Experiment#4:

ChemicalKinetics
By:SimonHagos
7767295
Partner:PatrickDing
7426216
CHM1311SectionC3
Demonstrator:
PhilipDumouchel
DONTPRINTTHISPAGEBECAUSEITISNOT
COVERPAGE
October22,2014
DepartmentofChemistry

UniversityofOttawa
Experiment4.ChemicalKinetics
Introduction:
Achemicalreactionisaprocessbywhichnewsubstancesareformeddueto
chemicalchanges.Thesereactionsoccuratparticularrates,whicharethoroughlystudied
intheareaofchemistryknownaschemicalkinetics.Chemicalkineticsisallabout
studyingparticularfactorsthataffectreactionrates.Theseparticularfactorsarecatalysts,
surfacearea,concentrationofreactantsandtheirchemicalnatureandtemperature.
Temperatureisanimportantfactorofreactionratesinthisexperiment.Whenthe
temperatureisincreased,reactionratesincreasebecauseofreallylargeincreasesinhigh
energycollisions(Clark).Graphicalanalysiscanbeusedtofindtherateofreaction.
Generally,therateofachemicalreactioncanbeexpressedasfollows.
Reactionrate(average)=r=c/t=changeinconcentration/elapsedtime[1]
Yet,theinitialrateofareactioncanbedeterminedusingthefollowingequation
where[X]and[Y]arethereactantsinitialconcentration,kistheratelawconstant,mand
n(powers)aretheordersofreactionwhichdescribehowthereactantsconcentration
affectstherate.
Y

[2],whereX+Y>Products

m
r=k [ X ]
Theoverallorderofthereactionisequaltom+n.Allofthevariablesintheratelaw
equationaredeterminedexperimentally.
Inthisexperiment,therateofreactionismeasuredempiricallyanalyzing
reactionsthatchangecolor.Theimportantanalyticaltoolknownasspectrophotometryis
usedinordertoproperlymeasurethesizeofthequantity(substance)presentbasedonits
lightabsorption.ThisspectrophotometricanalysisisalsoknownasBeerLambertslaw
andisexpressedinthefollowingequationwhereabsorbanceofasolutionisequaltothe
productsofthemolarabsorptivitycoefficient,the(path)lengthofsolutionthelight
passesthroughandtheconcentrationofthesolution.
A=bc [3]

ForthereactionoftheCr(III)saltandtheEDTAsolution,therateexpressioncanbe
expressedasfollows.
Rate=d[Cr(III)]/dt=d[Cr(III)EDTA]/dt=k[Cr(III)]a[H+]b[4]

Theequationabovecanbesimplifiedbecausethechangeinconcentrationofthe
EDTAcanbeneglected.
Whenusingspectrophotometry,transmittanceandabsorbancearethetwoimportant
measurementsusedindeterminingtherateofareaction.Transmittanceistheratioofthe
intensityoflightafterpassingthestudiedmedium(I),tothelightintensitybeforehitting
themedium(IO).Absorbanceisalogarithmicratiodescribingthemeasureoftheamount
oflightabsorbedbyasample,whichisrelatedtotransmittanceasexpressedbythe
followingequations.
T=I/IO[5]
%T=[(I)(IO)]x100%[6]
A=logT=log(I/IO)[7]
Duringtheexperiment,thepercenttransmittanceisgivenfromthemodern
spectrophotometersandtheabsorbancecanbedeterminedusingtheequationsabove.
Next,theabsorbanceoftheCr(III)saltcanbedeterminedbytheabsorbanceamountat
timeinfinitywhereallofthesalthasbeencompletelyreacted,andsubtractingthatbythe
absorbanceamountatanyspecificpointintheelapsedtimingoftheexperiment.
ACr(III)=AAT[8]

Overall,thelograteequation(informy=mx+b)isusedinordertodeterminethe
partialorderofthereactionwithrespecttoCr(III)asfollows.
LogRate=alog[Cr(III)]+logK[9],wherea=partialorder
Procedure:Asdescribedinthelabmanual(IfitWereDoneThenTwereWellitWere
DoneQuickly,Dr.RashmiVentateswaran,2013,Exp.4,p.5254).
DataTable:
Table1:RawData

