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OCR Chemistry A H432 Transition Elements and Qualitative Tests p. 1 Transition Elements Electron arrangements of the d-block elements The elements in between Group 2 and Group 3 are correctly referred to as the d-block elements. This is because the highest energy subshell (i.e. the subshell being filled) is a d-subshell. Recall that: ! the 3d subshell and the 4s subshell are actually very close together in energy, but 4s is slightly lower in energy, so the 4s fills before 3d ! a d-subshell contains five d-orbitals, so can hold up to 10 electrons ! electrons go one into each orbital first, before any orbital gets a second electron When we examine the electron arrangements of the first row of d-block elements we find two anomalies: Ca (20) 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 Sc (21) 1s2 2s2 2p6 3s2 3p6 3d1 4s2 Ti (22) 1s2 2s2 2p6 3s2 3p6 3d2 4s2 V (23) 1s2 2s2 2p6 3s2 3p6 3d3 4s2 Cr (24) 1s2 2s2 2p6 3s2 3p6 3d5 4s1 Mn (25) 1s2 2s2 2p6 3s2 3p6 3d5 4s2 Fe (26) 1s2 2s2 2p6 3s2 3p6 3d6 4s2 Co (27) 1s2 2s2 2p6 3s2 3p6 3d7 4s2 Ni (28) 1s2 2s2 2p6 3s2 3p6 3d8 4s2 Cu (29) 1s2 2s2 2p6 3s2 3p6 3d10 4s1 Zn (30) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 Ga (31) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p1 A rather simplistic and inadequate explanation for this is to say that having all the d-orbitals half-filled is an especially stable arrangement, so Cr has 3d and 4s all half filled rather that the expected 3d 4 4s 2 arrangement. Mo shows the same effect in Period 5. In the same way it can be suggested for Cu that having the 3d orbitals all full is more stable than having the expected 3d 9 4s 2 arrangement. In other periods, Ag and Au show the same effect. A more satisfactory explanation is beyond the scope of the A-level course. Electron arrangements of the ions of d-block elements Putting electrons into 3d shields the 4s orbital from the nuclear charge, and the 4s electrons now become easier to remove than the 3d i.e. 3d is now the lower energy subshell. As a result, when we start to remove electrons from the d-block atoms to form ions, we remove the 4s electrons before we remove any from 3d. d-block elements in Period 4

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TransitionElementsElectronarrangementsofthed-blockelementsTheelementsinbetweenGroup2andGroup3arecorrectlyreferredtoasthed-blockelements.Thisisbecausethehighestenergysubshell(i.e.thesubshellbeingfilled)isad-subshell.Recallthat:

! the3dsubshellandthe4ssubshellareactuallyveryclosetogetherinenergy,but4sisslightlylowerinenergy,sothe4sfillsbefore3d

! ad-subshellcontainsfived-orbitals,socanholdupto10electrons! electronsgooneintoeachorbitalfirst,beforeanyorbitalgetsasecondelectron

Whenweexaminetheelectronarrangementsofthefirstrowofd-blockelementswefindtwoanomalies: Ca (20) 1s22s22p63s23p64s2 Sc (21) 1s22s22p63s23p63d14s2 Ti (22) 1s22s22p63s23p63d24s2 V (23) 1s22s22p63s23p63d34s2 Cr (24) 1s22s22p63s23p63d54s1 Mn (25) 1s22s22p63s23p63d54s2 Fe (26) 1s22s22p63s23p63d64s2 Co (27) 1s22s22p63s23p63d74s2 Ni (28) 1s22s22p63s23p63d84s2 Cu (29) 1s22s22p63s23p63d104s1 Zn (30) 1s22s22p63s23p63d104s2 Ga (31) 1s22s22p63s23p63d104s24p1Arathersimplisticandinadequateexplanationforthisistosaythathavingallthed-orbitalshalf-filledisanespeciallystablearrangement,soCrhas3dand4sallhalffilledratherthattheexpected3d44s2arrangement.MoshowsthesameeffectinPeriod5.InthesamewayitcanbesuggestedforCuthathavingthe3dorbitalsallfullismorestablethanhavingtheexpected3d94s2arrangement.Inotherperiods,AgandAushowthesameeffect.AmoresatisfactoryexplanationisbeyondthescopeoftheA-levelcourse.Electronarrangementsoftheionsofd-blockelements Puttingelectronsinto3dshieldsthe4sorbitalfromthenuclearcharge,andthe4selectronsnowbecomeeasiertoremovethanthe3di.e.3disnowthelowerenergysubshell.Asaresult,whenwestarttoremoveelectronsfromthed-blockatomstoformions,weremovethe4selectronsbeforeweremoveanyfrom3d.

