Bansal Chemistry 1

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CONTENTS
KEY CONCEPT•................................................................ Page 2 -14
SOVLED EXAMPLE ......~ .....•................•..••...................... Page 15 - 21
EXERCISE-I..................................................................... Page 22 - 26
EXERCISE-II ............................................... ~ ................... Page 27 - 31
EXERCISE-Ill.................................................................. Page 32 - 33
. ANSWER KEy.......................................................•........... Page 34
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1.... ; JEE MAIN - 2014
c NITROGEN COMPOUND
(.
c
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C
L
C
L
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L
, ~'.'
NITROGEN 'COMPOUNDS
1. GENERAL CHARACTERISTICS
(a) If a hydrogen atom ofNH3 is replaced by an alkyl group then it is called primary amine
and possess -NH2(amino) group_
(b) Amines are called alkyl derivative ofNH3
(c) Aliphatic amine was discovered by 'Wurtz'.
(d) IftWo hydrogen atoms ofNH3 are replaced then it is called secoudary amine and it posses .
> NH (Imino) group_
(e) Ifall hydrogen atoms ofNH3 are replaced then it is called tert~ amine and has a nitrilo N
group_
(t) N is in sp3 hybridisation and tetrahedral geometry. .
(g) Bond angle increases from ammoni~ ~o ~o amines.
NH3 (l07°) < RNH2 < R2NH < R3N
(h) Aliphatic and aromatic amine shows chain, position, functional and metamerism.
GENERAL CHARACTERISTICS:
NH2
Ex.! Compound is a -
O N
I
CH 3
(A) 1° and 3° amine (B) Only primary amine

(C) 2° and 3° amine (D) Only secondary amine (Aus.A)
Sol. 3-Amino-N-methylpiperidine contains primary and tertiary amino groups.
Ex.2 The third member of homologous series of.dimethyl amine ;.

(A) CH3-CH2-NH-CH2-CH3 (B) CH;-NH-CH2-CH2-CH3_
(C) CH3-NH-CH(CH3h (D) 2 n and 3rd are correct (Ans.D)
Sol. Compounds 2nd an~ 3rd contains CH3-NH..;.. group. o
Ex.3 Tertiary butyl amine is a
(A)l°Amine (B) 2° Amine
(C)3°Amine (D) Quaternary salt (Aus.A)
Sol. (CH3)3C-N~ is primary amine
Ex.4 N-atom in quaternary ammonium halide will have the form- c

ED
(A) -N- (B) N (C) N~ (D) - N- H (Ans.A).
1\ I
I
Sol.
H H
Quaternary ammonium halide is an ionic compound. Hence N carries positive charge.
o
c
[2]
!j]!~~~~~ CM~~~!
10, lIko/ SchcJo,s
NITROGEN COMPOUNDS
,(~.
\J
G
Ex.S -CONH ""UU..uUII) -CH NH
2 2 2
In above reaction hybridisation state ofcarbon changes from ..... ~ ....... .
(A) sp ~ sp2 (B) sp ~ sp3
(C) sp2 ~ sp3 (D) sp2 ~ sp (Ans~C)
SoL Hybridisation state ofcarbon changes from sp2 to sp3.

\.
2. METHODS OF PREPARATION
2.1 FromAlkylchloride:
R-CI + H-NH2 CU20)
200.C
R-NH
2
+ HCI
Note: In the above reaction Cu20 neutralises the evolved HCI in form ofCuFl2 + H20 otherwise
HCI forms additional salt with amines.
2.2. From Grignard reagent:

R-Mg-Cl + CI-NH2 ) R-NH2 + ~gC12
2.3 From Alcohol:
r-------, ~g) R-NH2 + H 20
R'I'.:.9-'::!!J::!.:r NH2
(
' 2.4 By Aldehyde or Ketone (reaction with H2 and NH3 in presence of catalyst) :
Primary amme can be produced by passing a mixture ofaldehyde orketone and large excess ofammonia
and hydrogen under pressure (20-150 atm) over raney nickel catalyst at 40-150°C.
" R 1R 2C=0 + NH3 ~ RiR 2CHNH2
.Note: Small amount ofsecondary and tertiary amines are also produced in this method as by products.
2.5 By reaction ofAldehyde or Ketones (with ammonium formate orwith formamide and subsequent
hydrolysis ofprodu(:t)
Aldehyde and ketones when react with ammonium formate or formam ide or the formyl derivative of
primaty amine on hydrolysis yields primary amine and formate ions.
)C = ° + 2HC02NH4 ) )CH NHCHO + 2H20 + NH3 + CO2
(ammonium formate)
/'C =0 + 2HCONH2 ---7) )CH NH- CHO + CO2 + NH3

c
{ '"
/CH NH - CHO
2H20
inalkalinemedium
)'
/CH NH2 + H e
COO
( 2.6 From Alkanoic acid (Schimdt Reaction) :

(
'..
R-C-O-H + N3H cone. H2 S0 4 ) RNH + N2 + CO2
2
8
Note: Alkyl isocyanate can also be produced by heating the mixture of acyl halide and sodium azide,
alkylisocyanate, once it is formed, can easily be hydrolysed into primary amine and CO2,
C
C
[j~~~~A~ cy~~~~~ NITROGEN COMPOUNDS [3]
IdtoIforScholtll'S
L
I
C
t
Mechanism:
Ell
"~EIl H~-N=N
R- C -OH+HE!)-}R-C-OH~R-C-OH HN~NaN ~ R -c OH -H20
o
/I /:"11
~~H bH
I QH >
R-N~
( II~ R-N
. H20 -C-OH ( . ". II -Nz~. N=N
. ",0. . ' II
R-N-H , __;,c-OH R . C-OH
I
OH-C=O -H2 0
> R-N=C=O +H2<)
hydrolYSiS) RNHi + CO2
alkyl isocyanate
R- c -CI + NaN3 )
.r\fl
C!~~c-N1N=N ~O=C=N:""R OW >RNH2 + CO2
II \11 t . rearmngelllnl
o \..V ".
t '
2.7 From Acyl halide:

R - C - X + Na-N :: W = N- ~ R-C -N=N+ =N- Reearrangement tl. ) 2KOH + R-N=C=O
II II-N.!
o sodium azido 0
-K.,CO• .. R- NH2
Note : It is a good method for preparation ofalkyl amine. Reaction is called 'Curtius Reaction'.
2.8 From Alkanamide :

Ri-NH2 + Br2 + KOH > R-NH2 + KBr + K 2C03 + H 20
o
Note: The reaction is called 'Hoffmann Bromamide reaction' discussed earlier.
2.9 By Alkyl cyanide (By reduction) :

_ tlAlH.; )
R-C=N + 4H •. _.~.~.. R-CH2-NH2
Note: When (Na + Et.OH) is used as reducing agent then reaction is called 'Mandius Reaction'.
2.10 From Alkyl isocyanate (Alkalin~ Hydrolysis) :

R-N=C=O + 2KOH > R-NH2 + K 2C03
2.11 From Aldoxime (By Reduction) :
c
H H
c
I I 2H
R-C =N-OH + 2H tlAllt! )
R-c N - OH -H2 0 ) R-CH 2-NH2 0
~ ~ ()
1i'~~~A~C~~~~! NITROGEN COMPOUNDS -

[4] G
IdtoI for Schol4rs
c
c
2.12 From Phthalic acid:
o 0 0 0 0
II' II II II
@(
o -00
-00 ~ r(3YCi~-:-ff3>N_H ~ r(3YC'N_H~ r(3YC>_R~ R-NH2 + r(3YC-OH
~o ~c1 ____l:u
I
~c/ -HI ~c
II
~C-OH
II II II
(; 0 O. 0 0
phthalic anhydride phthalimide N-alkyl phthalimide
.Note: It is the best method for preparation ofaliphatic amines. The reaction is called 'Gabriel-Phthalimide
reaction'.
2.13 By reductiou of Nitro compouuds:
Nitro alkanes are reduced catalytically to primary amine.
(a) By LiAlH4
". (b) By Metal and acid (commonly used Sn + HCI or ,Fe + HCI)
RNO reduction) RNH + 2H 0
2 4H . 2 2
Note: (i) When reduction with metal is carried out in neutral solution e.g. with Zn dust & NH4CI solution,
nitro compounds are converted into N-alkyl hydroxyl amine.
RN02 Zn+) RNHOH + 2H20
N~CI
N-alkylhydroxyl amine
(ii) When reduction of nitroalkane is carried out with SnCl 2 and conc. HCI, a mixture of
N-alkyl hydroxyi amine and oxime are produced.
RCH NO sncl:!+) RCH NHOH + RCH = NOH
2 2 cone. HCI 2
N-Alkyl hydroxy amine Oxime
f
\, 3. PHYSICAL PROPERTIES
(a) Like ammonia, amines are polar compounds and except 3° amines can form intermoleculer H
r bonds that's why they have higher boilingpoints.
\.
(b) Unlike other organic compounds, amines are much more soluble in water. BecauseAll amines
c form a stronger H- bond with water.
(c) Solubility in water follow the order.
(,
1°. > 2° > 3° amine..
" This is all due to H- Bonding.

(
,-,.
(d) Boiling points ofamines are lesser than alcohols and acids ofcomparable mol. weight Because
H- bonding in amines is less pronounced in I ° and 2° than that in alcohols and carboxylic acids.
Because nitrogen is less electronegative than oxygen.
Thus every question regarding boiling point can be answered on the basis ofH - bonding.
c (e) Boiling points of 1°,2° and 3° amines follow the order.
1° > 2° > 3° amine.
[i!~~~.~~ CM~!~! IdullforSCholo"

NITROGEN COMPOUNDS [5]
. 4. CHEMICAL PROPERTIES
(a) Almost all chemical properties and reactions ofamines are governed by basicity ofamines..
(b) A lone pair ofelectron on n~trogen atom in each ofamines and ammonia makes them basic
in nature.
(c) Alkyl groups are electron releasing group which increases electron density on nitrogen atom
thus, we can expect the order of basicity ofammonia
'\
1° , 2° and 3° amines to be
3° > 2° > 1° > ammonia
(d) Some other factors like steric effect, Solvation or hydration and mainly crowding on nitrogen
atom by three bulky alkyl groups, decreases the basicity of3° amines to a great extent and
order follows
~NH > RNH2 > R3 N > NH3
(2°) . (1°) (30) (ammonia)
. . \
(e) This can be also explained on basis oflesser capacity of3° amine to form H- bonds with water
which stabilizes ~N'H on because it has only one H-atom
5. CHEMICAL REACTIONS
5.1 Alkylation:
+R~ >RNHRI +RzX

R-N X
) R-~-R2
RI 1+ x
RNH2 -HX -HX
t R2 +R3
-HX [ I
Ra
(quartenary ammo salts.) \ --'
5.2 Reaction with Grignard reagent: Since primary and secondary amines have active hydrogen, they
. on reaction with Grignard reagent give alkanes
RNH2 + CH3MgBr ether) CH4 + RNH.MgBr
R2NH + CH3MgBr CH4 + R 2N.Mg Br
ether)
Note: Tertiary do not react because of absence of active hydrogen.
5.3 Reaction with Aldehydes and K~tone:

RNH2 +CH3CHO ) RN = CHCH3 + H 20
(schiff's base or anil's base)
5.4 Acylation : 1° and 2° amines react with acetyl chloride or acetic anhydride to form acetyl derivatives.
R-NH2 + CH3COCI ) RNHCOCH3 + HCI
R-NH2 + (CH3COhO ) RNHCOCH3 + CH3COOH

c
(CH3hNH + CH3COCI ) (CH3hN - COCH3 + HCI c
Note: (a)
(b)
Tertiary amines donot undergo this reaction because ofabsence ofreplacable H- atom.
When Benzoyl chloride is used in place ofacetyl chloride reaction is called' Schotten - Baumann'
c
reaction. o
Ii!~~~!!~C~~~~! .ld<olforSch<>l4"
NITROGEN COMPOUNDS [6]" c
c
v
1 .
v
5.5 Oxidation: All three are Qxidised in different ways depending upon conditions ofoxidation.
(a) Primary Amine: Oxidised to aldehydes and ketones.
·RCHzNH:z~R.;.CH=NH H2
0
>R-CHO+ NH3 '
KMn04
aldimine aldehyde
~CHNH ~R-C=NH H2
0
>R·C=O+NH
, 2 KMn04 &"2 &"2 3
/ ketimine ketone
\
(b) Secondary Amine:
2R2NH ~ R 2N-NR2
KMn04 '
(tetra-alkyl hydrazine) .
/'
R2NH R 2N-OH
" (dialky I hydroxylamine)
(e) Tertiary Amine: Resistant to KMn04 but oxidised by neutral and aqueous H 20 2 in cold
to form trialkyl amine oxide.
Note: (i) NH2-NH2 is called hydrazine
(ii) NHrOH is called Hydroxylamine
f
\..
5.6 Salt formation: Amine forms salt with mineral acids ,
r
RNH2 +HCI) [RNH31 + CI
R2NH +HCl ) (R2NH2t cC
R3N + HCI ) (R3NHt CI-
These salts may undergo dealkylation at higher temp.
, +
For example: C2HSNH3 CI ~ C 2Hs CI + NH3
Reaction with HN0 2 : This reaction distinguishes 1°,2° and 30 alcohols.

(a) PrimaryAmime: Except methyl amine, reaction happens at ordinary temp. to evolve N2 Gas.
12
CHF1 NH2 + FlN02 ) CH3CH20H + N 2+ 0
112
Methylamine reacts in different way:
CH3NH2 + 2F1N02 )CH3-O-N ='0 + N2 + H 20
. methyl nitrite
2CH3Nfl2+ 2F1N02 --7CH3-O-CH3 + 2N2+ 3H20 ,
dimethyl ether
(b) SecondaryAmine: Form nitroso amines with FlN02 (No N2 gas is evolved)
~NH + FlN02 ) R2 .,... N - N = ° + H 20
(yellow)
Note: These nitroso amines formed, on warming with phenol and conc. H 2S04 give a brown or red colour
L changing to .blue or green on further addition ofan alkali, colour changes to red. This test is called
Libermann's nitroso test and used for identification of2° amines.
(
(e) Tertiary Amine: These are inert to I:IN0 2 but being basic in nature forms salts with it.
C (CH3)3N + HN02 ) (CH3)3 N - HONO
C:
t
5.8 Reaction with water: Amine gives alkyl anUnonium hydroxides which dissociate into ions
RNH2 +H20 .. '. ·RNH30H:::;;;::=::' RNH3++ OH
5.9 Isocyanide test or Carbylamine reaction:

Primary amines when heated with chlorofonn and ethanolic KOHsolution, alkyl isocyanides is produced"
which have characteristic foul smelt. This reaction is characteristic to the primary amine. This test is .
known as carbyl amine test or isocyanide test.
~ + CHCl3 + 3KOH >RNC + 3KCI + 3~O
The reaction proceeds via the formtion ofdichloro carbene (:CCI2). In the absence ofany lewis base
catalyst when HCCl3 reacts only with base, :CCI2 also produced, which is rapidly hydrolysed into CO,
HCO;-:- and cc. .
CHCl3 + OHa ) :CCI2 + H 20 + Cia
(dichloro carbene)
\- ~
e a
RNH2 + :CCI2 ---40) R- N == C + 2HCI
(alkyl isocyanide)
:CCI2 o~
H20
>co + HCO a + 2Cla
2
{
\
(
5.10 Reaction with Hinsberg reagent: This is a method for seperation of10 , 2 0 and 30 amines Hinsberg
Reagent is .
C6H s-S02-CI. (Benzene sulphonyl chloride)
RNH2 + CI - S02-C6HS -----? R-NH-S02-C6H s + HCl
(a) Primary amines form N-Alkyl benzene sulphonamide
@
~.
@
.0 -S02C1 + H-N-R
""'
H
I
) 0 -502 - N R + He!
N-alkyl benzene sulphonamide (ppt.)
(
\
~
1·smine
(b) Secondary amines form N, N-dialkyl benzene sulphonamide
o
@ "
-S°2CI+H-N-R >
@"
0 ~.
-S°2-N-R+HCI .
G
. ~. . N.N-dialkyl benzene sulphonamide (ppl)
2Q amlne ':
(c) Tertiary amines do not react because they do not possess a replacable Hydrogen atom.
5.11 Mustard oil reaction: Al 0 amine reacts with CS2 and then with HgCl2 tb form iso thiocyanate having
pungent smell ofmustard oiL .
2RNH2 +8= C
".
S~S =C(
NHR
HgCI2 ) R-N=C=S+RNH2 +HgS+2HCI
c
'~H .
alkyl isothiocyanate
()
NITROGEN COMPOUNDS
-
[8]
.
C
v
C
5.12 Reaction with Nitrosyl chloride (TILDEN'S REAGENT) :
R-NH2 + NOCI ) R-CI + N2 + H 20
·5.13 Reaction with Caro's acid [HzSOs1 :

With caro's acid, the oxidation products ofprimary amine are also dependent on the nature ofthe alkyl
group present in the amine.
/OH
RCH2NH2 [0).)
byH2S0S
RCH 2NHOH + RCH =NOH + R- c~ NOH
(N-alkyl (aldoxime) (hydroxamic acid)
hydroxyl amine)
~ R 2C
'\
R 2CHNH2 NOH (ketoxime)
byH2S0s
.R3CNH2 (oJ) R3CNO (nitrosoalkane)

byH2S0S
(
CHEMICAL REACTION
Ex.6 The smell ofmustard oil is given by the compounds
[ (A) Carbylaminoalkane (B) RN<:::S
I.,
(C) RCNO (D) RCNS (Ans. B)
( Sol. Alkyl isothiocyanate gives the smell ofmustard oil
Ex.7 R-C-NH2 Br./KOH) R~ CSH5

COC1
) R-NH -c C6HS
g ~
The reactions involved in the above reaction sequence are
r (A) Stephen and Schotten Boumann (B) Hofinann and Schotten Boumann
\
(C) Hofinann and Cannizaro (0) Gabriel and Schotten Boumann
( (Ans. B)
Ex.8 When. I-propane amine is treated with NaN02 and HCI the products will be
( (A) I-propanol, 2-propanol .
(B) Propene
(C) 2-Chioropropane, l-chloropropane
(0) All ofthese (Ans.D)
Sol. The products formed in the reaction between CH3CH2CH2NH2 and HN02 are
( 1- Propanol, 2 propanol, propene,
l-Chloropropane and 2-chloropropane
(
6. SEPERATION OF MIXTURES OF AMINES
( 6.1 Hinsberg method:
This involves the treatment ofthe mixture with benzene sulphonyl chloride (Hinsberg Reagent) and
(
KOH.
(a) . The primary amine forms N-alkyl benzene sulphonamide which forms a salt with KOH, which
C
is soluble in water.
L ~
CaHsS02CI + H-HNR ) <;Hs S02 -N-R + HCI
() benzene sulphonyl 1° amine N·alkyl benzene sulphonamide
chloride
C
C [I]~~~~,,~~ CL~~!~! NITROGEN COMPOUNDS [9)
IdeoIfot5<""klt'
{
"".
(b) The secondary amine gives N, N- dialkyl benzene sulphonamide which is insoluble in KOH
solution
(c) The tertiary amine does not react at all.
6.2 Hofmann method:

This involves the treatment ofthe mixture with diethyl oxalate..
(a) The prio:uiryamine fonns a dialkyloxamide, whic~ is a solid
,
(b) The secondary amine forms a dialkyl oxamic ester, which is an oily liquid.
(c) The tertiary amine does not react at all.
/-
6.3 Fractional distillatic)D :

The mixture ofprimary, secondary and tertiary amines, may be separated by fractional distillation
because their B.P's. are quite different. This method is extensively used in industry.
CYANIDES, ISOCYANIDES, ALKYL NITRITES AND NITRO ALKANES \
1.1 GENERAL CHARACTERISTICS:

(a) Compounds having the fonnula RCN are called alkyl cyanides or as nitrites ofthe acid which-they
()
produce on hydrolysis.
(b) According to IUPAC system, cyanides are named as alkane nitrites, i.e., in the name of parent '.
hydrocarbon 'nitrile' is suffixed. In naming the hydrocarbon part, carbon ofthe - CN group is also
counted.
Formnla As cyanide WPACname
CH3CN Methyl cyanide Ethane nitrile
(Acetonitrile)
!
\.
C2HsCN Ethyl cyanide Propane nitrile
(~
(propiononitrile) \../
C3H 7CN Propyl cyanide Butane nItrile

C 4H9CN Butyl cyanide Pentane nitrile
()
(c) The compounds having the formula RNC are called isocyanide or isonitriles. The nomenclature of
isocyanides is similar to cyanides.
Formula As isocyanides IUPAC names
(Commanname)
CH3NC Methyl isocyanide . Methylcarbylamine
(Methyl isonitrile) (Carbylamino methane)
C2HSNC Ethyl isocyanide Ethyl carbylamine
(Ethyl isonitrile) (Carbylamino ethane)
C3H7NC Propyl isocyanide Propyl carbylamine .
(propyl isonitrile) (Carbylamino propane)
c
(d) Isocyanides are also named as alkane isonitrile. c
CH3NC Methane isonitrile
C2HSNC Ethane isonitrile
()
C3H7NC Propane isonitrile
C
1i!~~~A~~ CL~~~~!
Itkal tOt Schoian
NITROGEN COMPOUNDS 110] C
c
(' ,
v
·(e) Hydrogen cyanide is known to exist as a tautomeric mixture. (Diad forms)
H - C == N ~ H - N =:!"C
Hence, it forms two types of alkyl derivatives which are known as alkyl cyanides and alkyl
isocyanides.
R-C==N R-N=:!"C
Alkyl cyanide Alkyl isocyanide
.1.2 ALKYL CYANIDES

Methods of Preparation
(i) From alkyl halides: The alkyl cyanides are prepared by refluxing an alcoholic solution
,
(
ofan alkyl halide with potassium cyanide. The disadvantage ofthis method is that a mixture
ofnitrile and isonitrile is formed.
RX + KCN (or NaCN) ~ RCN + RNC
Alkyl halide Nitrile Isonitrile
(Major product) (Minor product)
(11) From Grignard reagent: Grignard reagent reacts with cyanogen chloride to form alkyl
cyanides.
x
I'
\. ..
RMgX + CICN ~ RCN + M<
CI
Grignard Alkyl Cyanide
reagent
/Br
CH3MgBr + ClCN .~
CH3CN + M~
. I
(
Methyl Cyanogen Methylcyanide
rnagnisium chloride
bromide
(m) From acid amides : Pure nitriles are obtained by dehydration ofacid amides with phosphorus
r\. pentoxide. Arnides are distilled with phosphorus pentoxide, P 205'
RCONH z p~s ) RCN
-H20
C
CH3CONH z CH3CN + H20
Acetamide Methyl cyanide
Industrially, alkyl cyanides are prepared by passing a mixture ofcarboxylic acid and ammonia
C OVer alumina at 500°C.
r\. +
RcaOH + NH3 ~ RCOONH4
AI203.500"C RCONH2 ~RCN
-H20 Amide -H20 Alkyl
( '. Acid Ammonium Salt Cyanide
",.
t (Iv) From primary amines : J.lrimary amines are dehydrogenated when passed over copper
or nickel at high temperature to form alkyl cyanides. This is also a commercial method.
C Cu orNi ) RCN + 2H2
RCH2NHZ 500"C
(
Primary amine
C
C
1II!~~~!1~CL~~~~~
fdedlOf'ScMIors
t .
'L ..
c
,
11..../
CuorNi
CH3CHzNH2 500·C
CH3CN + 2Hz"
Ethylamine " Methyl cyanide
(v) From oximes : Aldoximes are converted into alkyl cyanides when distilled with phosphorus
pentoxide or acetic anhydride. The dehydration ofaldoximes occurs.
H
I P20S
R-C=NOH ----+
-H~.
R- CN + H20
Aldoxime Alkyl cyanide
1,3 Physical properties:
(a) Lower members containing upto 15 carbon atoms are liquids, while higher members ofcarbon
atoms in the molecule.
(b) Alkyl cyanides are neutral substances with pleasant odour, similar to bitter almonds.
(c) They are soluble in water: The solubility decreases with the increase in number ofcarbon atoms
in the molecule are solid.
(d) They are soluble in organic solvents.

(e) They are poisonous but less poisonous than HCN. c\
1.4 Chemical properties:
(i) Reaction with Grignard reagent: With Grignard's reagent, an alkyl cyanide forms a
ketone which further reacts to form a tertiary alcohol.
R' R' "

R-C N + R'MgX ~R -C
I
= NMgX 2H 20 )I R- I
C = 0 + NH + Mg(0H
3 . X
R' R' R'
I "I Hoi ,../OH
R-C o + R" MgX ~ R- C - OMgX 2.) R-c -OH + M~

I I X
R" R" c
Tertiary alcohol
(ll) Reduction: When reduced with hydrogen in presenceofPt or N~ or LiA1H4 (Lithium.aluminium
hydride) or sodium and alcoho~ alkyl cyanides yield primary amines.
RCN ~ RCH2NH2
Alkyl cyanide Primary amine
However, when a solution ofalkyl cyanides in ether is reduced with stannous chloride and
hydrochloric acid and then steam distilled, an aldehyde is formed (Stephen's reaction).
;H 0
R- C == N snCI2/Hel) =
RCH NH.HCI . 2 ) RCHO + NH4 CI
[2H] Imine hydrochloride Aldehyde
(ill) Hydrolysis: Alkyl cyanides are hydrolysed by both acid and alkalies. On partial hydrolysis
amides are formed while on complete hydrolysis acids are obtained.
RCN ~o
H+
) RCQNT-T_
'U k
H2
W
0
) RCOOH + NH3 c
Alkyl cyanide Amide Acid c
~o H20
CH3CN ~ CH3CONH2 H+) CH3COOH + NH3 ()
Methyl cyanide Acetamide Acetic acid u
[12]
Ii~~~~~~ CL~~~~!
IdeclJorSdloklrs
NITROGEN COMPOUNDS
c
c
(iv) Alcoholysis: When an alkyl cyanide is refluxed with an anhydrous alcohol in presence ofdry
HCI, an imido ester is formed, which on hydrolysis with water forms ester.
RCN + R'OH + HCI

NH2
+
~.[ R-8-0R'
1 CI "2° ) RCOOR' + NH.CI
. Ester
Uses: Alkyl cyanides are important intermediates in the laboratory synthesis ofa large number of
compounds like acids, amides, I:lster, amines, etc.
1.5 ALKYL ISOCYANIDES
Methods of Preparation
(i) From alkyl halides: The isocyanides are prepared by refluxing an alkyl halide solution in
alcohol with silver cyanide. The isonitrile is the main product but small amount ofnitrile is also
fonned.
R - X + Ag~l:l ----t RNC + RCN"
Alkyl halide Isocyanide Cyanide
(Isonitrile) (Nitrile)
( . Main product Minor product
CH3 CI + AgCN - - 7 CH3NC + CH3CN
Methyl chloride Methyl isocyanide
(" (Main product)
\
This method is, thus, suitable for preparing isocyanides.
(ii) From Primary Amines : (Carbylamine reacthm) :Alkyl isocyanides may be prepared by
heating primary amines with chloroform and alcoholic potash.
RN~ + CHCl3 + 3KOH ~ RNC + 3KCI+ 3H20
'- Primary Chloroform Isocyanide
,/ amine
\,
(iii) From N-alkyl fonnamides : N-alkyl fonnamides when dehydrated with POCI3 in presence of
( ) pyridine give isocyanides.
oII p~ _
R-NH-C H )R-N=C
Pyridine
N-alkyl formamide Isocyanide
Physical properties :
(
(a) Alkyl isocyanides are colourless, unpleasant smelling liquids.
(b) They are insoluble in water but freely soluble in organic solvents.
(c) 1}Ie boiling points ofisonitiriles are lowerthan corresponding alkyl cyanides.
c' (d) Isonitriles are much more poisonous than isomeric cyanides.
c Chemical properties:
(0 Hydrolysis: Alkyl isocyanides are hydrolysed by dilute mineral acids (but not by alkalies) to
fonn primary amines.
RN -C + 2H20 RN~ + HCOOH

Alkyl isocyanide Primary amine Fonnic acid
c.·
1iJ!~~~"Al CL~~!~! NITROGEN COMPOUNDS [131
Jd<o1""_
(
(n) Reduction: When reduced wifu nascent hydrogen or hydrogen in presence ofnickel. isocyaiIides
form secondary amines containing methyl as one ofthe alkyl groups.
R- N =C + 4H --+ RNHCH3
Alkyl isocyanide Secondary amine
(ru) Action of heat : When heated for sometime at 250°C. a small amount of isonitrile changes
into isomeric nitrile.
RNC heat) RCN
(iv) Addition reaction: Alkyl isocyanide give addition reactions due to presence ofunshared
electron pair on carbon atom.
+
R : N :::C : or R - N C
The following are some of~he addition reactions shown by alkyl isocyanides.
RNe + X 2 ) RNCX2 Alkyl iminocarbonyl halide
(Halogen)
RNC+ S ) RNCS Alkyl isothlocyanate
RNC+HgO-~ RNCO + Hg
(Alkyl isocyanate)
Distinction between Ethyl Cyanide and Ethyl Isocyanide
Test
Ethyl Cyanide
(C 2 Hs CN)
Ethyl isocyanide (C 2 H5 NC ) I
1. Odour Not unpleasant Extrem ely unpleasant
2. Solublity
Soluble Insoluble
in water
3. Hydrolysis Yields propionic aci Produces ethyl am ine

,.
4.Reduction Gives propylam ine Gives ethylm ethylam ine
(Prim ary am ine) (Secondary am ine)
5.Heating at No effect Changes to ethyl cyanide
250°C
CYNIDES AND ISOCYNIDES :
Ex.9 Alkyl halide reacts with AgCN to form

(A) Alcohol (B) Cyanide (D) Both B & C
(C) Isocyanide
(Ans.D)
Sol. In the above reaction major product is Isocyanide and minor product is Cyanide.
Ex.tO Amide on heating with P 205 gives

(A) Alkane nitrile (B) Alkyl halide (C)Amine (D) None (Ans.A) c
Sol. See text. ()
!i]~~~~A~CL~~~~! NITROGEN COMPOUNDS [14] /'

V
ItkoIlorSdtok1r1
c·
c
SOLVED EXAMPLES
Ex.1 An example ofa primary amine is

(A) n-Propylamine (B) Isopropylamine
(C) t-Butyl amine (D) All ofabove (Ans.D)
Sol. All the compounds given above are examples ofprimmy amine.
'.
CH3 ·
CH 3.......
I
CH3 CH2 CH2 - NH2 /CH-NH2 CH -C-NH
CH 3 3 I 2
n-propyl amine
. Iso propyl amine CH3
t- butyl amine
o
f'
II .
, Ex.2 For the elimination of - C- group ofamide following reaction is used

{A) Hofflnann hypobromite reaction (B) Kolbe reaction
(C) Hunsdiecker reaction (D) Liebermann's reaction (Ans.A)
\.."
Sol. For the formation ofRNH2 from RCONH2, NaOH and Br2 are used as reagent. It is called Hofmann
hypobromite reaction. .
('
\ ..
( Ex.3 Which of the following is hydrolysed to give secondary amine

" o
(A) Alkyl cyanide (B) H1-<~: (C) Nitro paratrms (D) Acid amide
(Ans.B)
( Sol.' The compound H-CO - N (CH3h on hydrolysis produces secondary amine.
(
o 0
'. II CH 3 H3C,,",u II
H-C~H + H 20 ) ~,«H+H-C-OH
3 H3 C
dimethyl amine Formic acid
c
c Ex.4 The structure of intermediate acetyl nitrene is
f
~.
(A) CH3 -CO-N: (B) CH 3-CO-N: (C) CH3-C0- N: (D) CH3 - CO= N: .
;!
'Ie
(Ans.C)
Sol. The structure of intermediate acetyl nitrene is CH3-CO--N. It is formed by the following reaction
(
NH2 NH-Br :N
I I I
CH3-C=O~CH3-C=O KOH) CHs-C=O+HBr
KOH
c Ex.S In hypobromite reaction of amide, carbonyl carbon atom is lost as

(A) CO (B) CO 2 (C) C03-2 (D) None of above
c (Ans.C)
[i!~~~A~~ CLI!!.~'~!
1deo1(<w$diofall
L .
\~
c
c'
Sol. In hypobromite reaction ofamide, carbonyl carbon atom is lost as C03-2 ion. The reaction takes
place as follows:
CH3CONH2 + Br2 + 4KOH ~ CHiN1I2 + 2KBr + K2C03 + H 20
K2C03 is an ionic compound and ionizes as K+ and C03-2 ions.
Ex.6 Which one of the following will give primary amine ot! hydrolysis
(A) Nitroparaffins (B) Alkyl cyanide (C) Amide (D) Alkyl isocyanide
(Ans.D)
Sol. Alkyl isocyanide on hydrolysis produces a primary amine. The reaction takes place as follows.
CHa-NC W
~ CHa-NH2 + H-C-OH
methyl isocyanide Hydrolysis
methjl amine
Ex.7 The correct set of the products obtained in the following reactions
redudioR ~ (I) CIi:}MgBr
(1) RCN (2) RCN
(iilH~
(3) RNC hydrolysis (4) RNH2

HN02 )
The answer is
1 2 3 4
(A) 2" Amine Methyl ketone. 10 Amine Alcohol
(8) 1° Amine Methyl ketone 1° Amine Alcohol
(C) 2° Amine Methyl ketone 2° Amine Acid
(D) 2° Amine Methyl ketone 2° Amine Aldehyde (Ans.B)
Sol. The products ofthe reaction 1,2,3 and 4 respectively are: 10 amine, methyl ketone, 10 amine and
alcohol (
\ /
Ex.S The reaction of an alkyl cyanide with sodium and alcohol to fonn an alkyl amine is known by the
name of - .
(A) Mendius reaction (B) Hofmann's reaction
(q Gabriel reaction . (D) Ammonolysis (Ans.A)
Sol. Cyanoallcanes are reduced to primary amines in the presence ofNa and ethanol. It is called
Mendius reacion
R-C == N + 4[H] Nafc2HsoH) RCH2-NH2
alkyl amine
Ex.9 FormaldoXime on reaction with Na/EtpH giveS

(A) 10Amine (B) 2 0 Amine (q 30 Amine (D) All above
(Ans.A)
Sol. Fonnaldoxime on reaction with NalEtOH gives

10 amine. The reaction is representated as follows: c
NatEtOH ) CH NH + H 0 l"
"-.J
H-CH=N-OH 4H 32 2
fonnaldoxime methyl amine c
This method is used for the preparation of primary amines.
c
[16]
1i!~~~A~\CLl!i~~~!
_~Sdlol."
NITROGEN COMPOUNDS .
(~
C
"
Ex.10 Which of the following compounds on reduction gives an amine

(A) Alkyl cyanide (B) Aldoxime (C) Alkyl isocyanide (D) All above
(Ans.D)
Sol. All the given compounds like alkyl cyanide,aldoxime, alkyl isocyanide on reduction gives an amine
4H
CH3-C=N ~ CH3 CH2NH2
SnlHel
acetonitrile ethyl amine
i~ 4H '
CH3-CH=NOH ~ CH3-CH2-NH2 + H2
" H20 ,
("
\
acetaldoxime ethyl amine
,, CH3-NC,
,
~
4H
SnlHCI
CH3-NH-CH3
methyl isocyanide dimethyl amine
'" (2° amine)
" Ex.ll An alkyl amine is prepared by the following reaction

()
RCOOH . + N 3H Conc~ H2 S0 4 ) RNH2 + CO2+2

N .
,...
Name ofthe above reaction is :
"
I
\,
(A) Schmidt reaction (B) Stephan's reaction
(C) Schotton-Baumann reaction (D) Reimer- tiemann reaction (Ans.A)
( Sol. The given reaction is represented as :
RCOOH + N H Cone. H2 S0 4
) RNH2 + CO2 + N2
3
alkanoic acid hydrazoic acid alkylamine
,
' The above reaction is known as Schmidt reaction. This is an important method ofpreparing primary
amines.
I
'",
( ~ Ex.12 N-Ethyl pthalimide on hydrolysis gives
(A) Methyl alcohol (B) Ethyl amine
(
'-~ I (C) Dimethyl amine (D) Diethyl amine (Ans.B)
E"" Sol. N- ethyl pthalimideon hydrolysis forms ethylamine. It is called Gabriel phthalimide reaction. It is
\./
an important method of preparing primaI)' amines.
c ~COOH
,--I
?'. o
©r
C~
CO
~-C2H5 + 2HzO )
0COOH
+
C2 H5 NH2
ethyl amine
(; N-ethyl phthalamide phthalic acid
C
Ex.13 Gabriel phthalimide reaction is used to prepare
() (A) PrimaI)' amine (B) Secondry amine
(C) Tertiary amine (D) All of above (Ans.A)
(
- b
C
( {I}!~~~A~~ CL~~~~~ NITROGEN COMPOUNDS [17]
_,Ior5<I>".",
c
Sol. Gabriel phthalimide reaction is used to prepare primary amine.
o
©X CO,"
CO
~H KO~)
"
©X
0 CO,
CO"
~-K+~
KI
" ©X
0
CO,
CO
~R 2HOH(HCI) )
phthalimide N-aJkyl phthalimide
R - NEl2 +
cr
alkyl amine (1 0)
". "'\
COOH
COOH
<E-(- - - '
phthalic acid
{--- ~
Ex.14 Assign number 1 for least to 4 for most to indicate the relative base strength of the following-
I II ill IV
C 6H SNIi2 p-N02C 6H4NH2 m-N02C 6H 4NH2 p-CH3OC6H 4NH2
I II ill IV ()
(A) 2 3 4
(B) 1 2 3 4
(C) 2 3 4 1
(D) 4 2 3 (Ans.A)
Sol. p-N02C 6H 4NH2 is the least basic due to electron withdrawing group at the p-position (in \
conjugation with NH2 group) p-CH30C6H 4NH2 is the most basic due to interaction oflone pair
ofelectron on oxygen atom of-OCH3 group with the benzene ring. As such lone pair of electron
on -NH2 group is more available.
Ex.IS Which compound is soluble in water

(A) [(CH3hNH2]+ CI (B) [CH3NH3]+ CI
(C)[(CH3)3NH]+ CI- (D) All the above (Ans.D) c"

'./
Sol. Amiiles salt are soluble in water.
Ex.16 Which compound will liberate CO~ from NaHC03 solution

(A) CH3CONH2 (B) CH3NH2 (D) CH3N~3CI-
(C) (CH3)4 WOH-
(Ans.D) r""
\....;
Sol. The compound which will liberate CO2 from NaHC0 3 solution is CH3N+ H 3CI-. The reaction
takes place as follows:
CH3W1I3CI- + NaHC0 3 ----+ CHr NH2-:1- NaCI + H 20 + CO2t
methyl amine methyl amine "
hydrogen chloride c
Ex.17 Which amine will not react with nitrous acid
(A) Metfiyl amine (B) Ethyl amine
(C) Dimethyl amine (D) N, N Dimethyl ethane amine (Ans.D) ""
Sol. Primary and secondary amines react with HN0 2, while tertiary amines do not react with HN0 2. e
Since N, N dimethyl ethane amine "
o
[18]"
[t]!~~A~~C~~~~!
- kkol fo, SchD10rs
NITROGEN COMPOUNDS c~
c
c
c
CH ' '
3)N _ CH2 - CH3 is a tertiary amine, hence it will not react with HN02.
CH '
3
Ex.18 Which gas will be evolved out when [CH3CH2NH2 +(CH3)2CHNH2] is treated with sodium
nitrite and HCI
(A) Chlorine (B) Ammonia (C) Nitrogen (D) N02 (Ans.C)
Sol. Primary amine and HN02 produces nitrogen gas.
RNH2 + HN02 ----7 ROH + N2 + H 20
Ex.19 Which ofthe following compound cannot be produced if I-propane amine is treated with NaN02 and
HCI
(A) Propane -1-01 (B) Propane-2-01
( (C) 2-Chloropropane (D) 2-Propaneamine (Ans.D)
Sol. In the reaction,
() CHr CH2- ffiCH2 and CHr ffi CH--CH3,
carbonium ions are formed.
(
As such I-propanol, 2-propanol, 2-chloro-propane, I-chloropropane and propene are the products
r while 2-propaneamine is not obtained.
\.
r
I, 'Ex.20 In the following sequence of reactions the product B, will be
NaN02
C H sMgBr '-'1I'n2) A ~ B
2 HCI
, (A)C 2H sOH (B) C2H SN0 2 (C) C2H 2 (D) All of the above
\..
(Ans.A)
Sol. In the given sequence of reactions, the product B, will be ethanol. The reaction takes place as
CINH2 HONO C
,\.
C2H SMgB r MgBrCl
) C2HSNH2 NaNOzIHCI'
) 2HsOH + N2 + H 20
'B' .
Ex.21 Which set of the follOWing compounds on reaction with an alkyl amine gives schiff's base:
.(A) HCHO, C6H sCHO, CH3CHO (B) HCHO, NH20H, NH2 - NH2
( • (C) CH3CHO, NH20H, NH2-NH2 ' (D) CH3COCH3, C2H sOH (Ans.A)
c Sol. The aldehydes e.g. HCHO, C6H sCHO and CH3CHO on reaction with alkylamine gives schiff's
t' base
" C6H sCHO +, H 2NCH3 ) C 6H sCH = N - CH3 + H 20
benzaldehyde methylamine schiff's base
Ex.22 Which ofthe following does not give a sulphur compound with a 10 amine
c (A) Hinsberg reaction (B) Mustard oil reaction
(C) Schotton - Baumann reaction (0) Con. H 2S04 (Ans.q
0
Sol. In Schotton - Baumann reaction a sulphur compound is not produced with a 1 amine
- C
R - NH2 + CI - CO - C6HS NaOH) R- NHCOC6H s + HCI
() alkyl amine benzoyl chloride . N-alkyl benzamide
[19]
!Il!~~~~~ CL~~~~~
ldeol'orSchokm
NITROGEN COMPOUNDS
{,
"
(
Ex.23 Ethylamine on oxidation with acidified KMn04 gives
(A) Acetaldehyde (B) Ethylamine oxide
(C) Ethanol (D) Acetamide (Ans.A)
Sol. Oxidation ofethylamine gives acetaldehyde.
Ex.24 Mustard oil reaction is given by

(A) Primary amine (B) Urea (C) Secondary amine (D) Acid amide
(Ans.A)
Sol. Mustard oil reaction is given by primary limine. It is known as Hoffinann's mustard oil reaction
R NH2 + S = C = S + HgCI 2 ·· > R - N ;= C = S + HgS-/' + 2HCI
alkyl isothiocyanate
This compound alkyl isothiocyanate has a smell resembling that of mustard oil.
Ex.25 Which of the following compounds has a smell of mustard oil

(A) Alkyl cyanate (B) Alkyl thiocyanate
(C) Alkyl isothiocyanate (D) alkyl isocyanate (Ans.C)
Sol. A primary amine condenses with CS2 in the presence of HgCl2 to forin an alkyl isothiocyanate. ( :
This compound has a smell resembling that of mustard oil. It is called as Hofmann's mustard oil.
reaction
R - NH2 + S = C = S + HgCl 2 ) R - N = C = S + HgS-/' + 2HCI
alkyl amine alkyl isothiocyanate
Ex.26 Which of the following amine does not react with Hinsberg reagent
(A) Neopentyl amine (B) Isopropyl amine
(C) Triethyl amine (D) Ethyl methyl amine (Ans.C)
Sol. Triethyl amine is tertiary amine. It does not react with Hinsberg reagent.
Ex.27 In which of the following sequence of reaction the end product does not exhibit tautomerism
(A) CH3CH2NH2 NOel) A9N0 2 ) (B) (CH3hCHNH2· NOCI) A9 N0 2 )
c
(C) (CH3)3CNH2 NOCI) Ag N0 2 ) (D) CH3CH(NH2)C2H S . NOCI) Ag N0 2 ) .
(Ans.C)
Sol In the 3rd reaction sequence the end product is a 3° nitro compound.
(CH3)3CN02 It does not have a-hydrogen as such tautomerism is not possible.
Ex.28 The acid used for the determination of molecular weights ofarnines is
(A) H 2PtCI 6 (B) Picric acid (C) HAuCl4 (D) H 2S04 (ADs.A)
Sol. The acid used is H 2PtCI6. It is a solution of platinic chloride, Pt Cl4 in con.HCI
.
2R-NH2 + H2 [PtCI6]
. +
) [R NH3h [ptCl6 r 2 c'
alkylamine platinichloride
Chloroplatinates on ignition leave a residue ofmetallic Pt. This reaction is employed in determining
molecular weight of amines.
o
~'t~~A~\CL~~~~!
fd<oItt..Sc/tokJ"
NITROGEN COMPOUNDS . [20) c
c
Ex.29 Methyl amine on reaction with chlorine in the presence ofNaOH gives
(A) Chlorofonn
(B) Methyl chloride
(C) N-Methyl chloramine
(D) Chloramine (Ans.C)
\.
Sol. Methyl amine reacts with Cl2 in the presence ofNaOH undergoes a substitution of a H-atom of
amino group by a CI group and N-methyl chloramine is fonned.
CH3NH2 + Cl 2 NaOH) CHrNHCI

NaCl,l-I:!O
N-methyl chloramine
(:
(
('
f
\
""
"""
(
"
c
c
c
(
C
C
(
C
C
( 1i~~~~A~~CL~~~~~
Itko4for ScboIors
(
,*,--,
t
"-..
c
EXERCISE-I
PREPARATION & GENERAL POINT

Q.l AmideonheatingwithP20sgives:
(A) Alkane nitrile (B) Alkyl halide (C)Amin~ (D) None
Q.2
.
R'-N < RlO
R
is a-
(A) Mixed 3° amine (B) Unsymmetrical amine
(C) Both 1st and 2nd (0) Quartenaty salt
Q.3 The alkanenitriles are isomeric with- .

(A) Primatyalkanamines (B) Secondary alkanamines
(C)AIkyI isp;:.anl~ (0) Nitroalkanes
,/? 4
Q.4..l' Mendius reaction involves the reduction of:

n
'" (A) Cyanoalkanes (B) Alkyl isocyanides (C)Oximes (0) Nitroalkanes
Q.5 CH3CONH2 PCIS)AHZO)B

(partial) .
.J, reduction
The functional groups ofB and C respectively are :
(A) -c -NH2, -NH2 (B) -c -NH2' -COOH

II. II .
a 0
(C) -CN, -NH- (D) -c-OH, -N-
" ...
\,/
Il . I
o
tAItt~-W
co"",
Q.6
@C /NH
CO
KOH ) A ~) B HOH)
w
C + D , C and D in the sequence are
C)
(A) Benzoic acid + aniline (B) Phthalic acid + ethylamine
.."
(C)Phthalic acid + aniline (0) Benzoic acid + ethylamine . ~ r eo ~ C
.. ---~
,'/ ~
... /
_c.::::,v
Which ofthe following is obtained by reducing methyl cyanide with Na + <;HsOH ~ d,""
~ (A) Methyl alcohol (B) Acetic acid (C) Ethyl amine (D) Methane J'-"J"
Q.8 Which ofthe following is optically active amine- ~ - cJJ,.:-.I'blt c
(A) CH3NH2 . (B) CH3NHCH3
(C) CH3CH2CH2N-C2H5 (0) Secondary butylamine
c
I
CH 3 c
Q.9 Which ofthe following would undergo Hoffinann bromide reaction to form primaty amine c
(A) RCONHCH3 (B) RCOONH4 (C) RCONH2 (D) RCONHOH ()
li'~~~A~~C~~~~!
IIkoIfcrSchokl,'
NITROGEN COMPOUNDS 122) c
c
c
Q.I0 Ethyl iodide on reaction with potassium nitrite gives
(A) Ethyl nitrite (B) Nitro ethane (C) Amine (D) Acid
Q.ll A reaction used in descending a homologous series would be

(A) RCON"H2 + Br2 + KOH (B) RCH2CI + KCN
(C) RNH2 + CHCl3 + KOH (D) None of the above
Q.12 Reaction for the preparation of 10 amine is

(A) Hofinann carbylamine reaction (B) Hoffinann mustard oil reaction
(C) Hofinann bromamide reaction (D) Lieberman nitroso reaction
Q.13 On reduction of Schiff's base we get

(A) Primary amine \j!DMcondary amine (C) Anils (D) Anilide
Q.14 In Hofmann degradation of amide the correct order of reagent is

(A) Br2, KOH, H20 ~OH, Br2, H20
(C) H20, KOH, Br2 (D) None of the these
( Q.15 Ethylamine can be prepared by the all except

(A) Curtius reaction (B) Hoffinann reaction
(
\ (C)"Mendius reaction ~duction of formaldoxime
Q.16 Alkyl halide reacts with AgCN to form

(A) Alcohol (B) Cyanide (C) Isocyanide (D) Both B & C
\
( Q.17 Grignard reagent reacts with cyanogen chloride to form

(A) Alkane nitrile (B) Alkyl halide (C) Amine (D) None
«)~/Nitrobenzene has a smell similar to that of:

(
(A) Benzaldehyde (B) Formaldehyde (C)Acetaldehyde (D) Salisylaldehyde
,
\.
oY1
, "fIiI:::>L
'"- ~-~~
Q.19 An example of nucleophilic aromatic substitution reaction is :
(A) C6H5N9/H2S04
(C) C6HJCH3ClIAICI3
(B) C6H50HIHN03
(D) C6H5NO/KOH
G
r
"-'
Q.20 In the reaction sequence identify the functional group present in A, B, C
(
A Sn/HCI )B HN02 >C C2HsO H ) Cl-T __
oOc 6~"6
(
(A) N02, NH2, N=N (B) N02• NH2• OH", (C) -OH -NH2• -N02 (D) -NH2' -N02, -N=N
" I
( . .
11- .. ~cl.-A'YA-- il"M.. A c:. :;:::.:,1"1/
Fast heating of urea YIelds : f4 ~
c vY (A) Cyanuric acid
---;7"/VI"f
(B) Carbamic acid (C) Parabanic acid
-- ,
(D) Barbituric acid
c Q:J" Ethylamine on oxidation with 'acidified KMn04 gives:

- C' . (A) Acetaldehyde (B) Ethylamine oxide "(C) Ethanol (D) Acetamide
"
C
·lIJ~~~~A~~ CL~~~~!
_foI:Sd",Io~
Ii'L "
c
(
Q.23 CH3CH2CONH2 N:~H) A '
Aqueous solution ofA:
(A) Turns blue litmus to red (B) TUrns red litmus to blue
(C) Does noteffect'the litmus' (D) Decolourisethe litmus
PHYSICAL PROPERTIES
Q.24 Which statement is not correct

(A) Methyl amine is more basic than NH3
(B) Amines from hydrogen bonds
(C) Ethyl amine has higher boiling points than propane
(D) Dimethyl amine is less basic than methyl amine
Q.25 The basic characterofamines can be explained

(A) In terms ofLewis and Arrhenius concept
(B) In terms ofLowry and Bronstcd concept ,r,
'- )
(C) In terms ofLewis and Lowry Bronsted concept
(D) Only by Lewis concept
Q.26 Amines are basic in nature because

(A) They produce OH- ions when treated with water
(B) They have replaceable H atoms on N atoms
(C) They have lone pair ofelectron on N atom
(D) None ofthese
Q.2 7 Suitable explanation for the order ofbasic character (CH3)3N < (CH3)2NH is
(A) Sterlc hindrance by bulky methyl group
(B) Higher volatility of3°amine
(C) Decreased capacity for H- bond formation with H20
(D) Decreased electron- density at N atom
Q.28 Which of the following diazonium salt is relatively stable of 0-5°C

_ ~~!2!3-N=N} @CC_ (B) CH3-C(CH3}-N=N}_@CI
~6H5-N=N} @CI (D) (CH3)3C-N=N} @el
. Q.29 Lowest boiling point will be of the compound

(A) Ethylamine (B) Etbylmethylamine
(C) I-Propaneamine (D) N,N-Dimethylmethanamine
Q.30 Which-of the following compound gives the smell of mustard oil
(A) Alkyl isocyanate (B) Alkyl isothiocyanate
(C) Alkyl isocyanide (D) Alkyl isonitrile
(\.3/ The odour ofalkyl cyanides is similar to :
11 (A) Bitter almonds (B) Acid (C) Fruity smell (D) None ()
Q.32 Minimum boiiing point would be of:

(A)Ethylmethylamine (B)Ethylamine (C) n-Propyl amine (D)Trimethylamine
o
i!~~~~~CM~~~!
_forSt;/""""
NITROGEN COMPOUNDS [24] c
c
o
'Q.33 Urea is insoluble in ether, because:
(A) Ure a shows polar character (B) Urea shows non-polar character
(C) Ure a is a neutral compound (D) None ofthe above
Q.34 Which one of the following compound is expected to be least soluble:

(A) CH3NH2 (B) (CH3)2NH (C)C6HSNH;! (D) (CH3)3N
Q.35 The minimum value of -logKb' will be for the compound:

(A) o-Nitroaniline (B) p-Nitroa,niline (C) p-Chloroaniline (D) p-Methoxyaniline
CHEMICAL PROPERTIES
Q.36 Match list I with list n and then select the correct answer from the codes given below the lists-
List I List II
0
(1) Isopropylamine (a) 1 amine with -NH2 ,on tertiary carbon
(2) Isopropyl alcohol . (b) Functional group isomers ofethylamethylamine,
(3) Trimethylamine (c) A seCondary alcohol
(4) Tertiary butylamine (d) A tertiary amine
\
Codes:
(A) lb 2d 3c 4a ~ 2c 3d 4a (C) Ib 2a 3d 4c (D) Ib 2c 3a 4d
(
Q.37 The number of 11: bonds present in CN-CH=CH-CN
(A) 5 (B) 4 (C) 3 (0) 2
Q.38 Hydrolysis ofalkyl isocyanide yields

( (A) Primary amine (B) Tert amine (C) Alcohol (0) Aldehyde
r
< Q.39 Which ofthe following does not form a sulphur compound with primary amine
f (A) Hinsberg's reagent (B) S\llphuric acid
~otten-Boumann reaction
\.
(D) Mustard oil reaction
Q.40 Butylamine reacts with sodium nitrite and aqueous solution ofa strong acid to form
C .(A) Two position isomers ofC4H8 having unbranched carbon chain
(B) I-butanol
l (C) 2-butanol
«' . (D) All compounds given in A, B and C
" QA) /Which ofthe following can be detected by carbylami~e reaction

(
L ( / (A) Urea (B) CH3CONH2 (C) C2HSNH2 (D) All the above
{
Q.42 Hinsberg's reagent is
(A) Oiethyl oxalate (B) Benzyl chloride
(C) Benzene sulphonyl chloride (D) None of these
.(
" Q.43 A mixture of 10 ,2° and 3° amine is formed in the-reaction

(' (A) 1°Amide + caustic potash + bromine (B) Methyl halide and ammonia
(C) Cyclic imide + H30+ (D) Alkyl isocyanide + H2
C
(
~!~~~A~~ CJA~~~!
_forScbolm1
l
Q.44 The presence of primary amines can be confIrmed by:
(A) Reaction withHN02 (B) Reaction with CHCl3 and ale. KOH
(C) Reaction with Grignard reagent (D) Reaction with acetyl chloride
Q.45 How many isomeric amines can have the formula C4H 11N
(A) Five (B) Six (C) Seven (D) Eight
-" .. ~.'
Q.46 Ethylamine can be prepared by the all except
. (A) Curtius reaction (B) Hofmann reaction
(C) Mendius reaction (D) Reduction offormaldoxime
Q.47 Which of the following method is generally not employed for the separation of primary, scondary
and tertiary amines ?
(A) fractional distillation (B) Hinsberg's method
(C) Hofmann's method (D) Filteration
Q.48 Which 'one of the following behaves both as nucleophile and as an electrophile ?
(A) CH3C=N (B) CHrOH (C) H2C=CH-CH3 (D) CHr NH3
Q.4 9 A primary nitroalkane is treated with nitrous acid, which ofthe following will be the main product:
(A) pseudonitrol (B) nitrolic acid (C) a primary amine (D) a primary alcohol
Q.50 C2HSNH2 cannot be prepared by the reduction of

(A) C2HsN0 2 (B) CH3CH=NOH (C) C2HSNC (D) CH3CN
, '
Q.51 Tilden's reagent is "

(A) C6H sS02CI (B) NOCI (C) CINH2 (D) (C 2H Sh Zn
Q.S2 CH3NH2 + CHC13 + 3KOH'-+ X + Y + 3H20; compounds X and Y are: r'

" J
(A) CH3CN + 3KCI (B) CH3NC + 3KCI

(C) CH3CONH2 + 3KCI (D) CH3NC + K2C03
Q.53 Acetonitrile has the structure:

(A) C2HSNC (B) C2HsCN (C)CH3NC (D) CH3CN
Q.54 The compound obtained by the reaction between primary amine and aldehyde is '.
(A) An amide (B) Imine (C) Nitrite (D) Nitro
E
CLASSES
L tM IT£: l)
NITROGEN COMPOUNDS [26] c
JckoI(f)t5('~1'$
EXERCISE-IT
Q.l The reaction

CH3Br + NH3(excess) ~ CH3NH2+HBr
is an example of a
" - (A) bimolecular electrophilic substitution reaction
(B) unimoleeular nucleophilic substitution reaction
(C) bimolecular nucleophilic substitUion reaction
(0) bimolecular free radical substitution reaction
Q.2 - A secondary amine is a compound which possesses

(A) two-NH2 groups
(B) one-NH2 group attached to a secondary carpon
(C) one-NH-group bonded to two'alkyl or aryl groups
(0) one-NH2 group attached to the second carbon ofthe main carbon chain
Q.3 The IUPAC name ofthe compound

( I
N
(._ ~~is-
( (A) N,3-dimethyl-N-propyl-3-propanamine (B) N-methyl-N-propyl-2-butanamine
" (C) s-butylmethyl-n-propylamiue (0) N, I-dimethyl-N-propyl-propanamine
Q.4 How many molecules ofmethyl bromide should react with ethylamine successively to convert the latter
into a quaternary ammonium salt?
(A) One (B) Two (C)Three (D) Four
(
" Q.5 Which ofthe following compounds on hydrolysis yields a carboxylic acid and a secondary amine?
(
' .. (A) CH3CH2NC (B) CH3CONHCH3 (C) PhNHCOCH3 (D) PhCONPh
(
. I
\. CH 3
(. Q.6 The end product (B) formed in the reaction
CHFH2Br AgCN) A I. NaGH, prolonged heat) B is
Hp'
{ (A) CH3CH2NHCH3 (B) CHFH2CH2NH2 (C) CH3CH2NH2 (0) CH3C~NHCOH
'-.
{ Q.7 Which ofthe following compounds possesses a chiral nitrogen atom?

". (A) CHFH 2 C HCH 3 (B) CHFH2NHCH2CH3
(
\..
I
NH2 .
(C) CH 3CH 2CH 2 N CH 2CH 3 (0) CHFH 2 NCH 2CH 3

. I I
( NH 2 CH3
C Q.8 An amine (X) on bemg heated with an excess ofmethyl bromide produces diethyldimethylammonium
.bromide. The amine (X) is-
C (A) C2HSNH2 , (B~)2NH (C) C2HsNHCH3 (D) C2HsN(CH3h
( li1~t~~,,~~CLIA~~~! .NITROGEN COMPOUNDS [27]

_fo<SdIo"'''
,(
\.
t
Q.9 Which one ofthe following.compounds will produce a water-insoluble yellow oily liquid ofnitrosamine
on reaction with NaN02 and dilute HCl at O°C ?
(A) Ethylamine (B) Methylamine (C) Diethylamine (0) Triethylamine
Q.I0 Whichofthe following compounds will liberate CO2from NaHC03 ?

(A) CH3CO~ (B) CH3CH2NH2 '(C) CH3NH/Cl (0) (CH3)4~-oH-
Q.II The reactionofRCONH2 with a mixture ofBr2 and aqueous KOH gives R.Nll2 as the main product
. The intermediate(s) involved in this reaction is(are}
(A) RCONHBr (B) RCON BrK+ (C) R-N=C=O (0) All ofthese
Q.12 The end product (B) formed in the reaction

I. Brl CCI, ) A I. LiAIH, ) B
CH2=CH2 2. KCN(excess) 2.H 30'
(A) CH2=CHCH2NH2 (B) H2N(CH2)4NH2

(C) CH3NH(CH2)2NHCH3 (D) NC(CH2)2CN
Q.13 In which of the following compounds are intermolecular hydrogen bonds not formed among its
molecules ?
.(A) (C2HshNH (B)C2HsOH (C) C2HsCOOH (0) (C2Hs)3N ,.
Q.14 Among the following compounds which onewill produce a Schiff base on reaction with-cyclohexanone?
(A)Q (B)ONHCH
3
{C)ONH
2
(0) ON( CH
:J2 '
H '"
\ .'
Q.15 Which ofthe following reactions does not yield an amine?
(A) RX+NH3 ~ (B) RCH=NOH ~

. <;H,OH
(C) RCN + .H20 (D)RCO~

L LiAIH,
2. H 20
c
Q.16 The product (A) and (B) ofthe reaction
CH3CH2NH2 + CH3MgBr ~ A + B
are-'
(A) CH3CH2CH3 and NH2MgBr (B) CH3CH2NHCH3 and MgBr2
(C) CH3CH2N(CH3h and MgBr2 (0) CH3CH2NHMgBr and CH4
Q.17 Which nitrogen is protonated readily in guanidine?

2 c
HN=C<~H2
NH2
(A) 1 (B)2 (C) 3 (0) All ofthese o
[28]
c
IIJ~~~~~~CM~!~'
• 1dtG1""S<boI.~
NITROGEN COMPOUNDS
t '.
\.../
If ~.
V
Q.18 Which ofthe following statements is not correct regardingethyJamine and aniline ?
(A) Each has a -~ group
(B) Both dissolve in HCI
(C) Each reacts with a mixture ofCHCl3 and KOH to fonn a bad smelling compound
(D) Each reacts with HN02 to give a hydroxy compound
Q.19 Which ofthe following is most basic?
(A) 6 NH2
(B) 0 .(C)Q
NH2
(D)
Jfl
"1.(
R
'Q.20 A compound (X) having the molecular fonnula C3H9N reacts with benzenesulphonyl chloride to fonn
a solid that is insoluble in alkalis. The compound (X) is ;
(
" (A) CH3CH2CH2NH2 (B) (~H3)2CHNH2
(C) CH3CH2NHCH3 (D) (CH3)~N
, .@ Which ofthe following may be prepared by Gabriel phthaIimide ~ynthesis ?

~phatic amines
(
(B) Aromatic amines (C) Aliphatic amides (D) Aromatic amides
@ When an organic compound was treated with sodium nitrite and HC) in the ice-cold condition. nitrogen
gas was evolved. The compound is :
r
.\
(A) a nitro compound (B) a primwy amine (C) a secondwy amine (D) a tertiwy amine
r
Q.23 Primwy amines on being heated with CS2 in the presence ofHgCl2 form alkyl/wyl isothiocyaruues. The
/
(~ reaction is known as
(A) Hofinann hypobromite reaction (B) Hofinann elimination reaction
/
, (C) Hofinann-Martius reaction (D) Hofinann mustard oil reaction
(
\ ~-aminO acids on heating with Ba(OH)z gives;
, (A) Basalt ofacid (B)Amine' (C) a-hydroxy acids (D) None ofthese
(
Q.25 . R-CI + NH3 (excess) -7 (X) (major product), the major product (X) is a ;
(A) 1° amine (B) 2° amine (C)3°amine (D)4°ammoniumsaIt
Q.26 In carbylamine reaction:
(A) the nucleophiIe i~ a ~ and electrophile is : CCl2
{
"-.
( (B) the nucleophile is primary amine and electrophile is Cell

(C) the nucleophile is CCI3- and the electrophile is primary amine
(
(D) the attacking reagent is electrophile
c Q.27 One mole ofan amine (A) consumes two moles ofmethyl bromide to give a quetemwy ammonium salt.
The amine (A) is :
(
(A) (CH3hCCH2NH2 (B) (CH3)2NCH2CH3
c (C) 0 (piperidine) (D)O(pyridine)
c ~
( NITROGEN COMPOUNDS [29]
c
I
~
(
Q.28 Which one ofthe following will not react with the Grignard reagent (C2HsMgBr) ?
C2 HS 0
H
(~) C2Hs-NH2 (B) C2 5)N-H (C) C2Hsi (0) CH 3-8-NH2
C2 HS
C2 HS
Q.29 An optically active compound (A) decolourises Br2/CCl4 and releases N2 with nitrous acid. The
compound (A) is :
(A) 6 (B)6 '.

NH2 NHCH3
(C)6
NH2
(0)
NHC2HS
6
I I
Q.30 How many products will be obtained when propane is subjected to vapour phase nitration?
W2 003 ~4 ~5 / .
Q.31 (A) H21Pt) 10 Amine (B) H,IPt) 2 0 Amine:

(A) and (B) respectively are:
(A) RNC, RNC (B) RCN, RCN (C) RCN, RNC (0) RNC, RCN
'Q.32 The products (A) and (B) formed in the given reaction is
RCOCI NaN~) (A) CgH sOHl4) (B) "
(A) RCON and RCN (B) RCN and RNC
(C) RCON 3 and RCN (0) RCON3 and RNCO
Q.3 3 CH3CH2NH2 contains a basic NH2 group, but CH3CONH2 does not, because :
(A) Acetamide is amphoteric in character
(B) In CHFH2NH2 the electron pair on N-atom is delocalised by resonance
(C) In CH3CH2NH2 there is no resonance, while in acetamide the lone pair ofelectrons on N-atom is
delocalised and therefore less available for protonation r'

\/
(0) None ofthese

'-.J
Statement Based question

Each ofthe questions given below consist of Statement - I and Statement - n. Use the following
Key'to choose the appropriate answer. ' C
(A) Ifboth Statement-I and Statement- II are true, and Statement - IT is the correct explanation
ofStatement-I.
(B) Ifboth Statement - I and Statement - II are true but Statement - II is noUhe ' correct explanation
of Statement -I.
(C) If Statement - I is true but Statement - II is false.
(0) If Statement - I is false but Statement - II is true.
Q.34 Statement-I In stronglyacidic solutions, aniline becomes more reactive, towards electrophilic
reagent o
Statement-II The amino group being completely protonated in strongly acidic solution, the
lone pair ofelectrons on the nitrogen is no longer available for resonance.. o
o
[30]
c
[j~~~A~~ CL~~~~! NITROGEN COMPOUNDS
/de(ll,""SdtoIa" C
\c.J
{ '.
v
Q.35. Statement-I . Ammonolysis ofalkyl halides is not a suitable method for the preparation of
pure primaty amines.
Statement-II Ammonolysis ofalkyl halides yields mainly secondaty amines.
Q.36 Statement-! The main product ofreaction ofalcoholic silver nitrite and ethyl bromide is
nitroethane.
Statement-II Silver nitrite is predominantly cOvalent compound.
Q.37 Statement-I Carbylamine reaction involves chemical reaction between 10 amine and
. chloroform in basic medium.
Statement-II : In carbylamine reaction, -NH2 group changes into -NC group.
(
\
"
{
"
I
\
'"
(.
(
,,-.
(
"
(
{ \
"
C
C
(~!~~~~~CIY~~!~!
. _""5d>o/a"
NITROGEN COMPOUNDS [31J
{
"
EXERCISE-III
SECTION-A
Q.l Reaction:
Primary amine + CHCI3+ KOH ) product, here product will be- [AIEEE-2002]
(A) Cyanide (B) Isocyanide (C)Amine (D) Alcohol
® Thecompound formed in the positive test for nitrogen withthe Lassaignesolution ofan organiccompound
is - [AIEEE-2004]
(A) Fe4 [Fe(CN)6h (B) Na3[Fe(CN)6] (C) Fe(CN)3 (D) Na4 [Fe(CN)sNOS]
Q.3 Which one ofthe foUowingmethods is neither meant for the synthesis nor for separation ofamines ?
{AIEEE-200S]
(A) Hofinannl11ethod (B) Hinsbergmethod (C) Curtius reaction (D) Wurtz reaction
6A) I' Reaction ofcyclohexanone with dimethylamine in the presence ofcatalytic amount ofan acid fonns a'
'0!)1 compound ifwater during the reaction is continuously removed. The compound formed is generally
known as - [AIEEE-200S]
(A) an enamine (B) a Schiff's base (C) an amine (D)an imine
Q.5 In the chemical reaction, CH3 ClIzNH2 + CHCI3 + 3KOH ~ (A) + (B) + 3~O, the compoUnds (A)
and (B) are respectively - [AIEEE-2007J
(A) C2HsCN and 3KCI (B) CH3CH2CONH2 and 3KCI

(C) C2HSNC and K2C0 3 (D) C2HSNC and 3KCI .
\.
. NH2 f'
(
. 1 .
Q.6 In the chemlca reactIOns: ~ lSJ'. NaN0 2
..~. --~,,)
A HBF
~ B, the compounds 'A' and 'B'
respectively are [AIEEE-2010J

(A) benzene diazonium chloride and fluorobenzene
(B) nitrobenzene and chIoro benzene
(C) nitrobenzene and fluorobenzene
(0) phenol and benzene
SECTION-B
Q.
VV
V The compound which on reaction with aqueo'Us nitrous acid at low temprature produces an oily ni-
trosoamineis . . [lIT 1981]
(A) Methylamine (B) Ethylamine (C)Triethylamine (D) Diethylamine
c
o
. Q.8 The compound is most reactive towards electrophillic substitution is : [IIT-84] C
(A) Toluene (B) Benzene' (C) Nitrobenzene (D) Benzoic acid
o
c
lIl~~~~A~C~~!~! NITROGEN COMPOUNDS [32] c
Idto'fo,$dI.okIrs
c
Q.9 Examine the following two structure for the anilinum ion and choose the correct statement from the one
gives below:· [IIT-93}
+
o---·-6I II
(A) (II) is not an acceptable canonical structure because carbonium ions are less stable than amonium
ion
(B) (II) is not an accepted canonical structure because it is non aromatic
(C) (II). is not an acceptable canonical structure because the nitrogen has 10 valence electron
(D) (II) is an acceptable canonical structure
Q.IO Increasing order ofbasic character is : [lIT Scr. 1994)
c\ (A) NH3 <C6HSNH2 < {C2HshNH <C 2HSNH2 < {C2HS)3N

(B) C6HSNH2 < NH3 < (C2Hs)3N <: (C2HS)2NH < C2HSNH2
,(
(C) C6HSNH2 < (C2HS)3N < NH3 < C2HSNH2 < (C2HS)2NH
(D) None ofthese
Q.ll Among the following the strongest base is {lIT 2000}

(A) C6HSNH2 (B) p. N0 2C6H4NH2 (C) m-N02:...c6H4NH2 (D) C6HsCH2NH2
Q.12 CH3N~ +CHCI3 +KOH---')-Nitrogencontainingcompound + KCI + ~O.

I
\
Nitrogencontaining compound is [JEE20061
- + +
(
{A)CH3-C=N (B) CH3-NH-CH3 (C) CH 3 - N == C (D)CH 3 N is C
c .
c 'Df InthereactiOnH,c-O-< .
(l) NaOHIBr1
(2)0-<o ) T the structureof theProductTis
NH2
c CI
{JEE20101
(,
"'-- \\ 'o-c
-Q-t,
o
(8)< )~ DCH,
II 0
(A) H3C 'I - '\ II

(
/I~
(
(
b 'f_~
°
f) 0
(
(C) H,C-{ }~-{ ) (D)
H3C
0 C\
NH-C
II
c
c
II
o
b
f ~
CjJ!t~~A~~CM~~~
. kkDlr...>dooIo"
NITROGEN COMPOUNDS (33)
(
ANSWER KEY
EXERCISE-I
QJ A Q.2 C Q.3 C Q.4 A Q.5 A Q.6 B Q.7 C
Q.8 C Q.9 C Q.10 A Q.ll A Q.12 C Q.13 B Q.l4 A
Q.15 A· Q.16 D Q.17 A Q.18 A Q.19 D Q.20 A Q.21 A
Q.22 A Q.23 B Q.24 D Q.25 C Q.26 C Q.27. A Q.28 A
Q.29 A Q.30 B Q.31 A Q.32. D Q.33 D Q.34 C Q.35 D
Q.36 D Q.37 A Q.38 A Q.39 D Q.40 D Q.41 C Q.42 C
Q.43· B Q.44 B Q.45 D Q.46 D Q.47 D Q.48 A Q.49 B
Q.50 C Q.51 B Q.52 B Q.53 D Q.54 B />-,
EXERCISE-'-ll
-~~.---<--.--
Q.l C Q.2 C Q.3 B Q.4 C Q.5 D Q.6 C Q.7 C

Q.8 D Q.9 C Q.I0 C Q.11 D Q.12 B Q.13 D Q.14 C
Q.l5 C Q.16· D Q.l7 A Q.18 C Q.19 C. Q.20 C Q.21 C
Q.22 D Q.23 D Q.24 B Q.25 A Q.26 A Q.27 C Q.28 C \.
' .
Q.29 A. Q.30 C Q.31 C Q.32 D ·Q.33 C Q.34 D Q.35 C
Q.36 A Q.37 A
EXERCISE-ill
Q.l B Q.2 A Q.3 D Q.4 A Q.5 D Q.6 A Q.7 D
Q.8 A Q.9 C Q.I0 C Q.11· D Q.12 D Q.13 C
{ .
\.
o
[341'
c
li!~~~A~CL~~!~!
tko' (or Scholor:f
NITROGEN COMPOUNDS
c
CONTENTS
KEY CONCEPT.......••..............••.•..........•..•........................ Page 2 - 27
EXERCISE-I..................~ .................................................. Page 28-33
EXERCISE-II ................................................................... Page 34-36
EXERCISE-III.;................................................................ Page 37-40
/
ANSWER KEy.................................................................... Page 41
"
C:
(
/
~
\.
(:.
JEE MAIN-2014
c CARBOXYLIC ACID &
( ITS DERIVATIVES
c
(.
6'
'-.
t
"
CARBOXYLIC ACID & IT'S DERIVATIVES
1. GENERAL INTRODUCTION
The organic compounds containing carboxyl (LH) group are known as carboxylic acids and the
tenn 'Carboxylic' was frrstly proposed by scientist 'Bayer'.
Resonance hybrid structure ofcarboxylic acid group is
~,o:
R-C"" .
··9
'0:
R-e(iI) '"
;0:..w 1
\.:9- H [
R·C·
\,1iE!)
9-H g.H
Resonance hWrid
due to resonance, the bond length value ofboth the bonds [C-O & C--O]are equal, which is 1.28 A.
1.1 Classification:
..
On the basis ofthe group to which-COOH group is attached.
(a) Aliphatic carboxylic acid = R-~-O:f-J; (R = H atom or alkyl group). r

\.
(b) Aromatic carboxylic acid =Ar-K-OH (Ar = Aryl group)
1.2 On the basic ofnumber of-COOH groups in their molecule.
No.of-COOHgroup
(a) Mono carboxylic acids 1

(b) Dicarboxylic acids 2
(c) Tricarboxylic acids 3
General fonnulais Cn~n02 orCn~n+1 COOH
Saturated and unsaturated mono carboxylic acids are also called fatty acids, because highel acids like
palmitic acid, steric acid, oleic acid, etc. were obtained by hydrolysis offats and oils.
Isomerism - Chain, positional, functional group and optical.
Hybridisation stateofC in tbe carboxyl group in sp2
2. METHOD OF PREPARATION
2.1 . By the oxidation ofalcohols, aldehydes and ketones:
(a) 1° Alcohol ~ corresponding carboxylic acids.
R...:cu
~ -'2
-OH+[O] KMn04°r"
K2Cf2Or
)R-CHO~R-~-OH .
(b) Aldehyde~ corresponding acids
0
R-CH=O + [0] Acidic K2Cr20 z ) R-~-OH C
.(C) Ketones ~ mixture ofacids oflesser no. ofC atoms than the ketone.
0
R-~-C~-R' + [0] Acidic ~2C!pr R-~-OH + R'-COOH
) C
C
lI't~~~~ CARBOXYLIC ACID & IT'S DERIVATIVES (2)
go
'L/
C
Ex. CH3-~-CH3 + 3[0] Acidic ~2C!20z CHr~-OH + HCOOH
HCOOH + [0] ) CO2 + ~O .
2.2 By the hydrolysis ofcyanides (nitriles) :
~. Cyanides on complete hydrolysis in the presence ofdilute HCI form carboxylic acids.
. . 0 oII
.
R - C .. N" + HOH ~ (?HJ
R-C=NH --+- R -C",,: N~ 1 HOH
-NH ) R -C- OH + NH3
3
Unstable
2.3' From hydrolysis ofacid derivatives:
R-~-Z + H-OH ) R-~-OH + HZ

,r (a) From acyl halides:
\
(: . + HOHR-~-CI ) R-~-OH + HCI

( ..
(b) From acid anhydride:
" 'if
('
R-c..., °H
/0 + H-OH---+2R-C-OH
R-C"
'. 8
Note: Formic acid cannot be prepared by these two reactions (a & b) because it's corresponding formyl
f
chloride and fonnic anhydride are unstable compounds.
\.
(c) From carboxylic ester:
R-~-OR' + HOH R-~-OH + R' -OH

(
)
(d) From acid amides:
c R-~-~+HOH dil. Hel ) R-~-OH + NH CI

4
(
2.4 By alkaline hy~rolysis ofalkylidyne trihalides :
<OK'
~
Cl ' . -3KCI 01. 0,
I
R- ~~. t 4"KOH -21-1 0) R-:- " HC') R -:-C- OH+ K91
2
Ct 0
(
2.5 From carboxylation ofgrignard's reagent:
( By passing CO2 in ether Solution ofGrignard's reagent
66 &J) &:9 66 JX
R~MgX + C'f'9 ~R-C-OMgx HOH ) R-C-OH+ M
"~
o
. n
0
. A ~OH
Note : Formic acid can not be prepared by this method.
c
[IJ!~~~A~~ C~~!~!
_fcrSdN>lors
CARBOXYLIC ACID & IT'S DERIVATIVES [3]
c
2.6 Partial decarboxylation ofgem dicarboxylic acids:
<
COOH
R-CH ..
[--, ~ R':"'CH2 -COOH+ C°iz
~Qg-J
Note : Formic acid is prepared from oxalic acid Qaboratory method) by heating at about 110° in the presence
ofglycerol.
yOOH GJyceroI) HCOOH + CO

eOOH 110 2
OOHll
In absence ofglycerol
b .
OOH
~ CO2 + CO + H2O
2.7 Carbonylation of:

(a) Sodium alkoxides or sodium hydroxide:
. H-ONa+CO ~g~ temp. ) H-COONa d.~~~I) H-~-OH

R £"'OON R- 9-OH
R-ONa+CO High temp.
High.p'ess
)
~ a
diL HCI
HOH) . J!;
(b) Alcohols:
R-OH+CO High
Bf3/HOH
temp. & press )
9
R-J!;-OH.
Bf3IHOH 9 { .
H-OH+CO High temp. & press ) H-8-OH "..
. (C) Alkenes [Koch Reaction] :
CH2=CH2 + CO + H 20 300-400t;;OJ9h press) CH3-CH2-E-OH (Propanoic a~id)'

CH3-CH=CH2 + CO + H2O 300-400?;~1gh press) CH 3-«H-CH3 (2-methyl Propanoic acid)
COOH
Note.: Formic acid and acetic acid can not be prepared by this method~
2.8' Oxidation ofalkenes andalkynes:
HN03 or GrO~: .
. R - CH =CH - R' + 410] or Acidic ~Cr2O: .R - COOH + R' - eOOH
CH2 =CH + 4[O} ~ 2 H OOOH ~ 2 CO2 + 2H20 ()

2
CH3 - CH = CH2 +-t1: [0] ~ CH3 COOH + CO: + Hp

C
R- C $il C - R' + 3 [0) + HOH ~., R ...; COOH + R' COOH
tJ
0
[i!¥,f~x~\CJA~'~! CARBOXYLIC ACID & IT'S DERIVATIVES [4] C

/dooIfo<Sdto/Qrs
c
c
3. PHYSICALPOPERTIES
3.1 Physical State: C1 to C3
Colour less pungent smelling liquids.
C4 to C9 = Liquids having goat's butter like smell.
CIO to C 10+ == Colourless & odourless waxy solids.

3.2 Solubility: Up to C4 == Highly soluble in water
With the increase in molecular weight ofcarboxylic acid, the solubility in water decreases.
Solubility oflower members ofcarboxylic acids family is due to the formation ofhydrogen bond between
-COOH group and water molecules.
Ii...... ~ . Ii'" lie lie. ~
M-O:-----H-O-C=O-----H-O·
. I ' 1 .' . .
H R h
As the alkyl group increases in size in acids, the water repelling(hydrophobic)tendency ofthe hydrocarbon
chain increases and it out weighs the effect ofhydrogen bonding. This is why solubility decreas.es in
('
higher members.
3.3 Boiling point (H.P.) :
B.P. ofacids> B.P.. ofalcohols
Because,A carboxylic acid molecular can enter into hydrogen bonding at two differentpoints. This leads
to the formation ofcyclic dimers in acids. This is the fact that lower acids occur as dimers in solution.
(
~-----H-O"
c/ ~C-R
R- "O-H-----~
3.4 Melting point (M.P.) :

( M.P.. ofcarboxylic acids do not vary smoothly from one molecule to another
,"
(
For first ten memebers M.P. ofC2n , > M.P. ofC2n+1
(n "" I, 2, 3, 4, 5) (n 0,1,2,3,4)
"
~
Reasons: In acids of even number ofcarhon at('ms term!nal-CHj and -COOH group lie on the
opposite side ofthe carbon chain.
cH; CH~£,QOOM Provide more effective packing ofthe molecule inthe lattice.
While in acids ofodd no. ofcarbon atoms
(' ./ CH2\ /CH2, Less effective packing

CH3 ' CH.2- '600H.
'.
(
4. CHEMICAL PROPERTIES : Carboxylic acids give following reactions :
I
~- 4.1 Due to alkyl group
r 4.2 Due to acidic hydrogen
\.. 4.3 Due to >C = 0 group
( 4.4 Dueto-OHgroup
4.5 Dueto-COOHgroup
4.6 Special reaction ofalkanoic acid
t
( .fIJ!,!~~!!~ C~S.,~!
likolf",_,.
c
4.1 Reactions due to alkyl group:
Halogenation: Acids having a. -H atom give this reaction. The a. -H atoms are easily replaced by
chlorine or bromine atoms, forming halogen derivatives ofacids.
H a
I CL. "0I
R-y-COOH --::Hct R - yH- COOH-HC!~ R-y-COOH
H CI CI
Note: (i) . The reaction is known as hell-volhard-Zelinisky (HVZ) reaction.

(n) In the presence ofphsophrous, monohalo product is formed as the main product.
R-CH1-COOH + Br2 ~ R-CH(Br)-COOH + HBr
(tit) Formic acid does not shown HVZ reaction due to absence ofalkyl group or a. - H atom.
4.2 Due to acidic hydrogen:

(a) Salt Formation: Carboxylic acids form salts with metals, metal oxide, hydroxides, carbonates,
bicarbonates and compounds showing basic nature.
Na 1
R - COONa + 2" H2
Na0H
R- COONa+ HaD
R-COOH I
N~O
. ,. 2RCOONa+I1:!O
-
NaHC03
R COONa + I1:!O + CO2
PbC03 _. (R-COOkPb+ CO +11:!0

2
~H40H_
RCOONH4 + I1:!O
'". "
Ca(OH}z.
(R - COO~ Ca + 211:!O
Note: A cids liberate CO2 with NaHC03• This reaction is used to distinguish carboxylic acid from phenol
which does not react with NaHC03•
(b) Reaction with Ketene:
R-C-OH + C = CH2' - - 4 R-C-O - C·~ CH 3

II ",I,
o/I 0 0 0··'
(Anhydride)
(c) Reaction with diazomethane : c

0·
II
R-C-OH+ CH1N2 ---)- R-C-OCH3 +N2
g Methyl ester c
Note : Diazomethane is a powerful methylating agent. So by this method methyl ester can be prepared. o
()
[t]!A~~A~~ C~~!E D
CARBOXYLIC ACID & IT'S DERIVATIVES . [6]
c
1d..lforSduJ/tl",
c
(d) Reaction with alkene and alkyne :
0 0 .
II SF II
R-C-OH + CH2 :::: CH 2 ~ R-C-OCH2 - CH3
oII .' .
R-C-OH + R - CH =CH 2 ~ R:... CH-CH 3
r
OCOR
~
R~C-OH + CH a CH "" CH· 0
II 2 II. .
CH-O-C-R
4.3 Reaction due to (>C = 0) group:
(a) R -~ - OH + 4 H NaBH
UAI~Qr) 4
R - CH - OH + H 0
.. 2 2
~
(b) R-C-OH+6HI
. A:~:1"'1 R-CH +2Hp+3Iz
. - 3
4.4 Reactions due to (-OH) group:
(a) With P10S (Dehydrations)
o o
II .....t71 II
R- C - '-1'"11
r~ 1 R-6>O + H20
R-C.f.OHI R-
II - - - II
o o
( (b) Esterification:
r----I . o
-~- OR'
(.
Conc.H;r§O4
\. R-CTOH+HTOR' R + H20 .
II - - - -
(
o
Note : The reaction is proton-catalysed esterification. In the reaction OH comes from the acid and H from the
c alcohol for release ofH 20.
(c) Reaction with Phosphrous Chlorides:
o o
( II II
~
3R-C-OH+PCla -----t 3R-C-Cl+H3Poa
t
" o o
II II
( R-C-OH+PC1s -----t R - C - CI +HCI +POCla
c (d) With Thionyl Chloride:
( o o
II II
R - C - OH + 80CI2 Pyrldlno l R-C-CI+Hct+S02 t
(
Note : In the reaction S02 is gas so escapes out and Hel is an acid, gets absorbed by basic pyridine and pure
c
acyl chloride is left. So its is best method for prepruing acyl chloride from acids.
c
i~~~~~~CM~~~~ /d""/,,",Schot.,,
c
(e) Formation ofacid Amides and Alkane Nitriles :
o 0 0
II /I II
IJ.
R-C-OH+ NH3 ~ R-C-ONH4 ~ R-C-NH2 ~o
2 •
R-CiliN+HO

2
(1) With Hydrazoic acid (Schmidt reaction) : N3H = Hydrazoic acid

o 0
fl II .
R-C-OH+HNa H2SO.) R-C-N3 +H20 ) R ~ N~ + CO2 + N2
The reaction is a modification of"curtius reaction".

Ex. CHrCOOH + HN3 HzS04) CH3-~ + CO2 + N2
Mechanism:
.~ . . '<if '0
CHa -~-<?H+N3H. lJ.o~CH3 .:..8.-:-N.3 ~ CH3 -8-.t'J;
Ethanolc aCId .(~).,. .... ..... '. :'1', ,.' ..
. ~~ent
CH 3 - NH2 ( co t CH3 - NH - COOH ( HaO CH3 - N == C = 0
Methanamin e 2 (Methytiso cyanate)
( .
4.5 Reaction due to (-COOH) group:
(a) Decarboxylation:
o
II
R-C-ONa N$OH+CaO .
+ ' Soda.
lime
' ) R - H ,. N82CCh
\../
. Alkane
t •
(b) Kolbe's electrolytic synthesis : '-... /
o R
II
R-C-OK I
R-C-OK
R +2C02 (AtAnode) c
II
o
2K + 2~O j 2'KOH + ~ (At Cathode)
Note : Kolbe synthesis undergoes free radical mechanism.

(c) Hundsdiecker reaction:
II
R-C-OAg+X2 R-X+ C02t+Agx.J,
(X =cr; or BI'2)
00. )
o
Note : In the reaction decarboxylative halogenation ofthe acid takes place. The reaction is useful in stepping
c
down a homologus series. o
c
[jj]'t~~A~~C~~~~!
_""S<I",I."
c.r
(d) Formation ofcarbonyl compounds [Dry distillation ofcalcium salt] :
o
II
R-C-O ' R
, >Ca-:4 >C ==O+CaCO)
R-C-O R '
II
°
,H-C-O>.
°II ' "
, Ca~ "
H -c - 0 HCHO + CaCOa
11 '
o
o
°II O-C-R
II
A
0
II
H-C:,O >ca +
Ca< ~ 2 RCH == 0 + R-C-R.+ HCHO + CaC03
H-C-O O.C-R ~
II
~
(e)
°
With Manganous oxide:
(
o ~(jj
( .. ,1',,1
II - - - - ... - Ui
\ ___ J __ _
MhO
aOO-C
',:R,'>
R' C= 0 +.H 0' +;CO
2, 2
R - C -bH+ H'-jO -'C .. R'
(
(carbonyl rompounds)
" 4.6 Special reaction ofalkanoic acid:

(a) Oxidation:
(
~ By Se02 a keto acid is fonned
~ By ~02 -OR group comes at p-C atom.
('
,
f .
CHa - CH;! - CH2
(Butanoic acid) ,
- COOH ~ CHa ~- z;:- CH2 - COOH ,
\.
(3-HydroxyButanoic acid)
(b) Pyrolysis:
CH2 -C=O AlPO", )

6OO'C
CH == C 0
2
=
It ~HI (Ketene)
SPECIALFEATURES OF FORMIC ACID

(a) Fonnic acid shows acidic character due to the presence of-COOR group as well as shown
reducing character diJe to the presence of-CRO group.
~
'"
H
II
C-O-H
'
J-H Alo~'H
'- COO!l group -CHOgroup
(b) It reduces Tollen's reagent and fonns silver mirror.

(c) It reduces mercuric chloride and fonns black pptofmercmy.
l
CLASSES CARBOXYLIC ACID & IT'S DERIVATIVES [9]
C 1d..1""_
LIM. Tt!!: D
,
{
c
(d) It decolourises the pink colour ofacidic KMnO4
(e) It fonns brown ppt ofMn02 with basic KMnO4
(f) Itconverts the orange colour ofacidic K2Cr20 7 into green colour.
(g) It reduces FeWingSQlution.
(h) Dehydration -HCOOH Cone:. ~S04 ) ~O + CO2
(i) Effect of heat :
160"C
(a) HCOOH A ~ C02+~
3BO'C COONa
(b) 2HCOONa ~21 +~
COONa
Sodium oxalate
6. DISTINCTION BETWEEN FORMIC ACID AND ACETIC ACID

S. NO. . . BeOOH . CHjCOOH
- - ---- ......
1. OeeomposiR! onheatJOgto giVErcsrbon Stable
dioxide and hydrogen; .
2. With concentrated sulphuric acid gives Stable
carbon monoxide and water.
3. With halogens, there is not action, Substituted acids are formed.

4. Reduces ammonical silver nitrate and No action.
Fehling's solution.
5. Calcium salt on heating gives formaldehyde. Calcium salt on heating gives acetpne.
6. Sodium salt on heating gives sodium oxalate No action.
hydrogen.
7. Sodium salt + soda lime gives hydrogen on Methane is produced.
r
I. .'
heating.
8. Electrolysis of alkali solution gives hydrogen; Ethane is obtained.

9. Oecoloulises acidifiedKMn04 solutiOn. No action.
10. Dichromate solution turns into green coloured No action.
solution.
()
7. FORMIC ACID (HCOOH)
1. Lab Reaction :
COOH Glycerol
tOOH' HCOOH + CO2
110' )
c
Note : B.P. ofHCOOH is lOOS, for removal ofwater from fonnie acid we can use PbC03 or PbO (L~ge)
and~S.
2HCOOH + PbC03 ~ (HCOO)2Pb + CO2 + H 20
(HCOO)2Pb + ~S 100·C ~ 2HCOOH + PbS (ppn
2. . Industrial method:
It is prepared on large scale by reaction CO with aqueous sodiron hydroxide under pressure 1 atm and
473K
(\
CO + NaOH
473K
'0'''') HCOONa
H2O
) HCOOH + NaOH v
~,~~~~Jt~~~~~! CARBOXYLIC ACID & IT'S DERIVATIVES [10] c

Id<DIrwSchDlc,.
,-"
{
c
'8. ACETIC ACID ClI.3COOH
Industrial methods:
(a) From ethyne: HC 5; CH + H20 :40% H;$O. >CH3·CHO

1% HqSO. (Acetaldehyde)
,
/'
MiigIioUs .""Iate
CH3COOH
1[O]alroxld'>
(b) From ethyl alcohol
(i) By dehydrogenation : CH3C~OH 3~~C) CH3CHO (Magnoi?lacelale» CH3COOH

(-li2) .
(u) By fermentation (Quick vinegar process)

Acetobeclor bacteria )
C~CH20H+02 (Mycoderma acetail) CH3COOH + ~O
c\ [dilute form 8 10% Called VINEGAR]
(IiI) FromCH30H
('
" CH30H+CO O~~h ) CH3COOH
('
\..,
f
. '"
(
,
,.
r,
c
c
(
<-.
c
()
C
i!~~~A~~CM~'~fId..lfor_
c
c
ACID DERIVATIVES
1. GENERAL INTRODUCTION
Replacement of-OH group ofthe -COOH group in a carboxylic acid by an atom or by auy other·
functional group give rise to certain new families ofcompounds. These compounds are called acid
delVatives.
+X(X=CI,Br,I» R-~-X (Acyl halide)

.,
-OH
o 0
R-~-OH +OCOR
...QH
) R _ ~_ 0 _ ~ -R (Acid Anhydride)
+NH . \1.
2 ) R-~-NH2 (AcldAmide)
~ >'R...:K_OR(Ester)
Acyl chlorides are the most ·importantacid halides. The fll'St member ofthis family is acetyl chloride
because fonny1chloride is unstable.
Similarly acetic anhydride is the representative member Qfthe acid anhydrides family, because fonnic
anhydride is unstable.
The first two members ofAcid Amide family are fonnamide andAcetamide. Acetamide is an important
acid amide.
f
Esters have functional group isomerism with acids. \.
/
R-~-Z [where Z=-x, -~, -OCOR, -:-OR]

* Order ofbasic character ofgroup Z
X- < 0- COR <-OR <~~
* Reactivity orderlRate ofhydrodysis
R-~-X> R-~-O-~-R> R-~-OR> R-~-~

* Order ofstability
R-~-~ > RCOOR> R-~-O-~-R> R-~-X
Derivatives regenerate the parent acid on hydrolysis.
2. ACETYL CHLORIDE rCH3-E-cI]

2.1 Method ofpreparation:
Laboratory method: 0
3CH3':"~-OH + PCl3 ~ 3CH3-~-CI + H P0

0
3 3
e
CH3-~-OH + PCl ~ CHr~-C1 + POCl3+ HClt
5 0
CH3COOH + SOCl2 ~ CH3-CO-CI + S02 + HCtt
~!~~~A~~C~~!~!
Id..l""_
CARBOXYLIC ACID & IT'S DERIVATIVES -
[12]
(
From Sodiumacetate :
CH3-COONa + PCls ~ CH3-CO-C1 + POCl3 + NaCI
3C~-COONa + PCI3 ~ 3CH3-CO-CI + N~P03
2CH3-COONa + POCI3 ~ 2CH3-CO-CI + NaP03 + NaCI
CH3-C00Na + SOC~ ~ C~3-CO-C1 + S02 + NaCI
,"
By the reaction ofsulpnryl chloride on calcium ethanoate :
o
n· . 0
CH 3 - C > " II
CH -C . Ca -tS02 Ci 2 -+ '2CH3 ...:C-:.Ci,+CaS04 ·
3 11
o
2.2 Physical Properties:
(i) Colourless liquid, having plUlgentodour.
(n) Slowly soluble in water, soluble in organic solvents like CHCI3, CCI4, CH3-CO-CH3, etc..
. (m) Produces bilster on skin and its vapour causes irritation in eyes.
(iv) Boilingpointi$51oC.
(v) Fumes strongly in moist air..
2.3 . Chemical properties :
(1) Hydrolysis :
( . 0 9
eH3 .... 8-CJ+HOH -t CHa -~-OH+HCJ .
\.
on alkaline hydrolysis
(
\.
o O.
(
..... CHa -8-CI+2NaOH -t CH3 -~-ONa~NaCI+H20
( (2) Rednction:
o H
CH3 -~-CI+H2 -b." ° + HCI
(
(i) :;:) CH 3
4
r-'
\' (Rosenmund's reduction. partial reduction)
f'
. '- . o
(n) CH 3 -~-CI;i-4H UAlH. ,.
CH3 - CH2 - OH + Hel
c «NaSH.
( Complete~uction)
c (3) Curtius Reaction:

o 0
c
"
CH3 -C-CI+ NaN3 ----+ CH3 -C- N3
Acetazide
" MHOH ) .CH:I - NH2 + N2 + CO2 .
(4) Friedel Craft's reaction:

(
o o
CH3 -~-Ct+H-C6H5 ~ CH3 -~-C6H6 +HCf
(Acetophenone)
c
( il!'!~~~~CL~~!!!Id<PlftwS<I>DI<m
CARBOXYLIC ACID & IrS DERIVATIVES [13]
{ .
. 'L
c
(5) With Grignard's reagent:
o o X
CH 3 -8~CI+R-M9X ~
CHa -~-R+M9<CI
(6) Halogenation:
0 ' 0
, CH II '
-C-CI+CI2 ~
M!Q"
Cf-CH2 -C-CI+HCI
" '
3
Chloroacetylchloride
(7) With Ether:
?i
CH 3 -C-CI+ c~s -0 C2HS ~
ZhCl.
CH3 - E- OC2Hs -+- C2HsCI
(8) With Sodium Ethoxide :

o o
II' ,
(9)
CH3 -C-CI+NaOC 2HS ~ CH3
With Sodium Acetate :
-
"
C - OC 2Hs + NaCI
oII '
00
II ' II-
0
II',·',
CHa ~C-CI + NaO-C-CHa,~ CH3 -C~O-C-CHa +NaCI
Aceticanhydride
(10) Acetylation ofCompounds having reactive hydrogen atom:
o 0
II - II
R-C-CI+H-Z ~ R-C-Z+HCI " "
, 0 I'
Ex. \,/
H +NH2 - + CH3 -~-NH2 (Acetamide),
H +NH - CHa ~ CHI! - CO - NH - CH (N-methylac.etamlde) 3
H +N{CHa);i - + CHa - CO - N ,(CH.3)2 (N. N-dim~thylacetamide) ()

o
II
CH 3 -c.Jcr + H +NH - CO - NH2 ---?' CHa - CO - NH'~ CO - NH2 (Acetylurl'!a)
H +NH - OH - + CH; :""cb - NH"- OK (Aoothydroxamic acid)
H +NH - NH2 - + CH 3 - CO - NH "'" NH2 (Acetic acid hydrazide)
H +S -' CH CH3~' co- S -

3
---? CHI! (Methylthloaretate) f'"
V
H +0 - C H. COOH (0) - + CH
8 3 - COOCsH. COOH(o) k:~tylsal!c;1lc a~d -or Aspirin)
C
o
II 8
L...._ _ _H....Jt OR ---? CH;t. -: C -:- QR (All<!" acef!3t~)
c
c
li't~~A~~CL~~!~!
IdtaI forSd>okur
CARBOXYLIC ACID & IT'S DERIVATIVES [14J
c
(11) With Alkene :
o o '0 ,"
II~ II '
II Anhyd. ) CHs -C-CH2 -CH2 ":'CI~ CHa -C-CH=CH2
CHs -C-CI+CH2 =CH2 AlCls •.
(4 -:- Chlorobufanone) (Methylvi~ylKetone)
3. ACETIC~YDErnOE [CH3-~-O-~-CH3]
o 0
W II II
CHs -C-OH OCOCHa
-OH ) CH,s -C-O-C-CHs
3.1 Method ofprepatation :

FromAcetyl chloride: '
(
o 0 0 0
II CI+H-O-C-CHs
CHs -C- " -+ II II
CHs -C-O-C-CHs +HCI
o 0" 0 0
II II II II
( CH 3 -C-CI+Na-O-C- CH 3 -+ CH3 -C-O-C-CHs +NaCt
I~
(Laboratory Method)
" FromAcetic acid:
o 0 o 0
(
\
II II II II
CHa -C-OH+ H-O C.-CHs ~ CHs-C-O-C-CHs+ Hp
!
"
By passing chlorine in a mixture ofSC~ and sodium acetate:
(
o 0
t II II
" 8CH3COONa + SCI2 + 2CI:----+4CHs -C-O-,C-CHs + 6NaCt + Na2 SO.
C From Ketene:
C H OH
I I AlP04
( CH 2 - C=0 0) CH = C = 0 + H20
600C 2
(ketene)
{
'
((
CH = C =0 + H-O-C- CH3 ----+ CH3 -C-O-C-CH3
" 2 II II ' "
o 0 0
c
3.2 Physical Properties :
(
(i) It is colourless liquid having pungent vinegarlike odour.
(it) Boiling point is 138°C.
(ill) Slowly soluble in cold water, but readily soluble in hot water
t
( Ij~L CLASSES CARBOXYLIC ACID & IT'S DERIVATIVES [15]
(
3.3 Chemical Properties :
Hydrolysis:
o 0
II /I
CH3C - 0 - C - CH3 + HOH ~ 2CHaCOOH
WithPCIs:
CHa- C
II
I a CI
>+p~a~
o
II
2CH3 -C-CI + poc~
CHa-C I
a
"o CI
WithN2 0 S :
o
II o
CHa- C o~ #0
~
CH3 -C""--
.."......0+
°
#
N-O-N
~
0
----+ 2CH3 -
"
C - 0 - N02 Acetyloilrate (explosive)
II
o
With Benzene {Friedel-Craft's Reaction] :
o 0 o
II II '.
CsHsH + CH3 - C - 0 - C - CH3 Anhyd.)
~a
CSH5 -
"
C - CH3 + CH3 - COOH
.
Acetophenone
With Acetaldehyde:
o 0
II "
CH3 - C - 0 - C - CH3 + CH3 - CHO ~ CHaCH(OCOCHa>2
Ethylidene diacetate
With Dry HClgas:.
0 0 0
II II II·
CH3 -C-O-C-CH3+ HC!--+- CH3 -~-CI + CH 3COOH c
Perkin's Reaction:
o 0 0 0 0
II II
CH3 -C-O-C-CH3+CSHS -CH --+ CH3 -C-O-C-CH=CHCsHs
IJ· II II
~~~~
HOH o
(Benzaldehyde) c
-+ CeHs - CH =
CH~COOH + CH3COOH
(Cinnamic acid)
0
C ,/
[i'~~~!!\CM~~~! CARBOXYLIC ACID & IT'S DERIVATIVES [16]

Id.oI ""S,hd<ns
C
Reduction:
o 0
II II UAI....
CH 3 - C - 0 - C - CH3 + 8H ) 2CH3 - CH2 - OH + Hp
With Compounds having reactive H-atom :

o 0 o
II /I II
CH, - C - 0 - C - CHa + H - Z ~ CH 3 - C - Z + CHaCOOH
Acety lderivative
Note: Products are similar as in case ofAcetyl chloride.

. ?
4. ACETAMIDE [CHr c-NH21

,/
o o
II II
(
\
CH - C - OH . +NHg ) CH3- C - NH2
3 -OH
( 4.1 Method ofPreparation :
FromAcetychloride:
(
o 0
.II . II .. ,
\. CH 3 - C - CI + 2NH3 ----+ CH3 - C - NHz + NH~CI
/. From Acetic Acid :
o o
II II .
CH3- C - OH + NH3 ~ CH 3 - C - NHa + HaO
/
\
From acetic Anhydride:
o 0 o
./
\ II II ,
II
CH 3 - C - 0 - C'-Cl1a .f'2H - NHz ---+ 2CH 3 - C - NH2 + HP
f
\ From Ethyl Acetate :
f o o
l ,,11 ..
(' "
CH, - C - OC;iHs +, NH3
Partial hydrolysis ofAcetonitrile :
---+ CH 3 ::' c- tilH2+CilHsOH
C o
II
(
\..
CH 3 - C =N + HOH Cone.HCI
H20 2
CH 3- C - NHg
By thermal decomposition ofAmmonium acetate:
C o 0
( II ':\ II ,.
CHa-C-ONH. ~CH3-C-NH2+ H20
C 4.2 Physical properties :

, (i) a
It is hygroscopic white crystalline solid.
C (n) . It has faint smell in pure state, but a rat like sinell in impure state.
(ill) It is soluble in water and alcohol, but sparingly soluble in ether.
-
C' (iv) Melting point 82°C and boiling pojnt is 222°C.
C
( CARBOXYLIC ACID & IT'S. DERIVATIVES [17]
(
'L
(
.(
L
4.3 Chemical properties:
Hydrolysis:
o
II
CHa - c- NH2+ H2Q + Hq ~ CH3- COOH + NH4CI
Dehydration: o
1/
3CH3 - C - NH2+ P205 ~ 3CH3CN + 2H3PO..
o
II
CH3 - C - NH~+ pct5 ~ (CH3 CCI2NH21+ POCI3 -2HCI) CH3 CN + 2HCI
o
II ..
CH3 - C - NH,+ POCI! ~ 3CH3 CN + H3PO.. + 3HCI
oII .
CH1 - C - NH2+ 80Clz ~ CH3 CN + 802 + 2HCI
Reduction:
ReducingAgent: Meta) Catalyst + ~,Na + Ethanol, LiAIH4 etc.
f •
o .
II . "
CH3 - C - NH2+ 4H ~ CH3 CHPH + NH3 ~ CH 3 - CH,2 NH2 + H20
With Nitrous Acid:
o ,
II "
CH3 - C - NH2 + HONO --+ CH3 - COOH .;. N2 +. H20
1./ "
\
Amphoter character:
Acetamids fOnDS salts on reacting with strong bases as well as strong a((ids. Therefore jt behaves like a
weak base as well as weak acid. i.e. it shows amphoteric character.
(i) Weak acidic behaviour:

o o c
II 110@
. 2CH3 - C - NH2+ 2Na ----7 2CH3 - C -.NH Na + H2
o o
II II
CHa - C - NH2 + NaNH~ --+ CHa - C - NHNa + NHa
o o
/I 1/
CHa - C - NH2 + (CHaCOO)2Hg --+ CHa - C ,. NH - Hg - OCOCHa + CHaCOOH
Acetamidomercuriacetate 0
(u) Weak basic behaviour: c
o o e
II II $0
CH3 - C - NH2 + Hel :)
CH3 - C - NHaCI
0
C
~~~~~A~~~~'~! CARBOXYLIC ACID & IT'S DERIVATIVES . [18]
_'forSt"""'' ("'
"-..1
c
Hofmann Bromamide Reaction or Hypobromite Reaction:
o
II
CH" - C - NHJ + Br1 + 4KOH ----+ CH3 - NH2+· 2
K CO
3
+ 2KBr + 2H20
(or NaOH}
(
Slightly Mechanism:
/'
Bromination:
CH 3 • C
I
=0 + Br -fer :; 'j"/~
--~~
) CH3 - C
I
=0 + KBr + H 0
2
:r·H;/ H )

:rH
Br
, Acetobromamide
\
Dehydrobromination :
,
('\
CHa-f=O
:N-Br
+ KOH - - - 4 0 r~fQl +m+H,O
Rearrangement(step3) ) CH - N = C = 0
3 ••
Methylisocyanate
r
\ I
H
(
" Hydrolysis:
CH 3 - N =C =0 + 2KOH ) CH3 - NH2 + K2 C03
Methylamine
Note: In the reaction decrease ofone carbon atom takes place. Therfore it can be used in decending down a
,. homlogous series and it is also called Hofinann degradation.
\
(
W
" 5. ETHYLACETATEAND ACETIC ESTER [CH3-c-OC2Hsl
(
o o
c II .11. .H
CH 3 -C-OH OCiHfi ) CHs -C-OC 5 2
c 5.1 Methods ofpreparation:
By liquid phase Esterification:
o
(
(
/I
CHs - C - OH + HOC2 Hs
. Cone.H2S04 °II
~ CHS - C - OC 2H5 + H20
By vapour phase Esterification:
o
{'
" 11
CHs - C - OH + HOC2 Hs
. ,. ThO
'. 2 )
J-I.
CHs - C
°'. +. H'O
OC2HS 2
c (vapour) (vapour)
c
r:
'-c. lIJ!~~~~~CL~~'~'
/<kQI""S<hoIa"
CARBOXYLIC AcID & IT'S DERIVATIVES [19]
c
(
I
'c
By Aceylation ofEthanol :
o o
II /I'
CH3 - C - CI + HOC2H5 Pyridine) CH3 - C - OC2HS + HCI
o
/I 0
CH" -, C" ,
<
CHa - C
'> - ,.
0 + HOC2 H$
" < 1/
AnhYd) CH~ - C -
ZoC/2
,;
09l'!$ + CHaCOOH
<
/- '~
/I
o
Tischenko Reaction:
H
CHa-C::O+O::C-CH3 Al(ORh) CHa,- C- 0 ·CH2 -CH3
I Anhyd.AlCI3 , II
H o
Ethyl acetate
Ethylatioli ofSilver halides:
o o
II
CHa,. C ,. OAg + 1- ~$
Ethanolysis ofEthanenitrile :
"
CHa - C ~ OC2H$ +AgIJ.
i'
o ',- .'
CH3 C == N + C2H50H + H20

II
- --~,) C~ - C - OC2HS + NH,
By addItion ofAcetic acid on Ethylene:

o Q
II SF If
CHI - C ,. OH + CH2:: CH; ~ CHa-C-O-CH2-CH,
By reaction ofsodium Ethoxide on Acetyl chloride:

o o
1/ II
CHa - C - CI + NaOC2Hs -----'<.-+) CHa - C - OC~s + NaCI
Baeyer-ViUiger Oxidation:
Ethyl acetate is fonned on reacting butanone with a peracid, Methyl propionate is also fonned in small
< amounts.
o 0 0 0
II
CHa-C-C2Hs
"
+ CHa-C-OOH ~ CHa .. C-OCtHs +
1/ 'II
CHJ-C-OH
c
Peracetic acid ' c
o 0
e
II
CH~ -C-CH2-CHa " -OCH,
+(0) - - 4 CH,-CHa-C
Methyl propionate o
fI~¥.f~~ CARBOXYLIC ACID & IT'S DERIVATIVES [201 c
c
(i) Colourless, sweet smellingsteamvolatile, inflammable liquid.
(n) Vel)' sparingly soluble in water, but soluble in organic solvents.
(m) Boiling point 78°.
5.3 Chemical Properties :
Hydrolysis :
aII .
.... CH3 - COOH + ~HsOH
S0
CH3 " C - OC2HS + HOH !"'2
aII -
0
II
CH3 - C - OC2HS + NaOH ~ CH3 - C - ONa + CzHsOH
Note : In esters caustic alkalies hydrolysis is rapid and complete. Alkaline hydrolysis ofesters is called
"Saponification".
(
Reduction:
o
II RedP+H1
( . CH3 - C - o.C:H5 + 4H . nr IIAIH.' ? 2 CH:PI-I,PH
I a
II
CH 3 - C - OC2HS +.4ti '. Na+~~50H) 2CH3CHPH
/
\.
(Bouveault-Blanc reduction)
(
Ammonolysis :
/
\.
o 0
II f}. II .
CHa - C - OC2HS + H - NH2 ~ CHs - C - NH:z + C2 HsOH
(
With Grignard's Reagent:
(
o 0
/ II II X .
l. CH 3 - C - OC2 Hs + R - Mg X ---+ CH3 - C - R+ Mg<
_ _ OC2HS
r'
\.-- Note : The product will be tertiary alcohol when 2 mole ofGrignard's reagent are taken.
( With Hydazine :
c o 0
1/ II
CH3 - C - OC2HS + Ii - NH - NH2 ----+ CHi - C - NH NH2 + C2HsOH
(
Acetyl hydrazine
( With HydroxylAmine:
c o a
II· .
(
CHa -C- OC2HS + H-NH:...QH ----+
"
CHa - C-NH-OH + C2 H50H
. Acetyl hydraxomlc add
t.'
CARBOXYLIC A~ID & q's DERIVATIVES

(. ~r SAL CLASSES
VATE LIH'TEO
ldeoIlor Sdtolon
[21]
(,
c
WithPCl5 :
o CI 0
II I/CI. II. . .,
CHa - C- 0 + P,- CI---+CH3 -C-CI + POCia + C2H~CI
r L- - - - - - - - - -L..""'c~
'

:C2Hs C(:
f __ .. __________ ~
Claisen Ester Condensation:
o 0 o 0
\I II /I II
CHa - C - OC2HS + H -CHz - C- OC2HS C?HsONa , CH3 - C- CH2 - C - OC2HS + C2 HsOH
Acetoaceticester
pYrolysis or Thermal decomposition:

('
o 0
CH3-~-OI H·
I
HSOO'-600"')CH3"':":~":;OA<I-CH':::iCH
. 2 2
ICHz -CH21
Acidolysis :
0 0 0
CH3 / IOCzH
1/ - OC H + C H - eOOH ~"CsHu - C';";
C . s + CH3 :.. C" .... OH
Z 5 5 10
/'
\.
o
,(~
G
1I!~~~6~~CL~~~~!
Idet.JIorS<hol<m
CARBOXYLIC ACID & IT?S DERIVATIVES' [22]
c
BENZOICACID
BENZOIC ACID (C/iHSCOOH)

