Chapter:8ThedandfBlockElements

POINTSTOBEREMEMBERED:
1. Theelementsofperiodictablebelongingtogroup3to12areknownasdBlockelements.
2. Thegeneralelectronicconfigurationoftheseelementsis(n1)d110ns12
3. dBlockelementsarecollectivelyknownasTransitionElementsbecausepropertiesofthese
elementsvaryinbetweensBlockandpBlockelements.
4. Atransitionelementshouldhavepartiallyfilled(n1)dorbital.
5. Group12elementsi.e.Zn,Cd,Hghavecompletelyfilled(n1)dorbitalinatomic&ionicstate&
thustheseelementsareconsideredasTypicalTransitionElements.
6. All these elements are metals. They are less electropositive than sblock elements & more
electropositivethanpblockelements.
7. The atomic radii decreases from group 3 to 6 (i.e. Sc to Cr) because of increase in effective
nuclearchargegradually.
8. Theatomicradiiofgroup7,89&10elements(i.e.Fe,Co,Ni)isalmostsamebecausepairingof
electronstakeplacein(n1)dorbitalcausingrepulsioni.e.shieldingof(n1)dorbital.
9. Group11&12elementsi.e.Cu&Znhavebiggersizeduetostrongshieldingofcompletelyfilled
(n1)dorbital.
10. Thetransitionelementsshowvariableoxidationstateduetosmallenergydifferencebetween
(n1)d&nsorbitalasaresultboth(n1)d&nselectronstakepartinbondformation.
11. Thehighestoxidationstateofanelementisequaltonumberofunpairedelectronspresentin
(n1)d&nsorbital.
12. Transitionelementshavehighenthalpyofatomization/sublimationBecauseoflargenumber
of unpaired electrons in their atoms, they have stronger interatomic interaction and hence
strongmetallicbondingispresentbetweenatoms.
13. Mostoftransitionelementsareparamagneticduetopresenceofunpairedelectronsin(n1)
dorbital.
14. Mostoftransitionelementsareusedascatalyst.Itisdueto(i)partiallyfilled(n1)dorbital(ii)
Variableoxidationstate(iii)Abilitytochangeoxidationstatefrequently.
15. Mostoftransitionelementsformcolouredcompoundsduetopresenceofunpairedelectrons
in(n1)dorbital&thustheycanundergoddtransition.
16. Mostoftransitionelementsformcomplexcompoundsdueto(i)smallsize(ii)highcharge(iii)
presenceofvacantdorbitalofsuitableenergy.
17. TransitionelementshavelowervalueofReductionPotentialduetohighionizationpotential,
highheatofsublimation&lowenthalpyofhydration.
18. Transitionelementsforminterstitialcompoundsbecausesizeofinterstitialvoidsissimilarto
sizeofnonmetalsC,N,O,H.
19. Transitionelementsformalloysduetosimilarionicradii.
20. TheoxidesoftransitionmetalsinloweroxidationstateareBASIC,intermediateoxidationstate
areAMPHOTERIC,highestoxidationstateareACIDIC.
LANTHANOIDS:
1. The14elementsafterLanthanumhavingatomicnumber58to71arecollectivelyknownas
Lanthanoids.
2. Thegeneralelectronicconfigurationoftheseelementsis[Xe]4f114,5d01,6s2.
3. Mostcommonoxidationstateoftheseelementsis+3,butCeshows+4,Eu+2,becausethey
acquirestableconfiguration.
4. ThesizeofLanthanoidsanditstrivalentiondecreasesfromLatoLuduetopoorshielding
of4felectrons.Itisknownaslanthanoidscontraction.
ACTINOIDS:
1. The14elementsafterActiniumhavingatomicnumber90to113arecollectivelyknown
asActinoids.

