1

SCHOOLOFCIVIL,ENVIRONMENTAL&CHEMICAL
ENGINEERING

AllassignmentsintheSchoolrequireastandardcoversheet.TheseareavailableonForms
forStudentsontheRMITintranet.

ProjectTitle

PROC2081/DataCollectionandAnalysis

SamMiddlebrook/s3378466
ZhenDaAlvinSiew/s3247781

Group20

4April,2017

LiamWard
 2

Summary

Inthisexperimentweweretryingtodeterminethereactionorderandthereactionrate
constantforthesaponificationofethylacetatebymeasuringthereactionconversionina
batchreactor.WealsoweretryingtodeterminethesamethingforaCSTRandthendraw
comparisonsanddeterminethestrengthsandweaknessesofthesedifferentreactors.The
conductivityofthereactionsolutioninthereactorchangeswiththedegreeofconversion,
andthisprovidesaconvenientmethodformonitoringtheprogressofthereaction.The
strengthsandweaknessesbasedontheMeasurementoftheReactionKineticsofthe
SaponificationofEthylAcetateinaBatchReactorandCSTRallowsustoselectthe
optimumreactorforthedesiredeffects.

Mostoftheinformationrequiredforthecorrectcompletionofthisexperimentcomesfrom
ourstudiesinreactionengineeringandappliedthroughthisexperiment.Muchofthe
experimentalworkintothesereactorsinvolvesoptimalstirringspeeds,correctand
effectivecatalysts,reactionkinetics,flowratesandalsotypesofflowwetheritbelaminar
orturbulent.Thereisanabundantamountofinformationavailableonlinehoweverallof
therequiredinformationcouldbefoundinthematerialprovidedtousinreaction
engineering.

The methodology and resources used were taken mainly from the notes givent to us in
reaction engineering but there was also a lot of material to be found online. The equations
used in our results were taken from various areas and allowed us to define the reaction
kinetics in a manor that seemed accurate. Combined with the experimental data recorded
during the experiment it was possible for us to determine the reation orders.
Thereactorsshowedvariousordersofreactionwhichisconcerningandsignallederrorsin
ourresultsorarithmeticalprocedure.HoweverinalltheresultsoftheCSTRwerequite
promisingandtheearlyreactionsinthebatchreactorsalsopointedtowardcorrectand
seemingly accurate experimentation. This report will clearly state our interpretion
combinedwithanalyticalmethodtoproducethedesiredreactionkinetics.
 3

Table of Contents
ThisTOCisgeneratedautomaticallyfromtheheadersinthesubsequentreport.You
updateitbyRightClickUpdateField/UpdateEntireTable.Donottypeoverit!

Summary................................................................................................................................
TableofContents...................................................................................................................
ListofFiguresandTables......................................................................................................
Introduction............................................................................................................................
LiteratureReviewandTheory................................................................................................
Experimental..........................................................................................................................
ResultsandDiscussion...........................................................................................................
ConclusionsandRecommendations.....................................................................................
References............................................................................................................................
 4

List of Figures and Tables

Figure1concentrationvtime

Figure2Concentrationvreactionratefor0.1M

Figure3Concentrationvreactionratefor0.05M

Figure4Concentrationvreactionratefor0.01M

Figure5ln(CA)vln(rA)for0.1M

Figure6ln(CA)vln(rA)for0.05M

Figure7ln(CA)vln(rA)for0.02M

Figure8timev1/CAfor0.1M

Figure9timev1/CAfor0.05M

Figure10timev1/CAfor0.02M

Figure11timevNaOHconcentration

Figure12Outletconcentrationvmolarflowrate

Table1

Figure13CSTR

Figure14ln(rA)versusln(outletconcentration)

Figure15ln(rA)versusln(outletconcentration)

Introduction
Inthisexperimentweweretryingtodeterminethereactionorderandthereactionrate
constantforthesaponificationofethylacetatebymeasuringthereactionconversionina
batchreactor. This experiment lookedatthesaponificationofethylacetate bysodium
hydroxidetosodiumacetateandethylalcohol.Thereaction,theoretically,isconsidered
first order when it is within a specific temperature. However with this particular
experimentthetemperaturewasambientandthereactionwasfirstorder.Batchreactors
are used in industry for noncontinuous, relatively smallscale specialist reactions
commonlyliquidphasereactions.Thisisseenparticularlyinthepharmaceuticalindustry.

