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EXPERIMENT1

REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
PURPOSE:
TodeterminetheRateLawandtheActivationEnergyforareactionfromexperimentaldata.
PRINCIPLES:
TheRateLawisamathematicalexpressionthatpredictstherateofareactionfromthe
concentrationofreactants.ThisRateLawistheproductoftherateconstant(k)andeach
reactantconcentrationtakentosomepower(almostalways0,1,2, 1,or0.5).
Thevaluesfortherateconstantandtheconcentrationpowershavetobedetermined
experimentally.
Anexampleofaratelawanditsrateconstantisshownbelow:
Considerthehypotheticalreaction:
X+2Y

Rateisthechangeofareactantorproductconcentrationperunittimeduringreaction(inM/s)

Mathematically:

D[X]
D[Y]
D[Z]
Rate= - = - =+
Dt
2 Dt
Dt
Rateofdisappearance
ofreactants

GeneralformforRateLaw:
m andn

Rateofformation
ofproduct

Rate=k[X]m[Y]n

arefrequently,butnotalwaysintegers(almostalways0,1,2, 1,or0.5).
mustbedeterminedexperimentally
RateConstant:

itsunitsdependupontheformofRateLaw
istemperaturedependent

Supposetheratelawwasthefollowing:
Rate=k[X][Y]2
Therateisfirstorderwithrespectto[X]whichmeans:
Rateisproportionalto[X]1
When[X]isdoubled,therateisdoubled. [2]1 =2
When[X]istripled,therateistripled
[3]1 =3
Therateissecondorderwithrespectto[Y]whichmeans: Rateisproportionalto[Y]2
When[Y]isdoubled,therateisquadrupled.
[2]2 =4
When[Y]istripled,therateisincreasedby9
[3]2 =9
NOTE:TheReactionOrdersarenot necessarilyequaltothecoefficientsintheoverallequation.
Theycouldbe(asitisthecaseinthisexample),butthatwillnotalwaysbeso.
TheReactionOrdersmustbedeterminedexperimentally

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
Therateconstant(k)iscalculatedfromoneoftheexperimentsafterwedeterminedthepowers
of[X]and[Y]
Tocalculatek: chooseanyexperiment,
plugintheconcentrations[X]and[Y]andthenthecorrespondingrateinto
theratelaw,
algebraicallysolvefork
ChangingthetemperaturecanalsochangetheRateofReaction.Duringareaction,thereisoften
aparticularstepintheoverallprocessthatslowstheentirereactiondown.Thisisoftena
difficultstepwherethemoleculesinvolvedmustcollidewithaminimumamountofenergyfor
thereactiontooccur.ThisminimumenergyrequirementiscalledtheActivationEnergy,Ea.
KnowingtheActivationEnergy,Eahelpsuspredictthereactionrateatothertemperature.
TheActivationEnergy,EamanifestsitselfthroughtheRateConstant,k.
PROCEDURE:
Inthisexperimentwewillobservehowtherateofreactiongivenbelowischangedby
variationsinreactantconcentrations,catalystconcentrationsandtemperature:
2I- +
S2O82 -
I2
+
2SO42 -
(Reaction1)
iodideionpersulfateioniodinesulfateion
Basedontheexperimentaldata,wewilldeterminetheTheRateLaw(PARTI)and
TheEffectofTemperatureonReactionRate(PARTII)
AnoverviewoftheProcedureisoutlinedbelow:
PartI: THERATELAW
A.EffectofConcentrationonReactionRate
1.
ReactantConcentrationsandCorrespondingReactionRates
2.
ReactionOrderswithrespecttoReactants:
(a)ReactionOrderwithrespectto[I-](m)
(b)ReactionOrderwithrespectto[S2O82-](n)
B.TheDeterminationoftheRateConstantk
C.TheEffectoftheCatalystonReactionRate
ReactionOrderwithrespecttoCatalyst(p)
PartII:EFFECTOFTEMPERATUREONREACTIONRATE
DeterminationoftheActivationEnergy,Ea
Thetableonnextpagesummarizesthevolumesofreactantsandthereactionconditionsunder
whichexperimentaldatawillbeobtained.