Benzoic aicd was first obtained by Schiele from gum benzoin. It is also present in Peru balsam and Tolu
balsam in the fonn ofits benzyl ester (f?enzyl benzoate).
C6HsCOOC~C6Hs Benzyl Benzoate
In combined fonn it is found as benzoylglycine in horse urine.
C6HsCONHC~COOH BenzoylgIycine
1.1 PREPARATION
.(1) Oxidation ofBenzyl Alcollol :
Benzoic acid is fonned on pennanganate oxidation ofbenzyl alcohol.
C6HsC~OH (Benzyl alcohol) + [0] ----+ C6HFHO(Benzaldehyde) ~ C6HsCOOH (Benzoic

acid)
(2) Oxidation ofBenzaldehyde :
( Oxidation ofbenzaldehyde takes place very readily and benzoic acid is fonned.
C6HsCHO~C6HsCOOH
f (3) Oxidation ofAralkanes and Their Derivatives :
'\,
A side chain (alkyl group or substituent alkyl group) bonded directly to the benzene ring is converted to
(
a carboxyl group on oxidation. Dilute nitric acid.or chromic acid or alkaline pennangante can be used as
/' oxidant
" r':':;:'l [0)
(
"
C6Hs ........... .,. ~C6HsCOOH
!C,i
Side chain
(
'"',
Benzoic acid is obtained on oxidation ofmany compounds like aralkanes (toluene, ethylbenzene,
n-propylbenzene, cumene, etc.) and their oxygenated derivatives (benzyl alcohol, benzaldehyde,
acetophenone, benzophenone, etc.) halogenated derivatives (benzyl chloride, benzal chloride,
benzotrlchloride etc) nitrogenated derivatives (cyanobenzene benzamide, etc.)
c (4) Carboxylation ofGrignard's Reagents ;
( Benzoic acid is fonned on hydrolysis ofthe product obtained by passing carbon dioxide in ethereal
solution ofphenylmagnesium bromide.
c
C6HSMgBr C02) C6HSCOOMgBr .
HOH) C6~-'-5
R COOH
(;
"", (5) Carboxylation ofBenzene :
c Benzoic acid is obtained on heating benzene and carbon dioxide in nitrobenzene medium in the presence
( ofanhydrous aluminium chloride.
ClIsH + CO2 Alec) C6HsCOOH

t
L
{I]!~~~A~~CL~~~~!
Scholars •
Ideal for
c
,
c
(6) Alkaline Hydrolysis ofBenzotrichloride :
Benzoic acid is fonned on hydrolysis ofbenzotrichloride by lime water in the presence ofiron catalyst.
C6HsCCl3 (Benzotrichloride) 3 OH- Ca<i:l2 ) C6H sCOOH + H20 + 3 Cl

(7) Hydrolysis ofBenzoyl Chloride:
Benzoic acid is obtained by hyrolysis ofbenzoyl chloride
C6HsCOCI + HOH ) C6H sCOOH + HCI
Benzoyl chloride is preparedby Friedel-Crafts chlororfonnylation ofbenzene, Benzoic acid is obtained

in 60% yield by the method.
C6HSH + CI-CO-CI A1CG) C6HsCOCI + HCI
Phosgene
(8) Hydrolysis of Cyanobenzene :

Benzoic acid is fonned on hydrolysis ofcyanobenzene i.e., benzonitrile by dilute hydrochloric acid.
C6H sCN + 2HOH -t HCI ) C6H sCOOH + NH4CI
(9) . Dehydroxylation ofHydroxybenzoic Acid :

Benzoic acid is fonned on dry distillation of0-, m-orp-hydroxybenzoic acid with zinc dust The ortho '. ,
isomer is c~lIed salicylic acid

HO-C6H4-COOH + Zn ) H-CEiH4-COOH + ZnO
Benzoic acid
D~arboxylation ofPhthalic Acid:

/'
(10) '-~
o-Benzendicarboxylic acid is called phthalic acid. On heating its zinc ofnickel or chromium salt at 200- ,,,. /
~
3000 with watervapours, benzoic acid is fonned by partial decarboxylation.
II
II
o
G
...." C-O,
C§rc_O...- zn
A
+1-l20) ©r
•••~'-"""
(.
. ~-
.).
COOH
+ Zno + CO2
Zinc phthalate c
(11) Hydrolysis ofBenzoic Acid Derivatives:
Benzoic acid is fonned on hydrolysis ofesters, anhydride, acid chloride and amide ofbenzoic acid.
C6H sCO-Z + HOH ) C6HsCOOH + Z-H
Benzoyl chloride and benzoic anhydride very readily get hydrolysed by water, but with little bit more
diffucilty as compared to aliphatic acid chlorides. Hydrolysis by alkali takes place faster.
o
C6HsCOCI + ~O ) C6H sCOOH + HCI
o
(C6HSCO)20 + ~O ) 2C6H sCOOH
Hydrolysis ofbenzoic esters takes place on heating with an alkali. e
C6HsCOOEt + NaOH ) C6HsCOONa + EtOH G
C
Ii!~~~~~Ch~~'~~
_r.r5dt<>Io"
c
c
Hydrolysis ofbenzamide takes place on boiling with dilute acid oralka1i solution.
C6HsCONH2 + ~O + HCI ) C6HsCOOH + NH4CI
C6HsCON~ + l'TaOH --~ C6HsCOONa + NH3
Liberation ofanimonia gas on heating the solution after adding sodium hydroxide solution is the test for
amides.
1.2 PHYSICALPROPERTIES
Benzoic acid is a crystalline solid (melting point 122<» which is sparingly soluble in cold water, but readily
soluble in hot water. It is also soluble in organic solvents like alcohol ether, etc. Its acid strength is more
than that ofthe alkanoic acids due to weak negative inductive effect ofphenyl group.
HCOOH> C6HsCOOH> CH3COOH
1.3 RESONANCE IN BENZOIC ACID
The COOH group present in benzoic acid is a strong electron-attracting group due to which the benzene
ring is deactivated and rate ofSE reaction decreases as compared to unsubstitued benzene. Therefore,
the COOH group exerts a deactivating effect on the benzene ring.
Dimerisation in Benzoic Acid due to Hydrogen Bonding:
r
Benzoic acid in liquid phase (in benzene solution or in molten form) exists in the form ofa dimer by
' ', association due to intermolecularhydrogen bonding in the same fashion as in alkanoic acids. This is the
I reason why the experimental value ofthe molecular weightofbenzoic acid is twice the calculated value.
"
\
Q--H........Q
CeHsC" . /C-CeHs
(
/ (}-Mm'H-o
\
Hydrogen bonded dimer of benzoic acid
/
1.4 REACTIONS
"
~ .. Benzoic acid gives the following two types ofreactionS.
\. (A) Reactions due to COOHgroup

(
(B) Reactions due to C6HS group
\.
(A) , .Reaction Due to Carboxyl Group:
c 1. With.Bases :
Many alkaline compounds form benzoate salts on reacting with benzoic aicd.
C6HsCOOH + NaOH. ) C6HsCOONa + ~O
( 2C6HsCOOH + N~C03 ) 2C6HsCOONa + ~O + CO2
'
C6H sCOOH + NaHC03 ) C6HsCOONa + H2O + CO2
c Phenol (a weak acid) does not react with sodium bicarbonate, whereas benzoic acid gives effelVescence
ofCO2, although both are acidic organic compounds toward litmus. Therefore, distinction between
( phenol and carboxylic acids can be done by using NaHC03.
I . 2C6HsCOOH + Ca(OH)2 ) (C6HsCOOhCa
\..
C6HsCOOH + NH3 ) C6HsCOONH4
C C6HsCOOH + NH40H ) C6HsCOONH4 + ~O
2. With Alcohols !
C An alkyl benzoate is formed by esterification on heating a mixture benzoic acid and an alkanol in the
presence ofa few drops ofconcentrated ~SO4'
t~
C6HsCOOH + HOR+ C6H4COOR + H20
C
iJ!~~!~~ CARBOXYLIC ACID & IT'S DERIVATIVES [25]
/
'l
t
3. With Inorganic Ch1o.ride :
Benzoyl chloride is fonned on the reaction ofbenzoic acid with phosphrous pentachloride or phsophrous
trichloride or thionyl chloride.
C6HsCOOH + PCls . ~ C6HsCOCI + POCl) + HCl
3C6HsCOOH + PC~ ) C6HsCOCI + H)P04
C6HsCOOH + SOCl2 ) C6HsCOCI (Benzoyl chloride) + S02 + Hel
4. WithPlOS :
Benzoic anhydride is fonned on heating benzoic acid with P20S'
2C6H sCOOH P,z~) (C6HsCO)20 + ~O

Acetic anhydride also dehydrates two molecules ofbenzoic acid to give benzoic anhydride.
S. WithAnunonia :
Benzamide is fonned on heating benzoic acid with ammonia.
A
C6HsCOOH + NH3 [C6HsCOONH4 J _~ C6HsCON~
)
Benzonitrile or cyanobenme can be obtained by heating benzamide with P20 S'

C6HsCON~ ~) C6H sCN + ~O
6. With Soda Lime:
~
. .Be ne is obtained on dry distillation ofsodium salt ofbenzoic acid with sodalime.
C6HsCOONa + NaOH ~ C6~ + N~C03
7 Dry Distillation ofCalcium Salt: .
Benzophenone is obtained on dry distillation ofcalcium salt ofbenzoic acid.·

. (C6HsCOOhCa ~ C6HsCOC6Hs + CaC03
8. Hunsdiecker Reaction:
Bromobenzene is fonned on heating the silver salt ofbenzoic acid with bromine in carbon tetrachlpride
solution
C6H sCOOAg + Br2 ~ C6HsBr + CO2 + AgBr
9. Reduction by Lithium Aluminium Hydride:
Benzyl alcohol is fonned on reduction ofbenzoic acid by lithium aluminium hydride (LiAlH,J.
C 6H sCOOH + 4H UAlH4) C6HsC~OH + H2O

10. Reduction by Sodium and Ethanol: .
Toluene is fonned on reduction ofbenzoic acid by sodium and ethanol.
C 6H sCOOH + 6H e~H) C6HSCH3 + 2~0

(B) Readuction Due to Aromatic Ring :
Hydrogenation by Sodium and Amyl Alcohol :
TIle COOH group is not affected on reduction ofbenzOic acid by sodium and amyl alc9hol but benzene
ring ofbenzoic acid is completely hydrogenated to fonn Cyclohexanecarboxylic acid.
H
c
( . ·).
~OH +6H
·6··
...........
Sodium +
Amyl alcohol
cS
Cydohexanecarboxylic Acid
o
1II!~~'6~~CJ~~~~~ CARBOXYLIC ACID & IT'S DERIVATIVES [26] c
_forSd>clon
c
('
v
Aromatic Electrophilic Substitution Reaction:
Meta substitution products are fonned on halogenation nitration and sulphonation ofbenzoic acid.
J:H 0H
lSJJ F~ )
©L
( ..-...)
····.... ··~Cl
m-Chlorobenzoic acid
~H
0H
.?;H
.'
lS2J
Conc.HN93
30°
©L
{.~.- ....)
.............
m-nitrobenzoic
N0
2
FumingHNOs
140·
Ol~-(~::ft-N02
3,5-Dinitrobenzoic acid
;t;H a1
\
<'
r
lSJJ
Cone. .yS04
A
V
m-Sulphobenzoic acid
S03H
(,
Note : Due to the presence ofa deactivatingm-directing COOH group in benzoic acid, the latter does not give
(
Friedel-Crafts reaction.
(
1.5 TESTS
1. Formation ofFerric salt :
(
A red-brown precipitate is obtained on adding a small amount ofneutral ferric chloride solution
in benzoic acid solution.
2. Esterification:
A sweet odour ofethyl benzoate is perceived on heating.benzoic acid after adding a few drops
ofethyl alcohol and concentrated sulphuric acid.
( 3. Decarboxylation:'
f'
Inflammable vapours ofbenzeneare libemtedouton heating benzoic acid after mixing it thoroughly
'- with soda lime.
1.6 USES
. Benzoic acid is used as follows:
( 1. As a germicide.
( 2. Benzoic acid and its salts are used in the fonn ofmedicines.
'l
3. Sodium benzoate is used as a preservative ofcanned food products.
( 4. Benzoic acid is used in the manufacture ofmany synthetic dyes, like aniline blue dye.
5. Ethyl ester ofbenzoic acid (ethyl benzoate) is used as a flavouring agent
(
'i..
c
(
c
/
'1.._ Ii',!~~~~CL~~~~!
kko/(Q( Sdl'oI.Qn:
CARBOXYLIC ACID & IT'S DERIVATIVES [27J
,
't
EXERCISE -I
Q.l In the reaction sequence :

CH -C=C-H CH3 MgBr) CH + (A) (i)co 2 ) (B)
3 :4 (ii)H20/He
(B)wiIlbe:
(A) CH3-C=C-CH3 (B) C~-C=C-MgBr
(C) CH3-C-=C-COOH (0) C~-CH=CH-COOH
Q.2 Which ofthe following products is fonned when adipic acid is heated
CH2-CH2~ CH -CH-
(A) I ~O (B) I 2 2~C=0
, CH 2 - CH2 CH 2 - CH2
CH2-CH2CO~ CH2 - CH2COOH

(C) I
. CH2 - CH 2CO---
0 (D) I
CH2 CH2COOH
Q.3 In the reaction sequence :

o
CH3 .,....~.-H . IBCN >(A) H 20/H
e
>Product, Product will be:
\
H Ii
OH OH
. I I
(A) CH 3 -?-COOH (B) HOOC-C- CH3
I
H H
OH OH
I I
(C)MixtureofCH3 -C-COOH and HOOC-C-CH3
I I
H H
OH
I
(0) CH3 -CH-CONH2 c
Q.4 Hydrolysis on,l, I-trichloro derivative (A) ofalkane gives a molecule (B) on alkaline hydrolysis which
produces red coloration with aqueous FeCI3. The compound (A) is

(A) CH3CH2CCl3 (B) CH3CCls ' (C) CHCl3 (D) None
,1\.1
.. Q.y/Inthegivenreaction~c,.,> bJ1 . ,'-
VV 3
.~
(ii)H20/H e / Ii
1A.-U1 -
,CH CHO (i) NaCN/HCI ).(A) (Fen;~) (B), (B) will be:
. ~g!\nt1
~ noYl . q-CrY'~
.1",- l<f'J1?'> r'
\.......
(A) Acetic acid (B) Oxalic acid (C) Pyruvic acid (0) Citric acid en. _ c.. ~
,'? '1.
Q.6 Which ofthe following is the best representation ofthe structure ofthe carboxylate ion- c
3+ 3- 8+
o '0 .......,...Q..
(A) R - cq::::: (B)R-<C: (C)R-C~o (0) None ofthese

o o
0- 3- &+ G
!i'~~~!!~ CARBOXYLIC ACID & IT'S DERIVATIVES [28]. c
c
, ,
~
Q.7 In the given reaction:
o
II {i}Br2 /KOH ) C~r3 + [Xl, [Xl will be.:
C('\Hs-C- CH 3
(ii}HtD
(A) Cl#s-CHO (B) C6HsCOOH (C) C6Hs-CH20H (D)C~COOH
: .Q.8 IdentifY Z in the sequence

CH COONH (i) heat ) y H~O(tr"» Z_
3 4 (ii)P20S
(A) CH3CH1CONH2 (B) CH3CN (C) CH3COOH (D) (CH3CO)lO
Q.9 Sodium bicarbocate reacts with salicylic acid to form:

OH ONa ONa
~OONa
(A)C6HsONa (B)lgJ . (C)@-COOH (D)@-COONa
r,
\. Q.IO . Which one ofthe following reacts with Grignard reagent to form an addition product which can be
/" hydrolysed to a carboxylic acid?
\.
W~ ~~ ~~ ~~
,
\.
.Q.II Which ofthe following compounds gives carbondioxidewith Na..QC03?
(
\.
(A) Acetic acid (B) Hexanol (C) Phenol (D) Acetylene
Q .12 A halogen compound' A' on hydrolysis with dilute alkali followed by acidification gives acetic acid. The
" compound A is
( (A)CICH2CH1CI (B)CH3CHCI1 (C)CICH1CHCI1 (D)CH3CCI3
/"
< Q. I ~ I Which ofthe following will not be soluble in sodium bicarbOnate solution?
(
f,././
W 02NO-,,-::::·N02~I
OH
~
6 COOH
~
~I
OH
ON02
~
~I 6 SQJlL-----
C Q.14 When malonic acid is heated, it gives ~

(A) FonniC acid (B) Oxalic acid (C) Acetic anpydride (0) Acetic acid
C
Q.15 Consider the given reaction: L
RCOOAg Br2 /a )R-Br
(
which one ofthe following acid will give maximum yield ofR-Br in the above reaction?
c (A) CH3 - CH -COOH
. I
. (B) CH3-CH2-CH2-COOH
CH 3
CH 3
t
.- t:
(SkCH3 -b COOH (D) All will give same yield
I
CH3
C
If'I.. 1i!~~~A~~ CL~~~~!
IdealforSdlokl,.
r:...
(.
Q.16 The acid D obtained through the following sequence ofreactions is
C H Br Alc.KOH)A~B~C H30·~j)
2 5 CCl4 (excess)
(A) Succinic acid (B) Malonic acid (C) Maleic acid (D) Oxalic acid

CHr CH2-COOH (i)AgN03 ) [X], [X] wiH be:
(ii)Br21 ~
(A) Ethyl bromide (B) Propyl bromide (C) Propyl propanoate (D) All ofthese
Q.18 Acetic acid exists as dimer in C6~due to

(A) Condensation reaction . (B) Hydrogen bonding
(C) Presence ofa carboxyl group (D) Presence ofhydrogen at a-carbon
Q:~J/ Carboxylic acid group can be detected by

(A) Sodium bisulphite test (B) Fehling's solution test
(C) Tollen's reagent (D) With NaHC03
Q.20 The pKavalues ofthe four carboxylic acids are given below. Which ofthe following is the weakest acid?'
(A) 4.38 (B) 2.87 (C) 1.26 (D) 0.64
Q.21 Which ofthe following will undergoes decarbo;XYlation on heating?

(A) Succinic acid (B) Phthalic acid (C) Malonic acid (D) Glutaric acid
Q.22 Which ofthe following is the weakest acid?

(A) Cl3CCOOH (B) Cl2CHCOOH (C) CICH2COOH (D)CH3COOH
Q.23 In which reaction major product is hydrocarbon?

(A) RCOOK Electrolysis) (B) RCOOAg 12/~ )
CH3
(C) CH3-CH3 CI 2 /hv (D) CH
I
-- C -- CI CzHsOH)
) 3
I
CH3
Q.24 Increasing pKa of0, m- and p-nitrobenzoic acid is?
(A) p<m <0 (B) 0 <m <p (C) o<p<m (D)m<p<o
6 COOH
H3, >[Xl. [XI will be:

o
c
(A) 6COBr
(B)6~'
COOH
(C) cj Br
H
(D)
c5
0H
)
~
o
[jJ'~~A~~CL~~~~! CARBOXYLIC ACID & IT'S DERIvATIVES [30] c
liI<ol",,_
t'
V
l'
Q .26 Amongst the acids, .

0) CH == CCOOH (ii) CH2 = CHCOOH and (iii) CH3CH2COOH,
the acid strength follows the sequence
(A)(i) «ii) > (iii) (B)(i) > (ii»(iii) (C)(i)=(ii)=(iii). (D) (i) = (ii»(iii)
CH -COOH (i) Br2/redP) [X] [Xl will be:

3 (ii)NaCN '
(iii)H 20IHE9 / <\
(A)CH3COOH (B) COOH-CH2-CH2-COOH

CHz-CO ~
O (D) CH2/ CO " 0
. (C) bH CO/
2 "CO/'
Q.28 Which ofthe following is a polyprotic acid

t·
(A) Acetic acid (B) Benzoic acid (C) Salicylic acid (D) Oxalic acid
\
Q.29 Arrange these esters in decreasing order ofease ofesterncation with CH30IIfII$ :
(
(I) CH3 -CH-COOH (II) CH3 - CH - CH2 - COOH
\
I I
r CH 3 CH3
CH .
3
I
\.
~
(III) CH3 -C-COOH (IV) (CH3--CH2)3C-C00H
I
( CH3
( (A) II> I> III> IV (B)I> II> Ill>IV (C)III>IV > II> I Q : v > Ill> II> I
Q.30 Which ofthe following acids combines the properties ofan aldehyde and an acid?
(A) Benzoic acid' (B) Acetic acid . (C) Fonnic acid (O) Oxalic acid
C:
. Q.31 Reducing property oftonnic acid is due to the presenceof:
o o
( II II
(A)-OH (B)-C-H (C) -C-OH (D) All ofthese
(
Q.3 2 Formic acid reacts with PCIs to fonn
M_' ...... o~
I' ,~
J-fcAr ~
..
}t..- c; --
~c:::;.
0(
(
(A) Acetyl chloride (B) Methyl chloride cL
-c (C) c::arbon monoxide and hydrogen chloride (D) fonnyl chloride cP.r11.!?..1
C Q.33 Which acid can be oXldised by Fehling solution:

(A) Malonic acid (B) Acetic acid (C) Oxalic acid (D) fonnic acid
t
C
,
{ [31J
'C CARBOXYLIC ACID & IT'S DERIVATIVES
CP~
Q.34 The Hell-Volhard Zelinsky reaction is used for preparing alan
(A) p-Haloacid (B)y-Haloacid
Q.3~J'l-Efuyl pthalimide on hydroiysis gives:

~ (A)Mefuylalcohol (B) Ethyl amine
(C) Acid halide
"(9L c. ~
(C)D~~ylam'
1-;
/'.-0 CIfY/,.,.-tM- /\_~n
roL'
;...r-- <;;
(D)Djefuyl~ine
-~
I-

.z.,rI\.41z.
Q.36 IdentifYZ in the following reaction sequenceCH31 ~X If"i),;J, y ~Z- ---'

E~ ~ RedP
(A) CH3COOH . (6) CH3COC)

I'-"~
(B) CH3MgI (D) CICH2COOH
Q.37 Which one ofthe following reactions can be used for the preparation ofP-hydroxy ester:
(A) Perkin reaction , (B) Refor:matsky reaction
(C)Aldol condensation (D) Claisen condensation\
Q.38 Ethyl alcohol can be obtained in one step from acetic acid by reduction with
(A) Zinc and a<;etic acid (B) Lithium-aluminium hydride
(6) III and red phosphorus (D) Nickel and hydrogen
-----=,
CH /NH2 COOC H
I 2
+ I 2 5
Pyridne .
CH '-...:NH COOC H ) [X], [X] will be .
2 2 2 5 .
H
¥ ~
N~C2Hs
(A) C ,).OC H
s
(B)CN:foI'
r
.~ 2
H
H
. /COOC 2Hs
r-N=C'COO~Hs,
(
N=c...,.cOO~HS CH2
(C) 'COOC2Hs I
NH2
(D) t,2 ...,.cOOC H
s 2
. N=C'COO~Hs
QAO Kolbe's electrolysis ofaqueous potassium ethanoate leads to the formation of
(A) Ethene (B) Methane (C) Ethane (D) Ethyne
QAl Carboxylic acids do not give the characterstic properties of

(A)R-group (B)-COOHgroup . (C»C=Ogroup (D) None is correct
QA2 Which ofthe following can be detected by carbylamine reaction:

(A) Urea (B) CH3CO~ (C) C2H5~ (D) All ofabove c
QA3 In the molecule CH3CHCI- CH2COOH; Cl atom is attached to
(A) a- Carbon atom (B) (3-Carbon atom (C) y-Carbon atom (D) ro-Carbon atom
()
c
~!~~~A~~~~~~~! CARBOXYLIC ACID & IT'S DERIVATIVES [32]
IdIDlforSdw/Dn
(;
C'
Q.44 Hydrolysis ofalkyl isocyanide yields:
(A) Primmy amine (B) Tert. amine (C)Alcohol (D) Aldehyde
·Q.45 Which ofthe following test is not carned out to examin the presence of-COOH groups
(A) Litmus test (B) Sodium bicarbonate test
(C) Ester test (D) Bromine water test
Q.46 Which ofthe following compound gives the smell ofmustard oil:
(A) Alkyl isocyanate (B) Alkyl isothioCyanate
(C)AIkyJ isocyanide (D)AlkyI isonitrile
Q.411 (CH3hC = CHCOCH3 can be oxidised to (CH3hC::' CHCOOH by - .

vV (A) Chromic acid (B) NaOI . (C) Cu at 300°C (D) KMn04
Select the compound which does not give acetic acid on hydrolysis
(A) CH3CCl3 (B) CH3CN . (C) CH3COCI (D) CH3CH2CI
The acid formed when propyl magnesium bromide is treated with CO2 is
(A) CH3CH2COOH (B) C 3H 7COOH
. (C) CH3CH2CH2CH2COOH (D) None
Which ofthe following skeleton gives the strongest acid ifCOOH is attached to the free valency
C
I
(A) C-C- (B)C-C-C (C)H- (D)C-C
,
" Q.~~ A ( CH3COOH ).B. What is not true for AandB-
,
/
W . red P
HJ
UAlH.,
," (A) A is hydrocarbon ofgeneral formula Cn H2n+2 while B belongs to alkanol
" (B) A can be obtained by reducing CH3CH2Cl while B by its hydrolysis

(C)A is alkene while B is alkanal
(D) A and B both belongs to different homologous series
c .W e product A, B, C and D in the reaction A + B ( Heat H-COOH Heat.)"
H2S0 4
C + D are given by
.
. the set
(A) CO, H 20, CO2, H2 (B) CO2, H 20, CO, H2
(C) CO2, H 2, CO, H20 (D) CO, H 2, CO2, H 20
(
Q.S3 Ozonolysis offatty acid is carried out to ascertain
( (A) Number of-OH group (B) Number of- COOH group
(C) Position ofcarbonyl group (D) Position ofdouble bond
C:
( Q~IY distillation ofcalcium acetate gives
(A)Aceta1dehyde. (B) Acetone (C)Ethane (D) Propane
C
. [33]
t IIJ~~~~~ CARBOXYLIC ACID & IT'S DERIVATIVES .
l
EXERCISE-II
Q.l Acetic acid can be used for the preparation of:

(A) Ethane (B) Methane (C) Acetone (D) ethanol
~
.. fH 3
redP ••
. .2 CH3 - C - COOH + Br2
I L\
) [Product] The product of the above
.
reactIon IS
. CH 3 ,~-.,
(A) f3-Dibromo acid (B) f3,f}' - Dibromo acid

(C) f3.f3' ,13"-Tribromo acid (D) No reaction takes place
Q.3 Consider the following reaction:

o
II He,,,0
CH3 -C-OH+CH3 -OH "" CH3 -C-O-CH3 +HOH
True about the above reaction is:
(A) Product is having smell like fruits
(B) Nucleophilic addition followed by elimination reaction
\
(C) follows AAC mechanism·
(D) it is irriversible reaction (
\.
Q.4 INZ reaction is specific for

(A) Replacementoff3 - hydrogen (B) Replacement of a - hydrogen
(C) Replacement of 13 - carbons (D) Replacement ofa - carbons
Q.5 Which one ofthe following compounds will give HVZ reaction?
H
XH
~COOH
(A)l0 8
(B)
CH3
(C) )-COOH (D) ljJ
1.6/ / Acetic anhydride is used as:
VV ~~vent 'YB5Dehydrating agent
()
~Acetylatingagent . (D) Antiseptic
Q.7 Arrange the following compounds in decreasing order ofacidity

CICH2CH2CH2COOH CH3CHCICH2COOH CH3 CH2CHCICOOH
I l l ' ill ( ,
G
(A) I > II > III (B) III > II> I (C) I > ill > II (D) III > I > II
c
8 Which compound will liberate CO2 from NaHC03solution:
(A) CH3CO NH2 (B) CH3~ (C) (C~)4WOH- (D) CH3N+H3Cr
Q.9 Arrange OHCH2COOH (I), HOCH2CH2COOH (II) and CH3COOH (ill) in order ofacidity - e
(A) I > II > III(B) III > II > I (C) I > III > II (D) II > III > I
G
C·
~~~'1~~~~~~~! kkclfc+-Schoklrs
C)
Q.IO Hofinann Bromamide degradation is given by:
(A) Imide (B) Acid chloride (C)Acidanhydride (D)Amide
Q.ll The rate ofesterfication ofHCOOH (1), CH3COOH (II), (CH3)zCHCOOH (Ill) and (CH3)3CCOOH
(IV) with ethanol follows in the order
(A) IV> III> II > I (B) I> II> 1lI> IV (C) II> I> IV > III (D) 1lI> IV > I > II
o
W II
CH 3 -C-O-CH2 -CH3
H3H I
........
a:, Ethanoic acid + Ethanol
Isotopic oxygen ofwater will be present with

(A) Ethanoic acid
(B) Ethanol
(C) After some time it will alsO' be present in soine molecules ofester
(D) None ofthese
-Q.13 In the electrolysis ofthe aqueous solution ofCH3CH2COONa, anion goes to anode the possibility
offormation offollowing compounds takes place
( (A) CH3 CH2 - tH2 - CH3 (B) CH2 = CH2,.CH3 - CH3
(C) CH3CH2COOC2H s (D) All the above
/
Q.14 Which ofthe following organic acid decolourises bromine water as well as forms anhydride
(A) HOOC - COOH (B) HOOC CH2 - COOH
H-C-COOH H-fl-cOOH
(C) H-~ COOH (D) HOOc-J-H
Q.15 The general formula ofdicarboxylic acid is

( (A) (COOHh (B) (CH2)n(COOHh
(C) (CH2)n-2 (COOHh . (D) (CH2)n-1 (COOHh
.~ The product A, Band C in the reaction sequence

~ (H-C-O)
II
Ca A NaOH) B Heat) Care - v
c
~~
2 . 360"C
o
c (A) HCHO, HCOONa, CH30H .
(C) HCHO, HCOONa, (COONa)2
"- (B) HCHO, Na]C03,NaHC03
(D) HCHO, HCOONa, Na2C03
(
~--' c..
Pi -.
q.l'} CH2COOH NaN0 2 IHCI ) CH COOH
2 II
( t/J I I
y C1 -- L
X
C
'-. glycine glycollic acid
( Here X and Y respectively are
(A) OR, NH2 (B) NH2• OH (C) Cl, OH (D) None
c Q.18 The carboxylic acid that does not undergo HVZ reaction is
(A) CH3COOH (B) (CH3hcHCOOH
(C) CH3CH2CH2CH2COOH (D) (CH3)3C COOH
c
c IIJ~~~~A~~CL~!! CARBOXYLIC ACID & IT'S DERIVATIVES [35]
(. -""-"
c
(,
,-.
(? Ih--~ ~ .
"I A"A _ ? . ? ~c.-:;:::ft-OX
IM/(,," -'> ~
&,p/ C'7 .
Q.19 The end pr~ct 'c' in the following sequence ofchemical reactions is
CH COOH . CaC03 ) A heat) B N~OH) C
3
(A)Acetaldehyde oxime (B) Fonnaldehyde oxime
(C)Methylni1rate (D)Acetoxime
Q.20 Which ofthe foHo..V:u'1g ca.-OOxylic acids uildergoes decarboxylation easiiy?

·CJI (A) C6Hs-CC}-CH2--COOH . (B) C 6Hs-CO--COOH
(C) CSH5 rH COOH (D) CaHs-yH-COOH
OH NH
2
Q .21 CH CH COOH ~ a A1c.KO~) b

3 2 redP
The compound b is
(A) CH3CH20H (B) CH3CH2COCl (C) CH2=CHCOOH (D) CH3--CHCI--cOOH
Q.22 A compound undergoes the following sequence ofreactions :

Hydrolysis Cig/P NH,;
C 3HSN ) C3~02 ) C 3H s 0 2 Cl ) C 3H 7N0 2
(a) (b) (c)
The compound C is
(A) I-Nitropropane (B) 2-Nitropropane
(C) 2-Aminopropanoic acid (D) 2-Hydroxypropanamide
Q.23 R - CH2 - CH20H can be converted into RCH2 CH2COOH. The correct sequence ofreagent is
(A) .PBr3' KCN, IF (B) PBr3' KCN, H2
(C) KCN, IF (D)HCN, PBr3' IF /
\, -"
~ a set ofthe given reactions, acetic, acid yields a product C

CH COOH + PCI -) A 9-10) B C2HsMgBr) C Product C would be
3 5 Anhy.AlCl
a Ether .
(A) CH3CH(OH)C2H s . (B) CH3COCoHs

(~
C2HS '--./
I ~
(C) CH CH(OH)C H6 s (D) CHiC-{OH)C6HS Jr~_
1/ 3 t.>,u. 'If)
~ _C
I
Q5"..!" the given reaction final compound (C) is Co J ~ ~ ..~l~

~ C02Et mNaOHlA ) (A) -4 (B) (C) .;,.. ~~
~'f
NaoH)
VV (ii)H30 + 0 .--C-A.-(f
(~
o¥o
<:>
.OH '
(A)~ (B)·)yy (C) )yy (D) J ('
\../
'""
~-t.t-~ -"
OHO
° c)
~
Q.26 Methyl malonic acid on heating to 160°C yields
(A) Fonnic acid (B) Propanoic acid (C) CO + CO2
(D) Acetic acid C:
Q.27 Which ofthe following has the highest PKa value?
(A) l? (B) ~~H (C) Nfv1eai

o
(D)~H G
~H ~~H
(~
[j]'~~~A~~CM~~! CARBOXYLIC ACID & IT'S DERIVATIVES [36]
-,""
c.;
c
EXERCISE-III
SECTION - fA)
Q.l End product ofthe following reaction is- [AlEEE-2002}

CH CH COOH ~ Alcoholic KOH.
3 2 redP
(A) CH 3yHCOOH (B) CH 2CH2COOH

I .
(C) CH2=CHCOOH (D) CH2-CH-COOH
I I
OH OH CI OH
Q.2 In the anion HCQO-the fwo carbon-oxygen bonds are found to be ofequal length. What is the reason for
it? (AlEEE-2003]
(A) The anion HCDO- has two resonating structures
(B) The anion is obtained by removal ofa proton from the acid molecule
(C) Electronic orbitals ofcarbon atom are hybridised
. \ .
(D) The C=O bond is weaker than the C-O bond
C
Q.3 Which one ofthe following does not have sp2 hybridized carbon 1 [AlEEE-2004]
/"
~ (A) Acetone (B) Acetic acid (C)Acetonitrile (D) Acetamide

I"
~
I
'. Consider the acidity ofthe carboxylic acids : [AlEEE-2004)
(

(a)PhCOOH (b) 0 - N02C6H4COOH

" (c) p - N02C6H4COOH (d) m - N02C6H4COOH
Which ofthe following order is correct 1
r
(A)a>b>c>d (B)b>d>c>a (C)b>d>a>c ~d>a
\.
Q. 5/The compound formed as a result ofoxidation ofethyl benzene by KMnO4 is - [AlEEE-2007]
(
\.
vV' (A) benzophenon~ (B) acetophenone (C) benzoic acid (D) benzyl alcohol.
(
» A liquid was mixed with ethanol and a drop ofconcentrated RaSO4 was added. A compound with a
fruity smell was formed. The liquid was : [AIEEE-2009]
(A) CH30H (B) HCHO (C) CH3COCH3 (D) CH3COOH
/'.
'-.
c
W A compound with molecular mass.I80 is acylated with CHFOCI to get a compound with:molecular
mass 390. The number ofamino groups present per molecule ofthe former compound is:
(A) 5 P ~- f . . d (B) 4 (C) 6 (D) 2 [JEE Main - 2013]
c ~ I~ 1.0 c...:......,., $/<'? .
c ~. The gas leaked from a storage tank ofthe Union Carbide plant in Bhopal gas tragedy was:
(A)Methylamine . (B)Amn:ionia [JEE Main - 2013]
(
'<.
(¢ Phosgene (D) Methylisocyanate
c Q J/f/An
(
organic compound Aupon reacting with NIl, gives B. On beating B give C, C in presence ofKOH
reacts with Br2to give CH3CRaN:H2. A is . .
( (A) CH3 CRaCH2COOH (B) CH:r-CH--COOH [JEE Main - 2013]
.I
t\:~ CHl
C Il/"b (C) CH3CRaCOOH (D)CH3COOH
( [I!~~~~CL~~'~'
_""s,_
"t
(. . "
(
SECTION - (B)
Q.I0 Acetamide is treated separately with the following reagents. Which one ofthese would give methyl
amine? [JEE 1983]
(A)PCIs (B) NaOH + Br2 (C)SodaJime (D) Hotconc. ~804
Q.ll Hydrogenation ofbenzoyl chloride in the presence ofPd and BaS04 gives [JEE 1992]
(A) benzyl alcohol (B) benzaldehyde (C) benzoic acid (D) phenol
Q.12 Which ofthe following carboxylic acids undergo deciutoxylation easily: [liT 1995]
(A) C6HsCO-C~COOH (B) C 6H sCOCOOH
(C) C 6H s CH2 -COOH (D) C 6 H s CH2 -COOH
I I
OH NH2
Q.13 The molecular weight ofbew..oic acid in benzene as determined by depression in freezing point method
corresponds to : HIT 1996]
(A) Ionization ofbenzoic acid (B) Dimerisation ofbenzoic acid
(C) Trimerisation ofbenzoic acid (D) Solvation ofbenzoic acid
- (
Q.14· When propionic acid is treated with aqueous NaHC03, CO2 is liberated. The 'C' ofCO2 comes from
(A) Methyl group (B) Carboxylic acid group
(C) methylene group (D) bicarbonate [lIT 1999]
Q .15 Benzoyl chloride is prepared from benzoic acid by: [I1T2000]

(A) CIz, hv (B) S02CIz . (C) SOCIz (D)CI2, ~O
Q.16 Which ofthe following acids has the smallest dissociation constant? [IIT2002]
(A) CH3CHFCOOH (B) FC~C~COOH
(C) BrC~C~COOH (D) CH3CHBrCOOH t
Q.17 An enantiomerically pure acid is treated with racemic mixture ofan~holhaving onechiral carbon. TIle
esterfo~edwil~be . It -+ @> ~ ~s o;c.o;P~"c,.~E2003]
(A) Optically active mixture tZl'S (B) Pure enan~mer - ~
(C) Meso compound . (D) Racemic mixture
~J
Q.18 When Benzamid is treated with POCl3, the product is: [liT 2004]
(A) Benzonitrile (B)Aniline (C) Chlorobenzene (D) BenzyIamine
(~
Q.19 When benzene sulphonic acid and p-nitrophenol are treated with NaHC03,the gases released
respectively, are .. [JEE 2006]
(A) 802' N02 (B) 802' NO (C) S02' CO2 (D) CO2, CO2
Q.20 The correct IUPAC name ofC6H sCOCI is

(A)Benzoyl chloride (B) J;3enzene chloro ketone
c
(C) Benzene carbonyl chloride (D) Chloro phenyl ketone [lIT 2006]
()
C'--'
[j!~~~A~CM~~!
/d.",,,,,S<hcI.,,
(../
(..,
C
D
.sr
, Q Which of!befullowingrea;:tants on.....:tion wi1hcone. NaOH fullowed by acidification gives !befullowing
lactone as the only product? [liT 2006]
'.
o
II
(Y)
V t - C H2
, '? ..-~
COOCH3 . ~P-~CCCOOH
" (B)
( (A)O::COOH # CHO
CHO COOH
C(
('
\
(C)CC (0) I '
CHO # COOH
( d~22 In the following reaction sequence, the correctstructures ofE. F .arid G are [JEE2008]
<~ 00
1
Ph~OH Heat) [E] u_:"n) [F] + [G]
,
\. (* implies I3C labelled carbon)
r o o
" (A)E=p~CH F=. hAeN~ G=CHI3
r 3 P 0 a
\.
o
r
(B)E=PhA
° * F- Ae e G =CHI3
" CH3 Ph. ONa
( o
(C)E=PhA
°* CH3 F=PhA8N~ *
G= CHI)
(
o o
(D)E Ph)~*CH, F- AeONae . *
G= CH)I
r Ph
". r\
Q~ IdentifY the binary mixture(s) that can be separated into individual compounds, by differential
extraction, as shown in the given scheme. [liT 2012]
C NaOH (aq) .1 Compound! 1+rcompound 21
Binary mixture containing I
( Compound 1 and Compound2
(
NaHCO,(aq) I ~~~~t'~~nu I I
+ Compound 21
(A) C6H sOH and C 6H sCOOH (B) C6H sCOOH and C 6H sCH20H
( (C) C 6H sCH20H and C 6H sOH . (D) C6HsCH20H and C6HsC~COOH .
jf(~~~
(
~., .......,
Lv1~ oJ~
ui;j..~~
.'7 c
('
f1Y\-' X ;:J
c ~~~~
!II!~~~A~~CL~~~~!'9 CARBOXYLIC ACID & IT'S DERIVATIVES [39]
_""S<lwioa
([
'--,
(
~41 IThe major product H ofthe given reaction sequence is : [lIT 2012]
\.1// CH -CT-i - CO -CH
.../ 3 ~'2 3
seN) G 95%H zS04 )
Heat
H
(A) CH3 -CH = C-COOH (B) CH3 -CH=C-CN

I . I
CH3 CH3
OH --.. ~-/
I
(C) CH3 -CH 2 C-COOH (D) CH3 -CH=C-CO-NH2
I I
CH3 CH3
® The compound that undergoes decarboxylation most readily under mild condition is : [lIT 2012]
COOH COOH P. ~~6
~CH2COOH ~O ./
(A) V (B) V
r""
\
COOH , CH2COOH
(C)OCOOH (D)c)o . I'
\..
.' .
\
o
c
c
c
c
f'
V
ANSWER KEY
EXERCISE-I
Q.1 C Q.2 B Q.3 C QA B Q.5 C Q.6 B Q.7 B
,
"
Q.8 C Q.9 B Q.I0 B Q.l1 A Q.12 D Q.13 C Q.14 D
Q.15 B Q.16 A Q.17 A Q.18 B Q.19 D Q.20 A Q.21 C
Q.22 D Q.23 A Q.24 C Q.25 B Q.26 B Q.27 A Q.28 D
, Q.29 A Q.30 C Q.31 B Q.32 C Q.33 D Q.34 D Q.35 B
\
Q.36 D Q.37 B Q.38 B Q.39 B QAO C QAl C QA2 C
QA3 B QA4 A ' QA5 D QA6 B QA7 B QA8 D QA9 B
Q.50 C Q.51 C Q.52 C Q.53 "D Q.54 B
EXERCISE-II
(
" Q.l ABCDQ.2 D

A'
Q.3 AB QA B Q.5 C Q.6 ABC Q.7 B
t· Q.8 D Q.9 Q.lO AD Q.ll B Q.12 AC Q.13D Q.14 C
" Q.15 B Q.16 C Q.17 B Q.18 D Q.19 ]) Q.20 A Q.21 C
( Q.22 C Q.23 A Q.24 D Q.25 D Q.26 B Q.27 A
(
\,
EXERCISE-III
I
\..
Q.l C Q.2 A Q.3 C QA B Q.5 C Q.6 D Q.7 A
(
l. Q.8 D Q.9 C Q.lO B QJl B Q.12 A Q.13 B Q.14 D
( Q.15 C Q.16 C Q.17 A Q.18 A Q.19 D Q.20 C Q.21 C
\.
Q.22 C Q.23 BD Q.24 A Q.25 B
(
C
C
C
(
./.-,-- ..
c
o
,j
,
/
,~ /
CONTENTS
BENZENE..............................................................................Page 01-07
" TOLUENE............................................................................... Page 07-10
,
PHENOL................................................................................ Page 11-18
"\ BENZALDEHyDE................................................................ Page 19-15
NITRO BENZENE............................................................... Page 16-19
ANILINE................................................................................Page 30-36
, SOLVED EXAMPLES........................................................... Page 37-41
\
EXERCISE-I..................................................................... Page 43-46
EXERCISE-II ................................................................... Page 47-51
(
EXERCISE-III.................................................................. .Page 52-58
(
\
ANSWER KEy................................................................... Page 59
(
(
(
,,
(
.(
c
c
JEE MAIN-2014··
(
AROMATIC COMPOUND
(
c
(
t;
C
C
(,
'<..,
(
'l.
c
AROMATIC COMPOUNDS
Benzene
[ij Aromatic compounds contain high percentage ofcarbon. They bum with smoky flame,
[i1l Aromatic compounds have the cyclic system and contain (4n + 2)1t electrons [Huckel rule].
--:--"
Where n = 0, 1,2,3, ............ .
Dipropylcyclopropenium n =0 21t-electron ,-,

perChlorate
Benzene, pyridine, pyrrole, n == I 61t-electron / -,
Furan, thiophen etc.

Napthalene n= 2 101t-electron
Anthracene n= 3 141t-electron
r
Aromatic Compounds: Main Source

Bituminous coal when subjected to destructive distillation in the absence ofair [1 00OO-1200°C] the ~
chief constituent obtained is coal tar.
Fractional distillation ofcoal tar: Different fractions are :'
Fraction Temperature . Main constituents

(
(a) Light oil 80 - 170°C Benzene, toluene, xylene etc.

(b) Middle oil 1700 -230°C Naphthalene,
.(carbolic oil) Phenol etc. r
(c) Heavy oil 230° 2700C Cresols, naphthalene " /
('
(d) Green oil 2700-360°C Anthracene \~
(-~
\.j
Benzene
. [i] Discoverer: Michael Faraday [ii] C-hybridisation : sp2

r
o
[iii] Geometry- Hexagonal [iv] Bond angle: 1200
[v] G-C Bond length: 1.39A [vi] C-HBond length: 1.09 A c
Metbods ofPreparation ofBenzene : c
[1]
[2]
Isolation From 'Ligbt Oil Fraction - Industrial method:
Decarboxylation ofSodium Benzoate- Laboratory Metbod :
c
Benzene is formed on dty distillation ofsodium benzoate with soda lime.
c
C H COONa + NaOH C H + Na CO
65.
Dry distillation)
. 66 . 23 c
[3] + Zn
Reduction ofPbenol •• C6H 5OIt Dry distillation) C H + Zno
Hydrolysis ofBenzene sulpbonicAcid: C6H5S03H + H 20 (steam)

6 6
C6~ + H 2S04
c
[4]
[5] Reduction ofBenzenediazonium Cbloride :
c
C6H5N 2Cl + C2H 50H .) C6H 6 + CH3CHO + N2 + HCI
. Hypophoshorus acid (H3P02) or sodium stannite (SnCI2 + NaOH) or formic acid can also be used for
e
reduction in place ofethanol.
G
C6H5N 2CI + H3P02 + H 20 ) C6H6 + H3P03 + N2 + HCl
C
[iJ~~~~ AROMATIC COMPOUND [2J
C
C'
C
C 6H SN2CI + 2H . ~:~~) C6H6 + N2 + HCI
C 6H SN2CI + HCOOH ) C6H6 + CO 2 + N2 + HCl
[6] Hydrolysis ofPhenylmagnesium bromide:
C 6H SMgBr + H 20 ) C6H6 + Mg(OH)Br
(7] Reduction ofChIorobenzene :

C 6H sCI + NaOH + 2H Nil AI > C 6H 6 + NaCI + H 20
,.
,
[8] Trimerisation ofAcetylene:
I .
3C2H 2 Ni(CO)4+{CSHSh P ) C6H6

In benzene
[9] Hydroforming ofn-Hexane:
CH3(CH2)4 CH3 Heavy metal oxides ) C6l-J- + 4H2

(' 500. ~"'6
'.
I
"- PhysicalProperties ..:
(
Benzene is a colourless liquid (boiling point, 80<», having a characteristic smell. It fonus a colourless
crystaline solid (melting point, 5.4°) on cooling. It bums with smoky or sooty flame. It is lighter than
( water (relative density, 0.8790) and is immiscible with water. Being nonpolar in nature. It is miscible with
'..
many organic solvents, like alcohol ether, acetone, acetic acid, carbon tetrachloride, carbon disulphide,
/
\ etc.
, Reaction:
" Benzene is a compound having very low reactivity, because it remains unaffected by many common
reagents, like HCI, KOH, NaOH, KMn0 4, K 2Cr 20 7, etc.
(
Benzene shows the following types ofreactions :
,
'(
[a] Addition·
[b] Electrophilic substitution
(
' [c] Oxidation
c Addition Reaction:
1. Halogenation:
c
..~
H
( c CI CI
OI+3CI2~~ ~I
(
(
~ H H
Benzene H CI
Benzene hexachloride
Benzene hexachloride is aJso known by many other names e.g., B.H.C., gammaxene, gammane,
t lindane 666 (triple six) and 1,2,3,4,5,6-hexachlorocyclohexane.lt was found that the 'Y isomer is a
very strong insecticide and pesticide, hence the names gammaxene and gammane.
t
Ij!,!~~~~c,,/~~~!! AROMATICCOMWOUND [3)
Ideal forS<holors
c
2.. Hydrogenation
0,
' I 3H2
Nilpt/Pd)
0 ,
Cyclohexane
Benzene
3. Ozonolysis :
~
, I + 303
Benzene
-----7
9H=O
3 CH=O + 3H20 2 '

Glyoxal
;"
3H20 2 + 3Zn ,-----7 3ZnO + 3H20
Electrophilic Substitution:
A continuous 1t cloud is spread above and below the benzene ring. Due to this, an electrophile is attracted
towards the benzene ring. This electrophile removes proton (the weaker electrophile) and take its place
in order to gain greater stability and fonns an electrophilic snbStitution product or SE product. This
'I
process is called aromatic electrophilic substitution.
0
,
+~
'Stronger---7
Benzene eleetrophile ,
6,
Substitued, benzene
(SE product)
+~
Weaker
eleclrophile
Nonaromatic intennediate carbocation formed in an aromatic electrophilic substitution reaction is known

'as Wheland intermediate.
'"
H
Mechanism ofAromatic SE reaction: "
',
/',
I: '
\ -'
H*"H + E+
Slow
.. 'HX;t!H
H
I '
~ H
H·
H
H
H
Cyclic Secondary carbocation
r'
~'
Cyclic secondary carboncation fonned is established by reSonance.
Xpt
~
:9(
H ,+H 'H' H H± H
0
1r! .. ~, I~ 'I -, ' ~ 'I
H ~'H H +'H H ~ H ( ,
'--'
H H H
0
HY,4H
H¥H H '
-H" • 6 c
e
This is called as SE2 mechanism i.e.; substitution electrophilic bimolecular reaction.
G
/',
\.....,.
li~~~!~ CL~~~! AROMATIC COMPOUND /4J
kleol""Schel."
C
C
C
4. Nitration:
© <6~' ©>6~'
,"-',
••
;62
~o2
~ ISo
1"-',
I" 2
,--" .
I"
\ ..J
~2
Fumm9H~0.
~
-H ' b -H 02 100" 02N' ....., 'N02
Nitro enzene m-Dinitrobei1zene -t! 1,2.3-Trinitrobenzene (TNB)
5. Haiogenation :
CI-CI + AICI3 ---7 ~, + CI-~'CI3

Chloronium ion '
@ @
C6HS-H + CI---7 C6Hs-C1 +H
f . Electrophlle Chlorobenzene
"
6. Snlphonation :
H2SO. ( ) S03 + ~O
(Cone.)
_6.,
(
H 0.e + f-fB
(
'-
:
l"~........ l
~
+ S03 -----".
8(¥--7
6
,.........,
.
:'~
\ ........l ~
Benzenesulphonic add
(
" 7. Friedel-Crafts Reaction:
(
Friedel-Crafts reaction involves replacement ofhydrogen atom ofan aromatic ring by a carbocation
(
species obtained from a compound in the presence ofanhydrous aluminium chloride. Fridel-Crafts
reaction is always carried out in nitrobenzene (boiling point 211 ~ medium and in the presence ofanhydrous
, AICI3,
\
( [iJ Friedel-Crafts Alkylation:

Anhyd AICIa
( C6'i> + CHj -- CI- ~CeH5 - CH;, + HCI
" Methyl chloride Toluene
f
",-.
C6He +~Hs -Cf Anhyd AICIa )C6Hs --~H5+HCI
Ethylbenzene
C6He + C~CH2CH2 -- CI Anhyd A1CIa ) C6HS - CH(CH;, }2+ C6He -- CH2CH2C~

'c' n-Propyl chloride Cumene (67%) n-Propylbenzene (33%)
(
. Note : A mixture ofcumene and n-propylbenzene is also obtained on taking propylene in,place ofn-propyl
C chloride in the above reaction, because intermediate 10 carbocation rearrange to give 2° carbocation
, Anhyd, H H'
2C6~ + CH2CI2 AICh) C6 ? -- CH2 -- C6 5 + 2HCI
. Dlphenylmethane
c
3C 6H 6 +CHCI 3
Anhyd
A10's) (C6Hs h CH +3HCI

Triphenylmethane
( [ii] Friedel-CraftsAcylation: (reaction with acyl chloride)
(:
(
(
\., Ii!~~,,~~C~~~~!
Id«JJ forSthoIors
AROMATIC COMPOUND [5)
c
fa] Acetylation:
C6H6 + CICOCH3 Anhyd.AICI:; ) CaHsCOC~ + HCI
Acetyl chloride Acetophenone
C6H6 + (C~COhO Anhyd.AlCI:; ) CaHsCOC~ + CH3COOH

Acetic anhydride Acetophenone
[b] Benzoylation:
C6H6 + CICOCaHs AnhydAICI:; ) CaHsCOCaHS + HCI __-,-"..
Benzoyl chloride benzophenone

/,- "
2CaHa + CICOCI Anhyd.AlCb ) CaHsCOCaHs + 2HCl
Benzene Phosgene Benzophenone
(Excess)
The above conversions can be carried out by taking many other compounds in place ofanhydrous
AICI3, e.g., FeCI3, FeBr3, SnCI2, ZnCI2, BF3, etc.
8. Mercuration : ..:
.r~,
Benzene on heating with mercuric acetateforms Acetoxymercuribenzene.

CH3CO~
Hg + H-CsHs - 7 CH3COOH + (.
CHacoo/ CH3 COOH9--CsHs
Phanylmen:urfe acetate
(AeBtoxymereuribenzeno)
Oxidation:
9. Catalytic Air Oxidation :
Oxidation ofbenzene by air in the presence ofvanadium pentaoxide can be carried outas follows:
Ii] At 3000 - Phenol is obtained as the major product
gA
H
A+IO]
~
V20S)
31)00 ",r·
Phenol
Iii] At 450 -'Maleic anhydride is obtained

0
as the major product {"
\..~./
0,9,01 ~. Q.2CO,.2H,0 £'\

\.../
r---,
Maleic anhydride "--"
10. Silver Oxide Oxidation: , ;t'
'-..--'
...,
Mainlyp-benzoquinone is formed when oxidation ofbenzene is carried out by silver oxide and lIN03
0+ 3[0]
A.Q-z.0
HNOa ¢ .~o r '
\...-.../
C
p-Benzoquinone
C
11. Combustion:
2CaHa +1502 ~ 12C02 +6H20 e
C
C'
'-'"
[I!~~~A~~ CL~~!~! AROMATIC COMPOUND {6J
f "
Ideo' for SebolDrt
' .... /
C
C
Catalytic Pyrolysis:
When the vapours of benzene are passed through red-hot copper or iron tube at 600 0 biphenyl is
fonned.
C6HS-H + H-C6HS ) C6HS-C6HS + H2
Uses of Benzene:
[1] As an industrial solvent. [2] In dry cleaning.
[3] As a constituent ofpower alcohol. [4] In the manufacture ofan insecticide and pesticide.
[5] In the manufacture ofan explosive. [6] In the manufacture ofdyes.
[7] In the manufacture ofmedicines. [8) In the manufacture ofperfumes.
[9] In the synthesis ofmany aromatic compounds. [10] As a fuel.
(
TOLUENE
Toluene. C6HSCH3
(~
\.. INTRODUCTION
/
~c
(
CH3-@
" (a) When a methyl group is directly attached with benzene ring, the compound is called Toluene.
,
(
(b) Toluene is a higher homologue of benzene.

(c) "It can be obtained by the light oil obtained from distillation of 'Coal-tar'.
(d) Toluene is the compound, which is more reactive than ben:zene in chemical reactions.
"'.
Methods ofPreparation
(
L "From 'LightOiP Fraction-Industrial Method :
'"
c Toluene fraction can be co Ilected by distillation at 1100 after separation ofbenzene from 90% benzol.
2. By Hydroforming ofn-Heptane:
~H3
CH3(CH 2)sCH3
HeavY metal
o:n~s )to +4H2
c 3. By Dehyd roxylation of Cresols :

{
\,
CH3 C6 H4 - OH +Zn Dry distillatiOn) CH -C H S+ ZnO
3 6
Cresol (0, m or p)
c 4. By Friedel-Crafts Methylation of Benzene :
( C6H,H + CI-CH3- ~ C6Hs-CH3 + H-CI

5. From Wnrtz-Fitting reaction :
A mixture of aryl & alkyl halide reacts in ether solution with sodium and forms toluene.
c
(
'I.. 1I1'~~~A~CL'A~!~!
fIJuIl (or Scholars
AROMATIC COMPOUND (71
(
"-~
(.
Q---t
f ' S r + 2Na + Sr t CH3 anhy.ehter D
) ~CH3 + 2Na Sr
bromo benzene bromo methane
6, By Decarboxylation ofToluicAcids:
, -
, CaO
CH 3 - C6H4 ~COONa +NaOH Dry distillation ) CHr C 6HS + Na2C03
Sodium toluate
(o,morp)
7 F.'om Grignardts reagent :

Phenyl magnesium iodide reacts with pure methyl iodide and forms toluene.
O-+M9I+I~C~3 ~ <O)-CH3+ Mg 12
r'
'-. ,,'
8. By Hydrolysis ofToluene Sulphonic Acids:

A
CH3 - C6H4 - S03H + HOH Cone. acid) CHT C 6H S + H 2S04
Toluene sulphonic acids
(o, m or p)
9. By Reduction ofBenzyl Chloride:
C6H s-CH2CI + 2H--7C6Hs-CH3 + HCI
f'
" ,
10. By Reduction ofToluenediazonium Chlorides :

"
( ,
"
CH3 -C6H4 -N2CI+2H --7 C6Hs-CH3 +,N2 + HCI

Toluenediazonium chlorides
c
(0, m or p)
Ethanol, hypophoshorous acid (H3P02)' sodium stannite (SnCI2 + NaOH) or formic acid can be used
as the reducing agents.
"
Toluene is a colourless liquid (boiling point 111°). It has benzene-like smell. It is lighter than water and (
',~
,immiscible with water. It is miscible with organic solvents, like a1coho~ ether, benzene, etc. It also bums
like benzene with smoky and sooty flame.
Chemical Propertes : ('. _/
Toluene mainly gives four type of reactions ;

1. Addition rea;;tions C 'j
2.
3.
Ring substitution reactions
Side chain substitution reaction
e
4. Oxidation reactions c
[I AROMATIC COMPOUND /8/ C
"
f
v
(;
C
Addition reaction (Reactions Due to Benzene Nucleus):
1. Catalytic Hydrogenation:
Ni/pt )
o-CH,+3H2 l\
O C H3
Melhylecydohexane
.Q
:.
2. Sulphonation :
6'·:
O,OH
: ~
w.........../
Cone.
H2S04 )
+
. .
.............#
0-Toluene sulphonic
acid S020H
p·Toluene sulphonic
acid
(
3.
.. .
Nitration:
.
& ~
' '
V
,
~
:~
(
©,........ .
"
HzS04
HNOa
)
••••
:'''~
.......-##
o-Nitrotoluene
NO.
+ ;:"" ..~
p-Nitrotoluene
....... _......
NO,
HzS04
HNOa
) I
••••
NO,
2.4-Dinitrotoluene
"
"..........: ,
NO. HzS04
HNOa
O,N ••••
{ .~
......- /
NO.
NO.
2.4.6-Trinitro toluene (TNT)
4. Alkylation:
(
,
,
I
'6·:_
.. ..
' .............
FeBr3)
A
~
••••
;'1
•••••••
CH,
+
o-Xylene
f
.,
f
"
5. Free Radical NucJearAdditive. Chlorination:
/ C 6H sCH.3 + 3C12 ~ CsHsCH3CIs

~ . ' Toluene hexachloride
6. Nuclear Electrophilic Substitutive Chlorination:
~
'
A
6 ··~-: . .
( ..... CI
l .. FeBrs
".........' CI2
.........",#
o·Chlorotoluene
+
¥ CI
p'·Chlorotoluene
/
Il... '
Reactions Due to Methyl Side Chain:

( 7. Free Radical Side Chain Substitutive Chlorination: .
( C6H s-CH 3 ~C6HS-C~C' ~ CaHs - CHCI2 1C~O ) CaHs - CCh

1 0 Benzyl chloride 110 Benzal chloride 1 Benzotrichloride
,{'
~
'" ~ {
8. Oxidation:
Benzoic acid is obtained on oxidation oftoluene by alkaline pennanganate or acidified dichromate
(
or dilute nitric acid.
(~.
,C6Hs-CH3 _ 3[0] ) C6H s-C00H + H20
C
(
'- [j'~~~A~CM~~!! ldeo'forSch.klt:
AROMATIC COMPOUND [9]
(
'
c
Ifmore than one side chain is present, then the same number of COOH groups will be formed for
example, phthalic acid is fanned from o-xylene.
H. 00H
CH.
3[0]
-H2 0 r(;C
....
t~·-"".
'••-' eaOH
o-Xylene Phthalic acid
Reaction due to Whole Molecule:

9. Combustion:
C6H,rCH3 + 902 ) 7C02 +4H20
Uses.:
[1] As a constituent ofaviation gasoline.
[2] As a solvent.
, '."
(
[3] .In the manufacutre ofexplosive.

I'
[4] In the manufacture ofdyes. '.
[5] In the manufacture ofmedicines.
" >
[6J In the manufacture ofperfumes.

[7] In the synthesis ofmany aromatic compounds.
(
\ . ~
"
c
(j
(jj)!~~~A\ CL~~~!!
I<I<oIfotSchcJar.r
AROMATIC COMPOUND 110}
c·
PHENOL (C 6H sOH)
Phenol is also known as carbolic acid or Benzenol or hydroxy benzene.
In phenol-OH group is attached to sp2 - hybridised carbon

,~
It was discovered by Runge in the middle oil fraction ofcoaltar distillation and named it carbolic ac id
(carbo coal; oleum = oil)
It is also present in traces in human urine.
Methods of preparation :
/'
"
(
[I} From Benzene sulphouic acid:
When sodium salt ofbenzene sulphonic acid is fused with NaOH phenol is obtained.
\
C6H sS03Na + NaOH -? C6H sOH + N~S03
r',
" [2) From benzene diazonium cbloride :

When benzene diazonium chloride solution is warmed phenol is obtained with evolution ofnitrogen.
( N=N~CI OH
\
(
@ "1' > @+N +HCI 2
"
[3] By distilling a phenolic acid: with sodalime (decarboxylation):
(.
/'
@Y00H
OH
N,OMO >
OH
@Na,Co, +
\, '
.Salicylic acid
(
[4) From Gignard reagent: The grignard reagent on reaction with oxygen and subsequent hydrolysis by
acid yields phenol
HMgBr~C
C6~~ 6HOMgBr
S H2
0
)CHOH+MgBrOH
6 S
(
[5] , From bezene :
(
C
@+[O] SOO"C
0
V2 S ~OOH
)~
,.
(
[6] Industrial preparation ofpbenol : Phenol can be prepared commercially by:

c [a] Middle oil fraction ofcoaltar distiHation [b] Raschig process
< [c] Dow's process Cd] ('umene
c
{ 1I1!~~~A~CL~~!!
Id«>Iw5<hold"
AROMATICCOMTOUND [11)
(
[.
\...
[a] Middle oil fraction ofcoaltar:
Coaltar ~~~~~ J Middle oil (172-230° C)
l (Pheool. cresols, Naphthalene)

Cool '
I
Naphthalene
(Solid crystals seperate out)
1
liquid
!Na6H
CaH.ONa
!CO:IHP
CaH.OH + Na2COa
[b] ,From cumene: (Isopropyl benzene) : Cunnene is oxidised with oxygen in to cumene hydro peroxide
in presence ofa catalyst This is decomposed by dil. H2S04 in to phenol and acetone.
o-OH
r"
CH CH I \ .
3"-CH/ 3 C(CH3)z OH
@ .,.,.'\. '@ '; ." ,@ CH'-g~Hl +

(
\,
/'
[c] Dow process: This process involves alkaline hydrolysis ofchloro benzene
OH ,.
r
C,H,Cl + NaOH ~~, @ + NaCI
2. Physical Properties:
( ,
• Phenol is a colourless, hydroscopic crystalline solid.. \
• It attains pink colour on exposure to air and light
C6H sOH ---'---------- ° < =' )=O--HOCJ-is

Phenoquinone (Pink colour)
()
• ~t is poisonous in nature but acts as antiseptic and disinectant
• Phenol is silghtly soluble in water, readily soluble in organic solvents.
• Solubility ofphenol in water'is much lower than alcohols because of larger hydrcarbon part in the
molecule. r"
'---'
• Due to intermolecular H-Bondfug, phenol has relatively high B.P. than the corresponding hydrocarbons,
aryl halides etc.
3. Chemical properties: Chemical properties ofphenol are classifi ed in the following four categories.
1 Reactions of-H atom of -OH group.
('
2 Reactions of-OH group of phenol. '-'
3 Reactions of Benzene ring.
4
Other Reactions.
{'
"-"
[i!~~~A~~CL~~~~! AROMATIC COMPOUND Ill]
kim' Ie< S<hok>"
c'
1. Reactions of -H atom of -OH group

2. Acidic Nature: Phenol is a weak acid. The acidic nature ofphenol due to formation ofstable phenoxide
ion in solution.
C6HsOH + H2O ~ C6HsO- + H+30
The phenoxide ion is stable due to resonance.
• The negative charge is spread through out the benzene ring which is stabilising factor in the phenoxide '
ion.
• Electron with drawing groups (-N02• -Cl) increase the acidity ofphenol while electron releasing
groups (--CH3 etc.) decrease the acidity ofphenoL
• Phenol is stronger acid than alcohols but weaker than the carboxylic acids and even carbonic acid.
The acidic nature ofphenol is ObselVed in the following:
[i] Phenol changes blue litmus to red.
t' [it1 Highly electron positive metals react with phenoL
\.
2C6HsOH + 2Na ~ 2C6HsONa + H2
[nij Phenol reacts'with strong alkalies to form phenoxides
(' C6HsOH + NaOH ~ C6HsONa + H20
',-
[vi] However phenol does not decompose N~C03 or NaHC03because phenol is weaker acid than carbonic
( acid.
(
C6HsOH + N~C03 or NaHC03 ~ No reaction
\
Reaction due to -OH group:
(
'"
[11 Reaction with PCls : Phenol reacts with PCIs to fDlm chloro benzene. The yield ofchlorobenzene is
poor and mainly triphenyl phosphate is formed.
(
\
C6HsOH + PCIs ~ C6HsCI + POCI3 + HCI
£
, 3C6HsOH + POCl3 ~ (C6Hs)3P04 2HCI
"
I
'
[21 Reaction with Zn dust: When phenol is distilled with zinc dust benzene is obtained.
r C6HsOH + Zn ~ C6H6 + ZnO
"
(~
[3] Reaction with NIl3 : Phenol reactS with NH3 in presence ofanhydrous ZnCl2to form aniline.
( , ZnCI'
C6HsOH + NH3 .2 ) C6HsNH2 + H20
(.
[4] Reaction with FeCl3 : Phenol gives violet colouration with FeC~ solution (netural) due to formation of
(
a complex.
( C6HsOH + FeCl3 ~ Voitet colour
'
* This reaction is used to differentiate phenol from alcohols.
c [5] Acetylation: Phenol reacts with acid chlorides or aci~ anhydrides in alkali solution to fOl1l1 phenyl
c esters.
C6H sOH + CICOCH3 NaOH ~ CaHsOrHa
c
[IJ!~~~A~~CL~~~~!
( ,
,,", AROMATICCOMWOUND [13J
IdtDI ftx 5<hcIon
(.
c
* C6H SOH + CI-C-C6H S 4-C6H SO-CC6H S
. A A
This reaction is called Schotten-Baumann reaction.
(6] Ethel' Formation: Phenol reacts with alkyl halides in alkali soJution to fonn phenyl ethers.
C6H sOH + NaOH ) C6HsONa -~aX I C6HsOR
* C6 HsOH + C~N2 ) C6H sOCH3 + N2t
[7] Reaction w~th P 285 :

5C6 H sOH + P2S S ) 5C6H sSH + P20 S
Reaction ofBenzne Ring: The -OH group is ortho and para directing. It activates the benzene nucleus..
[1] Halogenation: Phenol reacts with bromine in CCl4 to fonn mixture ofo-and p-bromo phenol.
A . OH
~
bBr
l.V + Br2~ ~ +
. *Phenol reacts with bromine water to from a white ppt. of2, 4, 6 tribromo phenol.
" .
OH
d5 + 3Bf2 ~B'~B' + 3HBr ('
[2] Nitration:
f
0
[a]
.Phenol
. reacts
.
with dil.
. HN03 at 5-10 C tofonn o-and p-nitro phenols.
\ /
OH 'OH OH
® cY ~"
'f)jl.n~'O.. ) N02
. . . . .1) ....
(40%)
(10%)
[b] When phenol is treated wtih ·conc. lIN03 in presence ofcone. ~SO4 2,4,6-trinitro phenol (picric
acid) is fonned.
OH
~. c-..HNO,
11,50,)
N02"r~N02
V
OOz
2. 4, 6-1'rinitropbenol
[3] .Sulphonation : Phenol reacts with conc.~SO4 to fonn mixture ofo-and p- hydroxy benzenesulphonic
acid
AsOJi
[iJ!~~~A~~CL~~~~~
d5 ~
AROMATIC COMPOUND
l.V
+
~ [14J
c
. 1d.lforScholQrs.
c
c
c
(4) FriedeI-Craft's reaction :-Phenol when treated with methyl chloride in presence ofanhydrous Alel3
~resol is main product.
~,
OH
& + CHaO ~ 0) H
3
(Main)
OH OB
&; + CH3 COCl

~ 0=\+ ~
0- and p-hydroxy acetophenone .I
[5] Gattermann aldehyde synthesis: When phenol is treated with liquid HCN and HC1 gas in presence
ofanhydrousA1C13 yields mainly p-hydroxy benzaldehyde.
HCI+HCN ~ HN=CHCI
& ~o
OH
~
o ~
I"
" + HN=CHO ~~') -1./11,
=NH
r
\ [6] Reimer-Tiemann reaction: Phenol on refluxing with chloroform and NaOH (aqueous) followed by
acid hydrolysis yields O-hydroxy benzaldehyde. When CCl4 is used salicylic acid is formed.
0H ~ONa
0=
0H
(
0= ° 0'
~CHO
~-r~': V-.:~ ~ COONa~.

/I'
~
CliO
N:JOH )
CHO
/
VooG;Y oNa 0=0H

Salicylaldehyde
"r
-" 0:
N!IOII(oq.) ° CC~
NaO!I
0
-
I!'
.COOH
Salicylic acid
c [7] Kolbe's Schmidt reaction =This involves the reaction ofC6HsONa with CO2 at 140°C followed by
c acid hydrolysis salicylic acid is formed.
o
( .ONa OCOONa OH OH
~ ~COONa ~COOH
c + cO2 1-u)"C ) 0
R<--!F""') ~ . I:~) .~
c Salicylic acid
( [8] Hydrogenation: Phenol when hydrogenated in presence ofNi at 150-200°C forms cyclohexanol.
(
OH
(
o 3~z
OH
+ 1»-:"(>
{'CH,
~L
H2e tH:
~ or
O' OH
'0;('
c
( [j'~~~A~~CL~~~~!
1deoI,.,
S<holors
AROMATIC COMPOUND [15}
c
c
[91 Fries rearrangement reaction:
When phenyl ester is heated in nitrobenzene solution, in the presence ofanhy. AICh then rearrangement
takes pJace in which acyl group is transferred at 0 - & p-positions ofphenolic group. Up to 60°C, para
product is obtained mainly and above 160°C ortho products are obtained as major product.
,..----.
C6H~OH + CH3 COCI C,Hs°COCH3
C6H!>OCOCH3
AICI,
C.Il,NO,
)
60°C
ct
OH
&COCH3
1000 C
[101 Coupling reactio~ :
[a] Phenol cOuples with benzene diazonium chloride in presence ofan alkaline solution to form a dye(p ,
('
hydroxy azobenzene)
N:Cl + (D-OH NaOIl) @=>-N.: N-CQ)- OH

p-hydroxy azobenzene (Orange dye)
/
[b] Phenol couples with phthalic anhydride in presence ofcone. ~SO4 to form a dye (phenolphthalien)
/0" rO~OH O={~~OH , ~
Cj "I~
~:S!?f) .. ill~OH
O""C
I I I I
~1.H~O!i L_.J .
Phenolphthalien (Colourless)
\ /
[111 Condensation witb formaldebyde : Phenol condenses with HCHO (excess) in presence ofNaOH to
form a polymerknown as bakelite.
o. OH
+ HCHO > (oj

~OH
OH
.+ &a-r.
OH
OH
(40%) rI. (200Q

0lymerisation
H~~OH
~~OH
. .
c
c
.
.
Polymer bakelite (PlleJ:lp1 formaldehyde resin)
e
rr '.
v
,( ,
o
1iJ!~~~A~~ CL~~'~f
1<1.."",$(","""
AROMATICCOMWOUND [16)
c
[12] Liberman's nitroso reaction: When phenol is reacted with NaN02 and conc. H2S04 it gives a deep
green or blue colour which changes to red on dilution with water. When made alkaline with NaOH
original green or blue colour is restored.
The reaction is used as a test ofphenol.
2NaN02 + ~S04 ) 2HN02 + N~S04
o OH
[i + H~NO
OH
NO
0
-~0 ~ rTll 1t~I) OrcenpheDol~, Red

YOH
Indophenol
,
i()n~ BlueSod. salt
,
- - ,Quinone mono-oxime (Reel colour)
,
(
113] Reaction with acetone:
~~~
M
( O~ OH
o 0
H ? H ~ Bi$ ~ Pheno)·A
CH3 - C· CHl p-p' isopropylidenediphenol
(
(
[14J Oxidation:
"
d5
./
\.
r'
[1 JIn presence of air: ~4... O=( )=0
\. Benzoquinone (red)
(
OH meso tartaric aciG
( A CH{OH) eaOH
[2) KMn04 : l.,V'-?'1 '
, CH(OH) COOH
(
c Test ofPhenol :
[1 ] Phenol turns blue litmus to red.,
(.
[2] Aqueous solution ofphenol gives a violet colour with a drop offerric chloride.
c [3] Phenol gives Lieber mann's nitroso test. '
(
, conc. H2 SO4 __
PhenoI ill NaN02
MO. _, . . ._ . _ . '
Red CO Iour ' NaOH excess I BIue coIour
(
"
[4] Aqueous solution of phenol gives a white ppt. of2,4,6 tribromophenol with bromine water,
(.
[5] Phenol combines with phthalic anhydride in presence ofconc. ~SO4to form phenolphthalein which
( , givespinkcolourwithalkali.
[6] With ammonia and sodium hypochlorite, phenol gives blue colour.
c fi'~~~A~~ CJA~!~!
/d",t for S<ho/a",
AROMATIC COMPOUND /17J
t
'L.
Differences between phenol and alcohol (C 2Hs0H) :
[I] Phenol is more acidic than aliphatic alcohol due to resonance in phenoxide ion.
[2] Phenol gives violet colour with FeCl3 while aliphatic alcohol does not give.
[3] Phenol gives triphenyl phosphate with PCIs while aliphatic alcohol gives alkyl chloride.
[4] Phenolhas phenolic odour whereas alcohol has pleasent odour.
[5] Phenol on oxidation gives quinone while alcohol gives aldehyde or ketone and acids.
Uses ofPhenol :
Phenol is used :
[1 ] As an antiseptic in soaps and lotions.

[2] In manufacutre ofazodyes, phenolphthalein, picirc acid (explosive), cyclohexanol (Solvent for rubber),
f',
plastic (bakelite) etc.
[3] In manufacture ofdrugs like aspirin salo~ phenacetin etc. I
(. /
[4] As preservation for ink.

Taltl Re.actlol1 Alcohol PhCllol
1 Utmustest No reacUon Blue l1tmus red
2 FeCls solution No reacUon Violet colour ,.
3 Benzene No reacUon Yellow or orange azo I
dlazonlum .salt dye ,~ ~
4 B12 water No reacUon 2.4.6 -trtbromophenoJ
{'"'
"-/
6
C
C
lI!~~~A~~ CM~~~~ AROMATICCOMWOUND [18J
IikoIfodcl>oJ,m
c
"
~"
o
BENZALDEHYDE
Benzaldehyde, C6H sCHO, Oil of bitterAlmonds

Benzaldehyde is present in the fonn ofglucoside .called amygdalin in bitter almonds. One molecule of
amygdalin is composed ofone molecule ofbenzaldehyde, two molecules ofglucose and one cyano
groups bonded to one another. Banzaldehyde is obtained on hydrolysis ofamygdalin by dilute acid or by
an enzyme emulase.
Method ofPreparation
[1 J By Oxidation ofBenzyl Alcohol: Benzaldehyde is obtained on oxidation ofbenzyl aclohol by dilutre
nitric acid
C6Hs CHzOH + [0] DU.HNOa) C6HsCHO +HzO
[2] By Catalytic Dehydrogenation ofBenzylAJcohol: Benzaldehyde is obtained on passing benzyl

(
\ alcohol vapour over copper catalyst or zinc oxide heated to 300°.
C6HsCH20H Cu 3o:x,-z:° » C6HsCHO + Hz
[3] By Alkaline Hydrolysis ofBenzal Chloride: Benzaldehyde is obtained by hydrolysis ofbenzal

chloride, Le., benzylidine chloride using dilute alkali.
(
C6HsCHCI2 + 2KOH ) [C6 H5 CH(OH)21 + 2KCI
' Unstable
,. [C 6HsCH(0H)2] ) C6H SCHO + H 20

\.
(
"-
.
[4) By Ozonolysis ofStyrene : A mixture ofbenzaldehyde and fonnaldehyde is obtained on ozonolysis of
styrene.
(
o
. _ /" 'to __
C CeHsCH-CH2 + 0 3 ) C6 Hs-CH CH 2 Zn) C6HsCH-0 + CHz-O
\ -' /
0-0
Styrene ozonide
(
[5) By Dry Distillation of Calcium Salts ofAcids : Benzaldehyde can be obtained by dry distillation of
( a mixture ofcalcium benzoate and calcium fonnate taken in equimolar ratio.
(C6HsCOO)2Ca + (HCOO)2Ca ) 2C6HsCHO + 2CaC03
( . Barium salts can also be used in place ofcalcium salts ofcarboxylic acids.
(
\...
[6] By Grignard's Reagent: Banzaldehyde is fonned by the reaction ofphenylmagnesium bromide with
( ethyl fonnate :
C6Hs-MgBr + EtO-~-H ) C6Hs-~-H + EtO-MgBr
L
( !i'~~~A\Cc~~~~~
ItkciIf,dcholD"
(
(
[7] By Rosenmund's Reaction: Benzaldehyde is formed by the reduction ofbenzoyl chloride in the
presence ofpalladised barium sulphate.
Pd
C6Hs- W--CI + H2 BaS04 ~ C6HS-W-H + HC!
o o
[8] By Stephen's Reaction: Benzaldehyde is obtained on reduction ofbenzaldimine, which is formed on
reduction ofbenzonitrile (cy;mobenzene) by stannous chloride and cone. HCI in ethereal solution.
. C6H s --C=N + 2H ) CsHs -CH=NH )C6Hs--CH=O

Benzaldimine
(9] By Oxidation ofBenzyl Chloride: Slow oxidation ofbenzyl chloride takes place on passing a stream
ofcarbon dioxide through the aqueous solution ofcopper nitrate or lead nitrate and benzaldehyde is
fonned.
H2<? Cu(NOa>2
C6HsCH2CI CDl) C6HsCH20H orPb(NOa>2 ) C6HsCHO r'··
[10] By Sommelet Reaction ofBenzyl Chloride: Benzyl chloride is refluxed with urotropine in aqueous
alcoholic solution, when a product is fonned. This productis subjected to hydrolysis by steam--distillation
after adding small amount ofan acid, when benzaldehyde is obtained.
C 6H sCH 2CI + (CH2)6N4 ~~ ) {C6HsCH2(CH2)6N4}+ CI- ~ [C 6H sCH 2

N=CH2] )
'- '
C6HsCH=N--CH3(N-Methylbenzaldimine) Di~~;on) C6HsCH=O '
/ '
\.'
[11] By Gattermann AJdehyde Synthesis: Benzaldehyde can also be obtained by heating benzene, HCN
(~
and HCI in the presence ofanhydrous AICI3• \.~ /
C6HSH + [HCN + HCI] ) C6HsCH=NH + HCI

C6HS
CH";NH H2
0
) C6HSCH=O
c
.
Physical Properties
Benzaldehyde is a colourless, volatile oily liquid (boiling point 179°) having characteristic odour ofbitter
almonds. It is miscible with organic liquids, like alcoho~ ether, etc., and immiscible with water. Its solu
bility in water is very low. It is poisonous and volatile in steam.
c
Reaction: Benzaldehyde gives the following two types ofreactions.
[AJ Reactions due to aldehyde group
[B] Reactions due to benzene ring G
[A] NecleophilicAddition on Aldehyde group: . ('
G
Nuck~ophilic addition on -CHO group in benzaldehyde takes place as follows.
Nu Nu
e
0+ 0- I T
C6Hs -'-CH=O + E- Nu ) CsHs -CH- 0- + ~
Oxide Ion
) CsHs - CH - OE
Adduct'
c
/-,
o
(I!~~~~~ CL~~f~f AROMATICCO~OUND [20)
_""5<1>0/0"
c
c
c
.[B) Electrophilic Substitution Reactions Due to Benzene Ring:
Aldehyde group bonded to the benzene ring is deactivating and meta-directing group due to strong
negative mesomeric effect (-M effect). Therefore, the attack ofan electrophile on aromatic ring of
benzaldehyde takes Place at slower rate as{;ompared to unsubstituted benzene. and m- SE substitution
product is formed under strong conditions, i,e., not easily.
[A] Reaction Due to Aldehyde GrouP!

[1] Reduction: Benzyl alcohol is formed on re!lction.ofbenzaldehyde by sodium amalgam + HCI or Zn +
HCI.
('
C6HsCHO + 2H ) C6HsCH20H
r'
[2] Oxidation: Benzoic acid is formed by slow auto-oxidation ofbenzaldehyde in the presence ofair and
light. Other oxidants bring about oxidation very fast.
C6H sCHO + [0] ) C6H sCOOH
(
\
Due to its easy oxidation, benzaldehyde behaves a s reducing agent. However. It is weaker reducing
agentas compared to aJiphatic aldehydes. Itrestores pink colour ofSchiff's reagent, gives white precipitate
turning grey with mercuric chloride solution, and it reduces silver ions ofTolien reagent, i.e., ammoniacal
( silver nitrate solution to metallic silver. But itdoes not give red precipitate ofcuprous oxide with Fehling's
" solution and Benedict's solution due to strong steric ·hindrance ofbenzene ring,
""
I
[3] With Sodium Bisulphite : The reaction ofsodium bisulphite with benzaldehyde gives benzaldehyde
sodium bisulphite adduct, which is a white crystalline solid.
\
C6HsCHO + NaHS03 ) C6HsCH(0H)S03Na
c [4] With Hydrogen Cyanide: Mandelic acid is obtained on hydrolysis ofmandelonitrile i.e., benzaldehyde
/ cyanohydrin, formed bY,addition ofhydrogen cyanide on benzaldehyde.
\
H H H
( I . I. I
C.H,,-C+HCN_ c.H.-C-CN~.CJ-Is-C-COOH
( "
o· I
·OH I
OH
Mandelonitrile Mandelic acid
[5] With Alcohols: An aromatic acetal is obtained on heating a mixture ofbenzaJdehyde and alcohol in the
c presence ofdry HCI gas.
( C6HsCHO + 2HOC2H s Dry HCI gas ) C6HSCH(OC2H~2 + ~O

The above aromatic acetal obtained from benzaldehyde and ethanol is called phenytal.
(
c [6J With Thiols : Aromatic thioacetals are formed by reacting benzaldehyde and thioalcohols in the presence
of dry HCI gas.
c C 6H s CHO + 2HSC2H s · Dry HCI gas) C6 HSCH(SC2HS)2 + ~O
c
[7J With Ammonia : On heating benzaldehyde with ammonia a complexcompound called hydrobenzamide
{ is formed.
f C;HsCH:j;O +'i1;iN+
- - - - I. .
!Hl A
CJJ$CH=N
I
. i
._....._._.
I ~CH-C;Hs
!
~
-3H 0 CH-C
, •.H<
2
C"HsCHtQ.!.!!dNtRJ. C.H~CH=N
C . Hydrobetl1.amide
C fi!~~~A~~~ ES AROMATIC COMPOUND [21J

.(
C~,
c
[8] With Primary Arnines : SchiflI's bases are fonned on heating benzaldehyde with primary amines. The
reaction ofbenzaldehyde and aniline gives a Schiff's base, named benzlideneaniline or benzalaniline of
N-phenylbenzaldimine.
C6Hs-CH=O + H2N -C6H S ~ CsHs - CH =N - CeHs + H 20

benzyiideneaniline
[9] With Hydroxylamin~ : Benzaldoxime is fonned by the reaction ofbenzaldehyde and N~OH.
C6Hs-CH=O + ~N-OH ) CeHs - CH = N - OH + H20

Benzaldoxime
[10] With Hydrazine : Benzladehydehydrazone is fonned by the reaction ofbenaldehyde and NH2NH2.
C6H s-CH=O + ~N-NH2 ) CsHs - CH =N - NH2 + H 20

Benzaldehydehydrazone
/
[11] With Phenylhydrazine : The reaction of benzladehyde and C6HSNHNH2 gives r,

benza!dehydephenylhydrazone.
-)..
C6HsCH=O + ~N-NHC6Hs ) CeHsCH = N-NHCeHs + ~O
bpnzaldehydephenylhydrazone r' ,
"~
[12] With Seinicarbazide: The reaction of benzaldehyde and semicarbazide gives benzaldehyde (
semicarbazone.
/-,
C6Hs-CH=O + ~N-NH-CO-NH2 ) CeHs - CH = N - NH - CO - NH2 + H20 "

Benaldehyde semicarbzaone ,
'-.
[13] With Phosphorus Pentachloride : Benzaldehyde reacts with PCIs to fonn benzal chloride, which is
.also called benzylidene dichloride.
(""
'-
C6H s-CH=O + PCIs ) C 6Hs,-CHCI2 + POCl3
C
· · ·
. '
[14] With Phenol: ./
. . I to
""'''1 f
Hj+'-...._..i
;-oH C
0\.. . .,' C,,_)
./ \ . CH+OJO-oi'
" "...........
t~j H
C
C
,
1~H10
Cone. H2S04
C
,·. . · · . A··.. ..-.'f-OH

..
C
0 \......-..)-CH~._...
,,":.
( ;-oH
0' '
........,-t'••
p.p'-Dihydroxytriphenylmethane
c
The above product is a triphenylmethan dye: e
c
('
v
[i~~~~A~~ CL~~~~!
!deDI,.,. Scholo"
AROMATICCOMWOUND [22J
C
' .
C
C
[15] With N,N-Dimetbylaniline : Ifthe reaction ofbenzIdehyde !Uld N,N-dimethyIaniline is carried out in
the presence ofa few drops ofconc. ~SO4 or anhydrous Znc~, then a green coloured triphenylmetbyl
dye, called Malachite green is obtained.
r-:.-.- ('\....,....... 1,•; .....,eH,

I -H'
I ~ _~.,
""-.CH)
..
(
"'*"..
I
I H.
~ b ""'"
~.... ~: "'
.I ""ClIs
"',,",,--
lIr
COII~. H~041-H'O
/.. .·.
. _
~
ON(CH 3
0
CH,
i :-CH
_'"~-,,/" ~: ...,") /CH~
• f lIr
"" ...........; ""CHJ
Malachite green
(p.p'-Bis-[dimethylamino]triphenylmethane)
[16] Cannizzaro's Reaction: Due to absece ofa hydrogen atom in benzaldehyde, oxidation ofone molecule
to benzoate ion and reduction ofthe second molecule to benzyl alcohol takes place on adding strong
solution ofcaustic alkali at room temperature
,
( 2C6HsCHO + OH- ) C6 HsCOO- + C6 HsCH20H
[17J Tischenko Reaction: When benzaldehyde is heated in the presence ofan aluminium alkoxide (ethoxide,
isopropoxide, etc.) taken in an inert solvent (CCI4, xylene, etc.), benzyl benzoate is formed by bimolecular
\.
addition.
( H H
I AI(ORh t
C,H,C + O=C-C6H5 :> C,;H~-C-O-C-CtH~
1/ I II I
o H 0 H
Benzyl benzoate
[18] Benzoin Condensation: When benzaldehyde is heated with aqueous alcoholic KCN solution, a ketonic
(: secondary alcohol benzoin is formed by bimolecular condensation.
( C6HsCHO + C6.HsCHO H0~C;H 1 C6HsCOCH(OH)C6Hs
. 2 J ,
(
\.. On Oxidation ofbenzoin with conc. nitric acid, the secondary alcohol group is converted to a ketone
group and a diketone, called benzilis formed.
(
.C6HsCOCHOHC6Hs + [0] . Conc. HN03 ) C6HsCOCOC6HS (Benzil) + H20
(
I<..
c [19] Claisen Reaction: An a, p-unsaturated aldehyde (or ketone)is formed on the condensation of
benzaldehyde with an aldehyde (or a ketone) having at least two a hydrogen atoms, in the presence of
( dilute alkali cinnamaldehyde is obtained on thecondeusation ofbenzaldehyde with acetaldehyde.
C6HsCH=0 + ~CH-CHO ) C6HsCH = CH - CHO + H20
Cinnamaldehyde
c
c .{i'~~~~~Ct~~~!!
_fwScho",,,
AROMATIC COMPOUND {23J
l
Benzaiacetone, i.e. benzIideneacetone is obtained on condensation ofbenzaldehyde with acetone.
/
C6HsCH=O + H2CHCOCH3 Oil.alkali) C6HsCH=CHCOCHa + H20

Benzafacetolle
0
[20J· Perkin's Reaction: When benzaldehyde is heated at 180 with an anhydride and the sodium salt ofa
carboxylic acid, then an unsaturated carboxylic acid is fonned. For example, Cinnamic acid is obtained
on the reaction ofacetic aDhydride and sodium acetate on benzaldehyde:
C.H.CH=O + HlCH-CO, CJhCQ~ C"H,CH=CH-CO, HOB :> C;H~CH=CH-COOH + CH.l-COOH

CHJ-~O',o -Hl» CRreO"" CiIUlllJlU~ a~ld
AcclJc ullhydridl! lknzalm':l.1:ic IInh\dride
[21] Knoevenagel Reaction: When benzaldehyde is heated with malonic ester in the presence ofpyridine.
then cinnamic acid is fonned in the following steps. \
/COOEt Pyridine /COOEt 2HOH /CooH A

C"H~CH=O + H~C, -H:<> ]) c.J1~CH=C,_ 2EIOU]) CJf~CH=C, . :.c<1:!]) C.Jt.CH=CH-COOH
COOEt "\,;ooEI CooH . CiulUuuic acid (
\.
MWOIlk ester Ben7.lllmalollic ester Benmlmlliollic acid
Malonic ester contains one reactive methylene group. whose two reactive hydrogen atoms take away
r
. the oxygen atom from benzaldehyde to fonn a water molecule. A reactive methylene group is present
between two strongly electronattracting groups (like CO. CN. etc.), due to which the hydrogen atoms
ofmethylene group acquire a tendency ofgetting released in the fonn ofprotons.
[22] . Reformatsky Reaction: When benzaldehyde is reacted with bromoacetic ester in the presence of "
zinc in dry ether. then cinnamic acid is obtained in the following steps.
Ether
C.J1rCH CH2-CooEI~ C,.H,-CH-CH,...,COOEt
II I· . I
o + Zn + Br . OZnBr
HOH
-7..II(OHulr CrH;-rn-CH2-COOEtHOH )0
OH -EIOH
. ~
C,.H,;-CH-CH2-CooH --? CJis-CH=CH-COOH

.OH CilUlOmic Ilcid
[BJ Reactions Due to Benzene Ring;

BellzaIdehyde gives the following SE reactions.
[23] Halogenation: m-Chloroben.za1dehyde (or m...,Bromobenzaldehyde) is fonned on heating benzaldehyde
with chlorine (or bromine) in the presence ofAICI3•
,c:o "" ~;:o

© \. ...,..1
~~
A1Cbl ..... )
..._.' I
o
{"
V
[I!~~~A~~ CL~~!~~
ldeolforSchokm
AROMATICCOMrOUND [24J
c
[24] Nitration:
m-NitrobenzaJdehyde is fonned on nitration ofbenzaldehyde by fuming nitric acid.
~
~:o
~
~
Fuming ~
HNClJ
( )
•••• ~....... N0
[25] Sulphonation : Benzaldehyde undergoes sulphonation on heating with conc. sulphuric acid to fonn m
fonnylbenzensulphonic acid..
/'
:©
,.~:.O
:...•••_ ..)
Cone,
fi2S0 4)
~
~.:.O
.....
~-••)
{•••
S020H
/"
\
[26J Friedel:..crafts Reaction: It should be noted that due to strong deactivation of benzene ring iti
benzaldehyde. Friedel-Crafts reaction does noUake place.
(
\..
USES: Benzaldehyde is used
/
[1] As a deodorant.
r" [2] In the manufacture ofsynthetic dyes, and
[3] In the synthesis ofmany aromatic compounds.
(
Some Important Point:
Uses :
S.No•. Fonnaldehyde Acetaldehyde Acetone
(
Disinfectant and preservati-..e for in the preparation of dyes polish,
( 1 Sol-..ent for cellulose,
. \. biological specimens. (formalin) , varniShes
c 2 Urotropine, a urinary antiseptic

In the manufacture of ethanol, In the preparation of sulphonals
acetic acid, synthetic rubber etc. " (hypotic)
c
c 3
. Formamint, for throat treatment
(formalin + lactose)
For the preparation of
metaldehyde {a solid fuel>'
In the preparation ofchlororform,
iodoform I
{
\..,
_ ....... _--_ .... _ - - "-_. __ _ - ...
( Distinction between Aldehydes and Ketones:
-c Test " Aldehyde Ketone

Schiffs reagent Pink colour X
Tollen's reagent Silver mirror X
Fehling Solution Red ppt. X
t
NaOH solution Brown resin X :
t, Mercuric chloride Black ppt. X I
C
fI]~~
I
\, AROMATICCO~OUND .[25)
f
\...
(
NITRO BENZENE
1 Introduction:
[a] Aromatic nitro compounds are obtained when hydrogen atom or atoms are ofaromatic compound
replaced by-N02 (nitro) group.
[b] Aromatic nitro compound are oftwo types.

[i] Those compounds in which nitro group is attached directly to the benzene ring ego nitrobenzene.
[ii] Those compounds, in which nitro group is attached to a side chain which is directly attached to the
benzne ring.
CH2 N0 2
© I
(nitro benzene) .
@
11
(phenyl nitromethane)
,r-"",
[c] Nitrobenzene is also called as 'oil ofmirbane' or 'artifical oil ofbitter almond's.
Cd] Ifhas a smell similar to benzaldehyde. \
2. Methods ofPreparation :
From Benzene (Nitration) :
o +HO-N02 conc.~SO.
60·
) 0
~
1
N02 + H 0 + energy
2
/' '.
vap.phase
Note:
[iJ The reaction species is +N02 (nitronium ion)
[ii] The above reaction is lab method ofnitrobenzene preparation.

t"
0'
3. Physical Properties:
[a] It is yellowish, oily liquid, insoluble in waterand soluble in organic solvents.
[b] It has odour like bitter almonds.
[c] It is steam volatile and poisonous in nature.
_.,
[d] Its boiling point is 211°C. ( .~
4. Resonance in nitrobenzene: .
[a] The groups which can attract the electron from benzene ring or deactivate the benzene ring or make
electron dificient to the benzene ring or shows -I effect or shows -M effect or -R effect are called as
meta directing groups. They do not show Friedel Craft reaction.

c
~O +
ego -N/"' -C-H. -C- OH. --SOaH. -C 5; N, -F, NH3
~o II . II
o
°
c
[I!~~~A~~ CJA~~! AROMATIC COMPOUND /26)
_""Scltolors
[b] The group which can donate the electron to the benzene ring or activate the benzene ring or make
electron efficient to the benzene ring or shows + I effect of+ M or +R effect are always ortho and para
directing groups.
H
.. i
ego , -NH2.-N-R.
.. -O-H. -O-R. -X:, - CH3 • -CH2 -CH 3 etc.
.'-
[cJ Resonating structures ofnitrobenzene.
0,::1 '0(7)
o~ ;;0
e 0 o o
0,/0' 0,/0 "/
"/ '/
eN ~ w ~ w
o~ · cO· ..
(1·'0$=0
ED
It is evident from the above structures that ortho and para positions are electron deficient and attacking
(
'- electrophilie is also electron deficient, so it does not attack on ortho and para positions but attacks at
meta position.
(
f'
'- 5. Chemical Reactions: Chemical reaction ofnitrobenzene are classified in three groups as follows:
( I. Reaction of-N02 group

2. Reaction ofBenzene ring
('
'- 3. Other reactions

{ 1 Reaction of-N02 group:
Reaductiou :
(
[a]' , Acidic medium:
Reagents: SnlHCI or SnCl/HCI or ZnlCH3COOH etc.
C6H 5NH2 + 2H20
c C6H5N02 +6H)
aniline
C' Propbale intermediate steps:
C C 6H 5-N02 -~~'b ') C 6H5NO +2H > C 6H 5NHOH _;!~) C6H5NH2
~ nitrosobenzene phenyl aniline
hydroxylamine
(
[b] Neutral Medium: Reagents: ZnlNH4Cl or ZnlCaCIz orAI-HglNH4CI etc.
c C 6 H 5N02 +4H) C 6H 5NHOH + H 20
( Phenyl
hydroxylamine
t
C
(
\.~ 1i~~~~A~~ CM~!~!
IdtaIi'«S<hcIDrs
AROMATIC COMPOUND ,/27}
(
[c] Alkaline Medium: Reagents: ZnlNaOH or SnC~lNaOH, or GlucoselNaOH etc.
• 2H
2CsHsN02 ~ Celis-N. ~ 0 ~
-ti.20 CsHs - . N
+ZH
=N - Celis CsHs - NH
11 I
CsH.s 'O'N 0 :. azobenzene CeHs - NH
·azoxyben~ne. hydrazobenzene
[d] Electrolytic reduction: [Medium: cone, ~S04]

f:.j~ ,.--'
c,H,NO, ;.:,. c,H,NHOH ~-. ~ (p- """" ,h",oI)
bH
. Reaction with AICIJ : Nitrobenzene behaves as weak base and makes a complex compound with
aluminium chloride.
@-~:_+"", ---+ <O>-~(:>AIC~ _. !

~
'
2. 0 Reaction ofBenzene ring:

Halogenation:
.0-. ,N02
OI
~
NO
2 +CI-CI
.
AICI,)~
lllO"C
CI
m-chloro nitrobenzene
.
f
"
Nitration:
o
N02
+ HO-N02
HzSO. (ronc.)
OO·C
& N02
m-dinitJ'obei1zene
(yellow crystalline solid)
c
.~.
N02
~
V
+ HO-N02 ,,100·C )
N02 N02
.I.N:e (e~pfosilie .ili nature) CO

\.J
Sulphonation :
N~ N~ 0
~O.·.
LSJ +.HO-SO H
3
~ ··~O·. .
1~e.o~.
o S0:iH e
fuming m-nitrobenzenesulphonic acid c
[i~~~~~~ LIMITEO
AROMATICCO~OUND [28J
I<kalforSdwIo"
c
c
3. OtherReactions: Nitrobenzene shows nucleophilic substitution reaction also. It is accomplishes in the
following way. Mechanism ofnucleopbillcsubstitution reaction - In nitrobenzene nucleophile attackes
at 0- & p- positions as these are the electron deficient centres.
o Co (\.f o
\+/
0
;,~~ N
~~ _~c&N".~
'N:t
A" r
Nu
fIr ....
O-~lV
H Nu Nu
Reaction with Solid KOH :
N0
NO, NO,· ~2
(e.
\.
@+KOH(soUd)~ @-OH + ~
OH
(0- &p-nitrophenol)
Reaction with Sodamide :
N02
\. N02 N02
.,
@ _ _.. ,@-NH,
+~
(
+
+ Na-NH2
\.
NH2
(0& p-nitro aniline)

( Reacti()n with Ethanol:
"
/
\.. NO.2
(
©
Test for Nitrobenzene:
+ C2HsOH ) o-and p-nitro phenetole
"-..
[Mulliken and Barker's method]
(. The alcoholic solution ofnitrobenzene Is heated with zinc powder and calcium chloride~ This hot mixture
/" on filtration in Tollen's reagent gives a black precipitate.
\..
C6H sN02 (alcoholic) +Zn +CaCI2 ~ [C6HsNHOH]filterinAgN03+NH40H ) 2Ag!
(
Black precipitate
{
t
t
ril'~~~A~\C~~~'!~
(
'-. AROMATIC COMPOUND [29J
I4uIr.,s.:h<>Ia..
t
ANILINE
1 Introduction:
[a] Aniline is called phenyl de.rivative ofammonia.
[b] ltwas initially obtained by the scientist 'Unverdorben'.
[c] Aniline is also called amino derivative ofbenzene because when a hydrogen atom is replaced by NH.z
group, aniline is obtained
2. Method ofPreparation :
From Nitrobenzene (Reduction in acidic medium) :
[a] Lab method:

~o
C6H5-N'~ + 6H Sn/HCI ) <:6Hs~
o ,-,
[b] Industrial method:
;0
CeHs-N'( .
~O
+

6H <:6HSNH2
.
From Benzamide :
<:6 H S-rr-
NH2 + Br2 + KOH (alc.) ) <:6HsN~ + K2<:03 + KBr + ~O
Note: The above reaction is called as 'Hofmann hypobromite reaction'. \.. ~ J
From <:hlorobenzene :
( - ~
[a] WithNH3:
<:6HS +ci+H+NH
..._._•••• .1 2 :..~~ )<:6HS NH2 + H<:l
Note: We use <:~O to neutralize the formed H<:l otherwise HG forms additional salt with aniline.
c
<:u20 + 2H<:1 ) <:u2<:12 + ~O
[b] With sodamide:

- ..- - - - - - , A
()
<:6Hs+.g:!J·~S:i-NH2 2000C) <:6HsNH2 + Na<:l
From Phenol:
J:.J +6H"+-fH-.NH
<:6~.as + J:.J 0
<:6HS-NH2~"'2
~.-•••--.. 2
anfly. inCIz )
300·C
c
('
From Grignsrd reagent: '-../
<:6Hs-fM.9QI~B-N~ ) <:6HsN~ + Mg<:12 e

chloramine
c
c
[iJ!~~~~~ CL~~~~! AROMATI<:<:OMPOUND {30}
{ .
Ideol for Scholors
'- ../
c
c
From pbenyl isocyanate (By al~line bydrolysis) :
r - ............... "'----'-,
K-O-H
CsHs - N =f: C =0 +, I --~) CsHsNH2 + ~ CO:!
L _ _ _ _K-O:r H
Note: The above method iscalledas 'wurtzmeibod'.
From Benzoic acid (Schimdt reaction) :
C,H, - &- °- H + N,H 1<OH.~c C,H,NH, + CO, + H,O + N,
By reudction ofazo and bydrazo compounds witb sodium ditbionite :
,
" CsHs - N =N - CsHs + 2 Na2$204 + 4Hp ) 2 Cr;HsNH z + 4 NaHS03
By curtius reaction:
(
CeHsCOCI + NaN3 ) CeHsCON3 + NaCI
/' CsHsCON3 + H20 - - - . . ? C6H5NH2 + CO2 + Nz
"
By Gabriel Pbtbalimide reaction:
r __ cn cQr"", C~e
©
\,
~ COOH cQr"~'! c~0 ~ ~ l KOH $'
11'
,~~
:
eOOH
f
-H2 0,. ':-- ccY -H 20 cQr
.~ CcY
--NH --~ "
',; CcY
NK
~
I
(
r
c
"
phthalic acid phthalic anhydride
phthalic acid + H2N - CsHs

phthalamide
( 2H,O
"
ex
"
'J
.'. -
Co,
~'"
Cv,
polassium phlhalamide
~N-CH
6, ' 5 , C"H;J J
c anilne N-phenyl phthalamide,
3. Pbysical properties:
c [a] Aniline is soluble in organic solvents as well as in water.
(. [b] Solubility in water is due to hydrogen bonding.
[c] It is colourless and poisonous liquid.
(
c· 4. Resonance in Aniline:
Aniline is less basic than ammonia and primary amine because it possess resonance
(
·· ~ 1:11 ill •• 0+
,(
'e C ~ ~ ~61
(0
NH2 " . . NH2
< )
NH2
~(
c)) ( ».u-
c:NH2
) 6·
NH2
50-01)
~H2
f.
'c V b ~ # ~
¢"
t:
C
( [tJ AROMATICCO~OUND [31)
c
It is evident from the above sturcutres that I.p. on N atom is delocalised and aniline behaves as a weak.
base. In these resonating structure, its ortho and para positions are electron richer (due to presence of
negative charge) so electrophile attacks on these positions only. That's why we can say it is ortho & para
directing.
5. Chemical Reaction:
Chemical reactions ofaniline are broadly classified in the following two ways:
5.1 Reaction of-N1l2 group
5.2 Reactions ofbenzene ring
5.3 Other reactions
5.1 Reactions of-NH2 group:

Alkyl~tion :
H H R'
R' l~
C6HS - ~- H + X- R' I-
t C6'1-1.' 5 - N R' X-R' I - R'
) CGHS - N
X-R'
• C;.,Hs
[
-t, -R' X
quaternary salt (
Acetylation:
H H r
I . I "
C6 Hs - N -H+CI-C-CHa Hel) C6 Hs - N - C-O"

A' - .A .~
N-phenyl acetamide Or acetanilide
Note: The product formed is important because it is used in preservation of-N1l2 group in aniline.
Schotten-baumann reaction:
H .H
I '., I
C6Hs -N -H+CI-C-CsHs -Hel) CsHs-N- C-CsHs
II II
o 0
N-phenyl benzamide or benzanilide

Reaction with Hinsberg reagent:
H H (~
I I '
CsHs - N - H + CI- 802 -CsHs ) CsHs - N - 802- CsHs C
()
C'
• "1
( ,
[i1~~~~A~~ CM~'" AROMATIC COMPOUND [32}

tor
ItkoI SChchlt
·c
C
0
Hoffmann Carbylamine reaction (Isocyanide test) :
C,H5 - N<: + CHCla + KOH (alc.) ) C,Hs - N ::; C + HCI+ Hp
There isocyanides has vel)' offensive smell. Reaction is used for testing ofprilUllI)' amines.
Reaction with Phosgene:' .
"
H H
I r--, I .
CaHs-Nr.!::!.C>
, , r±""- C,= 0
.
-2HCI ) ~.~.-.> C=O
C,Hs-N-
L
H c-'
I --
.
~~fH •
H
Rea~tion with Carbondisulphide :
[a] When aniline is in excess:

/.
~ H H
CH5-~C.H-H~K' I .
.CeHs- ,
6 + I + II S !C=S_--4 / c =S + Hp+ K2S
/
, I' II I
CsHs-N-
L H H---ClT.-K-, ceHs'- N
" I
H
- - - - .......
. I
"
N. N' - diphenyl thio urea
("
\ Ib] When aniline is in lesser quantity :
( rH.---H_O,rj(-'
L _ _ _+_ _ _:.r:- + S ~ C= s
I r----ilI T
~ CaHs - N =C =S + 2 H20 + K2S
CsHs -N-cl.:L _ .!::!.-OJI:~ _-'
"
phenyl iso thio cyanate
c Note: There isothiocyanate has odour like mustard oil so reaction is called 'Hoffmann-mustard oil
reaction.
c
Reaction with qrignard reagent: ,
'{
,,-, R- Mg -x + CaHs - N- H ) R - H +CeHsNHMgX
( ~
( Reaction with.8odium metal:

"'",
H
CgHs- N -'H+2Na
, I
~ CaHs- ~'-Na'
'
.
t H
N- phenyl sodamide
t,
AROMATIC COMPOUND . /33}
c
c
Reaction with HN02 and HCI (Diazotisation) :
CsHs - N r-H-+-0"* N -f OH + f-!1ci ----o:~ CSH5 - N = N - CI
rt-l
Iif___ -.J
J. benzene diazonium chlonde
.
Note: It is an important compound because we can obtain a number ofaromatic compounds from
benzene diazonium chloride like.
C2HsOHI L\
--..- - - - - - - - 7 C.H6 + N2 + HCI
HOH
--> C.HPH
HCIIcu 2CI2
~I
)
f--. - - . - - - - t C.HsCI
HBr!Cu2Br2
J
C.HsBr Sandmeyer reactions
HCN I CU2(CN)2
CoHs - N=N CI ---) C.HoCN j
KI I a '\ "
\ - - - - - - - - - - - 4 C.Ho!
HN02 ~,
t- ) C.H.N02
H (
SnlHCI I
C.Hs-N-NH2
B-nephtol
-----) orange ppt. (A dye)
Salt formation:
I
H + H ~CI-S
CSH5- N:
:,1
+6
f H
_
.")- 'Cf<.S:IjS·-N-7W
I
I
1+ CI ./
' ..
/---......
H con~ H ~-.
-arliil~ium chloride
2
( ,
I
H '['.' I
H' .'1+ . '--./
CsHs- N: + H2S04 ) C 6HS - N~ W SO4-2 I~-
~. . .:~ ..... '0--./
2
anilinium 5uJRhate ("
""j'
,"
H
I ' I.." ~.
CsHs- N: + H -+- Au-C14
H
I ']..+·
C6HS - N ~ H AuC I:;
I
H
)
,.1
·U- . c
(
",-,--,
snilinium chloraurate
1-'\
2 1;..../
I . ' [. .
C6Hs- ~:H + H pt CI6
2 ) C6H5 -
H
~ ~ H·1+ PtClii~V. c
H H 2
e
anilinium chloroplatinate ,
()
Note: By the. help ofthis salt we can calculate the mol. wt. ofpriinary amine.
c
[I]!~~~A~~ CL~~~~! AROMATICCOMWOUND [34J
Ickol 10;Scholars
C
C:
C
Reaction with Benzaldehyde:
C 6HSNH2 + C6HsCHO ) C6Hs-CH=N-C6HS
(schiffbase or anil)
5.2 Reaction of benzene ring:
Halogenation:
Aniline does not show halogenation or nitration directly due to presence ofactive hydrogen on -N~
group so for nitration, halogenations first we preserve~ group with acetyl chloride or by the fonnation
ofacetaniHde.
0 0
°C-CH3
CI }II
II °II II
©
H-NfH
+ -Hel)
.. ~C-CH,
0 CS,(nonpolar}
Br-8r{FeBr3}
©Y-
o Sr
CH
'
+
~C_CH'
Sr
~
~ c&B'
{
+ ,0 -CH3 COOH
(
~ Sr
(~
Note:
"( [i] Para product always yield more :
[ii] Ifreaction occurs in the presence ofpolar medium like bromine water, then product will be white ppt.
of2, 4, 6 tribromo aniline.
( [iii] Aniline on iodination gives para-iodo product only.
"
Nitration:
(
"
(
\.
.~
NH2
+ conc. HN03 - H2S04---'-~ ©-.. NH2
N02
(m-nftroaniHne)
Note: [i] Meta products is fonned because intennediate anilinium ion is fonned which is meta directing.
C [ii] Ifnilration occurs with conc. HN03 then product will be yellow ppt of2, 4, 6-trinilroaniline.
(
---
Sulponation :
( ill
(
"
(
'
@. H2S04 (fuming) --~@
NH3 HSo!
~160-2000C
(;i
,©
NHS03 H
._nM'_"" .~.
~ NH2
aniline hydrogen sulphate

S03H
( 5ulphanilic acid
Note: Sulphanilic acid is used as hypnotic drug.
(
II'~~~:\~ Cc~~!~!
f
\..~ AROMATIC COMPOUND {35]
1deo,r.,Schcl<m
L
Reductiou:
@
N~
+3H,
Pd/PI/Ni )
2OO"C
6 NH2
cyclo hexyJ amine
Reaction with benzene diazonium chloride:
NH2~ + CI N=N-@-
10"C
-HCI
~NH2-@-N:::N-@
, '
p-amino azobenzene
5.3 Other reactions:

Oxidation: Anilinefonns different compounds on oxidation as follows:
N~Cr2Or \ .
> aniline black

~nC;H2S04 ('
NSiCr20 7
dil.HzS04 crO=o
p-benzoquinone
H20 2 .500
Cs HsNH2 ~ 'i' Cs HsN02
CF3COOH
NaOCI
-~ H2N-@-oH
p-aminophenol f
"- \
H2SOS
CllsNO + CS H5N02
i
air oxidation \,
red-brown colour
(--'"
Test for Aniline:

N=N-+ ('
')~O
'---'
[a] Aniline ..~~oL ) C6HsN2CI 10%NaOH

+II-naphlhol ~
0 H
a-phenyl azo l3-naphthol (orange-;-ed dye) {, "

"'-'"
[b] Aniline + NaOCI ~ p-Aminophenol light) Purple--colour f
'-/
[c]Aniline cl(~~) Phenyl isocyanide (
',_/
'.
(most unpleasant smell)

c
G
C
P
'-/
(~
lip LCLASSES
'£ LIMITED
_"'S<~oIor.f
r, -j
c
c
SOLVED EXAMPLE
Ex. I Which of the following is not correctly matched

(A) Hydrolysis of phenyl magnesium iodide - benzene
(8) 'Y-Isomer ofBHC-lindane
(C) (2n + 4) 1£ Rule-- aromaticity
(0) Trimerisation ofpropyne-- mesitylene Ans.(C)
SoL The Huckel rule to account for aromaticity is closed ring of (4n + 2) 1£ electrons.
f
\
Ex.2 Benzene can be directly obtained from
(A) Acetylene (B) Ethene and butadiene
/ (C) Chlorobenzene (D) All the above Ans.(A)
~
Sol. See Text.
f Ex.3 Ozonolysis of benzene yields

(A) Glyoxal (B) Glycerine (C) Glycol (D) Glycerol (Ans.A)
,
(
Sol. Ozonolysis of benzene yields glyoxaJ. Benzene adds three molecules of ozone and forms benzene
( triozonide which on decomposition with water gives three molecules ofglyoxal
(
C6H 6 + 303 --~> C6H 6 0 9
" benzene ozone benzene triozonide
(
" +H 2 0 H-C=O
C 6H 6 0 9 ~ 3 I
H-C=O
benzene triozonide glYl)xal
c Ex.4 An aromatic compound contains .... 1£ electrons

(A) 4n (B) 4n + I (C) 4n + 2 (0) 4n + 3 (Ans.C)
Sol. An aromatic compound contains (4n + 2) 1£ electrons. It is according to Huckel's rule, which
represents the aromaticity of the molecules. Aromatic compounds possess a sweet smell which is
characteristic and different from other fragments.
The tenn aromatic compounds is now used for benzene ,and the compounds structuraJly related to
C benzene, even if they do not possess a sweet smell.
Ex.S Which of the following will show aromatic character-
c
c
{j
0)
I
o n
0
III
\)
IV
(A) I, II and III ~II~III ~n~N (0) All the four
c (Ans.C)
[I1~~~A~~CJA~~! AROMATIC COMPOUND 137J

Ideal"" Scho4ut
(
c
Sol. Benzene has 6n electrons (2 from each double bond) present in cyclic continous form.
o
benzene
\)
furan "'
Furan also has 6n electrons present in continous cyclic cloud, note that one of the pair of electrons
present in sp2 orbital does not involve in overlapping of the sextet; while the unused pair of
electrons present in p orbital is involved in overlapping forming sextet.
Ex.6 Which of the following is not a friedel craft's reaction

(A) C 6 H5 - OH + CI - COCH3 ~ C 6H50COCH3
(B). C 6 H6 + CICOCH3 AlGI,) C 6H 5-COCH3
(C) C 6 H6 + CH3CI AlGI,) C 6 H5 - CH3

(~
(D) C 6 H6 + C 2H5CI AlGI,) C 6H5 - C 2H 5 [Ans. AJ

(
Sol. Friedel craft reaction occurs in the presence of lewis acid. Note that carbon directly links with \.
benzene ring in friedel crafts reaction.
Ex.7 Toluene may be prepared by :

(A) Toluic acid (B) Cresol
(C) Toluene sulphonic acid (D) All the above [Ans. DJ
Sol. Toluene may be prepared by all the above compounds described earlier.
"
r'
" -"'
Ex.8 The chlorination oftoluene in presence of ferric chloride gives predominantly

(A) Benzyl chloride (B) m-Chlorotoluene " /
(C) Benzal chloride (D) 0- and p- Chlorotoluene [Ans. DJ (~

"j
A
f'
~OCH3CI
©
,-----,"
CI
Sol. Fe~13· G+~ c
("
CI \.../
("
In presence of halogen carrier, substitution occurs in benzene nucleus. \....J
c
Ex.9 Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH
gives - c
(B) P - Cresol
(A) 0 - Cresol
(C) 2,4-Dihydroxytoluene (D) Benz:'l alcohol [ADS. DJ
c
Sol. C6
H5 3 + CI 2
CH light ,heat ) C6
H5CH
2 CI aq.NaOH) C6
H5CH
2 OH e
c
c
[i!~~~A~~.CL~~!~! AROMATIC COMPOUND [38J {
IdeQI(DTkholors
v
c
c
Ex. 10 ~-CH3 Cr02C12 ) A ~O) B
[Where ~ = C6HS]
The functional group present in B and name ofthe reaction would be

(A) -CHO, Gattermann aldehyde synthesis (B) -CHO, Etard reaction
(C) -COCH 3, Friedel Crafts reaction (D) -CHO, Oxo reaction [ADS. BJ
Sol. The compound 'B' is benzaldehyde and the reaction is called Etard reaction.
Ex.ll The correct order ofreactivity towards electrophilic substitution is

(A) Phenol> Benzene> Chlorobenzene > Benzoic acid
(B) Benzoic acid> Chlorobenzene > Benzene> Phenol
(C) Phenol> Chlorobenzene > Benzene> Benzoic acid
(D) Benzoic acid> Phenol> Benzene> Chlorobenzene (ADs.A)
Sol. Presence of 0-, p- directing groups in benzene nucleus activates ring for SE reaction. Presence
,
(
of m-directing group deactivates ring for SE reactions. Also halogens are deactivating gpo due to
( - IE. inspite of o-and p-directing nature.
\.
Ex.12 Which among the following is the strongest 0-, p·directing group in benzene is
(
(A) -OH (B) -Cl (C)-OCH3 "(D) -CH3 (ADS.A)
Sol. -OH gpo posses the maximum tendency to throw electron pair towards benzene nucleus.
f
\.
Ex.13 The compound represented by the molecular formula C7HgO are
(
\. (A) Only alcohol (B) Only ether

(C) Only phenolic compound (D) All the three types of compounds (ADs.D)
f
\. Sol. Benzyl alcohol, anisole and 0 - , m-·, p-- cresols can be written by the molecular formula
C7HgO.
( Ex.14 Indenify A, B, and C in the following reactions-

\.
OH
,Z..,2 5
-+6
C
(a)~
H
~OH
C (b)~ +B (c) C ~
~L0
eOOH
(
(A) Sodalime, benzene, potassium phenoxide
( (B) Zn, benzene, sodium ethoxide
(C) Zn, cyc1ohexanone, sodium ethoxide
( (D) None of the above . (ADs.A)
( Sol. Sodalime, benzene, potassium phenoxide are the A, B and C compounds respectively.
C Ex.IS Rate of substitution reaction in phenol is

(A) Slower than the rate of benzene (B) Faster than the rate of benzene
(
(C) Equal to the rate of benzene (D) None (ADS.B)
t Sol. - OH group is activating group towards electrophilic substitution reactions.
C
[I]!~~1~ CJ~~~~~!
If
\... AROMATIC COMPOUND' {39)
IdeoIfotSchok'"
L
Ex.16 Which is least soluble in water
(A) Phenol (B) Ethanol (C) Benzoic acid (D) Benzene (Ans.D)
Sol. Benzene can not form H-bonding thus, it is least soluble.
Ex.I7 Which ofthe following reagen (s) cannot be used to distinguish between phenol and benzyl alcohol
(A) NaOH (B) NaHC03 (C) Br2 /CCl4 (D) FeCI 3 (Ans£)
Sol. Only phenol reacts with NaOH, NaHC03 and FeCl3 none of the two compounds react with
BriCCI4' .
Ex.IS Phenol condenses with formaldehyde to form

(A) Bakelite (B) Asbestos (C) Polyacrylaldehyde (D) Polyester (Ans.A)
. Sol. When phenol and formaldehyde react in presence of dilute alkali, p-hydroxybenzyl alcohol is
obtained as a major product on further heating for some time, a cross-linked polymer, called
phenol- formaldehyde resin or bakelite is formed.
/"'-..,..
Ex.19 @-OH + CHCI3 + NaOH - - + ~OH
. CHO
The above reaction is called

(A) Gattermann Kosch aldehyde synthesis
(B) Gattermann aldehyde synthesis
(C) Reimer Tiemann reaction
(D) Ledrer Mannase reaction (Ans.C)
Sol. The above reaction is Reimer Tiemann reaction.
Ex.20 In Etard's reaction toluene is oxidised to benzaldehyde using

(A) H 20 2 (B) Cl2
(C) Chromium trioxide or Cr02Cl2 . (D) KMn04 (Ans. C)
Sol.. cr03 or Cr02 C12 and a mixture of K2 Cr20 7 + H2 S04 + NaCI can also be used.
()
Ex.21 In Perkin reaction
(A) Benzaldehyde reacts with acetic anhydride in the presence ofsodium acetate forming cinnamic
acid.
(B) Benzaldehyde .reacts with acetaldehyde in the presence of sodium hydroxide to give
cinnamaldehyde.
(C) Calcium salt of benzoic acid on dry distillation gives benzophenone.
(D) None of these (Ans.A)
t'"
v
Sol. Perkin reaction can be shown as
C6Hs CHO + (CH3CO)20 CH3 COONa) CJIsCH = CH - COOH + CH3COOH t:'
V
. .
Ex.22 Benzaldehyde and formaldehyde differ from acetaldehyde in their reaction with
(A) NaOH (B) HCN c
(C) 2,4-Dinitrophenyl hydrazine (D) Semi carbazide (ADS.A)

c
[I] !~~~!~ CLL!t~!~!

