrbon doubIo bond + 5 m Is oxocyIIc.
CnIcuInfod:
mnx
vnIuo Is 234 m
Obsorvod:
mnx
vnIuo Is 235 m.
Quantitative appIication of UV spectroscopy
AbsorfIon of IIghf In bofh fho uIfrnvIoIof nnd vIsIbIo rogIons of fho oIocfromngnofIc
socfrum fnkos Inco whon fho onorgy of IIghf mnfchos fhnf roquIrod fo Induco In fho moIocuIo
nnd oIocfronIc frnnsIfIon nnd Ifs nssocInfod vIbrnfIonnI nnd rofnfIonnI frnnsIfIons subsoquonfIy.
Beer-Lambert's Iaw
Whon n bonm of IIghf Is nssod fhrough n frnnsnronf coII confnInIng n soIufIon of nn
nbsorbIng subsfnnco, fhon fho InfonsIfy of fho IncIdonf IIghf mny bo roducod.
1
2
3
4
5
I
o
I
t
Fig. 24.4 Reduction of the intensity of light by reflection at cell faces (rays 1-2),
absorption (ray 4) and scattering by particles (ray 5).
I
nbsorbod
= I
o
I
I
I
o
InfonsIfy of fho IncIdonf IIghf.
I
I
InfonsIfy of fho frnnsmIffod IIghf.
GenevuIIy \V expevIments uve done In quuvtz ceIIs us gIuss ubsovbs \V.
Tho frnnsmIffnnco (T) Is:
T =
I
I
I
o
nnd T Is gIvon by T =
l00 I
I
I
o
In l?60 !nmborf uf forwnrd fho roInfIon bofwoon I
I
nnd I
o
for vnrIous fhIcknossos (I) of
fho subsfnnco. ThIs roInfIonshI Is gIvon In shno of n Inw, whIch Is known ns !nmborf`s Inw.
Tho Inw Is sfnfod ns foIIows:
TLe vute oI decveuse In IntensIty oI IIgLt wItL tLIckness Is pvopovtIonuI to tLe
IntensIty oI tLe IncIdent IIgLt.
Whon fho Inw Is oxrossod mnfhomnfIcnIIy

J
JI
I
I
or
J
JI
I
= l
l
I
I
|l
l
roorfIonnIIfy consfnnf]
or
J
I
I
I
= l
l
JI
InfogrnfIng bofh sIdos:
I
I
= l
l
I + c
whon I = 0, c = In I
0
or In I
I
= l
l
I In I
0
or In
I
I
0
I
= l
l
I
or Iog
l0

I
I
0
I
=
l I
l
2303 .
wLeve, Iog
10
I
0
/I
t
Is cuIIed tLe ubsovbunce (A).
Absorbnnco Is rocIrocnI of common IognrIfhms of frnnsmIffnnco.
A = Iog
l0

I
I
0
I
= Iog
l0

l
T
= Iog
l0
T = 2 Iog ( T).
Ioor In l852 uf forwnrd nnofhor roInfIonshI whIch Is bofwoon nbsorbnnco nnd
conconfrnfIon whIch Is mnfhomnfIcnIIy oxrossod ns:
Iog
l0

I
I
0
I
=
l
2
C
2 303 .
Ioor`s Inw Is dofInod ns:
TLe IntensIty oI u beum oI puvuIIeI monocLvomutIc vudIutIon decveuses
exponentIuIIy wItL tLe numbev oI ubsovbIng moIecuIes. If mny bo sfnfod nIso ns: fho
nbsorbnnco Is roorfIonnI fo fho conconfrnfIon.
Tho combInnfIon of fhoso fwo Inws Ionds fo Ioor!nmborf`s Inw, whIch Is mnfhomnfIcnIIy
oxrossod ns:
A = Iog
l0
I
I
0
I
= oIc In whIch fho roorfIonnIIfy consfnnfs l
l
/2.303 nnd l
2
/ 2.303 nro
combInod fo fho sIngIo consfnnf 'o` whIch Is known ns ubsovptIvIty. Tho vnIuo of 'o` ns woII ns
Ifs nnmo doond on unIfs of conconfrnfIon. Whon 'c` Is In moIos IIfro
l
, 'o` Is cnIIod moIuv
ubsovptIvIty, formorIy known ns moIuv extInctIon coeIIIcIent ()
fhon fho oqunfIon fnkos fho form:
A = .I.c.
Whon fho nbsorbnnco Is monsurod for l (u/t) soIufIon In n l cm coII, fhon fho oqunfIon
fnkos fho form
A = A
lcm
l
.I.c.
A
lcm
l
Is known ns specIIIc ubsovbunce.
CoIovImetvIc unuIysIs Is nIso bnsod on Ioor!nmborf`s Inw. Horo fho IIghf usod Is
vIsIbIo ono nnd coIourod snmIos nro nnnIysod.
Infrared Spectroscopy
Whon Infrnrod IIghf Is nssod fhrough n snmIo of nn orgnnIc comound, somo of fho
froquoncIos nro frnnsmIffod fhrough fho snmIo wIfhouf boIng nbsorbod. If wo Iof fho orconf
nbsorbnnco or orconf frnnsmIffnnco ngnInsf froquoncy fho rosuIf Is Infrnrod (I!) socfrum.
MoIecuIar vibration
Af ordInnry fomornfuros orgnnIc moIocuIos nro In n consfnnf sfnfo of vIbrnfIon onch
bond hnvIng Ifs chnrncforIsfIc sfrofchIng nnd bondIng froquoncy nnd boIng cnnbIo of nbsorbIng
IIghf of fhnf froquoncy. Tho vIbrnfIons of fwo nfoms joInod fogofhor by n chomIcnI bond cnn bo
comnrod fo fho vIbrnfIons of fwo bnIIs joInod by n srIng, usIng fhIs nnnIogy wo cnn jusfIfy
sovornI froquoncIos of Infrnrod socfrum.
Two balls joined by a spring
Ior oxnmIo fo sfrofch srIng roquIros moro onorgy fhnn fo bond If; fhus sfrofchIng
onorgy of n bond Is gronfor fhnn fho bondIng onorgy nnd sfrofchIng nbsorfIons of n bond
nonr nf hIghor froquoncIos In fho Infrnrod socfrum fhnn fho bondIng nbsorfIon of fho
snmo bond.
CaIcuIation of vibrationaI frequencies
Wo cnn cnIcuInfo fho vIbrnfIonnI froquoncy of n bond wIfh n ronsonnbIo nccurncy, In fho
snmo wny ns wo cnn cnIcuInfo fho vIbrnfIonnI froquoncy of n bnII nnd srIng sysfom; fho oqunfIon
of cnIcuInfIon Is Hook`s Inw,
=
l
2.
l
n n n n
l 2 l 2
l/2
/ +
whoro = froquoncy, l = n consfnnf roInfod fo fho sfrongfh of fho srIng (fho forco consfnnf of
fho bond), n
l
, n
2
= fho mnssos of fwo bnIIs or nfoms, n
l
n
2
/n
l
+ n
2
Is known ns roducod mnss.
As nn oxnmIo, wo cnn cnIcuInfo fho nroxImnfo froquoncy of CH sfrofchIng vIbrnfIon
from fho foIIowIng dnfn,
l = 500 m
l
= 5 l0
5
gm s
2

l
n
= 5 l0
5
gs
2
l = l kg m/soc
2
= l000 gm s
2
n
C
= mnss of C-nfom = 20 l0
24
gm
n
= mnss of H-nfom = l.6 l0

24
gm
=
?
2 22
5 l0
20 l0 l6 l0 20 l6 l0
5 2
24 24 24
l/ 2

gs
g g ( )( . ) / ( . ) g
= 9.3 l0
l3
s
l
To oxross fhIs In wnvo numbors (
) wo uso roInfIonshI,
c
=

9 3 l0
3 l0
l3 l
8 l
. s
ms
whoro c = voIocIfy of IIghf
= 3.l l0
5
m
l
= 3l00 cm
l
So,
mnx.
for CH (Sfr.) Is 3l00 cm
l
.
Tho vIbrnfIonnI froquoncy of n bond Is oxocfod fo Incronso whon fho bond sfrongfh
Incronsos nnd nIso whon fho roducod mnss of fho sysfom docronsos. As for oxnmIo,
SfrofchIng : C = C > CC SfrofchIng :
C = O
> CO
l600 cm
l
l?00 cm
l
ll00 l300 cm
l
SfrofchIng : CH > CC SfrofchIng : OH > CO
3l00 cm
l
3500 cm
l
ll00l300 cm
l
l2 l
l3
<
l2 l2
24
l6 l
l?
<
l2 l6
28
Infrared spectroscopy
Infrnrod socfroscoy Is doondonf on modos of vIbrnfIon of fho nfoms In n moIocuIo nnd
fhoso hnvo boon shown In fho foIIowIng IIg. 24.5.
+ +

Symmetric Asymmetric Wagging Twisting
Out of plane
bending vibration
In plane
bending vibration
Stretching vibration
Scissoring Rocking
Fig. 24.5 Modes of vibration of the atoms in a molecule.
AppIications of IR spectroscopy
Tho I! socfrum cnnnof dIsfInguIsh n uro snmIo from nn Imuro snmIo.
Tho rogross of orgnnIc roncfIons cnn bo sfudIod wIfh I! socfrum.
ofocfIon of funcfIonnI grous In n moIocuIo.
IdonfIfy of fwo snmIos fhnf hnvo IdonfIcnI socfrn, gonornIIy If occurs In IIngor
rInf rogIon whIch Is l430 = 9l0 cm
l
ExampIes of some stretching and bending vibrations in aIkanes
mnx
CH sfrofchIng 2950 nnd 2820 cm
l
CH
2
bondIng l458 cm
l
CCH
3
bondIng l458l380 cm
l
IR Spectrum for ether and aIcohoI:
!oIncomonf of CH
2
In nIknno by 'O` rosuIfs In ofhor. Thoro Is nonrnnco of CO
sfrofchIng vIbrnfIon nf lll0 cm
l
In fho socfrum whon nn H nfom of n hydrocnrbon Is oxchnngod
for nn 'OH` grou, fho socfrum chnngos In n vory rodIcfnbIo wny, If now shows nbsorfIons
owIng fo 'OH` nnd 'CO` sfrofchIng vIbrnfIons In nddIfIon fo fho hydrocnrbon chromohorIc
grous rosonf i.e. for nIcohoIs:
OH sfrofchIng vIbrnfIon Is nf 3448 cm
l
(oIymorIc nssocInfIon of OH grous)
CO sfrofchIng vIbrnfIon Is nf l053 cm
l
In CCI
4
soIufIon OH sfrofchIng vIbrnfIon Is 3?88 cm
l
(ns fho dogroo of nssocInfIon
chnngos wIfh dIIufIon).
AIdeLyde und ketones: I! socfrn show nbsorfIon HC = O (sfrofchIng) nf l?40
20 cm
l
(sfrong); for n cycIIc kofono sfrofchIng vIbrnfIon Is nf l?25l?00 cm
l
(sfrong) (dIsfIncfIon
from CHO nnd C = O); CH (sfrofchIng) In CHO grou Is nf 28802625 cm
l
(wonk fo
modIum)(dIsfIncfIon from C = O).
AbsorfIon duo fo CH (doformnfIon) In
HCC = O
H
H
Is nf l365l355 cm
l
(shown by
nrrow) nnd In
CCC = O
H
H
Is nf l435l405 cm (sfrong).
AcIds: I! socfrn for
C OH
O
grou, C = O (sfrofchIng) Is nf l?25-l?00 cm