d-blockelementsinPeriod4

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e.g.ironformsgreenFe2+andorangeFe3+ions Fe 1s22s22p63s23p63d64s2 Fe2+ 1s22s22p63s23p63d6 -2x4selectronsremoved Fe3+ 1s22s22p63s23p63d5 -2x4selectronsand1x3delectronremoved e.g.vanadiumformsvioletV2+ionsandgreenV3+ions V 1s22s22p63s23p63d34s2 V2+ 1s22s22p63s23p63d3 -2x4selectronsremoved V3+ 1s22s22p63s23p63d2 -2x4sand1x3delectronremovedBUTZinconlyformscolourless2+ions, Zn 1s22s22p63s23p63d104s2 Zn2+ 1s22s22p63s23p63d10 -2x4selectronsremovedScandiumonlyformscolourless3+ions, Sc 1s22s22p63s23p63d14s2 Sc3+ 1s22s22p63s23p6 -2x4sand1x3delectronremovedWemightproposethatcolourintheseionsisassociatedwithhavingapartially-filledd-subshell,andexperimentationwouldprovideaphysicalbasisforthissuggestion.Wealsohavethebasisforthedefinitionofatransitionelement–whichisNOTthesameasad-blockelement:Atransitionelementisad-blockelementthatformsatleastonestableionwithapartiallyfilleddsub-shell.ThereforeinPeriod4,ZnandScared-blockelementsbutNOTtransitionelements,whereasTi-Cuarebothd-blockelementsANDtransitionelements.TransitionMetalChemistryThepartially-filledd-subshellintransitionelements,andtheeasewithwhichelectronscanberemovedfrom,oraddedtotheseorbitals,givesthemtheircharacteristicproperties: -formingcolouredcompoundsandcomplexes -actingascatalysts -havingcompoundswithmultipleoxidationstatesAlltransitionmetalsformcompoundswithionswith+2oxidationnumber;inmostcasesthisisduetolosingthetwoelectronsfromthe4sorbital.However,the3delectronscanalsobelostallowingtransitionmetalstoformstableionswithhigheroxidationnumbers.Thishappensbecausethe3dand4senergylevelsaresocloseinenergy.Ionsoftransitionmetalsalsoreadilychangefromoneoxidationstatetoanother,byacceptingordonatingelectronsfromthe3dsubshell.

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AnillustrationofcolourandmultipleoxidationstatesAsolutioncontainingvanadate(V)ionsisyellow,butwhenareducingagentsuchaszincisadded,theoxidationstatecanbereducedfrom+5instepsdownto+2withacorrespondingchangeincolourateachstage: VO2

+(aq) Oxidationstate:+5 Colour:yellow

VO2+(aq) Oxidationstate:+4 Colour:blue*

*usuallyanintermediategreensolutionisseencontainingamixtureofVO2+andVO2+ions

beforetheblueappears. V3+

(aq) Oxidationstate:+3 Colour:green V2+

(aq) Oxidationstate:+2 Colour:lilacIneachstage,thevanadiumhasbeenprogressivelyreduced.Atthesametime,thezinchasbeenoxidized(Zn(s)"Zn2+(aq))sothisisaseriesofredoxreactions.CatalyticbehaviorintransitionmetalchemistryCatalystsprovideanalternativereactionpathwaywithloweractivationenergy.Weclassifycatalystsashomogeneous(inthesamephysicalstateasthereactants)orheterogeneous(inadifferentphysicalstatetothereactants).Examplesofheterogeneouscatalysis! Iron(solid)isusedasthecatalystfortheHaberprocess:N2(g)+3H2(g)⇌2NH3(g)! Solidvanadium(V)oxide,V2O5,isusedasthecatalystforthestepintheContactprocessto

manufacturesulphuricacidthatoxidisessulphurdioxidetosulphurtrioxide:SO2(g)+½O2(g)⇌SO3(g)! Nickelisusedinthecatalystinthehydrogenationofmargarines,saturating(someof)thealkene

functionalgroupsinpolyunsaturatedvegetableoils: -CH=CH-+H2"-CH2-CH2-! Manganese(IV)oxide,MnO2,isusedtocatalysethedecompositionofhydrogenperoxideinto

oxygenandwater: H2O2(aq)"H2O(l)+½O2(g)! Thereactionbetweensolidzincandacids(producingazincsaltandhydrogen)iscatalyzedbythe

presenceofcopper(II)ionsinthesolution.Thecopper(II)ionsreactwiththesurfaceofthesolidzincinadisplacementreaction,formingcoppermetal.Thecoppermetalthenactsasthecatalystforthereactionbetweenthezincandtheacid.