IdtoI""SdtoIa"
AROMATIC COMPOUND {40]
Sol. Benzaldehyde (C6HS - CHO) and fonnaldehyde do not have a-hydrogen atoms so they give
disproportionation reaction with NaOH but CH3CHO does not give it.
Ex.23 When an aldehyde was heated with alkali, part of it was converted into an alcohol and part of it
into an acid. The aldehyde is
,-
\
(A) An aliphatic aldehyde other than fonnaldehyde
(B) An aliphatic aldehyde or salicylaldehyde
(
(C) An aromatic aldehyde other than salicylaldehyde
(D) An aromatic aldehyde or formaldehyde (Ans.D)
Sol. The aldehydes which do not have a.-hydrogen atoms show disproportionation reaction. These
f
aldehyde may be aliphatic aldehyde (fonnaldehyde) or aromatic aldehyde.
Ex.24 Product obtained on the addition of an aqueous alkali to benzaldehyde followed by acid hydrolysis
is
(
(A) Benzoic acid (B) Benzyl alcohol (C) Benzyl benzoate (D) All of the above
(Ans.D)
"
( Ex.25 Benzaldehyde reacts with acetaldehyde in the presence of a base to give
\
(A) Crotonaldehyde (8) Cinnamaldehyde (C) Crotonic acid (D) Cinnamicacid
(Ans.B)
Sol. Benzaldehyde reacts with acetaldehyde in the presence of a base to give cinnamaldehyde. It is
called crossed Aldol condensation or Claisen's condensation
(
~o ow ~::;CH.CHO
(
" 19J +CH3 CHO

~l9J
(
benzaldehyde acetaldehyde cinnamaldehyde
'"
Ex.26 In the reaction between benzaldeq.yde and fonnaldehyde, point out the wrong statement
/"
\" (A) Benzaldehyde is reduced to benzyl alcohol
(8) Fonnaldehyde is oxidised to fonnie acid
c (C) Benzyl fonnate is fonned
(D) The reaction is known as crossed aldol condensation
(ADS.D)
( Sol. In the reaction between benzaldehyde and fonnaldehyde the wrong statement is that the reaction
is known as crossed aldol condensation. Actually the reaction is called Crossed Cannizaro's reaction.
(
(1)OW
C6 HSCHO + HCHO
{ (2)HCI
benzaldehyde fonnaldehyde
(
C 6H sCH zOH + HCOOH
( benzylalcohol fonnic acid
c
(
fj}'~~~~~ CH!~~~! AROMATICCOMWOUND 141)

'(
IdeoIfIKSch<!k!t<
r
'L
(
/
't>
Ex.27 Which ofthe following will undergo aldol condensation-
Acetaldehyde Propanaldehyde
(1) (2)
Benzaldehyde rideuterosacetaldehyde
(3) (4)
(A) I (B) 1,4 (C) 1, 2, 4 (D) All of them (Ans.C)
--~/
SoL CH3CHO CH3CH2CHO

(1) (2)
C6HsCHO CD3CHO "

(3) (4)
Benzaldehyde has no a-hydrogen atom, remember that CH3CHO and CD 3CHO both behave
similarly in chemical properties.
'
('
"
(
('" "'
\'- .'
,r,
\
('
"/
('
'--"
(,
,--/
("
'--j
( "
\j
(----
'--'
c
c
c
e
o
c
liJ AROMATICCO~OUND [42)
c
~,
v
v"
(
EXERCISE-I
Q.I How many 1t electron are there in the following species :
~ (A) 2 (B) 4 (C) 6 (D) 8
W~trobenzene has a smell similar to that of:

(A) Benzaldehyde (B) FonnaJdehyde (C)Acetaldehyde (D) SalisylaJdehyde
\
Q.3 Benzene is a resonance hybridmainly oftwo Kekule structures. Hence:
(A) Halfofthe molecules correspond to one structure, arid halfofthe second structure
(B) At low temperatures benzene can be separated into two structures
( (C) Two structures make equal contribution to resonance hybrid
r~ c (D) An individual benzene molecule changes back and fortll between two structures
\c
r
\~
~ W SQlvent used in the, Friedel Craft's reaction is :
(A) Nftrosobenzene (B) Nitrobenzene ~ (C)Benzene (D) Toluene
Q.5 Which ofthe following is not an aromatic compound:

r
(A)Q (B)O' (C)o +

(D) 0o
(
Q.6 Benzene is obtained when phenol is distilled with
(
\~ (A) Copper turnings (B) Aluminium dust (C) Zinc dust (D) Pumice stone
( ~.~ ~~~fthe following group is divalent:

l'
'~-~~~YI (B) Benzyl (C)Benzal (D)p-Tolyl
\.
c· Q.8 Acetylene on polymerisation gives-

(A) Mesitylene (B) Benzene (C) Ethyl benzene (D) Propyle benzene
.Q. 9 The number ofbenzylic hydrogen atoms in ethylbenzene is:

c (A) 3 (B) 5 (C) 2 (D) 7
(. Q.IO Which one ofthe following is the most basic compound:

I (A) C6Hs-~ (B) C6HS-NHCH) (C) C6H s-N(CH)z (D) C6H sN(C zH s)z
t ~ ~
( . Q .11 Which one ofthe following statements is wrong

(A) Aromatic compounds are generally unstable
c (B) Aromatic compounds are richer in carbon content
(C) Aromatic compounds show substitution reactions
(D) Aromatic compounds bum with smoky flame
c
( AROMATIC COMPOUND [43)
(
'l.
c
Q.12 Which ofthe following is not the property ofbenzene:
(A) Characteristic smell (B) Inflammable
(C) Addition reactions (D) Colourless
Q.13 . The intennediate fonned in the reaction ofbenzene with an electrophile is
(A) Wheland intermediate (B) <1- complex ...
(C) Benzenium cation (0) All the above
Q.14 Friedel-Crafts' reaction does not occur in case .of

(A) Toluene (B) Benzene (C) Naphthalene (D) Pyridine
Q.lS Major product ofthis reaction will be :

CH3
@ .
CI:I3CI
AICI3 ,£1
)
. (A)o~xylene (B)p-xylene (C)Cwnene (D) m-xylene

['
\
Q.16 Toluene may be prepared by
(A) Friedel craft's reaction . (B) Wurtz-fitting reaction
(C) Grignard reagent- (D) All of the above
Q.17 For preparing monoalkyl benzene, acylation process is preferred than direct alkylation because
(A) In alkylation, a poisonous gas is evolved
(B) In alkylation, large amount ofheat is evolved
(C) In alkylation, polyalkylated product is formed
(D) Alkylation is very costly
Q.18 The main product ofthe reduction of benzaldehyde with Zn-Hglconc. Hel is - r •
\.,
. (A) Benzyl alcohol (B) C~!clohexylmethano!
(C) Toluene (D) None of these
r",
CH3COCI ) A Zn-Hg . ) B "-/
Q.19 C6H6
AICI] HCI
The end product in the above sequence is:·

c
"'\
(A) Toluene (B) Ethyl benzene (C) Both the above (D) None
Q .20 Which can be used in Friedel- Craft acylation

(A) CH3CO.O.COCH3 (B) CH3COCI ,'
L
(C) CH3CH2COCI . (D) All
C
Q.21 C6H6 +A . AICI 3 ) C6H5CON~
A in the above reaction is:
C
(A) ~CONH2 (B) CICO~ (C)CH3CON~ (D) C~(CI)CO~ e
0
C
II!~~~~~ CL~~! AROMATIC COMPOUND H4]
("
ldealforSdlOlo"
"-../
C
( "
v
Q.22 AnhydrousAICl3 is used in the Friedel- Craft's reaction because it is
(A) Electron rich (B) Soluble in ether
(C) Ionisable to chloride and aluminium ions (D) Electron deficient
Q.23 Nitration of toluene takes place at

/~ (A)o-Position (B) m -Position
\
(C) p - Position (D) Both 0- and p - positions
Q.24 Reaction ofS03 is easier in:

(A) Benzene '(B)Toluene (C) Nitrobenzene (D) chlorobenzene
Q.25 Which ofthe following will undergo sulphonation at fastest rate ?
" (A) 6 $)0 (C)C ~)o

Q.26 Ozonolysis oftoluene gives
(A) Two molecule ofglyoxaIe
(B) Three molecule ofglyoxaIe
(C) Two molecule ofgIyoxale and one molecule ofmethyl g1yoxale
(D) Two molecule ofmethyl glyoxale and one molecule ofg1yoxale
r
\
~henol is obtained in large scale from which fraction ofcoal-tar?
\
r , (A) Light oil fraction (B) Green oil fraction
(C) Pitch (D)Middle oil fraction
/
"( Q.28m-Bromotoluene is prepared by:

, (A) Brominationoftoluene
(B) Friedel Craft's reaction ofbromobenzene with CH3CI
c , (C) Bromination ofnitrobenzene and subsequent replacement of-N02 group with methyl group
c (D) Bromin~tion ofaceto-p-toluidine followed by hydrolysis and deamination
( Q .29 Phenol and ethanol are distinguished by the reaction with

(A) Red litmus (B) NaHC03 (C) FeCl3 (D) NaOH
(
'-'
Q.30 Phenol reacts with conc. HN03 in the presence ofconc. H2S04 to give
( (A) Meta nitrophenol (B) Ortho nitrophenol·
r
(C) Ortho and para nitrophenol (D) Picric acid
I,
'
Q.3 I In the Liebennann's nitroso reaction changes in the colour ofphenol occurs as:
(
(A) Brown or red-greenish red-deep blue (B) red-deep blue-green
( (C) red-green-white (D) white-red-green
Q.32 ReimerTiemann reaction involves

(A) Carbanion intennediate (B) A carbene intennediate
c (C) Carbonium ion intennediate (D) Free redical intennediate
(
li!~~!!~Ct~~!IdtQ/fwSd><>lo..
AROMATIC COMPOUND /45)
t
(
Q.33 Methyl group attached to benzene can be oxidised to carboxyl group by reacting with:
(A) Fe20) (B) AgNO) (C) KMn04 (0) crO)
Q.34 The fonnylating agent in 'Gattennann Koch' synthesis is

(A) CO + HCI (B) CO + H2 (C) HCI + HCN (0) CHCI3 + alc.KOH
CH=CHz
Q.35 A (- " @ KMmJ, .B
Compound A and B respectively are:

(A) 0- Bromostyrene, benzoic acid (B) p-Bromostyrene, benzaldehyde
(C) m.. Broniostyrene, benzaldehyde (0) Styrene dibromide, benzoic acid
Q.~/ Benzaldehyde is oxidised and reduced simultaneously in the presence of \. ~f
vV (A) NaHC0 3 (B) NaOH (C) Na2C03 (D) HCI
Q.31ftenzaldehyde and fonnaldehyde give a common reaction-

V (A) Cannizzaro's reaction (B) Benzoin condensation
(C) Claisen condensation . (D) Perkin's reaction
/
Q.38 Benzaldehyde can be converted to benzyl alcohol by-
(A) HCl (B) NaOH
(C) LiAJH4 (D) B and C are correct
Q.39 Benzaldehyde condenses with acetic anhydride to give cinnarnic acid in presence of '-,
(A) Sodium acetate (B) Sodium chloride {
'- _/
(C) Sodium benzoate (0) Sodium metal

r'
' ......
QAO HCHO and C6H sCHO can be distinguished by-.
(A) Fehling solution (B) Tollen's reagent (C) KMn04 (0) AU ofthese ('
'-./
' :
C j
/"
\.../
{'
,--,'
c
{
'-..J
"
c
c
e
o
c
li!~~~A~~ Cl~~~~~ AROMATIC COMPOUND {46]
Ideo/I., SdN>lc"
c
f"
v
t''
~
EXERCISE-II
Q.l C
6
HsNOi Sne12/HCI :;. A NaNOz/HCI) B ~ Benzene, In the above sequence B ~ Benzene is suitably
0°
V/ obtained
by using:
(A) Ethanol (B)H3P02 (C) Both the above (D) Methanol
Q.2 Aniline is purified by:

(A) Azeotropic distillation (B) Stearn distillation
(C) distillation in presence ofmagnesium (D) Fractional crystallisation
Q.3 C6 HsNH2, CHCI 3 and KOH give the main product :

(A) Phenyl cyanide (B) Benzyl cyanide (C) Benzyl carbylamine (D) Phenyl isonitrile
( ® Aniline on direct nitration produces:

f'
(A) o-Nitroaniline (B) m-Nitroaniline (C) p-Nitroaniline (D) 1 & 3 are correct
\.
[' Q.5 Which one ofthe following is not an azo compound :

,\.
(A) Methyl orange (B) Benzenediazonium chloride
(
(C) Phenolphthalein (D) p-hydroxyazobenzene
"
( Q.6 Nitration ofaniline is carried out after acylation, because:
(A) Oxidation can be avoided
(
(B) Reaction becomes manageaple
/
\.
(C) 0 and p-nitroanilines are obtained in good amount
(D)All the above
(
Q.7 Nitration ofaniline comes under:
," a
(A) Nu-addition
e
(B)N u-substitution
I'D
(C) E -addition (D) ~ -substitution'
(
W. Urethanes are esters of-
W (A) Carbamic acid (B) Citric acid (C) Malonic acid (D) Succinic acid
Q.9 'Which ufthe following on acidic hydrolysis gives prlmmy amint: :

( (A) CH3CN (B) CH3N02 (C) CH3CNO (D)CH3NC'
( Q.l 0 Reduction ofnitrobenzene with zinc and methanolic alkali gives mainly
(A)Aniline (B) p-Aminophenol (C)Azoxybenzene (D) Azobenzene
(
( Q .11 Choose the fIase statement:

(A) All the activating groups are 0-- & p--directing
(B) Halogens although deactivating' to some extent are 0, p directing
(C) Groups more deactivating than halogens are m-directing
t: (D) Nitration oft-butyl benzene is easier as compared to toluene
(
II~~~~~LECbl:'t~~~!
_forS<lo<>km
AROMATICCO~OUND 147J
!
ct,
(
\..
,Q.12 The order ofstability of an~line and anilinium ion is :
111 $
(A)C6Hs~ u C6HSNH3 (B)C6Hs~ <C6HSNH3
111 ,
(C) C6HSNH2> C6HS NH3 (0) None ofthe above
Q.13 C6HsNH2 812 /004 . Theproductis:

(A) Only o-bromoaniline (B) 2, 4, 6-triboromoaniline
(C) o-and p-bromoaniline (0) Only p-bromoaniline
Q.{t/niline can be prepared by

(a) Sclunidt reaction (b) Wurtz process
(c) Hofmann bromamide reaction (d) Reimer-TIemann reaction
Code is :
(A) Only a (B) a, band d (C) b, c and d (D) a, bandc , , >
Q.15 The well known insecticide, Gammexane is one ofthe stereoisomers ofhexachlorocyclohexane. The /---"
reagent useful for conversion of benzene into hexachlorocyclohexane is

(A) 3 HCI (B) 3CI2(AICI3) (C) 3CI2(ZnCI2) (D) 3CI2(hU)
~==='--
Q.16 Benzene does not react with the following except
(A) Bromine in carbon tetrachloride solution
(B) Aqueous potassium permanganate solution
(C) Hydrogen in the presence offmely divided nickel at high temperature and high pressure
(0) Dilute sulphuric acid in ethanolic solution
Q.17 Benzene easily shows

(A) Ring fission reaction since It is unstable [
(B)Addition reactions since it is saturated "

(C) ElectrophiHc substitution reactions due to stable ring and high 1t electron density ,_/ ;' ".
(0) Nucleophilic substitution reactions due to stable ring and minimum electron density
Q.18 An arene containing three primary, three secondary and three tertiary carbon atoms is
c
~ (A)Cumene (B) Cymene (C)Me~itylene (0) Styrene c
r'·
Q.19 Benzene does not undergo addition reactions easily because \cd'
(A) It has acyclic structure ("
~
(B) Double bonds in it are very strong
(C) Resonance stabilized system is to be preserved I'
",-j
(0) It has six hydrogen atoms
,
/ '
'---'
Q.20 Which ofthe following reaetions is not an example ofelectrophilic substitution
(A) C6H6 + -+:N02 -7 C6HSN02 + W (B) C6H6 + CH3CI Aleta )C6Hs CH3 + HCI G
(C) C6~ + Cl2 UVlighl) C6~CJ6 (0) C6Hs OH + CO + HCI Antri· C
Q.21 x ~ Benzotrichloride Hydrolysis) Y, X and Y respectively are e
(A) Benzene, Benzaldehyde
(C) Toluene, Benzoic acid
(B) Toluene, Benzaldehyde
(0) Benzene, Bel)zoic acid
o
,./
{'
1Il!~~A~~CJ!~~~!

-,...
AROMATICCO~OUND {48}
t'
v
c
()
Q.22 Which ofthe following statements is correct
(A) Bromination oftoluene occurs faster than that ofbenzene
(B) Nitration oftoluene is difficult than thatofnitrobenzene
(C) The bromonium ion is a good nucJeophile
(0) Effective nitrating agent is nitrate ion
~or explosion purpose T.N.T. is mixed with which ofthe following

( ~(A)Ammonium chloride (B) Ammonium nitrate
. (C)Ammonium nitrite (O)Ammonium sulphate
Q.24 Which ofthe following electrophilic substitution reaction is fastest

(A) Nitration ofchlorobenzene (B) Nitration ofbenzene
(C) Nitration oftoluene (0) Nitration ofbenzoic acid
( Q.7A.1 Salicylic acid, aspirin, nylon, plastics and picric acid h~ve"acommon raw material, namely-
/.
VV (A) Methane (B) Formic acid (C) Phenol (D) Alcohol
Q.26A~henol and benzoic acid can be distinguished by

\.
/
\. :::]' ~A)AqUeOUSNaHC03 . (B) Aqueous NaN03
(
(C)Aqueous NaOH (0) Conc. ~S04
\.
( Q.27 Phenol is converted into salicylaldehyde by

(A) Etard reaction (B) Kolbe reaction
( (C) Reimer- Tiemann reaction (0) Cannizzaro reaction
/
\. Q28 Phenol and cycJohexanol can be distinguished by using
(A) FeCI3 (B) Na (C) PCIs (D)CH3COCI
t
\.
Q.29 Benzaldehyde is used in all except

(
\. (A) In the manufacture ofperfinning agents (B) As an oxidising agent
(C) In the manufacture ofdyes "(0) In the manufacture ofcosmetics
(
~}j
Choose the wrong statement-
c (A) Smell ofbenzaldehyde and mirbane oil is not different
(B) Benzaldehyde undergoes Tischenko reaction
(C) Benzaldehyde reduces Fehling's solution
(,.
(0) Dry distillation ofcalcium benzoate gives a ketonic compound

(
Q.3){' Which aldehyde is used fu the manufacture ofperfinnes
( /' U (A)Cinnamaldehyde (B) Benzaldehyde {C)Propionaldehyde (D) Acryladehyde
[.
'l. Q.3 2 Which ofthe following is not a correct statement
(A) Acetophenone does not give a red colour precipitate with fehling's solution
( (B) Benzaldehyde gives a red coloured precipitate with Fehling's solution
(C) Benzaldehyde gives silver mirror with Tollen's reagent
t (D) Benzaldehyde gives a black grey precipitate with mercuric chloride solution
/
\...
li'~~~~ AROMATIC COMPOUND /49}
(~
f
\.
l
Q.33 The fmal product ofthe reaction
C6H6 + Cl2 is
(A) C6HsCI (B) o-C6H4C~ (C) p-C6H4C12 (0) C6H6Cl 6
Q.34 Among the following species, which one is expected to show the greatest stability ?
(A) O
e
~
(B) O
$
~
(C) 0 (D) 0.
,.6.35\
Which of the following is fonned as the major product when toluene (excess) reacts with CH3Cl at
" - / 80DC in the presence of AICl3 ?
(A)o-Xylene (B)p-Xylene (C) m-Xylene (0) Ethylbenzene
Q.3'J 3-Chloro-4-methylbenzenesulphonic acid reacts with superheated steam to give

\/I (A) m-chlorobenzenesulphonic acid . (B) toluene '--'.
(C) p-methylbenzenesulphonic acid (0) o-chlorotoluene
Q.37 Sodium benzenesulphonate is fused with solid NaOH and then acidified with dilute H2S04, The
product obtained is

/
(A) benzene (B) phenol
(C) 3-hydroxybenzenesulphonic acid (0) thiophenol
Q.38 When phenol is treated with a solution ofBr2 in carbon disulphide at OOC, the major product fonned
is
(A) 2, 4, 6-tribromophenol (B) o-bromophenol
(C) p-bromophenol (0) m-bromophenol
Q.39. Beznyl alcohol and phenol can be distinguished by using""':

(A) FeCl3 solution (B) Na
(C) CH3COCVpyridine (0) CH3MgJ/ether
~When calcium benzoate is heated with calcium fonnate, the major product fonned is
. (A) benzaldehyde . (B) acetophenone .
(C) beuzophenone (0) acetaldehyde
Q.41 In the Cannizzaro reaction:

2PhCHO PhCH20H + PhCOO
the slowest step is
(A) the attack of the OH- at the carbonyl group
(B) the transfer of the hydride ion to the carbonyl group
(C) the abstraction ofproton from the carboxylic acid c
(0) the deprotonation ofPhC~OH
c
li!~~~ CL~~!"
111«>1""_
[~
G
ASSERTION AND REASON TYPE QUESTION:
Each -of the questions given below consist of Statement - I and Statement - ll. Use the following Key
to choose the appropriate answer.
(A) Ifboth Statement- I and Statement-II are true. and Statement- II is the correct explanation of
, Statement- L
(B) Ifboth Statement - I and Statement -II are true but Statement - II is not the correct explanation
ofStatement - I.
(C) IfStatement - I is true but Statement - II is false.
(D) IfStatement - I is false but Statement - II is true.
Q.42 Statement-I : Phenol is more reactive than benzene towards electrophHic substitution.
Statement-II : In case of phenol, the intermediate carbocation is more resonance stabilized.
. ~~~t -I : p-nitrophenol is stronger aCid than o-nitrophenol.

~ement-ll
, \'"
: Iritramolecular hydrogen bonding makes ortho-isomer weaker acid than para isomer.
Q.44 Statement-I : Phenol is stronger acid than alcohols.

(
Statement-II : Phenol is stabilized by resonance whereas alcohols are not.
(
Q.45 Statement-I : Phenols undergo electrophilic substitution at the ring much more readily than aryl
\.
halides.
f"
Statement-II : In aryl halides electron density at the ring decreases due to resonance whereas in
" phenols it increases.
(
1- Q.46 Statement-I : --OR group in phenols cannot be substituted easily.
" Statement-II : C--O bond in phenols has partial double bond character due to resonance.
"
(
(
'
lil AROMATIC COMPOUND [51)

c
c
EXERCISE-III
(SECfION-A)
Q.l Bottles containing C6H51 and C6H5CH21 lost their original labels. They were labelled A and B for
testing. Aand B were sep8rately taken in test tubes and boiled with NaOH solution. The end solution in
each tube was made acidic with dilute HN03and then some AgN03 solution was added. Substance B
gave a yellow precipitate. Which one ofthe following statements is true for this experiment?
(A) B was C6HsI (B) Addition ofHN03 was unnecessary

(C) A was C6H51 (D) A was C6H5CH21 [AIEEE-2003J
Q.2 Which one ofthe following undergoes reaction with 50% sodium hydroxide solution to give the
corresponding alcohol and acid? [AIEEE-2004]
(A) Phenol (B) Benzaldehyde (C) Butana1 (D) Benzoic acid
Q.3 p---cresol reacts with chlorofonn in alkaline medium to give the compound A which adds hydrogen
cyanide to form, the compound. B The latter on acidic hydrolysis gives chiral carboxylic acid. The
structure ofthe carboxylic acid is - [AIEEE-2005J
.
/ '
"'/
~
CH 3
0
CH{OH)COOH
(B)
(A) VCH{OH)COOH b ' /
\
OH OH
CHa CH3
(D) OCH'COOH
(e) QCH' COOH
OH OH .
( ",
, ~
QA Fluorobeazelle (C6H5F) can be synthesized in the laboratory - [AIEEE 2006J

(A) from aniline by diazotisation followedby heatingthe diazonium saltwith HBF4
(B) by direct fluorination ofbenzene with F2 gas
(C) by reacting bromobenzene with NaF solution f'
"'---'
(0) by heating phenol with HF and KF
Q.5 Phenyl magnesium bromide reacts with methanol to give - .[AIEEE 2006J '.
(A) a mixture ofbenzene and Mg(OMe) Br (B) a mixture oftoluerie and Mg(OH)Br
(C) a mixture ofphenol and Mg(Me)Br (D) a mixture ofanisole and Mg(OH)Br c
OH O-Na+
Q.6 @0. + CHCIa + NaOH - 7 0
~CHO'
.
The electrophile involved in the above reaction is-
. e
[AIEEE 2006J e
(B) trichloromethy1anion ( ccr3)
(A) dichlorocarbene ( :CC12)
(1)
c
(C) fonnyl cation (~HO) (D) dichloromethyl cation (CHCf])
IElBANS. . AROMATIC COMPOUND [52} ( .

. ~PR'VA \J'
{'
'1.../
c
Q.7 The structure ofthe compound that gives a tribromo derivative on treatment with bromine water is
[AIEEE 2006}
(A)e ~OH
(D)0
CH3
(C)$
CH20H CH3
(B)~
oH
OH
Q.8 The reaction oftoluene with CI2 10 presence ofFeCI3 gives predominantly- [AIEEE 2007]·
(A) benzoyl chloride (B) benzyl chloride
(C) o-and p-chiorotoluene (D) m-chiorotoluene
~PhenoI, when it first reacts with concentrated sulphuric acid and then with concentrated nitric acid,
,
\,
gives- . . . [AIEEE 2008J
(
(A) o-nitrophenol(B) p-nitrophenol (C) nfuobenzene ~6-trinitrobenzene
Q.IO Toluene is nitrated and the reSUlting product is reduced with tin and hydrochloric acid. The product so
(
\.
obtained is diazotiseci and then heated with cuprous bromide. The reaction mixture so fonned contains
[AIEEE 2008]
(
(A) mixture ofo- and p-dibromobenzenes (B) mixture of 0- and p-bromoanilines

(
(C) mixture of0- and m-bromotoluenes (D) mixture of0- and p-bromotoluenes
\.
Q.ll The major product obtained on interaction of phenol with sodium hydroxide and carbon
\
dioxide is - . [AIEEE 2009]
(A) salicylaldehyde (B) saIicyclic acid (C) phthalic acid (D) benzoic acid .
(
" Q .12 . In the chemical reactions
,.
\.. NH2
c @ NaN°Z )
HCI,278K
A HBF4 >B
( the compound fA' and 'H' respectively are : [AIEEE-2010)

(A)Benzene diazonium chloride and fluorobenzene
( (B) Nitrobenzene and chlorobenzene
(C) Nitrobenzene and fluorobenzene
( (0) Phenol and benzene
,( Q.13 Phenol is heated with a solution ofmixture ofKBr and KBI03 . The major product,obtained in the above
reaction is: [AIEEE-2011)
( . (A)2-Bromopheonol (B)3-Brotnopheonol (C)4-Bromopheonol (D)2,4,6-Tribromophenol
(. Q.14 Which ofthe following reagents may be used to distinguish between phenol and benzoic acid?
[AIEEE-2011]
(A) Aqueous NaOH (B) Tollen's reagent (C) Molisch reagent (D) Neutral FeCI3
tI1!~~~A~~ CJ!~~~~!
_frKSchoion
,{
\.
Q.15 Ortho-Nitrophenol is less soluble in water than p- and m-Nitrophenols because: [AIEEE-2012]
(A) o-Nitrophenol shows intermolecular H-bonding
(B) Melting point ofo-Nitrophenol is lower than those ofm-and p-isomers.
(C) o-Nitrophenol is more volatile in steam than those ofm-and p-isomers.
(0) o..:Nitrophenol ~hows intramolecular H-bonding
Q.. 16 Aspirin is known as : [AIEEE-2012J

(A) Acetyl salicylate (B) Methyl salicylic acid
(C)Acetyl salicylic acid (0) Phenyl salicylate
Q.. 17 What is OOTamongthe following: [AIEEE-2012J

(A) Biodegradable pollutant (B) Non-biodegradable pollutant
(C) Greenhouse gas {D)Afertilizer
Q.. 18 Compound (A), CsH9Br. gives a white precipitate when warmed with alcoholic AgN03' Oxidation of
\
(A) gives an acid (B), Cs~O4' (B) easily forms aphydride on heating. Identify the compound (A).
/
(',
~CH
(A)~, 25
Br
(B)J;' (C)~
~O'CH2Br
CH3
(0)
~
o
"
CH2Br
' (
"
CH3
('
PEE Main-2013J
Q. ~ A solution of(-) - l--chloro -1- phenylethane on toluene racemises slowly in the presence ofa small
VII"'" amountofSbCls due to the formation of: : ' [JEE Main-2013J /
\.
(A)carbene (B)carbocation (C)freeradical (D)carbanion
r
(SECTION-B)
Q .20 The chlorination oftoluene in'presence offerric chloride give's predominantly - [I1T -1986]
(A) BenZyl chloride, (B) m-chlorotoluene (C) Bemal chloride (0) o-and- p-chlorotoluene c
Q.21 Chlorination oftoluene in the presence of light and heat followedby treatment with aqueous NaOH ,-..
G
gives- [lIT -1990J
(' "
(A) o-cresol (B) p-cresol v
(C) 2,4-dihydroxytoluene (D) Benzoic acid
c
Q..22 Aryl halides are less reactive towards nucleophilic substituion reaction as compared to alkyl halides
due to- ' [IIT-1990J c
(A) The formation ofless stable carbonium ion (B) Resonance stabilization ( ,
"'-'
(C) Longer carbon-halogen bond' ,(D) The inductive effect
c
~
Among the following statements on the nitration ofaromatic compounds, the false one is
(A) The rate ofnitration ofbenzene is almost the same as that ofhexadeuterobenzene C
(B) The rate ofnitration oftoluene is greater than that ofbenzene , [lIT -1997]
b
(C) The rate ofnitration ofbenzene is greater than that ofhexadeuterobenzene
(D) Nitration is an electrophiJic substitution reaction o
c
"LtJ!~~'A~CL~~~!
_,",S<ho/a"
AROMATIC COMPOUND {54]
c
{,
v
{'
v
Q.24 A new C - C bond is formed in - [IIT-1998]
(A) Cannizzaro's reaction (B) Friedel Crafts reaction
(C) Both (A) & (B) (D) None ofthese
Q.25 Benzyl chloride (C6HsC~Cl)can be prepared from toluene bychlorination with - [IIT-1998]
(A) S02Cl2hu (B) SOC~ (C) PCIs (D) NaOCI
Q.26 A solution of(+) -l-chloro-l-phenylethane in toluene racemises slowly in the presence ofsmall amonnt
ofSbCls' due to the formation of: [JEE 1999}
r~
(A)Carbanion (B)Carbene (C)Free-radical (D)Carbocation
Q.27 Amongst the following the strongest base is: [JEE 2000]
(A) C6HSNH2 (B) p-02NC6H4NH2 (C) m-02NC6H4NH2 (D) C6HsC~~
Q.28 IdentifY the correct order ofreactivity in electrophilic substitution reactions ofthe following compounds:
( ~ , CH3 . C! N02
" roO
(A) I> II> III> IV
006
(B) IV > III> II> I
~6
(C) II> I> III > IV
~6 ~~
(D) II > III> I> IV
( (CH3 )2 NH ) A (i)NaN02 HC) 0°-5°C) B

Q.29 F-@-N02 [JEE2003]
/
DMF (ii)H 2 Catalytic Reduction
\,
.H3 C
/
\. (A)02N-@--~ (B) ~
H3C/N-&~N~
'"
/
"
( H3C", ~~~ H3C",

(C) / N - & N 02 (D)
HC/
N~O
~~-N02
(- H2C , 3 .
I
NH2
(
/' H 0
OO
L
Me Br2 ~
Q.30 . 0 0 Me Fe
[JEE2004J
(
\.~ Major product ofabove reaction is:
~
( , o
~'O'Me
"
Me
( . Me
(B) 0 ~ M,
(A) 0 (' Br
{
(
(C)
Me
Br
.65 H
"'\ (
0
Me (D)
Me
~ ~ 0
o
1i~~~~A~~CJ1l~~~!
f AROMATIC COMPOUND [55J
'<.
, _forS<1IoI<m
f
\..
L
Q.31 Which ofthe following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of
sodium acetate? [JEE 2005]
(A) CH3 0 COONa (B) CH3 -< > + S03
(C) CH3 -< )- S03 Na + CH3COOH (D) CH3 -< )-S020. COCH3 + NaOH
·
Q.32
OI.,.,:;: +CI-CH 2CH2 - CH 3
The major products P and Q are

Aiel)
-----"--7
P 0)°2 1.1 >Q + Pheno I
(ii)Hp+ [JEE2006]
(A) 0 CH,C~CHO
and (B) 6 and CH,COCH,
(C) (5 and CH,COCH, (D) (5 and CH,CH,CHO (

\.
Q.33 In the following reaction, [JEE2007]
QI ..~
~. I N
'O
conc.HN0 3
>X
cone. H2S0 4
H ,.9
("
\. "
the structure ofthe major product 'X' is
QI~
'O 02N~~O
(A) ~ ~ ~I;l I.~
..
'<:::: NO2 . (B)
I H R' H· ,.,7
~.~o
~N ~ ~~O.
02N~~ 1'<::::
(C) H. I ,.9 N0 (D) H.d
Q.34 STATEMENT-l: Bromobenzene upon reaction with Br2 / Fe gives 1, 4-dibromobenzene

Vi and
as the major product.
STATEMENT-2: In bromobenzene, the inductive effect ofthe bromo group is more dominant·
than the mesomeric effect in directing the incoming electrophile.

G
(A) STATEMENT-l is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-l
(B) STATEMENT-l is True, STATEMENT-2 is True; STATEMENT-2 is NOTa co-;;'ect explanation

for STATEMENT-l
e
(C) STATEMENT-l isTrue, STATEMENT-2 is False c
(D) STATEMENT-l is False, STATEMENT-2 is True [JEE2G08]
iJ~~~~~\ CL~~'" AROMATIC COMPOUND {56] ( '.

I<koIf",Sc""I4r< v
c
ct31;. S!A1EMENT-l : Aniline on re~c~ion with NaN0 2/ HCI at OQC followed by coupling with p-naphthol
~lves a dark blue coloured precIpItate.
and
STATEMENT-2 : The colour ofthe compound fonned in the reaction ofaniline with NaN02 / HCI at O~
followed by coupling with f}-naphthol is due to the extended conjugation.
(A) STATEMENT-l is True, STATEMENT-2 is True; STATEMENT-2 is a correct explanation for
STATEMENT-l
(B) STATEMENT-l is True, STATEMENT-2 is True; STATEMENT-2 is NOT a correct explanation
for STATEMENT-l
(C) STATEMENT-I is True, STATEMENT-2 is False
(D) STATE1vlENT-l is False, STATEMENT-2 is True [JEE 2008]
Q.36 The compounds P, Q and S ° [JEE2010]
~OCH3 II~
~COOH
~,N
VO
(
"
HO~ H3C~
P Q
( 'I
S
'" ' were separately subjected to nitration using HN03 / I-IzS04 mixture. The major product formed in each
f
\ case respectively, is
II~
°
~COOH ~OCH3
(Y'~~
\
r~ (A)HO~ ~ H~~ 02N~
N02 NOz
{
\
~ °II rn
CX'~
( ~~yCOOH . ~OCH3
(B)HOA ANO
z H3C~ N02
c NO z
°II~N02
(
(C)HO~
~COOH ~OCH3
H3CAA~NOz
()~
C
NOz
c
c R~
~COOH ~ ~OCH3
H3CAA~N02
('0'~
V~ N92
(D)HO~
(: N02
C
fI'~~A~CLl!!.~~~!
I
\..- AROMATICCOMWOUND [57J
IdftJlftNSchol<Jn
c
{;
~- ~
c
9.3} Amongst the compounds given, the one that would fonn a brilliant colored dye on treatment with NaN02
V in dil. Hel followed by addition to an alkaline solution of~-naphthol is [JEE 2011]
r(Y'N(CH3)2 . r ( Y 'NHeH3
W~ OO~
r(Y'NH2
(C) N (D)~,NH'
H3C
Q.38 The major product ofthe following reaction is [JEE2011]
o
~H
. 0
. (i)KOH
(ii) Br-Q--cH2CI
')0
,
. . 0
o
cQ---Q----rn,el
/'
(A)~-eH,-o-Br
(B)
o o
o
(e)
cQ I ~
. O-CH2- o - B r
_
(D)~ cQl~ O~
F\ eRel
2
'
(
\.'
Q.39 Which ofthe following molecules, in pure from, is (are) unstable at room temperature ?[JEE 2012]
'r?l
(A) V , (8)0 (C)O o
0)6 o (,-'""
\.
c
Q.40 Themajorproduct(s)ofthefollowingreactionis(are) [JEE Advance 2013]
.¢~
I
OH
#
aqueous Br.(3.0 equivalents)
)
?
• c
(~
S03H
( '.
o
B~B'
B~B'
~ h(' G
I~ I~ I~ I~
0
Br.
#
B # Br B
#
r
C
S03H
p
Br Br S03H e
Q R S
(A)P (B)Q (C)R (D)S
u
c
[i AROMATIC COMPOUND [58J
(."
'0
c:
c
ANSWER KEY
EXERCISE-I
Q.l e Q.2 A Q.3 e QA B Q.5 B Q.6 e Q.7 e
e'
(
" Q.8 B Q.9 e Q.I0 D Q.ll A Q.12 e Q.13 D Q.14 D

Q.15 D Q.16 D Q.17 e Q.18 e Q.19 B Q.20 D Q.21 B
Q.22 D Q.23 D Q.24 B Q.25 B Q.26 e Q.27 D Q.28 D
Q.29 e Q.30 D Q.31 A Q.32 B Q.33 e Q.34 A Q.35 D
Q.36 B Q.37 A Q.38 D Q.39 A QAO A
EXERCISE - II
(
Q.l e Q.2 B Q.3 D QA B Q.5 e Q.6 A Q.7 D

Q.8 A Q.9 D Q.I0 A Q.ll A Q.12 B Q.13 B Q.14 e
Q.15 D Q.16 e Q.17 e Q.18 e Q.19 e Q.20 e Q.21 e
Q.22 A Q.23 B Q.24 e Q.25 e Q.26 A Q.27 e Q.28 A
Q.29 B Q.30 e Q.31 B Q.32 B Q.33 D Q.34 A Q.35 e
Q.36 D Q.37 B Q.38 e Q.39 A QAO B QAl B QA2 A
(' Q.43 A Q,44 B QA5 e QA6 A
\
(
\
EXERCISE-ill
Q.l e Q.2 B Q.3 A QA A Q.5 A Q.6 A Q.7 D
('
\.. Q.8 e Q.9 6 Q.I0 D Q.l1 B Q.12 A Q.13 D Q.14 D

Q.15 D 'Q.16 C Q.17 B Q.18 e Q.19 B Q.20 D Q.21 D
C Q.22 B Q.23 e Q.24 B Q.25 A Q.26 D Q.27 D Q.28 e
Q.29 B Q.30 D Q.31 e Q.32 e Q.33 B Q.34 e Q.35 D
Q.36 e Q.37 e Q.38 A Q.39 Be QAO B
C
C
(
f
\.,
(
AROMATIC COMPOUND [59J
feDlforScholars
"',
'"
<.
c
C)
CONTENTS
KEY CONCEPT................................;................................ Page 2 - 28
SOLVED EXAMPLE.................................................•....•.. Page 29 - 35
EXERCISE-I........~ ............................................................ Page 36 - 41
EXERCISE-II ................................................................... Page 42 - 49
EXERCISE-III.................................................................. Page 50 - 55
ANSWER KEy................................................................... 'Page 56
"
(
"
{'
\. ~
JEE MAIN - 2014
( ELECTROCHEMISTRY
/'
l,
c
(
('
t
ELECTRO-Ca.EMISTRY
ELECTROCHENUCALCELLS
Ail electrochemical cell consists oftwo electrodes (metallic conductors) in contact with an electrolyte
(an ionic conductor). An electrode and its electrolyte comprise an Electrode Compartment
Electrochemical Cells can be classified as:
. .(i) Electrolytic Cells in which a non-spontaneousreaction is driven by an external source ofC\UTent.
(il) Galvanic Cells which produce electricity as a result ofa spontaneous cell reaction
Electrochemical cell :
An electrochemical cell is a system consisting ofelectrodes that dip "into an electrolyte and in which a
chemical reaction either uses or generates an electric current.
A voltaic or galvanic cell is an electrochemical cell in which a spontaneous reaction generates an electric
current.
A voltaic cell consists oftwo half-cells that are electrically connected. Each halfcell is the portion ofan
electrochemical cell in which a half-reaction take place.
Asimple half-cell can be made from a metal strip that dips into a solution ofits metal ion. An example is
the zinc-zinc ion half-cell (often called simply a zinc electrode), which consists ofa zinc metal strip
dipping into a solution ofa zinc salt. Another simple half-cell consists ofa copper metal strip dipping into
.a solution ofa copper salt (copper electrode).
In a voltaic cel~ two half-cells are connected in such a way that electrons flow from one metal electrode
to another through an external circuit, and ions flow from one half-cell to another through an internal cell
connection. Figure given below illustrates an atomic view ofa vol~c cell consisting ofa zinc electrode
and a copper electrode. As long as there is an external circuit, electrons can flow through it from one
electrode to another. Because zinc tends to lose electrons more readily than copper, zinc atoms in the 1-<"..,
'-.,
zinc electrode lose electrons to produce zinc ions. These electrons flow througb the external circuit to the
copper electrode, where they react with the copper ions to produce copper metal, and an electric
currentflows through the external circuit.
Cathode ofCu
(+ve electrode)
The two half-cells must be connected internally to allow ions to flow between them. As zinc ions continue
to be produced, the zinc ion solution begins to build up a positive charge. Similarly, as copper ions plate
out as copper, the solution builds up a negative charge. The halfcell reactions will stop unless positive
ions can move from the zinc half-cell to the copper half cell, and negative ions from the copperhalf-cell
can move to the zinc half-cell. It is necessary that these ion flow occur without mixing ofthe zinc ion
and copper ion solutions. Ifcopper ioricome in col1mcfwitli"tlui zmc metal: for eXample:" direct~action
would occur without an electric current being generated. The voltage would drop, and the battery ()
would run down quickly.
c
[tJ~~~A~C~~~~~~" ELECTROCHEMISTRY [2J {
IdcclforSchoklr$
"--'J
c
The two half-cells ofa voltaic cell are connected by a salt bridge. A salt bridge is a tube ofan electrolyte
in a gel that is connected to the two half-cells ofa voltaic cell; the salt bridgeaUows the flow ofions but
prevents the mixing ofthe different solutions that would allow direct reaction ofthe ceJl reactants. The
half-cells are connected externally so that an electric current flows.
The two half-cell reactions, as noted earlier, are
Zn(S) --) Zn2+(aq) + 2e- (oxidation half-reaction)
Cu 2+(aQ) + 2e---) Cu(S) (reduction half-reaction)
The fIrst half-reaction, in which a species loses electrons, is the oxidation half-reaction. The electrode
at which oxidation occurs is called the anode. The second half-reaction which a species gains electrons,
is the reduction half-reaction. The electrode at which reduction occurs is called the cathode. These
definitions ofanode and cathode hold for all ele~trochemical cells, including electrolytic cells.
Note that the sum of the two half-reaction
Zn(S) + Cu2+(aq) --) Zn2+(aq) + Cu(S)
The net reaction that occurs in the voltaic cell, it is called the cell reaction.
Once you know which electrode is the anode and which is the cathode, you can determine the
/
direction of electron flow in the external portion ofthe circuit. Electrons are given up by the anode
\ (from the oxidation half-reaction) and thus flow from it, whereas electrons are used up by the cathode
(by the reduction half-reaction) and so flow into this electrode. The anode in a voltaic cell has a
" negative sign, because electrons flow from it. The cathode in a voltaic cell has a positive sign.
.J
( -dfU..
"
Note:
\
~ 1. The salt-bridge contains solution ofstrong ionic salts like NaCI, NaN03, KN03, KCI etc.,
which is soaked in a colloidal solution ofagar-agar gel which permits the movement ofions
ofsalts only.
£
\ 3. Salt bridge carries whole ofthe current across the boundary; more over the K+and N03- ions
have same speed. Hence, salt bridge with uniform and same mobility ofcations and anions
r
\ . completes the electrical circuit & permits the ions to migrate.
2. I~ maintains the electrical neutrality ofthe solutions in the two half-cens. In the absence ofsalt
(
'
bridge, a reverse potential difference is set up in the two half-cells which results in breaking the
continuous supply ofvoltage.
In a galvanic cell, cathode is positive With respect to anode.
c REPRESENTATION OFA CELL ( IUPAC CONVENTIONS) :
Letus illustmtethe convention taking the example ofDanielcell.
( (i) Anodic half ceJl is written on left and cathodic half cell on right hand side.
( Zn(s) IZnS04 (sol) II CuS04 (sol) 1Cu(s)
(it) Two half cells are separated by double vertical lines: Double vertical lines indicate salt bridge or any type
( ofporous partition.
(fu) EMF (electromotive force) may be written on the right hand side ofthe cell.
( (iv) Single vertic~llines indicate the phase separation between electrode and electrolyte solution.
Zn I Zn 2+ II Cu2+ I Cu .
(v) Inert electrodes are represented in the bracket
( Zn I ZnS04 11 H+ I H2, (Pt)
CLASSES
TED ELECTROCHEMISTRY [3J
.': I!~ I
JOtOll(Jts;;;;;;;,u;
t
c
Ex.1 Writing the cell Reaction from the Cell Notation
(a) Write the cell reaction for the voltaic cell
2
TI(S) I TI+(aq) II Sn (aq) I Sn(S)
(b) Write the cell reaction forthe'voltaic cell

/~
Zn(2) I Zn2+(aQ) II Fe3+(aq)' Fe2+(8q) I Pt

Problem strategy: The cell notation gives the species involved in each half-reaction. Complete the
balance each half-reaction, then mUltiply by factors so that when you add the half-reactions, the
electrons cancel. The result is the cell reaction.
Sol. (a) The half-cell reactions are
TI(S) - - ) 0 TI+(aq) + e-, Sn2+(83) + 2e- - - ) 0 Sn(S)
Multiplyingthe anode reaction by 2 and then summing the half-cell reactions gives
2TI(S) + Sn2+(aq) - - ) 0 2Tl+(a9) + Sn(s)
(b) The halfcell reactions are
Zn(S) - - ) 0 Zn2+(aq) + 2e-. Fe3+(aq) + e-- - ) 0 Fe2+(aq) and the cell reaction is :
Zn(S) + 2Fe3\aq) - - ) 0 Zn2\aq) + 2Fe2\aq)
ELECTRODEPOTENTLAL:
When a metal is placed in a solution ofits ions, the metal acquires either a positive or negative charge
with respect to the solution. On account ofthis, a defmite potential difference is developed between the'
metal and the solution. This potential difference is called electrode potential.
The potential difference is established due to the formation ofelectrical double layer at the interface of
metal and the solution. The development ofnegative charge (as on zinc plate) or positive charge (as on
copper plate) can be explained in the folloyving marmer.
(a) Oxidation: Metal ions pass from the electrode into solution leaving an excess ofelectrons and thus
a negative charge on the electrode.
M(s)--)o Mn (aq.) + ne
(b) Reduction: Metal ions in .solution gain electrons from the electrode leaving a positive charge on the
electrode.
Mn+(aq.)+ne---)o M (s)
,~
"
The magnitude ofthe electrode potential ofa metal is a measure of its relative tendency to undergo
oxidation (loss ofelectrons) or reduction (gain ofelectrons). The magnitude ofpotential depends on the
following factors :
(i) Nature ofthe electrode, (n) Concentration ofthe ion is solution
(Iii) Temperature.
, [j]'~~~A~~C~,~~~~!
lIkolr...SdIoIoIS
ELECTROCHEMISTRY /4J
c
Depending on the nature ofthe metal electrode to lose or gain electrons, the ele9trode potential may be
oftwo types :
(i) Oxidation potential: When electrode is negatively charged with respect to solution, Le., it
actsc as anode. Oxidation occurs.
M~Mn++ne-
(ii) Reduction potential: When electrode is positiv~ly charged wit respect to solution. i.e., it acts
as cathode. Reduction occurs.
( Mn++ne-~M
it is not possible to measure the absolute value ofthe single electrode potential directly. Only the difference
(. in potential between two electrodes can be measured experimentally.
( CONCEPT OF ELECTROMOTIVE FORCE (EMF) OFA CELL

Electron flows from anode to cathode in external circuit due to a pushing effect called or electromotive
force (e.m.f.). EMF is called as cellpotential. Unit ofe.m.f. ofcell is volt.
(. EMF ofcell may be calculated as :
\
Eeell = reduction potential ofcathode - Reduction potential ofanode
C Similarly, standard e.m.f. ofthe cell (EO) may be calculated as
P cell = Standard reduction potential ofcathode - Standard reduction potential ofanode'
~
( '.'
. ... \ l ".' ...•. " "
" ,J :_<~ <. Which electrode ofa galvanic cell orresponds to the higb~r potential energy.
( < i
( SIGN CONVENTION OF EMF

f
EMF ofcell should be positive otherwise it will not be feasible in the given direction.
" Zn 1ZnS04 J1 CuS04 1Cu E = +1.10 volt (Feasible)
{ Cu 1Cuso411 ZnS041Zn E = -1.10 volt (Not Feasible)
"
( RELATIONSHIP BETWEEN .6.GAND ELECTRODE POTENTIAL
Let n, Faraday charge is taken out from a cell ofe.m.f. (E), then electrical work done by the cell
may be calculated as,
Work: done =Charge x Potential = nFE
From thermodynamics, we know that decrease in Gibbs free energy ofa system is a measure of
reversible or maximum obtainable work by the system.
: . .1.G=-nFE
( Under standard state .1.GO == -nFEo ~)
(i) From thermodynamics we know, .1.G = negative for spontaneous process. Thus from eq.(i) it is
( clear that the EMF should be +ve for a cell process to be feasible or spontaneous.
( (it) When .1.G = positive, E = negative and the cell process will be non spontaneous.
Reactions .6.G E
(. Spontaneous .(-) (+)
Non-spontaneous (+) (-)
C Equilibrium 0 0
Standard free energy change ofa cell may be calculated by electrode potential data.
Substituting the value of EO (Le., standard reduction potential ofcathode- standard reduction potential
c ofanode) in eq. {i) we may get .1.Go.
jjJ~~~~A~ CM~~~! ELECTROCHEMISTRY [5) ,

ldeolfDl5dlokm
c
NERNSTEQUATION
WalterNemst derived a relation between cell potential arid concentration orReaction quotient
aG=aGo+RTlnQ .. (1)
where aG and aGo ~ free energy and standard free energy change; 'Q' is reaction quotient.
:. -aG = nFE and -AGO = nFEo
Thus from Eq. (i),we get -nFE = -nFEo + RT InQ

-
At 25°C, above equation may be written as E Eo - 0.0591 gQ

1
--0
n
Where On' represents number of moles ofelectrons involved in process.
In general, for a redox cell reaction involving the transference ofn electrons
aA + bB ----7 cC + dD, the EMF can be calculated as:
E EO 0.0591 [C]c[D]d
"
,< ,
Cell CeU--- --log , ,

n [A]a[B]b
What will happen to the cell emfas cell start operating from standard condition.
(
"
Can the Nernst equation be used at temperature other than room temperature? What
-'- .
will happen to cell emfas temperature is increased slightly?
THERMODYNAMIC TREATMENT OF NERNST EQUATION

(i) Prediction and feasibility ofspontaneity ofa cell reaction. (' --'.
\ "
Let us see whether the cell (Daniell) is feasible or not: i.e. whether Zinc will displace copper or not.
Zn I(s) I ZnS04 (sol) II CuS04 (sol) I Cu(s)
E~2+/zn =- 0.76volt ; E~u2+ ICu =+ 0.34volt

r"
v
.E° cell °
= ECu2+/Cu _EO
Zn2+IZn
= 0.34 -(-0.76) =+1.10 volt
Since EO = +ve , hence the cell will be feasible and zinc will displace copper from its salt solution. In the.
other words zinc will reduce copper.
r',
(ii) Determination ofeqUilibrium coustant : We know, that ~
E= E o - -
0.05911
- o gQ ..(i)
n
At equilibrium,the cell potential is zero because cell reactions are balanced, i.e. E = 0 c
:. FromEq.(i), we have
e
0:::: EO 1
--0
'1 { nEo ]
' K eq=antlo-
0.0591 gK q or
n e 0.0591
.[i~~~~!!~CL~~~~!
{"
ELECTROCHEMISTRY {6] v
_1""5<1",.,,,
c
DIFFEREN1' TYPES OFHALF-CELLS AND THEIR REDUCTION POTENTIAL
(1) Gas-Ion HalfCell:
ill such a half cell, an inert collector ofelectrons, platinum or graphite is in contact with gas and a solution
containing a specified ion. One ofthe most important gas-ion half cell is the hydrogen-gas-hydrogen ion
halfcell. ill this halfcell, purified ~gas at a constant pressure is passed over a platinum electrode which
/-~
is in contact with an acid solution.
H+(aq) + e- 112 H2
r~
"
I' E + = EO + _ 0.0591
--log
~H2)\1/2
H /H 2 H IH
2 1 [H+]
,
(
(2) Metal-Metal Ion Half Cell:

This type ofcell consist ofa metal M in contact with a solution containing~ ions.
(
Mn+(aq) + ne- ~ M(s)
°
/~
"c E n+
M 1M
=E n+
M 1M
0.0591
-- -log--
n
1
[Mn+]
(
(3) Metal-Insoluble Salt-Anion Half Cell:
" ill this halfcell, a metal coated with its insoluble salt is in contact with a solution containingthe anion ofthe
r
insoluble salt. ego Silver-Silver Chloride HalfCell:
" This halfcell is represented as CI-/AgCl/Ag. The equilibrium reaction that occurs at the electrode is
(
AgCI(s) + e- ~ Ag(s) + Cl-(aq)
(
1:;' EO 0.0591 I "[CI-]
'""CO AgCll Ag cO AgClI Ag -1- - og
(
potentialofsuch cells depends upon the concentrationofanions. Such cells can beused as Reference Electrode:
.
(
(
(4) Oxidation-reduction HalfCell:
'--/ This type ofhalf cell is made by using an inert metal collector; usually platinum, immersed in a solution
which contains two ions ofthe same element in different states ofoxidation. ego Fe2+- Fe3+" halfcell.
Fe 3+(aq) + e- ~ Fe2+(aq)
2
EF 3+ 2+ = EO 3 _ 0.0591 I [Fe +]
( e /Fe Fe +/Fe2+ og --~
1 . [Fe3+]
( CONCENTRATION CELL
The cells in which electrical current is produced due to transport ofa substance from higher to lower
( concentration. Concentration gradient may arise either in electrode material or in electrolyte. Thus there
are two types ofconcentration cell. For such cell, EOCell = O.
( (i) Electrode Gas concentration cell :

Pt, ~(P \) I H+(C) I ~(P2)' Pt
Here, hydrogen gas is bubbled at two different partial pressures at electrode dipped in the solution of
same electrolyte.
(
[i!~~~~~CM~!~!
ldtoJfor$(ho1on
ELECTROCHEMISTRY [7}
(
c
Cell process: 1I2H2 (Pt) ---+ H+ (c) + e - (Anode process)
+
H (c) + e ---+ 112 H2 (P2)(cathode process)
1/2H2 (PI) ~ 1/~ H 2 (P2) (Net reactions)
112
E= 2.303RT log P2
F [ PI ]
or At 25°C E = 0.0591 1
, 2F og P2
[.!l]
For spontanity ofsuch cell reaction, PI>P2 ,--'.
(ii) Electrolyte concentration cells:

Zn(s) I Zn804 (C I) II Zn804 (C 2) I Zn(s) , '
'\
In such cells, concentration gradient arise in electrolyte solutions. Cell process may be given as,
,-
Zn{s )-,~,zn2+{Cl)+2e
,
(Anodic process)
Zn 2 +(C 2 )+2e ---'---» Zn(s) (Cathodic process) I'

'-
'
Zn 2 +(C 2 ) ¢ Zn 2+(C,) (Over all process)
From Nernst equation, we have
E= 2.303RT IOg[C Z ]
2F CI
For spontanity ofsuch cell reaction, C 2> C,
c
Can you Explain Why?
(i) Like other thermodynamic properties, ~H , ~8 and ~G, the sign orEo changes
but the magnitude of EO remains the same when we reverse the cell reaction.
(ii) Changing the stoichiometric coefficients ora half-cell reaction does not affect
the value of ED.
Ex~2 Using the standard electrode potentials predict the reaction, ifany, that occurs between the following:
(a) Fe3+(aq) and I-(aq) (b) Ag+(>q) and Cu(S)
(c) Fe3+(aq) and Br(aq) (d)A~s) and Fe +(aq)
3
(e) Br2(aq) and Fe2+(>q)

Given: EOFe3+ IF.2+ == +O.77V, E i1/r == +O.54V EOAg+1 Ag +O.80V, EOCul+ leu := +O.34V
EOBr2/Br- + l.08V
~,~~~~~C~~~~! Ithol tOt $cbokm

ELECTROCHEMISTRY [8} f'
"---'
c
Sol. (a) . Here I-(og) loses electrons and Fe3+(aq) gains electrons. Thus
~idationhalfcellreaction 2I-~ 12 + 2e-, EO =- 0.54V
Reduction halfcell reaction [Fe3++ e- ~ Fe2+] x EO = +O.77V
( -
Overall reaction 21- + 2Fe3+~ I2 + 2Fe2+' EOcell = 023V
•
\
Since E~II is +ve, the reaction is spontaneous i.e., the reaction does take place.
r
(b) Here CU(S) loses electrons and Ag+(aq) gains electrous. Thus
Oxidation halfcell reaction: Cu ~ Cu2++ 2e-, EO =- 0.34V
Reduction half cell reaction [Ag+ + e-~ AgJ x 2, EO = +O.80V
Overall reaction Cu + 2Ag+ ~ Cu 2++ 2Ag, E°cell= 0.46V
(
Since EOcell is +ve, the reaction is spontaneous
" (c) Here Br(aq) loses electrons and Fe3+(og) gains electrons. Thus
c Oxidation halfcell reaction 2Br~ Br2 + 2e-, EO =-l.OSV
( Reduction half cell reaction 2Fe3++ 2e-~Br2 + 2Fe 2+, EO == +O.77V
( Overall reaction 2Br + 2Fe 3+~ Br2 + 2Fe2+' EO""II 0.31 V

( Since EOcell is -ve, the reaction is non-spontaneous, i.e., reaction does not take place.
(d) HereAg loses electrons and Fe3+(aq) gains electrons. Thus
(
Oxidation halfcell reaction Ag ~ Ag+ + e-, EO = O.SOV
( Fe3++e- ~ Fe2+, EO = +0.77V
Reduction halfcell reaction
(
Overall reaction Ag + Fe3+~ Ag+ + Fe2+, EOeel' - 0.03V
c Since EOcdl is -ve, the reaction is non-spontaneous, i.e., reaction does not take place.
(e) Here Fe2+(aq) loses electrons and Br (aq) gains electrons. Thus
2
Oxidationhalfcellreaction 2Fe2+~ 2Fe3++ 2e-, EO =':..- 0.77

Reduction halfcell reaction Br2 + 2e- ~ 2Br, EO=+1.08V
c Overall reaction 2Fe2++ Br ~ 2Fe3++ 2Br EOcen +O.3IV
2 '
(
'-- Since EOcell is +ve, the reaction is spontaneous, i.e., the reaction does not take place.
(
Ex.3 Calculate the values for cell
2+11- CU aq2+1'Cn (i) cell reaction and

Zn IZnaq (ii) . c.m.f. of cell
c 1M 1M
( Given : E~l+ICu =+O.35V; E~l+IZn =-O.76V
Sol. (i) E~ forCu/Cu 2+=-0.35V
Egp for ZnlZn2+= +O.76V
-[iJ'~~~~~ ELECTROCHEMISTRY f9]

(
f
\.
c
More is E~p, more is tendency to show oxidation and thus Zn will oxidize and Cu2+ will reduce.
Anode Zn - 7 Zn2++ 2e
Cathode : Cu2+ + 2e-- 7 Cu
Cell reaction Zn + Cu2'" - 7 Zn2+ + Cu

(ii) Also, E~u = E~plnlZnl+ +E~Col + ICu 0.76'1- 0.35 =1.I1V
Ex.4 Calculate the standard e.m.f. ofthe reaction Fe3++ 3e- -4 Fe(S) EJ =?
Given Fe3++ e--4 Fe2+ EO1 =0771V

. Fe2++2e--4Fe(s) EO2 =-044V
.
Sol. With the help ofcalculation offree energy
l1G~ =-nFEo =-(I)(F)(O.771V)=-O.771V
LlG~ =-(2)(F)(0.44) =0.88FV

toG~ =-(3)(F)(EO)= -3FEOV
The free energy change for the unknown process can be obtained as ( ,
toGo3 = toGoI + toGo2

-3FEO -0.771F+0.88F=0.109F
('
or EO _ 0.109 -0.036V
3
Ex.S The standard electrode potentials of the electrode Cu2+ICu and Ag+IAg are 0.34V and 0.7991 V
respectively, What would be the concentration ofAg+ in a solution containing 0.06M ofCu2+ ion such
that both the metals can be deposited together. Assume that activity coefficients are unity and both silver (
and copper do not dissolve among themselves. " /
Sol. The individual reactions are : ('
Cu2++ 2e- - 7 Cu(5) .

' "
Ag+ + e- - 7 Ag(s) "
The electrode potentials given by Nernst equation
E(Cu
2+ 0.0591 ° 1 (00591)
ICu)=E =-2- log [Cu 2+]=0.037 . '2
1
logO.06 =0.037-0.036=0.301
E(Ag+ I Ag)= 0.7991- 0.0591 Iog _1_

1 [Ag+]
Two metals will be deposited together when the electrode potentials are equal i.e.
1 1 0.7991-0.301 =8.428
0.301 ::::0.7991-0.059I1og-+ i.eJog [Ag+]
. [Ag ] 0.0591
_1_=10 8.428 ('

~'
[Ag+]
or [Ag+] = 10-8.428:::: 0.37 X 10-8 mol dm-3
Ex.6 Calculate the equilibrium constant for the reaction,

Zn2++4N~-7 [Zn(NH3)4Y+ o
EO(Zn +IZn):::: - 0.763 and EO [Zn(NH3)4]2+IZn + N~) = 1.03V
2
{'
't..J
c
1i1~~~~.~~cy~~~~~
l(koJ (Of ScOOl4ts
ELECTROCHEMISTRY [10} c
c
Sol. The electrode reactions for the given electrodes, can be written as
Zn 2++ 2e- ~ Zn EY =-0.763V
[Zn(NH)4]2+ + 2e- ~ Zn + 4~ EY =-1.03V

Reaction (1) - (2)
Zn2++4NH3~ [Zn(NH )4P

3
The standard emfofthis reaction = EY -Eg = -0.763V -(-1.03) = 0.267V

i
According to Nemstequation E = EO _ RT In a[Zn{NH')4J"

(
2F a Zn,. 'a
(
. eqUl'I'b
Ifthe process IS 0.0591
1 rium, E = 0 at 25°C - - .- 1og
K == 0.267
2
,
" 10 K = (0.267)(2) 9.036
g (0.059)
{
"
(
K =10-0.36109 = 1. 09 X 109
The equilibrium constant is also called the "Stability Constant" ofthe complex. Ifthe reaction is written
\.
in a reverse manner, it will be "instability constant".

c Ex.7 To fmd the standard potential of M3+1M electrode, the following cell is constituted.
, Pt IM I M3+ (0.0018 mol-1L) IIAg+ (0.01 mol-1L) lAg
", The emf of this cell is found to be 0.42 volt. Calculate the standard potential ofthe halfreaction,
" M3+ + 3e- ---,)0 M EI)

Ag+/Ag
= 0.80 volt.
(
'. Sol. The cell reaction is: M + 3Ag+ ---,)0 3Ag + M3+
Applying Nemst equation,
(
0.0591 lM3+ J
( Eeell = E!n - - 3 - log [Ag+]3
(
\.
0.42
° 0.0591 (0.0018)
E cell - 3 log (0.01)3.
(
E~ell- 0.064
EOcell -- EOcathode
-
EOanode
EOanode -- EOcathode - EOcell = (0.80 - 0.484) = 0.32 volt

{
\. Ex.S Calculate the pH ofthe following half-cells solutions.
(a) Pt(H2) IH+(HCI) E=0.25 volt
(
latm
( (b) Pt(H ) IHI< (H2S04) E= 0.3 volt
2
latm
( Sol. (a) H2 ---,)0 2HI< + 2 e
( EH m+
°
= EH 2 IH+ -
0.0591
--log P
[H+f .
= 0.0 -
[H+]
0.0591 log -
2 2 H2 I
0.25 = 0.0591 pH
C 0.25
pH = 0.0591 = 4.23
C
C lll~~~~,,~~ CL~~~~!
IdtolfcrSd>oIo~
ELECTROCHEMISTRY Ill)
f
\.>
(
"
L
o 0.0591 [H+f
(b) EH IW = EH m+ - - log - p
2 2 2 H2
[H+]
= 0.0 -- 0.0591Iog-
". 1
0.3 = 0.0591 pH
0.3
pH = 0.591 = 5.076 .
Ex.9 What is the standard potential ofthe TP+{f1 electrode?

TP++2e- ~ n+ EO= 1.26 volt]
Tl++ e - - ) n EO=--0.335 volt ,
Sol. TP+ + 2e- - ) TJ+ nFEo = 2 x 1.26 x F = 2.52 F
Tl+ e--- ) Tl nFEo = 1 x (-0.336) x F=- 0.336 F ',/
,"'.
~.
addition TP++3e Tl 2.52F-0.336F = 2.184 = 0.728 volt
EO= nF 3 i '
Ex.tO Calculate the emfofthe following cell at 25°C.

Pt Hz I HCI I Hj't / .
2a1m lOatm
'.
0.0591 2
Sol. EcelJ = - 2 - log 10
0.0591 2
= - 2 - log 10 ( ,
'-/
= -- 0.0206 volt
Ex.ll Calculate the emfofthe cell Zn-Hg (C t )/Zn2+ (aq) IZn- Hg (C2) at 25°C, ifthe concentration of the
zinc amalgam are C 1 = 2 gm per 100 gm ofHg and C z = 1 gm per 100 gm ofHg.
Sol. At cathode: Zn 2++ 2e-- ) Zn(C2) (,
At anode: ZIt(C 1) - ) Znz+ + 2e- V
Net reaction Zn(C t) - ) Zn (C2)
E 0.059 log C z =-0.29510g(~) = 8.8x 10-3 V
2 C1 . 2
COMMERCIALVOLTAIC CELLS
Batteries can be classified as primary and secondary. Primary batteries can not be returned to their
. orjginal state by recharging, so when the reactants are consume,d, the battery is "dead" and mllst be
discarded. Secondary batteries are often called storage batteries or rechargeable batteries. The reactions
in these batteries can be reversed; thus, the batteries can be recharged.

e
[I]~~~~.~~CHL,~~~~~ ELEctROCHEMISTRY [12J

Idtol 10l'.smotor.J
"v
c
PRIMARY BATTERIES:
DRY CELLSAND ALKALINE BATTERIES
Zinc serves as the anode, and the cathode is a graphite
rod placed down the center ofthe device. These cells
are often called "dry cells" because there is no visible
liquid phase. However, water is present, so the cell
contains a moist paste ofNHFI, ZnCl2 and Mn02.
The moisture is necessary because the ions present must
be in a medium in which they can migrate from one
electrode to the other. The cell generates a potential of
1.5 V using the fol1owinghal:f..reactions:

Cathode, reductions: 2NH4+ (aq) + 2e- ---). 2NH3(g) + ~(g)
Anode, Oxidation: Zn (s) ---). Zn2+(aq) + 2 e
(
'," The two gases formed at the cathode will build up pressure and could
cause the cell to rupture. This problem is avoided, however, by two
other reactions that take place in the cell. Ammonia molecules bind to
{ Zn2+ ions, and hydrogen gas is oxidized by Mn02 to water.
" Zn2+(~q) + 2NH3(g) + 2C1- (aq) ---). Zn(NH3hCI2(s)
2Mn02 (s) + H2 (g) ---). Mn20 3(s) + ~O(l)
(
LeClanche cells were widely used because oftheir low cost, but they have several disadvantages. If
"
(
current is drawn from the battery rapidly, the gaseous products caunot be consumed rapidly enough, so
" the cell resistance rises, and the voltage drops. In addition, the zinc electrode and ammonium ions are in
( contact in the cell, and these chemicals react slowly. Recall that zinc reacts with acid to form hydrogen.
The ammonium ion, NH/ (aq), is a weak Bronsted acid and reacts slowly with zinc. Because ofthis
( reaction, these voltaic cells cannot be stored indefinitely. When the zinc outer shell deteriorates, the
battery can leak acid and perhaps damage the appliance in which it is contained.
(
At the present time alkaline batteries are used the chemistry ofalkaline cells is quite similar to that in a
( LeClanche cell, except that the material inside the cell is basic (alkaline). Alkaline cells use the oxidation
ofzinc and the reduction ofMn02to generate a current, but NaOH or KOH is used in the cell instead
c ofthe acidic salt NH4Cl.
Cathode, reductions: 2Mn02 (s) + ~O(l) + 2e- ---). Mn20 3(s) + 20H-0(aq)
Anode, Oxidation: Zn (s) + 20H-(aq) ---). ZnO(s) + H20(l) + 2 e

( Alkaline cells, which produce 1.54 V (approximately the same voltage as the LeClanche cell), have the
further advantage that the cell potential does not decline under high current loads because no gases are
c formed.
(
SECONDARY OR RECHARGEABLE BATTERIES
t An automobile battery - the lead storage battery - is
probably the best - known rechargeable battery figure.

( The 12 -V version ofthis battery contains six voltaic
cells, each generating about 2V. The lead storage battery
can produce a large initial current, an essential feature
c when starting an automobile engine.
!IJ!~~~A~~CL~~~~!
Id¢al fw SdullofS
ELECTROCHEMISTRY [13J
(
(
When the cell supplies electrical energy, the lead anode is oxidized to lead (II) sulfate, an insoluble
substance that adheres to the electrode surface. The two electrons produced per lead atom move through
the external circuit to the cathode, where Pb02 is reduced to p1J2+ ions that, in the presence of~SO4,also
fonn lead (lI) sulfate.
Cathode, reduction: Pb02 (s) + 4H+(aq) + SO/- (aq) + 2e- ~ PbS04(s) + 2 ~O(I)
Anode, oxidation: Pb(s) + SOl-(aq) ~ PbSOis) + 2e
Net cell reaction Pb(s) + Pb02(s) + 2~SOiaq) ~ 2PbS04(s) + 2H20(1)

<'1."b' <
~ The discharging process of the storage cell is based on the principles of electrochemical
~ cell, whereas the charging process is based upon the principles of electrolytic cells.
f -,
, "
f-,,
"
Nickel- Cadmium ("Ni - Cad n) batteries, used in variety ofcordless appliances such as telephones,
video camcorders, and cordless power tools, are lightweight and rechargeable. The chemistry ofthe cell
utilizes the oxidation ofcadmium and the reduction ofnickel (ill) oxide under basic conditions.
o
Cathode, reduction : NiO(OH) (s) + ~O(I)+ e-~Ni(OHMs) +OH-(aq) I x 2 '\
Anode, Oxidrition: Cd(s) + 2 OH ~ Cd(OH)2(s) + 2e

Net cell reaction: 2NiO(OH)(s) + Cd(s) + H 20 (I) ~ 2Ni(OH)2 (s) + Cd(OH)2 (s)
As the active masses ofall reaction components are independent oftheir amount. The cell delivers
constant EMF throughout.
FUELCELLS AND HYBRID CARS

An advantage ofvoltaic cells is that they are small and portable, but their size is also a limitation. The
amount ofelectric current produced is limited by the quantity ofreagents contained in the cell. When one t'<
V
__ ()fJQ~< r~~ctan~js_~ompleteLyconsumed, the cell will no longer generate a current. Fuel cells avoid this
limitation because the reactants (fuel and oxidant) can be supplied continuously toe the cell from an
externalteservoir.
t'
G
~~~~§~~CL~~~~!
_ktSchoJD"
o
In a Hydrogen - Oxygen fuel cell figure, hydrogen is pumped into the anode ofthe cell, and 02 (or air)
is directed to the cathode where the following reactions occur:
Cathode, reduction: 0ig) + 2 H 20(l) + 4 e- --t 40H-(aq) EO = 1.23 V
Anode, Oxidation: H2(g) --t 2W (aq) + 2 e- EO == 0 V
Schematic diagram
of a modern
hydrogen-oxygen
fuel cell.
Commonly used
electrolytes are
NaOH solution,
phosphoric acid, or
" , solid oxides. A
major limitation of
any oxygen
consuming fuel cell
is the slow rate of
the reduction of
this element at a
cathode. The best
cathode surfaces
are usually made
r
\ of platinum, 'which
is a major {;ost
factor in fuel cell
( , design.
/
',-
EFF1CIENCY OFA FUELCELL : (.1G) x100
11
r
(m)
CORROSION CELLS AND REACTIONS
( Corrosion can be defined as the deterioration ofmaterials by chemical processes. Ofthese, the most
" important by far is electrochemical corrosion ofmetals, in which the oxidation process M --t M+ + e- is
( facilitated by the presence ofa suitable electron acceptor, sometimes referred to in corrosion science as
a depolarizer.
( In a sense, corrosion can be viewed as the spontaneous return ofmetals to their ores; the huge quantities
ofenergy that were consmned in mining, refining, and manufacturing metals into useful objects is dissipated
(
'
by a variety ofdifferent routes.
The special characteristic ofmost corrosion processes is that the oxidation and reduction steps occur at
separate locations on the metal. This is possible because metals are conductive, so the electrons can
flow through the metal from the anodic to the cathodic regions. The presence ofwater is necessary in
{
\., order to transport ions to and from the metal, but a thin film ofadsorbed moisture can be sufficient.
A corrosion system can be regarded as a short-circuited electrochemical cell in which the anodic process
is something lik~
Fe(s) ~ Fe2+(aq) + 2 e
(
and the cathodic steps can be any of
02 + 2 H 20 + 4e- --t 4 OH
H+ + e- --t ~ H2(g)
( M2+ + 2 e- ~ M(s)
where M is a metal. Which parts ofthe metal serve as anodes and cathodes can depend on many
( factors, as can be seen from the irregular corrosion patterns that are commonly observed. Atoms in
regions that have undergone stress, as might be produced by forming or machining, often tend to have
l
higher free energies, and thus tend to become anodic.
"
c
~~~~~!!~ CL~~~~~
/ckol lorS,hoIon
ELECTROCHEMISTRY [15)
('
\..,
c
CONfROL OF CORROSION
Since both the cathodic and anodic steps must take place for corrosion to occur, prevention ofeither
one will stop corrosion. The most obvious strategy is to stop both processes by coating the object with
a paint or other protective coating. Even ifthis is done, there are likely to be places where the coating is
broken or does not penetrate, particularly ifthere are holes or screw threads.
, A more sophisticated approach is to apply a slight negative charge to the metal, thus making it more
difficult for the reaction M ~ M2+ + 2 e-to take' place.
SACRIFICIAL COATINGS
Oile way ofsupplying this negative,charge is to apply a coating ofa more active metal. Thus a very
common way ofprotecting steel from corrosion is to coat it with a thin layer ofzinc; this process is
known as galvanizing.The zinc coating, being less noble than iron, tends to corrode selectively. Dissolution
ofthis sacrificial coating leaves behind electrons which concentrate in the iron, making it cathodic and'
thus inlubitingits dissolution.
Negative charge in iron inhibits /

" ,
dissolution of Fe'l.+
Sacrificial coating Noble coating

("
The effect ofplating iron with a less active metal provides an interesting contrast. TIle common tin-plated \.
can (on the right) is a good example. As long as the tin coating remains intact, all is well, but exposure of
even a tiny part ofthe underlying iron to the moist atmosphere initiates corrosion. The electrons released
from the iron flow into the tin, making the iron more anodic so now the tin is actively promoting corrosion
"
ofthe iron! You have probably observed how tin cans disintegrate very rapidly when left outdoors.
\.. ~J
CATHODIC PROTECTION
A more sophisticatedstrategy is to maintain a continual negative electrical charge on a metal, so that its
dissolution as positive ions is inhibited. Since the entire surface is forced into the cathodic condition, this
. method is known as cathodic protection. The source ofelectrons can be an external direct current
power supply (commonly used to protect oil pipelines and other buried structures), or it can be the
corrosion ofanother, more active metal such as a piece ofzinc or aluminum buried in the ground nearby.
ELECTROLYSIS
The decomposition ofelectrolyte solution by passage ofelectric current, resulting into deposition of
metals or liberation ofgases at electrodes is known as electrolysis.
ELECTROLYTIC CELL
This cell converts electrical energy into chemical energy. f'
Anode
o
t...-~amoae (-)
The entire assem bly except that ofthe external battery is
known as the electrolytic cell
Electrolytic cell
[i]'~~~A~~ SES ELECTROCHEMISTRY {16]
c
ELECTRODES
The metal strip at which positive current enters is called anode; anode is positively charged in electrolytic
cell. On the other hand, the electrode at which current leaves is called cathode. Cathodes are negatively
charged.
Anode Positive Loss ofelectron Positive
j-
or oxidation current
takes place enters
/-
Cathode Negative Gain ofelectron . Current

or reduction leaves
takes place
ELECTROLYSIS OF MOLTEN SODIUM CHLORIDE

NaCI(molten)--7 Na+ + Ct"
Reactions at anode (oxidation) cathode (reduction)
2Cl---7 C12(g) + 2e-: . 2Na+ + 2e- --7 2Na(l)
There are two types ofelectrodes used in the electrolytic cell, namely attackable and non - attackable.
The attackable electrodes participitate in the electrode reaction. They are made up ofreactive metals
like Zn, Cu, Ag etc. In such electrodes, atom ofthe metal gets oxidised into the corresponding cation,
which is passed into the solution. Thus, such anodes get dissolved and their mass decreases. On the
(
other hand, non-attackable electrodes do not participate in the electrode reaction as they made up of
" unreactive elements like Pt, graphite etc. Such electrodes do not dissolve and their mass remain same.
".
ELECTROLYSIS OF SODIUM CHLORIDE SOLUTIONS:
( When you electrolyze an aqueous solution ofsodium chlori<~e, NaCl, the possible species involved in
( half-reactions are Na+, Cl- and ~O. The possible cathode half-reactions are
"
Na\,q) + e- --7 Na(S) EO=-2.71V
c 2Hp(l) + 2e- --7 HZ(g) + 20H-(aq) EO -O.83V
(
" Under standard conditions, you expectHp to be reduced in preference to Na+, which agrees with what
you observe. Hydrogen is evolved at the cathode.
2CI-(aq) --7 C12(g) + 2e- EO ::: - 1.36V
2~O(l) --7 02(g) + 4H+(aq) + 4e . p::: -1.23V
(; Under standard-state conditions, you might expect H20 to be oxidized in preference to
CI-. However, the potentials are close and over voltages at the electrodes could alter this conclusion. It
( is possible nevertheless to give a general statement about the product expected at the anode. Electrode
potentials, as you have seen, depend on concentrations. It turns out that w~en the solution is concentrated
enough in Cl-, C~ is the product; but in dilute solution, Oz is the product. To see this, you would simply
( apply the Nemst equation ofthe CI1C~ half reaction.
2Cl-(aq) --7 C1 2(g) + 2e

(
Starting with vel)' dilute NaCI solutions, you would fmd that the oxidation potential ofCI-is vel)' negative,
( so ~0 is reduced in preference to Cl-. But as you increase the NaCI concentration, you would find that
the oxidation potential ofCl- increases until eventually CI- is oxidized in preference to ~O. The product
changes from 02 to Clz'
c
< {I!~~~~~ cy~~~~~ ELECTROCHEMISTRY {17]
1de.llbrSdi<>k>"
c
c
The half-reactions and cell reaction for the electrolysis ofaqueous sodium chloride to chlorine and
hydroxide ion are as follows:
2 ~O(l) + 2e- ~ H2(g) + 20H-(aq) (cathode)
2 CI-(aq) - - ? C~) + 2e- (anode)
2Hp(l) + 2CI-(aq) - - ? ~(g) + CI2(g) + 20H-(aq)

Because the electrolysis started with sodium chloride, the cation in the electrolyte solution is Na+. When
you evaporate the electrolyte solution at the cathode, you obtain sodiufl.l hydroxide NaOH.
QUALITATIVE ASPECfS OF ELECTROLYSIS

(i) Of the two cations, that cation is liberated at the cathode which has higher reduction potential.
Ofthe two anions, that anion will be discharged at the anode which has lower reduction potential.
(ii) Ifelectrode is active at cathode, metal goes on depositing on cathode and at ap.ode metal is. \ /
dissolved.
(iii) It must be noted that itis not the SRP ofa cation that decides its discharge, but its reduction
potentiaL The SRP's should be used only when the concentration of ions are 1M. For
concentrations other than 1M, the reduction potentials for each cation at the concentration is
/
calculated and then the discharge ofan ion can be predicted. \ ~
(iv) The discharge of NO;, PO!- and SO~- ions at anode does not commonly take place from
aqueous solution.
(
\.
Electrolysis ofwater is often done with a small amount ofsulphuric acid added to water.
Why?
FARADAY'S LAWS OF ELECTROLYSIS: /',

\_-'"
(i) First law ofelectrolysis :
Amount ofsubstance deposited or liberated at an electrode is directly proportional to amount ofcharge
passed (utili.zeid) through the solution.
wacQ
W=.weight liberated, Q= charge in coulomb
w=ZQ
c
Z = electrochemical equivalent
when Q= 1 coulomb, then w = Z
Thus, weight deposited by 1 coulomb charge is called electrochemical equivalent.
Let I ampere current is passed till 't' seconds.
Then, Q"'" It :. w = ZIt
c
1 Faraday = 96500 coulomb = Charge ofone mole electrons
One faraday is the charge required to liberate or deposit onegm equivalent ofa substance at
. corresponding electrode.
Let 'E' is equivalent weight then 'E' gm will be liberated by 96500 coulom b.
C
I Coulomb will liberate 96~OO gm; By defmition, Z= 96~OO ( j'\
fi]!~~~A~C,~~~!
Idtolfor SchoJDrt
ELECTROCHEMISTRY /18J r
"-..,;
rv o
'
JtE
W
96500
When a gas is evolved at an electrode, then above fonnula changes as,
ItV e
V=--
96500
where V =volume ofliberated gas, Ve = equivalent volume ofgas.
Equivalent volume may be defmed as:
The volume ofgas liberated by 96500 coulomb at latm & O°C.
(ii) Second law ofelectrolysis :

When same amount ofcharge is passed through different electrolyte solutions connected in series then
weight ofsubstances deposited or dissolved at anode or cathode are in ratio oftheir equivalent
weights. i.e. w/w2 =E/E2
Ex. 12 How much electric charge is required to oxidise :

(a) ImoleofHz0to02 (b) ImoleofFeOtoFep3?
( Sol.- (a) The oxidation reaction is:
T-l o~ 10
L'-.! 2 2 + 2H+ + 2e
\"
I mole 2 mole
(
Q = 2F = 2 x 96500 = 1.93 x lOs C
"
(b) The oxidation reaction is
FeO+ 1HP~ 1Fe203+H++e
Q =F 96500 coulomb
Exactly 0.4 faraday electric charge is passed through three electrolytic cells in series, first containing
AgN03' second CuS04 and third FeCI3 solution. How many gram ofeach metal will be deposited
assuming only cathodic reaction in each cell.
The cathodic reaction in the cell are respectively,
Ag+ + e- ~ Ag
1 mole 1 mole
108 g 1F
Cu 2+ + 2e- ~ Cu
1 mole 1 mole
63.5g 2F
and Fe3 + + 3e- ~ Fe
1 mole 1 mole
56~ 3F
Hence, Ag deposited = 108 x 0.4 = 43.2 g

63.5
Cu deposited = -2- x 0.4 = 12.7 g
56
and Fe deposited = 3 x 0.4 = 7.47 g
(I]'~~~A~~ ELECTROCHEMISTRY /19]
t
-"
,.
(
L
Ex.14 An electric current of 100 ampere is passed through a molten liquid ofsodium chloride for 5 hours.
Calculate the volume ofchlorine gas liberated. at the electrode at NlP.
Sol. The reaction taking place at anode is
2CI- ~ Cl2 + 2e

71.0 g 71.0 g 2 x 96500 coulomb
1 mole
. Q = i x t 100 x 5 x 60 x 60 coulomb
_
.. _/ "'
The amount ofchlorine liberted by passing 100 x 5 x 60 x 60 coulomb ofelectric charge.
1
=xlOO x 5 x 60 x 60 = 9.3264 mole
2x96500
Volume ofCI 2 liberated atNTP= 9.3264 x 22.4=208.91 L
Ex.IS What current strength in ampere will be required to liberate 109 of chlorine from sodium chloride
solution in one hour? f'
, /
Sol. Applying E = Z x 96500 (E for chlorine = 35.5),

35.5 = Z x 96500 \ "
35.5
or. Z= 96500
Now, applying the formula
W=Zxixt
35.5
Where W 109, Z = 96500' t = 60x60 3600 second
/',
lOx 96500
i= 35.5x3600 =7.55 ampere
Ex.16 A current of2.68 ampere is passed for one hour through an aqueous solution ofcopper sulphate using \.
copper electrodes. Calculate the change in mass ofcathode and that ofthe anode. (at. mass ofcopper
;' ,
63.5).
Sol. The electrode reactions are :
Cu2+ + 2e- ~ Cu (cathode)
1 mole 2 x 96500 C
Cu ~ Cu2+ + 2 e- (Anode)
Thus, cathode increases in mass as copper is deposited on it and the anOde decreases in mass as copper
from it dissolved.
Charge passed through cell = 2.68 x 60 x 60 coulomb
63.5
Copper deposited 'or dissolved = 2 x 96500 2.68 x 60 x 60:= 3.174 g
Increase in mass ofcathode = Decrease in mass ofanode = 3.174 g

,
Ex.17 In a zinc maganese dioxide dry cell, the anode is made up ofzinc and cathode ofa carbon rod surrounded
by a mixture of Mn02' carbon, NH4CI and ZnC1z in aqueous base.
The cathodic reaction may he.r.epresented-as
[-'
2Mn02(s) + Zn2+ + 2e- ~ ZnMnp4(s) ~-,.-'
Let there be 8 g Mn02 in the cathodic compartment. How many days will the dry cell continue to give '\
a current or 4 x 10-3 ampere.
[jJ ~~~~!!~C~.~~~~!
IckDlfors<hokl,s
ELECTROCHEMISTRY [20} ("
~
.
Co/"
(
"-"
Sol. When Mn02 will be used up in cathodic process, the dry cell will stop to produce current.
Cathodic process:
+4 +3
2Mn02 (s) + Zn2+ + 2e- ~ ZnMn 20 4
Molecular mass 87
Equivalent mass ofMn02= Change in oxidation state ::::: -1 =87
Fromfirst law ofelectrolysis,

4 x 10-3 x t x 87
W=~ 8=----
96500=> 96500
2218390.8
2218390.8 second 25.675 day
3600x24
CONDUCTANCE
Introduction:
Both metallic and electrolytic conductors obey Ohm's law
i.e. V=IR
where V ::::: Potential difference in volt; I = Current in ampere; R::::: resistance in Ohm
( We know, resistance is directly proportional to length ofconductor and inversely proportional to
cross sectional area ofthe conductor.
"
\, I I
Roc A or R= Pp: ( p = Specific resistance)
Specific resistance is the resistance ofa conductor having lengths of I cm and cross sectional
area on cm2•
Unit ofR is ohm and unit of specific resistance is ohm cm
' Reciprocal of resistance is called as conductance and reciprocal ofspecific resistance is called
as specific conductance.
1 IA A
-:::::-- or C=K
f R pi I
" where C::::: conductance ohm-I; K specific conductance ohm-1cm- 1 •
c Mho and siemens are other units ofconductance
c K~C
A
Specific conductance= Cell constant x Conductance
SPECIFIC CONDUCTANCE IS CONDUCTANCE OF 1 CM3 OFAN ELECTROLYTE SOLUTION.
( In case ofelectrolytic solution, the specific conductance is~efined as the conductance ofa solution of
defmite concentration enclosed in a cell having two electrodes ofunit area separated by I cm apart.
( 1. Equivalent Conductance
Equivalent conductance is the conductance ofan electrolyte solution containing I gm equivalent
( ofelectrolyte. It is denoted by A •
A Kx V
(
(A = ohm-l cm- xcm 3 ohm-I cm2)
1
" Usually concern ration ofelectrolyte solution is expressed as C gm equivalent per litre.
(
V_IOOO
Thus, ~C-
{Volume having I gm equivalent electrolyte in the solution} Thus, A=K x I O~O

t
f
'L (jJ~~~~A~~C~~~~~~
!d<olfotS"",ID,,
ELECTROCHEMISTRY {21)
(
,r
\.
L
2. Molar Conductance
Molar conductance may be defined as conductance ofan electrolyte solution having 1 gm mole
electrolyte
. in a litre. It is denoted by A m •
A =KxV
m '
Usually concentration ofelectrolyte solution is expressed as 'M' gm mole elecrtrolyte per litre.
V_lOOO
Thus,
M
IOOO
Hence, A =Kx
m M
Relation between A and Am: Am=n X A
DETERIVIINATION OF A~ OR A 0
A plol of Am VS JC as found experimentally is as shown below graphically.
AO
mr..
.........
Am
I, !' -~
~
JC-
The ~ vs JC plot ofstrong electrolyte being linear it can be extrapolated to zero concentration.
Thus, Am values ofthe solution of the test electrolyte are determined at various concentrations the
concentrations should be as low as good. \,,/
Am values are then plotted against JC when a straight line is obtained. This is the extrapolated to zero r-- .,
concentration. The point where the straight line intersects Am axis is A~ ofthe strong electrolyte.
However, the plot in the case weak electrolyte being non linear, shooting up suddenly at some low
concentration and assumingthe shape ofa straight line parallel to ~ axis. Hence extrapolation in this
case is not possible. Thus, Ao ofa weak electrolyte cannot be determined experimentally. It can, however,
be done with the help ofKohlrausch's law to be discussed later.
c
Is electrolytic conductance depends on temperature?
,./"
(
( "
Kohlrausch's Law oflndependent Migration oflons '"