ThestrengthsandweaknessesbasedontheMeasurementoftheReactionKineticsofthe
Saponification ofEthyl Acetate in aBatch Reactor andCSTRallows us to select the
optimum reactor for the desired effects. This experiment also explores the chemical
kineticsofawelldocumentedhomogeneousliquidreactionwhichallowsustomakethe
rightdecisionswhendecidingonareactor.
 5

Thereactioncarriedoutinabatchreactorisallowedtoproceedclosetocompletion.The
conductivityofthereactionsolutioninthereactorchangeswiththedegreeofconversion,
andthisprovidesaconvenientmethodformonitoringtheprogressofthereaction.These
twomethodsinvolvetwodifferentequationsandmethodsofanalysis.
 6

Literature Review and Theory

Stoichlometry
The stoichiometry of the reaction can be written as:

Sodium Hydroxide + Ethyl Acetate Sodium Acetate + Ethyl Alcohol

A + B C + D

Rate of Reaction
The rate of reaction is defined as
-rA = -rB = rC = rD = - (1)

For equal feed concentrations, CA0 = CB0, and since the reaction stoichiometry is 1:1, the
reaction rate may be simplified to:

Therearetwoparticularmethodforconductingthisexperimentthebatchreactorwhichis
fairlysimpleandtheCSTR.

Thefirstwhichisthebatchreactorinwhichreactantswhereaddedtocontainor. Batch
reactorsareexamplesofclosedreactorsthatisonesthat,onceprimed,receivenofurther
inputs of mass or energy and permit no outputs of waste materials. In some case the
unreactedreactantsarerecycledbackintothereactorsotoavoidewasteandoptimisethe
reactorsprofitability.Theparticularreactionbetweenethylacetatebysodiumhydroxideis
usuallyconsideredafirstordereactionbutwhenthefeedstreamshaveaequimolarnature
the reaction kinetics follow a second order nature overall. The differential or integral
methodcanbeusedtodefinetherateconstant.Whenwedothiswefindthattherate
constantis:

For an irreversible reaction the general form of the rate law is often given as:

-rA = kCAnCBm

This means the reaction rate is given by,

-rA = kCAm

Where: r=reaction rate

k=rate constant
Ci = molar concentration of reactant i
n, m = appropriate powers (based on experimental data)

Theintegralmethodisdifferenttothedifferentialmethod.Thekeydifferencebetweenthe
twoliesinthetreatmentofthedifferentialdesignequation.Theintegrationmethodis
definedbytheequation,
 7

Afterdeterminingthisbyusingthedifferentialmethodandwefindthenecessaryequation
whichis,

Thereforewefindthatthe

Anaturalplotoflogreactionrateversuslogconcentrationwillgiveastraightlineofslope
equal to the power of the relationship. This equation allows us plot the concentration
againstreactionrateanddetermineavaluethatissuitableforkwithreferencetoasecond
orderequation.

ForaCSTRreactantsarefedintothereactorandreactedinsideandproductsexitthe
reactorthroughtheoutletstream.CSTRshaveanincreasedlevelofsafetyduetothefact
thattheyhavenoaccumulationofproducts.Theyproduceaproductquickerhoweverthey
oftenhaveadecreasedyieldincomparisontoabatchreactor.Theyalsohaveaveryhigh
capitalcostbuttheproductismoreconsistentthenthatofabatchreactorandthisisoften
considereasignificantbenefit.
 8

Experimental
i) Todeterminetheoverallreactionorderandthereactionrateconstantforthe
saponificationofethylacetatebymeasuringthereactionconversioninabatch
reactor.

Makeup0.5litresbatchesof0.1Msodiumhydroxideinwater,and0.5litrebatchesof
0.1Methylacetateinwater.Ensuretheconductivityprobeandtemperaturesensorshave
beeninstalled.Chargethebatchreactorwith0.5litresofthesodiumhydroxidesolution.
Switchonthereactoragitatorandadjustthespeedsettingto7.00Carefullyaddtothe
reactor0.5litresofethylacetatesolutionandstartthecollectionofdata.Wethenusedthe
IFDchannelhistorywindowtomonitortheprogressofthereaction.Theprocesswasthen
repeatedwithequimolarconcentrations0.05Mand0.02M.alloftheseprocesseswhere
carefullumonitoredandrecordedonexcelspreasheets.

ii) Todeterminetheoverallreactionorderandthereactionrateconstantforthe
saponification of ethyl acetate by measuring the reaction conversion in a
continuousreactor(aCSTR).