2. Thegeneralelectronicconfigurationoftheseelementsis[Rn]5f114,6d01,7s2.
3. ThesizeofactinoidsanditstrivalentiondecreasesfromActoLwduetopoorshielding
of5felectrons.Itisknownasactinoidscontraction.
4. TheelementsafterU(92)aremanmadeknownastransuranicelements.
POTASSIUMDICHROMATE:
Preparation:Ittakesplaceinthreesteps
(i) Conversionofchromiteoretosodiumchromate.
(ii) Conversionofsodiumchromatetosodiumdichromate.
(iii) Conversionofsodiumdichromatetopotassiumdichromate
Followingreactiontakeplace:
4FeCr2O4+4Na2CO3+7O2
2Na2CrO4+2Fe2O3+8CO2
2Na2CrO4+2H+
Na2Cr2O7+2KCl

Na

2Cr2O7+2Na

++H O
2

K2Cr2O7+2NaCl

ThechromatesanddichromatesareinterconvertibleinaqueoussolutiondependinguponPhof
thesolution.
A) InAcedicmedium(PH<7)
2CrO42+2H+Cr2O72+H2O
B) Inbasicmedium(PH>7)
C) 2CrO72+2OHCr2O42+H2O

POTASSIUMPERMANGNATE:
Preparation:

Ittakesplaceintwosteps:
(i) Conversionofpyrolusiteoreintopotassiummagnate
(ii) Conversionofpotassiummagnatetopotassiumpermaganate
Followingreactionstakeplace:
2MnO2+4KOH+O2
2K2MnO4+2H2O
2
+
3MnO4 +4H
2MnO4+MnO2+2H2O

QUESTIONANSWERS
(TWOMARKQUESTIONS)
Q.1Explainbrieflyhow+2oxidationstatebecomesmoreandmorestableinthefirsthalfofthe
firstrowtransitionelementswithincreasingatomicnumber.
A.1In M2+ ions, 3dorbitals get occupied gradually as the atomic number increases. Since, the
numberofemptydorbitalsdecreases,thestabilityofcationsincreasesfromSc2+toMn2+.Mn2+is
moststableasalldorbitalsaresinglyoccupied.

Q.2Explainwhytransitionelementshavemanyirregularitiesintheirelectronicconfigurations?
A.2Inthetransitionelements,thereisalittledifferenceintheenergyof(n1)dorbitalsandns
orbitals. Thus, incoming electron can occupy either of shell. Hence, transition elements exhibit
manyirregularitiesintheirelectronicconfigurations.
Q.3WhataredifferentoxidationstatesexhibitedbyLanthanides?
A.3The common stable oxidation state of lanthanides is +3.However some members also show
oxidationstatesof+2&+4.
Q.4How isthe variabilityin oxidation statesof transition metals different from that ofthe non
transitionmetals?Illustratewithexamples.
A.4The transition elements useits (n1)d, ns and np orbital and the successive oxidation states
differbyunity.Forexample,Mnshowsalltheoxidationstatesfrom+2to+7.Onotherhandnon
transitionelementsuseitsns,npandndorbitalsandthesuccessiveoxidationstatesdifferbytwo
unitse.g.Sn2+,Sn4+etc.
Q.5Whydotransitionelementsshowvariableoxidationstates?
A.5Thetransitionelementsshowvariableoxidationstateduetosmallenergydifferencebetween
(n1)d&nsorbitalasaresultboth(n1)d&nselectronstakepartinbondformation.
Q.6WhyareMn2+compoundsmorestablethanFe2+compoundstowardsoxidationto+3state?
A.6TheelectronicconfigurationofMn2+is[Ar]3d5,i.e.allfivedorbitalsaresinglyoccupied.Thus
thisisstableelectronicconfiguration and further loss ofelectronrequireshighenergy.onother
hand side the electronic configuration of Fe2+is [Ar] 3d6, i.e. Loss of one electron requires low
energy.
Q.7To what extend do the electronic configuration decide the stability of oxidation state in the
firstseriesofthetransitionelements?Illustrateyouranswerwithanexample.
A.7Inatransitionseries,theoxidationstatewhichleadtoexactlyhalffilledorcompletelyfilled
orbitals are more stable.e.g. the electronic configuration of Fe is [Ar] 3d6 ,4s2. It shows various
oxidationstatebutFe(III)ismorestablethanFe(II).
Q.8Whatismeantbydisproportionation?Givetwoexamples.
A.8Thosereactionsinwhichsamesubstanceundergoes oxidationaswellasreductionarecalled
disproportionationreactions.e.g.
2Cu+Cu2++Cu
3MnO42+4H+2MnO4+MnO2+2H2O
Q.9Whichmetalinthefirstseriesoftransitionmetalsexhibits+1oxidationstatemostfrequently
andwhy?
A.9Copperwithconfiguration[Ar]3d104s1exhibits+1oxidationstate.Copperloses4s1electron
easilyandachievedastableconfiguration3d10byformingCu+.
Q.10Whatareinnertransitionelements?
A.10Thefblockelementsinwhichthelastelectronaccommodatedon(n2)fsubshellarecalled
innertransitionelements.Theseincludeatomicnumbers58to71andfrom90to103.
Q.11 The paramagnetic character in 3dtransition series elements increases upto Mn and then
decreases.Explainwhy?
A.11 In the 3dtransition series as we move from Sc (21) to Mn (25) the number of unpaired
electronsincreasesandhenceparamagneticcharacterincreases.AfterMn,thepairingofelectrons
inthedorbitalstartsandthenumberofunpairedelectronsdecreasesandhence,paramagnetic
characterdecreases.
Q.12 Comment on the statement that elements of the first transition series possess many
propertiesdifferentfromthoseofheaviertransitionmetal
A.12Thefollowingpointsjustifythatthegivenstatementistrue:
(i)Ionizationenthalpiesofheaviertransitionelementsarehigherthantheelementsof3dseries.
Consequently,heaviertransitionelementsarelessreactiveincomparisonto3delements.
(ii)Meltingpointsofheaviertransitionelementsarehigherthan3delements.
(iii) Higher oxidation states of heavier transition elements are stable whereas lower oxidation
statesarestablein3delements.
Q.13What are transition elements? Which dblock elements are not regarded as transition
elementsandwhy?