l
(s) (ns
fhnf of ncyIIc C = O), OH (sfrofchIng) Is nf 3650-3500 cm
l
(s) (m) (Iowor fhnn fhnf for
nIcohoIs), sfonrIc ncId In CCI
4
soIufIon gIvos
mnx
nf 29?4 cm
l
(OH sfr. Is hIddon by CH sfr),
l?06 cm
l
for C = O sfr., CH (dof.) nf l460 cm
l
. SfonrIc ncId In soIId sfnfo gIvos
mnx
nf
2940, l460 nnd l3?0 cm
l
(bnnds for nujoI) C = O sfrofchIng nf l?09 nnd l3l2, l295, l2?9,
l258, l235, l220 nnd ll88 cm
l
. Thoso bnnds nro chnrncforIsfIc of Iong chnIn n-nIkyI comounds,
In fho soIId sfnfo. Tho nbsorfIons of sfonrIc ncId In CCI
4
soIufIon nnd In soIId sfnfo show n
dIfforonco In I! socfrum of fho comound.
stevs: Ior CH
3
C
O
OCH
2
CH
3
mnx
nro:
l?42 cm
l
(C = O sfr. In soIId nIIhnfIc osfors)
l24l cm
l
(CO sfr. In ncofnfo)
l3?0 cm
l
(CH dof. In CH
3
)
3003 cm
l
(CH sfr. In CH
3
or, CH
2
)
l449 cm
l
(CH dof. In CH
3
or, CH
2
)
AcId unLydvIdes: C = O sfr. In ncyIIc nnhydrIdo nro l840-l800 (s) nnd l?80-l?40 cm
l
(s).
Thoro Is nIso n bnnd In fho rogIon ll80-l030 cm
l
(s) duo fo CO sfr In fho grouIng
COC.
mnx
for vnrIous sfr. nnd dof. of bonds In nn nnhydrIdo nro shown boIow wIfh fho
nrrows.
HCCCCOCCCCH C C O film
8 14
H H H H H H
H H H H H H O O
1035 (str.)
def. in the 1879
1818 1748 2985 2890 1460 1408 (deformations)
(str.) (str.) (str.) (str.)
AII fho vnIuos nro In cm
l
.
-dIketones:
HCCCCCH
H
H
O H H O
H H
[1725-700 cm
1
single stretching
with greater intensity (as there
are two carbonyl groups)
in IR spectrum]
HCC = CCCH
H
H
H H
H
Absorption at 1655 cm
1
(s)
OH O
C = O in enols for
, unsnfurnfod kofonos confnIn grouIng
C = CC = O
1685-1665 cm (s)
1
onoIs confnIn fhIs grouIng,
buf fho shIff fo l655 cm
l
fhnf occurs In fhoso comounds Is nffrIbufod fo HbondIng
OH----O = C
. Truo nIcohoIIc OH nbsorfIon bnnd nonr 3?00 cm
l
In onoIs nro nbsonf, buf
fhoro Is nbsorfIon bnnd nonr 2?00 cm
l
(e) whIch Is nffrIbufod fo fho OH grou (e) IndIcnfos
sfrong nbsorfIon, (n) IndIcnfos modIum nbsorfIon.
AmInes: IrImnry nnd socondnry nmInos confnIn H bond, bofh fyos nbsorb In fho
rogIon 3500 3300 cm
l
(t) buf fho fwo nro dIsfInguIshod by fho fncf fhnf rImnry nmInos show
fwo bnnds In fhoIr rogIon, whorons socondnry nmInos gonornIIy show onIy ono. If fhoro Is H-
bondIng, fhon fho rogIon Is 3400 3l00 cm
l
(e) C sfr. l200 l020 cm
l
In nIIhnfIc nmInos
(u n), C sfr. + 200 l020 cm
l
In nromnfIc nmInos (e), H dof l650l590 cm
l
(e n) In
rImnry nmInos, H dof l650 l550 cm
l
(e).
Iocnuso of fho ovorIn of fhoso rogIons, If Is nof ossIbIo fo dIsfInguIsh fho fyos of
nmInos In fhIs wny.
AvomutIc Compounds: AromnfIc comounds roduco n Inrgo numbor of nbsorfIon
bnnds In fho I! rogIon. Tho foIIowIng rogIons nro nrfIcuInrIy usofuI for rocognIsIng fho rosonco
of bonzono, oIynucIonr nromnfIcs nnd bonzono dorIvnfIvos.
CH 3080 3030 cm
l
(u) (sfr) nnd fho bnnds for C = C (In Inno vIbrnfIon) nro
l625 l600 cm
l
(t), l590 l5?5 cm
l
(t) nnd l525 l4?5 cm
l
(t).
SubsfIfuonf grous show vory IIghf offocf on fho nbovo bnnds, buf now bnnds nro
Infroducod nccordIng fo orIonfnfIon of fho grous. Howovor, bocnuso of n gronf donI of
ovorInIng of fho vnrIous bnnds In fho rogIon l2259?0 cm
l
; fhIs rogIon Is nof vory usofuI.
On fho ofhor hnnd, fhoso Isomors In fho nromnfIc sysfom mny bo rondIIy dIsfInguIshod by
fho bnnds duo fo (CH) (ouf of Inno) doformnfIon l, 2 Isomor shows
mnx
??0 ?35 cm
l
(e)
l, 3 Isomors nf
mnx
800 ?50 cm
l
nnd ?25 680 (m) ; l, 4 Isomor nf
mnx
840 8l0 cm
l
(e);
mono-subsfIfufod bonzono rIng shows
mnx
nf ??0 ?30 cm
l
(e) nnd ?l0 690 cm
l
(e) (Two
bnnds dIsfInguIsh If from l, 2 Isomor):
mnx
for sfr. nnd dof. of fho bonds nro shown by fho nrrows.
1, 2-dIsubstItuted benzene:
C H
C H
def. at 1376 cm
1
1600 cm
and 1493 cm
1
1
1462 and 1449 cm
1
C H
8 10
Alkenes or = CH (Ar.) show
stretching at 2941 cm
1
def at 3024 cm
1
1, 3-dIsubstItuted benzene:
C H
H
H
H
2941 cm (def )
1
str. min Ar or C = CH
C
H
H
H
1370 cm (def)
1
C = C (Ar) sfr. Is nf l6l3, l58?8 nnd l490 cm
l
nnd l450 cm
l
for CH dof In CH
3
nnd ??2 nnd 654 cm
l
(e) for l, 3-dIsubsfIfufIon
1, 4-dI-substItuted benzene:
C H
H
H
C
H
H H
def or for
1626 and 1515 cm
1
for
C = C str (Ar)
1449 cm C = C str (Ar)
1
1370 and 798 cm (s)
1
H
2941
str
cm
1
1, 4 disubstituted benzene
AbbvevIutIons:
mnx
wnvo numbor cm
l
, e-sfrong, u-wonk, n-modIum,
sfr. (sfrofchIng), dof. (doformnfIon), t (vnrInbIo)
Some IR Spectra:
3 4 5 6 7 8 9 10 11 12 13 14 15
100
80
60
40
20
0
4000 3000 2000 1500 1000 900 800 700
T
r
a
n
s
m
i
t
t
a
n
c
e
%
cm
1
Wavelength ( m) m
Fig. 24.6 R spectrum of carbon disulphide (0.1 mm cell).
3 4 5 6 7 8 9 10 11 12 13 14 15
100
80
60
40
20
0
4000 3000 2000 1500 1000 900 800 700
T
r
a
n
s
m
i
t
t
a
n
c
e
%
cm
1
Wavelength ( m) m
Fig. 24.7 R spectrum of carbon tetrachloride (0.1 mm cell).
3 4 5 6 7 8 9 10 11 12 13 14 15
100
80
60
40
20
0
4000 3000 2000 1500 1000 900 800 700
T
r
a
n
s
m
i
t
t
a
n
c
e
%
cm
1
Wavelength ( m) m
Fig. 24.8 R spectrum of chloroform (ethanol-free) (0.1 mm cell).
Wavelength (Microns)
4000 3000 2000 1500 1000 900 800 700
100
80
60
40
20
0
3 4 5 6 7 8 9 10 11 12 13 14 15
100
80
60
40
20
0
T
r
a
n
s
m
i
t
t
a
n
c
e
(
%
)
cm
2
Fig. 24.9 Di--butyl ether, liquid film.
Wavelength (Microns)
4000 3000 2000 1500 1000 900 800 700
100
80
60
40
20
0
3 4 5 6 7 8 9 10 11 12 13 14 15
100
80
60
40
20
0
T
r
a
n
s
m
i
t
t
a
n
c
e
(
%
)
cm
2
Fig. 24.10 Lauryl alcohol, liquid film.
NucIear Magnetic Resonance (nmr) or Proton Magnetic Resonance (pmr)
spectroscopy
nnr Is n oworfuI nnnIyfIcnI fochnIquo fo ovnIunfo fho sfrucfuros of cnrbon comounds.
Tho fochnIquo Is usod (i) fo IdonfIfy unknown comounds, (ii) fo chock for ImurIfIos nnd
(iii) fo sfudy fho shnos of moIocuIos. In modIcIno, mngnofIc rosonnnco ImngIng usos nnr fo
dofocf fho hydrogon nucIoI In fho humnn body, osocInIIy In wnfor nnd IIIds. Tho form 'nucIonr`
Inforrofs fho fochnIquo fhnf dofocfs nucIoI of nfoms such ns hydrogon-l (rofon). Tho form
'mngnofIc` Inforrofs fho nucIoI fhnf ncf IIko fIny mngnofs fhnf cnn IIno u oIfhor In fho snmo
dIrocfIon or In fho oosIfo dIrocfIon fo nn oxfornnI mngnofIc fIoId. Tho form 'rosonnnco` Is fho
nbsorfIon of onorgy In fho form of rndIo wnvos wIfh fho froquoncy corrosondIng fo fho sIzo of
onorgy jum ns fho nucIoI fII from ono nIIgnmonf In n mngnofIc fIoId fo fho ofhor (IIg. 24.ll).
Tho nfomIc nucIoI sIn nbouf fhoIr nxos. ow sInco n rofnfIng chnrgod shoro Is nIwnys
nssocInfod wIfh If n mngnofIc momonf, fhon nII fho chnrgod nrfIcIos In n nucIous wIII mnko
fhnf nucIous fo bohnvo IIko n fIny bnr mngnof, wIfh Ifs mngnofIc momonf nIong fho nxIs of
rofnfIon of fho nucIous. Tho nnguInr momonfum of fho sInnIng nucIous cnn bo rorosonfod In
forms of sIn numbors (I). Thoso numbors cnn nffnIn fho vnIuos 0,
l
2
, l,
3
2
ofc. (I = 0 donofos no
sIn). Tho nucIonr mngnofIc momonf Is donofod by fho symboI '`.
Inch rofon nnd noufron In n nucIous hns Ifs own sIn nnd I Is n rosuIfnnf of fhoso
sIns. If fho sum of rofons nnd noufrons Is ovon, I Is 0 or, InfogrnI (l, 2, ofc.), If fho sum Is odd
I Is
l
2
InfogrnI i.e.,
l
2
,
3
2
,
5
2
. If bofh rofons nnd noufrons nro ovon numborod fhon I Is 0. Thnf
Is why, bofh C
l2
nnd O
l6
hnvo no rosuIfnnf nucIonr mngnofIc momonf nnd gIvo no nnr sIgnnI.
SovornI nucIoI H
l
, I
l9
, C
l3
hnvo n sIn numbor I of
l
2
nnd n unIform shorIcnI chnrgo dIsfrIbufIon.
ucIoI wIfh sIn numbor I of l or hIghor hnvo n non-shorIcnI chnrgo dIsfrIbufIon.
If n mngnofIc nucIous Is Incod In n unIform mngnofIc fIoId If Is soon fhnf fho mngnofIc
dIoIo nssumos onIy n dIscrofo sof of orIonfnfIons. Tho sysfom Is snId fo bo qunnfIsod. Tho
mngnofIc nucIous cnn nffnIn nny ono of fho ossIbIo orIonfnfIons IndIcnfod by (2I + l).
Thus n rofon (I =
l
2
) cnn nssumo onIy ono of fho fwo ossIbIo orIonfnfIons corrosondIng
fo fho onorgy IovoI of H
o
. Ono wIfh rosocf fo fho dIrocfIon of fho nIIod mngnofIc fIoId nnd
fho ofhor Is nIIgnod ngnInsf fho dIrocfIon of fho nIIod fIoId (IIg. 24.ll).
E
n
e
r
g
y
H
0
(Applied magnetic field)
Fig. 24.11 Energy levels of a proton.
Tho frnnsIfIon of n rofon from ono ossIbIo orIonfnfIon fo nnofhor Is offocfod by fho
nbsorfIon or omIssIon of n dIscrofo nmounf of onorgy such fhnf,
I = I = 2 H
o
whoro, = froquoncy of oIocfromngnofIc rndIon nbsorbod or omIffod
I = IInnck`s consfnnf
= nucIonr mngnofIc momonf
H
o
= nIIod mngnofIc fIoId.
Ior rofons If n mngnofIc fIoId l4000 Cnuss Is nIIod fho froquoncy of such onorgy
romnIns In fho rndIo froquoncy rogIon (60 mogncycIos or socond).
!nIoss fho nxIs of fho nucIonr mngnof Is orIonfod oxncfIy nrnIIoI or nnfInrnIIoI wIfh
fho nIIod mngnofIc fIoId (IIg. 24.ll), fhoro wIII bo n corfnIn forco by oxfornnI mngnofIc fIoId
fo so orIonf fho sInnIng nucIous. Iuf bocnuso fho nucIous Is sInnIng, fho offocf Is fhnf Ifs
rofnfIonnI nxIs drnws n cIrcIo orondIcuInr fo fho nIIod fIoId. Such nn offocf Is shown In
IIg. 24.l2. ThIs mofIon of fho nucIous Is cnIIod PvecessIon.
Precessional orbit
Axis of rotation
Spinning nucleus
H
o
Applied magnetic field
Fig. 24.12 Precession.
Theory of nucIear resonance
A rofon In n sfnfIc oxfornnI mngnofIc fIoId mny nssumo onIy fwo ossIbIo orIonfnfIons
corrosondIng fo fho onorgIos of + H
o
. Tho Iow onorgy orIonfnfIon corrosonds fo fhnf sfnfo In
whIch fho nucIonr mngnofIc momonf Is nIIgnod nrnIIoI fo fho oxfornnI mngnofIc fIoId, nnd fho
hIgh onorgy orIonfnfIon corrosonds fo fhnf sfnfo In whIch fho nucIonr mngnofIc momonf Is
nIIgnod nnfInrnIIoI (oosod) fo fho oxfornnI mngnofIc fIoId. If Is ossIbIo fo fho Induco
frnnsIfIons bofwoon fhoso fwo orIonfnfIons. Tho froquoncy of oIocfromngnofIc rndInfIon
nocossnry for such n frnnsIfIon Is gIvon by
= 2H
o
/I
whoro H
o
Is fho sfrongfh of fho oxfornnI or nIIod mngnofIc fIoId nnd I Is IInnck`s consfnnf.
Tho rocossIonnI froquoncy of fho sInnIng nucIous i.e., nucIonr mngnof Is oxncfIy oqunI
fo fho froquoncy of oIocfromngnofIc rndInfIon nocossnry fo Induco n frnnsIfIon from ono nucIonr
sIn sfnfo fo nnofhor. Tho nucIonr frnnsIfIon corrosonds fo n chnngo In fho nngIo fhnf fho nxIs
of fho nucIonr mngnof mnkos wIfh fho nIIod mngnofIc fIoId. ThIs chnngo cnn bo broughf
nbouf fhrough fho nIIcnfIon of oIocfromngnofIc rndInfIon whoso mngnofIc vocfor comononf
Is rofnfIng In n Inno orondIcuInr fo fho mnIn mngnofIc fIoId. Whon fho froquoncy of fho
rofnfIng mngnofIc fIoId nnd fho froquoncy of fho rocossIng nucIous bocomo oqunI, fhoy nro snId
fo bo In rosonnnco, nnd fho nbsorfIon or omIssIon of onorgy by fho sInnIng nucIous fhon occurs.
Thus n nucIeuv vesonunce wIII occur whon n nucIous (I > 0) Is Incod In n sfnbIo mngnofIc fIoId
nnd subjocfod fo fho oIocfromngnofIc rndInfIon of nrorInfo onorgy.
Tho oIocfromngnofIc rndInfIon Is suIIod by nn oscIIInfor wIfh Ifs mngnofIc fIoId nf
rIghf nngIos fo fho nIIod fIoId nnd sInco fho osIfIon of nbsorfIon onk, fhnf Is, whoro
rosonnnco occurs, doonds on fho froquoncy of fho oscIIInfor or fho sfrongfh of fho nIIod
mngnofIc fIoId. If Is ossIbIo fo chnngo from fho Iowor fo hIghor onorgy IovoI by omIoyIng n
vnrInbIo froquoncy wIfh n fIxod nIIod mngnofIc fIoId or vIco vorsn. In rncfIco If Is onsIor fo
vnry fho mngnofIc fIoId rnfhor fhnn fho froquoncy, fho rosuIf Is fho nnr socfrn whIch Is
usunIIy n grnh of sIgnnI InfonsIfy (ordInnfo) ngnInsf fho mngnofIc fIoId (nbscIssn) oxrossod In
mIIIIgnuss nf n fIxod froquoncy (IIg. 24.l?).
Instrumentation
Radio
frequency
oscillator
Detector Computer Recorder
N S
Probe at room temperature containing
the sample, which is spun at 20 times
per second to average any inhomogeneity
in the sample glass tube
Magnet
Fig. 24.13 Diagram of an H spectrometer.
ShieIding, DeshieIding and ChemicaI Shift
If mIghf bo oxocfod fhnf fho rosonnnco froquoncy for n gIvon mngnofIc fIoId doonds
onIy on fho nnfuro of nfomIc nucIous concornod. ThIs, howovor, Is nof fho cnso. Tho nIIod
mngnofIc fIoId cnusos oIocfrons surroundIng n nucIous fo cIrcuInfo In n Inno orondIcuInr fo
fho nIIod fIoId, nnd fhIs gonornfos oIocfrIc curronf fo roduco n mngnofIc fIoId In oosIfIon
fo fho nIIod mngnofIc fIoId (IIg. 24.l3). Thus fho offocfIvo mngnofIc fIoId 'H` oxorIoncod by
fho nucIous Is smnIIor fhnn fho nIIod mngnofIc fIoId (H
o
). Tho roInfIonshI bofwoon fho fwo
Is oxrossod ns:
H = H
o
(1 ) Is cnIIod fho sLIeIdIng ov,
scveenIng constunt (whIch Is nondImonsIonnI) nnd
hns n osIfIvo vnIuo. Iuf If mny bo nognfIvo i.e., fhon
fho offocfIvo mngnofIc fIoId Is Inrgor fhnn fho nIIod
mngnofIc fIoId fo orIonf fho nucIonr mngnofIc. In fhnf
cnso fho rofon Is snId fo bo desLIeIded. SInco fho
numorIcnI vnIuo of doonds on fho chomIcnI
onvIronmonf of n gIvon nucIous, fho shIoIdIng or
doshIoIdIng vnrIos wIfh Ifs oIocfronIc onvIronmonf.
Thon nf n gIvon rndIofroquoncy, nII rofons nbsorb nf
fho snmo offocfIvo fIoId sfrongfh, buf fhoy nbsorb nf
dIfforonf nIIod fIoId sfrongfhs.
Fig. 24.14 Diamagnetic electronic
circulation about a nucleus.
Inch sof of oquIvnIonf rofons In n comound wIII hnvo n sIIghfIy dIfforonf oIocfronIc
onvIronmonf from ofhor sof of rofons nnd honco wIII nbsorb nf n sIIghfIy dIfforonf nIIod
fIoId sfrongfh fo roduco fho snmo offocfIvo fIoId sfrongfh whIch cnn cnuso fho 'rosonnnco` fo
occur.
ShIoIdIng cnusos n shIff of fho rosonnnco froquoncy fo hIghor vnIuos of fho nIIod fIoId
(H
o
), fhnf Is , fho shIff Is upIIeId. On fho ofhor hnnd, doshIoIdIng cnusos n shIff of fho rosonnnco
froquoncy fo Iowor vnIuos of fho nIIod fIoId, fhnf Is, fho shIff Is downIIeId. Tho mngnIfudo of
fhIs shIff Is cnIIod cLemIcuI sLIIt. SInco fho vnIuo of fho nIIod fIoId oxorIoncod by fho
orgnnIc comound cnnnof bo doformInod nccurnfoIy, chomIcnI shIffs nro monsurod roInfIvo fo
somo sfnndnrd comound whIch confnIns fho nucIous undor consIdornfIon. TofrnmofhyIsIInno
|TMS, (CH
3
)
4
SI] Is nrfIcuInrIy usofuI for rofon mngnofIc rosonnnco (pnr). TMS confnIns
fwoIvo oquIvnIonf rofons. Tho pnr socfrum of fhIs comound shows n sIngIo shnr IIno
whIch occurs nf hIghor fIoId fhnn nny ofhor rofons In mosf of fho common orgnnIc comounds.
Thnf Is, mosf pnr sIgnnIs occur downfIoId wIfh rosocf fo TMS.
CH SiCH
3 3
CH
3
CH
3
(TMS)
Fig. 24.15 Shielding of an acetylenic proton in terms of paramagnetic effects.
Tho chomIcnI shIff mny bo roorfod In vnrIous wnys. Tho rosonnnco froquoncy of fho
rofon of fho comound Is doondonf on fho sfrongfh of fho nIIod mngnofIc fIoId. Tho shIff
mny bo roorfod ns unIfs of fho mngnofIc fIoId In mIIIIgnuss. Howovor, fho mngnofIc fIoId cnn
nIso bo oxrossod ns Horfz (Hz) or cycIos or socond (cs). Tho sonrnfIon In Hz Is nIso
roorfIonnI fo fho froquoncy of fho oscIIInfor, e.g., If fho sonrnfIon bofwoon n rofon sIgnnI
nnd sIgnnI of TMS Is 60 Hz nf 40 MHz fho sonrnfIon nf 60 MHz wIII bo 90 Hz. Thoroforo If Is
dosIrnbIo fo ronrf chomIcnI shIffs In such unIfs fhnf nro Indoondonf of fho oornfIng condIfIons
of fho socfrohofomofor. ThIs cnn bo dono vory onsIIy by dofInIng chomIcnI shIff by fho
oxrossIon
=
SonrnfIon In Hz
OscIIInfor froquoncy
l0
6
Tho fncfor l0
6
Is Infroducod In ordor fo rocord fho chomIcnI shIff ns n convonIonf vnIuo.
ThIs Is usunIIy In fho rnngo l-l0 nnd Is oxrossod In m.
Tho doondonco of fho chomIcnI shIff of fho oscIIInfor froquoncy Is shown In fho foIIowIng
oxnmIo,
=
60
40 l0
6
l0
6
= l.5 m.
=
90 l0
60 l0
6
6
= l.5 m.
If Is now bocomIng common rncfIco fo oxross chomIcnI shIffs In (fnu) vnIuos, dofInod by:
= l0-.
l0 m Is nssIgnod fo fho IIno of TMS In nnr socfrum. Mosf rofons hnvo osIfIvo
vnIuo i.e., < l0. Sfrong ncIdIc rofons hnvo nognfIvo vnIuo i.e., > l0.
Position of signaIs (chemicaI shifts)
Tho gronfor fho shIoIdIng of nucIous fho Inrgor Is vnIuo (fho smnIIor Is ). SInco fho
dogroo of shIoIdIng doonds on fho oIocfron donsIfy surroundIng fho rofon nny sfrucfurnI
fonfuro fhnf docronsos fhIs oIocfron donsIfy cnusos n docronso In shIoIdIng (doshIoIdIng) wIfh
consoquonf IoworIng of fho vnIuo (fho chomIcnI shIffs) movosdown fIoId. Thus oIocfronognfIvIfy
(m) (m)
CH
3
I ?.83 CH
3
C 9.l2
CH
3
Ir ?.35 CH
3
?.85
CH
3
CI 6.98 CH
3
O 6.?0
CH
3
I 5.?0
of fho nfoms nffnchod In fho comounds In fho coIumn grndunIIy Incronsos ns such fhoro Is
grndunI doshIoIdIng nnd vnIuo docronsos In fho coIumn.
SI Is Ioss oIocfronognfIvo fhnn cnrbon, so fho rofons of CH
3
grous In TMS nro moro
shIoIdod fhnn fhoso In CCH
3
.
ExampIes of ShieIding and DeshieIding
H
C
C
H
R
H
C O
H
0
H
0
p-electron circulating
at right angles
to the field
(a) (b)
Fig. 24.16 (=) Shielding of an acetylenic proton and (>) deshielding of an aldehydic
proton in terms of diamagnetic anisotropic effects.
nduced field
opposing the applied
field, circulating
electrons act to
shield the protons.
This effect is called
diamagnetic
anisotropy.
H H
H
0
Ring current
Resultant
paramagnetic
field
Induced
diamagnetic
field
Fig. 24.17 The deshielding of aromatic protons due to a ring current effect.
The nucIear magnetic spectrum
Af n gIvon rndIo froquoncy, nII fho rofons wIII nbsorb nf n snmo offocfIvo fIoId sfrongfh,
buf fhoy nIso nbsorb nf dIfforonf nIIod fIoId sfrongfhs. Tho nIIod fIoId sfrongfh Is monsurod
nnd Ioffod ngnInsf fho nbsorfIon of rndInfIon; fho rosuIfs nro sIgnnIs nnd fho socfrum Is
cnIIod n nucIonr mngnofIc rosonnnco socfrum (IIg. 24.l8(o) nnd (I)).
A
b
s
o
r
p
t
i
o
n
Downfield
Lowfield Upfield
(a) (b)
Fig. 24.18 (=) 4 spectrum for ethanol at low resolution, (>) a signal.
Informations predicted by the spectrum
Tho numbor of sIgnnIs IndIcnfo fho dIfforonf fyos or sof of rofons rosonf In fho
moIocuIo.
Tho osIfIons of sIgnnIs rodIcf somofhIng nbouf fho oIocfronIc onvIronmonf of onch
kInd of rofon.
Tho InfonsIfIos of sIgnnIs IndIcnfo how mnny rofons of onch kInd Is rosonf.
Tho sIIffIng of fho sIgnnIs Info sovornI onks IndIcnfos fho onvIronmonf of n rofon
wIfh rosocf fo ofhor nonrby rofons.
NSTRUMENTAL METHODS OF ANALYSES 533
Number of signaIs
A sof of rofons wIfh fho snmo onvIronmonf nro snId fo bo oquIvnIonf. Tho numbor of
sIgnnIs In fho nnr socfrum foIIs us, fhoroforo, how mnny sofs of oquIvnIonf rofons, how
mnny kInds of rofons.
Judging the equivaIent protons
Inch rofon In n moIocuIo Is In furn fo bo roIncod by somo ofhor nfom Z. If roIncomonf
of oIfhor of fwo rofons by Z wouId yIoId fho snmo roducf or onnnfIomorIc roducfsfhon fho
fwo rofons nro chomIcnIIy nnd mngnofIcnIIy oquIvnIonf.
xumpIe. CH
3
CH
2
CI (CH
3
rofons nro non-oquIvnIonf fo fho CH
2
rofons)
Tho onvIronmonf of fhoso fwo rofons nro noIfhor IdonfIcnI nor mIrror Imngos of onch
ofhor, mngnofIcnIIy fhoso rofons nro non-oquIvnIonf nnd wo oxocf fho nnr sIgnnI from
onch ono.
CH
3
Cl
H H
H Cl
1
Cl
H Z
H Cl
Z H
H Cl
CH
3
Cl
CH
3
Cl
1, 2-dichloropropane ( ) a ( ) b
Cl nro dInsforoomorIc, mngnofIcnIIy non-oquIvnIonf nnd gIvo sonrnfo nnr sIgnnIs
xumpIes: Tho numbor of sIgnnIs IndIcnfo fho rosonco of fho numbor of sofs of
mngnofIcnIIy nonoquIvnIonf rofons In fho moIocuIo of fho comound.
CH CHCI CH
3 3
o I o
2 nmr sIgnnIs.
C = C
CH
3
CH
3
H
H
a
a
b
b
2 nmr sIgnnIs.
CH CH CH CI
3 2 2
o I c
3 nmr sIgnnIs.
3 nmr sIgnnIs.
C = C
H
Cl
H
Hc
b
Vinyl chloride
a
3 nmr sIgnnIs.
4 nmr sIgnnIs.
H Cl
H H
Cl
CH
3
c d
a
1, 2-dichloropropane
b
4 nmr sIgnnIs.
Peak area and Proton counting of a Compound
TofnI sfo hoIghfs (IIg. 24.l9) for l6 rofons of fho comound l, 4-mofhyI forfInry
bufyIbonzono = 8.8 2.9 3.8
o I c
+ + = l5.5 unIfs i.e., fho numbor of squnros wIfhIn nn InfogrnfIon In
nn nnr socfrn (IIg. 24.l9) for fho comound, C
ll
H
l6
fhon
l6H
l5.5
= l.03 H Is fho numbor of
rofons or unIf. Thon numbor of o rofons, I rofons nnd c rofons In fho comound nro:
oH = l.03 8.8 = 9.l
IH = 2.9 l.03 = 3
cH = l.03 3.8 = 3.9l4
i.e., CH
3
CH
3
c c
b
c c
C
CH
3
CH
3
a
a
a C H
11 16
(I)
l,4-MofhyI forfInry bufyIbonzono
c
CH
3
CCH
3
b
a Integration
c 4H
3.8
b 3H
2.9
8.8
c 9H
400 300 200 100 0
c 90
2
8
3
7
4
6
5
5
6
4
7
3
8
2
9
1
10 r
0 d
CH
3
CH
3
Fig. 24.19 NMR spectrum of 1, 4-methyl tertiary butylbenzene (Proton counting).
SpIitting of signaIs; Spin-spin coupIing
CHCH
2
Secondary (2) proton
tertiary (3) proton
Tho mngnofIc fIoId fhnf n 2 rofon (eH) fooIs nf n nrfIcuInr Insfnnf durIng nmr Is
sIIghfIy Incronsod forfInry or sIIghfIy docronsod by fho sIn of noIghbourIng forfInry rofon
(I.H), Incronsod If fho I.H hnons nf fhnf Insfnnf fo bo nIIgnod wIfh fho nIIod fIoId; or docronsod
If fho I.H hnons fo bo nIIgnod ngnInsf fho nIIod fIoId for hnIf of fho moIocuIos. Thon,
nbsorfIon by n eH Is shIffod sIIghfIy downfIoId nnd for nnofhor hnIf of fho moIocuIos fho
nbsorfIon Is shIffod sIIghfIy ufIoId. Tho sIgnnI Is sIIf Info fwo onks n doubIof wIfh oqunI
onk InfonsIfIos.
Signal from
uncoupled H
H
o
Spin combination
for adjacent c
Signal is 1:1 doublet
H
o
,
Signal from
uncoupled
proton
Spin combination
for adjacent CH
2
Signal is 1:2:1 triplet
H
o
, ,
, ,
Spin combinations
for adjacent CH
3
Signal from
uncoupled H
Signal is 1:3:3:1 quartet
xumpIes:
CHBr CH Br
2 2
CH CHBr
3 2
Upfield doublet ( + 1) n
Downfield triplet ( + 1) n
Upfield doublet
Downfield quartet
( = 2) n
( = 1) n
( = 3) n
( = 1) n
Compound (A)
Compound (B)
SIgnuI spIIttIng Is detevmIned by tLe numbev oI neIgLbouvIng pvotons (). TLe
numbev oI peuks >( + 1).
Ionk nron rofIocfs fho numbor of nbsorbIng rofons nnd fho muIfIIIcIfy of sIIffIngs
rofIocfs fho numbor of noIghbourIng rofons (IIgs. 24.l9 nnd 24.20).
Wo mny oxocf fo obsorvo sIn sIIffIng onIy gIvos fho non-oquIvnIonf noIghbourIng
rofons. Iy non-oquIvnIonf rofons, wo monn rofons wIfh dIfforonf 'chomIcnI shIffs`. Iy
noIghbourIng rofons wo monn mosf commonIy rofons on ndjnconf cnrbons.
FIg. 24.20 The observed multiplicity of a given group of equivalent protons clearly depends
on the number of proton on adjacent atom. The multiplicity of a given group by
the expression ( + 1), where is the number of protons on adjacent atoms.
Mass spectrometry
IntvoductIon: Mnss socfromofry Is nn nccurnfo InsfrumonfnI fochnIquo for doformInn-
fIon of veIutIve utomIc musses nnd roInfIvo moIocuInr mnssos. Muss spectvometvy cun
uIso LeIp to detevmIne tLe moIecuIuv stvuctuves und to IdentIIy unknown compounds.
Basic principIes
In fho sImIosf mnss socfromofor, nn orgnnIc moIocuIo Is bombnrdod wIfh oIocfrons nnd
Is convorfod fo hIghIy onorgofIc osIfIvoIy chnrgod Ions (moIocuInr Ions or nronf Ions, M
.
+
),
whIch bronk u Info smnIIor Ions (dnughfor Ions). Tho Ioss of nn oIocfron from n moIocuIo Ionds
fo n rndIcnI cnfIon (M
.
+
); nnd fho whoIo rocoss cnn bo rorosonfod ns foIIows:
M M
.
+
+ 2e
(OrgnnIc moIocuIo) (MoIocuIo Ion)
Tho moIocuIo Ion (M
.
+
) gonornIIy docomosos fo n puIv oI Ivugments, whIch mny bo
oIfhor rndIcnI Ius or n smnII moIocuIo Ius n rndIcnI cnfIon. Thus,
M
+
(MoIocuInr Ion) Ion (rndIcnI)
. .
+
+
n n
l 2
( )
or
n n
l 2
.
+
(rndIcnI cnfIon) (smnII moIocuIo)
+
Tho moIocuInr Ions, fho frngmonf Ions nnd frngmonf rndIcnI Ions nro sonrnfod by
dofIocfIon In n vnrInbIo mngnofIc fIoId nccordIng fo fhIs mnss nnd chnrgo, nnd gonornfo n curronf
(fho Ion curronf) nf fho coIIocfor In roorfIon fo fhoIr roInfIvo nbundnncos. A muss spectvum
Is u pIot oI veIutIve ubundunce uguInst tLe vutIo muss to cLuvge (tLe m/z vuIue). Ior
sIngIy chnrgod Ions, fho Iowor fho mnss fho moro onsIIy Is fho Ions dofIocfod In fho mngnofIc
fIoId. oubIy chnrgod Ions nro occnsIonnIIy formod, fhoy nro dofIocfod much moro fhnn sIngIy
chnrgod Ions of fho snmo mnss; nnd fhoy nonr In fho mnss socfrum nf fho snmo vnIuo ns
sIngIy chnrgod Ions of fho hnIf, sInco,
2
2
n
c
n
c
=
oufrnI nrfIcIos roducod In fho frngmonfnfIon, whofhor unchnrgod moIocuIos (n
2
) or
rndIcnIs (n
2
.
) cnnnof bo dofocfod dIrocfIy In fho mnss socfromofor.
Instrumentation
Thoro Is n hIgh vncuum InsIdo n mnss socfromofor fo roduco nnd sfudy IonIsod nfoms
nnd moIocuIos IncIudIng frngmonfs of moIocuIos.
Anode (+ve)
Vaporized
sample
Electric accelerating field
Heated
cathode
To vacuum pump
Recorder
or vdu
Computer
Amplifier
Detector
Magnetic
field
+
Fig. 24.21 Diagram of a mass spectrometer.

ScLemutIc vepvesentutIon Iov pvoductIon oI u muss spectvum:
Injection of a small amt. of
sample into the instrument
Vapourisation
Sample
vapour
Bombarding with a beam of
high energy electrons
Production of molecular
ions M
+
.
Deflection of moving stream
of ions with a magnetic field
to focus ions with a particular
mass on the detector.
Acceleration of the
positive ions in an
electric field
Feeding the signal from the
detector to a computer which
prints out the mass spectrum
as the magnetic field steadily
changes over a range of values
to focus the series of ions with
different masses (m/z) one by
one in the detector.
20
40
60
80
23 24 25 26 27
Mass of the positive ions detected
%
a
b
u
n
d
a
n
c
e
Fig. 24.22 Mass spectrum of magnesium.
Tho Insfrumonf noods cnIIbrnfIon usIng n roforonco comound wIfh n known sfrucfuro
nnd moIocuInr mnss so fhnf fho comufor cnn rInf n scnIo on fho mnss socfrum.
Tho mnss socfrum for nn oIomonf dIsInys fho roInfIvo nbundnnco of dIfforonf Isofoos
of fho oIomonf. ThIs mnkos If ossIbIo fo cnIcuInfo fho roInfIvo nfomIc mnss for fho oIomonf
(soo IIg. 24.22).
AppIications
Stvuctuve eIucIdutIon
Whon n moIocuInr comound Is boIng nnnIysod, fho onk of fho Ion wIfh hIghosf mnss Is
usunIIy fho whoIo moIocuIo IonIsod Is known ns 'moIocuInr Ion` or nronf Ion (M
.
+
), whIch Is fho
roInfIvo mnss (moIocuInr woIghf) of fho comound.
NItvogen vuIe. If n moIocuInr Ion hns nn ovon moIocuInr woIghf, If ossossos oIfhor no
nIfrogon or nn ovon numbor of nIfrogon nfoms. An odd moIocuInr woIghf comound roquIros
nn odd numbor of nIfrogon nfoms.
Tho buse peuk Is fho mosf Infonso IIno of fho socfrum.
MetustubIe Ions. IrngmonfnfIon (n
l
+
n
2
+
+ n
3
) In gonornI occurs In fho Ion sourco
of fho mnss socfromofor boforo fho osIfIvo Ions nro nccoIornfod nnd fhoroforo n dIsfIncf onk
rosuIfs for onch frngmonfnfIon.
So mnss socfrum Is n 'frngmonfnfIon nfforn`. Tho comufor hns n dnfnbnso of mnss
socfrn so If cnn IdonfIfy nn unknown comound by mnfchIng Ifs socfrum wIfh ono In Ifs
dnfnbnso.
A chomIsf who synfhosIsos now comounds cnn sfudy fhoIr frngmonfnfIon nfforn In n
mnss socfromofor nnd doformIno Ifs sfrucfuro wIfh fho hoI of ofhor socfrn IIko Infrnrod
socfroscoy (I.r.) nnd nucIonr mngnofIc rosonnnco (n.m.r.).
Tho combInnfIon of gns-IIquId chromnfogrnhy (gIc) wIfh mnss socfromofry Is of gronf
Imorfnnco In modorn chomIcnI nnnIysIs. IIrsf gIc sonrnfos fho comononfs In nn unknown
mIxfuro, such ns n snmIo of oIIufod wnfor, fhon mnss socfromofry (ms) dofocfs nnd IdonfIfIos
fho comononfs.
HIgLIIgLts:
Tho nronf onk (M
.
+
) Is fho mosf Infonso In sfrnIghf-chnIn comounds, fho InfonsIfy
roducos wIfh Incronsod chnIn brnnchIng.
In n homoIogous sorIos, fho InfonsIfy of M
+
docronsos wIfh Incronso In moIocuInr
woIghf.
In brnnchod chnIn hydrocnrbons cIonvngo Is roforrod nf fho bond ndjnconf fo fho
brnnch; fhus gIvIng rIso fo forfInry (3) cnrbocnfIons ns 3 Is moro sfnbIo fhnn 2,
whIch In furn Is moro sfnbIo fhnn l cnrbocnfIons.
urIng rorosonfIng fho frngmonfnfIon, n ono oIocfron shIff Is rorosonfod by n
'fIsh hook` nrrow ' ` nnd n fwo oIocfron shIff In fho usunI mnnnor by ' ` .
xumpIes. Ior MofhyIonfnnos:
CH CCHCH CH
3 2 3
CH
3
CH
3
CH
3
.
+
CH CHCH CH CH
3 2 2 3
CH
3
.
+
CH C + CHCH CH
3 2 3
CH
3
CH
3
CH
3
+
.
CH C + CH CH CH
3 2 2 3
CH
3
H
+
.
m z / 57
m z / 43
Tho robnbIIIfy of fho oxIsfonco of n sfrong M
.
+
onk Is hIgh for unsnfurnfod or cycIIc
sysfoms rosonf In fho moIocuIo. As In cnrbocnfIon chomIsfry fho cnrbocnfIons formod
nro sfnbIIIsod.
AIkyIbonzonos cIonvo nf fho CC bond fo fho nromnfIc rIng rosuIfIng In n hIghIy
sfnbIIIsod cnrbocnfIon. Mosf nIkyIbonzonos gIvo fho moro sfnbIo frooIIum Ion (I) rnfhor
fhnn fho IonzyI cnfIon (II).
CH R
2
.
+
R
R
.
+
CH
2
.
+
+
+ R
.
(II) (I)
CycIIc nIkonos offon undorgo gonornIIy n vetvo-IeIs-AIdev IIssIon.
.
+
.
+
+ CH = CH
2 2
m z / 54
Comounds such ns nIcohoIs, morcnfnns, nmInos, osfors cIonvo nf CC bond fo
fho hoforo nfom.
RCXH
..
.
+
CXH
+
..
R +
.
C = XH
..
+
(Resonance stabilisation)
Cleavage
Q. 1. WLut Is utomIc spectvoscopy?
Ans. Gvound stute oI un utom monns If Is wIfh normnI oIocfronIc confIgurnfIon. In
fhIs sfnfo fho nfom romnIns In Ifs Iowosf onorgy sfnfo nnd fhIs Is fho mosf sfnbIo sfnfo of fho
nfom. xcIted stute oI un utom rofors fo fho oIocfronIc confIgurnfIon nvnIIod by nn nfom
nffor nbsorbIng corfnIn dofInIfo nmounf of onorgy. Tho vnIonco oIocfrons nro romofod fo somo
hIghor ormIffod onorgy IovoI by nbsorfIon of onorgy. In fho oxcIfod sfnfo, fho nfom Is unsfnbIo
nnd fho oxcIfod oIocfron fonds fo como bnck fo fho orIgInnI osIfIon i.e., ground sfnfo. Affor
nbouf l0
4
soc. fho oIocfron rofurns fo fho ground sfnfo by omIffIng fho nmounf of onorgy
nbsorbod durIng oxcIfnfIon. Tho onorgy Is omIffod or nbsorbod In fho form of oIocfromngnofIc
wnvos of dofInIfo froquoncy i.e., of dofInIfo wnvoIongfhs. ThIs rocoss of oxcIfnfIon nnd rofurn
fo fho ground sfnfo Is fho bnsIs of socfroscoIc nnnIysIs of nfomIc nbsorfIon, omIssIon nnd
nfomIc fIuorosconco.
Q. 2. WLut Is utomIc ubsovptIon spectvoscopy?
Ans. ThIs Is fho nnnIyfIcnI fochnIquo bnsod on fho honomonon of IIghf nbsorfIon (!V
or vIsIbIo). If Is nIIcnbIo bofh fo qunIIfnfIvo nnd qunnfIfnfIvo nnnIysos.
Q. 3. WLut uve tLe puvumetevs Iov expvessIng tLe ubsovptIon?
Ans. TrnnsmIffnnco Is fho rnfIo of fho InfonsIfy of IIghf frnnsmIffod fo fho InfonsIfy of
IncIdonf IIghf.
(TrnnsmIffnnco) T =
I
I
o
T (orconf frnnsmIffnnco) =
l00 I
I
o
A = Iog
l0

