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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE PURPOSE: ToverifyaproposedmechanismforthehydrolysisoftButylChloride. PRINCIPLES: OncetheRateLawforareactionhasbeenexperimentallyestablishedthenextstepisitsexplanationin termsofaReactionMechanism. Thisisasequenceofelementarysteps,whichdescribeindetailthe actualinteractionsamongtheatomsandthemoleculesduringthereaction whichwouldleadtotheobservedratelaw. Inthisexperiment,youwillverifyaproposedmechanismforthehydrolysis(waterbreaking)oft butylchloridebydeterminingtheratelawoftheslowerstepinvolvedinthemechanism.

Thereactionoftbutylchloridewithwaterproceedsasshowninthetwostepreactionbelow: CH3 CH3 C


+

STEPONE: SLOW

CH3

k CClCH3

+Cl-

CH3 CH3 tbutylchloridecarboniumionchlorideion

CH3

CH3 CH3 COH+H+

STEPTWO: FAST

CH3

C+ +OH

CH3 H CH3 carboniumionwatertbutylalcohol Intheoverallreaction(obtainedbysimplyaddingStepsOneandTwo),tbutylalcoholand hydrochloricacidarethetwoproducts: CH3 CH3 C OH+HCl

OVERALL:

CH3 CCl+OHCH3

CH3 H CH3 tbutylchloridewatertbutylalcoholhydrochloric acid orsimply: RCl + H2O ROH + HCl

whereRisanabbreviationforthe(CH3)3C (tbutylgroup).

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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE Thecommonlyacceptedmechanismsuggeststhatthefirststepistheslowerstepandtherefore determinestheoverallrateofreaction.Oneofthemostimportantpiecesofevidenceinfavorofthis reactionmechanismisthekineticratelawthatthisreactionfollows. Ifthefirststepinthereactionsequenceisindeedtheratedeterminingstep,then: TheRateofOverallReaction=RateofSlowerStep=RateofStep1 SinceStep1isaunimolecularreaction,itfollowsthat: RateofOverallreaction=RateofStep1=Rateofdisappearanceoftbutylchloride(RCl) D [RCl] Rate= - =k[RCl] Equation1 D t where: [RCl] =istheConcentrationoftbutylchloridesinmolesperliter k =RateConstant nRCl V =numberofmolesoftbutylchloride =thevolumeofthesolutioninliters

If:

Then:

nRCl [RCl] = V

Equation2

DuringtheveryshorttimerequiredforRCltochangeby D[RCl],thevolumeofthesolutionremains constant. IfwesubstituteEquation2intoEquation1,weget: DnRCl V1 DnRCl 1 Rate= - = - =knRCl () D tV D tV

Equation3

DividingbothsidesofEquation3by(1/V),weobtaintheRateLawinaformmoreconvenientforour purposes: DnRCl DnRCl - =knRCl or = -k Dt Equation4 D t nRCl

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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE
0 Iftheinitialnumberofmolesoftbutylchlorideattime0isn RCl andthenumberofmolesattimetis nRCl,integrationofEquation4betweentheselimitsgives:

DnRCl = -k Dt nRCl

Equation4

nRCl ln ( )=-kt 0 n RCl

and

0 ln(nRCl)= -kt+ln(n RCl)

Equation5a

Equation5b

Respectively: nRCl -kt - kt 0 log ( )= and log(nRCl)= +log(n RCl) 0 n RCl 2.3032.303

Equation6a

Equation6b

Equations5band6baresimilartotheequationofastraightline(y=b+mx) -k log(nRCl)= t 2.303

0 +log(n RCl)

Equation6b

y =mx + (vertical(slope)(horizontal coordinatecoordinate)

b (Intercept)

Equation6bpredictsthatifthereactionrateiscorrectlygivenbyEquation1(Rate=k[RCl]), aplotof log(nRCl)versustshouldbelinearwith slope=m= -k/2.303

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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE Inthisexperimentthestudyofthehydrolysisoftbutylchloridewillbecarriedoutina5050mixture (byvolume)ofisopropylalcoholandwater. Thereasonforstudyingthereactioninthissolvent,ratherthaninpurewater,istwofold: 1. tbutylchlorideisnotverysolubleinpurewater,and 2. thehydrolysisreactioninpurewaterproceedstoorapidlytobefollowedconveniently. + TheprogressofthereactionmaybefollowedbyfollowingtheproductionoftheH ion RCl + H2O
+ ROH +H +Cl-

