You are on page 1of 41

Chapter14 ChemicalKinetics

bv,272009

I.Introduction
Gasolineandairinacarengineexplodeviolently,butleftuntouched,theywillnotreactforyearsata time.Meatleftoutwillinvitebiochemicalreactionsthat,amongotherthing,generatebadsmelling gases.Ifkeptatlowertemperatures,thesereactionstakeamuchlongertimetooccur.Enzymatic reactionsoccurslowlyatlowtemperaturesandathightemperatures,butrapidlyatintermediate temperatures.Whydosomeoccurquickly,whileothersslowly?Whydosomereactionsoccuratall whileothersdonot?Inotherwords,whatcontrolschemicalreactivity? Chemicalreactivityiscontrolledbytwobroadfactors:thermodynamicsandkinetics.Thermodynamics considersthequestion:whichstateismorestable,reactantsorproducts.Thermodynamicsanswersthe question:shouldthisreactionoccur?Kineticsthesubjectofthischapterconsidersthequestion:what controlstherateofareaction?

Inorderforareactiontooccurinapracticalsense,itmustbeboththermodynamicallyandkinetically favored.Thesearerelativeterms:thereactionmustbethermodynamicallyfavoredenoughtoformthe amountofproductdesired,anditmustbekineticallyfavoredenoughtobecompleteonthetimescale required. Thermodynamiccontrolofreactionsarisesfromenthalpy,entropyandthetemperature.Kineticcontrol ofareactionarisesfromthemannerinwhichthereactiontakesplaceitsmechanism,theenergy barrierrequiredtobeovercometheactivationenergy,theconcentrationofreactants,andagainthe temperature.Inthischapterweanalyze:

howconcentrationcontrolsreactionrate themathematicsconnectingconcentration,rateandtime howactivationenergycontrolsreactionrate howtemperaturecontrolsreactionrate howeachoftheseisrelatedtothereactionsmechanism

II.CollisionTheory
Collisiontheoryrelateshowwethinkofreactionstothereactionratesweobserve.Theideaofcollision theory,isthatmoleculesarecollidingallthetimeandsomefractionbutnotallofthosecollisionswill leadtotransformationofthereactantstotheproducts. 1.Themoleculesmustcomeintocontact.Thisisacollision. 2.Theymustcollidewithenoughenergytoovercomeanenergybarriertoreactioncalledthe activationenergy. 3.Theymustcollideinanorientationthatallowsthenecessarybondbreakingandforming neededtotransformthereactantstotheproducts. Relationshipstoreactionrate: 1.Collisions:Thisissimple.Ifsomefractionofcollisionswillleadtocreationofproducts,thenthemore collisionspersecond,thefasterthereactionwillproceed.Thiscollisionrequirementdoeshavealarge effectonwhatmediaarechosentoperformchemicalreactions.Solidstendtobeveryslowreactors becauseonlytheatomsonthesurfacecanhavecollisionswithotheratomsonothermolecules.Ever noticehowslowironrusts?Mostreactionsaredoneeitherinsolutionorinthegasphasewhere freedomofmovementofthereactantmoleculesallowsthemtoeasilycomeintocontact. Conclusion:Themorecollisions,thefasterthereaction. 2.OvercomingtheActivationBarrier:AnysampleofreactantswillhaveaBoltzmanndistributionof molecularenergies.Somemoleculeswillhavehighenergy;somelow;manyintermediate.Onlythose withenergiesgreaterthantheactivationenergywillbeabletoreact.Figure15.1ashowsBoltzmann plotsforasetofreactantsattwodifferenttemperatures.Onlythosereactantswithenergygreaterthan (totherightof,intheplot)theactivationenergywillbeabletoreact.Becauseagreaterfractionof moleculesinthehightemperaturesampleexceedtheactivationenergy,thehightemperaturesample willhaveeffectivecollisionsandwillexperienceafasterreactionrate.

Figure15.1a:Boltzmanndistributionsofmolecularenergiesatdifferenttemperaturesshow thatmoremoleculesexceedtheactivationenergyathighertemperature.b:Atagiven temperature,moremoleculesexceedaloweractivationenergythanahighone. Figure15.1bshowsaBoltzmanndistributionofmolecularenergiesforasinglesample,butshowstwo differentactivationenergies.Agreaterfractionofthesamplemoleculesexceedtheenergyofthelower activationenergythandothehigheractivationenergy.Therefore,thosereactantmoleculeswill undergothereactionwiththeloweractivationbarriermorerapidlythanwouldwiththehigher activationbarrier. Conclusion:Thehigherthetemperatureandthelowertheactivationenergy,thefasterthe reaction. 3.CollisionOrientation:ConsiderthereactionwhereachlorideionbondstoanelectrondeficientC atomintheunstableC(CH3)3+carbocation.ThereactionintermsofLewisstructuresisshowninFigure 15.2a.

Figure15.2a Thereactionismoreclearwhenviewedusing3dimensionalmolecularmodels.Theseareshownin Figure15.2bandc.In(a)theClionapproachestheC(CH3)3+ionfromtheopenside,sotheCllonepair ofelectronscanreachtheopensiteonthecentralCatomandformthebondtomaketheproduct.

Figure15.2bandc In(c)theCl ionapproachesfromtheendandisblockedbyoneoftheCH3groups.Itcollides,butnotin therightplace.So,noreaction.Inthisreactionmanyofthecollisionswillbeintheproperorientation butmanywillnot.Orientationeffectsslowthereaction,butnotbymuch.Somereactionsinvolvevery largemoleculeswithveryspecificreactionsites,andinthesealowfractionofcollisionsoccurringlead toproducts. Conclusion:Themorespecificareactionsite,theslowerthereaction.

II.ExpressingReactionRate
Howfastisareaction?Weknowitwhenweseeit,buthowisitexpressedquantitatively?Wedothisby writingaratioofchangeinconcentrationoverchangeintime.ConsiderFigure15.3,whichshowsthe changesinconcentrationoveraperiodof8secondsforareaction,A 2B.ReactantAstartsata concentrationof0.50Manddropsto0Mover8seconds.ProductBstartsat0Mandincreasesto1.0 Mover8seconds.Therearethreecommonwayswemeasurerate.

Figure15.3ConcentrationTimeplotsduringthe courseofthereactionofA 2B

AverageRateOverTime Onewaywecouldexpresstherateisthechangeinconcentrationovertheperiodof8seconds.Therate ofproductionofBwouldbe1.00M/8s,or0.125M/s.Thisisnotparticularlyusefulbecausethereaction wasalreadydone.Betteristolookattherateofthereactionwhileitisoccurring.Ifwelookattheplot inmoredetail,weseethatthechangeinconcentrationinthefirstsecond,is:

Inthefirstsecond,theconcentrationofBchangesfrom0Mto0.50M.Therateofchangeistherefore,

[ B ] ( 0.50M 0.0M ) = = 0.50M / s 1.0s 0.0s t

Likewise,inthefirstsecond,theconcentrationofAchangesfrom0.50Mto0.25M.Therateofchange ofAistherefore,

[ A] ( 0.25M 0.50 M ) = = 0.25M / s 1.0 s 0.0s t

Whythenegativesign?Ratesarealwaysconsideredtobepositive.Whenexpressingarateintermsofa reactants(forwhichtheconcentrationdecreases)wechangethesigntomakesuretheratecomesout positive.Rule:Ratesexpressedforproductsdontusethenegativesign;thoseforreactantsdo.

