Determinationofan

EquilibriumConstant
Introduction
Whenchemicalsubstancesreact,thereactiontypicallydoesnotgotocompletion.
Rather,thesystemgoestosomeintermediatestateinwhichtheratesoftheforwardand
reverse reactions are equal. In this state, the reactants and the products have
concentrationswhichdonotchangewithtime.Suchasystemissaidtobeinchemical
equilibrium.Wheninequilibriumataparticulartemperature,areactionmixtureobeys
theLawofChemicalEquilibrium,whichimposesaconditionontheconcentrationsof
reactantsandproducts.ThisconditionisexpressedintheequilibriumconstantK cforthe
reaction.
In this experiment ( purpose) we will study the equilibrium properties of the
reactionbetweeniron(III)ionandthiocyanateiontofindtheequilibriumconstant:
3+ 2+
Fe (aq)+SCN (aq) FeSCN (aq)
3+
WhensolutionscontainingFe ionandthiocyanateionaremixed,theyreacttosome
2+
extent,formingtheFeSCN complexion,whichhasadeepredcolor.Asaresultofthe
3+
reaction,theequilibriumamountsofFe andSCN willbelessthantheywouldhave
2+ 3+
beenifnoreactionhadoccurred;foreverymoleofFeSCN formed,onemoleofFe

andonemoleofSCN willreact.TheequilibriumconstantexpressionK cforReaction1
is:
[FeSCN 2 ]
Kc
[Fe3 ][SCN ]
ThevalueofKc isconstantatagiventemperature. Thismeansthatmixtures
3+
containingFe andSCN willcometoequilibriumwiththesamevalueofK c,nomatter
3+
whatinitialamountsofFe andSCN wereused.Ourpurposeinthisexperimentwill
betofindKcforthisreactionforseveralmixturesthathavebeenmadeupindifferent
ways,andtoshowthatKc indeedhasthesamevalueineachofthemixtures. The
reactionisaparticularlygoodonetostudybecauseK cisofaconvenientmagnitudeand
2+
thecolorofFeSCN ionmakesforaneasyanalysisoftheequilibriummixture.
The mixtures will be prepared by mixing solutions containing known
concentrationsofiron(III)nitrate,Fe(NO3)3,andpotassiumthiocyanate,KSCN. The
2+
color of the FeSCN ion formed will allow us to determine its equilibrium
concentration. Knowing the initial composition of a mixture and the equilibrium
2+
concentrationofFeSCN ,wecancalculatetheequilibriumconcentrationsoftherestof
thepertinentspeciesandthendetermineKc.

2+
MethodforDetermining[FeSCN ]

21
 2+
Inthisexperiment,youwilluseaspectrophotometertodetermine[FeSCN ]in
theequilibriummixtures.
2+
TheFeSCN complexabsorbsbluelight. Thatiswhyithasareddishorange
color.Itabsorbsthemostlightatawavelengthof447nm.Therefore,atthiswavelength
2+
absorbance measurements will have the highest sensitivity to [FeSCN ]. In this
experiment,youwillmeasuretheabsorbanceofallsolutionsat447nm.
Inthefirstpartoftheexperiment,youwilldeterminetherelationshipbetweenthe
2+
absorbanceand[FeSCN ]at447nm.Youwilldothisbymeasuringthetransmittance
2+
ofthreestandardsolutions,inwhich[FeSCN ]isknown.Thereisaproblemhere:how
2+ 2+
can known concentrations of FeSCN be obtained? FeSCN participates in the
3+
equilibrium with Fe and SCN ions. Known amounts of the reactants will not
necessarilyyieldaknownamountoftheproduct.
This difficulty can be avoided. According to Le Chteliers principle, a net
reaction from left to right (that is, in the forward direction) occurs when more of a
reactantisadded.Asmoreandmoreofthesamereactantisadded,moreandmoreofthe
productwillbeformed.Itispossibletoaddsomuchofthisreactantthatessentiallyall
oftheotherreactantwillbeconvertedtoproduct. Youwilluselimitingquantitiesof
3+ 2+
SCN andoverwhelmingamountsofFe toproduceknownamountsofFeSCN in
2+
yourstandardsolutions.TheamountofFeSCN thatisformedwillthenbeessentially
equaltothestartingamountofthelimitingreactant.
Onceyouhavemeasuredthetransmittanceofthestandardsolutions,youwillplot
2+
the absorbances against the concentrations of FeSCN on a graph, or calibration
curve.Thepointsonthecalibrationcurvewillfallonastraightline,whichhasaslope
of b,theconstantofproportionalitybetweenabsorbanceandconcentration. Youcan
2+
usethiscalibrationcurvetofind[FeSCN ]inothersolutions.
Inthe secondpart oftheexperiment,youwillmeasurethetransmittanceofa
differentsetofsolutions,inwhichsubstantialamountsofbothreactantsandtheproduct
arepresent.Youwilluseyourcalibrationcurvetoconvertthemeasuredabsorbanceto
2+
theequilibriumconcentrationofFeSCN ineachsolution In preparing each of the
+
mixturesinthisexperimentyouwillmaintaintheconcentrationofH ionat0.5M.The
hydrogeniondoesnotparticipatedirectlyinthereaction,butitspresenceisnecessaryto
2+
avoidtheformationofbrowncoloredspeciessuchasFeOH ,whichwouldinterfere
2+
withtheanalysisof[FeSCN ].

