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InorgChem d-Block Elements

Properties
TRANSITION ELEMENTS are elements, which forms at least one compound in which the element has in incompletely filled inner d su!shell "lements with at least one o#idation state in which the element has incompletely filled inner d su!shell $i.e. w/1 to 9 e%& 'candium $'c& ( )inc $*n& are not transition elements as !oth has only one o#idation state 'c+, ( *n2,, which !oth has no incompletely filled d su!shell d-BLOCK ELEMENTS are elements whose highest energy electron / last filled electron is found in the d or!ital "lement atoms with electronic configuration - .$n+1&s2nd x /irst transition series0 'c, 1i, 2, 3r, 4n, /e, 3o, 5i, 3u, *n

Electronic configuration:
6toms of d !loc7 elements are characteri)ed !y inner !uilding of d su!shells 4ost contains the configuration - .nd x$n+1&s2 "#cept0 3r $*829&0 -6r.+d59s1 and 3u $*829&0 -6r.+d1:9s1 1he 2, ions of d !loc7 elements ha;e no e% in the ;alence s or!ital 3onfiguration0 - .nd x

Typical properties of Transition elements:

Properties similar to s !loc7 elements 4etals <ood conductor of electricity ( heat 4P =P Properties different from s !loc7 elements >ard, strong, high 0 'trong ( closely pac7ed struct. due to delocali)ation of 9s ( +d e% 'imilar chemical properties0 ?utermost su!shell 8 9s2 2aria!le o#idation state0 'uccessi;e @" are close 6!ility of formation of comple#es0 6;aila!ility of low lying d ;acant or!itals 3pds are colored0 'plitting of d su!shell into different energy le;els after comple# formation 3atalytic !eha;ior0 6!ility to form comple#es ( the e#istence of ;aria!le o#idation states 'c ( *n do not e#hi!it typical properties of transition elements

Variation of Properties
Ionization Enthalpy:
d =loc7 elements has 9d su!shell filled !efore +d su!shell =efore filling, 9s has lower energy than +d 6fter filling d or!ital, +d has lower energy than 9s e% in d or!ital screens 9s as it is more penetrating Ahen d !loc7 metal ioni)es, the 9s e% are first remo;ed Bifference in energy !tw +d ( 9s su!shells is small, successi;e @" increases gradually 6cross the 1st transition series, @" increases slightly 6dditional e% is added to inner +d su!shell and screens the 9s e%, which is !eing ioni)ed 'creening effect cancels most the increase in "53 1st @" of 'c C *n > 1st @" of D ( 3a as the "53 inc. Bue to the small ( gradual increase in @", transition elements ha;e similar chemical properties

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Metallic Radius:
/actors affect the metallic radius of d !loc7 metals0 "53 on the outermost e%0 inc. from 'c to *n Eepulsion !tw the d electrons0 inc. from 'c to *n 6ll d !loc7 metals ha;e smaller atomic radii than s !loc7 in same period due to the inc. of "53 6cross the period from 'c to *n, 6tomic radius dec. slightly from 'c to 3r0 'light increase of "53 3r to 5i ha;e nearly constant atomic radius0 @ncreasing "53 ( repulsion cancelled out 6tomic radius inc from 5i to *n0 Eepulsion !tw e% increases as * increases ?;erall ;ariation in atomic radius is small $:.12 % :.16 nm&0 e% is in inner +d su!shell

Ionic Radius:
2ariation of ionic radius of d !loc7 elements is similar to that of atomic radius 6ll d !loc7 metals ha;e smaller ionic radii than s !loc7 due to the inc. of "53 6cross the period, the ionic radius from 'c to 3u dec. slightly as the slightly inc. of "53 @onic radius of *n2, is slightly larger than e#pected as the full filled +d1: produces a larger electronic repulsion

Melting Point & Hardness:

4P ( >ardness of metal 4etallic !ond strength d =loc7 elements usually ha;e higher 4P ( hardness =oth s ( d e% are delocali)ed to the electron sea and ta7e part in the metallic !ond 'trong metallic !ond 4ost d !loc7 elements are closely pac7ed $3oordination num!er 8 12& 6tomic radii of d !loc7 elements are smaller 4P =P as only small fraction of metallic !onds has to !e !ro7en in melting !ut all metallic !onds are !ro7en in !oiling $i.e. =oiling 8 6tomi)ation& /actor affecting the 4P ( hardness of 'c to *n 'maller atomic radius 'tronger metallic !ond 4ore unpaired d e% 4ore delocali)ed e% in metallic !ond 'tronger metallic !ond 3loser pac7ing of atoms 'tronger metallic !ond >alf filled or full filled d su!shell are e#tra sta!le 6cross the period from 'c to *n, the 4P ( hardness @ncreased from 'c to 2 as the no. of unpaired d e% inc. ( atomic radius dec. 4etallic !ond strength increases Becreased from 2 to 4n as 3r ( 4n has e#tra sta!le +d5 4etallic !ond strength dec. @ncreased to a ma#. at /e, 3o, 5i as unpaired d e% are more in;ol;ed in metallic !ond Becreased from 3u to *n as !oth has e#tra sta!le +d1:

Density:
d =loc7 elements usually ha;e higher densities than s !loc7 elements as the atoms are closely pac7ed 1he density increases from 'c to 3u as the relati;e atomic mass increases while atomic radii are appro#imately constant *n has a lower density than 3u as the +d ( 9s e% are less in;ol;ed in metallic !ond Farger atomic radius

Electronegativity:
6cross the period from 'c to *n, "53 increases "lectronegati;ity generally increases "ase of formation of metal ions dec. 4etallic character dec. d =loc7 elements are less electropositi;e / more electronegati;e than s !loc7 elements d =loc7 cations are less li7ely to form than s !loc7 4n has a lower electronegati;ity than e#pected Bue to low ioni)ation enthalpies0 "#tra sta!ility of 4n2,0 -6r.+d5 *n has particularly low electronegati;ity

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Bue to low ioni)ation enthalpies0 "#tra sta!ility of *n2,0 -6r.+d1: 1he standard electrode potential $" & has a similar ;ariation with electronegati;ity Ahen "53 on the outermost e% increases, " !ecomes more positi;e or less negati;e

!idation "tates:
1ransition metals show ;aria!le o#idation states0 'c ,1, ,2, ,+ 'c+, 1i ,1, ,2, ,+, ,9 1i2,, 1i+,, 1i?2 2 ,1, ,2, ,+, ,9, ,5 22,, 2+,, 2?2,, 2?2, 3r ,1, ,2, ,+, ,9, ,5, ,6 3r2,, 3r+,, 3r9,, 3r?+ 4n ,1, ,2, ,+, ,9, ,5, ,6, ,7 4n2,, 4n$?>&+, 4n?2, 4n?92%, 4n?9% /e ,1, ,2, ,+, ,9, ,5, ,6 /e2,, /e+, 3o ,1, ,2, ,+, ,9, ,5 3o2,, 3o+,, -3o/6.2% 5i ,1, ,2, ,+, ,9 5i2,, 5i+,, 5i2?+, 5i?2 3u ,1, ,2, ,+ 3u,, 3u2, *n ,1, ,2 *n2,
G 3omple# only 4ost sta!le state ?#idation states

1he e#istence of ;aria!le o#idation states due to gradual increases rather than sharp rapid rise of successi;e @" of transition metal 6cross the 1st transition series, /rom 'c to 4n, the highest possi!le ?5 8 1otal no. of e% in +d ( 9s 4a#imum ?5 found in 4n$2@@& =y remo;al of all +d ( 9s electrons from 4n /rom 4n onwards, the highest ?5 decreases as the no. of unpaired e% decreases 'ta!ility of a particular ?5 is related to e#tra sta!le state of half/full filled d or!ital 4n2, ( /e+, are particularly sta!le as they ha;e -6r.+d5 config. *n2, is particularly sta!le as it has -6r.+d1: config. "nthalpy of formation of an ion0 >f 8 >atom , @" , >hyd 6n ion of lower >f is energetically sta!le 6n energetically sta!le ion $e.g. 3u,& may !e unsta!le w.r.t. disproportionation0 3u$s& 3u,$aH& >f 8 ,6:6 7Imol%1 3u$s& 3u2,$aH& >f 8 ,971 7Imol%1 $less sta!le& Bisproportionation0 23u,$aH& 3u$s& , 3u2,$aH& > 8 %291 7Imol%1 ?ccurs spontaneously ( energetically fa;ora!le