I
I
o
A = 2 Iog T
whoro A = Absorbnnco, I
o
= InfonsIfy of IncIdonf IIghf,
I = InfonsIfy of frnnsmIffod IIghf.
CombInnfIon of !nmborfIoor`s Inw gIvon
A = A
l cm
l
Ic.
A = Absorbnnco, A
l cm
l
= Absorbnnco of l (u/t) soIufIon for nfh Iongfh of l cm,
I = fhIcknoss (cm), c = conconfrnfIon (g/l00 mI)
(moInr oxfIncfIon cooffIcIonf) =
A moIocuInr wf.
l0
l cm
l
.
Q. 4. CuIcuIute tLe concentvutIon oI u substunce A In un etLunoIIc soIutIon oI
wLIcL tLe ubsovbunce In u 1 cm ceII ut Its
mux
241 nm wus Iound to be 0.B90. TLe A
(1", 1 cm) Is 540 ut 241 nm.
Ans. A = A
l cm
l
Ic.
0.890 = 540 l c
C = 0.00l65 g/l00 mI.
Q. 5. CuIcuIute tLe concentvutIon In g mI
1
oI u soIutIon oI substunce B (moI.wt.
204.2) In 0.1 (M) HCI, sLowIng ubsovbunce ut Its
mux
2?? nm oI 0.613 In u 4 cm ceII.
TLe moIuv ubsovptIvIty ( ) ut 2?? nm Is 5432.
Ans. Horo fho workIng formuIn Is A = Ic.
0.6l3 = 5432 4 c
c = 2.82 l0
5
moI I
l
= 2.82 l0
5
204.2 gI
l
= 0.005?6 gI
l
= 5.?6 g mI
l
.
Q. 6. WLut Is moIecuIuv spectvoscopy?
Ans. Tho InfornnI onorgy (I) of n moIocuIo Is gIvon by:
I = KInofIc onorgy + IofonfInI onorgy + I
rof
+ I
vIb.
+ I
frnns
.
Tho moIocuInr socfroscoy mnInIy donIs wIfh fho sfudy of InforncfIon bofwoon rndInnf
onorgy nnd fho moIocuIo. In gonornI moIocuInr socfroscoy Is nbsorfIon socfroscoy.
Q. ?. WLut uve tLe dIIIevent eIectvonIc tvunsItIons tLut tuke pIuce on ubsovptIon
oI \V IIgLt?
Ans. Whon n moIocuIo, socInIIy orgnnIc moIocuIo, nbsorbs !V rndInfIons fho oIocfrons
nro oxcIfod fo hIghor onorgy IovoIs. In fho dIngrnm boIow fho oIocfrons nro rorosonfod
C = O
:
:
n (nonbonding)
R
H
s
s
s
p
Tho foIIowIng oIocfron frnnsIfIons fnko Inco:
* (nnfIbondIng), n *, n * (nnfIbondIng)
*
Thoso oIocfronIc frnnsIfIons nro rosonsIbIo for !V nbsorfIon of n moIocuIo.
Q. B. MentIon tLe uppIIcutIons oI \V.
Ans. (o) QuuIItutIve:
ofocfIon of conjugnfIon
ofocfIon of funcfIonnI grous
ofocfIon of goomofrIcnI Isomors.
(I) QuuntItutIve:
AnnIysIs of vnrIous snmIos (drugs, dyos ofc.)
Q. 9. Cun \V dIIIeventIute etLyIbenzene Ivom styvene?
Ans.
CH
2
CH
3
Ethylbenzene
CH = CH
2
Styrene
Ixfondod conjugnfIon Is mnxImum In cnso of sfyrono. So sfyrono wIII nbsorb nf n hIghor
wnvoIongfh.
Q. 10. WLIcL oI tLe IoIIowIng compounds wIII Luve gveutev
mux
?
(i)
NH
2
:
(ii) NH Cl
3
+
.
Ans. Comound (i) shows gronfor
mnx
vnIuo ns fho Iono nIr on nfom comos Info
rosonnnco wIfh fho bonzono rIng fo oxfond fho conjugnfIon. In (ii) fhoro Is no such oIocfron
nIr.
Q. 11. WLIcL oI tLe IoIIowIng compounds wIII Luve gveutev
mux
?
Ans. (i) CH
3
O
C
CH
3
(ii)
CCH
3
O
Comound (ii) wIII show gronfor
mnx
ns fhoro Is conjugnfIon In bonzono rIng ns woII ns
C = O grou romnIns In conjugnfIon wIfh fho bonzono rIng.
Q. 12. WLut uve tLe pvIncIpIes oI IR?
Ans. Tho nfoms In n moIocuIo bond nro In n sfnfo of consfnnf vIbrnfIon nnd rofnfIon.
Thoy mny bo comnrod wIfh fwo bnIIs (nfoms) joInod by srIng (bond). On nbsorfIon of I! fho
bond mny sfrofch, bond ofc., ns shown boIow. So sfrofchIng nnd bondIng of bonds nro rosonsIbIo
for I! nbsorfIon.
stretching
bending or
deformation
Q. 13. WLut Is tLe vunge oI InIvuved vudIutIons? CovveIute tLe dIIIevent unIts
used In I.R. spectvoscopy.
Ans. I.!. rogIon IIos bofwoon 0.8 fo 20 m or 80020,000 nm of oIocfromngnofIc rndInfIon.
Tho rogIon bofwoon 0.8 fo 2.5 m Is cnIIod fho nonr I.!. rogIon nnd l5 fo 20 m Is cnIIod fnr I.!.
rogIon. Tho rogIon bofwoon 2.5 l.5 m Is fho roor I.!. rogIon.
ConornIIy wnvo numbor (u) whIch Is fho numbor of vIbrnfIons of fho rndInfIon or cm.
Tho corroInfIon bofwoon fho dIfforonf unIfs usod In I.!. Is gIvon boIow:
l m = l0
6
m = l0
4
cm
So, =
l l0
4
m
=
cm
l
Q. 14. WLut uve IunctIonuI gvoup und IIngevpvInt vegIon In I.R.?
Ans. Tho IunctIonuI gvoup vegIon Is 2.5 fo ?.4 m (4000l430 cm
l
). In fhIs rogIon
funcfIonnI grous of orgnnIc comound Is dofocfod. Tho IIngevpvInt vegIon Is ?ll m (l430
9l0 cm
l
) gIvos n good donI of InformnfIon nbouf fho moIocuIo bosIdos fho funcfIonnI grous
of fho comound. Tho fIngorrInf rogIon cnn Iond us fo IdonfIfy nn orgnnIc comound.
Q. 15. How Is un I.R. spectvum vecovded?
Ans. (o) IR souvce: A ornsf gIowor, n rod of nn nIIow of ZIrconIum, YffrIum nnd
IrbIum oxIdos. Tho rod Is oIocfrIcnIIy honfod fo l?50 K.
(I) !ock snIf dIsc or KIr dIsc Is usod ns gInss nnd qunrfz nbsorb I.!.
(c) SumpIe pvepuvutIon: IIfhor fho snmIo wIfh KIr Is mndo fo oIIof or ujoI muII Is
usod. ujoI Is hydrocnrbon In nnfuro.
(J) RecovdIng oI spectvu: Tho snmIo Is Incod In !ock snIf coII In fho nfh of I.!. Tho
chnngo of InfonsIfy of IIghf frnnsmIffod drnws n grnh whIch Is I! socfrum.
Q. 16. How wIII you dIstInguIsL CH
3
COOH Ivom CH
3
COCH
3
wItL tLe LeIp oI
I.R. spectvu?
Ans. C = O (sfr.) onks wIII bo obsorvod In bofh fho socfrn In fho rogIon of l?00 cm
l
. Iuf
nn nbsorfIon bond nf 25003000 cm
l
(brond) wIII bo obsorvod In socfrum of CH
3
COOH duo
fo dImorIc nssocInfIon of CH
3
COOH moIocuIos fhrough hydrogon bondIng.
Q. 1?. GIve tLe stvuctuve oI moIecuIuv IovmuIu C
3
H
B
O Ivom tLe IoIIowIng dutu:
I.R. (NuJoI)
mux
2950 und 2B20 cm
1
, 1110 cm
1
.
Ans. Throo Isomors for fho moIocuInr formuIn nro:
(i) CH
3
CH
2
CH
2
OH, (ii) CH
3
CHOH CH
3
nnd (iii) CH
3
O CH
2
CH
3
As fhoro Is no onk nonr 3300 cm
l
fho fIrsf fwo nro ruIod ouf. Tho onk nf lll0 cm
l
Is
CO (sfr.) for ofhor IInkngo nnd 2950 nnd 2820 cm
l
for CH (sfr). So fho comound Is
CH
3
OCH
2
CH
3
.
Q. 1B. WLut Is nucIeuv mugnetIc vesonunce (n.m.v.)?
Ans. Irofons nnd noufrons In fho nucIous sIn. If fho nrfIcIos In n nucIous don`f hnvo
fhoIr sIns nIrod, fhoro Is n nof sIn. Chnrgod nrfIcIos IIko rofon whon sIn wIII gonornfo
mngnofIc fIoId nnd mngnofIc momonf nIong fho nxIs of sIn. Thus n rofon or nucIous ncfs IIko
n fIny bnr mngnof. ucIoI wIfh ovon mnss numbors
8
C
l2
,
8
O
l6
hnvo no rosuIfnnf sIn nnd honco
fho mngnofIc roorfy. Tho mngnofIc roorfy of fho nucIous Is rosonsIbIo for nucIonr mngnofIc
rosonnnco. Tho rocIssIonnI froquoncy of fho sInnIng nucIous whon oqunIs fho froquoncy of
fho nIIod mngnofIc fIoId (oIocfromngnofIc rndInfIon), fho nucIous chnngos Ifs sIn sfnfo from
ono fo fho ofhor nnd fho nbsorfIon or omIssIon of onorgy fhon fnkos Inco by fho nucIous nnd
nucIonr rosonnnco fhon occurs. Tho nbsorfIon of onorgy Is rocordod In n grnh nnd Is known
ns n.m.r.
Q. 19. WLut uve equIvuIent und non-equIvuIent pvotons In n.m.v.?
Ans. Irofons rosonf In n moIocuIo hnvIng fho snmo onvIronmonf nbsorb nf fho snmo
mngnofIc fIoId sfrongfh. Such rofons nro cnIIod oquIvnIonf rofons.
And rofons whIch hnvo dIfforonf onvIronmonfs In n moIocuIo nbsorb nf dIfforonf mngnofIc
fIoIds, such rofons nro cnIIod non-oquIvnIonf rofons. AII oquIvnIonf rofons gIvo ono sIgnnI
In fho n.m.r. socfrum. on-oquIvnIonf rofons gIvo dIfforonf sIgnnIs.
Q. 20. GIve u scLemutIc dIugvum oI pmv spectvum.
Ans. Soo foxf.
Q. 21. IdentIIy equIvuIent und non-equIvuIent pvotons In tLe IoIIowIng moIecuIes
und Lence tLe numbev oI sIgnuIs und spIIttIng.
(i) CH
3
CBv
2
CH
3
und (ii) CH
3
CH
2
CI
Ans. (i) CH
3
o
CIr
2
CH
3
o
AII nro oquIvnIonf rofons. So n.m.r. socfrum wIII show ono sIgnnI i.e., n 6H, e (sIx
rofon, sIngIof)
(ii) CH CH CI
3 2
o I
2 l
2 rofons In Cl nro oquIvnIonf nnd 3 rofons In fho C2 nro oquIvnIonf; buf fho
rofons of Cl nnd C2 nro non-oquIvnIonf ns dosIgnnfod by 'o` nnd 'I`. So fwo sIgnnIs nro
obfnInod In fho n.m.r. socfrum. Tho ufIoId sIgnnI Is n frIIof (3H, I). Tho downfIoId sIgnnI Is
qunrfof (2H, qunrfof). 'CH
2
` rofons gIvo downfIoId sIgnnI ns fho C2 Is nffnchod fo
oIocfronognfIvo 'CI` nfom (Soo foxf).
Q. 22. WLut uve sLIeIdIng und desLIeIdIng oI pvotons?
Ans. In fho M! socfrum of n comound, fho oIocfrons nround fho rofons nIso Iny
fhoIr roIo. Whon n comound Is Incod In n mngnofIc fIoId, fho oIocfrons nround fho rofons
gonornfo nIso n mngnofIc fIoId known ns Inducod mngnofIc fIoId. ThIs Inducod mngnofIc fIoId
mny roInforco or ooso fho nIIod fIoId. So fwo cnsos mny nrIso:
(i) If fho Inducod fIoId oosos fho nIIod fIoId nnd fhus fho offocfIvo mngnofIc fIoId 'H`
oxorIoncod by fho nucIous Is smnIIor fhnn fho nIIod mngnofIc fIoId (H
o
). H Is
roInfod fo H
o
ns H = H
o
(l ) whoro, n nondImonsIonnI qunnfIfy known ns
shIoIdIng or scroonIng consfnnf nnd hns n osIfIvo vnIuo.
Tho rofon Is snId fo bo shIoIdod by fho oIocfrons. A gronfor nIIod fIoId Is roquIrod for
fho oxcIfnfIon of rofons.
(ii) If fho Inducod fIoId roInforcos fho nIIod fIoId (horo Is nognfIvo), nn onhnncod fIoId
sfrongfh wIII bo oxorIoncod by fho rofon nnd rofon Is snId fo bo doshIoIdod In fhIs
cnso.
SLIeIdIng cnusos n shIff of fho rosonnnco froquoncy fo hIghor vnIuos of fho nIIod fIoId
(H
o
) i.e., fho shIff Is ufIoId. On fho ofhor hnnd desLIeIdIng cnusos n shIff of fho rosonnnco
froquoncy fo Iowor vnIuos of fho nIIod fIoId i.e., fho shIff Is downfIoId. Tho mngnIfudo of fhIs
shIff Is cnIIod cLemIcuI sLIIt.
Q. 23. MutcL tLe numbev oI sIgnuIs oI tLe compounds gIven:
ConpounJe Signole
(i) H C
3
CCH
3
CH
3
CH
3
l
(ii) C
2
H
5
OH 3
(iii) CH
3
OCH
3
3
(it) CH
3
OCH
2
CH
3
3
Ans. Comound (i) wIII roduco fhroo sIgnnIs bocnuso fhoro nro fhroo fyos of rofons
i.e., CH
3
rofons on fho Ioff sIdo of fho rIng, mofhyI rofons on fho rIghf sIdo of fho rIng nnd
rIng rofons. SInco fhoro Is no non-oquIvnIonf rofons In fho moIocuIo, nII fho onks wIII bo
sIngIof nnd no sIIffIng wIII fnko Inco.
Comound (ii) wIII roduco fhroo sIgnnIs ns fhoro nro fhroo fyos of rofons. If wIII bo n
frIIof for CH
3
rofons, n qunrIof for CH
2
rofons nnd n sIngIof for OH rofon.
Ior comound (iii) onIy ono sIgnnI wIII bo obfnInod In cnso of 3rd comound ns fhoro nro
onIy ono fyo of rofons nnd honco If wIII bo n sIngIof.
Comound (it) wIII roduco fhroo sIgnnIs. Thoro nro fhroo fyos of rofons. Honco n
sIngIof for OCH
3
rofons, n qunrfof for CH
2
rofons nnd n frIIof for CH
3
rofons.
Q. 24. TvunsIute tLe IoIIowIng set oI NMR spectvuI dutu to u compound. MoIecuIuv
IovmuIu C
9
H
12
, sIngIet 3.22, 3H; sIngIet ?.?5, 9H.
Ans. (i) Tho formuIn C
9
H
l2
corrosonds fo fho gonornI formuIn of nromnfIc hydrocnrbon
C
n
H
2n6
. Thus fho comound wIII confnIn n bonzono rIng wIfh somo ofhor subsfIfufIons.
(ii) Tho comound gIvos fwo sIgnnIs nnd fhus If IndIcnfos fho rosonco of fwo fyos of
rofons. Thoso condIfIons nro snfIsfIod onIy by fho sfrucfuro:
H C
3
CH
3
CH
3
1, 3, 5-trimethyl benzene
ThIs sfrucfuro oxInIns fho oxIsfonco of sIngIof 3.22 duo fo fhroo rIng rofons nnd sIngIof
?.?5 duo fo nIno CH
3
rofons.
Q. 25. Count tLe numbev oI sIgnuIs Iov tLe IoIIowIng compounds:
(l)
CH
3
, (2) CHCI
2
CH
3
Ans. (i) Tho fIrsf comound confnIns fwo fyos of rofons, fho rIng rofons nnd CH
3
rofons, honco fwo sIgnnIs wIII bo obsorvod.
(ii) Tho socond comound confnIns fwo kInds of rofons ns IndIcnfod by o nnd I (boIow).
CHCI CH
2 3
o I
So, fwo sIgnnIs wIII bo obsorvod.

Q. 26. Stute tLe sIgnIIIcunce oI peuk uveu.
Ans. Ionks obfnInod In fho M! socfrum mnko dIfforonf nrons wIfh fho bnso IIno. If
hns boon obsorvod fhnf nron undor nn M! sIgnnI Is dIrocfIy roorfIonnI fo fho numbor of
oquIvnIonf rofons fhnf gIvo rIso fo fhnf sIgnnI. Iy comnrIng fho nron subfondod by dIfforonf
sIgnnIs, wo cnn cnIcuInfo fho roInfIvo roorfIon of dIfforonf fyos of rofons. As for oxnmIo,
In fho cnso of onks obfnInod for bonzyI nIcohoI, fho rnfIos of fho nrons undor fho onks nro
l:2:5, IndIcnfIng fhnf fho fhroo fyos of rofons nro In fho rnfIo l:2:5. Thoro nro ono OH
rofon, fwo mofhyIono rofons nnd fIvo rIng rofons.
Q. 2?. MentIon tLe vuvIous uses oI n.m.v. spectvum.
Ans. M! socfroscoIc fochnIquo Is nIIod In dIfforonf cnsos.
(i) Iov IdentIIIcutIon oI IunctIonuI gvoups. Ivory funcfIonnI grou gIvos n
chnrncforIsfIc sIgnnI In fho M! socfrum. Iy sfudyIng fho chomIcnI shIff of
comound, If bocomos ossIbIo fo osfnbIIsh whnf kInd of funcfIonnI grou Is rosonf
In fho moIocuIo.
(ii) Iov stvuctuve detevmInutIon oI un unknown compound. If Is ossIbIo fo oIucI-
dnfo fho sfrucfuro of nn unknown comound from fho n.m.r. sfudIos. ThIs Is duo fo
fho rofons whIch undor dIfforonf onvIronmonfs gIvo dIfforonf chomIcnI shIffs.
Iy obsorvIng doubIofs, frIIofs or muIfIIofs, If Is ossIbIo fo Inco hydrogons nf n-
rorInfo Inco In fho formuIn nnd honco n sfrucfuro cnn bo osfnbIIshod.
(iii) Iov compuvIson oI two compounds. M! socfrum Is IIko fIngorrInf of n
comound. Two comounds whIch show snmo n.m.r. socfrum musf bo IdonfIcnI In
sfrucfuros.
Q. 2B. Iscuss tLe uppIIcutIons oI muss spectvoscopy.
Ans.
oformInnfIon of moIocuInr mnss of n comound (known nnd unknown).
oformInnfIon of moIocuInr sfrucfuro nnnIysIng fho frngmonfnfIon nfforn nnd
fnkIng fho hoI of !V, I.!., nmr socfrn.
Tho combInnfIon of gns IIquId chromnfogrnhy (gIc) wIfh mnss socfromofry (ms)
Is of gronf Imorfnnco In modorn chomIcnI nnnIysIs. IIrsf gIc sonrnfos fho
chomIcnIs In nn unknown mIxfuro, ns for oxnmIo, oIIufod wnfor, whon fho ms
dofocfs nnd IdonfIfIos comononfs.
Q. 29. TvunsIute tLe IoIIowIng set oI spectvu to tLvee IsomevIc ovgunIc
compounds.
oscrIfIonCoIourIoss IIquId (b.. 80C); moIocuInr formuIn C
4
H
8
O; I.!.
mnx
fIIm
(cm
l
)
l?l5 (e), M! (nonf IIquId) l.06 (3H, I), 2.l4 (3H, e), 2.43 (2H, q).
Ans. Tho I! bnnd nf l?l5 cm
l
IndIcnfos fhnf fho comound ossossos n C = O grou.
ThIs ovIdonco, fnkon wIfh fho moIocuInr formuIn C
4
H
8
O, suggosfs fhnf fho comound Is oIfhor
nn nIIhnfIc nIdohydo or n kofono.
Tho M! socfrum rondIIy oxcIudos nro nIdohydo ns fhoro Is no rosonnnco nf nbouf
9.5 nnd confIrms fho sfrucfuro ns bufnn-2-ono (mofhyI ofhyI kofono).
CH CH
3
A
2

O
C
CH
3
I
MofhyI grou (A) nnd fho mofhyIono grou nonr rosocfIvoIy ns fho oxocfod frIIof
nnd qunrfof. MofhyI grou (I) nnd mofhyIono grou nro bofh doshIoIdod (movod fo downfIoId)
by fho ndjnconf C = O grou. Tho rIncInI Ions In fho mnss socfrum of bufnn-2-ono nro
CH
3
C O
+
(n/c 43) nnd CH
3
CH
2
C O
+
(n/c 5?), nnd moIocuInr woIghf M
.
+

?2.
EXERCISES
1. (o) MonfIon fho wnvoIongfhs for vIsIbIo, !V nnd I.!. rndInfIons.
(I) nmo fho dIfforonf socfroscoIc fochnIquos whIch nro omIoyod for fho oIucIdnfIon of sfruc-
furos of orgnnIc comounds.
2. Whnf do you monn by:
(o) nbsorfIon socfrum (I) omIssIon socfrum
3. Sfnfo Ioor-!nmborf`s Inw nnd doduco mnfhomnfIcnI oxrossIon for fho snmo.
4. Whnf nro fho dIfforonf oIocfronIc frnnsIfIons fhnf fnko Inco on fho nbsorfIon of !V IIghf
5. IxInIn fho forms:
(i) chromohoro (ii) nuxochromo (iii) bIuo shIff (it) rod shIff.
6. MonfIon fho nIIcnfIons of !V socfroscoy.
?. CnIcuInfo fho moInr nbsorfIvIfy of fho soIufIon of conconfrnfod l l0
4
moI I
l
, gIvon A = 0.20
nnd nfh Iongfh = 2.5 cm. (Ans. 8000 dm
3
moI
l
cm
l
)
B. MonfIon fho rIncIIos of I.!. socfrum.
9. IndIcnfo whofhor you wIII uso I.!. or !.V. socfroscoy for dIsfInguIshIng fho foIIowIng nIrs of
comounds:
(o) CH
2
= CHCH
2
OCH
3
nnd CH
3
CH
2
COCH
3
(I) CH
3
OCH
3
nnd CH
3
CH
2
OH
(c) CH
2
= CHCH
2
OH nnd CH
3
CH
2
CHO
10. Whnf Is nucIonr mngnofIc rosonnnco
11. Whnf nro oquIvnIonf nnd non-oquIvnIonf rofons
12. Whnf Is monnf by shIoIdIng nnd doshIoIdIng of n rofon
13. Whnf Is chomIcnI shIff
14. Why do wo soIocf fofrnmofhyI sIInno (TMS) ns n sfnndnrd subsfnnco In n.m.r.
15. Whnf do you monn by sIIffIng of sIgnnIs
16. Whnf Is mnss socfroscoy Whnf Is fho rIncIIo of m.s.
1?. CIvo nIIcnfIons of:
(i) !V (ii) I.!. (iii) n.m.r. (it) m.s.
#
2DJ?DAEIJHO
548
In nImosf nII chomIcnI roncfIons fho moIocuIos fhnf fnko nrf nro gonornIIy In fhoIr ground
oIocfronIc sfnfos. In hofochomIcnI roncfIons, fho roncfnnf moIocuIos nro rovIousIy romofod
by nbsorfIon of IIghf fo fhoIr oIocfronIcnIIy oxcIfod sfnfo. !Ighf of nny wnvo-Iongfh Is nssocInfod
wIfh nn onorgy vnIuo donofod by I = I, whoro I Is IInnck`s consfnnf nnd Is fho froquoncy of
IIghf. !Ighf of nrfIcuInr froquoncy corrosondIng fo nrfIcuInr onorgy cnn cnuso fho oIocfron
of n moIocuIo fo movo fo hIghor onorgy IovoI. Honco nn nmounf of IIghf onorgy wIII bo nbsorbod
nnd fho rosf of fho onorgy wIII bo frnnsmIffod. Socfrohofomofor Is nn Insfrumonf whIch
comnros fho InfonsIfy of frnnsmIffod IIghf nnd IncIdonf IIghf nnd gIvos fho nmounf of onorgy
nbsorbod by fho soIufIon of n comound. Tho onorgy of oIocfronIc frnnsIfIons corrosonds fo
IIghf In vIsIbIo, !V nnd fnr !V rogIon. ConornIIy fho coIorod comounds nbsorb In fho vIsIbIo
rnngo, nnd ossoss n coIor comIomonfnry fo fhnf of whIch Is nbsorbod.
Far UV
150 nm 200
UV
400
Visible
800 1000
Near I.R.
15 2.5
1 0.8 m m
Fig. 25.1 UV, visible and l.R. portions of spectrum.
!ndor normnI condIfIons, fho moIocuIos nro consfnnfIy vIbrnfIng nnd rofnfIng nnd fhoso
mofIons cnn bo qunnfIzod. Thus fho moIocuIos nro nof onIy In n gIvon oIocfronIc sfnfo buf nIso
In n vIbrnfIonnI nnd rofnfIonnI sfnfo. Comnrod fo fho dIfforonco bofwoon fho fwo oIocfronIc
IovoIs fho dIfforonco bofwoon fho fwo ndjnconf vIbrnfIonnI or rofnfIonnI IovoIs Is much smnIIor.
A snmIo mny confnIn Inrgo numbor of moIocuIos nII In fhoIr ground oIocfronIc sfnfos, buf fhoy
mny bo dIsfrIbufod nmong vIbrnfIonnI nnd rofnfIonnI sfnfos. Thus whon n nrfIcuInr wnvo-
Iongfh of IIghf Is nbsorbod fhoro wIII bo mnny ossIbIo frnnsIfIons whIch mny gIvo rIso fo n
brond bnnd, rnfhor fhnn gIvIng n shnr onk. Tho hoIghf of fho onk of nbsorfIon doonds on
fho numbor of moIocuIos mnkIng frnnsIfIon nnd Is roorfIonnI fo Iog whoro Is fho oxfIncfIon
cooffIcIonf.
mny bo oxrossod ns = I/cl.
whoro c = conconfrnfIon of moIocuIos In moIos or IIfro,
l = coII Iongfh In cm, nnd
I = Iog I
o
/I whoro I
o
nnd I nro fho InfonsIfIos of IncIdonf nnd frnnsmIffod IIghf rosocfIvoIy.
Tho wnvoIongfh whoro fho nbsorfIon Is mnxImum Is donofod by
mnx
. !V or vIsIbIo nbsorfIon
onk Is duo fo fho frnnsIfIon of nn oIocfron from fho ground sfnfo fo n hIghor onorgy orbIfnI.
Tho funcfIonnI grou whIch cnusos such nbsorfIon Is cnIIod n cLvomopLove. IuroIy vIbrnfIonnI
PHOTOCHEMlSTRY 549
frnnsIfIons roquIro much Ioss onorgy nnd nro found In I.!. rogIon whorons rofnfIonnI frnnsIfIons
nro found In fnr I.!. rogIons.
SingIet and TripIet States
In orgnnIc moIocuIos fho oIocfrons In fho ground sfnfo nro nIrod nnd hnvo oosIfo
sIn. Iy nbsorbIng onorgy whon oIocfrons nro romofod fo nn orbIfnI of hIghor onorgy fho
oIocfrons no Iongor shnros nn orbIfnI nnd fhoso fwo unnIrod oIocfrons mny oIfhor hnvo snmo
sIn whIch Is cnIIod n 'IripleI` or fho sIns mny bo nIrod whIch Is cnIIod 'eingleI`. Tho onorgy for
fho frIIof sfnfo Is Iowor fhnn fho corrosondIng sIngIof nccordIng fo Hund`s !uIo. Thus n
dIfforonf nmounf of onorgy i.e., dIfforonf wnvoIongfh Is roquIrod fo romofo nn oIocfron from
ground fo fho oxcIfod sIngIof or frIIof sfnfo. Any fyo of frnnsIfIons nro nof ormIffod rnfhor
frnnsIfIons bofwoon onorgy IovoIs nro govornod by soIocfIon ruIos nnd sovornI fyos of frnnsIfIons
nro forbIddon. Two of fho fyos of forbIddon frnnsIfIons nro Imorfnnf:
(o) Spin forIiJJen IroneiIionefrnnsIfIons In whIch sIn of nn oIocfron chnngo Is
forbIddon, i.e., frnnsIfIons bofwoon IdonI sIngIof nnd frIIof sfnfos nro sfrIcfIy forbIddon.
(I) S,nneIr,-forIiJJen IroneiIionen* frnnsIfIon In formnIdohydo Is forbIddon sInco
ovorIns of orbIfnIs nro forbIddon.
Notation for Excited States of Organic MoIecuIes
Tho oxcIfod sfnfos of moIocuIos nro dIfforonf from fho orIgInnI ground sfnfos. Honco
nomoncInfuro of fhoso oxcIfod sfnfos sonrnfoIy Is Imorfnnf.
Ono common sysfom for fhnf Is fo donofo fho muIfIIIcIfIos, S for sIngIof nnd T for frIIof.
Tho ground sfnfo Is donofod by so nnd hIghor oxcIfod sfnfos ns S
l
, S
2
, S
3
, T
l
, T
2
, T
3
ofc.
M. Knshn hns dovoIood nnofhor sysfom of oxrossIng fho oIocfronIc sfnfos In forms of
InIfInI nnd fInnI orbIfnIs InvoIvod In frnnsIfIon. Thoro nro four fyos of moIocuIos:
(i) Snfurnfod moIocuIos wIfh MoIocuInr orbIfnIs (MO), e.g. nrnffInIc hydrocnrbons.
(ii) Snfurnfod moIocuIos wIfh nnd non of bondIng MO, e.g. CH
3
I, H
2
O.
(iii) !nsnfurnfod moIocuIos wIfh nnd MOs, e.g., C
2
H
5
, nromnfIc hydrocnrbons, CO
2
ofc.
(it) !nsnfurnfod moIocuIos wIfh , , nnd n MOs, e.g., nIdohydos, kofonos, yrIdIno, ofhor
hoforocycIIcs ofc. MOs nro formod by ovorInIng of e nnd p
c
orbIfnIs IIko ep, ep
2
,
ep
3
ofc.
MOs nro formod by ovorInIng of p
x
nnd p
,
or hybrIdIzod orbIfnIs fo form doubIo or
frIIo bonds.
n MOs nro uro nonbondIng orbIfnIs confnInIng nonbondIng oIocfrons. Honco fho fyos
of oIocfronIc orbIfnIs nro , , n, * nnd *. IhofochomIsfs dosIgnnfo by nn nrrow from Iowor fo
hIghor onorgy sfnfo frnnsIfIons ns n
*
,
*
, n
*
, o
*
ofc.
Tho n * frnnsIfIons hnvo Iow robnbIIIfy nnd honco gIvo wonk nbsorfIon bnnds
whorons * frnnsIfIons nro mosf Imorfnnf nnd gIvo Infonso chnrncforIsfIc nbsorfIon (for
conjungnfod hydrocnrbons).
Properties of the Excited States
A moIocuIo In fho oIocfronIcnIIy oxcIfod sfnfo mny bo n comIofoIy dIfforonf socIos from
fho orIgInnI ono. SInco fho chnrgo donsIfIos nro dIfforonf If shows dIfforonf chomIsfry from
fhnf of fho ground sfnfo moIocuIo, nIso bocnuso If hns oxcoss onorgy buf wonkor bonds. Ofhor
hysIcnI roorfIos IIko dIoIo momonf, K vnIuos, rodox ofonfInIs nIso dIffor.
A frnnsIfIon of oIocfrons from fho bondIng fo fho nnfIbondIng orbIfnI cnusos n frIIo
bond fo bocomo doubIo, n doubIo bond fo bocomo sIngIo nnd n sIngIo bond fo dIsruf. If nIso
Ionds fo Incronso In bond dIsfnncos by nbouf l5 nnd nIso Inrgo chnngos In bond nngIos.
IormnIdohydo moIocuIo hns n Innnr goomofry In fho ground sfnfo. On oxcIfnfIon nn
oIocfron on O-nfom Is frnnsforrod fo nnfIbondIng MO nnd honco fho moIocuIo cnn fwIsf nIong
fho CO bond. SImIInrIy for conjugnfod sysfoms IIko ofhyIono or bufndIono, froo rofnfIon In
fho oxcIfod sfnfo Ionds fo cie-Irone IsomorIznfIon. Ior e.g. ncofyIono, whIch Is IInonr In ground
sfnfo hns n Irone goomofry wIfh ep
2
cnrbons In (, *) sfnfo.
H
C C
H
CO
2
, CS
2
, HC nro IInonr In fhoIr ground sfnfo buf bonf In oxcIfod sfnfos, whorons
rndIcnIs IIko H
2
, HCO nnd O
2
moIocuIos nro bonf In fhoIr ground sfnfo buf IInonr In oxcIfod
sfnfos.
IxcIfod honoI Is moro ncIdIc nnd nIso orfho-nrn dIrocfIng fownrds subsfIfufIon In
bonzono rIng. Tho rofoIyfIc oquIIIbrIum consfnnf K
o
for fho roncfIon Is l0 nnd 5.? In fho
ground nnd oxcIfod sfnfos. In confrnsf fo fhIs, nromnfIc cnrboxyIIc ncIds oxhIbIf n docronso In
ncIdIfy In oxcIfod sfnfo roInfIvo fo ground sfnfo. In gonornI, honoIs, fhIoIs nnd nromnfIc nmInos
bocomo sfrongor ncIds on oxcIfnfIon whorons cnrboxyIIc ncIds, nIdohydos, kofonos nnd
hoforocycIIcs bocomo sfrongor bnsos.
Tho dyos IIko mofhyIono bIuo nnd fhIonIno show sfrIkIng dIfforonco In rodox ofonfInIs
bofwoon ground nnd oxcIfod sfnfos.
In fho oxcIfod sfnfo, fho dIoIo momonf nof onIy hns dIfforonf mngnIfudo, buf dIfforonf
dIrocfIon nIso. IhofochomIcnI bohnvIour of n moIocuIo vnrIos wIfh fho chnngo In soIvonf for fho
nbovo ronson.
HIgLIIgLts:
Iuws oI PLotocLemIstvy:
CroIIIure-Dropper Lou (IireI lou).
OnIy fhnf IIghf whIch Is nbsorbod by n sysfom cnn cnuso chomIcnI chnngo.
SIorl-1ineIein Lou (2nJ lou).
Ono qunnfum of IIghf Is nbsorbod or moIocuIo of nbsorbIng nnd roncfIng subsfnnco
fhnf dIsnonrs.
Wignerè epin coneertoIion rule.
In nny nIIowod oIocfronIc onorgy frnnsfor rocoss, fho ovornII sIn nnguInr
momonfum of fho sysfom shouId nof chnngo.
PhotoIysis
Tho dIrocf dIssocInfIon of n moIocuIo on nbsorfIon of n qunnfum of rndInfIonnI onorgy
bocomos robnbIo whon fho onorgy nbsorbod Is oqunI fo or moro fhnn fho bond dIssocInfIon
onorgy nnd fhIs dIssocInfIon from nn oxcIfod sfnfo Is cnIIod pLotoIysIs. Throo sIfunfIons cnn
Iond fo cIonvngo of n moIocuIo.
(l) Tho romofIon mny brIng fho moIocuIo fo n vory hIgh vIbrnfIonnI IovoI whIch IIos
nbovo fho rIghf hnnd orfIon of fho curvo I
2
In IIg. 25.2 nnd honco fho moIocuIo cIonvos nf Ifs
fIrsf vIbrnfIon.
PHOTOCHEMlSTRY 551
E
2
E
1
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
Internuclear distance
r
2
r
1
r
0
V
3
V
2
V
1
V
0
V
0
V
1
V
2
A
Fig. 25.2 Energy curves for a diatomic molecule. Two possible transitions are shown. When an
electron has been excited to the point marked A, the molecule may cleave.
(2) Whon fho romofIon Is fo n Iowor vIbrnfIonnI IovoI t
l
or t
2
whIch IIos wIfhIn fho curvo
I
2
, fho moIocuIo mny cIonvo. Irom fho curvo In IIg. 25.2, wo fInd fhnf fho oquIIIbrIum dIsfnnco
Is gronfor for oxcIfod sfnfo fhnn In ground sfnfo.
Ivunck-Condon pvIncIpIe sfnfos fhnf romofIon of nn oIocfron (l0
l5
soc) Is much
fnsfor fhnn fho sIngIo vIbrnfIon (l0
l2
soc). Honco whon nn oIocfron Is suddonIy romofod fho
dIsfnnco bofwoon fho nfoms romnIns unchnngod nnd honco fho bond bohnvos IIko n comrossod-
srIng, fho condIfIon Is suddonIy roIIovod by bronkIng fho bond.
(3) In somo cnsos ns In IIg. 25.3, fho oxcIfod sfnfo onfIroIy Ionds fo dIssocInfIon. 1.g., Is
fho * romofIon In hydrogon moIocuIo IondIng fo cIonvngo. Tho hofoIyfIc cIonvngo mny
bronk fho moIocuIo Info fwo smnIIor moIocuIos or Info froo rndIcnIs. Iroo rndIcnIs bohnvo In n
sImIInr wny IIko froo rndIcnIs roducod In ofhor rocossos, oxcof fhnf fho formor nro In oxcIfod
sfnfo. !nroIy fho moIocuIo bronks Info fwo Ions.
E
1
E
2
V
2
V
1
V
0
P
o
t
e
n
t
i
a
l
e
n
e
r
g
y
Internuclear distance
Fig. 25.3 Promotion to a dissociative state results in bond cleavage.
Types of PhotophysicaI Pathways
A moIocuIo oxcIfod fo n hIghor onorgy sfnfo musf rofurn fo fho ground sfnfo. IromofIons
nro from S
0
fo S
l
sfnfos, ns romofIon from S fo frIIof sfnfos Is 'forbIddon`. IromofIon fo ofhor
hIghor sIngIof sfnfos IIko S
2
fnkos Inco, buf In IIquIds nnd soIIds fhoso hIghor onorgy sfnfos
nro shorf IIvod (l0
l3
fo l0
ll
soc.) nnd usunIIy dro bnck fo S
l