Kohlrausch determined Ao values ofpairs ofsome strong electrolytes containing same cation say Kf
and KCI, NaP and NaCI etc., and found that the diffe~ence in· Ao values in each case remains the same:
.(
A~(KCI) - A~ (KF) = A~ (NaCI) - A~ (NaP) \;,
He also detemined Ao values ofpairs ofstrong electrolytes containing same anion say KF and NaP, KCI
and NaCI etc.and found that the difference in Ao values in each case remains the same. c
A~ (KF) - A~(NaP) = A~ (KCI) - A~ (NaCl) e
This experimental data led him to fonnulate the following law called Kohlrausch's law ofindependent
migration ofions.
/'
,,-,
I
~~~~~~~~~~~~~
• Jd<GlforSdw>lo"
[,
v
At infmite dilution whendissociation is complete, every ion makes some defmite contribution towards
molar conductance ofthe electrolyte irrespective ofthe nature ofthe other ion which with it is associated
and that the molar conductance at infinite dilution for any electrolyte is given by the sum ofthe conmbution
ofthe two ions. Thus,
1\ 0 = ').,0 +').,0
m +
Where A.~ is the contribution ofthe cation and A.~ is the contribution ofthe· anion towards the molar
conductance at infinite dilution. These contributions are called molar ionic conductances at infinite dilution.
Thus, A.~ is the molar ionic conductance ofcation and A.~ is the molar ionic conductance ofanion, at
infmite dilution. The above equation is, however, correctonly for binary electrolyte like NaC~ MgSO4 etc.
Application ofKohlrausch's law:

(l) Detennination of I\~ ofa weak electrolyte:
In order to calculate I\~ ofa weak electrolyte say CHFOoH, we detennine experimentally I\~ values
ofthe following three strong electrolytes:
(' (a) A strong electrolyte containing same cation as in the test electrolyte, say HCI
(b) A strong electrolyte containing same anion as in the test electrolyte, say CH3COONa
(c) A strong electrolyte containing same anion of(a) and cation of(b) i.e. NaCl.
i I\~ ofCH3COOH is then given as:
"
I
I\~ (CH3COOH) = I\~ (HCI) + I\~ (CH3COONa) - I\~ (NaCl)
'-
Proof:
I\~ (HCI) A.~
!'
\ + A.
CI
- ......................(i)
I\~ (CH3COONa) =A.~H3COO- +A. Na +

~
\" '
...................... (ii)
f'
I\~ (NaCl) = A.~a+ +A.~I_ ...................... (iii)
" Adding equation (i) and equation (ii) and SUbtracting (iii) from them:
0
o (HCI) +
I\m
0
I\(CH 3 COONa) -
1\ -
(NaCO -
1.0(H+) + 1.0(CH)COOo ) - 1\
- 0(CH3 COOH)
( (2) Detennination ofdegree ofdissociation (a) :

"-."
No.ofmoleculesionised I\m
a=
totalnumberof moleculesdissolved I\~
( (3) Detennination ofsolubiliJ:y ofsparingly soluble salt
The specific conductivity ofa saturated solution ofthe testelectrolyte (sparingly soluble) made in
( conductivity water is detennined by the method as described above. From this the specific conductivity
ofconductivity water is deducted. The molar conductance ofthe saturated solution is taken to be equal
(
to I\~ as the saturated solution ofa sparingly soluble salt is extremely dilute. Hence fromequation (4).
(
o _ IOOOK
I\m - C '
(
where C is the molarity ofsolution and hence the solubility.
c
1i~~~~A~~ CL~~~~!
,<
\... ELECTROCHEMISTRY [23J
Oi<alforkhol<m
c
Ex.18 1.0 N solution of a salt surrounding two platinum electrodes 2.1 cm apart and 4.2 sq cm in area
was found to offer a resistance of50 ohm. Calculate the equivalent conductivity ofthe solution.
Sol. Given 1= 2.1 cm, a = 4.2 sq. cm, R = 50 ohm
Specific conductance, K =~ . ~
2.1 1 I
or K = 4.2 x 50 = 0.01 ohm- cm-1
Equivalent conductivity = K X V
V == the volume containing 1 g equivalent = 1000 ml
So Equivalentconductivity== 0.01 x 1000
== 10 ohm-I cm 2 equiv-I
Ex.19 Specific conductance ofa decinorm'al solution of KClis 0.0112 ohm-1 cm-I. The resistance ofa cell
containing the solution was found to be 56. What is the cell constant?
Sol. We know that
Sp. conductance = Cell constant x conductance
Sp. conduc tan ce
or Cell constant =
Conduc tan ce
Sp. conductance x Resistance
= 0.0112 x. 56
0.6272 cm I
Ex.20 The specific conductivity of0.02 M KCI solution at 25 °C is 2.768 X 10--3 ohm-I em-I. The resistance of
f
this solution at 25 OC when measured with a particular cell was 250.2 ohms. The resistance of0.0 1 M
CuS04 solution at 25°C measured with the same cell was 8331 ohms. Calculate the molar conductivity
/
ofthe copper sulphate solution.
Sp. condo of KCI
Sol. Cell constant C ond uctan ce 0 f KCI
2.768 x 10-3
11250.2
2.768 x 10-3 x 250.2
For 0.01 M CuS04 solution
c
Sp. conductivity = Cell constant x conductance
= 2.768 X 10-3 x 250.2 x 8331
1000 f
Molar conductance = Sp. condo x C \./
2.768 x 10-3 x 250.2 1000

== x-
8331 1/100
= 8.312 ohm-I cm mole-I
[i!~~~~CM~!~'
1duI,.,_ . ELECTROCHEMISTRY [24] c
Ex.21 A 0.05 N solution ofa salt occupying a volume between two platinum electrodes separated by a distance
of 1.72 cm and having an area of 4.5 cm 2 has a resistance of 250 ohm. Calculate the equivalent
conductance ofthe solution.
Sol. Specific conductance = conductance x cell constt.
I 1 I 1 1.72
K=Cx A =- x-
- 250 x 4.5
R A
= 1.5288 X 10-3 ohm-I cm- I
A =K x 1000 1000
e = 1 5288 X 10-3 x = 30.56 ohm-I cm2 eq-I
N . 0.05
Ex.22 The equivalent conductances ofsodium chloride, hydrochloric acid and sodium acetate at infinite
dilution are 126.45,426.16 and 91.0 ohm-1 cm2 equiv-l, respectively at 25 "C. Calculate the equivalent
conductance ofacetic acid at infmite dilution.
i
\
SoL According to Kohlrausch 's law,
r' Aa:>CH3COONa ACH3coo- + ANa+ = 91.0 .......(i)
\
" Aa:>HCI = AH+ + ACI- = 426.16 ......(ii)
Aa:>NaCI ANa+ + AC)- 126.45 .......(iii)

f
" Adding equations (i) and (ii) and substracting (iii),

i'
" ACH3coo- + ANa+ + AH+ + ACI- ANa+ - Act-'
(
= 91.0 + 426.16 -126.45
"
ACH3COO- + AH+ = A",CH3COOH = 390.7 ohm-I cm2 equiv-I
f '
,-
:' Ex.23 A decinonnal solution of NaCI has specific conductivity equal to 0.0092. lfionic conductance ofNa+
and CI- ions at the same temperature are 43.0 and 65.0 ohm- 1 respectively, calculate the degree of
( dissociation ofNaCI solution.
Sol. Equivalent conductance ofN!1 0 NaCI solution
Au = Sp. conductivity x dilution
( = 0.0092 x 10000
92 ohm-l
Au;; = ANa+ + Acl
( = 43.0 + 65.0 = 108 ohm-I
'
( Degree ofdissociation, ex. = Au = 92 0.85

Aoo 108
C -Ex.24 The specific conductivity of a saturated solution of silver ch~oride is 2.30 x 10-{i mho cm- 1
at 25°C. Calculate the solubility of silver chloride at 25°C ;
if A + = 61.9 mho cm2 mol-I and A
cr
76.3 mho cm 2 mol-I.
( Ag
[IJ ELECTROCHEMISTRY [25J
(
"
/
"
So). Let the solubility ofAgCI be 5 gram mole per litre
.. 1000
DIlUtion -5
AooAgCl = '"Ag+
+ "'CI
= 61.9 + 76.3
= 138.2 mho cm2 mol- 1
Sp. conductivity x dilution = AooAgCI = 138.2

-6 1000_
2.30 x 10 x s - 138.2
2.30 x 10-3 . 5 •
5 = 138.2
= 1.66
.
x 10- mole per htre
= 1.66 X 10-5 x 143.5 gL-l
= 2.382 X 10-3 gL-l
ELECTROCHEMICAL SERIES:
S.NO. Reduction half cell reaction EO in volts at 25°C
1. F 2 + 2e- ---+ 2F"' + 2.65
2. S20i- + 2e- ---+ 2S0~ + 2.01
3. Co3+ + e- ---+ Co 2+ + 1.82
4. Pb02 + 4H+ + SO!- + 2e----+ PbS0 4 + 2H20 + 1.65 (
<
5. MnO-4 + 8H+ + 5e----+ Mn2+ + 4H20 + 1.52
!- "'
6.. Au 3+ + 3e----+ Au + 1.50 " -~
7. Cl 2 + 2e- ---+ 2CI- + 1.36

8. Cr20~- + 14H+ + 6e- ---+ 2Cr3+ + 7H20 + 1.33
9. O2 + 4H+ + 4e'- ---+ 2H20 + 1.229
10. Br2 + 2e- ---+ 2Br- + 1.07
11. NO) + 4H+ +3e ---+ NO + 2H20 + 0.96
12. 2Hg2+ + 2e- ---+ Hg~+ + 0.92
13. Cu2+ + 1- + e- ---+ Cui + 0.86
14. Ag+ + e----+ Ag + 0.799
15. Hg;+ + 2e- ---+ 2 Hg + 0.79
16. Fe 3+ + e- ---+ Fe2+ + 0.77
17. 12 + 2e- ---+ 21- + 0.535
18. Cu+ + e- ---+ Cu + 0.53·
19. Cu 2+ + 2e- ---+Cu + 0.34
20. Hg2Cl 2 + 2e----+2Hg + 2CI + 0.27 c
21. AgCI + e- ---+Ag + CI- + 0.222
22. Cu2+ + e- ---+ Cu+ + 0.15
Sn4+ + 2e- ---+ Sn 2+ + 0.13
23.
c
Iil~~~~~~C~,~~~~~
ldfolfo( S(hoklrs
ELECTROCHEMISTRY {261
(~
v
24. 2H+ + 2e- ----+ H 2 0.00
25. Fe 3+ + 3e- ----+ 'Fe - 0.036
26. Pb2+ + 2e- ----+ Pb -0.126
27. Sn 2+ + 2e- ----+ Sn - 0.14
28. AgI + e- ----+ Ag + 1- - 0.151
29. Ni 2+ + 2e- ----+ Ni -0.25
30. Co 2+ + 2e- ----+ Co - 0.28
31. Cd 2++ 2e- ----+ Cd - 0.403
32. cr3+ + e- ----+ cr2+ -0.41
33. Fe 2+ + 2e- ----+ Fe - 0.44
34. Cr3+ + 3e- ----+ Cr -0.74
35. Zn 2+ + 2e- ----+ Zn - 0.762
36. 2H20 + 2e-----+ H2 + 20H- - 0.828
(
37. Mn 2+ + 2e- ----+ Mn - 1.18
\
38. AI3+ + 3e-----+ Al - 1".66
39. H2 + 2e- ----+ 2H- -2.25
40. Mg2+ + 2e- ----+ Mg -2.37
{'.
, . 41. Na+ + e- ----+ Na - 2.71
42. Ca2+ + e- ----+ Ca - 2.87
43. Ba2+ + 2e- ----+ Ba -2.90
( 44. Cs+ + e- ----+ Cs -2.92
" 45. K+ + e-----+ K -2.93
46. Li+ + e- ----+ Li -3.03
(
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CLASSES
t.t ~ I T£ D .ELECTROCHEMISTRY (27)
Id<oI for SdKIIon
(
ATLAS
Some Basic Concept
-1
(1) Electrolytes,
(2) Electrolysis~
(3) Conductance
1
Electrochemical Cells Electrolytic conductance
1
1.
I Electrolytic Celli Galvanic Cell
I
I
\. J
('
\. j
1. Set up of cell L(a) Set up of cell 1. Conductance of solutions

(b) Cell Notations
2.Types of electrodes (c) Cell potential &
2. Equivalent and molar
(' ,
Nearest equation
conductivity & relationship \./
3. Faraday's laws of (d) Relationship between
between them
electrolysis standard free energy &
equlibrium constant
3. Variation of molar
4. Qualitative aspects conductivity with
of electrolysis 2. Types of half cells I electrodes concentration
t' ~."
\.../
3. Concentration cells 4. Kohlrausch's law &
(a) Electrode concentrations cells it's application
(b) Electrolyte concentration cells
4. Type of batteries
c
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SOLVED EXAMPLES
Ex.1 Consider the cell corresponding to reaction

Zn + 2Ag+ -7 Zn2+ + 2Ag given that EZn .Zn 2+ = 0.76 volt and
E Ag.Ag+ =-0.80 V .
Find the e.m.f ofthe cell.
Sol. The cell is ZnIZn2+IIAg+IAg.

P = the standard e.m.fofthe cell == Reduction potential ofR.H.S. electrode
- Reduction potential ofL.H.~. electrode
== + 0.80 - (-D. 76)
+ 0.80 + 0.76 =1.56 V
The data provides the oxidation potential ofZn andAg electrodes; in order to obtain the
reduction potential ofboth the electrodes, the sign is to be reversed.
The standard e.m.f ofthe cell EO can also be determined by adding the oxidation potential of
(' Zn (= 0.76) and reduction potential ofAg (=+ 0.80).
That is, EO = 0.76 + 0.80 = 1.56 V. '
Ex.2 Calculate the electrode potential ofa copper wire dipped in 0.1 M CuS04 solution at 25°C.
The standard electrode potential ofcopper is 0.34 V.
Sol. The electrode reaction is Cu2+ + 2e- -7 Cu(s).
\ B Y usmg 0.0591
. E = EO - -
. N ernst equation, - Iog { 2 ]
2 Cu +
0.0591 I
Or E 0.34 - 2 og 0.1 = 0.34 - 0.02955
( , 0.31045 V
\,
Ex.3 Consider the cell
"',
<'
'
Zn1Zn2+ (aql.OM~ICu2+ (aq 1.0M)Cul
('
\ ..... /
The standard reduction potentials are 0.350 V for Cu2+ (aq) + 2e- -7 Cu and
( 0.763 V for Zn2+ (aq) + 2e- -7 Zn
(a) What is the cell reaction?
( (b) Cal~ulate the e.m.f ofthe cell.
( (c) Is the cell reactionspontaneous?

Sol. Anodic reaction: Zn -7 Zn2+(aq) + 2e
(. Cathodic reaction: Cu 2+ (aq) + 2e- -7 Cu
( Overall reaction: Zn +Cu2+ (aq) -7 Zn2+ + Cu ,
'
?--, e;m.fofthecell E~ell==E~ Er 0.350-(-0.763)=1.113 V
'\..
Since E~II is positive, the LlG ofthereaction (=-nEF)will be negative and so the reaction is
c spontaneous.
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ELECTROCHEMISTRY {29]
(
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Ex.4 The e.m.fofa ce11 corresponding to the reaction
Zn(s) + 2H+(aq)-+ Zn2+ (0.1 M)+ H2 (g) (1 atm.) is 0.28V at 25°C. Write the halfceU
reactions and calculate the pH ofthe solution at the hydrogen electrode.
( EO:::;:
Zn 2+.Zn
-0.763 v)
Sol. The halfcell reactions are
(anode) Zn -+ Zn2+ + 2e- ( cathode) 2H+ + 2e- -+ ~
The cell reaction is Zn + 2W -+ Zn2+ + ~ (g)
Nemst equation for the cell reaction is
2
RT
(Zn + ][PH ]
E=Eo- log 2 where EO = EO _Eo
2F (H+ ]2 H+H 2 Zn 2+. Zn
0- (-0.763) = 0.763 V
0.0591 [0.1].1
Or E=0.763--- log (H+f
'0.0591 ~
Or 0.28 = 0.763 - -.~2- log [H+]2
Or
+ - .l[2(0.763-0.28) 10 (o.OJ
-log [H ] - 2 (0.0591) g
1
= -[16.33 + 1] = 8.67
2
Ex.S A cell contains two hydrogen electrodes. The negative electrode is in contact with a solution of
10-6 M hydrogen ions. The e.m.fofthe cell is 0.118 Vat 25°C. Calculate the concentration of
hydrogen ions at the positive electrode.
Sol. The cell is
PtIH2(g)(1 atm)IH+ (10-6M)IIH+1 H 2(g) (1 atm)IPt
1
At anode: "2' H2 -+ (H+)L + e- ('
" J
1.
At cathode: (H+k + e- -+ "2 H2
r
",-"
Overall reaction (W)R -+ (H+)L
. l'IS E cell = EOeel!

The ce II potentia RT I
- - og-+(
\
(H+ )L
.... ~. -H~R
0.059 10-6
Or 0.118 V = 0 - '-1- log [H+ ]
Or [H+] = 10-4 M
",
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ELECTROCHEMISTRY {30J ~
Ex.6 The standard reduction potential of Cu 2+ICu and Ag+IAgeJectrodes are 0.337 V and
0.799 V respectively. Construct a working cell with positive e.m.f. Ifthe concentration ofCu2+
ions is 0.01 M, then for what concentration ofAg+ will the e.m.fofthe cell be zero a.t25°C?
Sol. Since the reduction potential ofsilver electrode. E~g+Ag is higher than copper electrode, the half
cell Ag1Ag will constitute the cathode ofthe cell and the cell is
CuICu2+IIAg+IAg
The cell reaction is Cu + 2Ag+ ~ Cu2+ + 2Ag and the standard e.m.f
EO = 0.799 - 0.337 = 0.462 V.
The Nernst equation for the cell is
0.0591 I [Cu 2+ ]
E = EO
cell cell - 2 - og [Ag+J2
00591 {O.O}]
Or Ecell = 0 0.462 - .2 log [Ag+]2
( [0.01] _ 0.462x2 15.6345

\ Or
log [Ag+ J2 - 0.0591
(
Or 2 log [Ag+J = log [0.01] -15.6345
( = -2-15.6345=_8.8173
Or [Ag+] = 1.523 x 10-9 M

/. Ex.7 Zinc granules are added in excess to 500 mL of 1.0 M nickel nitrate solution at 25°C until
equilibrium is reached. If the standard reduction potential of Zn 2+.Zn and
\
f Ni2+.Ni are -0.75 V and -0.24 V respectively, calculate the concentration ofNP+ in the solution
" at equilibrium.
f
\. Sol. The cell reaction is Zn + Ni2+ ~ Zn2++ Ni.
EO, the standard e.m.f, is -0.24 -(-0.75) = 0.51 V.
The equilibrium constant ofthe reaction K is [AGo = -nE°F =-RTln K],
".\.. given by the expression
nEO F _ (2 x 96500Cmol- I )(0.51) .

10gK= 2.303 RT - (2.303)(8.314JK- I )(298)
c'
\..
OrK 1.78 x 10- 17
(
'\.. Let 'x' be the concentration ofNi 2+ ions. Then
Zn(s) + Ni 2+(aq)r==='Zn2+ (aq) + Ni(s)

LO-x x
c 17
[Zn 2+] x
K= 1.78 x 10- = [Ni 2+] (l.O-x) orK.l.O-K.x=x
(
\.
x = K.1.0 ::=l.OM
I+K
2
( [Ni 2+J "" [Zn +] l.OM 5.6x to-18 M
K 1.78xtO I7
r
'
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Ex.8 . For the cell Zn1Zn 2+ (0.1 M)I\Cu 2+(0.01 M)ICu,
a graph between Eceuand log ~~:::~ is foundto be linear. The intercept on Eceu axis is 1.10 V.
Calculate the e.m.f ofthe cell.
Sol. . The cell reaction is Zn + Cu2+~ Zn2+ + Cu.

2
K= [zn )ku 2+]=[0·%.0l]=10
o )0.0591 [Zn 2+]
Or K = (Ecell - - 2- log [cu 2+]
This expression is the same as y =mx + c, where c = intercept = E~II = 1.10 V.

r
, J
0.0591
So, Ecell = 1.10- - 2 - log 10
= 1.1 0 -
0.0295 t'
1.0705 V ''\ ."
Ex.9 How many coulombs ofelectrici1y are required for the following reactions?
(i) l.OmolofCu2+toCuand
(n) 1.0 mol ofKMn04 to MnS04
Sol. The reaction is Cu 2+ + 2e- ~ Cu and for this the quantity of electricity required is
/'
2 Faradays, as two mole ofelectrons are involved. Therefore, 2 x 96500 = 193000 coulombs
ofelectrici1y is required.
(it) For the reaction Mn0 4- to Mn2+, 5 mQles of electrons are involved
Mn 7+ + 5e- ~ Mn2+ and for this the quantity of electricity required is
5 x 96500 = 482500 coulombs.
Ex.10 When a current of2 A flows for 30 minutes iJ:.l an electrolytic cell containing CuS04, copper
is deposited at the cathode. Find out the amount ofcopper deposited.
.Sol. Totalquanti1y ofelectrici1ythatflows across the solution ofCuS04 = 2 x 30 x 60= 3600
coulombs. ".
Considering the reaction Cu2++ 2e- ~ Cu, two moles of electron, that is, 2 Faraday of
electricity equivalent to. 2 x 96500 coulombs deposit one mole of copper equal to
63.5 x 3600
635 goo. Therefore, 3600 coulombs will deposit = 2x96500 =1.184 gm
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ELECTROCHEMISTRY /32/
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E:x.ll How much time in hours is required for a current of 2 A to electrolytically decompose
18 gm ofwater?
Sol. The anodic and cathodic reactions are
2H20 -4 02 + 4H+ + 4e- ......... (1)
2H20 + 2e- -4 H2 + 20H- or 4H20 + 4e- -4 2H2 + 40H ......... (2)
On adding (1) and (2), 6H20 -4 2H2 + O2 + 4H+ + 40H
Or 6H20 -4 2H2 + O2 + 4H20
Or 6H20 - 4H20 = 2H20 -4 2H2 + O2
that is, the passage of4.0 moles ofelectrons de(:ompose 2 moles or 36 g ofwater. So, for the
decomposition of IS gm ofwater only 2 mole of electrons are required, or the quantity of
< e Iectnclty
.. reqUIre
. d'IS 2 x 96500 C. There11ore, the tune
<. . d'IS 2 x 2A
requrre 96500 965 00 second s
= 26.8 hours.
(' Ex.12 How long a current of3 A has to be passed through a solution ofsilver nitrate to coat a metal
surface of SO cm 2 with a 0.005 mm thick layer. Density of silver is
('
10.5gcm-3.
Sol. Volume ofmetal to be deposited =(80 cm2) (0.0005 cm) =0.04 cm 3
Mass ofmetal to be deposited (10.5)(0.04) = 0.42 gm
0.42 -3
Amount ofsilver to be deposited = --=3.S89x I 0 moles
10S.0 <
Amountofelectricitynecessaty = 3.889 x 10-3 x 96500 C mol-I = 375.27 C

< (moles)
( Time for which 3 A current is to be passed

(
'-<
Ex.13 In a fuel cell, hydrogen and oxygen react to produce electricity. In the process, hydrogen gets
(
oxidisedat the anode and oxygen gets reduced at the cathode. If67.2 L ofH2 at STP reacts in
( 15 minutes, what is the average current prodU(~ed? Ifthe entire current is used for electro
deposition ofcopper from copper (II) in solution, what mass ofcopper is deposited?
(
Anode reaction: H2 + 20H- ---7 2H20 + 2e
r Cathode reaction: O 2 + 2H20 + 4e- -4 40H
t<
( 67.2 3 I
Sol. Amount ofhydrogen oxidised = = rna es
22.4 <
c Amount ofelectrons produced = 2 x 3 moles ofelectrons
, Electricity produced = 2 x 3 x 96500 C

~ CUrrent produced = 2 x 3 x 96500/15 x 60 643.33 A
1.0 mole ofcopper gets deposited by the absorption of2 moles ofelectrons
Amount ofCu deposited = 3 moles
c Or, mass ofCu deposited = 3 x 63.5 = 190.5 gm
, [i!~~~A~~ C~~~~!
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Ex.14 During the discharge ofa lead storage battery, the density ofsulphuric acid fell from 1.294 g m
L-l to 1.139 gmL-I. Sulphuric acid ofdensity 1.294 gmL- is 39% H 2S04 by mass and ~atof
density 1.139 g mL- is 20% H 2S04 by mass. The-battery holds 3.5 L ofacid and the volume
remains practically constant during the discharge. Calculate the number ofampere hour for
which the battery has been used. The reactions are
Pb + SO42- ~ PbS0 4 + 2e- (charging)
Pb02 + 4H+ + SO4 2- + 2e- ~ PbS04 + 2H2 (discharging)
Sol. Mass ofH 2S04 (initially) = 3.5 x 103 x 1.294=4529 gm
39
Actual mass ofH 2S04 = 100 x 4529 = 1766.3 gm
Mass of H 2S04 in the end = 1.139 x 3.5 x 103 = 3986.5 gm
20 I'"
Actual mass ofH 2S04 = 100 x 3986.5 = 797.3 gm
Mass ofH 2S04 consumed = 1766.3 -797.3 = 969.0 gm
969
Moles ofH 2S04 consumed = 98 = 9.888 moles
Amount ofH+ consumed = 2 x 9.888 moles (since ~SO4 has 2H+). In the discharge reaction,
4 moles ofH+ are consumed per 2 moles ofelectrons. Therefore, electrons discharged (2 x
9.888) x 2/4 = 9.888 moles of electrons. So, the amount of electricity discharged = 9.888 \. ,
moles x 96, 500 C = 954192 C.

/' ."
Battery has been used for = 954192/60 x 60 = 265.05 ampere hours. \ J
('
Ex.IS 19.0 grams of molten SnCl2 is electro lysed for some time by using inert electrodes, until
( ...
0.119 g ofSn is deposited at the cathode. No substance is lost during electrolysis. Find the ratio
'-_/
ofmasses ofSnCl2 and SnCl4 after electrolysis. (-,
'-J
Sol. Cathode: Sn2+ + 2e- ~ Sn ; Anode: Sn2+ ~ Sn 4+ + 2e-
Since 0.119 g ofSn is deposited at cathode then 0.119 g ofSn4+must have formed at anode (see c
the electrode reactions). So, a total of2 x 0.119 g ofSn2+ are lost from the solution. (',
o
MSnCI
Mass ofremaining SnCl2 =19g- 2 xm
M Sn " -'
\
\.
Sn
189.6
, ...
'\..J
= 19- --x2x0.119
119
r'"'
'<....;
= (19 - 0.379) = 18.621 g
M SnCI 260.2
c
Mass ofSnCl4 formed = ._.4 x ms = - - x 0.119 = 0.26 g ~
MSn n 119 V
("
m(SnCI 2) 18.621 71.62 V
---'-_--="!" =- - =-
m(SnC1 4 ) 0.260 1 f ...
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ELECTROCHEMISTRY [34J c
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Ex.16 How many grams ofsilver could be plated out on a serving tray by electrolysis ofa solution
containing silver in +1 oxidation state for a period ofS hours at a current ofS.46 amperes. What
is the area ofthe tray ifthe thickness ofthe silver plating is 0.00254 em? The density ofsilver is
10.5 g/cm3•
It M (S.46)(Sx60x 60)(1 07.S)
Sol.
m= p' z (96500 C mol-I) 272.1S g
• m 272.18
VolumeofsilverplatedoutV= p = ~ =25.92cm 3
_ 25.92 _ 2
Area oftray plated - 0.00254 - 10204.7 cm
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EXERCISE-I
Q.I Which ofthe following statements abOut galvanic cell is incorrect

(A) Anode is positive
(B) Oxidation occurs at the electrode with lower reduction potential
(C)Cathode is positive
\ ': .: T....
(D) Reduction occurs at cathode
Q.2 Which ofthe following energy changes occur in galvanic cell-'

(A) Electrical energy -7 Chemical energy (B) Chemical energy -7 Electrical Energy
(C) Chemical energy -7 Internal energy (D) Internal energy -7 Electrical energy
Q.3 Which ofthe following is not true about e.m.f. ofa cell
(A) It is maximum voltage obtainable from the cell ' (
(B) It is responsible for the flow ofsteady current in the cell
(C) Work calculated from it is not the maximum work obtainable from the cell
(D) It is the potential difference between two electrode when no current is flowing in circuit
Q.4 Saturated solution ofKN03 is used to make 'Salt - bridge' because

(A) Velocity ofK+ is greater than that ofN03
/
(B) Velocity ofN03- is greater than that ofK+
(C) Velocities ofboth K+ and N03- are nearly the same
(D) KN03 is highly soluble in water
Q.5 In galvanic cell the salt bridge is used to

(A) Complete the circuit (B) Reduce the electrical resistance in the cell " .'
(C) Separate cathode from anode (D) Carry salts for the chel1)ical reaction
Q.6 The cell reaction for the cellZn IZn2+ (l.OM) II Cd2+ (l.OM) ICd is given by
(A) Cd -7 Cd2+ + 2e- (B) Zn2+ -7 Zn 2e
(C) Cd + Zn2+ -7 Zn + Cd2+ (D) Zn + Cd2+ -7 Zn2+ + Cd
Q.7 The cell reaction Zn + 2Ag+ -7 Zn2+ + Ag is best represented by

(A)Ag IAg+ II Zn IZn2+ (B)ZnIZn2+ IIAg+ lAg
(C) 2Ag 1Ag+ II Zn 1Zn2+ (D) Zn 1Zn2+112Ag I Ag+
Q.8 The Cell reaction Zn + Cu+2 -7 Zn+2 + Cu is bestrepresented by

(A)Cu I Cu+2 11 Zn+2 1Zn (B)Zn IZn+211 Cu+2 1Cu
(C) Cu+2 1CU II Zn I Zn+2 (D) Pt IZn+2 11 Pt I Cu+2
Q.9 EO forF2 +2e 2r-is 2.8 V, EO for Y:zF2 +e-=r-is

(A) 2.8 V (B) 1.4 V (C) -2.8 V (D)-1:4 V
Q.lO EORP for Fe+2 1Fe and 8n+2 1 8n are-0.44 and-D.l4 volt respectively. The standard emf for cell
Fe+2 + 8n -7 8n+2 + Fe is '
(A) +0.30 V (B)-0.58 V (C) +0.58 V (D) -D30 V ~,
Q.11 The standard electrode potentials ofZn2+ IZn and Ag+IAg are -D.763 V and + 0.799 V respectively.
The standard potential ofthe cell is
(A) 1.56 V (B) 0.036 V (C) -1.562 V (D) 0.799 V
[i~~~~,,~~CL~~~~! ELECTROCHEMIS.TRY [36/

_1fI>'Sdw/cn
Q.12 The cell reaction of a cell is Mg(s) + Cu 2+(aq) ---? Cu(s) + Mg2+ {aq). If the standard reduction
potentials ofMg and Cu are -2.37 and + 0.34 V respectively. The emfofthe cell is
(A) 2.03 V (B)-2.03V (C)+l71V (D)-2.7IV
Q .13 The standard reduction potentials for the following half-cell reactions are
Zn ---? Zn2+ + 2e-; EO 0.76 V; Fe ---? Fe2+ + 2e-; EO = -0.44 V
The e.m.f. for the cell reaction Fe2+ + Zn ---? Zn 2+ + Fe will be
(A) -O.32V (B) + 0.32 V ~ .20 V (D) -1.20 V
Q.14 Thestandardeell potential of Zn IZn2+ (aq) II Cu2+ (aq) leu cell is 1.10 V
The maximum work obtained by this cell will be
(A) -106.15 kilo joule (B) - 212.30 kilo joule

(C) - 318.45 kilo joule (D) -- 424.60 kilo joule
<::ll}. ;rhe single electrode potential E of0.1 M solution ofW ions [Eo = -2.36 V] is
"iYv (A) + 2.41 . . (B) - 2.41 (C) - 4.82 (D) +4.82
Q.l6 The emffor the cell Ni I Ni2+ (l.OM) II Au 3+ (l.OM) IAu (EO for Ni 2+ I Ni =-0.25 V. EO for Au3+ I
f Au 1.50V) is
~
(A) 1.25 V (B)-4.0 V (C) 1.75 V (D) -1.75 V
Q.17 What is theemfofthe cell Crl Cr3+ (1.0M) II C02+(l.OM) I Co [EO For cr3+ ,Cr=-O.74 V &C02+,
, Co = -0.28V]
\
(A) -0.74 -(:-0.28) -0.46 V (B)-O.74 +(-0.28) -1.02V
(C) -0.28 -{-O.74) = + 0.46 V (D)-O.28 (x2)-{-O.74) x(C) = + 1.66 V
2W (aq) + 2e- ---? H2 (g). Standard electrode potential for the above reaction (in volts) is
(A) 0 (B) +1 (C) -I (D) None of these
The halfcell reduction potential ofa hydrogen electrode at pH = 10 will be

(A) 0.59 V (B) - 0.59 V (C) 0.059 V (D) - 0.059 V
A standard hydrogen electrode has zero electrode potential because:

(A) Hydrogen is easiest to oxidise (B) The electrode potential is assumed to be zero
c (C) Hydrogen atom has only one electron (D) Hydrogen is the lightest element
( Q.21 TheemfofaDanielcell at298KisE l Zn IZnS041l CuS041 Cuwhenthe concentrationofZnS04 is l.OMand

"
(O.OIM) (l.OM)
( that ofCuS04 is 0.0 I M the emfchanged to E 2. What is the relationship between El and E2
( (A)~=O:;<:El (B)EI>~ (C)EI<E2 (D)E1=E2
(.
Q .22 Stronger is oxidizing agent, greater is the

(
\. (A) Standard reduction potential (B) Standard oxidation potential
(' (C) Ionic nature (D) None
" Q .23 Zinc displaces copper from the solution ofits salt because
(
(A) Atomic number ofzinc Is more than that ofcopper
(B) Zinc salt is more soluble in water than the copper salt
t:
(C)Gibbs free energy ofzinc is less than that ofcopper
( (D) Zinc is placed higher than copper in electrochemical series
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Q.24 In theelectrochemicalceIIH2(g) 1 atom I W(1 M) II Cu2+(l M) I Cu(s) Which.one ofthe following
statements is true
(A) H2 is cathode; Cu is anode (B) Oxidation occurs at Cu electrode
(C) Reduction occurs at H2 electrode (D) H2 is anode; Cu is cathode
Q .25 One ofthe following is false for Hg

(A) It can evolve hydrogen from H2S (B) It is a metal
(C) It has high specific heat (D) It is less reactive than hydrogen
Q.26 The values ofthe standard oxidation potentials for some reactions are given below:
....
Zn ~ Zn2+ + 2e- , EO + 0.762 VFe ~ Fe2+ + 2 e-, EO = + 0.440 V
Cu~ Cu2++ 2e- , EO ~0.345 VAg~Ag++e-, EO=- 0.800 V
Which one ofthe following is most easily reduced
(A) Fe2+ (B)Zn2+ . (C)Cu2+ (D)Ag+l
Q.27 The reaction Zn2+ + 2e- ~ Zn has a standard potential of- 0.76 V. This means
(A) Zn can't replace hydrogen from acids (B) Zn is reducing agent
(C) Zn is an oxidising agent (D) Zn2+ is a reducing agent
Q.28 KCI cannot be used as a salt bridge for the cell Cu(s) ICuSOiaq) II AgN03 IAg(s) because
(A) CuCI2 gets precipitated (B) CI2 gas is evolved
(C)AgCI gets precipitated (D) None ofthe above
Q.29 A gas X at 1 atm is bubbled through a solution containing a mixture of 1MY- and 1 M Z- at 25°C. Ifthe
reduction potential ofZ> Y> X, then
'"
(A) Y will oxidize X and not Z (B) Y will oxidize Z and not X \.
(C) Y will oxidize both X and Z (D) Y will reduce both X and Z
Q.:jO The standard reduction potentials of4 elements are given below. Which ofthe following will be the most
suitable reducing agent
1=- 3.04 V II - 1.90 V III=O.V IV 1.90V
(A) III (B)U (C)I (D)JV
\
Q.31 EO value of Mg2+ I Mg, Fe2+I Fe and Zn2+ I Zn are -2.37 V, -0.44 V and -0.76 V respectively.
The correct statement is
(A) Mg oxidizes Fe (B) Zn oxidizes Fe (C) Zn reduces Mg (D) Zn reduces Fe2+
Q.3 2 Silver from silver nitrate is deposited by copper because

(A) EO (Cu2+, Cu)<EO(Ag+,Ag) (B)EO(Ag+,Ag) <Eo (Cu2+, Cu)
2
(C) EO (Cu +, Cu) = EO (Ag+ ,Ag) (D) None ofthese
Q.33 The standard reduction potential values ofthree metallic cations, X, Y, Zare 0.52, - 3.0': and - 1.18V
respectively. The order ofreducing power ofthe corresponding metals is
(A)Y>Z>X (B)X>Y>Z (C)Z>Y>X (D)Z>X>Y
Q .34 When a copper wire is placed in a solution ofAgN03' the-solutionacquires blue colour. This is due to
the foonation of
(A) Cu+2 ions (B) Cu + ions
(C) Soluble complex ofCu with AgN03 (D) None
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Q.35 Standard reduction potentials at 25° C of Li+ I Li, Ba2+ I Ba, Na+ I Na and Mg2+ I Mg are
-3.05, -2.90, -2.71 and - 2.3 7 volt respectively. Which one ofthe following is the strongest oxidising
agent
(A) Na+ (B)Li+ (C) Ba2+ (D) Mg2+
Q.36 Out ofCu, Ag, Fe and Zn, the metal which can displace all others from their salt solution is
W~ ~~ ~~ ~~
Q.3 7 The degree ofdissociation ofan electrolyte does not depends on

(A) Nature ofelectrolyte (B) Catalytic action
(C) Dilution (0) Temperature
Q.3 8 Solid NaCI is a bad conductor ofelectricity because

(A) Solid NaCI is covalent
~'
(B) In solid state there are no ions
(C) In solid NaCI, there is no migration ofions
/' (0) In solid NaCI, there are no electrons
" Q.39 Which one ofthe following will not conduct electricity
(A) Crystalline NaCI (B) CuS04 solution
r (C) Graphite (0) NaCI crystal having defects
" Q.40 In the electrolysis ofNaCI
/
\
(A) CI- is oxidized at anode (B) CI- is reduced at anode
(C) CI- is reduced at cathode (0) CI- is neither reduced nor oxidized
" Q.41 Which one ofthe following reaction occurs at the cathode
r
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(A) 20H- ~ H20 + + 2e- ° (B)Ag~Ag++e-
(C) Fe2+ ~ Fe3+ + e- (D) Cu2+ 4- 2e- ~ Cu
(
Q.42 When electric current is passed through a cell having an electrolyte, the positive ions move towards the
" cathode and the negative ions towards the anode. Ifthe cathode is pulled out ofthe solution
/ (A) The positive and negative ions will movetowards the anode
'-,
(B) The positive ions will start moving towards the anode, the negative ions will stop moving
( (C) The negative ioils will continue to move towards the anode and the positive ions will stop moving
(0) The positive and negative ions will start moving randomly
Q.43 Which is responsible for electrical conduction ofmolten sodium chloride

( (A) Free electrons (B) Free ions
(
(C) Free molecules (0) Atoms ofsodium and chlorine
'I. '
Q.44 A so lution ofsodium sulphate in water is electrolyzed using inert electrodes. The products at the cathode
{
"', and anode are respectively
t (A) H2, 02 (B) 02' H2 (C) 02' Na (0) 02' S02
t
Q.45 Water is nonelectrolyte but~onducts electricity on dissolving a small amount 6f:
( (A) NaCI (B) Sugar (C)Acetone (0) Oxygen
C Q.46 The cathodic reaction in electrolysis ofdilute sulphuric acid with platinum electrode is:
(A) Oxidation (B) Reduction
( (C) Both oxidation and reduction (0) Neutralization
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Qo4 7 At cathode, the electrolysis ofaqueous Na:zS04 gives
(A)Na (B)H2 (C) S03 (D)S02
Qo48 Ofthe following metals that cannot be obtained by electrolysis ofthe aqueous solution oftheir salts are:
(A) Ag and Mg (B) Ag and AI (C) Mg and AI (D) Cu and Cr
Qo49 The unit ofelectric charge is equal to

(A) Faraday I Avogadro number (B) Faraday x Avogadro number
(C)Avogadro numberlFaraday (D) None ofthese
~ The number ofelectrons required. to deposit 1 gm atom ofaluminium (at. wt. = 27) from a solution of
Waluminium chloride will be (where N is Avogadro's number) .
wm ~m. ~lli ~~
Q.51 How many faraday are needed to reduce a mole ofMn04- to Mn2+
W4 ~5 ~3 ~2
Q.52 A current of5 ampere is passed through the solution ofzinc sulphate for 40 minutes then the amount of
deposited zinc on cathode will be
(A) 40.65gm (B) 4.065 gI1.l (C) 004056 gm (D) 65,04 gm
Q.53 When 0.04 faraday ofelectricity is passed through a solution ofcaS04, then the weight ofCa+2 metal
deposit~d atthe cathode is
(A) 0.2 g (B) 004 g (C) 0.6 g (D) 0.8 g
Q.54 The amount ofelectricity required to deposit 0.9 g ofaluminium, when the electrode reaction is
A13+ + 3e- ~ AI
(A)9.65xl03C (B)1.93xl04C (C)9.65xl0 4C (D)4.34xl04C
Q.55 A certain current liberated 0.504 g ofhydrogen in 2 hours. How many grams ofcopper can be liberated
by the same current flowing for the same time in copper sulphate solution , J
(A)12.7g (B) 16.0 g (C) 31.89 (D) 63.5 9
Q.56 What is the amount ofchlorine evqlved, when 2A ofcurrent is passed for 30 minutes in an aqueous
c
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solution "'j
ofNaCI ,>
5
A A) 1.32g (B) 4.56 g . (C) 9.81 g (D) 12.6 g '-J
~~en a lead battery discharges, which ofthese occurs : r'

v
. (A) Pb is formed (B) Sulphuric acid is consumed ('
2
(C) PbS04 ~ Pb + + SOl- (D) PbS04 + H2 ~ Pb + H 2S04 \....J
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Q.58 When lead storage battery is charged '-./
(A) Pb02 is dissolved (B) H 2S04 is regenerated
(C) PbS04 is deposited on lead electrode (D) Lead is deposited on lead electrode
c
Q.5 9 When a solution ofan electrolyte is heated the conductr.nce ofthe solution - c
(A) Increases· beeause oftheeleetrolyteeonduets better ( "\
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(B.) Decreases because ofthe increased heat .
(C) Decreases because ofthe dissociation ofthe electrolyte is suppressed c
(D) Increases because the electrolyte is dissociated more
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Q.60 The conductivity ofstrong electrolyte
(A) increases on dilution slightly (B) does not change on dilution
(C) decreases on dilution (D) depends on density 'Ofelectrolyte
Q.61 Which ofthe following is a poor conductor of electricity
(~
(A) CH3COONa (B) C 2H s OH (C) NaCI (D) KOH
Q.62 The relationship between equivalent conductivity (A), specific conductivity (K) and normality (xN) ofa
solutionis
(A)K= 1000xx (B) A = 1000 x K K A

A x (C)A= 1000 x x (D) 1000 x x
The cell constant is the product ofresistance and
(A) conductance (B) molar conductance
(C) specific conductance (D) specific resistance
A conductance cell was filled with a 0.02 M KCI solution which has a specific conductance of
2.768xl0-3 ohm- l cm- I • Ifits resistance is 82.4 ohm at 25°C, the cell constant is
(A) 0.2182 cm- l (B) 0.2281 cm- I . (C) 0.2821 cm- I (D) 0.2381. cm- I
The resistance of 1 N solution of acetic acid is 250 ohm when measured in a cell ofcell constant
1.15 cm-I • The equivalent conductance (in Ohm- I cm 2 equiv- I) ofl N acetic acid is
(A) 4.6 (B) 9.2 h (C) 18.4 (D) 0.023
The specific conductance ofa NIl 0 KCI at 25°C is 0.0112 ohm-l cm-I . The resistance ofcell containing
solution at the same temperature was found to be 55 ohms. The cell constant will be
(A) 0.0616 cm- l (B)0.616cm- 1 (C) 6.16 cm- I (D) 616 cm-I
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EXERCISE-II
Q.I Consider the given data :

Half cell reaction EO
"
1. Crp/- + 14H+ + 6e- ~ 2Cr3+ + 7Hp + 1.33 V
-, ,
2. Cr3+ + 3e- ~ Cr -0.74 V
3. Cu++e-~Cu, +0.52 V
4. Cu2++ 2e- ~ Cu 0.34V
EO for the reaction, 2Cr(s) + 3Cu2+(aq) ~ 2Cr3+ + 3Cu IS:
(A) - 1.08 V (B) - 0.70 V (C) 1.08 V (D) 2.50 V
Q.2 For a cell reaction, 2Ag+ + Cu~ Cu+2+ 2Ag " ,
schematic diagram indicating migration ofcation, anion and electrons is :

("
e--- e--- , /
anion ( ,
'I,
cation--.
(A) (B)
('
(C) both (A) and (B) (D) none ofthese
Q.3 Consider the following equations for a cell reaction

A+B ....----
----""C+D EO=x volt' eKq =K I
2A+2B~2C+2D EO=yvolt,K
, eq
=K2 then: /'
'
(A) x = y, Kl = ~ (B) x = 2y, Kl = 2~ (C) x = y, K/ = ~ (D) x 2 = y, Kl2 = K2
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Q.4 When has maximum potential for the half-cell reaction?
2H++2e-~~
( j

(A) 1.0MHCI
(C) pure water
(B)asolutionhavingpH4
(D) 1.0 M NaOH
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Q.5 For the half-cell given below,

(~
Pt(H2) I pH = 2 , celJ potential is :
1 atm ()
(A) 0.0591 V (B) 0.0295 V (C)0.1182V (D) O.OOV (
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Q.6 Fortlie cell prepared from electrode A and B ;
Electrode A : Crp/-I Cr3+, EOred=+ 1.33 V and electrode B ; Fe3+ IFe2+, EOred = 0.77 V. Which ofthe
G
following statements are correct? ('"
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(A) the electrons will flow from B to A when connection are made
(B) the emfofthe cell will be 0.56 V c
(C) A will be positive electrode
o
(D) none ofthese
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~ Consider following sets
CuSO•. CuSO. II CuSO, III

(blue) (blue) (blue)
Blue colour solutions changes to colourless (or fades) in :

(A) I, II. III (B) I, II (C) II, III CD) I, IIf
~ Consider following sets
"
ZnSO. II MgCI, III
(colourless) (colourless) (colourless)
Colourless solution changes to blue coloured solution in :
(A) I (B) II (C) m (D) I,m
Q.9 For the cell prepared from electrode A and B;

tV Electrode A : Crp/-I 0.3+, EOn:/=+ 1.33 V and electrode B; Fe3+IFe2+, E°red O.77V. Which ofthe
fo Howing statements are correct?
(A) the electrons will flow from B to A when connection are made
(B) the emfofthe cell will be 0.56 V
(C)A will be positive electrode
(
(D) Bone ofthese
" .Q.IO For the half-cell given, Pt(HJ IpH = 2, cell potential is:
c 1 atm
c (A) 0.0591 V (B) 0.0295 V (C) 0.1182 V (D) O.OOV
Q.ll Pt(~) IO.OIMH+ II O.IMH+l Pt(I\). IfEceu =O.OOV ,than is:
( y
xatm yatm
(.
(A) 100 (B) 10 (C) 0.01 (D) 0.1
(' Q(f2jAythe Pb2+concentration is maintained at 1.0 M, what is the [Cu2+] when the cell potential drops to
0fvlzero? EOceU = 0.473 V, Pb I Pb2+ (1.0 M) II Cu2+(LQ X 10-4 M) I Cu(s)
(
(A) 1 x 10-16 M (B) 1 x 1016M (C) 1.0 x 10- 14 M (D) 1.0 X 10 14 M
{ Q.13 In the following electrochemical cell: Zn I Zn+2 11 H+ ,Pt(H 2 ) ; EOcen= Ecen'
H (+)
( . This will be when:
(A) [Zn2+J = [H+] = 1M and Pm = latm
6 (B) [Zn2+] = 0.01 M, [H+J = 0.1 M and PH2 = latm
(C) [Zn2+] = 1 M, [H+] = 0.1 M and PH2 = 0.01 atm
t
(D) all ofthe above
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ELECTROCHEMISTRY [43}
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Q9c?lectrode potentials ofthe given half-celIs :
Pt~) IH+ (C l); Pt(CI2) ICI- (C2) ; AgIAg+(C 3)
PI P2
(I) (II) (III)
(A) will increase on increasing C l, C2& C3 (B) will decrease on increasing C r, C2 & C3
(C) both (A) and (B) (D) none ofthese
Q.15 1 mol of electrons passes through each ofthe solution ofAgN03' CuS04 andAIC~ when Ag, Cu and
AI are deposited. Their molar ratio will be :
(A) 1 : I : I (B) 6: 3 : 2 (C) 6: 3 : 1 (D) I : 3 : 6
Q.16 Following behaves as S.H.E.atapressure Pt,~I~O:

(A) I atrn (B) 10-7 atm (C) 107 atrn (D) 10-14 atrn
,'0
Q.l7 For the cell, Zn(s) I2n2+11 Cu2+j Cu(s), the standard cell voltage, E°cell is 1.l0V. When a cell using these (,
reagents was prepared in the lab, the measured cell voltage was 0.98 V. One possible explanation for
the observed voltage is : \ <
(A) there were 2.00 mole ofCu2+butonly l.00molofZn2+

(B) the Zn electrode had twice the surface ofthe Cu electrode
(C) the [Zn2+] was Jargerthan the [Cu2+]
(D) the volume ofthe Zn2+ solution was larger than the volume ofthe Cu2+ solution.
Q.18 Thee.m.fofthe following three glvaniccells:

(1) Zn1Zn2+ (1 M) II Cu2+(1M) ICu /"
(2) Zn lZn2+(0.1 M) II Cu2+(1 M) ICu

\,
(3) Zn1Zn2+(1 M) II Cu2+(0.1 M) leu

'-,"
are represented by E 1, E2 and E3. Which ofthe following statement is true ?
(A) E2 > El > E3 (B) E3 > E2> El (C) EI > E2 > E3 (D) E3> El > E2 "-/ " /
(~
Q.19 Ifthe pressure ofhydrogen gas is increasedfrom 1atm to 100 atm, keeping the hydrogen ion concentration '-j
constant at 1 M, the voltage ofthe hydrogen half cell at 25°C will be:
(A) -0.059 V (B) + 0.059 V (C) 5.09 V (D) 0.259 V
f"
~
Q.20 The reduction potential ofa half cell consisting ofa Pt electrode immersed in 1.2 M Fe2+ and 0.012 M
('0
Fe3+solution at 25°C is (Eo Fe3+lFe2+= 0.770) '-J
(A) -0.326 V (B) 0.652 V (C) 0.326 V (D) -0.652 V / '

~
~
2 i Prequivalent conductance ofl M benzoic acid is 12.8 ohm-1 cm2 and ifthe conductance ofbenzoate ion c~
ctndH+ ion are 42 and 288.42 ohm-1 cm2respectively, its degree ofdissociation is :
(A) 3.9 % (B) 0.039% (C)39% (D) 0.39% c
( ,
Q .22 Number ofelectrons lost during electrolysis of0.355 g ofCI- is : b
0.01
(A) 0.01 (B) 0.01 No (C) 0.02 No (D) 2No c
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Q.23 Schematic diagram ofan electrolytic-cell is :
(A) (B)
(C) (D) none is correct presentation'
' ..
<@~~e2+lfe is
(
XI' EOFe3+lfeis x 2• then EOfe3+1fe2+ will be :
-V0A) 3Xz 2x t (B) Xz - Xl (e) Xz + Xl

(D) 2Xl +3Xz
Zn + eU 2+(aq)' ~ eU + Zn2+ (aq)

(
' Q.25
(
Reaction quotient is Q = f~:::~ . Variation of Eceu with log Q is plotted on graph then intercept
OA 1.10V.,Ecen will be 1.159Vwhen:

(
\ [eu 2+] [Zn 2+ ] [Zn 2+] [Zn 2+]

(A) - [ 2+] = 0.01 (B) 2+ = 0.01 (e) --2+- 0.1 (D) [Cu 2+]
( Zn [eu ] [eu ]
"
OH °
,
'- Q.26 For the half cell, r:QJ ~ ~ ~
+ 2H' + z.- .E' 1.30 V
(.
OH Y
At pH = 2. electrode potential is :
(A) 1.36V (B) 1.30 V (C) 1.42 V (D) 1.20 V
(
Q.27 Cu2++2e~eu.For this graphbetween log (eu +) versus Ercdis a straight line of intercept 0.34
2
( V then electrode potential ofthe half-cell CulCu2+(0.1 M) will be :
(
(A) 0.34 + 0.Oi91 (B) - 0.34 - o.or 1 (C) 0.34 (D) 0.34 + 0.Oi 91
( Q.28 In acidic medium Mn04- isanoxidisingagent. Mn04- +8H++ 5e---+ Mn2++4Hp. If H+ ion
concentration is doubled, electrode potential ofthe half-cell Mn04-, Mn2+IPt will :
(
(A) increase by 28.46 m V (B) decrease by 28.46 m V
(C) increase by 142.3 mV (D) decrease by 142.30 mV
.(
Q.29 Assume that during electrolysis ofAgN03' only ~O is electro lysed and 02 is formed as :
2Hp--+ 4H+ + 02 +4e
02 formed at NTP due to passage of2 amperes ofcurrent for 965 s is :
c (A)0.1l2L (B)0.224L (C)11.2L (D) 22.4 L
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Q.30 A 9Qnducting wire carries a current of 0.965 ampere. Rate of flow ofelectrons per second at a given
point is :
NO
(A) 1 x 10-5 No (B) No (C) 0.965 No

(0) 0.965
Q.31 A quantity ofelectrical charge that bringS about the deposition of4.5g Al from AP+ at the cathode will
also produce the following volume (STP) of~(g) from H+ at the cathode:
(A) 44.8 L (B) 22.4 L (C) 11.2 L (0) 5.6 L
Q.32 1 g equivalent of Na metal is formed from electrolysis of fused NaCI. Number of mol of Al from
fused N~AlF6 will be ;
(A) 1 (B) 3 (C) 1/3 (D) 2
~ i 00 mL ofa buffer of 1 M ~(aq) ·and 1 M NH/ (aq) are placed in two· voltaic cells separately. A
\AIcurrent of 1.5 A is passed through both cells for 20 minutes. Ifelectrolysis ofwater only takes place
2~0 + 02 + 4e- ~ 40H- (RHS)
2~0 ~ 4H+ + 02 + 4e- (LHS)
then pH ofthe :
(A) LH8 halfcell will increase (B) RH8 half-cell will increase
(C) both half-cells will increase (0) both half-cells will decrease
Q.3t'Duringdischarging oflead-storage acid battery following reaction takes pl'lce :
\/../ Pb(s) + Pb02(s) + 2H2804 ~ 2Pb804(s) + 2Hp
If 2.5 amp ofcurrent is drawn for 965 minutes, ~804 consumed is :
(A) 0.75 mol (B) 3.00mol (C) L50mol . (0) 4.50 mol
Q.35 When a dilute aqueous Li 2804 solution is e lectro lysed , the products formed at the anode and
cathode, respectively, are:
(A) 8 and Li (B) 02 and Li (C) 802 and ~ (D) 02 and ~ ,
2 I
Q.36 The limitingmoIar conductivities N for NaCl, KBr and KCl are 126, 152 and 150 S cm mol- respectively..
The N for NaBr is : {'
,~ j
",
(A) 278 S cm2 mol:- I (B) 178 S cm2mol- I (C) 1288 cm 2 mol- I (0) 306 8 cm2mol- I
..,
Q•3 7 A NH 4 Cl -- 130 """
",,-I cm 2 mol- I
o

A""
NaOH
=220 0- cm2mol-I
A""
NaCI
= 1100-1 cm2 mol-I
.
If Am ofNHPH at a given concentration is 12.00-1cm2mol-I,what is its percentage dissociation?
(A) I % (B) 2% (C) 3 % (D) 5%
Q.38 Sp~ific conductance of 0.01 N solution of an electrolyte is 0.00419 mho em-I. The equivalent
conductance ofthis solution will be :
(A)4.19mhocm2 (B)419mhocm2 (C) 0.0419 mhocm 2 (O)0.209mhocm2 .
r~
Q.39 Ksp ofBaS04is 1 x 10-10, Ifthe ionic conductances ofBa+2and S04-2 ions are 64 and 80 ohm-I cm2 v
mot-I respectively, then its specific conductan~s : ' . t- '\
'b-'
(A) 1.44 x 10-& ohm-I cm- I (B) 144 x 10-& ohm-I cm- I
(C) 1.44 x 108 ohm-I cm-I (D) 144 x 108 ohrD- 1 cm- 1
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Q.40 One gm metal M+2 was discharged by the passage of I.81 x I<p2 electrons. What is the atomic weight
ofmetal?
(A) 33.35 (B) 133.4 (C) 66.7 (0)55
QAI Salts ofA (atomic weight 7), B (atomic weight =27) and C (atomic weight = 48) were electrolysed
underidentical conditions using the same quantity ofelectricity. It was found that when 2.1 g ofA was
deposited, the weights of Band C deposited were 2.7 and 7.2 g. The valencies of A,B and C
respectively are
(A) 3, I and 2 (B) 1,3 and 2 (C)3, I and 3 (D)2,3 and 2
Q.42 The density ofCu is 8.94 gCfll-3. The quantity ofelectricity needed to plate an area 10 cm:x IOcm to
a thickness ofIo-2 cm using CuS04 solution would be
(A) 13586 C (B) 27172 C (C) 40758 C (D) 20348 C
Q.43 During electrolysis ofan aqueous solution ofsodium·sulphate, 2.4 L ofoxygen at S1P was liberated at
anode. The volume ofhydrogen at STP, liberated at cathode would be
(A) 1.2 L (B) 2.4 L (C) 2.6 L . . (D) 4.8 L
~uring electrolysis ofan aqueous solution ofCuS04 using copper electrodes, if2.5 g ofCu is deposited
at cathode, then at anode ,
(A) 890 ml ofCl2 at S1P is liberated (B) 445 ml of02 at S1P is liberated
(
, (C) 2.5 g ofcopper is deposited (D) a decrease of2.5 g ofmass takes place
Q.45 The charge required for the oxidation ofone mole Mn30 4 into MnO~- in presence ofalkaline medium is
(A) 5 x 96500 C (B) 96500 C (C) 10 x 96500 C (D) 2 x 96500 C
Q.46 A solution ofsodium sulphate in water is electro lysed using inert electrodes. The products at the cathode
and anode are respectively.
( (A) H 2, 02 (B) 02'~ (C) 02' Na (0) none
( Q.47/)Vhen an aqueous solution oflithium chloride is electrolysed using graphite electrodes
" W (A) CI2 is liberated at the anode.
c (B) Li is deposited at the cathode

(C) as the current flows, pH ofthe solution around the cathode remains constant
(D) as the current flows, pH ofthe solution around the cathode decreases.
(
\..
Q.48 A standard hydrogen electrode has zero electrode potential because
(A) hydrogen is easier to oxidise
( (B) this electrode potential is assumed to be zero
{
(C) hydrogen atom has only one electron
'-. (0) hydrogen is the lighest element.
( Q.49 Ifthe pressureof~ gas is increased from I atrn to 100atrn keepingH+ concentration constant at 1M,
the change in reduction potential ofhydrogen halfcell at 25°C will be
(
(A) 0.059 V (B) 0.59 V (C) 0.0295 V (D) 0.118 V
(
~ Q.5u The equilibrium constant for the reaction
Sr(s) + Mg+2 (aq) ~ Sr+2 (aq) + Mg(s) is 2.69 x 10 12 at 25°C
~
't=
The EO for a cell made up ofthe Sr1Sr+2 and Mg+2/Mg halfcells
( (A) 0.3667 V . (B) 0.7346 V (C) 0.1836 V (D) 0.1349 V
(
~!~~~~~CM~~~!
Ickott'otScho1otS
ELECTROCHEMISTRY {47J
r
\.
e A silver wire dipped in 0.1 M Hel solution saturated with AgCI develops oxidation potential of-0.25 V.
If.Eo I
Ag Ag
+ = - 0.799 V, the ~p ofAgel in pure water will be
(A) 2.95 x 10-11 (B) 5.1 x 10- 11 (e) 3.95 x Hrll (D) 1.95 x 10- 11
Q.52 eonsiderthe following Galvanic celJ;

i,,_,... _.. __ i
-CI2(g)
Pt(s)
Anode Cathode
By what value the cell voltage change when concentration ofions in anodic and cathodic compartments
both increased by factor of 10 at 298 K
(A) +0.0591 (B)4).Q591 (C)-O.1182 ~D)O
Q.53 For the cell ,-'

Pt I H2(O.4atm) I H+(pH=I) IIH+(pH=2) I H2 (0.1 atm) IPt
The measured potential at 25°e is
(A)-O.1 V (B)-O.5 (C)-O.041 (D) none 'J
Q.54 The standard reduction potentials of eu2+I eu and eu2+I eu+ are 0.337 and 0.153 V respectively. The
standard electrode potential ofru+I eu halfcell is
(A)0.184V (B)0.827V (C)0.521 V (D) 0.490 V
Q~ j\ The resistance of0.5 M solution ofan electrolyte in a cell was found to be ~O ~. I~the ~lectrodes in the
v cell are 2.2 cm apart and have an area of4.4 cm 2 then the molar conductlVlty (m S m2 mol-I) ofthe
solutionis
(A) 0.2 (B) 0.02 (C) 0.002 (D) None ofthese " ,
'- ,"
Q.56 Equivalent conductance of0.1 M HA(weak acid) solution is 10 Scm2equivalenrl and that at infinite
dilution is 200 Scm2equivalenr l Hence pH ofHA solution is ~ J
(A) 1.3 (B) 1.7 (C) 2.3 (D)3.7

r -,
\._j
Q.57 Ifx is specific resistance ofthe electrolyte solution and y is the molarity ofthe solution, then Am is given
by o
. 100Qx 1000 xy
(A) y (B) 1000 Y.. (C)~
x (D) 1000
v"
Q.58 The dissociation constant ofn-butyric acid is 1.6 x 10-5 and the molar conductivity at infmite dilution is
380 x 1(f4 Sm2mol-1• The specific conductance ofthe 0.01 M acid solution is
(A) 1.52 x 10-5 Sm-I (B) 1.52 x 10-2 Sm- I
3
(e) 1.52 x 10- Sm- I (D) None
WThe conductivity ofa saturated solution ofAg3PO4 is 9 x 10-6 S m-1 and its equivalent conductiv.ity is G
1.50 x 10-4 S m2 equivalenrl. The Ksp ofAg3PO4 is f'
: (A) 4.32 x 10-18 (B) 1.8 x 10-9 . (e) 8.~~ __~1 0-13 (D) None ofthese V
t' "
Q.60 Equal volumes of0.015 MeH3eOOH&0.015 MNaOHaremixedtogether. What would be molar b-
conductivity ofmixture ifconductivity ofeH3eOONa is 6.3 x 10-4 Scm-I

(A) 8.4 S cm2 mol-I (B) 84 S cm2 mol-I (e) 4.2 S cm2 mol-I (D) 42 S cm 2 mol-I
c
c
ELECTROCHEMISTRY /48) r
~
c
,c ,
v
Assertion & Reasoning type questions
Q.6I Statement -1 : The voltage ofmercury cell remains constant for long period oftime.
Statement -2 : It is because net cell reaction does not involve active species.
(A) Statement-I is true, statement-2 is true andstatement-2 is correct explanation for statement-I.
(B) Statement-I is true, statement-2 is true and statement-2 isNOTthe cqrrect explanation for statement-I.
(C) Statement-l is true, statement-2 is false.
(D) Statement-I is false, statement-2 is true.
Q.62 Statement-I: The SRPofthree metaUic ions A+,B2+, C3+ are-O.3,-O.5, 0.8 volt respectively, so
oxidising power ofions is C3+ > A+ > B2+.
Statement -2 : Higherthe SRP, higher the oxidising power.
(A) Statement-I is true, statement-2 is true and statement-2 is correct explanation for statement-I.
(B) Statement-I is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-I.
(C) Statement-! is true, statement-2 is false.
(D) Statement-l is false, statement-2 is true.
Q.63 Statement -1 : We can add the electrode potential in order to get electrode potential of net reaction.
Statement -2 : Electrode potential is an intensive property.
(A) Statement-I is true, statement-2 is true and statement-2 is correct explanation for statement-I.
(B) Statement-I is true, statement-2 is true and statement-2 is NOTthe correctexplanation for statement-I.
(C) Statement-} is true, statement-2 is false.
(D) Statement-I is false, statement-2 is true.
c
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ELECTROCHEMISTRY /49}
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EXERCISE-III.
SECTION-A
Q.l EMF ofa cell in tenns ofreduction potential ofits left and right electrodes is [A1EEE 20021
(A) E = E left - E right (B) E = EI«ft + E right (C) E = E right E 1eft (D) E = -(Bright + E left)
Q.2 When KMnO4 acts as an oxidising agent and ultimatelyfonns [MnO4r2, Mn02, Mn20 3, Mn+2 then
the number ofelectrons transferred in each case respectively is (A1EEE 2002]
(A) 4, 3, 1,5 (B)1,5,3,7 (C)1,3,4,5 (D) 3, 5, 7, I
Q.3. Conductivity (unit Siemen's) is directly proportional to area ofthe vessel and the concentration ofthe
slution in itandis inversely proportional to the length ofthe vessel then the unit ofthe constant of
proportionality is (AIEEE 2002]
(A) Sm mol- I 2
(B) Sm mol- I (C) S-~~mol (D) S2m2mo12
Q.4 What will he the emffor the given cell Pt jH2(p1)1 W(aq) II H 2(p2)1 Pt [A1EEE 2002]
RT PI RT I RT P
(A) -log p.
. f 2 (B) 2f og P2 (C) flog 1\2 (D) None ofthese
Q.S Which ofthe following reaction is possible at anode (AIEEE 2002]

(A) 2Cr3+ + 7H20 -4 Cr20l-+ 14W (B) F2 -4 2r
(C) )1202 + 2H+ -4 H 20 (D) None ofthese
Q.6 When the sample ofcopper with zinc impurity is to be purified by electrolysis, the appropriate electrodes
are: (A1EEE 2002]
Cathode Anode
(A) Pure zinc Pure copper

(
(B) hnpure sample Pure copper " ~'
(C) hnpurezinc
(D) Pure copper
Impure sample
Impure sample
c
£-...,
U
Q.7 Fora cell reaction involving a two-electrons change, the standrard emfofthe cell is found to be 0.295V
at~5°C. The equilibrium constant ofthe reaction at 25°C will he: [A1EEE 2003] ./
(A) 1 x 10- 10 (B) 29.5 x 10- 2 (C) 10 (D) I x 10 10

,--"
\.."j
Q.8 Which one ofthe following nitrates will leaves tiehing a metal on strong heating: (A1EEE 2003]
(A) Ferric nitrate (B) Copper nitrate c
(C) Manganese nitrate (D) Silvernitrate
Q.9 Sereval blocks ofmagnesium are fixed to the bottom ofa ship to [A1EEE2003]
()
(A) Keep away the sharks (B) Make the ship lighter
(C) Prevent action ofwater and salt (D) Prevent puncturing b under-sea rocks 'j c
Q.IO Standard reduction electrode potentials ofthree metals A, B and C are respectively + O.Sv, -3.0V and
-1.2 V. The reducing powers ofthese metals are [A1EEE 2003]
t"
(A)B>C>A (B)A>B>C (C)C>B>A (D)A>C>B V
....
[i~~~~1l~ C..~~~~!
. - Jd<,j/fC( SdN>/4t:1
c
f. -c·
V
~~
r ~e
v. n
:
basis ofthe infonnation available from the reaction
*'1
j
Al + 02 --+ A~ 03' dG =-827 kJmol-1 of02, the minimumemf required to carry outan electrolysis
ofA 12°3 is(F 96500C mol-I) {AlEEE200J]
(A) 8.56 V (B)2.14 V (C) 4.28 V (D) 6.42 V
(
Q.12 Then during electrolysis ofa solution ofAgN03' 9650 coulombs ofcharge pass through the electroplat
ing bath, the mass ofsilver deposited in the cathode will be [AlEEE 2003]
(A) 1.08 g (B) 10.8 g (C) 21.6 g (D) 108g
Q.13 For the redox reaction:

Zn(s)+ Cu2+ (0.1 M)--+ Zn2+ (1M) +Cu(s) taking place in acel), EOeell is 1.1 0 volt. Eeell forthe-cell will
be
, ( 2.303 RFT = 0.0591)_ [AlEEE 2003)

" (A)2.14 volt. (B) 1.80 volt (C) 1.07 volt (D) 0.82 volt
/'
" Q.14 The EOM3+1M2+ values for Cr, Mn, Fe and Co are-OAl, +1.57,+0.77 and + 1.97Vrespectively. For
(
"- which one ofthese metals the change in oxidation state from +2 to +3 is easiest? [AlEEE 2004]
( W~ ~~ ~Th ~O
\
Q.15 The standard e.m.f. ofa cell, involving one electron change is found to be 0.591 Vat 25°C. The equilib
rium constant ofthe reaction is (F =96,500 C mol-I; R ~ 8.31.4 JK- I mol-I) [AIEEE2004)
(A) 1.0 xl 0 30 (B) 1.0 x 10 5 (C) 1.0 x 1010 (D) 1.0 x 10 1
( ,
Q.l6 The limiting molar conductivities N for NaCI, KBr and KCl are 126, 152 and 150 Scm 2 mol-I respec
tively. The N for NaBr is [AlEEE 2004]
(
(A) 302 S cm 2 mol- I (B) 176 S cm2 mol-I
" (C) 278 S cm 2 mol-I (D) 128 S cm 2 mol-I
(
"
Q.l7 In a cell that utilises the reaction Zn(s) +2H+(aq)--+ Zn2+ (aq) + H 2(g) addition ofH 2S04 to cathode
( ..
'l compartment, will [AlEEE 2004]
(A) increase the E and shift equilibrium to the left
C (B) lower the E and shift equilibrium to the right
(C) increase the E and shift eqUilibrium to the right
(D) lower the E and shift eqUilibrium to the left
( Q.18 Consider the following EO values [AlEEE2004)
EOFe3 +lFe2+ +O.77V
c EOSn2+/Sn -0.14V
(
\. Under standard conditions the potential for the reaction
Sn(s) + 2Fe3+(aq) --+ 2Fe2+(aq) + Sn2+ (aq) is
{ (A) 0.63 V (B) lAo (C) 0.91 V (D) 1.68 V
Q.19 In a hydrogen-oxygen fuel cell, combustion ofhydrogen occurs to [AlEEE2004] .

(A) remove adsorbed oxygen from electrode surfaces
~ (B) create potential difference between the two electrodes
(C) produce high purity water
(
(D) generate heat
c SAL CLASSES
PRIVATE LlMI'f£D ELECTROCHEMISTRY {51J
( kRol(otSth¢IDtJ
'c.
(
~e highest electrical conductivity ofthe following aqueous solutions is of [AlEEE 2005]
(A) 0.1 M acetic acid (B) 0.1 M chloroacetic acid
(C) 0.1 M fluoroacetic acid (D) 0.1 M difluoroacetic acid
Q.21 Aluminium oxide may be electrolysed at 1OOO°C to furnish aluminium metal (at. mass == 27 amu; 1 ,I .',
Faraday == 96.500 Coulombs). The cathode reaction is

A13+ + 3e- -? Alo
To prepare 5.12 kg ofaluminimum metal by this method would require [AIEEE 2005]
(A) 5.49 x 107 C ofelectricity (B) 1.83 x 107 C ofelectricity
(C) 5.49 x 104 C ofelectricity (D) 5.49 x 1010 C ofelectricity (
Electrolyte
(Sem 2 mol-1)
Calculate using appropriate molar conductances ofthe electrolytes listed above at infmite dilution in H20
at 25"C. [AIEEE 2005]
(A) 517.2 (B) 552;7 (C)390.7 (D)217.5
Q.23 The molar conductivities l\~aOAc and I\~CI at infmite dilution in water at 25"C are 91.0 and 426.2 S cmll
mol respectively. To calculate I\~OAC the additional value requried is [AIEEE 2006]
"(A) I\~CI (B) A~aOH (C) A~aci (D) A~20
Q.24 The equivalent conductances oftwo strong electrolytes at infmite dilution in HzO (where ions move
freely through a solution) at 25°C are given below: [AIEEE 2007]
A0 CH3COONa =91.0 S cm2 I equiv

" "
A0 Hel =426.2 S em 2 I equiv

What additional information/quantity one needs to calculate A0 ofan aqueous solution ofacetic acid?
(A) The limiting equivalent conductance of H+ (/.. 0 +)
H
c
(B) A ofchloroacetic acid (CICHzCOOH)
0
(~~)
(C) A0 ofNaCI
(D) Ao ofCH3COOK
Q.25 The cell Zn I Zn2+ (1 M) II Cu2+ (1M)1 Cu (E~ll == 1.1 Ov) was allowed to be completely discharged at
2
[Zn +JJ ()
2 2 [AIEEE 2007]
298K The relative concentration ofZn + to Cu +
[[Cu is2+ ]
(A) 1037.3 (B) 9.65 X 104 (C) antilog (24.08) (D) 37.3
Given EO ~
Q.26
" C + ICr
= -O.72V [AIEEE2008]
c
EO 2+ ;;; -0.42V {;
Fe IFe
The potential for the cell
Cr/Cr3+ (0.1 M) II Fe2+ (0.0 I M) IFe is :
(A)-O.339 V (B)-O.26V (C) 0.26 V (D) 0.339
c
1i~~~~A~~CL~~!~! ELECTROCHEMISTRY [52J
Id<:ol""_
c
c
Q.27. The correct order ofEO M2+JM values with negative sign for the four successive elements Cr, Mn, Fe
and Co is : [AIEEE 201OJ
(A) Cr> Mn> Fe> Co (B)Mn >Cr> Fe> Co
(C) Cr > Fe > Mn > Co (D) Fe > Mn > Cr > Co
( .. Q.28 The reduction potential ofhydrogon haIf-cell will be negative if [AIEEE 2011]
(A) P(H2) = 1 atm and [H+J = 2.0 M (B) p(H2) 1 atm and [H+] 1.0 M
(C) p~) = 2 atm and [H+] = 1.0 M . (D) P(H2) = 2 atm and [H+] = 2.0 M
Q.29 The standard reduction potentials for Zn2+I Zn; Ni 2+INi, and Fe2+I Fe are -0.76, -0.23 and 0.44 V
respectively. The reaction X +y2+ - t X2+ + Y will be spontaneous when:
(A) X = Fe, Y = Zn (B) X = Zn, Y = Ni [AIEEE 2012]
(C) X=Ni, Y=Fe (D)X=Ni, Y=Zn
Q.30 Given [JEE main 2013]
(.,
EOCr3+ fer = -0.74 V'' EO
n
a-1M 2+ = 1.51V
M 4 n
\
E~r2a~-/C?+ = 1.33 V ; E~lIcC =1.36V

Based on the data given above, strongest oxidising agent will be:
(A)Cr3+ (B)Mn2+ (C) Mn04- (D)CC
SECTION-B
(
\.
Q.31 AgasXat 1 atm is bubbled through a solution containing a mixture ofl MYand 1 MZat2S°C. Ifthe
reduction potential ofZ > Y>X, then
(A) Y will oxidise X and not Z (B) Y will oxidise Z and X
(
(C) Y will oxidise both X and Z (D) Y will reduce both X and Z. [JEE 1999]
\.
Q.32 For the electrochemical cell,M IM+ I X-I X,EO{M+JM) 0.44 V and EO (XlX-) = 0.33V. From this
( data, one can deduce that
f (A) M + X ~ M+ + X- is the spontaneous reaction
\.
(B) M+ + X- ~ M + X is the spontaneous reaction
(C) Eeen= 0.77 V
(D) Eeen= -0.77 V [JEE2000J
(
Q.33 The reaction,
( 3CIO-(aq)~ CIO) (aq) + 2CI-(aq)
(
\.. ... is an example of
(A) Oxidation reaction . (B) Reduction reaction
(
\ (C) Disproportionation reaction (D) Decomposition reaction [JEE200l]
( .
Q.34 The correct order ofequivalent conductance at infmitedilution ofLiCI, NaCI and KCI is
( (A) LiCI > NaCI > KCI (B) KCI > NaCI > LiCI
(C)NaCI> KCI> LiCI {D) LiCI > KCI> NaCI [JEE2001J
c
(.
iJ~~~~A~~cg~~~~~
_fc<s<_~
ELECTROCHEMISTRY /53}
(
\ ..
~.
Q.35 Saturated solution ofKN03 is used to make salt bridge because
(A) velocity ofK+ is greater than that of NO;
(B) velocity of NO 3" is greater than that ofK+
(C)velocities ofbothK+ and NO; are neartythe same
(0) KN03 is highly soluble in water [JEE2001]
Q.36 Standard electrode potential data are useful for understanding the suitablilty ofan oxidant in a redox
titration. Some halfcell reactions and their standard potentials are given below: [JEE 2002]
MnO~ (aq) + 8H+(aq) + 5e- ~ Mn2+ (aq) + 4~O (I); EO = 1.51 V
Cr20~-(aq) + 14 H+ (aq)+ 6e-~ 2Cr3+(aq) +7~O (I); EO = 1.38 V

Fe3+ (aq) + e- ~ Fe2+ (aq); EO = 0.77 V
C~ (g) + 2Cl- (aq); EO = 1.40 V
1'-,
Identify the only incorrect statement regarding quantitative estimation ofaqueous Fe(N03)2
(A) MnO~ can be used in aqueous HCl (B) Cr20~- can be used in aqueous HCI
(C) MnO~ can be used in aqueous H 2S04 (D) Cr20~- can be used in aqueous ~S04
Q.3 7 In ·the electrolytic cell, flow ofelectrons is from: rJEE 2003 J

(A) Cathode to anode in solution (B) Cathode to anode through external supply
(C) Cathode to anode through internal supply (D) Anode to cathode through internal supply.
Q.38 Zn IZn2+(a= 0.1M) II Fe2+ (a O.OIM)IFe. The emfofthe above cell is 0.2905 V. Equilibrium
constant for the cell reaction is [JEE 2004] /"
(A) 10°.3210.0591 (B) 100.32/0.0295 (C) 10°·26/0.0295 (D) eO.32/0.295 '- ..

;"
\
Q.39 Thehalfcell reactions for rusting ofiron are: [JEE2005]
;
1 . \..;
2H+ + 2 02 + 2e- ~ ~O; EO + 1.23 V, Fe2+ + 2e- --+ Fe; EO = -0.44 V
AGO (in kJ) for the reaction is:
(A)-76 (B)-322 (C)-122 (D)-176 ( "
\j
Q.40 Electrolysis ofdilute aqueous NaCI solution was carried out by passing 10 milli ampere current. The time
required to liberate 0.01 mol of~ gas at the cathode is (1 Faraday = 96500 C mol-I)
(A) 9.65 x 104 sec (B) 19.3 x 104 sec (C) 28.95 x 104 sec (D) 38.6 x 104 sec C:
[JEE2008]
Q.41 Forthe reduction ofN03- ion inan aqueous solution, EO is +0.96 V. Values ofEO for some metal ions
are given below
V2+(aq)+2e -'tV EO=-1.19V
3
Fe + (aq) + 3e -'t Fe EO = - 0.04 V
Au 3+(aq) + 3e- -'t Au EO = + 1.40 V
Hg2+ (aq) + 2e -'t Hg EO =+ 0.86 V
The pair(s) ofmetal that is(are) oxidised by N03- in aqueous solution is(are) [JEE 2009] c
(A) V and Hg (B) Hg and Fe (C) Fe and Au (D) Fe and V
[i~~~~A~~ C~~~~!
Idu1 for Scbolors
,?\
C
G
Q.42 Among the following, the intensive property is (properties are) [JEE2010]
(A) molar conductivity (B) electromotive force
(C)resistance (D) heat capacity
Q.43 Consider the following cell reaction: [JEE2011]

2Fe(s) + 02 (g) + 4H+ (aq) ----7 2Fe2+ (aq) + 2~0 (I) EO == 1.67 V
2 3
At [Fe +) = 10- M, P(02) = 0.1 atrn and pH = 3, the cell potential at 25° C is
(A)I.47V (B) 1.77 V (C)1.87V (D) 1.57 V
W An aqueous solution ofX is added slowly to an aqueous solution ofY as shown in List I. The variation
~ in conductivity ofthese reactions is given in List II. Match List I with List II and select the correct using
J5;?{I" the code given helowthe lists: . [JEEAdvance 2013]
List I List II
(P) (C2HShN+ CH3COOH (1) Conductivity decreases and then increases
I ,,-. . .~ .... '.
\
X Y
(Q) KJ(O.IM) +AgN~(Q.,.oIM) (2) Conductivity decreases and then does not
( ''y."~. .,....,. 1} '"
". :X . . y~
change much
(R) CH3COOH + KOH (3) Conductivity increases and then does not
i y change much
/
(8) NaOH+HI (4) Conductivity does not change much and then
., Y
X increases
Codes:
( p Q R S p Q R S
(A) 3 4 2 1 (B) 4 3 2 1
(
(C) 2 3 4 CD) 1 4 3 2
(
\ Q.45 The standard reduction potential data at 25°C is given below. [JEE Advance 2013]
EO (Fe3+, Fe2+) = +0.77 V; EO (Fe2+, Fe) =-0.44 V

(. EO (Cu2+, Cu) = +0.34 V; EO (Cu+, Cu) = + 0.52 V
EO [02(g) + 4H+ + 4e- ~ 2~0] = + 1.23 V; EO [02(g) + 2H20 + 4e- ~ 40H-] = +0.40 V
C EO{Cr 3+,Cr)=-0.74V;· EO(Cr2+,Cr)=-O.91 V
( Match EO ofthe redox pair in List I with the values given in List II and select the correct answer using the
\.,
code given helowthe lists:
;(
\.,
List I List II
(P) EO (Fe3+, Fe) (1) -0.18V
'
(Q) EO (4~0 ~ 4H+ + 40H) (2) 0.4 V
(R) EO (Cu2+ + Cu ~ 2Cu+) (3) - 0.04 V
- C (S) EO (cr3+, Cr2+) (4) - 0.83 V
Codes :
t P Q R S P Q R S
(A) 4 1 2 3 (B) 2 3 4 1
(C) 1 2 3 4 CD) . 3 ,4 2
(
{
\..
I
'"
(
{
\. ..
ANSWER KEYS
EXERCISE-I
Q.1 A Q.2 B Q.3 C QA C Q.5 A Q.6 D Q.7 B
Q.8 B Q.9 A Q.I0 D Q.ll A Q.12 C Q.13 B Q.14 B
Q.15 B Q.16 C Q.17. C Q.18 A Q.19 B Q.20 B Q.21 B
Q.22 A Q.23 D Q:24 D Q.25 A Q.26 D Q.27 B Q.28 C
Q.29 A Q.30 C Q.31 D Q.32 A Q.33 A Q.34 A Q.35 D
Q.36 C Q.37 B Q.38 C Q.39 A QAO A QAl D QA2 D
QA3 B Q.44 A Q.45 A Q.46 B Q.47 B Q.48 C Q.49 A
Q.50 C Q.51 B Q.52 B Q.53 D Q.54 A Q.55 B Q.56 A
Q.57 B Q.58 C Q.59 D Q.60 A . Q.61 B· Q.62 . B Q.63 C
Q.64 B Q.65 A Q;66 B
. - ~-
EXERCISE-II
Q.l C Q.2 B Q.3 C QA A Q.5 C Q.6 AC Q.7 D

Q.8 A Q.9 AC Q.lO C Q.ll C Q.l2 A Q.13 D Q.14 D
Q.15 B Q.16 D Q.17 C Q.18 A Q.19 A Q.20 B Q.21 A
Q.22 B Q.23 B Q.24 A Q.25 B Q.26 C Q.27 D Q.28 A
Q.29 A Q.30 A Q.31 D Q.32 C Q.33 B Q.34 C Q.35 D
Q.36 C Q.37 D Q.38 B Q.39 B QAO C QAl B Q.42 B
Q.43 D Q.44 D QA5 C QA6 A QA7 A QA8 B Q.49 A ,I - ~.
Q.50 A Q.51 B Q.52 C Q.53· C Q.54 C Q.55 C Q.56 C

;- ,
Q.57 C Q.58 B Q.59 A Q.60 B Q.61 A Q.62 A Q.63 D " /
-~.
EXERCISE-ill
Q.l C Q.2 C Q.3 B QA B Q.5 A Q.6 D Q.7 D

Q.8 D Q.9 C Q.IO A Q.ll B Q.12 B Q.13 C Q.14 D
( .,
Q.15 C Q.l6 D Q.17 C Q,18· C Q.19 D Q.20 D Q.21 A \.j
Q.22 C Q.23 C Q.24 C Q.25 A Q.26 C Q.27 B Q.28 C

Q.29 B Q.30 C Q.31 A Q.32 B Q.33 C Q.34 B Q.35 2
Q.36 A Q.37 C Q.38 B Q.39 B Q.40 B QAl ABD Q.42 AB ()
QA3 D Q.44 A QA5 D
C
y
b
C
L
Ii~~~~!!~C.:L,~~~~~
{ '.
ELECTROCHEMISTRY {56} x..J

Idull()l$choklll
.:,.
C
I~
CONTENTS,
KEY CONCEPT •••...;............................ ~ .............................. Page 2 - 23
EXERCISE-I ................... ~................................................... Page 24 - 26
I
\ EXERCISE-II...................................................................... Page 27 - 33
("'
\.
I EXERCISE-III ............................. ~ ..................................... Page 34 - 35·
"
(
ANSWER KEY ......................... :.......................................... Page 36
\.
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\..
c
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'..'
JEE MAIN - 2014

(
( CARBONYL COMPOUND
/
I,.
c
( .
(;,
\.
C i'l" ,f,
(
{
'<-.
CARBONYL COMPOUND
1. INTRODUCTION:
(a) Organic compounds in which - C- group is present are called'Aldehyde & Ketone'.
II
(b)
°
The group - C- is called as carbonyl group so, compound are also called carbonyl "
°"
compounds. If H atom is attached with this carbonyl group then compound is called
aldehyde and if alkyl group is present on both sides then compound is called Ketone.
(c) In ketone ifboth alkyl group are same then they are called simple ketone, ifdifferent then
called mixed ketone.
(d) Their general formula is CriH200. Hybridisation state of carbon is sp2 and C ° bond
length is 1.23 AO.
(e) The ratio ofC, H & ° in formaldehyde is I : 2: I (CH 20). It is called simplest sugar.
(f) Aldehyde shows chain, position and functional isomerism.
(g) Ketone shows chain, position, functional and metamerism also. Aldehyde and ketone both
are functional isomers with each other.
2. GENERAL METHODS OF PREPARATION

2.1 From Alcohol (By Oxidation) :
H H
I
R-C-O+[O]
"dO
Crz07/Pyn me ) R -c =
I
°
I I
H H aldehyde
"
primary alcohol
R R
I Cr20 7 /P'yridine I
R-C-O+[O] ~R-C=O
I I
HH ketone
secondary alcohol
NOTE :
In this reaction ifwe take acidic KMn04 or K2Cr207 then reaction will not stop on aldehyde or ketone
because they are strong oxidising agent. They further oxidise aldehyde, ketone into acid. So, to stop the
reaction on aldehyde & ketone, we usemild oxidant Cr207 in pyridine solution. For better yield, we can
use cr03 in 3° butyl alcohol. For 2° alcohol we can use aluminium tertiary butoxide [(CH3)3 COh Al
R" CH 3" R~C=O+ CH~3,

CH-OH+ c=o [(CH:!hCOhAI ) /HOH
R
,/ .C , /
~
oppenaueroxidation. , /
R CH 3 c
[2J
[i~~~'A~~ CL~~'~!
Ideolfor$d!oltJrs
CARBONYL COMPOUND
2.2 From Alcohol ( By Catalytical Oxida tion ) :
When vapours ofa primary alkanol (or secondary alkanol) are passed over heated copper (or zinc
oxide) at 3000 then alkanals {or alkanones) are formed.
R - CH 0H Cuf300') R - CHO + H2
2
,
{
R"
/,CH-OH Cuf300' R"
/,C=O+H
R'/'
R' /' 2
2.3 From Alkene (Ozonolysis) :

Desired alkanals and alkanonescan be obtained by ozonolysis ofappropriate alkenes.
;:.<~<
R CH = CH - R'~ R-CH I CH-R Zn/H 2 0 ) R - CHO + R'CHO
. I I I -H20 2
0-1-0
I
R" /R' R", ;:.<2< /R' R", /R'

°
,
< ~
C=C
"R' ~ R/1O-L-O
C
I'"
I C
R'
Zn/H 2 0
-~02
)- ~
c=o+o=c
"R'
( 2.4 From Alkyne :
/
Acetaldehyde is fonned on passing acetylene in 40% aqueous solution ofHzSO4 at 60° in the presence
\
of] % HgS04 .1t is called Kucherov's reaction.
,, CH CH + HOH HgS04fdil.~S04) CH =CH-OH rearrangement) CH -CHO

" 2 3
(
rearrangement
R - C == C - H + HOH H9S04fdil.~S04) R' - C = CH2 )- R-C- CH 3
. I II
. OH o
(,NOTE: Methanal cannot be formed from the above reaction.
( :2.5 From Grignard's Reagent: -

Alkanal is fonned byreaction offonnic ester and an alkylmagnesium halide.
(
R R
( I
-R •
~ Mg-X + R'-C-O-R" ) I
R'-C-O-R" H:zO ) R'-C ::: 0
( II I'
o b-Mg-X
c Ketones are obtained from acetic and higher esters. Acid chlorides and amides can be taken in place of·
esters. However HCOCI cannot be taken because it is unstable.
R-MgX + C2H sO-CO--R' ~ R-CO-R' + CzHsO--MgX
R-MgX +CI-CO-:-R' ~ R-CO--R' + MgXCI
C R--:MgX + H 2N-CO-R' ~ R-CO-R' + Mg(NH2)X
f ~OTE : Fonnaldehyde cannot be fonned from the above reaction.

'.
(]] ~~~~A~\CL~~'~~ CARBONYL COMPOUND 13l
tJeoIfOt'Schololl
(
2.6 From Nitroalkane ( Nef reaction) :
By Nefreaction, formaldehyde can be obtained fi'om nitromethane, acetaldehyde from nitroethane
and acetone from 2-nitropropane.
H 0-
R-6 t ~+~j NaOH
~ /0 H+
R-C= N,O ~ R-C=O !'
H-OH 7
1-' " 0
H -H+ I
H
aldehyde
2.7 From Vicinal Glycol (Oxidation) :-
Carbonyl compounds are obtained on oxidation orvicinal alkane'diols by periodic acid or lead
tetraacetate
R-CH-OH
I + [0] H104 or H' H 0
(CH3COO)4 Pb ) 2R-C 0 + 2
R-CH-OH
"
\
~ (
.... \. .
~
*
R-C-OH
I H104'or I
R-C-OH + [0] (CH3COO)4 Pb ) 2R-C=O + H2 O \.
I
R
rom Calcium or Barium salt of Carboxylic acid :,

When calcium salts ofalkanoic acids are subjected to dry distillation, then carbonyl compounds,
are formed. The yield increases on taking barium, manganese and thorium salts ofalkanoic acids. \.
Formaldehyde is formed on taking calcium formate (R == H) and acetone is formed on taking calcium (
acetate (R = CH3). "

o
H II .-----.:
C+O,
1 'CarI fl
1---1 / --00C) H-C-H+CaC03
H}C-O I , II ('
I II I o '-J
10
L_________ 1
I
c
oII r..;..-----I
10 I
CH3 -Ct '"

,___I ~cal
I A
CH -C-CH3 +CaC0 3
rrr- 3
AA _ _ _ )
Clls ! II
'I______
0 ' ---~I °
Acetaldehyde carl be formed by taking a mixture ofcalcium formate and calcium acetate.
?! 0
c
CHa-C-O,_ /0-8-H
/"Ca+Ca ~ CH
CHO + HCHO + CH COCH + CaC0
CHa - C - 0 ...........0 - C - H 300.c
3 3 3 3
II II
o 0
C ~/
CARBONYL COMPOUND I"

/4J (~
c
2.9 From Carboxylic Acid: - When vapours ofcarboxylic acid are passed on mangnese oxide MnO
at 300°C, then carbonyl compounds are formed.
Formaldehyde is prepared fi'om formic acid (R == R' == H), acetone from (R R' = CH3), and
acetaldehyde from a mixture of acetic acid (R' == CH3) and formic acid (R = H).
II
H-C-·O-H
°
MoO
+ 300"C ~ H-C-H+C0 2 +H 20
H-C-O':"H II
If
°
(
\ °
II
CH3-C-O-H
°
MoO
, + 300"C > CH 3 -C- CH 3 +C0 2 + H 2 0
" CH3-C-O-H II
(
\
II
°
°
2.10 FromAlkyne(Hydroboration) :
When a dialkylborane is reacted with an alkyne, then dialkylvinylbroane adduct is formed, which
on reacting alkaline hydrogen peroxide solution forms a carbonyl compound. Alkanals are formed
( fi'om terminal alkynes, and alkanones from nonterminal alkynes.
\
I-Alkyne ~ Aldehyde
( Other alkynes ~ Ketone
.( (i) CH3-C '" CH e~ ) (CH3-CH=CH-hB 0 /0H

H2 2 ) [CH 3-CH=CHOH]
/
~CHrCH2-CHO
'" ~ H2 0 2 /Q;
(IQ .CH3-C",C-CH 3 ~ [CH3-C=CH-CH3]
f
~ I
OH
(
,,-. J,
2-Butanone
(2.11
From Hydrolysis of oximes and acetals :-
Carbonyl compounds are formed froni hydrolysis ofoximes and acetals.
CH3CH=NOH ~o) CH3CHO + NH20H ..
Acetaldoxime
( (CH3)2C=NOH H20 ) (CH3)2C=O + NH20H
( Acetone-oxime
CH3CH(OC2H5)2 H2 0 ) CH 3CHO + 2C2H50H
( Acetal
C.12 From Hydrolysis of gemdihalide :-
Carbonyl compounds are formed on heating alkylidene dihalides with aqueous caustic alkali solution.
>CCI NaoH.) > C(OHh -H 2o ) >C=O

2
~ CH3CHCl2 NaOH) -H 20 ) CH3-CHO
C. CH3
CCI
2CH
3 NaOH ) -H20
)(CH
32 ) C-O

l
~'~~~A~~C~~f~! IdeDlfo<Schoiors
CARBONYLCO~OUND {51
3. METHODS OF PREPARATION ONLY FORALEDHYDES
3.1 Stephen's Method:
By dissolving an alkyl cyanide in ether and reacting it with stannous chloride and conc. hydrochloride,
aldimine chlorostannate salt is obtained. Alkanal is formed on hydrolysis ofthis salt.
III
R-CsN HCI) R-C=N+HCI SnCI2 ) [R -'CH = Nli!hSnCI
Acid nitrile HCl Aldimine chiorosfannale
(,
[R-CH==NHhSnCI6 +2H20 ~ 2R-CH =0 + (NH4)2SnCI6
, Alkanal
Taking the example ofacetonitide (methyl cyanide) Stephen reaction can be shown expressed as follows.
" .
CH3 -C:; N+2H SnCI2
;.CH3 -CH = NH HOH )CH3 -CH 0
HCI
Acetonitrile Acelaldimine Acetaldehyde
3.2 Rosenmund Reaction:

Aldehydes are formed on reduction ofacarboxylic acid chloride in boiling xylene medium by
hydrogen and palladised barium sulphate.
o 0
R-~-CI + H2 Rl-H + HCI
Acetaldehyde is formed on taking acetyl chloride (R CH 3). Formaldehyde cannot be prepared by
Rosenmund reaction, because HCOCI is not a stable compound, BaSO4acts as a catalyst poison and
decreases the catalytic efficiency ofPd catalyst, due to which fmiher reduction ofacetaldehyde formed
to primary alcohol cannot take place.
\
3.3 Oxo-reaetion :-
When a mixture ofan alkene, carbon monoxide and hydrgen is passed over cobalt catalyst at high
temperature and pressure, then alkanals are formed. Dicobalt octacarbonyl [C02(CO)gJ can be used
as a catalyst in place ofcobalt. Due to addition ofhydrogen and formyl group on ullsaturated carbon
atoms ofalkene, this reaction is called hydroformylation.
Co or
C02 (COJa
CH2==C~ + CO+~ High ~ yH2iH2

temperature
and pressure H CHO
Propanal
CH3-CH=CH2 + CO + H2 ) CH3 - CH2 - CH2 - CHO + CH 3

, l HO
H-CH 3
n-Butyraldebyde Isoblityraldehyde
4 METHODS OF PREPARATION ONLY FOR KETONES

4.1 From Alkyl Cyanide: -
Alkanones are formed on hydrolysis after reaction ofan alkylmagnesium halide with ethyl cyanide
or its higher homologue.
R'
6+ 6- 6- l5+ I
0
R- C:; N+R-+- Mg-X~R-C=N-MgX H2 )R-C-R'
II
-0
In this reaction ifwe take HCN with G.R., product will be aldehyde but major product will be alkane
because HCN is an example ofactive H compound and with active hydrogen compound GR forms o
alkane.
(jj) ~~~~~~CLl!!~!~i CARBONYLCOMWOUND [6]'

c
IdNlforSdlolms
."". 4.2 Dialkyl cadmium with acid chlorides :
A ketone and an alkylcadm ium ch loride are fonned on reacting a dialkylcadmium with an acid ch loride.
R-Cd-R +CI-CO,...R' >R-CO-R' + R-Cd Cl
Dialkylcadmium are obtained by the reaction ofcadmium chloride with a Grignard's reagent.
. 2R-Mg CI + CdCl2 ) R-Cd-R + 2MgCl2
4.3 Oppenaur Oxidation: In order to prepare alkanone easily, Oppenauer oxidation ofsecondary alkanols
is done. In this process, a secondary alkanols is refluxed with aluminum tert-butoxide in excess amount
in acetone. Acetone is reduced to isopropyl alcohol.
R-CHOH+CH 3 -co [(CH3)3C~OhAI ) R-CO+ CH 3 -CHOH

I I I I.
R CH 3 R CH 3
( .
\ METHODS OF PREPARATION:
Ex.1 Choose the compound whose oxime on hydrolysis yields ethanal
(A) HCHO (8) CH3CHO
(C) CH 3 CH 20H (D) CH3COCH 3 (Ans.B)
Sol. Oxime ofethanal on hydrolysis gives ethanal
CH3CH = NOH . H20 ) CH3CHO + NH 20H
.Ex.2 On dipping red hot coper wire in isobutyl alcohol, we get

\.
(A) An alkene (B) A ketone
" (C) An aldehyde (D) None ofthe above (Ans.C)
Sol. Isobutyl alcohol contains primary alcoholic group -CH20H which on oxidation converts to-CHO
group
( Ex.3 CH 3COCI Pd/BaS0 4 ) A

[H21
The isomers of CH3COCI and A will be respectively

(' (A) CHzCICHO, oxirane (B) Chloral, vinyl alcohol
(C) a-chloroethyl alcohol, epoxyethane (D) None of the above (Ans. A)
(~ol. a-chloroacetaldehyde and oxirane ethane are the isomers ofCH3 COCI and CH3CHO respec
tively.
(
( .
\.' PHYSICAL PROPERTIES
(a) Aldehydes are colourless with pungent smell liquid while ketones are pleasant smell liquids
( but fonnaldehyde is gaseous in nature. .
( (b) . Lower carbonyl compounds are soluble in water. It is due to polarity in carbonyl group.
(c) Higher carbonyl compounds are insoluble in water due to more covalent character.
( (d) Melting point & Boiling point .:x:Molecular mass
.:x: No of branches
(
(e) Melting point and boiling point ofcarbonyl compounds are more than to corresponding
alkanes due to dipole-dipole attraction present between molecules -in carbonyl compounds.
[SAL CLASSES
fA iT£'
D
CARBONYLCOMWOUND [7J
(
\.
l
(f) Reactivity ofcarbonyl compound is dependent on alkyl group which is linked with carbonyl
group.
~ ~ m
H- FJH> CH -+-IC,:t> CH
3 3 -+ IT)
~~ ~~ o~
(g) 40% solution of formaldehyde is known as 'FORMALIN' (40% HCHO. 54-56% H 20, ( ,
4-6% methanol) .
(h) Mixture of formaldehyde and lactose sugar is called 'FORMAMINT' which is used in
medicine ofthroat infection.
(i) Boiling point of carbonyl compounds are as under
Compound Boiling Point

l. Fonnaldehyde - 21°C
2. Acetaldehyde + 2loC
3. Acetone 56°C
6. CHEMICAL PROPERTIES :
Main reaction ofcarbonyl compounds are nucleophilic addition reaction.

H H H H
I I H
R-Co$ +Eo$ I less stable - - 7 R CI - Nu - -E+

Nu°E> ---? R_CE& ~ R C$ I
- - 7 R-C-Nu
(II
OoE>
IE)
0 E 0 b I
OE
'-
More Stable r'
\- ;
Rate ofnucleophilic addition reaction ofcarbnyl compounds decreases in the following order:
\....
HeHO > CH3CHO > CH3COCH3 > C6Hs-CHO
6.1 Reaction with Hydrogen Cyanide:
H H H
,l.. /i ll+ 0- I
R- if + H -t CN ) R - C - CN. R-6-CN
b~' 6- I
OH
cyanohydrin
,.
',------""
NOTE:
(a) IfR = H then product will be formaldehyde cyanohydrin .
"
.(b) Cyanohydrin is an important compound which gives the following product on hydrolysis and
{'
reduction. 'C7
CARBONYL COMPOUND f8]

c
4 H " ....OH
) /C'CH2NH~
(i-Amino alcohol
" ",OH Pal1ial " -yOH
/C'CN Hydrolysis ) /c.....CONH2
Cyanohydrin (X,-HydroXY_~lmide
C\lmplete" ... 0 I:I

HYdrolySi.s > /C'COOH
(X,-Hydroxyadd
(i)SuC1 2 + Hel " .... OH
I..-----,>C
(Ii) HOB / 'CHO
n-Ihdroxyaldehyde
l 4H CH 3 ".. ",OB
--.,) C
( H/ 'CH~NH=
I-Amiuo-2-propallol
(
CH.I , - CH~, /OH~10H CHI".. ;,OH
( C=O--'7 C, C...
\ H./ HeN H/ CN' H/ CONH:
. 2-H,vdJoxypropilll<imiuc
f
\
A.:etaldehydt: A.:elaldehvde
cyanohydrin 2BOH CH~" ;,DB .
> H/c:.. COOH
Luetic IIcid
f
(2-Hydroxypropanoic acid)
f
"-
SIlCb -rHCI CHl, ;.OH
(
H<:>H > B/C'CHO
2:..Hy4fOX)prOpalml
(
Acetone cyanohydrin is fonned on reacting acetone with HeN.
C
('.
CH)-CO-CHj + H-CN ----,»- Cfb-C-CH,
'j, '
f\cetQne BO· eN
" Acc.nmCCYlInoh\'ddll
( • >~ • •
( CH)-C-CH.1
~t'cN
r 1
f
" Acetone CYcillohydrin
4H
(
" . . lHOH
(
CH:r-"'C-CH3 CH:cC-CHJ CH1-C-CR.
/, . /, J' .
HO .CH2NH~ HO CONH; HO. (,DQH
. •. . . 2-!iydnJxy.J; 2~ft.ydroW~2-
l-Annno-2-methvl-2 'Il' IpmpaUaljJl.'dt:.
c '. .
propano I" me
- tV - . lll.;:tllylprollauQil;.ucid
(i'~~!!~Ct~~~~!
/deQI forSdlolms
CARBONYLCO~OUND [9)
(
'
c
6.2 Reaction with Sodium bisulphite :
Carbonyl compound form a white crystalline addition product with sodium bisulphite called
Aldehyde I Ketone sodium bisulphite adduct. "
H HOH H H
"?!+li&- " I
R-C-S0 3 Na
_...,.-_ _-") I I
0
R - C + H - S03Na - - + -NaHSO 4 I - OH
R- C -- - '7 R-C
I I aldehyde
H O-H OH
white crystalline solid
NOTE:
(a) Bisulphite adduct is an important compound because it gives carbonyl compound on further
hydrolysis:
(b) The above reaction is used in purification of carbonyl compound.
6.3" Reaction with Ammonia derivatives:

Addition of nitrogenous nucleophile on carbonyl gl'OUp takes place according to the following
mechanism. ,
f"
H H
I I I I
C + :N-Z --7 -C-N-Z
II I I
o H OH
Adduct
The end product is formed by elimination ofwater fi'om the adduct under appropriate energy condition.
H (
I j
-C-N-Z ~
-H 0
-C=N-Z
I
I
2
OH
In theabove two steps, it appears that an unsaturated condensation prod uct is formed by liberation of
the water molecule from carbonyl group and nitorogenous nuc1eohile.
!J,.
-C=O + H2N-Z -=---7 -C=N-Z
I -H 20 I
(i) With Hydroxylamine: o

)C=O+H2NOH -H 0»C NOH"
2
Oxime
(ii) With Hydrzaine :

'\.' "
/C=O +1-I 2Nl\f}-h

-""
-lchO - '" "

/G=NNH:.
Hydrar:qll~
(' )
(iii) With Phenylhydrazine:
'\" "" ~, N"

iC=O +H~NNHCJ':f~~Ri() ,J /C= NHC.Hs
J·h~l\ylhyilra?,i)lie
c
CARBONYL COMPOUND {101 c
C
G
(iv) With 2,4-Dinitrophcnylhydrazine:
\.
+(~I~N~-~
/C=O --7)0 )C::N-NH
...H
I
-Ii,"
':.
O'~
-.:....
. / .
NO; NO:
2.4-Dinilr(mI11:IlylhyUrllZ(1I1t!
(
\
(v) With Semicarbazide :
,
\
;c=o + H2NNHCONH~ . ' ) ) C'=:NNHCONH,.
Scmicarbilzolic
On reacting a carbonyl compound with 2,4-dinitrophenylhydrazine, a yellow precipitate of

2,4-dinitrophenylhydrazone derivative is obtained. White precipitate is obtained by the reaction with
r
\ hydroxylam ine, hydrazine phenylhdrazine and semicarbazide. The pure parent carbonyl compound can
be obtained by hydrolysis ofthe above five derivatives.
(
\. \.
/C=N-Z + HOH --"::")0 /C=O + H:i"--Z
C
6.4 Reaction with Alcohol: In the presence ofcatalyst (HgO·BF 3) aldehyde form acetal with alcohol
while ketone from ketal with alcoho1.
(
' H H H
I 0+ 1'>- HgO.BF I I
R co+ + H -+- 0 - R' J " R - C - OR' R -C-OR'
( ~~ <: I I
OH OR'
/ hemiacetal acetal
'
/ R R R
"- I 0+ 0- HgO.BF, I R'OH I
R - CO+ + H -+- 0 - R' . " R - C - OR' <: ." R -C-OR'
/
" cg&- <: 6H I
OR'
hemi ketal ketal
(
"
6.5 Reaction with Alkane Thiol: Aldehyde fonn thio acetal with alkane thiol while ketone fonn thio
( ketal with alkane thiol.
C R, .---H-=i.S-R' ZnclidryHCI R" / S -R'

C i::O + I • ('
H-- 11__ --_1
H ..1S-R' H------S..:.R'
thio acetal I mercaptals
(
R, .---H~=i.S-R' ZnclidryHCI R" -/ S - R'
Ci::O+ I ~ C
(: R-- H ..1S-R'
11_____ 1 R-- -"S-R'
thio ketal I mercaptols
(
"- These are important compounds because they forms sulphonyl compounds on oxidation which are
( used as hypnotic drugs.
(
R" /SR'
~
R" /S02-R'
H--C--SR' H.-:c-.. S02- R'
sulphonal
~
( R" /SR'
~
R, /S02- R'
R--C--SR' R--~S02-R'
sUlphone
ctIl!~~~~~~ CL~~f~! CARBONYLCOMWOUND [Ii]

_(0'5<_"
r
'
6.6 Aldol Condensation:
In the presence ofsmall amounts ofhydroxide ions two molecules ofthe carbonyl compound containing
a-hydrogen atoms, give a ~-hydroxy carbonyl compound. This reaction is normally called Aldol
condensation.Aldol condensation oftwo identical carbonyl compounds is called simple aldol condenstaion.
As a source ofhydroxide ions, a few drops ofvery dilutt< aqueous solution ofK2C0 3, N~C03' NaOH,
. KOH, Ca(OH)2' Ba(OH)2 etc. are added.
H H E> H H
I 'I « . . lo\V'IOH / . 1 I
CH,-C + CH---CH=O' ) CHcC-CH-CH=O
. > II I ' . I., .
o H OH
. Acctal<ichyut:: Accta!(!ol
(twomnksJ
Aa,f3-Unsaturated aldehyde crotonaldehyde is formed by the elimination ofa water molecule on heating
acetaidol (3-hydroxybutanal)
L1
CH)-CH- CH-CH=O -~-7> CH,-CH= CH-CH=O
I I -H20 -
Crotonaldehycle
OH H
(2-Butenal)
Acetaldol
CBs H
I I
CH3'
I" Llw C(H3 ¥ yH 3
CH3-C + Cl-l'-C=O ~e" , CH..3....,Cf -CH-C=O
II J .
OJI
[OTj] OR
, AcetOI1~ hiacet{)iJ.yJal.tohdl·
(TW9 ·mQles) (4~Hydroxy-4-1~ethyl-2-pentauone)
CH)CH3
I '. I
jA -H2Q
CH)""'-C=CH-C=O·
M~ityl oxiatt .
(4'"lI4t4hyl-3-l'enttn"'4'-One)
Aldol condensation oftwo non identical carbonyl compounds is called mixed orcrossed aldol condensation. c
Theoretically four products can be fonned from aldol condensation ofthe carbonyl compounds A and B.
C~ - CHO+ C~ - CH 2 - CHO ~ CH3iH-9H-GHO

Actaldehyde
OH CH3
c
3-Hydroxy-2-methylbutanal
C~CH2 -CHO+CHsCHO ) CH:,cHr«H-GH 2CHO G

Propionaldehyde 6H t~ "\
3-Hydoxypentanal V
t,
[iJ!~~~A~ CARBONYLCOMWOUND [12J c

c
~
6.7 Cannizaro Reaction: Carbonyl compound in which a H atoms is absent, when react with strong
base like NaOH or KOH then fonns sodium and pottasium salt ofcarboxylic acid and alcohol. It is an
example ofthe reaction in which one mole ofthe compounds is reduced. Such type ofreaction is called
disproportionation reaction, also known as cannizaro reaction. In this reaction elimination ofhydride ion
takes place. In this reaction oxidation numbercbanges from 0 to +2 and () to-2.
Compounds showing cann izaro reaction are
(a) 2H-C-H +NaOH~ H-C-O-Na+H-CH2 -OH
II 1/
o 0
(b) 2C6H5 -C-H

~ + KOH C6 H5COOElK@ + C6H 5CH20H
CH 3 CH3 CH 3
I I I
(c) 2 CH 3 - C - C - H + K - O H 7 CH 3 - C - C - OK + CH 3 - C - CH 2 - OH
I II I II I
CH 30 CH 3 0 CH 3
(
6.8 Tischenko Reaction:
When an aldehyde is heated with an anhydrous alumin ium alkoxide in the presence ofanhydrous AICI 3,
" then a carboxylic acid ester having twice the number ofcarbon atoms is formed. All aldehydes give this
(
reaction.
H . H
I AJ(ORl? I
/
\. R-C + O=C-R :> R-C-O-C-R
II I AJCh II I
o H - 0 H
Aldehyde (Two moles) Esler (One Inole)
/
"
H H
( I Al(OC:!H:;)3 ., /
\ CH,-C + O=C-CH3 > CFI3-C-G-C-CH)
" I Aiel] II I
('
\.
0» Q H
Acetaldehyde Ethyl aGet.'lte
, nWO liloleS) (Olle'nlole)
( 6.9 Qxidation : Aldehyde on oxidation fonns respective acid while ketone forms less carbon carboxylic
acid on oxidation according to popoff's rule (As discussed in Alcohol theory)
(
R-C-H+[O] acidlcKMnO. ) R-C-OH
{ /I II
'- o o
(
\.
R - C - CH 3 + [ 0 J acidicKMnO.
~ R - C - OH + CO 2 + H20
( II II '
o o
( NOTE: *-fr:~#: .
(ayA ising agent is seJenium oxide Se02 then, a-methylene group ofcarbonyl compound
( \ //oxidises
' into -l(- group and resultant dicarbonyl compound will be fonned.
o
f,-,
cil~~~~A~~ ~~!~! IdeoIforS<llolors

CARBONYL COMPOUND [13J
t
H- C
II - H + [ 0 ]<
Se0 2 ) NO reaction
o
ex. - methylene group is absent.
H-C~- c H + [ 0] se0 2 ) H C-C-H

~ ~ ~
glyoxal
(dicarbonyl compound)
Se0 2
H C~ - C - CH3 + [ 0 ] ~ H C - C CH3
~ ~ ~
pyruvic aldehyde
(methyl glyoxal)
(b) If the oxidising agent is performic acid then aldehyde oxidises into respective acid while
ketone oxidises into ester. The reaction is called 'Baeyer-villiger Oxidation'.
Other peroxy acid also give same product.
ego CH3COOOH, C6 H5 COOOH, MCPBA, CF3 COOOH
(' <
H
I
H-C H+O-O-C-H~H c OH + HCOOH
I II
~ H 0 8
H
I
CHrC-H+ 0 - 0 C -H~CH3- C -OH + HCOOH
~ ~ . ~ ., ~
CI
(
••• MCPBA -> meta chloro perbenzoic acid r§l. C03H
H
I
CHrc -C H3 + O-O:.....C -H ~ CH3-c -O-CH3
. ~ ~ ~
)
6.10 Reduction: Aldehyde on reduction form primary alcohol while ketone on reduction form secondary
alcohol.
R C - H + 2H ) R - CH 2 - OH
.~ ["'.
G
R- C - R + 2H ) R - CH R (;
~ 6H '"-_/
secondary alcohol.
{,
v
CARBONYL COMPOUND . · .1. {141
-'---
IdeoIforSchol."

c
"'-~ ~
f,
V
NOTE:
(a) In the above reaction ifreducing agent is Na + C2 HsOH then reaction is called <Bouveault
- Blanc Reaction'.
(b) Ifreducing agent is NaH reaction is called 'Darzen's Reaction'. We can also use LiAlH4
in this reaction.
(c) If reducing agynt is (red P / HI) then product will be alkane.
(d) If reducing agent is Zn-Hg/conc. HCI then product will be alkane. Reaction is called
<Clemmenson-Reduction' .
(e) If reducing agent is alkaline solution ofhydrazine, product will be alkane. Reaction is called
, Wolf - kishner Reduction'.
(f) The percentage yield ofalkane can be increased by using diethylene glycol in wolfkishner
reduction then reaction is called 'Huang-Millan Conversion'.
(g) Ifreducing agent is aluminium iso propoxide (CH 3 C H -O-)3AI, then product will be
I
CH)
alcohol. Reaction is called <Meerwein-PondorffVerley Reduction'.
6.11 Polymerisation Reactions: A Idehyde shows addition as well as condensation polymerisation reactions
while ketone shows only condensation polymerisation reactions.
(
\
" 6.11.1 Addition Polymerisation reaction of Formaldehyde:

\
( (a) When aqueous solution offormaldehyde is heated then it converts into a white crystalline
\
solid called 'Paraformaldehyde'.
n HCHO !'J. " >(HCHO)n n > 6, n < 100
evaporaUon .
paraformaldehyde
(
\,
If n :::; 50 Linear structure polymer
Ifn> 50 Cyclic structure polymer
(
(b) Ifformaldehyde is kept with cone. H2S04 at room temperature then it forms a cyclic trimer
c called meta formaldehyde or trioxane.
3C~O::::() ) (CH2--O)3
(
MClafotlnaJdehydc
C 0/
CH,
"'-0 or
Trio:\}'melhylene
( II or
H~C< /CH~
1.:U·Tlioxan
c o or
~:vm-Trioxall
( ,
(c) Ifaqueous solution offormaldehyde is kept with lime water in dark room for 5-6 days then
( it converts into a sweet solution called 'FARMOSE
It is an example oflinear polymer.
~
6HCHO Ca(OHk /Ba{OH)2
C6H 120 6
C dark, 5~days
farmose
!
'L
(JIU~~~~~\CL~~~~~
SdioIo.. /deQI for
CARBONYL COMPOUND [15J.
c
£'
.....
6.11.2 Condensation Polymerisation reaction of Formaldehyde :
(a) With Ammonia:- When formaldehyde is heated with NH3 then a: white crystalline heterocyc1 ic
compound is formed called 'Hexamethylene tetramine' or urotropene' or'Aminoform'.
6HCHO + 4NH3 ~ (CH2)6N4 + 6H20
/~'~
CH'l yI-h Cf"h
I y"./
(tI1
N/' 1
ell1 •
'N
Urott(Jpine-
~ /'
CH 2
It is used in medicine or diabities or urinary infection.
(b) With Phenol: - In presence ofdilute alkali formaldehyde fii'st fonn 0- & p- hydroxy benzyl
alcohol with phenol which on selfcondensation form a cross link polymer called 'Bakelite'.
@
phenol
+ HCHO
formaldehyde
Bakelite
,/
"
'
,/
( .
Bakelite is electric and thennal resistant. So, used in fonnation ofelectric appliances. Reaction "
is called 'Lederer-Manasse Reaction',
·6.11.3 Addition Polymerisation ofAcetaldehyde :

(a) When acetaldehyde is kept with conc. H 2 S0 4 at room temperature then it form a cyclic
trimer called paraaJdehyde.
3 CH3C HO Room temp.

Cone. H2S04 ) (CH3CHO)3 (paraldeye
h' d )
I '.
\....:
(>araldehyde has nonaromatic heterocyclic structure and it is called 2A,6-trimethyl-l ,3,5-trioxan.
C)
CH~
I .
<I1H
0/-"""'0
br '~H Paraldehyde or 2,4,6-trimethyl-l ,3,5-trioxan
/,/'-. .
CHl 0 CHI
Paraldehyde is used as mild hypnotic.
(b) If ac.etaldehyde is kept with highly conc. HCI at low temperature then it forms a cyclic
tetramer called metaaldehyde.
Dry HCI gas
4CH3CHO o· ~(CH3CHO)4
I'-~,
c
.[16J
~!~~~~~C~~~~~~
JdeJlforSchtJI."
CARBONYL COMPOUND c
c
c
Metaldehyde has the following nonaromatic eight-memebred heterocyclic structure. _
/CH 3
O CH
CH 3/ - ",
'CH 0
I 6H
o "
"CH-O/ CH 3
/
CH 3
NOTE: Metaldehyde is used as smokeless powder and Para aldehyde is used as a sedative while meta
aldehyde is used as a solid fuel.
6.11.4 Condensation Polymerisation of Acetaldehyde:

(a) Aldol condensation - Discussed earlier.
(b) Reaction with NH3 :
H
Clh, CH 3 , /OH I
/C=O+NH., ) /C, -H 0
2
~ CH 3 - C NH
H H NH:
f Acela Idehy<I'Ntllllnonia
\.
Acetaldimine is fOlmed by theelimination ofwater molecule on heating acetaldehyde-ammonia, which

undergoes polymerisation to form a nonaromatic heterocylic addition trimer, namer 2,4,6
trimethylhexahydro--l,3,5-triazine trihydrate as the main product.
f
\. 6.11.5 Condensation Polymerisation ofAcetone:

(a) Ifacetone is heated with conc. H2 S04 then an aromatic compound is formed called 1,3,5
trbnethyl benzene or mesitylene.
(
\.
Conc. H2S04
,/
CH)COCH) /j.
'-
CH 3
Mesitylene
(b) Ifacetone would be in excess in ketal condensation or catalyst (ZnCI 2 ' dry Hel) is used
( then three moles ofacetone undergoes condensation polymerisation and form a compound
called 'Phorone'.
C
CH3
( I -----1 CH 3
CH3 - C !: 0 H"--.
I
: ~H CH3 -C=CH ...........
(' 1~--Ij-
r----l ""'c-o

ZnCI2 )
C=O
(
I-
0
CH 3 - CI =r1___ ...rcW
H"""-f.....
1::1_
/
-
dry. HCI CH3 -C=CH/
I
CH3
,
'C:""
CH 3
[molecular wt. of phorone = 3 mole of acetone - 2 mole of H 20 ]
(
~~~~~A~~~~~~~! ~ I~ SchoIots
CARBONYL COMPOUND 1I7}
,{
\..
t
'L
6.12 Reaction with pels:
Carbonyl compound fonn gemdihalide with PCl y
R'C[~-:-~~~=tCI_=~R,c . . . . . CI
H.. . . . . c;7' ~CI

II ___________ H/ 'CI
gemdihalide
/ \
6.13 With RMgX :

CH 3,
CH3CHO CHaMgBr H20 )
CH /CHOH
3
6.14 With sodium acetylide :

CH3CHO + HC=CNa -7 CH3 -CH C CH ~ CH3 -CH-C CH
I
ONa 6H
6.15 With primary amine':-,:
CH3CH=O + H2NC 6H S -7 CH3-CH=NC 6 H s
Schiff's base
(CH3hC =O + H2NC 6 H S h
~ (CH 3 C=NC 6H s
7. REACfIONS SHOWN BY ALDEHYDES ONLY

7.1 Red ucing nature ofAldehyde: Aldehyde are reducing in nature, they can reduce Tolien 's reagent,
Fehling solution and mercuric chloride solution.
(a) Reaction with ToileD's Reagent: - Ammonical silver nitrate solution is called Tollen 's
reagent. Aldehyde reduce the tollen's reagent and form silver mirror. Aldehyde oxidises itself
into carboxylic acid.
AgN03 + NH40H ) [Ag(NH 3h ]-OH
( ,
!NH;.
2AgOH-":"" A9 2 0
" "
-H,Q
(simplest reacting species)
o
R- 8- H + A9 20 ) R - C - OH + AgJ,
II
o
NOTE: In the above reaction oxidation number ofAg varies from +1 to 0.·
(b) Reaction with Fehling Solution: It is the mixture"oftwo solution called Fehling solution
A and Fehling solution B.
Fehling Solution A : Aqueous solution ofCuS04 (blue)
Fehling Solution B : Alkaline solution of Roschelle salt (sodium potassium tartarate)
~ ~ /--"
L,
H-O-C-C-O-K
I
H -O-C -c-o- Na
I II
H 0
(C 4H 40 6NaK)
c
r 1il!~~~A~~CN~~~~! CARBONYL COMPOUND [18J
c
IdeoIIOfS<hoIon
c
By the mixing ofboth solution we get a dark blue colour solution called final fehling solution. Reacting
species of this solution is cupric oxide CuO.
R - C H + CuO ~ R - C - OH + CU20J,
II II
° . °
(red ppt.)
NOTE: Oxidation number of copper varies from +2 to + 1
(c) Reaction with Mercuric Chloride solution : Aldehyde reacts with mercuric chloride so
lution and initially form white ppt. ofmercurous chloride solution, which further react with
excess of aldehyde and form black ppt of mercury.
R-ff-H + HgCI 2 + HzO ~ R-fi-OH+HCI+H92Clz(J,)
,
° ° (white)
\ R-C-H + Hg 2CI 2 +HP ~ R-C-OH+HCI+Hg{J,)
(
\
°" °" (black)
(d) Benedict solution:
\"
[A-CuS0 4 soln, p-NaOH, Sodium citrate]

r
\ CHJCHO + 2CuO ~ CU20 + CHJCOOH
(e) Schiff's reagent:
r Megenta dye Colourless solution CHp~O) Pink colour restored

8. REACTIONS SHOWN BY KETONES ONLY
(a) Reaction with NH3 : If acetone is heated with ammonia then it forms diacetone am ine.
CHs H CHsH
I I /l, I I
CHa-C + NHa + H-C-C-CHa ~ CHa-C-C-C-CHa+H20
/
" °" I
H °II I I
NH2 H, 0.
II
r
\ If acetone and ammonia would be in eXcess then product would be tri acetone amine. If
tri acetone amine is heated at high temperature then it converts into a hetrocyclic compound
by the elimination ofwater.
Reaction with Nitrous Acid:
Oximinoacetone is fonned by liberation ofa water molecule on reacting acetone with nitrous
acid.
-H-----· -
"K!:
CHs - C - C 0
° . H_____
II
I + T N - OH ~
1
1.
A · CHS - C - CH

-H20
°1/
= N - OH
oximino acetone
Bimolecular Reduction:
Pinac6\ is formed on reduction ofacetone in an inert medium (like benzene) by using magnesium
amalgam and hydrogen.
OH
~ C~-C-C~
I _
CHa-C-CHs Mg-Hg/HCI
+ +2H I
( CHs - fr -
CHa
dry Celis C~-C-C~
- I
OH
( ° pinacol
Qj~~~~,,~~ CJ!~~~~~
kko/(orScl>olats
CARBONYLCOMTOUND [191
(
c
CHEMICAL REACTION:
ExA What would be the product wl)en carbonyl compound reacts with HCN
(A) Cyanohydrin (B) Hydroxy acid
(C) Hydroxy amide (D)Amino alcohol (Ans.A)
~ H H.
Sol. R-CO+ + HO+-.e;N ) R-6-CN ~ R-t-CN :' - \
~5- . 6- bH
(cyanohydrin)
Ex.5 What would be the product when acetaldehyde reacts with HCN and the product is partially
hydrolysed
(A) Lactamide (B)Methyl glyconamide
\
(C) Both A & B (D) None (Ans.C)
(
CH 3--.. __ OH _..!.H!£::20==--_---7
CH 3_ _OH , "
Sol. CH 3 C = 0 + HCN C
H........ H--C--"CN H/ '~-NH2
o
lactamide or methyl glyconamide
Ex.6 Which carbonyl compound will be purified with sodium bisulphite

(A) 2-Pentanone (B) 3-Hexanone
:,
(C) 4-Heptanone (D) All abpve (Ans.A)
Sol. The reaction is used in purification ofall types ofaldehydes and methyl ketones only because the
ketones having bulky alkyl group form unstable adduct.
Ex.7 Reaction involving formation oftrioxane from methanal is called:
(A) Aldol condensation (B)~ddition polymerisation
(C) Condensation polymerisation . (0) Cannizzaro's reaction (Ans. B)
Sol. 3CH20 dil.H2 S0 4 ) [CH20h trioxane [addition polymer]
Ex.8 >C - CN group is called
OH.
I o
(A) Hydroxy nitrile (B) Hdroxy cyanide . (0) Hydroxy isocyanide
(C) Cyanohydrin
. (Ans. C)
Sol. Carbonyl compound on addition with HCN gives a compound containing cyanohydrin group.
Ex.9 Butanone does not show any reaction with the reagent
(A) $ - NHNH2 (B) CH3NH2
(C) [Ag (NH 3)2t (D) NH20~ (Ans. C)
Sol. Tollen's reagent does not react with ketone.
t~·.
V
c
CARBONYL COMPOUND [20J c
c
CARBONYL COMPOUNDS
Chemical properties
HCN
R'C/ OH
r"
R/ 'CN
Methods of preparation
!
\ NaHS03 R, /OH
C
I~
Alkenes Ozonolysis R/ 'S03Na
\.
,
\ Alkynes di!. H,SO, I HEilIHO
2 . R'C/ OH
R/ 'OR
( Gem-dihalides
'. Hill/ROH R, /OR
R/C'OR
,
\..
Alchols
H2N-Z R,
R/C=N-Z
( R-CH 2-OH (Ammonia
derivatives)
"
\. (9
R-CH-R OH
I 0: H containing
< OR carbonyl compounds
Carbonyl Compounds
r il>
give Aldol reaction
\. R-COOH [Aldehydes, Ketones] ill
OH
( Aldehydes without
o:ll give cannizaro
(RCOO)2Ca reaction
(
. G Zn-Hg
(. ~ters Alkane
Cone. HCI
/:" ,
\. G
Alkyl cyanide LiAIH4
Alcohol
HIl)
( RCOCI
( Oxidation
Acids
r RCaCI
\. Hydrolysis
( RMgX
I
.. Alcohols
(
(~ Tischenko
Ester
reaction
C
{
"-.
Ql~~~~,,~~ CH~~~~~ CARBONYLCO~OUND [21J

kIeoIfo<Schoiolt
C
PERKIN CONDENSATION
In Perkin reaction, condensation reaction take place between aromatic aldehydes and aliphatic acid
anhydrides in the presence ofsodium or potassium salt ofcorresponding acid ofthat anhydride, to yield
a, p-unsaturated aromatic acids.
C6H5-CHO+ CH) -C-O-C-CH) (i)CH]COONa,a ) C6H5 -CH=CH-COOH +CH3COOH

II . II . (ii)H+ !H20,A
o 0 ,"
CH3-C-O
Mech. CH r C-O-C-CH3 o1/ A ~e

CH -C-O-C-CH 3
. II II
o 0
~HrCOOH
;».
,2 8 8
Ph-CH-CH,,-C-0-C-CH3
. 'OH
I ~ II
0 0
II
4'
CH -C-OH
J
~
r
II.
I
.
II
0-
Ph-Cf
II
g
Ph-CH-CH2-C-O-C-CH3
0
-
0
f
\ .
. -CH~-C~OH
, II jU1'1 H,O ~
o
A
Ph-CH-CHz-C-OH - - - - '_30
-H 20
Ph-CH=CH-COOH
.
I II (
OH 0
f3-Hydroxy acid
KNOEVENAGELREACTION
Reaction ofactive methylene group with aldehyde & Ketones is known as knoevenagel reaction.
Z
Gl
RCHO+CH( Pyridine) RCH = C(COOR)2 (i)H2 0 !H ) R CH:::: CH - COOH
or piperidine (ii)a,-C02
"'ZI
Zcanbe·
(-;
o j
II . . .
CHO, COOMe, CN, N02, C - R, SOR, S02R, S020R etc.
( '.
Mechanism: "
•• E!1 '·9
R3N + H2C(COOR)2 ~ R3 NH + HC(COOR}z
e
O . Ef) • OH 0
CII ~e I RNH I .
R-Ct!' + CH(COOR)2 ~ R-C-CH(COORh """ 3 :", R-C-CH(COORh -H 20
I . 1 ~~ I
H H .H
A
c
0/HGl
R-CH = C(COOR) (i)H2 ) R - CH = CHCOOH
2 (ii)A,-C02
High reactivity ofthe methylene group ofthe active methylene compound prevents self-condensation of
the aldehyde.
c:
fiIU~~~~~~Ch~~~~'
IdeolforSchof<l"
CARBONYL COMPOUND [22] . C
c
BENZIL-BENZILIC REARRANGEMENT OR BENZILICACID REARRANGEMENT
The base catalysed reaction of J, 2-diketones to a salt of -2-hydroxy carboxylic acid is known as
Benzilic acid rearrangement, this reaction generally take place when aryl group is present on both carbonyl
carbons.
o OH
Ph C
1/
C - Ph (i)OW ~
I
HO-C-C-Ph
II (ii}H+
1/ I
o o Ph
(Benzil) (Benzilic acid)
Mechanism:
~eOH)~Ph_C_C_Ph~
,~
I -C-C-Ph l~
HO
OH)b
I II I
09
P1 '. a ~-T-Ph ~
(~ o Ph ~
OH OH
(
\ I Htt7 e I
HO-C C Ph +----- 0 C C Ph
" II I II I
0 Ph 0 Ph
(Benzilic acid)
TISCHENKO REACTION I TISCHENKO CONDENSATION

(I) This reaction takes place between two molecules ofaldehydes.
/ . (2) Reaction is catalysed by aluminium ethoxide.
\ . (3) This is a two-step reaction, i.e., redox reaction followed by ester formation. Thus this reaction is
, . extension ofCannizzaro reaction.
'~
R-CHO+R-CHO (C2HsOhAI
~
> R-CH2 -O-C-R
a
C Mechanism:
H ~
{ I.~ ED e 1/n· e
,,~ R
..
C = 0 + AI(OC zHs)3 ¢ Ri=c9-Al (OC Hs 2 )3
':.
R-,-CH=O ') R "H
~ v
( $
0 - C - 0 - Al(O
I U
C H)
2
.
S 3
H R
I
( HYdride ion
transfer
o
( II
R CH2-0-C-R + AI(OC 2HJ3
Ester
(
{-'
"<,~ <
(11!~~~!!~ CN!~~~! CARBONYLCONWOUND [23J

IdeOIftKSdIoIors
/
~
l
,
'2... ~-g p,etdJ Fr -z:;::;
..::::::::;::::
EXERCISE -.1
METHODS OF PREPARATION OF CARBONYL COMPOUNDS
Q.l The best method for the conversion ofethanol to ethanal is
(A) By passing ethanol vapours over Cu at 578 K
(8) By oxidation with acidic potassium dichromate
(C) By oxidation with mangenese dioxide at 3000C .r"
(D) By oxidation with acidic KMn04
Q.2 When propyne reacts with 20% H2S04 & 1% HgS0 4 , we get
(A) Acetaldehyde (8) Propanaldehyde (C) Acetone (0) Formic acid
Q.3 The product formed by the reaction ofpropyne with dil. H2S04 in the presence ofHg2+ can not be
prepared by the following reaction- .
(A) Dry distillation ofcalciwn ethanoate
(B) By passing vapours ofethanoic acid over MnO at 300°C
(C) By ozonolysis of2- Butene
(0) By alkaline hydrolysis ofisopropylidene chloride
Q.4 Except acetylene, other alkynes react with H20 to give

(A) Aldehyde (8) CH3CHO (C) Ketones (D) A lkanal.
Q.5 When CH3Mgf reacts with CH3CN and the product is hydrolysed, we get- .
(A) Propanal (B) Acetone (C) Formaldehyde (0) Acetaldehyde
Q.6 Ethylidene chloride (CH3CHCI2) on hydrolysis with NaOH gives

(A) CH3CHO (B) CH3COCH3 (C) CH3CH(OH)2 (O)C 2H s OH
,." ,
Q.7~HCOO)2Ca + (CH3COOhCa
VJiI' (A) Propanone (8) Methanal
Drydistillation)"A:'_ PrortuctA is-
(C) Ethanal (0) Oneofthe above
"
~/When calcium.acetate is heated with calcium formate then, w~ get

(A) Methanol (8) Acetic acid (C)Acetaldehyde (0) Acetone
~
Q.9 Partial oxidation ofmethane gives
"r ~
(A) HCHO (B) HCOOH (C) H20 and CO2 (O)COandH2
r',
Q.I0 Thereaction- \. "~
CH3COCl+H2 CH3CHO + HCI is

(A) Stephen's reaction (8) Rosenmuhd reaction
(C) Hoffinann reaction (0) Cannizzaro's reaction
Q.l1 Acetone will be obtained by the ozonolysisof~

(A) I-Butene (8) 2-Butene (C) Isobutene (0) 2-Butyne
. Q.IJ/ What is the function ofBaSO4 in Rosenmund reaction - .'