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
Summaryof VolumesofReactants,VolumeofCatalystandReactionConditionsforall
ReactionRuns
Run Temp
250mLReactionFlask
50mLFlask
No.
KI
Na2S2O3
KClSoluble (NH4)2S2O8 (NH4)2SO4 CuSO4
(0.200M)(0.00500M)(0.200M)Starch (0.100M)(0.100M)(0.100M)
1 Room 20.0mL10.0mL0.0mL34drops 20.0 mL0.0mL0.0mL
Temp
2 Room 10.0mL10.0mL10.0mL34drops 20.0mL0.0mL0.0mL
Temp
3 Room 20.0mL10.0mL0.0mL34drops 10.0mL10.0mL
0.0mL
Temp
4 Room 20.0mL10.0mL0.0mL34drops
5.0mL15.0mL0.0mL
Temp
5 Room
8.0mL10.0mL12.0mL34drops 20.0mL0.0mL0.0mL
Temp
6 Room 15.0mL10.0mL5.0mL34drops 15.0mL5.0mL0.0mL
Temp
7 Room 20.0mL10.0mL0.0mL34drops 20.0mL0.0mL4drops
Temp
8 Room 20.0mL10.0mL0.0mL34drops 20.0mL0.0mL2drops
Temp
9
about 20.0mL10.0mL0.0mL34drops 20.0mL0.0mL0.0mL
400C
10 about 20.0mL10.0mL0.0mL
34drops 20.0mL0.0mL0.0mL
0
10 C
11 about 20.0mL10.0mL0.0mL34drops 20.0mL0.0mL0.0mL
00C

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
PARTI:DETERMINATIONOFTHERATELAW
A.TheEffectofConcentrationonReactionRate
TheReactionRateforReaction1canbemeasuredthroughtheformationofelementaliodine,I2,
sincethepresenceofevensmallamountsofiodinecanbedetectedbyvirtueoftheintensely
bluecoloredcomplexformedbetweeniodineandstarch:
2I- +
S2O82 -
I2
+
2SO42 -
(Reaction1)
iodideionpersulfateioniodinesulfateion
Iodine

StarchIodineComplex
(deepblue)
OnecreativewayofmeasuringtherateofformationofIodineistocouplethereactioninwhich
theIodineisformed(Reaction1)withamuchfasterreactionthatconsumesalloftheIodine
(Reaction2)
I2

2S2O32-
thiosulfateion

Starch

2I-

S4O6 2-

(Reaction2)

Reaction2immediatelyconsumestheI2 generatedinthefirstreactionuntilalloftheS2O32-
(thiosulfateion)isusedup.Whenthe S2O32- isconsumed,I2 buildsupandreactswithstarchto
formthedeepblueStarchIodineComplex,accordingtoReaction1givenabove:
2I- +
S2O82 -
I2
+
iodideionpersulfateioniodine
reactswithstarchtoform
adeepbluecomplex

2SO42 -
sulfateion

(Reaction1)

Theappearanceofthedeepbluecomplextellsusthatatthispointintime(tcolor), sufficientI2
hasbeenproducedbyReaction1touseupalloftheS2O32- (thiosulfate)ionoriginallyadded.
FromthisobservationwecaneasilycalculatetheconcentrationofIodineproducedby
Reaction1,byobservingthataccordingtothestoichiometryofReaction2,1moleofI2 reacts
with2molesofS2O32-(thiosulfate),or moleI2 reactswith1moleofS2O32- (thiosulfate).
Itfollows,thatatthetimethedeepbluecolor(tcolor)appears:
[S2O32-]originally addedandusedup
[I2]produced =
2
KnowingthemolarconcentrationofI2 ataspecific,exactlymeasuredtimegivesustheRateof
formationofI2 whichinturn permitsustocalculatetheRateofReaction1foranycombination
ofreactionconditions,aslongastheamountoftheS2O32- iskeptconstant.
2I-
+
S2O82 -
I2
+
2SO42 -
(Reaction1)
iodideionpersulfateioniodinesulfateion
4

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
Thedifferencebetweentheinitialandthefinalconcentrationsof I2dividedbytheamountof
timeneededforthischangetooccuristheRateoftheReaction.