A.13Anelementwhichhaspartiallyfilled(n1)dorbitalisknownastransitionelements.Group
12 elements i.e. Zn, Cd, Hg have completely filled (n1) dorbital in atomic & ionic state & thus
theseelementsarenotconsideredasTransitionElements.
Q.14What are interstitial compounds? Why are such compounds well known for transition
metal?
A.14Compoundsoftransitionmetalwithrelativelysmallernonmetalsareknownasinterstitial
compounds.Thesecompoundsarewellknown fortransitionmetalsbecausesizeofC,N,O,andB
issimilartosizeofinterstitialvoidsoftransitionmetal
Q.15ForthefirstrowoftransitionmetalstheE0valuesare:
E0values V
Cr
Mn
Fe
Co
Ni
Cu
M2+/M
1.18
0.91
1.18
0.44
0.28
0.25
+0.34
Explaintheirregularityintheabovevalues.
A.15TheE0(M2+/M)valuesarenotregularwhichcanbeexplainedfromtheirregularvariationof
ionizationenergyandsublimationenergyofMnduetohalffilledorbitals.
(THREEMARKQUESTIONS)
Q.1Decidegivingreasonwhichoneofthefollowingpairsexhibitsthepropertyindicated:
(i)Sc3+orCr3+exhibitsparamagnetism
(ii)VorMnexhibitsmorenumberofoxidationstates
(iii)V4+orV5+exhibitscolour
A.1(i)Sc=[Ar]3d14s2;
Sc3+=[Ar];ithasnounpairedelectronsodiamagnetic
Cr3+=[Ar]3d3;ithasthreeunpairedelectronsparamagnetic
Cr=[Ar]3d54s1;
3
2
(ii)V=[Ar]3d 4s
Mn=[Ar]3d54s2 ThusVexhibitoxidationstatesof+2,+3,+4,+5
WhereasMnexhibitoxidationstatesof+2to+7.
(iii)V4+=[Ar]3d1coloured
V5+=[Ar]colourless
Q.2(a)Describethegeneraltrendsinthefollowingpropertiesofthefirstseriesofthetransition
elements:
(i)Stabilityof+2oxidationstate
(ii)Formationofoxometalions
(b)WritestepsinvolvedinthepreparationofKMnO4fromK2MnO4
A.2(a)iTheelementsoffirsttransitionseriesshowdecreasingtendencytoformdivalentcation
aswemovelefttorightintheseries.Thistrendisduetogeneralincreaseinthefirstandsecond
ionizationenergy.ThegreaterstabilityofMn2+isduetohalffilledd5configurationandthatofzinc
isduetod10configuration.
(ii)AllmetalexceptScfromoxideoftypeMOwhicharebasic.Thehighestoxidationnumberinall
oxide,coincidewiththegroupnumberandisattaininSc2O3toMn2O7.Formationofoxoanionsis
duetohighelectronegativityandsmallsizeofoxygenatom.
2(b)Ittakesplaceintwosteps:
(iii) Conversionofpyrolusiteoreintopotassiummangnate.
(iv) Conversionofpotassiummangnatetopotassiumpermanganate.
Followingreactionstakeplace:
2MnO2+4KOH+O2
2K2MnO4+2H2O
2
+
3MnO4 +4H
2MnO4+MnO2+2H2O
Q.3(a)WritethestepsinvolveinthepreparationofK2Cr2O7fromchromiteore.
(b)WhatistheeffectofpHondichromateionsolution?
A.3(a):Ittakesplaceinthreesteps
(iv) Conversionofchromiteoretosodiumchromate.
(v) Conversionofsodiumchromatetosodiumdichromate.
(vi) Conversionofsodiumdichromatetopotassiumdichromate
Followingreactionstakeplace:
4FeCr2O4+4Na2CO3+7O2
2Na2CrO4+2Fe2O3+8CO2
Na2Cr2O7+2Na++H2O
2Na2CrO4+2H+
Na2Cr2O7+2KCl
K2Cr2O7+2NaCl

