ORIGINOFCOLOUR IN TRANSITIONMETALCOMPLEXES

FOR CAPEUNIT1STUDENTS
INCLUDESTHE6MAINPOINTSTOGETYOUFULLMARKSINANYCAPEQUESTION.
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YOUWILLLEARN 1. 2. CrystalFieldTheoryandLigandField Theory yofcolour. 6mainpointstobeusedinansweringa CAPEquestionontheoriginofcolourin transitionelementcomplexes. p

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OriginOfColour

Thisis Thi i explained l i dby b the th Crystal C t lField Fi ldTheory Th andtheLigandFieldTheory.

Thesetheoriesregardthecomplex(ion)asan agglomerationofacentralionsurroundedby otherionsormoleculeswithelectricalfields.

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OriginOfColour

Theelectrical Th l t i lfield fi ldof fthe th central t lion i will illaffect ff t thesurroundingligands,whilstthecombined fieldoftheligandswillinfluencethe arrangement g ofelectronsinthecentralion.

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OriginOfColour

Thesplitting Th litti of fth thefi fivedorbitals bit l of fth the centralionintotwogroupsisoneofthe fundamentalideas.Inafreeion,asintheFe3+ ion,thefivedorbitalsaredegenerate g ,i.e. energeticallyalike.

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OriginOfColour Thefivedorbitalsarenot, ,however, ,allalikein shapeandthatiswhytheysplitupintotwo energeticallydifferentgroupsunderthe influenceoftheligandfield.

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OriginOfColour Thetwog groups p consistofthreeorbitals( (the t2g group)andoftwoorbitals(theeg group). Theextentandnatureofthedifferencein energybetweenthetwogroupsdependson thefieldstrengthoftheligandsandontheir geometricalarrangementaroundthecentral ion.
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OriginOfColour Andthearrangement g ofelectronsinthe centralionisdecidedbytheenergydifference betweenthet2g orbitals. 2 andeg groupsoforbitals

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OriginOfColour Thecolourofap particulartransitionmetalion dependsuponthenatureoftheligands (eitherneutralmoleculessuchaswaterwhich containlonepairsornegativeionssuchasthe chlorideion)bondedtotheion. ion

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OriginOfColour Thep palebluehydrated y copper(II) pp ( )ionchanges g todarkblueinthepresenceofammoniaand togreenifsufficientchlorideionsareadded; copper(II)chloridesolutionisthereforeeither blueorgreen green,dependingupontherelative concentrationsofwatermoleculesand chlorideions.
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OriginOfColour Thecolourofatransitionmetalionis associatedwith: (a) Anincompletedlevel(between1and9 delectrons) electrons). (b) Thenatureoftheligandssurroundingthe ion.
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OriginOfColour

Acompletetheoryofcolouris verycomplex but,putsimply,itisduetothemovementof electronsfromonedleveltoanother.

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OriginOfColour

Sincethe Si th five fi separate t 3dorbitals bit l are orientateddifferentlyinspaceanelectron(or electrons)whichisclosetoaligandwillbe repelled p andhencetheenergy gyofsuchorbitals willberaisedrelativetotheothers.

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OriginOfColour

Thedegeneracy Th d of fthe th 3dlevels l l is i therefore th f destroyed;thisisrepresentedpictorially,for thecopper(II)ion,inthefollowingdiagram.

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OriginOfColour

Thesplittingofthe3dorbitalsoftheCu2+ ioninan octahedralenvironmentofwaterligands.

Itwillbeseenfromtheabovediagramthat twoofthe3dlevelsareraisedinenergy relativetotheotherthree,theenergy differencebeing E .

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OriginOfColour

Theaboveorbitaldiagramdepictsthecolours absorbedintheexcitationofthedelectronto thehigherlevel level.

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OriginOfColour

Sincethe Si th degree d of fsplitting litti of fthe th 3dlevels l l dependsupontheparticularligands themselves,thevariationincolourofionsofa particulartransitionmetalisexplained. p p

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OriginOfColour

Thisseriesofoctahedralchromium(III)complexesillustrateshowthe energygapbetweenthet2g andeg orbitalgroupsaffectscolour.

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OriginOfColour

Absorption Ab ti spectra t show h th thewavelengths l th absorbedbyagivenmetalionwith differentligandsandbydifferentmetalions withthesameligand. g Fromsuch data,werelatetheenergyoftheabsorbed lighttothe values,andtwoimportant observationsemerge:
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OriginOfColour 1. Foragivenligand,thecolourdepends onthe th oxidation id ti state t t of fth themetal t li ion. Asolutionof[V(H2O)6]2+ ionisviolet,and asolutionof[V(H2O)6]3+ ionisyellow.

Solutionsof[V(H2O)6]2+ (left)and[V(H2O)6]3+ (right)ionshavedifferentcolours.

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OriginOfColour 2. Foragivenmetalion,thecolour d depends d onth theli ligand. d Even E asingle i l ligandsubstitutioncanhaveamajor effectonthewavelengthsabsorbedand, thus,thecolour,asy youcanseefortwo Cr3+ complexionsbelow.

Achangeinevenasingleligandcaninfluencethecolour.The[Cr(NH3)6]3+ ionisyellow orange(left);the[Cr(NH3)5CI]2+ ionispurple(right).

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CAPEhasaskedthis questiononly q ytwicein thelast10years. y

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CAPEhasaskedthis questiononly q ytwicein thelast10years. y

(Infacttheyveonlyaskedittwice inthehistoryoftheexams.)
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In2009itwentlikethis: Usethedistributioninthedorbitalsto accountf forcolourintransitionmetalions. [2marks]

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In2009itwentlikethis: Usethedistributioninthedorbitalsto accountf forcolourintransitionmetalions. [2marks]

andin2007itwentlikethis: Accountfortheoriginofcolourintransition metalcomplexes. [4marks]

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NEVERMINDTHEDIFFERENCE INMARKSALLOCATED. ALLOCATED

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NEVERMINDTHEDIFFERENCE INMARKSALLOCATED. ALLOCATED

Onceyouusethefollowing6pointsinyour answer,evenifthequestioncountsfor6 marks,y youregetting g gallofthem.

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MainPointsForAnsweringACAPEQuestion

1 Iftheionhaspartiallyfilleddorbitals 1. orbitals,it willbecoloured.Sc3+ andTi4+ haved0 structures andCu+ andZn2+ haved10 and structures, soarenotcoloured.

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MainPointsForAnsweringACAPEQuestion

2 dorbitals pointindifferentdirectionsin 2. space,andsointeracttodifferentextents withtheelectronsintheligands. ligands

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MainPointsForAnsweringACAPEQuestion

3.

Thiscausesasplittingofthedorbitals intotwogroupsofhigherenergyand lowerenergy. gy

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MainPointsForAnsweringACAPEQuestion

4.

Whenwhitelightisshone intothe substance,adelectronismovedfrom thelowerenergy gytothehigher g energy gy level.

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MainPointsForAnsweringACAPEQuestion

5.

Thefrequencyofthelightthatcauses thisjump isinthevisiblerange,sothat colouratthisfrequency q yisremoved from thewhitelight.Thecolournotremoved isseenasthecolourofthecomplex(ion).

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MainPointsForAnsweringACAPEQuestion

6.

Thecolourdependsonthesizeofthe energygap whichvarieswiththemetal ionandwiththetype yp ofligand. g

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