EXPERIMENT3 THEEQUILIBRIUMCONSTANT PURPOSE: 1. Toexaminetheeffectofchangingreactantconcentrationsonachemicalequilibrium. 2. Todeterminetheequilibriumconstantforthefollowingequilibrium: 3+ - 2+ Fe (aq) + SCN (aq) FeSCN (aq) PRINCIPLES: Whenchemicalreactionsoccur,reactantsareusedupandproductsareformed. Formanyreactions,thisprocessisirreversible(reactiongoestocompletion)andproductsform totheextentof100%.Thenetresultisthatonlyproductsandnoreactantsarepresentinthe system.

Thesetypesofirreversiblechangesoftenhappenwhenaninsolublesolidforms (precipitationreactions)orwhenoneoftheproductsisagas. A + B C + D

Forotherchemicalchanges,theproductscanreacttoreformtheoriginalreactants.Thesetypeof reactionsaresaidtobereversible.Inthissituation,boththeforwardreaction(formationof products)andthereversereaction(reformationofreactants)areoccurringsimultaneously.

forward

B
reverse

Thesetwosimultaneousprocessescontinuetooccuruntilequilibriumisreached.Atequilibrium bothreactantsandproductsarepresentinthesystem (A,B,C,D)butnotnecessarilyinthe sameamounts. Atequilibrium,therateoftheforwardreactionisequal totherateofthereversereaction: RateofForwardReaction = RateofReverseReaction

Therateofanyreactionisproportionaltotheconcentrationofthereactingspecies. Itfollowsthat: RateofForwardReaction=kf [A][B] RateofReverseReaction= kr [C][D]

where:kf andkr areproportionalityconstantscalledRateConstants. SincechemicalequilibriumisdefinedasthestateofthesysteminwhichtheRateoftheForward ReactionisequaltotheoftheReverseReaction,thenthefollowingmustbetrue: kf [A][B]= kr [C][D] Thisequationcanberewrittenbycollectingallthereactantandproductconcentrationsonthe samesideoftheequationandtheRateConstantsontheotherside: kf [C][D] = =Keq =EquilibriumConstant kr [A][B] 1

EXPERIMENT3 THEEQUILIBRIUMCONSTANT InthisexperimentyouwilldeterminethenumericalvalueoftheKeq (theequilibriumconstant) 3+ forthereactionbetweentheferricion(Fe )andthethiocyanateion(SCN-)toformthered 2+ orangecoloredFeSCN complexion:

3+ Fe (aq) paleyellow

SCN-(aq) colorless

2+ FeSCN (aq) redorange

3+ TheFe (aq)ionsarederivedfromanaqueoussolutioniron(III)nitrate,Fe(NO3)3,andthe - SCN (aq)ionsarederivedfromanaqueoussolutionofsodiumthiocyanate,NaSCN. + Thenitrateions,NO3- andthesodiumions,Na arespectatorions,andassuchtheydonot participateinthereaction.

Notethatforthisequilibrium:
2+ [FeSCN ] = 3+ - [Fe ][SCN ]

Keq

3+ Youwilldeterminetheeffectofincreasingtheconcentrationof[Fe ]ontheextentofformation 2+ oftheredorangecoloredcomplexofFeSCN . 2+ TodeterminetheconcentrationoftheredorangecoloredcomplexofFeSCN atequilibrium,an instrumentcalledaspectrophotometerisused. Thespectrophotometerisaninstrumentthatmeasuresnumericallythecolorintensityof solutionsbymeasuringhowmuchlightisabsorbed(Absorbance,A)and/ortransmitted (Transmittance,T)byacoloredsolution. Thehigherthecolorintensityofasolution(higherconcentration),thehighertheAbsorbance,A ofthesolution(morelightisabsorbedbythesolution)andthelowertheTransmittance,Tofthe solution (lesslightistransmittedthroughthesolution). RangefortheAbsorbance: A=0.0 2.0 (dimensionlessnumber) RangeforTransmittance, T=100 0% (expressedasapercentorasadecimal)

Notethatwhenallofthelightisabsorbed(A=2.0),nolightistransmitted(T=0%) Conversely,whennolightisabsorbed(A=0.0),allofthelightistransmitted(T=100%) Absorbance,A,andTransmittance,Tarerelatedbythefollowingrelationship: 1 A= log Tisexpressedasadecimalinthisequation! T Theaboverelationshipisuseful,sinceTransmittance,T,readingsareeasiertoreadfromthe spectromotometerthanAbsorbance,A,readings.However,thequantity thatisdirectlyrelatedto theconcentrationofacoloredsolutionistheAbsorbance.Inthisexperimentyouwillbereading theTransmittanceofsolutionsofdifferentunknownconcentrations,andthenwillconvertyour TransmittancereadingtoAbsorbancereadings. 2