Example1. Forthedecompositionofhydrogenperoxideindilutesodiumhydroxideat20oC 2H2O2(aq) 2H2O(l)+O2(g) thefollowingdatahavebeenobtained: Time,minutes [H2O2],mol/L 0 9.12x102 434 5.66x102 868 3.51x102 1302 2.18x102 WhatistheaveragerateofdisappearanceofH2O2overthetimeperiodfrom0minto434min? Solution: Therateovertimeisgivenbythechangeinconcentrationoverthechangeintime.Fora reactant,weaddaminussigntomakesuretheratecomesoutasapositivevalue.

Rate =

[ H 2O2 ] time

( 5.66 102 M 9.12 102 ) 434 min 0 min

= 7.97 105 M / min

WecanrelatetheratesofchangeofAandBusingthereactionequation.Because2molofBare producedforeachmolofAreacting,thechangeinconcentrationsofAandBarerelatedbyafactorof 2.

[ B] [ A] = 2 t t

Example2. Forthedecompositionofhydrogenperoxideindilutesodiumhydroxideat20oC 2H2O2(aq) 2H2O(l)+O2(g) theaveragerateofdisappearanceofH2O2overthetimeperiodfromt=0tot=516minis foundtobe8.08x105M/min.WhatistherateofappearanceofO2overthesametimeperiod? Solution: ThereactionequationshowsthatforeverytwomolesofH2O2thatreact,onemoleofO2is formed.ThereforetherateofformationofO2ishalftherateofH2O2consumption.

[ O 2 ] 1 [ H 2O 2 ] 1 8.08 105 M = = = 4.04 105 M / min t 2 t 2 min

InstantaneousRate Weareofteninterestedinhowfastareactionisgoing,rightnow.Thisiscalledtheinstantaneousrate andisequaltotheslopeoftheconcentrationtimecurve.Ifdrawtangentsonthecurveatthe2second pointandmeasuretheirslopes,weseethattheinstantaneousrateat2secondsis+0.130M/sforthe productionofBand0.065M/sforconsumptionofA.

InitialRate Theinitialrateistheinstantaneousraterightwhenthereactionstarts.Thisisofinterestexperimentally becauseitistheeasiesttimeforustoknowtheexactconcentrationsofthedifferentspeciesinsolution. Afterthereactiongoesawhile,weneedtomakeinstantaneousmeasurementstoknowwhatthe concentrationsare.Sometimesthatseasy,butsometimesnot.Buttheconcentrationsatthestartof thereactionarealwayseasytoknow.Youmadethesolutions,afterall.

Theinstantaneousrateistheslopeoftheconcentrationtimecurveatthetime=0point.Again,though, weseethattherateofproductionofBistwicetherateofconsumptionofA. AFinalPoint Youcanuseaconcentrationtimecurvetosayalotaboutareaction.Wevealreadynotedthatthe concentrationtimecurveidentifiesAasareactantbecauseitdecreasesinconcentrationovertime,and Basaproductbecauseitincreases.Wecanalsoseethat2molofBareformedforeachmolofAthat reactsbecauseBgoesuptwiceasmuchasAgoesdown.

Butwecanalsoseeinthisplotthatthereactionslowsdownasitproceeds.Notallreactionsdo.What thistellsusisthatthereactionratedependsontheconcentrationofAavailabletoreact.Noticethat when[A]islarge,theslopeofthecurveissteep.Thereactionisfastwhen[A]islarge.Laterinthe reaction,[A]ismuchsmaller,andsoistheslope.ThereactionslowsdownasAisusedup.Thereisa concentrationdependenceofrateonconcentration.Which,notcoincidentally,isthesubjectofthenext section.

III.ConcentrationEffects
Thefrequencyofcollisionswasthefirstconsiderationweexaminedwhenthinkingaboutwhatcontrols reactionrates.Themorecollisions,thefastertherateshouldbe.Andthatsgenerallybutnotalways true.Therearetwowaystoincreasethefrequencyofcollisionsbetweenmolecules:crowdmoreof themtogetherinaspaceormakethemmovefaster.Movingfasterisaccomplishedbyraisingthe temperature,andwelldealwiththatlater.Asforcrowdingmoremoleculestogether,weretalking aboutconcentration.Thegreatertheconcentrationofacompound,themoremoleculeswillbepresent inthesamevolume,andthemorecollisionswilloccur.Thisiswhycrowdeddancefloorsarepopular, andemptyonesarenot.Inadditiontothatbeingtruebydefinition,ofcourse. Thedependenceofarateontheconcentrationofthereactantsisexpressedinaratelaw(orsometimes calledarateequation).ConsiderthedecompositionreactionofNH4NCO. NH4NCO(aq) (NH2)2CO(aq)

Theratelawforthereactionis Rate=k[NH4NCO]2

Theratelawhasthreeparts:

Whatdoesthismean,anyway?Well,forthisreaction,itmeansthattherateofthereactionis proportionaltothesquareoftheconcentrationofthereactant.Youmightthinkthatifyoudoublethe reactantconcentration,theratewoulddouble.Inthisreaction,nottrue.Itwillquadruple. Moreexamples: Reaction(allgasphase) 2N2O5 4NO2+O2 NO2+CO NO+CO2 2NO+O2 2NO2

RateLaw Rate=k[N2O5] Rate=k[NO2]2 2 Rate=k[NO2] [O2]

OverallOrder firstorder secondorderinNO2,zeroorderin CO,secondorderoverall secondorderinNO,firstorderin O2,thirdorderoverall

Acouplethingstonoticeintheexamplesabove: 1.Theratelawsarenotderivedfromthereactionequations.Sometimestheymatch. Sometimestheydonot. 2.Althoughtherateconstantisreallyanumberwithunits,whendescribingageneralratelaw, weusuallyjustwritek.Thisisbecausetheratelawistrueatalltemperatures,butany numericalkvalueistrueonlyatonetemperature.Weindicateanumberwhenwewanttouse theratelawincalculations. AnnoyingBoxAbouttheUnitsofk Assumingtimeismeasuredinseconds,therateofareactionisalways expressedintermsofM/s.Whataretheunitsofk?Well,itdependson thereactionorder. ZeroOrder Ifthereactioniszeroorder,theratelawis, Theunitsofkmustbethesameasthatofrate,M/s. FirstOrder Inafirstorderreaction,theratelawis, Rate=k[A] Rate=k

Intermsofunits,thisis SecondOrder

M = k M .Theunitsofkmustbe1/s,ors1. s

Inasecondorderreaction,theratelawis, Rate=k[A]2

Intermsofunits,thisis M1s1.