Notethatforeverymoleoftbutylchloride(RCl)consumedintheoverallreaction1moleofHCl(and + therefore1moleofH and1moleofCl -)isproduced.ThereforethenumberofmolesofHCl producedduringthecourseofthereactionisameasureofthenumberofmolesof tbutylchloride(RCl)reacting. Furthermore,thenumberofmolesofunreactedtbutylchlorideisequaltothetotalnumberofmolesof 0 tbutylchloride(RCl)initiallypresent(n RCl)minusthenumberofmolesofHClproduced. Summarizing:

nHClproduced =nRCl reacted 0 nRClunreacted (remaining) =n RCl -nHClproduced


TherateofproductionofHClcanbetrackedbydeterminingthevolumeofstandardNaOHsolution requiredfortheneutralizationoftheH+. Thisisdonebyaddingafewdropsofphenolphthaleinindicatortothetbutylchloridesolutionatthe startoftheexperiment.AnamountofNaOHsolutionwillthenbeaddedsothatthetotalnumberof molesofOH - ,nOH,isinitiallyinexcessofthenumberofmolesofH+,nH+ ,thusfarproduced. AsthereactionproceedstheamountofH+ ionproducedincreases.Aftersometimettheamountof H+ producedwillbejustsufficienttoreactcompletelywiththeamountofOH - ionaddedtothe solution.Atthistime,thephenolphthaleinindicatorwillchangefrompinktocolorless. RecallthathereactionbetweenH+ ionandOH - ioninsolutionis: H+ +OH- H2O Hence,atthetimetatwhichtheindicatorchangescolor:

nRCl reacted =nH+ =nOH-

0 + 0 - nRClunreacted (remaining) =n RCl -nH =n RCl -nOH

Equation7 Afterthefirstcolorchangehasbeenobserved,sufficientNaOHsolutionisaddedtothetbutyl chloridesolutiontoreturnthepinkcolorofthesolution,andtheobservationofthetimeatwhichthe indicatorturnsfrompinktocolorlessisrepeated.Inthisway,alargeamountofdatagivingthenumber ofmolesoftbutylchlorideremaininginthesolutionatvarioustimesmaybecollected.Inorderto calculatethenumberofmolesoftbutylchlorideremainingattimet(nRCl) ,itisnecessarytoknow thenumberofmolesoftbutylchloridepresentatthestartofthereaction(n0RCl): 0 nRClremaining=n Equation8 RCl(initially present)- nRCl
0 Thenumberofmolesoftbutylchloridepresentatthestartofthereaction(n RCl)isdeterminedby titratingthereactionmixturewiththestandardNaOHsolutionafterasufficientlapseoftimesothat practicallyallofthetbutylchloride(RCl)hashadtimetoreact.

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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE PROCEDURE: 1. Obtaininaclean,drybeakerapproximately60mLof0.250MNaOHin5050isopropyl alcohol watersolution. 2. Rinseyourburettwicewith34mLportionoftheisopropylalcohol watersolution. 3. FillyourburetcompletelywiththeNaOHsolution,makingsurethatnobubblesaretrapped intheburettip. 4. Clamptheburetinaverticalpositionand setyourburettoexactly0.00ml. Theburetshouldthenbecappedwithaloosefittingtesttubeorsmallbeakertopreventthe evaporationofthealcoholfromtheNaOHsolutionandtheabsorption ofCO2 fromtheair. 5. Inyourgraduatedcylinder,measureout100mLof5050isopropylalcohol watersolution andemptythisintoaclean,dry250mLErlenmeyerflask. Addfivedropsof phenolphthaleinindicatorsolutiontotheflask. 6. Addapproximately1mLoftbutylchloridetotheflaskandswirlimmediatelytodissolve tbutylchloride(RCl)inthesolventmixture. Thetbutylchloridereagentwill beprovidedwithaPasteurpipetwhichwillbemarkedto indicatethelevelofliquidcorrespondingtoabout1mLoftbutylchloride. Startyourstopwatchtheveryinstantatwhichthetbutylchlorideisaddedtothe solventmixture. VERYIMPORTANT: DONOTSTOPYOURSTOPWATCHUNTILYOUFINISHEDTHEEXPERIMENT! 7. Immediatelyreturntoyourbenchandaddtotheflaskabout1mLofNaOHsolutionfrom theburet.Swirltomix.Ifthesolutiondoesnotturnpink,addasecondmilliliterofNaOH solution.Recordtheburetreadingtothenearest0.01mL Watchthetbutylchloridesolutionclosely.Usingyourstopwatch,note,readandrecord thetimein minutesand secondsthetimeatwhichthepinkcolor ofthesolutiondisappears (timeofcolordischarge) VERYIMPORTANT: DONOTSTOPYOURSTOPWATCHUNTILYOUFINISHEDTHEEXPERIMENT! Whenyouarefinishedwiththeexperiment,yourtimereadings(inminutesandseconds) willbeconvertedinseconds(timeelapsed,t ). Thiswillmakeiteasiertoplotthegraph. 8. Addanother1mLportionofNaOH,swirltomix,andrecordthenewburetreadingand thetimeInminutesandseconds) atwhichthepinkcolordisappearsagainfromthesolution. VERYIMPORTANT: DONOTSTOPYOURSTOPWATCHUNTILYOUFINISHEDTHEEXPERIMENT!