ExamplesofhomogeneouscatalysisInsolution,transitionmetalcompoundscanprovideanalternativereactionpathwayforredoxreactionsbyreactingwithonereactant,thenbeingregeneratedinthereactionwiththeotherreactant.e.g.ifAreactswithBinaredoxreaction,withAbeingoxidisedandBreduced,thealternativepathwaymightconsistofAbeingoxidizedbythecatalyst,whichisitselfreduced,thenthecatalystreducingB,andbeingoxidizedbacktoitsoriginalform.

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! Hydrogenperoxideoxidisestartrateionstocarbondioxidegasandmethanoateions.Thereactionproceedsveryslowlyifthereisnocatalyst,evenatelevatedtemperatures.

Thepresenceofcobalt(II)ionsinsolutioncatalysesthereaction. ThehydrogenperoxideinitiallyoxidisesthepinkCo2+,togreenCo3+,andisreducedtowater. Thecobalt(III)ioncausesoxidiationofthetartarateion,andasaresultofwhichtheCo3+is reducedbacktoCo2+andthepinkcolourreturns.

PracticalRochellesaltreactionwithhydrogenperoxide,catalyzedbyCo2+(aq)–seeClassicChemistryDemos.! Thereactionbetweeniodideions,I-,andperoxydisulphateions,S2O8

2-formssulphateionsandiodine: 2I-(aq)+S2O8

2-(aq)"2SO4

2-(aq)+I2(aq)

Thisformationofiodinecanbehighlightedbytheadditionofstarch,whichformsablue-black complexwiththeiodine.ThereactioniscatalyzedbythepresenceofFe2+(aq),andwhenasmall amountofthisisaddedtheblue-blackcolourformsmuchmorequickly,withtheFe2+ionsleft unchangedattheendofthereaction. Step1: S2O8

2-(aq)+2Fe2+(aq)"2SO4

2-(aq)+2Fe3+(aq) reactioninvolvingcatalyst

Step2: 2I-(aq)+2Fe3+(aq)"I2(aq)+2Fe2+(aq) regenerationofcatalystComplexesandColourThesolidcompoundsandaqueousionsoftransitionmetalshavecharacteristiccolours: Cu2+(aq)ionsareblue Co2+(aq)ionsarepink Fe2+(aq)ionsarepalegreen Fe3+(aq)ionsareyellow-orange Mn2+(aq)ionsarepalepinkBycontrast,compoundsofZnandScarewhite(colourlessinsolution).ThisisbecauseZn2+ionshavea3d10electronarrangement,andSc3+haveno3delectrons,soneitherhastheincompletelyfilledd-orbitalsnecessaryforcolourintransitionmetalcompounds.However,considercopper(II)sulphate.Itisbluewhenhydratedcrystalsorinsolution,butwhitewhenanhydrous.Thecopperionsare[Ar]3d9ineverycase.Wemustconcludethattheunfilledd-subshellisonlyoneofthenecessaryrequirementsforcolour.Wheninsolutionandinthehydratedcrystallattice,thetransitionmetalionsarenotmerelydissolvedinwater,buttheyareactuallybondedtoanumberofwatermolecules,bydativecovalentbondsformedfromalonepaironwater'soxygenatomtothemetalion.