Volumeof
EDTA
Solution(mL)
Temperatureof
WaterBath
(C)
Numberof
Dropsof
Cr(III)into
EDTA
Solution
%T=5mins
%T=10mins
%T=15mins
%T=20mins
%T=25mins
%T=30mins
%T=35mins
%T=40mins
%T=45mins
%T=50mins
%T=55mins
%T=60mins
%T=65mins
%T=70mins
%T=75mins
%T=80mins
%T=85mins
%T=90mins
%T=95mins
%T=100mins
Timewhen
cuvette
solutioncooled
afterheated

pH=4.0

pH=4.5

pH=5.0

50.0

50.0

50.0

22.1

22.1

22.1

78.0
74.0
67.5
62.5
59.0
55.0
51.0
47.5
45.5
43.5
41.0
40.5
39.0
39.0
36.0
36.0
36.0
35.0
34.0
34.0
11.0

87.0
85.5
83.5
81.5
79.0
77.5
75.0
73.0
71.0
69.5
68.0
68.0
66.5
65.0
62.5
62.5
62.5
62.0
61.0
61.0
16.5

82.0
81.0
78.5
77.5
74.0
71.5
70.0
68.0
63.5
63.0
62.5
62.0
61.0
60.0
57.5
56.5
56.0
56.0
55.0
54.0
5.0

Observations:
Initially,theEDTAsolutionsconsistingofpHs4.0and4.5weretransparent,
whereasthe5.0pHsolutionwasadarkgreyishcolor(slightmixofblackandpurple).

OncemixedwiththeaddeddropsofthedarkishblueCr(III)solutiontotheEDTA,the
followingqualitative(color)observationswerenoticedrespectivetothepH,slight
purple,moderatemix(sufficientlybetweenbothcolors)anddarkpurple.Overall,allthe
solutionsinthecuvettesweregraduallyturningpurplethroughouttheirtimeinthewater
bathandaswellinhotbath.Atrendobservedwasthatthecolorofthecuvettesappeared
moreconcentratedasthepHoftheEDTAsolutionsobservedincreased.
Adecreaseinthepercenttransmittancethroughoutthefirst75minutesofthe
experimentoccurredandafter,thepercenttransmittanceremainedrelativelyconstantfor
theremaining25minutesbeforethetenminutehotbath.However,thepercent
transmittancesignificantlydecreasedafterplacedfortenminutesinthehotbathand
cooledintheinitialwaterbathplaced.ThereactionwiththeEDTAsolutionandthe
Cr(III)solutionappearedcompleteoncethetoneofthecuvetteappearedsignificantly
concentrated(dark).

Table2:DataandResultsinanalysisofcuvettesolutionoverelapsedtimeforpHof4.0.

Tim
e
%T
(min
s)
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
70.0
75.0

AT
78.0
74.0
67.5
62.5
59.0
55.0
51.0
47.5
45.5
43.5
41.0
40.5
39.0
39.0
36.0

ACr(III)
0.108
0.131
0.171
0.204
0.229
0.260
0.292
0.323
0.342
0.362
0.387
0.393
0.409
0.409
0.444

0.851
0.828
0.788
0.754
0.729
0.699
0.666
0.635
0.617
0.597
0.571
0.566
0.550
0.550
0.515

log[ACr(II
I)]

RateInstantan

Log[RateInstanta
neous]

-0.070
-0.082
-0.104
-0.122
-0.137
-0.156
-0.176
-0.197
-0.210
-0.224
-0.243
-0.247
-0.260
-0.260
-0.288

0.425
0.414
0.394
0.377
0.365
0.349
0.333
0.318
0.308
0.299
0.286
0.283
0.275
0.275
0.257

-0.371
-0.383
-0.405
-0.423
-0.438
-0.457
-0.477
-0.498
-0.511
-0.525
-0.544
-0.548
-0.561
-0.561
-0.589

-1
eous (m )

80.0
36.0
0.444
0.515
-0.288
0.257
85.0
36.0
0.444
0.515
-0.288
0.257
90.0
35.0
0.456
0.503
-0.299
0.251
95.0
34.0
0.469
0.490
-0.310
0.245
100.0
34.0
0.469
0.490
-0.310
0.245

.
11.0
0.959
0.000

Table3:DataandResultsinanalysisofcuvettesolutionoverelapsedtimeforpHof4.5.