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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE 9. Repeatstep8untilatotalof 161mLadditionsofNaOHsolutionhavebeenmade,andthe correspondingtimesofcolordischargehavebeenrecorded. Ifyoushouldmissnotingthetimeofanycolorchange,simplyignorethisdatapoint, addanotherincrementofNaOHsolution,andcontinuewiththeexperiment. VERYIMPORTANT: DONOTSTOPYOURSTOPWATCHUNTILYOUFINISHEDTHEEXPERIMENT! 10. Measureandrecordthesolutiontemperature.
0 11. Fillalarge600mLbeakerhalffullofwaterandheatthewatertoabout40 C. Note: Youmaywanttodothiswhenyoustarttheexperimentindoingso, youll have 0 thewaterheatedto40 Cwhenyouneedit. Thiswillsaveyouwaitingtime. Measureoutabout50mLofthiswarmwaterinyourgraduatedcylinder,addittothetbutyl chloridesolutionintheflaskandswirltomix.Thenstoppertheflaskandimmerseitinthe largebeakerofwarmwater. Allowtheflasktoremaininthebeakerforabout1hour,turningitoccasionallyand periodically.WarmthewaterwithahotplateoraBunsensoastokeepthetemperature 0 0 between35 Cand45 C.Donotoverheat. Theadditionoftheextrawaterandtheincreaseintemperaturespeedupthehydrolysisof tbutylchloride(RCl)sothatattheendof1hour,virtuallyallof thetbutylchloridehas reacted.

12. Removetheflaskfromthebeakerofwarmwater,unstopperit,andtitratethesolution withthestandardNaOHtoafaintpinkendpoint. Recordthefinalburetreading Becarefulnottoovershoottheendpointinthisfinaltitration,sincetheaccuracyofall yourcalculationsdependsontheaccuracyofthistitration.

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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE CALCULATIONS: 1. Convertallyourtimereadingssincethetbutylchloridewasfirstaddedtothesolventmixture (recordedinminutesandseconds)intoseconds(t elapsed). 2. FromyourburetreadingandthemolarityoftheNaOHsolution,calculatethetotalnumber ofmolesofNaOH,(nOH-)thathadbeenaddedtothesolutionforeachtimeatwhich thecolor dischargewasobserved. 3. Fromtheresultofthefinaltitration,calculatethenumberofmolesof tbutylchloride(RCl) 0 whichwereinitiallypresent(n RCl) 4. FromEquation8,calculatethenumberofmolesoftbutylchlorideremaininginthe solution(nRCl)ateachtimet. 5. PlotlognRCl versust 6. FromtheslopeofthecurvemandEquation6bdeterminetherateconstantkandthe halflifet1/2forthereaction 7. AnswerQuestion4ontheReportForm

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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE Name:_________________________ Partner:________________________ REPORTFORM ConcentrationofNaOH:____________M Averagetemperature:____________0C

DATATABLE Time Time ofcolor elapsed discharge t (min&sec) (sec) 00:00 0 TotalmL ofNaOH added 0.00 nRCl reacted nRCl remaining 0 (MolesNaOHadded) (n RCl nRCl reacted) 0 (MolesofHClproduced) Seebelowforn RCl (UseEquation8) 0 0 lognRCl (3decimals)

FINALTITRATION: . TotalNumberofmolesofNaOHadded: Showcalculationsbelow:

________________mLNaOH ________________moles

TotalMolesofHClproduced
0 NumberofmolesofRClinitiallypresent(n RCl):

_______________moles

________________moles 8

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EXPERIMENT2 THEHYDROLYSISOFtBUTYLCHLORIDE 1. PlotlognRCl versust(seconds)ongraphpaperprovided.Attachthegraphtoyourreport. Intheupperrighthandsideofthegraphprovideatablethatincludeshedatabeingplotted. Recallthateverygraphmusthaveatitle. Drawthebeststraightlinethroughtheexperimentalpoints Findtheslopeoftheline. Showcalculationsfortheslopeonthegraphandincludeunits. Slope=m= 2. CalculatetheRateConstant,kfortheHydrolysisoftButylChloridefromyourexperimental data.Includeunits. Showcalculationsbelow:

k=

3. CalculatetheHalfLife(t1/2)fortheHydrolysisoftButylChloride. Showcalculationsbelow.Includeunits.

t1/2 = 4. Fromyourexperimentaldata,calculatethetimeinhourswhichwouldhavebeenrequiredfor 99.9%ofthetbutylchloridetohydrolyze,ifthereactionhadbeenallowedtoproceed withouttheadditionofextrawaterorheating.

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