M = k M 2 .Theunitsofkmustbe1/Ms,or s

Example3: Methylacetatereactswithhydroxideionaccordingtothefollowingequation, CH3CO2CH3+OH CH3CO2+CH3OH

withtheratelaw, Ratek[CH3CO2CH3][OH]

Whatistheorderofreactionforeachreactant,andtheoverallreactionorder? Solution: Becausethetherearenosuperscriptstotherightofeachconcentrationintheratelaw,it meanstheyareeachfirstorder.ThereactionisfirstorderinCH3CO2CH3andfirstorderinOH.It issecondorderoverall,because1+1doesequal2. DeterminingRateLawsUsingtheMethodofInitialRates Ratelawsarenotderivedfromthereactionequation.Nomatterhowmanytimeswesay,peoplekeep thinkingitstrue.Butitsnot. Ratelawsarederivedfromexperimentaldata.Therearetwomethods:themethodofinitialrates,and thegraphicalmethod.Herewecoverthemethodofinitialratesinwhichareactionisrunmultipletimes withdifferentinitialconcentrationsofeachreactant.Theinitialratesofeachexperimentarecompared totheinitialconcentrationsofthereactantstodeterminetheorderofeach.Themethodismostoften performedinthefollowingway: 1.Foreachreactant,runapairofreactionsinwhichthatreactantsconcentrationisdoubledwhileall otherreactantconcentrationsareheldconstant.Thisisolatestheeffectonratetothatsinglereactant. 2.Mostoftenoneofthreethingshappenstotheinitialratewhenthereactantconcentrationis doubled: a.Theratedoesnotchange:thismeanstherateisindependentofthatreactant.Thereactionis zeroorderwithrespecttothatreactant. b.Theratedoubles:thismeanstherateisproportionaltotheconcentrationofthatreactant. Thereactionisfirstorderwithrespecttothatreactant. a.Theratequadruples:thismeanstherateisproportionaltothesquareoftheconcentrationof thatreactant.Thereactionissecondorderwithrespecttothatreactant. 3.Oncetheorderforeachreactantisfound,takeanyoftheexperimentsandpluginconcentration valuesandthemeasuredratetodeterminethenumericalvalueofk.

Example4. Areactionisperformedbetweentworeactant,AandB, A+B C

Thefollowingdatawasobtainedfortheinitialrateofthereactioninfourseparateexperiments.

Whatistheratelawforthereaction,andwhatisthenumericalvalueofk? Solution: Theideaistoidentifytwotrialsforwhichonereactantconcentrationisdoubledandtheotheris heldconstant. ForA,thepairtouseisTrial1andTrial2.Noticethe[B]isconstantat0.252M.When[A]is doubled,therateincreasesfrom0.0204M/minto0.0817M/min.Thisisanincreaseof4times. Thereactionratequadruples,soweknowthatthereactionissecondorderinA. ForB,thepairoftrialstouseisTrial1andTrial3.[A]isheldconstantat0.213Mwhile[B]is doubled.When[B]isdoubled,therateincreasesfrom0.0204M/minto0.409M/min.Therate doubleswhen[B]isdoubled,sothereactionisfirstorderinB. Theratelawisthen,Rate=k[A]2[B] Finally,wefindthevalueofkbychoosinganyofthetrials,insertingthevaluesforrate,[A],and [B],andsolvingfork.ChoosingTrial4(fornoparticularreason),wesee, 0.0901M/min=k[0.761M]2[0.630]

k=

0.0901M / min = 0.247 M 2 min 1 2 [0.761] [0.630]

ConcentrationTimeRelationshipsforSingleReactantReactions
Forreactionsthatinvolveasinglereactant,wehavederivedmathematicalequationsthatrelatethe concentrationatanytimeduringthecourseofthereactiontotheinitialconcentrationandtherate constant.Thesearecalledintegratedrateequationsbecause,perhapswithoutsurprise,theyare derivedbyintegrationoftherateequation.Becausetherateequationsdependonthereactionorder, sodotheintegratedrateequations.Table13.1showsthethreeequationsintwoforms.Thefirstisthe regularequation.Thesecondisaversionintheformofastraightlineequation.Wellusethatlaterto makestraightlineplots,whicharealwaysusefulinscience.Ineachcase,[A]orepresentsthe concentrationofAbeforethereactionstarts.[A]trepresentstheconcentrationofAaftertimetpasses. Twoalgebraicversionsaregivenforthefirstordercase,becausebothareuseful. Equation/Order RateLaw IntegratedRate Equation ZeroOrder Rate=k [A]o[A]t=kt FirstOrder Rate=k[A] SecondOrder Rate=k[A]2

ln

[ A ]t [ A ]o

= kt
kt

1 1 = kt [ A]t [ A]o

[A]t =[A]o e
LinearForm [A]t=kt+[A]o y=mx+b

ln[A]t = kt + ln[A]o
y=mx+b

1 1 = kt + [ A ]t [ A ]o
y=mx+b

StraightLinePlot

y=[A] x=time slope=k

y=ln[A] x=time slope=k

y=1/[A] x=time slope=k

Theseequationsaregenerallyusefulinthreeways: 1.Topredicttheconcentrationatsomefuturetime,givent,kand[A]o. 2.Determinethetimerequiredfor[A]otodecreaseto[A]t. 3.Todeterminetherateconstant,k,given[A]oand[A]tattimet.

Example5. Thedecompositionofnitrousoxideat565oC 2N2O 2N2+O2

issecondorderinN2Owitharateconstantof1.10x103M1s1.Ifthereactionisinitiatedwith [N2O]equalto0.108M,whatwillitsconcentrationbeafter1250shaveelapsed? Solution Becausethereactionisfirstorder,weusethefirstorderintegratedrateequation.

1 1 = kt [ A]t [ A]o

Weknow[N2O]o,k,andt.Wesolvefor[N2O]t.

1 1 = (1.10 103 M 1s 1 ) 1250 s [ N 2O]t 0.108M 1 = 9.26M 1 + 1.38M 1 [ N 2O]t


[N2O]t=0.940M

Example6.Findingthetimerequiredfor[A]otoDecreaseto[A]t Theisomerizationofmethylisonitriletoacetonitrileinthegasphaseat250oC CH3NC CH3CN

isfirstorderwitharateconstantof3.00x103s1.IftheinitialconcentrationofCH3NCis0.107 M,howmuchtimemustpassfortheconcentrationofCH3NCtodropto0.0142M? Solution Becausethereactionisfirstorder,weusethefirstorderintegratedrateequation.Theversion bettersuitedtofindingtime(ork,forthatmatter)is,

ln

[ A]t [ A]o

= kt

Weknow[CH3NC]t,[CH3NC]o,andk.Wesolvefort.

ln

[CH3 NC]t [CH3 NC]o

= ln

0.0142 M = 3.00 103 s 1t 0.107 M

2.02 = 3.00 103 s 1t

t=

2.02 = 673 s 3.00 103 s 1

Example7.DeterminingtheValueofk Thegasphasedecompositionofdinitrogenpentoxideat335K 2N2O5 4NO2+O2

isfirstorderinN2O5.Duringoneexperimentitwasfoundthataninitialconcentrationof0.249 Mdroppedto0.0496Min230s.Whatisthevalueoftherateconstant,k,ins1? Solution: Becausethereactionisfirstorder,weusethefirstorderintegratedrateequation.Theversion bettersuitedtofindingkis,

ln

[ A ]t [ A ]o

= kt

Weknow[N2O5]t,[N2O5]o,andt.Wesolvefork.

ln

[ N 2O5 ]t [ N 2O5 ]o

= ln

0.0496 M = k s 1 230 s 0.249 M

1.61 = k s 1 230 s

k=

1.61 = 7.02 103 s 1 230 s

HalfLifeandRadioactiveDating Theconceptofhalflifeisusefulfordescribingtheroughspeedofareaction.Thehalflifeofareactionis thetimeittakesforofthereactantstoturnintoproducts.Considerthefirstorderdecompositionof hydrogenperoxide.ThetablebelowshowstheconcentrationofH2O2inincrementsof654min.The dataareplottedaswell.