-0.589
-0.589
-0.600
-0.611
-0.611

Time
log[ACr(I RateInstanta Log[RateInstant
%T
AT
ACr(III)
-1
(mins)
II)]
neous (m )
aneous]
5.0
87.0
0.060
0.722
-0.141
0.361
-0.442
10.0
85.5
0.068
0.714
-0.146
0.357
-0.447
15.0
83.5
0.078
0.704
-0.152
0.352
-0.453
20.0
81.5
0.089
0.694
-0.159
0.347
-0.460
25.0
79.0
0.102
0.680
-0.167
0.340
-0.468
30.0
77.5
0.111
0.672
-0.173
0.336
-0.474
35.0
75.0
0.125
0.658
-0.182
0.329
-0.483
40.0
73.0
0.137
0.646
-0.190
0.323
-0.491
45.0
71.0
0.149
0.634
-0.198
0.317
-0.499
50.0
69.5
0.158
0.625
-0.204
0.312
-0.505
55.0
68.0
0.167
0.615
-0.211
0.308
-0.512
60.0
68.0
0.167
0.615
-0.211
0.308
-0.512
65.0
66.5
0.177
0.605
-0.218
0.303
-0.519
70.0
65.0
0.187
0.595
-0.225
0.298
-0.526
75.0
62.5
0.204
0.578
-0.238
0.289
-0.539
80.0
62.5
0.204
0.578
-0.238
0.289
-0.539
85.0
62.5
0.204
0.578
-0.238
0.289
-0.539
90.0
62.0
0.208
0.575
-0.240
0.287
-0.541
95.0
61.0
0.215
0.568
-0.246
0.284
-0.547
100.0
61.0
0.215
0.568
-0.246
0.284
-0.547

16.5
0.783
0.000
Table4:DataandResultsinanalysisofcuvettesolutionoverelapsedtimeforpHof5.0.
Time
log[ACr(I RateInstanta Log[RateInstant
%T
AT
ACr(III)
-1
(mins)
II)]
neous (m )
aneous]
5.0
82.0
0.086
1.215
0.085
0.607
-0.217
10.0
81.0
0.092
1.210
0.083
0.605
-0.218
15.0
78.5
0.105
1.196
0.078
0.598
-0.223

20.0
25.0
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
70.0
75.0
80.0
85.0
90.0
95.0
100.0

77.5
74.0
71.5
70.0
68.0
63.5
63.0
62.5
62.0
61.0
60.0
57.5
56.5
56.0
56.0
55.0
54.0
5.0

0.111
0.131
0.146
0.155
0.167
0.197
0.201
0.204
0.208
0.215
0.222
0.240
0.248
0.252
0.252
0.260
0.268
1.301

1.190
1.170
1.155
1.146
1.134
1.104
1.100
1.097
1.093
1.086
1.079
1.061
1.053
1.049
1.049
1.041
1.033
0.000

0.076
0.068
0.063
0.059
0.054
0.043
0.042
0.040
0.039
0.036
0.033
0.026
0.022
0.021
0.021
0.018
0.014

0.595
0.585
0.578
0.573
0.567
0.552
0.550
0.548
0.547
0.543
0.540
0.530
0.527
0.525
0.525
0.521
0.517