PrelabQuestion

22
 Astudentdoesanexperimenttodeterminetheequilibriumconstantforthesame
reactionthatyouwillstudy,butatahighertemperature.
3+ 2+
Fe (aq)+SCN (aq) FeSCN (aq)
3
Thestudentmixes5.00mLof2.0010 MFe(NO3)3solutionwith5.00mLof
3
2.00 10 M KSCN solution, heats the mixture, and finds that the equilibrium
2+ 5
concentrationofFeSCN inthemixtureis5.0010 M.
Calculate the equilibrium constant for the reaction under the conditions in this
experiment.
Leavespaceandshowyourcalculationhere

ExperimentalProcedure
2+
Part1:Findingtherelationshipbetweenabsorbanceand[FeSCN ]
Label3mediumsizedtesttubes.Table1showstheamountsoftheconcentrated
3
0.20MFe(NO3)3(in1MHNO3)solution,2.0010 MKSCNsolution,andpurified
waterthatshouldbeaddedtoeachtube.Pipettheapproximateamountofeachsolution
intoeachtube.(Recordtheexactamountofeachsolutionthatyouactuallyadd.You
willneedtousetheseactualamountsinyourcalculations.)
ObtainarubberstopperClosethetopofthetesttubewiththestopperMixeach
solutionthoroughlybyinvertingthetesttubeseveraltimes. Zero the spectrophotometer.
Then,measureandrecordthetransmittanceofeachsolutionat447nm.

2+
Graphingtherelationshipbetweenabsorbanceand[FeSCN ].
2+
AssumingthatalloftheSCN ionshavebeenconvertedtoFeSCN ions,
2+
calculate[FeSCN ]ineachofthesolutionsinPart1.Forexample,intesttube12,1.0
3
mLofa2.00 10 MKSCNsolutionwasdilutedto10.0mL. Theconcentrationof
2+
SCN that results from this dilution is the one to use for determining [FeSCN ].

Because of the 1:1 stoichiometry, that initial concentration of SCN is equal to
2+
[FeSCN ].

2+
PlotafullpagegraphoftheabsorbanceagainsttheconcentrationofFeSCN in
allstandardsolutions.Usearulertodrawthebeststraightlinethatcomesclosesttoeach
ofyourfivedatapoints.Yourlineshouldpassthrough(0M,0).(Why?)Thisgraphis
yourcalibrationcurve.Whenyoumeasuretheabsorbanceofasolutionthatcontainsan
2+
unknownconcentrationofFeSCN ions,youcanusethiscalibrationcurvetodetermine
theunknownconcentration.Youcanuseyourgroupsdataortheclassaveragedata.

23
Table1Compositionofsolutionsforpreparingthecalibrationcurve.
Volumeof Volumeof Volumeof [FeSCN+2] %/T ABS
3
concentrated 2.0010 purified
Test 0.20MFe(NO3)3 MKSCN water
Tub in1MHNO3(mL) (mL) (mL)
e
11 5.0 0.50 4.5 1.0E4 42 0.3767
12 5.0 1.0 4.0 2.0E4 16 0.7958
13 5.0 1.5 3.5 3.0E.4 5 1.301

24
25
Part2:Determiningtheequilibriumconstant.
3
Label5mediumsizedtesttubes.Table2showstheamountsof2.0010 M
3
Fe(NO3)3 (in1MHNO3)solution,2.00 10 MKSCNsolution,andpurifiedwater
thatshouldbeaddedtoeachtube.Pipettheapproximateamountofeachsolutioninto
eachtube.(Recordthe exactamountofeachsolutionthatyouactuallyadd.Youwill
needtousetheseactualamountsinyourcalculations.)
Mixeachsolutionasbeforethoroughlybyinvertingthetesttubeseveraltimes.
Measureandrecordthetransmittanceofeachsolutionatthe447nm.