Noticethatinthefirst654min,theconcentrationdropsfrom0.020Mto0.010M.Thatis,itdropsin half.Thehalflifeofthereactionistherefore654min.Then,whenanother654minpasses(fromt=654 tot=1308)theconcentrationdropsinhalfagain:from0.010Mto0.0050M.Thehalflifeisstill654 min.Successivehalflivescuttheoriginalconcentrationtofractionsof, #halflives 1 2 3 4 5 6

fractionremaining

1 2

1 4

1 8

1 16

1 32

1 64

Example8. Thefollowingdataareforthedecompositionofsulfurylchlorideat383oC. SO2Cl2 SO2+Cl2 0 5.18x103 166 2.59x103 332 1.30x103

time,min [SO2Cl2],M

Whatisthehalflifeofthereactionstartingattime0min,andattime166min? Solution: Theconcentrationdropsinhalffromto2.59x103overthefirst166minofreaction.Therefore thehalflifestartingatt=0minis166min(bydefinition). Startingat166minutes,theconcentrationdropsfrom2.59x103to1.30x103of166min(from 166minto332min).Thisisagaindroppinginhalfoverthatsametimeperiod.Thehalflife remains166min.

MathematicalRelationshipsforHalfLifeandk Foranyfirstorderreaction,thehalflifecanberelatedtotherateconstantinthefollowingway: Atthehalflife,theconcentrationforreactantAisofwhatitwasatthestartofthereaction.So,

[ A ]t ln [ A ]o
ln

1 [ A ]o 2 = ln [ A ]o

1 = kt 2

Therefore,

ln(0.5) = kt1/ 2 0.693 = kt1/ 2

t1/2 =

0.693 and k

k=

0.693 t1/2

RadioactiveDecay Allradioactiveisotopesdecayviafirstorderreactions.Forthesecaseswewritetheratelawandtime basedequationsintermsofnumbersofatomsoramountpresentinsteadofconcentration,wherethe letterNisusedtodenotehowmuchoftheradioactiveisotopeispresentatanyparticulartime.

ln

[ N ]t [ N ]o

= kt

[N]t =[N]o e kt
Example9. Theisotope32Phasahalflifeof14.3days.Ifasamplecontains0.884gof32P,whatmassof32P willremainafter22days? Solution: Thepathforthisproblemistousethehalflifetodeterminetherateconstantk.Thenusethe firstorderconcentrationtimeequationtodeterminethefinalamount.

k=

0.693 0.693 = = 0.0485 days 1 t1/ 2 14.3 days


1

N t = N o e kt = 0.884 ge (0.0485days

)(22 days)

= 0.304 g

RadioactiveCarbonDating Carbonexistsasmostly12C,withabout1%of13C,andaverysmallfractionofradioactive14C.Itisformed intheupperatmospherebyreactionof14Nwithhighenergysolarradiation.Becauseitisconstantly decayingandbeingreformedintheupperatmosphere,thereisarelativelyconstantconcentrationof 14 CpresentasCO2intheatmosphere.ThatCO2,likeallCO2,canbesequesteredbyphotosynthesisto formplants.Thoseplantslivetheirplantlikelife,sometimesbeingeatenbyanimals,sometimesjust dying.AsaplantoranimallivesitkeepsexchangingCwiththeatmosphere,andthefractionof14Cin theplantoranimalstaysequaltothatintheatmosphere. Oncethethingdies,however,itsCcontentislockedanditnolongerreceivesnew14C.Becausethe14C isradioactive,thefractionofitpresentinthedeadthingstartstodecrease.Ifwecomparethefraction presenttodaywiththefractionwepresumetobethesteadystate14Camount,wecanestimatethe timesincedeath.ThisisshowninFigure14.5.

Theactualexperimentinvolvesmeasuringthe14Cradioactivityfromasample.Itisgenerallyreported inunitsofcountsperminutepergramofC.Thehalflifeof14Cis5730years,andthistechniqueisgood fordatingitemsasoldas50,000years.

Example10. AwoodenbowlisfoundinacaveinFranceisfoundtohavea14Cradioactivityof10.2countsper minutepergramofcarbon.Livingwoodhasanactivityof13.6countsperminutepergramof carbon.Howlongagodidthetreedie? Solution. Tomakethiscalculation,wemaketheassumptionthatthefractionof14Cintheatmospherehas beenconstantovertime.Therefore,theactivityatt=0isassumedtohavebeen13.6 counts/ming.Becausetheradioactivityofasampleisdirectlyproportionaltotheamountof radioisotopepresent,theratioof14Cpresentnowandthenisequaltotheratioofradioactivity nowandthen.So,

ln

Nt = kt No

0.693 = 1.21 104 y 1t 5730 y 10.2 ln = 1.21104 y 1t 13.6 0.288 = 1.21 104 y 1t t = 2380 y k=
DeterminingtheRateLaw:TheGraphicalMethod Concentrationtimeplotscanbeusedtodetermingtheratelawforsinglereactantreactions.Thelinear formsoftheconcentrationtimeequationsforzero,first,andsecondorderreactionspredictdifferent formsofequationsthatwillyieldalinearplot. Equation/Order LinearForm ZeroOrder [A]t=kt+[A]o y=mx+b FirstOrder SecondOrder

ln[A]t = kt + ln[A]o
y=mx+b

1 1 = kt + [ A ]t [ A ]o
y=mx+b

StraightLinePlot

y=[A] x=time slope=k

y=ln[A] x=time slope=k

y=1/[A] x=time slope=k

Thegraphicalmethodfordeterminingratelawsinvolvesthesesteps: 1.Collectconcentrationtimedatawhilethereactionproceeds. 2.Makethreeplots:[A]vs.t,ln[A]vs.t,and1/[A]vs.t. 3.Determinethereactionorder: if[A]vs.tislinear,thereactioniszeroorder ifln[A]vs.tislinear,thereactionisfirstorder if1/[A]vs.tislinear,thereactionissecondorder

4.Theslopeoftheplotthatgivesastraightlineistherateconstantforthereaction.

Example11. Concentrationvs.timedataiscollectedforthedecompositionofH2O2. 2H2O2(aq) 2H2O(l)+O2(g)

Usethesedatatodeterminetheratelaw,andthenumericalvalueoftherateconstant. Solution ThefirststepistoenterthedataintoagraphingprogramsuchasExcelandusethecalculation functionstocreatecolumnsforln[H2O2]and1/[H2O2].

Next,createthreeplots:[H2O2]vs.t,ln[H2O2]vs.t,and1/[H2O2]vs.t.

Theln[H2O2]plotgivesastraightline.Thismeansthatthereactionisfirstorderandtheratelaw is, Rate=k[H2O2] Finally,thenumericalvalueoftherateconstantistheabsolutevalueoftheslopeofthestraight lineplot.TheslopecanbefoundinExcelbyrightclickingononeofthedatapoints,and choosingAddTrendline/Linear/DisplayEquationonChart.

Inthisreaction,k=0.00106min1.

IV.ActivationEnergyandTemperature
Weallhavethefeelingthatreactionsgofasterathighertemperatures,andthatstrue.Givenequal concentrations,allreactionswillproceedmorerapidlyastemperatureincreases.Why?Allreactions haveanactivationbarrier,anenergytheymustovercomebeforeproceedingtoproducts.Consider thecaseofthereactionofthisorganiciodidecompound.