#ormation of $olored $pds:

4ost s !loc7 metals form colorless cpds !ut most d !loc7 metals form colored cpds "#ception0 'c+,, 1i9, 3u,, *n2, Ahen transition metal forms cpd, 1he electrons in s shell is remo;ed d shell !ecomes the outermost shell 1he d or!itals may split into different energy le;els in cpd 1he splitting is due to the electronic repulsion !tw d e% and FP e% of anion / ligand @f the metal ion has d shell neither full filled nor empty, e% in lower energy le;el can Jump to a higher or!ital 6!sor!s electromagnetic radiation of a particular freHuency 6!sorption in the ;isi!le light region ma7es the ion colored 3olor of aHueous ion0 'c+, 3olorless 1i+, Purple 1i9, 3olorless 22, 2iolet 2+, <reen 2?2, =lue 2?2, Kellow 2?+% Eed 2, +, 3r =lue 3r <reen 4n2, Pale pin7 4n$?>&+ =rown 4n?2 =lac7 4n?92% <reen 4n?9% Purple /e2, <reen /e+, Kellow 2, 3o Pin7 5i2, <reen 3u, <reen 3u2, =lue *n2, 3olorless 'ome transition metals show colored flame when !urned as the e#citation of e%

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Eadiation in ;isi!le spectrum is emitted when the e% falls !ac7

Reaction %ith %ater:

d =loc7 metals usually react slowly with water 1he low reacti;ity of d !loc7 metals is due to its high @" ( >atom "#ception0 'c , hot water 'c$?>&+$aH& , >2$g&

Vanadium & Manganese

&anadium:
2anadium is a soft ( sil;ery white metal 3ommon o#idation states0 ,2, ,+, ,9, ,5 Kellow 2?2,, =lue 2?2,, <reen 2+,, 2iolet 22, respecti;ely 2anadium can react w/o#idi)ing acids >5?+ ( >2'?9 2anadium$2&0 Bio#o;anadium$2& ion 2?2, is produced !y dissol;ing ammonium polytrio#o;anadate$2&0 5>92?+$aq& , 2>,$aq& 2?2,$aq& , 5>9,$aq& , >2?$& 2?+%$aq& , 2>,$aq& 2?2,$aq& , >2?$& 5either 25, nor -2$>2?&6.5, e#ists as the charge density is e#tremely high >ydrolysis occurs0 25,$aq& , 2>2?$aq& 2?2,$aq& , 9>,$aq& @t is a sta!le o#idation state of 2 2anadium$2& o#ide, 22?5, is an amphoteric o#ide0 22?5$s& , 2>,$aq& 22?2,$aq& , >2?$& 22?5$s& , 6?>%$aq& 22?9+%$aq& , +>2?$& 2anadium$@2&0 ?#o;anadium$@2& ion 2?2, can !e produced !y reacting 2?2, with metal0 *n$s& *n2,$aq& , 2e% 2?2,$aq& , 2>,$aq& , e% 2?2,$aq& , >2?$& 5either 29, nor -2$>2?&6.9, e#ists as the charge density is e#tremely high 2anadium$@@@& ( 2anadium$@@&0 2+, and 22, ions can !e produced !y reducing 2?2, !y metal0 2?2,$aq& , 2>,$aq& , e% 2+,$aq& , >2?$& 2+,$aq& , e% 22,$aq& =y adding e#cess *n granules or *n amalgam in acidic condition $conc. >3l&, 2?+%$aq& 2?2,$aq& 2?2,$aq& 2+,$aq& 22,$aq& =oth 2+, and 22, ions are reducing and readily o#idi)ed !y air or water