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e.g.theblueCu2+(aq)ionisactually[Cu(H2O)6]2+(aq) Thisisanexampleofacomplex.Becauseithasanoverallcharge,wecallitacomplexion.Becausetransitionmetalionsaresmalltheyhaveastrongelectricfieldaroundthemthatattractselectron-richspecies.Speciesthathavealonepairavailabletodonatecanformdativecovalentbondstothetransitionmetalion.WecallsuchspeciesLIGANDS.Aligandisamoleculeorionthatcandonatealonepairtoformadativecovalentbondtoatransitionmetalion.Itisthepresenceoftheseligandsaroundthecentraltransitionmetalionthatistheothernecessaryrequirementforcolour.Examplesofligands: H2O: :NH3 :Cl- :CN- :SCN- :OH- water ammonia chloride cyanide thiocyanate hydroxideThedativecovalentbondsaroundthetransitionmetalionrepeloneanother,andsoarearrangedaroundthetransitionmetalioningeometricarrangementspositioningthemasfarapartaspossible(likeinVSEPRTheory).Thenumberofdativecovalentbondsarrangedaroundatransitionmetaliscalledtheco-ordinationnumber.Complexionswithaco-ordinationnumberof6tendtobeoctahedralComplexionswithaco-ordinationnumberof4aretetrahedraloroccasionallysquareplanarDrawingcomplexes,andwritingformulaeFormulaeforcomplexionsarewritteninsquarebracketswiththeoverallchargeonthebrackets.Noindividualchargesonligandsorthemetalionareshown.Ligandsareinbracketsunlesssingleatoms,withthenumberofeachligandafterthebracketifmorethanone.Complexionsaredrawnin3Dusingshadedandwedgebondstorepresentbondsintoandoutoftheplaneofthepaper.Thebondsbetweenligandsandthetransitionmetalionaredativecovalentbonds,sowesometimesuseanarrowtoindicatethedirectioninwhichtheelectronpairhasbeendonated(towardsthetransitionmetalion),butthisisoptional.Aswiththeformula,squarebracketsareusedandtheoverallchargewrittenatthetopright.Examples:1) [Cu(H2O)6]2+ octahedral paleblue Name:hexaaquacopperIIion

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Aqueoussolutionsofallthetransitionmetalions(withnootherligandspresent)haveaco-ordinationnumberof6andareoctahedral.2) [CuCl4]2- tetrahedral yellow Name:tetrachlorocuprateIIionItisthesizeoftheligandsthathasthemostsignificanteffectonthegeometryofthecomplexions–chlorideionsaremuchlargerthanwatermolecules,soonlyfourchlorideionswillpackaroundthesmalltransitionmetalion,wheresixwatermoleculeswillfit.3) [Fe(H2O)5SCN]2+ octahedral bloodred Name:pentaaquathiocyanatoironIIIionTheligandsdon’tallhavetobethesame,herefivewaterligandsandathiocyanateligandformdativebondstotheiron(III)ion.Noticealsothattheoverallchargeonthecomplexionis2+eventhoughtheironisin+3oxidationstate,becauseofthe1-chargeontheSCN-ion.CrystallisingcomplexesComplexionsarenotfoundontheirown–thereisalwaysanoppositely-chargediontobalancethechargesalthoughwemayignoreitmuchofthetime.Wemayfocusonthe[Cu(H2O)6]2+ionwhenwedissolvecopper(II)sulphateinwater,forgettingtheSO4

2-ionisalsopresentinequalconcentrations.Similarlywhenweform[CuCl4]2-bytheadditionofhydrochloricacidtocoppersulphatesolution,wehavetwoH+ionspresentforevery[CuCl4]2-ion.Thisisofnoconsequencewhenweareconsideringsolutions–the"other"ionsarespectators,butwhenweevaporatethewaterandformcrystals,theseotherionsbecomepartofthegiantioniclatticealongwiththecomplexions.e.g.K3Fe(CN)6containsthecomplexion[Fe(CN)6]3-andthreeK+ionstobalancethecharges.Name:potassiumhexacyanoferrate(III)TypicalionswemayfindinthisroleincludeNa+,K+orNH4

+.TheseotherionsareNOTligandsandareNOTbondedtothecentralmetalion.LigandSubstitutionWhenanewligandisaddedtoasolutioncontainingacomplex,thenewligandcanreplacetheoriginalligandtoformanewcomplex.Thisisknownasligandsubstitution.