sfnfo. Tho onorgy Iosf by fhoso
dros from S
2
, S
3
fo S
l
sfnfos Is gIvon u fo fho onvIronmonf by coIIIsIon wIfh ofhor noIghbourIng
moIcuIos nnd fho rocoss Is cnIIod enevgy cuscude. Tho docny from fho hIghor onorgy sfnfos
InIfInIIy ouInfos mnny vIbrnfIonnI IovoIs of S
l
, buf fInnIIy comos down fo fho Iowosf vIbrnfIonnI
IovoIs of S
l
, whIch Is fhoroforo fho onIy Imorfnnf oxcIfod sIngIof sfnfo. ThIs sfnfo cnn undorgo
dIfforonf hysIcnI nnd chomIcnI rocossos. Tho nfhwnys nro shown nnd IIsfod In modIfIod
JnbIonskI dIngrnm (IIg. 25.4) nnd In TnbIo 25.l.
vc
S
0
h
p
n
h
f
n
hn
hn
vc
S
2
IC
IC
S
1
ISC
vc
ISC
vc
T
1
Fig. 25.4 Modified Jablonski diagram.
PHOTOCHEMlSTRY 553
TabIe 25.1 Physical processes undergone by excited molecules
The superscript v indicates vibrationally excited state: excited states higher
than S
1
or T
1
are omitted.
S
0
+ I S
l
t
IxcIfnfIon
S
l
t
S
l
+ honf VIbrnfIonnI roInxnfIon
S
l
S
0
+ I IIuorosconco
S
l
S
0
+ honf InfornnI convorsIon
S
l
T
l
t
Inforsysfom crossIng
T
l
t
T
l
+ honf VIbrnfIonnI roInxnfIon
T
l
S
0
+ I
t
Ihoshorosconco
T
l
S
0
+ honf Inforsysfom crossIng
S
l
+ A S A
(S ) 0
0
+
(S )
l
SIngIof-sIngIof frnnsfor
(hofosonsIfIznfIon)
T
l
+ A S A
(S ) 0 (T
0
+
l
)
TrIIoffrIIof frnnsfor
(hofosonsIfIznfIon)
(l) Inorgy nbsorfIon mny romofo moIocuIo fo n hIghor onorgy sfnfo IIko S
2
, S
3
, ofc. or
fo hIghor vIbrnfIonnI IovoIs of S
l
wIfhIn l0
5
soc. oboyIng Irnnck-Condon rIncIIo. Tho oIocfronIc
onorgy of fho hIghor sfnfos or oxcoss vIbrnfIonnI onorgy of S
l
sfnfo Is quIckIy Iosf fo fho
surroundIngs by n mochnnIsm cnIIod InfornnI convorsIon (IC).
(2) Tho moIocuIo In fho S
l
sfnfo cnn dro fo somo Iow vIbrnfIonnI IovoI of S
0
nf onco
gIvIng off fho onorgy In fho form of IIghf wIfhIn l0
9
soc. cnIIod IIuovescence. ThIs rocoss Is
sIow nnd nof vory common oxcof for nromnfIcs nnd dInfomIc moIocuIos.
0 - 0
S
1
S
0
V
4
V
3
V
2
V
1
V
0
V
4
V
3
V
2
V
1
V
0
Promotion Fluorescence
Fig. 25.5 Promotion and fluorescence between S
1
and S
0
states.
(3) Intevsystem cvossIng (ISC), InvoIvos non-rndInfIvo frnnsIfIon from sIngIof fo
frIIof sfnfos (S
l
T
l
) whIch Is n 'forbIddon` nfhwny. SInco n sIngIof sfnfo usunIIy hns n
hIghor onorgy fhnn fho corrosondIng frIIof nnd honco onorgy musf bo gIvon u. Tho
moIocuIo fhus mIghf cross from S
l
fo T
l
sfnfos nf n hIgh vIbrnfIonnI IovoI nnd fhon cnscndo
down fo Ifs Iowosf vIbrnfIonnI IovoI of T
l
. ThIs cnscndo Is vory rnId (l0
l2
soc).
(4) MoIocuIo from fho T
l
sfnfo mny rofurn fo S sfnfo by gIvIng u honf (rovorso Inforsysfom
crossIng) or IIghf (rndInfIvo hoshorosconco omIssIon). Iuf duo fo sIn rosfrIcfIon (forbIddon)
bofh fho rocossos nro sIow (l0
3
fo l0
l
soc). Thus T
l
sfnfo hns much Iongor IIfofImo.
(5) Tho Insf ofIon Is fhnf n moIocuIo In nn oxcIfod sfnfo (S
l
, T
l
) mny frnnsfor Ifs fofnI
onorgy fo nnofhor moIocuIo of fho onvIronmonf. Tho rocoss Is cnIIod pLoto-sensItIzutIon,
fho donor moIocuIo Is cnIIod pLotosensItIzev, nnd fho nccofor ronchos Ifs oxcIfod sfnfo.
* + A * +
ThIs onorgy frnnsfor fnkos Inco nccordIng fo Wigner-epin coneertoIion rule, whIch sfnfos
fhnf fho fofnI oIocfron sIn doos nof chnngo nffor fho onorgy frnnsfor.
AccordIng fo WIgnor-ruIo fwo Imorfnnf fyos of hofosonsIfIznfIon nro:
A A
T S T S
l 0 l 0
+ + (TrIIof-frIIof frnnsfor)
A A
S S S S
l 0 l 0
+ + (SIngIof-sIngIof frnnsfor)
SIngIof-sIngIof frnnsfor cnn fnko Inco ovor Iong dIsfnncos (40 ) whorons frIIof-frIIof
frnnsfor roquIros coIIIsIon bofwoon fho moIocuIos. SInco frIIof sfnfos nro usunIIy dIffIcuIf fo
ronro by dIrocf IrrndInfIon honco frIIof-frIIof frnnsfor Is nn Imorfnnf rocoss of frnnsforrIng
onorgy by hofosonsIfIznfIon.
Ior n roncfIon hofosonsIfIzor shouId bo choson such fhnf If doos nof nbsorb IIghf In fho
snmo rogIon ns fho nccofor sInco fwo mIghf fhon comofo.
HIgLIIgLts:
(i) Ifforoncos In chnrgo dIsfrIbufIon In vnrIous onorgy sfnfos of n moIocuIo cronfo
dIfforoncos In fho chomIcnI nnd hysIcnI roorfIos of oxcIfod nnd ground sfnfo
moIocuIos.
(ii) IIocfronIc frnnsIfIons bofwoon onorgy sfnfos nro govornod by Irnnck-Condon
rIncIIo.
(iii) Coomofry of fho moIocuIos mny chnngo on oxcIfnfIon whIch hns nn Imorfnnf
offocf on fho hofochomIsfry of fho moIocuIo.
(it) A frnnsIfIon mny bo forbIddon duo fo
ConsorvnfIon of sIn momonfs
Symmofry rosfrIcfIons.
(t) Affor nbsorbIng n hofon, nn nfom or n moIocuIo, If doos nof nrfIcInfo In
hofochomIcnI roncfIon, cnn rofurn fo ground sfnfo by nny of fho mnny
hofohysIcnI nfhwnys, somo of whIch nro rndInfIvo nnd somo nro nonrndInfIvo.
PhotochemicaI Processes for Excited MoIecuIes
IxcIfod sIngIof socIos hnvo vory shorf IIfofImo (>l0
l0
soc) nnd honco gonornIIy undorgo
ono of fho mnny hysIcnI rocossos nIrondy dIscussod. Tho frIIof sfnfos hnvo much Iongor
IIfofImo nnd honco fhoy roncf chomIcnIIy. Thus hofochomIsfry Is fho chomIsfry of tvIpIet
stutes.
Thoro nro sovornI fyos of chomIcnI roncfIons whIch cnn occur wIfh oxcIfod moIocuIos.
Tho rImnry roncfIons nro boIng dIscussod whIch mny bo foIIowod by socondnry roncfIons sInco
fho roducfs of fho rImnry roncfIons nro froquonfIy rndIcnIs or cnrbonos.
(l) SImpIe cIeuvuge Into vudIcuIs. AIdohydos nnd kofonos nbsorb In 230 fo 330 nm
rogIon, whoroby n* sIngIof-sIngIof frnnsIfIon occurs nnd fho cnrbonyI comounds cIonvo. In
cnso of kofonos, fhIs roncfIon Is cnIIod NovvIsL type I veuctIon whIch InvoIvos -cIonvngo
gIvIng rIso fo nn ncyI nnd nn nIkyI rndIcnI. Tho ncyI rndIcnI Is ossonfInIIy docnrbonyInfod nf
hIgh fomornfuro.
!O
O
!
I
!C
O
+ !
PHOTOCHEMlSTRY 555
ThIs dIssocInfIon Is fnvourod If n roInfIvoIy sfnbIo nIkyI rndIcnI Is formod nnd usunIIy
fnvourod In vnor hnso rnfhor fhnn In soIvonf.
Tho ofhor oxnmIos nro cIonvngo of CI
2
fo CI nfoms, cIonvngo of OO bonds In oroxy
comounds, nnd C bonds In nIIhnfIc nzo comounds (sInco sfnbIo
2
Is fho roducf).
(2) ecomposItIon Into moIecuIes. AIdohydos cnn nIso cIonvo fo form CO nnd nIknno.
!C
O
H
I
!H + CO
CnrbonyI comounds ossossIng -hydrogon nfoms rocood by n shIff of H fo oxygon
wIfh subsoquonf cIonvngo fo nn oIofIno nnd nn onoI. ThIs Is NovvIsL type II veuctIon.
!
2
CHC!
2
C
O
!
I
!
2
C = C!
2
+ !
2
CHC
O
! !
2
C = C!
OH
Tho roncfIon cnn occur from bofh fho oxcIfod sIngIof nnd fho frIIof sfnfos. SomofImos
fho InformodInfo cnn nIso cycIIzo fo n cycIobufnnoI ns sIdo roducf. CnrboxyIIc osfors, nnhydrIdos
cnn nIso gIvo fhIs fyo of roncfIon.
R C
2
CR
O
H
hn
R C
2
CR
O
H
Singlet/triplet
.
R C
2
CR
OH
.
diradical
CR = CR + HOCR
2

2
CR
2
O = CR
CHR
2
R OH
R R
R R
R R
.
*
3. IntvumoIecuIuv veuvvungement. TrImosIfyI comound fo onoI ofhor
ArCHCAr
Ar O
ArCH = CAr
OAr
Where Ar is
Me Me
Me
hn
4. PLotoIsomevIzutIon. Tho common oxnmIo Is fho cie-Irone IsomorIznfIon of sfIIbono.
C = C
Ph
H
Ph
H
C = C
Ph
H Ph
hn
H
cis-isomer trans-isomer
In fhIs cnso In fho oxcIfod sfnfo, bofh In S
l
nnd T
l
of oIofIns fho goomofry Is orondIcuInr
rnfhor fhnn Innnr nnd so no cie-Irone Isomors for oxcIfod sfnfos. Whon fho oxcIfod moIocuIo
rofurns fo fho ground sfnfo (S
o
) oIfhor of fho Isomor cnn bo formod.
5. Hydvogen utom ubstvuctIon. Ionzohonono whon IrrndInfod goos fo S
l
sfnfo nnd
fhon fo T
l
sfnfo whoroby If nbsfrncfs ono H nfom from fho soIvonf IsoroyI nIcohoI nnd fhon
subsoquonfIy nnofhor H fo form bonzhydroI or If mny dImorIzo fo form bonzInncoI.
PhCPh
O
hn
PhCPh
O
(S
1
)
PhCPh
O
(T
1
)
PhCHPh
OH
PhCCPh
Ph
OH
Ph
OH
PhCPh
OH
Isopropanol
6. PLotodImevIzutIon
hn
O
O O O
O
+
Dimerization of cyclopentenone
Photosynthesis
IhofosynfhosIs InvoIvos n sorIos of comIox roncfIons In fho chIoroInsf of Innfs wIfh
fho ovornII convorsIon of wnfor nnd cnrbon dIoxIdo fo cnrbohydrnfos nnd dIoxygon.
nCO
2
+ nH
2
O
680 nm
I
(CH
2
O)
n
+ nO
2
ChIorohyII
AII fho oxygon comos from H
2
O.

Tho roncfIon Is InIfInfod by vIsIbIo soInr rndInfIon
(600?00 nm) nnd If Is ondofhormIc. Tho hofosysfom consIsfs of fwo nrfsnn nnfonnn comIox
consIsfIng of chIorohyII moIocuIos whIch nbsorb fho soInr onorgy nnd fho socond nrf Is
hofochomIcnI roncfIon confro, whIch Is n frnnsmombrnno rofoIn-Igmonf-cofncfors comIox.
Tho nnfonnn i.e., fho IIghf-hnrvosfIng Igmonf comIox (!HC) nbsorbs IIghf qunnfn nnd wIfhIn
Icosocond frnnsfors fho onorgy fo fho roncfIon confro. Tho ovornII hofosynfhofIc convorsIon
InvoIvos IIghf nbsorfIon nf fwo dIfforonf wnvoIongfhsIhofosysfom I (IS-I) nnd Ihofosysfom
II (IS-II)IIghf roncfIons. IS-I nnd IS II nro IdonfIfIod ns I?00 nnd I 680 Igmonfs rosocfIvoIy.
(u) PLotosystem I (P ?00). I?00 Is oxcIfod nnd If frnnsfors nn oIocfron fo bound
forrodoxIn (Io-S rofoIn). Tho bound forrodoxIn In furn frnnsfors fho oIocfron fo soIubIo-
forrodoxIn, whIch ngnIn frnnsfors If fo AI
+
formIng AIH (IIg. 25.6).
PHOTOCHEMlSTRY 557
P700
photosystem I
Photon
hn
Bound
ferredoxin (P430)
Soluble
ferredoxin
NADPH
+0.4
+0.2
0
0.2
0.4
0.6
R
e
d
o
x
p
o
t
e
n
t
i
a
l
(
V
)
Fig. 25.6 Formation of NADPH by photosystem I.
on-oxygon ovoIvIng hofosynfhofIc bncforIum confnIns IS-I onIy.
(b) PLotosystem II. In oxygon-ovoIvIng sysfoms IS-I nnd IS-II nro sorInIIy

IInkod fo
roduco AIH nnd ATI by n fwo-sfo rocoss.
0.6
0
+0.4
+0.8
R
e
d
o
x
p
o
t
e
n
t
i
a
l
(
V
)
Q (weak reductant)
e
proton
gradient
ATP
Photosystem
P680
II
H O
2
O
2
+ 4H
+
photon hn
(weak oxidant)
Photosystem
P700
I photon
hn
e
NADP + H
+ +
NADPH
Bound (strong reductant)
ferredoxin
(strong oxidant: Mn-containing,
water-splitting enzyme)
Fig. 25.7 Electron transport and oxidation of H
2
O in noncyclic photo-phosphorylation (Z-scheme).
Iy nbsorbIng IIghf IS-II Is rnIsod fo oxcIfod sfnfo nnd nn oIocfron Is frnnsforrod fo Insfo
quInono (or) whIch In furn frnnsfors If fo cyfochromo I 559. Tho fInnI oIocfron-cnrrIor from
IS-II fo IS-I Is n InsfocynnIn (Cu confnInIng rofoIn). IS-I nccofs oIocfrons from IS-II. Iy
monns of fwo-sfo oIocfron-onorgIsIng rocossos, cnfnIysod by onch hofosysfom, oIocfrons nro
fInnIIy frnnsforrod from H
2
O fo fho fInnI nccofor bound-forrodoxIn I430 (IIg. 25.?). !Ighf
onorgy cnusos oIocfrons fo fIow from H
2
O fo AIH.
Tho rocossos of hofosynfhofIc sysfom of I680 nnd I?00 nro summnrIzod In IIg. 25.8.
Stroma side
= +ve Dm
H
+
Photon, hn
2H
+
Thylakoid
membrane
PSII
P680
2e
Lumen side
= ve Dm
H
+
Plasto-
quinone
loop
PQH
2
PQ
Cyt b -f
6
2e
PC
Photon, hn
NADP + H
+ +
NADP
ADP+Pi ATP
PSI
P700
2e
ATPase
H O
2
0.5O + 2H
2
2H
+
nH
electrochemical
proton gradient
+
PO = Plastoquinone; PC = Plastocyanin;
electron transport by electron carriers PQ and PC
Fig. 25.8 Schematic representation of energy transduction by reaction centres PS-II and PS-I in the
noncyclic photosynthetic reaction process (According to Tanz and Zieger, "Plant Physiology Benjamin/
Cummings, Redwood City, CA. (1991).
Tho oIocfron frnnsorf rocoss cronfIng oIocfro-chomIcnI rofon grndIonf ncross fho
fhyInkoId mombrnno drIvos fho synfhosIs of ATI from AI nnd I
i
by ATI synfhnso.
2H
2
O + 2AI
+
+ 3AI
3
+ 3HIO
2