W (A) To stop further oxidation ofaldehyde (8) To stop further reduction ofaldehyde
(C) Act as a poisonous catalyst (0) It checkS the reactivity ofpd.
{i~~~~A~~ C~,~~!~~ IdeolforScholors

CARBONYLCOMWOUNDS [24J c
\
Q.13 The slow partial oxidation ofethyl alcohol is Iikelyto form
(A)C02+H20 (B) Acetic acid (C)CH + H 20 (D) Acetaldeh yde
Q.14 Reaction ofethyl formate with excess ofCH3 MgI followed by hydrolysis gi~-/~ q,
'11 c_o-{..J- «r- ../
(A) n-Propyl alcohol (8) Ethanal - 11:. < y, .1 .P
(C) Prop anal (0) Isopropyl alcohol '
f" ~-lfh~h
PHYSICAL PROPERTIES
±~~~
'Q.15 Compound used for preserving dead bodies is
tt)rrCH20 (40%) (B)CH3CHO (10%)
4j -C?1--vJt,'
(C) CH 30H (25%) (D) C 2H sOH (40%) ~~
Q.16 Which fo the following forces is correctlydescribed about boiling point ofAldehydes & ketones
(A) Hydrogen bond (B) Vanderwall force
(C) Dipole-dipole attraction (D) None ofthese
( Q.17 Which aldehyde is insoluble in H20

(A) Propanal (B) Ethanal (C)ButanaJ (D) Heptanal
(
" CHEMICAL PROPERTIES
Q.18 The general order ofreactivity ofcarbonyl compounds for nucleophi Iic addition reactions is
(A)H 2C 0>RCHO>ArCHO>R2C 0 > Ar2C=0 ' ~?t-c;,.,.o,,?,~c=--=?I'?f<.::.ho
(B) ArCHO > Ar2C = 0> RCHO > R 2C "" 0 > H 2C 0 V
r
\,
°°
(C) Ar2C = >R2 C =0 >ArCHO > RCHO > H 2C
(0) H 2C = > R 2C = 0 > Ar2C =0> RCHO > ArCHO
° 0
Ak'2- '="o
"
C Q.19 Least reactive towards nucl€ o philicadditonis
(A)CH2=0 (B) CCls -C - CfIs (C) CH3 C - Clis (D) CHs-C-H
(
~ II
o ~
C Q.20 What would be the product when acetaldehyde reacts with HCN and the product is further hydrolysed
(A) 2-Hydroxy propanoic acid (B) ~cticacid
(
(C) Both A & B (0) None ofthese
(
Q.21 Reaction ofammonia derivative with carbonyl compound is an example of
( (A) Addition and Substitution (B) Substitution and Elimination
(C) Addition and Elimination (0) Addition and intramolecular substitution
(
( Q.22 The vapour density of a compound is 29, which reacts with iodine and NaOH to form a yellow
compound.The compound is- .
C (A) CH3COOH (B) CH3COCH3 (C) CH 3CHOHCH3 (0) CH30H
( Q.23 Stephen reaction is the reaction involving:

(A) Reduction ofalkanoyl chloride with PdlBaSO4.
c~ (B) Reduction ofalkyl isocyanide with sodium and alcohol.
(C) Reductio~ ofalkyl yyanide with SnC12 and HCI and hydrolysing the intermediate aldimine.
(0) Reduction ofcarbonyl compound with zinc amalgam and HC!.
(.
'L
{iJ~~~~A~~C~~!~! CARBONYLCOMWOUNDS [25J

ldealforSd>ofo"
t
L
Q.24 Acetone gives test with
(A) 2,4 Dinitro phenyl hydrazine (B) Fehling solution
(C) Schiffs reagent (D)All
Q.25 Aldol condensation between the following cOmpounds followed bydehydmtion gives methyl vinyl ketone-
J (A) HCHO and CH3COCH3 (B) HCHO and CH3CHO
(C) Two molecules ofCH3CHO (D) Two molecules ofCH3COCH3 C'
Q.26 In Cannizzaro reaction

(A) Aldehyde is converted into alcohol
(B) Alcohol is converted into aldehyde
(C) Primary amine is converted into isocyanide
(D) Acid is converted into amine "
Q.27 Which is most difficult to oxidise

(A) HCHO (B) CH3CHO (C) CH3COCH3 (D) CH3CH2CHO
Q.28 ForthereactionRCH=O+2[H] -..?RCH20H

the catalyst is
(A) Ni only (8) Pd. only (C) Pc only" (D) Any ofthe above
Q.29 Acetone shows similarity with acetaldehyde in reacting to

(A) Schiffs reagent (B) Fehling solution (C) Grignard reagent (D) Tollen's reagent
Q.30 Which ofthe following combinations give t-butyl alcohol when treated with Grignard reagent
(A) CH3MgBr+CH3COCH3 (B) C2HS MgBr+CH3COCH3
,
(C) CH3MgBr + (CH3)3C, OH (D) CH3MgBr + CH3CH2CHO \. ."
Q.31 Which ofthe following can be used to differentiate between ethanal and pro.p~~
(A) AmmonicaiAgN03 ~ ~
(B) Ammonical AgN03 in presence oftartrate ions
(C) I2 in presence ofbase ./
(D) AmmonicaIAgN03 in presence ofcitrate ions
Q.32 Which ofthe following does not tum schiff's reagent to pink
(A) Formaldehyde (B) Benzaldehyde (C)Acetone' (D) Acetaldehyde
/
c
liJ!~~~!!~C~~~~f CARBONYLCOMWOUNDS [26) c

ldeo'fcrSdlOhm
L)
EXERCISE - II
Q.l, I An aldehyde isomeric with allyl alcohol gives phenyl hydrazone. Pick out a ketone that too gives
\)1 a phenyl hydrazone containing the same percentageofnitrogen: I!. ~ '2C t:.;1-~
(A) Methyl ethyl ketone ~mettiYI ketone J,

( (C) 2- Butanone (D) 2-Methyl propanone '1'151~ :J1
f. . IJ-j.l)f~
Q.2 Aldehydes and ketones form hydrocarbons by; :.r JJL
(A) The Clemmensen reduction (B) The Cannizzaro reaction (1.+
~ - ( --'''>
(C) The Rosenmund reduction (D) Aldol condensation t
Q.3 Acetaldehyde oxidises.:
('
\. (A) Fehling's solution. (B)Ammoniacal AgN03 solution

(C) NaOL (D) None of these
(
ow .
Q.4 C 6 HsCHO + CH3COCH3 ) C6 H s CH(OH)CH2CQCH 3 ~ C 6Hs
CH CHCOCH3 This
reaction is known as:
c (A)Aldol condensation ~ross aldol condensation

( (C) The Claisen-Schmidt reaction (D) None of these
(4
!\ \
Feh! ing sol ution is made by mixing two separate solutions. One ofwhich is a solution ofcopper sulphate
only while the other contains:
(A) NaHC03 (B).N~C03 (C) KNaC 4H40 6 (D) KHC0 3
r
" Q.6 -....
Dry distillation ofcalcium formate and subsequent treatment with dilute KOH gives the mixture of:
( , (A) CH30H,'HCOO~ (B)CH3CHO, HCOOK C.J::I-cedz,-C'<l, ~ 1/- ~-11
r (C) HCHO, HCOOK (D) None of the a b o v e , A ?
( ~~~
("OJ! The conversion CH3CHO ~ OHC - CHO can be effected by: C3fj-=c11
. '.f
(A) cr03 ~ (B) Se02 (C) Br2/NaOH (D) KMn04 Jfc-c>o-
C , t' J.1. - ( - 11 . ~3 H_ c. - C -H' .
. ~ ~ . ~ ~ ,
Q.8 Match List I with Jist II and then select the correct answer from the codes given below the lists:
List I List II
( (1) C6H 5CHO (a) Mesitylene
(.
(2) CH3COCHO (b) Paraldehyde
\.
(3) CH3COCH3 (c) Iodoform reaction
( (4) CH3CHO (d) Cannizzaro reaction
Codes
2 3 4
(A) d c b a
(B) d b c a
'=-~ (C) a c b d
(0) d c a b,
(
'"I
(ci~~~A~~ CN~~~~! CARBONYL COMPOUNDS ! [27J

ldealf..-schohm
1'"·
c
o
Q.9 CH 3-CHO ~ CH 3CH(OH)CH 2CHO In the aldol condensation of acetaldehyde
represented above, which of the following intermediate species are obtained?
0° o
I o II
(A) CH2=C-H (B) :CH2 - C-H
09 0 r '.
. I II
(C)CH3 -C-CH2 -CH (D) All above
~
~nversion ofacetone into 2,3-dimethylbutane-2, 3-diol can be achieved by:
(A) ZnJHglHCI (B) Wolff-Kishner reduction
(C) Mg/Hg/H 20 (D) The conversion is not possible.
Q.ll Which ofthe following statements is wrong:

(A) All methyl ketones give a positive iodoform test.
(B) Acetaldehyde is the only aldehyde that gives iodoform test.
(C) All secondary alcohols give positive iodofonn test.
(D) Any alcohol that can be oxidised to an acetyl group gives a positive iodoform test.
Q.12 Arrange [(CH3)3ChCO (I), [(CH3)2CHhC=O (II), (CH3)2C=O (III) and CH 3CHO (IV) in order
ofreactivity towards nucleophilic attack:
(A) I > II > III > IV (B) I > III > IV > II
(C) IV > III > II > I (D) II > I > III > IV
,
(
Q.13 Which ofthe following statements is correct: (
(A) All primary al~hol give iodoform reaction. '.

(B) All secondary alcohols give iodoform reaction.
(C) Ethanol is the only primary alkanol that gives positive iodoform test.
(O)All aldehydes with a hydrogen atoms give positive iodoform reaction: c
Q.14 Both Fehling's solution and Benedict's solution give this compound when treated with acetalde
hyde: .
(A) CuO (B) Cu20 (C) Cu(OHh (D) Cu(CO)4
Q)i Aldehyde not containing a-hydrogen atom reacts with aqueous alkali to form:
(A) An a, f3 unsaturated aldehyde.
(B) An a, f3 unsaturated acid.
(C) Corresponding alcohol and corresponding carboxylate anion.
(0) Corresponding carboxylic acid.
Q.16 Formaldehyde reacts with 50% aqueous alkali to form:

(A) A mixture ofmethanol and sodium acetate. {"
'c7
(B) A mixture ofethanol and sodium formate.
(C) A mixture ofmethanol and sodium formate. c
(0) A resinous mass.
1i CARBONYL COMPOUNDS [28J c

c
c
Q.17 CH 3CH=CH-CHO may be reduced to CH3CH=CHCH20H using:
(A) H/Pt (B) NaBH4
(C) [(CH3hCHOh Al (D) Zn-Hg/HCI
Q.18 How many aldols will be formed by CH3CHO and CHr CH2-CHO
(A) 2 (B) 3 (C) 4 (D) 1
r
.( Q.19 An organic compound reduces Tollens reagent and Fehling's solution. It can be
(A) CH3CH2CHO (B) C 6HsCHO (C) CH3COCH2CH 3 (D) (CH3)3CCOCH3
Q.20 Methyl ethyl ketone can be reduced to n-butane by

(A) Meerwein-Ponndorfreduction (B) Wolff-Kishner reduction
( (C) Mg-Hg, H20 (D) HI I red phosphorus at A23 K
"
( Q.21 In the reaction CH 3CHO + HCN ~ CH 3CHOHCN the product obtained is
I
(A) a meso compound (B) a levorotatory compound
\
(C) a dextrorotatory com pound (0) a recemic mixture
(
Q.22 Cannizzaro reaction does not take place with
(
< )-CHO
'\
(
\
(A)(CH3)3CCHO (B) (C) O-CHO
o
(D) CH 3CHO
( Q.23 Bakelite, a polymer, is formed by either acid or base-catalysed condensation offormaldehyde with
\
(A) benzaldehyde (B) 2-~hthol (C) phenol e
(D) acetaldehyde
(. ~ +)1ULc .~ ·--f(CJr~---y;y-~+·
Q.~/Inthereaction' ~'""t ~ l ~_J~ ~
( .CH3COCH3 + Se02 ~ P + Se + H20 J" " . (
the product {P) is
c (A) CH3COOCH3 (B) CH3COOCH20H
c· (C) CH3COCHO (D) CH30COOCH3
(,Q.25 The reagent that can be used to distinguish acetophenone and benzophenone is
(A) 2,4-dinitrophenylhydrazine (B) aqueous NaHS03
(
(C) Benedict's reagent (D) 12 and N~C03
CQ .26 An alkene C7H14 on reductive ozonolysis gives an aldehyde with formula C3 H60 and a ketone. The
C ketone is-
(A) 2-butanone (B) 2-pentanone (C) 3~pentanone (D) propanone
C
( Q.27. Identify the compounds A and B in the following reaction sequence
(CH hC = ° NaCN) a H30 + ) b

8 3 HCI Heat
(A) a = CH3C02H, b = (CH3COhO (B) a = (CH3)2C(OH)CN,·b = (CH3hC(OH)C02H

C
(
(C)· a = CH3CHO, b = CH3C02H (D) a = (CH3)2C(OH)CN, b = (CH3hC = °

(~N~!!~ CL~~~~~ IdeoIfMSch<JJo..
. CARBONYLCO~OUNDS [29)
(
\...
- (
Q.28 Necleophilic addition reaction will be most favoured in
o
II
(A) CH 3CHO (B) CH 3-CH 2-CH 2 C-CH3
(C) (CH3hC ° (D) CH3CH 2CHO
Q.29 The increasing order of the rate ofHCN addition to compounds a - dis /'-'<
(a) HCHO (b) CH3COCH3

(d) PhCOCH3 (d) PhCOPh ~-----
(A) a < b < c < d (B) d < b < c < a (C) d < c < b < a (D) d < a < c < b
Q.30 Predict the product '8' in the seuqnece ofr~action

HC = CH A NaOH) B
HgS0 4 .
(A) CH3COONa (B) CH3COOH

(C) CH 3CHO (D) CH3CH(OH)CH 2CHO
Q.31 Which one ofthe following on treatement with 50% aqueous sodium hydroxide yields the correspondnig
alcohol and acid

(A) CH3CO CH3 (B) C 6HsCH2CHO (C) C 6HsCHO CD) CH3CH2CH 2CHO
Q.32 Among the following compounds which one will react with acetone to give a product that contains
carbon-nitrogen double bond
(A) C6HSNHC6HS (B) (CH3h N (C)O' (D) C6H SNHNH2
N·
H , r'
\;. -;:
Q.33 Which ofthe following reagents may be used to accomplish the conversion / '
J C6Hs CH = CH CH20H ) C6H s CH = CHCHO " "
(A) [(CH3)3COh AI, (CH3hCO (13) @N:.- H CICrOs
(C) Mn02 (D) All ofthese

c
Q.~4t /The major product obtained from photochemical chlorination ofethylbenzene (in eXcess) is hydrolyzed I'·
l..1/ with aqueous KOH and the product is then oxi~ized with pce. The final product formed is
,,~
(A) P~H2CHO (B) PhCOCH3 (C) PhCOO (D) PhCOOH c

Q~~ _ M~-ij- ~GM-U";J ~ r;;r ~ --<-¥j .
Q.35 A compound (A), C 4H sC12, on~drolysis gives a product (B) which forms a 2, 4-DNP derivative
( ,
'- ....
but does not reduce Tonens reagent. The compound (A) has the structure {'\
V
(A) CH3CH2CHCICH2CI (13) Clf3CH2CCI2CH3
(C) CH3CH2CH2CHCl2 (D) CH3CHCICHCICH3 ()
Q.36 wfich ofthe following compo~nds does no.t react with NaHS03 ?
, '.
v
~) C 6HsCHO (13) C6HsCOCH3 (C) CH3COCH3 (D)C2H sCOC2H s
c
c
'IIJ~~~~~~C~~~~~
-CARBONYL COMPOUNDS-- {37J] c
Sch%"
_ (or
r·
'\J
Q.37 Which ofthe following will not undergo aldol condensation?
(A)Acetaldehyde (B)i>ropionaldehyde
(C) Trideuterio acetaldehyde (D) Benzaldehyde
Q.38 In the Cannizzaro reaction: 2PhCHO . ow ) PhCHzOH + PhCOO- the slowest step is
(A) The attack of OH- at the carboxyl group
(B) The transfer of hydride to the carbonyl group
(
\ (C) The abstraction of proton from the carboxylic acid
(0) The deprotonation ofPhCHzOH
Q.39 A cyanohydrin ofa compound (X) on hydrolysis gives an a-hydroxy acid which shows optical activity
after resolution. The compound (X) is
(A)Acetone (B) Formaldehyde
f
(C) Oiethyl ketone (D) Acetaldehyde
\
. f1, _ (' - c.-l1
Q.40 Phenylglyoxal, C 6 H5COCHO, on heating with concentrated NaOH gives '1. l.b
(A) C 6 H sCOONa and CH3 0H (B) C 6 H5CH20H and HCOONa J';v'~
/
\ (C) C 6 HsCHOHCOONa (D) C 6 H 5COONa and HCOONa
(
\ QA1 The most appropriate reagent for the conversiqn of2-pentanone into butanoic acid is
fI,,-f1- cocr
~-~
(A)Chromic acid ~ ~ ~(B)Acidified KMn04
~~
,(C\..M1(aline
~. _.. -
KMn04 ~hfh"
j.r,.>
J-~~) Sodium hypochlorite
~J.J\"'f"""
~~
Q.4;/ Which ofthe following gem ina I diols is the most unstable?
{ \£r
, F3C" /OH CI 3C" /OH ~OH OH
(A) /C, (B) /C, . (C) V"OH
(0) CH3"C/
F3C OH H OH CH3/ 'OH
(
Q.43 The reaction
(
\. CHO
o
C§:( + conc. NaOH ~
CHO
( produces
..'... .
~
"
(A) ©:CH{OH}2
(B)@CO
(C) (§XCHPH (D)CSC=
( CH{OHh COO COO-
Q.44 2-Methylcyclohexanone is allowed to react with metachloroperoxobenzoic acid. The major product
formed in the reaction is ~ vi.!'~_ ~I'd~~
c o o o
~H'
Ha\-e.0
(A)a
CHO
(B)C\H' (C) (0) U
C Q.45 The possible number ofstereoisomers that may be produced by the reaction ofracemic s-butyl methyl
ketone with ethylmagnesium bromide and subsequent hydrolysis is
(A) Two (B) Three (C) Four (0) Six
C{i)!~~~..~~CL~~~~! CARBONYL COMPOUNDS [31/

,( IdeoIfor5chok'"
'--~
Q.46 Consider the following sequence ofreactions.
CH COCH Ba(OH)2) A ~S04) B NaB~ ) C The final product (C) is
3 3 heat heat
(A) (CH3)2C(OH)CH2COCH3 (8) (CH3)2C CHCOCH3

(C) (CH3)2CHCH2CHOHCH3 (D) (CH3)2 C = CHCHOHCH3
.Q.47 Among the following compounds, the one which can undergo both aldol condensation and Cannizzaro ( '.
~)2C"t!CHO (B) HCHO (C) C6HsCHO' (D) CH3CHO

.~ c4::)~~~ j:.l.o.~~A~j~ ~ .
Q.48 Consider the following sequence ofreactions.
. H
Ketone A
1.C2H SM gBr
2.H20
)
.B
H2S04 heat
-H20
. >C
2.Zn.H20 ~/~
o 0
The ketone (A) is
(A)~ (B)~ (C)vy (D)Y

o o o ('
o
Q.49 An organic compound (A), CSHlOO, reacts with hydrazine to form a hydrazone derivative (B). The
hydrazone (B) on being heated with KOH at about 180°C, gives n-pentane. The compound (A) does
not respond positively to Tollens reagent and to the iodoform test. The compound (A) is
,.
~
o o
(A)~H ~.J
(D)~
( .,
\
Q.50 The reaction of C6HsCH = CBGHO with NaBH4 gives
(A) C6HsCH2CH2CH20H (B) C6HsCH CHCH20H \,
(C) C6HsCH2CH2CHO (D) C6HsCH2CHOHCH3

...~
c
Q.51 B ( Raney
N~H2 ct
. t,NaBH4• CH 30H
PI.1 (equi.)H2 ) A
C
c
A, Band Care:
(A) d H
in all cases (B) 0 in ~Il cases c
("'Y0H . ~ OH OH
(C) Il./ in all cases (D) A: V ' B: ~ ,C:()
c
c
lIJ~~~~A~CL~~~~~ " CARBONYl.. COMPOUNDS /32J c
c
Ideo/forSd>ol<>rs
( '.
v
Q.52 The aldehyde which shows Cannizzaro's reaction is
(A) HCHO (B) C6 Hs CHO (C) CCI3-CHO (0) all ofthese
Q.53 The product fonned in the following reaction will be-

CHO NaOH
I )0 product-
CHO
(A) CH 20H (B) CH 2 0H (C) COONa (D) AU ofthese

I I I
CH 20H COONa COONa
.:
\
Q.54 Mixture ofC6HsCHO and HCHO is treated with NaOH then cannizzaro's reaction involves
(A) Oxidation ofHCHO
(B) Reduction of HCHO and Oxidation ofC6HsCHO
( (C) Reduction ofG 61I#'H C6 YI>c.)1P
(O)BothA&C
Statement Based Question

/'
\, Each ofthe questions given below consistofStatement -1 and Statement- 2. Use the following Key to
choose the appropriate answer.
I
(A) Ifboth Statement-l and Statement-2 are true, and Statement-2 is the correct explanation of
(
Statement- 1.
'.
(B) If both Statement-l and Statement-2 are true but Statement-2 is not the correct explanation
ofStatement - I.
(C) IfStatement -I is true but Statement-2 is false.
(D) IfStatement - 1 is false but Statement-2 is true.
( Q.55 Statement-l Carbonyl compounds take part in nucleophilic addition reactions.
"
(,
Statement-2 These reactions are initiated by nucleophilic attack at the electron deficient
carbon atom.
I'
\.
Q.56 Statement -1 : The.addition ofammonia derivatives on carbonyl compounds is carned in weakly
ct).~ acidic medium.
,Statement-2 In weakly acidic medium attacking nucleophile is also protonated~
(
/" Q.57 Statement-l . Fonnic acid reduces mercuric chloride solution.
\.
Statement -2 : Fonnic acid has reducing aldehydic group.
r
'(
Q.S8 Statement-l Acetaldehyde undergoes aldol condensation with dilute NaOH.

(
Statement-2 Aldehyde which do not contain a-hydrogen undergoes aldol condensation.
;' ,
'-..
Q.S9 Statement-l Crossed CannizZaro reaction between fonnaldehyde and benzaldehyde give
( benzyl alcohol and [onnate ion.
Statement-2 Fonnaldehyde is a better hydride donar than benzaldehyde.
c {jij!~~~,,~~CL~~~~! IdeoIforSdlOlO,.
CARBONYLCO~OUNDS [33J
EXERCISE III
SECTION-A
Q.l Which one of the following is reduced with zinc and hydrochloric acid to give the corresponding
hydrocarbon? [AIEEE-2004] .
(A) Ethyl acetate (B) Acetic acid (C)Acetamide (D) Butan-2-one

I "
(3) The best reagentto convert pent-3-en-2:-01 into pent-3-en-2-one is. - IAIEEE-200S]
(A) Acidic dichromate (B) Acidic permanganate
~nium chloro-chromate (0) Chromic anhydride in glacial acetic acid
Q.3 The increasing order ofthe rate ofHCN addition to compounds A - Dis - [AIEEE 2006]
(a) HCHO (b)CH3COCH3 (c)PhCOCH3 (d)PhCOfJf:k
(A) d < b < C < a (B) d < C < b < a (C) c < d < b < a (D) a < b < C < d
Q.4 Which ofthe folowing on heating with aqueous KOH, produces acetaldehyde? [AIEEE 2009] " /
(A) CH3COCI (B) CH3CH2Cl (C) CH2ClCH2CI (D) CH3CHCI 2 /'
Q.5 Todofonn can be prepared from all except: [AIEEE 20121

(A) 3-Methyl-2-butanone (B) lsobutyl alcohol
(C) Ethyl methyl ketone (D) Isopropyl alcohol
o:)fI In the given tran~ormation, which ofthe following is the most approptiate reagent? [AIEEE 20121
CH-CHCOCH3 DCH CHCH 2CH 3
Reagent)
00 D 00 .
(A)Na,Liq.NH3 (B) NaBH4 (C)~NH2' OH (D)Zn-HgfHCI
,- .-'
/'
SECTION-B
Q.7 The formation ofcyanohydrin from a ketone is an example of- [lIT -1990]
(A) Electrophilic addition (B) Nu~leophilic addition
(-'.
(C) Nucleophilic substitution (0) Electrophilic substitution '-/
f·'
Q.8 The enolic form ofacetone contains - [IIT-1990]

(A) 9 sigma bonds, 1 pi bond and 2 lone pairs (B) 8 sigma bonds, 2 pi bonds.and 2 lone pairs
(C) 10 sigma bonds, 1 pi bond and llone·pair (0) 9 sigma bonds, 2 pi bonds and I lone pair
J
Q.9 Which ofthe following will give yellow precipitate with IJNaOH? [IIT-1997] f
(A) ICH2COCH2CI\ (B) CI\COOCOCH3

(C) CI\CON~ (0) CH3 CH(OH)CH2CI\
I{mong the following compounds, which will react with acetone t~ give a product containing >C=N- c
iTy\L
,.. 411\.,
W 1\[ [IIT-1998]
.. (A) (C6Hs)3N (B) (C~)3N (C) C6H SNHC;;Hs {)Y'-'6HSNHNH2 .
c
( ,
'0
!ji]!~~~A~~ C~~~~! CARBONYL COMPOUNDS·· {34J

IdeofforSdw/"n
c ~.
v
Q.ll Which ofthe following will not undergo aldol condensation- [I1T-l 998]
(A) Acetaldehyde (B) Propanaldehyde
(C) Benzaldehyde (D) Trideutero acetaldehyde
a)--c.MO
Q.12 Which ofthe following will react with water- [IIT-1998]

(A) CHCl3 (B) Cl 3CCHO (C) CCI., (O)CIC~C~CI
~~
Q.13 Which ofthe following has the most acidic hydrogen - [IIT-2000]
(A) 3-hexanone (8) 2,4-hexanedione (C) 2,5-hexanedione (D) 2,3-hexandione
(
9.11; Which ofthe reage~t is used to convert 2-Butanone into propanoic acid - [I1T- 2005]
\.ff (A) NaOH , 121 H ( B ) Tollen's reagent
(C) Fehling solution (D) NaOH , Nail H+
(' Q.15 T~e smallest ketone and its next homologue are reacted with ~OH to form oxime.
(A) Two different oximes are fOimed (B) Three different oximes are formed
(C) Two oximes are optically active (D) All oximes·are optically active [JEE 2006)
(
".' Q.16/;;yclohexene on ozonolysisfollowed by reaction with zinc dust and wa.ter gives compound E. Compound
( LJf/ E on further treatment with aqueous KOH yieJds compound F. Compound F is [JEE 2007]
(
(
(A) U- CHO (B) o-CHO (C) o-COOH (D) Cg;:~ .
Q.l} fltatement-l: Glucose gives a reddish-brown precipitate with Fehling's solution.
" vc/'
t'
because .
Statement-2: Reaction ofglucose with Fehling's solution gives CuOand ~luconicacid.
(A) Statement-..1 :s True, Statement-2 is True; Statement-2 is a correct explanation for Statement-I.
( (B) Statement-l is True, Statement-2 is True; Statement-2 is NOTa correct explanation for Statement-I.
'
(C) Statement-l is True, Statement-2 is False.
c (D) Statement-l is False, Statement-2 is True. [JEE2007]
(
,~
c
(
"
c·
c
(
(til ~~~~!!~ CLI!!~~~!

ldeo/forScholor1
CARBONYLCO~OUNDS /35J
/
"-
ANSWER I<EY
EXERCISE-I
Q.l A Q.2 e Q.3 e QA e Q.5 B Q.6 A Q.7 D
Q.8 e Q.9 A Q.I0 B Q.l1 e Q.12 0 Q.13 D Q.14 D
Q.16 e Q.19 e - / "
Q.15 A Q.17 0 Q.18 A Q.20 C Q.21 C
Q.22 B Q.23 e Q.24 A Q.25 A Q.26 A Q.27 C Q.28 D
Q.29 e Q.30 A Q.31 e Q.32 e
EXERCISE - II I'
" '
Q.l B Q.2 A Q.3 D QA e Q.5 C Q.6 A Q.7 B

( ,
Q.8 D Q.9 D Q.l0 e Q.ll e Q.12 e Q.13 e Q.14 'B
Q.15 e Q.l6 C Q.17 e Q.l8 e Q.19 A Q.20 B,O Q.21 D "
\ /"
Q.22 D Q.23 e Q.24 e Q.25 0 Q.26 A Q.27 B Q.28 A

-
I"
l
-".
Q.29 e Q.30 D Q.31 e Q.32 D Q.33 D Q.34 B Q.35 B
('
Q.36 D Q.37 0 Q.38 B Q.39 0 QAO e QAl 0 QA2 D

QA3 e QA4 e QA5 e QA6 0 QA7 A QA8 B QA9 C (,
Q.50 B Q.51 0 Q.52 0 Q.53 B Q.54 0 Q.55 A Q.56 C

Q.57 A Q.58 e Q.59 A
, '
I" J
EXERCISE - III
Q.l 0 Q.2 0 Q.3 B QA D Q.5 B Q.6 e Q.7 B ('
\.,-,
Q.8 A Q.9 D Q.I0 A Q.l1 e Q.12 B Q.13 B Q.14 A

!'
Q.15 B Q.16 A Q.17 e \ -'
()
c
c
c
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8
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[i]~~~~A~~ C~,~~~~!
Ideol fa< SchoJors
CARBONYL COMPOUNDS C
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,,--CONTENT· ,#
S.No Pages
1. Theory (KTG & THERMODYNAMICS) 1 -24
2. Exercise-I . 25 - 34
3. Exercise-II 34-40
,
(
4. Exercise-III 41 - 48
5. Exercise-IV (Section-A) 48- 50
(Section-B) 50 - 55
(
6. Answer Key 56 - 57
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JEE MAIN - 2014
C
",.
FLUID MECHANICS
(
'
L
, /
)
FLUID MECHANICS
Definition ofFluid :
The term fluid refers to a substance that can flow and does not hav~ a shape ofits own. For example
liquid and gases.
Fluid includes property -7 (A) Density (B) Viscosity (C) Bulkmodulus ofelasticity (D) Pressure (E)
specific gravity
Pressure in a Fluid:
The pressure p is defined as the magnitude ofthe normal force acting on a unit surface area.
.1F
" P= M ~F =normal force on a surface area M.
The pressure is a scalar quantity. This is because hydrostatic pressure is transmitted equally in all direc
tions when force is applied, which shows that a definite direction is not associated with pressure.
(
~F .~
\.
,
~.
(
M
(
( Variatio~ ofPressure with height:
V/eight ofthe small element dh is balanced by the excess pressure. It means = pg.
P h
Jdp=pgJdh => P Pa +pgh
,
(
Pa 0
(,
"
c
1 'Iliiil~~:il
~~~~H;H;~mHHH
( hI ";:;;!HH!H,;;1!,
(
C
( Pascal's Law:
c~ Ifthe pressure in a liquid is changed at a particular, point the change is transmitted to the entire liquid
without being diminished in magnitude. In the above case ifPa is increase.d by some amount than P must
( increase to maintained the difference (P - PJ::;: hpg. This is Pascal's Law which states that Hydraulic lift
is common application ofPascal's Law.
{~~
[j]!~~~A~~CL~~!~!
"-
FLUID MECHANICS [lJ
c Ideal (01 Scholars
(
<--/
Hydraulic press:
f W W
P = - = - or f= - x a
a A A,
as A»a then f«W.
TIlls can be used to lift a heavy load placed on the platfonn oflarger piston or to press the things placed
between the piston and the heavyplatfonn. The wor done byapplied force is equal to change in potential
, ...
enrgy ofthe weight in hydraulicpress.
f J Applied !w
~ rNee
•~
:'1'::"
~
. ..
~.
..
~
:::f:':::
.....
110m,'
~
... .
.. ~
~ :t~~:TifmT~~;;; m1i ~~A

ht:i£ii;_
Hydraulic Brake:
Hydraulic brake system is used in auto-mobiles to retard the motion.
Hydrostatic Paradox: , .
Pressure is directly proporti~nal to depth and by applying pascal's law it can be seen that pressure is
L'ldependent ofthe size and ~~ape ofthe containing vessel.
I.,
;"\"';\""""""';"C'1 .:m~m§1EEm _:::.~:::'

~i\~~~~~~~~~~~~r 1IIIJIIllflmm ;f!II/b!::,
ABC
PA=PB=Pc
Atmospheric Pressure:
Ue.fmition :
The atmospheric pressure at any pOint is numericallyequal'to the weight ofa cOlumn ofair ofunit cross
, sectional area extending from that point to the top ofthe atmosphere. "
At O°C, density ofmercury = 13.595 g cm-3, and at sea level, g::::: 980.66cm g-2
NowP=hpg.
G
Atmospheric pressure = 76 x 13.595 x 980.66 dyne cm-2 == 1.013 x 10-5 N-m2 (Pa)
I' ,
'--"
[i'4~~A~~CL~~!~~
Ideal for SchoIors
FLUID MECHANICS, [2J (
'---'
.
c
Measurement ofAtmospheric Pressure:
1. Mercury Barometer.
To measure the atmospheric pressure experimentally, tomcelli invented a mercury barometer in 1643.
Pa =hpg
The pressure exerted by a mercuryColumn of Imm high is called 1 Torr.
1Torr = 1 mmofmercurycolumn
. Torricelli
Mercwy
Trough
2. Open tube Manometer:

Open-tube manometer is used to measure the pressure gauge.
When equilibrium is reached, the pressure at the bottom ofleft limb is equal to the pressure at the bottom
ofright limb.
l
~ r- - - .
~fY=Y'-Yl.hlP,
.
P Y2
( p+y,pgtYl hIlP.+Y2Pg
i.e. p + YI pg = Pa + Y2 pg
'\. p-pa= pg (Y2 -Yl) = pgy
p-pa= pg (Y2 -Y1) = pgy
(
p = absolute pressure, p - pa gauge pressure.
( Thus, knowing Yand p (density ofliquid), we can measure the gauge pressure.
"
I
\, 3. Water Barometer:
/ . Let us suppose water is used in the barometer in stead ofmercury.
\.
1.013 x 105
hpg = 1.013 x lOs or h = - - -
pg
( The height ofthe water column in the tube will he 10.0 m. Such a long tube cannot be managed easily,
thus water barometer is not feasible.
C
Ex. A vertical U-tube of uniform cross-section contains mercury in both arms. A glycerine
( (relative density = 1.3) column oflength 10 cm is introduced into one ofthe anns. Oil ofdensity 800 kg
( m-3is poured into the other arm until the upper smface ofthe oil and glycerine are at the same horizontal
leveL Find the length ofthe oil column. Density ofmercury is 13.6 x 1Q3 kgm-3.
c· Sol. Pressure atA and B must be same
( Pressure atA = Po + 0.1 x (1.3 x 1000) x g HIlle
where Po = a1mospheric pressure
"
~ Pressure at B Po + h x 800 x g + (OJ - h) x 13.6 x 1000 g O.l-H

L Po + 0.1 x 1300 x g
Po + 800 gh + 1360 g 13600 x g x h
~Bl
{
'L
or h=9.6cm
[i]!~~~A~~CLL,~~~!!
Ideal (()f SchoIol$
FLUlDMECHAMCS [3J
(
t
Ex. For the arrangement shown in the f!gure, what is the density ofoil?
c
D=12.3~
oil' f
1=135MM
At )Bl
So]. Psurface Po + Pw·gl
Psurface = Po + Poil (l + d) g
_ pro'l 1000(135)
=> r oil - (I +d) = (135+12.3) 916 kg/m

fr ~
\- /
ARCIDMEDES PRINCIPLE:
According to this principle, when a body is immersed wholly or partially in a fluid, it loses its weight
which is equal to the weight ofthe fluid displaced by the body.
Upthrust buoyancy=Vp~ V =volume submerged
PI = density ofliquid.
Relation between density ofsolid and liquid:

Weight ofthe floating solid = weight ofthe liquid displaced
PI V2
VI PI g V 2 P2 g => -=
P2 VI
Density of solid Volume of the immersed portion of the solid "
I
,
\. ..
or Density of liquid = Total volume of the solid
This relationship is valid in accelerating fluid also. Thus, the force acting on the body are
(1) Its weight Mg which acts downward and ()

(n) Net upward thrust on the body or the buoyant force (mg).
Hence the apparent weight ofthe body =Mg -mg =weight ofthe body - weight ofthe displaced liquid.
.Or Actual weight ofbody -Apparent weight ofbody =weight ofthe liquid displaced.
The point through which the upward thrust or the buoyan~force acts when the body is immersed in the (,
'~/
liquid is called its centre ofbuoyancy. This will coincide with the centre ofgravity ifthe solid bodyis
homogeneous. On the other hand ifthe body isnot homogeneous, then the centre ofgravity may not lie
on the line ofthe upward thrust and hence there may be a torque that causes rotation in the body.
Ifthe centre ofgravity ofthe body and the centre ofbuoya:Qcy lie on the same straight line, the body is in
equilibrimn.
If the centre ofgravity ofthe body does not coincide with the centre of buoyancy (Le., the line of
upthrust), then torque acts on the body. This torque causes the rotational motion ofthe body.
c
[I ~~~~A~~ CI.L,~~!~~
Idea/forScholars
FLUIDMECHANICS. [4J
{ ,
'--'"
Ex. A pipe ofcopper having an internal cavityweighs 264 gm in air and 221 gm in water. Find the volume of
the cavity. [Density ofcopper is 8.8 gmlcc.]
Sol. The buoyant force on the copper piece, F = v pg
. F (264-221)g
Hence, volume ofthe copper plece V = - 43 cc
crg .1 xg
~' The volume ofthe material ofthe copper piece
V = mass of copper piece . .:. 264 _ .
o density of material - 8.8 - 30 cc
Hence, volume ofthe cavity = V -Yo 43-30 13 cc
Ex. A piece ofbrass (ailoy ofcopperand zinc) weighs 12.9 gm in air. When completely immersed in water,
it weighs 11.3 gm. What is the mass ofcopper contained in the alloy?
[Specific gravities ofcopper and zinc are 8.9 and 7.1, respectively.]
c Sol. Let the mass ofcopper in alloy = x gm.
F
Amountofzinc=(12.9-x)gm
" x x
Volume ofcopper, VCu = 8 9 and
PCu •
f Volume ofzinc V = (12.9-x)
Zn 7.1
/"
Total volume ofthe alloy, V = VCu + VZn
,,
V = (12.9-x) + ~
"' or
7.1 8.9
... (i)
(
Buoyantforce F = Vpg = loss ofweight
( = (12.9 - 11.3)g = 1.6 g
Substituting the value ofV in equation (i), we get
x=7.6gm ]
f'
\..
( Ex. A cubical block ofiron ofedge 5 cm is floating on mercury in a vesseL

(a) What is the height ofthe block above mercury level?
( (b) Water is poured into the vessel so t1!at it just covers the iron block. What is the height ofthe water
(
c, column?
{Relative densityofHg = 13.6 and that ofFe = 7.2] .
C' Sol. (a) Let h be the height ofthe iron block above mercury.
( In case offlotation,
Weight ofthe block = buoyant force
~
Le., x3 pg = [(x - h) crg] x2 .
C
or h = x (1- 1:)cr = 5 (1- 7.2)
13.6
= 2.3 5 cm
.
[j~~~~~~ (t~~!~~ Ideo! f<K

SdIo/a1$
FLUID MECHANICS 15]
(b) Letybe the height ofthewaterlevel.
For equilibrium ofthe block,
x 3 pg = [O"wgy + crHgg(x-y)] x 2
xcr=(x-y) crHg +ycr

w
or y = x[ crHg -cr
O"Hg -crw
J= 5 (13.6 - 7.2J
13.6 - 1
2.54 cm ] c,
Ex.
The 'tip ofthe iceberg' in popul'lf speech has come to mean a small visible fraction ofsomething that is
mostly hidden. Forreal icebergs, what is this fraction? (Pice = 917 kg/m3, P seawater = 1024 kg/m3)
Sol.
W.lee =pV.g,W
1 I seawater
=pwVw.g
Forfioatation, P;Yig = PwV~
Vj-Vw 917
Fraction ofthe volume submerged = V. = 1- 1024 107 = 10.45% ]
. I 1024
,r"~\
Ex. Ablock ofwood weighs 12 kg and has relative density 0.6.1t is to be in water 0.9 of its volume
immersed. What weight ofa metal ofa metal is needed (a) Ifthe metal is on the top ofwood, (b) Ifthe
\
metal is attached below the wood? [RD ofmetal = 14]

Sol. (a) When the metal is on the top ofwood, .
M +m 1=0.9V a=0.9-P
w . Pw
[asv. PMJ w
m, =M [O.9=~-IJ
Pw
12 [0.9 -IJ
0.6
= 6 kg
,. ,
(b) When the metal is attached at the bottom ofwood,
(M + 1l1:z) = (0.9 Vw + V~ cr
or M+m= 0.9-+- [0 mass]

M' m2] crasp=-
[ Pw Pw vo~.
0
or In, [1-P:]=M[O.9= P: -IJ .

1
or m 0[1 __ J=12[0.9 -'IJ =6kg
2 14 0.6
14x6
or ~=O=~·~kg
b
c
,
I
'---
[i~~~~~~CL~~!~~ Ideal forScho/on
FLUIDl'dECHANICS {6/ r
l-.-'o
0
Pressure in Case ofAccelerating fluid:
(i) Liquid Placed in elevator:
flo
When elevator accelerates upward with acceleration llo then
pressure in the fluid, at depth 'hI may be given by, . --·······l.t Ir
h
p=hp [g+ao] .-.......,~
and force ofbuoyancy, B = meg + ao)

(n) Free surface ofliquid in horizontal acceleration:
ao
w~ mg
tanS=
g
PI - P2 = Ipao where PI and P2 are pressures at point 1 and 2.
lao
Then hl-~
g
/
,,
Ex. A vessel containing liquid accelerates to the right, with acceleration 'llo'. What is the angle made by the
free surface ofthe liquid with the horizontal?
(' Sol. The shaded element accelerates to the right.
\
~ PIllS - p2LlS mao = (pillS) ao ..... (1)
/'
\. PI = hlpg +Po; P2 = ~pg+ Po
or PI -P2 (hI -~) .... (2)
From (l),
(PI - P2) = p/ao
r ' or (h;
-~) pg= p/a
o
h1 -h 2 ao
or
I g
80
r'
" From (2),
c tanS (a/g)
i"
'z___
FLUID DYNAMICS:
c Streamline Flow:
The path taken by a particle in flowing fluid is called its line offlow. In the case ofsteady flow all the
"
\.. particles passing through a given point follow the same path and hence we have a unique line offlow
( passing through a given point which is also called streamlin~.
" Characteristics ofStreamline :
{.
' 1. A tangent at any point on the stream line gives the direction ofthe velocity ofthe fluid particle at that
point
(
2. Two steamIines never intersect each other.
(
Laminar flow:
( Ifthe liquid flows over a horizontal surface in the fonn oflayers ofdifferent velocitities, then the flow of
liquid is called Laminar flow. The particle ofone layer ~o not go to another laye. In generaI, Laminarflow
f: is a streamline flow.
C
Turbulent Flow:
(
The flow offluid in which velocity ofall particles crossing a given point is not same and the motio ofthe '
fluid becollles disorderly or irregular is called turbulent flow.
lIJ~~~!!~ CL~~!~~ FLUID MECHANICS [7J
c Ideal forSdIo/ars
RREYNOLD'S NUMBER:
According to Reynold, the critical velocity (vJ ofa liquid flowing through a long narrow tube is
(1) Directly proportional to the coefficient ofviscosity (11) ofthe liquid
(ii) Inversely proportional to the density p ofthe liquid and
(ill) Inversely proportional to the diameter (D) ofthe tube."
. 11 ." Rll vcPD

That IS Vc OC. pD "or Vc = pD orR = -11 ...... (1) ,..,
where R is the Reynold munber.

JfR <2000, the flow ofliquid is streamline or laminar. IfR> 3000, the flow is turbulent. IfRlies between
2000 and 3000, the flow is unstable and may change from streamline flow to turbulent flow.
al,v l
1. Equation ofContinuity
The equation ofcontinuity expresses the law ofconservation ofmass in fluid dynamics.
a1v 1 ~V2
In general av = constant. This is called equation ofcontinuity and states that as the area ofcross section
ofthe tube offlow becomes larger, the liquid's (fluid) speed becomes smaller and vice-versa.
2. Energy ofa liq uid

A liquid can posses three types ofenergies:
\ /
(i) Kinetic energy :

The energy possessed by a liquid due to its motion is called kinetic energy. The kinetic energy of i
'~ >'
1 ('
aliquidofmassmmovingwithspeedvis 2 mv2•
1
-mv2
... K.E. per urnt
. mass _2 =.!.V 2
- m 2
(Ii) Potential energy :
The potential energy ofa liquid ofmass m at a height h is m g h.
mgh .
:. P.E. per unit mass = - - =gh
m
(m) Pressure energy :
The energy possessed by a liquid by virtue ofits pressure is called pressure energy. f"
\...7
Consider a ves~l fitted with piston atone side (figure). Let this vessel is filled with a liquid Let
'A' be the area ofcross section ofthe piston and P be the pressure experienced by the liquid.
The force acting on the piston =PA 8

Ifdx be the distance moved by the piston, then wor~ done by the force =PA dx = PdV
where dV =Adx, volume ofthe liquid swept.
(.
v
fj~~~~A~~C~~~~! ldeolf...SdtokJrs
FLUIDMECHANICS [8J
c
lbis work done is equal to the pressure energy ofthe liquid.
Pressure energy ofliquid in volume dV = PdV.
Themass ofthe liquid having volume dV = pdY, p is the density ofthe liquid.
PdV' P
Presure energy
. per unit mass ofthe liquid = dV = -- .
p p
3. Bernoulli's Theorem:
It states that the sum ofpressure energy, kinetic eriergy and potential energy per unit mass or per unit
(
volume or per unit weight is always constan~ for an ideal (Le. incompressible and non-viscous) fluid
" havingstream-line flow.
P 1
i.e. p + 2 V2 + gh = constant.
P2
r
/
"
f
"
(
,
/
4. Application ofBemoulli's Theorem:
\ (0 13unsenburner
r Cn) Lift ofan airfoiL
',
(m) Spinning ofa ball (M"agnus effect) v
(iv) The sprayer.
(v) Aping-pong ball in anairjet
(
~'
(VI) Torricelli's theorem (speed ofefflux)
( At pont A, PI = P, VI = 0 and hi h
At point 13, P2 = P, V2 =v(speed ofeffiux) and h= 0
(
"
Using 13emoulli's theorem ~ + ghl + ~ vi

c = -
P2
+O'h
1 2
= - v wehave
p 0"''2 2 2'
p p 1
- +gh+O= ~ =0+ -v2
p p 2 => 2"1 V2

= gh hI
orv = ,,2gh
c
(
(j]!~~~~~ CL~~~~~ FLUlDMECHANICS [9J
c Ideal for Scholc,.
c
(vii) It is a gauge put on a :flowpipe to measurethe :flowofspeed ofa liquid (figure). Let the liquid of
density P be :flowing t11!0ugh a pipe ofarea ofcross section AI' Let ~ be the area ofcross
section at the throat and a manometer is attached as shown in the figure. Let VI and PI be the
velocity ofthe flowandpressure at point A, v2 and P2 be the corresponding quantities at pointB.
;, ~.'
{ ~ VI ~ ~!t!V"1-----
',AI ~~,
"I D • ---"'~ •
~@"Pm
Using Bernoulli's theorem:
PI 1 2 P2 1 2
- + gh + - v = - + oh + - v we get
p I 2 I P &""2 2 2'
PI 1 2 P2 1 2
-+gh+- v =-+gh+-v (since hi =h2 =h)
p 2 1 P 2 2
or (PI P 2) (2 2)
21 P v 2 -VI ....... (1)
According to continuity equation,A1vl = ~ v2
or V,~ (~J,
Substituting the value ofv2 in equation (1) we have
(P _ P ) = .!. P
I 2 2
[(~)2 vt _VI2J21 P v2 [(~J2 -1]
A2 I A2
{~-
-Since Al >~, therefore, PI > ~2
2A~(PI - P2 )
('-
2 2(P1 - P2 ) - /
or
v, ~ {( ~:r -IJ ~ p(A; -A~)
where (P1- P2) = Pm gh and h is thy difference in heights ofthe liquid leves in the two tubes.
2Pmgh
v=
{(~J -1]
I
The :flowrate (R) i.e., the volume ofthe liquid flowing per second is given by R =VIAl'
[i~~~~A~~-CL~~!~!
Idea/f,llScholars
FLUID MEClIANlCS flO)
(.J
(viiI) Duringwindstorrn,
The velocity ofairjust above the roofis large so according to Bernoulli's theorem, the pressure
just above the roof is less than pressure below the roof Due to this pressure difference an
upward force acts on the roof which is blown ofwithout damaging other parts ofthe house.
(lX) When a fast moving train corss a person standing near a railway trace, the personhas a tendensy
to fall towards the train. This is because a fast moving train produces large velocity in airbetween
person and the train and hence pressure decreases according to Bernoulli's theorem. Thus the
(
excess pressure on the other side pushes the person tQwards the train.
Ex. A bent tube is lowered into the stream as shown. The velocity ofthe stream relative to the tube, is equal
to V. The closed upper end ofthe tube is located at height ho' To what height h will the water jet spurt?
f'
\
('
\
("
\
f
Sol. Let tube's entrance be a depth 'y'belowthesurface. Take point 1 a!entryandpoint2atthe maximum
\
height ofthe fountain. This is a tube offlow. Now let's apply Bernoulli's theorem,
(
\ 1 1
PI + pgh I + -2 pv I2 P2 + pol.
0'':2
+ -2 pv22
(
Taking, hI =0, ~ = (y+ ho + h), VI =V, V2 = 0
( PI = Po + pgy, P2 = Po'
.
( SubstItuting, Po+ pgy+ pg x 0 + '21 , 1
pV2 = Po + pg (y+ ho + h) + 2 P X 02
/
C =>
1
2 pV2=pg(ho+h) or
(V
h=l2g
2
- ho
J ]
Ex. Water enters a house through a pipe with inlet diameter of 2.0 cm at an absolute pressure of
4.0 x lOS Pa(about4 atin).A 1.0 cm diameter pipe leads to the second floor bathroom 5.0 above.
When flow sneed at the inlet pipe is 1.6 mis, find the flow speed, pressure and volume flow rate in the
( bathroom.
Sol. Let point 1 and 2 be at the inlet pipe and the bathroom, then frpmcontinuity equation
c a)v) = ~V2 => v2= 6.0 mfs
( Now, applying Bemoulli's equation at the inlet(y=O) and at the bathroom(Y2 =5.0m).
1 2
c As p + -ov +agy = constant
2
(
Hence, p
2='21 P (2 2) .
V2 -VI -pg(Y2 -Y1)
~
Which gives P2 = 3.3 x lOs Pa
c
Thevolumeflowrate=~v2 =A)v) : (0.1)2 6=4.7 x 1O-4 m3/s.
[i!~~~.ArCblA~~~!
Ideal for Scholars
FLUID MECHANICS , [llJ
"
\.~,
Ex. . Water coming out the jet having across sectional area a, with a speed v strikes a stationary plate and
stops after strildng. Find the force exerted by the water jet on the plate.
Sol. The change ofmomentum ofwater in tinie "dt=0-pav2dt i =-pav 2dti where i isaunitvectorinthe
.direction ofthe velocity ofthe jet. The rate ofchange ofmomentum ofwaterjet = -pav 2 i
Thus the force exerted on the water jet by the plate = _pv 2 i
Thus the force exerted on the water jet by the plate = -PGlV 2 i
The force exerted on the plate by the water jet = pav i.

2
Ex. Water flows in a horizontal tube as shown in figure. The pressure of water changes by 600N/m2
betwen A and B where the areas of cross-section are 30cm2 and 15 cm2 respectivley. Find the
rate of flow of water thi:ough the tube.
A ~__~~=-
-- ----
---------~~----~~
Sol. Let the velocity at A = v A and that at B = vB'
VB 30 cm 2
By the equation of continuity, -v = 15 - =2
" " A cm r-"'.

By Bernoulli's equation,
1 2 _ 1 2
PA + "2 pv A - PB + "2 pv B
113 2
or, PA - PB = 2 P (2vA)2- "2pv2A = 2 pv A
or, 600~2 = ~(1 000 kg3 )vi \ ..

m 2 "m
or, vA = .JOAm 2 15 2 = 0;63m 15.
The rate of flow = (30 cm2) (0.63 mls)
= 1890 cm3/s. "
Ex. A siphon tube is used to remove liquid from ~ container as shown in fig. In order to operate the /
siphon tube, it must initially be filled with the liquid.

c
H ()
Datum I~ II I
h
B
y
(I) Determine the speed of the liquid through the siphon.

(n) Determine the pressure at the point C.
Sol. (I) Applying Bernoulli's equation at points A and D, we get
PA + ~pv2A + PgyA = PD + ~pv2D + P~D

Assuming datum for potential energy at the free surface, we have
yA = 0; YD = - (h + y);
c
PA = PD = Patm vi I>:; 0; VI;> = Y
1
Patm + 0 + 0 = Patm + "2 pv2 = pg [-(h+y)]
[I]~~~~A~~ C~,~~!~! . FLUlDMEC1lANICS /12J

Idealfor S<hcIors
c
? ~~<
'l/.
or V::: .J2g(h+y)
(n) Applying Bernoulli's equation at A and C, we get
1 1
PA + 2"PV2A +PgyA=PC+ 2 p v2c+pgyc
Here, Yc = + H; vc::::: V (according to the continuity equation)
. . 1
Patm + 0 + 0 = PC + 2" pv2 + pgh
or, Patm = Pc + pg (h + y) + pgh
or, Pc = Patm - pg (h + H + y)
( Ex. A liquid flows out of a broad vessel through a narrow vertical pipe. How are the pressure and the
velocity ofthe liquid in the pipe distributed when the height ofthe liquid level in the vessel is H
from the lower end of the pipe and the length of the pipe is h ?
Sol. Let us consider three points 1,2,3 in the flow ofwater. The positions of the points are as shown
in the figure.
=-;1
~
IIII
xlIII
1111 h
\. ! 11.-211
1111
I
I It I
\
Applying Bernoulli's theorem to points 1, 2 and 3
(
\
Po 1 2 p2 1 2 .
-+-V1 +gH =-+-V2 +g(h-x)
I
\
p 2 p 2
( - Po +J..V~ +0
- p 2 .
( By continuity equation
AIvI = A2 v2 = A 2v 3
c Since Al »A2 , vI is negligible and
v2 = v3 = v (say)
c
,{
Po +gH= P2 +J.. v 2+g(h-X)
'- p p 2
( = Po +J.. V2
P 2
c v = .J2gH (1)
and Po +gH = P2 +gH+g(h':"x)

p p
=> Po::::: P2 + pg (h x)
,..
{
=> P1 = Po - pg (h-x) (n) .
(7
Thus prssure varies with distance from the upper end of the pipe according to equation (ii) and
C velocity is ~ constant and is given by (i).
I];]BANSAL C •____ FLUID MECHA.NICS 113J

(' ~PR'VATE
,,-. L.tMITE.O
•• ., Scholars
",
(!
",-.
Ex. Water is flowing through two horizontal pipes ofdifferent diameters which are conn~ted together.
In the first pipe the speed of water is 4 rn/s and t1;le pressure is 2.0 x 104 N/m2. Calculate the
speed and pressure of water in the second pipe. The diameters of the pipes are 3 cm and 6 cm
respectively.
Sol. IfA is the area of cross-section of a pipe at a point and \) is the velocity of flow of water at that
point, then by the principle of continuitY, we have
AU = Constant
or A}\)I=A2\)2
or (1Crl }Ui = (1Cri }02
or \)2 (;:J \)1
Here rl = 1.5 cm 1.5 x 10-2 m, r2 =3 cm =3 x 10-2 m and \)1 = 4rn/s

2
1.5x 10-2 .
\)2 = ( 3 x 10-2 ) x 4 = 1 rn/s
1 2 1 2 122
Bernoulli's theorem: Pi + '2 POi P2 +'2P02 P2 = Pi +'2 P(01 -02)
for water p = 1 x 103 kg/m 3, \)1 = 4 rn/s,

\)2 = 1 rn/s and PI = 2.0 x 104'N/m2
P2 = (2.0 x 104) +'21 x (lxI03) x (42 _12)

104) + (0.75 x 104) = 2.75 x 104 N/m2
= (2.0 x
Ex. The pressure difference between two points along a horizontal pipe, through which water is flowing,
is l.4cm of mercury. If due to non-uniform cross-section, the speed of flow of water at the point
of greater cross-secti0n is 60 crn/s, calculate the speed at the other point.
F'-...,
Sol. By Bernoulli's theorem·~
1 2 1 2
PI + '2 P01 = P2 + '2P02
( .,
,./
2(P1 P2 )
or O~ -o~ = P
2
The speed of water will be greater at the place when the cross-section is smaller.:. o~ = P
{PI - Pz} +o~

Here PI - P2 = 1.4 cm of mercury
= (l.4 x 10-2 m) x (13.1) x 103 kg/m3)
x (9.8 N/kg)
= 1.866 x 103 N/m2,
p = Ix 103 kg/m3, \)1 = 60 cmlsec = 0.6 mlsec.
2 .
o~ = (1x10 3 ) x (1.866 x 10 )
3 + (0.6)3
= 4.092
or \)2 = 2.023 rn/sec
(j]~~':'~1!~CM~!~!
• 1deD1f0t SdIo/a,.
FLUIDMECHAN1CS /14)
c
Ex. Water flows into a horizontal pipe whose one end is closed with a valve and the reading of a
pressure gauge attached to the pipe is3 x 105 N/m2 . This reading of the pressure gauge falls to
1 x 105 N/m 2 when the valve is opened. Calculate the speed of water flowing into the pipe.
Sol. According to Bernoulli's theorem :
1 2 1· 2
PI + 2'Pu 1 = P2 +'2'PU 2
"
or 1 2
-P[U2 2
-U1] = P I - P2
2
Here \)1 = 0 (the value is initially closed, and so the velocity of water is zero)
2 2
U2=p (PI - P 2)
2
/
U~ =--3 X (3 x 105 - lxlO5)
"
r- ,
1x10
\ =2 x 2 xl 02 = 400
( \)2 = 20 mls
Ex. A horizontal tube has different cross-sectional areas at point A and B. The diameter ofA is 4 em
(
\
and that of B is 2 cm. Two manometer limbs are attached at A and B. When a liquid of density
I 0.8 g/cm3 flows through the tube, the pressure-difference between the limbs of the manometer is
\
8 cm. Calculate the rate of flow of the liquid in the tube. (g = 980 cmls2)
(
\
I
2gh
( Sol. Q = Al A2
Af-A~
\
(
Here Al = n~l n x (~r = 4n cm2,
(
A2 = nr} = n x (2'2)2 = n cm2, _
g = 980 cmlsee2. h = 8 cm
2x980x8
2x980x8
r
'---- Q = 4n x n 11 (4n)2 _(n)2 = 4n 15
= 4 x 3.14 x 32.3 = 406 cm3/sec
c Ex:. Water tank has a hole in its wall at a distance of 10m below the free surface of water. The
diameter of the hole is 2 mm. Compute the velocity ofefflux of water from the hole and the rate
( of flow of water.
{' Sol. The velocity of efflux ofwater is

'--
v == J2gh = ~2x9.8m/s2 x10m = 14 mls The rate of flow ofwateris = A x v = rcr2 xv
3.14 x (1 xl0-3 m)2 x 14 mlsec
= 4.4 x 10-5 m 3/sec
(
f,
\..
r~
/
\--
tIJ!~\c~~~ ldealfor SchoialS
FLUID MECiIANICS [151
r
'l.
VISCOSITY:
When a solid body slides over another solid body, a frictional force begins that between them. This force
opposes the relative motion ofthe bodies. Similarly, when a layerofa lquid slides over another layer of
the same liquid, a :frictional-force acts between them :which opposes the relative motion between the
layers. 11lls force is called 'internal frictional-force'
Velocity Gradient and Coefficient ofViscosity : / --,
The property ofa liquid by virtue ofwhich'an opposing force (internal frrction) comes into play when
ever there is a relative motionbetweenthe different layers ofthe liquid is called viscosity. Consider a flow
ofa liquid over the horizontal solid surface as shown in figure. Let as consider two layers AB and CD
v
moving with velocities v and + dv at a distance x and (x + dx) respectively from the fixed solid
surface.
According to Newton, the viscous drag or back ward force (F) betwen these layers depends.
(i) Directly proportional to the area (A) ofthe layer and (ii) directly proportional to the velocity gradient
( ::) between the layers.
dv dv
c£ V'+f ~~fdX
A
~
II
(
\
"
i.e. F oc A dx or F = -11 A dx ...(1) .. x , «
;
\
11 is called coefficient ofviscosity. Negative sign shows that the direction IIII/III//;;m7ll7lnnJ MJi~
ofviscous drag (F) is just opposite to the direction ofthe motion ofthe
liquid
\ ,
Similarities and Differences between viscosity and slid friction similarities:
VIscosity and solid friction are similar as
1. Both oppose relative motion. Whereas viscosity opposes the relative motion between two adjacent
< liquid layers, solid friction opposes the relative motion between two solid layers.
('
2. Both come into play, whenever there is relative motion between layers ofliquid or solid surfaces as
thecase may be.
3. Both are due to molecular attractions.

Effect oftemperature on the viscosity:
The viscosity ofliquids decrease with inc~ease in temperature and increase with the decrease in tem
1
perature. Thatis, 11 oc -ff' On the otherhand, the value ofviscosity ofgases increases with the increase
in temperature and vice-versa. That is, 11 ex:: -ff .

Stoke's Law:
Stokes proved that the viscous drag (F) on a spherical body ofradius r moving with velocity v in a fluid
ofviscosity 11 is given by' F = 61t 11 rv. This fs called Stoke's law.
,~<
Terminal velocity : v
When a body is dropped in a viscous fluid, it is first accelerated and then its acceleration becomes zero
and it attains a constant velocity called tenninal velocity.
[16J
[jJ~~~~A~~ CL~~~~! Ideal {or SdtoIars
FLUID JJfECllANICS
Calculation ofTerminal Velocity :
Let us consider a small ball, whose radius is r and density is p, falling freely in a liquid (or gas), whose
density is cr and coefficient ofviscosity 11. When it attains a tenninal velocity v. It is subjected to two
forces:
(i) effective force acting downward
4._~
=V(p-cr) g='3m- (p-cr)g,
, (ii) viscous force acting upward

\
=61t11rv
Since the ball is moving with a constant velocity v Le., ther is no acceleration in it, the net force actin on
it must be zero.
That is
4 v!
6n 11 rv = 3" p i' (p - cr)g
(
\
4/31tl"](p-o)g
2 r2(p-cr)g
(
\ or v =--...::!'---.....:.=
9 11
(
\ Thus, tenninal velocity ofthe ball is directly proportional to the squareofits radius.
( Ex. A metal plate 0.04 m2 in area is lying on liquid'layerofthickness 10-3 mandco-efficient ofviscosity 140
" poise. Calculate the horizontal force neededto move the plate with a speed of0.040 mfs.
(
"
Sol. Areaofthe plate, A =0.04 m2
Thickness, ~x = 10-3 m
(
~ is the distance ofthe free surface with respect to the fixed surface.
,
\
VieOCI t::..v= -
I 'tygradient, - 0.04
-3= 40-
s
1
/ ~ 10-
"
-
Co-efficient ofviscosity, 11 = 14 kg ms-1 S-I

( Let F be the required force.
c ~v
Then, F=11n -=22.4N
~
C Ex. A cylindrical vessel of(radius r) (~ontaining a liquid spins continously
C with constant angular velocity 0) as shown in the figure. Shown that the
pressure at a radial distance r from the axis is'

(
1
( p = Po + '2 rro2f2 ,
(
where Po =atmospheric pressure.
(" Sol. Consider a partice1 ofthe fluid at a point P(x, y) w.r.t. the corrdinate axes as shown in the figure. The
force acting on This particle are mro2x (the centrifugal force) and the weight mg.
(
The net force F acting at P should be perpendicular to the free surface, so that
~ ..
mro 2 x ro 2 x
( tan8=--=
mg g
(
(
f4jlBANSAf
~
CUtSSES
PR'fVATE .... 'MJTED
FLUID MECHANICS [17J
/deQI for Scholars
t'-..
dy moo 2
or, -=-- [.; slope = tan 9 =: d Y]
dx g dx
00 x2
or, y= 2g
F,
2
ro
This equation represents a parabola; for which the elevation from origin at x =r will be Y= -2- r2
. g
pro 2r2
.
Pressure P (r) . Po + pgy = Po + - 2
Ex. The viscous force acting en a solid ball moving in air with tenninaI velocity v is directly propertional
to
(A) JV (B) v . (C) lIJV (D) v2
Sol. Since F = 6 1t 11 r v so F a:: v
Ex. The velocity of a small ball of mass M and density dI, whcim dropped in a container filled wHh
glycerine becomes constant after some time. If the density of glycerine is d 2, then find viscous
force acting on the ball. .
M
. Sol. Since Effective force = V (d 1 - d 2) g but d
1
= V
(
so effective force will be Mg ( 1 - ~: J

Ex. A drop of water of radius 0.0015 mm is falling in air. It the co-efficient of viscosity of air is
1.8 xlO-5 kg m-1s-l. What will be the terminal velocity of the drop, density of air can be
neglected. ,'
\.
2 r2 (p-cr) 9
Sol.. VT =9 given r = 0.0015 mm, p = 103 kg m-3, cr 0,
11
11 ,;" 1.8 x 10-5 kg m-1s- f
. [
2x 15x10- I x1C 3 x9 8
4 ')2 c
1000 ) .
VT = 9x1.8x10-5
VT = 2.72 x 10-4 m/sec.

Ex. The relative velocity between two layers of water is 8.0 cm/s. If the perpendicular distance
.between the layers is 0.1 cm, find the velocity gradient.
/.1v
c
-Bol. . VelocitY gradient /.1;
Here Avx (relative velocity between layers) = 8.0 cm/s and distance between the layers
6
Az = 0.1 cm
r"
. . 8.0 em's V
Veiccity gradIent = 0.1em 80 per sec
c
[i't~~~~CL~~!!! /IJeaf {or Sella/DIS
c
c
Ex. There is a 1 mm thick layer ofglycerine between. ~ flat plate ofarea 100 cm2 and a big plate. If the
coefficient ofviscosity ofglycerine is 1.0 kg(m-s), then how much force is required to move the plate
with a velocity of 7 cmls ?
Sol. To move the plate with a constant velocity, the necessary force will be equal to the viscosity force
ilVx
F(say). Now F == 1)A ilZ '
Here 1) = 1.0 kg/(m-s), A = 100 cm2 = 10-2 m2,

2
1.0x10-2x(7x10-2)
3
7 x 1<>-' mlsec and I1z = 1 mm = 1<>-' m'.. F =
I1vx = 10-3 = 0. 7 N
Ex. A drop of water of radius 0.0015 mm is falling in air. if the coefficient of viscosity of air is
1.8 x 10-5 kg/m-s), what will be the terminal velocity of the drop?
(Density of water = 1.0 x 103 kg/m 3 and g = 9.8 Nlkg,) Density of air can be neglected,
Sol. By Stokes' law, the terminal velocity of a water drop of radius r is given by
r'
v = r2(p-cr)g ,
2 ---'''---..:....=.
9 "
/
\, ,
Here p density of water, cr is the density of air and 11 the coefficient of viscosity of air. Here cr
is negligible and r 0.0015 mm 1.5 x 10-3 mm = 1.5 x 10-6 m . Substituting the values:
(
\.
2 (1.5x1O-<if(1.0x10 3 )x9.8
/'
v= 9' X 1.8x10-5
'"
/
\.
= 2.72 x 10--4 m/s
(
Ex. A metallic sphere of radius 1.0 x 10-3 m and density 1.0 x 104 kg/m3 enters a tank of water,
\
after a free fall through a distance of h in the earth's gravitational field. Ifits velocity remains
,.
\.
unchanged after entering water, determine the value of h. Given: coefficient ofviscosity of water
.0 x 10-3 N-s/m 2 , g = 10 m/s 2 and density of water = 1.0 x 103 kg/m3. .
(
\. Sol. The velocity attained by the sphere in falling fr~ly from a height h is
(
\, ' v =.j2gh ............. (i)
This is the terminal velocity ofthe sphere in water. Hence by Stokes' law, we have
( 2 r2(p-cr)g
v= 9 T)
(.
,'" Where r is the radius ofthe sphere, p is the density ofthe material of the sphere, cr (=1.0 x 103
( kg/m 3) is the density of water and 11 is coefficient of viscosity of water
f
',
('
2 x(1.0 X 10-3)2(1.0x104 -1.0 x103)x10
v= 9x{1.0x10-3)
"
f
" = 20 mls
2
' (') h h v
fr om eq, 1 we ave = 2g
20 x 20
=, 2x10 = 20 m
.
(
"-
I!~~~A~~CL~~!~!
ldealfot SdtoIafS
FLUID MECHANICS {19J
'
(
'L
. EL An air bubble of radius 1. cm rises up in a liquid column with terminal velocity of
0.21 cm/s. If the density ofliquid be 1.47 x 103 kg/m3, then calculate the coefficient ofviscosity
ofthe liquid. Density of air is negligible. (g 9.8 m/s2)
Sol. The weight ofthe air bubble is negligible. Two forces act upon it : (i) upthrust ofthe liqui~ ~ 1tr3 og,
where r is the radius of the bubble and C1 is the density ofthe liquid and (ii) viscous force 61C11rv.
Since the bubble has acquired terminal velocity,
4
Therefore 61C11rv 1tr3ag
3
2 r209
or 11 = 9 v
Substituting the value

2 (1 x 10-2 m)2 (1.47 x 10 3 kg/m 3 )x9.8m/s2 )
11 =9 . O.21x10-2 m/s
1.52 x 102 kg/(m-s)
::::: 1.52 x 103 poise
SURFACE TENSION:
Surface tension is a property ofliquid at rest by virtue of
which a liquid surface gets contracted to a minimum area and behaves
like a stretched membrane. Imaginary
Surface tension ofliquid is meausured by force peronit length on either Line

side ofany imaginary line dra~ tengentitally over the liquid surface, ~:=::§~
force being nonna! to the imaginmy line as shown in the figure.
i.e. surface tension
(T) = total force on either of theimginary line (F)
. Length of the line (£)

( "
' .. ~
Units ofsurface tension ~

In C.G.S. system the unit ofsurface tension is dyne/cm (dyne em-I) and SI system its units is Nm-i
Explanation of some observed phenomena:
1. Lead ball are spherical in shape.
o
2. Rain drops and a globule ofmercury placed on glass pate are spherical.
3. Hiar ofa shaving brush/painting brush, when dipped in water spread out, but as soon as it is taken out.
Its hair stick together. .
4. A greased needle placed gently on the free surface ofwater in a beaker does not sink.
5. Similarly,insects can walk on the free surface ofwater:without drowining.
6. Bits ofCamphor gum move irregularly when placed on water surface.
Surface Energy :
We know that the molecules on the liquid surface experience net downward force. So to bring amolecle
from the interior ofthe liquid to the free suCrace, some work is required to' be done against the intermo
lecular force ofattraction, which will be stored as potential energy ofthe molecules on the su:..face. The
. potential energy ofsurface molecules per unit area ofthe curface is called surface energy. Unit ofsurface
energy is erg cm-2 in C.G.S. system and Jm-2 in S1 system. Dimensional formula ofsurface energy is
[ML0]'-2] surface energy depends on number ofsurfaces e.g. a liquid drop is having one liquid air
surface while bubble is having two liquid air surface.
[20J
[j}~~~~~~ CL~~!~!
Ideal Sc/u)lors
(or
FLUIDMECHANICS {
v
,
EXCESS PRESSURE INSIDEALIQID DROP AND A BUBBLE :
Inside a bubble:
Consider a soap bubble ofradius r. Let p be the pressure
insdie the bubble and Pa outside. Theexcesspressure=P-Hf
Imagine the bubble broken into two halves, and consider
one halfofit"as shown in fig. Since there are two surfaces,
inner and outer, so the force due to surface tension is
F = surface tension x length =T x 2 (circumference ofthe bubble) = T x 2 (2T n r) ...(1 )

The excess pressure (p -- pa) acts on a cross-sectional area p r, so the force due to excess pressure
.
is
=> F = (p - pA) m2 ... (2)
The surface tension force given by equation (1) must balence the force due to excess pressure given by
equation (2) to maintain the equilibrium. i.e.
(p - Pa)nr = T x 2 (2m)
(
I'
4T
\, or (p - Pa) = r = Pexcess
f
\. above expression can also be obtained by equation ofexcess pressure ofcurve by putting R J =~.
( inside the drop!
{ ill a drop, there is only one surface and hece excess pressure can be written as
'-.
(' 2T
\ (n-p)=
\..t' aJ r =pexcess
\
Inside air bubble in a liquid:
f'
,
(P-Pa) = 2T
Pexcess
r
~
I
t! A charged bubble:
\.,
Ifbubble is charged, its' radius increases.
l'
\ ..
Bubble has pressure excess due to charge too.
c 4T
fuitiallypressureinsidethe bubble = Pa +-;
(
",.
4T 0"2
(' For charge bubble, pressure inside =Pa + r. '2 E •
\. 2 0
( where cr surface is surface charge density. Taking temperature remains constant then from boyle's law
( 2
4TJ 4 3 =[ Pa +-----
4T cr ]4
( Pa +'Ii- -prj
3 r2
-pr23
2 Eo 3
From above expression the radius ofcharged drop may be calculated. It can conclude that radius of
E'
charged bubble increases, i.e. r2 :> II
\,
f
,,-,
f [i]~!~~A~~CL~~~~! FLUID MECHANICS [21J
". Ideal (01 SdroIIm
(
.'-....
Excess of Pressure Inside a Curved Surface:.
Plane Surface: • T
• T
..
Ifthe surface ofthe liquid is plane [as shown in figure], the molecule on
the liquid surface is attracted equally inall directions. Theresultant force
due to surface tension is zero.
The pressure, therefore, onthe liquid surface is nonnaI.
Plane Surface
Concave Surface:
Resultant
Ifthe surface is concave upwards [as shown in fIgure], there will be . T t T
upwards resultant force due to surface tension acting ont he molecule.
Since the molecule on the surface is in equilibrium, there must be an
:::::::: B ::::::::
excess ofpressure on the concave side in the downward direction to
2T
balance the resultant force ofsurface tensi.on pA - PB = -; /
Concave Surface \ .
Convex Surface: A
Ifthe surface is convex [as shoWn in fIgure], the resultant force due to
•
surface tension acts in the downward direction. Since the molecule on
the surface are in equilibrium, there must be an excess ofpressur~ on the

::::1\-:: i- ResiJtaiii:.
..... - .........
::::::_._ B ::::::
. concave sideofthe surface acting in the upward directionto balance the
downward resultant force ofsurface tension, Hence there is always an
excess ofpressure on cOlicave side ofa curved surface over that on the Concave Surface
2T
convex side. PB-PA =-;-
Capllary Rise:
The force of cohesion:
<.
The force ofattraction between the molect¥es ofthe same substance is called cohesion.
In case ofsolids, the force ofcohesion is vety large and due to this solids have definite shape and size.
.on the otherhand, the force ofcohesion in case ofliquids is weak:erthan that ofsolids. Hence liquids do
not have definite shape but hav~ defInite volume. The force ofcohesion is negligible in case ofgases.
Because ofthis fact, gases have neither fixed shape nor volume.
Example:
. (i) Two drops ofa liquid coalesce into one when brought in mutual contact becuase ofthe cohesive force.
(11) It is difficult to separate two sticky pates ofglass wetted with water because a large force has to be
applied against the cohesive force between the molecules ofwater.
(IiI) Itis vety difficult to break a drop ofmercUty into small droplets because oflarge cohesive force between
mercUtymolecules. .
Force ofAdhesion :
The force ofattraction between molecules ofdifferent'substances is called adhesion. (, ,
'--'
Example
(i) Adhesive force enables us to write on the black board with a chalk.
(Ii) Adhesive force helps us to write on the paper with ink:.
(IiI) Large force ofadhesion between cement and bricks helps us in construction work. o
(IV) Due to force ofadhesive, water wets the glass plate.

(v) Fevicol and gum are used in gluing two surfaces together becuase ofadhesive force.
[i~~~~A~~C~~~!~!
Ideal"" Sc/Jolo,..
FLUIDMECHAMCS [22J
Angle ofcontact: "
The angle which the tangent to the liquid surface at the point ofcontact makes with the solid surface
inside the liquid is called angle ofcontact. Those liquids which wet the walls ofthe container(say in case
ofwater and glass) have meniscus concave upwards and their value ofangle ofcontact is less than 90°
(also called acute angle), However, tho.:;e liquids which don't wet the walls ofthe container(say in case
ofmercmy and glass) have meniscus convex npwards and their value ofangle ofcontactis greaterthan
90° (also called obtuse angle), The aDgIe ofcontact ofmercmy with glass about 140°, whereas the angle
/'-
ofcontact ofwater with glass is about 80 , But, for pure water, then angle ofcontact S with glass is taken
as 0°,
Glass Glass
,
\
Point of Point of
:.!::
conact conact
( Water Mercury
Capillarity :
A glass tube ofvery fine bore throughout the length ofthe tube is called capillary tube, Ifthe capillary
tube is dipped in water, the water wets the inner side ofthe tube and rises in it{shown in figure a]. Ifthe
.:
same capillary tube is dipped in the mercury, then the mercury is depressed [shown in figure b]. The
~ phenomenonn ofrise or fall ofliquids in a capillary tube is called capillarity
J&
water
~
MerCUryW
( _---. . ~
...... .... .......
......... ..
.~~~~H!~~~mmff
.......................
.. .......... ........ ............
................... ...........
.............................." -
.,
............................
........................................
"' ............................
" (a) (b)

/
\ - Capillary Rise (Height of a Liquid in a Capillary Tube) Ascent Formula:
Consider the liquid w~jch wets the wallsofthe tube, fonns concave meniscus shown in figure. Consider
(
\ a capillary tube ofradius r dipped in a liquid ofsurface tension T and desnity p. Let h be the height
through which tbe liqUid rises in the"tube. Letp be the pressure on the concave side ofthe meniscus and
c pa be the pressure on the convex side, ofthe

meniscus. The excess pressure (p pa) is given by
(' 2T
(P-Pa) = R
(.
( Where R is the radius ofthe meniscus. Due to this excess pressure, the
" liquid will rise in the capillarytube till it becomes equal to the hYdrostatic
( pressure hpg. Thus in equilibrium state.
( 2T
Excess pressure = Hydrostatic pressure or R = hpg
(
Let S be the angle ofcontact and r be the radius ofthe capillary tube shown in the figure.
(
"-- " OC - "·r 2TcosS
From ilOAC - = cosS or R :::: - - :=;. h :::: - -
, OA cosS rpg
This expression is called Ascent fonnula.
(
f
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Scholors
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FLUIDMECHANICS [231
!
'L
Ex. A meniscus drop ofradius 1cm is sprayed into 106 droplets ofequal size. Calculate the energy expended
ifsurface tension ofmercury is 435 x 10-5 N/m.
Sol. Energy expended will be the work done against the increases in surface area, i.e.
nC4nr2) - 4nR2
E=W=TAS
r/-"
== T.4n(nr2- R2)
But the total volmne remains constant -,
4 4 R
I.e. -1tR3 =n-1tt or r=-W
3 3 ~)
E == 41tR2T (n l13 -1) = 4 x 3.14 x (1 x lO-2)2 x 435 x 10-3 (102 -1)

= 54.1 x 10-3 J
Ex. Under isothermal condition two soap bubbles ofradii a and b coalesce to from a single bubble ofradius ,-,
c.lfthe external pressure is Po show that surface tension,
3 3
T- po(c _a 3 _b )
- 4(a 2 +b 2 _c 3)
Sol. As excess pressure for a soap bubble is (4T/r) and exteranal pressure Po.
Pi = Po + (4T Ir)
so Pa == [Po + :T]. Pb [Po + :T] and Pe == [Po + :T] ...(i)
4 4 4
and V = -1ta 3 V = -1tb 3 and V == -1tC 3 ...(li)
a 3 ' b 3 e 3
Now as mass is conserved ,
I.e.,
aaVa
- -+-
Rta
abVb -aeVe
-=
RTb
--
RTc
[aspy =".IRT,I.e.,~=
. PV]
;RT
As temp, is constant, i.e., Ta = Tb == Tc ; the above expression reduces to
Pa Va + PbVb = PeVc
Which in the light ofEqn. (i) and (li) becomes
[po + :rI~1ta3J+[po+ :rI~1tb3J=[Po+ 4;I~1tC3J

)+',7$
i.e., 4T (a2+b2 -c2) = po(c3-a3-b3) ..:srt} ..J
3 3 3
\: tV ~" 1-y"'V
T= Po(c a _b )
i.e., 4(a 2 +b 2 _c 2 ) •
[24].
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. FLUIDMECHANICS-
{ ,
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EXERCISE-I
Q.l A unifonnaly tapering vessel shown in Fig. is filled with liquid ofdensity 900 kg/m3• The force that
acts on the base of the vessel due to liquid is (take g = 10 m/s2)
AREA ;, 1Q-3 m2
"
f'
AREA =2 x 1o-3m2
(A) 3.6 N (B) 7.2 N (C) 9.0 N (D) 12.6 N

Q.2 Two stretched membranes of areas 2 and 3 m2 are placed in a liquid at the same depth. The ratio
of the pressure on them is
(A) 1 : 1 (B) 2 : 3 (C) J2 : .J3 (D) 22 : 3 2
Q.3 The height of a barometer filled with a liquid of density 3.4 glcc under normal condition is
approximately
(
\
(A) 8 m (B) 5 m (C) 3 m (D) 1 m
Q.4 If 1 g of substance ofrea1tive density 2 and 4g ofanother substance ofrelative density 3 are mixed
together, then the relative density ofthe mixture is
(A) 2.4 (B) 2.5 (C) 2.7 (D) 2.8
Q.5 Atmospheric pressure shown by a barometer placed in a moving lift will be
\.
(A) greater if lift descends with acceleration. (B) less if lift descends with retardation
(
(C) greater if lift descends with retardation (D) less iflift ascends with constant velocity
Q.6 The value of g at a place decreases by 2%. The barometric height of mercury
(A) Increases by 2% (B) Decre~ses by 2%
(C) Remains unchanged (D) Sometimes increases and sometimes decreases
(
'-
Q.7 Three identical vessels are filled with equru masses of three different liquids A, Band
( C (pA > PB > pd· The pressure at the base will be
(A) Equal ill all vessels (B) Maximum in vessel A
(C) Maximum in vessel B (D) Maximum in vessel C
(' Q.8 Pressure applied to an enclosed fluid is transmitted undimihished to every portion ofthe fluid and
" the walls ofthe containing vessel. This law was first formulated by
(A) Bernoulli (B) Archimedes {C) Boyle (D) Pascal
Q.9 A piston of cross-section area 100 cm is used in a hydraulic press to exert a force of 107 dynes
2
(
011 the water. The cross-sectional area of the other piston which supports an object having a mass
i 2000 kg. is '
\. 2
(A) 100 cm (B) 109cm2 4
(C) 2 x 10 cm 2 IO
(D) 2 x 10 cm 2
£'
\. Q.I0 A blQck of ice floats on a liquid ofdensity lo2in a beaker then level ofliqUid when ice completely
melt
( (A) Remains same (B) rises (C) Lowers (D) (A), (B) or (C)
Q.l1 !ftwo liquids of same masses but densities PI and P2 respectively are mixed, then density of
mixture is given by
(A) P = PI +P2 PI +P2 2PIP2_ PIP2

f 2 (B) P= 2PIP2 (C) P = PI+P2 (D) P= PI +P2
\,..
,
\..
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FLUID MECHANICS '{25J
Q.12 If two liquids of same volume but different densities and are mixed, then density of mixture
is given by
(A) P = PI +P2 CB) P = PI +P2 (C) P = 2PIP2 (D) P = PIP2
2 2PIP2 PI +P2 PI +P2
Q.13 Three liquids ofdensities d, 2d and 3d ar~ mixed in equal volumes. Then the density ofthe mixture
is
(A) d (B) 2d (C) 3d (D) 5d

Q .14 A boy is carrying a bucket of ~ter in one hand and a piece ofplaster in the other. After transfering
the plaster piece to the bucket (in which it floats) the boy will carry
(A) same load as before
(B) more load than before
(C) less load than before
(D) either less or more load, depending on the density of the pla~ter
Q.15 A sample of metal weighs 210 g in air, 140 g in water and i20 g in an unknown liquid. Then
(A) the density of the metal is 3 g/cm3
(B) The density of the metal is 7 g/cm3 .
(C) density ofthe metal is 4 times the density of unknown liquid
(D) the metal still float in water
Q.16 A boat having a length of 3 metres and breadth 2 metres is floating on a lake. The boat sinks by
one cm when a man gets on it. The maSs of the man is

(A) 60 kg (B) 62 kg (C) 72 kg CD) 128 kg .
Q.17 The density ofice is 0.9 g/c.c. and that ofsea water is·t.l g/c.c. An ice berg ofvolume Vis floating
in sea water. The fraction of ice berg above water level is - ,
'. .
(A) 1111 (B) 2/11 (C) 3/11· . (D) 4/11 .
Q .18 A uniform rod ofdensity P is placed in a wide tank containing a liquid of density po(Po > p) . The
depth of liquid in the tank. is halfthe length ofthe rod. The rod is ill equilibrium, with its lower end
resting on the bottom of the tank. In this position the rod makes an angle a with the horizontal , ..
/
(./
(A) sina = !...~Po 1P (B) sin a =!.... Po (C) sin a= ~pl Po CD) sina = Polp
2 2 P
Q.19 A cubical block ofwood to em on a side floats at the interface between oil and water with its
lower swface horizontal and 4 cm below the interface. The density of oil is 0.6 gem-I. The mass
'ofblock is
e
(A) 706 g (B) 607 g (C) 760 g (D) 670 g o
c
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FLUID MECHANICS (
'-./
.
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Q.20 A hollow sphere of volume V is floating on water surface with half immersed in it. What should
be the minimum volume of water poured inside the sphere so that the sphere now sinks into the
water
(A) VI2 (B) V/3 (C) V/4 (D) V
Q.21 Water is flowing through a cylindricB:l pipe of cross- section area 0.09 1t m 2 at a speed of 1.0 mI
s. Ifthe diruneter of the pipe is halved, then find the speed of flow of water through it
(A) 4.0 mls (B) 6.0 mls 2 (C) 4.0 mls2 (D) 6.0 mls
Q.22 Water is flowing through a horizontal tube of nonuniform cross- section. At a place the radius
ofthe tube is 0.5 cm and the velocity ofwater there is 20 cmls. What will be the velocity at another
7
, place where the r~dius of the tube is 1.0 cm?
( (A) 3 cmls (B) 7 cmls (C) 5 cmls (D) 0.5 cmls
Q.23 Water is flowing in a horizontal pipe ofnon- uniform area of cross- section. The velocity ?f water
at a place, where the radius ofpipe is 0.01 m is 25 mls. What will be the velocity of water where
the radius of pipe is 0.02 111?
(A) 7.25 mls (B) 6.75 mls (C) 6.25 mls (D) None of these
Q.24 Water is flowing through a horizontal pipe of nonuniform cross- section. The speed of water is
30 cmls at a place where pressure is~ 10 cm(ofwater). Calculate the speed of water at the other
(
place where the pressure is half ofthat of the first place-
I~
,~
(A) 100.4 cmls (B) 101.4 cmls (C) 102.4 cmls (D) 103.4 cmls
Q.25 Water enters a horizontal pipe ofnon- uniform cross-section with a velocity of 0.5 wJs and leaves
(
the other end with a velocity of 0.7 mls. The pressure of water at the first end is
'" 103 N/m 2. Calculate pressure at the other end. (Density of water 1.0 x 103 kg/m3)
(
"- (A) 980 N/m2 (B) 880 N/m2(C) 800 Nlm (D) None of these
Q.26 A water tank has a hole in its wall at a distance of 40 m below the free surface of water. Compute
the velocity of flow of water Jrom the hole. If the radius of the hole is
(
1 mm., find the rate of flow of water
(
~
(A) 26 mls , 8.8 x 10-5 m 3/s (B) 28 mis, 8.8 x 10-5 m 3/s
(C) 28 mis, 6.8 x 10-5 m 3/s (D) 26 mis, 9.8 x 10-5 m 3/s
( Q.27 The relative velocity between two .parallellayers ofwater is 8 cmls and the perpendicular distance
between them is 0.1 cm. Calculate the velocity- gradient-
I
\.
(A) 90/s (B) 80.5 Is (C) 80 Is. (D) None of these
(
Q .28 Water is flowing through ahorizontal pipe ofnon-uniform cross-section. At the extreme narrow
portion ofthe pipe, the water will have
(A) Maximum speed and least pressure ~ (B) Maxim1ll?1 pressure and least speed
c
(
(C) Both pressure and speed maximum (D) Both pressure and speed least
'
(
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Q.29 A liquid flows in a tube from left to right as shown in figure. Al and
A" are the cross~sections ofthe portions ofthe tube as shown.
Al Al
Then the ratio ofspeeds V/V2 will be
(A)A/A" - (B)A"IA 1
. (C) JA21 fA: (D) fA: I JA;.
- Q.30 An application ofBemoulli's equation for fluid flow is found in
(A) Dynamic lift ofan aeroplane (B) Viscosity meter
(C) Capillary rise (D) Hydraulic press
Q.31 -The Working ofan atomizer depends upon
(A) Bernoulliis theorem (B) Boyle's law
(C) Archimedes principle (D) Newton's law ofmotion
Q.32 Molecular force are
(A) only adhesive (B) only cohesive
(C) only repulsive (D) cohesive and adhesive
Q.33 The net force acting on a molecule inside the liquid is~
(A) directed upwards at the liquid surface. (B) directed inwards at the liquid surface.
. (C) zero (D) infinite.
Q.34 The lIquid surfaces have a tendency to contract, this phenomenon is due to
(A) surface tension (B) viscosity (C) friction (D) dispersion
Q.35 Surface tension may be defined as the mechanical work required to create an additional unit area
of the liquid under \", .
(A) isobaric conditions (B) isothermal conditions

(C) adiabatic conditions (D) isometric conditions.
Q.36 The surface tension of a liquid depends on
(A) contamination (B) impurity dissolved in the liquid
(C) temperature (D) all the above.
Q.37 If we increase the surface area of a soap film, the surface tension ofthe film -
(A) increases (B) decreases
(C) remains the same (D) becomes infinite
Q.3 8 When the temperature
.
ofliquid is increased/current
. flows through a liquid, then its surface tension- f '\
\...../
(A) remains constant (B) increases

(C) decreases. (D) first increases then decreases
Q.39 The soap and the detergent make water suitable for washing clothes because they
(A) make it rich in lather (B) increas.e its density c
(C) reduce its hardness (D) reduce its surface tension
e
Q.40 . Which of the following liquids has the maximum value of surface tension 6 •
\.y
(A) water (B) soap-solution (C) alcohol (D) mercury
f '.
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FLUID MECHANICS {28]

[I]~~~~~~C~~~~!
Ideal/or ScholDrs
c
Q.41
At critical temperature, the surface tension of a liquid
(A) is zero
(B) is infinity
(C) is the same as that any other temperature.
(l?) can not be determined.
Q.42
On wearing a rain coat on which some greasy material is coated, a person does not wet in rain
because
(A) the rain coat absorbs water
(B) the cohesive force of water is more.
(C) the adhesion between the rain coat and water becomes less.
(D) none of these.
Q.43 If there is a thin layer of water between two parallel plates then it is easier to seperate the plates
by
f (A) displacing them
" (B) applying force perpendicular to the surface ·ofthe plates
(
" (C) applying force in the some direction

( (D) none of the above.
Q.44 W is the work done in forming a bubble of radius r, the work done in forming a bubble ofradius
2r will be
(A) 4W (B) 3W (C) 2W (D) W
Q.45 IfW is the amount ofwork done in fonning a soap bubble ofvolume V, then the amount of work
(
done in forming a bubble of volume 2V from the same solution will be
(C) J2 W (D) 4 113 W
(
(A) W/2 (B) 2W
"
L Q.46 A big drop of water whose diameter is 0.2 cm, is broken into 27000 small drops ofequal volume.
\c
Work done in this process will be - (surface tension ofwater is 7 x 10-2 N/m).
(
\
(A) 5 x 105 joule (B) 2.9 x 10-5 joule
(C) 2.55 x 10-5 joule (D) zero
(Q.47 The work done in blowing a spherical soap bubble of diameter 2cm will be if the surface tension
( of soap solution is 2 x 10-2•
(A) 50.2 x 10-6 Joule (B) 50.2 Joule.
(
(C) 50.2 x 10-6 erg. (D) zero
(
~.48 A soap bubble has radius r. The surface tension ofthe soap film is T. The energy needed to double
( the diameter of the bubble without change oftemperature is
(
(A) 4 1t r2 T (B) 2 1C r2 T (C) 12 1C r2 T (D) 24 1C r2 T
tq9 The surface energy of a liquid drop is u. It is sprayed into 1000 equal droplets. Then its surface
( . energy becomes
(
(A) u (B) 10 u ,<C) 100 u . (D) 1000 u
50 Suppose that 64 raindrops combine into a siligle drop. The ratio of the total surface energy of the
64 drops to that of a single drop is- (For water T = 0.72 N/m = 0.072 Joule/m2.)
C (A) 4 (B) 10 (C) 2 (D) 8
(
le~~A~~ CL~~!~!
1Uf!tJ, lIN Scholots
FLUIDMECHANICS {29]
l
\.
Q.51 A liquid drop of diameter D is divided into 27 equal droplets. If the surface tension is T then the .
change in energy will be
tA ) 3 'Jt D2 T (B) 1t D2 T (C) 2 'Jt D2 T (D) 4 'Jt D2 T
Q.52 When two soap bubble:; coalesce to form a single bubble then its radius will be-
r
(A) 0 (B) CQ (C) "2 (D) .fir
Q.53 The liquid rise in capillary
(A) is directly proportional to the thickness of glass
(B) is inversely proportional to the thickness of glass
(C) is proportional to the square of the thickness of glass
. (D) does not depend on the thickness of the glass
Q.54 The volume of two soap bubbles are in the ratio 8: 1. Then ratio of excess pressure inside the
soap bubbles is- .
(A) 8 : 1 (B) 1 : 8 (C) 2 : 1 (D) 1 : 2

Q.55 The excess of pressure inside a water drop is Pd and that inside an air bubble of same radius in
water is Pb' Which of the following relation is correct?
(A) P d == Pb (B) 2 Pd = Pb
(C) P d = 2Pd (D) none of the above
Q.56 What will be the difference ofpressure inside and outside a drop ofwater ofradius 1.0 nuri?
(The surface tension ofwater is 73 dyne/cm-)
(A) 146 N/m 2 (B) 73 N/m2 (C) 7.3 N/m2 . (D) 200 N/m2
Q.57 The pressure inside a small air bubble 6fO.l mm radius is
\,~
[T = 0.072 N/m and atmospheric pressure = 1.013 x 105 N/m2].

(A) 2.027 x 105 N/m 2 (B) 1.013 x 105 N/m2 ,
['
(C) 2 x .072 x .001 N/m2 (D) 1.027 x. 105 N/m2 \.~ /

"
Q.58 Ifr, V and P are respectively the radius, volume and excess of pressure, for a bubble (or drop)
then
(A) PV ex r . (B) PV ex lIr (C) PV ex r2 (D) PV ex lIr2
cf!)/ 7he radius ofcu:vature '?f common surface formed by contact of two' soap bubbles of radii 3cm
, ~~ 4cm respectIvely, Will be- . .
(A) 7cm .. (B) lcm (C) Scm· (D) 12 cm
o
Q.60 The angle of contact for pure water and clean glaSs is
(A) {)O (B) 90° (C) 1800 (D) 3600
Q.61 If a liquid neither rises nor falls in a capillary, its angle of contact is - c
(A) 0° (B) 1800 (C) 900 (D) 45 0
Q.62 The excess pressure inside an air bubble of radius r just below the surface ofwater is Pl' The
excess pressure iJ1side a drop. of the same radius just outside the surface is P2' If T is surface. c
tension then
(A) PI = 2P2 (B) PI == P2 (C) P2 = 2PI (C) P2 = 0, PI =I: 0
c
,-
[30] o
i~~~~A~\C~~~~!IdeolfotScholan
FLUID MECHANICS
Q.63 Two soap bubbles of radii 3 cm and 4 cm are kept in contact, then the radius of curvature of
common surface will be
(A) 5 cm (B) 7 cm (C) 9 cm {D) 12 em
Q .64 A capillary tube (A) is dipped in water. Another identical tube (B) is dipped in a soap-water solution.
Which ofthe following shows the relative nature ofthe liquid columns jn the two tubes?
r'
Bg
(A)
(B) I;;;;;;;"f,it.;;;mj Illml!!I~!mmfilj
~
_
."n:~J: : : : : _."""~
, .
"
(C) (D) ............. "' .
. ~HEHH~:H:~HH~~~H
J,,"",,"
~~..............
:::::::::::::: ::::: iEEE

~ ........... -................. "' . .
H~H~~H:H!~~HHH~~
H:::::::::::::;:::;:::
{
Q.65 The surface tension ofa liquid is 5 N m- I • Ifa thin fIlm is formed on a loop ofarea 0.02 m2 , then its
\
surface energy will be
(A) 5 x 10-2 J (B) 2.5 X 10-2 J (C) 2 x 10-1 J (D) 3 x 10-1 J
,
( Q .66 A disc ofpaper ofradius R has a hole ofradim r. It is floating on a liquid ofsurface tension T. The force
ofsurface tension on the disc is
(A)T.3nR (B) T.2n (R + r) (C) TAn (R + r) (D) T.2n (R - r).
( Q.67 A soap bubble has radius r. The work done in increasing its radius to three times its original radius,
, without any rise oftemperature, is (Given: surface tension ofsoap solution is 1)
,\
(A) 12nr2T (B) 16nr2T (C) 64 nr2T' (D) 48nr2T
£
" Q.68 The energy E supplied to a soap bubble ofradius r and surface tension.-doubles the radius offue soap
( bubble under isothermal conditions. The value ofE is
(A) 8nr2cr (B)12nr2cr (C)'16nr2cr (D) 24nr2cr
(
Q.69 If two soap bubbles of different radii are connected by a thin tube with each other then
(' (A) Air flows from the larger bubble'into the smaller one until the two bubble are of equal size
/'
'l., (B) Air flows from the smaller bubble into the larger one and the larger bubble grows at the
expense of smaller Oli.e. '
(
(C) The size of bubbles remain the same
{
(D) Air may flow from anyone bubble into the other depending on the temperature
"
Q.70 An air bubble is fonned at depth h below the surface ofwater. The pressure inside the bubble is
c.
(Po = atmospheric pressure, r = radius of bubble)
(
(A) 4T (B) 2T
( . r r
t (C) Po + UP hg + 2T (D) Po + 1<P hg + 4T

r r
C Q.71 The pressure inside two soap bubbles is1.0! and 1.02 atmosphere if surrounding pressure is 1
atm., then ratio of their volume is
(A) 1;02: L01 (B) (1.02)3 : (1.01)3 (C) 8 : 1 (D) 2 : 1
{
I1!~~~A~~ CN~~~~~ ideaUo, Sdo%"
FLUID MECHANICS /31J
'
(
Q.72 A soap bubble is very slowly blown on the end of a glass tube by a mechanical pump which
supplied a ftxed volume ofair ~very time whatever be the pressure against which it pumping. The
excess ofpressure inside the bubble varies with time as shown by which of the graph
(A) tp •
t -------...
• (B) jPI V tpll. jp
t ---...
(C)
t ---...
(D) v
t ---...
•
Q.73 A ring of radius r and weight W is lying on a liquid surface. If the surface tension ofthe liquid is
T, then the minimum force required to be applied in order to lift the ring up
(A) W (B)2W (C) W + 4mT (D) W + 2mT
Q.74 A thin wire ring of radius of 2m is placed on the surface a liquid. If a force of 4N is required to
pull this ring from the surface of liquid (before the liquid ftlm breaks) then the surface tension of
liquid is
(A) 4 N/m . (B) 2N/m (C) Iht N/m (D) 1I2n: N/m
Q.75 A soap ftlms formed over a frame ABCD as shown n figure.
AII!I###IB
I
Wire PQ can slide without friction. Surface tension for soap is \. c
.045 J/m 2 and density of material of wire is

8.96 x 103 kg/m3 • If wire PQ is in equilibrium then its diameter QI IP
shall be '
(A) 0.6mm (B) 0.6 em D c

«C) 1.2mm (D) 1:2 cm
'
Q.76 1000 drops of water, all ofsame' size join together to form a single drop and the energy released
raises the temperature ofthe drop. Given.that T is the surface tension of water, r the radius of each
small drop, p the density of Jiquid, J the mechanical equivalent of heat. What is the rise in
.temperature
(A) T/Jr (B) 10 T/Jr 'c (C) 100 T/Jr (D) None of the above
Q.77 .Liquid drops are falling slowly one by one from a vertical glass tue. Establish a relation between
the weight of a drop w, the surface tension T and the radius r of the tube
(fI.ssume the angle of contact to be zero)
(A) w ;;: n:r2T (B) w= 2mT (C) w = 21tr2T (D) w = 4/3 1tr
Q.78 There is a small hole in a hollow sphere. The water enters in it when it is taken to depth of 40
em under water. The surface tension of water is 0.07 N/m. The diameter of hole is
(A) 7mm (B) 0.07 mm (C) 0.0007 mm (D) 0.7 m
Q.79 A ring is cut from a platinum tube 8.5 c~ internal and 8.7 cm external diameter. It is supported
horizontally from a pan of a balance so that it comes in contact with the water in a glass vesse~ .
.If an extra 3.97 gm-wt. is required to pull it away from water, the surface tension or'water is
(A) 70.07 dyne/cm (B) 70.80 dyne/cm (C) 63.35 dyne/cm (D) 60 dyne/cm U
FLUID MECHANICS [32)

II!~~~!!~C~~!~!idea/fIN SdJoIors
c
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'--'
Q.80 A straight capillary tube is inunersed.in water and the water rises to 5 cm. Ifthe capillary is bent
as shown in figure then the height of water column will be
!h
(
(A) 5 em (B) less than 5 cm .(C) greater than 5 cm (D) 4 cos a.

Q.81 Two parallel glass plates are dipping perpendicularly in a liquid of density p. The separation
between the plates is d and the surface tension is T. The angle of contact for glass is O. The
capillary rise of the liquid between the plates is:
(A) (T cos O/p d) (B) (2T cos O/p gd) (C) (2T/p gd cos 0) (D) (T cos O/p gd)
Q.82 There isa 1 nun thick layer of oil between a flat plate of area 10-2 m 2 and a big plate. How much
force is required to move the plate with a velocity of 1.5 cm/s2? The coefficient of viscosity of oil
,
I
is 1 poise
/
\ (A) 1.5 x 10-3 N (B) 1.3 x 10-5 N (C) 1.5 x 10-2 N (D) 1.5 x 102 N
Q.83 A steel shot of diameter 2 nun is dropped in a viscous liquid filled in a drum. Find the terminal ~
\
(
ofthe shot Density of the material of the shot = 8.0 x UP kglm3, de!lSity of liquid = l.Ox 103 kgI m3,
" Coefficient ofviscosity ofliquid 1.0 kgI(m-s), g = 10 m/s2
(
\ (A) 1.55 cm/s (B) 1.455 Cmls (C) 5.1 cm/s (D) None of these
Q.84 An air bubble (radius 004 nun) rises up in water. If the coefficient of viscosity of water be
1 x 10-3 kg/(m-s), then determine the terminal speed .of the bubble density of air is negligible~
(A) 0.843 mls (B) 3.048 mls (C) 00483 mls (D) 0.348 mls
(
\
Q.85 Ifan oil drop of density 0.95 x 103 kg/ m 3 and radius 10-4 cm is falling in air whose density is
1.3 kmlm3 and coefficient of viscosity is 18 x 10--6 kg/(m-s). Calculate the terminal speed of the
drop.
(
(A) 0.00015 cm/s (B) 0.0005·cm/s (C) 0.0115 cm/s (D) None of these
( Q.86 Velocity of water in a river is
(A) Same everywhere
(B) More in the middle and less near its banks
(
(C) Less in the middle and more.near its banks
( (D) Increase from one bank to other bank
I Q.87 As the temperature ofwater increases, its viscosity
"
('
(A) Remains unchanged
(B) Decreases
I
~ (C) Increases
(D) Increases or decreases depending on the external pressure
Q.88 A good lubricant should have
c (A) High viscosity (B) Low viscosity
, (C) Moderate viscosity (D) High density
\.,
(
[I!~~~A~~ CL~~!~!
IdeolforScholars
FLlllDMECllANICS [33J
l
\... ..
Q.89 The relative velocity oftwo consecutive l~yers is 8 cm/s. If the perpendicUlar distance between the
layers is 0.1 cm, then the velocity gradient will be
.(A) 8sec- 1 (B) 80 ~ec-t (C) 0.8 sec- 1 (D) 0.08 sec- 1
Q.90 We have three beakers A, B and C containing glycerine, water and kerosene respectively. They
are stirred vigorously and placed on a table. The liquid Which comes to rest at the earliest. is
(A) Glycerine (B) Water r"'
(C) Kerosene (D) All of them at the same time

Q .91 A lead shot of Imm diameter falls through a long column ofglycerine. The variation of its velocity
v. with distance covered is represented by
t
If If
t t
If
(A) V (B) I/ (C) 1,/ (D)

Distance covered -+ Distance covered -+ Distance covered _ Distance covered
Q.92 A small spherical solid ball is dropped from a great height in

A
a viscous liquid: Its journey in the liquid is best descri~ed in 8
the diagram given below by the C
D
(A) Curve A
TIme (t)
(B) Curve B
(C) Curve C
(D) Curve D ,,~
Q.93 A small drop of water falls from rest through a large height h in air; the final velocity is ,
(A) ex:; Jh (B) oc h
(C) oc (l/h) (D) Almost independent ofh ( "
\./
EXERCISE-II
Q.I In a U-tube the radii of two columns are respectively rt and r2 and
if a liquid of density d filled in it has level differ~nce ofh then the
surface tension of the liquid is - .

(r2>r1)
(A) T =
hdg
r -r
2 I
(B) T = (rl - rl)hdg
2
"l~ ~ -_
(rl + r2 )hdg hdg (rlr2 )
(C) T = 2
. (D) T = - 2 r2 -rl
( .
'-..j
"Q.2 The U-tube with limbs of diameter 5 mni and 2 mm contains water of surface tension
7 x 10-2 N/m, angle of contact is zero an~ density of water is 103 kg/m3 • Then difference in level
in the two limbs is
(A) 8.4 cm (B) 8.4mm (C) 0.84 mm (D) 0.84 cm

(j]~~~~A~~CL~~!~!
Ideal(orSdtoIats
c
Q.3 A bucket contains water filled upto a height = 15 em. The bucket is tied to a rope which is passed over
a frictionless light pulley and the other end ofthe rope is tied to a weight ofmass which is halfofthat of
the (bucket + water). The water pressure above atmosphere pressure at the bottom is
(A) 0.5 kPa (B) 1 kPa (C) 5 kPa (D) None ofthese
QA The area ofcross-section ofthe wider tube shown in figure is
800 cm2• Ifa mass of 12 kg is placed on the massless pisto~ the h I':U I 12kg
difference in heights hin the level ofwater in the two tubes is:' }~.;,:::,:
(A) 10 cm (B) 6 em ,:':' eo'",
....... ...
......eo,_- ..........................
... eo;:':::':':.
~~~-.-
(C) 15 cm (D) 2 em:;'::'::;'::';;;'::'::;'::';;;';

Q.5 An open cubical tank was initially fully filled withwater. When the tank was accelerated on a horizontal
plane along one ofits side it was fOlUld that one third ofvolume ofwater spilled out. The acceleration was
(A) gl3 (B) 2g13 . (C) 3g/2 (D) None
Q.6 Some liquid is filled in a cylindrical vessel ofradius R. Let F1 be the force applied by the liquid on the
bottom ofthe cylinder. Now the same liquid is poured into a vessel ofuniform square crss-section ofside
R. Let F2 be the force applied by the liquid on the bottom of this new vessel.(Neglect atmosphere
pressure) Then:
( F2 L
(A) FI = 1tF2 (B) FI- (C) FI = -v1tF2 (D) FI = F2
1t
Q,7 AV-tube having horizontal arm oflength 20 cm, has uniform cross-sectional area = Icm2• It is filled
with water ofvolume 60 ee. What volume ofa liquid ofdensity 4 glee should be poured from one side
into the U- tube so that no water is left in the horizontal arm ofthe tube?
(A) 60 cc (B) 45 cc (C) 50 cc (D) 35 cc
Q, 8JI A li~t semi cylindric~ gate ofradius ~ is ~io,,:ed at its ~d point 0, of
V the diameter as shown ill the figure holding hqUld ofdensIty p. The force
( F required to prevent the rotation ofthe gate is equal to
" (A) 21tR3pg (B)2pgR3/
2R2/
(C) 3 pg (D) none ofthese
Q,9 The pressure at the bottom ofa tank ofwater is 3P where P is the atmospheric pressure. Ifthe water is
( drawn out till the level ofwater is lowered byone fifth., the pressure at the bottom ofthe tank will now be
( (A) 2P (B) (13/5) P (C)(8/5) P (D)(4/5)P
" Q.I0 An open-ended V-tube ofuniform cross-sectional area contains water
(
"-. (density 1.0 gramlcentimeter3) standing initially 20 centimeters from the
h'IUI~
bottom in each arm. An immiscible liquid ofdensity4.0grams!centimeter3
( is added to one arm until a layer 5 centimeters high forms, as shown in
the figure above. What is the
(
ratio ~lhl ofthe heights ofthe liquid in the two arms?
! (A) 3/1 (B) 5/2
"
(C) 2/1 . (D) 3/2
(. Q.J 1/ I A heavy hollow cone ofradius R and height h is placed on a horizontal table surface, with its flat base on
(
\IV the table. The whole volume inside the cone is filled with water ofdensity p. The circular rim ofthe
cone's base ~as a watertight seal with the table's surface and the top apex ofthe cone has a small hole.
~. Neglecting atmospheric pressure find the total upward force exerted by water on the cone is
(A) (2/3}1tR2hpg (B) (1I3)1tR2hpg (C) 1tR2hpg (D) None
.''
,-. (I !~~~A~~CN~~~~~
( Ideal(or Scholors
FLUID MECllANICS . [35)
'-,
'-"
/
\
Q.12 Two cubes ofsize 1.0 m sides, one ofrelative density 0.60 and another ofrelative density = 1.15 are
connected by weightless wire and placed in a large tank: ofwater. Underequilibrium the lighter cube will
project above the water surface to a height of
(A) 50 cm (B) 25 cm . (C) 10 cm (D) zero
Q.13 A cuboidal piece ofwood has dimensions a, b and c. Its relative density is d. It is floating in a large body
.ofwater such that side a is vertical. It is pushed down a bit and released. The time period ofSHM
executed by it is :
~
(A) 21tVg (B) 21t{dag (C) 21t/dgbC (D) 2"lga
Q.14 A slenderhomogeneous rod oflength 2L floats partlyimmersed in
water, being supported by a string fastened to one ofits ends, as
.-~-.
shown. The specific gravity ofthe rod is 0.75. The length ofrod
that extends out ofwater is : .
1 1· :-:: .~ :-. -.. :-::

:''':;~-
..~.. ~:::~~:
(A)L (B) - L (C) 4 L (D)3L
2
Q.I5 Two bodies having vollimes Vand 2V are suspended from the two anns ofa common balance and they
are found to balance each other. Iflarger body is immersed in oil (density d l = 0.9 gmlcm3) and the
smaller body is immersed in an unknown liquid, then the balance remam in equilibrium. The density of
unknown liquid is given by:
(A) 2.4 gmlcm3 (B) 1.8 gm/cm3 (C) 0.45 gmlcm3 (D) 2.7 gm/cm3
Q.16 A boy carries a fish in one hand and a bucket(not full) ofwaterin the other hand. Ifhe places the fish in
the bucket, the weight now carried by him (assume that water does not spill) :
(A) is less than before (B) is more than before
(C) is the same as befor~ (D) depends upon his speed
Q.I7 Acork ofdensity05gcm-3 floats onaca1m swimtningpool. The :fraction ofthe cork's volume which is
under water is
(A) 0% (B) 25% (C) IQ% (D) 50%
Q.17'/fwo cyllind~rs ofsame cross-section and length L but made oftwo material ofdensities dl and ~ are
V(/ cemented together to fonn a cylinderoflength 2L. The combination floats in a liquid ofdensity d with a
. length U2 above the surface ofthe liquid ~dl > ~ then:
3 d d
(A) d} > 4 d (B)2' > d} (C) 4 > d 1 (D) d < d 1
Q .19 The frequency ofa sonometer wire is f, but when the weights producing the tensions are completely
immersed in water the frequency becomes ff2 and on immersing the weights in a certain liquid the
frequency becomes f13. The specific gravity ofthe liquid is:
4 16 ]5 32
Wi ~~ ~12 ~n
Q.20 A small ball ofrelative density 0.8 falls into water from a height of2m. The depth to whichthe ball will
sink is (neglectviscous fo~s): .
(A)8m . (B)2m (C)6m (D)4m
Q.21 A small wooden ball ofdensity p is immersed in water ofdensity cr to depth h and then released. The
height H above the surface ofwater up to which the ball will jump out ofwater is
crh
(A) ~
p
(a
(B) --1 h
p .
J (C)h (D) zero
(IJ~~~~~G~~~*! FLUlDMECHAMCS
136J
IdeoIfor SchoIors
Q.22 A hollow sphere ofmass M and radius.r is immersed in a tank ofwater (densitypw)' The, sphere would
float ifitwere set free. The sphere is tied to the bottom ofthe ~ by two wires which makes angle 45°
with the horizontal as shown in the figure. The tension T1 in the wire is :
4 "
-1tR 3pwg- M g
~)~:~-:m
Rl
(A) -=3_----::=::--_ (B) 32 1tR3Pwg-Mg
.fi
4 1tR3 ...
(C) 3 Pwg-Mg (D) 3-nR3pwg+Mg
-- 5°45 :-::
2
Q.23 Asphere ofradius R and made ofmaterial ofrelative density a has a concentric cavity ofradius r. It just
floats when placed in a tank full ofwater. The value ofthe ratio Rlr will be
(A) (~)"3 (B) (<r;I)'" (C) (a; 1)'" (0) (a_I)1!3

a-I 0-+1
Q.24 A body having volume V and density p is attached to the bottom ofa
----
mf
container as shown. Density of the liquid is d(>p). Container has a ..............
constant upward acceleration a..Tension in the string is :~ :-.-. :~: fa
---........
- .--.....
(A)V[Dg-p(g+a)] (B)V(g+a)(d p) (C)V(d p)g(O)none
Q.25 A beaker containing water is placed on the platform ofa spring balance. The balance reads 1.5 kg. A
",.
\
stone ofmass 0.5 kg and density 500 kg/m3 is completely immersed in water without touching the walls
ofbeaker. What will be the balance reading now?
(A) 2 kg (B) 2.5 kg (C) 1 kg (D) 3 kg
Q.26 There is ametal cube insidea blockofice which is floating on the surface
ofwater.1be ice melts completely and metal falls in the water. Water
/ -,
"
I"
I.,
level inthe container
(A) Rises
(C) Remains saine
.
(B) Falls
(0) Nothing can be concluded

Q.21 I Acylindrical block of area ofcross-section A and ofmaterial ofdensity
.:.JV p is placedin a liquid ofdensity one--,third ofdensity ofblock. The block
o
compresses a sprmg and compression in the spring is one-third ofthe
c lengthofthe block. Ifacceleration due to gravity is g, the spring constant

ofthe spring is:
(A) pAg (B) 2pAg (C) 2pAg/3 (D) pAg/3
(
c
c
Q.28 A cubical box ofwine has a small spout located in one of
the bottom comers. When the box is full and placed on a
.level surface, opening the spout results in a flow ofwine

with a initial speed ofvo (see figure). When the box is half
v,
:
JIII
:
:~ ~ i?=:
:3t:::iE:
~\\o ·..:!·:·it:
empty, someone tilts it at 45° so that the spout is at the
( •~..~~
if.~.
.
lowest point (see figure). When the spout is opened ",
c the wine will flow out with a speed of ~..