Manganese:
4anganese is a hard, pin7ish grey metal 3hemically acti;e and rapidly attac7ed !y hot water, steam or acid0 4n$s& , 2>2?$& 4n$?>&2$s& , >2$g& 4n$s& , >2?$g& 4n?$s& , >2$g& , 4n$s& , 2> $aq& 4n2,$aq& , >2$g& 3ommon o#idation state0 ,2, ,9, ,7 4anganese$@@&0 1he pale pin7 4n2, ion is ;ery sta!le in acids $partly due to +d5 config.& @t forms comple# -4n$>2?&6.2, in water and undergoes slight hydrolysis -4n$>2?&6.2,$aq& -4n$?>&$>2?&5.,$aq& , >,$aq& @n al7aline medium, 4n2, would !ecomes white 4n$?>&20 -4n$>2?&6.2,$aq& , 2?>%$aq& -4n$?>&2$>2?&5.$s& , 2>2?$& 1he 4n$?>&2 in al7aline is readily o#idi)ed !y ?2, >2?2, ?3l% to unsta!le 4n$?>&+$s& and finally to 4n?2$s&0 94n$?>&2$s& , ?2$g& , 2>2?$& 94n$?>&+$s& 24n$?>&+$s& , $n%+&>2?$g& 4n2?+n>2?$s& 24n2?+n>2?$s& , ?2$g& 94n?2$s& , $2n&>2?$& 24n$?>&2$s& , ?2$g& 24n?2$s& , 2>2?$&

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4anganese$@2&0 4n?2 is a dar7 !rown amphoteric solid w/strong o#idi)ing property0 4n?2$s& , 9>,$aq& , 2e% 4n2,$aq& , 2>2?$& 4n?9 can o#idi)e 3l% in >3l$aq&0 4n?2$s& , 9>3l$aq& 4n3l2$aq& , 2>2?$& , 3l2$g& 4n?9 can !e o#idi)ed !y strong o#idi)ing agent in !asic medium0 +4n?2$s& , 6?>%$aq& , 3l?+%$aq& +4n?92%$aq& , +>2?$& , 3l%$aq& 24n?2$s& , 9?>%$aq& , ?2$g& 24n?92%$aq& , 2>2?$& 4anganese$2@@&0 4n2?7 is acidic co;alent compound Purple manganate$2@@& ion 4n?9% is a powerful o#idi)ing agent0 6cidic medium0 4n?9%$aq& , 8>,$aq& , 5e% 4n2,$aq& , 9>2?$& 6l7aline medium0 4n?9%$aq& , 2>2?$& , +e% 4n?2$s& , 9?>%$aq& 4n?9% can react w/iron$@@@& ion0 4n?9%$aq& , 8>,$aq& , 5/e2,$aq& 4n2,$aq& , 9>2?$& , 5/e+,$aq&

Complexes
$omple!:
6 comple# $coordination compound& is formed when a central metal ion/atom is attached !y ligands in which the no. of ligands is greater than the normal ;alance of the central ion/atom 1he metal ion/atom acts as an electron pair acceptor $Fewis acid or electrophile& 1he metal ion/atom ought to !e has high positi;e charge density to attract the ligands 1he ligand acts as an electron pair donor $Fewis !ase or nucleophile& COMPLEX0 6 central metal ion/atom surrounded !y and dati;ely !onded to other ligands LIGAND0 6n ion or molecule containing at least one atom ha;ing a lone pair of electrons which can !e donated to the central cation or atom to form a dati;e co;alent !ond COORDINATION NUMBER of the central ion is the num!er of ligands !onded to the central ion d =loc7 metal has strong tendency towards comple# formation as the a;aila!ility of low lying ;acant or!itals ena!les metal ions to accept FP e% from ligands