EXPERIMENT3 THEEQUILIBRIUMCONSTANT TheAbsorbancereadingswillthenbeusedtocalculatetheconcentrations. 2+ 2+ AslightpassesthroughtheredorangecoloredsolutionofFeSCN ,itinteractwiththeFeSCN ions.Theseionswillabsorblightofacertainwavelength(linnanometers).Thelightthatisnot 2+ absorbedbytheFeSCN ionsistransmittedthroughthecoloredsolutionandisseenbytheeye. Thistransmittedlighthasacharacteristiccolorwhichwecallthecolorofthesolution. 2+ Thetotal Absorbance,Aisdeterminedby boththesolute(FeSCN )andthesolvent(water). Inaddition,thecontainer (calledacuvet),usedtoholdthecoloredsolutionforthe Absorbancemeasurements,alsoabsorbslight. Total Lightabsorbed Light=by 2+ Absorbed FeSCN Lightabsorbed Lightabsorbed +by+by Watercuvet

TheAbsorbance,A,ofwaterandofthecuvetareautomaticallycorrectedforduringthe measurements(seeProcedure) 2+ TheconcentrationoftheFeSCN canbecalculatedfromAbsorbancemeasurementsusing BeersLaw. BeersLawstatesthattheAbsorbance,a,ofacoloredsolutionisdirectlyproportionaltothe concentration,C,ofthecoloredsolution: AaC 2+ TheAbsorbance,A,ismeasuredatthewavelengthofthemaximumabsorbanceofFeSCN , whichis449nm. AsimpleapplicationofBeersLawwillbeusedinthisexperimenttocalculatetheunknown 2+ concentrationsoftheredorangeFeSCN complexinyoursolutions.Youwillpreparea 2+ referencestandardthathastheMaximumConcentrationofFeSCN (Cref)andrecordits absorbancevalue,Aref . Aref =ConstantxCref
2+ whereCref =MaximumConcentrationof SCN =2.00x10 -4 M

Forsolutionofunknownconcentration,C1 (ExampleSolution1),A1 isdetermined experimentally.ApplyingBeersLaw: A1 =ConstantxC1 Aref A1 Constant= = Cref C1 whereC1 isunknown A1 x Aref

Rearrangingtofindtheunknown: C1 =Cref

Forexample: Theabsorbanceat449nmoftheReferenceStandard: TheconcentrationoftheReferenceStandard: Theabsorbanceofasolutionofunknownconcentration: Theconcentrationofsolutionx:

Aref =0.901 Cref =2.00x10 -4 M Ax =0.612 Cx =?

EXPERIMENT3 THEEQUILIBRIUMCONSTANT Ax 0.612 Cx =Cref x = 2.00x10 -4 Mx =1.36x10-4 M Aref 0.901 2+ OncetheequilibriumconcentrationoftheredorangecomplexofFeSCN isknown,the 2+ - equilibriumconcentrationsofthereactants(Fe eq andSCN eq)canbecalculated,asitsishown below:
3+ Fe (aq)

- SCN (aq)

2+ FeSCN (aq)

Initial Concs:80.0xx10 -4 M

2.00xx10 -4 M

Change: 1.36x10 -4 M

1.36x10 -4 M

+ 1.36x10 -4 M

Equil. Concs:80.0x10 -4 M 2.00x10 -4 M 1.36x10 -4 M1.36x10 -4 M 78.6x10-4 M 0.64x10-4 M

0+ 1.36x10 -4 M 1.36x10-4 M

Once,theequilibriumconcentrationsareknown,theEquilibriumConstant,Keq canbeeasily calculated:

3+ [Fe ]eq = - [SCN ]eq = 2+ [FeSCN ]eq =

78.6x10-4 M 0.64x10-4 M 1.36x10-4 M

Keq

2+ [FeSCN ]eq 1.36x10-4 M -1 = = =270M (2SigFigs) 3+ [Fe ]eq [SCN ]eq (78.6x10-4 M)(0.64x10-4 M)

EXPERIMENT3 THEEQUILIBRIUMCONSTANT PROCEDURE: I. Turningonthespectrophotometer. 1.Makesurethatthesamplecompartmentisempty 2.PressVISonthespectrophotometer(DONOTPRESSUV).Thelampwillturnon 3.Letthelampwarmupforatleast10minutes. II. PreparationofReactionMixtures 1.Thoroughlycleanfive(5)testtubes(18mmx150mm). 2.Rinsewithdeionizedwaterandallowtodrainasdryaspossible. 3.Labelthetubes:1,2,4,8,andXS(excess) 4.Addthereagentsaccordingtothetablebelow:
3+ PreparationofmixturesofFe andSCN - inafinalvolumeof15.0mL Tube Relative Fe(NO3)3 NaSCN HNO3 3+ -2 -4 label [Fe ] (0.10M) (6.00x10 M) (6.00x10 M) 1 x1 1.00 5.00 9.00 2 x2 2.00 5.00 8.00 4 x4 4.00 5.00 6.00 8 x8 8.00 5.00 2.00 3+ PreparationofmixturecontaininganexcessofFe Tube Relative Fe(NO3)3 NaSCN 3+ label [Fe ] (0.10M) (6.00x10 -4 M) 10.00 5.00 XS excess