ThefirststepinvolvesthebreakingoftheCIbond.Thisisanendothermicprocessandrequiresenergy tomakehappen.Eventhoughlaterstepsinvolvebondformationandareexothermic,andcanmakethe overallreactionexothermic,energymustbeusedtogetthefirststeptooccur. ReactionCoordinateDiagrams Theenergeticchangesthatoccurduringtheprogressofareactionareoftendisplayedgraphicallyusing areactioncoordinatediagram.Thisisaplotwithenergyofthechemicalsystemontheyaxisandthe progressofthereactionfromreactantsonthelefttoproductsontherightalongthexaxis. Figure14.5showsrepresentativereactioncoordinatediagramsfortwosimplereactions,one exothermicandtheotherendothermic.

Figure14.5Reactioncoordinatediagramsforanexothermicreactionandanendothermicreaction.

Importantfactsaboutreactioncoordinatediagrams: Energymustbegainedbythereactantsinordertoreachtheactivatedcomplex(alsocalledthe transitionstate) Theenergyrequiredisthereactionsactivationenergy,andthesymbolgivenisEa. Theactivationenergyisalwaystheenergydifferencebetweenthatofthereactantsandthatof theactivatedcomplex. o Activationenergyisalwayspositive. Theenergychangeforthereaction(E)istheenergydifferencebetweenthereactantsandthe products. o Ecanbeeitherpositiveornegative

Whenintroducingcollisiontheory,wesawthatanysampleofreactantswillhaveaBoltzmann distributionofmolecularenergies.Onlythosewithenergiesgreaterthantheactivationenergywillbe

Figure14.6aandb.Boltzmanndistributionsofmolecularenergiesatdifferenttemperatures showthatmoremoleculesexceedtheactivationenergyathighertemperature.b:Atagiven temperature,moremoleculesexceedaloweractivationenergythanahighone. abletoreact.Figure14.6ashowsBoltzmannplotsforsamplesatlowandhightemperature.Agreater fractionofmoleculesexceedtheactivationenergyinthehightemperaturesample.Thisleadstoa greaterfrequencyofeffectivecollisionsandafasterreactionrate.Figure14.6bshowshowactivation energyaffectsrate.Highactivationenergyleadstoasmallerfractionofmoleculesthatcanreact,anda slowerrate. Temperatureandactivationenergythereforeplayoffeachothertocontrolreactionrate.Greater activationenergydecreasesthefractionofcollisionswithsufficientenergytoreact.Buthighactivation energycanbeovercomewithhighertemperatures. ConsidertheconcentrationtimecurvesinFigure14.7a.Iftworeactionsarerunatthesame temperature,theonewiththegreateractivationenergywillbeslower.Figure14.7bshowsthatasingle reactionwillproceedfasteratahighertemperature.

Figure14.7aTworeactionsrunatthesametemperature,butwithdifferentactivationenergies. Thehighactivationenergycasegivestheslowerreaction.

Figure14.7bThesamereactionrunattwodifferenttemperatures.Thehightemperaturecase givesthefasterreaction. Remembertheratelaw?Itwassupposedtocontrolrate,andsoitstilldoes.Recallthatforasimplefirst orderreaction,A B,theratelawis, Rate=k[A]

Temperatureandactivationenergyeffectsarepartoftherateconstant,k,asdescribedbythe Arrheniusequation.

TheArrheniusequationshowsusthat: UsingtheArrheniusEquation ThetwopointversionoftheArrheniusequationis ahigherfractionofcollisionswithcorrectorientationleadstolargervalueofAandafasterrate (wegenerallydonotreportvaluesofAforreactions,buttheydomatter) isthefractionofcollisionsexceedingtheactivationenergy decreasesandtherateisslower

asEaincreases,

asTincreases, increasesandtherateisfaster thefractionEa/Tcontrolsrate:thesmallerthisfraction,thefastertherate

ln

E 1 1 k2 = a k1 R T2 T1

andismostoftenusedintwoways: 1. predictingtherateofreactionatadifferenttemperatureifyouknowEaandtherateatanother temperature 2. determiningtheactivationenergy

Example12.FindingkataNewTemperature Theactivationenergyforthegasphasedecompositionoftbutyl propionateis164kJ. Whatofthiscanwecontrol? C2H5COOC(CH3)3 (CH3)2C=CH2+C2H5COOH Althoughwediscusshowchangesin Therateconstantat528Kis3.80x104/s.Whatwillthe Eawillaffectreactionrate,the rateconstantbeat569K? activationenergyisinherenttoany reaction.Wecancontrolthe Solution: temperature,butnotEa.Forsome Inthiscase,weknow: reactions,Eacanbeloweredthrough useofacatalyst,butnotina T1=528K controlledway.Ifyouwanttochange T2=569K reactionrate,youchangeeither k1=3.80x104/s concentrationortemperature. k2=? Ea=164kJ/molandR=8.314x103kJ/Kmol WeinserttheseintotheArrheniusequation,

ln ln

E k2 = a k1 R

1 1 164kJ / mol 1 1 = 3 569 K 528 K 8.314 10 kJ / K imol T2 T1

k2 = 2.69 3.80 104 / s k2 = e 2.69 = 14.8 4 3.80 10 / s

k2=5.61x103/s

Example13.FindingEa Forthegasphasedecompositionofethylchloroformate, ClCOOC2H5 C2H5Cl+CO2 therateconstantat470Kis1.05x103/sandtherateconstantat508Kis1.11x102/s.Whatis theactivationenergyforthisreaction? Solution: Inthiscase,weknow: T1=470K T2=508K k1=1.05x103/s k2=1.11x102/s Ea=? R=8.314x103kJ/Kmol

WeinserttheseintotheArrheniusequation,

ln

Ea 1.11 102 / s 1 1 = 3 3 508 K 470 K 1.05 10 / s 8.314 10 kJ / K imol Ea 1.59 104 / K 2.36 = 3 8.314 10 kJ / K imol

Ea=123kJ/mol GraphicalDeterminationofEa TheArrheniusequationcanbewrittenintheformofastraightlineequation.

ln k =

Ea 1 + ln A R T

y=mx+b Inastraightlineplot,y=lnk,x=1/T,andtheslope=Ea/R.TodetermineEa,werunthereactionata seriesoftemperaturesandmeasuretherateconstantateach.Thenweplotlnkvs.1/T.

Example14.

Solution: Thefirststepistocreateaplotofthenaturallogofthemeasuredrateconstantsvs.theinverse temperature.ThiscanbedoneinExceloranothergraphingprogram.Findtheslopeusingleast squaresanalysis(inExcelthisiscalledatrendline).

Theactivationenergyisgivenby, Ea=Rxslope=(8.314x103kJ/Kmol)(1.22x104)=102kJ/mol

V.ReactionMechanisms
Chemicalreactionsinvolverearrangingatoms.Atomsononemoleculeenduponanother;some moleculesfallapart;othermoleculesform.Areactionmechanismisadetaileddescriptionofthebond breakingandformingstepsinvolvedinthepathwayfromreactanttoproducts.Anoverallreactionis composedofaseriesofindividualsteps.Eachofthesediscretestepsiscalledanelementarystep.

