Documente Academic
Documente Profesional
Documente Cultură
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
(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