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ChemicalKinetics

Chemistry1121
WesleyR.HarrisandKeithJ.Stine

Objectives
(a)Tomeasuretherateofachemicalreactionundervariousconditionstodeterminetherateequation
forthereaction.
(b)Tousetherateequationfrompart(a)todeterminetherateconstant.
(c)Tousetheinformationfromparts(a)and(b)topredicttherateofareactionunderanewsetof
conditions.

Introduction
Chemicalkineticsinvolvesthestudyofhowrapidlyareactionproceeds.Consideragenericchemical
reaction

A+BC

(1)
Therateofthereactionisexpressedasthechangeintheconcentrationofareactantorproductperunit
time.Wecanselectanygivenreactantorproducttomeasuretherate.Basedontheproductofthe
reaction,C,therateofthereactionineq(1)canbedefinedas

Rate

[C ]

(2)

Theratelawisamathematicalequationthatdescribestherelationshipbetweentheconcentrationsof
thereactantsandtherateofthereaction.Forthisexample,theratelawis

Rate

[C ]
k[ A]x [ B ] y
t

(3)

Thevaluesfortheexponentsxandyineq(3)arenotbasedonthestoichiometriccoefficientsineq(1).
Theymustbedeterminedexperimentally.Themostcommonvaluesfortheseexponentsare0,1or2.
Theseexponentsrepresenttheorderofthereactionwithrespecttoaspecificreactant.Thusifthe
exponentforreactantAis1,thenthereactionisfirstorderinA.Iftheexponentis2,thenthe
reactionissecondorderinA.

Iftheexponentforareactantineq(1)is1or2,thentherateofthereactionwillincreaseasthe
concentrationofthereactantincreases.ConsiderthesampledatainTable1.

Table1.Sampledataset1
ExperimentNo.
[A](Molarity)
[B](Molarity)
rate(M/s)

0.1

0.1

1x103

0.2

0.1

2x103

0.1

0.2

4x103

IfwecompareExperiments1and2,theconcentrationofBstaysconstant,whiletheconcentrationofA
doubles.WhentheconcentrationofAdoubles,theratealsodoubles.Thiscanbetrueonlywhenx,the
exponentforAineq(3),isequalto1.IfwecompareExperiments1and3,theconcentrationofAstays
thesame,whiletheconcentrationofBdoubles.WhentheconcentrationofBincreasesbyafactorof2,
therateincreasesbyafactorof4.Thisindicatesthaty,theexponentforBineq(3),mustbe2.Thus
wecanwriteanexperimentallydeterminedratelawforthisreactionas

(4)
Rate
k [ A][ B ]2
Itisgenerallypossibletodeterminetheorderofthereactionbyinspectionofthedata.Alternatively,
onecancalculatethevalueofxory.Assumingthatwemeasuretherateattwodifferent
concentrationsofAwhilekeepingtheconcentrationofBconstant,theorderofthereactionwith
respecttoAcanbecalculatedas

rate1
log

rate2

[ A]1
log

[ A]2

(5)

Theexponentforaspecificreactantmaybezero,inwhichcasetherateofthereactiondoesnotchange
whentheconcentrationofthereactantchanges.Considerasecondsetofsampledataforeq(1)shown
inTable2.

Table2.Sampledataset2
ExperimentNo.
[A](Molarity)
[B](Molarity)
rate(M/s)

0.1

0.1

1x105

0.2

0.1

2x105

0.1

0.2

1x105

Inthisexample,therateofthereactiondoubleswhentheconcentrationofAdoubles,sotheexponent
xforAineq(3)is1,andthereactionisfirstorderinA.However,whentheconcentrationofBdoubles,
theratestaysthesame.ThustheexponentyforBineq(3)iszero,andthereactioniszerothorderinB.
Insuchcases,itiscommonpracticetodeletethatreactantfromtherateequation.Giventhatthatx=1
andy=0,thentherateequationwouldbe

(6)
Rate k [ A]1[ B ]0 k[ A]
WecandroptheBtermineq(6)becauseanyvalueforthe[B]raisedtothezeropowerisequalto1.