Thereactoragitatorwasadjustedtoaspeedsettingof7.00andtheCSTRwasallowed
tofillwithequimolaramoutsofwith0.1Msodiumhydroxideand0.1Methylacetate.The
feedpumpsweresetto80mL/minandtheconductivitywasmeasuredatasamplingrate
ofevery10secondsandwassampledcontinuouslyuntilthereactorachievedasteady
state.Theflowratewasdecreasedbyanintervalof10mL/mineachtimethereaction
achievedasteadystate,takingapproximately15minuteseachtime.

iii) Riskassessment

Theriskassessmentfoundthattherewereinsignificantrisksthereweresomeelectrical
risks anddueto thecorrosive nature ofthesodium hydroxideprotective gear(safety
glasses,labcoat,enclosedfootwear)hadtobewornincaseofspills.Therewasalsoa
veryminorslippinghazard.
 9

Results and Discussion

Batchreactor
Three different concentrations of equimolar volumes of sodium hydroxide and ethyl
acetatewererecordedIthreedifferentrunseachconcentrationwasmadeupwithwater
andplacedinsidethebatchreactor.Withdecreasingmolaritythebatchreactorsnecessary
reactiontimeincreases.Usingthemeasuredconductivityaplotofconcentrationagainst
timecouldbefound.

Concentrationandtime

Theconcentrationsofthereactantsdecreasesexponentiallywhichsuggestsanincreasein
products.Howeverwithdecreasingconcentrationthereactiontimewillincrease.

Figure1concentrationvtime

Theconcentrationdecreasedramaticallyinthefirsttwominuteshowevertheydosteady
outovertime.
 10

Rateandconcentration

By ploting the concentration and reaction rate against concentration it is possible to

determineakvaluethatissuitableforthereactionkinetics.

-rA = -rB = rC = rD =

For 0.1M the data can be represented in the following way

Figure2Concentrationvreactionratefor0.1M

ThechangeinconcentrationwasdividedbythechangeintimeandIexcludedtheoutling
data points in order to give an equation that is y=0.0035x3e05. When we take into
accountthefactthatthereareanumberofoutliersthisisasuitableresult.

For0.05Mthedatacanberepresentedwiththegraph

Figure3Concentrationvreactionratefor0.05M
 11

ThechangeinconcentrationwasdividedbythechangeintimeandIexcludedtheoutling
datapointsinordertogiveanequationthatisy=0.0018x1E05.Thisisafairlysimilar
reactionratetoconcentrationwhichsuggestsaconsistencyintheresults.

For0.02Mthedatacanberepresentedwiththegraph

Figure4Concentrationvreactionratefor0.01M

Thechangeinconcentrationwasdividedbythechangeintimeanditwasdecidedto
excludetheoutlingdatapointsinordertogiveanequationthatisy=0.0008x1E05.This
isfairlysimilartotheotherresultshoweverduetothemoreextensivetimeframeitvaries
aittle.Thisisbroughtaboutduetothefactthatthemolarconcentrationsaresignificantly
reduced.

Errorcouldhaveoccurredbecauseofanumberoffactorsincludinghumanerrorinthe
precisionofmeasurementcouldhaveresultedinlessormorevolumethandesirablebeing
addedtothebatchreactor.Alsothetemperaturemayhavefallenbellowthedesiredrange
ofabout2040Cwhichmanyhavealsoresultedinsomefairlysubstaintialerrors.However
due to the fairly consistent results obtained it was concluded that the results were
acceptable.
 12

Reactionrateandconcentrationlogarithmically

Toconcludeonthecomprehensivenatureofthereactions orderascattergraphofthe
naturallogneedstobeused.Thiswillalsodeterminethekvalueanddemonstrateafairly
conclusiveresult.Howeverduetosomeerrorsmentionedbeforetheresultswillvaryabit.
TheR^2valueshowwhetherthereultsarefeasible.