Table2Compositionofsolutionsfordeterminingtheequilibriumconstant.
Volumeof Volumeof Volumeof %T ABS [FeSCN+2]
3 3
2.0010 2.0010 purifiedwater
Test MFe(NO3)3 MKSCN (mL)
Tube in1MHNO3 (mL)
(mL)
21 5.0 1.0 4.0 74 0.1308 3.72E5
22 5.0 2.0 3.0 59 0.2291 5.99E5
23 5.0 3.0 2.0 49 0.3098 7.86E5
24 5.0 4.0 1.0 37 0.4318 1.07E4
25 5.0 5.0 none 30 0.5229 1.28E4

Determiningtheequilibriumconstant(Type2Problem)
CalculatethevalueoftheequilibriumconstantforReaction(1)fromyourdatafor
eachofthefivesolutionsinPart2.Youmayfindithelpfultoorganizeeachofyourfive
calculationsinanequilibriumtablesuchasthisone:
3+ 2+
Fe (aq) + SCN (aq) FeSCN (aq)
Initialconcentration(M) 0.001 2.0E4 0
Changeinconcentration(M) 3.27E5 3.72E5 +3.72E5

Equilibrium concentration 9.63E4 1.62E4 3.72E5

(M)

Kc=[FeSCN2+]/[SCN][Fe3+]
Kc=3.72E5/1.62E4*9.63E4

26
Kc=238.5
Kc=2.4E2
3+ 2+
Fe (aq) + SCN (aq) FeSCN (aq)
Initialconcentration(M) 0.001 4.0E4 0
Changeinconcentration(M) 5.99E5 5.99E5 +5.99E5

Equilibrium concentration 9.40E4 3.40E4 5.99E5

(M)
Kc=[FeSCN2+]/[SCN][Fe3+]
Kc=5.99E5/3.40E4*9.40E4
Kc=187.4
3+ 2+
Kc=1.9E2 Fe (aq) + SCN (aq) FeSCN (aq)
Initialconcentration(M) 0.001 6.0E4 0
Changeinconcentration(M) 7.86E5 7.86E5 +7.86E5
Equilibrium concentration 9.21E4 5.21E4 7.86E5
(M)
Kc=[FeSCN2+]/[SCN][Fe3+]
Kc=7.86E5/5.21E4*9.21E4
Kc=163.8
3+ 2+
Kc=1.6E2 Fe (aq) + SCN (aq) FeSCN (aq)
Initialconcentration(M) 0.001 8.0E4 0
Changeinconcentration(M) 1.07E4 1.07E4 +1.07E4

Equilibrium concentration 8.93E4 6.93E4 1.07E4

(M)
Kc=[FeSCN2+]/[SCN][Fe3+]
Kc=1.07E4/6.93E4*8.93E4
Kc=172.9
Kc=1.7E2
3+ 2+
Fe (aq) + SCN (aq) FeSCN (aq)
Initialconcentration(M) 0.001 0.001 0
Changeinconcentration(M) 1.28E4 1.28E4 +1.28E4

Equilibrium concentration 8.72E4 8.72E4 1.28E4

(M)
Kc=[FeSCN2+]/[SCN][Fe3+]

27
Kc=1.28E5/8.72E4*8.72E4
Kc=168.3
Kc=1.7E2
ThecalculationsforPart2aremosteasilydonebyfollowingSteps1through5
3+
Step1. FindtheinitialconcentrationsofFe andSCN inthemixturesintesttubes2
1through25.Youwillneedtoaccountfordilutionsofthestocksolutions.
Step2. Usethemeasuredabsorbancesofthesesolutionsandyourcalibrationcurveto
2+
findtheequilibriumconcentrationof[FeSCN ]inthesesolutions.
2+
Step3. Find the change in concentration of FeSCN . Deduce the changes in
3+
concentrationofthereactants,Fe andSCN .Thechangesinconcentrationof
allthreespeciesshouldbeconsistentwiththestoichiometryofthereaction.
3+
Step4. Findtheequilibriumconcentrationsofthereactants,Fe andSCN .
Step5. CalculateKcforthereactionforeachofthemixturesbysubstitutingvaluesfor
3+ 2+
the equilibrium concentrations of Fe , SCN , and FeSCN into the
equilibriumconstantexpression.

Usetheabovetable(copy)andrepeatforthefoursetsofdata.
CalculatetheaverageKcforthereaction.

Question.
2+
InPart1ofthisexperiment,youmadetheassumptionthattheFeSCN concentrations

inyourstandardsolutionswereequaltotheinitialconcentrationsofSCN ions.
Now that you know the value of the equilibrium constant, calculate the actual
3+ 2+
equilibriumconcentrationsofFe ,SCN ,andFeSCN inmixtureintesttube12.
(Howgoodwastheassumption?)(leavespaceandputyouranswerhere)
Conclusion:

28