'omenclature:
3oordination compounds are named according to the nomenclature recommended !y @LP63 @onic coordination compounds0 3ation is name !efore the anion 1he ligands and central metal are named together as one word ?rder of ligands0 6nionic, 5eutral, 3ationic "#ample0 -Pt3l2$5>+&9.2, 8 Bichlorotetraammineplatium$@2& 5ames of anionic ligands end in %o 5ames of neutral ligands are the names of the molecules, e#pt 5>+, >2?, 3?, 5? 5ames of common ligands0 LIGAND PREFIX LIGAND PREFIX =romide =r% =romo 6mmonia 5>+ 6mmine 3hloride 3l% 3hloro Aater >2? 6Hua 3yanide 35% 3yano 3ar!on mono#ide 3? 3ar!onyl /luoride /% /luoro >ydro#ide ?>% >ydro#o 'ulphate$2@& '?92% 'ulphato 6mide 5>2% 6mido @f the no. of a particular ligand is more than one, the num!er is indicated w/<ree7 prefi#0 Aithin each type of ligand, the ligands are arranged in alpha!etical order, ignoring the num!ering prefi#es NUMBER PREFIX NUMBER PREFIX 1wo Bi /i;e Penta 1hree 1ri 'i# >e#a /our 1etra @f the comple# is anionic, the name of the metal ends in %ate

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"#ample0 -/e$35&6.+% 8 >e#acyanoferrate$@@@& 5ames of common metals in anionic comple#es0 METAL NAME METAL NAME 1itanium 1itanate 5ic7el 5ic7elate 3hromium 3hromate 3opper 3uprate 4anganese 4anganate *inc *incate @ron /errate Platinum Platinate 3o!alt 3o!altate @f the comple# is cationic or neutral, the name of the metal is unchanged "#ample0 -3r3l2$>2?&9., 8 BichlorotetraaHuachromium$@@@& 5eutral coordination compounds0 1he name of the comple# is the name of the cpd

(onding & "ta)ility:

Figand contains FP e% which forms dati;e !onds with the central metal Bifferent ligand has different tendency to donate their unshared electrons to form dati;e !ond 1he strength of the dati;e co;alent !ond of differs as the ligands differ 6 ligand can !e replaced !y another ligand which form more strong dati;e !ond i.e. the ligand that of higher tendency to donate the electrons Ahen a stronger ligands present, the wea7er ligand would !e replaced0 -/e$>2?&6.2,$aq& , 635%$aq& -/e$35&6.9%$aq& , 6>2?$& -5i$>2?&6.2,$aq& , 65>+$aq& -5i$5>+&6.2,$aq& , 6>2?$& @n the displacement of ligands of the comple#, usually there would !e color change 1he formation of comple# or displacement of ligand is a stepwise reaction @n -3u$>2?&6.2,$aq& , 95>+$aq& -3u$5>+&9$>2?&2.2,$aq& , 9>2?$&0
-3u$>2?&6.2,$aq& , 5>+$aq& -3u$5>+&$>2?&5.2,$aq& , 5>+$aq& -3u$5>+&2$>2?&9.2,$aq& , 5>+$aq& -3u$5>+&+$>2?&+.2,$aq& , 5>+$aq& -3u$5>+&$>2?&5.2,$aq& , >2?$& -3u$5>+&2$>2?&9.2,$aq& , >2?$& -3u$5>+&+$>2?&+.2,$aq& , >2?$& -3u$5>+&9$>2?&2.2,$aq& , >2?$& D1 8 1.911:9mol%1dm+ D2 8 +.161:+mol%1dm+ D+ 8 7.771:2mol%1dm+ D9 8 1.+51:2mol%1dm+

[-3u$5> & $> ?& . ] = D D D= [-3u$> ?& . ] [ 5> ]

2+ + 9 6 2 2 2+ 9 1 2 +

D1, D2, D+, D9 are called stepwise sta!ility constant 1he eHuili!rium constant of o;erall reaction0
2

D+ D 9

D is called the sta!ility constant of the comple# and it gi;es a measure of the sta!ility of the comple# ion 1he comple#es with large sta!ility constant is sta!le