(A)vo (B) vo/2 (C) vo/..fi (0) vo/ifi
Q.29 Water is flowing steadily through a horizontal tube ofnon uniform cross-section. Ifthe pressure ofwater
C is 4 x 1()4 N/m 2 at a point where cross-section is 0.02 m2 and velocity offlow is 2 mis, what is p~ssure
at a point where cross-section reduces to 0.01 m2•
(A) 1.4 x 104 N/m 2 (B) 3.4 x 104N/m2(C) 2.4 x 10~ N/m2 (0) none ofthese
(
FL um MECHANICS
1I!~~~A~~ CH~~~~~
Ideal for Scholars
[37J
Q.30 Alarge tank is filled with water to a height H. Asrnall hole is made at the base ofthe tank. It takes TI time
to decrease the height of water to Hill, (11 > 1) and it takes T2time to take out the rest ofwater. If
TI = T2 , then the value ofll is:
W2 ~3 ~4 ~2h
Q.31 In the case ofa fluid, Bernoulli's theorem expresses the application ofthe principle of conservation of:
. (A)linearmomentmn ~)energy . (C) mass (D) angularmomentum
Q.32 Fountains usmiIly seen in gardens are generated by a wide pipe with an enclosure at one end having
.many small holes. Consider one such fountain which is produced by a pipe of internal diameter
2 cm in which water flows at a rate 3 ms-I. The enclosure has 100 holes each ofdiameter 0.05 em. The
velocity ofwater coming out ofthe holes is ( i~ ~I):
WM8 ~% ~~. ~~
Q.3 3 A fire hydrant delivers water ofdensity p at a volume rate L. The water
r
travels vertically upward through the hydrant and then does 90° turn to
emerge horizontally at speed V. The pipe and nozzle have unifonn
crosssection throughout. The force
exerted by the water on the corner ofthe hydrant is
(A)pVL . (B)zero (C)2pVL (D)J'ipVL.
Q.34 Avertical tank, open at the top, is filled with a liquid and rests on a smooth horizontal surface. Asmall hole
is opened at the centre ofone side ofthe tank. The area ofcross-section ofthe tank is N times the area of
the hole, where N is a large number. Neglect mass ofthe tank itself. The initial acceleration ofthe tank is
g g g g
(A) 2N (B) ..fiN (C) N (D) 2JN
Q.35 Two water pipes P and Q having diameters 2 xlO-2m and 4 x 1O~2m, respectively, are joined in series
with the main supply line ofwater. The velocity ofwater flpwing in pipe P is \. /
(A) 4 times that ofQ (B) 2 times that ofQ

,,
(C) 112 times ofthat ofQ (D) 1/4 times that ofQ
Q.36 Alarge tank is filled with water (density= 1()3 kglm3).Asmall hole is made ;
at a depth 10m below water surface. The range ofwater issuing out of
the hole is Ron ground. What extrapressure must be applie4 on the water ....;..,...........
",
'
surface so that the range becomes 2R (take 1 atm = 105 Pa and g = 10 mI

s2):
W9~ ~4~
~5~ ~3~ r R
a
Q.37 A sufficiently long close organ pipe haS small hole at its bottom. Initially the pipe is empty. Water is
poured into the pipe at a constant rate. The fundamental frequency ofthe air column in the pipe
(A) continuouslyincreasing (B) first increases and them becomes constant·
(C) continuously decreases. (D) first decreases and them become constant
Q.38 A water barrel stands on a table ofheight h. Ifa small hole is punched in the side ofthe barrel at its base,
it is found that the resultant stream ofwater strikes the ground at ahorizonatl distance Rfrom the barrel.
The depth ofwater in the barrel is
R R2 R2 h
(A) 2' (B) 4h (CY
h (D) '2
Q.39 A cyclindrical vessel of cross-sectional area 1000 cm2;is fitted with a frictionless piston of mass /
1..,•./
'\
10 kg, and filled with water completely.Asmall hole ofcross-sectional area 10 l1lin2is openedat a point 50
cm deep from the lower surface ofthe piston. The velocity ofefflux from the hole will be
(A) 1O.5m1s (B)3.4m1s (C) 0.8 mls (D)0.2m1s
[38J
[jJ~~~~A~~CL~~!~~ . FLUIp MECHANICS
/deJJ/ fDr SchoIa"
Q040 Arectangular tank is placed on a horizontal ground and is filled with water to a height H above the base. A
small hole is made on one vertical side at a depthD below the level ofthe water in the tank The distance x
from the bottom ofthe tank at which the waterjet from the tank will hit the ground is
1
(A) 2,jD(H-D) (B) 2.JDH (c) 2,JD(H + D) (D) 2" .JDH
QA1 Equal volumes oftwo irrimiscible liquids ofdensities p and 2p are filled
in a vessel as shown in figure. Two small holes are punched at depth hI2 --------
................
.......... - & ...........
'"' ...........
...
and 3h12 from the smface oflighter liquid. Ifv1 and v2 are the velocities h :e;.:-: :-:-: ~ :-:-: ;':-/11- VI
ofa flux at these two holes, then v/v2 is : --------
.................. ........
'"
.I h i~:j f=:: ~ ~:~ ~:--H- V2

1
(A) 2.Ji
1
(B) 2
1
(C) 4 (D) .Ji
;-: ;.:-: :-:-: ~ ~:~ ~~
Q.42 Ahorizontal pipe line canies water in a streamline flow. Atapoint along the tube where the cross-sectional
area is 10-2 m 2, the water velocity is 2 ms- I and the pressure is 8000 Pa. The pressure .of water at
another point where the cross-section~ ~ea is 0.5 x 10-2 m2. is :
(A) 4000 Pa (B) lOOOPa (C) 2000 Pa (D}3000 Pa
c
Q.43 A cylindrical vessel filled with water upto height ofH stands on a horizontal plane. The side wall ofthe
vessel has a plugged circular hole touching the bottom. The coefficient offriction between the bottom of
vessel and plane is f.t and total mass ofwater plus vessel is M. What should be minimum diameter ofhole
so that the vessel begins to move on the floor ifplug is removed (here density ofwater is p)
,
~ ~
\
2f.tM f.tM f.tM
~
(A) I-H
-
V1tp (B) -2
1tp
H (C) ·-H
P ,
(D) none
Q.44 Which ofthe following is not an assumption for an ideal fluid flow for WhichBemoulli's principle is valid
, (A) Steady flow (B) Incompressible (C) Viscous (D) Irrotational
\
Q.45 A Newtonian fluid fills the clearance between a shaft and a sleeve. When a force Qf800N is applied to
the shaft, parallel to the sleeve, the shaft attains a speed of1.5 em/sec. Ifa force of2,4 k:N is applied
instead, the shaft would move with a speed of
C (A) 1.5 em/sec (B) 13.5 em/sec (C) 4.5 em/sec (D) None
C Q.46 A solid metallic sphere ofradius r is allowed to fall freely through air. Ifthe frictional resistance due to air
is proportional to the cross-sectional' area and to the square ofthe velocity, then the tenninal velocity of
t.lJ.e sphere is proportional to which ofthe following?
( (A) r2 (B) r (C) f312 (D) r I12
(
, .
Q.47 Two drops ofsame radius are falling through air with steady velocity of v cmJs. Ifthe two drops
coalesce, what would be the tenninal velocity?
\.. (A) 4 v (B)(4) 113 V (C) 2 v (D) 64 v
C Q.48 A cubical block ofside'a' and deIisity 'p' slides over a fixedihclined
.£j
plane with constant velocity 'v'. There is a thin film ofviscous fluid of
thickness '1' between .
the plane and the block Then the coefficient ofviscosity ofthe thin film will be:
(A) 3pagt (B) 4pagt (C) pagt (D) none ofthese

5v 5v v
I
\..~
r
~.
[IJ!~~~~~CL~~!~!
iIk<l/for SchoIats
FLUlDMECHANICS [39J
c
Q.49 Which ofthe following graphs best represents the motion ofaraindrop?
(A)k O3<k. (C)~ (D)~

Q.50 Which ofthe following is the incorrect graph for a sphere falling in a viscous liquid?
(Given at t.= 0, velocity v = 0 and displacement x = 0.)
(A) "b::, (B)'~, . (C)'~" (D)

Xld 1 I
l
Q.51 The displacement ofa ball falling from rest in a viscous medium is platted against time. Choose a possible
!/V (D)u,
option
(A)!/ /
~
O3)b (C)
Q.52 There is a 1mm thick layer ofglycerine between a flat plate ofarea 100 cm2 & a big fixed plate. Ifthe
coefficient ofviscosity ofglycerine is 1.0 kglm-s then howmuch force is required to move the plate with
a Velocity of7 cm/s? .
(A) 3.5 N (B) 0.7 N (C) 1.4 N (D) None

Q.53 A container, whose bottom has round holes with diameter 0.1 mm is filled with water. The maxunum
height in cm upto which water can be filled without leakage will be what?
Surface tension = 75 x 10-3 N/m and g = 10 m/s 2 :
(A) 20 em (B) 40 cm (C) 30 cm (D) 60 cm

Q.54 Iftwo soap bubbles ofdifferent radii are connected by a tube,
(A) air flows from the bigger bubble to tD.e smaller bubble till the sizes become equal
(B) air flows from bigger bubble to the smaller bubble till the sizes are interchanged /-- ~"
(C) air flows from the smaller bubble to the bigger

(D) there is no flow ofair. / '
Q.55 Aliquid is filled!n a spherical container ofradias R till a height h. At this

positions the liquid surface at the edges is also horizontal. The contact
angle is
(A) 0
. (R-h)
(B) cos-1 ~ Q r'·
(h-R)
(C)cos-1 .~ (R-h)
(D) sin-l ~
Q.56 Alongcapillmytyubeofradius'r'isinitiallyjustverticallycompletelyimergedinsidealiquidofangle of
contact 00. Ifthe tube is slowly raised then relation between radius ofcurvature ofofminiscus inside the
.
'capillmytube and displacement (h) oftube can be represented by
(A) RL h
03) ~L
h
(C)RL
h
(D)RC h
C
I •
~

[i)~~~~A~~ ("
c
EXERCISE-III
Q.l An incompressible fluid flows steabily through a cylindrical pipe whlch has radius 2R at point A and
radius R at point B further along the flow direction. Ifthe velocity at point A is v, its velocity at
point B will be
W~ ~v ~~ ~~
Q.2 Water is flowing in a horizontal pipe ofnon-uniforin cross - section; At the most contracted place
of the pipe
(A) Velocity ofwater will be maximum and pressure minim\lIll
(B) Pressure of water will be maximum and velocity minimum
(C) Both pressure and velocity of water will be maximum
(0) Both pressure and velocity ofwater will be minimum
Q.3 Water is flowing in a tube ofnon-uniform radius. The ratio of the radii at entrance and exit ends
of tube is 3 : 2. The ratio ofthe velocities of water entering in and exiting from the tube will be
(A) 8 : 27 (B) 4 ; 9 (C) 1 : 1 (D) 9 : 4
QA Water from a tap emerges vertically downward with an initial speed of 1.0 ms-I . The cross-section
area of the tap is 10-4m2. Assumed at the pressure is constant throughout the stream of water and
r
\ that the flow is steady. The cross-sectional areal of the stream 0.15 m below the tap is
,
("-- (g = 10 mls 2)
(A) 5.0 x 10-4 m 2 (B) 1.0 x 1O-~ m 2 (C) 5.0 x 10-5 m 2 (D) 2.0 x 10-5 m 2
Q.5 The velocity ofasmall ball of mass M and density d I , when dropped in a container filled with
glycerine becomes c.onstant after some time. lithe density of glycerine is d2, the viscous force
acting on the ball will be-
I
Md19
M9(1-:~ J
\.
(B) M(d1 + d2 )
(A) d;- 9
(C) (D) M d l d2
(
Q.6 Bernoulli's theorem based upon
(A) Conservation of momentum .(B) Conservation of energy
(
\
(C) Conservation mass (D) None of these
Q.7 There is a gale over a house. The force on the roof of the house due to the gale is:-
(
(A) Directed downward (B) Directed upward
C (C) Zero (D) None of these
Q.8. A tank has an orifice near its bottom. The volume ofthe liquid flowing per second out of the orifice
'- does not depend upon
( (A) Area of the orifice (B) Height of the liquid level above the orifice
'.
(C) Density of liquid (D) Acceleration due to gravity
(
'.
Q.9 The rate of flowing of water from the orifice in a wall of a tank will be more if the orific is
( (A) Near the bottom
(B) Near the upper end
(
(C) Exactly in the middle
(0) Does not depend upon the position of orific
c Q.1O A tank is filled with water to a height H. A hole is made in one of the wans at a depth D below
"- ...
the water surface. The distance x from the foot of the wall at which the stream ofwater coming
c out of the tank strikes the ground is given by-
tf
(A) x = 2 [D(H - D)]I12 (B) x = 2 (gD)I12
"-.
(C) X = 2 [D(H + D)] 112 (D) None of these
(
( [jJ~~~~~~ CL~~~~!Ideal fly Scholars
FLUID M.ECllANICS [41J
"'"" F
c
Q.l1 A small lead ball is falling freely in a viscous liquid. The velocity of the ball
(A) goes on increasing
(B) goes on decreasing
(C) remains. constant
(D) first increases and then·becomes constant I'
Q.12' The terminal velocity ofa spherical ball.of radius r falling through a viscous liquid is proportional
to
(A) r (B) r2 (C) r' (D) r- 1
Q.13 The viscous force acting on a solid ball moving in air with terminal velocity v is directly proportional
to
1
(A) ..Iv (B) v (C) ..Iv (D) v 2
Q.14 A small spherical solid ball is dropped in a Viscous liquid. Its journey in the liquid is best described
, .
in the figure by -
\'''' "
----c
D
x )
DISTANCE TRAVELLED
(A) Curve A (B) CurveB (C) Curve C (D) Curve D

Q.15 The terminal velocity ofa ball in air is v, where acceleration due to gravity is g. Now the same ball is
taken in a gravity free space where all other conditions are same. The balHs now pushed at a speed
vv, then
(A) The terminal velocity ofthe ball will be vl2 (B) The ball will move with a constant velocity
(C) The initial acceleration ofthe ball is 2g in opposite direction ofthe ball's velocity
(D) The ball will finally stop (Given that density ofthe ~l p=2 times the densityofaircr)
Q.16 A tank is filled up to a height 2H with a liquid and is placed on a platform ofheight H from the ground.
The distance x from the ground where a small hole is'punched to get the maximwn range R is
(A)H (B) 1.25H (C) 1.5 H (D) 2H
Q.17 In a cylindrical vessel containing liquid ofdensity p, there are two holes in the side walls at heights of
hI and ~ respectively such that the range of efflux at the bottom ofthe vessel is same. The height ofa
hole, for which the range ofefflux would be maximum, will be- C
(A)h2 -hi (B)h2 + hI
(C) h2 -:h1 (D) h2+h1

c
2 2
c
FLUIDMECHANICS [42J·
[I~~~~~~CM~!~! Ideolfor Sch%,. c
c
Q .18 Two drops ofsame radius are falling through air With steady speed v. Ifthe two drops coalesce, what
would be the tenninal speed
(A) 4v (B) 2v (C) 3v (D) None ofthese
Q.19 A large tank is filled with water (density = 10 kglm ). A small hole is made at a depth 10m below
3 3
, water surface. The range ofwater issuing out ofthe hole is R on ground. What extra pressure must be
applied on the water surface so that the range becomes 2R .
(take 1 atm = 105 Pa and g = 10 mls2)=
~U!!~~~~
=;gg:==.1
;~5~~~·tM..
r
·,,~~~~'f~~m!l~I:t.~ii1i>il<1~~F
~\
'4iI R ....
W9~ ~4~ ~5~ ~3~

Q.20 A ball ofrelative density 0.8 falls into water from a height of2m. The depth to which the ball will sink
/
is,(n.eglectviscous forces)
"
(
(A) 8m (B)2m (C)6m (D)4m
" Q.21 When a sphere is taken to bottom ofsea 1 km deep, it contracts by 0.01 %. The bulk modulus of
/
\ .
elasticity ofthe material ofsphere is :
(Given DenSity ofwater = 191cm3Y
(A) 9.8 x 1010 N/m 2 (B) 10.2 x 1010 N/m2 (C) 0.98 x 1010 N/m 2 (D) 8.4 x 1010 N/m 2
Passage: ( Q.No. 22 to 24)
AU-tube ofbase length L contains a liquid ofdensity p in it. The tube is rotated about one of its
vertical end with angular velocity. (() as shown. The diameter ofthe tube is negligible. Take Po as
(
\ atmospheric presure.
( ~(l)
( h,
h,
( ::::::==::::::-:-:-:-:-:-:-:~-:==-=
14 L ~I
Answer the following questions:
C Q .22 What is the force at B due to rot&tions ofthe u-tube ?
2 2
(
\.. (A)Ap(()2 (B) A p(()2L2 (C) Apro L2 (D) Apro L2
2 4
Q.23 What is the presure at B from left band side.

(
(A)Po+h I pg (B)P + h1pg
o (C) 2Po+ hI pg (D)Po+h pg+
I
pro~L2
( 2 2
Q.24 The value ofho is
ro 2L 2[2
roo ro 2 L2 ro 2 L2
(A) ~g (B)2g (C) 3g (D)~
(
(
(
[i!~~~A~~ CL~~!~~
IdeDlfor SdroIars
FLUID MECHANICS [43)
',
(
Q.25 A block of mass 2kg and specific gravity 5/2 is attached with a spring of force constant
K = 100 N/m and is half dipped in the water. Ifextension in the spring is 1 cm, the force exerted by
. the bottom ofthe tank on block is
(Take g = 10 mls 2)
(A)20N (B) 19N (C) l5N (D) 16N

Q.26 A stone is placed.inside a container. The nonnal reaction b~t~een the stone and the container is N l'
Now a liquid is poured inside the container such that normal reaction between stone and the container , '-,
{
isN2 then
(Assume no liquid between stone and container at the contace surface)
(A)N2 <N 1 (B)N2 >N 1 (C)N2=Nl (D) None ofthese
Q.27 Ifthe radii oftwo soap bubbles are Rl and ~, then the ratio ofthe respective masses ofair in them will
be (cr = surface tension and Po = atmospheric pressure)
R 40
R, ~
oR
I PO*[RI]3 I.
(A) R2 (B) Ii; (C) P, 40- (D) R 40- R2

o R2 OR 2
Q@ IfFe and FA denote cohesive and adhesive force on a liquid molecule near the surface ofa solid, then the
·surfuce ofliquid is convex if
Fe Fe . Fe
(A) FA> Ji (B) FA = J2 (C) FA <Ji (D) FA <Fe
Q.29 The lower end ofa capillary tube is at a depth of 12 cm and the water rises 3 cm in it. The mouth
pressure required to blow an air bubble at the lower end will be x cm ofwater column, where x is
(A) 12 (B) 15 (C) 3 (D) 9
Q.30 A film of soap solution is trapped between a vertical frame and a light wire ab oflength 0.1 m. If
g = lO m g-2 and 0' =25 x l0-3 N m- I, then the load W that should be suspended from the wire to keep
it in equilibrium is
II II II
(;
II II
II II
C
al Ib
C
(D)O.Sg
C
(A)O.2g (B) O.3g (C) OAg
FLUIDMECHANlCS [44J
~~~~~A~~~~~~!Ideal (",Scholars
,'
C
Q.31 A hollow sphere has a small hole in it. On loweringthe sphere in a tank ofwater, it is observed that water
enters into the hollow sphere at a depth of 40 em below the surface. Surface tension of water is
7 x lo-2Nm- 1• The diameter ofthe hole is
1 . 1 1 1
(A) 28 nun (B)-mm (C) 14mm (D)7 mm.
21
Q .32 The excess pressure due to surface tension itisid;e a spherical drop is 6 units. Ifeight such drops combine,
then the excess pressure due to surface tension inside the larger dropis
(A) 3 units (B) 6 units (C) 12 units (D) 48 units.
Q.3 3 A capillary tube ofradius ris immersed in aliquid. The liquid rises to a height h. The corresponding mass
is m. What mass ofwater shall rise in the capillary ifthe radius ofthe tube is doubled ?
Wm ~h ~h ~~
Q.34 Consider a vertical tube ofsemi-circular cross-section dipped in a liquid. Assume that the wetting ofthe
tube is complete. The forces ofsurface tension on the flat part and on the curved part ofthe tube are in
~
/ era'o
" ( 2 : 1t (B) 1 : 1t . (C) 3 : 1t '. (D) 2.7 : 1t

Q.35. iquid in a capillmy tube rises to a height h. The tube is filled with the liquid in the horizontal position. If
r .the length ofthe tube is greaterthan 2h, then the column ofliquidwhich remains in the capillarytube when
" held in the vertical position is . a:~
h r.~~
Wh ~i ~Th ~~ ~
(
Q.36 The addition ofsoap changes the surface tension ofwater to 0'1and that ofsalt changes to 0'2" Then
(A) 0'1 > 0'2
( (B)cr l <0'2
( (C) 0'1 =0'2
'-
(D) it is not possible to prediCt the above.
( Q@ Anumber ofdroplets, each ofradius r, combine to form a drop ofradius R. 1fT is the surface tension,
then the rise in temperature will be
(
c (A) 2T 3T
(B)R (C) 2T[;~ !] (D) 3T[.!-~]
r r R
Q.38 A glass rod ofradius r l is inserted symmetrically into a vertical capillmy tube ofradius r2such that their
( lower ends are at the same level. The arrangement is now dipped in water. The height to which water will
rise into the tube will be((J' = surface tension ofwater, p = density ofwater)
f
" 200 a 200 200

(A) (r _lj)pg
2
(B) (r2 -lj)pg (C) (r + lj}pg (D) (ri _lj2)pg
2
( Q. 3~ f A drop ofliquid ofdensity p is floating half-immersed in a liquid ofdensity d. If(J' is the surface tension,
\..01 then the diameter ofthe drop ofthe liquid is .
(
~ ~ 1200
(A) { g(2;- d) (B)V~ (C)V~ (D) 11 g(2p - d)
(
r:
\.
, [i!~~~A~~ CL~~~~! FLUIDMECHAMCS {-I5]

'- Ideal for S<ho/a,.
Q.(4(h A drop ofwater ofvolume V is pressed be~ween the two glass plates so as to spread to an areaA. 1fT
V is the surface tension, the nonna! force required to separate the glass plates is
(A) TA2 (B) 2TA2 (C) 4TA2 TA2

V , V V, (D) 2V
Q@ Alarge number ofdroplets, eachofradius a, coalesce to fonn a biggerdrop ofradius b.Assume that the
energy released in the process is converted mto the kinetic energy ofthe drop. The velocity ofthe drop
is (cr = surface tension, p = density)
(A) [ ;
1 I)J1I2
( a --;;
. [2 (1 I)J
(B); a --;; J
/2
(C)
[3 ( 1
;
I)J"2
a --;;
[6 (I I)J1I2
(D); a --;; ,
QG 125 water droplets, each ofradius r, coalesce to fonn a single drop. The energy released raises the
V temperature ofthe drop. Ifcr represents surface tension, p represents density, S represents specific heat
and J represents mechanical equivalent ofheat, then the rise in temperature ofthe drop is
,/
120' 120'p 20'p'
(A) 5JrpS (B) 7JrS (C) SJr (D) Zero
Q® Two spherical soap bubbles coalesce. IfV is the consequent change in volume ofthe contained air, S is
the total change in surface area 8nd cr is the surface tension ofsoap solution, then
(A) PeV +4Scr= 0 (B) 3PoV +4crS= 0 (C) 4PoV + 3crS = 0 (D) PoV -crS=O \. --
[Here Po represents atmospheric pressure.]
QUestions No. 43 to 45 are based on the following paragraph.
Two vertical parallel glaSs plates are partially submerged in water. The distance between the plates is d
and theirw :idth.is I. Assume that the water between the plates does not reach the upper edges ofthe
Q8
plates and that the wetting is complete.
The water will rise to height (p = density of water and 'cr = surface tension ofwater)
20' 30' 20'p

(
\..~
,
-/
(A)- (B)~·
(C) SJr (D) Zero
pgd pgd
, dt45\ ,The force ofattraction between the plates i~
,.~ 1 1 'Ipg
(A) pg h 2 (B) pg. h (C) Ipg
(D)2/; f- '"
2 , 2 2 '...7
[Here h represents the height to which the liquid rises.]

Q.46 Ifwater is replaced by another liquid ofsurface tension 2cr, then the force F ofattraction between two
plates would become
(A)2F (B) 4F (C) 8F (D)I6F

c
Q.4 7 Statement-I: Air flows from a small bubble to a large bubble when they are connected to each other
by a capillary tube. .'
Statement-2: The excess pressure inside a bubble due to surface tension is inversely proportional to
the radius ofthe bubble. '
(A) Statement-l is false, Statement-2 is true. ,

(B) Statement-l is true, Statement-2 is true; Statement-2 is a correct explanation for Statement-I.
(C) Statement-I is true, Statement-2 is true; Statement-2 is not is a correct explanation for Statement-l.
(D) Statement-l is true, Statem~nt-2 is false. 1.
t'
\.....
f46] ,
[j]~!~~~~CL~~!~! FLUID MECHANICS (
\.....
Ideal forSdJD/ors
c
Q.48 Statement-1: A needle placed carefully on the surface ofwater may float whereas a ball ofthe same
material will always sink.
Statement-2: The upthrust on an object depends both on the material and shape ofthe object.
(A) Statement-l is false, Statement-2 is true.

(B) Statement-I is true, Statement-Z is true; Statement-2 is a correct explanation for Statement-I.
(C) Statement-l is true, Statement-2 istrue; Statement-2 is no~ is a Correct explanationfor Statement-I.
(D) Statement-I is true, Statement-2 is false. I.
Q.49 Statement-1:The shape ofaliquid drop is spherical.
Statement-2: The pressure inside a drop is greater than outside.
(A) Statement-I is false, Statement-2 is true..

(B) Statement-I is true, Statement-2 is true; Statement-2 is a correct explanation for Statement-I.
(C) Statement-l is true, Statement-2 istrue; Statement-2 is not is a correct explanation for Statement-I.
t'
(D) Statement-I is true, Statement-2 is false. 1.
" Q.50 Statement-1: Detergents decrease both the angle ofcontact and surface tension.
Statement-2: The molecules ofa detergent are hair-pin shaped.
f
(A) Statement-I is false, Statement-2 is true.
" (B) Statement-I is true, Statement-2 is true; Statement-2 is a correct explanation for Statement-I.
(
(C) Statement-I is true, Statement-2 is true; Statement-2 is nofis a correct explanation for Statement-I.
t'
\
( Q.51 Sta tement-1: The surface tension ofa liquid decreases with rise in temperature.
Statement-2: Density and viscosity increase with rise in temperature.
(A) Statement-l is false, Statement-2 is true.
(B) Statement-l is true, Statement-2 is true; Statement-2 is a correct explanation for Statement-I.
( (C) Statement-I is true, Statement-2js true; Statement-2 is 11,0t is a correct explanation for Statement-I.
( (D) Statement-l is true, Statement-2 is false. 1.
"
Q.52 Statement-1: Whena glass capillarytube ofinsufficientlengthis dipped vertically inwater, water finally
overflows.
C Statement-2: According to Jurin's law, the smaller the radius ofa tube, greater is the rise or fall ofliquid
in the tube. .
C (A) Statement-l is false, Statement-2 is true. .
( (B) Statement-l is true, Statement-2 is true; Statement-2 is a correct explanation for Statement-I.
( (C) Statement-l is true, Statement-2 is true; Statement-2 is not is a correct explanation for Statement-I.
c·· Q.53 Statement-1: Amercury barometer always reads less than the actual value ofpressure.
( Statement-2: Mercury falls in a glass capillary tube.
U (A) Statement-I i~ false, Statement..2 is true.
(B) Statement-l is true, Statement-2 is true; Statem~nt-? is a correct explanation for Statement-I.
l
(C) Statement-l is true, Statement-2 istrue; Statement-2 is not is a correct explanation for Statement-I.
t (D) Statement-l is true, Statement-2 is false. 1.
(
,[
[I~~~~~~ CN!~~~~
IdeolforSdloion
\..
l
Q.54 Statement-I: Mercury does not wet glass.
Statement-2: The force ofcohesion among molecules ofmercury is greater than the force ofadhesion
between molecules ofmercury and molecules ofglass.
(B) Statement-I is true~ Statement-2 is true; Statement-2 is a correct explanation for Statement-I.
(C) Statement-I is true, Stateme~t-2 is true; Statement-2 is not is a correct explanation forStatement-l.
(D) Statement-I 'is true, Statement-2 is false. 1.
Q.55 Statement-I: Greased cotton soaks less ilian ordinary cotton.
Statement-2: Presence ofgrease increases surface tension.
.<'-~

(B) Statement-I is true, Statement-2 is true; Statement-2 is a correct explanation for Statement-I. (' .
(C) Statement-I is true, Statement..:2 is true; Statement-2 is'not is a correct explanation for Statement-I.
,(D) Statement-I is true, Statement-2 is false. 1.
EXERCISE-IV
(
QUESTIONS FROM LAST YEARS AIEEE & nT-JEE PAPERS ',.
SECTION-A
Q.I Acylinderofheight20miscompletelyfilledwithwater.ThevelocityofefIluxofwater(inms-1)tbrougha / '
\
small hole on the side wall ofthe cylinder near its bottom is - [AIEEE-2002]
(A) 10 mls (B) 20 mls (C) 25.5 mls (D) 5 mls
Q.2 Which one ofthe following represents the correctdimensionsofthe coefficientofviscosity? (
\..
,
[AIEEE-2004]
(A)ML-1r-1 (B)ML~I (C)ML-1r-2 (D)ML-2r-2
Q.3 Spherical balls ofradius 'R' are falling in a viscous fluid ofviscosity '11' with a velocity 'v'. The retarding
viscous force acting on the spherical ball is- [AIEEE-2004]
(A) inversely proportional to both radius 'R' and velocity 'v'

(B) directly proportional to both radius 'R"and velocity 'v'
(C) directly proportional to 'R' but inverselyproportional to 'v'
(D) inversely proportional to 'R~ but directlyproportional to velocity 'v'
Q.4 Iftwo soap bubbles ofdifferent radii are connected bya tube- [AIEEE-2004]
(A) air flows from the smaller bubble to the bigger
(B) air flows from bigger bubble to the smallerbubble till the sizes are interchanged
(C) air flows from the bigger bubble to the smallerbubble till the sizes become equal
(D) there is no flow ofair
Q.5 A 20 em long capillary tube is dipIJOC in water. The water rises upto 8 cm. Ifthe entire arrangement is
put in a freely falling elevator the length ofwater column in the capillary tube will be
[AIEEE-2005]
(A) 8 em (B) 10 cm (C) 4 cm (D) 20 cm C'. . --,
FLUIDMECHANICS (48)
, [I~~~~A~Cb~~~~!
/detJtfor SJ:ho/Ofj
c
")
Q.6 Ifthe tenninal speed ofa sphereofgold (density = 19.5k:g1m3) is 0.2 mls in a viscous liquid
(density= L5 kg!m3), find the tenninal speed ofa sphere ofsilver{density = 10.5 kg/m3) ofthe same size
in the same liquid- [AlEEE-2006]
(A)O.lm1s (B)0.2m1s (C)OAmls. (D) 0.133 mls
Q.7 Ajar is filled with two non-mixing liquids 1 and 2having densities PI and
P2, respectively. Asolid ball, made ofamaterial ofdensity P3, is dropped
inthejar. It comes to equilibrlumintheposition shown inthe figure. Which
ofthe following is true for PI' P2 and P3 ? [AIEEE-2008]
(A) PI > P3 > P2

(B) PI < P2 < P3
(C) PI < P3 < P2
(D) P3 < PI < P2 ~
Q.8 A capillary tube (A) is dipped in water. Another identical tube (B) is dipped in a soap-water solution.
(
\
Which ofthe following shows the relative nature ofthe liquid columns in the two tubes?
("
[AIEEE-2008]
" A A B
/
\
(
~ )
r---i-I·... ···j
-;c.:-;c.:~-.::-:
~~:~~lIt;~~~~~~~~
- - .. -....
- :-;c.:~.;c.:-:;
A ... .......;,,...... . -:......-_ _... .:-.---."':. r···-·~i-I~~·"·'I

.--.. _- ------
------ - -------
:~:~~:~~~: ~ :~~:~~~:~~
-::::~::~:;;·;v~:::::~::::~
(B)
";...-.;;;;'-.- ";;,;,,..---.-.-
r'~~~n~
WIW·'_~~n~~~r ·'W.,! r.ml~· noml
~-:~~~-:-:- -:-:~~~~~-
~~~~~~~ ~~~:~~~~~~~
\
...::-:.:-:...::-:-~-::-:-::-:-:-:. ~ .
:-:-:-:...~:;.~ ~:~...:-~.::-:...: ~~~~::::::~~€~~€::::~ . .:f::~~€::~€::::~~€::~~:
(
A B A B
-
,~
.
\~
"
------- r'~~:i·:««·:"'1
(C) -:;:::::t:~:: :::;;::::::::~
-----.. --------
_._........ -------,.._ ... _--
-----"":---"":-""!..- -
----............. -------
----:::---:..---_"":..
r··I~i·m·
------- -- -------
-:~:~-:-~:-
~~~~t~~; ~ ~~~~~~~
1
:-:-:-:-:~-:-
r'·'·i~·mml
(D) -------
-;;-;-;:~;;~-;;: -------
~~~~i~~ ~ ~~~~
-;,:~..,;:,;:-:-:~
L··-·llli·-~~--
I:~~~-:-
------- - -----
~~~~~~~? ~ ~~i~i~
:-:~~':-:-;:
_..._ -...-_-_.';.-_-_-:.-...................~.._......_:. _-••_-.:::-.:'..1'~rI";".Il".,:.,..::'....- .. .......-.:t:r_-_.._-.::"t:'_-.:
:~:~;E:~:::t~:~==~}:::~
~I..:_ ~
( -=..:. ..=...:-:-:::-:-.:-:..:.:-:.:!-~..::; . ..
~ :oo!:~~~ ~~~-!~*!..:~ ..:... ..
-r~~--::-.:: :~~~ :~~~~-:
"
( Q.9 A spherical solid ball ofvolume V is made ofa material ofdensity PI' It is falling through a liquid of
'--"~
density P2 (P2 < PI).Assume that the~liquid applies a viscous force on the ball that is proportional to the
c square ofits speed U, i.e., F . = - ku2 (k> 0). The terminal speed ofthe ball is [AIEEE-2OD.8]t.v' ~ P1
VISCOUS ~" 1:: J 'l..-tJ
c (A) V!'" (B) t~1 (C)Vg(P~ -p,) (D) tg(p~-1'2) .:'.=~ ~
(
Q.1O A baIl is made ofa material ofdensity P where P~il < P < Pwater with Poil and Pwater representingli~
( densities ofoiland water, respectively. The oil and waterare immiscible. Ifthe above ball is in equilibrium vfi7-:::..
in a mixture ofthis oil and water, which o(the folloWing pictures represents its equilibrium position? vr-a-).t1(..}.,1..
( ~ . . {AlEEE-2010). ~
,/1::,"'", v=
/fiA
~4;
( k.
.................
. . . ..............,.. ..
................
( : : :W~fri': : : : :E>J~ ::::: :..... .-:w.a!~r:
.... ..- .....
."-. : :Q!l: :
..... _--- .. ..
.., ........... - .
'"'
(A) ...............
... .. . ... .. .. . . ..
(B) ...............
.. .. .. .. .. .. -., ...
(D)
: : QiJ:
(C) . ...
. . . .. .~ .; .,'"~ ..~
M'~te!:
.: :- ~t : ... ~il' :WJtj~r;
..... ..... ... -
::: -.... .............
t .. ..-........
....... ..
,.. . -.
............ .
f
"'-
Iii
{
L CLASSES
LIMITED
FLUID MECHANICS /49/
c IdeaIfor Scho/O,.
Q.11 Work done in increasing the size ofa soap bubblefrom aradius (lf3 cm to 5 cm is nearly (surface tension
ofsoap solution = 0.03 Nm-I): . [AIEEE-2011]
(A) 4nmJ (B) 0.2nmJ (C) 2.mnJ (D) O.4nmJ
Q.12 Water is flowing continuously from a tap having an internal diameter 8 x 10-:3 m. The water velocity as
it leaves the tap is 0.4 ms-). The diameter ofthe water stream at a distance 2 x 10-1 m below the tap is
close to : [AIEEE-2011]
(A) 5.0 x 10- m 3 (B) 7.5 x 1O~3 in (C) 9.6 x 10- m 3 (D) 3.6 x 10-3 m
Q.13 A uniform cylinder oflength L.and mass M having cross-sectional area A is suspended, with its length
vertical, from a fixed point by a massless spring, such that it is half submerged in a liquid ofdensity at cr
equilibrium position. The extension Xo ofthe spring when it is in equilibrium is :
Mg(
(A)T I-
LAcr) Mg(l_ LAO) Mg(
(C)T l+M
LAcr) (D)T
Mg
M (B) k 2M
(Here k is spring constant) [JEE Main-20 13]
Q.14 Assume that a drop ofliquid evaporates by decrease in its surface energy, so that its temperature remains
unchanged. What should be the minimum radius ofthe drop for this to be possible? The surface tension
is T, density ofliquid is p and L is its latent heat ofvaporization. [JEE Main-20 13]
(A) .,jT/pL (B) T/pL (C) 2T/pL (D) pL/T
SECTION - B
Q.1 A tube oflength L is filled completely with an incompressible liquid ofmass M and closed at both
the ends; The tube is then rotated in a horizontal plane about one of its ends with a uriiform angular , ,
velocity roo The force exerted by the liquid at the other end is - [IIT-92] ,c"
2 2 2
(A) Mro L (B) Mro2L (C) Mro L (D) M:0 L2
2 4 2 .
Q.2 A horizontal pipeline carries water in a streamline flow. At a point along the pipe where the cross-
sectional area is 10 cm2, the water velocity is 1 m s-1 and the pressure is 2000 Pa. The pressure
ofwater at another point where the cross-sectional area is 5 cm2 is (Density ofwater = 103 kg m-3)
[IIT-94]
(A) 500 Pa (B) 1000 Pa . (C) 250 Pa (D) 750 Pa
Q.3 Water from a tap emerges downwards with an initial speed of 1.0 ms-t. The cross-sectional area
'of the tap is 10-4m2• Assume that the pressure is constant throughout the stream of water, and the
flow is steady. the cross-section area of the steam 0.15m below the tap is : .
[IIT-98]
(A) 5.0 x 10-4 m2 (B) 1.0 x 1O-5m 2 (C) 5.0 x 10- m5 2 (D) 2.0 x 10-5 m2
Q.4 A large open tank has two holes in the wall. One is a square- hole of side L at a depth y from
the top and the other isa circular hole ofradius R at a depth 4y from the top. When the tank is
completely filled with water, the quantities ofwater flowing out per second from both holes are the
same. Then, R is equal to - [IIT-2000]
L L
(A) Ji; (B) 2nL (C) L (D) 21t'
FLUID MECHANICS [50}

[t]~~~~A~~ C~~!~! !
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Q.5 /'/A vessel filled with water upto height 3m. There is a hole at height 52.5 em from the bottom. Ratio
ofarea of cross section ofhole to vessel is 0.1. Then square of velocity of the water coming out
of hole in (m/s)2 [IIT-2005] ,
(A) 50 (B) 50.5 (C) 51 (D) 40
Q.6 Statement -1 :The stream ofwater flowing at high speed from a garden hose pipe tends to spread
like'a fountain when held vertically up, but tends to narrow down when held vertically down.
Statement - 2 : In any steady flow of3Q incompressible fluid, the volume flow rate ofthe fluid
remains constant.
(A) Statement - 1 is True, Statement- 2 is True; Statement -2 is a correct explanation for Statement -1
(B) Statement - 1 is True, Statement- 2 is True; Statement -2 is NOT a correct explanation for
Statement -1
(C) Statement-l is True, Statement-2 is False
(D) Statement-l is False, Statement-2is True
( Q. 7 Water is filled up to a height h in a beaker ofradius R as shown in the figure. The density of water
is p, the surface tension of water is T and the atmospheric pressure is Po. Consider a vertical
section ABCD of the water column through a diameter of the beaker. The force on water on one
side of this section by water on the other side of this section has magnitude
[IIT-2008]
,
(
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!h
(
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(A) 12PoRh + JrR2 pgh - 2RTI (B) 12PoRh+R2pgh -2RTI
(C) IPo1ZR2 + Rpgh2 - 2RTI 2

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(D) /PoJrR + Rpgh2 + 2RT/
Q.8 A glass tube of uniform internal radius (r) has a valve separating the two identical ends. Initially,
C
the valve is in a tightly closed position. End I has hemispherical soap bubble ofradius r. End 2 has .
C subhemispherical soap-bubble as shown in figure. Just after opening the valve. Figure :
[IIT-2008]
(
(
'-.
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c 2····
( (A) air from end 1 flows towards end 2. No change in the volUme of the soap bubbles
'v
(B) air from end 1 flows towards end 2. Volume of the soap bubble at end 1 decreases
L (C) no change occurs
(D) air from end 2 flows towards end 1. Volume of the soap bubble at end 1 increases
t
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C [i]~~~~A~~ CL~~~!~ FLUID MECllANICS [51J

IdeoUctSd1%rs
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Paragraph for Question Nos. 9 to 11
A small spherical monoatomic ideal gas bubble ( Y = i) is trapped inside a liquid ofdensity Pe (see
figure).Assume that the bubble does not exchange any heat with the liquid. The bubblecontains n moles
ofgas. The temperature ofthe gas when the bubble is at the bottom is To, the height ofthe liquid is Hand
the atmospheric pressure is Po (Neglect surface tension). '
Figure:
Po
/--'
Q.9 As the bubble moves upwards, besides the buoyancy force the,following forces are acting on it
(A) Only the force ofgravity "
(B) The force due to gravity and the force due to the pressure ofthe liquid
(C) The force due to gravity, the force due to the pressure ofthe liquid and the force due to viscosity of
the liquid '
.r~-
(D) The force due to gravity and the force due to viscosity ofthe liquid [JE E 2008]
Q .10 W hen the gasbubbJe .isatahe:ighty from thebotlDm ,.1istem pexatum.is
PO + pegH)2/5 (B) To(PO + Peg(H - y»)2/5
. (A) To ( Po+Pegy Po +PlgH
315
PO+PlgH , (D) To(PO :Plg(H_y»)3/5
(C)To(po +p,gy ) [JEE2008]
"'o+Pt'gH. /~ "'
Q.ll The buoyancy forCe acting on the gas bubble is (Assume R is the universal gas co~tant)[JEi3 2003]
,
(Po +PlgH) 215
Pl nRgT.0
(A) PlnRgTo (Po +Plgyf /5 (B) (Po +PegH/15[Po +Pt'g(H-y)i I5
3/5 PenRgTo
(Po+PlgH)
(C) PlnRg T0 (Po +Pegy) 815 (D) (Po + PegH)3/5[Po + Peg(H _ y)]2/5
Q.12 A cylindricalvessel ofheight 500mmhas an orifice (small hole) at its bottom. The orifice is initiallyclosed
arid water is filled in it up to heightH. Now the top is oompletely sealed with a cap an4the orifice at the
'bottom is opened. Some water comes out from the orifice and the water level in the vessel becomes
steady with height ofwater coluinn being 200 inm. Find the fall in height (in mm) ofwater level due to
opening ofthe orifice. '
[Take atmospheric pressure = 1.0 x 1.05 N/m2, density ofwater = 1000 kg/m3 and g = 10 ~S2. Neglect
any effect ofsurface tension.] [JEE-2009]
{ '.
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[i ~~~~A~~CL~~!~! IdeaIfolSt:h"~rs
Q.1 J TW3 soap bubbles A and B are kept in a closed chamber where the air is maintained at pressure SN/rn2•
The radii ofbubbles A and B are 2 em and 4cm, respectively. Surface tension ofthe soap-water used to
make bubbles is 0.04 N/m. Find the ratio nJnA' where nA and nB are the number ofmoles ofair in
bubbles A and B, respectively. [Neglect the effect ofgravity] [JEE-2009]
/' -"
Paragraph for Questions 14 to 16

When liquid medicine ofdensity p is to be put in the eye, it is done with the help ofa dropper. As the bulb
on the top ofthe dropper is pressed, a drop fonns at the opening ofthe dropper. We wish to estimate the
size ofthe drop. We first assume that the drop fonned at the opening is spherical because that requires
a minimum increase in its surface energy. To detennine the size, we calculate the net vertical force due to
the surface tension T when the radius ofthe drop is R. When this force becomes smaller than the weight
;'
ofthe drop, the drop gets detached from the dropper.
\
Q.14 Ifthe radius ofthe opening ofthe dropper is r, the vertical force due to the surface tension on the drop of
("
radius R (assuming r« R) is
(C) 21tr2T (D) 21tR2T

" (A) 2mT (B) 21tRT
"
/
R r
" Q.15 Ifr= 5 x 10-4 m, p 10-3 g= lOms-2T=0.11 Nm'l, the radius ofthe drop when it detaches from the
dropper is aproximately [JEE-20 10]
(A) 1.4 x 10-3 m (B) 3.3 X 10-3 m (C) 2.0 x 1O-~ m (D) 4.1 x 10-3 m
( Q .16 Aft~r the drop detaches, its surface ene:gy is [JEE-2010]
(A) l.4x lO-6J (B) 2.7 x 10-6 J (C) 5.4 X 10-6 J (D) 8.1 X 10-6 J
( ~. Q .17 A tiny spherical oil drop canying a net charge q is balanced in still aire with a vertical unifonn electric field
81. _ .
ofstrength 7 x lOS V m-I . When the field is switched off, the drop is observed to fall with tenninal
(
f
velocity 2 x 10-3 m S-I. Given g = 9.8 ms-2, viscosity ofthe ~r = 1.S x 1O-s Ns m-2and the density ofoil
\. ..
= 900 kg m-3, the magnitude ofq is [JEE-20 10]
(A) 1.6 x 1O-19C (B) 3.2 x 1O-19C (C) 4.8 X 1O-19C (D) 8.0 x 10-19C
(. . Q .18 Four point charges, each of +q are rigidly fixed at the four comers ofa square planar soap film ofside
( 'a'. Thesurfacetensionoftheso~pfilmisy. The system ofcharges and planar film are in equilibrium, and
2]IIN
c a= k [~ , where 'k' is a constant. Then N is . [~rEE-2011 ]
c
i
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I. FLUID MECHANICS
IdeoIforSd!ckJrs
(
Paragraph for Questions 19 to 21
Phase space diagrams are useful tools in analyzing all kinds ofdynamical problems. Theyare especially
useful instudyingthe changes inmotion as initial positionand momentumare changed. Here we consider
some simple dynamical systems in one-dimension. For such systems, phase space is a plane in which
position is ploatted alonglorizontal axis and momentum is plotted along vertical axis. The phase space
diagram is x(t) vs. pet) curve in this plane. The arrow on the curve indicates the time flow. For example,
.the pbase space diagram for a partiCle moving with constant velocity is a straight line as shown in the
figure. We use the sign convention in which position OF momentumupwards (or to right) is positive and
downwards (or to left) is negative.
1
• ~ J w
.0
~
;:;.s '1.--_ _ _ __
Position
Q.19 The phase space diagram for a ball thrown vertically up from ground is [JEE-2011]
Momemtum Momemtum Momemtum Momemtum
Position
(A) Position (B) (C) Position (D)
Position
Q.20 The phase Space diagram for simple hannonic motion is a circle centrered at the origin. In the figure, the
two circles represent the same oscillator but for different initial conditions, and EI and Ez are the total
mechanical energies respectively. Then [JEE-2011]
,f "
Momemtun
r~
\._j
Position
(A) E} =J2E2 (B) EI = 2 Ez (C) El =4 Ez (D) E} = 16Ez
FLUID MECHANICS [541

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'x, . Consider the spring-mass ~ystem, with the mass submerged in water, as shown in the figure. The ph(;lSe
diagram for one cycle ofthis system is [JEE-20ll] ,
Momemtum Momemtum
(A) (B) 'osition
(
Momemtum Momemtum
"
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I
, Q.22 Two solid spheres A and B ofequal volumes but ofdifferent densities dAand ~ are connected by a
string. They are fully immersed in a fluid ofdensity~. They get arranged into an equilibrium state as
(
'.
hownin !he figure with a tension in the string. The sinmgement is possible only if [JEE-2011]
( (A)dA<~ (B)~>~ (C)dA>~ (D)dA+~=2~

Q.23 A thin unifonncylindrical shell, closed at bothends, is partiallyfilled with water. It is floating vertically in
( water in half-submerged state. IfPc is the relative density ofthe material ofthe shell withrespectto water,
then the correct statement is thatthe-shell is [JEE-20l2] ,
(
(A) more than half-filled if Pc is less than 0.5 (B) more than half-filled ifPc is more than 1.0
( (C) half-filled ifPc is more than 0.5 (D) less than half-filled ifPc is less than 0.5
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FLUID MECHANICS /55J
(
ANSWER-KEY
EXERCISE-I
Q.2 A Q.3 C Q.4 C Q.5 B

Q.1 B
A Q.7 A Q.8 D Q.9 C Q.10 A
Q.6
D. Q.12 A Q.13 B Q.14 A Q.15 A·
Q.ll
Q.16 A Q.17 B Q.18 A Q.19 C Q.20 A
Q.21 A Q.22 C Q.23 C Q.24 D Q.25 B
Q.26 B Q.27 C Q.28 A Q.29 B Q.30 A
Q.32 D Q.33 C Q.34 A Q.35 B
Q.31 A
Q.37 C Q.38 C Q.39 D Q.40 D
Q.36 D
A -Q.42 C Q.43 A Q.44 A Q.45 D
Q.41
Q,46 C Q.47 A Q,48 D Q.49 B Q.50 A
Q.51 C Q.52 D Q.53 D Q.54 D Q.55 A
Q.57 C Q.58 C Q.59 D Q.60 A
Q.56 A
Q.61 ·C Q.62 B 'Q:63 D Q.64 C Q.65 C
Q.67 C Q.68 D Q.69 B Q.70 C , '
/'
Q.66 B ~
Q.71 C Q.72 C Q.73 C Q.74 D Q.75 B

Q.77 B Q.78 A Q.79 A Q.80 A
Q.76 D
Q.82 C Q.83 C Q.84 D Q.85 C
Q.81 B
Q.86 B Q.87 B Q.88 B Q.89 B Q.90 A
Q.91 A Q.92 B Q.93 D
EXERCISE-II
Q.2 B Q.3 B Q.4 C Q.5 B
Q.1 D i
\. ~
D Q.7 D Q.8 D Q.9 B Q.10 C
Q.6
Q.ll A Q.12 B Q.13 D Q.14 A Q.15 B ('
Q.16 C Q.17 D Q.18 A Q.19 D Q.20 A

Q.23 A Q.24 B Q.25 B ", ..
Q.2l B Q.22 A
Q.27 B Q.28 D Q.29 B Q.30 C
Q.26 B
Q.32 D Q.33 D Q.34 C Q.35 A
Q.31 B
Q.37 B Q.38 B Q.39 B Q.40 A
Q.36 D
Q.42 C Q.43 A
Q,44 C Q.45 C
Q.41 D·
Q.47 B Q.48 A Q.49 C Q.50 C
Q,46 D
Q.52 B Q.53 C Q.54 C Q.55 B
Q.51 D
Q.56 B
EXERCISE-III ('
',,"
Q.3 B Q.4 C Q.5 C

Q.1 D Q.2 A
B Q.8 C Q.9 A Q.I0 A
Q.6 B Q.7
Q.13 B Q.14 C Q.15 D
Q.ll D Q.12 B
Q.18 A. Q.19 D Q.20 A
Q.16 C Q.17 D
Q.23 D Q.24 D Q.25 B
. Q.21 A Q.22 C
Q.28 C Q.~9 B Q.30 D
Q.26 B .Q.27 D
Q.33 B Q.34 C Q.35. C
Q.31 C Q.32 A
Q.38 A Q.39 D Q.40 B c- :
Q.36 B Q.37 D "-../
Q.43· B Q.44 A Q.45 A
QA1 D Q.42 A
Q.48 B Q.49 C Q.50 C
Q,46.B Q.47 B
Q.53 B Q.54 B Q.55 D
Q.51 D Q.52 A
C
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EXERCISE-IV
QUESTIONS FROM LAST YEARS AIEEE & IIT-JEE PAPERS
SECTION-A
Q.l B Q.2 C Q.3 B Q.4 A Q.5 D

Q.6 A Q.7 C Q.8 B Q.9 D Q.I0 D
Q.1l D Q.12 D Q.13 B Q.14 C
SECTION - B
Q.l A Q.2 A Q.3 C Q.4 A Q.5 A
,
/
Q.6 A Q.7 B Q.8 B Q.9 D Q.I0 B
Q.ll B Q.12 6 Q.13 6 Q.14 C Q.15 A
Q.16 B Q.17 D Q.18 3 Q.19 D Q.20 C
Q.21 B Q.22 D Q.23 A·
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( ERRORS IN MEASUREMENTS
& INSTRUMENTS
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ERRORS
Measurement is the process ofdeterrninationthe value ofa physical quantity experimentally with the help
ofspeciaLtechnical means called measuring instruments. Almost all measurements are subject to both
random and systematic uncertainties.
(a) Systematic (Determinate) errors

(b) Random (Indeterminate) errors
a) Systematic errors:
It has definite direction and magnitude (+ive or - ive).
It has same size in all measurements.
It has assignable cause (their cause can be determined).
It can be eliminated. <;)
Cannot !:Ie revealed by repeating the measurements.
Possible causes for systematic errors are :
Error in the procedure,
,r Instrumental measurement errors: faulty calibration ofscale.

Choosing certain standard value in calculation having lesser significant digits.
Flaw in design ofexperiment (Methodological errors):
C b) Random errors: Theword random indicates that they are inherently unpredictable and its expected
value or arithmetic mean is zero. It can be minimized by repeating the measurement several times, and
,
('
taking average ofit but cannot be eliminated. Random errors have no fixed sign or size.
Sources ofrandom error are:
small errors during interpolating - reading between scale markings (because ofoperator).
(
small disturbances ofthe apparatus (such as mechanical vibrations),
" Limitation ofmeasuring instrument - sometimes experiment cannot be perfonned more than
r'
(
" once.
( Problem ofdefinition and several others.
The effect ofrandom error can be some what reduced by taking the average ofmeasured values.
A measurement with relatively small random error is said to have high precision. A measurement with
( small random error and small systematic error is said to have high accuracy.
Absolute Error
( Error may be expressed as absolute measures, giving the size ofthe error in a quantity in the same units
as the quantity itself.
(
". Least Count Error :- Ifthe instrument has known least count, the absolute erroris taken to be halfofthe
( least count unless otherwise stated. For measuring the time elapsed, the error in the stop watch is taken
"-,
to be the least count.
(
Relative (or Fractional) Error
C Error may be expressed as relative measures, giving the ratio ofthe quantity's error to the quantity itself.
absolute error in a measurement
In general, Relative error
size of the measurement
c We should
. know the error in the measurement because these errors propagate
. through the calculations
( to produce errors in results.
( '[i!~~A~~CL~~~~! mOl11){ Scholars

Errors in Measurements & Instruments /1)
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Straight sum (provisional) rule for random & systematic error:
Rule Formula .s.ysternatic Random
r+dr or r tlr r±dr
Addition R=x+y dR=dx+dy dR=dx+dy
subtraction R=x-y dR=dx-<{v dR=dx+dy

(dx tiv \ aY ')
Product R=x.V dR=R( -+....::- r dR=R{"d~ +-,'
"x v I ..,'
,'\ .},
Quotient R_
-
x
dR=RI---~
I'dx til") dR=R~-+-
(dr ely)
Y \ x Y.l X Y
dR dx dR dx
POlver R=Xll -=a- -=a-
R x R x '. '
Quotient r"
1 1 1 dR dx dy dR dx ely
R=-~-
xv -=-+ --~=-?--
R'" x y:1 - R2 =-1 2
R x y X Y ,,-'''.
x+y
Examples
1. A student fmds the constant acceleration ofa slowly moving object with a stopwatch. The equation used ( ,
( ~
is S = (1I2)AT2. The time is measured with a stopwatch, the distance, S with a meter stick. What is the
acceleration and its estimated error?
S = 2 ± 0.005 meter.
T = 4.2 ± 0.2 second. \../
Sol: We use capital letters for quantities, lower case for errors. Solve the equation for the result, a. ('
2 .• a 2t s
A 2S/ T . Its random-error equation IS A T + S ; ,
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Thus A = 0.23 ± 0.02 mls2•
SIGNIFICANT DIGITS
Significant figures are digits that are statistically significant. There are two kinds ofvalues in science:
1. Measured Values
2. Computed Values
The way that we identifY the propernumherofsignificant figures in scienceare different for these two types.
MEASURED VALUES
IdentifYing a measured value with the correct number ofsignificant digits. reqUires that the instrument's r· ,
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calibration be taken into consideration. The last significant digit in a measured value will be the first
estimated position.For example, a metric ruler is calibrated with numbered calibrations equal to 1 cm. In
addition, there will be ten unnumbered calibration marks between each numbered position. (each equal
to 0.1 cm). Then one could with alittle practice estimate between each ofthose marking. (each equal to
0.05 cm). That first estimated positionwould be the last significant digit reported in the measuredvalue. Let's
say that wewere measuringthe lengthofatube, and itextendedpastthe fourteenth numbered calibrationhalf
way rernreen thethird and fourth unnumbered mark. The metric rulerwas a meter stick with 100numbered
()
calibrations. The reported measured length would he 14.35 cm. Here the total number ofsignificant digits
will be 4.
L
Errors in Measurements &: Instruments [2J
[I] ~~~~A~ CLL,~~!~!
Ideal (or Schalors
COMPUTED VALUE
The other type ofvalue is a computed value. The proper number ofsignificant tigures that a computed
value should have is decided by a set ofconventional rules.However before we get to those rules for
computed values we have to consider how to detennine how many significant digits are indicated in the
numbers being used in the math computation.
A. Rules for determining the number ofsignificant digits in number with indicated decimals.
.1'
"., 1. All non-zero digits (1-9) are to be counted as significant.
2. Zeros that have any non-zero digits anywhere to the LEFT ofthem are considered significant zeros.
3. All other zeros not covered in rule (ii) above are NOT be considered significant digits.
For example: 0.0040000
The 4 is obviously to be counted significant (Rule-I), but what about the zeros? The first three zeros
would not be considered significant since they have no non-zero digits anywhere to their left (Rule- 3).
The last four zeros would all be considered significant since each ofthem has the non-zero digit 4 to their
left (Rule-2). Therefore the number has a total offive significant digits.
Here is another example: 120.00420
The digit 1,2, 4 and 2 are all considered significant (Rule-I). All zer9s are considered significant since
they have non-zero digits somewhere to their left (Rule-2). So there are a total ofeight significant digits.
Ifin the question, we are given a number like 100, we will treat that the number has only one significant
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digit by convention.
B.
Determining the number ofsignificant digits ifnumber is not having an indicated decimal.
The decimal indicated in a number tells us to what position ofestimation the number has been indicated.
But what about 1,000,000?
Notice that there is no decimal indicated in the number. In other words, there is an ambiguity concerning
the estimated position. This ambiguity can only be clarified by placing the nUlTl.ber in exponential notation.
For exampJe : In write the number above in this manner.
I' • 1.00 x 106
~.
I have indicated that the number has been recorded with three significant digits. On the other hand, in
( write the same number as : 1.0000 x 106
('
I have identified the number to have 5 significant digits. Once the number has been expressed in exponential
'" . notation form then the digits that appear before the power often will all be considered significant. So for
example: 2.0040 x 104 will have five significant digits. This means that unit conversion will not cbange
. the number ofsignificant digits. ThusO.OOOOlOkm = l.0 cm=O.OlOm= l.0 x 10-2m 1.0 x 10-5 km
( Rule for expressing proper number ofsignificant digits in an answer from multiplication or division
(
.~
For multiplication AND division there is the following rule for expressing a computed product or quotient
with the proper number ofsignificant digits.
( The product or quotient will be reported as having as many significant digits as the number
( involved in the operation with the least number ofsignificant digits.
Fotexample: 0.000170 x 100.40 = 0.017068
c The product could be expressed with no more that three significant Jigits since 0.000170 has only three
significant digits, and 100.40 has five. So according to the rule the product answer could only be expressed
c with three significant digits. Thus the answer should be 0.0171 (after rounding oft)
c· Another example: 2.000 x 104 /6.0 x 10-3 0.33 x 107
(
ALCLASSES Errors in Measurements & Instruments 13)

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The answer could be expressed with no more that two significant digits since the least digited nwnber
invoIved in the operation has two significantdigits.
Sometimes this would required expressing the answer in exponential notation.
For example: 3.0 x 800.0 2.4 x 103
The number 3.0 has two significant digits and then number 800.0 has four. The rule states thatthe answer
can have no more than two digits expressed. However the answer as we can all see would be 2400.
How do we express the answer 2400 while obeying the rules? The only way is to express the answer in
exponential notation so 2400 could be expressed as : 2.4 x 103
Rule for expressing the correct number ofsignificant digits in an addition or substraction:
The.rule for expressing a sum or difference is considerably different than the one for multiplication of
division. The sumordifferencecanbeno moreprecisethan the leastprecisenumberinvolvedinthe mathernatica1
operationPrecision has to do with the number ofpositions to the RIGHT ofthe deciIm>1. The more position
to the right ofthe decimal, the more precise the number. So asumor difference can have no more indicated
positions to the right ofthe decimal as the number involved in the operation with the LEAST indicated
positions to the right ofits decimal.
For example: 160.45 + 6.732 = 167.18 (after rounding off)
The answer could be expressed only to two positions to the right ofthe decimal, since 160.45 is the least
precise.
Another example : 45.621 +4.3-6.41 =43.5 (after rounding off)
The answer could be expressedonly to one position to the right ofthe decimal, since the number 4.3 is the
least precise number (i.e. having only one position to the right ofits decimal). Notice we aren't really
determining the total riumber ofsignificant digits in the answer with this rule.
\
Rules for rounding off digits: j
There are a set ofconventional rules for rounding off. ,

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I. Determine according to the rule what the last repOlted digit should be.· ( ,
2. Consider the digit to the rigl!t ofthe last reported digit.
3. Ifthe digittothe right ofthe last reported digit is less than 5 round it and all digits to its right off.
4. If the digit to the right ofthe last reported digit is greater than 5 round it and all digits to its right off and
r'·
increased the last reported digit by one. ',,-_/
5. Ifthe digit to the right ofthe last reported digit is a 5 followed by either no other digits or all zeros, round r- ",
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it and all digits to its light offand ifthe last reported digit is odd round up to the next even digit Ifthe last
'.
reported digit is even then leave it as is.
For example ifwe wish to round offthe following number to 3 sigrificant digits: 18.3682
The last reported digits would be the 3. The digit to its right is a 6 which is greater than 5. According to
(
the Rule-4 above, the digit 3 is increased by one and the answer is : 18.4 'J
Another example: Round off4.565 to three significant \
digits. c
The last reported digit would be the 6. The digitto the right is a 5 followed by nothing. Therefore (
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according to Rule-5 above since the 6 is ever! it remains so and the answer would be 4.56.
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Errors in Measurements & Instruments [4J

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EXPERIMENTS
(i) Measurement oflength
The simplest method measuring the length ofa straight line is by means ofa meter scale. But there exists
some limitation in the accuracy ofthe result:
(i) the dividing lines have a finite thickness.
(ii) naked eye cannot correctly estimate less than 0.5 mm
For greater accuracy devices like
{a) Vernier callipers (b) micrometer scales (screw gauge) are used.
VERNIER CALLIPERS:
(
\
USING VERNIER CALIPER ONE CAN MEASURE
A) INNER DIAMETER OF OBJECT
B) OUTER DIAMETER OF OBJECT
C)DEPTH OF OBJECT
(
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Vernier Scale
Main Scale
(
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(
C D Vernier Callipers
(
The instrument can have systematic error in it. The diagrnm below shows different situations in this case.
( a) No error: Zero ofmain scale is coinciding with the zero ofvernier scale.
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"~[I!~~~!!~ Cl.~~~~! Errors in Measurements & Instruments [51
( Tor Scho/Qrs
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b) Positive elTor: c) Negative ElTor:
Vernier scale zero to right ofmain scale zero. Vernier scale zero to left ofmain scale zero.
Least count ofVernier Caliper:

Just as meter scale has least count of1mm, vernier caliper also has its least count.
Imm 9mm
r\
0.9mm
a) Count the number ofdivision in VS (lOin above figure)
b) Match the zero ofVS with zero ofMS.
c) See where 10th division ofVS coincides with MS.
In this case it is 9 mm. [:. 10 division ofVS has 9 mm length]

, 9
d) ,Reading of I division in VS = least count VS = 10 = 0.9 mm I
,
"
[This is also called I vernier scale division (1 vsd)] ;(
e) Least count ofthe instrument = I.Omm-0.9mm 0,1 rom \
Ofcourse, this value is consecutive distance between smaller divisions on VS. In the figure above, ('
we can see that zero ofMS and VS are coinciding. Thus, there is no elTor in the instrument. \ /
Least count (LC) of Vernier Callipers (in general)
The least count or Vernier constant (v. c) is the minimum value ofCOlTect estimation oflength without eye
f~
estimation. IfN division ofvernier coincides with (N-I) division ofmain scale, then '-../
Nt
N (VS) = (N - 1) ms => I VS = N ms
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N-I) 1ms
Vernier constant = 1 ms - 1 vs = ( 1 N ms = N' which is equalto the value ofthe smallest
/'
~ ~-'
division on the main scale divided by total number ofdivisions on the vernier scale.
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Errors in Measurements & Instruments {6J

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How to calculate zero error:
Ifthe zero marking ofmain scale and vernier calipers do not coincide, necessary correction has to be
made for this error which is known as zero error ofthe instrument.
a) postive zero error
,(
coinciding
En-or = 4 x LC 0.4 mm
This is already reading some positive value. Thus, when we measure length, then it will measure more
length than what actually it is. Thus, we should subtract the error in the final answer.
(
When the caliper is in the position shown, then the zero error will be determined by where the MSD and
\
VSD are coinciding (call it Inl).
positive zero error = n x LC
b) Negative zero Error
(
\
("
coinciding
( Error 6 x LC = - 0.4 mm
" negative zero error=-[Total no. ofvsd-vsdcoinciding] x L.C
( Length as measured by Vernier Callipers

Mainsca1ereading: MSD
("
Verniersca1edivisioncoinciding with amainscale division: LCD
'" The formula for measuring the length is L:
= MSR + LC ofvernier scale x LCD - zero error
Do not try to read the main scale at the point where the lLlles match best. Thi3 has no meaning. Read
,
\.
from the vernier scale instead. Sometimes it is difficult to tell whether the best match oflines is for
vernier marks 9, 0, or 1. Make your best estimate, but realize that the final result including the vernier
( must round offto the result you would choose ifthere was no vernier. Ifthe mark is close to 3.20 on the
(
main scale, but the vernierreading is 9, the length is 3.19 cm. Ifthe mark is close to 3.2 on the main scale
and the vernier is 1, the length is 3.21 cm.
(
"'-"
(
I"
~" [j]~~~~A~~ CL~~~~! Errors in Measurements & Instruments [7J

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Reading without zero error:
coinciding (= 6 x LC = 0.6 mm)

The above vernier caliper has LC of0.1 mm.
" VS zero is little ahead of22nd reading ofMS
" Vernier scale's 6th reading is coinciding with the MS.
" Reading = 22.0 + 6x 0.1 = 22.6 mm
SCREW GAUGE ,<~R MICROMETER SCREW)

In general vernier callipers can measure accurately upto 0.01 cm and ['\
for greater accuracy micrometer screw devices e.g. screw gauge,

" '
spherometer ar~ used. These consist ofaccurately cut screw which can
be moved in a closely fitting fixed nut by turning it axially. The instrument
is provided with two scales:
Screw head
Direction+ ~~ ~
of motion
"
Screw Gauge "\, ./
Principle of a micrometer
.The instrument can have systematic error in it. The c1.iagram below shows differ~nt situations in tfljs case.
a) b) c)
'"
o
graduation
E
E Positive zero error Negative zero error
(2 division error) i.e.,+O.002 cm (3 division error) i.e.,-O.003 cm
Screw gauge with no zero error
(zero of main scale is visible) (zero of main seale is hidden)
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Errors in Measurements & Instruments f8]

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Ideollor Scholars
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Least count of Micrometer:
Generally micrometer has two scales. Along with the scales I am also mentioning their least count.
a) Main scale: LC 0.5 mm (see consecutive readings)
Pitch distance b/w two consecutive threads = LC of main scale.
distance moved by screw for one complete rotation of cap.
number of main scale

(
'.
pitch
number of rotation made
b) Vernier scale on rotating screw: It has 50 divisions.
When I give the screw one complete rotation(Le. rotate by 50 divisions), then the measuring rod
moves by 0.5 mm.
( 1 division ~ 0.5/50 mm = 0.01 mm = LC of vernier scale

(
Le
number of division on main scale
"
(
meaSuring rod
/
\
d=O.OO mm
( How to calculate zero error:

Ifthe zero marking ofmain scale and vernier calipers do not coincide, necessary correction has to be
made for this error which is known as zero error ofthe instrument.
a) postive zero error
(
(
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:2345
(
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(
(
False reading = 0+ 1 xO.Ol =0.01 mm
t: That means we are already reading something, when the jaws are touching. Thus, in the final answer, We
should subtract the false reading.
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b) Negative zero error: In this case the zero ofmain scale is hidden.
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Figure shows:
a) Jaws are touching
b) 49th reading coincides with graduation line
:. Negative Error 0....:(50-49)xO.Ol = - 0.01 nun
Reading using micrometer:
1"···T·r.·,·,·~.1-- 0
45
'_ 40
Reading = 3.00 + 49 x 0.01 = 3.49 mm I

\ /
SIMPLE PENDULUM
AIM
To study dissipation ofenergy ofa simple pendulum by plotting a graph between square ofamplitllde.
and time.
APPARATUS
Ticker timer, paper tape, meter scale, thread, clamp, metallic brick as bob, clamps, split cork and a
spring balanc~.
c
THEORY
The energy ofa simpJe harmonic oscillator is directly proportional to its amplitude. When the bob of
a simple pendulum is set into vibrations, its amplitude goes on decreasing with time due to friction of .
air and friction at the point ofsupport. Such vibrations whose amplitude decreases with time due to
some dissipative force are called damped vibrations. The vibrations ofsimple pendulum are also
damped vibrations.
At any time t the energy Et is given by Et E.e-At, where Ais the decay constant and energy E is given
by E ~ KA 2 where A is the amplitude and K is force constant.
Errors in Measurements & Instruments flO]

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.
,
( Clamps
Metallic
Brick
Ticker I Irto//
Timer
PROCEDURE
1. Find the mass ofthe metallic brick by the spring balance.
2. Fix the clamp stand on the edge ofthe table with the help ofclamps.
3. The one end ofthe thread with the metallic brick and pass the other end ofthe thread through the split
(
cork hold the cork in the clamp stand.
( 4. Fix the ticker timer at the same height above the ground on the brick is attach the paper tape at the
" centre ofthe brick with the help ofthe cello tape.
(
5. Pull the brick towards the ticker timer and taut the paper tape. Start the ticker timer and release the
"
( brick.
" 6. As the brick reaches the outer extreme switch offthe ticker timer.
( 7. Remove the paper tape. The pattern ofdots obtained on the tape will be as shown below
(
Paper tape
(
c 8. Mark the central dot A and the extreme dots B and C corrensponding to the extreme positions ofthe
mettllick brick.
c 9. Measure the distance ofthe dots from the central dot A.
(, OBSERVATIONS
,.
{, Least count offor spring balance ....... kg
Corrected mass ofthe metallic block m= ...... kg
( Time period ofticker-timer (one tick) = ...... sec
( Length ofsimple pendulum, = L = ..... , .. m
( Side from central dot S. no. ofdot from Displacement from (AmPlitude)zl .Time Interval
( central dot (A) central dot A (m) t = No. of dot x time period
Amplitude
I
Right 2
c 3
I
c Left 2
3 I
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Errors in Measurements & Instruments {llJ
L
GRAPH
y
A2
L,-----~x
o t---'" , ..
From the graph it is clear that Energy ex; (Amp? and the energy ofthe pendulum decreases with time.
PRECAUTIONS
1. An inextensible and string thread should be used for making the pendulum.
(
2. The lower faces ofthe split cork should lie in the same horizontal plane. '
3. The amplitude ofocsillation should be kept small. ,r--,
4. The experiment should be performed at a place which in free from any air disturbance.
/",
S. The metallic brick should be suspended close to the ground. \ .

6. The metallic brick should move along the refrence line without any j erkey motion.
RESULT
This shows that the energy is being transferred from kinetic to potential and vice versa. From the
above graph it is proved that there is dissipation ofenergy during SHM ofsimple pendulum. ,
PRECAUTIONS ,
'- ~
1. Pendulum support should be rigid.
2. The anlplitude should remain small. "". /
3. Pendulum should be sufficiently long (about 2 metres)

4. Pulling string should be used to avoid spinning ofthe me1cllic block.
(",
S. Paper tape should be attached to the centre ofthe bottom of the block. \.../
SOURCE OF ERROR
c
1. The support may not be fully rigid.
2. Movement ofmetallic block may not be proper. c
( ,
\.../
METRE SCALE
AIM C· "' j
To determine the mass ofa given body using a metre scale by principle ofmoments. ( ,
\..../
APPARATUS
A metre scale, a broad heavy wedge with sharp·edge, a weight box, a body ofunknown mass.
c
THEORY c
Metre scale as a beam balance:
(a) Introduction: Like a physical balance, a metre scale can be.used as a beam balance making use of
e
t "..,
the same principle ofmoments. V
Besides it has adjustable power arm and weight arm about fulcrum whose length can be adjusted. ('
\..../
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(b) Diagram: See fig.
Mg
Figure (a) Metre-scale balance.
Power and weight arms of equal length.
Mg
Figure (b) Metre-scale balance.
Power and weight arms of unequal length.
( (c) Construction (Arrangement) : The metre scale is balanced by putting its 50 cm mark over the
sharp edge ofa heavy broad wedge which works as fu1cr.nn. In this position the weight ofthe metre
scale and reaction ofthe wedge, balance each other.
(d) Working: The body is tied to a strong and light thread loop and suspended on the left ofthe wedge
gIl: some fixed mark. (Say 20 em in diagram)
Alight paper pan is suspended by a strong and light thread on the right. Weights are put on the pan.
f
The position ofthe loop of the pan and weight in it are so adjusted that the metre scale becomes
horizontal again.
Position ofthread ofthe loops and the amount ofweights in the pan are noted.
Mass ofthe body is calculated using following theory.
,.
(
(e) Theory: Ifm and M be the mass ofthe body and mass of the weight used and a 1 and ~ be the
( distance oftheir loops from wedge. Then, power (mass) arm = a 1, weight arm 8:l
\ ..
From principle ofmoments mg a 1 Mg 8:l
or m = Ma2 , which can be calculated.
al
(1) Two different methods:

( (i) Ann lengths fixed and equal and weight adjustable.
The thread loops are suspended at position forming both ami ofequal length. Weights in the paper
(
pan are adjusted till the metre scale becomes horizontal. (figure (a».
In this case a} = ~ = a
C
Hence, mga} = Mg~
or m=M
( A physical balance makes use ofthis method.
(ii) Masses and power ann fixed and weight arm adjustable.
t Mass is suspended at a fixed distance aI'
Length ofpower mm is adjusted by moving weight loop thread in and out till the metre scale becomes
C horizontal (figure (b»
C In this case a l a, ~ A
( [I~~~~A~~CL~~~~~
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Hence mga l = Mga2, becomes mg a MgA
A
or m=M
a
PROCEDURE
(i) First method
1. Arrange the metre scale horizontally by supporting it at the sharp edge ofthe broad heavy wedge at
50cmmark.
2. Suspended the body ofunknown mass by a loop thread at a fixed mark on the left ofthe wedge.
3. Suspended paper pan at same distance on the right ofthe wedge with some weights in it.
4. Adjust the weights in paper pan till the metre scale becomes horizontaL
5. Note the mass ofthe weights in the pan.
6. Repeat steps 2 to 5, three time by increasing the length ofthe arms in equal steps keeping the lengths
equal.
7. Record the observations as given below in table.
OBSERVATION AND CALCULATIONS
S. No. Length of weight Mass ofW eight in th e Unknown mass
f'
(or power) arm Paper pan (body)
a (cm) M(g) meg)
I. 30 MI '"'20 ml =Ml 20
2. 35 M2 =20 m2 M2 20
, 3. 40 M3 "'20 m3 M3 20
-
(Note: Observations are as sample)

_ illl +m2 +m3
Mean mass, m- g ... g
3 '
It will be found that Ml = M2 = M3 m in all cases. \., ,
RESULT
The unknown mass ofthe body, m = 20 g
(ii) Second method
1, 2. Step 1 and 2 offirst method.
f"
3. Suspend the paper pan on the right ofthe wedge with some known weight in it.
4. Adjust the distance ofthe paper pan till the metre scale becomes horizontal.
5. Note the position ofthe paper pan and thus length ofthe weight arm.
6. Repeat steps 2 to 5, three times by increasing the ma~s ofthe weights by equal amount.
7. Record the observations as given below in table.
OBSERVATIONS AND CALCULATIONS
Fixed length ofpower arm = a = 25 cm
S.No. Mass ofweight Length ofthe Unknown mass
in the paper pan Weight arm (body)
M(g) A(em) m(g)
MIAI
1. 20 Al =30 ml =--=24
a
MA
ffi2 == _2_2 = 24
2. 30 A2 =20
a
M3A.3
3. 40 A3 = 15 m3=-- =24
a
(Note: Observations are as sample) ('
{14] "-'
Errors in Measurements & Instruments
[I ~~~~~~ CLL,~~!!!Ideal (or Scholal'$
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v
ml +m2 +m3 .
Mean mass, m= ,.,
;)
g=,..g
It will be found that m l = m2 m3 = m in all cases.
RESULT
The unknown mass ofthe body, m = 24 g
PRECAUTIONS
, 1. The wedge should be broad and heavy with sharp edge.
\
2. Metre scale should have uniform mass distribution.
3. Threads used for loops should be thin, light and strong.
SOURCES OF ERROR
1. The wedge may not be sharp.

2. Metre scale may have faulty calibration.
3. The threads used for loops may be thick and heavy.
SURFACE TENSION
AIM
(
To determine the surface tension ofwater by capillary rise method.
(
" APPARATUS
/
Three capillary tubes ofdifferent radii and a tipped pointer clamped in a metallic plate with a handle,
" travelling microscope, clamp and stand, a fine motion adjustable height stand, a flat bottom open dish,
(
clean water in a beaker, thermometer.
/
~
THEORY
( Rise ofliquid level in a capillary tube (Ascent formula):
( Let a capillary tube be dipped in a liquid which makes concave meniscus in the tube. Due to surface
\.
tension, the tube molecules exert a force T on the liquid molecuies in the unit iength of the circle of
( contact ofthe liquid surface with the tube. This force acts at an angle e (angle ofcontact) with the wall
ofthe vessel [fig. (a)]. Components T sin e perpendicular to the wall ofthe tube cancel for the whole
circle. Component T cose along the wall ofthe tube become added. For the tube ofradius r, the circle
{
'-.
ofcontact has circumference 2nr and the upward force on all molecules becomes 2nrT cos e.
It is this upward force that pulls the lkluid upward in the capillary tube. The liquid rises in the capillary
( tube upto a height till the weight ofthe liquid risen equals this force.
t:
~
Let the liquid rise upto a height h(as measured for the lower meniscus B) and let the meniscus ABC
have hemispherical shape [Fig. (b)].
Then, voume ofthe liquid risen upto lower meniscus = 1tr2h.
( Volume ofliquid in meniscus above B [Fig. (b)]
"'-..
= Volume ofcylinder ofradius and height r - Volume ofhemisphere ofradius r
( 2 1
= nr2. r- '3 nr3 = 3 nr3
C
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Errors in Measurements & Instruments [15)
'-..
Tcos e Tcos e
A.•••••L .....?-......L ....9

:
:
r
(a)
Fig. : Water level rising in a glass capillary tube

("
\ "
Total volume ofthe liquid risen

,,:
= nr4h + ~ nr3 nr2 [h + ~J

Ifliquid has a density p, then
mass ofliquid risen == nr2 [h +~JP

\
and weight ofthe liquid risen = nr2 [h + ~Jpg /- "
Forequilibrium,
nr2'[h +~ pg = 2nr T cos e

J h = 2Tcos9 r
or
rpg 3
[From above we find that hoc.!.r , i.e., liquid rises more in.a capillary tube ofsmall
_
radius]
Also, T = (h +r /3)rpg
2cos9
Measuring height h ofliquid risen in capillary tube and knowing other quantities, surface tension of (
"-'
liquid (T), can be calculated.
[In practice, ~ is neglected as compared to h, then T = 2~~:e ]

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[I~~~~}l~ C~~~~! Errors in Measurements & Instruments /16J

Ideal for ScholarS
TRAVELLING MICROSCOPE
Compound Microscope
R
( p
\,
Fig: Travelling microscope
/ A travelling microscope is a device which is used for the accurate measurement ofvery small distances.
Basically, it is a compound microscope fixed on a strong metallic horizontal platform which can be
/'
'- balanced with the help oflevelling screws L and L' [Fig. (2)]. The compoand microscope has ability
,/ , to slide or travel both along horizontal and vertical levels. Due to the horizontal or vertical travelling of
\.
the microscope, we have named it as a travelling microscope.
( The compound microscope consists oftwo convex lenses called objective 0 which is placed clos~d '
to the object and eye-piece E placed near the eye ofan observer. The objective 0 is a simple convex
c lens small aperture and a small focal length. These two lenses are placed in two distinct tubes placed
( coaxially. To focus object the tubes can be moved by using a rack and pinion arrangement R. The
microscope has a crosswire in front ofeye-piece which serves as a reference mark. The object to be
, seen i3 placed in front ofthe objective a..,d the image is viewe.d through the eye piece. The image
( fomed is virtual, magnified and inverted.
The distance through which the microscope moves can be read with the help ofa vernier scale (V)
c moves with the microscope along with the scale engraved on the frame work. The horizontal movement
ofmicroscope is done with the help ofscrew P in the [Fig. 6. (2)] and the vertical movement of
(
microscope is done with the help ofscrew Q whereas the horizontal and vertical shifting for fine
(\ adjustment microscope can be done with the help offine screws pr and Qt.
(
t,
[jJ~~~~A~ CL~~~~! < Errors in Measurements & Instruments /17/

Ideol for Scholars
l
PROCEDURE
DIAGRAM
Metallic
plate
Dish
Fig. : Measurement of surface tension by capillary rise method
(a) Setting the apparatus

1. Place the adjustable height stand on the table and make its base horizontal by levelling screws. (
, .
2. Take dirt and grease free water in an open dish with flat bottom and put it on the top ofthe st~d.
3. Take three capillary tubes ofdifferent radii (ranging from 0.05 mm to 0.15 mm).
4. Clean and dry them, clamp the capillary tubes in a metallic plate in order ofincreasing radius. Also
clamp a pointer after third capillary tube. " (
t~-· ,
5. Clamp the horizontal handle ofthe metallic plate in a vertical stand, so that the capillary tubes and the
pointer become verticaL I'
6. So adjust the height ofmetallic plate that the capillary tu!Jes dip in watcr in open dish.
7. Adjust the position ofthe pointer, such that its tip just touches ~e water surface.
(b) Measurement of capillary' rise
8. Find the least count ofthe travelling microscope for the horizontal and the vertical scale. Record the
same in the note-book.
9. Raise the microscope to a suitable height, keeping its axis horizontal and pointed towards the capillary
tubes.
10. Bring the microscope in front offirst capillary-tube (which has maximum rise).
11. Make the horizontal cross wire just touch the central part ofthe concave meniscus (seen convex
through microscope [fig. (b)]
12. Note the reading ofthe position ofthe microscope on the vertical scale.
13. Now move the microscope horizontally and bring it in front ofthe second capillary tube.
14. Lower the microscope and repeat steps 11 and 12. c
15. Repeat steps 13 and 14 for third capillary tube.
16. Lower the stand so that pointer tip becomes visible.
17. Move the miscroscope horizontally and bring it in front ofthe pointer. G
18. Lower the microscope and make the horizontal cross wire touch the tip ofthe pointer. Repeat step
12. C
Errors ill Measuremellts & Instruments [18J
[j1 ~~~~A~~CN~~!~~
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(c) Measurement of the internal diameter of the capillary tube.
•~.':.':.':.':.·.·".':.':::.':;:.':.1.·:::t::.·.':.~':.·.·:::::;":'·.':.~
!fA: Capillary
B tube
Fig. (a) Fig. (b) Fig.(c)
19. Place the first capillary tube horizontally on the adjustable stand.
20. Focus the microscope on the end dipped in water. A white circle {inner bore) surrounded by a green
circular strip (glass cross-section) will be seen [fig. (c)].
21. Make horizontal cross-wire touch the inner circle at A. Note microscope reading on vertical scale.
22. Raise the microscope to make the horizontal cross-wire touch the circle at B. Note the reading (the
difference gives the vertical internal diameter AB ofthe capillary tube).
23. Move the microscope on horizontal scale and make the vertical cross wire touchthe inner circle ~t C.
, Note microscope reading on horizontal scale.
" 24. Move the microscope to the right to make the vertical cross-wire touch the circle at D. Note the
reading {the differencegives thehorizontal internal diameter CD ofthe capillary tube).
25. Repeat steps 19 to 24 for other two capillary tubes.
26. Note temperature ofwater in dish.
(
27. Record your observations as given below.
(
OBSERVATIONS
( Least C0unt oftravelling microscope (L.C.) ..... cm.
( Table for height ofliquid rise
'- .'
Reading ofMeniscus Reading of Pointer Tip

Serial Total Total Height
No. of M.S.R V.S.R. Reading . M.S.R V.S.R. Reading hI -h2
Capillary N n x (L.c.) N + n(L. C.) N n x (L.C.) N + n{L. C.)
tube (cm) (cm) (c:u) (em) =h (cm)
hI {cm) h2 (cm)
(
(1) (2a) (2b) (2c) (3a) (3b) (3c) (4)
( 1.
2.
(
3. I
(
C
(
(.. Ij]!~~~,,~~ C~~~~! laNllor Scholors

Errors in Measurements & Instruments /19/
/
'
Table for internal diameter of the capillary tube
Microscope Read ing for cross

Internal Diameter
Serial Wire in position
Internal radius
No. of I
Mean
Capillary Vertical Horizontal d
tube
(A) (8) (q (D)
AB CD
AB+CD -=r(cm)
2
(cm) (cm) (cm) (cm) 2
(em) (em)
d(cm)
(I) (2a) (2b) (2c) (2d) (3a) (3b) (3e) (4)
l.
2.
3.
Temperature ofwater, (t) .... 0C.
Density ofwater at observed temperature, P .... gcm-3
Angle ofcontact ofwater in glass, 9. 8°
1.e., cos 9 0.99027 taken as L

1/---,
CALCULATIONS
From fonnula,
T = r(h +r /3)pg
2cos9
Put values ofh (column 4-fIrst table) and r (column 4-second table) for each capillary tube separately
and find the value ofT (in dynes cm-I ).
Find mean value,
T = TJ +T2 +T3 \"
3
-~ ....... dynescm-I..
,,- '"
, "
RESULT
The surface tension ofwater at tOC = ... ,... dynes cm-I .
PRECAUTIONS
1. Capillary tube and water should be free from grease.
2. Capillary tube should be set vertical.
3. Microscope should be moved in lower direction only to avoid back lash error.
4. Internal diameter ofcapillary tube should be measured in two mutually perpendicular directions. ,(
5. Temperature ofwater should be noted. ( ,
'J
SOURCES OF ERROR f'

i..J
Water and capillary tube may not be free from grease. { ,
,-,
(:;
(.
'-../
c
Errors in Measurements & Instruments 120J c
[I] !~~~A~~ CL~~!~~
Ideo' for Scha/o"
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COEFFICIENT OF VISCOSITY
AIM
To determine the coefficient ofviscosity ofa given viscous liquid by measuring the terminal velocity of
a given spherical body.
APPARATUS
A halfmetre high, 5 cm broad glass cylindrical jar with millimetre graduations along its height, transparent
viscous liquid, one steel ball, screw gauge, stop clock/watch, thermometer, clamp with stand.
THEORY
Terminal velocity :
(a) Definition: The maximum velocity acquired by the body, falling freely in a viscous medium, is called
terminal velocity.
(b) Expression: Considering a small sphere ofradius r ofdensity p falling freely in a viscous medium
(liquid) ofdensity cr, The forces acting on it are :
The weight ofthe sphere acting downward = ~ nr3pg

(
The upward thrust = Weight ofthe liquid displaced by the sphere ~ nr3crg
/
" The effective downward force,
l'll$ = ! nr3pg - ! nr3crg

3 3
(
" 4
= nr3(p - cr) g
3
( Upward force ofviscosity, F 6lt11rv
"
When the downward force is balanced by the upward force ofviscosity, the body falls down with a
( constant velocity, called terminal velocity.
Hence, with terminal velocity,
c 4
6lt11rV = 3" ltr3 (p - cr) g
( 2
. al 1 . 2 r (p -cr)g
or 11ermm ve OClty, v = 9" 11
This is the required expression,
( 2
'al veIOCI'ty
11ermm v 2 r (p-cr)g
-
( 9 11
( or 11 v
knowing r, p and cr, and measuring v, 11 can be calculated.
(
(
if
~. [j] ~~~~A~~ CL~~~~~ Errors in Measurements &lnstruments {21J

Ideal tDr Schelars
DIAGRAM
1«111-- Thermometer
Stand ---+ :-:-:.:.:.:.:.:.:. -~-I-

:':':':':':':':0:':':'--.:: Liquid
~.. .. • .. ..... • .- r
:
\ >
:.:.:.:.:.:.:-:- ~i-- Steel ball
a ~ '1:=:=:=:=:=:=:=:::::=:::: -
::::::::::::::::::::::::::::~+- Glass
...tttttt~I~ cylinder
':·I::::::::::::::::::::::::::::~+- Scale
::::.:-:::::::::::::::::::::::::::;
..... - - ........................ 1
PROCEDURE
1. Clean the glassjar and fill it with the viscous liquid, Which must be transparent.
2. Check that the vertical scale along the height ofthe jar is clearly visible. Note its least count.
3. Test the stop clock/watch for its tight spring. Find its least count and zero error (if any)
4. Find and note the least count and zero error ofthe screw gauge.
5. Detennine mean radius ofthe ball.
6. Drop the ball gently in the liquid. It falls down in the liquid with accelerated velocity for about one-
third ofthe height. Then it falls with unifonn tenninal velocity.
7. Start the stop clock/watch when the ball reaches some convenient division (20 cm; 25 cm; ..... ).
8. Stop the stop clock/watchjust when the ball reaches lowest convenient division (45 cm).
9. Find and note the distance fallen and time taken by the ball. .
/
~
10. Repeat steps 6 to 9 two times more. ( "".

11. Note and record temperature ofthe liquid.
12. Record your observations as given ahead. "
/' '
OBSERVATIONS
Least count ofvertical scale = .... mm.
Least count ofstop clock/watch .... s.
Zero error ofstop clock/watch .... s.
r' '.
Pitch ofthe screw (P) Imm. V
Number ofdivisions on the circular scale 100 '-.
_ 1
Least count ofscrew gauge (L.C.) - 100 = 0.01 mm
Zero error ofscrew gauge (e) .... mm.
zero correction ofscrew gauge (C) = (--e) .......... mm
Diameter ofspherical ball
(I) Along one direction, D) = .... mm

{ ,
(li) In perpendicular direction, D2 =.... mm '-.j
Terminal velocity of spherical ball

Distance fallen S = .... cm
c
Time taken, t1 = .... s ()
f:2 .... s
13 = .... s
Errors in Measurements & Instruments /22}
iJ~~~~A~~ CL~~~~~
Ideal for Scholars
c
CALCULATIONS
Mean diameter D
2 mm
o .... cm
Mean radius r 2 mm
Meantime t 3 = .... s
Mean terminal velocity, v

s .... cm s-1
(-
" From fonr..ula, 11 = 9v = .... c.G.S. units.
RESULT
The coefficient ofviscosity ofthe liquid at temperature (eOC) = .... C.G.S. units.
PRECAUTIONS
1. Liquid should be transparent to watch motion ofthe ball.
2. Balls should be perfectly sphericaL
3. Velocity should be noted only when it becomes constant.
SOURCES OF ERROR
/
\ 1. The liquid may have nonuniform density.
("
2. The balls may not be perfectly spherical.
3. The noted velocity may not be constant.
"
I
SPECIFIC HEAT CAPACITY
,,- AIM
To determine specific heat ofa given solid (lead shots) by method ofmixtures.
APPARATUS
Solid (lead shots), copper calorimeter with copper stirrer and lid, calorimeter jacket (wooden box
c: with coating ofinsulating material inside), hypsometer, heating arrangement tripod, burner and wire
gauze or a hot plate, two Celsius thermometers graduated in O.2°C. Water and a physical balance,
weight box and milligram fractional weights.
( THEORY
(
The law ofmixtures states that when two substances at different temperatures are mixed, i.e., brought
c,
in thermal contact with each other, then the heat is exchanged between them, the substance at higher
( temperature loses heat and that at lower temperature gains heat. Exchange ofheat energy continues
till both the substances attain a common temperature called equilibrium temperature.
( The amount ofheat energy lost by the hotter body is equal to the amount ofheat energy gained by
( colder body, provided (i) no heat is lost to the surroundings and (ii) the substances mixed do not react
chemically to produce or absorb heat. In brief, the law mixtures is written as :
On mixing oftwo substances at different temperatures, if no heat is lost to surroundings; at the
equilibrium temperature,
Heat gained Heat lost

(
~
(~ [i]!~~~A~~CL~~!~!lC1eQl1Ol SdJoIon
I"
~-
I
,-.
For a body ofmass Ill, and specific heat 5, when its temperature falls by 68, the amount ofheat lost by
it is given as
6Q = m.s.66
The same formula is used for the amount ofheat gained by colder body where L\6 would be the rise in
temperature.
SP.ECIFIC HEAT
Specific heat ofa substance is the amount ofheat required to raise the temperature ofunit mass of
substance through one degree celsius.
S.L unit ofspecific heat is J kg- l K-I . Convenient measures ofmass in the lab is gram and temperature
is °C so we express specific heat as J g-l °C-I.
O+-CeJsius thermometer TA
TB' range O°C to IOOOC.

(O.2°C least count)
II' Cotton
Stirrer
'" Jacket
Hypsometer for generating steam and Fig.: Calorimeter containing known mass ofwater,
heating the given solid. stirrer and a thermometer placed inside a jacket.
PROCEDURE
1. To ensure that two thermometers read the temperature ofa body exactly the same, one is compared
with the other one which is taken as the standard thermometer.
Mark the thermometer used for measuring temperature ofwater in calorimeter at room temperature
as TA and the other used in hypsometer as TB' Suspend them side by side from a clamp stand and'
note their readings. The error in the temperature measured by thermometer B, is
e=TB-TA
The correction is (- e)., r'·
~
The correction (- e) isalgebracally added to readings oftemperature recorded by thermometer TB.
used hypsometer.
2. Take about 100 grams oflead shots in the tube ofhypsometer and add sufficient quantity ofwater in
the hypsometer.
3. . Insert the thermometer marked TB in the tube such that its bulb is surrounded by lead shots and fix the ()
tube inside the mouth ofhypsometer.
Errors in Measurements & Instruments f24]

[I] ~~~~A~~CLL,~~~~!
Ideo! for ScOOI""
c
4. Place the hypsometer on the wire gauze placed on the tripod and start heating it using the burner.
Note: Alternatively, hot plate may be used in place oftripod and burner arrangement.
MEASURING MASSES
5. Ensure that the physical balance is in proper working condition and on turning the knoQ, the pointer
moves equal divisions on the left and right sides ofthe zero mark ofthe scale provided at the back of
pointer.
6. Check that the calorimeter is clean and dry. Use a piece ofcloth to rub it and shine its surface. Weigh
the calorimeter along with stirrer, note the reading as mc'
7. weigh the calorimeter with stirrer and lid. Record it as mI'
8. Place few pieces of ice in a beaker containing water such that its temperature becomes 5 to 7°C
below the room temperature. Fill 2/3 ofthe calorimeter with cold water from the beaker and ensure
that no moisture from air should condense on the surface ofthe calorimeter, clean the surface ifat all
the drops appear.
9. Weigh the calorimeter with stirrer, lid and water in it.
10. Place the calorimeter in the jacket. Insert thermometer labelled asA through the lid cover ofcalorimeter
r
~.
and hold it in a clamp provided on the jacket such that the bulb ofthermometer is well immersed in
water but does not touch the bottom ofthe calorimeter.
11. Note and record the temperature ofwater in the calorimeter.
f 12. Observe the temperature ofthe solid in hypsometer at intervals oftwo minutes till the temperature
becomes steady. After the temperature becomes steady for about 5 minutes, record it as 8 2, Apply the
correction (- e) to it and write the corrected temperature ofsolid.
"
f
13. Note the temperature ofcold water in the calorimeter once again. This is to be taken as the reading for
calculations. Immediately after this, remove the cork along with thermometer from the copper tube of
hypsometer. Take out the tube, raise the lid ofcalorimeter and transfer the hot solid quickly to water
in the calorimeter without any splash ofwater.
14. Stir the water in the calorimeter till the temperature ofthe mixture becomes steady. Note the equili brium
( temperature reached by the hot solid and the cold water in the calorimeter.
15. Gently take the thermometer out ofthe water in the calorimeter. Take care that no water drops come
c out ofthe calorimeter along with the thermometer.
16. Take out the calorimeter from the jacket and weigh the calorimeter with stirrer, lid, water and solid in
(
it. Record it as m 3.
c
(
OBSERVATIONS
'. Room temperature reading by thermometer A, TA = ..................... °C
( Room temperature reading by thermometer B. TB = ..................... °C
(
Correction required for thermometer B, e TA-T B
\.
Mass ofcalorimeter + stirrer, m ...................... g
(
,- Specific heat ofthe material ofcalorimeter,copper from tables, sc = 0.4 J/g/oC,
Specific heat ofwater s= 4.2J/g/°C
W ,. ';, ',.
( Water equivalent ofcalorimeter, W = m} (sc/sw)
C * when Sw for water is taken as I cal/g/°C
(, ..
W = m x sl otherWIse wrIte Was W m x
(0.4) g
4.2
Mass ofcalorimeter + stirrer + lid = m l = ................... g
c [iJ~~~~~~CL~~~~~ Errors in Measurements & Instruments [25J

'..
f lOeOJ ror Scholars
Mass ofcalorimeter + lid + cold water = m2 = ................... g
Temperature ofcold waterin calorimeter, 9 = ................... g
1
Steady temperature ofsolid in hypsometer by thermometer B, W2 = ................... °C
Corrected temperature ofsolid, 92 92 "" 9 2 + (- e) = ................... °C
Final, i.e. equilibriwn temperature ofthe mixture ge

................... °C
Mass ofcalorimeter + stirrer + lid + water + solid = m3 = ................... g
CALCULATION
(a) Let the specific heat ofsolid be S J/g/°C
Mass ofcold water in calorimeter, mw = m2 - m] =.................... g
Water equivalent ofcalorimeter + stirrer, W mx s

w
Rise in temperature ofcold water and calorimeter and stirrer, 9e - 9 1 = .............. °C
Amount ofheat gained by cold water and calorimeter = (mw + W) x Sw x (ge

- ( 1) = .............. J
....(1) where specific heat ofwater = Sw = 4.2 J/g/oC
(b) Mass ofsolid added to cold water, ms = m3 - m2 =

............. g
1'.0",>,
Rise in temperature ofsolid, 92 - ge

= ............. °C
Asswned value ofspecific heat ofsolid, s = ............. J/g/°C
Heat lost by hot solid = mass x sp. heat x fall oftemperature (m] m2) s (92 ge
) ... (2)
Applying law ofmixtures, keeping in view the conditions,
Heat lost Heat gained
Equating (2) and (l)
(m3 - In2) S (9 2 ge) = (mw + W) SW (ge ( 1)
(mw + W) (Oe -9 j ).sw . .
s = (m3 m2) (9 -g ) = ...................... J/gl°C
2 e
s may be written in S.I. unit as J/kg/°C, by multiplying the calculated value above by 1000.
I '
. RESULT
Specific heat ofgiven (solid), s ............... J/kg/°C
Value from tables St = ............ J/kg/oC
s-s
Percentage Error in the value ofS = -S_I x 100 =........... %
PRECAUTIONS
1. Physical balance should be in proper working condition
2. Sufficient quantity ofwater should be taken in the boiler ofthe hypsometer
3. The calorimeter should be wiped clean and its surface should be shining so as to minimise any loss
ofheat due to radiation.
4. The thermometers used should be ofthe sa~ne range and their least counts be compared before
starting the experiment. Cold water in calorimeter should not be so cold that it forms dew droplets on
the outer surface ofcalorimeter. Solid used should not be chemically reactive with water.
S. Hypsometer, burner ano heating system should be at sufficient distance from the calorimeter so
that calorimeter absorbs no heat from them.
/" .
"-.j
i~~~~A~~ CL~~~~! {26J
IdeolforScholars
c
6. The solid should be heated such that its temperature is steady for about S to 7 minutes.
7. The solid should be transferred quickly so that its temperature when dropped in water is the same
as recorded.
8. Water should not be allowed to splash while dropping the solid in water in the calorimeter.
9. After measuring equilibrium temperature, the thermometer when removed should not have any
water droplets sticking to it.
10. Cold water taken in the beaker should be as much below temperature as the equilibrium temperature
after adding solid is expected to go above it. This is to take care ofheat absorbed from surroundings
I
I,
by cold water or that lost by warm water during the course ofexperiment. It would be of interest to
know that this correction had been thought of by count Rumsfort in 19th century.
(
SOURCES OF ERROR
1. Radiation losses can be minimised but cannot be completely eliminated.
2. During transfer ofhot solid into calorimeter, the heat loss cannot be accounted for.
/
3. Though mercury in the thermometer bulbs have low thennal capacity, it absorbs some heat and
" -lowers the temperature to be measured.
SPECIFIC HEAT CAPACITY

c AIM
( . To detennine the specific heat ofa given liquid (kerosene or turpentine oil) by method of mixtures.
APPARATUS
(
\. A calorimeter with stirrer and lid cover. The lid cover having provision of two holes for passing
(
thermometer and stirrer. Ajacket for calorimeter. A thermometer having o.soc least count. Given
\.
liquid (it should be non-volatile) kerosene oil or turpentine oil. A cylindrical piece ofmetal (about 6 to
8 cm long and about 1 cm diameter), cotton thread about 20 cm long to tie the metal piece with it and
it should be non-slipping. Beaker with water, tripod stand, wire gauze, burner or hot plate, physical
c balanc~ and weight box and fractional weights.
(: THEORY
c Specific heat: The heat capacity ofa substanCe ofany kind is defined as the amount ofheat required
to raise the temperature ofits unit mass through 1 kelvin.
(
Symbol used for it is 3 or c and S.I. unit ofspecific heat is J per kg per K. (J kg- l K-I)
( Note: To determine the specific heat ofa solid in the lab, it is convenient to measure mass in gram and
temperature in °C. Therefore; the value ofspecific heat is detennined as Jg-l °C-i and then converted
(
into SJ. unit J kg- l K-l.
(
C
t
c
(
(
~~~~~A~~C~~~~~!
10.alfoESmolars
Errors in Measurements & Instruments {27/
(
Ill" Thermometer
Thread - - H (OOC 100°C) in OSC
..,.:1 Boiling Water
if-_· : :I Solid (metal piece)
Copper stirrer
:,/.. , Heating set up
Felt or glasswool
r---uil (experimental Liquid)
Calorimeter
Figure (A): Experimental set up for determining specific heat of given liquid (kerosene oil)
Water Equivalent of Calorimeter : Itis the equivalent amount ofwater which will need the same
amount of heat for certain rise oftemperature as required by the calorimeter for the same rise of
temperature. ( ,
,
Water equivalent is generally written as W. For a calorimeter ofmass m and of specific heat of its
material as s, its water equivalent:
Sc (material of calorimeter, copper)
W =m x
Sw (water)
400Jkg- 10 C- 1
-m
-
X
4200kg- I "CI (
\
= m x 0.095 g
Method of mixtures: In this method a hot substance is added to a cold substance such that both the
substances mutually exchange heat till they reach an equilibrium temperature common to both. Care is ()
usually taken that no heat is lost to the surroundings.
Law of mixtures: In very brief, in method of mixtures when no heat is lost anywhere else to
surrounding etc. at thermal equilibrium.
Heat gained by colder body = Heat lost by hotter body
The amount ofheat exchanged 'AQ' m.s.AS where m is mass, ofthe substance, s thermal specific
. heat and AS is change in temperautre ..
For a colder body, AS is rise in temperature (se - 6 1) Se and 6 1being equilibrium temperature and initial
temperatures respectively.
For hotter body, AS is fall in temperature (S2 - Se) S2 and Seare respectively the initial temperature ofhot
C
body, and equilibrium temperature ofthe mixture.
Method ofmixtures is used for determining specific heat ofsubstances; solids or liquids.
c
Errors in Measurements & Instruments {l8i
[jj]~~~~A~~ CL~~!~~
Ideal Scholars
(or
c
PROCEDURE
1. Set the beaker, tripod, wire gauze and burner as shown in fig.( A) and fill the beaker to half of its
volume with tap water and start heating the water.
2. Tie the cylindrical metal piece tightly using one end ofmachine thread. Make sure that the thread does
not slip from the piece and about 10 cm ofthread is there for suspending the metal piece in water.
3. Weigh the calorimeter with stirrer, in physical balance, Record its mass as mi'
4. Fill the calorimeter (3/4) with given liquid whose specific heat is to be determined.
5. Weigh. the calorimeter + stirrer + given liquid (oil). Record the mass as~.
6. Read the temperature ofoil in the calorimeter and record it as 1 DC. °
7. Wet the metal piece, shake it and weigh it in physical balance. Record the mass as m3.
,
8. The metal piece is suspended by thread and placed in the beaker ofwater. Start heating the water and
boil it with metal piece inside for about 20 minutes.
9. When the sample has been in boiling water for enough time duration (say, 15 minutes) such as to attain
temperature ofboiling water (100°C), once again note the temperature ofoil in the calorimeter, lift the
(
metal piece by thread and transfer it quickly to the calorimeter. .
,
10: Ensure that there is minimum loss ofheat during transfer ofmetal piece, to achieve this, the jacket of
(
\. calorimeter is held close to the hot water bath and sample ofmetal is transferred quickly without
splashing any oil.
11, It is advisable to given metal piece a little shake to remove any adhering hot water just before transfering
\.
it to liquid.
Also the metal piece is made wet before weighing with a view not to add any weight ofadhering water
(point 7).
12. The lid cover is kept over the calorimeter immmediately after transfer ofhot solid in the oil and the
\.
mixture is well stirred till final steady temperature (equilibrium temperature, is reached).
(
13. Record the equilibrium temperature as 0e'
" Record your readings and observations as follows:
(
( OBSERVATIONS
1. Mass ofcalorimeter + stirrer, mI g
.................................
(.
\.. 2. Mass ofcalorimeter + stirrer + oil, m2 .............. ~ .................
g
,',
"
3. Temperature ofoil in the calorimeter, 1
°
= ................................. °C
4. Mass ofthe cylindrical piece tied to thread, m3 = ................................ g
( 5. Temperature ofboiling water in the beaker, Le., temperat'Jre ofmetal piece 2

= lOO°C °
6. Steady equilibrium temperature ofmixture 0e ................................ °C
( CALCULATIONS
Water equivalent ofcalorimeter,
Specific heat of material of calorimeter
W mass x
c .
SpeCIfic heat of water
( of copper
So:
m x 400
-m x I 4200 - m. x 0.095
- I Sw of water
Mass ofoil, m=m 2 -m. = ........................ g
Water equivalent ofcalorimeter, W m l x 0.095 (for copper calorimeter)

Temperature ofoil in calorimeter oJ ............................ °C
(
Equilibrium temperature 8e = ............................ °C
r: .
\..
/
[i!~~~A~~ Cl.l!!.~!~~ Errors in Measurements & Instruments [29J
IUf:UII{Jf Scr.a1ats
\.
{
"-
Rise in temperature ofcalorimeter, stirrer and oil (..1.9)1 = ge 91
Heat gained by calorimeter =W x (ge 91
)
Heat gained by oil, = (m2 - m 1) x Sf x (ge 9 1)
=ms(9-9) f e I
Total heat gained, (..1.Q)1 = (W + m.s,") (ge - 9t ) •••• (1)
Temperature ofhot solid, cylinder piece 9 1 = 100°C
'l'b'
EqUl 1 nurn temperature 9e -- ..................... ..
°C
Fall in temperature (..1.Q)2 = (l00 - ge) = ....................... °C
Mass ofsolid piece, m3 = ....................... g
Specific heat ofmetal ofsolid piece ofmetal ( .... name ofthe metal used) from tables
S -- ...................... . J g-l °C-I
Heat lost by hot solid,
(..1.Q)2 = m) x S x (9 2 ge) = m3 x S x (l00 ge

) .... (2)
Applying law ofmixture : equating (1) and (2)
(g e -9 1) (W + m.se ) = m3 x S x (l00 ge)

m3·s(100 . 9~) W ,,,
Specificheatofliquid, Sl = m(g -9 ) --;; = ................ J g-l °C-I
e 1
Sf value may be written in S.L unit, J kg- 1 °C-I by multiplying the above value by 1000.
! -,
RESULT
Specific heat ofgiven oil (kerosene oil) Sf = .................... J kg-I K-I
Value ofspecific heat ofkerosene oil from tables, Sl = .................... J kg-I K-I
Note: To write the value in S.L unit, kelvin is used for temperature, so °C is replaced by K.
Percentage error in value ofS t

Se -SI
-s-x 100= .................. %
'."
I
,
PRECAUTIONS
1. Solid piece is weighed before heating in boiling water. ( ,
'.J
2. Sufficient amount ofliquid (at least halffilled calorimeter) should be taken
3. The calorimeter should be wiped clean and its surface should be shining so as to minimise loss ofheat
due to radiation.
4. Solid should be heated in boiling water for sufficient time duration so as to attain the steady temperature
ofboiling water.
5. The solid should be transferred quickly, so as not to lose much heat and it should be transferreq
carefully not to splash and lose any mass ofliquid.
SOURCES OF ERROR
1. Even though the metal piece is kept in boiling water, it may not exactly attain its temperature. c
2. Small losses ofheat due to radiation to atmosphere during transfer ofsolid to oil or from the surface { ,
~.
ofthe calorimeter are inevitable.