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Examples:1)AdditionofexcessconcentratedammoniasolutiontoCu2+(aq)resultsintheformationasolutioncontainingadarkbluecomplexion. [Cu(H2O)6]2++4NH3"[Cu(NH3)4(H2O)2]2++2H2O bluedarkblue octahedral octahedral2)IfconcentratedhydrochloricacidisaddedtoasolutioncontainingCu2+(aq),thesolutionturnsgreenandprogressivelymoreyellowaschlorideligandsreplacethewatermolecules.Thenewcomplexisyellow,butthesolutioncontainingbothcomplexesappearsgreen. [Cu(H2O)6]2++4Cl-⇌[CuCl4]2-+6H2O blue yellow octahedral tetrahedralPractical: Nuffield19.2aPart1experiments1-4 ClassicChemistryDemonstration#8p.16MultidentateligandsAlltheligandswehaveseensofarhaveformedasingledativecovalentbondtothetransitionmetalion.Werefertotheseasmonodentateligands.Largermoleculesmayhavemorethanonesitethatisabletodonatealonepair,andsomaybeabletoformmorethanonedativecovalentbondtothetransitionmetalion.Examples:salicylate(2-hydroxybenzoate)ions Salicylicacid(abenzeneringwithanadjacent–OHand–COOHgroup)doesnotactasaligand,butthesalicylateiondoes(presumablybecauseitismoreelectron-rich).TheOofthe–OHgroupandthe–O-ofthe–COO-groupeachhavealonepairwhichcanformabondtothetransitionmetalion,sotwodativecovalentbondsareformed.Thisasabidentateligand.Whenthisisaddedtoasolutioncontainingyellowaqueousiron(III)ions,thesixwaterligandsarereplacedwiththreesalicylateligandstoformadeeppurplecomplexofiron(III)salicylate.(Notethatthiscomplexhasnocharge–itisnotacomplexion,justacomplex).

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[Fe(H2O)6]3+(aq)+3HOC6H4COO-(aq)"[Fe(HOC6H4COO)3](s)+6H2O(l)

yellow purpleEDTA(ethylenediaminetetraaceticacid) ThisligandexistsincomplexesastheEDTA4-ion.Ithassixlonepairswhichcanformdativecovalentbonds,andishenceahexadentateligand.EDTAisusedtobindmetalions,removingthemfromsolution,andisreferredtoasachelatingagent.Usesincludebindingcalciumandmagnesiumionstoreducewaterhardness,orbeingaddedtobloodtotreatpatientssufferingfromleadormercurypoisoning.Practical:NuffieldExpt19.2aPart2(omitting1,2-dihydroxybenzene)ethane-1,2-diamine NH2CH2CH2NH2

ThishastwoNatomseachwithalonepairthatcanformabondtothetransitionmetalion.Thisisthereforeabidentateligand.Forexample,nickelformsanoctahedralcomplexwithco-ordinationnumber6whenitbondswiththreeoftheseligands: [Ni(NH2CH2CH2NH2)3]2+ ethanedioateions C2O4

2- Theethanedioateionisabidentateligand.EachO-canformadativecovalentbondtothetransitionmetalion.

Cr3+formsanoctahedralcomplexwithtwoethanedioateionsandtwowatermolecules. [Cr(C2O4)2(H2O)2]-

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PtO

OOH

C OOC

C

O

O

OH

C OO OC

O C

O

OPt

OH

C OOCC

O

O O

O

O

H

C O O

CC

O

O O

O

Wemightbegiventhestructureofacomplexandaskedtoworkoutanddrawtheligandspresent,indicatinghowtheyactasligands.Todothisweneedtobreakthedativecovalentbondstothetransitionmetalionandrestorethelonepairtotheatomsintheligandthatformedthebond:e.g.[Pt(C2O4)(HOC6H4OCOO)]-1)Takethecomplexionapart:2)Lookforatomswhosevalencyisnotsatisfiedwithbonds–onetoofewbondsindicatesanegativeion.3)Addinthelonepairswhichformedthedativecovalentbondstothemetalions

-

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BiologicalroleofligandsubstitutionHaemaglobininbloodisresponsibleforthetransportofoxygentocellsforrespiration,andthetransportawayofcarbondioxide.Haemaglobinisacomplexprotein,containingfournon-proteincomponentscalledhaemgroups,eachofwhichhasanFe2+ionatitscentre,andfourdativecovalentbondsbetweentheironandfourN-atomsinthehaemstructure,andafurtherdativecovalentbondtotheproteinglobin.

Oxygencanbindtotheironinthehaemgroupasaligand,givingaco-ordinationnumberof6,inordertobetransported.Thecolourofthecomplexwhenoxygenisboundasaligandistherichredofoxygenatedblood.Carbonmonoxidecanalsobindtotheironatthesamebindingsiteastheoxygenwould,thestabilityconstantforthiscomplexisgreater(seelater)sothebondbetweentheironandtheCOisstrongerandmuchlesslikely