(b)Dichromateionisorangeinacidicsolution(pH<7)andturnsyellowinbasicsolution.Itisdue
tointerconversionofdichromateiontochromateion.Followingreactionstakeplace:
2Cr042(yellow)+2H+Cr2O72(orange)+H2O
Cr2O72(orange)+2OH2Cr042(yellow)+H2O.
Q.4(a)Whatislanthanidecontraction?Whateffectdoesithaveonthechemistryoftheelements,
whichfollowlanthanoids?
(b)Thechemistryofactinoidelementsisnotsomuchsmoothasthatoflanthanoids.Justifythese
statementsbygivingsomeexamplesfromtheoxidationstateoftheseelements.
A.4 (a)The size of Lanthanoids and its trivalent ion decreases from La to Lu. It is known as
lanthanoidscontraction.
Cause:Itisduetopoorshieldingof4felectrons.
Consequencesoflanthanidecontraction:(i)BasicstrengthofhydroxidedecreasesfromLa(OH)3
TOLu(OH)3.(ii)Becauseofsimilarchemicalpropertieslanthanidesaredifficulttoseparate.
(b)Lanthanoidsshowlimitednumberofoxidationstatesi.e.+2,+3,+4(outofwhich+3ismost
common) . This is because of a large energy gap between 4f, 5d and 6s subshell. The dominant
oxidationstateofactinidesisalso+3buttheyshowanumberofotheroxidationstatealsoe.g.+4,
+5,and+7.Thisisduetosmallenergydifferencebetween5f,6dand7sorbitals.
Q.5 Give examples and suggest reasons for the following features of the transition metal
chemistry:
(i)Thelowestoxideoftransitionmetalisbasic,thehighestisamphoteric/acidic.
(ii)Atransitionmetalexhibitshighestoxidationstateinoxidesandfluorides.
(iii)Ofthed4species,Cr2+isstronglyreducingwhilemanganese(III)isstronglyoxidizing.
A.5(i)Theoxideoftransitionmetalsinloweroxidationstatesaregenerallybasicwhilethosein
thehigheroxidationstatesareacidic.Acidiccharacterincreaseswithincreaseinoxidationstateis
due to decrease in size of metal ion and increase in charge density.e.g. MnO (basic), Mn3O4
(amphoteric),Mn2O7(acidic).
(ii)Atransitionmetalexhibitshigheroxidationstatesinoxidesandfluoridesbecauseoxygen and
fluorinearethemostelectronegativeelementsandthuseasilycanunpairelectronsofmetalatom.
(iii)BecauseoxidizingandreducingpropertydependsonE0value.SinceE0 valueofCr3+/Cr2+is
negativewhilethatofMn3+/Mn2+ispositive, asaresultCr(II)actasreducingagentandMn(III)is
strongoxidizing.
Q.6ForM2+/MandM3+/M2+systems,theEovaluesforsomemetalsareasfollows:
Cr2+/Cr
0.9V