ReactionforthisLab
Inthisexperiment,thereactiontobestudiedis

3I(aq)+H2O2(aq)+2H+(aq)I3(aq)+2H2O(l)

(7)

Thisisaredoxreaction.ThehydrogenperoxideoxidizestwoIionstoI2,moleculariodine,whichthen
combineswithathirdIioninanonredoxreactiontoformtheI3anion.Wewillexpresstherateofthis
reactionintermsoftheformationofproductas

Rate

[ I 3 ]

(8)

[ I 3 ]
Rate
k[ I ]x [ H 2O2 ] y [ H ]z
t

(9)

Theratelawforthisreactionis

Theexponentsx,y,andzmustbeestablishedexperimentally,bychangingtheconcentrationofoneof
thereactants,andthenassessingthedegreetowhichtheexperimentalreactionratechanges.To
simplifythislab,allthereactionswillberuninthepresenceofalargeexcessofH+.Becauseofthis
excess,the[H+]willnotchangesignificantlyduringthecourseofanyifthereactions.Sincethe[H+]will
beconstantforallthereactions,wecaneliminate[H+]fromtherateequation,soeq(9)canbe
simplifiedto

Rate

[ I 3 ]
k[ I ]x [ H 2O2 ] y
t

(10)

Notethatthevalueofkthatappearsineq(10)maybevalidonlyatthe[H+]usedinthisexperiment.If
thezexponentineq(9)isnotzero,thentherateofthereactionwouldbedifferentifweranthe
reactionatadifferentpH.

Todeterminetherateofthereactionasdefinedineq(10),weneedsomeexperimentalmethodto
determinethechangeinthe[I3]asafunctionoftime.Therearevariouswaysonecoulddothis.For
example,I3absorbsvisiblelight,sowecouldmeasuretheabsorbanceofthesolutionasafunctionof
time.Butthisrequiresexpensiveequipment.Instead,wearegoingtouseagimmick,whichwillallow
youtomeasurethereactionratesusingonlyyoureyesandastopwatch.

Whenyourunthereactionshownineq(7),youaregoingtoaddtwoextrareagents,i.e.compounds
thatdonotappearasreactantsorproductsineq(7).Oneisthiosulfate(S2O32).Thecriticalpropertyof
thiosulfateisthatitreactsveryquicklywithI3,reoxidizingittoIasshownineq(11).

2S2O32(aq)+I3(aq)3I(aq)+S4O62(aq)

(11)

Theotherextrareagentisstarch(apolymerofglucose),whichreactswithanyI3thatremainsinthe
solutiontogenerateadeepbluecolorthatisveryeasyforyoutosee.

Whenthereactionbegins,peroxidewillbegintooxidizeItoI3,butthisI3willbeimmediately
consumedbythethiosulfate.SincenoI3willbeaccumulatinginthesolution,thereisnoreactionwith
thestarch,andthesolutionremainscolorless.Theexperimentisdesignedsuchthatthiosulfateisthe
3

limitingreagent.Thismeansthattheconcentrationsofbothperoxideandiodidearemuchgreaterthan
theconcentrationofthiosulfate,sothatthethiosulfateisdepletedbeforethereisanysignificantchange
intheconcentrationsoftheotherreagents.Assoonasthethiosulfateisdepleted,theI3thatisbeing
generatedbyeq(7)accumulatesinthesolution,reactswiththestarch,andproducesadeepbluecolor.
Thusyoucanliterallyseewhenthethiosulfatehasbeendepleted.

Inthisexperiment,the[S2O42]ineachsolutionis8mM.Basedonthestoichiometryineq(11),8mM
thiosulfatewillbeconsumedaftertheproductionof4mMofI3.Thustherateofthereactionfromt=0
tothetimethatthebluecolorappears(t)canbecalculatedas

Rate

[ I 3 ] 0.004 M

t
t

(12)

StockSolutions
1.0Msulfuricacid(H2SO4)
3%hydrogenperoxide(H2O2)
0.08Msodiumthiosulfate(Na2S2O4)
0.2Mpotassiumnitrate(KNO3)
0.2Mpotassiumiodide(KI)
0.1MdisodiumEDTA
1%starchsolution

ExperimentalProcedure
PartA.DataCollection
1.StarchandEDTAsolutionswillbeavailableindropperbottles.Transferasmallaliquotofeachofthe
otherstocksolutionstoabeaker/flaskfromyourlabdrawer.Allthesolutionsarecolorless,sobe
suretolabeleachbeaker.Forthisexperiment,youwillneedthefollowingapproximatevolumes.
Pleasedonottakemoresolutionthanyouneed.

sulfuricacid
75ml

sodiumthiosulfate
75ml

potassiumiodide
125ml

hydrogenperoxide
75ml

potassiumnitrate
400ml

2.Eachreactionshouldberunina125mlErlenmeyerflask.Runthereactionforthefoursetsof
conditionslistedinTable3.Foreachreaction,thefinalsolutionshouldcontain1ml(~20drops)of
thestarchindicatorand5dropsofEDTA.TheEDTAbindsanymetalionsthatmightbepresentin
thesolutionsandpreventsthemfromaffectingtherateofthereaction.