tobreak.COwillthereforebindpreferentiallyifbothcarbonmonoxideandoxygenarepresentinthelungs;thebindingisirreversible,sothathaemaglobinbecomesuseless.Sincetobaccosmokingproducescarbonmonoxide,andthisisoneofthereasonswhysmokersbecomeshortofbreath.IsomerismincomplexionsStereoisomerismariseswhentheligandscanbearrangedindifferentspatialarrangements.Incomplexes,aswithorganicsubstances,wewillseebothcis-transisomerismandopticalisomerism.Cis–TransisomerismForexamplewhenacomplexcontainsfourofoneligandandtwoofanother,wecanhavecisandtransisomers.e.g.cobaltformsanoctahedralcomplexofformula[Co(NH3)4Cl2]+.Thecobaltisinoxidationstate+3here.Itwasfoundthatagreensaltandapurplesaltbothwiththesameformulacouldbecrystallized.Thiswasclearevidencefortwodifferentisomers:

cis-isomer trans-isomerpurple green

Clat90°tooneanother Clat180°tooneanother (adjacent=cis) (opposite/across=trans)

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Cis-transisomerismisalsopossibleinsomecomplexeswithco-ordinationnumber4iftheyhaveasquare-planarconfiguration.Nickelformsasquareplanarcomplex[NiCl2(NH3)2].Thishasnooverallcharge,asthenickelisinthe+2oxidationstate. cis-isomer trans-isomerAsimilarcomplexofplatinum[PtCl2(NH3)2]isoneofthemosteffectivedrugsinchemotherapyforcancer.Itisthecis-formofthecomplexwhichisbiologicallyactive.Thedrugisaliquid,usuallyadministeredintravenouslyasadrip,andgoesunderthenameofcis-platin.Theimportanceoftheexactshapeandstructureofthemoleculeisemphasizedbythefactthatthetrans-formisineffective.Thebenefitofusingcis-platintotreatcanceristhatitworksbybindingtotheDNAoffast-growingcancercells,changingtheDNAstructureandpreventingthemfromdividingtoreproduce.Chemotherapyhasunpleasantsideeffects,however,andanewgenerationofcancer-treatmentdrugsrequiringlowerdosesandwithfewersideeffectsthancis-platinhavebeendeveloped,e.g.carboplatin.OpticalisomerismOpticalisomerismariseswithoctahedralcomplexescontainingmultidentateligands,wherethesecanbearrangedaroundthecentraltransitionmetalatomasnon-superimposablemirrorimages.Recallthatopticalisomersrotateplane-polarisedlightdifferently–oneisomerwillrotateittotheright,andtheothertotheleft.Anequalmixtureofisomerswillhavenoeffectonplanepolarizedlightbecausetherotationscancelout.Examples: [Ni(en)3]2+-acomplexwiththreebidentateligands

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[Co(en)2(H2O)2]2+-acomplexwithtwobidentateligandsandtwomonodentateligands.Complexeslikethiswillhavecisandtransisomers,buttherewillbetwocisisomerareopticalisomersofeachother.TwocisisomersThetrans-isomerCasestudiesinTransitionMetalchemistryReactionsofcoppercompoundsi)Cu2+(aq)withsodiumhydroxideBlueaqueouscopper(II)ionsreactwithhydroxideionstoformablueprecipitateofcopper(II)hydroxide.Theprecipitateisinsolubleinexcesssodiumhydroxide. Cu2+

(aq)+2OH-(aq)" Cu(OH)2(s)

ii)Cu2+(aq)withammoniasolutionRememberthatammoniaformsanequilibriumreactingwithwaterwhenitdissolves,NH3(aq)+H2O(aq)⇌NH4

+(aq)+OH-

(aq)soammoniasolutionisbothasourceofNH3andOH-ligands.InitiallyitistheOH-ionsthatreactwiththeaqueouscopper(II)ions,formingabluecopperhydroxideprecipitateasabove.Whenexcessammoniasolutionisadded,thecopperhydroxideprecipitateredissolvesundergoingaligandsubstitutionreactiontoformadarkbluesolutioncontainingtheoctahedraltrans-complexof[Cu(NH3)4(H2O)2]2+Overall: [Cu(H2O)6]2+(aq)+4NH3(aq)" [Cu(NH3)4(H2O)2]2+(aq)+4H2O(l)

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iii)Cu2+(aq)withconcentratedhydrochloricacidWhenconcentratedhydrochloricacidisaddedtoblueaqueouscopper(II)ions,ayellowsolutioncontainingtetrahedral[CuCl4]2-(aq)isformedinaligandsubstitutionreaction,althoughagreencolourisoftenseenwhenboththeaqueousionsandthenewcomplexionarepresentinsolution.Asthisisanequilibrium,thecolourofthesolutionchangesastherelativeconcentrationsofchlorideionsandwaterpresentchange. [Cu(H2O)6]2+(aq)+4Cl-(aq)⇌[CuCl4]2-(aq)+6H2O(l)iv)Cu2+(aq)withiodideionsAqueouscopper(II)ionsreactwithiodideionsinaredoxreactionthatformsbrownaqueousiodineandawhiteprecipitateofcopper(I)iodide.Notethatthecopper(I)ionhasa3d10electronarrangement,soitisnotsurprisingwithnopartiallyfilledd-subshellthatitiswhite. 2Cu2+