Reactionmechanismscannotbecalculatedorpredictedwithassuredness.Instead,allreaction mechanismsmustbedeterminedexperimentally.InsectionsVfandVgwereviewsomeofthemethods usedtoelucidatemechanisms. Va.TypesofMechanismSteps Molecularity Chemicaleventscanbecategorizedsimplybythenumberofreactingspeciesinanelementarystep. Almostalleventsareunimolecular,involvingasinglereactant,orbimolecular,involvingtworeactants. Ofthemillionsofchemicaleventsobserved,onlyahandfulinvolvetermolecularsteps,inwhichthree speciesreacttogetheratthesameinstant.Therefore,wewilldealwithunimolecularandbimolecular steps,butnottermolecularsteps. Fromamorechemicalperspective,anyreactionweobserveisthesumofaseriesofeventsthatoccurin sequence.Therearethreekindsofchemicalevents: bondbreaking bondforming concertedbondbreakingandforming

Abondbreakingstepinvolvesasingleentitybreakingupintotwopieces.Intheexamplebelow,aCO bondbreaks.Asinglereactantformstwoproducts.Becauseonlyonereactantmoleculeisinvolved,this stepisalsotermedunimolecular.

Abondformingstepinvolvesbringingtwomolecularfragmentstogethertoformasingleproduct.In theexamplebelow,aCObondisformed.Tworeactantsformasingleproduct.Becausetworeactant moleculesareinvolved,thisstepisalsotermedbimolecular.

Aconcertedbondbreakingandformingstepinvolvesonebondbreakingwhileanotherisforming.In theexamplebelowaCFbondisformedwhileaCClbondbreaks.Tworeactantsformtwoproducts. Thisstepisalsobimolecularbecausetworeactantmoleculesareinvolved.

Vb.ExamplesofSingleStepReactions Manychemicalreactionsaresimpleeventsthatoccurinasinglestep.Manyoftheseyouhaveseen before.Acidbasereactionsmostlyoccurinasinglestep.Theprotonationofammoniabyhydroniumion involvesthetransferofanH+ionfromH3O+toNH3.Thissinglestepisaconcertedbondbreakingand formingprocess. H3O+(aq)+NH3(aq) H2O(aq)+NH4+(aq)

ThedecompositionofN2O4isasinglebondbreakingstep. Vc.MultistepReactions,IntermediatesandCatalysts Mostchemicalprocessesthatweobserveoccurinaseriesofelementarysteps.Herearesomerules: 1.Theoverallreactionisthesumofthereactionsteps. 2.Aspeciesthatisformedinonestepandthenusedupinalaterstepisanintermediate. 3.Aspeciesthatisusedinonestepandthenreformedinalaterstepisacatalyst. 4.Neitherintermediatesnorcatalystsareseenintheoverallreactionequation. 5.Acatalystwillnormallybeseeninthereactionsratelaw,butanintermediateisnot.

Thedecompositionofozonetakesplaceintwosteps. Step1.O3(g) O2(g)+O(g) unimolecular,bondbreaking bimolecular,concertedbondformingandbreaking

Step2.O3(g)+O(g) 2O2(g)

WhenstudyingHesssLawinChapter5weintroducedtheideaofaddingaseriesofreactionstogivea netreaction.Thesametechniqueisusedheretodeterminetheoverallreactionthattakesplaceina seriesofsteps.Thisisperformedbyaddingallthereactantstotheleftofthereactionarrowandallthe oftheproductstotherightofthereactionarrow,andcancellinglikeitemsthatarepresentonboth sides.Inthiscase,theO(g)ispresentonbothsides. Step1.O3(g) O2(g)+O(g) Step2.O3(g)+O(g) 2O2(g) 2O3(g)+O(g) 3O2(g)+O(g) 2O3(g) 3O2(g)

Overallreaction:

LetsnotjustyetcompletelywriteoffthatO(g)atom.Sure,itdoesntappearintheoverallreaction equation,butthatdoesntmeanitdoesnotexistatleastforalittlewhile.Achemicalspeciesthatis formedinonestepofamechanismandthenusedinalaterstepiscalledanintermediate. Intermediatesneverappearintheoverallreactionequation.Sometimestheycanbeobservedwhilethe reactionprogresses,butothertimestheyareformedandusedupsoquicklytheyarenotseen,nor heard. Thedecompositionofhydrogenperoxideinthepresenceofiodideionoccursintwosteps. Step1.H2O2(aq)+I(aq) IO(aq)+H2O(l) bimolecular,concerted

Step2.IO(aq)+H2O2(aq) I(aq)+H2O(l)+O2(g) bimolecular,concerted overallreaction2H2O2(aq) 2H2O(l)+O2(g)

Inthiscase,theIOionisformedinthefirststepandthenconsumedinthesecondstep.IOisan intermediateinthisreaction.Conversely,Iionisusedinthefirststepandthenreformedinthesecond step.Iisacatalyst.

Example15. Chlorofluorocarbonsbreakdownintheupperatmospheretogivechlorineatoms.Theseare involvedinthebreakdownofozoneviathefollowingmechanism. Step1.Cl(g)+O3(g) ClO(g)+O2(g) Step2. ClO(g)+O3(g) Cl(g)+O2(g)

a.Whatisthemolecularityofeachstep? b.Whatistheoverallreactionequation? c.Identifyanyintemediatesand/orcatalysts. Solution: a.Bothstepsinvovletworeactants.Theyarebothbimolecular. b.Theoverallreactionisfoundbeaddingthetwostepsandcancellinglikespeciespresenton bothsides.Inthiscase,bothClOandClarecancelled. OverallReactionbeforecancelling: OverallReactionaftercancelling: Step1. Cl(g)+O3(g) Step2. ClO(g)+O3(g) Cl(g)+ClO(g)+2O3(g) 2O3(g) ClO(g)+O2(g) Cl(g)+O2(g) Cl(g)+ClO(g)+2O3(g) 3O2(g)

c.Cl(g)isareactantintheStep1,butisregeneratedinStep2.Clisthereforeacatalyst.ClOis generatedinStep1,butisconsumedinStep2.ClOisthereforeanintermediate. ReactionCoordinateDiagramsandMechanisms Reactioncoordinatediagramsareusedtorelatetheprogressofareactiontotheenergyofthesystem atanyparticularstep.Figure14.8showsreactioncoordinatediagramsfora1stepanda2step reaction.

Figure14.8ReactionCoordinatediagramsfor1step(R P)and2step(R In P)reactions.

Intheonestepreaction,theenergyofthereactants(R)mustincreasetothatofthetransitionstate beforeprocedingtoformproducts(P).Inthetwostepreaction,atransitionstatemustfirstbereached toallowthereactants(R)toundergoesthefirststeptoformtheintermediate(In).Theintermediatelies inanenergywell.Asecondactivationbarriermustbeovercomefortheintermediatetoreactfurtherto formthefinalproducts(P).Anyreactionsoverallactivationenergyistheenergydifferencebetweenthe reactantsandthetransitionstateofhighestenergy. Vd.ComplexReactionMechanismsandConcentrationTimeCurves Consideratwostepreaction. Step1. A B Step2. B C OverallReaction: A C HowwilltheconcentrationsofA,B,andofCchangeovertime.Clearlytheconcentrationofthereactant Awilldecreaseasthereactionproceeds,andtheconcentrationoftheproductCwillincrease.Butwhat abouttheconcentrationoftheintermediate,B?Itisformedinonestepandconsumedinanother.Its concentrationmustbezeroatthestartofthereaction,andmustbezerowhenthereactioniscomplete, butnonzeroinbetween.Thisisbestobservedbyexaminingconcentrationtimecurves.Figure14.9 showsconcentrationtimecurvesforA(red),B(yellow),andC(blue)forthreecases.

a. b.

c.

