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ChemicalKineticsReactionRates
Chemicalkineticsisthebranchofchemistrywhichaddressesthequestion:"howfastdoreactions
go?"Chemistrycanbethoughtof,atthesimplestlevel,asthesciencethatconcernsitselfwithmaking
newsubstancesfromothersubstances.Or,onecouldsay,chemistryistakingmoleculesapartand
puttingtheatomsandfragmentsbacktogethertoformnewmolecules.(OK,soonceinawhileone
usesatomsorgetsatoms,butthatdoesn'tchangetheargument.)Allofthisistosaythatchemical
reactionsarethecoreofchemistry.
IfChemistryismakingnewsubstancesoutofoldsubstances(i.e.,chemicalreactions),thenthereare
twobasicquestionsthatmustbeanswered:
1.Doesthereactionwanttogo?Thisisthesubjectofchemicalthermodynamics.
2.Ifthereactionwantstogo,howfastwillitgo?Thisisthesubjectofchemicalkinetics.
Herearesomeexamples.Considerthereaction,
2H2(g)+O2(g)2H2O(l).
WecancalculaterGoforthisreactionfromtablesoffreeenergiesofformation(actuallythisoneis
justtwicethefreeenergyofformationofliquidwater).WefindthatrGoforthisreactionisvery
largeandnegative,whichmeansthatthereactionwantstogoverystrongly.Amorescientificwayto
saythiswouldbetosaythattheequilibriumconstantforthisreactionisveryverylarge.
However,wecanmixhydrogengasandoxygengastogetherinabulborothercontainer,evenintheir
correctstoichiometricproportions,andtheywillstaythereforcenturies,perhapsevenforever,
withoutreacting.(Ifwedropinacatalystsayatinypieceofplatinumorintroduceaspark,oreven
illuminatethemixturewithsufficientlyhighfrequencyuvlight,orcompressandheatthemixture,the
mixturewillexplode.)Theproblemisnotthatthereactantsdonotwanttoformtheproducts,theydo,
buttheycannotfinda"pathway"togetfromreactantstoproducts.
Anotherexample:considerthereaction,
C(diamond)C(graphite).
IfyoucalculaterGoforthisreactionfromdatainthetablesofthermodynamicpropertiesyouwill
findonceagainthatitisnegative(notverylarge,butstillnegative).Thisresulttellsusthatdiamonds
arethermodynamicallyunstable.Yetdiamondsarehighlyregardedasgemstones("diamondsare
forever")andareconsideredbysomefinancialadvisorsasagoodlongterminvestmenthedgeagainst
inflation.Ontheotherhand,ifyouweretovaporizeadiamondinafurnace,underaninert
atmosphere,andthencondensethevapor,thecarbonwouldcomebackasgraphiteandnotas
diamond.
Howcanallthesethingsbe?
Theansweristhatthermodynamicsisnotthewholestoryinchemistry.Notonlydowehavetoknow
whetherareactionisthermodynamicallyfavored,wealsohavetoknowwhetherthereactioncanor
willproceedatafiniterate.Thestudyoftherateofreactionsiscalledchemicalkinetics.
Thestudyofchemicalkineticsrequiresnewdefinitions,newtypesofexperimentaldata,andnew
theoriesandequationstoorganizethedata.Webeginwiththedefinitionofreactionrate.

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ReactionRates
Considerthereaction,
2NO(g)+O2(g)2NO2(g).
Wecanspecifytherateofthisreactionbytellingtherateofchangeofthepartialpressuresofonethe
gases.However,itisconvenienttoconvertthesepressuresintoconcentrations,sowewillwriteour
ratesandrateequationsintermsofconcentrations,wheresquarebrackets,[],meanconcentrationin
mol/L.
Wemighttrytowritetheratevariouslyas,

oras

butthesearenotthesamebecauseeachmoleculeofO2givestwomoleculesofNO2.Toarriveatan
unambiguousdefinitionofreactionratewedefinethe"reactionvelocity,"v,as

(1)
Thisisunambiguous.Thenegativesigntellsusthatthatspeciesisbeingconsumedandthefractions
takecareofthestoichiometry.Anyoneofthethreederivativescanbeusedtodefinetherateofthe
reaction.
Forageneralreaction,
aA+bBcC+dD,(2)
thereactionvelocitycanbewritteninanumberofdifferentbutequivalentways,

(3)
Asinourpreviousexample,thenegativesignsaccountformaterialthatisbeingconsumedinthe
reactionandthepositivesignsaccountformaterialthatisbeingformedinthereaction.The
stoichiometryispreservedbydividingtherateofchangeofconcentrationofeachsubstancebyits
stoichiometriccoefficient.