(aq)+4I-(aq)" 2CuI(s)+I2(aq)Oxidationstates: +2-1+1-10Copper(I)compoundsareunstableinsolution.Whensolidcopper(I)oxidereactswithhotdilutesulphuricacid,abrownprecipitateofcopperandabluesolutionofcopper(II)sulphateareformedinadisproportionationreaction: Cu2O(s)+H2SO4(aq)" CuSO4(aq)+Cu(s)+H2O(l)Oxidationnumbers: +1 +2 0 +1 Reactionsofironcompoundsi)Fe2+(aq)andFe3+(aq)withsodiumhydroxidePalegreeniron(II)ionsinsolutionreactwithsodiumhydroxidetoformadirtygreenprecipitateofiron(II)hydroxide.Onstandingtheprecipitateturnsbrownatitssurfaceasiron(II)hydroxideisoxidizedtoiron(III)hydroxide. Fe2+(aq)+2OH-

(aq)" Fe(OH)2(s)Paleyellowiron(III)ionsinsolutionreactwithsodiumhydroxidetoformanorange-brownprecipitateofiron(III)hydroxide.Fe3+(aq)+3OH-

(aq)" Fe(OH)3(s)Neitherprecipitateredissolvesonadditionofexcesssodiumhydroxide.ii)Fe2+(aq)andFe3+(aq)withammoniasolutionItisonlythehydroxideionsintheammoniasolutionthatreactwithiron(II)andiron(III)ionstoformiron(II)hydroxideandiron(III)hydroxideexactlyasabove.Thereisnofurtherreactionwiththeammoniapresent,andtheprecipitatesdonotredissolve.

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iii)oxidationofiron(II)withacidifiedmanaganate(VII)Palegreenaqueousiron(II)ionswilldecolourisepurplemanagante(VII)ionsinacidicsolutioninaredoxreaction.Theiron(II)isoxidizedtopaleyellowaqueousiron(III)ions,whilethemanganate(VII)isreducedtopalepinkaqueousmanganese(II)ions. MnO4

-(aq)+8H+

(aq)+5Fe2+(aq)" 5Fe3+(aq)+Mn2+(aq)+4H2O(l)iv)reductionofiron(III)withiodideionsPaleyellowaqueousiron(III)ionscanbereducedtopalegreeniron(II)ionsbyredoxreactionwithcolourlessaqueousiodideions.Inthisreactioniodineisformedinaqueoussolution,whichisbrown,andmasksthecolourchangeoftheironions. 2Fe3+(aq)+2I-(aq)" I2(aq)+2Fe2+(aq) Reactionsofmanganesecompoundsi)Mn2+(aq)withsodiumhydroxidePalepinkaqueousmanganese(II)ionsreactwithsodiumhydroxidetoformapalebrownprecipitateofmanganese(II)hydroxide,whichdarkensonstandinginair.Theprecipitateisdoesnotredissolveorreactfurtheronfurtheradditionofsodiumhydroxide. Mn2+

(aq)+2OH-(aq)" Mn(OH)2(s)

ii)Mn2+(aq)withammoniasolutionItisonlythehydroxideionsintheammoniasolutionthatreactwithmanganese(II)ionstoformmanganese(II)hydroxideexactlyasabove.Thereisnofurtherreactionwiththeammoniapresent,andtheprecipitatesdonotredissolve.ReactionsofchromiumcompoundsThecolourofthecomplex[Cr(H2O)6]3+(aq)ispalepurple.Thismaybeasurprisesincewehaveconsistentlyreferredtothecolourchangewhenacidifieddichromate(VI)ionsareusedasanoxidizingagentasorangefordichromate(VI)andgreenforchromium(III).Thisisbecausethechromium(III)ionformedinthepresenceofsulphuricacidisactuallynot[Cr(H2O)6]3+but[Cr(H2O)5(SO4)]+andthisisthegreenionwehavebeenreferringtoasCr3+(aq).i)Cr3+(aq)withsodiumhydroxidePalepurpleaqueouschromium(III)ionsreactwithsodiumhydroxidetoformagreen-greyprecipitateofchromium(III)hydroxide. Cr3+(aq)+3OH-

(aq)" Cr(OH)3(s)Onadditionofexcesssodiumhydroxide,thisprecipitateredissolvestoformadarkgreensolutioncontainingthecomplexion[Cr(OH)6]3-(aq). Cr(OH)3(s)+3OH-

(aq)" [Cr(OH)6]3-(aq)ii)Cr3+(aq)withammoniasolutionInitiallyitistheOH-ionsthatreactwiththeaqueouschromium(III)ions,formingagreen-greychromiumhydroxideprecipitateasabove.