3.Theorderinwhichyoumixthereagentsmatters.Youdontwantthereactiontostartprematurely.
MixthereagentsastheyappearfromlefttorightinTable3.Thereactionwillstartwhenyouadd
theperoxide.MakesureyouhaveaddedthestarchandtheEDTAbeforeyouaddtheperoxide.

4.Inordertomeasurethevolumesasaccuratelyaspossible,youneedtousegraduatedcylindersof
theappropriatesize.Volumesof5mlshouldbeaddedusinga5mlgraduatedcylinder.Volumes
between6and10mlshouldbeaddedwitha10mlgraduatedcylinder.Ifyouhavetouseasingle
graduatedcylinderformorethanonesolution,besuretorinseitwithdistilledwateranddryitas
bestyoucanwhenswitchingfromonesolutiontotheother.

TheKNO3solutioncanbeaddedwitha50or100mlgraduatedcylinder.Thissolutionisaddedas
neededtomaintainaconstantvolume.Therateofthereactiondependsontheionicstrengthofthe
solution,soasolutionofKNO3isusedforthispurposeratherthanjustaddingdistilledwater.The
KNO3doesnotdirectlyparticipateinthereaction.

5.Mixallofthereagentsexcepttheperoxideintoa125mlErlenmeyerflask.Addtheperoxidewith
swirlingtomixthereagentsandstartthestopwatchimmediately.Oncethesolutionisthoroughly
mixed,placetheflaskonawhitesheetofpapersothatyoucanseethecolorclearly.Duringthe
reaction,watchthesolutionclosely.Thebluecolorwillappearverysuddenly.Stopthestopwatchat
thefirstappearanceofabluecolor,andrecordthetimeinTable4.Ifyouarelookingawaywhenthe
colorappearsandfailtogetanaccuratetime,repeatthereaction.Foreachsetofconditions,obtain
threereliablereplicatevaluesoft.

Afterthereactionsolutionsturnblue,theshadeandintensityofthecolormaychange.Ignoreany
suchchanges.Thecorrecttimeforthereactioncorrespondstotheinitialappearanceontheblue
color.

PartB.DetermineRateEquation
6.Useeq(12)tocalculatethereactionratecorrespondingtoeachofyourvaluesfort,andenterthe
valuesfortheratesinTable5.Foreachsetofreactionconditions,calculatetheaveragereaction
rateandrecordthisvalueinTable5.

7.CalculatethemolarityofKIandH2O2presentineachofyourreactionsolutions.Thisisadilution
calculationbasedonthegeneralformulaM1V1=M2V2.Giventhatthefinalvolumeforeachsolution
is50ml,theconcentrationofeachreagentcanbecalculatedas

[ X ]reaction solution

[ X ]stock solution Vstock solution (ml )


50 ml

(14)

AddthecalculatedconcentrationsofperoxideandiodidetoTable5.

8.Table5nowcontainstheconcentrationsofperoxideandiodideandthereactionrates.Analyze
thesedatatodeterminetheorderofthereactionwithrespecttoiodideandwithrespectto
peroxide.Recordthereactionsorders(thexandyexponentsineq10)belowTable5.Insertthese
exponentsintoeq(10)andwritetheresultingrateequationbelowTable5.
5

PartC.DetermineRateConstant
9.Oftheparametersinyourrateequation,youshouldnowhavedeterminedvaluesfortherate,[I],
[H2O2],xandy.Theonlyremainingparameterintherateequationistherateconstant,k.Useyour
rateequationwiththeaveragerateforeachsetofsolutionstocalculatetherateconstantforthis
reaction,andrecordtheserateconstantsinTable5.Calculatetheaveragerateconstantforallthe
solutionsandrecordthisvalueinTable5.

PartD.DesignanExperimenttoGivet=120s
10.Basedoneq(12),avalueoft=120swouldcorrespondtoareactionrateof3.33x105M/s.Thus
youcanrewritetherateequationas

(15)
Rate 3.33 x 105 M / s k[ I ]x [ H 2O2 ] y
usingthevaluesofxandythatyoudeterminedinPartB.