Rate1

D[I2]
=+
Dt

Ifweknowthestartingconcentrationof S2O32 - (thiosulfate)andrememberthatitisallusedup


whenthecolorofthereactionchanges,thenwealsoknowthathalfthatamountof I2 wasalso
consumedinthereaction.
ThismeansthatthechangeintheI2concentrationisequaltohalfthestarting(initial)
concentrationof S2O32 - (thiosulfate):
[S2O32 -]initial
D[I2]=
2
Thetimeofthecolorchange(tcolor) isalsothetimethatpassedduringthereaction(Dt)
ItfollowsthattherateoftheFirstReactioncanbecalculatedas:

Rate1

[S2O32 -]0

D[I2]2[S2O32 -]0
= - = =
Dt
Dt2tcolor

1.ReactantConcentrationsandcorrespondingReactionRates
Thetablebelowsummarizesthevolumesofreactantstobeusedinmakingupsixdifferent
mixtures:
Table1:KineticRunsatVaryingConcentrations
Rxn
Run
No.
1
2
3
4
5
6

250 mLReactionFlask
KI
(0.200M)
20.0mL
10.0mL
20.0mL
20.0mL
8.0mL
15.0mL

50 mLFlask

Na2S2O3
KCl
(0.00500M)(0.200M)
10.0mL
0.0mL
10.0mL
10.0mL
10.0mL
0.0mL
10.0mL
0.0mL
10.0mL
12.0mL
10.0mL
5.0mL

Soluble
(NH4)2S2O8
(NH4)2SO4
Starch(0.100M)(0.100M)
34drops
20.0mL
0.0mL
34drops
20.0mL
0.0mL
34drops
10.0mL
10.0mL
34drops
5.0mL
15.0mL
34drops
20.0mL
0.0mL
34drops
15.0mL
5.0mL

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
Theactualprocedureforcarryingouteachreactionwillbemuchthesameanditwillbe
describedindetailforReactionRun1:
(a). Fillingthe250mLErlenmeyerFlask(ReactionFlask)
Useaburettoaddexactly 20.0mLof0.200MKIintothe250 mLErlenmeyer
whichwewillcalltheReactionFlaskandwhichwillserveasthecontainerforthe
reaction.
Useaburettoaddexactly 10.0mLof0.0050MNa2S2O3 intothisflask.
Add3or4dropsof starchsolutiontotheflask
(b).

Fillingthe50mLErlenmeyerFlask
Useaburettoaddexactly 20.0mLof0.100M(NH4)2S2O8 intothisflask

(c).

TemperatureReading
Readthetemperatureofthesolutioninthe250 mLreactionflaskwitharinsed,dried
thermometer.
Removethethermometer,rinseanddryit,andmeasurethetemperatureofthesolutionin
the50mLflask.Thesolutionsinbothflasksshouldbeatthesametemperature 0.20C.
Ifnecessary,adjustthetemperaturebyexternalwarmingorcoolingtosomeconvenient
pointintherangeof200C250C,bestplacebeingroomtemperature.
Recordthistemperaturetothenearest0.10C.
Removethethermometerfromtheflask,rinseanddryit.

(d).MixingandTiming(haveastopwatchavailable)
Pourthesolutionfromthe50mLflaskintothereactionflask(youcanleavethe50ml
flaskoverthemouthofthereactionflask).Notethetimeatwhichthesolutionswere
mixed.
Swirlthesolutionstomixthemthoroughly.
Continueswirlingthesolutionuntilthebluecolorappears.
Noteandrecord thetimeatwhichattheinstantthebluecolorappears(itshouldtakeless
thana minute).Recordalltimestothenearestsecond(nofractionsofsecondsshouldbe
recorded).
Notethatthetimeelapsedforthebluecolortoappear(tcolor)isthetimeintervalrequired
toconsumealloftheS2O32 - (thiosulfate)ion.
Checkthetemperatureagain.Ifthetemperaturehaschangedbymorethan 0.5,or
ifthetimingwasfaulty,repeattheentirerun.
(e). Repeattheexperimentwiththeothermixturesinthetable
Theflasksusedshouldberinsedwithdistilledwaterbetween experimentsanddrained
beforebeingusedagain.
Buretsshouldbeusedinmeasuringthevolumesofallthefivesolutions:
KI, Na2S2O3,KCl,(NH4)2S2O8, and (NH4)2SO4
NOTE: Although KCl and(NH4)2SO4],donotenterthereactiondirectly,thesereagents
servetomaintaintheeffectiveconcentrationsofallions(ionicstrength)ata
constantlevel.Holdingtheionicstrengthconstantremovesthedependenceof
thereactionrateonvariationsinthesolvent.
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09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
2.ReactionOrderswithrespecttoReactants
Once,experimentaldataisavailableforseveralconcentrationsandcorrespondingReaction
Rates,theReactionOrderswithrespecttoReactantscanbedeterminedbycalculations:
2I-+
S2O82 -
I2
+
2SO42 -
Rate=k[I-]m [S2O82-]n
where:

mandnaretherespectiveReactionOrders,
kistheRateconstant
Toobtainmandntwodifferentreactionrunsinwhichtheconcentrationofonereactant
isthesamewillbedividedbyeachother.Thiswillpermitcancellationofseveralidenticalterms
andwillyieldanequationinwhichthereactionorder(morn)istheonlyunknown.
Solvingtheequationwillyieldm,respectivelyn.
B.TheDeterminationoftheRateConstant k
TheRateConstantkischaracteristicforthisreactionandisindependentoftheconcentration
ofthereactants.However,kistemperaturedependent.
Assuch,kcanbecalculatedfromanyofthesixexperiments,sincethetemperaturehasbeen
maintainedessentiallyconstant(Roomtemperature)
TocalculatekplugintheConcentrationsof [I-] and[S2O82-]andthecorrespondingRateinto
theRateLawandthensolvealgebraicallyfork.
Theclosenessofthesixvaluesthatyouwillobtainforkisindicativeoftheprecisionofyour
experimentaldata.
C.TheEffectoftheCatalystontheReactionRate
Anotherwayofcontrollingtherateofareactionisbytheadditionofacatalyst.Catalystschange
theindividualstepsinvolvedintheoverallreactionandavoidtheslowsteps.
Asaresult,catalystsareoftenincorporatedintheratelawandacceleratethereaction.
Metalliccations(suchasCu2+)haveapronouncedcatalyticeffectontherateofthisreaction.
PerformReactionRuns7and8asReactionRun1,includingthesametemperature(room
temperature),exceptaddsmallvolumesof 0.1MCuSO4 solutiontothe50mLflask,just
beforepouringthecontentsintothereactionflask.
Recordthetemperaturesandthereactiontimes.
ReactionMixtureswithvaryingamountsofCatalyst
Reaction
ReactionMixture
Temperature
Cu2+
Run#
(0.1M)
7
sameasinRxn.Run#1 Roomtemperature
4drops
8
sameasinRxn.Run#1 Roomtemperature
2drops
Determinetheorderofthereactionwithrespecttocatalystconcentration p
Note: Tofindp,youdonotneedtocalculatetheactualconcentrationofthecatalystin
theReactionFlaskforReactionRuns7and8.
Notingthatoneconcentrationistwiceaslargeastheotherone,willallowyouto
cancelouttheconcentrationof[Cu2+]
7

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
PARTII:THEEFFECTOFTEMPERATUREONREACTIONRATE
ChangingthetemperaturecanalsochangetheRateofReaction.Duringareaction,thereisoften
aparticularstepintheoverallprocessthatslowstheentirereactiondown.Thisisoftena
difficultstepwherethemoleculesinvolvedmustcollidewithaminimumamountofenergyfor
thereactiontooccur.ThisminimumenergyrequirementiscalledtheActivationEnergy,Ea.
KnowingtheActivationEnergy,Eahelpsuspredictthereactionrateatothertemperature.
TheActivationEnergy,EamanifestsitselfthroughtheRateConstant,k.
ArrheniusEquation
Ea
-
RT
k=Ae

k=therateconstantintheratelaw
A=aconstantforthereactionatalltemperaturesandconcentrations
Ea=theActivationEnergy
R=theuniversalgasconstant=8.315J/Kxmol
T=absolutetemperature
e=2.718