HNO3 (0.10M) 0.00

5.Cover(seal)eachtesttubewithapieceofsaranwraporparafilm 6.Mixthecontentsofeachtubebyinvertingtubesseveraltimes. 7.GotothenextstepIMMEDIATELY! NOTE: ReadtheAbsorbanceofthesolutionswithin10minutes.Thesolutionsarenotstable soyoucannotstorethesolutionbeyondthattimeperiod.

III.

AbsorbanceReadings 1.Preparingthecuvet (a)Obtainacuvetandholditwithtissuepaper(yourfingerprintswouldaffect yourreadings). (b)Rinsethecuvetthoroughlywithdeionizedwaterandfillit2/3fullwith deionizedwater. (c)Setalargebeakerforwastenexttothespectrophotometerandplaceyour washbottlenearby.

EXPERIMENT3 THEEQUILIBRIUMCONSTANT 2.Zeroing (a)WipetheoutsideofthecuvetgentlywithaKimWipetoremoveanyexcess water. (b)Liftthedoorofthesamplecompartmentofthespectrophotometerandplace thecuvetinthesamplecompartmentintheproperorientation. ASKYOURINSTRUCTORABOUTTHEPROPERORIENTATION OFTHECUVET. Closethesamplecompartment. (c)Setthewavelength(l )onthespectrophotometerto449nm. Note:yourlabinstructormayhavealreadydonethisforyou. (d)PressCALIBandwaituntil0.000appearsontheAbsorbancedisplay. (100%T) PressCALIBagainifthenumberappearstodrift.Waituntilfurtherdrift stopsandpressCALIB. NOTE:Dependingonthetypeofspectrophotometeravailablethisstepmay beslightlydifferentHowever,keepinmindthatthepurposeofthis stepistoautomaticallycorrecttheAbsorbance,A,of waterandof thecuvetforfurthermeasurements. Assuch,aftercompletingthisstep,thespectrophotometershouldread: Absorbance=0.000and Transmittance=100% (e)Liftthedoorofsamplecompartmentandremovethecuvet.Closedoor. (f)Pourthewateroutintothewastebeakerandshakeanyexcessoutofthecuvet. 3.MeasuringtheAbsorbanceofthesolutions (a)Usingsolution1(withtheleastamountofcolor),carefullypourthesolution intothecuvetto2/3full. Pourthisbackintothetubeandrepourthesolutionintothecuvetto2/3full. Thiswillmixinanddiluteanytracesofwaterleftinthecuvet. (b)WipetheoutsideofthecuvetgentlywithaKimWipetoremoveanyexcess solution.Thisisaprecautionincaseyouaccidentallyspilledsolutiononthe outsideofthecuvetortouchedthemwithyourhands. (c)Liftthedoorofthesamplecompartmentandplacethecuvetinitinthe properorientation.Closethesamplecompartment. DONOTPRESSANYKEYS! (d)RecordtheAbsorbanceofthesolution. Ifyouspectrophotometeryouareusinghasadigitalreadout,readthe Absorbancedirectly.Ifthereisnodigitalreadout,readtheTransmittancein %andconvertittoAbsorbancereadings(Seepage2) (e)Repeatsteps(a)through(d)withtheothersolutions. (f)Removethecuvetfromthespectrophotometer. (g)ShowyourAbsorbance(transmittance)readingstoyourinstructor.

EXPERIMENT3 THEEQUILIBRIUMCONSTANT NAME:__________________________ PARTNER:_______________________ REPORTFORM PartI:CalculatingtheInitialConcentrationoftheReactantsinthe15.0mLReactionMixture 3+ Foreachtesttube,calculatetheInitialConcentrationsofthetworeactants(Fe andSCN-) Useexponentialnotationandexpressallofyourcalculatedconcentrationsin: #x10-4 M Usepropersignificantfigures. Sincethetotalvolumeineachtesttubeis15.0mL,thisvolumemustbetakenintoaccountin calculatingtheinitialconcentrationsofthetworeactants. Forexample,intesttube1,sincethe1.00mLof6.00x10 -2 MFe(NO3)3 addedreactsinatotal 3+ volumeof15.00mL,theinitialconcentrationof[Fe ]canbecalculatedtobe: 1.00mL 3+ [Fe ]=6.00x10 -2 Mx = 40.0x10-4 M 15.00mL
3+ Carryoutsimilarcalculationsforallotherinitialvaluesof[Fe ]and[SCN-]