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Whenexcessammoniasolutionisadded,thechromiumhydroxideprecipitateredissolvesundergoingaligandsubstitutionreactiontoformapurplesolutioncontainingtheoctahedralcomplex[Cr(NH3)6]3+Overall: [Cr(H2O)6]3+(aq)+6NH3(aq)" [Cr(NH3)6]3+(aq)+6H2O(l)iii)oxidationofchromium(III)withalkalinehydrogenperoxideHotalkalinehydrogenperoxideisapowerfuloxidizingagent,andreactsinaredoxreactiontooxidiseaqueouschromium(III)ions(greenorpalepurple,dependingontheligandsbondedtothechromium)toyellowchromate(VI)ions. 3H2O2(aq)+2Cr3+(aq)+10OH-

(aq)" 2CrO42-(aq)+8H2O(l)

iv)reductionofdichromate(VI)withzincunderacidicconditionsThedichromate(VI)ionisorangeinaqueoussolution.Itcanbereducedinaredoxreactionwithareducingagentsuchaszincmetalunderacidicconditions,formingchromium(III)ionsinsolution.Thechromium(III)ionformedislikelytobegreen,asaligandfromtheacidwillformpartoftheCr3+(aq)complex. Cr2O7

2-(aq)+14H+

(aq)+3Zn(s)" 2Cr3+(aq)+3Zn2+(aq)+7H2O(l)Ifanexcessofzincisused,thechromium(III)ionsinsolutioncanbereducedinafurtherredoxreactiontopalebluechromium(II)ions. Zn(s)+2Cr3+(aq)" Zn2+(aq)+2Cr2+(aq)QualitativeTestsforIonsTestsforanionsWehavealreadymetthetestsforcarbonate,sulphate,chloride,bromideandiodideions.Therearespecificprecautionstobetakeninpreventinginterferingionsfrominvalidatingtheresultsofthesetests,andanorderinwhichthetestsshouldbedoneifthesamesampleistobeusedforallthetests. Carbonate: addH+

(aq) observefizzing Sulphate: addBa2+(aq) observewhiteprecipitate Chloride: addAg+(aq) observewhiteprecipitate,solubleindiluteammoniasolution Bromide: addAg+(aq) observecreamprecipitate,solubleinconc.ammoniasolution Iodide: addAg+(aq) observeyellowprecipitate,insolubleinammoniasolutionTestsforcationsInthistopicwehaveseenthattheprecipitationreactionsoftransitionmetalswithsodiumhydroxidesolutionwillallowustoidentifycopper(II),iron(II),iron(III),chromium(III)andmanganese(II)ionsinsolutionbasedonthecolouroftheprecipitateandtheactionofexcesssodiumhydroxideonit. Copper(II) addNaOH(aq) blueprecipitatethatdoesnotredissolveinexcessNaOH(aq) Iron(II) addNaOH(aq) dirtygreenprecipitatethatdoesnotredissolveinexcessNaOH(aq) Iron(III) addNaOH(aq) orange-brownprecipitatethatdoesnotredissolveinexcessNaOH(aq) Manganese(II) addNaOH(aq) palebrownprecipitatethatdoesnotredissolveinexcessNaOH(aq)

Chromium(III) addNaOH(aq) green-greyprecipitate,redissolvesinexcesstogiveagreensolution

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Ifaprecipitatedoesnotformwhensodiumhydroxideisadded,thecationpresentmightbetheammoniumion,NH4

+.Thepresenceofammoniumionsistestedbywarmingthesolutionwithsodiumhydroxide.Thiscausesanyammoniumionspresenttoreactwiththehydroxideionstoproduceammoniagas. NH4

+(aq)+OH-

(aq)" NH3(g)+H2O(l)Theevolutionofammoniagaswillcausedampredlitmuspaperheldatthemouthofthetesttubetoturnblue.