Calculations:
ThefollowingsampleconversionandcalculationsisdoneforanyarbitrarypHvalue
(pH=4.5att=20mins).
T=%T/100
=81.5/100
=0.815
AT=logT
=log(0.815)
=0.0888
A=logT
=logT
=log[%T/100]
=log[16.5/100]
=0.7825
ACr(III)=AAT
=0.78250.0888
=0.6937

-0.225
-0.233
-0.238
-0.242
-0.247
-0.258
-0.259
-0.261
-0.262
-0.265
-0.268
-0.275
-0.279
-0.280
-0.280
-0.283
-0.287

Thefollowingsamplecalculationsalsocompletedusingthesameconditions(pH=4.5at
t=20mins)aretodisplayhowthepointsforthecurves(logAvstandlogRatevslogA)
aredetermined.
log[ACr(III)]=log0.6937
=0.1588
RateInstantaneous=y/x
=ACr(III)/x
=ACr(III)/2mins
=0.6937/2
=0.3469min1
RateInstantaneousobtainedfromgraph=0.3859min1
logRate=log(0.3469)
=0.4599
OrdercalculationsPleaserefertograph3.
Regardingtheorderoutcome,thepartialorderwithrespecttotheCr(III)ionfrom
theslopeofgraph3isinthefirstorder.
Discussion:
Themainobjectiveoftheexperimentwasusingtheprinciplesofabsorbance,
transmittance,reactionratesandspectrophotometrytodeterminetheinstantaneousrate
onthelogRatevslogACr(III)graphandsignificantly,thepartialorderwithrespectto
Cr(III)ion.Theexperimentwentaccordinglyusingtheproceduresfromthelabmanual,
whichseemedstraightforwardandthenotionwasdeterminedthatthedata
experimentallydeterminedwasreproducible.Asaresult,eventhoughthemeasurements
ofthevolumesoftheEDTAsolutionandCr(III)dropsmayseemadequateandwerenot
theprimaryemphasis(techniquerequired)fortheexperiment,volumeandtemperature
measuresareimportantforthisexperiment.Thosetwomeasurementswereimportant
becausetheymustbeconstantforthisexperimentandinaddition,weighingrelated
measurementsareusuallywhereadeviationoccursinthelab(backtodata).Aswell,the
concentrationofCr(III)saltwillchangeifvolumeisnotconstant.
Next,thespectrophotometerwasmanuallyalteredtotheappropriatestandardby
thelabdemonstratormakingallofthespectrometersusedthesame.Ifaparticularsource
oferrorwerereallyobserved,itwouldbethedecreaseinthetemperatureofthewater
bathusingtapwaterthroughouttheelapsedtimeoftheexperiment.Thetemperature
experiencedsomeinconsistencyshiftingfrom22.1Ctoaroundapproximately19.4C.
whicheffectedtherateofreactioncausingadecreaseintheACr(III)vstgraph.Aswell,
sincethetimingfortheexperimentwasnotimpeccableandthetimesatwhenthepercent
transmittancewasrecordedwereafterthespectrophotometerreading,thedatasaccuracy