Cr3+/Cr2+

0.4V
2+
Mn /Mn1.2VMn3+/Mn2++1.5V

Fe3+/Fe2+
+0.8V
Fe2+/Fe0.4V
Usethisdatatocommentupon:
(i)thestabilityofFe3+inacidsolutionascomparedtoCr3+orMn3+and
(ii)theeasewithwhichironcanbeoxidizedascomparedtoasimilarprocessforeitherchromium
ormanganesemetal.
A.6(i)EoforCr3+/Cr2+is0.4Vi.e.negative,thismeansCr3+ionsinthesolutioncannotbereduced
toCr2+easilyi.e.Cr3+isstable.AsMn3+/Mn2+is+1.5Vi.epositivemeansMn3+caneasilyreducedto
Mn2+ionsincomparisontoFe3+ions.Thusrelativelystabilityoftheseionsis:
Mn3+<Fe3+
<Cr3+
(ii)Theoxidationpotentialsforthegivenpairswillbe+0.9V,+1.2Vand0.4V.Thus,theorderof
theirgettingoxidizedwillbeintheorderMn>Cr>Fe.
Q.7Accountforthefollowingstatements:
(i)Cobalt(II) isstableinaqueoussolutionbutinthepresenceofstrongligandsandair,itcanbe
oxidizedtoCo(III).
(ii)Thed1configurationisveryunstableinions.
(iii)Oneamongthelanthanides,Ce(III)canbeeasilyoxidizedtoCe(IV).
A.7 (i) Strong ligands force cobalt (II) to lose one more electron from 3dsubshell and thereby
inducedd2sp3hybrisation.

(ii) The ion with d1 configuration try to lose the only electron in order to acquire inert gas
configuration.
(iii)TheconfigurationofCeis[Xe]4f1,5d1,6s2.Thereisnomuchdifferencebetweentheenergyof
4f, 5d and 6s orbitals and thus, Ce can utilize electrons present in these orbitals and hence
oxidationstateof+4.
Q.8Comparethechemistryofactinideswiththatofthelanthanoidswithspecialreferenceto:
(i)electronicconfiguration(iii)oxidationstate
(ii)atomicandionicsizesand(iv)chemicalreactivity

A.8ComparisonofLanthanoidsandActinides
Properties Lanthanoids
Actinides
Electronic
[Xe]4f114,5d01,6s2
[Rn]5f114,6d01,7s2.
configuratio
n
Atomic/ioni SizedecreasesfromLatoLu,
SizedecreasesfromActoLw,and
csizes
andsizeismorethanactinides. sizeissmallerthanlanthanoidsdue
topoorershieldingof5felectrons
Oxidation
Commonoxidationis+3where Commonoxidationis+3where
states
otheroxidationstatesare+2,
otheroxidationstatesare+2,+4,+5
+4.Itisduetoalargeenergygap and+7duetoduetosmallenergy
between4f,5dand6ssubshell
differencebetween5f,6dand7s
orbitals
Chemical
Theearliermemberquite
Theactinideshighlyreactive
reactivity
reactivebutwithincreasing
,especiallyinfinelydivided.
atomicnumbertheybehavelike
aluminum.
Complex
Lesstendencytoformcomplex
Moretendencytoformcomplexdue
formation
duetolesschargedensity.
tohighchargedensity.