4 I
2H
+
+ O
2
+ 2AIH + 3ATI
4
ChIoroInsfs cnn nIso synfhosIzo onIy ATI wIfhouf roducIng AIH InvoIvIng cycIIc
hofohoshoryInfIon.
uvk veuctIons. Tho AIH nnd ATI formod by fho 'IIghf roncfIons` nro ufIIIzod for
synfhosIzIng cnrbohydrnfos from CO
2
In sfromn for whIch sunIIghf Is nof roquIrod. Thoso CO
2
fIxIng roncfIons nro cnIIod HIII veuctIons, whIch cnn fnko Inco In dnrk.
IInnfs gonornfo gIycornIdohydo-3-hoshnfo (CAI) ns fho sfnrfIng mnforInI for hIghor
cnrbohydrnfos from fhroo moIocuIos of CO
2
by ufIIIsIng 9 ATI nnd 6 AIH. ThIs mofnboIIc
nfhwny for cnrbohydrnfo synfhosIs Is cnIIod CuIvIn-Benson cycIo.
3CO
2
+ 9ATI + 6AIH + H
2
O CAI + 6AI
+
+ 8 I
i
+ 9 AI.
PHOTOCHEMlSTRY 559
Chemistry of vision
Ihoforocofor coII In vorfobrnfo oyo consIsfs of:
(i) Oufor sogmonf consIsfIng of sfnck of mombrnno dIscs In rods nnd conos, whIch ncfs
ns nnfonnno for rocoIvIng hofons (confnInIng IIorofoIn comIox, whIch Is socInIIsod
for hofon rocofIon).
(ii) Innor sogmonf of mofnboIIc nnd nucIonr sourcos.
(iii) SynnfIc rogIon for confncfIng wIfh norvo coIIs of rofInn.
Tho oufor sogmonf of fho rod coII confnIns n frnnsmombrnno chromorofoIn cnIIod
vLodopsIn comosod of n gIycorofoIn opsIn nnd n chromohoro vetInuI.
AbsorfIon of IIghf Ionds fo fho hofo-IsomorIsnfIon of cie-rofInnI fo Irone Isomor, whIch
dIssocInfos sonfnnoousIy fo nII-Irone-rofInnI nnd osIn. Tho schomo Is:
Rhodopsin, Rh
11- -retinal + H N-(CH ) -opsin cis
2 2 4
H
+
hn
RC = N(CH ) -opsin + H O
2 4 2
cis-retinal Isomerisation
Trans-retinal C = N(CH ) -opsin
2 4
H
+
H
Spontaneous
dissociation
All- -retinal + Opsin trans
SIgnuI tvunsductIon. A gonornI schomo of hoforoncfIon Is:
(i) AbsorfIon of n hofon of IIghf cnusIng ll-cie-rofInnI fo nII-Irone-rofInnI form nnd
conformnfIonnI chnngo of osIn.
(ii) CIonvngo of nII-Irone-rofInnI from osIn. !hodosIn !h Is ncfIvnfod fo !h
*
.
(iii) Tho hoforocofor ofonfInI In fho rod coII mnInfnInod by cIosuro of n
+
Ion chnnnoIs.
IhofonbsorfIon nIfors fho mombrnno ofonfInI nnd conducfnnco of n
+
, rosuIfIng In
frnnsIonf oonIng of n
+
chnnnoI nnd n
+
Ion InfIux.
(it) Chnngo In mombrnno ormonbIIIfy fo Cn
2+
cnusos cIosuro of fho chnnnoI nnd rosfo-
rnfIon fo rosfIng sfnfo.
AbsorfIon of n sIngIo hofon bIocks fho InfIux of mIIIIon of n
+
Ions by cIosIng hundrods
of n
+
chnnnoIs In fho mombrnno. ThIs sIgnnI nmIIfIcnfIon Is nchIovod by onzymo cnscndo
InvoIvIng cycIIc CMI.
PevceptIon oI coIov Is by (o) oJJiIite nnd (I) euIIrocIite proceeeee.
In nddIfIvo rocoss orcofIon of coIor Is by mIxIng of rImnry coIors, rod, bIuo nnd
groon. CombInnfIon of rImnry coIors (fwo) gIvos socondnry coIors whIch ngnIn cnn bo mIxod fo
gIvo fho fuII rnngo of coIors.
In subfrncfIvo rocoss, Igmonfs nbsorb corfnIn coIors nnd rofIocf bnck ofhor coIors. In
fhIs rocoss, fho rImnry coIors nro mngonfn, yoIIow nnd bIuo-groon. Inch Igmonf nbsorbs
ono rImnry coIor nnd rofIocfs bnck fho ofhor fwo. IorcofIon of coIor Is qunnfIfnfIvo nnd
subjocfIvo, If dIffors nmong IndIvIdunIs.
HIgLIIgLts:
Tho InIfInI hofon nbsorfIon gIvos rIso fo n shorf IIvod sIngIof sfnfo whIch
subsoquonfIy nssos fo Iong-IIvod frIIof sfnfo, whIch ncfunIIy nrfIcInfos In rodox
chnIn.
IhofosynfhosIs InvoIvos n sorIos of comIox roncfIons wIfh fho ovornII convorsIon
of wnfor nnd cnrbon dIoxIdo fo cnrbohydrnfos nnd dIoxygon In fho chIoroInsf.
EXERCISES
1. Sfnfo: (o) Croffhurs-rnor Inw (I) Sfnrk-IInsfoIn Inw.
2. IxInIn: (o) Irnnck-Condon rIncIIo.
3. MonfIon hysIcnI rocossos undorgono by oxcIfod moIocuIos.
4. Whnf Is onorgy cnscndo
5. Whnf nro ISC nnd IhofosonsIfIzor
6. CIvo oxnmIos of somo hofochomIcnI roncfIons.
?. Whnf Is orrIsh fyo I roncfIon CIvo oxnmIo.
B. IxInIn fho chomIsfry of vIsIon.
9. Whnf nro fho nrk nnd HIII roncfIons
10. CIvo n schomnfIc rorosonfnfIon of onorgy frnnsducfIon In fho noncycIIc hofosynfhofIc roncfIon
rocoss.
11. IxInIn hofosynfhosIs In fho IIghf of hofochomIcnI roncfIons.
561
$
RoIe of MetaIs in BioIogy
MofnI Ions nro roquIrod for mnny crIfIcnI funcfIons In bIoIogIcnI sysfoms. Tho normnI
conconfrnfIon rnngo for onch mofnI In bIoIogIcnI sysfom Is nnrrow, wIfh bofh dofIcIoncIos nnd
oxcossos cnusIng nfhoIogIcnI chnngos. Tho oIomonfs
roquIrod In humnn nufrIfIon cnn bo grouod Info
buIk nnd tvuce grous. Tho buIk oIomonfs nro
roquIrod In oxcoss of l00 mg/dny, whorons fho frnco
oIomonfs nro roquIrod In nmounfs nof gronfor fhnn
n fow mg/dny. Tho frnnsIfIon mofnIs for whIch
bIoIogIcnI sforngo nnd frnnsorf nro sIgnIfIcnnf nro
In ordor of docronsIng nbundnnco: Iron, zInc, coor,
moIybdonum, cobnIf, chromIum, vnnndIum nnd
nIckoI. Tho form of fho mofnIs Is nIwnys IonIc, buf
fho oxIdnfIon sfnfos cnn vnry on bIoIogIcnI noods. Tho
mofnIs nro gonornIIy found oIfhor bound dIrocfIy fo
rofoIns or In cofncfors such ns orhyrIns or
cobnInmIns. IrofoIns wIfh whIch frnnsIfIon mofnIs
nnd zInc nro mosf commonIy nssocInfod cnfnIyzo fho
Infrn nnd InformoIocuInr ronrrnngomonf of oIocfrons.
In fhIs rosocf, fho rodox roorfIos of fho mofnIs
nro Imorfnnf, In ofhors mofnIs nonr fo confrIbufo fo fho sfrucfuro of fho ncfIvo sfnfo. An
ossonfInI mofnI Ion mny funcfIon ns n ofonf oIocfron-wIfhdrnwIng ngonf nf somo oInf In fho
cnfnIyfIc funcfIon of onzymos whIch roquIro mofnI Ions for fhoIr ncfIvIfIos nnd nro cnIIod
mofnIIoonzymos (TnbIo 26.l).
TabIe 26.1: Some Enzymes Containing or Requiring Essential lnorganic Elements as Cofactors
Io
2+
or Io
3+
Cyfochromo oxIdnso
CnfnInso
IoroxIdnso
Cu
2+
Cyfochromo oxIdnso
Zn
2+
A oIymornso
CnrbonIc nnhydrnso
AIcohoI dohydrogonnso
Mg
2+
HoxokInnso
CIucoso 6-hoshnfnso
Mn
2+
ArgInnso
K
+
Iyruvnfo kInnso
(nIso roquIros Mg
2+
)
I
2+
!ronso
Mo Ifrnfo roducfnso
So CIufnfhIono oroxIdnso
EIements required in Human
nutrition
IuIk oIomonfs
CnIcIum
MngnosIum
SodIum
IofnssIum
Trnco oIomonfs
Coor
Iron
Mnngnnoso
MoIybdonum
SoIonIum
ZInc
Iron
Iron Is fho mosf nbundnnf frnnsIfIon oIomonf In fho Inrfh`s crusf nnd In gonornI In nII
forms of IIfo. Tho fofnI nmounf of Iron In humnns Is quIfo Inrgo, nvorngIng 3 fo 5 gm for n
honIfhy nduIf. Iron Is nbsorbod In Ifs forrous form (Io
2+
). AbsorfIon nnd oxcrofIon of Iron nro
roInfIvoIy sIow nnd confroIIod by dIfforonf fncfors. Iron rosonf In dIfforonf food vnrIos In fhoIr
nbsorfIon chnrncforIsfIcs, such ns Iron Is bosf nbsorbod from monf, Ioss nbsorbod from coronI
grnIns.
Mosf of fho Iron Is rosonf In LuemogIobIn, fho Insmn oxygon-frnnsorf rofoIn, whoro
Iron funcfIons fo doIIvor oxygon for rosIrnfIon. A much smnIIor nmounf Is rosonf In
myogIobInwhIch Is n muscIo oxygon-frnnsorf rofoIn. If Is rosonf In cytocLvomes nnd
cytocLvome oxIduse. Iron frnnsorf from fho sforngo sIfos fo IocnfIons whoro coIIs synfhosIzo
Iron confnInIng rofoIns Is dono by nn Iron-confnInIng rofoIn cnIIod tvunsIevvIn. In fho fIssuos
If Is sforod In fho form of IevvItIn, nn Iron-rofoIn confnInIng forrIc hydroxIdo nnd forrIc
hoshnfo. Tho IIvor, sIoon nnd bono mnrrow confnIn much forrIfIn. Iron Is oxcrofod from fho
body LE= bIIo nnd fnocos nnd monsfrunI bIood. SInco durIng monsfrunfIon, Iron Ioss bocomos
doubIo or frIIo, honco Inrgo nmounf of Iron Is roquIrod for womon comnrod fo mon.
Intestine
Only 510%
of ingested Fe
is absorbed
Intestinal cells
(stored as ferritin)
Fe carried
by transferrin
Blood
Liver
(Fe stored as
ferritin)
Muscles
(myoglobin;
cytochromes)
Other
tissues
(cytochromes)
Bone
marrow
Red blood cells
(haemoglobin)
Loss in
menstrual blood
Food
Fe in bile
inhibits
absorption
Transferrin
Blood
Transferrin
Transferrin
Transferrin
Transferrin
Fig. 26.1 lron absorption and transport.
ROLE OF METALS lN BlOLOGY 563
Tho rocossos nnd roncfIon In whIch Iron nrfIcInfos nro crucInI for fho survIvnI of
orgnnIsms nnd fhoy IncIudo A synfhosIs, rosIrnfIon, hofosynfhosIs, nIfrogon roducfIon,
oxygon frnnsorf nnd oxygonnfIons.
ofIcIoncy of Iron Ionds fo Ivon-deIIcIency unemIu, In whIch fho numbor of rod bIood
coIIs nro normnI buf fho nmounf of homogIobIn In fho coIIs Is Iow.
Copper
Coor Is ossonfInI In fho dIof bocnuso If Is InvoIvod In fho roor ufIIIznfIon of Iron
osocInIIy for fho synfhosIs of cyfochromo oxIdnso, whIch confnIns bofh Iron nnd coor. If Is
roquIrod fo fho oxfonf of 2.5 fo 5 mg/dny nnd Is found In monf, sonfood, nufs, nnd vogofnbIos.
Coor nnd Iron rofoIns nrfIcInfo In mnny of fho bIoIogIcnI roncfIons:
for cyfochromo oxIdnso synfhosIs whIch cnfnIyzos fho frnnsfor of oIocfrons from wnfor
fo dIoxygon durIng rosIrnfIon.
rovorsIbIo bIndIng of dIoxygon, AC homogIobIn, homocynnIn ofc.
ncfIvnfIon of dIoxygon.
dIsmufnfIon of suoroxIdo by Cu or Io ns fho ncfIvo mofnI.
!so of sforod Iron Is roducod by coor dofIcIoncy, whIch suggosfs fhnf Iron mofnboIIsm
mny doond on coor rofoIns.
Coor Is nIso rosonf In fho ncfIvo grou of IysyI oxIduse, nn onzymo rosonsIbIo for
cross-IInkIng In coIIngon nnd oInsfIn. Honco nnImnIs fhnf nro coor dofIcIonf dovoIo dofocfIvo
coIIngon moIocuIos (duo fo nbsonco of cross-IInkIng) IondIng fo rufuro of nrforIos.
In fho hofosynfhofIc oIocfron frnnsorf, fho ncfunI cnrrIor of oIocfrons Is fho bIuo coor
rofoInInsfocynnIn. Horo fho coor nfom cnrrIos fho oIocfron undorgoIng Cu(I)Cu(II) cycIos.
Zinc
ZInc Is nn ossonfInI comononf of nonrIy nbouf 80 fo l00 dIfforonf onzymos ns nrf of
fhoIr rosfhofIc grous. Tho onzymos IncIudo nIcohoI dohydrogonnso, cnrbonIc nnhydrnso, A
nnd !A oIymornsos, cnrboxy ofIdnso. If Is nIso rosonf In mnny A nnd AI IInkod
dohydrogonnsos whIch romofo fho frnnsfor of hydrIdo Ions from subsfrnfos fo A
+
/AI
+
.
As n nrf of fho cnrbonIc nnhydrnso, If cnfnIyzos fho hydrnfIon of CO
2
fo H
2
CO
3
, whorons
In cnrboxyofIdnsos, If nrfIcInfos In rofooIyfIc ncfIvIfy. ZInc Is found In hIgh conconfrnfIon
In sorm coIIs, rosfnfo gInnd nnd oyos. Tho hormono InsuIIn Is sforod comIoxod wIfh zInc.
ZInc nIso hns n roIo In fho funcfIonIng of fnsfo nnd smoII rocofors rosocfIvoIy of fonguo
nnd noso.
Mechanism
ZInc hns such nn Imorfnnf roIo ns fho rosfhofIc grou of Inrgo numbor of onzymos
sInco If cnn co-ordInnfo wIfh four, fIvo or sIx IIgnnds wIfhouf nny roforonco. Tho IIgnnds cnn
bo onsIIy oxchnngod wIfh ono wnfor moIocuIo. ZInc ncfs ns n !owIs ncId, If doos nof chnngo Ifs
rofoIn IIgnnd nor doos If chnngo Ifs oxIdnfIon sfnfo buf onIy chnngos fho co-ordInnfIon shoro
on fho sIdo oxosod fo wnfor/soIvonf. ZInc hns n hIgh nffInIfy for nIfrogon, oxygon nnd suIfur. If
Is fhoroforo found fo bo bound fo hIsfIdInos, gIufnmnfos or nsnrfnfos. If doos nof nIwnys
nrfIcInfo In fho cnfnIyfIc sfos buf Ifs rosonco Incronsos cnfnIyfIc rnfo. Thus from nbovo If
cnn bo snId fhnf zInc Inys bofh sfrucfurnI nnd roguInfIng roIos for fho onzymos.
nIIy roquIromonf of zInc for nn nduIf Is l5 mg. If Is rosonf In nbundnnco In monf, ogg,
son foods, mIIk nnd IIvor buf In Iow nmounf In fruIf nnd groon vogofnbIos.
Manganese
Mnngnnoso Inys n crIfIcnI roIo In oxygon ovoIufIon cnfnIysod by fho rofoIns of fho
hofosynfhofIc roncfIon confor. How fho muIfIIo mnngnnoso nfoms nrfIcInfo In fho romovnI
of four oIocfrons nnd rofons from wnfor Is yof fo bo InvosfIgnfod. Tho supevoxIde dIsmutuse
of bncforIn nnd mIfochondrIn nndpyvuvute cuvboxyIuse In mnmmnIs nIso confnIn mnngnnoso.
Mnngnnoso Is nIso rosonf In uvgInuse whIch hydroIyzos nrgInIno fo uron, whIch Is fho ond
roducf of humnn nmIno grou mofnboIIsm. Mn
2+
nIso sorvos ns n cofncfor for hoshnfo-
frnnsforrIng onzymos.
CobaIt
CobnIf Is n vIfnI nrf of vIfnmIn I
l2
moIocuIo nnd honco Is roquIrod by fho mIcro-orgnnIsms
for Ifs synfhosIs. In dIfforonf nnImnIs nIso Co Is roquIrod for fho synfhosIs of I
l2
by fho
mIcroorgnnIsms of fho C.I. frncf.
Tho mosf common fyo of roncfIon In whIch cobnInmIno onzymos nrfIcInfo rosuIfs In
rocIrocnI oxchnngo of H nfoms If fhoy nro on ndjnconf C nfoms.
!nIIko mosf nnImnIs, rumInnnfs hnvo n hIgh nufrIfIonnI roquIromonf for cobnIf.
ofIcIoncy of cobnIf mny Iond fo Iowor roducfIon of I
l2
whIch mny Iond fo nnnomIn.
NickeI
IckoI Is n comononf of uronso, hydrogonnso, CO dohydrogonnso, S-mofhyI CoM
roducfnso, whIch cnfnIyzos fho formInnI sfo In mofhnno roducfIon by mofhnnogonIc bncforIn.
AII I-rofoIns nro obfnInod from Innfs nnd bncforIn. IckoI Is n comononf of uveuse whIch
wns fho fIrsf onymo crysfnIIIzod In l926. IckoI mny nIso bo found In fho nucIoIc ncId bIndIng
rofoIns.
VunudIum nnd cLvomIum hnvo sovornI fonfuros In common. IIoIogIcnI roIos of onch
romnIn InrgoIy unknown nnd fhoy nro bofh rosonf In onIy smnII nmounfs In orgnnIsms. In
rofoIns, vnnndIum Is n cofncfor In nn nIgnI bromooroxIdnso nnd In corfnIn roknryofIc
nIfrogonnsos. If Is nIso found In bIood coIIs of n rImIfIvo vorfobrnfo buf Ifs roIo Is uncIonr. If Is
found fo funcfIon In fho ncfIvo sIfos of corfnIn fInvIn dohydrogonnsos. If Is nIso noodod for
roor growfh of bono nnd connocfIvo fIssuos of humnn.
ChromIum Is InvoIvod In fho gIucoso ufnko by nnImnI fIssuos, buf IIffIo Is known nbouf
fho comIoxos or fncfors of chromIum from Innfs, nnImnIs nnd bncforIn.
MoIybdenum rofoIns cnfnIyzo fho roducfIon of nIfrogon nnd nIfrnfos ns woII ns
oxIdnfIon of nIdohydos, urInos nnd suIfIfo. Mo rofoIns nro nIso Io-rofoIns wIfh Iron confros.
Somo Mo-rofoIns confnIn nddIfIonnI cofncfors such ns fInvIns, AC In xnnfhIno oxIdnso nnd
nIdohydo oxIdnso. XnnfhIno oxIdnso cnfnIyzos fho oxIdnfIon of urIno fo yIoId fho oxcrofory
roducf urIc ncId. Tho numbor of rodox confros In Mo-rofoIns oxcoods fho numbor of oIocfrons
frnnsforrod.
SeIenIum combInod In nn nmIno ncId Is nn ossonfInI comononf of fho rosfhofIc grous
of sovornI onzymos IncIudIng gIufnfhIono oroxIdnso, whIch funcfIons wIfh gIufnfhIono fo rofocf
coIIs ngnInsf fho dosfrucfIvo ncfIon of hydrogon oroxIdo. Tho forrous (Io II) of fho hnomogIobIn
Is rondIIy oxIdIsod by H
2
O
2
fo mofhomogIobIn (InncfIvo oxygon cnrrIor). ThIs Is rofocfod by
gIufnfhIono oroxIdnso whIch confnIns soIonocysfoIno In whIch fho S of cysfoIno Is roIncod
by So.
!IffIo Is known nbouf fho bIoIogIcnI sforngo of nny mofnI oxcof Iron whIch Is sforod In
forrIfIn. Howovor, zInc nnd coor nro bound fo mofnIIofhIonoIn In n form whIch mny bo sforod.
ZInc, coor, vnnndIum, chromIum, mnngnnoso nnd moIybdonum nro frnnsorfod ns sImIo
snIfs or IoosoIy bound rofoIn comIoxos. Iuf for Iron, hIgh-nffInIfy choInfors or rofoIns nro
roquIrod for frnnsorf.
Coor, cobnIf, zInc, mnngnnoso nnd nIckoI, nIfhough ossonfInI In fho dIof, nro nIso foxIc
In oxcoss nnd cnuso honIfh hnznrds. ChromIum In fho form of chromnfo Is mufngonIc In bncforInI
nnd mnmmnIInn sysfoms.
!nsfIy sIIIcon, ubIquIfous ns sIIIcn (SIO
2
) nnd ns cnIcIum nIumInIum sIIIcnfo, Is fho
mnjor comononf of cIny nnd Is roquIrod by rnf, chIck nnd ofhor nnImnIs fod wIfh synfhofIc
dIof. Tho funcfIon of sIIIcon Is nof known, buf If occurs In gronfosf conconfrnfIon In bono nnd
connocfIvo fIssuos of nnImnIs In nn orgnnIc form.
CaIcium and Magnesium
Tho nduIf humnn body confnIns moro fhnn n kIIogrnm of cnIcIum, nonrIy nII of whIch Is
conconfrnfod In bonos nnd foofh nIong wIfh hoshnfo nnd ns InsoIubIo crysfnIIIno cnIcIum
hydroxynnfIfo. CnIcIum nIso Inys n vory Imorfnnf roIo In nII coIIs ns nn InfrncoIIuInr roguInfor
nnd mossongor, modInfIng n wIdo rnngo of bIoIogIcnI rocossos IIko muscIo confrncfIon, socrofIon,
gIycoIysIs nnd gIuconoogonosIs, Iron frnnsorf, coII dIvIsIon; nnd growfh.
Cn
2+
nnd fho cyfoInsmIc Cn
2+
-bIndIng rofoIns (AC. CnImoduIIn) funcfIon ns InfrncoIIuInr
mossongors for dIfforonf hormonos. Iroo Cn
2+
rosonf In fho cyfosoI Is vory Iow nbouf l0
6
M.
TrnnsIfory Incronso In fho Cn
2+
conconfrnfIon whIch rosuIfs from hormonnI ncfIon on n
mombrnno rocofor Ionds fo fho conformnfIonnI chnngos of fho Cn
2+
bIndIng rofoIns. Thoso
rofoIns In furn sfImuInfo dIfforonf rofoIn kInnsos whIch nro InvoIvod In dIfforonf coIIuInr
ncfIvIfIos.
Affor fhoso rosonsos nnofhor Imorfnnf cInss of frnnsorf rofoIns (Cn
2+
ATInsos)
frnnsorf fho oxcoss InfrncoIIuInr Cn
2+
(roIonsod from dIfforonf sourcos) ncross fho mombrnno
nnd mnInfnIn fho orIgInnI Iow conconfrnfIon of Cn
2+
.
Cn
2+
Ions nro nIso known fo Iny vnrIous roIos oufsIdo coIIs. In fho Innfs Cn
2+
forms IInk
bofwoon IndIvIdunI coIIs nnd Is roquIrod for mnInfnInIng fho rIgIdIfy of whoIo Innfs.
CnIcIum Is nbundnnf In foods IIko mIIk, chooso, coronI grnIns, Iogumos, nufs nnd
vogofnbIos. AbsorfIon of Cn from InfosfIno Is confroIIod by comIox fncfors IIko H, Cn:I rnfIo
In dIof, rosonco of fnffy ncIds nnd vIfnmIn In dIof.
Irognnnf nnd IncfnfIng womon nnd chIIdron roquIro moro cnIcIum (l200 mg/dny)
comnrod fo normnI humnn (800 mg/dny). Tho cnIcIum rosonf In fho coronI grnIns Is nof
rondIIy nbsorbod.
Tho body confnIns nbouf 25 g of mugnesIum mosfIy rosonf In bonos. ConconfrnfIon
of mngnosIum Is rnfhor hIgh In nII fho coIIs, EA 5-l0 mM, sInco If Inys n vIfnI roIo on fho
ncfIon of n Inrgo numbor of onzymos InvoIvod In fho gIycoIysIs nnd ATI frnnsorf mochnnIsms.
Mg
2+
forms comIoxos wIfh fho hoshnfo grous of fho gIycoIyfIc InformodInfos nnd AI/
ATI nnd fho subsfrnfo bIndIng sIfos of mnny of fhoso onzymos nro socIfIc for Mg
2+
comIoxos
of hoshoryInfod InformodInfos. MngnosIum Is nbundnnf In chIorohyII of groon Ionfy
vogofnbIos. Tho rocommondod mngnosIum Infnko Is 350 mg/dny for nduIfs. AIcohoIIcs nnd
oIdorIy ooIo nro found fo bo mngnosIum dofIcIonf.
EIectron Transfer
!oncfIons In whIch oIocfrons nro frnnsforrod from ono moIocuIo fo nnofhor nro rodox
roncfIons. !oducIng nnd oxIdIsIng ngonfs funcfIon ns conjugnfo nIrs (rodox nIrs).
oIocfron donor A

+ oIocfron nccofor
Throo fyos of rodox confros nro found In bIoIogyrofoIn, smnII moIocuIos nnd rodox
cofncfors. MnInIy In fho cInss of smnII moIocuIos for oIocfron frnnsfors nIcofInnmIdo nnd quInono
coonzymos nro found In bIoshoro.
IcofInnmIdo ndonIno dInucIoofIdo (A) nnd AI nrfIcInfo wIfh fho 4-osIfIon of
fho yrIdIno rIng boIng ncfIvo.
Coonzymo A, nIso cnIIod ubIquInono, found In nII coIIs bofh In froo nnd In rofoIn bound
forms funcfIons ns foIIows:
O
O
H CO
3
CH
3
H CO
3
[CH
2
CH = CCH ] H + 2H + 2
2 n
+
e
CH
3
OH
OH
H CO
3
CH
3
H CO
3
[CH
2
CH = CCH ] H
2 n
CH
3
MofnIIorofoIns ncf ns oIocfron-frnnsfor rofoIns, nIso cnIIod 'oIocfron frnnsfornsos`,
ossoss somo chnrncforIsfIcs IIko:
(=) Iossoss n suIfnbIo cofncfor whIch ncfs ns oIocfron sInk.
(>) Iossoss ono hydrohobIc shoII cIoso fo cofncfor whIch forms hydrogon bonds wIfh fho
hydrohobIc onvIronmonf fo sfnbIIIzo fho oxIdIsod nnd fho roducod forms.
(?) SmnII sfrucfurnI chnngos nccomnnyIng oIocfron frnnsfor. Thoso frnnsfornsos nro of
four cInssosfInvodoxIns, bIuo coor rofoIns, Iron-suIfur rofoIns, cyfochromos.
Tho fInvodoxIns confnIn orgnnIc rodox cofncfor fInvIn mononucIoofIdo (IM). Thoy nro
found mnInIy In bncforIn nnd nIgno. IM cnn ncf ns l or 2 oIcfron rodox confor nnd funcfIons ns
Me
Me
N
N
CH (CHOH) CH OPO
2 3 2 3
2
N
NH
O
O
Me
Me
N
N
CH (CHOH) CH OPO
2 3 2 3
2
N
NH
O
O
H
Me
Me
N
N
CH (CHOH) CH PO
2 3 2 3
2
N
NH
O
O
H
H
Tho bIuo coor rofoIns funcfIon In bncforIn nnd Innfs. Tho goomofry of fho coor
sIfo Is frIgonnI Innnr nnd fhroo IIgnnds bInd fo coor nnd hnvo n roInfIvoIy hIgh roducfIon
ofonfInI.
Tho Iron-suIfur rofoIns Iny Imorfnnf roIo ns oIocfron cnrrIors In nII IIvIng orgnnIsms
nnd nrfIcInfo In fho Imorfnnf funcfIons IIko Innf hofosynfhosIs, nIfrogon fIxnfIon, sforoId
mofnboIIsm, oxIdnfIvo hoshoryInfIon ofc. Tho sImIosf Is rubrodoxIn found In nnnorobIc
bncforIn. Tho forrodoxIns (2Io-2S) nro found In Innf chIoroInsfs nnd mnmmnIInn fIssuos.
Tho ofhor fyos of forrodoxIn (4Io-4S) nro found In mnny sfrnIns of bncforIn. In fhoso fho Io Is
co-ordInnfod fo fho S of cysfoIns.
!nsfIy, fho cyfochromos nro fho mosf fhoroughIy chnrncforIzod oIocfron frnnsfornsos.
Cyfochromo confnIns homo cofncfors nnd nccordIng fo fho fyo of homo EA homo =, homo >
nnd homo ?, cyfochromos nro nIso cInssIfIod. CInss I cyfochromo ? hnvo n dIsfIncfIvo roIo In fho
mIfochondrInI oIocfron frnnsfor In mnmmnIInn sysfom. CInss II cyfochromo ? nro found In
hofosynfhofIc bncforIn. CInss III cyfochromo ? confnIn four homos whIch nro nssocInfod wIfh
fho cyfoInsmIc mombrnno of suIfnfo-roducIng bncforIn.
IIocfron frnnsfor roncfIons Iny koy roIos In bIoIogIcnI rocossos IIko coIIngon synfhosIs,
sforoId mofnboIIsm, Immuno rosonso, drug ncfIvnfIon, nourofrnnsmIssIon, nIfrogon fIxnfIon,
rosIrnfIon nnd hofosynfhosIs. Irom fho oInf of gIobnI bIoonorgofIcs, norobIc rosIrnfIon
nnd hofosynfhosIs nro comIomonfnry rocossos (IIg. 26.2).
CO
2
Catabolic cycles Anabolic cycles
Organic
compounds
Aerobic
respiration
Photosynthesis
ATP ADP+P
i
2H O
2
ATP
P+ADP
i
2H O
2
O
2
Fig. 26.2 Aerobic respiration and photosynthesisComplementary processes.
Tho oxygon ovoIvod by hofosynfhosIs Is consumod by norobIc bncforIn nnd nnImnIs.
SImIInrIy, fho ond roducfs of norobIc rosIrnfIon (CO
2
nnd H
2
O) nro fho mnjor nufrIfIonnI
roquIromonfs of hofosynfhofIc orgnnIsms.
Tho onorgy oxfrncfod from fho orgnnIc comounds by sovornI cnfnboIIc nfhwnys (AC.
cIfrIc ncId cycIo) InvoIvos oxIdnfIon of fhoso comounds fo CO
2
nnd H
2
O wIfh concomIfnnf
roducfIon of wnfor soIubIo roducfnnfs IIko AH nnd succInnfo. Thoso roducfnnfs donnfo
oIocfrons fo fho comononfs of mIfochondrInI oIocfron frnnsfor chnIn IondIng fo roducfIon of O
2
fo H
2
O.
In norobIc sysfom fho formInnI oxIdnnf Is O
2
nnd In nnnorobIc sysfom If Is fho InorgnnIc
suIfnfos nnd nIfrnfos. Thoso roncfIons nro couIod fo ATI synfhosIs (cnIIod oxIdnfIvo
hoshoryInfIon).
EIectron Transport and Oxidative PhosphoryIation
Iectvon tvunspovt Ivom NAHIIocfrons nro frnnsorfod from AH fo oxygon
nIong fho oIocfron frnnsorf chnIn (rosIrnfory chnIn). AH nssos oIocfrons fo AH-
dohydrogonnso, n Inrgo rofoIn comIox confnInIng IM nnd fwo fyos of IoS rofoIns. IM
nccofs fho oIocfrons nnd Is convorfod fo IMH
2
nnd fhon nssod fo IoS. Thon oIocfron from
AH dohydrogonnso nssos fo coonzymo = convorfIng If fo CoQH
2
nnd fhon fo fho cyfochromo
>?
l
comIox. Cyfochromo >?
l
In furn nssos fho oIocfrons fo cyfochromo ? whIch ngnIn In furn
nssos fhom fo cyfochromo oxIdnso. IInnIIy cyfochromo oxIdnsos nss four oIocfrons fo moIocuInr
oxygon fo form fwo moIocuIos of wnfor.
AII fho oIocfron cnrrIors In fho oIocfron frnnsorf chnIn Inforncf nccordIng fo fhoIr rodox
ofonfInIs nnd If Is obvIous fhnf fho noxf oIocfron nccofor hns n hIghor nffInIfy for oIocfron
fhnn fho donor. Thus fhoro Is n unIdIrocfIonnI fIow of oIocfrons from AH fo O
2
. Tho fhroo
mnIn rofoIn comIoxosfho AH dohydrogonnso, cyfochromo >?
l
nnd cyfochromo oxIdnso
ncf ns H
+
um drIvon by oIocfron frnnsorf nnd cronfo nn H
+
grndIonf ncross fho Innor
mIfrochondrInI mombrnno fo Informombrnno snco. ofnII of fho oIocfron frnnsorf Is doIcfod
In IIg. 26.3.
NADH
NAD
+
FMN
FMNH
2
Fe S
2+
Fe S
3+
CoQ
CoQH
2
Cyt.b
Fe
2+
Cyt.b
Fe
3+
Fe S
3+
Fe S
2+
Cyt.c
Fe
1
2+
Cyt.c
Fe
1
3+
Cyt.c
Fe
2+
Cyt.c
Fe
2+
Cyt.a
Fe
Cu
3+
+
Cyt.a
Fe
Cu
3+
2+
Cyt.a
Fe
Cu
3
3+
2+
Cyt.a
Fe
Cu
3
2+
+
H O
2
O
2
H
+
FADH
2
FAD
Fe S
3+
Fe S
2+
NADH dehydrogenase Cytochrome bc complex
1
Cytochrome oxidase
Succinate
dehydrogenase
H
+
H
+
Fig. 26.3 Details of electron transport.
Iectvon tvunspovt Ivom IAH
2
: IAH
2
whIIo goffIng rooxIdIsod fo IA donnfos fwo
oIocfrons fo succInnfo-CoQ-roducfnso, whIch In furn nssos fho oIocfrons fo ubIqnInono (CoQ).
Thoso oIocfrons onfor fho mnIn oIocfron frnnsorf chnIn sImIInr fo fhnf from fho oxIdnfIon of
AH.
EIectron transport inhibitors
Rotenone nnd umytuI InhIbIf oIocfron frnnsorf of AH dohydrogonnso.
AntImycIn A InhIbIfs fho cyfochromo >?
l
.
CyunIde (C
), uzIde (
3
) nnd cuvbon monoxIde (CO) nII InhIbIf cyfochromo oxIdnso.