forthetime(x)valuesdecreased.Inaddition,anothersourceoferrorcouldbewhen
wipingthecuvettespriortoinsertingthemintothespectrophotometersslotbecausethe
effectivenessoftheKimwipesabilitytowipegreaseorfingerprintswithgooddurability
isquestionable.Anyoilordirtcouldinterferewiththelightspassingthroughthesample
thatcouldbeadisfavorfortheexperimentsinceitcouldpossiblyincreasetheACr(III)
values,followinganincreaseinvaluefortheorderofthereactionwithrespecttoCr(III)
andoverallrate.
Ingraph1,theformulausedtocalculatetheinstantaneousratewasy/x,which
wasapproximatedinsteadofsimplybeingy/x.Theapproximationthatwascarriedout
wasacceptabletousebecauseintheend,theapproximationisagoodaid/(time
efficient)methodofthecalculation.Thepartialorderofthereactionwithrespectto
Cr(III)ionisdeterminedinthe3rdgraphandsincedividingtheyvaluesby2minutes,the
timeinterval(x)whichisconstantandusedeverytime,itmaintainsthecertaintyofthe
rateatwhichtheyvalueschange.Determiningtheinstantaneousrateforanyvalueofy
wasnotnecessary.
Inaddition,thereweredifferencesbetweenthe3samplesthataffectedthevalues
inthelab.ThepHvaluesandvaluesofthehydrogenionconcentrationvariedinthe
samples.Ingraph1thefirsttwotrialswerelinearandthethirdtrialwithapHof5.0was
acurvedplot.Therelationshipbetweenbothvariablesnoticedexplainshowthe
differencesineachsampleaffectthevalues.Therelationshipbetweenbothvariables
noticedishowasthepHincreases,therateofthereactionincreasesandviceversa
appliestothevaluesofACr(III)andinterestinglytheH+concentration(bothdecrease).Asa
result,thepredictioncanbemadethatthepartialorderwithrespecttothehydrogenionis
negative(duetoproportionalityrelationshipwhere[H+] 1/Reactionrate).
Ingraph2,forthetwotrialsofpH=4.0and4.5,thegraphswerelinearandthe
slopesforbothbestfitlineswerenegativedisplayinghowthereactionisoverallpseudo
firstordersincethedecreaseintheconcentrationofCr(III)ionsslowedovertheelapsed
time.
Ingraph3,thegraphplottedhelpedinconfirmingthepartialorderofthereaction
withrespecttoCr(III)ionbydeterminingtheslopeofthegraph(sinceitisequaltothe
partialorder).Theslopewasequaltoaround0.992and0.921respectivelyfortrials1
and2.
Rate=k[Cr(III)a[H+]b[EDTA]c=k[Cr(III)]a
and
logRate=logK+a[logACr(III)]
y=b+m[x],whereaisslopewhichis
partialorderwithrespecttoCr(III)ion.
Depictingthegraphtellshowthereactionisfirstorder.Also,literatureinformationwas
obtainedonlinewhichfoundthereactiontobefirstorder(AbdelMessih).

Also,whenthereactionwasforcedattheendoftheexperiment,itwasreally
evidenthowaftertenminutesatahighertemperature,theboilinghotwaterbathrapidly
madeasignificantqualitativechangeincolor(increaseindarkpurpletone).
Conclusion:
Inconclusion,thepartialorderofthereactionwithrespecttoCr(III)ionwas
foundtobepseudofirstorderandtheslopemeasuredittobe0.992and0.921
respectively,fromthesolutionswithpH=4.0and4.5.Yet,theslopesthatshouldhave
beengottenwereavalueof1,resultinginpercenterrorsof7.9and0.83forthe2trials.
Inaddition,anincreaseinthefollowingfactors;EDTAconcentration,temperatureand
pHresultinamoreacceleratedreactionrate.Moreover,themeasureoftheconcentration
oftheCr(III)ionwhichisalsoknownastheabsorbanceoropticaldensity,forallvalues
ofpH,decreasesasafunctionofelapsedtime.
Reference:
Clark,Jim."TheEffectofTemperatureonRatesofReaction."TheEffectofTemperature
onRatesofReaction.ChemGuide,1Oct.2013.Web.27Oct.2014.
<http://www.chemguide.co.uk/physical/basicrates/temperature.html>.
IfitWereDoneThenTwereWellitWereDoneQuickly,Dr.Rashmi
Ventateswaran,2013,Exp.4,p.5254.
Messih,M.F.Abdel."KineticsandMechanismofInteractionbetweenChromium(III)
andEthylenediaminetetra3PropinateinAqueousAcidicMedia."Advancesin
ChemicalEngineeringandScience2013.98104(2012):99,103.Scientific
ResearchPublishing.SCIRP.Web.26Oct.2014.
<http://dx.doi.org/10.4236/aces.2013.31012>.
Silberberg,Martin,SophieLavieri,andRashmiVenkateswaran.Chemistry:The
MolecularNatureofMatterandChange.1sted.McGrawHillRyerson,2013.
Chapter14.Print.