Q.9(a) What is actinides contraction? What effect does it have on the chemistry of the
elements,whichfollowactinides?
(b)Nameanimportantalloy,whichcontainssomeofthelanthanidemetals.Mentionitsuses.
A.9(a)ThesizeofactinoidanditstrivalentiondecreasesfromActoLw.Itisknownaslactinides
contraction.
Cause:Itisduetopoorshieldingof5felectrons.
Consequencesofactinidescontraction:(i) Basicstrengthof hydroxidedecreasesfromAc(OH)3
ToLw(OH)3.(ii)Becauseofsimilarchemicalpropertieslactinidesaredifficulttoseparate.
(b) An important alloy containing lanthanoid metals is mischmetal, which contains 95%
lanthanide metal and 5% Fe along with traces of S, C, Ca and Al. It is used in Mgbased alloy to
producebullets,shellsandlighterflint.
Q.10Completefollowingreactions:
(i)MnO4+H++Fe2+

++

(ii)MnO4+C2O42+H+

++

(iii)MnO4+OH+I

++

A.10(i)MnO4+8H++5Fe2+

Mn2+

(ii)2MnO4+5C2O42+16H+

2Mn2+

(iii)2MnO4+H2O+I

2MnO

+5Fe

3++4H

2O

+10CO2+8H2O

2+2OH +IO3

(FIVEMARKQUESTIONS)
Q.1Explaingivingreasons:
(i)Transitionmetalsandmanyoftheircompoundsshowparamagneticbehaviour.

(ii)Theenthalpiesofatomisationofthetransitionmetalsarehigh.
(iii)Thetransitionmetalsgenerallyformcolouredcompounds.
(iv)Transitionmetalsandtheirmanycompoundsactasgoodcatalyst.
(v)Transitionmetalshaveastrongtendencytoformcomplexes.
A.1 (i)Transition metals and many of their compounds show paramagnetic behaviour due to
presenceofunpairedelectronsin(n1)dorbital.
(ii) The enthalpies of atomisation of the transition metals are high Because of large number of
unpairedelectronsintheiratoms,theyhavestrongerinteratomicinteractionandhencestrong
metallicbondingispresentbetweenatoms.
(iii) The transition metals generally form coloured compounds due to presence of unpaired
electronsin(n1)dorbital&thustheycanundergoddtransition.
(iv)TransitionmetalsandtheirmanycompoundsactasgoodcatalystItisdueto(i)partiallyfilled
(n1)dorbital(ii)Variableoxidationstate(iii)Abilitytochangeoxidationstatefrequently.
(v)TransitionmetalshaveastrongtendencytoformcomplexesMostoftransitionelementsform
complexcompoundsdueto(i)smallsize(ii)highcharge(iii)presenceofvacantdorbitalof
suitableenergy.
Q.2Givereasonsforthefollowing:
(i)FehashighermeltingpointthanCu.
(ii)[Ti(H2O)6]3+iscolouredwhile[Sc(H20)6]iscolourless.
(iii)The4dand5dseriesoftransitionmetalshavemorefrequentmetalmetalbondingin
theircompoundthandothe3dmetals.
(iv)Transitionmetalssometimeexhibitverylowoxidationstatesuchas+1and0.
(v)Hgisnotconsideredatransitionmetal.
A.2(i) This is because Fe (3d6, 4s1) has four unpaired electrons in 3dsubshell. While Cu
(3d10, 4s1) only one unpaired electron in 4s shell. Hence metallic bonding is stronger in Fe than
thoseinCu.
(ii)TheoxidationstateofTiin[Ti(H2O)6]3+is+3anditsconfigurationis[Ar]3d1i.eoneunpaired
electronandhenceitiscoloured.WhereastheoxidationstateofScin[Sc(H2O)6]3+is+3andits
configurationis[Ar]3d0i.enounpairedelectronandhenceitiscolourless.
(iii)Inthesamegroupofdblockelements,the4dand5dtransitionelementsarelargersizethan
thatof3delements.Hence,thevalenceelectronsarelesstightlyheldandformmetalmetalbond
morefrequently.
(iv)+1oxidationstateisshownbyelementslikeCubecauseafterlossofoneelectron,itacquire
stable configuration. Zero oxidation state is shown in metal carbonyl, because electrons
donatedbyCOareacceptedintotheemptyorbital.
(v)The characteristic properties of transition metal are due to partially filled dorbitals.Hg has
completelyfilleddorbital,asaresultitdoesntshowpropertiesoftransitionmetalsandhenceis
notconsideredastransitionmetal.
Q.3(a)writeelectronicconfigurationofelementhavingatomicnumber101.
(b)Whichelementshowmaximumoxidationstatein3dtransitionseries?
(c)Whatismischmetal?
(d)ExplainwhyCu+ionisnotstableinaqueoussolution?
(e)Namethetransitionmetalwhichiswellknowntoexhibit+4oxidationstate?
A.3(a)[Rn]5f13,6d0,7s2.
(b)Mn,Whichshows+7oxidationstateinKMnO4.
(c)Itisanimportantalloy,whichcontains95%lanthanidemetaland5%Fealongwithtraces
ofS,C,CaandAl.ItisusedinMgbasedalloytoproducebullets,shellsandlighterflint.
(d) Water is a good complexing agent and thus Cu forms complex by losing one more electron
from3dorbital.
(e)Cerium(Z=58)
Q.4(a)Writethepreparationofpotassiumdichromatefromironchromite.Whathappenswhen
potassiumdichromatereactswith(i)Hydrogensulphide(ii)FeSO4?
(b)WhydoZrandHfexhibitalmostsimilarproperties?
(c)WhyisLa(OH)3strongerbasethanLu(OH)3.