OxIdutIve pLospLovyIutIon: OxIdnfIvo hoshoryInfIon Is ATI synfhosIs IInkod fo fho
oxIdnfIon of AH nnd IAH
2
vIn fho oIocfron frnnsorf chnIn. Tho mochnnIsm wns orIgInnIIy
roosod ns chomIosmofIc hyofhosIs. Inorgy IIbornfod by oIocfron frnnsorf Is usod fo um
H
+
Ions ouf of fho mIfochondrIon nnd cronfo nn oIocfrochomIcnI rofon grndIonf. Tho rofons
fIow bnck Info fho mIfochondrIon fhrough fho ATI synfhnso whIch synfhosIzos ATI. Abouf 3
moIocuIos of ATI nro synfhosIzod or AH oxIdIsod nnd fwo ATI moIocuIos or IAH
2
oxIdIsod. IIocfron frnnsorf Is fIghfIy couIod fo ATI synfhosIs so fhnf rosIrnfory confroI
onsuros oIocfron fIow onIy whon ATI synfhosIs Is roquIrod.
HIgLIIgLts:
CuIcIum Is mnInIy conconfrnfod In bonos nnd foofh nIong wIfh hoshnfo. CnIcIum
nIso Inys nn Imorfnnf roIo In nII nnImnI coIIs ns InfrncoIIuInr roguInfor
or mossongor.
If hoIs fo roguInfo fho ncfIvIfy of skoIofnI muscIo, honrf nnd mnny ofhor fIssuos.
MugnesIum Inys nn Imorfnnf roIo In fho ncfIon of fho onzymos of gIycoIyfIc
nfhwny nnd nIso In ATI-doondonf roncfIons.
Coppev Is ossonfInI In fho dIof sInco If Is InvoIvod In fho roor ufIIIznfIon of Iron,
dovoIomonf of connocfIvo fIssuos nnd bIood vossoIs.
Ivon Is roquIrod for fho synfhosIs of hnomogIobIn, cyfochromos ofc.
ZInc Is ossonfInI for ovory nduIf In hIs dIof nnd ncfs ns fho rosfhofIc grou of
nbouf 80 onzymos.
NIckeI, vunudIum, cLvomIum nnd sIIIcon nro noodod for fho roor growfh of
bono nnd connocfIvo fIssuo.
SeIenIum Is nn ossonfInI comononf of gIufnfhIono oroxIdnso.
MoIybdenum Is fho nrf of fho rosfhofIc grou of xnnfhIno oxIdnso.
Somo Innfs hnvo shown roquIromonfs for bovon nnd uIumInIum.
Q. 1. WLut uve metuIIopvoteIns?
Ans. IrofoIns whIch confnIn mofnI Ions IIko Io, Co, Zn, Cu, Mg ofc., AC coruIoInsmIn
(Cu).
Q. 2. WLut Is tLe dIIIevence between metuI-uctIvuted enzymes und metuIIo-
enzymes?
Ans. In mofnI-ncfIvnfod onzymos fho mofnI Is nof fIghfIy hoId by fho onzymo nnd cnn bo
onsIIy oxchnngod wIfh ofhor cnfIons, AC, ATInso (Mg
2+
nnd Cn
2+
).
In mofnIIoonzymos fho mofnI Is hoId fIghfIy by fho onzymo nnd cnnnof bo rondIIy
oxchnngod, AC, xnnfhIno oxIdnso (Mo).
Q. 3. WLIcL uve tLe pvIncIpuI eIements oI tLe body?
Ans. Tho sovon rIncInI oIomonfs consfIfufo 60-80 of fho body`s InorgnnIc mnforInI.
Thoy nro Cn
2+
, Mg
2+
, I, n
+
, K
+
, CI
, S.
Q. 4. WLut uve tLe Iuctovs pvomotIng Cu ubsovptIon?
Ans. VIfnmIn (cnIcIfroI), nrnfhyroId hormono, Iow H (ncIdIc), Incfoso nnd nmIno
ncIds IIko IysIno nnd nrgInIno romofo Cn nbsorfIon.
Q. 5. WLut Is tLe sIgnIIIcunce oI Cu:P vutIo?
Ans. Tho Cn:I rnfIo Is Imorfnnf for cnIcIfIcnfIon of bonos. Tho roducf of Cn I (In
mg/dI) shouId bo nround 50 for nduIfs.
Q. 6. WLut uve tLe bIocLemIcuI IunctIons oI Mg?
Ans. Mg Is roquIrod for fho formnfIon of foofh, If sorvos ns fho cofncfor for dIfforonf
onzymos IIko dIfforonf kInnsos nnd ndonyInfo cycInso. Mg Is nIso roquIrod for nouromuscuInr
funcfIons.
Q. ?. In wLut Iovm Is suIIuv pvesent In ouv body?
Ans. SuIfur In our body Is mosfIy rosonf In fho orgnnIc form. If Is rosonf In fho rofoIns
In nmIno ncIds nnmoIy cysfIno, cysfoIno, mofhIonIno.
Q. B. WLy Is Ivon cuIIed tLe one-wuy substunce?
Ans. Iron mofnboIIsm occurs In n cIosod sysfom. If Is nof InncfIvnfod or oxcrofod durIng
mofnboIIc rocossos IIko ofhor vIfnmIns or orgnnIc nnd InorgnnIc subsfnncos rnfhor If Is Iosf
from fho body onIy fhrough bIIo, swonf, bIood Ioss nnd hnIrIoss. Honco onIy fho onfry of Iron In
fho body by nbsorfIon Is confroIIod nnd honco If Is cnIIod fho ono-wny subsfnnco.
Q. 9. WLut Is LemocyunIn?
Ans. HomocynnIn Is n coor-rofoIn comIox whIch funcfIons IIko hnomogIobIn In
Invorfobrnfos.
Q. 10. WLut Is IIuovosIs?
Ans. IIuorosIs Is cnusod by oxcossIvo Infnko of fIuorIno. MnnIfosfnfIons nro dIscoIornfIon
of foofh, hyorcnIcIfIcnfIon of IImb bonos, IIgnmonfs nnd sIno IondIng uIfImnfoIy fo crIIIng
of nn IndIvIdunI.
EXERCISES
1. Whnf nro fho funcfIons of mInornIs In our body
2. How nro mInornIs cInssIfIod nccordIng fo fhoIr roquIromonfs
3. Whnf nro fho rIncInI funcfIons of Cn In our body
4. nmo fho dIsonsos roInfod fo Cn In our body.
5. Whnf nro fho dIfforonf rofoIns nssocInfod wIfh Iron In our sysfom
6. Whnf nro fho bIochomIcnI funcfIons of Cu
?. nmo fho onzymos whoso funcfIons nro doondonf on zInc nnd moIybdonum.
B. Why nro Mn nnd Co roquIrod In our body
9. Whnf Is IysyI oxIdnso
10. IxInIn fho roIo of Zn In fho body.
11. Zn hns much Imorfnnf roIo ns fho rosfhofIc grouoxInIn.
12. Whnf do you monn by buIk nnd frnco grous
13. Whnf nro cofncfors CIvo oxnmIos.
14. Whnf Is fho roIo of Iron In fho body
15. Whnf do you monn by Iron dofIcIoncy nnomIn
16. IxInIn fho roIo of foIIowIng oIomonfs In fho body:
(=) I (>) V (?) Cr (@) Mo (A) So ( B ) SI
1?. Whnf Is oIocfron frnnsfor
1B. IIocfron frnnsfor roncfIons Iny koy roIos In bIoIogIcnI rocossosoxInIn.
19. Whnf nro oIocfron frnnsorf nnd oxIdnfIvo hoshoryInfIon
20. Whnf nro mofnIIoonzymos
%
PoIIution Prevention and Waste Minimisation
IoIIufIon mny bo dofInod ns fho oxcossIvo dIschnrgo or nddIfIon of undosIrnbIo subsfnncos or
unwnnfod foroIgn mnffors Info fho onvIronmonf, fhoroby ndvorsoIy nIforIng fho nnfurnI qunIIfy
of fho onvIronmonf, nnd cnusIng dnmngo fo humnn, Innf or nnImnI IIfo. !sIng fho form
onvIronmonf wo monn nIr, wnfor nnd soII.
Our onvIronmonf Is n comIox nnd dynnmIc sysfom InvoIvIng nII forms of IIfo whIch nro
vIrfunIIy Infor-doondonf. Humnn boIng, fho bosf form of IIfo on onrfh, Is ruIIng fho onrfh nnd
for hIs comforf, owor nnd fhIrsf for knowIodgo hns boon consfnnfIy chnngIng fho nnfurnI
chnrncforIsfIcs by nddIng foxIc comononfs fo fho onvIronmonf nnd ns n consoquonco ovory
IIvIng orgnnIsm Is fncIng onvIronmonfnI hnznrds. Tho rIncInI cnusos of fhoso hnznrds nro
(i) ouInfIon oxIosIon, (ii) doforosfnfIon nnd doIofIon of forosf covor, (iii) rnId urbnnIsnfIon,
(it) doIofIng surfnco nnd ground wnfor rnIdIy, (t) omIssIon of honf, nrfIcIos nnd foxIc gnsos
from IndusfrIos, (ti) no rocycIIng of wnsfo roducfs. Anrf from nII fhoso mnn-mndo robIoms
nnfurnI fncfors IIko voIcnnIc orrufIons, rndIoncfIvIfy nnd nnfurnI dIsnsfors nIso confrIbufo fo
oIIufIon.
AIR POLLUTION
AIr Is n mIxfuro of gnsos fhnf form fho nfmoshoro. Tho cIonn nIr Is comosod of fho
gnsos hnvIng conconfrnfIon
O
2
20.92,
2
?8.l, Ar 0.9325
CO
2
0.03, H
2
0.0l, o 0.00l8
Ho 0.0005, Kr 0.000l
AIr oIIufIon hns bocomo nn Imorfnnf fncfor of onvIronmonfnI dogrndnfIon. Tho
IncronsIng IndusfrInIIsnfIon, urbnnIsnfIon, oxcossIvo burnIng of fuoI ofc. roduco n Inrgo nmounf
of oIIufIng subsfnncos, fhnf hnvo dnmngIng offocf fo humnn, Innfs nnd nnImnI IIvos. Isonsos
IIko bronchInI nsfhmn, Iung cnncor, honrf nnd brnIn dnmngos ofc. hnvo bocomo rovnIonf duo
oIIufod nIr.
Air PoIIutants
AIr oIIufnnfs nro oIfhor In soIId, IIquId or gnsoous forms. AccordIng fo modo of formnfIon,
oIIufnnfs whIch onfor fho nIr dIrocfIy nro cnIIod pvImuvy poIIutunts, nnd fhoso whIch nro
cronfod In fho nIr from oIIufnnfs undor oIocfromngnofIc rndInfIon from fho sun nro cnIIod
seconduvy poIIutunts.
(E) Carbon monoxide (CO)
Cnrbon monoxIdo Is n coIourIoss, odourIoss, hIghIy foxIc gns roIonsod by fho nrfInI
combusfIon of fuoIs from nufomobIIo, IndusfrIos, oII rofInorIos, conIs, woods ofc. Abouf 290
mIIIIon fonnos of CO Is dIschnrgod Info fho nfmoshoro nnnunIIy, 90 of whIch orIgInnfos from
571
oxIdnfIon of mofhnno roducod by docnyIng orgnnIc mnffor. Ouf of mnn-mndo CO omIssIon,
90 of If nrIsos from frnnsorf socfor. CO Is nIso roducod In Inrgo qunnfIfIos In fhormnI owor
Innfs by burnIng conI.
CO cnusos foxIc offocfs IIko hondncho, vIsunI dIsfurbnncos, nrnIysIs nnd ovon donfh. If
combInos wIfh hnomogIobIn In humnn bIood fo form cnrboxyhnomogIobIn, whIch ImnIrs oxygon
frnnsorf. Irosonco of 2-5 of cnrboxyhnomogIobIn nffocfs fho normnI funcfIonIng of fho norvous
sysfom. CO nIso nffocfs fho cnrdIovnscuInr sysfom, cnusIng honrf dIsonsos.
(EE) SuIfur dioxide (SO
2
)
SO
2
Is n coIourIoss gns wIfh n suffocnfIng nnd sfrong ungonf odour. On n gIobnI scnIo,
hnIf of fho nmbIonf SO
2
orIgInnfos from fho oxIdnfIon of H
2
S gIvon off by docnyIng orgnnIc
mnffor. AnnunIIy 90 mIIIIon fonnos of SO
2
Is oIsonIng fho nIr of onrfh. MnIn confrIbufors nro
burnIng of suIhur-confnInIng conI nnd dIosoI In fhormnI owor Innfs. Ofhor sourcos nro
ofroIoum Indusfry, oII rofInorIos, suIfurIc ncId Innfs, suIfIdo oro ronsfIng Innfs.
!ong form or chronIc oxosuro fo SO
2
cnusos rosIrnfory dIsonsos IIko bronchIfIs,
nrfIcuInrIy In young chIIdron. If cnusos IrrIfnfIon fo fhronf nnd oyos, chosf consfrIcfIon,
hondncho, vomIfIng nnd donfh. If cnusos corrosIon of mofnIs. SO
2
cnusos mombrnno dnmngo,
chIorohyII dosfrucfIon, mofnboIIsm InhIbIfIon, growfh yIoId roducfIon In Innfs.
(EEE) SuIfur trioxide (SO
3
)
If Is formod by fho oxIdnfIon of SO
2
undor fho offocf of sunIIghf. SO
3
, ovon nf fho
conconfrnfIon of l m, cnusos bronfhIng robIom nnd rosIrnfory robIoms.
Iofh fho oxIdos of suIfur nro convorfod fo suIfurous nnd suIfurIc ncIds In fho nfmoshoro
wIfh wnfor vnours whIch Is fho cnuso of ucId vuIn nnd Is hnrmfuI for nII IIvIng nnd non-IIvIng
forms on fho onrfh.
(EL) Nitrogen oxides (NO, NO
2
etc)
AII fho oxIdos of nIfrogon, e.g., O, O
2
, nro rorosonfod by O
x
. On n gIobnI bnsIs, 60
of O
x
Is roducod from bIomnss burnIng, fIxnfIon by IIghfnIng, InfIow from fho sfrnfoshoro,
chomIcnI convorsIon from H
3
In fho frooshoro nnd Ioss of O
2
from fho soII. Tho ofhor
sourcos IncIudo combusfIon of fuoIs IIko conI, dIosoI, ofroI, mofor vohIcIo oxhnusfs, ncId
mnnufncfurIng ofc.
O
x
hnvo vnrIous dIrocf nnd IndIrocf offocfs on humnn. Thoy InhIbIf cIIInry ncfIon so
fhnf soof nnd dusf onofrnfo fho Iungs fo cnuso bronchIfIs nnd rosIrnfory dIsonsos. O
x
rondIIy
combInos wIfh wnfor formIng HO
3
whIch forms ncId rnIn. If nIso cnusos oyo IrrIfnfIon. In
rosonco of sunIIghf O
x
nnd hydrocnrbons (combusfIon roducfs of ofroIoum) form smog
nnd fhIs smog ngnIn cnusos oyo IrrIfnfIon, bronfhIng dIffIcuIfIos nnd IImIfs vIsIbIIIfy of ronds.
AnnunIIy nbouf l0 mIIIIon fonnos of O
x
nro onforIng fho nfmoshoro.
AcId RuIn
Ovor fho Insf fow docndos, sImIo rnInfnII hns fnkon on n fhronfonIng comIoxIfy In
somo nrfs of fho worId. Tho rnIn nnd snow fnIIIng down Is goffIng oIIufod wIfh nfmoshorIc
oxIdos of suIfur nnd nIfrogon formIng suIfurIc ncId nnd nIfrIc ncId nnd wnfor. ThIs Is known ns
ncId rocIIfnfIon or ncId rnIn.
SO
2
+ H
2
O H
2
SO
3
, 2SO
2
+ O
2
+ 2H
2
O 2H
2
SO
4
4O
2
+ 2H
2
O + O
2
4HO
3
.
Tho Iongor fho SO
x
nnd O
x
romnIn In fho nfmoshoro fho gronfor Is fho chnnco of fhoIr boIng
convorfod fo H
2
SO
4
or HO
3
by vnrIous cnfnIyfIc nnd hofochomIcnI roncfIons.
POLLUTON PREVENTON AND WASTE MNMSATON 573
!nIns fond fo bo ncIdIc nnfurnIIy duo fo fho dIssoIufIon of nfmoshorIc CO
2
fo yIoId
H
2
CO
3
. Ofhor nfmoshorIc subsfnncos from voIcnnIc orufIons, forosf fIros ofc. nIso confrIbufo
fo fho ncIdIfy. Iuf sfIII fhon fho nmounf of ncIdIfy Is suffIcIonf fo dIssoIvo mInornIs In fho
onrfh`s crusf nnd mnko fhom nvnIInbIo fo nnImnIs nnd Innfs buf nof dnmngIng fo IIvos. Howovor
fho confrIbufIons of SO
x
nnd O
x
oIIufIng fho nfmoshoro confrIbufos fo dIsfurb fho bnInnco
In fho ncIdIfy, cnusIng dnmngo fo fho onvIronmonf.
HnrmfuI offocfs of fhIs ncId rnIn IncIudo (i) dnmngo fo froshwnfor IIfo, (ii) cnusos IrrIfnfIon
fo oyos nnd mucous mombrnnos, (iii) nccoIornfos corrosIon of rocks, mInornIs nnd mofnIs,
(it) dnmngo fo buIIdIngs, brIdgos ofc. cnusIng fnsfor wonfhorIng, (t) dIssoIvos ouf mofnIs nnd
snIfs fhnf Incronso fho confonf of fhoso In nnfurnI wnfor rosourcos fo ovon foxIc IovoIs, (ti) In
mIsf form dnmngos fho Innfs.
Tho rncfIcnI nronchos fo counfor fho robIom of ncId rnIn nro
(i) Inorgy consorvnfIon IondIng fo roducod fuoI consumfIon nnd honco Iossor oIImInnfIon
of SO
x
nnd O
x
.
(ii) osuIfurIsnfIon nnd donIfrIfIcnfIon of fuoIs IondIng fo Iowor omIssIons of SO
x
nnd
O
x
.
(iii) SubsfIfufIon of fossII fuoIs wIfh ofhor nIfornnfIvo sourcos of onorgy.
SO
x
omIssIon Is roducod by conI cIonnIng, bIo-dosuIfurIsnfIon of IIquId fuoI nnd ofhor
mofhods of dosuIfurIsnfIon.
O
x
omIssIon Is roducod by modIfyIng fho dosIgns of furnnco nnd burnor nnd usIng
cnfnIysfs for dIfforonf rocossos ofc.
AcId rnIns nro IIkoIy fo occur moro In cIfIos nnd IndusfrInIIsod nrons nnd nIso In fho
socfors whoro Inrgo nmounfs of fhoso oxIdos nro omIffod by fho nufomobIIos.
(L) Carbon dioxide (CO
2
)
CO
2
Is nof n oIIufnnf IfsoIf. If comos mnInIy from fho burnIng of fossII fuoIs, oxIdnfIon
of cnrbon sforod In fho froos nnd soII humus, nnd roIonsod whon forosfs nro fIrod for shIffIng
cuIfIvnfIon. IncronsIng ouInfIon on onrfh Is cnusIng fnsfor Incronso In fho conconfrnfIon of
CO
2
In fho nfmoshoro. Thus CO
2
Is usod ns mnIn food sfock for fho hofosynfhosIs of groon
vogofnfIon. oforosfnfIon Is IondIng fo fho Ioss of bnInnco of fhIs CO
2
cycIo. Tho oxcoss of CO
2
In fho nfmoshoro cnusos rosIrnfory dIsordors nnd suffocnfIon. CO
2
nIso hns mnny IndIrocf
offocfs IIko cIImnfIc chnngos, Incronso In gIobnI fomornfuro. ThIs Incronso In gIobnI fomornfuro
furfhor brIngs nbouf fho chnngo In rnInfnII nfforn, moIfIng of Ico In fho oInr rogIon rosuIfIng
In rIso of son IovoI, chnngos In fIsh roducfIon, forosf nnd wnfor suIy.
Af rosonf, fho conconfrnfIon of CO
2
In fho nfmoshoro Is nrox. 350 m nnd fho
nnnunI Incronso rnfo Is nbouf l.5 m. Honco by fho mIddIo of fho noxf confury, CO
2
conconfrnfIon In fho gIobnI nfmoshoro wIII bo nroxImnfoIy doubIo fho rosonf conconfrnfIon.
Gveen House IIects
Tho onrfh Is honfod by sunIIghf nnd somo of fho honf Is nbsorbod whIIo fho rosf Is rndInfod
bnck Info fho snco. Tho gnsos IIko CO
2
, wnfor vnour, CH
4
nnd mnn-mndo chIorofIuorocnrbons
ncf ns gInss In n groon-houso nnd nIIow fho sunIIghf comIng In buf sfrongIy nbsorb fho Infrnrod
rndInfIon gIvon ouf by fho onrfh`s surfnco. Tho nof rosuIf Is fho honfIng of fho onrfh`s surfnco
cnIIod fho groon-houso offocf.
AcfunIIy, fho groon-houso gnsos nro rosonsIbIo for kooIng our Innof wnrm nnd
susfnInIng IIfo, ofhorwIso fho fomornfuro of fho onrfh wouId hnvo gono down fo sub-zoro
IovoI. Iuf, howovor, If fho conconfrnfIon of fhoso groon-houso gnsos Is foo much, fhoy frn foo
much of honf fhnf mny uIfImnfoIy fhronfon fho IIfo on onrfh, e.g., CO
2
In fho nfmoshoro of
Vonus Is 60,000 fImos fhnf of onrfh nnd nvorngo fomornfuro of Vonus Is 425C mnkIng
oxIsfonco of IIfo ImossIbIo.
If Is osfImnfod fhnf nfmoshorIc CO
2
confonf hns Incronsod by 25 durIng Insf fwo
confurIos, whIch hns rnIsod fho gIobnI fomornfuro nIrondy. If Is osfImnfod fhnf wIfhIn 50l00
yonrs fho fomornfuro mny Incronso by 4 fo 5C whIch wIII Incronso fho surfnco wnfor
ovnornfIon nnd chnngo fho cIImnfo whIch mny fInnIIy InfIuonco fho growIng of cros.
CIobnI wnrmIng mny nIso frIggor moIfIng of gIncIors rosuIfIng In rIsIng of son IovoI. If
nIso cnusos fIoods, hurrIcnnos, fornndoos, nnd Incronsod broodIng of osfs.
To mInImIso fho groon-houso offocf If Is roquIrod fo roduco fho uso of fossII fuoIs, uso of
nIfornnfIvo sourco of onorgy. ConsorvnfIon of forosfs, roducfIon In uso of nufomobIIos, bnn on
CIC`s nnd nucIonr oxIosIons, oncourngIng nnd dovoIoIng groon fochnoIogIos nnd chockIng
ouInfIon growfh nnd nwnrIng ooIo nro fho ofhor nIfornnfIvos fo chock fho groon-houso
offocf or gIobnI wnrmIng.
epIetIon oI Ozone Iuyev (O
3
)
Ozono Is nn Imorfnnf chomIcnI socIos rosonf In fho sfrnfoshoro, i.e., nbovo 20 km
from fho onrfh`s surfnco nnd Ifs conconfrnfIon Is nround l0 m. If Is formod In fho sfrnfoshoro
by hofochomIcnI roncfIon:
O
2
+ I (242 nm) O + O
O + O
2
+ M (such ns
2
or O
2
) O
3
+ M
Tho socIos M nbsorbs fho oxcoss onorgy IIbornfod In fho roncfIon nnd fho moIocuIo of
ozono Is sfnbIIIzod. If Is consfnnfIy formod. If Is dosfrucfIvo fo fnbrIcs, rubbor goods, cros ofc.
Af fho snmo fImo If ncfs ns n rofocfIvo shIoId for fho IIfo on onrfh, by sfrongIy nbsorbIng
!V-rndInfIons comIng from fho sun (220-230 nm) whIch Is hnrmfuI for IIfo on onrfh.
Ozono Is dosfroyod by CI
2
, roIonsod duo fo voIcnnIc ncfIvIfy nnd nIso by roncfIons wIfh
(i) O, (ii) nfomIc oxygon, (iii) roncfIvo OH rndIcnI rosonf In fho nfmoshoro.
ChIorofIuorocnrbons (CICs) como ouf from jumbo jofs nnd suorsonIc nIrcrnff, nucIonr
oxIosIons, CICs nro nIso usod ns cooInnfs In rofrIgornfors, nIr condIfIonors, norosoIs, InsfIc
fonms. CIC`s oscno nnd nccumuInfo nf hIgh nIfIfudo, undorgo docomosIfIon, undor !V IIghf,
fho docomosIfIon roducf boIng CI
2
. Inch nfom of CI roncfs wIfh moro fhnn 0.5 moIocuIos of
oxygon In chnIn roncfIon convorfIng ozono fo oxygon nnd fhoroby Ionds fo doIofIon of ozono
Inyor.
CI + O
3
CIO + O
2
CIO + O CI + O
2
Tho onvIronmonfnI hnznrds duo fo fho CICs woro rocognIzod In l9?0 nnd fho dofocfIon
of ozono hoIo ovor AnfnrcfIcn In l985. Tho uso of CICs woro IImIfod sInco fhon.
Tho SO
x
nnd O
x
nIso roncf wIfh ozono
SO
2
+ O
2
SO
3
+ O
2
O + O
3
O
2
+ O
2
Honco omIssIons of nII fhoso oIIufnnfs nro nIso noodod fo bo mInImIsod.
Tho doIofIon of ozono Inyor nIIows fho hnrmfuI !V rndInfIons fo ronch onrfh whIch
fInnIIy cnusos skIn cnncor, sunburns, bronsf cnncor, cnfnrncf, IoukomIn, Iung cnncor, vIsunI
ImnIrmonf, romnfuro ngIng, A dnmngo nnd ovon mny Iond fo donfh.
(LE) Hydrogen fIuoride (HF)
If Is gIvon ouf from hoshnfo forfIIIsor IndusfrIos, nIumInIum IndusfrIos, mofnIIurgIcnI
rocossos, brIck kIIn nnd conI burnIngs. ThIs cnusos fIuorosIs In cnffIo broodIng on nffocfod
Innfs nnd nIso cnusos bono, foofh nnd skoIofon dIsordors nnd rosIrnfory dIsonsos In humnn.
(LEE) Hydrocarbons
Ifforonf fyos of hydrocnrbons In hIgh conconfrnfIons rosonf In fho nfmoshoro cnuso
mnny sorIous robIoms IIko IrrIfnfIon fo mucous mombrnnos, rosIrnfory robIoms, Iung cnncor,
norvous sysfom dIsordors nnd ovon mny cnuso donfh If In foxIc IovoI. AddIfIonnIIy, dIfforonf
mufngonIc orgnnIc comounds nffocf A roIIcnfIon nnd ncf ns ofonfInI cnrcInogons.
(LEEE) Lead oxide (PbO)
!ond oxIsfs In n vnrIofy of chomIcnI comounds wIfh dIfforonf chnrncforIsfIcs. Tho
nfmoshorIc Iond confnmInnfIon comos from fho nufomobIIos. 2 fo 4 g of Iond Is rosonf or
IIfro of fuoI. !ond Is Ingosfod nnd InhnIod nnd nbouf hnIf of If Is nbsorbod, somo onfors fho
bIood, somo onfors fho bonos. Advorso offocfs of Iond nro found In ouInfIon wIfh bIood IovoIs
of l0 mg/dI of Ib. !ond oIsonIng Ionds fo nnnomIn, brnIn dnmngo nnd Ioss of kIdnoy funcfIon.
!ond nIso onfors fho nfmoshoro from sourcos ofhor fhnn fho nufomobIIos, i.e., from mInIng of
Iond bonrIng oros, Iond IumbIng nnd soIdorIng, uso of nInfs nnd cornmIc gInss nnd Iond-zInc
bnffory dIsosnI.
ParticuIates as poIIutants
(i) ust. Thoro nro Inrgo numbor of sourcos of dusf In fho nfmoshoro, somo of fhoso
IncIudo mInos, furnncos, vohIcIos, cornmIc fncforIos, forosf fIros, housohoId dusfs,
rubbor fyro nbrnsIon, nnfurnI wInds ofc. usf cnusos rosIrnfory nnd nIIorgIc rob-
Ioms. SIIIcn confnInIng dusfs cnuso sIIIcosIs.
(ii) Smoke. Smoko Is roducod duo fo IncomIofo combusfIon of fuoI, nnd fho sourcos
nro IocomofIvos, owor Innfs, IncInornfors, dIosoI nnd gnsoIIno ongInos, oon fIros,
furnncos ofc.
Smoko Ionds fo Ioss of fuoI, soIIngo of oxforIors of buIIdIngs nnd ovon If cnn cnuso
cnncor.
(iii) Smog. If Is n combInnfIon of smoko nnd fog In droIofs. If Is of fwo fyos:
(o) LonJon enog. If Is conI smoko nnd fog. Tho Inffor consIsfs of n mIxfuro of SO
2
nnd SO
3
. In rosonco of sunIIghf fho oxIdnfIon of SO
2
fo SO
3
Is fncIIIfnfod whIch
foIIowod by roncfIon wIfh wnfor droIofs forms suIfurIc ncId norosoI. ThIs fyo of
smog cnusos rosIrnfory robIoms, oyo IrrIfnfIon ofc., nnd If nIso roducos fho
vIsIbIIIfy.
(I) Loe Angelee enog (pIoIocIenicol enog). IhofochomIcnI smog Is InIfInfod by fho
hofochomIcnI dIssocInfIon of O
2
nnd fho socondnry roncfIons of fhoso wIfh
unsnfurnfod hydrocnrbons, froo rndIcnIs Iond fo fho formnfIon of oroxIdos nnd
ozono. ThIs Is fncIIIfnfod In sunny dnys. IhofochomIcnI smog nIso cnusos oyo
IrrIfnfIon nnd roducos vIsIbIIIfy nnd If nIso dnmngos Innfs nnd rubbor goods.
(it) Asbestos. ThIs fIbrous sIIIcnfo mnforInI Is usod mnInIy for Ifs mochnnIcnI sfrongfh
nnd InsuInfIng roorfIos. Tho fIny nsbosfos fIbros onofrnfo fho Iung fIssuos nnd
mucous mombrnnos nnd sfny fhoro for n Iong orIod. SomofImos If gIvos rIso fo cnncor.
(t) Heuvy metuIs. !ond, Morcury nnd CndmIum nro fho gonornIIy found honvy mofnIs
In fho nfmoshoro fhnf cnuso foxIcIfy.
!ond Is mnInIy omIffod from fho nufomobIIos ns If Is nddod fo gnsoIIno fo Imrovo
nnfIknock roorfIos nrfIcuInrIy In fho form of fofrnofhyI Iond. Irosonco of hydrocnrbon grou
hoIs If fo nss fhrough fho mombrnnos In our body; If mnInIy conconfrnfos In bIood, bonos ofc.
If roncfs wIfh fho ncfIvo SH grous of onzymos roducIng hnomogIobIn nnd honco Ionds fo
nnnomIn.
SImIInrIy, morcury nIso roncfs wIfh SH grou of dIfforonf ossonfInI rofoIns nnd InhIbIfs
onzymnfIc ncfIvIfIos. ToxIcIfy of morcury doonds on Ifs sfnfo. Iuro morcury, InsoIubIo InorgnnIc
morcury comounds hnvo Iowor foxIcIfIos whorons soIubIo snIfs of morcury, morcury vnour
nnd orgnnIc morcury comounds IIko dImofhyI morcury ofc. cnuso morcury oIsonIng. Ifs
hnrmfuI offocfs IncIudo soro gums, Iooso foofh, brnIn dnmngo, IrrIfnbIIIfy nnd omofIonnI
dIsfurbnncos.
Morcury In nnfurnI wnfor rosorvoIrs nro mofnboIIsod by corfnIn mIcro-orgnnIsms formIng
dImofhyI morcury whIch mny bo onfon u by smnII fIshos nnd fhoroby If mny onfor fho food
chnIn cnIIod bIomugnIIIcutIon nnd uIfImnfoIy ronch hIghor nnImnIs.
Tho bosf romody for fhoso honvy mofnIs Is fronfIng wIfh choInfIng ngonfs IIko ofhyIono
dInmIno fofrnncofnfo whIch romovos honvy mofnIs from fho bIood by formIng comIoxos.
NCH CH N
2 2
OOCH C
2
OOCH C
2
CH COO
2
CH COO
2
EDTA
PoIIution from internaI combustion engines
Ono of fho mnjor oIIufIon of fho nfmoshoro Is duo fo fho InfornnI combusfIon ongInos
of fho nufomobIIos. IuoIs usod such ns dIosoI, ofroI ofc., confnIn InrgoIy fho hydrocnrbons
wIfh ofhor S nnd confnInIng ImurIfIos. IurnIng or IncomIofo burnIng of fhoso fuoIs cnusos
roIonso of CO
2
, CO, SO
2
, O
2
, hydrocnrbons ofc. AII fhoso oIIufo fho nfmoshoro, form smog
nnd cnuso dnmngo fo IIvos.
ThIs fyo of oIIufIon cnn bo mInImIsod by usIng (i) boffor nnd oIIufIon-froo fuoIs,
(ii) usIng ongInos wIfh boffor orformnncos, (iii) usIng cnfnIysfs for fho convorsIon of oIIufnnfs
fo Ioss hnrmfuI subsfnncos by joInIng n dovIco In fho oxhnusf sysfom of nn nufomobIIo. Tho
dovIco Is known ns cutuIytIc convevtev (IIg. 2?.l), (it) by mIxIng oxhnusf gnsos wIfh moro
nIr for boffor combusfIon.
Out to
the air
N
2
N
2
O
O
2
CO/CO
2
NO
X
C H
X Y
From the
engine
Thin coating of catalyst
on the ceramic
Ceramic block with many
fine tubes
Fig. 27.1 Catalytic converter.
HIgLIIgLts:

PoIIutIon:
(i) Tho oxcossIvo dIschnrgo or nddIfIon of undosIrnbIo subsfnncos or unwnnfod
foroIgn mnffor Info fho onvIronmonf, fhoroby ndvorsoIy nIforIng fho nnfurnI
qunIIfy of fho onvIronmonf, nnd cnusIng dnmngo fo humnn, Innfs or nnImnI
IIfo.
(ii) MuJov AIv PoIIutunts:
Cnsos IIko SO
2
, SO
3
, H
2
S, O, O
2
, CO, CO
2
, hydrocnrbons.
InrfIcuInfos IIko dusf, smoko, smog, Iond, morcury, cndmIum.
(iii) ContvoI oI AIv PoIIutIon:
!sIng chImnoys
!sIng cycIono sonrnfor, oIocfrosfnfIc rocIIfnfor
Iy cIonnIng fho fuoIs IIko conI, ofroIoum
Iy fronfIng fho oxhnusf gnsos
Iy InnfnfIon of froos
(it) Impovtunt eIIects oI AIv PoIIutIon:
l. AcId rnIn
2. Croon-houso offocf
3. oIofIon of ozono Inyor
4. IhofochomIcnI smog formnfIon
5. Honvy mofnI oIsonIng
Air poIIution controI
AIr oIIufIon cnn bo confroIIod by rovonfIng fho formnfIon of fho oIIufnnfs nf fho
sourco. Somo of fho foIIowIng romodIos cnn bo hoIfuI:
l. (o) IoIIufIon duo fo emIssIons Ivom uutomobIIes cnn bo mInImIsod by usIng cnfn-
Iysfs fo nId fho offocfIvo combusfIon.
(I) Iy urIfyIng fho fuoI, romovIng suIfur by bIo nnd normnI mofhods of do-
suIfurIznfIon nnd nIso by roducIng fho omIssIon of SO
2
In fIuo gnsos by fronfIng
wIfh IIq. H
3
, nIk. KMnO
4
ofc.
2. (o) Tho IndusfrInI rocoss cnn bo Imrovod by modIIyIng tLe oId mucLInevIes so
fhnf oIIufIon duo fo Imorfocf convorsIons cnn bo corrocfod.
(I) InstuIIutIon oI uIv tveutment Innfs for fho urIfIcnfIon of vonf gnsos confnInIng
objocfIonnbIo oIIufnnfs.
3. Tho uso of tuII stucks ov cLImneys roducos fho conconfrnfIon of nIr oIIufnnfs In
fho ground IovoI. Tho gnsos dIschnrgod fhrough fhoso gof dIIufod nnd nro dIsorsod
fo n hoIghf fhnf roducos oIIufIon In ground IovoI.
4. AItevnutIve souvce oI enevgy Is fo bo frIod Insfond of convonfIonnI fuoIs cnusIng
oIIufIon.
5. InstuIIutIon oI devIces
(o) CycIone coIIectov. If Is usod for rocIonnIng of nIr for romovnI of dry nrfIcuInfos
of sIzo rnngIng from 520 m. Tho nIr/gns Is nssod fhrough n fIghf cIrcuInr
sIrnI-fIffod chnmbor. Tho confrIfugnI forcos fhrow fho nrfIcuInfos fownrds fho
wnII from whoro fhoy soffIo down duo fo grnvIfy. Tho coIIocfod nrfIcIos nro
orIodIcnIIy romovod. Tho ncfIon of cycIono sonrnfor Is ns shown In IIg. 2?.2.
Outlet for clean gas
Inlet for gas
containing
particulates
Circular
spiral
Particulates move
outwards due to
centrifugal force
Chamber
Outlet for deposited
particulates
Fig. 27.2 A cyclone collector.
(I) CottveII eIectvostutIc pvecIpItutov. Smoko ns woII ns fho nrfIcuInfos cnn bo
romovod by fhIs dovIco. Smoko Is n coIIoIdnI susonsIon of nognfIvoIy chnrgod
cnrbon nrfIcIos In nIr. Smoko/nIr Is nssod fhrough n chnmbor mnInfnInod fo n
vory hIgh ofonfInI of 30,000 voIfs. !ndor fho InfIuonco of sfrong oIocfrIcnI fIoId
fho nrfIcIos (chnrgod) gof nffrncfod fownrds oosIfo chnrgo nnd fho hof gns
nssos nwny.
Positive D.C. voltage
Point electrodes
Clean gas outlet
Dirty gas
inlet
Ground
Settled dust, carbon, etc.
Fig. 27.3 Cottrell electrostatic precipitator.
(c) usf Is oIImInnfod by extvuctIon ventIIutIon. Tho nIr confnInIng dusf Is nssod
nf vory hIgh sood nnd fho rnfo Is suddonIy roducod whoroby fho dusf nrfIcIos
soffIo ouf.
(J) IIItevs. CIofh bngs ncfIng ns fIIfors nro usod fo sonrnfo fho nrfIcuInfos from
fho sfnck gnsos In oIocfrIc owor Innfs.
(e) Scvubbevs. Thoso nro usod fo romovo nrfIcIo ns woII ns ncIds nnd chomIcnI
fumos. Tho oIIufod nIr Is nssod fhrough n fowor fIIIod wIfh coko nnd fIno mIsf
of wnfor srInkIod whIch romovos nbouf 99 nrfIcIos nnd 80-95 SO
x
.
6. PIuntutIon oI tvees. Troos osocInIIy brond Ionvod Innfs hoI fo roduco oxcoss CO
2
of fho onvIronmonf nnd nIso hoI fo doosIf fho susondod nrfIcIos from fho nIr nnd
mnko nIr Ioss oIIufod.
?. ZonIng. To nvoId nIr oIIufIon robIoms, fhoro shouId bo buffor zonos bofwoon fho
roor IndusfrInI zonos nnd domosfIc nrons. Thus dIIufIon of fho oIIufod nIr fnkos
Inco boforo ronchIng common ooIo.
8. nIovcement oI AIv (PveventIon und ContvoI) PoIIutIon Act, 19B1. AIr qunIIfy
sfnndnrds ns rocommondod by fho ConfrnI IoIIufIon ConfroI Ionrd musf bo sfrIcfIy
ImIomonfod.
WATER POLLUTION
Wnfor from nnfuro Is usod by mnn for drInkIng, domosfIc, ngrIcuIfurnI, frnnsorf nnd
IndusfrInI urosos. PoIIutIon oI wutev Is dofInod ns fho rosonco of foroIgn orgnnIc, InorgnnIc,
bIoIogIcnI, rndIoIogIcnI nnd hysIcnI subsfnncos fhnf fond fo dogrndo Ifs qunIIfy nnd consfIfufo
honIfh hnznrds or docronso Ifs qunIIfy.
Wnfor mny bo confnmInnfod by fho foIIowIng:
l. IssoIvod gnsos IIko H
2
S, CO
2
, H
3
,
2
ofc.
2. IssoIvod mInornIs IIko sodIum, cnIcIum, mngnosIum snIfs.
3. Susondod ImurIfIos IIko cIny, snnd, mud, orgnnIc mnffor.
4. MIcro-orgnnIsms IIko bncforIn, vIrusos, rofozon.
5. ConfnmInnfod wIfh rndIoIogIcnI subsfnncos.
Sources of Water PoIIution IncIude
l. omestIc sewuge. Tho domosfIc nnd munIcInI wnsfos consIsfIng of humnn
oxcrofIons, kIfchon wnsfos nnd ofhor orgnnIc wnsfos drnIn ouf Info fho cnnnI nnd
fhrough If fo fho rIvors nnd ofhor nnfurnI wnfor rosorvoIrs doforIornfIng Ifs qunIIfy
nnd nIso ncf ns n sourco of food for mIcro-orgnnIsms. ThIs fInnIIy Ionds fo vnrIous
dIsonsos of sfomnch nnd skIn for humnn.
2. IndustvIuI wutevs. AcIds, nIknIIos, mofnIs, snIfs nnd numorous ofhor chomIcnIs
oIIufo fho wnfor. InrfIcuInrIy, fho wnsfo wnfor from nor, sugnr, son, foxfIIos,
Ionfhor fnnnorIos, hnrmncoufIcnIs, oII rofInorIos ofc., confrIbufos n Iof of oIIufnnfs
fo fho wnfor.
3. IevtIIIzev pIunts. Thoso Innfs ndd nIfrnfos, hoshnfos, nmmonIn ofc., fo wnfor.
4. AgvIcuItuvuI dIscLuvges. IosfIcIdos, InsocfIcIdos, Innf dobrIs, forfIIIzor mnnuros
ofc., nro fho oIIufnnfs.
5. NutuvuI poIIutunts Ivom otLev souvces. CIny, fInos of soII, oII, doforgonfs, bncfo-
rIn, vIrusos, rofozon, dond bodIos of nnImnIs nnd humnn ofc., cnuso wnfor oIIufIon
whIch fInnIIy cnusos oufbronk of InfocfIous dIsonsos.
6. IrocossIng of vudIouctIve mutevIuIs cnusos wnfor oIIufIon.
ControI of Water PoIIution
Tho robIom of wnfor oIIufIon cnn bo confroIIod by ndofIng fho foIIowIng rocoduros:
l. Iy roducIng fho wnsfo nf sourco.
2. IIufIng fho wnsfo wnfor from dIfforonf sourcos boforo dIschnrgIng sInco fho dIs-
soIvod oxygon of dIIufIng wnfor hoIs In bIodogrndnfIon of dIfforonf foxIc chomIcnIs
by mIcro-orgnnIsms fo Inocuous chomIcnIs boforo mIxIng wIfh nnfurnI wnfor.
3. Iy chomIcnI fronfmonf fho oIIufod wnfor cnn bo mndo snfo.
4. Iy hysIcnI mofhods IIko rovorso osmosIs, oIocfrodInIysIs, Ion-oxchnngo ofc., oIIufod
wnfor cnn bo urIfIod.
5. Iy rocycIIng of wnsfo wnfor boforo dIschnrgIng InvoIvos fronfmonfs IIko uso of ncfI-
vnfod sIudgo, frIckIIng fIIfor ofc.
6. !ocInmnfIon of wnsfo wnfor: sowngo wnfor cnn bo mndo usonbIo for IrrIgnfIon, fIsh-
fnrm rnIsIng, ns If confnIns ossonfInI nufrIonfs.
Sewage and its Treatment
Sowngo Is fho IIquId wnsfo from domosfIc nnd munIcInI wnsfo wnfor, IndusfrInI wnsfo
wnfor, ground wnsfos ofc. omestIc-sewuge hns objocfIonnbIo odour duo fo S nnd confnInIng
comounds nnd n groy fo groon coIor duo fo fho rosonco of dIschnrgos from kIfchons, bnfh nnd
InvnforIos.
IndustvIuI wustes hnvo dIfforonf coIor or odour doondIng on fyos of IndusfrIos rosonf
nnd fho chomIcnI consfIfuonfs nIso vnry nccordIngIy. Tho fronfmonfs consIsf of uevobIc und
unuevobIc oxIdnfIons, whIch nro broughf nbouf by fho norobIc or nnnorobIc bncforIn rosonf
In fho sowngo.
Tho norobIc bncforIn oxIdIzo fho orgnnIc comounds rosonf In fho sowngo by fho dIssoIvod
oxygon IondIng fo fho formnfIon of nIfrnfos, suIfnfos nnd hoshnfos whIch Is cnIIod norobIc
oxIdnfIon.
Sewage
+
Air (to
supply dissolved
oxygen)
Oxidation by
Aerobic bacteria
Nitrates, sulfates,
phosphates etc.
Aerobic oxidation
In fho nbsonco of fho suIy of froo oxygon, fho nnnorobIc bncforIn convorf fho orgnnIc
comounds In fho sowngo fo mofhnno, H
2
S, nmmonIum suIfIdo ofc. (offonsIvo odour).
In fhIs fyo of nnnorobIc oxIdnfIon rocoss fho roquIrod oxygon Is suIIod by fho nIfrnfos,
suIfnfos nnd orgnnIc comounds.
Sewage
Oxidation by
Anaerobic bacteria
Oxidation to
produce H S,
PH , CH etc.
2
3 4
Anaerobic oxidation
BioIogicaI Oxygen Demand (BOD)
IO of n sowngo Is dofInod ns fho nmounf of froo oxygon roquIrod fo oxIdIzo fho orgnnIc
mnffor rosonf In fho sowngo by fho norobIc bncforIn rosonf In If nf 2?C for n orIod of
3 dnys. Tho unIf of IO Is m or mg/IIfro. IO, fhoroforo, gIvos nn Idon of fho IovoI of
oIIufIon of fho sowngo ns If Is nn Indox of fho nmounf of docomosnbIo orgnnIc mnffor. HIghor
fho IO, gronfor Is fho dogroo of oIIufIon. An nvorngo sowngo hns n IO IovoI l00l50 m.
Determination of BOD
Tho IO fosf Is bnsod on mnInIy bIo-nssny rocoduros whIch monsuros fho dIssoIvod
oxygon consumod by mIcro-orgnnIsm whIIo nssImIInfIng nnd oxIdIsIng fho orgnnIc mnffor undor
norobIc condIfIon.
A known voIumo of snmIo Is dIIufod wIfh dIIufIon wnfor (whIch Is nornfod fo n known
dIssoIvod oxygon conconfrnfIon). If Is Incubnfod nf 2?C for 3 dnys In dnrk. Affor fhIs fho
dIssoIvod oxygon conconfrnfIon Is doformInod, fho rIncIIo of whIch Is gIvon boIow. Tho
dIfforonco bofwoon fho InIfInI nnd fInnI dIssoIvod oxygon gIvos fho IO.
PrincipIe for DO
If Is fho modIfIod WInkIor mofhod. Iy fhIs mofhod n f of mnngnnous hydroxIdo Is
formod fIrsf whIch rnIdIy nbsorbs oxygon dIssoIvod In wnfor formIng n hIghor oxIdo.
MnSO
4
+ 2KOH Mn(OH)
2
+ K
2
SO
4
2Mn(OH)
2
+ O
2
2MnO(OH)
2
On ncIdIfIcnfIon In rosonco of IodIdo, I
2
Is IIbornfod In n qunnfIfy oquIvnIonf fo fho
dIssoIvod oxygon rosonf.
MnO(OH)
2
+ 2KI + H
2
O Mn(OH)
2
+ I
2
+ 2KOH
Tho IIbornfod I
2

Is fIfrnfod wIfh sfnndnrd sodIum fhIosuIfnfo soIufIon usIng sfnrch soIufIon
ns IndIcnfor.
I
2
+ 2S
2
O
3
2
S
4
O
6
2
+ 2I
l
.
ChemicaI Oxygen Demand (COD)
If Is n monsuro of fho oxIdIznbIo ImurIfIos rosonf In fho sowngo. If rorosonfs bofh fho
bIoIogIcnIIy oxIdIznbIo ns woII ns bIoIogIcnIIy non-oxIdIznbIo ImurIfIos rosonf nnd honco fho
vnIuo Is hIghor fhnn fho corrosondIng IO of fho sowngo. If Is ndvnnfngoous fo monsuro
CO fo nssoss fho IovoI of ImurIfIos sInco CO doformInnfIon fnkos onIy 3 hrs.
Determination of COD
250 mI of fho snmIo of wnfor Is rofIuxod for l
l
2
hrs. wIfh n known oxcoss of l K
2
Cr
2
O
?
nnd dII H
2
SO
4
nnd n IIffIo Ag
2
SO
4
ns cnfnIysf. Affor fho oxIdnfIon Is ovor fho oxcoss K
2
Cr
2
O
?
Is
fIfrnfod bnck wIfh sfnndnrd Mohr`s snIf soIufIon. Tho oxygon oquIvnIonf of K
2
Cr
2
O
?