Tube Label 1

3+ [Fe ],M

[SCN-],M

Sameasintesttube#1

Sameasintesttube#1

Sameasintesttube#1

3+ XSFe

Sameasintesttube#1

EXPERIMENT3 THEEQUILIBRIUMCONSTANT
2+ PartII:CalculatingtheEquilibriumConcentrationoftheProduct(FeSCN )fromAbsorbance Readings

DATATABLE#2 Tube Label Transmittance (%) (ifneeded) Absorbance Calculations (seePage3forSample Calculation) Equilibrium Concentration 2+ ofFeSCN (M) #x10-4

XS (reference)

3+ 3+ *Inthereferencetube(excessFe ),thelargeexcessofFe speedsuptheforwardreactionand thereforeshiftstheequilibriumallthewaytotheright.AlloftheSCN- presentwillbeboundin 2+ theFeSCN form. - 2+ SincetheSCN- isthelimitingreagent,then: [SCN ]initial =[FeSCN ]equilibrium ThisisexplainedintheEquilibriumTablebelow: 3+ - Fe (aq) + SCN (aq) ReactantinexcessLimitingReactant 2+ FeSCN (aq)

InitialConcslargeexcess Change: X

X+X X

Equil.ConcslargeexcessX0

EXPERIMENT3 THEEQUILIBRIUMCONSTANT PartIII:CalculatingtheEquilibriumConcentrationoftheReactants 3+ - 2+ 1. Complete[Fe ]initial,[SCN ]initial,and[FeSCN ]equil fromdataobtainedinPartIand PartII(DataTable#1andDataTable#2) DATATABLE#3 3+ 2+ 3+ - - Tube [Fe ]initial [FeSCN ]equil [Fe ]equil [SCN ]initial [SCN ]equil Label (M) (M) (M) (M) (M) 1 2 4 8 XS
3+ - 3+ - 2+ 2. Calculate[Fe ]equil and[SCN ]equil from [Fe ]initial,[SCN ]initial,and[FeSCN ]equil byusingtheEquilibriumTablesprovidedbelow(seePage4foranexample)

Tube#1
3+ Fe (aq)

- SCN (aq)

2+ FeSCN (aq)

Initial: Concs: Change: Equil Concs: Tube#2

3+ Fe (aq)

- SCN (aq)

2+ FeSCN (aq)

Initial: Concs: Change: Equil Concs:

EXPERIMENT3 THEEQUILIBRIUMCONSTANT Tube#4

3+ Fe (aq)

- SCN (aq)

2+ FeSCN (aq)

Initial: Concs: Change: Equil Concs:

Tube#8
3+ Fe (aq)

- SCN (aq)

2+ FeSCN (aq)

Initial: Concs: Change: Equil Concs

3+ - 3. Enteryourcalculatedvaluesfor [Fe ]equil and[SCN ]equil intheappropriateDataTable#3

PartIV:CalculatingtheEquilibriumConstant(Keq) (SeePage4forasamplecalculation) DATATABLE#4 Tube Label

3+ [Fe ]equil,M - [SCN ]equil,M 2+ [FeSCN ]equil,M -1 Kequil (M ) (2SigFigsallowed) (carryoneadditional SigFigtobedropped inthenextstep)

1 2 4 8 10

EXPERIMENT3 THEEQUILIBRIUMCONSTANT PartV:CalculatingtheAverageValueoftheEquilibriumConstant(Keq) Answershouldbegivenin decimalnotation(notexponential)and 2SignificantFigures!

PARTVI:InterpretingthedatainviewofLeChateliersPrinciple 1. Completethefollowingtableandtheblanksbelowthetablebyentering:increased, decreased,stayedthesame,totheright, totheleft,asappropriate Considerthetrendgivenbyyourdataingoingfromtube#1 >tube#8

3+ Fe (aq)

- SCN (aq)

2+ FeSCN (aq)

Stress(Change):

EquilibriumShift:

NewEquilibrium: (5) 2. HowdoesthedatafromthisexperimentillustrateLeChateliersprinciple? Answerbycompletingtheblanks. (10) Astheconcentrationof _________ is____________theequilibrium_________________ Asaresult: Theequilibrium concentrationof ___________ is ________________ Theequilibrium concentrationof ___________ is ________________ Theequilibrium concentrationof ___________ is ________________ TheEquilibriumConstant,Keq _________________________________

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EXPERIMENT3 THEEQUILIBRIUMCONSTANT

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