Prepareanewreactionsolutionthatwillgiveavalueoft=120s.Use5mlofH2SO4,5mlof
thiosulfate,and3mlofperoxideasshowninTable6.Assumingthatthetotalvolumewillbe50ml,
useeq(14)tocalculatetheconcentrationofperoxidethatwillbepresentinthisreactionsolution
andrecordthisconcentrationaboveTable6.Insertthisperoxideconcentrationandtheaveragerate
constantfromTable5intoeq(15)andcalculatetheconcentrationofI.ThisistheconcentrationofI
neededtogivet=120s.RecordthisconcentrationaboveTable6.

11.Useeq(14)tocalculatethevolumeofKIstocksolutionthatmustbeaddedtoyour50mlreaction
mixturetogivethedesiredconcentrationofKI,andrecordthisvolumeinTable6.Lastly,calculate
thevolumeofKNO3youmustaddtoreachafinalvolumeof50ml,andrecordthisvalueinTable6.

12.PrepareanewreactionsolutionbasedonthevolumeslistedinTable6andmeasurethereaction
time.Repeatthisproceduretogive3replicatevaluesoft,andrecordthesevaluesinTable6.
CalculatetheaveragetforthisreactionandlistthisvaluebelowTable6.

Name_____________________________________
PartA.DataCollection
Table3Reagentvolumestopreparereactionsolutions.*(Allvolumesinml)

orderofadditionAddlast

Set#

vol.H2SO4

vol.KNO3

vol.S2O3

vol.KI

volH2O2

32

27

10

29

24

10

BesuretoaddthestarchandEDTAbeforeyouaddtheperoxide.

Table4.Recordofexperimentalreactiontimes
Set#

tvaluesforreplicatetrials(seconds)

trial1

___________________________

___________________________

___________________________

___________________________

trial2

trial3

PartB.DetermineRateEquation
Table5.Calculatedreactionrates
Set#

Reactionratesforreplicatetrials(M/s)

trial1

_________________________________________________________

_________________________________________________________

_________________________________________________________

________________________________________________________

trial2

trial3 avg.rate(M/s)[KI](M)[H2O2](M)k

averagek=________

OrderofreactionwithrespecttoI:x=_____
OrderofreactionwithrespecttoH2O2:y=_____
Experimentalratelaw=___________________________________

PartC.DesignanExperimenttoGivet=120s.
[H2O2]=______________

[I]=___________________

Table6.Volumestoproducet=120sec
VolH2SO4

VolKNO3

VolS2O32VolKI

VolH2O2

MeasuredtValues

5ml

______

5ml ______

3ml

_____________________

averaget

_______

Name______________________________________
PreLaboratoryAssignment
1.(3points)Thefollowingdatawerecollectedat293Kforthereaction

acetone(C3H6O)+H++Br2bromoacetone(C3H5BrO)

[Br2](M)
0.01
0.01
0.02
0.02

[acetone](M)
0.25
0.13
0.25
0.25

[H+](M)
0.10
0.10
0.10
0.40

rate(M/s)
1.0x103
5.0x102
1.0x103
1.6x104

Whatistheorderofthisreactionwithrespecttoeachofthethreereactants?

2.(1point)ConsiderthereactionA+2BC.Theratelawforthisreactionwouldbe

rate=k[A]x[B]y

BasedjustonthestoichiometriccoefficientsforAandBinthebalancedchemicalreaction,whatcan
yousayabouttheexponentsxandyintherateequation?

2.(1point)WhatisthepurposeoftheKNO3intheexperimentyouwillperformthisweek?

3.(1point)Howmanymolesofperoxidemustreactbeforethesolutionturnsblueinthisweekslab?

Name__________________________________
PostLaboratoryAssignment
1.(1point)WhyisitimportanttoadjustthevolumeofKNO3tomaintainaconstantvolumeinthis
experiment?

2.(1point)Whaterrorhaslikelyoccurredifthesolutionturnsblueimmediatelyuponadditionofthe
peroxidesolutiontothereactionflask?

3.(1point)Whataretheunitsfortherateconstantthatyoudeterminedinthisexperiment?Explain
howyouarrivedatyouranswer.

4.(1point)Thisreactionwasrunat0.1Msulfuricacid(~0.2MH+).Assumingthereactionisfirstorder
inH+,howmuchfasterorslowerwouldthereactionbeifrunatpH2?

10