Figure14.9a.Step1fasterthanStep2.b.Step2alittlefasterthanStep1.c.Step2mustfasterthan Step1. In(a)thefirststepissomewhatfasterthanthesecondstep.Initially,asA Boccurs,therateof formationofBisgreaterthanitsrateofconsumptioninStep2.So,theconcentrationofBincreases overtime.Then,asreactantAisdepletedandtheconcentrationofBincreases,therateofformationof Bdecreasesanditsrateofconsumptionincreases.Atthispoint,theconcentrationofBstartsto decrease.EventuallytheconcenrationsofbothAandBdroptonearzeroasthereactionnears completion. Part(b)showsacasewhereStep2issomewhatfasterthanStep1.Inthiscase,Bisconsumedmore quicklyanditsconcentrationdoesnotbuildupasmuchasinPart(a).

Part(c)showsacasewhereStep2ismuchfasterthanStep1.Inthiscase,Bisconsumedalmost instantlyasitisformed.TheconcentrationofBneverrisestoanappreciablelevelandBmayneverbe concentratedenoughtoobserveinanexperiment. Youmightwonder,ifacaselikePart(c)occurs,howwouldweeverknowtheintermediateeverexisted? Insomecasesweneverdo.Inothercases,wedesignexperimentstoshowthattheintermediatewas present,evenifnotdirectlyobserved.Oneprimemethodforthisisatrappingexperiment.Ifwe suspectedsuchanintermediatewaspresent,weaddanotherreagentthatwepredictwillreactwiththe intermediate.Ifweseetheproductofthatexpectedreaction,thenwehaveevidencethatthe intermediatewaspresent.Inoursimpleexample, A B B+D E

weaddreagentD,whichinterceptsintermediateBbeforeiscanformproductC.Itinsteadforms productE,whichwecanobserveasitbuildsupinsolution. Ve.ReactionsTooComplextoDescribeWithMechanisms Reactionsthatinvolvemorethanonephaseareinherentntlycomplexandaregenerallynotwrittenas mechanisms.Takeforexampletheformationofsolidesilverchloridethatformswhensolutionsofsilver nitrateandsodiumchloridearemixed.Theoverallreactionandnetionicequationsarebothsimple: AgNO3(aq)+NaCl(aq) AgCl(s)+NaNO3(aq) Ag+(aq)+Cl(aq) AgCl(s)

Thisreactionseemsprettysimple.Twoionscometogetherandformasolid.Butitisthesolidthat makesitcomplex.Thesolidthatformsishugeonthemolecularscale,containingbillionsofions.Each crystalformsbyaddingmoreandmoreAg+andClions.

Intheimagehere,thecrystalgrowsbyafewaddedions.Thereisnoclearwaytowriteamechanismfor thisprocess.Itinvolvesbillionsofstepsandalthoughthegeneralprocessisalwaysthesame,the intemediatecrystalsinvolvedaredifferenteachtimethereactionisrun.

Vf.RelatingMechanismstoaReactionsRateLaw Thepathareactiontakeshasaneffectonhowrapidlythereactiontakesplace.Therateofanoverall reactionisequaltotherateofthatreactionssloweststep,whichiscalledtheratedeterminingstep(or sometimestheratelimitingstep).Acommonmisperceptionisthattheratelawisdirectlyderivedfrom thereactionequation.Thisisnottrueremovethatthoughtfromyourmind.Theratelawisinstead deriveddirectlyfromthechemicalequationoftheratedeterminingstep.Thereareonlythreetypesof steps: Theexperimentallydeterminedratelawisoneofthemostusefultoolsintryingtodeterminea mechanism.Theprocessinvolvesthreesteps: 1.Proposeamechanism,includingwhichstepwillberatedetermining. 2.Predicttheratelawusingtheratelawoftheslowstep. 3.Measureandcomparetheexperimentalratelawtothatpredictedforthemechanism.Ifthey donotmatch,thentheproposedmechanismiswrong.Iftheydomatch,thentheproposed mechanismmightbecorrect.Butitmightnotbecausemultiplemechanismscanleadtothe samepredictedratelaw. unimolecular A D 2A D A+B D Rate=k[A] Rate=k[A]2 Rate=k[A][B]

bimolecular,onereactant bimolecular,tworeactants

Example16. AnoxygenatomtransferreactionoccursbetweenNO2andCO. NO2(g)+CO(g) NO(g)+CO2(g)

Therearetwoproposedmechanisms: MechanismA. Step1. NO2(g)+CO(g) NO(g)+CO2(g) ratedeterminingslowstep

MechanismB. Step1. 2NO2(g) NO3(g)+NO(g) ratedeterminingslowstep fastsecondstep

Step2. NO3(g)+CO(g) NO2(g)+CO2(g)

Theexperimentallydeterminedratelawisrate=k[NO2]2. Whichofthesetwomechanismsissuppportedbytheexperimentalevidence? Solution TheratelawpredictedforMechanismAisthatforthesinglestep.Becausethatstephasboth NO2andCOasreactants,thepredictedratelawforthatstepandtheoverallreactionis: rate=k[NO2][CO]

Thisdoesnotmatchtheexperimentalratelaw,sothismechanismiswrong. TheratelawpredictedforMechanismBisthatfortheslow,firststep.Thisstepinvolvestwo moleculesofNO2,sothepredictedratelawforthatstepandtheoverallreactionis: rate=k[NO2]2

Thisdoesagreewiththeexperimentalratelaw,sothismechanismissupportedbutnotproved correct. MechanismswithReversibleSteps Somereactionstepscanreactinboththeforwardandreversedirections.Thatis,reactantscangoto formproducts,butthoseproductscanbackreacttoreformthereactants.Ifbothstepsarefast,they quicklyformanequilibriumstate,wheretheratesoftheforwardandreversereactionsproceedatthe samerate. Bromineandhydrogenreacttoformhydrogenbromide.Theoverallreactionis Br2(g)+H2(g) 2HBr(g).

Theproposedmechanismis:

Step 1.

k1 Br2 (g) 2 Br(g) k 1 k2 Br(g) + H 2 (g) HBr(g) + H(g) k3 H(g) + Br2 (g) HBr(g) + Br(g)

fast in both directions slow fast

Step 2. Step 3.

Inthismechanismdepiction,wewritetherateconstantforeachstepalongwithitsreactionarrow.The stepnumberiswrittenasasubscriptforeachstep.Thereversiblefirststepiswrittenwithadouble arrow,withtherateconstantforthereversestepbeingdenotedwithaminissign.Notethatk1isnot equaltok1.The1justmeansitstherateconstantforthereverseofstep1. Theratelawfortheoverallreactionistheratelawfortheslowstep: Rate=k2[Br][H2]

However,Brisnotareactantandweneverknowitsconcentration.Inordertoobtainthepredicted ratelawfortheoverallreactionweneedtoexpresstheconcentrationofBrintermsofspecieswedo know.TodothiswesolvetheratelawforStep1for[Br].ThekeytothisisthatthereversibleStep1is atequilibrium,astatewheretheforwardandreversereactionratesareequal(nottherate constants).So,

k1[Br2 ] = k1[Br]2 k [Br ] k [Br] = 1 2 = 1 k1 k1


Wetheninsertthissolutionfor[Br]intotherateequationfortheslowstep2.
1/ 2

[Br2 ]1/2

k Rate = k2 1 k1

1/2

[Br2 ]1/2 [H 2 ]

Experimentally,wecouldnotdifferentiatebetweenthecollectionofkvaluesandtheywouldcollapse intoasingle,measuredrateconstant. Rate=k[Br2]1/2[H2]

Theoverallreactionorderis3/2.