"tereostructure:
1he spatial arrangement of ligands around the central metal is related to the coordination num!er 1he coord. no. is determined !y0 'i)e of the central metal 5o. and nature of ;acant or!itals for forming dati;e !onds F <enerally the coord. no. is constant for a particular metal atom / ion F F 3ommon coordination num!ers0 2, 9, 6 4 F F 3oordination num!er 8 60 @n comple#es with coord. no. of 6, the structure usually is octahedral0 F +, +% "#ample0 -3r$5>+&6. and -/e$35&6. F F 4 3oordination num!er 8 9 F F F @n comple#es with coord. no. of 9, the structure usually is tetrahedral0 "#ample0 -*n$5>+&9.2, and -3o3l9.2% 4 F 6 few four coordinated comple#es are ha;ing sHuare planar structure0 F F "#ample0 -3u$5>+&9.2, and -3u3l9.2% 1he -3u$5>+&9.2, and -3u3l9.2% comple# should !e si# coordinated and in octahedral structure, !ut the two >2? is loosely !onded and ignored usually >2? 53 35 @somerism occurs in the comple#es0 3u 'tructural isomers0 Bifferent ligands coordinated to the central metal 35 53 >2?

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"#ample0 -3o$5>+&5=r.2,'?92% and -3o$5>+&5'?9.,=r% <eometrical isomer0 Bifferent geometrical arrangement of ligands 'Huare planar comple#es0 a a ! ! 4 4 and -4a2!2.0 a ! ! a a a c c 4 4 and -4a2!c.0 a ! ! a d ! c d ! d 4 4 4 , and -4a!cd.0 a a ! a c c

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?ctahedral comple#es0 a ! a a 4 and -4a9!2.0 ! a a a ! ! a a 4 and -4a+!+.0 ! a a a

! ! 4 a a ! ! 4 a !

Catalysis
$atalytic action:
d =loc7 elements and their cpds are common catalysts in industry ( !iological systems =y pro;iding suita!le reaction surfaces, or =y forming unsta!le intermediates 3ommon catalysts0 22?5 or 2?+%0 3ontact process, 2'?2$g& , ?2$g& +'?+$g& /e or /e2?+0 >a!er process, 52$g& , +>2$g& 25>+$g& 4n?20 Becomposition of hydrogen pero#ide, 2>2?2$& 2>2?$& , ?2$g& 5i0 4anufacture of margarine, E3>83>2 , 2>2$g& E3>23>+ Pt0 4anufacture of nitric$2& acid, 95>+$g& , 5?2$g& 95?$g& , 6>2?$&

Heterogeneous catalysis:
@n heterogeneous catalysis, the catalyst and reactants are in different phases Lsually, the catalyst are finely di;ided solids 1he heterogeneous catalyst pro;ides a suita!le reaction surface for reactants to come close together and react "#ample, catalysis of gaseous reaction on solid surfaces li7e >a!er process ?utlined mechanism0 1he gaseous reactant diffuse to the catalyst 1he catalytic surface adsor!s one reactant $3at , E1 3at%E1& 1he catalytic surface adsor!s another reactant $3at , E2 3at%E2& =ond !rea7ing ( forming !tw catalyst ( reactants $3at%E1 , 3at%E2 3at%E2%E1%3at& 1he products desor!ed and diffused away $3at%E2%E1%3at E1%E2& 1he a!undance of ;alence e% and a;aila!ility of ;acant or!itals in d !loc7 elements facilitate the surface adsorption of reactants 1he adsorption !rought the reactants within close pro#imity to cataly)e reaction

Homogeneous catalysis:
@n homogeneous catalysis, the catalyst and reactants are in same phase 1he catalyst form an intermediate with the reactants to cataly)e reaction Eeaction mechanism is changed such that "6 is lower "#ample0 '2?82%$aq& , 2@%$aq& 2'?92%$aq& , @2$aq& is slow due to 7inetic factors /e+, can cataly)e the reaction as /e2,$aq& , e% /e2,$aq&0 2@%$aq& , 2/e+,$aq& @2$aq& , 2/e2,$aq& 2/e2,$aq& , '2?82%$aq& 2'?92%$aq& , 2/e+,$aq& /e+, o#idi)es iodide ions and gi;es /e2,, !ut /e2, reduces pero#odisulphate$2@& and gi;es /e+, 1he catalyst is unchanged at last