TodetermineEaexperimentallyweneedtofocusontheeffectofEaontheRateConstant,k.
Thisisdoneby:
holdingthereactantconcentrationsconstant,sothatalltheratechangesareduetochanges
intheRateConstant,k,and
measuringhowtheReactionRaterespondstotemperaturechanges
Thecalculationscanbegreatlysimplifiedbysubstitutingthevalueof kfromtheArrhenius
EquationintotheexpressionoftheRateLaw,andthentakingthenaturallogarithmofboth
sideoftheequation:ReactionRate:
Ea
-
RT
- m
- n
Rate=k [I ] [S2O8 ]
Rate= Ae
[I-]m [S2O8-]n

Ea
-
RT
- m
- n
Rate= A[I ] [S2O8 ] e

constants
groupedtogether

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
Recallthatthelogarithmofaproductisequaltothesumoftheindividuallogarithms:
ln(XY)
=
lnX +lnY

Ea
-
RT
Rate= A[I-]m [S2O8-]n e

constant

variable

ln(Rate)=lnA[I-]m [S2O8-]n

Ea
-
RTEa
+lne=lnA[I-]m [S2O8-]n - lne
RT
1

TheresultingEquationissimilartotheequationofastraightline(y=b+ mx):

- m

ln(Rate)=lnA[I ] [S2O8 ]

Ea
-
R

y=
b
+mx
(vertical
(Intercept)
(Slope)(horizontal
coordinate)coordinate)
Fromaplotof lnRateasafunctionof 1/T,theslope ofthegraphcanbeeasilydetermined.
Fromtheslope,theActivationEnergy,Eaiscalculatedbyalgebra.
OnceEahasbeendetermined,itispossibletopredictreactionratesatanytemperaturesandany
setofconcentrations.
ToobtainexperimentaldatareflectingthedependenceoftheReactionRateonTemperature,the
reactionwillbecarriedoutatseveraldifferenttemperatures,butwiththesameconcentrationof
allreactants.

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
Thetablebelowindicatesthereactionconditions:
ReactionMixturesatDifferentTemperatures
ReactionRun#
1
9
10
11

Temperature
Roomtemperature
about400C
about100C
about00C

ReactionMixture
sameasinRxn.Run#1
sameasinRxn.Run#1
sameasinRxn.Run#1
sameasinRxn.Run#1

ReactionRun#1:

DatafortheReactionRateisalready available(PartI)

ReactionRun#9:

Thereactioniscarriedoutbyaddingthesamevolumesofthesame
solutionsasinReactionRun#1.
Slowlyswirlthe250mLandthe50mLflasksseparatelyfor
approximately3minutesinalargebeakerofwateratatemperatureof
about400C.Recordtheexacttemperature(nearest0.10C)ofthe
solutioninthe250mLreactionflask.
Whenthetemperaturesinbothflasksareabout400Candnearlythe
same,mixthesolutionstogetherbypouringthecontentsofthe50mL
flskinthereactionflaskasinpreviousruns.Notethetimeofmixing.
Keepthereactionflaskimmersedinthebeakerfortheentirereaction
intervalinordertomaintainasconstantatemperatureaspossible.
Recordthetimeatwhichthecolorchangeoccursandthetemperature
ofthemixtureatthatpoint.

ReactionRun#10: Repeattheexperimentatabout100C,coolingallreactantsinalarge
beakertothattemperaturebeforestartingthereaction.
Recordthetimerequiredforthereactionandthefinaltemperatureof
thereactionmixture.
ReactionRun#11: Repeatonceagainatabout00C,thistimeusinganicewaterbathto
coolthereactantsolutions.
CalculatetheActivationEnergy(Ea)fromtheexperimentaldata.