consumod
for fho oxIdnfIon roncfIon Is fho monsuro of CO.
l mI of l K
2
Cr
2
O
?
0.008 gm of oxygon.
MunicipaI Sewage Treatment
IsosnI of sowngo hns bocomo of rImo Imorfnnco ns If cnusos undosIrnbIo nnd hnrmfuI
offocfs on IIvIng boIngs nnd fho onvIronmonf. Tho mnIn objocfIvos of sowngo fronfmonf nro
(i) romovnI of comounds cnusIng bnd odour, (ii) romovnI of ImurIfIos cnusIng ubIIc honIfh
robIom, (iii) rondorIng fho sowngo fInnIIy snfo fo bo dIschnrgod fo nnfurnI wnfor rosorvoIrs
such fhnf nqunfIc IIfo Is nof dIsfurbod.
MunIcInI sowngo fronfmonf rocossos nro cnIIod sownrngo nnd If InvoIvos fho foIIowIng
sfos:
(i) PvImuvy tveutment. IIrsf fho sowngo Is subjocfod fo mochnnIcnI rocossos IIko
fIowIng, dIIufIon nnd sodImonfnfIon fo romovo fho conrso soIId mnforInIs. If Is nssod fhrough
n sorIos of fIIfors of grndod oonIngs nnd fhon fIows fo n sodImonfnfIon fnnk. Conrso mnforInIs
coIIocf nf fho sodImonfnfIon fnnk cnIIod sIudgo. Tho IIquId offIuonf fhon undorgoos socondnry
fronfmonf.
(ii) Seconduvy tveutment. ThIs Is n uroIy bIoIogIcnI fronfmonf hnvIng fwo hnsos
norobIc nnd nnnorobIc. Tho norobIc rocoss InvoIvos norobIc dIgosfIon of sIudgo by rocossos
IIko frIckIIng fIIfors, oxIdnfIon onds nnd ncfIvnfod sIudgo rocoss.
In fho tvIckIIng IIItev pvocess fho offIuonf from fho rImnry fronfmonf Is nIIowod fo
fIow fhrough 6l0 ff doo bod of crushod sfono, grnvoI, conI ofc. If Is srnyod ovor fho bod whon
If gofs snfurnfod wIfh norInI oxygon nnd fho mIcro-orgnnIsms rosonf sfnrf norobIc dIgosfIon
whIIo fho wnfor nssos fhrough fho fIIfor bod, dogrndIng fho orgnnIc comounds nnd fInnIIy
rondorIng fho offIuonf hnrmIoss whIch coIIocfs nf fho boffom nnd onfors fho forfInry fronfmonf
(IIg. 2?.4).
Rotating arms
Sewage distributor
Ground level
Sewage
inlet
Effluent
outlet
Under drainage
system
Coarse aggregate
(filtering media)
Fig. 27.4 Trickling filter.
In fho oxIdutIon ponds whIch nro shnIIow onds fho wnfor Is oxosod fo nfmoshoro
whoroby fho nIgno CIlorello p,renoiJoeo grow nnd fhoIr growfh hoIs In mnInfnInIng fho
norobIc condIfIon In fho sowngo nnd fho mIcroorgnnIsms rosonf dIgosf fho orgnnIc mnffors
rosonf nnd rondor fho wnfor hnrmIoss.
In fho ncfIvnfod sIudgo rocoss fho sowngo Is vIgorousIy nornfod nnd duo fo fho rosonco
of mIcroorgnnIsms coIIoIdnI nggrognfos of ''fIoccuIos` nro formod whIch fInnIIy soffIo down nffor
n Iong-fImo. ThIs soffIod sIudgo Is fho 'ncfIvnfod sIudgo` whIch consIsfs of n Inrgo numbor of
vory ncfIvoIy mofnboIIzIng bncforIn, yonsfs, moIds nnd rofozon. Whon fhIs ncfIvnfod sIudgo Is
nddod fo fho frosh bnfch of nornfod sowngo, fIoccuInfIon fnkos Inco In vory shorf orIod nnd
honco fho whoIo rocoss fnkos vory shorf fImo. ThIs mofhod Is nIso known ns uctIvuted sIudge
pvocess. Iuf dIsosnI of fhIs ncfIvnfod sIudgo Is n robIom.
Anaerobic Digestion
Tho sIudgo coIIocfod nffor rImnry fronfmonf Is nddod fo fho nnnorobIc dIgosfIon fnnk
whIch Is n cIosod fnnk nnd fho mIcro-orgnnIsms dIgosf fho orgnnIc comounds In fho nbsonco of
oxygon for nbouf 30 dnys. Tho gnsoous roducfs consIsf of 60-?0 CH
4
, 20-30 CO
2
, smnII
nmounf of H
2
S, H
2
,
2
. ThIs gns cnn bo usod ns n fuoI for owor gonornfIon or for cIfy suIy.
400 fo 600 IIfros of gns Is roducod or kg. of soIId sIudgo.
(iii) TevtIuvy tveutment. Tho offIuonf from socondnry fronfmonf confnIns nIfrnfo,
hoshnfo ofc. ThIs Is subjocfod fo chomIcnI fronfmonf. Affor fho chomIcnI fronfmonf fho
wnfor Is chIorInnfod fo froo If from mIcro-orgnnIsms. Affor fhIs forfInry fronfmonf fho wnfor Is
snfo for humnn uso (IIg. 2?.5).
Raw
sewage
Screening
Alum
Sedi-
mentation
Activated
sludge
Trickling
filter
Treated
discharge
Sedi-
mentation
Chlorination
Anaerobic Aerobic
Primary treatment Secondary treatment
or
Fig. 27.5 Flow diagram for sewage treatment.
Wnfor oIIufIon cnn bo rovonfod by:
(o) IrovonfIng fho uso of chomIcnI forfIIIzors
(I) !sIng bIo-dogrndnbIo doforgonfs.
(c) Iroor fronfmonf of sowngo boforo drnInIng fo nnfurnI rosorvoIrs.
(J) PLyto-pIunkton, n Inyor of fho fIny nnImnIs nnd Innfs fhnf IIvo on fho surfnco of
son wnfor. Thoy nro cnnbIo of nbsorbIng fIonfod mInufo nrfIcIos, dIrf nnd hoI fo chock wnfor
oIIufIon. Tho oIIufIon In wnfor hnmors fho growfh of Innkfon nnd nffocfs mnrIno IIfo.
SOIL POLLUTION
Tho confnmInnfIon of soII or Innd wIfh rnIn, oxcoss of forfIIIsors, wrong forfIIIsors,
InsocfIcIdos nnd horbIcIdos Is cnIIod soII oIIufIon.
Sources of SoiI PoIIution
l. !oonfod nnd oxcoss uso of forfIIIzors nnd osfIcIdos cnuso soII oIIufIon. Iy oxcoss
uso of (H
4
)
2
SO
4
, fho SO
4
2

Ion nccumuInfos Info fho soII nnd mnkos If InforfIIo duo
fo ncIdIfy. SImIInrIy, roonfod uso of forfIIIzors confnInIng KO
3
, nO
3

ofc., cnusos
nccumuInfIon of n
+
, K
+
nnd Ionds fo nIknIInIfy of fho soII.
2. SoII Is oIIufod by fho cysfs of onfnmoobn, nscnrIs, Igworm ofc., whIch onfor fho food
chnIn nnd Infocf humnn boIng.
3. Tho sowngo confnInIng humnn nnd nnImnI oxcrofn, soIId nnd IIquId wnsfos
oIIufos soII.
4. SrnyIng of InsocfIcIdos nnd horbIcIdos for fruIfs nnd vogofnbIos nIso cnusos soII
oIIufIon. Thoso nIso onfor fho food chnIn nnd fhoroby onforIng humnn nnd nnImnI
bodIos. ThIs cnn bo fnkon cnro of by roorIy wnshIng fho vogofnbIos, fruIfs, soods
wIfh suffIcIonf wnfor boforo fhoIr Infnko.
5. AcId rnIn Is nIso n sourco of soII oIIufIon.
6. SoII orosIon fnkos Inco duo fo doforosfnfIon, unInnnod IrrIgnfIon nnd dofocfIvo
mofhods of cuIfIvnfIon.
?. SoII Is orrodod duo fo romovnI of uor forfIIo Inyor.
8. umIng of wnsfos from mInos, owor gonornfIon Innfs nnd mofnI smoIfIng cnuso
Innd oIIufIon.
9. !ndIoncfIvo wnsfos dIschnrgod from IndusfrInI nnd rosonrch confros cnuso oIIufIon.
l0. AII sorfs of chomIcnIs In fho nfmoshoro, InsfIc bodIos uIfImnfoIy Iond fo soII oIIufIon.
ControI of SoiI PoIIution
l. ConfroI uso of forfIIIzors nnd osfIcIdos.
2. Ioforo dumIng fho sowngo fho hnrmfuI chomIcnIs shouId bo romovod.
3. oforosfnfIon Is fo bo mInImIsod nnd InnfnfIon cnrrIod ouf.
4. AvoIdIng fho sIIIngo of gnrbngo, nsh, sIudgo, boffIos, InsfIcs ofc.
5. IndusfrInI wnsfo fo bo fronfod roorIy boforo dIsosnI.
6. IrocnufIon fo bo fnkon fo noufrnIIso ncId rnIn.
?. Tho wnsfo gnsos roIonsIng from nufomobIIos nnd IndusfrIos shouId bo urIfIod boforo
ronchIng fho ground.
8. Tho dIggIng of Inrgor Ifs or groovos In vIow of grnnIfo mInos, nquncuIfuro, nddIfIon
of vnrIous chomIcnIs fo grow wnfor bodIos ofc., nro fo bo nvoIdod fo rofocf fho soII
oIIufIon.
RADIOACTIVE POLLUTION
ThIs Is mnInIy duo fo (i) nucIonr oxIosIons, (ii) dIschnrgos from nucIonr roncfors.
Thoy omIf rndInfIons whIch nro hnrmfuI for IIvIng boIngs bocnuso fhoy brIng nbouf
chnngos In chromosomnI As nnd Iond fo gonofIc dIsordors, nnd dIsonsos. Thoso rndIo-nucIIdos
nro somofImos vory shorf IIvod nnd somofImos orsIsf for fhousnnds of yonrs nnd honco cronfo
bofh shorf fImo nnd Iong fImo hnznrds. Thoso hnznrds nro nof confInod fo fho oxIosIon sIfos
onIy bocnuso fhoy nro cnrrIod by nIr, wnfor ofc., by dIfforonf roufos fo dIfforonf nrfs of fho
onrfh nnd fhrough fho food chnIn fhoy onfor fho bIoIogIcnI rocossos.
umuges duo fo rndIoncfIvo rndInfIons IncIudo:
(o) InfhoIogIcnI dnmngoroducIng dIsonsos IondIng fo donfh nIso.
(I) ConofIc dnmngorndInfIons Iond fo chromosomnI dnmngo fo nny IIvIng sysfom cnusIng
ormnnonf chnngos for gonornfIons.
(c) !ndInfIons nIso cnuso Ioss of ImmunIfy, Ioss onzymIc ncfIvIfIos nnd honco cnuso honIfh
robIoms.
RudIouctIve wustes cun be:
(o) HIgL IeveI wustes. Thoso wnsfos nro rodomInnnfIy usod ns fuoI. Thoy nro InfonsoIy
rndIoncfIvo nnd somo of fhom hnvo Iong hnIf-IIvos e.g., IIufonIum-239, hnIf-IIfo 24,000 yonrs.
Ixfromo rocnufIons nro fo bo fnkon fo nvoId such hIgh IovoI confnmInnfIon In nIr, wnfor ofc.
(I) Iow IeveI wustes. Thoso nro roInfod fo nucIonr onorgy roducfIon, wnsfos from
urnnIum rofInorIos.
IsposuI oI vudIouctIve wustes
AccIdonfs from rndIoncfIvo rnys hnvo Incronsod ubIIc concorn worIdwIdo fo Iond fo snfo
dIsosnI of fhoso wnsfos. On-sIfo sforngo of fhoso wnsfos ovor shorf form nnd fhon fInnI dIsosnI
for Iong form InvoIvo Innd, nIr nnd wnfor.
l. Gvound dIsosnI Is bofh chon nnd onsIor. Tho wnsfos nro oIfhor burrIod doo In fho
ground nwny from dwoIIIng nrons, In vncnfod conI-mInos, In snIf-hons (snIfs nbsorb
rndIoncfIvo rnys) InsIdo mInos. Tho nrons for dIsosnI shouId hnvo Iow rnInfnII.
2. AIv. ConornIIy rndIoncfIvo gnsos nro sforod In fnnks, burIod In fho ground nnd fInnIIy
vonfod fo nIr so fhnf fhoro Is Iow IovoI of ncfIvIfy In fho nIr, ofhorwIso If mny bo
InhnIod nnd mny onfor fho IIvIng sysfom.
3. Wutev. Ior Iong form dIsosnI uIfImnfoIy fho wnsfos nro oncnsod In non-corrosIvo
Iond, fIfnnIum or coor confnInors nnd burrIod doo Info fho oconn. If musf bo so-
curod or If mny nffocf fho nqunfIc IIfo, fIshos nnd onfor fho food chnIn or onfor fho
ground wnfor.
RadionucIides
!ndIonucIIdos nro fho roducfs of fho nnfurnI docny of urnnIum. !rnnIum fnIIIngs confnIn
n vnrIofy of rndIoncfIvo nfoms or rndIonucIIdos IIko, !n-226, Th-230, Ib-2l0 ofc.. Somo of fhoso
hnvo Iong hnIf IIvos, e.g., Th-230 hns n hnIf IIfo of 80,000 yonrs. oondIng on fho H of fho
fnIIIngs, fhoso nucIIdos bocomo soIubIo nnd nvnIInbIo.
Tho mnIn oxosuro nfhwnys for rndIoncfIvIfy from fnIIIngs nro rndInfIon, InhnInfIon
of rndIoncfIvo nrfIcuInfos, rndIonucIIdos onforIng fho food chnIn. Thoro nro moro fhnn l000
rndIonucIIdos In fho nfmoshoro. Iofh fho Iong IIfo nnd shorf IIfo fyos of nucIIdos nro of
concorn for ubIIc honIfh robIoms. Tho fnbIo boIow IndIcnfos fho ncfIvo sIfos for nnd fho hnIf-
IIfo of dIfforonf rndIonucIIdos.
TabIe 27.1. Some mportant radionuclides and their half -lives
IoJionucliJe TorgeI Iieeue Holf-life
CnIcIum-45 Iono l65 dnys
Cnrbon-l4 WhoIo body 5?60 yonrs
CnosIum-l3? Soff fIssuo, gonIfnI orgnns 2? yonrs
IodIno-l29 ThyroId l? mIIIIon yonrs
IodIno-l3l ThyroId 8 dnys
IIufonIum-239 Iono, IIvor, sIoon 24,400 yonrs
!ndIum-226 Iono l620 yonrs
SfronfIum-90 Iono 28 yonrs
TrIfIum (
3
H) WhoIo body l2.3 yonrs
NOISE POLLUTION
Iscomforf cnusod by honrIng unIonsnnf, undosIrnbIo sound nf wrong Incos nnd nf
wrong fImos Is cnIIod noIso oIIufIon``. oIso oIIufIon Is oxrossod In ocIboI unIfs (dI). Tho
smnIIosf sound unIf nudIbIo nnd undIsfurbIng fo n honIfhy orson hnvIng good honrIng cnncIfy
Is ''ono docIboI.
Crowdod cIfIos, mochnnIsod frnnsorf, honvy IndusfrIos, modos of onforfnInmonf cnuso
noIso oIIufIon.
Sources of Sound PoIIution
Honvy nufomobIIos, scoofors, frnIns, noroInnos, horns, sIrons, fncforIos, Ioud sonkors,
rndIo, TV, nIr condIfIonors, gonornfors, dIfforonf funcfIons nnd moofIngs nro fho dIfforonf sourcos
of noIso oIIufIon.
WHO hns rocommondod fhnf n orson cnn sIoo ufo 35 dI noIso, ?5 dI Is fho oxIosIvo
IImIf, 80 dI Is hnrmfuI, dnmngIng fho honrIng sysfom.
Effects of Noise PoIIution on Man
l. oIso oIIufIon cnusos dIscomforf nnd Ioss of offIcIoncy.
2. IroIongod oxosuro Is hnrmfuI for confrnI norvous sysfom nnd nffocfs momory.
3. oIso oIIufIon cnusos Incronso In honrf rnfo, dnmngo fo brnIn, kIdnoy, IIvor.
4. Cronfos omofIonnI dIsfurbnncos.
5. InrfInI or ormnnonf honrIng Ioss.
6. IInfnfIon of uII of oyos.
?. Cronfos hondncho.
8. ocronsos workIng offIcIoncy.
9. Isfurbs sIoo.
l0. !onds fo vIoIonco, fIrodnoss, docronsod coIour orcofIon, dorossIon ofc.
ll. HIgh Ifchod noIso Ionds fo rond nccIdonfs.
l2. !onds fo hyor nnd hyogIycnomIn, hyoknInomIn, oosInohIIIn duo fo chnngo In
bIood nnd body fIuIds.
ControI of Noise PoIIution
l. oIso oIIufIon duo fo nufomobIIos cnn bo mInImIsod by fIffIng sIIoncors.
2. SoffIng IndusfrIos nwny from rosIdonfInI nrons.
3. !osfrIcfIng fho uso of Ioud sonkors.
4. ImosIng Inws fo confroI noIso.
5. IInnfIng Ashok, oom, IucnIyfus froos on bofh sIdos of hIghwnys, bosIdo schooI,
coIIogo, IndusfrInI buIIdIngs.
6. Tho wnIIs of IIvIng housos, offIco buIIdIngs, cInomn hnIIs shouId bo covorod wIfh sound
nbsorbors.
?. oIso cronfIng mnchInory shouId oIfhor bo IubrIcnfod roguInrIy or covorod wIfh Insu-
InfIng mnforInIs.
8. WonrIng of onrIugs, onr muffs for workors nnd ofhors fo mInImIso noIso offocfs.
THERMAL POLLUTION
Tho roIonso of hof vnours from nucIonr owor Innfs, IndusfrInI offIuonfs, nucIonr
roncfors, conI fIrod owor Innfs, hydrooIocfrIc Innfs rnIsos fho nfmoshorIc fomornfuro nnd
cnusos fhormnI oIIufIon. Honco duo fo fhormnI oIIufIon fho nvorngo fomornfuro of cIfIos
nro nbouf l0C hIghor fhnn fho vIIIngos. Tho dIssoIvod oxygon conconfrnfIon of wnfor bodIos
bocomos Iow duo fo rIso In fomornfuro. ThIs In furn cnusos hnrm fo fIshos, nqunfIc Innfs nnd
fo norobIc nqunfIc mIcroorgnnIsms.
Iy fho combusfIon of conI nnd ofroIoum roducfs CO
2
conconfrnfIon In nfmoshoro
Incronsos whIch rosuIfs Incronsod fomornfuro of fho onrfh nnd groon-houso offocf.
HIgLIIgLts:
(i) Souvces oI wutev poIIutIon
omosfIc sowngo
IndusfrInI offIuonfs
AgrIcuIfurnI dIschnrgos confnInIng osfIcIdos ofc.
OIIs, gronsos from nufomobIIos, mnchInos.
!ndIoncfIvo wnsfos.
(ii) MunIcIpuI sewuge tveutment
l. IroIImInnry mochnnIcnI fIIfrnfIon
2. SoffIIng In sodImonfnfIon fnnks
3. IIoIogIcnI fronfmonf
(o) AorobIc rocoss InvoIvIng (i) TrIckIIng fIIfors, (ii) OxIdnfIon onds, nnd
(iii) AcfIvnfod sIudgo rocoss
(I) AnnorobIc rocoss.
(iii) OtLev types oI poIIutIon
SoII or !nnd IoIIufIon
!ndIoncfIvo IoIIufIon
oIso IoIIufIon
ThormnI IoIIufIon
(it) BO
IIoIogIcnI oxygon domnnd Is fho nmounf of froo O
2
In mg roquIrod for fho
bIoIogIcnI oxIdnfIon of fho orgnnIc mnffor rosonf In l IIfro of sowngo.
(t) CO
ChomIcnI oxygon domnnd Is n monsuro of oxIdIsnbIo ImurIfIos rosonf In
sowngo.
Q. 1. WLut Is PoIIutIon?
Ans. Soo foxf ngo no. 5?l.
Q. 2. WLut uve tLe pvIncIpuI cuuses oI poIIutIon?
Ans. (i) IouInfIon oxIosIon.
(ii) !nId urbnnIznfIon.
(iii) !nId IndusfrInIIznfIon.
(it) oforosfnfIon.
(t) nfurnI dIsnsfors.
Q. 3. WLut uve tLe undesIvubIe eIIects oI excess oI oxIdes oI suIIuv In tLe
utmospLeve?
Ans. Soo foxf ngo no. 5?2.
Q. 4. WLut Is ucId vuIn?
Ans. Tho oxIdos of suIfur nnd nIfrogon formod duo fo nIr oIIufIon dIssoIvo In fho moIsfuro
rosonf In fho nfmoshoro fo form fho corrosondIng ncIds, whIch fnII wIfh fho rnIn sIowIy on
onrfh nnd Iowors fho H of fho rnIn wnfor boIow H = 5.
Q. 5. WLut Is gveen-Louse eIIect?
Ans. Cnsos such ns CO
2
, CH
4
, O ofc., do nof nIIow fho rndInfIng Infrnrod rnys from fho
onrfh`s surfnco fo nss fhrough fhoroby IncronsIng fho nfmoshorIc fomornfuro of fho onrfh
whIch Is cnIIod groon-houso offocf. ThIs Ionds fo nbouf 0.05C rIso of fomornfuro or yonr.
Q. 6. WLut Is tLe Impovtunce oI ozone Iuyev?
Ans. Ozono nf nn oIovnfIon of 30 km from fho onrfh`s surfnco nbsorbs fho mosf hnrmfuI
!V rndInfIon comIng from fho sun nnd fhoroby rofocfs fho IIvIng boIngs on onrfh.
Q. ?. WLut uve tLe cuuses oI 'ozone LoIe'?
Ans. ChIorofIuorocnrbons comIng ouf from fho oxhnusf of fho suorsonIc jofs nnd from
fho rofrIgornfors, norosoIs ofc., Iond fo fho bronkdown of ozono Info oxygon by n chnIn roncfIon
nnd cnuso fho doIofIon nnd fhoroby formnfIon of ozono hoIo ovor AnfnrcfIcn.
Q. B. WLut Is pLotocLemIcuI smog? MentIon Its eIIects.
Ans. Soo foxf ngo no. 5?5.
Q. 9. WLut uve eIIects oI puvtIcuIute muttev on Lumun?
Ans. Irosonco of oxcossIvo nrfIcuInfo mnffor In nIr Ionds fo nIIorgy nnd rosIrnfory
dIsonsos In humnn. Tho fwo mosf common dIsonsos fnkIng Inco nro bronchInI nsfhmn nnd
Iung cnncor.
Q. 10. WLut Is sewuge?
Ans. Tho IIquId wnsfo, whIch IncIudos humnn nnd housohoId wnfors, IndusfrInI wnsfos,
sfroof wnshIng ground wnsfos confnInIng mnInIy wnfor nnd ofhor orgnnIc nnd InorgnnIc mnffors
Is cnIIod sowngo.
Q. 11. WLut Is BO?
Ans. Tho nmounf of froo oxygon In mg roquIrod for fho bIoIogIcnI oxIdnfIon of fho orgnnIc
mnffor rosonf In l IIfro of sowngo Is cnIIod Ifs bIoIogIcnI oxygon domnnd (IO).
Q. 12. WLut Is CO?
Ans. ChomIcnI oxygon domnnd (CO) Is n monsuro of oxIdIsnbIo ImurIfIos rosonf In
sowngo.
Q. 13. WLut Is tLe Impovtunce oI BO ov CO meusuvement?
Ans. IO or CO Is vory Imorfnnf In sowngo fronfmonf sInco If IndIcnfos fho nmounf
of oxIdIsnbIo orgnnIc mnffor rosonf In fho sowngo. Honco gronfor fho vnIuo of IO, hIghor Is
fho oIIufIon IovoI of fho sowngo.
Q. 14. WLut Is 'wutev tubIe' und Low does It IuII?
Ans. Tho dofh In fho soII boIow whIch soII Is fIIIod wIfh bod of wnfor onIy.
Tho wnfor fnbIo fnIIs whon fho rnfo of umIng ouf of wnfor Is gronfor fhnn fho rnfo of
rnInwnfor orcoInfIon.
Q. 15. How Is veIovestutIon Impovtunt In contvoIIIng utmospLevIc poIIutIon?
Ans. IInnfs ufIIIzo fho CO
2
of nIr for fhoIr hofosynfhosIs nnd gIvo ouf O
2
In fho nIr,
fhoroby roducIng fho Iond of CO
2
In nIr nnd onrIchIng If wIfh O
2
.
Moroovor, nIr fIowIng fhrough fho froos In fho forosfs sIows down IondIng fo doosIfIon
of nrfIcuInfo mnffors cnrrIod by fho nIr.
Q. 16. How cun we decveuse tLe Ieud poIIutIon due to uutomobIIes?
Ans. !ond oIIufIon duo fo fho nufomobIIos cnn bo docronsod by usIng unIondod ofroI
ns fuoI.
Q. 1?. WLut Is eutvopLIcutIon?
Ans. AIgno In rIvors, Inkos muIfIIy rnIdIy by forfIIIzors from fnrmInnd or by nufrIonfs
from sowngo. Thus formod fhIck Inyors of nIgno bIock ouf fho IIghf fo Innfs growIng boIow fho
surfnco so fhnf fhoy cnn no moro roduco oxygon, nnd nqunfIc IIfo bocomos ondnngorod. Tho
honomonon Is known ns oufrohIcnfIon.
EXERCISES
1. MonfIon fho hnrmfuI offocfs of fho nIr oIIufnnfs: SO
2
nnd CO.
2. Whnf Is groon-houso offocf nmo n fow groon-houso gnsos.
3. Whnf Is fho dIfforonco bofwoon norobIc nnd nnnorobIc oxIdnfIons of sowngo
4. oscrIbo fho ncfIvnfod sIudgo rocoss for fronfmonf of sowngo.
5. Whnf nro IO nnd CO IndIcnfo fhoIr sIgnIfIcnnco In sowngo fronfmonf.
6. WrIfo down fho rIncIIos InvoIvod In fho doformInnfIon of IO nnd CO.
?. IxInIn fho cnuso of doIofIon of ozono Inyor. Why Is fho ozono Inyor Imorfnnf for us
B. WrIfo fho sourcos of rndIoncfIvo oIIufIon. How cnn If bo confroIIod
9. WrIfo nofos on:
(i) TrIckIIng fIIfor mofhod.
(ii) IIocfrosfnfIc rocIIfnfor nnd Ifs uso.
(iii) AcfIvnfod sIudgo rocoss.
(it) AcId rnIn.
(t) IhofochomIcnI smog.
(ti) CycIono sonrnfor.
10. Whnf Is noIso oIIufIon How cnn If bo mInImIsod
11. Whnf nro fho sourcos of wnfor nnd soII oIIufIon
12. IxInIn (o) IoIIufIon confroI cnn bo offocfod by roforosfnfIon (I) IO Is fho monsuro of oIIufIon
of wnfor.
13. Sfnfo fho monsuros fo bo fnkon fo confroI:
(o) AIr oIIufIon (I) Wnfor oIIufIon (c) oIso oIIufIon
(J) SoII oIIufIon (e) !ndIoncfIvo oIIufIon.
14. Iscuss fho mofhods of munIcInI sowngo fronfmonf.
15. How cnn oIIufIon from InfornnI combusfIon ongInos bo confroIIod

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C8d:\N-engche\ TITLE.

Atoms and MoIecuIes

whoro x Is cnIIod quonIun nunIer nnd Is oqunI fo l, 2, 3 ... .

(a) (b) (c)

orbIfnI IIo nIong fho x nnd , nxos whIIo fhoso of Jc

VaIency and ChemicaI Bonding

Ions. Thoso Ions

(nnfIbondIng) moIocuInr orbIfnIs rosuIfIng from fho combInnfIon of fwo

Fig. 2.24 -Bonding.

.I. no. of oIocfrons In bondIng moIocuInr orbIfnIs.

Fig. 2.28 M.O. diagram for N

Q. 10. WIoI ie IIe epeciol feoIure of o cotolenI IonJ:

Fig. 2.37 (>) Forces of attraction during H

uo fo hydrogon bondIng, fhoro Is moIocuInr nssocInfIon In HI nnd offocfIvo moIocuInr

Tho rosonf rnfIo of !

, fhon fho nbovo oqunfIon wIII fnko fho form,

whoro q Is moInr honf of frnnsIfIon from ono hnso fo nnofhor.

. ThIs oqunfIon Is fho fnmous CIupeyvon-CIuusIus equutIon.

Irom 3rd Inw, S

InfogrnfIng bofh sIdos,

from (ii) nnd (iii), wo hnvo

C Is n consfnnf ns C Is n sfnfo funcfIon

(C) = 393 lJ nol

= consfnnf for such rocoss.

Ions roncf In onch cnso.

(ti) HydroIysIs of nn osfor:

Socond ordor roncfIon l =

So, If wo cnn doformIno fho fwo rnfo consfnnfs l

= 24.09 + l0.?9 = 34.83

Horo, I = 30 mIn o = l00

. ColculoIe IIe ocIitoIion energ, of IIie reocIion.

whoro A Is cnIIod fho ArrhonIus fncfor nnd I

whoro l = rnfo consfnnf nnd fho ordor of fho roncfIon + + .

oxorImonfnIIy obsorvod fncf.

Progress of reaction (one-step process)

gonornfod. Thus nddIfIon of n bromIno moIocuIo fnkos Inco fo n doubIo bond:

, fho bnso durIng roncfIon.

) occurs on n cnrbonyI cnrbon IondIng fo nn nddIfIon

nffncks nnd forms n now bond.

Primary (1) carbocation Tertiary (3) carbocation

(I) IuncfIonnI grou (i) C

) Is n nucIoohIIIc rongonf, nnd subsfIfufIon of X

, i.e., subsfIfufIon of wonkIy bnsIc grou fnkos Inco by n sfrongIy bnsIc

Is u weukIy busIc gvoup und OH

Is n wonk bnso ns Ifs conjugnfo ncId HX

fnkos Inco by nucIoohIIIc H

, ns If hns Iono nIrs C

und IsocyunIdes wItL AgCN?

In fho nbsonco of such romofIon by Ag

wouId fnko Inco wIfh oqunI rondInoss from oIfhor

romnIns unsoIvnfod nnd oworfuI nucIoohIIo cnn nffnck.

fo gIvo !X. So, fho roncfIon Is

l9 8l Snyfzov Tho nIkono wIII rodom-

95 5 Hofmnnn Tho nIkono whIch hns

, (it) fho nnfuro of fho soIvonf.

So, suIhonnfIon of bonzono Is nn oIocfrohIIIc subsfIfufIon.

Ions. If Is woII known

Ions nro snmo nnd OH

Is dorIvod from n bnso, so wo

Ions. Tho dofInIfIon of ncIds nnd bnso noods fo bo oxfondod.

. Somo AcId/Inso conjugnfo nIrs nro shown In fho foIIowIng fnbIo.

HydroIysIs roncfIon Is oxInInod ns foIIows nccordIng fo Ironsfod !owry concof:

is o sIrong Iose os iIs conjugoIe ociJ, oceIic ociJ

Ions wIII rondIIy nccof rofons from wnfor moIocuIos