A.4(a)Preparation:Ittakesplaceinthreesteps
(i) Conversionofchromiteoretosodiumchromate.
(ii) Conversionofsodiumchromatetosodiumdichromate.
(iii) Conversionofsodiumdichromatetopotassiumdichromate
Followingreactiontakesplace:
4FeCr2O4+4Na2CO3+7O2
2Na2CrO4+2Fe2O3+8CO2
2Na2CrO4+2H+
Na2Cr2O7+2KCl

Na

2Cr2O7+2Na

++H O
2

K2Cr2O7+2NaCl

Reactions:(i)Cr2O72+8H++3H2S2Cr3++7H20+3S
(ii)Cr2O72+14H++6Fe2+2Cr3++7H20+6Fe3+.
(b)Becausebothhavesimilarionicsize
(c)Due to lanthanoid contraction size of La3+ is smaller than Lu3+ as a result LuO bond will
strongerthanLaObond.
Q.5Givereasonsforthefollowing:
(i)Transitionmetalshavehighenthalpyofhydration.
(ii)Zn,CdandHgarenotregardedastransitionmetal.
(iii)dblockelementsexhibitalargenumberofoxidationstatethanfblockelements.
(iv)Thesecondandthirdmembersineachgroupoftransitionelementhavesimilaratomicradii.
(v)K2[PtCl6]iswellknowncompoundwhereasthecorrespondingNicompoundisnotknown.
A.5(i)Transitionmetalionsaresmallerandhavehighercharge,thereforehavehighenthalpyof
hydration.
(ii)Group12elementsi.e.Zn,Cd,Hghavecompletelyfilled(n1)dorbitalinatomic&ionicstate
&thustheseelementsarenotconsideredastransitionelements.
(iii)Thedifferenceintheenergyof(n1)dorbitalandnsorbitalisverysmallandthusbothsub
shellsareusedforbondformation.Whereasinfblockelements(n2)forbitalslieunderneathand
hencearenotavailableforbondformation.
(iv)Thesecondandthirdmembersineachgroupoftransitionelementhavesimilaratomic radii
duetolanthanoidcontraction.Itarisesduetopoorshieldingofdandfelectron.
(v)The oxidation state of Pt in is +4 which is stable for Pt. The +4 oxidation state for Ni is very
difficult to achieve because the sum of first four ionization energies is very high. Hence ,the
correspondingNi(II)compoundisknown.