Foraconcentrationof0.1M

Figure5ln(CA)vln(rA)for0.1M

Fortheinitialconcentrationof0.01MtheR^2valuewasat0.8284thissuggeststhatthe
resultsarefeasible.Theratelawthatwasfoundgavethefollowingvalues:

K(rateconstant)=1.1845

n(reactionorder)=2.3382

Afterformulatingthesevalueswecandeterminetheratelawwhichisfoundtobe:

rA=1.2[CA]2

Thisisthemostaccuratevaluefork,andn,duetotheR^2valuebeingclosestto1.0outof
alloftheresultsgiven.Thisisbecauseitistheleastinfluencedbytheoulingfactorsand
theincreasedexposuretotheerrorspresentearilier.
 13

Foraconcentrationof0.05M

Figure6ln(CA)vln(rA)for0.05M

Fortheinitialconcentrationof0.01MtheR^2valuewasat0.6023thissuggeststhatthe
resultsarefeasiblehowevertheyarenotasaccurateasthosepresentedinFigure5.The
ratelawthatwasfoundgavethefollowingvalues:

K(rateconstant)=3.5276

n(reactionorder)=1.8203

Afterformulatingthesevalueswecandeterminetheratelawwhichisfoundtobe:

rA=3.5[CA]2

This resultsuggests that thekconstant is notas correct as the 0.1M reaction butthe
reaction remains second order which is correct. With decreasing accuracy comes a
decreaseinthevalidityoftheratelaw.Howeverthisisobviousandisclearlyvisiblefrom
theseresults.
 14

Foraconcentrationof0.02M

Figure7ln(CA)vln(rA)for0.02M

Fortheinitialconcentrationof0.01MtheR^2valuewasat0.1268thissuggeststhatthe
resultsarenotfeasible.Thisismostlikelyduetoerrorsandtheresultsshouldbedismissed
ifanaccurateratelawistobedetermined.Theratelawthatwasfoundgavethefollowing
values:

K(rateconstant)=9.4377

n(reactionorder)=0.5909

Afterformulatingthesevalueswecandeterminetheratelawwhichisfoundtobe:

rA=9.4[CA]

This rate law should be ignored due to the inaccuracy that was found to be present.
Thereforethemostaccurateratelawistheonethatisfoundfromthe0.1Mreaction.

IntegralAnalysis

Afterrearrangingtheequation:

andplotingtheappropriatevariablesweobtainvaluesfork.theresultinggraphsshowthe
desiredvaluesandtheyarerecordedbeloweachgraph.Thesevaluesaredifferenttothe
valuesrecorededfromdifferentialanalysis.
 15

Figure8timev1/CAfor0.1M

Thereforeln(k)isequalto8.86

Figure9timev1/CAfor0.05M

Thereforeln(k)isequalto8.585
 16

Figure10timev1/CAfor0.02M

Thereforeln(k)isequalto9.01

Theseresultsdiffersignificantlyanditcouldbeconcludedthatthisisbecauseofanumber
ofreasonssomeofwhichincludeoperatorerror.Thepreferredmethodthatwouldbeused
toanalysethisparticularbatchreactorsefficiencywouldbethedifferentialmethodand
because of the trial aspect associated with it. However I believe I made an incorrect
assumptionwhencalculatingtheseresultsandthereforemycalculatedresultsfromthe
integralcalculationsandthereforemyreactionordermaybeincorrect.

The differential method provedfarsuperior andandallowed foraccurate detection of

inaccuracy which allowed for the greater validation of these results. Because of these
reasonsitisconsideredthatthedifferentialmethodisfarbetterwithrespecttodetermining
thecorrectvalueforthekconstant.
 17

CSTR

Figure11timevNaOHconcentration

Eachofthesepeaksrepresentsachangeinthemolarflowratethatprogressivelyshifts
from8040cm^3/minwitheachprogressionbeing10cm^3/min.Theseshiftscauseana
sharpdecreaseintheconcentrationoftheNaOHstream.Thiscanbedemonstratedbya
volumetricflowratevNaOHconcentrationgraph.