RateLaws
Aratelawisanequationthattellsushowfastthereactionproceedsandhowthereactionrate
dependsontheconcentrationsofthechemicalspeciesinvolved.Aratelawisanequationoftheform,

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(4)
Equation4isgivesusafirstorderdifferentialequationintbecausethereactionvelocityisrelatedtoa
timederivativeofoneoftheconcentrations(asinEquation3).
Theratelawmaycontainsubstanceswhicharenotinthebalancedreactionandmaynotcontainsome
thingsthatareinthebalancedequation(evenonthereactantside).
Usuallyratelawstaketheform,
(5)
wherex,y,z,aresmallwholenumbersorsimplefractionsandkiscalledthe"rateconstant."Thesum
ofx+y+z+...iscalledthe"order"ofthereaction.

Commontypesofratelaws:
1.FirstOrderReactions
Inafirstorderreactiontherateisproportionaltotheconcentrationofoneofthereactants.Thatis,
v=rate=k[B],(6)
whereBisareactant.IfwehaveareactionwhichisknowntobefirstorderinB,suchas
B+otherreactantsproducts,
wewouldwritetheratelawas,

(7)
Theconstant,k,inthisrateequationisthefirstorderrateconstant.

2.SecondOrderReactions
Inasecondorderreactiontherateisproportionaltoconcentrationsquared.Forexample,possible
secondorderratelawsmightbewrittenas
Rate=k[B]2(8)
oras
Rate=k[A][B].(9)
Thatis,theratemightbeproportionaltothesquareoftheconcentrationofoneofthereactants,orit
mightbeproportionaltotheproductoftwodifferentconcentrations.

3.ThirdOrderReactions
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Thereareseveraldifferentwaystowritearatelawforathirdorderreaction.Onemighthavecases
where
Rate=k[A]3,(10)
or
Rate=k[A]2[B],(11)
or
Rate=k[A][B][C],(12)
andsoon.
Wewillseelaterthatthereareother,more"interesting"ratelawsinnature,butalargefractionofrate
lawswillfitinoneoftheabovecategories.

Integratedformsofratelaws
Inordertounderstandhowtheconcentrationsofthespeciesinachemicalreactionchangewithtime
itisnecessarytointegratetheratelaw(whichisgivenasthetimederivativeofoneofthe
concentrations)tofindouthowtheconcentrationschangeovertime.
1.FirstOrderReactions
Supposewehaveafirstorderreactionoftheform,
B+....products.(13)
Thenwecanwritetheratelawandintegrateitasfollows(recallthatthederivativeisnegative
becausetheconcentrationofthereactant,B,isdecreasing):

(14a,b,c,d)
Thefirstorderratelawisaveryimportantratelaw,radioactivedecayandmanychemicalreactions
followthisratelawandsomeofthelanguageofkineticscomesfromthislaw.TheformofEquation
14discalledan"exponentialdecay."Thisformappearsinmanyplacesinnature.Oneofits
consequencesisthatitgivesrisetoaconceptcalled"halflife."

Halflife
Thehalflife,usuallysymbolizedbyt1/2,isthetimerequiredfor[B]todropfromitsinitialvalue[B]o
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to[B]o/2.
Usingtheintegratedformofthefirstorderratelawwefindthat

(15a,b)
Takingthelogarithmofbothsidesgives,

(16a,b)
or

(17)
(Youcanalsowrite

(18)
whichmayactuallygivealittlemoreinsightintowhatismeantbyhalflife.Thisequation
demonstratesclearlythattheconcentrationdropsbyafactoroftwoforeveryt1/2incrementintime.)
Forfirstorderprocessesitiscommontodefinea"relaxationtime.",by

(19)
sothatonecanwritetheintegratedformoftheratelawas
(20)
isthetimerequiredfor[B]todropfrom[B]oto[B]o/e.Sometimesiscalledthe"oneovere"time.
Althoughthehalflifeisalmostalwaysusedtodescribethedecayrateofradioactiveelements,itis
commonforchemiststotalkabouttherateoffirstorderprocessesinchemistryintermsofthe
relaxationtime.
WRS
Fromhereyoucan:
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