10

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION

NAME:__________________________
PARTNER:_______________________
REPORTFORM
PARTI:DETERMINATIONOFTHERATELAW
A. TheEffectofConcentrationonReactionRate
1.ReactantConcentrationsandcorrespondingReactionRates
Foreachkineticrun,calculatetheinitialconcentrationsforthetworeactantswhichreact:
[I-]and[S2O82-].
Sincethereactionwhoserateisbeingmeasuredtakesplaceinatotalvolumeof50.0mL,
thisvolumemustbetakenintoaccountincalculatingtheinitialconcentrationsofthe
tworeactants
ForexampleinRun1,sincethe20.0mLof0.200MKIaddedreactsinatotalvolumeof
50.0mL,theinitialconcentrationof[I-]canbecalculatedtobe:
20.0mLsolution
-
[I ]1 =0.200MKI =0.0800MKI
50.0mLsolution
Similarly,inRun1,theinitialconcentrationof[S2O82-]is:
[S2O82-]1

=0.100M(NH4)2 S2O8

20.0mLsolution
=0.0400M(NH4)2 S2O8
50.0mLsolution

Carryoutsimilarcalculationsforallotherinitialvaluesof [I-],[S2O82-]and[S2O32 -]
andcompletetheappropriatecolumnsintheDataTable.
[S2O32-],M

AllRuns

11

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
[I-]

Run1 0.200MKI

[S2O82-]

20.0mL
20.0mL
= 0.0800M 0.100M(NH4)2 S2O8 =0.0400M
50.0mL
50.0mL

Run 2

Run3

sameasinRun1

sameasinRun1

Run4
sameasinRun1

Run5

sameasinRun1

Run6

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09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION

Table1:ReactantConcentrationsandcorrespondingReactionRates

(NH4)2 S2O8
Time
RATE*
[I-]0,M mLM
[S2O82 -]0, M (t color) [S2O32 -]0
added

(s)
2tcolor
20.00.200 0.0800 20.00.100
0.0400

10.00.20020.00.100

20.00.20010.00.100

20.00.2005.00.100

8.00.20020.00.100

15.00.20015.00.100

RunTemp
KI
No.(0C)mLM
added

Rate*

ExpressRateas(Ax10-6)andin3significantfigures

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09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
2.ReactionOrderswithrespecttoreactants
SummarizetherelevantdatafromTable1intoTable2.
Table2:ReactantConcentrationsandcorrespondingReactionRates
Run
[I2]produced
Time,
Rate*
[I-]0
[S2O82-]0
No.
(at tcolor)
(tcolor)
[I2]
(M)
(M)
(M)
(seconds)
(M/s)
tcolor
1
2
3
4
5
6
Rate*
ExpressRateas(Ax10-6)andin3significantfigures
(a)CalculatingtheReactionOrderswithrespectto[I-]
FromRun1andRun2:
ThegeneralformulasfortheRateLawforRuns1and2are:
Rate1 =k[I-]m [S2O82-]n
Rate2 =k[I-]m [S2O82-]n
Substitutetheknownconcentrationsof[I -]and[S2O82 -]ionsandtheknown
ReactionRatesfortheseruns.Includereactionorders,mandn

Dividethefirstequationbythesecondandcanceloutidenticalterms.

Notethatyouhaveobtainedandequationinvolvingonlymasanunknown:
Tosolveform,takethelogofbothsidesoftheequationandthensolveform

m1,2
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EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
FromRun1andRun5
DothesamecalculationyoudidforRuns1and2,butuseinsteadthevaluesfor
Runs1and5toobtainm
Thensubstitutetheknownconcentrationsof[I -]and[S2O82 -]ionsandtheknown
ReactionRates.Includereactionorders,mandn.Showallcalculations.

m1,5
FromRun2andRun5
DothesamecalculationyoudidforRuns1and2,butuseinsteadthevaluesforRuns2
and5toobtainm.Showallcalculations

m2,5

Calculatetheaveragevalueform:
m1,2
m1,5

m2,5

maverage :____________(ascalculated)

maverage =
15

(roundedofftoaninteger)
09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
(b)CalculatingtheReactionOrderswithrespectto[S2O82-]
Applyingthesameapproachyouusedforthecalculationofmfindthevalueofn
FromRuns1and3:

n1,3
FromRuns1and4:

n1,4
FromRuns3and4:

n3,4
Calculatetheaveragevalueforn
n1,3
n1,4

n3,4

naverage :__________(ascalculated)
naverage =

(roundedofftoaninteger)