(7
( '.
V
/ '.
~

c
[jJ~~~~A~~ CH!.~~~!
Ideal for Scholars
c
PLOTTING A COOLING CURVE
AIM
To study the relationship between the temperature ofa hot body and time by plotting a cooling curve.
APPARATUS
Newton's law ofcooling apparatus (a thin-walled copper calorimeter suspended in a double walled
enclosure) two thermometers, clamp and stand, stop clockiwatch.
THEORY
Newton was the first person to investigate the heat lost by a body in air. He found that the rate ofloss
ofheat is proportional to the excess temperature over the surroundings. This result, called Newton's
law ofcooling, is approximately true in still air only for a temperature excess 0120 K or 30 K.
Consider a hot body at a temperature T plac-ed in surroundings at temperature To'
dQ
Rate ofloss of heat
dt
(
Using Newton's law ofcooling, -" ~; oc (T - To)
/
\,
or ~; = - k (T To), where k is a constant ofproportionality whose value depends upon the area and
nature of surface ofthe body.

If the temperature ofthe body falIsby a small amount dT in time dt, then
(
\ dQ=mcdT
(
is
wherem the mass ofthe body and c is the specific heat ofthe material ofthe body.
\
/ Now, mc ~~ = -k(T To)
I
\.
or dT _ k (T To)
dt mc
(
'
, or dT =-K(T
dt
To) [Here, K =;c cons tan! J
"
The negative sign indicates a decrease in temperature with time.
(
\...
Again, ~ Kdt
T-To
(
Integrating, f~ T To dT - K fdt
(
or 10ge(T To)=-Kt+C ...... (1)
'
where C is a constant ofintegration.
~ y
(
- ( ,......
0
E
I
( C
~
t -+ X
"
~. [I~~~~~~ CL~~~~!
(
Errors in Measurements & Instruments /31/
IOeol101 SdwIors
\.
(
This is the equation ofa straight line having nagative slope (- K) and intercept C on Y-axis. Figure
shows the graph ofloge (T - To) versus time 1. While t has been treated as the x-variable, loge (T
To) has been treated as the y-variable.
1fTm is the maximum temperature ofhot body, then at t = 0 from equation (i)
10g(Tm To)=C
.. log (T - To) log (Tm- To) = - kt
T To) _ kt
log ( Tm -To
T..,.To
e-kt
Tm -To
so (T - To) (Tm To) e-kt
Clamp ..
To A T
If Stirrer
~~~~;( Lid
!
\,
-:...:11 Hot water
Stand .E"
,
I.. I -Calorimeter \,
~.. Double walled

container
Cooling Calorimeter
PROCEDURE
1. Fill the space between double wall ofthe enclosure with water and put the enclosure on a laboratory
table.
2. Fill the calorimeter two-third with water heated to about 80°C. (

'-'
3. Suspend the calorimeter inside the enclosure along with a stirrer in it. Cover it with a wooden lid
having a hole in its rnidqle.
4. Suspend from clamp and stand, one themlOmeter in enclosure water and the other in calorimeter
water.
5. Note least count ofthe thermometers.
- 6. Set the stop clock/watch at zero and note its least count.
7. Note temperature (To) ofwater in encll)sure.

c
8. Start stirring the water in calorimeter to make it cool uniformly.
Errors in Measurements & Instruments [32)

[I] !~~~A~~ C~~!~!
Ideol fOf Scholors
( ,
'-'"
9. Just when calorimeter water has some convenient temperature reading (say 70°C), note it and start
the stop clock/watch.
10. Continue stirring and note temperature after every 5 minutes. The temperature falls quickly in the
beginning.
11. Note enclosure water temperature after every five minutes.
12. When fall oftemperature becomes slow note temperature at interval oftwo minutes for 10 minutes
and then at interval of5 minutes.
, 13. Stop when fall oftemperature becomes very slow.
14. Record your observations as given ahead.
( OBSERVATIONS
Least count ofenclosure water thermometer = ............. °C
Least count ofcalorimeter water thermometer = ............. °C
Least count ofstop clock/watch = ............ s.
Table for time and temperature

('
"
f
\ Serial No.
Time for cooling Temperature of Temperature of water Difference
ofObs.
t(min) water in calorimeter in enclosure of temperature iog1o(T - To)
(TtC (To) DC (T - To)OC
(" (1) (2) (3) (4) (5) (6)
\
I
( 2
\
3
/
\ 4
5
\. 6
7
( 8
'
9
( J 10
C
" CALCULATIONS
(
1. Temperature ofwater in enclosure will be found to remain same. Ifnot then take its mean is To'
( 2. Find temperature difference (T - To) and record it in column 5 ofthe table.
3. Plot a graph between time t (column 2) and temperature T (column 3), taking t along X-axis and T
(
along Y-axis. The graph comes to be as shown in given figure. It is called 'cooling curve' of the
( liquid.
",
Graph between time and temperature (Cooling curve)
(. Scale:
{ X - axis: 1 em = 5 minutes oft
\.
Y-axis: 1 em = 5° C ofT
c
c
(
,(
~"[I~~~~~~ C~~~~~ Errors in Measurements &: Instruments [33J

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(
65
60
i 55
50
(T Tn)
45
40
35
30
0 5 10 15 20 25 30 35 45 X
Time (t) in minute ~
[COOLING CURVE]
RESULT (
\
The temperature falls quickly in the beginning and then slowly as difference of temperature goes on
decreasing.
This is an agreement with Newton's law ofcooling.
PRECAUTIONS
1. Double-walled enclosme should be used to maintain surrounding at a constant temperature.
2. Stining should remain continuous for unifonn cooling ""
SOURCES OF ERROR
1. Surrounding temperature may change.
2. The stirring ofhot liquid may nut be continuous.
RESISTANCE BY OHM's LAW
AIM
Verify Ohm's law for the given unknown resistance (say a 60 cm constantan wire). Plot a graph of" "
c
potential difference versus current. From the slope ofthe graph and length ofthe wire, calculate the "
resistance per cm ofthe wire.
K Battery
r-------;f'.) + I1-11
(
G
"
Voltmeter r'
\....,
Fig. Circuit diagram
[I ~~~~A~~ CLL,~~!~! Errors !n Measurements & Instruments /34J

Ideo/lor Scholars
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E, E2
Fig. Assembly circuit diagram

(
APPARATUS
Resistance wire (60 cm constantan wire or a standard resistance coil) ; an ammeter (1. SA ran~e);
D.C.voltmeter (1.S V range); Rheostat; one way plug key, An accumulator or dry cells or a battery
eliminator and connecting copper wires.
"
/~
THEORY
" Ohm's Law states that when a steady current flows through a conductor, the ratio ofthe potential
(
\
difference between the ends ofthe conductor and the current flowing through it is a constant, provided
the physical conditions ofthe conductor such as length, temperature, density etc., do not change.
IfV represents the potential difference between the two ends ofa conductor and I the current flowing
,
[
in!t, then
( V oc I
.. rV-;;;;-R!l where R is the constant ofproportionality. ~
or ~ R ; R is the resistance ofthe conductor.
c When the potential difference V is measured in volts and the current I in amperes, the resistance R is
measured in ohms.
To establish current-voltage relationship (or Ohm's Law) it is to be shown that a change in potential
(
'- difference at the two ends ofa conductor means a corresponding change in current in such a manner
( Potential difference . t t
that the IS a cons an .
current
/
A graph drawn with potential difference along X-axis and current along Y-axis should be a straight
" line. This line is termed as the characteristic ofthe conductor having resistance and will have different
c inclinations for different conductors.
(
" .PROCEDURE
1. Draw a neat circuit diagram showing the connections to be made as shown in Fig. (11.1 )
t 2. Arrange the apparatus on the working table in the laboratory and assemble the circuit connections as
shown in Fig 11.2.
(
'--~
[i] ~~~~A~ CL~~~~~! Errors in Measurements & Instruments {35}

( Ideol (Of Scholar,
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"'"~
3. The ammeter is connected in series with the given resistance wire (R) or standard unknown resistance
and the voltmeter is connected in parallel i.e., across it. The current must enter the ammeter and the
voltmeter through their terminals marked +ve. The rheostat must be connected through one of its
lower terminals and the upper terminal.
4. Note the zero-errors ofthe ammeter and voltmeter, it any Also before sending the current through the
circuit note the least count ofthe voltmeter and the ammeter and record these in the observation
tables.
5. Insert the plug key K, slide the rheostat contact starting from the left end to the right end see that the
deflections in the voltmeter and ammeter are such as to give at least ten independent sets of
observations.
6. Now start the rheostat contact at one end so that a small current passes in the resistance wire or the
standard resistance coiL Note down the potential difference between the ends ofthe experimental
resistance wire i.e., voltmeter reading and the current flowing in it i.e., ammeter reading.
Shift the rheostat contact slightly so that both the voltmeter and ammeter give full division readings
(not in fractions). Note down these voltmeter and ammeter readings.
7. Take at least ten sets ofsuch independent observations.

8. Measure the length ofthe experimental wire just outside the binding terminals.
9. Plot a graph showing the potential difference between the ends ofthe experimental wire along the y ( ,
axis and the current through the conductor along the X -axis selecting proper scales.
OBSERVATION AND CALCULATIONS

Value ofeach small division on ammeter
(or least count ofammeter) ""....................... ampere
zero correction for ammeter "" ..................... ampere
Value ofeach small division on voltmeter (or least count ofVoltmeter) = ................... .Yolt. " ,
Zero correction for Voltmeter = ...................... Volt /',
·
Smce the Potential difference comes a constant quantity,
. h ence current-vo Itage reIatlOns
' h'Ip IS
.
current
established i.e., voltage (V) C£; current (I) or Ohm's Law is verified.
( ,
" /
S.No. Voltmeter reading V (volt) All'IIileter reading I (Arq» Potential difference

(potential difference) (Current) (Current)
f'
v
Observed Corrected Observed Corrected V
- =' a constant ( ,
(V) in volts (I) in amperes I "-~
= R(in ohms)
(Unknown resistance)
I.
'-'
2.
3. C
4.
f'
5. v'
6.
/ "
7. G
8.
<' '
9. V
10. - ( ,
v
t
v
Errors in Measurements & Instruments /36J
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14.. Scholars
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V
, '
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Since the graph between the potential difference and c:urrent is a straight line (Fig. 11.3), the law has
also been verified graphically or the voltage-current relationship i.e., voltage oc current is also verified
grapIlIC ~
• ally. In lact t h e ratIO
. Potential difference.IS th '
e resIstance f h . I"
0 t e expenmenta WIre III 0
hmS.
current
Y
i jY;_·_·__····.9 (X". YQ) Scale: Along X-axis

.5 ........ DIY. = ........amperes
~ 1 Along Y-axis
I
..............................P ·........···..·....·~T
~

Yp j(Xp,Yp) 1 ........ DIY. ........... volts
~ i ~
"6
-;;;
'p
!j
c:; I
Ilxp
Ix
1Q X
( o Current (I) in amperes
('
\ Fig.
Calculation of resistance per em ofthe given resistance wire from the slope ofthe graph:
The slope ofa graph at a given point is the slope ofthe tangent to it at that point. The graph between
( the
'.
potential difference (V) in volts and current (1) in amperes is a straight line (Fig. 11.3 ). To measure the
/'
.slope of this straight line, select two points P(X p , Y p) , Q(XQ' Y Q) on the. line, not necessarily
( observational points which are well separated record from the graph. Ifthe values ofYp,Xp (at P) and
\
ofYQ and XQ (at Q).
/
\. Tnen the slope is :
( YQ-Yp QT = ....... v =R
xQ -Xp TP ...... .A
( = ........... ohm
gives the resistance (R) in ohms ofthe given resistance wire.
(:
Length ofthe wire outside the terminals L = ...... cm
.
. . ReSIstance per cm 0 f t he WIre
. = -R = ......ohm ...... 0 hm / cm
L ........cm
(. '
(
\. RESULT
(
·)
C1
s·Illce the raho. Potential .difference . so 0 hm' s 1aw gets ven'fiIed .
comes a constant quantIty
current .
( (Ii) The graph ofpotential difference versus current is a straight line and the slope ofthis line gives the
resistance R ofthe given resistance wire in ohms.
C Here R = .......... ohm.
{ Length ofthe wire = L = ........ cm
'
:. Resistance per unit
length ofthe wire = ~ ...........ohmlcm
L
(
"-.
[iJ~~~~A~~ cy~~~~~ Errors in Measurements & Instruments [37J

(. ldealfor ScholDrS
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PRECAUTIONS
1. Clean the ends ofthe cOIll1ecting wire with sand paper.

2. Ammeter and voltmeter should be ofproper range.
3. A low resistance rheostat should be used. Rheostat must be connected through one of its lower
terminals and the upper terminal.
4. Ammeter is to be connected in series with the circuit and the voltmeter in parallel with the unknown
('- .....
resistance i.e., the given resistance wire.

5. Positive ofthe ammeter and voltmeter should be connected to positive electrode ofthe battery.
6. The connections should be tight, short and straight.
7. The wires should only be connected at the terminals and not in between.
8. Get your circuit connections checked by the teacher before passing the current.
9. Do not pass current into the wire for a longer interval oftime otherwise due to large heatfng, the ratio
V II may not remain constant.
10. Measure only that length ofexperimental resistance wire which is just outside the binding terminals. ,/- ~
r,
HALF DEFLECTION METHOD
AIM {
To find the resistance ofa galvanometer by halfdeflection method and find its figure ofmerit.
APPARATUS
A weston type moving coil galvanometer, a cell, two resistance boxes, two one-way keys, a voltmeter,
connecting wires and a sand paper.
E KJ R ! \~ /'
--4 ----1+1
.. !- (• )-----[]]J
,',
f
\..- /'
( ,
'j
G J ~ ~ I' '1.,-_/
s c
f'
\..j
Fig. : Half deflection method

o(' '.
THEORY
r'''·
The connections for finding the resistance ofa galvanometer by the halfdeflection method are shown \..../
in Fig. 14.1. When the key, KI is closed, keeping the key K2 open, the current Ig through the r'
',--,
galvanometer is given by .
E
c
Ig = R + G where E = E.M.F. ofthe cell. ('
o
R = Resistance from the resistance box R.B .
G = Galvanometer resistance.
e
Ife is the deflection produced, then
c
E
R+G = ke .... (1) c
c
[I] ~~~~A~~ CL~~~~~
Ideal for Scholars c
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G
Ifnow the key K2 is closed and the value ofthe shunt resistance S is adjusted so that the deflection is
reduced to halfofthe first value, then current flowing through the galvanometer I~ is given by
, E (S) kB
Ig R+~ G+S) 2
(G+S)
ES k9
or rg R(G+S)+GS 2
.... (2)
Comparing (1) and (2), we get
(R + G) 2S = R(G + S) + GS
or (R - S) G = RS
or IG=~1
Ifthe value ofR is very large as compared to S, then R~s is nearly equal to unity. Hence
~
r: FIGURE OF MERIT
'<
Figure ofmerit of a galvanometer is that much current sent through the galvanometer in order to
" produce a deflection ofone division on the scale.

Ifk is the figure ofmerit ofthe galvanometer, and '9' be the number ofdivisions on the scale, then
Current (Ig) through the galvanometer is given by
r
\
IIg == kB
PROCEDURE
"
I
1. Draw a diagram showing the scheme of connections as in Fig. l4.1 and make the connections
accordingly.
I 2. Check, the connections and show the same to the teacher before passing current,
" 3. Introduce a high resistance R from the resistance box (R.B.), close the key K} anu adjust the value of
['
'-< R till the deflection is within scale and maximum. Note the deflection and the value oftPe resistance R.
4. Close the key K2 and adjust the value of the shunt resistance S so that the deflection is reduced
(
exactly to halfthe fust value. Note this deflection and the value ofthe resistance S.
5. Repeat the experiment three times taking different deflections ofthe galvanometer.
(
6. To find the figure of merit:
" (i) Find the e.m.f. ofthe cell by a voltmeter. See the positive ofthe cell is connected to the positive
( marked terminal ofthe voltmeter.
(ii) Connect the cell E, the galvanometer Q the resistance box R.B. and the key KI in series as shown
I
" in Fig.(14.2)
c 1- --fee)
K}
c G })-_ _+-_ _...J
( Fig. Figure of Merit

/
~- [i~~~~A~~CL~~~~! Errors in Measurements & Instruments [39J

( Idea' (Of Scholars
L
take out 5,000 ohms plug from the resistance box and make all other plugs tight. put in the key K1 and
adjust the value ofthe resistance R from the resistance box so that a deflection 9, near about 30 divisions
is indicated in the galvanometer. Note the deflection 9 in the galvanometer and also the value ofthe
resistance R from the resistance box.
(iii) Adjust the value ofR from the resistance box to get a deflection ofabout 20 divisions and again
note the deflection and the resistance.
(iv) Increase the number of cells to two. Find the e.m.f. and the value of the resistance R tv get a ,'-".
deflection ofabout 30 and again about 20 divisions as in the previous step.

(i) RESISTANCE OF GALVANOMETER:
S.No. Resistance Deflection Shunt Half deflection Galvanometer Resistance

R Resistance
~
(ohms) S
(ohms)
(~) G =
R -s
(ohms)
r o
."
\ /
1.
2.
3.
4. I
Mean value ofG = ............. ohms

,,~
(ii) FIGURE OF MERIT:

Galvanometer resistance (G) = .............. ohms.
No. ofdivisions on the galvanometer scale = .....................
S.No. Number e.m.f. (E) of cell Resistance Deflection (9) Figure of Merit ,,
(
/
ofcel1s (volts) in the res istance

E ( .,
(volts) box(R) K= '--...../
(R +0)9
(ohms)
r'
v'
1. One
2. One ;"-~
,"
3. two ('
'-J
4. two
( "
,-J
r'
PRECAUTIONS ' "--....
1. The value of'R' should be large.
2. To decrease the deflection, the shunt resistance should be decreased and vice-versa.
c
(,
3. In this method it is assumed that the deflection is proportional to the current. This is possible only in a ~
weston type moving coil galvanometer.

4. The connections must be tight and the ends of connecting wires should be cleaned. e
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FOCAL LENGTH OF CONVEX MIRROR
AIM
To fmd the focal length ofa convex mirror using a convex lens.
APPARATUS
An optical bench with four uprights, a convex mirror, a convex lens, a knitting needle and a half meter
scale.
THEORY
Suppose a convex lens L is interposed between a convex mirror M and an object needle 0 as shown
in Fig. 15(A).1 When the relative position ofM, L and 0 are adjusted in such a way that there is no
parallax between the object needle 0 and its image I. then in that position, the rays will fall normally
on the convex mirror M. The rays which fall on the mirror normally should meet at the centre of
curvature C ofthe mirror when produced (Fig.) The distance MC gives the radius ofcurvature R.
Halfofthe radius ofcurvature gives the focal length f ofthe mirror.
"
\,
~
/
" (a) c
/
"
J+-R )10:
\
(
\
(
\..~
(b) ~ K ~ f'
~
/
"
(
Fig. Focal length ofthe convex mirror using a convex lens
(
Now without disturbing the positions ofthe object 0 and the lens L, the convex mirror is removed
( and another needle is placed in the position ofthe image!' ofthe object 0, formed by the lens L by
using parallax method as shown in Fig.
(
R MI'
Measure MI', Now, f= 2 = 2
(
~~ ~~~~~A~~~~~~~~
\. IdealfOl Scholors
PROCEDURE
I. Mount the convex mirror M, a convex lens L and the object needle 0 on an optical bench as shown
in Fig. (a). Look for the inverted image of 0 through the system ofthe lens L and the mirror M by
adjusting the position of 0 or L with respect to that ofthe mirror. When the inverted image is not
obtained, a convex lens oflarger focal length should be used.
2. Remove the parallax between the object needle 0 and its inverted image and note the position of 0,
Land M on the bench scale.
3. Remove the mirror M and do not disturb the lens Land 0 at all. Take another needle It and pla<;:e it on
the other side ofthe lens [Fig. (b)].
Adjust the position ofthe needle so that there is no parallax between the needle I' and the inverted
image ofthe object needle 0 formed by the lens. Note this position ofthe needle It on the optical
bench.
4. Take five sets ofobservations for different positions of 0 and L.
5. Determine the index correction between the mirror M and the image needle 1'.

Index correction
Length ofthe knitting needle, y = ............. cm (
\
Observed distance with the needle between M and I' ~ x = ............. cm

.. Index correction between M and I' = (y-x) = ............. cm.
Table Determination of Focal Length
No.of Position ofobject I Position ofJens L Position of Position ofimage

Observed
Obs needle 0 Mirror M needle I'
di~ta!lc.e,
MI'
(em) I .-(~;) . (em) (em)
(em)
2. ("
, ~
3.
4.
5.
Mean, MI' =................ cm
Corrected distance, Ml' = ................ cm

f ..:.-;.-----
2

cm
Corrected MI' - ....................
RESULT
Focal length ofthe given convex mirror = ..•..•.............. cm
....................m
PRECAUTIONS
1. The linejoining the pole ofthe mirror, the centre ofthe lens Land the tip ofthe needle, should be
parallel to the length ofthe optical bench.

[I] ~~~~}l); C~~~~~
/deal for Scholars
2.. The auxiliary lens L must have sufficiently large fbcallength.
3. The parallax should be removed tip to tip while removing the parallax, the eye should be kept at the
least distance ofdistinct vision i.e., 25 cm away from the needle.
4. In the second part ofthe experiment Le., after removing the mirror M, the positions ofL and 0 should
not
be disturbed at all.
CONCAVE MIRROR
AIM
To find thevalueofv for different values ofu incase ofconcave mirror and to find its focal length.
APPARATUS
An optical bench alongwith three uprights, one mirror holder, two needles, concave mirror, a knitting
needle and a meter scale.
THEORY
( The relation between the object distance u, the image distance v and the focal length f ofa concave
. . .
c mIrror IS gIven as
I 1 1
=~+ .... (i)
f u v
uv
or ....(ii)
u+v
In the case of concave mirror, for real image both u and v are negative as per new cartesian sign
convention. The focal length fis also negative.
( PROCEDURE
TO FIND THE ROUGH FOCAL LENGTH:
1. First ofall find the rough or the approximate focal length ofthe given concave mirror. It can be done
,<
\. by the following method:
Obtain a clear and distinct image ofsome far offobject like that ofthe sun or ofa distant tree on a
(
white paper with the given concave mirror. Adjust the distance between the white paper and the
mirror so that a sharp image is focussed on the paper. Measure this distance between the white paper
and mirror with a meter scale, this distance is the approximate focal length f ofthe mirror.
L
( TO SET MIRROR AND NEEDLE:
"
I. U .1
(
Image of 0
'I. .
~o( F• Ji' v .,1
C
( o I'
c
I
'\. OPTICAL BENCH
,<
~
[IJ~~~~A~~ CL~~~~~
ldeolfor Scholars·
1. Hold the concave mirror in the clamp ofone ofthe three uprights. Mount it in the clamp holder in such
a way that the principal axis ofthe mirror is horizontal and parallel to the length ofthe optical bench.
For this, shift the upright carrying the mirror near one end ofthe optical bench and look into the mirror
keeping your eye vertically above the bed ofthe optical bench. Now turn the mirror slowly in such a
way that the image ofyour eye is obtained at the centre ofthe mirror. This ensures the principal axis of
mirror being parallel to the length ofthe bed.
2. Mount the two needles on the uprights and adjust their heights in such a way that the tips ofthe two
needles and the pole (i.e., the centre ofthe mirror) lie in the same straight line parallel to the length of
the optical bench. After this adjustment, the tips ofneedles will be at the same height as the pole ofthe
mirror. Make a distinction between the object needle and the height as the pole ofthe mirror. Make a
distinction between the object needle and the image needle by putting some distinguishable mark on
them. To do this, a paper flag may be fixed on one ofthe needle-say on the object needle '0'.
3. Mark the position ofa point which is at a distance equal to the approximate focal length, from the pole
P ofthe mirror as shown in Fig. 15(B).1 Label this point as F (i.e, the focus).
4. Shift the object needle towards the pole P ofthe mirror to a position that lies beyond the focus F
" /'-"
-
-'-. /
but remain between F and C (the centre ofcurvature ofthe mirror). The point C lies at a distance
,~-
equal to 2ffrom the pole P of the mirror. Since the object is situated between F and C, so a real \
and inverted image ofthe object needle will be formed beyond C as shown in Fig. You can see_
this inverted image in the mirror by closing your one eye and keeping the other eye along the
optical bench at the height ofthe pole of the mirror.
5. Now mount the second needle on the upright and shift this needle to the position I ofthe image ofthe
object needle. Remove the parallax between this second needle and the image I ofthe object needle.
In the position ofno parallax, the second needle locates the position ofthe image ofthe object needle.
"- /
For this very reason the second needle is termed as the image needle 1'. ( -
'--
6. Note and record the position ofthe mirror, the object needle and the image needle on the b~nch scale.
/" "
7. Repeat the above steps for five different position ofobject needle (i.e., for five different values ofu) '-- /
and record your observations as detailed below: r"'

\../
OBSERVATIONS
C)
1. Rough focal length ofthe concave mirror = ............... cm r,
\:......7"
2. Length ofthe knitting needle, x = ............... cm (--
\...j
3. Observed distance between L;e mirror and the object needle 0 when the knitting needle is introduced
(-',
in between them y = ............... cm ~"- --,,'
4. Observed distance between the mirror and the image needle I' when the knitting needle is introduced in (
\....j
between them,
z = ............. cm c
5. Indexerrorforu, e}=(y-x) = ............. cm ( -

'---./
Index correction for u, = (---e}) = ............. cm
6. Index error for v, e 2 = (z-x) = ............. cm e
Index correction for v, = (---e 2) = ............. cm

(~
r\..../-
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i~~~~A~~ CL~~~~!
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7. Table
Object distance Image distance v

Positions of
No. u (em) (em)
of Corrected Corrected I I
Obs. The mirror Object Image Obsd.
u u'+
Obsd.
v=v'+ - f=~ -
(P) needle (0) needle (I') (P-O) =u' (P-I') =v' u v u+v
(-el) (-e2)
r
(em) (em) (em) (cm) (em) (em) (em) i (em-I) (em-I) (cm)
1.
2.
3.
4.
5.
-
Mean valueoff= ............... cm.
8. Plotting Graphs and Calculation off
(a) u and v graph: Choose suitable but the same scale to represent u along x -axis and v along y-axis. In
(
'- this case, according to Coordinate Sign Convention, both u and v will be negative. Plot the points for
various sets ofvalues ofu and v from the observation table. The graph will be a rectangular hyperbola
as shown in Fig.
r.
'
x'
...;f---- u(em) P - "IV
1ft x
(
'. /: 2f
~
,
Hyperbola ~ ff
··
.. --.--...... "t' ... ----... R
(-2f, -;11)
\
(
/
/
/
/
/
/
1:
t
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c /
el
:
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( Fig. Graph ofu vs. v for a concave mirror (rectangular hyperbola)
( Findingffrom this graph: Draw a line OQ bisectingtheangleX'OY' and cutting the graph at point
Q. The coordinates ofthis point are (-2f, -2f) as shown in Fig. Note the distances ofthe foot ofthe
perpendiculars QP and QR respectively on x and y-axis. The distance QP OR -2f. Halfofthese
distances gives the focal length ofthe concave mirror. Thus,
-QP
( f= -2-= .......cm
_ QR
Also f--""2 ..... em
Take the mean ofthese two values off.

c
(
"-.
( li!~~~A~~ C~~~~! Errors in Measurements & Instruments f451

\. . Ideal for Scholars
(b) ~u and I graph: Choose a suitable but the same scale to represent ~ along X -axis and I along Y_
v . u v
axis, taking 0 as origin (0,0). Plot the graph between I and

. u
J..v . The graph would be a straight line
as shown in fig. 15(B).3. This straight line graph cuts the two axis at an angle of 45° (fig. 15(B ).3)
making equal interapts (OA) and DB) on them.
I
f=- OA ................... cm
f - OB = .................. em
takes the mean ofthese two value off.
(-I
IT'O
J A+-~(cm
I )-1
10
x' "
t
(
< I
I ('
B(O,~lJ
" ,
y'
\.- /
Fig. Graph of I
u
VS. ~v for a concave mirror
PRECAITTIONS
1. The principal axis ofthe mirror should be horizontal and parallel to the length ofthe scale.
2. The uprights supporting the needles and the mirror should be rigid
3. The tips ofthe needles and the pole ofthe mirror should be at the same horizontal level.
4. Parallax ofthe image and object needles should be removed tip to tip
5. The object and the image needles should be clearly distinguished from each other by putting a paper , "
flag on one ofthem and they should not be interchanged for different sets ofobservations. ~J
6. Index corrections for both u and v, should be properly determined and must be applied.
RESULT
Mean value offocal length by computation = ........... cm
F ocallength ofthe given concave mirror as determined from the graph in figure 15(B). 2 f= ...............cm
( ,
and from the graph in figure 15.(B). 3 f= .................... cm \.J
c:
Errors in Measurements & Instruments [46]

[j]~~~~A~~ CL~~~~!
(deal fOl ScholaI'S
L
CONVEX LENS
AIM
To find the focal length ofa convex lens by plotting ofgraphs between u and v and between 1Iu and 1/
v.
APPARATUS
A convex lens ofshort focal length (say 15 to 20 cm.), two needles, three uprights, one clamp, an
optical bench, a half meter rod and a knitting needle.
THEORY
Position ofthe image fonned by a convex lens depends upon the position ofthe object with respect to
the lens. Fig. 15(C). 1 shows the different positions ofthe images fonned by a convex lensfor different
object positions.
The relation between u, v and ffor a convex lens is
I 1 I
- ---
f v u
(
{
PROCEDURE
" 1. Find the rough focal length ofthe given convex lens by focussing a sharp, clear and inverted image
ofa distant object on a white paper and measuring this distance between the lens and the white paper
with a meter scale.
(
\ 2. Ifthe optical bench is provided with levelling screw, then level it using a spirit level.
3. Mount the convex lens (held in its holder) on the central upright ofthe optical bench.
Also mount the two needles on the remaining two uprights. Arrange the tips ofthe needles at the same
\. vertical height as the centre ofthe lens.
r,
Image ofAB
2F ~
~ Image
Needle
( Object needle
CD
AB D
u
( Fig. (C) Two pin method for determining the focal length f of a convex lens.
(Arrangement on the optical branch)
{
\.
4. Mark one needl~ asAB object needle and the other one CD as image needle and distinguish between
them by rubbing tip ofone ofthe needles with a piece ofchalk or putting a paper flag on it.
( S. Find the index corrections for u and v using a knitting needle.
6. Shift the position ofthe object needle AB to a distance greater than 2ffrom the lens. Look from the
C other side ofthe lens along its principal axis near the end ofthe bench. Ifthe setting is correct, an
C inverted, realimageNB' is seen. Now adjust the position ofthe second needle CD such that parallax
('
between the image ofthe object needle and the image needle is removed. The position ofthe second
'"" needle is so adjusted that parallax is removed tip to tip as shown in Fig.15(C).2
F
; [j]~~~~A~~ CL~~~~~ Errors in Measurements & Instruments {47/
\. ldealfor Scholo"
7. Note the positions ofthe lenses, the .object needle and the image needle on the bench scale and thus
find the observed values ofu and v. Apply index corrections to get the corrected values for u and v.
8. Repeat the above steps for 5 different positions ofthe object by placing it beyond 2F and between F and
2F.
Record your observations as detailed below:
OBSERVATIONS
(i) Approximate focal length ofthe lens f = ..... ,..... cm
(ii) For index correction
Actual length ofthe knitting needle x = ........... cm
(a) Foru
1. Observed distance between the object needle and the lens
when knitting needle is inserted between them, y = ................ cm
2. Index error for u, e j (y - x) = ................ cm
3. Index correction foru, (-et)=(x-y) = ................ cm
'(b) For v
4. observed distance between the image needle and the lens
when knitting needle is inserted between them, z = ................ tm

(
\ .
2. Index error for v, e2 = (z - x) = ................ cm
3. Index correction for v, (-e2)=(x-z) = ............ :... cm
Table
Position of Object distance u (cm) Image distance v (cm)
No. Lens Object Image Observed Corrected u Observed Corrected
of at 0 needle needle (O-A)= u' I=u'+ (-el) (C-O) = v' v= v'+(-e2) -uI -I
v
Obs. atA at C
-I -I
(cm) (cm) (cm) (cm) (cm) (cm) (cm) (cm ) (cm )
I.
",
2.
3.
4.
5.
6.
6. Plotting Graphs and Calculations off

(a) u-v Graph :
(i) Choose a suitable but the same scale to represent u along x-axis and v along y-axis. Remember
that u is negative and v is positive for a convex lens, according to the coordinate sign convention used
these days.
(n) Plot the points for various sets ofvalue ofu anJ v from the observation table. The graph will be a
rectangular hyperbola as shown in fig. 15(C).3 c
I '\
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i~~~~A~~ S~~~~~!
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(-2f, 2fj' i :,::,--------- 8
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X' 1 "'10 x
u (em)<II-- y'
Fig Graph ofu vIs v for a convex lens (rectangular hyperbola)

Finding ffrom this graph: Draw aline OC bisecting the angle X' OY and cutting the graph at point
C. The coordinates ofthis point are (-2f, 2f) as shown in fig. Note the distances ifthe foot of the
I perpendiculars OA and OB respectively on X and Y axis. Halfof these distances given the focal
length ofthe convex lens. Thus
,
" f= OA -- ............ .. .... cm
2
:') 08
also 2 = .................. Clll
;
\
take the mean ofthese two values off.
(b) Calculation off from graph between lIu and lIv : Choose a suitable but the same scale to represent
J.u along x-axis and .!.v
along y-axis, taking 0
-
as the origin (0, 0). Plot the graph between 1 and.!..
u v
The graph would be a straight line as shown in figure. 15(C).4. This straight line graph cuts the two
axis at an angle of45 0 (figure 15(C).4) making equal intercepts (OA and OB) on them.
[
measureAO and OB. Then
" I I
[
\
f= OA OB = .................... cm
(
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r
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o
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1 10
y'
x
c- Fig. Graph of lIu vs. lIv for a convex lens

e
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~ .
[i]!~~~A~~CLI!!~~!~
Idealfor Scholars
RESULT
The focal length ofthe given convex lens as detennined from the graph of
(i) (u, v) Fig. = .................cm
(ii) (~)-) Fig. = .................cm .
,u v
PRECAUTIONS
1. The tips ofthe needles should be as high as the optical centre ofthe lens.
2. The uprights carrying the lens and the needles should not be shaky.
3. Parallax should be removed tip to tip.
4. The eye should be placed at such a position that the distance between the image needle and the eye is
more than 25 cm.
S. The image and object needles should not be interchanged for different sets ofobservations.
6. A pieceof chalk may be rubbed on the tip of the object needle or a paper flag put on it, so as to
distinguish it from the image needle.
MINIMUM DEVIATION
AIM
To detennine the angle ofminimum deviation for a given glass prism by Plotting a graph between the
angle ofincidence and angle ofdeviation and hence find the refracti ve index ofthe material ofthe
prism.
APPARATUS
A drawing board, a sheet ofpaper, glass triangular prism, pins, a halfmeter scale, a graph paper and
a protractor
THEORY
Refraction Through a prism (angle ofminimum deviation)
A
....... T
Nt
E H
{
Figure Refraction ofIight through a prism "
Minimum Deviation - In (Fig.), ABC

represents the principal section of a glass prism. Let EF be a ray of light that is incident on the .
refracting faceAB ofthe prism. The straight path FG represents the refracted ray through the prism
and GH represents the emergent ray. FN 1 and GN 2 are drawn normal to the refracting faces AB and
AC at points F and G respectively. Incident ray EF Produced to PT, as as result ofrefraction through
the prism ABC emerges along GH. The incident ray shown as EF (extruded as dotted line FPT)
deviates and follows the path PGH. The angle ois the angle between the incident ray EFPT (produced)
shown dotted and the emergent ray GH (produced backwards) to meet EFT at the the point P. This
angle 5 is known as the angle ofdeviation. The angle BAC ofthe prism (Le., the angle between its two
i!~~~A~~ C~~~~! Ideo! for !khokm

Errors in Measurements & Instruments . [50J
refracting faces) is called the angle ofthe prism and it is denoted by the letter 'A'. It can be proved
from simple geometrical considerations that
LA + La Li+ Le .... (i)
and A=r) + r2 .... (ii)
where i angle ofincidence
e = angle ofemergence
r l
= angle ofrefraction at faceAB
r2 = angle ofrefraction at face AC. .
The relation (i) clearly shows that angle ofdeviation 8 varies with the angle ofincidence i.
The variation ofangle 0 with angle i is represented graphically in Fig.
It is obvious from Fig. That the angle 8 decreases with the increase in the value of i initially, till a
particular value ( 0 ) ofthe angle ofincidence is reached. For this value ofangle of incidence, the
corresponding value ofthe angle ofdeviation is minimum and it is denoted by the letter Om' This angle
ofdeviation is called the angle ofminimum deviation. When a prism is so placed with respect to the
incident ray that the angle ofdeviation produced by it is minimum, then the prism is said to be in the
(
\. position ofminimum deviation. In this position, the following relation holds between the angles.
.£
i.e., Li Le and Lr) = Lr2 ....(iii)
In this position, the incident ray and the emergent ray are symmetrical with respect to the prism and
!
\,
the ray passes through the prism is parallel to its base. Refractive index ofmaterial ofprism is given as,
(
\. . (A+Om)
Sin 2
J.l sinA/2
( Where om is the angle ofminimum deviation and A is the angle ofthe prism
(
y
(
i 48
46
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lib
~ 44

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'~ 40
f
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( <C om
36
(
341 X
( 20 30 40io 50 60 70 80
Angle of incidence (i)/ degree
- ( )00
Variation of angle of deviation with angle of incidence for refraction through a prism
(
(' [I~~~~A~~ CL~~~~~

"- Ideal for Scholars
PROCEDURE
1. Fix the sheet ofthe white paper on the drawing board with cello-tape or drawing pins.
2. Draw a straight line XY nearly at the centre ofthe sheet parallel to its length. Mark points marked as
o at suitable spacing on this line XY and draw normal to the line XY at points 0 as shown in Fig.
Draw straight line PQ corresponding to the incident rays that are drawn at angles ofincidence ranging
from 30° to 60°, i.e., for angles of 30°,40°,50° and 60° using a protractor.
3. Place the prism with one of its refracting surfaces on the line XY and trace its boundary ABC as
shown in Fig.
/ '
T
"
Fig. (
\,
,
4. Fix two pins P and Q about 8 cm apart on the incident ray line and view its image with your one eye
closed from the face Be ofthe prism. Fix two pins R and S on the paper such that the tips ofthese \ /
pins and the tips ofthe images ofthe incident ray pins P and Q all lie on the same straight line.
5. Remove the pins Rand S and encircle their pin pricks on the paper. Remove the pins P and Q and
also encircle their pin pricks. , .
i
6. Join the points (Le., pin pricks) Sand R and produce it backwards to meet the incident ray PQ
(
produced (shown by dotted lines). Thus RS is the emergent ray corresponding to the incident ray PQ.
Draw arrow heads to show the direction ofthe rays. /
\ /
7. Measure the angle ofdeviation S with a protractor.

r ".
S. Repeat the steps (3 to 7) for different values ofangle ofincidence (Fig.) and measure the corresponding \./
angles ofdeviation S. Take at least seven values ofangle i ranging from 30° - 60°. ('
'--./
Measurement of refracting angle 'A' ofthe prism.
1. Draw a line XY on the drawing sheet as depicted in Fig. o
G J H
c
,---,.
f '
C
f'
'-/
L ~y
x C'
Fig. Measurement the refracting angle A of the prism 0
C
( ,
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Errors in Measurements & Instruments [52]
[i~~~~A~~ CL~~!~!
Ideo! (or Scholars
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2. Mark points 0 in the middle ofXY and E and F on either side of0 equidistant from E such that OE
OF (say 1 cm each).
3. Draw three vertical lines EO, 01 and FH through E, 0 and F respectively, such that these are parallel
to each other.
4. Place the prism with its refracting edgeAon the line OJ such that BC is along XY. The points E and F
would be symmetric with respect to edges B and C.
5. Draw the boundary ABC ofthe face ofprism touching the board.
6. Fix pins PI and P2 vertically, 4 cm apart, observe their reflection in the face AB and tlx the pin P 3 such
that the images ofP l' P 2 and P 3 are in a straight line. Fix another pin P4 such that prick ofP4 is also in
the same straight line. Join the pricks ofP 3 and P 4 by line LK and produce it backward. KL is
reflected ray of incident ray OK.
7. Similarly locate NM by joining P:3 P 4. as the reflected ray ofincident ray HM. Draw NM backward to
meet the line LK produced backward at point P. The point P should lie on the line OJ ifobservations.
are correctly taken.
(
\
8. The angle LPN is equal to 2 LA (it can be proved geometrically from the tlgure). Measure the angle
LPN and determine LA, the angle ot-prism.
r~
OBSERVATION
(
(i) Table for angles i and 8
(
\.
,
(
1 30°
!
2 35°
\.
3 40 Q
/
\.
4 45°
t'
\. 8 60°
( (li) plotting the graph between Li and L8 Plot a graph between angles i and 0 for various sets ofvalues
recorded in the observation table. The graph will be a curve as shown in Fig.
( (iii) For angle' N ofthe prism
r'· LPN ........... 0 = 2A
\.. o
or AngleA =
(
(. CALCULATIONS
,.
Determine the angle ofminimum deviation 13m from the graph.
(
RESULT
(
(i) The angle ofdeviation 8 tlrst decreases with the increase in the angle ofincidence, attains a minimum
(
\.. value and then increases with further increase in the angle ofincidence as indicated in the (&-i) graph
Fig.
(
- C: PRECAUTIONS
1. A sharp pencil should be used for drawing the boundary ofthe prism.
( 2. The separation between the pins should not be less than 3 Cffi.
e 3. The angle ofincidence should lie between 3'()0 to 60°.
,:(~----------------~----~~--------~---------------=----~~~
[j]!~~~A~~ CLL,~~~~! . Errors in Measurements & Instruments {53}
'\... .. .. _ ..
c
4. The same angle ofprism should be used for all the observation. So an ink mark should be placed on
it to distinguish it as the refracting angle A ofthe prism.
S. The pins should have sharp tips and fixed vertically and the pin pricks should be encircled immediately
after they are removed.
6. Proper arrows should be drawn to indicate the incident, the refracted and the emergent rays.
7. A smooth curve practically passing through all the plotted points should be drawn.
REFRACTIVE INDEX OF A GLASS SLAB

AIM
To determine the refractive index ofa glass slab using a travelling microscope.
APPARATUS
A piece ofpaper, a marker, glass slab, travelling microscope, lycopodium powder.
THEORY
Refraction is a phenomenon ofpropagation oflight from one transparent medium into the other medium
such that light deviates from its original path. The ratio ofvelocity oflight in the first medium to that in
the second medium is called refractive index ofsecond medium with respect to the first. Usually the
first mediumis air.
The bottom surface ofa vessel containing a refracting liquid appears to be raised, such that apparent c
depth is less than the real depth. Refractive index ofrefracting liquid is defined as the ratio ofreal
depth to the apparent depth.
. IIy, RefractIve
Mathematica . .mdex Jl = ------''---
real depth
apparent depth
For accurate measurements ofdepths, a travelling microscope [Fig. (a)] is used.
Ifreading ofreal depth at the bottom ofthe slab is r1' ifreading at cross due to refraction is r2 and at
\
the top ofslab ifreading is r3' then
real depth = r3 - r" and
apparent depth r3 - r2 ·
. . . . . . . . . . . . . ii
Therefore, refractive index ofglass (material vf slab) Jl =

r3 f2
.................... _ _ _ a. _ _ ..
(~
Q)
0.. .................c::::rfh
R
~~ 0
e
<.)
R
.§ R
b.O
:.E
Q)
~
J:::
"
'0
E Lycopodium
$I Powder
t/.)
---;..-..- Glass slab

o
(a) (b) (c) G
Fig. : Travelling microscope taking reading (a) atthe cross mark
(b) at the cross mark with slab placed on it (c) at powder sprinkled on the top of the slab

lI~~~~!!~ CL~~~~f
Ideal for Sch<JIol'I
c
c
PROCEDURE
For accurate measurement ofdepths, travelling microscope is used [for travelling microscope turn to
page no. 41]
1. Note the number ofdivisions ofvernier which coincide with number offtill scale divisions.
2. Find the value ofeach main division and hence least count ofthe microscope scale as (1 M.S.D. - 1
VS.D.).
3. Set the microsc0pe in its stand such that it is capable ofsliding vertically up and down as the screw
attached to rack and pinion is turned.
4. On a sheet of white paper, mark a cross and place it below the objective of the microscope.
5. Move the microscope very gently. Using the screw, focus the eye piece on cross mark and bring the
cross in focus such that the cross wires, coincides with the marked cross on the paper. Note the
reading ofthe microscope as r l [Fig. (a)].
6. Place the given glass slab on the cross mark. You would observe that the cross mark appears to be
raised.
7. Move the microscope gradually and gently upward to bring the cross mark in focus and on cross of
cross wires. Record the reading as r2 [Fig (b)].
, 8. Sprinkle some fine lycopodium powder on the glass slab and move the microscope upward till the
powder particle come into focus. Record the reading on the scale as r3 [Fig. (C)].
9. Difference ofreadings r3 and r I i.e. r3 -r l gives the real depth whereas r3 - r2 gives the apparent
/
\
depth.
10. Record your observations as follows and calculate the value ofrefractive index m.
i
.OBSERVATIONS
.,Least count oftravelling microscope.
,
10 Vernier Scale Division = 9 Main Scale Divisions
"
(
(Scales may differ from instrument to instrument).
Value ofone main scale division = 1 mm i.e. 0.1 cm.
(
." 10 V.S.D. 9 M.S.D. (VS.D. Vernier Scale Division, M.S.D. Main Scale Divisions)
( .'. 1 V.S.D. = to9 M.S.D.

9 1 1
L.C. = 1 M.S.D. - 1 V.S.D. = 1 M.S.D. 10 M.S.D. = 10 M.S.D. or 10 x 0.1 cm = 0.01 cm.
Reading ofmicroscope focussed on

(
Cross mark without slab Cross mark with slab placed on it Powder sprinkled on top ofslab
No.
( Main Vernier Reading Main scale Vernier Reading Main Vernier! Reading
of
scale diy. N+n x reading(N) diy. N+n x scale diy. N+n x
Obs.
( reading· Coinciding L.C. = rl Coinciding . L.C. = r2 reading Coinciding L.Co = r3
(N) (N)
(
\.. (em) n (cm) (cm) n (em) (cm) n (cm)
( 1.
2.
c 3.
(
I _._
Mean values r l = .......... cm, r2 = .............. cm and r3 ..........cm
~. ~.------------------~------~----------~----------------------~~-
(
[I!~~~. ~. ~ CL~~~~~ Errors in Measurements & Instruments [55J
\.. Ideo! for Scholars
CALCULATIONS
Real depth d r = r3 - r l = .......... cm.
(1) ..... ,.. cm; (2) ........ cm and (3) ......... cm; Mean d r
= ...... cm
Apparent depth = d a = r3 - r2 = ........ cm.
(1) ......... cm (2) ......... cm (3) .......... cm; Mean d a =

.............. cm
. . Real depth d
RefractIve mdex ~ = = _r =
Apparent depth da
/~
PRECAUTIONS
1. Least count ofthe scale oftravelling microscope should be carefully calculated.

2. Microscope once focussed on the cross mark, the focussing should not be disturbed throughout the
experiment. Only rack and pinion screw should be turned to move the microscope upward.
3. Eye piece should be adjusted such that cross wires are distinctly seen.
4. Cross wires, cross should be set on the ink cross mark on the paper.
S. Only a thin layer ofpowder should be spread on the top ofslab.
6. Express your result upto significant figures keeping in view the least count ofinstrument.
RESULT
The refractive index ofthe glass slab by using travelling microscope is determined as ...........(no units
required as it is simply a ratio).
\
CHARACTERISTIC CURVES OF A P-N JUNCTION

AIM "
To study the static and dynamic curves ofa p-njunction diode in forward bias and to determine its " ..
static and dynamic resistances (- '-
". /"
REQUIREMENTS
A p-n junction diode, a three volt battery, a high resistance rheostat, 0-3 volt voltmeter, one
milliammeter, one way key and connecting wires.
r'
v
THEORY
When a junction diode is forward biased, a forward current is produced which increases with increase c'
in bias voltage. This increase is not proportional. c
The ratio of forward bias voltage (V) and forward current (I) is called the static resistance of
c
. ductor d'10d
semicon e, 'I.e., R VF
-.;-.
c
In case ofa varying bias voltage and varying forward current, the ratio ofchange in forward biase ( ,
'-'
voltage (6.V) and corresponding change in forward current (6.I) is called the dynamic resistance
c
r = !J..VF)
( !J..IF . c
To find the static and dynamic resistance ofsemiconductor diode, a graph has to be plotted between
forward bias voltage (V) and forward bias current (1). This graph is called the characteristic curve of
e
semicondctor diode. G
( ,
v
G
[I~~~~A~~CH~~!~~
IdealTor Scholars
C
C
PROCEDURE
Diode
+
Battery -= Rh ~( Voltmeter I V
+
rnA) Milliammeter
(
\
K
,r' ,
(a) Make the connections as shown in figure.
(b) Keep the moving contact of the rheostat to the minimum and insert the key K. Voltmeter and
f
\. milliammeter will show a zero reading.
c (c) Move the contact towards the positive to apply the forward bias voltage V = 0.1 V. The current
•
remamzero
(
( (d) Increase the forward bias voltage to 0.3 V in steps. The current will still be zero. (This is due to the
junction potential barrier of0.3 V).
(e) Increase V to 0.4 V. Record the current.

(
(I) Increase V in step of0.2 and note the corresponding current.
(
\.
<..
(g) At V = 2.4 V. The current increases suddenly. This represents 'the forward breakdown stage.
(
(h) Draw a graph of! on y-axis and V on x-axis. The graph will be as shown in figure
(
(,. RE~ORD OF READINGS
(1) Least count ofvoltmeter = ......................... V Zero error ofrnA = ........................ rnA
C (ii) Least count ofmilliammeter = ................. rnA Zero error of voltmeter = ................... V
(;
(
o o
(
' 2 o
o
c 3
4
(
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l
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(
- fj]~~~~A~~ CL~~~~~ Errors in Measurements & Instruments [57J
C Ideof(Of Sch%rs
l
GRAPH
1-!r
c
~
! t.<i:.................--......................-.
. . . -.. . -.. . . . .-..-.-. . . . rT
5 B
11 ~
01 ! ::r=! .!A'l. )to x
Forward bias voltage Vp (V) , /
CALCULATIONS
.(i) For static resistance (R)
vF
R=
IF
. OA'
From the graph R = ON' = .......... , ohm
Diode used...... (specifY the code)

(ii) For dynamic resistance (r)
/').vF
r
/').JF
AC .
. . From the graph r = BC ohms
RESULT
c
(1) The static resistance ofthe given semiconductor diode = ........... ohm
(ii) The dynamic resistance ofthe given semiconductor diode = ......... ohm
PRECAUTIONS
(i) Make all connections neat, clean and tight
(ii) Key should be used in circuit and opened when the circuit is not in use
(ill) Avoid applying forward bias voltage beyond breakdown

c
POSSIBLE SOURCES OF ERRORS c
(i) The connection may not be tight
(ii) The junction diode may be faulty
c
f '
~
[58}
i ~~~~A~~CL~~~~~
1dea1f0f S<holors
c
c
CHARACTERISTIC CURVES OF A ZENER DIODE
AIM
To draw the characteristic curves ofa zener diode and to determine its reverse breakdown voltage.
APPARATUS
A Zener diode (with reverse breakdown voltage of6 V), a ten volt battery, a rheostat, two voltmeters
(range 0, 10 V), one milliammeter, one 200 resistance, one way key, connecting wires.
THEORY
Zener diode is a semiconductor diode in which the n-type sections are heavily doped, This heavy
doping results in a low value ofreverse breakdown voltage.
The reverse breakdown voltage ofZener diode is called Zener voltage (V z)' The reverse current that
results after the breakdown, is called Zener current (lz).
The circuit diagram is given in figure
Vi Input voltage
Vo = Output voltage
(
\ R j = Input resistance
r Ii = Input current
\~
Iz =
Zener diode current
IL Load current
IL = Ii -
Iz
Vo=V.-RI.
I I I
(
\ Vo RLIL
Initially as Vi increases, Ii increases hence V 0 increases linearly. At break-down, increase ofVj increases
(
Ii by large amount, so that V 0 = Vi - RjI i becomes constant.
This constant value ofV0 Which is the reverse breakdown voltage, is called Zener voltage.
(. CIRCUIT DIAGRAM
r
'" IL
,
\.-'
lz
f
+ +
'" IOV_
Zener
RL Vo
diode
(
N758 A
( VI) Vi
.~__~________~________________________~~____~~____J
(
'1...
! ..
(
!"~
'l.
c
(
"
:. [i~~~~A~CL~~~~~ Errors in Measurements & Instruments [59)
\.. Ideolfor St;hcIorS
c
PROCEDURE
(a) Make the connections as shown in figure above making sense that zener diode is reverse biased
(b) Bring the moving contact to rheostat to the minimum and insert the key K. Voltmeter and ameter will
read zero
(c) Move the contact a little towards positive end to apply some reverse bias voltage (VJ Milliammeter
reading remains zero.
(d) As Vi is f11rther increased, Ii starts increasing and Vo becomes less than Vi. Note the values ofVi' Vo
and I·I
_._-/
(e) Keep increasing Vi in small steps of 0.5 V. Note the corresponding values ofli and Vo
(f) At one stage as Vi is increased, Ii increases by large amount and Vo does not increase. This is reverse
break down situation
(g) As Vi is increased further, Ii will increase keeping Vo constant. Record your observation in tabular
column
(h) Draw graph ofoutput voltage V0 along y-axis and input voltage along x -axis. The graph will be as
shown in figure
(i) Draw graph ofinput current along" y":axis and input voltage along x-axis. The graph will be as shown
in figure
GRAPHS
( ,
\
"
,,
Input voltage (V) volt
(

o; Zener
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Input voltage (V) volt
c
( ,
RECORD OF READINGS '--'
Least count or'voltmeter VI = ............ V
Least count ofvoltmeter V2 = ............ V c
Least count ofmilli-ammeter = ......... mA c
c
(\
v
c
{60J
c
1i~~~~A~~ CLL,~~~~~ Ideal (or Scholars c
c
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2 0.5
4 1.5
( RESULT
The reverse breakdown voltage ofgiven Zener diode is 6 volts.
(
\~
PRECAUTIONS
(i) Use voltmeter and milliammeter ofsuitable range.
(li) Connect the zener diode p-n junction in reverse bias.
(iii) The key should be kept open when the circuit is not in use.
CHARACTERISTIC CURVES OF A
TRANSISTOR
r ~
AIM
" To study the characteristics ofa common emitter n-p-n or p-n-p transistor and to find out the values
( ofcurrent and voltage gains.
(. REQUIREMENTS
( An n-p-n transistor, a 3 V battery, a 30 V battery, two rehostats, one 0--3 V voltmeter, one 0-30 V
voltmeter, one 0--500!-lAmicroammeter, one 0-50 mAmilliammeter, two one way keys, connecting
wires.
(
THEORY
( A transistor can be considered as a thin wafer ofone type ofsemiconductor between two layers of
(
another type. A npn transistor has one p-type wafer in between two n-type. Similarly p-n-p the .
\.
.transistor has one n-type wafer between two p-type.
( 1n a common emitter circuit, the emitter base makes the input section and the collector base the output
section, ~th emitter ba~e junction, forward bias and the collector base junction, reverse biased.
(
The resistance offered by the emitter base junction is called input resistace Rj and has a low value.
( ~.. The resistance offered by the collector base junction is called output resistance Ro and has high value.
Due to the high output resistance, a high resistance can be used as a load resistance.
L
.
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Ideal for Sdiolars
The ratio ~ or ~ measures the resistance gain ofthe common emitter transistor.
Rj Rj
The ratio ofchange in collector current to the corresponding change in base current, measures the
current gain in common emitter transistor and is represented by 13.
13 = Alb
The product ofcurrent gain and the reistance gain measures the voltage gain ofthe common emitter
transistor.
FORMULA USED
Input resistance, Rj :::: Alb
·
Output resIstance, AV
R 0 =: _ c
_
Alc
Resistance gain, Rj
Current gain, f3 Alb
Voltage gain = Current gain x Resistance gain
(" "
Ro
i.e. AV f3R. !
CIRCUIT DIAGRAM
\~/
Ie ;:'- ".
( '-.
- .."c<::Rh +
+
-=-3V 30V
Rh ~><I.r---
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'-d
K. Ib Ie K2
PROCEDURE
( ,
(a) Make circuit diagram as shown in given figure (A) v
(b) Drag the moveable contact ofrheostat to the minimum so that voltmeters V I and V2 read zero volt
e
FOR INPUT CHARACTERISTICS t ".
V
(c) Apply the forward bias voltage at the emitter base junction note the base voltage (y b) and the base "
current(I~
(d) Keep increasing Vb till Ib rises suddenly
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(e) Make collector voltage 10 V and repeat the above steps
(f) Now make collector voltage 20 V, 30 V and repeat the above steps. Note the value ofV band Ib in
each case
FOR OUTPUT CHARACTERISTICS

(g) Make all reading zero. Keep the collector voltag~ zero.
(h) Make base current Ib 100 ~IA by adjusting the base voltage. You will be able to read some collector
current even though the collector voltage is zero
(i) Make the the collector voltage 1Ov, 20V, 30V, etc. and note corresponding collector currents. Record
your observations in the tabular fonn as given below
0) Make the current Ib equal to 200 ~A, note the values ofIe corresponding to the different values ofV e
RECORD OFREOBSERVATIONS
Least count ofvoltrneter, VI .......... V
Leastcountofvoltrneter, V2
= .......... V
Least count ofmilliammeter = ............. rnA
( Least count ofmicroammeter ............... ~A
(
\ Table-l For base voltage and base current
Table-2 For collector voltage and collector current
3
(
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4
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5
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\- GRAPHS
{ I. (For Input Characteristics)
Draw a graph ofbas~ voltage (Vb) on the x-axis and base current (Ib) on the y-axis from table no. 1.
( The graph will be as shown in figure.
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f [j]~~~~A~~ Ct:~~!~~ Errors in Measurements & Instruments [63J

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<u4 ~
400 ,-7 ,<U ~
~'" -7 ry<U S
~ ····.···l-··.····-.-..-·-·-...... 4<:'-7
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~~
~
f_..._:...J_...
~~
Dt
-...-.-----..
Ii.
4<:.
50
.......- I I I I "X
-0.5 1.5 2 2.5 3

Base voltage (Vb) V
The slope ofthe graph gives the value of d1b and its reciprocal gives the value ofinput resistance R i. "
dVb ,/
,r--"
i
b
R = dV~= ........... ohms
..1.Ib
\
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,,-,
f
"\.. .i
II. For Output Characteristics

Draw the graph between collector voltage Ve and collector current Ic for lOrnA base current Ib
taking Vc along x-axis and Ie along y-axis from table no.2. The graph will be as shown in figure.
15;- /" I Ib=400 !!A ' "
1:5 ' ~
Q)
....~ ~ 1511 /4AL Ib=300 !!A '' ~

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B~
~~
;:::::
l°tf /..'! Ib=200 !!A
o
u
5-111 ..- i lb= 100 !!A
I'
''--.7
. X
5 10 20 25
Collector voltage (V c) V ( '.
"
From the graph the slope gives the value of dIe and its reciprocal gives the output resistance. C',
.........../
dVe
Ro= ~~e = ................. ohm
c
III. For Calculation ofCurrent Gain G
Plot a graph ofbase current (Ib) on x-axis and collector current Ic on y-axis. The graph will be as v"
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shown in figure. f .
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The slope ofthe graph will give the value of 41: which is thevaIue ofcurrent gain (~).
y
1:: -r- 20
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....,
0
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. . . . . . . . . . ('
1
<1.)"-'
15
() TID B
.... 'C
!. Alb .,
v _! _ I , I
200 300 400 .. X

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Base Current (lb) JlA
r AC= ................................. rnA
\~
................................. A
BC::::: ................................. J..lA
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\, ................................. A
c 13 = ~~ = ................. .
For calculation ofvoltage gain (Av)

"
\, Voltage gain = Current gain x Resistance gain
{ Ro
~
A=~x ~
y I·
(
C'. RESULT
For the given common eIhittertransistor, Current gain 13 = ................... .
Voltage gain Ay = ....................
PRECAUTONS
(i) Use voltmeter and milliammeter ofsuitable range
( (ri) The key should be kept open when the circuit is notin use
( POSIBLESOURCESOFERRORS
(
\. (l) Voltmeter and ammeter may have a zero en'or
(ri) All the connections may not be tight
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{65J
IDENTIFICATION OF DEVICES
AIM
To identi fy a diode, a L.E. D., a transistor, a resistor and a capacitor from a mixed collection ofsuch
items
APPARATUS
A multimeter and a collection ofajunction diode, L.E.D., a transistor, a resistor, a capacitorand
integrated circuit.
THEORY
For identification ofdifferent items, we have to consider both, their physical apperarance and working
1. AnIC (integrated circuit) is in the form ofa chip (with flat back) and has multiples terminals, say 8
or more. Therefore, it can easily be identified.
2. A transistor is a three terminal device and can be sorted out just by appearance
3. A resistor, a capacitor, a diode and an LED are two teminal devics. For identifying these, we use
the following facts :
(i). A diode is a two terminal device that conducts only when it is forward biased
(ii). An LED is a light emitting diode. It is also a two teminal device which conducts and emits light
only when it is forward biased.
(iii). A Resistor is a two teminal device. It conducts both with d.c. and a.c.voitage. Further, a
resistor conducts equally even when teminals ofd.c. battery are reversed
(iv). A capacitor is a two terminal device which does not conduct with d.c. voltage applies either
way. But, conducts with a.c. voltage
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Resistor
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L.E.D.
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Diode Transistor
PROCEDURE
1. Looks at the given mixture ofvarious components ofelectrical circuit and pick up the one having
more than three terminals. The number ofterminals may be 8, 10, 14, or 16. This component will have
a flat face. This component will be the integrated circuit Le., IC.
2. Now find out the component having three legs or terminals. It will be a transistor ( "
'--'
3. The component having two legs niay either be a junction or capacitor or resistor or a light emitting
diode. These items can be distinguished from each other by using a multimeter as an ohmmeter.
4. Touch the probes to the two ends ofeach item and observe the deflection on the resistance scale.
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After this, interchange the two probes and again observe the deflection
5. (i) Ifthe same constant deflection is observed in the two cases (before and after interchanging
the probes), the item under observation is a resistor
(Ii) Ifunequal deflections are observation, it is a junction diode
(ill) Ifunequal deflections are observed in the two cases along with emission oflight in the case
when deflection is large, the item under observation is an LED
(iv) On touching the probes, ifa large deflection is observed, which then gradually decreases to
" zero the item under observation is a capacitor
In case the capacity ofthe capacitor is ofthe order ofpicofarad, then the deflection will become zero
within no time
RESULT
When the item is observ~d physically
S. No. Number oflegs (or pins) ofthe item Inference

I More than three The item is an Ie
2 Three The item isa transistor
3 Two junction diode, L.E.D.,
(
res istoror capacitor
""
("
With multimeter as an ohmmeter:
I"
"" S.No. Possible deflection before and after interchanging tile Inference
probes
1 Same cosntant deflection The item is a resistor
t.e '
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2 Small deflection in one case and large deflection in the The item is a junction diode
(
other
\", 3 Small deflection in one case and large deflection in the The item is an LE.D,
( other along with emission of light
\
4 Large deflection, which gradually falls to zero The item is a capacitor ofsmall
capacity
- - - - - ............. - - - - --_
........... _ - - - - -
(
PRECAUTIONS
" ' Observe all those precautions which were related to multimeter and explained at the end of multimeter.
(
MULTlMETER
'(
AIM
( Use ofmultimeter to :
(a) IdentifY base oftransistor.
(b) Distinguish between N-P-N and P-N-P type transistor.
C, (c) IdentifY terminals ofan IC.
(d) See the unidirectional flow ofcurrent in case ofa diode and LED.
(e) Check whether the given elecrroniccomponent(e.g., diode, transistor or IC) is in working order.
{
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APPARATUS
A multimeter, P-N-P transistor, N-P-N transistor, an IC,junction diode, L.E.D., etc
THEORY
Multimeter : It is an electrical instrument which can be used to measure all the three basic electrical
quantities i.e., electrical resistance, current (a.c. and d.c.) and voltage (direct and alternating). Since it
can measure Ampere (A) (unit ofcurrent), Volt (V) (Unitofe.m.f.) and Ohm (unit ofresistance), that
is why it is also called as AVO meter. In this way, this single instrument will replace the Voltmeter and
Ammeter.
CONSTRUCTION
The most commonly used form ofmulti meter is shown in figure, which is basically a pointer type
moving coil galvanometer. The pointer ofthe multimeter can move over its dial, which is marked in
resistance, current and voltage scales ofdifferent ranges. The zeros ofall the the scales are on the
('
extreme Ieft, except that ofresistance scale, whose zero is on the extreme right. A dry cell of 1.5 V is \, /
provided inside "it. When the multi meter is used as an ohmmeter, the dry cell comes in closed circuit.
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(-,
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Selector switch ~ Cj l'l "r

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Jack socket 1,,0
Figure: Multimeter
1. Circuit jacks: In the multimeter shown in fig. there are two circuit jacks, one each at the extreme
comers ofthe bottom ofthe multimeter. The jack at right comer is marked positive ( + ), while the
other at left corner is marked negative ( - ). In certain multimeters, the positive circuit jack is not /"
\_j
'~
provided but circuit jacks are provided in front ofall the markings in regions A, E, C and D. When the
range switch is turned in any region, then all the circuit jacks in that region act as the posi tive circuit
()
jacks.
Two testing leads (generally one black and the other red in colour) are provided with a multimeter.
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Each lead carries two probes (one smaller than the other) as its two ends.The smaller probe ofred \.-/".
lead is inserted injack marked positive, while the smaller probe ofblack lead is inserted injack (,,/"
marked negative.
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It may be pointed out that the battery cell remains connected to the meter only, when the range switch
is in region A. Further, actually the positive ofthe battery cell is connected to the negative circuit jack
and the negative ofthe battery cell is connected to the positive circuit jack.
2. Zero ohm switch: This switch is provided at the left side ofthe multimeter. However, in some
multimeters, the zero ohm switch is also provided on its front panel. This switch is set, while measuring
a resistance. In order to set this switch, the smaller probes are inserted in the two jacks and the bigger·
probes are short circuited. This switch is worked, till the pointer comes to zero mark, which lies at the
right end ofresistance scale. The action ofmultimeter as different types ofmeters is explained below
(i) Ammeter: The galvanometer gets converted into d.c. ammeter when range switch lies in the
region B ofthe multi meter panel. When range switch is in region B, it can be used as d.c. ammeter of
range 0 to 0.25 mA, 0 to 25 rnA and 0 to 500 rnA by bringing the knob in front ofthe desired mark
when the range switch is in the region B, a very small resistance called shunt resistance whose value is
different for different range, gets connected in parallel to the galvanometer. In this position, the battery
(
cell is cut offfrom the meter.
l
r (li) Voltmeter: Multimeter can be used to measure both direct and alternating voltage
(a) d.c. Voltmeter: The galvanometer gets converted into d.c. voltmeter when the range switch lies
in the region C ofthe multimeter panel. With different positions ofrange switch in this region, it can be
used as d.c. voltmeter ofranges 0-0.25 V, 0-2.5 V, 0-10 V, 0-50 V and 0 to 1000 volts. Whf;ll the
range switch is in region C, a high resistance, whose value depends upon the range selected, gets
(
. connected in series to the galvanometer. In this case the battery cell is not in circuit with the meter.
(b) a.c. Voltmeter: The galvanometer gets converted into a.c. voltmeter when the range switch is
(
turned and it lies in the region D ofthe multimeter panel. With the different positions ofthe range
switch in this region, multimeter can be used as a.c. voltmeter ofrange 0 to 10 V, 50V, 250V and
(
IOOOV. A solid state crystal diode rectifier is incorporated in the circuit so as to use it for a.c.
"
measurement.
(iii) ohm-meter: When the knob in the lower part ofthe multimeter Le., the range switch is turned so .
( as to be in the region A ofthe multimeter panel, the galvanometer gets converted into a resistance
( .
meter. When range switch is in front ofa small black mark against x KQ mark, it works as resistance
-=-'
meter of range
oto 50 KQ and when the knob is in front of x MQ mark, it works as a resistance metre ofrange 0 to .
( 50 x 106 ohm. When the range switch is in region A, a battery cell of0.5 V and suitable resistor
\.
whose value is different for xKQ and xMQ marks, gets connected in series to the galvanometer.
(
"
(. PROCEDURE
(
(1 )Take a multimter and plug in the smaller probe3 ofthe testing leads into jack sockets marked as
\..
positive (+) and negative (- ).
- C (2) Tum the selector switch in the region A, so that it points towards the small black mark against
xMQ or xKQ. Adjust the zero ohm switch till the pointer ofthe multimeter comes to zero mark of
(.
the resistance scale (on extreme right), when the two probes are short ciruited.
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Errors in. Measurements & Instruments {69/
(a) To identify the base of transistor :
..-----~
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Transistor J
(3)In most of the cases the central lead ofa transistor is base lead but in some cases it may not be so.
In order to identify the base lead, touch the two probes to the extreme two legs ofthe transistor. Note
the resistance oftransistor between these two legs. Now, interchange the probes touching the two
extreme legs ofthe transistor again and note the resistance oftransistor between these legs. i'
I,
Ifin both cases the resistance oftransistor is high, then the central leg is base oftransistor and the
two extreme legs are emitter and collector, because emitter collector junction offers high resistance in
both directions.
But ifthe resistance is high in one direction and low in the other direction, then one ofthe extreme
legs is base oftransistor.
(4)To find, which ofthe extreme legs is base, touch one probe to the left: leg and the other to the
central leg. Note the resistance between these two legs. Now interchange the two probes and again
note the resistance.
In case the resistance is low in one direction and high in other direction, then the left leg is base
/
otherwise the right leg is base ofthe transistor. \ /
(b) To find whether the given transistor is N-P-N or P-N-P :

(5) First find the base oftransistor as explained above
(6) Now touch the probe ofblack wire to the base and the probe ofthe red wire to anyone of the / ."
remaining two iegs and note the resistance from the multimeter
(7) In case the resistance ofthe transistor is low, it is an N-P-N transistor, otherwise P-N-P
(c) Flow ofcurrent in a junction diode: .
(8)Touch the two probes of the multi meter with the two legs of the diode and note the value of
resistance. Now interchange the two probes and note the resistance. If in one case resistance is low
and in other case resistance is high, then it shows the unidirectional flow ofcurrent through a junction
diode.
Flow of current in a L.E.D.

(9) Touch the two probes ofthe multimeter with the two legs of the L.E.n. and note the value of .
resistance. Now interchange the two probes and note the resistance. Ifin one case resistance is low
and in other case resistance is high, also the L.E.n. will glow by emitting light when its resistance is
low, then it shows the unidirectional flow ofcurrent through a L.E.n.
(d) Check whether the given diode or transistor is jll working order:
(10) Set the multimeter as resistance meter as explained in steps 1 and 2. Now touch the probes
with the two legs ofthe junction diode and note the value ofresistance. Now interchange the probes
and again note the resistance. Ifin one case resistance is low and in the second case resistance is high,
then the junction diode is in working order. Ifin both cases the resistance is low, then the junction'
diode is spoilt.
Errors in Measurements & Instruments {70]

[I] ~~~~A~~ CN~~!~~
Ideal for Scholors
FORA TRANSISTOR
(II) Confinn the base, emitter and collector ofthe given transistor. Find the resistance ofE-B juncti on
andB-Cjunction usingthemultimeter, keeping in mind either the given transistorisP-N-Por N~P-N .
. Again find the resistance ofE-B junction and B-C junction by interchanging the probes. Ifin both
directions the resistances ofboth the j unctions come to be low, then the given transistor is spoiled ifin
one direction resistance is low while in other direction the resistance is high, show that the transistor is
in working order.
PRECAUTIONS
The following precautions should be observed while using a multi meter.
(1) The electrical quantity to be measured should be confirmed each time before starting the
measurement otherwise the multimeter may get damaged ifone starts measuring voltage and the
selector switch is in the region ofcurrent or resistance etc.
(2)The instrument should not be exposed to high temperature and moisture for long time, otherwise it
will get damaged.
(3) When order ofthe magnitude ofvoltage or current is not known, measurement is always started
on the highest range and then adequate lower range is selected in gradual steps.
(4) while handling high voltages, probes should be held from their insulating covers.
(5) Due to to high sensitivity ofthe instruments, it should not be given big shocks/vibrations.
(6) Batteries out oflife should be immediately replaced by new ones. Otherwise components inside
will get corroded by leakage ofthe electroiyte.
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Errors in Measurements & Instruments /71)
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EXERCISE-I
Q.l In a meter bridge set up, which ofthe following should be the propelties ofthe one meter long wire?
(A) High resistivity and low temperature coefficient
(B) Low resistivity and low temperature coefficient
(C) Low resistivity and high temperature coefficient
(D) High resistivity and high temperature coefficient ,,--~
Q.2 IdentifY which ofthe following diagranls represent the internal construction ofthe coils wound in a
resistance box or PO box?
(A)
=4 f§
/
I (B)
-3-r,T- -1--'----,r,-
p
... .
----c::~.
-:-
.~
j
'L-....f-
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/
I (C)
~
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P Ii
(D)
Q.3 In a meter bridge experiment, we try to obtain the null point at the middle. This
(A) reduces systematic error as well as random error. /
\.
'
(B) reduces systematic error but not the random error. .' .
eC) reduces random error but not the systematic error.
(D) reduces neither systematic error nor the random error.
QA An approximate value of number of seconds in an year is 1t x 107 • Determine the % eITor in this
\. .
value.
(A) 0.5 % (B) 8% (C) 4% (D) 15 %
Q.5 While studying the dissipation of energy of a simple pendulum by plotting a graph between square
of amplitude and time which of the following apparatus is not essential?
(A) ticker timer (B) meter scale (C) paper tape CD) stop watch
. Q.6 In an experiment to find loss of energy w.r.t. time in the case of swinging simple pendulum the
correct graph between (ampp and time is
t
~_ fL(C) f~
2t / U
2
a
a
(A) (B) (D)
t--.. t --.. t--.. t --J>.
Q.7 Amplitude of vibrations of simple pendulum is A. It becomes ~ after 20 seconds. The amplitude
after 60 seconds will be
e
A
(B) -~
A A
(A) 6 8 (C) 9" (D) 27
,[j]!~~~A~~ CL~~~~!
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Errors in Measurements & Instruments [72J (.
v
Q.8 Variation of energy ofthe bob E moving in viscous medium as function oftime t is shown graphically
as -
(B)r'~
Eo
~
Eo E.
(A) E
t (C) E
t t
(D) E
) )
01 t ---+ 01 t ---+ 0 t ---+ 01 t ---+
Q.9 In an experiment to find mass of a body with the help of meter rod. Following data is recorded
where length of fixed arm (power arm) is 25 cm
mass at weight pan (g) length of weight arm is (cm)
20 30
/
32 20
" 60 10
the calculated Ipass is
\.
/
(A) 42.5 g (B) 42.3 g (C) 24.8 g (D) 24.5 g
Q.IO In Searle's apparatus we have two wires. During experiment we study the extension in one wire.
(
The use of second wire is
(A) to support the apparatus because it is heavy and may not break single wire
(B) to compensate the changes in length caused by changes in temperature of atmosphere during
experimentation
(C) to keep the apparatus in level so that extension is measured accurately
(D) all the three above
Q.ll The air bubble in sprit level in Searle's apparatus is at centre. With increase in length ofexperimental
(
wire towacds your right hand, the air bubble wiIi shift towards yOUi'
C (A) right towards experimental wire (B) towards compensating wire
( , (C) towards either of them (D) does not shift
"
Q.l2 The teacher allows all the students of a class to perform the experiment to determine the Young's
(
'- modulus of elasticity with the same experimental wire. It does not give correct result to the last
{ student because of
" (A) elastic limit (B) elastic fatigue
(
"" (C) plasticity (D) permanent set

(
\.. Q.13 To mesure the height of water level a student sees the pointer tip through the travelling microscope
he must have seen this image
C
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(A) (B) (C) (D)
[i~~~~1!~ C~,~~!~! Errors in Measurements & Instruments [731

( ldealloT Schc/ars
0.14 While !Jerforming the experiment to find out the surface tension of water, Ajay got the height of
the water 6 cm during winter. Repeating the same experiment during summer, the height would be
(A) h> 6 (B) h = 6 (C) h < 6 (D) h 12

0.15 To observe, how is the surface tension ofwater affected on dissolving a detergent in it experimentally,
student must observe that

(A) pure water rises to a higher level in the same capillary tube whereas detergent solution rises
to a lesser height
(B) the height of detergent solution is more than the rise of water in an identical capillary tube
(C) same rise of water and detergent solution in both the tubes
(D) water rises in the capillary tube but detergent solution depressed in the tube
0.16 While performing an experiment to find coefficient of viscosity the ball should be
(A) centrally dropped in the glass jar
(B) dropped along the calibrated side of glass jar
(C) dropped along the opposite side of calibrations
(D) dropped in any manner but slowly
0.17 While performing an experiment to fmd coefficient of viscosity to avoid the formation ofair bubble
around the surface of steel balls - ( ,
(A) the balls should be kept absolutely dry before dropping them
(B) the balls should be rinsed with acetylene
(C) the balls should be wetted with the used viscous liquid \ ~ .'
(D) the balls should be dropped gently

0.18 \\lhile measuring the speed ofsound by performing a resonance column experiment, a student get's
the first resonance condition at a column length of 18 cm during wimer. Repeating the same
experiment during summer, she measures the column length to be x cm for the second resonance.
Then
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(A) x > 54 (B) 54 > x > 36 (C) 36> x > 18 (D) 18>x \.,
Q.19 To find the value of resistance R using Ohm's law, we are given four voltmeters as below. Which
one will you prefer to be connected in the circuit ?
(A) 1.5 V, 10,000 Q (B) 2.0 V, 20,000 Q (C) 1.5 V, 1000 Q (D) 10 V, 20,000 Q
Q.20 In above question which ammeter will you prefer?

(A) 1 A, 10 Q (B) 2 A, 0.01 Q (C) 1 A, 0.001 Q (D) 10 A, 1 Q
Q.21 Variation of cutrent passing through a conductor as the voltage supplied across its ends as varied
is shown in the adjoining diagram. If the resistance (R) is determined at the points A, B, C and
D we will find that
v I
(A) Rc = RD (B) RB"> RA (C) Rc> RB (D) RA > Rc

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Q.22 In the measurement of resistance ofa wire using Ohm's law, the plot between V and I is drawn
<
as shown.
V(volt)
,,"(3,3)
,
(1, L21,"Q (2,2.2)
, <
>if, '
,
I" ) I(amp)
The resistance of the wire is

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(A) 0.833 Q (B) 0.9 n' (C) 1 Q < (D) None of these
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Q.23 In the experiment, to find the resistance of a given wire by using Ohm's law, teacher recommends
that +ve terminals of ammeter and voltmeter both should be connected to +ve terminal of the
battery but you have connected +ve of ammeter with -ve of voltmeter. Your circuit diagram is
(A) correct
,
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(B) terminals of ammeter be reversed

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, (C) terminals of voltmeter be reversed
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, (D) terminals of ammeter and voltmeter may be connected in any order
Q.24 In Wheatstone bridge experiment as shown in figure

B
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(A) Key Kl should be pressed first and then K2
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' A
(B) Key K2 should be pressed first and then Kl R~WX
l~K2
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, (C) any key can be pressed in any order
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\ (D) both keys should be pressed simultaneously.
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" Q.25 In a metre bridge experiment null point is obtained at 20 em from one end of the wire when
( . resistance X is b. llanced against another resistance Y If X < Y, then where will be the new position
of the null point from the same end, if one decide to balance a resistance of 4X against Y
( (A) 50 em (3) 8{) em (C) 40 em· (D) 70 em

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Q.26 For the given circuit diagram student records the voltmeter reading and measures length A1. He
plots a graph between voltmeter reading V plotted on y-axis and length of potentiometer wire
AJ = f on x-axis then the shape of the graph is
E Rh K,
+I~~•
.e .. )
Af t
'B
±cy)=---J
v,y
v' Y
i
, -,.
.....
t
---..
(A) ~ (B) ~
~S,I/
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''':::-
·0" :x :x
f (in cm)--+ f(in cm)-....
v· Y V, y r
\ .
t
---.
..... '"""
.....
t
(C) ~ (D) ~ ( ,
s::
~I ~5JI
01 e(in cm)-.... x f (in cm)-....
:x
Q.27 A potentiometer wire is mad~ of constantan or manganin because it has - \.J
(A) high specific resistance, Jow temperature coefficient ,',

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(B) low specific resistance, hlgh temperature coefficient ( ,
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(C) low specific resistance, low ttmperature coefficient

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(D).hlgh specific resistance. high temperature coefficient o
Q.28 Which of the following statements is not wrong? (~: ./
(A) To increase sensitivity of a potentiometer increase current through potentiometer wire.

(B) To increase sens:tivity increase external resistance in battery circuit connected to potentiometer,
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(C) To increase sensitivity increase battery voltage c
(D) To increase sensitivity increase the emf of battery. (\
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Q.29 We use a high resistance box in series with battery in half deflection method r'
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(A) to bring the deflection of galvanometer within the scale
(B) to minimize power loss c
(C) because high resistances are easily available c
CD) none of these
c
Q.30 To find the galvanometer resistance we should adjust the value of the shunt resistance so that
deflection of the galvanometer becomes c
, -.
(A) almost same of the previous value (B) double of the previous value l/
(C) half ofthe previous (D) exactly same of the previous value
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Q.31 In half detlection method a student performs experiment the deflection goes out of the range of
galvanometer. What should he do to bring the deflection within the range
(A) The shunt resistance should be increased
(B) The shunt resistance should be decrease
(C) Should check the connections
(D) Should change the keys used by him
Q.32 A student while measuring resistance of galvanometer uses a high resistance box (HRB) in series
with galvanometer and a low resistance box (LRB) in parallel to galvanometer. He introduces
resistance R 100012 from HRB for deflection e. When he closes key K2 in the figure shown
below and introduces resistance S = 60 12. Then resistance of galvanometer is about-
IIr--.-KI
t
K2
(A) 56 12 (B) 60 12 (C) 64 12 (D) 94012
~
Q.33 A student plots a graph between the resistance R and the reciprocal of deflection e for the given
galvanometer. The graph obtained is as shown in figure. From the graph he can calculate the
resistance of galvanometer as
1
f
e
-7
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( R
" (A) ratio of slope to intercept
c (B) ratio of intercept to slope
(C) product of slope and intercept
(
(D) galvanometer resistance can not be calculated from it.
'-. Q.34 A galvanometer is connected as shown in figure. It has resistance of 100 12. What should be the
t'
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I k12=R
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( (A) 10012 (B) 9912 (C) 91 12 (D) 9012

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Q.35 Which of the following statement is false
(A) the bench correction is always equal to the negative of bench error
(B) larger the distance between the two objects larger the magnitude of parallax
(C) parallax disappear if the positions of two objects coincide
(D) parallax can occur between any two objects
Q.36 The focal length of a convex mirror is obtained by using a convex lens. The following observations
are recorded during the experiment
object position = 5 cm
lens 35.4 cm
Image 93.8 cm
Mirror 63.3 cm
Bench error = -0.1 cm
then the focal length of mirror will be
(A) 7.5 (B) 8.4 cm (C) 15.3 cm (D) none of these
Q.37 A student gets a graph u versus v for a mirror. Point plotted above the point P on the curve are
for values of v
v
l' '.
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(A) smaller than 1 (B) smaller than 21 (C) larger than 2f (D) larger than 1
Q.38 In an optics experiment, with the position of the object fixed, a student varies the position of a "
convex lens and for each position, the screen is adjusted to get a clear image of the object. A graph
r
between the object distance u and the image distance v, from the lens, is plotted using the same \. i
scale for the two axes. A straight line passing through the origin and making an angle of 45° with c
the x-axis meets the experimental curve at P. The coordinates ofP will be r"
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(A) (2f, 2f) (B) (~,~) (C) (f, f) (D) (4f, 4f)
Q.39 ~ In an experiment for a small angled prism, angle of prism A, the angle of minimum deviations (0)
( ,
varies with the refractive index of the prism as shown in the graph '-~~
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1...'_ _
fJ.-+
(A) Point P corresponds to fJ. = 1

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(C) Slope = 2A
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(D) None of the above statements is true
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QAO A parallel beam of light is incident on a prism as shown in figure. Such that the rays get reflected
from opposite faces. The angle ofdev.iation <5 between reflected rays from facesAB andAe is
(A) A (B) 2A
(e) A (D) Non relation between A and 8

2
QAl An experiment is performed to find the refractive index of glass using a travelling microscope in
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this experiment distances are measured by
(A) a standard laboratory scale
(
(B) a meter scale provided on the microscope
(C) a screw gauge provided on the microscope
(D) a vernier scale provided on the microscope
I
QA2 A mark on a table top is seen by a student through a microscope at a distance of 30 cm from the
'-
microscope. Seeing along same vertical path he puts a slab in between microscope and table top
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at any position. He finds that he is to move the microscope by 5 cm, away from the slab to see
the focussed image ofthe same mark. Ifrefractive index of glass slab is 1.5. The thickness of glass
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(A) 15 qn (B) 5 cm (e) 30 cm (D) 20 cm
QA3 A student in an experiment gets following observations.
Reading for the bottom of an empty beaker = 12.324 cm.
( Reading for the bottom of the beaker when partially filled with the liquid 12.802 cm.
Reading for the liquid surface = 13.895 cm.
The refractive index would be

(A) 1.232 (B) 1.389 (e) 1.28{) (D) 1.437
f
'" . QA4 In an experiment, microscope is focused on a scratch on the bottom of a beaker. Turpentine oil
is poured into the beaker to a depth of 4 cm, and it is found necessary to raise the microscope
through a vertical distance of 1.28 cm to bring the scratch again into focus. The refractive index
"\. of the turpentine oil would be
( (A) 1.28 (B) 1.82 (e) 1.47 (D) 3.12
( Q.45 Mark the correct statement(s)
(A) Diode, LED and transistor are two leg devices
(B) Diode, LED and resistor are two leg devices
C (C) Transistor and Ie are 3 leg devices
(D) Ie and transistor are having same number of legs but not three
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Q.46 continuity test is made with multimetet: by keeping the selector switch ON at
(A) voltage position (B) current position
(C) resistance position (D) None of these
Q.47 A two terminal device when connected in series with a battery and a galvanometer in series with
it through a two way key as shown in figure. The galvanometer shows maximum deflection which
gradually decreases to zero, when key k] is close and k2 open. Now key k] is open and k2 is
closed. Now battery is disconnected and galvanometer is directly connected to the same device,
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the deflection in galvanometer is maximum and reversed and decreases to zero gradually. The
device is
Device Device
k2 (
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(A) p-njUilction (B) resistance (C) LED (D) capacitor
Q.48 A student is given a transister. He is asked to find out the terminals ofp-n-p traI1sistor as emitter,
c
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base and collector. He is told that the terminal marked with red dot is emitter. He touches red " /
(,
probe with known terminal as emitter and marks other two lead wires as A and B. He measures '-/
resistance between emitter and lead A. Then measured resistance between emitter and lead B and
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finds that resistance increases. This shows

C
(A) A is base and B is collector (B) A is collector and B is base
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(C) either can be collector or base (D) multimeter cannot be used to test the terminals
C
Q.49 A working transistor with its three legs marked P, Q and R is tested using a multi meter. No
C
conduction is found between P and Q. By connecting the common (negative) terminal of the
multimeter to R and the other (positive) terminal to P or Q, some resistance is seen on the multimeter, C
which of the following is true for the transistor? C
(A) it is an n-p-n transistor with R as base (B) it is a p-n-p transistor with R as collector r'
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EXERCISE-II
QUESTIONS FROM LAST YEARS AIEEE & IIT-JEE PAPERS
SECTION-A
Q.l The length ofa gi ven cylindrical wire i5 increased by 100%. Due to the consequent decrease in
diameter the change in the resistance ofthe wire will be : [AIEEE-2003]
(l) 200% (2) 100% (3) 50% (4) 300%
Q.2 While measuring the speed ofsound by performing a resonance column experiment, a student gets the
first resonance condition at a colunm length of 18 cm during winter. Repeating the same experiment
during summer, the measures the column length to be x cm for the second resonance. Then:
[AIEEE-2008]
(1)18>x (2) x > 54 (3) 54 > x > 36 (4)36>x> 18
Q.3 A student measures the focal length ofa convex lens by putting an object pin at a distance u from the
lens and measuring the distance v ofthe image pin. The graph between u and v plotted by the student
should look like : [AIEEE-2008]
r
~ )r=~=)
v(cm) v(cm) v(cm)
"
(1) /
u(cm)
(2)
u(cm)
(3) (4)
~ u(cm)
In an experiment the angles are required to be measured using an instrument. 29 divisions ofthe man
scale exactly coincide with the 30 divisions ofthe vernier scale. Ifthe smallest division ofthe main scale
is half-a-degree (= 0.5°), then the least count ofthe instrument is: [AIEEE-2009]
(1) one minute (2) halfminute (3) one degree (4) half degree
The respective number ofsignificant figures for the numbers 23.023,0.0003 and 2.1 x 10-3 are
[AIEEE-201O]
(A)5,5,2 (B)4,4,2 (C) 5, 1,2 (D)5,1,5
A screw gauge gives the following reading when used to measure the diameter ofa wire.
Main scale reading 0 mm.
Circular scale reading 52 divisions
Given that 1 mm on main scale corresponds to 100 divisions ofthe circular scale. The diameter ofwire
( from the above data is : [AIEEE-2011]
( (1) 0.52 ern (2) 0.052 em (3) 0.026 ern (4) 0.005 ern
Q.7 A spectrometer gives the following reading when used to measure the angle ofa prism.
(
Main scale reading: 58.5 degree
( Vernier scale reading: 09 divisions
Given that I division on main scale corresponds to 0.5 degree. Total divisions on the vernier scale is 30
(
and match with 29 divisions ofthe main scale. The angle ofthe prism from the above data:
C [AIEEE-2012]
(1) 58.65 degree (2) 59 degree (3) 58.59 degree (4) 58.77 degree
(
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SECTION-B
Q. , The edge ofa cube is a 1.2 x 1O~2 m. Then its volume will be recorded as : [JEE2003]
(A) 1.7 x 10-6 m 3 (B) 1.70 x 10-6 m3 (C) 1.70 x 10-7 m3 (D) 1.78 x 10-6 m3
Q.2 Ina vemiercallipers,ndivisions ofits main scale match with(n + 1) divisions on its vernier scale. Each
division ofthe main scale is a units. Using the vernier principle, calculate its least count. [JEE 2003]
Q.3 A wire has a mass 0.3 ± 0.003 g, radius 0.5 ± 0.005 mm and length 6 ± 0.06 cm. The maximum
percentage error in the measurement ofits density is [JEE 2004]
(A) 1 (B) 2 (C) 3 (D) 4

Q.4 In a Searle's experiment, the diameter ofthe wire as measured by a screw gauge ofleast count 0.00 1 cm
is 0.050 cm. The length, measured by a scale ofleast count 0.1 cm, is 110.0 cm. When a weight of50
N is suspended from the wire, the extension is measured to be 0.125 cm by a micrometer ofleast count
0.001 cm. Find the maximum error in the measurement ofYoung's modulus ofthe material ofthe wire
from these data. [JEE 2004]
Q.5 The pitch ofa screw gauge is 1mm and there are 100 divisions on the circular scale. While measuring the ('
diameter ofa wire, the linear scale reads I mm and 47 th division on the circular scale coincides with the
reference line. The length ofthe wire is 5.6 cm. Find the curved surface area (in cm2) ofthe wire in
appropriate number ofsignificant figures. [JEE 2004]
Q.6 Draw the circuit for experimental verification ofOhm's law using a source ofvariable D. C. voltage, a
main resistance of 100 Q, two galvanometers and two resistances ofvalues 106 Q and 10-3 Q respectively.
Clearly show the positions ofthe voltmeter and the ammeter. [JEE 2004]
Q.7 An unknown resistance X is to be determined using resistances
Rl' Rzor R3 • Their corresponding null points are A, B and C.

Find which ofthe above will give the most accurate reading and why?
[JEE2005] ABC
R=RI or Rz or R)
Q.8 In a resonance column method, resonance occurs at two successive level of 11=30.7 cm and
12 63.2 em using a tuning fork of 512 Hz. What is the maximum error in measuring speed ofsound
using relations v = fA & A= 2(12 II) [JEE 2005)
(A) 256 cm/sec (B) 92 cm/sec (C) 128 cmJsec (D) 102.4 cm/sec .
Q.9 The side ofa cube is measured by vernier callipers (10 divisions ofa vernier scale coincide with 9
divisions ofmain scale, where 1division ofmain scale is 1 mm). The main sca1e reads lOmmandfirst
division ofvernier scale coincides with the main scale. Mass ofthe cube is 2.736 g. Find the density 6f
the cube in appropriate significant figures. [JEE 2005]
Q.lO Graph ofposition ofimagevs position ofpoint object from a convex lens is shown. Then, focal length
. ofthe lens is I[:~m [JEE2006]
~ _':,:
(A) 0.50 ± 0.05 cm
(B) 0.50 ± 0.10 cm
- I
(C) 5.00 ± 0.05 cm ._-_..- ! ,'.,
u em ,,,,,,,,,,, , . (-9 +9)
-31 -30 -20 -10 0 '
(D) 5.00± 0.10 cm
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Q.11 The circular divisions ofshown screw gauge are SO. It moves O.S nun on main scale in one rotation. The
diameter ofthe ball is [JEE 2006]
~.. =I
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(A) 2.2S mm (B) 2.20 nun (C) 1.20mm (D) 1.2Smm
Q.l2 A student perfurms an experiment for detennination of { = ~:/ Jb>1m and he commits an error of61.
For the experiment takes the time ofn oscillations with the stop watch ofleast count.6.T and he conmrits
a human error of0.1sec. For which ofthe following data, the measurement ofg will be most accurate?
fl.l fl.T n Amplitude of oscillation [JEE 2006]
(A) Smm 0.2 sec 10 . Smm
(B) Smm 0.2 sec 20 Smm
(C) Smm 0.1 sec 20 1mm
(0) 1mm 0.1 sec SO 1mm
(. Q.13 In an experiment to detennine the focal length (f) a concave mirror by the u-v method, a student places
the object pin A on the principal axis at a distance x from the pole P. The stUdent looks at the pin and its
/
\ inverted image from a distance keeping hislher eye in line with PA. When the student shifts hislher eye
(
towards left, the image appears to the right ofthe object pin. Then, [JEE 2007]
(A) x </ (B)/< x < 2/ (C) x = 2/ (D) x > 2/
" Q.l4 A student uses a simple pendulum ofexactly 1m length to determine g, the acceleration due to gravity. He
(,
uses a stop watch with the least count of 1 sec for this and records 40 seconds for 20 oscillations. For
I
\
this observation, which ofthe following statement(s) is (are) true ?
(A) Error.6.T in measuring T, the time period, is O.OS seconds
(B) Error .6.T in measuring T, the time period, is 1 second
(C) Percentage error in the detennination ofg is S%
(D) Percentage error in the determination ofg is 2.S% [JEE~20 10]
( . Q.lS A Vernier calipers has 1 mm marks on the main scale. It has 20 equal divisions on the Vernier scale which
match with 16 main scale divisions. For this Vernier caplipers, the least count is
(
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(A) 0.02 nun (B)O.OSmm (C) 0.1 mm (D)0.2nun [JEE-20IO]
Q.l6 The density ofa solid ball is to be determined in an experiment. The diameter ofthe ball is measured with
( a screw gauge, whose pitch is O.S mrtl and there are SO divisions on the circular scale. The reading on the
(' main scale is 2.S nun and that on the circular scale is 20 divisions. Ifthe measured mass ofthe ball has a
" .' relative error of2%, the relative percentage error in the density is [JEE~20 11 ]
(A) 0.9% (B) 2.4% (C) 3.1 % (D) 4.2%
Q.l7 A meter bridge is set-up as shown, to detennine an unknown resistance 'X' using a standard 10 ohm
( resistor. The galvanometer shows null point when tapping-key is at S2 cm mark. The end-corrections
I'
are 1 cm and 2 cm respectively for the ends A and B. The <ietennined value of'X' is [JEE-2011 ]
\
( X IOQ
- C (A) iO.20hm (B) 10.6.ohm (C) 10.8 ohm (D) 11.1 ohm
C
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C[l!~~:A~~ CLIt~!~~ Errors in Measurements & Instruments [83J

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Q.l8 In the detenninationofYoung's modulus (Y = 4~d~g JbyusingSearle'smethod,awireoflength
L 2m and diameter d = 0.5 mm is used. For a load M = 2.5 kg, an extension 1== 0.25 mm in the length
of the wire is observed. Quantities d and I are measured using a screw gauge and a micrometer,
respectively. They have' the same pitch of0.5 rnrn. The number ofdivisions on their circular scale is 100.
The contributions to the maximum probable error ofthe Y measurement [JEE-20 12]
(A) due to the errors in the measurements ofd and I are the same
(B) due to the error in the measurement ofd is twice tl:at due to the error in the measurement of I.
(C) due to the error in the measurement of I is twice that due to the error in the measurement ofd.
(D) due to the error in the measurement ofd is four times that due to the error in the measurement of I.
Q.19 The diameter ofa cylinder is measured using a Vernier Callipers with no zero error. It is found that the
zero ofthe Vernier scale lies between 5.10 cm and 5.15 cm ofthe main scale. The Vernier scale has 50
divisions equivalent to 2.45 cm. The 24th division ofthe Vernier scale exactly coincides with one ofthe
main scale divisions. The diameter ofthe cylinder is [JEE-20 13]
/-""'-..
(A)5.112cm (B) 5.124cm (C)5.136cm (D) 5.148cm

Q.20 Using the expression 2d sin e = A., one calculates the values ofd by measuring the corresponding angles (
\
e in the r811ge 0 to 900. The wavelength A. is exactly known and the error in e is constant for all values of
"
e,As e increases from 00 , [JEE-2013] /
(A) the absolute error in d remains constant

(B) the absolute error in d increases
, /
(C) the fractional error in d remains constant

(D) the fractional error in d decreases.
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CONTENTS
KEY CONCEPT ••.•..••..•........•........•.•.•...............••........•.••...• Page 2 - 26
EXERCISE-I •••••.•••••.••••••••..•...••.•.•..••..•••••.•.•.•••.••....••••......•. Page 27- 35
EXERCISE-II•.•.•.••.•...•....•........•....•.•...•....•..••.....••.•.••...•...•. Page 36 - 39
I~
'- EXERCISE-III .................................................................... Page 40 - 44

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AN'SWER 'KEy.................................................................... Page 45

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JEE MAIN - 2014
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CO-ORDINATION COMPOUND
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CO-ORDINATION
, COMPOUNDS
INTRODUcnON
(a) The concept ofcoordination compounds arises from the compl€tx formation tendency oftransition
elements. ; "
(b) These compounds playa vital role in our life. Haemoglobin of animal blood and chlorophyll of
plants are also coordination compounds ofFe and Mg respectively.
, . .
MOLECULAR OR ADDITION COMPOUNDS
(a) When'solutions containing two or more sirr!ple stable compounds in molecular proportions are
allowed to evaporate, cry~tals of new sub~tances are obtai~ed. These substances are tenned
molecular or additi<;m compounds. :
(b) Some common examples ~e as follows.

CUS04 + 4NH3 ~ CU S04· 4NH3
AgCN + KCN ~ KCN. AgCN
simple stable Addition or
compounds molecular
cQmpounds /--,
., .-"
4 KCN + Fe(CN)2 ~ Fe(CN)2.4KCN

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~S04 + Al2 (S04)3 + 241\0 ~ ~S04' AI2(~04)3' 24 ~O \.
Alum
(c) The molecular or addition compounds are of two type Double salts lattice compound and
coordination or complex compound
Double salts or lattice compounds
(a) The addition compounds which are stable in solid state only but are broken down into individual
constituents when dissolved in water are called double salts or lattice compounds.
(b) Their solution have the samepi:operties as the mixture ofindividual compounds
(c) For example when carnallite (KCl. MgCI 2• 6H20) is dissolved in water it exhibits the properties of
KCI and MgCl2
Coordination or complex compounds
(a) The addition compounds in which some ofthe constituent ions or molecules lose their identity and
when dissolved in water they do not break up completely into individual ions are called coordination (''.
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compounds
(b) The properties of their solutions are different than those of their constituents.
(c) In such compounds there is complex ion whjch is a central metal ion with lewis bases attached to ,.
'- /
it through coordinate covalent bonds.

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(d) On the basis ofstability ofcomplex ion, complex ions are further divided.as follows. \
(i) Perfect complexes; Those in which complex ion is fairly stable and is either not dissociated or
feebly dissociated in solution state, e.g.
K 4[Fe(CN)6] ~ 4K+ + [Fe(CN)6]4
( ,
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F e2++6Qr
\...../
1-'
(feebly dissociated) "-.j
The ferrocyanide ion [Fe(CN)6]4- is so insignificantly dissociated that it can be considered as ,,'-- '\
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practically undissociated and does not give the test of Fe2+or C~ ions
(ii) Imperfect complexes: Those in which complex ion is less stable and is reversibly dissociated to
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give enough simple ions and thus imparts their tests, e.g.
~{Cd(CN)4] ~ 2K+ + [Cd(CN)4]2

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Cd2++4CN
(appreciably dissociated)
Note: An imperfect-complex may be too unstable to exist and may be completely dissociated in
solution, it then becomes a double salts
VARIOUS TERMS USED IN CO-ORDINATION COMPOUNDS

(a) Complex ion:
An aggregate ofmetal ion with anions, cation or neutral molecules is called as complex ion.
(b) Central metal ion: ,
(i) The metal ion which fonns complex ion in.combination with anions or neutral molecules is
called as central metal ion.
(ii) . Central metal ion acts as an electron pair acceptor and forms coordinate bond with ligands.
(c) Coordination Number:
(i) The number of atoms ofthe ligands that are directly bond to the central· metal atom or ion
by coordinate bonds is known as the coordination number ofthe metal atom or ion.
(n) It is actually the number ofcoordinate covalent which the ligands fonn with the central metal
atom orion
(iii) Some common coordination numbers exhibited by metal ions are 2,4,6. The light transition
metals exhibit 4 and 6 coordination numbers while heavy transition metals may exhibit
coordination number more than 6
(iv) For example, the coordination number ofNi in the complex [Ni(NHJ4]CI2 is 4 and that ofPt
in the complex ~[PtCI6] is 6 .
(d) Coordination sphere-(entity) :
(i) The central metal atom and the ligands directly attached to it are collectively tenned as the
corrdination sphere.
(ii) Coordinatiori sphere is written inside square bracket, for example [Co(NHJ6P+
(iii) The part outside the bracket is called ionisation sphere.
(iv) The species present in the coordination sphere are nonionizable.
(v) The species present in the ionization sphere are ionisable.
Central metal ion Coordination sphere
.\~~........_...7-· <-...~
c ([CuCNH )4]S04")
....•..7..,-·..•. Ionization sphere
. . ......
3
, /
. . --..'-
~ ..
( Ligand Coordination number
/ (e) Oxidation state :
'" (i) It is number which represents the electric charge ion the central metal atom of a complex
ion.
(ii) Ex. the oxidation number ofFe, Co and Ni in [Fe(CN)6]4-, [Co(NH3)6]3+ and Ni(CO)4 is +2,
+3 and zero respectively.
(1) Charge on the complex ion:
It is the algebraic sum ofthe total charge ofthe ligands and central metal ion.
( .(g) Ligands:
(i) The anions or neutral molecules which combine with central metal ion to fonn complex ion
C are called as ligands.
(
(ii) They act as electron pair donor Lewis bases, but strong crystal field ligands like CO, CN
\.. etccan ae<;ept electron pair from the metal ion, because these ligands are 1t-acids.
(. lIl'~~~A~C~~!~!/deQI for Sdloktrs

Co-ordination Compounds [3J
Types ofLigands on the basis of number ofdonor atoms pre~ent in them:
(A) ~ono-or un identate ligands: They have one donor atom, i.e. they supply only one electron pair
-to .central metal atom or ion.
Examples: F-, CI-, Br-, ~O, NH3, ~, N02-, OIr,CO, Py, H
(B) Bidentate ligands: Ligands which have two donor atoms and have the ability to link with central metal
ion at two positions are called bidentate ligands. Some examples are :
CH2--N~
I
CH2--N /
H " / H
-0/ 'b-
"c-/
©r
o
0
c- o
~
H / ""-H o/ '\.0 (sac)
salicylato
Ethylenediamine (en) Oxalate (ox)
"
o 0
11 I
C C
CH/
3 'CH~ 'CH3 .' - "
(acac)
1,10-Phenanthroline (o-phen) acetylacetonato
H
I
(
'-./
CH 2 --N-H
I ~
/\
-a-c-o-
C 0-/ II / '
II o
o ,
~~j
'
Glycinato (Gly) 2,2' -Dipyridyl oJipy) Carbonato
(C) Tridentate ligands: The ligands having three donor atoms are called tridentate ligands. Examples
are:
r "
H" /H
H-N N-H ( ,
/"./\ 't~.1
H21 l IH2
i'
t
'.J
. H2C - - N-H2C I
\../
.. I·
H {'
'--../'
Diethylene triamine (Dien) 2,2' ,2"-Terpyridine

f '\
(terpy) "-..-I
~ ,
~./
[IJ Co-ordination Compounds {4} C

./
v
~'~."
V
~ (Di Tetradentate ligands: These ligands possess four donor atoms. Examples are:
H H
I I
/CH2COO /N-(CH2 r N,
N~CH,COO~ ~~*'{l-
~
~N
"";/
/\ /
01!
~
CH2COO-/ . ./ N",
H/ ~ ~ H·
(Nitrilotriacetato) Triethylene tetramine

(NTA) (Trien)
'(E) Pentadentate ligands: They have five donor atoms. For example, ethylenediamine triacetate ion.
O--c=o
o=c-o-
I /~
~/
a
.
CHrN--(CH2)2 - N - CH2
I
II
O--C-CH2
I ..
H·
Ethylenediamine triacetato ion (EDTA)-3
/' (F) Hexadentateligands:Theyhavesixdonoratoms.Themostimportantexampleisethylenediaminetetraacetate

< .
iOIl
~-<:Hr-CH7~ "
/
"
CH2 ~ / CH2 "'
/ I _/; ,_ I CH2
H2C O=c-6~~=O /
~C-O- ~O--C
II II
o 0
(
Ethylenediamine tetraacetato ion {EDTA)4
(
'. (G) Chelating ligands.

(
(a) Polydentate ligands whose structures permit the attachment oftwo or more donor sites to
( the same metal ion simultaneously, thus closing one or more rings are called chelating
,(
ligands and the compounds formed are known as chelate compounds.
\.
(b) A chelate may be defined as a ring structure formed by the combination of a polydentate
.- ligand having two or more donor atoms with a metal ion forming part ofthe ring .
it...
(c) The process offormation ofchelates is called chelation.
t (d) Chelate complexes are more stable than ordinary complexes in which the ligand is a
C monodentate
CtIJ~¥,I~~~CL~~~!! Ideal f()( Sdtohlrs

c
(e) This increased stability ofthe compound due to chelation is called the chelate effect
(f) In the complex ion given below, 5 membered rings are fonned. So all these are called chelate
2+
complexes
. [CH2-H 2 N............
I' CU
/' NH2-CH~
CHr-H2N............. 'NH2-CH2
(g) Generally the chelate complexes with 5 or 6 membered, rings are more stable.
(h) Out of these, 5 merpbered rings are very stable when they involve saturated ligands. / ~.
(i) On the other hand 6,membered ring structures acqujre ~imum stability when they involve
unsaturated ligands containing conjugate double bond. This is due to the resonance effects
involving metal d-orbitals and ligand p-orbital eleptrons.
Classification of ligands on the basis of donor an~ acceptor properties of the ligands f'-
(A) Ligands having one (or more) lone pair (or pairs) of electrons
(a) . Ligands which contain vacant x-typ~ orbitals that can receive back donated x electron
from metal ion in low oxidation stat~.
e.g.: CO, NO, CN, NC, R-N=C, RsP, RsAs
a,a-:-dipyridyl, o-phenanthroline
(b) All these ligands also have filled donor orbital in addition to vacant x-type acceptor orbitals.
(c) Thus in there complexes both metal and ligand function as donors and acceptors
(M ( L) (J )
It
(d) Ligands which do not. have vacant orbitals to receive back donated electron from metals
Ex.~O,~,F.
(-..
(B) Ligands having no lone pairs of electrons but have x bonding electron \.J
Ex. Ethylene, benzene, cyclopentadienyl-ion ;' "'.
Note: (1) Polydentate ligands have Flexidentate character it is not necessary that all the donor atoms
present in the polydentate ligands should form coordinate bonds with central metal atom or f' '.
ion. '--/
"
(2) There are certain ligands which have two or more donor atoms but during formation of
complexes only one donor atom is attached to metal ion. Such ligands are called
ambidentate ligands such as CN, CNS
Werner's coordination theory

Alfred Werner (considered as the father of coordination chemistry) studied the structure of
coordination complexes such as CoCI3. 6NH3 and CuS04• 4NH3 in 1893 .
. According to him :
( "
(a) Each metal in coordination compound possesses two types ofvalencies : '-'
(i) primary valency or principal valencies or ionisable valencies.

(ii) Secondary valency or nonionisable valencies
(b) Primary valencies are satisfied by anions only. The number ofprimary valencies depends
upon the oxidation state of the central metal. It may change from one compound to other.
These are represented by dotted lines between central metal atom and anion.
Iil !~~~~~CL~~!~! Co-ordination Compounds [6) c

Ideal (",Scholo"
'-"
(c) Secondary valencies are satisfied only by electron pair donor, the ions or the neutral species.
These are represented by thick lines.
(d) Each metal has a fixed number ofsecondary valencies also referred as coordination number.
The coordination number depends mainly on the size and the charge on the central atom. The
maximum number ofions or molecules that,the central atomcan hold by secondary valencies is
known as coordination number.
(e) The ions attached to primary valencies possess ionising nature whereas the ions attached to
secondary valencies do not ionise when the complex is dissolved in a solvent
(f) EveI)' central ion tends to satisfy its primary as well as secondary valencies.
(g) The secondary valencies are directional and are directed in space about the central metal ion.
The primary valencies are nonMdirectional. The presence ofsecondary valencies gives rise to
stereoisomerism in complexes.
(h) , Initially, Werner had pointed out coordination number ofa metal atom to be four orsix.
(i) The six valencies were regarded to be directed to the comers of a regular octahedron
circumscribedaboutthemetal ion. Formetalshavingfour coordination number, the foUr valencies
are either arranged in a planar or tetrahedral nature.
0) Thus on the basis ofwerner theory, the CoCI3. 6 NH3 is called hexamminecobalt (Ill) chloride
because there are six ammonia ligands and the cobalt is in the +3 oxidation state, i.e. cobalt has
three primary valencies and six secondary valencies. The complex can therefore be represented
['
, as shown.
CI
H3N~ i/NH,
\.
H3N
;/
CI ••••
H3N
.......
.. Co
'"
.
:
;
CI
'"
I[
NH3
NH3
[CO{NH 3)6]CI 3
Note: Now, it has been proposed that coordination number ofa metal may be any whole number between
( 2 and 9
( 'Effective atomic number' (E.A.N.) rule or sidwick rule.
According to sidwick, metal atom present in coordination compound continues to accept electron
(
pairs donated by the ligands till the total number ofelctrons on metal atom and those donated by
ligands reaches to next noble gas configuration. This is known as Effective atomic number'
(E.A.N.) rule or sidwick rille.
r
"- It is calculated by the following formula
I E.A.N. =Atomic number - Oxidation number + Coordination number x 2 I
(
\.
(
\.-,
Ex. Effective atomic number ofcobalt in [CO(NH3)6]3+ can be calculated as follows:

(
"-- Atomic number of cobalt = 27
{
"-~
Oxidation state ofcobalt in complex = +3
Number of electrons in CO+3 ion are (27-3 = 24)
c During coordinate covalent bonding, CO+3 ion gains 6 pairs ofelectrons.
(
',- Thus Effective atomic number ofcobalt in (Co(NH3)6J+3is 24 +12 = 36
c~~~~~~C~~~~!
c /deoIforSe/lor.m
Co-ordination Compounds [7)
'-)
f
V
Complex Metal Atomic Coordination Effective atomic number
(Oxidation State) Number of Metal number (E.A.N.)
K4[Fe(CN)6] +2 26 6 (26-2) + (6 x2) = 36 [Kr]

[Cu (NHJ4]S04 +2 29 4 (29-2) + (4x2) = 35
[Co (CH3)6]C13 +3 27 6 (27-3) + (6 x 2) =36 [Kr]
Ni(CO)~ 0 28 4 (28-0) + (4x2) = 36 [Kr]
~[Ni(CN)4] +2 28 4 (28-2) + (4x2) = 34
~[PtCI6] +4 78 6 (78~2) + (6 x 2) =86 [Rn]
~[(;r(C104)3] +3 24 6 (24-3) + (6 x 2) =33
"
~[Fe(C104)3] +3 26 6 (26-3) + (6 x2) = 35
~[HgI4] +2 80 4 (80-2) + (4x2) =86 [Rn]
[Ag~)l]CI +1 47 2 (47-1) + (2x2) = 50
\. /'
~[PdCI4] +2 46 4 (46-2) + (4x2) = 52
I.U.P.A.C. NAMING OF COORDINATION "',

"
COMPOUNDS '
Due to wide variety of coordination compounds it is ess~ntial to use a unified system of

/ '~'.
\. ,
nomenclature. Though a lot of compounds a;re known by their trivial names only, but I.U.P.A.C.
has introduced rules for the naming ofcoordination compounds as follows
The order of listing the ions
(a) In common salts cation is named first and then the anion.
(b) In the complex ion (Cation or anion) ligands are named first followed by the
name ofcentral atom '
(c) The oxidation state of the central metal is indicated by Roman numeral in
brackets immediately after its name; (0) in dicates zero oxidation state.
(d) In case the complex is non ionic, it is named as one word e.g. [Ni(CO)4] is called tetracarbonyl
nickel (0)
(e) The suffix - ate is added to the name ofcentral metal fonning anionic complex"ion. In cationic
complex ion, the name ofmetal (usual name) is fallowed by the oxidation number in bracket.
However in some metals Latin names are preferred in place ofEnglish names e.g. iron as fenate, c
lead as plumbate and silver as argentate.
Name of the ligand:
(a) If there are two or more different kinds of ligands, they are ,named in alphabatical order
without separation by hyphen.
(b) When there are several ligands ofsame kind, they are listed alphabetically
(c) Anionic ligands ending with' ide' are named by replacing 'ide' by suffix '0'.
Symbol Name as ligand Symbol Name as ligand

CI- Chloro/Chlorido N3- Nitrido
Br BromolBromido 0 22- Peroxo
CN- Cyano S2- Sulphido
0 2- Oxo NW~ imido
OH- Hydroxo NHa- amido
H- , Hydrido
C'.'
[i]!~~~~~cy~~~! Co-ordination Compounds [B)

Ideol fer SCholo"
c
G
Ligands whose names end in'ite' or 'ate' become 'ito' Le.;byreplacingtheending 'e' with 'o'as
follows.
C023
Carbonato SO32 Sulphito
C02
2 4
Oxolato· CH 3
COO- Acetato
SO42 Sulphato. NO2 (bonded through oxygen) nitrito
N0 3 Nitrato .(bondedthrough nitrogen) nitro
S20- 3
2 Thiosulphato
,f) Names ofpositive ligands ends in 'ium' e.g.

r NO+ Nitrosylium
~NH3+Hydrazinium
7
\
(g) Ifthe number ofa particular ligand is more than one in the complex ion, the number is indicated by
using Greek numbers such as di,tri, tetra, penta, hexa, etc. However, when the name ofthe ligand
includes a number, e.g. dipyridyl, ethylene diamine, then bis, tris, tetrakis are used in place of di,
tri, tetra, etc
( ,h) In case ofchelating ligands or ligands having di, tri, tetra, etc, in their name the prefixes bis, tris,
(. tetrakis are used before ligands placed in paranthesis
\.
(i) In poly nuclearcomplexes, the bridging group is indicated in the formula ofthe complex by separating it
( from the rest ofcomplex by hyphens and adding beforeits name or in poly nuclearcomplex (a complex
. with two ormore metal atoms) bridging ligands (which links two metal atoms) is denoted by the prefix J.!
before its name.
(
" S.No. Complex Compounds IUPACName

(
\.
,r
(i) K 4[Fe(CN)(J Potassium hexacyanoferrate (II)
" (ii) ~[PtCIJ Potassium hexachloroplatinate (IV)
(m) [Co(NH3)6]CI3 Hexammine cobalt (III) chloride
( (iv) [C~0)4CI2]CI Tetra aqua di chloro chromium (ill) chloride
(v) [Pt(NH3)2CI4] Diammine tetrachloroplatinum (IV)
(vi) [Co(N~)3CI3] Triammine trichloro cobalt (III)
(
(vii) ~[Co(N0')6] Potassium hexanitro cobaltate (ill)
~
(viiI) Na3[Fe(CN) sNO] Sodium pentacyano nitrosyl ferrate(II)
C (IX) [NiCI4]-2 Tetrachloro nickelate (II) ion
(
\. (x) [Ru~)5CIY2 Pentammine chlororuthenium (III) ion
r
I..
(xi) [Fe(en)j]CI3 Tris (ethylenediamine) iron (III) chloride
(xii) [Ni(GlY)2] Bis (glycinato) nickel (II)
C
{,)OMERISM IN COMPLEXES
(a) Compounds which have the same molecular formula, but differ in their properties due to the
C difference in structure are called as Isomers.
[IJ) Isomerism is commonly considered, to be the characteristic ofonly organic compounds, it is also
found although less frequency among inorganic substances.
l
Q]~~~l~~CL~~~~! I<k4I fer Sdtok;,.
Co-ordination Compounds {9}
(
,--.
(c) Classification ofisomerism :
Type of isomerism
i
+
Structural isomerism
l
Stereo isomerism
i
+ + f
Ionization Hydrate
+ +
Coordination Coordination Linkage
+
Geometrical
+
Optical
position
STRUCTURAL ISOMERISUM
It arises due to the difference in the type of ch~micallinkages and distribution ofligands within and
outside the coordination sphere.
Ionisation isomers: .... ,' '.,' "
The type ofisomerism is due to the exchange ofgroups ofor ion between.the CQpr4inating spher:e (
and the ionisation sphere
Ex.
(a), Co(NH3)4Br2804 can represent
(i) [Co(NH3)4Br2] 804 (red violet)
(ii) [Co(NH)4] 804] Brired). \. .
These complexes give sulphate ion and bromide ion respectively
(b) [Pt(NH3)4CI2] Br2 and [P~)4Br2]CI2
(c) [Co(NH3)4(N03)2] 804 and [Co(N~)4804]{N03)2
Hydrate isomers :
""
This type of isomerism is due to presence of different number of water molecules inside a
coordination sphere.
Ex. C~0)6CI3 hasthree possible structure
(i) [Cr(~0)6]CI3 violet
(li) [Cr(~O)sCI] Clr H 20 green
(iii) [Cr~0)4CI2] Cl. 2~0 dark green.
These complexes differ from one another with respect to the number ofwater molecules acting as
c
ligands. " '
Other hydrate isomers are ...,.
(i) [Co(N~)4~0 CI] Cl2 (ii) [Co(NH3)4 C12] Cl. H20
Linkage or salt isomers:

(a) This type ofisomerism arises due to presence ofambidentate ligands like N02- CN- and 8CN
(b) These ligands have two donor atoms but at a time only one atom is directly linked to the central
metal atom ofthe complex. Ci
(c) Such type of isomers are distinguished by infra red (I.R.) spectroscopy.
Ex. (i) [Co(NH3)sN02] Cl2 and [Co(NH)sONO] Cl2 o
(ii) In N02 ligand, The coordinating sites are nitrogen (Le., N02-Nitrogen ligand) or
through oxygen (Le. ONO Nitrogen ligand)
(iii) The nitro isomer is yellow and is stable to acids whereas nitrito ismoer is red c
and is decomposed by acids.
[IJ~~~~A~~CL~~~~~ Co-ordination Compounds [10J c

IdeoIforSchol."
c
Coordination isomers :
(a) This type of isomerism is exhibited when the complex has two complex ions in
it, cationic and anionic.
(b) This type ofisomerism is caused by the interchange ofligands and metal ions betweenthe two
complexionsofthesame.complex.
Ex. (J.) [Co(NHJ6] [Cr(CN)61
[Cr{NH3)J [CO(CN)6]
(ii) {Co(NH3)6] [Cr(C20 4)3]

[Cr(NH3)6] [CO(C20 4)3]
\ STEREO ISOMERISM
~' (a) They have same molecule formula, same constitution, they differ only with respect to the
spatial orientation ofligands in space around the metal ion.
(b) The two stereo isomers which are possible are - Geometrical and opticaL
( Geometrical or cis - Trans isomers :
(a) The ligands occupy different positions around the central metal ion.
(b) When two identical ligands are coordinated to the metal ion from the same side then it is cis
f isomer.
"
('
(Latin, cis means same).
\, (c) If the two identical ligands are coordinated to the me~l ion from opposite side then it is
('
Trans isomer (in Latin, Trans means across)
\
(d) These geometrical isomers differ in physical as well as inchemical properites.
(e) Geometrical isomerism is most important incompoundswithcoordinationnumbers 4 and 6.
(f) 4-coordinated complexes with tetrahedral geometry do not exhibit cis-Trans isomerism.
(g) It is exhibited by 4-coordinated complexes with square planar geometry.
( Geometrical isomers with coordination number = 4 (Square planar co~plexes)

( (i) Complexes with general formula, Ma2b2 (where both a and bare monodentate) can have
, Cis:-and trans isomers.
(
"
( a~.•;;!a a~"7c
: M : : M-':
(
bk:...~C
Cis-isomer
:
~~
. '.:
b: •....••••••••• : a
Trans-isomer
f (ii) Complexes with general formula Ma2bc can have Cis-and trans-isomers.
~
a~ .•;;!a a~
..........;....
; !:b

" : M :
'.. M
.:
bk:...-~b
=
! /";
( b ~a
k..........
Cis Trans
{
(iii) [Pt (NH3)2 C12]
(
HaN
~'''?:
NHa
.
CI
.~ , ..NHa
'"''''''''?:'''''''
.! Pt - i :. Pt !
i,/ .
CI~··..~CI HaN
L:.····..·..~CI
(
\. Cis(Cis-platin) anti cancer Trans
(rjJ ~~~A~~C~~~~~ IdeolforSchoklrs

Co-ordination Compounds [11)
(
,,-.
c
l
(iv) [pt(NH,)lClBr]
CI~•..~NHaj B. ~""7NH3
: ,Pt : : Pt ;
Br~""~NHa HaN
~""~CI
Cis ' Trans
(v) Complexes with g~era1 fonnula, Mabcd can have three i~mers.
a~- •••••••. ;....;! b a~"71d a~······71c
·:
. t
.i
I
M/!:
-----(
·~
:.
M
~I
d' •.••.•.••••••• c
. !
c:.~~
:
M !
I
.......................: b
:C
i /' " !
biL•••••.•.~d
(i) (ii) (iii)

(vi) Diglycinato platiuDl (ii) complexes
(
CH2-NH~ /,NH2-CH2 CH2-NH~ / ' 6 -co

I ., Pt· I ,I Pt 1 ---,
co-a/'" '6-co co-a/'" 'NH;-CH2
/
(Cis) (Trans) f
Geometrical isomers with coordination number =6 "
(i) [Fe(NH3)4C~]
CI
NHa
H3N~+~NH3
H3i"",f-~c'
! Fa......! ! Fa......! c
~.L..:-:J
HajL+·-··~ CI
HaN 1 NHa ·r'
CI NHa
Trans Cis f'
'- ~
(ii) Facial and Meridional isomerism (Ma3bJ
b r••• b
a {\.....................,. b
". . ,.a 1\. :::;::w b
r~'
\::7
a ....... ~.......-= }'
-.
~I a
(
•••••••••••••••••••
\../
a
Facial (fac) Meridional (Mer)
Optically isomers : r •
~
(a) Optically active complexes are those which are nonsuperimposable over the mirror
image structure. c
(b) Anoptica1lyactivecomplexis one which isasymmetric in nature i.e.,notdivisible into two identical (
o

halves.
(c) The complex which rotates plane polarised light to left hand side is laevo rotatory i.e., 'i' or
'-' and ifthe complex rotates the plane polarised lightto right hand sidethenitisdextrorotatory ,V -.
'd' or'+'.
(d) Thus complexes which have same physical and chemical properties but differ in their ,
f "
o
action towards plane polarised light are called as optical isomers.
!il~~~~A~C~~'~! Co-ordination Compounds {12] c
Ideo! (or 5"'",k",
c
,V"
(e) The'd' and 'R' isomersofa compound are called as Enantiomers or Enantiomorphs.
Only those 6-coordinated complexes in which there are chelating agents i.e.
(f)
bidentate ligands,exhibit optical isomerism. This isdue to the absenceof elements ofsymmetIy
in the complex.
(g) optical isomerism is not found in square planar complexes on account ofthe presence ofaxis of
synnnetly.
, Jptical isomer with Coordination number = 6
(i) [Ma2b2c2]n+ -+ [Pt(PY)2(NHJ2 CI2]2+
2+ 2+
py py
( ,
j",i·/ipy
P7~-.---I-~/i------:1
. * , .
CI
.
,I I
/ Pt / / Pt l
~
/ /' ' l •
CI.::C•••• -+.~H3 H3N l_··········I_\1a

/ NHs NH3
"
r Cis-d-isomer Mirror Cis-i-isomer

\
(ii) [Mabcedf] -+ [Pt(py)NH3N02ClBrI]

-.
Br py
i",i./i NO, 7~·I·/iNO'
"
(
/ Pt l l Pt· /
/ /'
.L::::::'_·I··YCI
'
-+\.~H3
(
\.
CI.::C-•• H3N
(
\,
I
I
d-isomer
Mirror i-isomer
(iii) [M (AA)3]n+ -+ [Co(en)3]3+
3+ 3+
( en
(
"-. en!,(',
I -~~~~-f-7-'-'-'---# . ,
ej\J.. / 1
c
,
,
•
I
i
, C:t.'
V
l
"
Co
#
'en
l
/
/'
.l
1E3" '
.----------
I· -
Co
...........
I
,
l
en ,
r
\,
d-form Mirror i-form
r (iv) [M(AA)2ab]n+ -+ [Co(en)2NH3C1j2+
"
( 2+ 2+
en
CI~~
(
enl<t--- -----;;;7:-------I CI
C r-/j # /.
•
:'
1
C ~
HaN f._ ..___~
/ Co"/
~'
, .•
/
~,NH3
Co
. #
J
l
e~--------- -----
(
\.
Cis-d-isomer Mirror Cis-i-form
"BANSAL
J;>RIVXfE
CLASSES
LIMITED
/deQ/torSdtOknf
L
(v) LM (A B )3] ~ [Cr(gIY)3]
r
gly
gly
',.
f.:1 .._.....
/".r--/j._
Cr l
gly//,--B # '\ / I/~
~
ll l
I) / Cr
l ......_.. .. ~ gly .V
' l ••••~.-... ~.
._•• ~t)'
.
l
l
gly . .
Cis or trans~is~mer Mirror Cis or tran~i-isomer
(vi) [M (AA)b2~2] ~ [Fe~)2(en)C~J

:
CI CI
!'~:::~-t-71c,
CI r'=········I··~-·--····
i i I" '" '-,\
NH,~l-----
enl Fe en
"/~
i____+_~------ i NH,
NH3 Mirror NH3
Cis-d-isomer Ci~i·isomer
(vii) [M(AA)2b21 ~ [Fe(en)2C~]
en~
.i, ••
.,
~*•••••••• •••• 71
. . . _..
- : CI
.,
!
~------- ---~
I
l k
. 9 ' Fe •
CI CI
en
Mirror
Cis -d-isomer Cis -i·isomer
(I) Trans- [Fe(en)2 C~] do not show optical activity due to superimposition oftheir mirror image.
(u) Some more examplesare opticallyactive:
[Cr(ox)3Y-;[Fe(dipY)3]2+; [Cr(ox)2~O)2; [pt(en)3]4+ etc.
BONDING IN COORDINATION COMPOUNDS

Valence Bond Theory
The salient features ofthe theory are summarised below.
(a) The central metal ion has a number ofempty orbitals for accommodating electrons donated
by the ligands. The number ofempty orbitals is equal to the coordination number of the
metal ion for the particular complex.
(b) The atomic orbitals (s, p or d) of the metal ion hybridize to form hybri4 orbitals with
definite directional properties. These hybrid orbitalsnowoverlap with the ligand orbitals to form
,
strong chemical bonds. ~
~!~~A~C~~'~' Co'-ordination Compounds [14] c

IdMI(orS<:hol<m
c
(c) . The d-orbitals involved in the hybridization may be either inner (n -1) d orbitals or outer
nd-orbitals. The complexes formed in these two ways are referred to as low spin and high spin
complexes, respectively.
(d) Each ligand contains a lone pair ofelectrons. .
(e) A covalent bond is formed by the overlap ofa vacant hybridized metal orbital and a filled
orbital of the ligand. The bond is also sometimes called as a coordinate bond.
(f) Ifthe complex contains unpaired electrons, it is paramagnetic in nature, while ifit does not
contain unpaired electrons, it is diamagnetic in nature..
(g) The number ofunpaired electrons in the complex, points out the geometry ofthe complex
as well as hybridisation of central metal ion and vice -versa. In practice, the number of
unpaired electrons in a complex is found from magnetic moment measurements as illustrated
below.
J.l = .In (n + 2) , where n = no of unpaired electron
Thus the knowledge of the magnetic moment can be p{ great help in ascertaining the type
ofcomplex .
(h) Under the influence of a strong .ligand, the electrons 'can be forced to pair up against the
r·
Hund's rule ofmaximum multiplicity.
"
DC.lW back of valence bond Theory
( (i) It describes bonding in coordination compounds only qualitatively
\-. (ii) It does not offer any explaination for the optical absorption spectia of complex
( (iii) It does not describe the detailed magnetic properties of coordination compounds.
Crystal field Theory

( This is the more advanced theory and satisfactorily explains the optical absorption spectra and
r magnetic properties ofcomplexes which were not explained by V.B.T. But its details are beyond
" the scope of this text.
r
"
The shape of complexes depends upon hybridization state of central atom, it is described as
(. follows:
- :>ctahedral complexes:
C
On the basis ofhybridized orbitals it can be oftwo type as d2sp3 ( inner orbital) or sp3d2 (outer orbital)
.
( .• hybridized .
~er orbital complexes:
. We have already discussed that in these type ofcomplexes the d-orbitals used are oflower quantum
( number i.e~ (n - 1) various examples are as follow
( (a) Complexes formed by the use of inner orbitals are diamagnetic or have reduced paramagnetism.
\.
(b) These are called as low spin or spin paired complexes

(
If-(CN)
\.. ' 6
J4
{
(a) electronic configuration ofFe26 = [Ar] 3d64s2
I...
_ C.. (b) electronic configuration ofFe+2 = [Ar] 3d6 = 11~11 11 1111 I 01L..- ...L--.I...---I
. (c) 2
electronic configuration ofFe+ after rearrangement
c =1r1-.....-~11~~
"""--'1 0
1-1l-~1 L..-I...L--.I...---I
d2
c sp3
1r~'!~S~~~~~~~!
( Ide:alforSdool4rs
Co-ordination Compoun{ls. 115J
c
(d) 'The above rearrangement is due to p~nce ofcyanide ligand
(e) In this state Fe2+ undergoes d2sp3 hybridisation to from six d2sp3 hybrid orbitals, each ofwhich
accepts electron pair donated by CN- ions.
(t) The resultant complex is inner octahedral as shown in figure and it should be diamagnetic as it
hasnounpairedelectron.Fonnationof[Co~)6]3+takesplaceinthesamemanner
NH3
,H 3N
K ··+""7! NH3,
i . Co+3 !
H3Nt/...+••~ NH3
NH3
Octahedral shape of [f0(NH3)6]3+
[Fe(CN)(,13
3d 4s 4p
(a) Fe26 111 11 11 11 11 1ill] r--I-r-I--'---'1 /-- -....
3d 4s 4p (
(b) Fe3+ 11 11 11 11 1I0 ,--.--,--.-----.
J /
\
(c) 3
Fe +(rearranged due to presence ofCN) ,
'\
3d 4s 4p /' ,
111 11111 I I01""-.. .1--"1

.. '
\
';'sp3 ~i%ation
(d) The resulting complex is octahedral due to d2sp3hybridization
(e) due to presence of unpaired electron it is paramagnetic
[Cr(NHJ6]3+ ..
3d5 4s1 4d
(a) Cr24 11 11 11 11 11 I[JJ r--I~I --r---I
(b) Cr3+ 11 11 )1 I I0 L.-....I.-.....

L...-.-II
(c) Cr3+ in d2sp3hybridized state

1111111 1101
d 2sp3 ~disalion
(d) This d2sp3 hybridisation leads to octahedral geometry, the complex [Cr(NH3)6J3+ will be ,o '
octachedral in shape
(e) Since the complex ion has 3 unpaired electrons so it must be paramagnetic.
(f) . Other complexes ofchromium with similar inner structure are [Cr(CN)6]3- and [C~O)6]3+
c
~!~~~A~~C~~~~! Co-ordination Compounds [16} o
_""Sd>oII1,.
c
f '
L
Outer orbital complexes•
.(a) In these complexes s, p as well as d orbitals involved in hybridization, belong to the highest
quantwn number (n)
(b) complexes formed by the use of outer n, d orbitals will be paramagnetic.
(c) These complexes are called highspin or spin free complexes
(d) The outer orbital complexes have greater number ofunpaired electrons.
\ [CoF,]3
(a) C027
3d 4s 4p 4d
I[illl II
~11lI1"'"':"'"11llr--'111~11r- '11 1""'-1"--1"--1"--1 I
"""""'1
(b) C0 3+ ion
11lj111 11 11 1DI I I II 11I I1

(c) C0 3+ ion in sp3d 2hybridised state
11111 111111 ID1 1 I 1 r--I'--1'----'11""'-'1""'-'1

( sp3d2
(d) Due to octahedral orientation ofsix sp3d2hybridised orbitals shape [CoFJ~- complex ion is
octahedral
(e) Due to presence offour unpaired electrons in 3d orbital [CoFJ3- ion has paramagnetic character
(f) Other examples are [FeF6]3-, [Fe(NH)6]2+, [Ni(NH3)6]2+, [Cu(NH3)6]2+, [C~O)6]3+
/ Tetrahedral Complexes:
" These are formed by Sp3 hybridisation. Complexes ofZn2+are invariable tetrahedral ,because they
C involve Sp3 hybrid orbitals
((~11~)4]1+
"
( (a) configuration of~o
"", 3d 4s 4p
(
(
11~11~11~11~lnl [ill I IT
(b) electronic configuration ofZn2+
(
3d 4s 4p
(
(
11~ 11~ 11~ 11~ 11~ 1 D I I I I
\..,
(c) Zn2+in Sp3 hybridised state

c
C 11~ 11~ 11~ 11~ 11~ I D 1.-1
.....L--..L-..J
t: Sp3 hybridised
(d) [Zn(NH3)4]2+
C
f
11~ 11~ In In 11~ I GJ 1.. 1· ·1· ·1
C NH3 NH3 NH3 NH3
)ij Co-ordination Compounds [17J

c
c
(e) Since the complex is fonned by Sp3 hybridisation, it is tetrahedral
(f) Since all electrons are paired it is diamagnetic
[Ni{CO)41
(a) N~8
3d 4s 4p
11~ 11~ 11~ 11 11 1 [ill 1 1 I

(b) Ni after rearrangement
3d 4s 4p
11~ 11~11~11~ 11~1 D 1 I 1
(c) The empty one 4s and three 4p orbitals mix to fonn four Sp3 hybridised orbitals
(d) each orbital accepts one electron pair from carbon monoxide molecule forming [Ni(CO)4]
(e) The shape ofnickel tetra carbonyl is tetrahedral as shown below
(f) It is diamagnetic in nature
co
I
Ni~
/ ' \.~~

co '\ co <
co
Square planar complex.
These are fonned due to dsp2 hybridisation. (
\,
These complexes tend to be fonned when the central ion has only one d orbital available in the
inner shell {
'- /
[Ni(CN)41~
{'
(a) . electronic configuration ofNi
3d 4s 4p
,',
11~ 11~ 11~ 11 11 I [ill I I 1 "'-~
. (b) electronic configuration ofNP+
3d 4s 4p
""'-:11~-'-11---r~1-1~ ~11~""""'I---'1 D 1-.-1.;.&.-1

---'----I
dsp2
(c) The rearrangement is due to presence of strong ligand CN-. The. four orbitals make dsp2
hybridisation
(d) The shape ofresulting complex is square planar ( ,
v
(e) Due to paired electrons it is diamagnetic.
( ,
u
c
(jj] '¥.'~ll~CL~~!~!
IdHI (I)rSdIo/dtt
Co-ordination Compounds {lB]
c
STABILITY OF COMPLEX
(a) A complex is formed in solution by the stepwise addition ofligandsto a metal ion
(b) Thiscan be expressed as followsM + L '< >. ML, where M =metal and L is ligand
(c) The stability constant K for this reaction is as shown

ML
K= [M][L]
(d) This metal can again get a ligand

" >.
ML+~ c::::::: ML2
"
(e) The forthcoming stability constant K t then K. = r~~;! 1 its value is less thanK
(f) The higher the value ofstability constant stabler is the complex.
c (g) The value ofstability constants for someofthe complexes are given below:
Complex Stability constant
[CU(NHJJ2+ 4.5 x 1011
(
[Ag(NH3)2Y 1.6 X 107
[Co(1\rfI3)6]2+ 1.12 x 106
[Co(1\rfI3)6P+ 5.0 X 1033

,
r
[AgC~r 1.11 x lOs

r,
[AgBr2r 1.28 x 107
, [Ag(CN)2r 1.0 x 1022
\
(
[CU(CN)4P- 2.0 X 1027
\
[Fe(CN)6]3- 7.69 x 1043
(
" Factors influencing the stability ofcomplex

(~~ature ofcentral ion
(a)
. . .
The complex Will be more stable for higher values ofcharge densIty
' . (Charge)
radius
c (b) The higher the electronegativity ofthe central ion, .the greater is the stability ofits complexes
(, (c) The higher the oxidation state ofthe metal the more stable is the compound
\
f Nature ofligand
t, (a) A basic ligand is likely to easily donate its electroqs. Thus a more basic ligand will form more
( stable complex.
(b) Chelating ligands form more stable complexes as compared to monodentate ligands.
C
ORGANOMETALLIC COMPOUNDS
(
Compounds containing at least one metal-carbon bond may be called organometallic compounds. These
c compounds may be defined as those compounds in which the carbon atoms oforganic groups are linked
to metal atoms. The compounds ofelements such as boron, phosphorus, silicon, germanium, tellurium
c and antimony with organic groups are also included in the organometallics.
(
'L.
(1i1'~~A\C~~!~!
I _forSdlolars
Co-ordination Compounds [191
'-..
c
a-bond organometallic compou..ds :
In O'-bonded compound organic group is bonded to metal atoms through a normal 2 electron covalent
bond. Some example ofO'-bonded organometallic compounds as below are
Al2 (CH3)6' AliC6HS)6' Pb(CH3)4' Pb(C2Hs)4' Zn(C2Hs)." (CHJ4Sn etc.
Examples:
R-Mg-X (Cl\CI\)2Zn
Grignard reagent Diethyl zinc
(Alkyl magnesium halide)
(CH3)4 Si (CI\)4Sn
Tetramethyl silane Tetramethyl tin
(C2Hs)4 Pb (CHJ2Cd
Tetraethyllead Dimethyl cadmium
Trimethylalumirrium exists ~ stabledimet: In this, two methyl groupsact as bridges between two alurrrinium
atoms. The alkyl bridge is formed bymulticentrebonding.
1t-bonded organometallic compo~nds :

This type ofcompounds are generally formed by transition metals. Some examples of1t-complexesare
: . ,~
( ,
"
Transition metals usually form the1t-oondedcomplexes. Fenoceny, Dibenzene chromium, Zeise's salt,
etc. are some well known examples ofthe complexes belonging to this class.
0'- and7t-bonded organometallic compounds : .

Metal carbonyls oftransition metals constitute another important class oforganometallic compounds.
The first metal carbonyls, Ni(CO)4andFe(CO)s were discovered by A.Mond in 1890 and 1891. Few
moreexamplesofmetalcarbonyls are Cr(CO)6' MO(CO)6' maddition to mononuclearofmetalcarbonyls
mentioned above, transition metals form various polynuclear metals carbonyls such as Fe(CO)12'
~(CO)IO' The metal carbonyl bond in metal carbonyls posses both 0' and 1t character.
Application ofOrganometallic Compounds:
(a) Ziese's salt is used in the treatment ofcancer.
"
(b) Nickel tetracarbonyl is used in purificationofnickel. C j
(c) Ethylmercuricchloride is used as afimgicide.

(d) As homogeneous Catalyst
Wilkinsons catalyst for hydrogenation ofolefins is [P(PbJ3RhCI]
(e) As heterogeneous cat8J.yst

Zeigler-Natta Catalyst (~AI + TiCI4)
(Tri alkyl Aluminium + Titfnium tetrachloride) used for polymerisation ofalkene.
(f) Organic synthesis: OMC like RMgX, ~Cd, CHlLi etc. are used for preparation of
almost all type oforganic compounds.
(g) Cyclopentadienyl manganesetricarbonyl and TEL (Tetraethyllead) is used as antiknock
c
agent in petrol.
(h) In medicine - Organo arsenic compounds are used as medicine for syphilis disease.
(i) In agriculture- Seeds are treated with ethy mercury Chloride commercially known as
CERESSAN to protect the plants against infection. u
IIJ~~~~A~~CL~~'~!
IdeoIrorSd>clar1
C
.. SOLVED EXAMPLES
Ex. I In the compound CoCl305NH3
(A) all the CI show primary valency (PV) only
(B) two CI show (PV) and one CI secondary valency (SV)
(C) two CI show (PV) and one CI (PV) as well as (SV)
(D) all the CI show (SV)
Jol. (C)
[Co(NH3)srl]CI2 ----t These two CI show PV
This one CI show PV as well SV

\, ·~x.2 ~oNH2 although possesses two electron pair for donation but not acts as chelating agent. Why?
( 801. The co-odrinating by NH2.~ leads to a three member highly unstable strained ring and thus it does
not acts as chelating agent
NH2 -NH2
c
, ..
~~Three member highly
".
f
unstable strained ring
"Ex.3 Square planarcomplexeswith co-ordinationnumberfour exhibitgeometricalisomerismwheras tetrahedral
complexes do not. Why?
Sol. In tetrahedral complexes, the relative position ofatoms with respect to each other is same thus these do
'\.
not show geometrical isomerism. Square planar complexes show cis, traIis isomerism.
,
"~x.4 Select correct code about complex [Cr(N02)(NH3)S] [ZnCI4]
r
\
(I) IUPAC name ofthe :compound is Pentaamminenitrito-N-chromium (111) tetrachloridozincate(IT)
(II) It shows geometrical isomerism
( (Ill) It shows linkage isomerism
(IV) It shows co,-ordination isomerism

( (A) III, IV (B) I, III & IV (C) II, III & IV (D) I, II, III & IV
(~ol. (B)
\...'
(I) [Cr(N0 2)(NH3)s][ZnCI4]
c IUPAC name ofthe compoundis Pentaamminenitrito-N-chromium (III) tetrachloridozincate (II)
(III) It shows linkage isomerism due to presence ofambidented ligands

c [Cr(N0 2)(NH3)s] [ZnCI4]
(, [Cr(ONO)(NH3)S][ZnCI4]
(IV) Because both complex ions have different ligands

(~x.5 Platinum (IT) forms square planar complexes and pl~tinum (IV) gives octahedral complexes. How
(
\. ..
many geometrical isomers are possible for each ofthe following complexes? Describe their structures
(a) [Pt(NH3)3Clt (b) [pt(NH3)CI s r
L (c) [Pt(NH3hCIN02] (d) [Pt(NH3)4ClBr]2+
(~ol. (a) Square planar complex ofthe type M~b shows no isomerism.
- c cl ""'···········:7j NH3
+
i
c I i
Pt/""
( H3N !L'......'::::~/NH3
(~!~~~~CL~~'~! Ideo/lorSchoIIlrs
Co-ordination <;ompounds I21}
(
t
(b) An octahedral complex pfthe type MaPS shows no isomeri~.
NHs
Clr~::~::~..t········:::ry/ CI
I Pt~··
CI L:::::::+~a
CI
(c) A square planarcomple;x ofthe type M~bp exists as cis and trans isomers
(
Cli~····~ NH3 Cll'··-·~ NH3
.
•
. Pt·'
. • ,Pt /
.
(~
: ~; fL.'
,. ~;
ON'.••_••_
f L . •... _. •NH H N • -.-._.......... •NO
2 Cis 3 s Trans 2
(d) An octahedral complex ofthe type Ma4bc shows cis and trans isomerism.
NH3 CI
HsNi',:-··+······:;.:::; CI
: "Pt"""""'- i
H3Ni~~+~NH3 l
: Rt
k::::....L~r
I
H3N ,r H3 NfL.·t'·~NH3
, ('
NH3
Br
Cis
Trans
" '
\.
Ex.6 Howmany geometrical isomers with fonnula [MABCD] e.g., [Pt(NH3)P~OH)N02]+ arepossihle?
Sol. Three isomers
NH3 NH3
NH3
~'--"/1
PY
f':....../1NH,OH f':'''--/1
Py
! !Pt i Pt i i
!..)f
Pt
,,!
!
~.....~ ~......~py HO~• '2Ntc...····..······~' NO

. 2
NO, NH20H NO,
Ex.7 What are facial and meridional isomers? Explain with examples.
Sol. For the complexes ofthe type ~ h3] e.g., [Co(NH3)3CI3]3+ and [Rh(PY)3CI3]3+; the isomer is called
facial (fac) when all similar ligandsoccupysame face ofan octahedronas shown below. When all similar
ligands are not on the same face then isomer is called meridional (mer).
CI CI
I
N~'!."'?j
NH3
!':'.'7;C' • II" !
CI
! M ! i Ca+ ! (~
NH3k::t~CI NH3 k:.·t·~ NH3
NHs CI
facial meridional c
,
rI Co-ordination Compounds , '[22J c
c
EL8 [Fe(CN)614-is diamagentic while{FeF614:-is strongly pa,I1Ullagnetic. Why?
Sol. CN-is strong field ligand and so it pairs up the electrons leading to the fonnation oflow spin complex
which is diamagnetic.
[Fe(CN)6]4-;
d2sp3
4s
B 1"1"1"
Octahedral, diamagnetic complex
r is weak field ligand so it fomls high spin p~etic complex.
, [FeF6I4-: .
Sp3d2
11~ 11 11 11 11 I b 1.. 1.. 1.. ll.I .. 1 I I

Octahedml, paramagneticcomplex
CEx.9 Ifexcess ofAgN03 solution is added to 100 mL ofa 0.024 M solution ofdichlorobis (ethylene diamine)
(
cobalt (III) chloride, how many mol ofAgCI be precipitated: .'
" (A) 0.0012 (B) 0.0016 (C) 0.0024 (D) 0.0048
Sol. (C)
(
[CoP2(en)2]Gl· AgNOJ) [CoCI2(en)2]N03 + AgCI
" Mole of [CoClien)2]CI =molarity x v(Lt.)
0.0024 mole of [CoClien)2]CI gives
100
- - x 0.024 = 0 0024 mole ofCI

"
(
1000 .
Which precipitate 0.0024 mole ofAgN03 because 1 mole Ag+ required 1 mole CI- to precipitate
('
" Ex.1O [Fe(CN)6]3- is weakly paramagnetic while [Fe(CN)6]4- is diamagnetic, why?
(Sol. [Fe(CN)6]3- involves d2sp3 hybridization
d s p
(.' 3
Fe +(d S
) Itit It I t It I ,0 o=I
l [Fe(CN)6P- lulul t I : I : I IT] I: I: I : I

~
(
Rearrangement ctsp3hybridization
( One d-orbital is singly occupied, hence it is weakly paraniagnetic in nature.
[Fe(CN)6]4- involves also d2sp3hybridization but it has Fe1+ ion as central ion
d s p
C Fe +(d6)
2
lui tit I tit I 0 I I I
C [Fe(CN)6]4-ltJ-lhltJ-1 : j': I IT] I : I : I : I

~
- C Rearrangement ctsp3hybridization
All orbitals are doubly occupied, hence it is diamagnetic in nature.

t
l:aJ!~~A~~CL~~~~~ /d<olforScho/Qrs
.'. Co-ordination Compounds .··[23)
(
L
ELll Find out the hybridization, geometrY and magnetic moment ofthe complexes :
(i) [Co(NH3)61 3+ (ii) [Cr(CN)6P
Sol. (1) The oxidation state ofcobalt in the complex is +3. The electronic configmation ofCo3+ ions is
3d 4s 4p
C 0 3+ = It-l-I tit Itit I 01 II I
3cl4s 4p
[Co~)J3+ It-l-It-l-It-l-I ': I : 1ml : 1: 1:.1
~
Rearrange~~mt : cfsp~ybrkflZ8tion
Octahedn;lI. zero magnetic moment
(n) The oxidation sm.te ofclpumipm in the conwlex is +3. TheelectrooicoonfigurationofCr3+ion is

,". l '
3d 48 4p
[Cr(CN)J3- =I tit It I: I' 1D I I t I
Itltltl:I:1 IT] r:l:l:1
~
,Rearrangement cfsp3hybridizaton c
Octahedral, magnetic moment
= .J3x(3+2) = J15 = 3.87 B.M. (
Ex.I2 The magnetic moment of[MnCIJ2-is 5.92RM On the basicofits magnetic momenf; write configmation (
\,
ofMn2+ in this complex.

SoL For an atom/ion
Magnetic moment (J.t) = .In(n +2) \ ,
(n =No. ofunpaired electrons)
Given that J.1 = 5.92 B.M.
:. 5.92 = .In(n + 2)
or n=5
Thus in this complex Mn contains five unpaired electrons and soits possible configmation maybe Mn2+
in [MnCI4j2-= [Ar] 3d54so
so hybridisation ofMn2+ in the given complex mustl1e sp3.
3d5 it ..•••••••..••••••..
48 ••••••••...·····,
4p !
[MncIJ 2
-1 tit Itit 1t Iim I : I.....:-.........
,.................. I :11;.
~.-
sp3hybridization
'Ex.I3 All the octahedral complexes ofNi2+are outer orbital complexes, why?
s
c
3d
Sol. NP+ : It-I-It-I-It-1-1 tit I
Thus only one vacent 3d-orbital is available after pairing up ofelectrons due to strong field ligand.
Therefore, d2sp3 hybridisation is not possible. Only spJd2is possible which represent outer complex.
[i't~~A~~CM~!~!/deolforScltolan
Co-ordination Compounds 1lJtlI G
( ,
v
'Ex.14 Ni(CO)4 possesses tetrahedral geometry while [Ni(CN)4]j2- is square planar, why?
Sol. In the fonnation ofNi(CO)4' nickel undergoes sp3 hybridization, hence it is tetrahedral in shape. '
6
3d 45 4p
Ni(O)3d 8
: It.J-lt.J-lt.J-1 t It I [ill CD
Ni(CO)4 >lnlt.J-lnlt.J-lt.J-1 m J : I: I: I
, I
Sp3 hybridization
In the formation of[Ni(CN)J 2- , Ni2+ ion undergoes dsp2 hybridisation, hence it is square planar in
shape.
6
:' ' 3d 4s 4p
NP+ : It.J-lt.J-lt.J-1 tit I 0 CD
[Ni(CN)4]2-: lult.J-lhlt.J-1 : I m [J]TI
2
Rearrangement dsp hybridization
,
{
r
"Ex.IS Consider the following complexes
(i) KzPtCl6 (ii) PtC14.2NH3 (iii) PtC14.3NH3 (iv) PtCI4.5NH3
Theirelectrica1 conductancesinaq. solutions are
(J\)256,0,97,404 (B) 404, 0, 97, 256 (C) 256, 97, 0,404 (D) 404, 97,256, 0
C 301. (A) Coordination number ofPt is 6 hence
I Kz[PtCI6] - Three ions
II [Pt(NH3)2CI4] - Zeroions
\.
III [Pt(NH3)3CI3]CI - Two ions
(
N [Pt(NH3)sCI]CI3 - Fourions
Conductivity oc no. ofions
Ex.16 Determine the oxidation state ofmetal in the complex ion, [ptCI6]2-.
("
'--Jot Charge on the complex ion = Oxidation state ofmetal + charge on ligands
-2=x+6 x (-1)
orx=+4
The oxidation ofPt in the complex ion is +4.
C~x.17 The pair in which both species have same magnetic moment (spin only value) is
(
(J\) {Cr(~O)J2+, [CoC14]2- (B) [Cr(H20 )6]2+, [Fe(H20 )J 2+
'
(C) [Mn(H20)6]2+, [Cr(Fl20)6]2+ (D) [CoC14 ]2-, [Fe(H20)6]2+
(Sol. (B) Same magnetic moment = same number ofunpaired electrons = ~n(n +2)
/
\
where n=numberofunpairedelectrons
",
(
Co2+ = 3d7, 3 unpaired electrons
cr2+ = 3d4, 4 unpaired electrons
Mn2+= 3ds, 5 unpaired electrons
L Fe2+= 3d6, 4 unpaired electrons
C
(lJ't~~~~CM~~~! Id«II forSdloIors
(
L
Ex.18 The colour ofHg2C~ changes from white to black when treated with NH3, Why?
Sol. Hg2C~ reacts withNH3 to give blackcomplex,
l%C~ +2NH40H ~ Hg+ H~)Cl +NH4CI+2H20

(Black)
Ex.19 Write the forrnulaofthe following complexes.
(i) Pentamminechlorocobalt (TIl) ion
(n) Lithium tetrahydr.idoalurninate (Ill)
Sol. (i) [Co(NH3)sCI]2+; (ii) Li[AlHJ
Ex.20 Identity the complexes which are expected to be coloured and explain.
(A) n(N03)4 (B) [Cl,l(NCCH3)4]+ BF4
(C) [Cr (NH3)6]3+ 3CI- (D) K3 [VF6]
Sol. in
(C) and (D) are coloured because cr3+ [Cr(NH3)6]3+ and V 3+ in [VF6]3- have 3d3 and 3d2
configuration respectively and thus show d-d ~ition.
Ex.21 Write the IUPAC name ofthe given compound,~
( ,
,,/
,
(NH3)4 c1OR'co(en),] Cl4
f .
OH
(
Sol. Tetraamine cobalt (III) di-J.l-hydroxo bis ethyl~nediamine cobalt (III) chloride.
Ex.22 Explain the following with appropriate reasons :

[Fe(CN)6]3- ion has magnetic moment 1.73 BM, while [Fe~O)J3+ has a magnetic moment 5.92 BM. ( .
SoL 1. 73 = ~n(n + 2) 5.92 = .In(n + 2) { ,

\.
n=1 n=5
~
---<=
11
3+ 3+
Fe~ Fe 1 1 1 {~
Due to strong filed ligands (eN) Due to weak ligands (:140)
[I] ,~~~~~CL~~~~!
IdeoI (Q, Sdldal$
Co-ordination Compounds [26) c'
EXERCISE # I
COORDINATION COMPOUNDS AND TERMINOLOGY
Q.l For the complex [Cr(C204)2~0)2]-' the oxidationnwnberofCr is ................and the coordination
nwnberofCr is ..................... ..
(A) +3, 6 (B) +3, 4 (C) +2,6 (D) +2, 4
(! Q.2 How many EDTAmolecules are required to make an octahedral complex with a Ca2+ ion?
(A) Six (B) Three (C) One (D) Two
" Q.3 In the coordination compound K4[Ni(CN)J, the oxidation state ofnickel is:
\
(A)-l (B) 0 (C) +1 (D) +2
QA Formulaofferroceneis:
(A) [Fe(CN)6]4- (B) [Fe(CN)6]3+ (C) [Fe(CO)s] (D) [Fe(CSHS)2]
, i Q.5 Which ofthe following species is not expected to be a ligand

C (A)NO+ (B) NH~ (C) NHz-NH; (D) CO
Q.6 . Which ofthe following is not a double salt but is acomplexsalt.,- ,

(A) KCl.MgCI2. 6H20 (B) FeS04·(NH4)2S04·6H20
( (C) K2S04.AI2(S04)3.24H20 (D) 4KCN.Fe(CN)2
"
( . Q.7 The solution ofthe complex [Cu(NH3)4] S04 in water
(
(A) Will give the tests ofCu2+ions (B) Will give the tests ofNH3
\
(C) Will give the tests ofSO42- ions (D) Will not give the testS ofany ofthe above species
( \
" Q.8 The donor atoms in EDTA are-

f
(A) Two N and Two ° (B) Two N and four °
\..
(
\.
(C) Four N and Two I
°. (D) Three N and three °
(\ Q.9 Whichofthe following ligands is not a chelatingagent
(A) EDTA (B) ethylenediamine (C) Oxalate (D) Pyridine
f
~) Q.l 0 The oxidation number ofplatinwn in [Pt(NH3)5 CI]CI3is

(i (A) 2 (B) 3 (C) 4 (D) 6
( Q.11 An ambidentate ligand is.one which

(A) is linked to the metal atom at two points
(
'. (B) has two donor atoms but only one ofthem has the capacity to form a coordinate bond
( (C) Has two donor atoms but either ofthe two can form a co-ordinate bond
(D) fonns chelate rings
(,
Q.12 All ligands are-
C; (A) Lewis acid (B) Lewis base (C) Neutral (D) None ofthese
{ 1
".' Q .13 In SCN ligand ifN is attached to central atom, the name ofligand is
( , (A) Thiocyanato-N (B) Cyanato-N (C) Thiocyanato-S (0) Cyanato-S
Ci [i!~~~~~CL~~~~! Co-ordination Compounds 127]

Ideal for SdIokJrs
~ Bidentate ligand is
(A) CN- (B) Ethylene diamine (C) EDTA4- (D) SCN
Q .15 The neutral ligand is

(A) ChIoro (B) Hydroxo (C)Ammine (D)Oxalato
Q .16 Glycinato ligand is C> ...
- ~ -Oh--N»t.
(A)~<NH2~ l?~ ' r ; / ' (B) Bidentateligapd
.~
(C) Two donor sites N and 0- (D) All ofthese
Q .17 Triphenyl phosphine is
(A) Neutral and monodentate li~d (B) Neutral and tridentate ligand
(C) Uninegative and unidenfate ligand (D)Trinega~veaBdtridentateligand
Q .18 The coordination number ~d oxic:lation numb;r ofthe central metal ion in the complex [Pt(en)2]+2 is
(
(A) C.N. = 2, O.N. = +2 . . ; (B) C.N. = 6, O.N. = +4
(C) C.N. = 4, O.N. = +4 (D) C.N. = 4, O.N. = +2 /
i~;~~e addition compounds, which retain their indentity in solution are called
. V" (A)Doublesal~ j~ sP·U - . (B) Complex compounds ..,rJ I~ :.SfZI}./
(C) Coordination compounds (D) (B) and (C) both
"
Q .20 The total number ofLigands attached to the central metal ion through coordinate bond is called-
j'
(A) Valency ofthe metal ion (B) Oxidation state ofthe metal ion
(C) Coordinatin number ofmetal ion (D) None ofthe above
\
Q.21 The co-ordination number and oxidation number of X in the compound [X(S04)(NH3)5] will !'
~ .-"
be
(A) 10 and +3 (B) 1 and +6 (C) 6 and +4 (D) 6 and +2
Q.22 To form a coodination bond, one needs a ligand. Which ofthe following species cannot be a ligand
(i)NH/ (ii)NO+ (iii) CsHsN c
(A)ionly (B) i & ii only (C) i&iii only (D) i, ii & iii only
Q.23 The co-ordination number ofcobalt in [Co(enhBr2] Cl2 is

(A) 2 (B) 4 (C) 6
J (D) 8
Q.24 In which ofthe following complexes Ni etal is in highest oxidation state

(A) Ni(CO)4 (B) K2NiF6 (C) [Ni(NH3)6] (BF4h (D) K4[Ni(CN)6]
Q.25 The number ofdonor sites indime1hyl gly . e, glycinato, diethylene triamine andEDTAare respectively:
(A) 2, 2,3 and 4 (B) 2, 2, 3 and 6 (C) 2, 2, 2 and 6 (D) 2, 3, 3 and 6
Q.26 The oxidation number and coordinati~h number of chromium in the following complex is
[Cr(C20 4) 2 ( N H 3 ) 2 ] - 1 ' C
(A) O.N. = + 4, C.N. = 4 (B) O.N. = +3, C.N. = 4
(C) O.N. = - 1, C.N. = 4 . (D) O.N. = + 3, C.N. = 6
[j!~~~l!~CL~~~~! Co-ordination Compoun,ds 128J

ld""lfQfS<hoIor;
c
WERNER'S THEORY
Q.27 WhichoneisthemostlikelystructureofCtCI3~~Oifl/3 oftotalchlorine ofthe compound is precipitated

by adding AgN03 to its aqueous solution:
(A) CrClf6H20 (B)[crCI3(H20)3HH20)3
(C) {crCI2(H20 )4]'CI'2H20 (D) [CrCI(H20)s]C~ 'H20
@/Wllichofthe following is non-conducting ofelectricity?
VI;(A) CoCI3.6NH3 (B) C<~CI3·5NH3 (C) CoCI3.4NH3 (D) CoCI3.3NH3
I~
Q.29 When AgN03 is added to a solution ofCo(NH3)sCI3, the precipi~te ofAgCI shows two ionisable
\
chloride ions. This means - "
(A) Two chlorine atom satisfy primary valency and one chlorine atom satisfies primary valency as well
~---- - ~ ~
as secondary valency.
(B) One chlorine atom satisfies primary valency.
" (C) Two chlorine atoms satisf.¥ secondary valency.
(D) Three chlorine atoms satisfy secondary valency.

(
Q.30 A co-ordinationcomplexofcobalthas molecularfonnula containing five ammonia molecules, one nitro
r"
" group and two chlorine atoms for one cobalt atom. One mole ofthis compound producesthree mole
ions inanaqueous solution. In reacting this solution with excess ofsilver nitrate solution, two moles of
AgCI get precipitated. The ionic fonnula ofthis complex would be
' (A) [(Co(NH3)4.N02CI].[(NH3)CI] (B) [(Co(NH3)5CI].[CI(NO~]
(C) [(Co(NH3)s(NO~]CI2 (D) [(Co(NH3)s]·[(N02)2CI2]
( ~.31 Which ofthe following complex will give white preCipitate with barium chloride solution
(A) [Cr(NH3)5CI]S04 (B) [Cr(NH3)S04]CI
(C) [Co(NH3)6]Br3 (D) None ofthese
,.
'- Q.32 Which isomer ofCrCI 3.6H20 is dark green in colour and fonns one mole ofAgCI with excess of
(
\"
AgN03 solution
(A) [Cr(H20)6]CI3 (B) [Cr(H20)5CI]CI2~H20
(
{C) [Cr~O)4CI2]C1.2H20 (D) [Cr(H20 )3 CI3]·3H20
I
" Q. 33 Give the correct increasing order ofelectrical conductivity ofaqueous solutions offollowing complex
entities
( 1. [Pt(NH3)6]CI4 II. [Cr(NH3)6]CI3 UI. [Co(NH3)4CI2]CI IV. K2[PtCI6]
(A) III < IV < II < I (B) IV < II < III < I (C) II < I < IV <III (D) I < II < IV < III
(
,. Q .34 When potassium hexachloroplatinate (IV) is dissolved in water. The solution
" (A) Contains 6 ions per molecule (B) Reacts with AgN03 to give 6moiesofAgCI
C (C) Does not contain any CI- ion (D) Contains K+, Pt4+ and CI- ions
"(}35 The fraction ofchlorine pricipitated by AgN03 solution from [Co(NH3)5CI]C12 is
(A) 1/2 (B) 2/3 (C) 1/3 (D) 1/4
t
(Q.36 Which ofthe following has the highestmolar conductivity in solution
(A) [Pt(NH3)6]CI4 (B) [pt(NH3)5C1]C13 (C) [pt(NH3)4C12]CI2 (D) [Pt(NH3)3 CI3]Cl
(
{~~~--------------------~--~----~-------------------------
~i ~¥.'~~~~~~l~ Co-ordination Compounds {29J
Q.3 7 The number ofions given by [CO(NH3)~C13 41 aqueous solution is
W2 ~3~1 ~4
Q.38 A complex ofplatinum, ammonia and chlorine produces four ions per molecule in the solution. The
structure consistent with the observation is -" .'
(A) [pt(NH3)4]CI4 (B) [Pt(NH3)2CI4]

(C) [pt(NH3)sCI]CI3 (D) [Pt(NH3)4CI2l Ch . (.
Q.39 Match List I with List IT and select the ~orrect answer using the codes given below the
lists-
List! List II
(Equivalent conductance) . (Formula)

(1) 229 (i) [Pt(NH3)sCI]CI3 .
(2)97 (ii) [Pt(NH3)3CI3]CI
(3) 404 (iii) [Pt(NH3)4CI2]C12

(4) 523 ~iy) [Pt(NH3)~CI4 ..
' ..- . .', ~.-.~
"~.O\.., . "
.,.'., .
Code: " .
\ .
(I) (2) ~(3) ." (4)
-
;"-'_M ,"" .~, ,.,: :_ '". •
·(A). m i i :i
. (B) 1 iv iii i [',
(C) 1 iii iv 1
"
(
(D) m ii i 'II '.
Q040 Which ofthe following is most likely fonnula ofplatinum complex, if ~ oftotal chlorine ofthe com
pound is precipitated by adding AgN03 to its aqueous solution- (
\
(A) PtCI4.6H20 (B) PtCI4.5H20 (C) PtCI4.2H20 (D) PtCI4.3H20 (
'.
Q Al The number ofions fonned, when bis (ethane-l ,2-diamine) copper (TI) sulphate is dissolved in water
will be
(A) 1 r(B)2(C) 3 (D) 4 (
Q .42 The no. ofions given by [Pt(NH3)4CI2]CI2 in aqueous solution is- ",
W2 003 ~4 ~5 ( ,/
IUPAC NOMENCLATURE
QA3 The lUPAC name for the. coordinationcompoundB~rFJ2is '.
(A) Bariumtetraf1uorobromate (V) t1B)Barium tetrafIuorobromate (III)
,-ttC) Barium bis (tetranuorobrorilate) (IIi) ,~) none ofthese
<@ The fonnula ofthe complex hydridotcimetboxidoborate(lll) ion is:

, (A) [BH(OCHJ3]2-. lB) [B~(OCH3)3]2-
(C) [BH(OCH3)3]- (D) [BH(OCH3)3]+
n,
Q.45 The correct ruPAC name ofthe complex Fe(C sH s)2 is- G
(A) Cyclopentadienyl iron (TI) (B) Bis (cyclopentadienyl) iron (TI)

(C) Dicyclopentadien ferrate (TI) (D) Ferrocene
c
Q.46 The IUPAC name of [CoCI(N02)(en)2] CI is
(A) Chloronitro bis (ethylene diarnmine) cobalt(11l) chloride ',
(B) Chloronitro bis(ethylenediammine) cobalt (II) chloride C
I _~:
(C) Chloro bis (ethylene diammine) nitro cobalt (III) chloride

(D) Bis (ethylene diammine) chloronitro cobalt (Ill) chloride
c
1iJ~~~~A~CL~~~~!
IdeoII'orSdlolo,.
, "
c
Q.47 IUPACname of[Pt(NH3)3(Br)(N00CI]CI is
(A) Triamminechlorobromonitroplatinum(IV) chloride
(B) Triamminebromonitrochloroplatinum (IV) chloride
(C) Triamminebromochlororutroplatinum (IV) chloride
(D) Trlrirriminemtrochlorobromoplatinuin (IV) chloride
Q.48 Thecorrect name of[Pt(NH3)4CI2] [PtC14] is
(A) Tetraammine dichloro platinum (IV) tetrachloroplatinate (ll)
/'
(B) Dichloro tetra ammine platinium (IV) tetrachloro platinate (IT)
(C) Tetrachloro platinum (ll) tetraammine platinate (IV)
(0) Tetrachloro platinum (ll) dichloro tetraamine platinate (IV)
( Q.49
,
- The IUPAC name ofK2[Cr(CN)202(Oh(NH3)] is
(A) Potassiumamminedicyanodioxoperoxo chromate (VI)
(B) Potassiumamminecyanoperoxodioxo chromium (VI)
(C) Potassiumamminecyanoperoxodioxo chromium (III)
(0) Potassiumamminecyanoperoxodioxo chromate (IV)
Q~50 Th~JJ)J>AQ name [Co(Nf!3)6] [Cr(CN)61 is
(A) Hexaammine cobalt (III) hexacyanochromate (III)
(B) Hexacyanochromium cobalt hexaammine (VI)
C' (C) Hexaammine cobalt (III) hexacyanochromium (VI)
,/ (D) Hexacyanochromium (III) hexaammine cobalt (III)
(' Q.51 'The IUPAC name for [Co(NCS)(NH3)5]CI2 is
, (A) Pentaammine (thiocyanato-N) cobalt (III) chloride
C (B}Pentaammine (thiocyanato-S) cobalt (Ill) chloride
( (C) Pentaamine (isothiocyanato-N,S) cobalt (III) chloride
" (D) Pentaammine (mercapto-N) cobalt (Ill) chloride
G ~~complex, ~[HgIJ, canl)t~ named as :
r ~WPotassium tetraiodidohydragyrate (ll) (B) Dipotassium tetraiodidohydragyrate
", (C) Potassium tetraiodidohydragyrate (-2) ,(O)AlI ofthese
C~.53 The IUPAC name for K2[OsCI 5N] is
(A) Potassium pentachloroazidoosmate (VIII) (B) Potassium pentachloroazidoosmate (VI)
c (C) Potassium pentachloronitridoosmate (VI) (D) Potassium nitroosmate (III)
.54 /Ille IUPAC name ofFe(C,0)5 is
c:f.54>,
( ,~v(A) Pentacarbonyl ferrate (0) (B) Pentacarbonyl Ferrate (Ill)

(C) Pentacarbonyl Iron (0) , (0) Pentacarbonyl Iron (II) ,
(Q.55 K3[Fe(CN)6] is
( (a) Potassium hexacynoferrous (III) (b) Potassium hexacynoferrate (III)
(c) Potassium ferricyanide (d) Hexa cyno ferrate (Ill) potassium

c Correct answer is - '
(A) Only (a) and (b) (B) Only (b) and (c) ,
(C) Only (a) and (c) (0) Only (b) and (d)
c
Q.56 ThelUPAC name ofthe complex [CrCI2(H20)4]N03 is
(, (A) Dichlorotetraaquachromium (III) nitrate (B) Tetraaquadichlorochromium (III) nitrate
(C) Chromium tetra aqua dichloro nitrate (0) Dichlorotetraaquachromium nitrate
/~------------------------~--~~--~----~----------------~~
~rIJ~~~~~~C~~~!! Co-ordination Compounds {31J
C IdMlforSdaolc..
Q.57 In brown ring complex compond [Fe(H20)5NO]SO4' the oxidation state oife is
(A)+2 (B) + 3 (C)+4 ' ~+ 1
Q.58 Give the IUPAC name ofthe complex compound [Co(NH3)4(H20)Br](N03h

(A) BromoaquatetraamineCobalt (III) nitrate .
(B) BromoaquatetraaminoCobalt (III) nitrate
(C) BromoaquatetraammineCobaltate (llI) nitrate
(D) TetraammineaquabromoCobalt (Ill) nitrate
Q.59 The chIoro-bis (ethylenediamine) nitro cobalt (Ill) i~n is

,(A) [Co (NO~2 {en)2 Cl 2t (B) [CoCI (N02)2 (en)2 t
(C) [Co (N02) CI (enht (D) [Co (en)CI 2(N02h]
Q~ W
hich ofthe following statement is iIicorrect~ut [Fe(H20)5NO]S04
(A) It gives brown ring test for nitrates . (B) Oxidation state ofFe is + 'I
(C) It exhibits geometrical isomeris~/ (0) Charge on NO is + 1
Q.61 What is the oxidation number ofchromium in ~e dimeric hydroxo bridged species c
.,
~ /0H .........
(H20)4 Cr ,~/cr(H20)4
J4+"
"
(A)+6 (B)+4 (C) + 3 (P)+2 \"
( .
,
Q .62 In the complex Fe(CO)x' the value ofx is, ifit follows sidwickEAN rule :
W3 ~4 ~5 ~6
ISOMERISM '
Q .63 [Co(en)3P+ ion is expected to show c

(A) two optically active isomers: d apd 1fonns
(B) three optically active isomers: d, llUld meso forms
(C) four optically active isomers: cis, d and 1isomers and trans d and 1isomers
(D) none ofthese
Q .64 Ofthe following configurations, the optical isomers are
II, q CI :U
CI
("
,-j
CI CI Cl
en e
I II III IV
(A) I and II (B) I and III (C) II and IV (O) II and III
c
Q .65 Which ofthe following is pair ofionizatiqn isomers
(A) [Co(NH3)5Br]S04 and [Co(NH3)5S04]Br
(B) [Cr(H20)5CI]CI2.H20 and [Cr(H20)4.CI2]C1.2H20
(C) [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
c
(O) cis-[Pt(NH3hC12] andtrans-[pt(NH3)2CI~
, '
"'--'
C
[32J
!il ~~~~,,~~CL~~~~!
ldeo/forSdlokln
Co-ordination Compounds
C
Q.66 mcoordination compounds, the hydrate isomers differ
(A)Inthenmnberofwatermolecules ofhydrationonly
(8) In the number ofwater molecules only present as ligands
(C)Both (A) and (B)
(D) II) their coordination nmnber ofthe metal atom
Q .67 GeOmetrical isomerism in coordination compounds is exhibited by

(A) Square planar and tetrahedral complexes
(8) Square planar and octahedral complexes
(C) Tetrahedral and octahedral complexes
(D) Square planar, tetrahedral and octahedral complexs
r
,
Q.68 Which ofthe following is not optically active
(A) [Co(en)3P+ (8) [Cr(oX)3]3- (C) cis-{CoCI2(en)2t (D) trans-[CoCI2(en)2]+
Q.69 Which one ofthe following octahedral complexes will not show geometrical isomerism (A and B are
(
monodentate ligands)
"
(A) [MAsB] - (B) [MA2B4] (C) [MA3B3] (D) {MA4B2]
(
\..
Q.7O Which would exhibitco-ordination isomerism
(A) [Cr(NH3)6][Co (CN)J (B) [Co(en)2CI2t
(C) [Cr(NH3)6][C13 (0) [Cr(en)2CI2]+
Q.71 A complex shown below- .

" A
FI< AB
'
E 1£ " C
(
o
(
\ (A) Optical isomerism only (B) Geometrical isomerism only
(C) Both optical and geometrical isomerism (D) None
,
(
{, Q.72 The phenomenon ofoptical activity will be shown by

\..
B~A 8' A[£DA A

(
(
(A)
8
M.
8
(B)
B'
M en (C) ef I r l)n (0)
.... "8
A
A B
('
"
Q.73 A square planar complex represented as it will show which isomerism
(
/
CH:z
NH2
l8t.
·..•...••.. .......•
/NH:z'\.
CH
I '..' I 2
CH ' . ••••••••••••:--............ CH
2 2
"-H r/ 2 H2 w'
(A) Geometrical isomerism (B) Optical isomerism
(
"-. (C) Linkage isomerism (D) None ofthese
(
[33J
L (j]!~~A~~CM~~~! Co-ordination Compounds
_""SdIoIoI!;
c
Q. 74 Cis-trans-isomerism is f01pld in square planar complexes of the. molecular fonnula( a and b are
monodentate ligands) .
W~ ~~ ~M~ ~~
Q. 75 Out ofthe following which will not show geometrical isomerism -:
(A) [Pt(NH3)2 (H2oht2 (B) [Cr(NH3)5 01] Cl2
(C) [Co (enh C1 2] CI CD) [Co(NH3)4CI2]Cl
Q.76 The complexes given below are

A en
en
A
. (A) Geometrical iSomers . (B) Position isomers
(C) Optical isoIl1ers CD) Identical
Q.77 Theoritically the No. of geometrical isomers expected for octahedral complex [Mabcdef]
is
(A) Zero (B) 30 (C) 15 CP)9
Q.78 [Pd(C6Hs)2 (SCN)2] and [Pd(C6Hs)2(NCS)2] are:

(A) Linkage isomers (B) Co-ordination isomers
(C) Ionisation isomers . CD) Geometrical isomers
VALANCE BOND THEORY
'.
Q.79 A complex ofcertain metal has the magnetic moment of4.91 BM whereas another complex ofthe same
metal with same oxidation state has zero magnetic moment The metal ion could be
W~ ~~ ~~ ~~
Q.80 Point out the correct statements amongst the following
(A) [Cu(CN)4P- has tetrahedral geometry and dsp2 hybridization
(B) [Ni(CN)J4- is octahedral and Ni has d2sp3 hybridization (."'
(C) [ZnBr4F- is tetrahedral and diamagnetic
. (D) [Cr(NH3)61 3+has octahedral geometry and sp3d2hybridization
Q .81 The complex ion [Cu(NH3)4]2+ is....;'

(A) Tetrahedr3l and paramagnetic (B) Tetrahedral and diamagnetic
(C) Square planar and paramagnetic CD) Square planar and diamagnetic
C)
Q .82 The complexions [Fe(CN)613-and [Fe(CN)614
(A) Are both octahedral and paramagnetic
(B) Are both octahedral and diamagnetic
(C) Have same structure but different magnetic character
(D) Have different structures but same magnetic character
Q .83 Which complex has square planar structure

(A) Ni(CO)4 (B) [NiCI4]2- (C) [Ni(H20)6]2+ (D) [Cu(NH3)4]2+ ( ,
"--'
Co-ordination Compounds [34]

'~~~~~A~~~~~~~!
Idea' k1r SdIo/Q,.
, [ "
'--'
Q.84 Complexes with CN-ligands are usually
(A) High spin complexes (B) Low spin complexes
(C) Both (A) and (B) (D) None ofthese
Q.85 Which order is correct in spectrochemical seri~s ofligands
(A) CI- < P- < C 20 4 2- <NO 2-<CN- (B) CN- < CO 2- < CI- > NO -<F
2 4 2
( C) C2
0 2- < 4 > NO -<CN-
P- < CI-2 (D) P- < CI- <NO2
- < CN-<C
24 0 2
Q.86 Hexafluorocobaltate(III) ion is found to be high spin complex, the hybridisation state ofcobalt is
(A) d 2sp3 (B) sp3 (C) sp3d (D) sp3d 2
Q.87 The number ofunpaired electrons calculated i~, [Co(NH3)6P+ and [CoF6P- are :
(A)4and4 (B) oand 2 (G) 2 and 4 (D) oand 4
"\
" \. CRYSTAL FIELD THEORY
\ \
~ .. Q~~~~~the fOllowin~ coordination entities, the magnitude of ~o [CFSE in octahedral field] will be
( (A) [Co(CN)6P- (B) [Co(C20J3P- (C~ [Co(H20)6P+ (D) [Co(NH3)6P+

C Q.89 . The~agneticm~mentofasaltcontainingZn2+ ion is :
(A) 0 (B) 1.87 (C) 5.92 (D) 2
f
\.
Q.90 In an octahedral crystal field, the t2g orbitals are
(
(A) Raised in energy by 0.4 L\o (B) Lowered in energy by 0.4 L\o
( (C) Raised in energy by 0.6 L\o (D) Lowered in energy by 0;6 L\o
( Q. 91 If L\o < P, the correct electronic configuration for d 4 system will be

, (A) t~g e~ (B) t~g e~ (C) tgg t~ (D) t~g e;
"
( Q.92 Match List-I (Complex ions) with List-II (Number of Unpaired Electrons) and select the
correct answer using the codes given below the lists
( List - I List - II
( (Complexions) (Number ofUnpaired Electrons)
(1) [CrF6]4- (i) One
C (2) [MnF6]4- (ii) Two
(3) [Cr(CN)6]4- (iii) Three

c (4) [Mn(CN)6]4- (iv) Four
( (v) Five
(
Code: I 2 3 4
(A) (Iv) (i) (Ii) (v)
( (B)V (Ii) (v) (iii) (I)
(C) . (iv) (v) (Ii) . (i)

C (D) (n). (i) (iii) (v)
(. Q.93 Forthe t~g e; system, the value ofmagnetic moment (J!) is
- c (A).2.83 ~.M. . (B) 1.7.3 B.M. .(C) 3.8~ B.M. (D)4.92~.M..
C Q.94 Which oftlle follwomg electroruc arrangement gives the highest value ofthe magnetic moment m case of
octahedral complex?
( (A) d6, strong field (B) d 7,highspin (C) d4, weak field (D) d 2, strong field
;-
~..
[i]~~~~A~~C~~~~~!
IdealforScholars
c
EXERCISE # IT
Q.1 A solution containing 0.319 g ofCrCI3.6~Owas passed througll a cation exchange resin in the acid
form, and the acid liberated was titrated with a standard solution ~fNaOH. This required 28.5 cm3of
0.125 MNaOH. The correct formula ofthe Cl;(IIl) complex is '
(A) [C~O)JCI3 (B) [crCI(~O)5]CI2.H20
r (C) [CrC12(H20)5]C1.2~O (D) [crCI3·(H20 lJ.3H20
@ ,Which ofthe following is considered to be anapticancer species ?
CA)
C)
Pt<CH,·
[ trH2]
8
C~
(B) . )Pt<
Cl] 2
[
Cl CI Cl Cl
,
(C)
,H3
[H3)N <CI]
Pt
Cl
0) [H:)pt(] 3
Q.3 The correct order ofmagnetic moments is :

(A) [MnCIJ 2-> [CoCI4]2-> [Fe(CN)6]4- (B) [MnCIJ2- > [Fe(CN)6]4- > [CoCI4]2- c:
(C) [Fe(CN)6]4-> [MnCIJ2-> [CoCI4]2- (D) [Fe(CN)J4-> [CoCI4]2-> [MnC14]2~ r '
\.
Q.4 Thetotal number ofpossible coordination isomers ofthe compound [Cull(NH3)4] [PtITCI4] are:
W3 ~5 ~4 ~6 "
\.
Q.5 Which ofthe following is an outer orbital complex
(A) [Fe(CN)6]3- (B) [Fe(CN)6]4- (C) [peF6]3- (D) [Cr(CN)J 3
!'
Q.6 Which ofthe following complexes has the least molar conductivity in the solution-
(A) CoCI3. 3NH3 (B) CoCI3. 4NH3 (C) CoCI3. 5NH3 (D) CoCI3· 6NH3
Q.7 The complex CoC13.5NH3 is aqueous solution ionizes to give a total number ofions equal to ('
"---'
(A) 0 (B) 2 (C) 3 (D) 4
c
Q.8 The number ofgeometrical isomers for [Pt(NH3)2Clii is
(A) Two (B) One (C) Three (D) Four
Q.9 The geometIy ofsome complex ions are given against them
(1) [Ag(NH3)2]+ -:- Linear (2) [MnCI4f- -Tetrahedral
(3) [Cu(NH3)4f+ - Square planar (4) [Ni(CN)4]2- - square planar
The correct match is

(A) land 4 (B) 1,2 and 3 (C) 1,3 and 4 (D) 1,2,3 and 4 ('"
~.7
Q.I0 Which one is the most likely structure ofCrC13.6H20 if 1/3 oftotal chlorineofthe compound is precipitated
by adding AgN03 to its aqueous solution
(A) CrC13.6H20 (B) [Cr(H20 )3 C13]·(H20 )3 '
(C) [CrCI2(H20)4]C1.2H20 (D) [CrCl(H20 )s]CI2.H20
c
t(i),_ ~e complex ion which bas no 'd' electrons in the central metal atom is
~~) [Mn04r (B) [CO~3)6]2+ (D) [Cr(H:~O)6]3+
f'
~
(C) [Fe(CN)6]3-
.iiJ!~~~~~C~~~~ Co-ordination Compounds {36J

--zq .c;?-
, /deQl forSchol<l"
r;:::;:::;'
e L
c
. Q.12 The complex that violates the EAN rule
(A) Potassium ferrocyanide (B) Potassium fenicyanide
(C) Tetracarbonyl Nickel (D) Hexamine cobalt (Ill) chloride
Q.13 Which one ofthe following pairs ofisomers and types ofisomerism are correctly matched
(a) [Co(NH3)s(N0:0]CI2and (Co(NH3)s<0NO)]CI2.... Linkage
(b) [OJ(NH3)4](PtCI4)] and [Pt(NH~J (CuCI4]······co-ordination
(c) [Pt(NH3)4CI:0J Br2 and [Pt(NH~4 Br:0]Q2......Ionization
Select the correct answer using the codes given below

(A) band c (B) a, b and c (C) a and c (D) a and b
f
~. ~.14 Match List I with List II and Select the correct answer using the codes given below the lists
List-l List-2
Complex ions Magnetic Momentin
BohrMagnetons·
a. [Fe(CN)6]-4 1. 1.73
b. [Fe(CN)6]3+ 2.5.93
r
c. [Cr(H2O}6]3+ 3.0.00
, d. (Ni(H20)6]2+ 4.2.83
\.
3.
e. [FeF6t . 5.3.88
Code: a b c d e
(A) 1 2 .3 '~ 4 5
(B) 3 1 5 4 2
(C) 2 3 4 5 1
\
(D) 4 5 1 2 3
( Q.15 Correct fonnula ofdiammine silver (l) chloride is
. (A) Ag(NH3}CI (B) Ag(NHz}Q (C) [Ag(NH3}2]CI (D) Ag(NHz}2]CI
Q.16 The fonnula ofsodium nitroprusside is

(/ (A) Na4[Fe(CN)sNOS] (B) Naz[Fe(CN)sNO]
(C) NaFe[Fe(CN)6] (D) Naz[Fe(CN)6NOz]
A
I< >I B
f
\...~. 17 The isomer of can be marked as
( BI<" "A
c A
c (A) Dextro isomer (B) Laevo isomer (C) Cis isomer (D) TtanS isomer
(1· 18 The fonnula ofpotassiumdicyano bis (oxalato) nickelate (ll) is

(A) K4(Ni(CN}z (Ox}z] (B) K3iNi2(CN}z (Ox}z]
L (C) K [Ni(CN) (Ox}z] (D) K2[Ni(CN)2(Ox}z]
(Q.19 The valency ofcopper ion in cuprammonium ion is

"( (A) +4 (B}+2 (C}-2 (D}-4
c~~~~----------------~--~--~~----~----------------~
fi]!~~~~~ C~~~~! Co-ordination Compounds [37J
""",,_Sc/IoIon
{
"'
Q.20 The complex diaquatriam.tlljne chlorocobalt (Iij) chloride is~nted as-
o t
(A) [Co(NH3)3%O)3]CI2 (BHCo(NH~3(H;20)2]CI2

(C) [CoCI(NH3)3(fI20)2]CI3 (I»[CoCI(NH3)3(fI2(»~CI2
Q.21 Match List-I with List-II and select the correct answer using codes given below the lists
List-I List-n.
Metal ions Magnetic moment(B.M,.)
(1) cr3+ i. J35

(2) Fe2+ iiJ30 ·1 :
(3) Ni2+ iiiJ24
(4) Mn2+
iv.Jf5
v.Fa
code: (1) (2) (3) (4)
(A) 1 iii v iv
(B) 1 iii v i
(C) PI iii v i
(I» iv v iii i
Q.22 The species having tetrahedral shape is-

(C) [pd(CN)4f
r '
(A) [pdCI.J2- (B) [Ni(CN)4]2- (P) LNiC14]2- \. ,
Q .23 In nitroprusside ion the iron and NO exist as Fell and NO+ rather than FellI and NO. These forms can
be differentiated by - .
(A) Estimating the concentration ofiron (B) Measuring the concentration ofCN
(C) Measming the solid state magnetic moment (D) Thermally decomposing the compound , ,
Q .24 Which ofthe following coIPplexes are paramagnetic in nature

[Fe(CN)6]3- [Fe(CN)6]4- [CoF6]3- Ni(CO)4 ,'
I
'-.j
I II ill IV
(A) Only I (B) I and II (C) I and ill (I»ill and IV
Q.25 Among the complex ions given below which is/are outer-orbitals complex
[Co(CN)6]4- [Fe(fI20)6]2+ [FeF6]3':" [CoF6]3
I II ill IV c
(A) II, ill, IV (B) II, ill only (C) I, IV only (I» II only
Q.26 In which offollowing pairs ofspecies the number ofunpaired electrons are same
(A) [CoF6]3-, [FeF6 ] 3 - ' (B) [Fe(CN)6]3-, [Fe(CN)~4-
,r ,
(C) [Fe(CN)6]3-, LNi(CN)4]2- (0) [CoF6]3-, [Fe(fI20)6]2+ '-J
Q .27 A reagent used for identifying nickel ion is

~otassiumfe1TOcyanide(B) Phenolphthalein
I ~imethylglyoxime (I»EDTA
c
Q.28 The IDPAC name ofthe red coloured complex [Fe(C4H70 2N 2)2] obtained from the reaction ofFe2+ e
and dimethyl glyoxime
(A) bis (dimethyl glyoxime) ferrate(lI) (B) bis(dimethyl glyoximato) iron (II)
o
. (C) bis (2, 3-butanediol dioximato) iron (II) (I» bis (2, 3-butanedione dioximato) iron (II)
G
II~~~~~~ CH!~~!
IdeoIf;JrSdlol/lf$
Co-ordination Compounds {38J
c
'-.a'
Q.29 Zn (ll) ion:firstgives a white precipitate with NaOH whichdissolves in excess ofNaOH. This is due to
the fonnattonofa complex. Theoxidation sateofzinc in this complex will be.
(A) Zero (B)+n (C)+IV (D)+VI
~Ofthefullowingis correctlymatcbed?
! Column I Column IT Columnm . [
c (A) [Cr(CO)6] Paramagnetic Octahedral, sp3d ..
(B) [Fe(CO)s] Paramagnetic Trigonal bipyramid, sp3d
(C) [Co(CO)4]- diamagnetic t.:.trahedral, sp3
f
(D) [Ni(CO)J diamagnetic spuare planar, dsp2
/
\
~
f·
\...
,.
,"
'...
\.- ..
\.
(
r
I..
(
"--
\.
(
'.
C
C
C
(
(
C
\..
f
~j~-----------""",,------------------
fij]. ~~~~~~ CL~~!~! Co-ordination Compounds [39}
( j lde!1/{orSchoto,.
(
~
EXERCISE # III
SECTION-A
Q.1 fu [Cr(C20 4)3]3-, the isomerism.shown is- .. [AlEEE-2002]

- jCA)Ligand (B) Optical (C) Geometrical (D) Ionization
9Jfl i
fu the complexes {Fe~O)J3+,{Fe(CN)J3+, {Fe(C20 4)3]3- and {FeCIJ3-, more stability is shown ~y- .
. g/ [AIEEE-2oU#]
(A) {Fe(I\0)J3+ yY{Fe(CN)6]3+ (C) (Fe(C20")3]3- (D) [FeCIJ3- . "
Q.3 One mole ofthe complex compound Co~sC~, gives 3 moles ofions on dissolution in water. One
mole ofthe same complex reacts with two mol~ ofAgN03 solutiqnto yi~ld two moles ofAgCl(s). The
structure ofthe complex is- . . [AlEEE-2003]
(A) [Co(NHJ3CI3].2NH3 (B) [Co(NHJ4C12] Cl.~

(C) [Co(NH3)4CI] C~.NH3 (D) [Co(NH3)sCl] C~
Q.4 fu the coordination compound K4[Ni(CN)4], the oxidation $te ofnickel is- [AlEEE-2003]
(A) 0 (B) +1 (C) + 2 " , ; (D)-1
Q.5 The number of3d-electrons remained inFe2+(At. no. ofFe 26) i~'::' [AlEEE-2003]
(A) 4 (B) 5 : (C) 6 (D) 3
Q~Ammonia fODDS the complex ion [Cu(NH,)J" ion with copper ions in a1kaline solutions butnotin ""I!lie
VV solution. What is the reason forit - [AlEEE-20~3]
(A) fu acidic solution hydration protects copper ions

(B) fuacidic solutionsprotons coordinate with ammoniamolecu1es funning NH/ ionsand ~ molecules
are not available
(C) ill 8lkaline solutions insoluble Cu(OH)2 is precipitatedwhich is soluble in excess ofanyalkali
(0) Copper hydroxide is an amphoteric substance
Q.7 Among the properties (a) reducing (b) oxidising (c) complexing, the set ofproperties shown byCN-ion
towards metal species is - [AIEEE-2004]
(A) c, a (B) b, c (C) a, b (D) a, b, c
Q.8 The coordination number ofa Central metal atom in a complex is determined by - [AlEEE-2004] ( ':j
(A) The number ofligands around a metal ion bonded by sigma and pi-bonds both
(B) The number ofligands around a metal ion bonded by pi-bonds
(C) The number ofligands around a metal ion bonded by coordinate bonds
(0) The number ofonly anionic ligands bonded to the metal ion
Q.9 Which one ofthe following complexes is an outer orbitals complex- [AlEEE-2004]
(A) [Co(NH3)6]3+ (B) [Mn(CN)6]4- (C) [Fe(CN)6]4- (D) [Ni(NHJ6]2+
(Atomic nos. : Mn = 25; Fe = 26; Co = 27; Ni = 28)
Q.I0 Coordinationcompounds have great importance inbiological systems. ill this contectwhich ofthe following c
statements is incorrect? [AlEEE-2004] .
(A) Cyanocobalamin is vitamin Bt2 and contains cobalt
(B) Haemoglobin is the red pigment ofblood and contains iron L
(C) Chlorophylls are green pigments in plants and contain calcium r
L
.
(0) Carboxypeptidase-A is an enzyme and contains zinc

c
[I!~~~~ CL~~~~! Co-ordination Compounds {40j
/deQJ for Sd>oI<m (~
c
Q.l1 The oorrect order ofmagnetic moments (spin only values in B.M.) among is - [AIEEE-2004]
(A) [Fe(CN)6]4- > {MnCI4]2- > {CoCI4]2- (B) IMnCI4]4- > (Fe(CN)6]4- > lCoCI4]2
(C) [MnCI4]2-> [CoC14]2- > lFe(CN)6]4- (D) (Fe(CN)6]4->JCoC14]2- > [MnCI4Y
(Atomic nos: Mn = 25 ; Fe = 26 ; Co = 27 ; Ni = 28)
Q .12 The value ofthe 'spin only' magnetic moment for one ofthe following configumtions is 2.84 BM . The
correct one is - . [AIEEE-2005]
4
(A) d (in strong ligand field) (B) d' (in weak ligand field)
3
(C) d (in weak as well as in strong field) (D) d' (in strong ligand field)
I .
Q.13 The IUPAC name for the complex [Co(N02)(NH),] C~ is - [AIEEE-2006]

(A) petaammine nitrlto-N-cobalt (II) chloride (B) pentaammine nitrito-N-cobalt (III) chloride
(C) nitrito-N-pentaammineoobalt (Ill) chloride (D) nitrito-N-pentaammineoobatl (Il)chloride
Q.14 Nickel (Z = 28) combines with a negative monodentate ligand X- to fonn a paramagnetic complex
[NiXJ2-. The numberofunpaired electron in the nickel and geome1:tyofthis oomplex ionare respectively
[AIEEE-2006]
r
(A) one, square plrutar (B) two, square planar (C) one, tetrahedral . (D) two, tetrahedral
" Q.15
(
In Fe(CO)" the Fe-C bond possesses - [AIEEE-2006]
'. (A) ionic character (B) O"-characteronly (C) n-character (0) both 0" and n character
Q.16 HowmanyEDTA(ethylenediaminetetraacetateion) molecules are required to make an octahedral oomplex
, with a Ca2+ion? ' [AIEEE-2006]
(.
W~ ~~ ~~ ~~
Q.17 The "spin-only" magnetic moment [in units ofBohrmagneton] ofNF+ in aqueous solution would be (At.
r
\. No. Ni = 28) - [AIEEE-2006]
t (A) 0 I (B)1.73 (C) 2.84 (D) 4.90
\ 1
Q.18 Which one ofthe following has a square planar geometry - (Co = 27, Ni = 28, Fe = 28, Fe = 26,
Pt = 78) - [AIEEE-2007]
( (A) [CoC1 4
]2- (B) [FeC1 ]2-
4
(C) [NiCI 4
]2- (D) lPtCI4
]2
(_ Q.19 The coordination number and the oxidation state ofthe element 'E' in the complex [E(en)lC20 4)] N02
\..
(where (en) is ethylene diamine) are, respectively - [AIEEE-2008]
(A) 6 and +2 (B) 4 and +2 (C) 4 and +3 (D) 6 and +3
( Q .20 In which ofthe following octahed~ complexes of Co (at. no. 27), will the magnitude of £\0 be the
{ highest? [AIEEE-2008]
'- (A) [Co(CN)6]3- (B) [CO(C20 4)3]3- (C) [Co(H20)6P+ (D) [Co(NH~6]3+ .
( ,
Q .21 Which ofthe following has an optical isomer [AIEEE-2009]

(A) [Co(en)(NH3)2f+ (B) [Co(H20)ien)]3+
t (C) [Co(en)2(NH3)2]3+ (D) [Co(NH3)3Clt
Q .22 Which ofthe following pairs represents linkage isomers ? [AIEEE-2009]
(A) [Pd (P Ph3)2(NCS)2] and [Pd (P Ph3)2 (SCN)2]
(B) [Co(NH3)sN03] S04 and [Co(NH3)sS04] N03
( (C) [Pt Cl2 (NH3)4] Br2 and [Pt Br2 (NH3)4] Cl2
(D) [Cu(NH3)4 [PtCI4]] and [Pt(NH3)4] [CuC14]
[411
(. ~~~~~A~~~~~~~!
Co-ordination Compounds
, kkoIforSdlo/ars
L
. ~"
Q .23 A solution containing 2.675 g ofCoCI3.6NH3(molar mas = 267.5 g mol-I) is passed through a cation
exchang~r. The chloride ions obtained in solution were treated with excess ofAgN03 to give 4.78 g
ofAgCI(molarmass= 143.5 gmol-I ). Thefonnulaofthecomplexis: [AIEEE-2010]
(Atomic mass ofAg = 108 ~)
(A) [Co(NH3)6]CI3 . \ (B) [CoC~ (NH3)4]Cl
(C) [CoCI3(NH3)3] . (D) [CoCI(NH3)s]CI2
Q.24· Which one ofthe following has an optical isom,er ? (en = ethylenediamine) [AIEEE-2010]
(A) [Zn(en)(NH3)2]2+ . . (B) [Co(en)3P+
(C) [Co(H20)4(en)]3+ (0) [Zn(en)i!2+
Q.25 Which ofthe following facts about the complex [Cr(NH3)J Cl3is wrong? [AIEEE-20ll]
(A) The complex involves d2spJ hybridisation and is octahedral in shape.
(B) Thecomplex is paramagnetic
(C) The complex is ali outer orbital complex. ,.
(D) Thecomplex gives white precipitatewith silver nitrate solution.
Q.26 The magneticmoment (spin only) of[NiC14] is [AIEEE-20ll]
(A) 1.82 BM (B) 5.46 BM (C) 2.82 BM (D) 1.41 BM
Q .27 Whichofthe following complex species is not expectedto exhibit optical isomerism?
(A) [Co(en)2C~r (B)[Co(NH3)j.CI3] [.lEEMain-2013]
. (C) [Co(en)(NHJ)2C~]+ . (D) [Co(en)3] +
',_/
SECTION-B
Q.28 The oxidation state ofFe in brown ring complex, [F~O)SNO]S04is .[JEE19S7]
(A) +1 (B) +2 (C) +3 (D)~4
Q.29 Amongst [Ni(CO)J, [Ni(CN)4f- and [NiCIJ2- . [JEE 1991]

(A) [Ni(CO)J and [Ni(CN)4]2- are diamagnetic and [NiC14]2-is paramagnetic
(B) [NiCIJ2- and [Ni(CN)J 2- are diamagnetic and [Ni(CO)J is panimagnetic
(C) [Ni(CO)4]' [NiCIJ2-and [Ni(CN)4]2- are diamagnetic.
(D) [Ni(CO)4] is diamagnetic and [Ni(CN)J2- ,[NiCI4f-'-areparamagnetic
Q.30 The numberofd-electron is [Cr(H20)6]J+ [AtNo. ofCr = 24] is [JEEI993]
W2 003 ~4 ~5
Q.31 Which ofthe follwoing is an organometalliccompound [JEE 1997]
(A) Lithium methoxide (B) Lithium acetate (C) Lithium dimethylamide (0) Methyllithimn
Q.32 The geometry ofNi(CO)4 and Ni(pPhJ)2C~ are [JEE 1999]
(A) both square planar (B) tetrahedral and square planar
(C) both tetrahedral (D) square planar and tetrahedral
Q.3 3 The correct order ofhybridisation ofthe central atom in the following species. [JEE2001]
. NHJ, [PtCI4]2-, PCls and BCIJ is [At No. Pt = 78]
(A) dsp2,spJd,sp2 and spJ (B) spJ,dsp2, spJd, sp2
(C) dsp2,sp2,spJ and spJd (D) dsp2, spJ,Sp2 and spJd (j
Q.34 The species having tetrahedral shape is : [JEE2004]

(A) [PdCI4]2- (B) [Ni(CN)4F- (C) [Pd(CN)4]2- (D) [NiCI4f

c
[j]~~~~~Cl.~~!!!
Idr<tI(QrScholors
Q.3S The compound having tetrahedral geometry is [JEE2004]

(A) {Ni(CN)4]2- (8) (Pd(CN)4]2- (C) [pdCI4]2- (D) [NiCIJ2
Q.36 Spin only magnetic momentofthe compound Hg [Co(SCN)J is [JEE2004]

(A) Jj (B) .Jl5 (C).fi4 (D)-J8
Question No. 37 to 39 (3 questions) . [JEE2006]
The coordination number ofNi2+ is 4.
NiCl2+ KCN(excess)-+A(cyanocomplex)
NiC~ + KCI (excess) -+ B (chloro complex)
Q.37 The IUPAC name ofA and Bare

(A) Potassium tetracyanidonickelate 00, potassium tetrachloridonickelate 00
(B) Tetracyanidopotassiunmickelate 00, teterachloridopotassiunmickelate 00
(C) Tetracyanidomickel 00, tetrachloridonickel (ll)
(D) Potassium tetracyanidonickel 00, potassium tetrachloridonickel 00
r~ Q.38 Predict the magnetic nature ofA and B.

(A) Both are diamagnetic.
(B) Ais diamagnetic and B is paramagnetic with one unpaired electron.
r (C) Ais diamagnetic and B is paramagnetic with two unpaired electrons.
'\
(D) Both are paramagnetic.
Q.39 The hybridization ofAand B are
( (A) dsp2, sp3 (B) sp3, Sp3
(
(C) dsp2, dsp2 (D) sp3d2, d2sp3
( QAO Ifthe bond length ofCO bond in carbon monoxide is 1.128~ then what is the value ofCO bond length
in Fe(CO)s?
( (A) l.ISA (B) 1.128A
(C) l.72A (D)1.118A [JEE2006]
QAI Match the complexes in Column I with their properties listed in Column II. Indicate your answer by
C darkening the appropriate bubbles ofthe 4 x 4 matrix given in the ORS.
Column I Column II [JEE 2007]
(A) [Co(NH3)iH20)2]CI2 (P) Geometrical isom~
(B) ~)2CI2] (Q) Paramagnetic
(C) [Co~O)5CI]CI (R) Diamagnetic
(
". (D) [Ni(H20 )6]CI2 (S) Metal ion with 2+ oxidation state
( ~. 42 The spin only magnetic moment value (in Bohr magneton units) ofCr(CO)6 is [JEE2009]
( (A) 0 (B) 2.84 (C) 4.90 (D) 5.92
\..
( Q .43 The correct structure ofethylenediaminetetraacetic acid (EDTA) is [JEE2010]
( HOOC-CH2 CH -COOH
" / 2
- C' (A) N-CH=CH-N
HOOC-CH2/ "CH2-COOH
(
\.,
(liJ!~~~A~~CL~~~~!
l _forSc/lolaJs
Co-ordination Compounds /43J
C
HOOC, /COOH
(B) N-CH2-CH2-N
HOOo/ 'COOH
HOOC-CH2 CH -COOH
, / 2
(C) N-CH2-CHr N
HOOC-CH( 'C~-COOH
·1
/COOH
HOOC-CH2
, CH2 ·
1
N-CH-CH-N
/
H
(0) /
H
I 'CH -COOH
CH 2
/2
HOOC
Q.44 Among the following complexes (K-P) [JEE2011]

K 3[Fe(CN)6] (K), [Co(NH3)6]CI3 (L), N~[Co(oxalate)3] (M), [Ni(H20 )6]CI2 (N),
.~(Pt(CN)4] (0) and [~O)6] (N03)2 (P)
the diamagnetic complexes are
W~~~N ~~~~p ~~~~P~~~~O
r
"
,.-"'\
('-'"
(~
Co-ordination Compounds (44)

c
Ii!'!'.'~~~CL~~~~!
IdeolfQ,Sdu>lcrs
--
\
AN'SW'ER KEY'S
EXERCISE # I
; Q.l A Q.2 C Q.3 B QA D Q.5 B Q.6 D Q.7 C

Q.8 B Q.9 D Q.10 C Q.ll C Q.12 B Q.13 A Q.14 B
Q.15 C Q.16 D Q.17 A Q.18 D Q.19 D Q.2() C Q.21 D
'Q.22 A Q.23 C Q.24 B Q.25 B - Q.26 D Q.27 C Q.28 D
Q.29 A Q.30'C Q.31 A Q.32 C Q.33 A Q.34 C Q.35 B
r
\ Q.36 A Q.37 D Q.38 C Q.39 D QAO D QAl B QA2 B
(Q.43
, -,B QA4 C QA5 B QA6 C QA7 C QA8 A ,QA9 A
Q.50 A Q.51 A Q.52 D Q.53 C Q.54 C Q.55 B Q.56 B
I'
'Q.57 D Q.58 D Q.59 C Q.60 C Q.61 C Q.62 C . Q.63 A
Q.64 C Q.65 A Q.66 C Q.67 B Q.68 D Q.69 A Q.70 A.
"Q.71 C Q.72 B Q.73 D Q.74 C Q.75 B Q.76 D Q.77 C
\ Q.78 A Q.79 C Q.80 C Q.81 C Q.82 C Q.83 D Q.84 B
C~.85 A Q.86 D Q.87 D Q.88 A Q.89 A Q.90 B Q.91 B
Q.92 C Q.93 A Q.94 C
f ' EXERCISE # II
"
( :l.1 A Q.2 C Q.3 A QA C Q.5 C Q.6 A Q.7 C
Q.8 A Q.9 D Q.10 C Q.ll A Q.l2 B Q.13 B Q.14 B
(Q.15 C Q.16 B Q.17 D Q.18 A Q.19 B Q.20 D Q.21 C
(~.22 D Q.23 C Q.24 C Q.25 A Q.26 D Q.27 C Q.28 B
rQ.29 B Q.30 C
\.
"
\
EXERCISE # III
I"~
~~.1 B Q.2 B Q.3 D QA A Q.5 C Q.6 B Q.7 A

(J.8 C Q.9 D Q.I0 C . Q.ll C Q.l2 A Q.13 B Q.14 D
(Q.15 D Q.16 A Q.17 C Q.18 D Q.19 D Q.20 A Q.21 C
Q.22. A Q.23 A Q.24 B Q.25 C Q.26 C Q.27 B Q.28 A
(~.29 A Q.30 B Q.31 D Q.32 C Q.33B . Q.34 D Q.35 D
(1.36 B Q.37 A Q.38 C Q.39 A QAO A
"/ Q.41 (A) P, Q, S; (B) P, R, S; (C) Q, S; (D) Q, S QA2 A QA3 C QA4 C
\...
(,~~----------------~~~~~--~----------------
~1!'!'.'~~~2t!!~ Co-ordination Compounds {45)
,{ .
c
\
J
~\
)

Bansal Chemistry 1

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r-) :

KEY CONCEPT•................................................................ Page 2 -14

SOVLED EXAMPLE ......~ .....•................•..••...................... Page 15 - 21

EXERCISE-II ............................................... ~ ................... Page 27 - 31

. ANSWER KEy.......................................................•........... Page 34

(A) 1° and 3° amine (B) Only primary amine

Ex.2 The third member of homologous series of.dimethyl amine ;.

Ex.4 N-atom in quaternary ammonium halide will have the form- c

SoL Hybridisation state ofcarbon changes from sp2 to sp3.

2.2. From Grignard reagent:

/'C =0 + 2HCONH2 ---7) )CH ­ NH- CHO + CO2 + NH3

( 2.6 From Alkanoic acid (Schimdt Reaction) :

2.7 From Acyl halide:

2.8 From Alkanamide :

2.9 By Alkyl cyanide (By reduction) :

2.10 From Alkyl isocyanate (Alkalin~ Hydrolysis) :

1i'~~~A~C~~~~! NITROGEN COMPOUNDS -

phthalic anhydride phthalimide N-alkyl phthalimide

2.13 By reductiou of Nitro compouuds:

Nitro alkanes are reduced catalytically to primary amine.

RNO reduction) RNH + 2H 0

" This is all due to H- Bonding.

[i!~~~.~~ CM~!~! IdullforSCholo"

3° > 2° > 1° > ammonia

+R~ >RNHRI +RzX

(quartenary ammo salts.) \ --'

RNH2 + CH3MgBr ether) CH4 + RNH.MgBr

R2NH + CH3MgBr CH4 + R 2N.Mg Br

Note: Tertiary do not react because of absence of active hydrogen.

5.3 Reaction with Aldehydes and K~tone:

(schiff's base or anil's base)

R-NH2 + CH3COCI ) RNHCOCH3 + HCI

R-NH2 + (CH3COhO ) RNHCOCH3 + CH3COOH

Note: (i) NH2-NH2 is called hydrazine

(ii) NHrOH is called Hydroxylamine

R3N + HCI ) (R3NHt CI-

These salts may undergo dealkylation at higher temp.

Reaction with HN0 2 : This reaction distinguishes 1°,2° and 30 alcohols.

CH3NH2 + 2F1N02 )CH3-O-N ='0 + N2 + H 20

5.9 Isocyanide test or Carbylamine reaction:

C6H s-S02-CI. (Benzene sulphonyl chloride)

RNH2 + CI - S02-C6HS -----? R-NH-S02-C6H s + HCl

(a) Primary amines form N-Alkyl benzene sulphonamide

(b) Secondary amines form N, N-dialkyl benzene sulphonamide

R-NH2 + NOCI ) R-CI + N2 + H 20

·5.13 Reaction with Caro's acid [HzSOs1 :

.R3CNH2 (oJ) R3CNO (nitrosoalkane)

Ex.7 R-C-NH2 Br./KOH) R~ CSH5

6.2 Hofmann method:

6.3 Fractional distillatic)D :

CYANIDES, ISOCYANIDES, ALKYL NITRITES AND NITRO ALKANES \

1.1 GENERAL CHARACTERISTICS:

Formnla As cyanide WPACname

CH3CN Methyl cyanide Ethane nitrile

C3H 7CN Propyl cyanide Butane nItrile

CH3NC Methyl isocyanide . Methylcarbylamine

(Methyl isonitrile) (Carbylamino methane)

C2HSNC Ethyl isocyanide Ethyl carbylamine

(Ethyl isonitrile) (Carbylamino ethane)

C3H7NC Propyl isocyanide Propyl carbylamine .

(propyl isonitrile) (Carbylamino propane)

Alkyl cyanide Alkyl isocyanide

.1.2 ALKYL CYANIDES

atoms in the molecule.

/'C =0 + 2HCONH2 ---7) )CH NH- CHO + CO2 + NH3

[i!~. CM~!~! IdullforSCholo"

Ex.9 Alkyl halide reacts with AgCN to form

Ex.tO Amide on heating with P 205 gives

Ex.1 An example ofa primary amine is

, Ex.2 For the elimination of - C- group ofamide following reaction is used

( Ex.3 Which of the following is hydrolysed to give secondary amine

c Ex.S In hypobromite reaction of amide, carbonyl carbon atom is lost as

The answer is

Ex.9 FormaldoXime on reaction with Na/EtpH giveS

Ex.10 Which of the following compounds on reduction gives an amine

" Ex.ll An alkyl amine is prepared by the following reaction

Ex.IS Which compound is soluble in water

Ex.16 Which compound will liberate CO~ from NaHC03 solution

Ex.24 Mustard oil reaction is given by

Q.ll A reaction used in descending a homologous series would be

Q.12 Reaction for the preparation of 10 amine is

Q.13 On reduction of Schiff's base we get

Q.14 In Hofmann degradation of amide the correct order of reagent is

( Q.15 Ethylamine can be prepared by the all except

Q.24 Which statement is not correct

Q.25 The basic characterofamines can be explained

Q.26 Amines are basic in nature because

Q.28 Which of the following diazonium salt is relatively stable of 0-5°C

. Q.29 Lowest boiling point will be of the compound