Vg.AdvancedMethodsforDeterminingMechanisms Alargepartofthechemistsworkisdeterminingthepathwaybywhichareactionoccurs.Ifyoure luckyandyoureusuallynotsomeeasyexperimentscanhelpdetermineamechanism.Ifnot,more advancedmethodsareemployed.Somecommonmethodsaredescribedbelow. 1.Reactiontotheexperimentalratelaw.Thiswasdescribedintheprevioussection. 2.Detectionofanintermediate.ThiswasdescribedinSectionVd.Detectionisusuallydone spectroscopically,byobservingabsorptionofradiationintheUV,VIS,orIRregions.SometimesNMR spectroscopyisused.Themainobstructiontodetectingintermediatesisthattheyareunstableand tendtoreactquickly.Thatswhytheyareintermediates.But,sometimestheystickaroundawhileand youcanseethem. 3.Trappingexperiments.Theseexperimentsareusedtochemicallydetectintermediatesbyhavingthe intermediatereactwithasecondaryreagenttoproduceanidentifyableproduct.Thatis,youdesignan experimenttohighjackanintermediateandcutofftherestofthemechanismunderstudy.

Inthereactiondiagramsabove,theproposedmechanisminvolvesthreesteps,withformationoftwo intermediates,BandC.Inthetrappedmechanism,areagentRisaddedtosiphonoffintermediateC.If additionofRleadstoformationofEandoflessD,thatsupportstheproposedmechanism.IfnoEis observedandDisstillformed,thatmeanstheproposedmechanismiswrong.Thisallassumesyouare surethetrappingreaction(C+R E)bothoccursandoccursfasterthanconversionofC D.Butyou canknowthatwithreasonablecertainty,soitsok. 4.Isotopiclabeling.Inthistypeofexperiment,oneofthereactantsissynthesizedcontainingaparticular minorisotopeofoneofthereactingatoms.Youcanthentrackwherethatisotopicallylabeledatom endsupintheproducts.Inoxidationreactionsinvolvingmetaloxides,itisunclearwhethertheoxygen thatisaddedtothespeciesoxidizedcomesfromthemetaloxide,orjustfromwaterinsolution. Todeterminethis,themetaloxidecanbesynthesizedusingtherareisotope18O,inasolutionwherethe watercontainsalmostall16O.Iftheproductcontains18O,youknowitcomesfromthemetaloxide.Ifit contains16O,youknowitcomesfromthewater.Tobesurethisexperimentisvalid,youneedtomake surethemetaloxideandwaterdonotexchangeOatoms.

Vh.Catalysis Catalysisisthetechniqueofusingacatalysttoinfluencetherateofareaction.Catalystsserveoneof twofuncitons:makingreactionsfasterormakingthemmoreselective.Ineithercase,thecatalyst providesanalternativemechanisticpathwayforthereaction,whichchangestheactivationenergyand changestherate. IncreasingReactionRate. Earlier,wesawthemechanismoftheIioncatalyzeddecompositionofH2O2.Thereactioncanbe observedtooccuroverashortperiodonceaniodideisadded.However,H2O2canalsodecomposeall onitsown,thankyouverymuch.Ifyouhaveanunopenedbottleofhydrogenperoxidethathasbeenon theshelfforafewmonths,payattentionwhenyoufirstopenittherewilloftenbeaswooshofair escaping.ThisisduetothebuildupofO2gasthathasformedinthedecompositionovertime. Figure14.10showsareactioncoordinatediagramforthisreaction,bothwithacatalystpresent,and withoutone.Theloweractivationenergyinthecatalyzedcaseleadestoafasterreaction.

Figure14.10ReactionCoordinatediagramsfortheuncatalyzedand thecatalyzeddecompositionofhydrogenperoxide. IncreasingSelectivity Welietoyou.Youvesuspectedit.Wetendtowritechemicalreactionsasiftheywilloccuraswritten andgoallthewaytocompletion.Oftentimes,though,reactionsaremessy.Oneformofthemessinessis thatasetofreactantscanoftenundergodifferentreactionstoformdifferentsetsofproducts.Thats bad.Youalwayswantonesetofproductsbecauseitisdifficultandexpensivetopurifytheproductsofa mixedreaction.Thesemultiplereactionsoccurwhenbothmechanisticpathwayshavesimilaractivation energies.Selectivityisameasureofhowmuchthereactioncreatesonesetofproductsoveranother. (Uptillnowwehavebeenassumingallreactionsareperfectlyselective.) Acatalystcanincreaseselectivitybychangingthepathwayofonereactionpathandnottheother. Whenthishappens,thereactiontoformonesetofproductswillincreasewhiletheotherstaysslow. Thereactionprefersthefasterformedproductsandismoreselective.Figure14.11showsreaction coordinatediagramsrepresentinghowthisworks.

Figure14.11ReactionCoordinatediagramsshowingtheprogressfortwosimultaneousreactionsthat occurfromasinglesetofreactants.Thetwosetsofproducts(AandB)areshowntoeithersideofthe reactants,whichareinthecenterofthediagram. Intheuncatalyzedcase,thetworeactionshavesimilaractivationenergiesandproceedatclosetothe samerate,formingsignificantquanitiesofproductsforbothcases.Additionofthecatalystdecreases theactivationenergyforformationofproductsetB,butnotproductsetA.Inthiscase,formationofBis muchfasterthanformationofA,sothereactionisselectiveforformationofB. TypesofCatalysts Catalystsaregenerallyhomogeneousorheterogeneous.Homeogeneouscatalystsaresoluble compoundsthatareaddedtosolutionsalongwiththereactants.Thesehavetheadvantageofbeing chemicallymodifiedtoagreatdegree.Chemistsareverygoodatsynthesizingsmallmoleculesandcan generallycreatesmall,solublecompoundsthatactinveryspecificways.Homogeneouscatalystsare goodatmodifyingreactionsinahighlyselectiveway.Themaindisadvantageofhomogeneouscatalysts isthattheymustberemovedfromsolutionwhenthereactioniscomplete.Thatis,oncetheproducts areformed,theyarestillmixedwiththecatalystandthetwomustbeseparated.Thisisoften expensive. Heterogeneouscatalystsaresolidsthatserveasareactivesurfaceuponwhichreactantsineitherthe gasorsolutionphasecanreact.Thesehaveadvantagesanddisadvantagesthatareoppositefrom homogeneouscatalysts.Theyareeasytoseparatefromthereactionproducts:justfilteroffthesolid. Theyare,however,muchmoredifficulttomodify.Becauseofthesedifferences,homogeneouscatalysts aremoreoftenusedforreactionsinwhichgreatselectivityisneeded;heterogeneouscatalystsare neededwhereselectivityisnotanissue.