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09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
B. DeterminationoftheRateConstantk
Havingfoundmandn,thespecificrateconstantkcanbecalculatedby
substitutionofmandnandtheknownratesandreactantconcentrationsintothe
RateLaw.WritetheequationfortheRateLaw,bysubstitutingthevaluesformandn:
Recall:mandnareintegers

Rate=

EvaluatekforReactions1through6.Includeunitsinyourcalculations
Run1
Run2
-
2-
-
[I ]1 =
[S2O8 ]1 =
[I ]2 =
[S2O82-]2 =
Rate1 =
Rate2 =

k1 =
Run3
[S2O82-]3 =

[I ]3 =
Rate3 =

k2 =
-

[I ]4 =
Rate4 =

k3 =
Run5
[S2O82-]5 =

[I ]5 =
Rate5 =

Run4
[S2O82-]4 =

k4 =
-

[I ]6 =
Rate6 =

k5 =

Run6
[S2O82-]6 =

k6 =

SummaryofRateConstantskforRunsatRoomTemperature
RunNo.
1
2
3
4
5
6
k
(
)
k(Average)
(
)
WritetheRateLawforthereactionstudied,bysubstitutingthevaluesform,nandk:
Includeunits!
17

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
C. TheEffectoftheCatalystontheReactionRate
Cu2+ isacatalystinthereactionstudied.Assuch,theRateLawofthecatalyzedreaction
couldbewrittenas:
Rate=k[I-]m [S2O82-]n [Cu2+]p
wherethereactionordersmandnarethesameasintheuncatalyzedreaction.
Todetermineifthereisaquantitativerelationshipbetweenreactionrateandcatalyst(thatis
p,thereactionorderwithrespecttothecatalyst),summarizeyourdataforReactionRuns
withthesameconcentrations,atthesametemperature,butwithvaryingamountsofcatalyst
added.
Inthismanner,theeffectoftheconcentrationofcatalystontheReactionRatesmaybe
evaluatedindependentofotherfactors.
ReactionMixtureswithvaryingamountsofCatalyst
Run
Temp. Dropsof
Time
RATE
[S2O32-]
0
No.
( C)
CuSO4
(tcolor)
M
[S2O32 -]0
(0.1M)
(s)

2tcolor
7
8
Fromthedatainthistable,calculatep,thereactionorderwithrespectto[Cu2-]
(nearestwholenumberorzero).
Thecalculationsaresimilartothosedoneforthereactionorderwithrespect
to[I-](m)and[S2O82-](n)
Showcalculationsbelow:

p
(roundedofftothenearestintegerorzero)
WritethecompleteformoftheRateLaw(includebothreactantsandthecatalystwiththeir
respectiveordersofreaction)andsubstitutekwiththeexperimentallydeterminedvalue.
Includeunits!Rate=
18

09/16/2002

EXPERIMENT1
REACTIONRATE,RATELAW,ANDACTIVATIONENERGY
THEIODINECLOCKREACTION
PARTII:THEEFFECTOFTEMPERATUREONREACTIONRATE
Todeterminethequantitativerelationshipbetweenreactionrateandtemperature,summarize
yourdataforReactionRunswiththesameconcentrationsofallreactantsbutrunatdifferent
temperatures.Inthismanner,thecorrespondingreactionratesfortheserunswillbeaffected
bytemperaturechangesonly.

Run Temp. Temp.


No.
(0C)
(K)

1
T
(K-1)

Time
(tcolor)
(s)

[S2O32-]
M

RATE
[S2O32-]

2tcolor

ln
(RATE)

1
9
10
11
ToevaluatetheActivationEnergy (Ea),makeagraphof ln(Rate)vs.1/T(Xx10-3) ongraph
paperprovided.Intheupperrighthandsideofthegraphprovideatablethatincludesthat
data beingplotted.Recallthateverygraphmusthaveatitle.
Findtheslopeofthelineobtainedbydrawingthebeststraightlinethroughthe4experimental
points.Showcalculationsforslopeonthegraph

Slope

Fromtheslope,calculatetheActivationEnergy(Ea).RecallthatR=8.315J/Kxmol
Showcalculationsbelow.Pleaseincludeunitsinyourcalculations.

Ea

J/mol

Ea
19

kJ/mol
09/16/2002