Figure12Outletconcentrationvmolarflowrate
 18

Usingtheequation:x=(CA0CA)/CA0 wecandeterminethereactantsconversionleveland
afterwehaveobtainedthiswecanusearelatedequation:

Combinedwith,

Oncewehaveourreactionratewecanusethesevaluestographthereactionratev
theoutletconcentrationandthenwecanalsographthenaturallogsofbothto
obtainthereactionsorder.Therewereafewissuesthatresultedinusstartingthis
experimentagainwhichincludedthelossofpowertotheCSTRduringtheearly
stagesoreaction,howeverthiswasaneasyfixandwejustbegantheexperiment
again.

Volumetric Outlet Inlet Reactant Reactionrate

flowrate concentration concentration conversion

80 0.051781 0.052 0.004075 0.000017

70 0.042107 0.052 0.19025 0.000692

60 0.04065 0.052 0.218269 0.000681

50 0.039708 0.052 0.236385 0.000615

40 0.038576 0.052 0.258154 0.000537

Table1
 19

Figure13CSTR

Wethenplotthelogofouletconcentrationandthereactionratetodetermineavaluefork.

Figure14ln(rA)versusln(outletconcentration)

Thisgraphwasobtainedbytakingthenaturallogoftheoutletconcentrationandthe
naturallogofthereactionrate.Thetrendlineshowstheorderofthereactioncanbe
recognised,alongwiththereactionconstant.Theoverallorderofthereactionis
givenas49.273.Thisisnotcloseto2whichistheexpectedresulthoweverthe
outliermadeitdifficult.

Figure15ln(rA)versusln(outletconcentration)

Aftersomeminorcorrectionswhichincludedtheeliminationofonedatapoinitwasfound
thatthekvaluewasequalto2.072.thisvalueisincrediblycloseto2andistheexpected
resultfortherateconstant.
 20

Conclusions and Recommendations

TheexperimentshowsthebasicconceptsanddifferencesbetweenaCSTRandaBatch
Reactorandhowtousethetwodevicestodeterminereactionrates.Bygraphimgthelogs
andtakingintoaccountthenecessaryequationsitwaspossibletocalculatethereaction
rateconstantsandtodefinetheorderofthereactionduetothefactthatitdifferswith
respecttoreactionconditions.Inordertogathermoreaccurateandconclusivedatarepeat
experiementswouldneedtobeconductdsothatthedatawouldyieldamorelevelresult.

ThevariablesinvolvedinboththeCSTRandbatchreactorneedtobetakenheavilyinto
accountwhenexaminingthedatapresentedherebecausetheeffectwerenoticible.CSTR
reactorsareverygoodatproducinglareamountsofproductshowevertheiryieldisgratly
reducedincomparisontothatofbatchreactors,howeverthiscouldbeaddressesthrough
theintroductionoflargerreactionvessilesandslowerfeedstreams.TheCSTRprovedto
besubstaiallyunsuitableforareactionofthissizeandwouldonlybeapplicableonamore
commercialscale.Itisforthisreasonthatthebatchreactorprovedtobeamoreacceptable
reactorforthisparticularexperiment.

Theequationsusedinourresultsweretakenfromvariousareasandallowedustodefine
thereactionkineticsinamanorthatseemedaccurate.Combinedwiththeexperimental
datarecordedduringtheexperimentitwaspossibleforustodeterminethereationorders.
By doing this we gathered valuable knowledge on the relaionships involved with the
kineticpresentinthesereactortypes.

Thereactorsshowedvariousordersofreactionwhichisconcerningandsignallederrorsin
ourresultsorarithmeticalprocedure.HoweverinalltheresultsoftheCSTRwerequite
promisingandtheearyreactions inthebatchreactorsalsopointedtowardcorrectand
seeminglyaccurateexperimentation.
 21

References
1) http://www.umich.edu/~elements/asyLearn/bits/cstr/

2) http://www.cs.montana.edu/webworks/projects/stevesbook/contents/chapters/chapt
er008/section002/blue/page002.html

3) http://www.chemeng.queensu.ca/courses/CHEE321/lectures/documents/Module5.
pdf

4) https://lms.rmit.edu.au/bbcswebdav/pid4643627dtcontentrid
8350005_1/courses/PROC2083_1350/CRE%20Week%201%20%202013.pdf