Chapter13:ChemicalKinetics

EffectsofConcentration

EffectsofTemperature

EffectsofSurfaceArea

EffectsofCatalysts

ChemicalKinetics
Thermodynamicsdealswithspontaneityandtheposition
ofequilibrium,butdoesnotpredicthowquickly
equilibriumisachieved
Kineticsdealswithreactionrates

Energy

Transition
States
Reactants

Kinetics
Thermodynamics
Products

ReactionCoordinate

Ea
E

RatesofReaction
Forareaction,aA+bBcC+dD,wecandefinethe
instantaneousrateofreactionas:
1 d[A]
1 d[B] 1 d[C] 1 d[D]
rate =
=
=
=
a dt
b dt
c dt
d dt

where[A]and[B]areconcentrationofAandB,andtis
time

ThenegativesignsareneededbecauseAandBdisappear
duringreaction
Theaveragerateoveraperiodtis:
1 [A]
1 [B] 1 [C] 1 [D]
rate =
=
=
=
a t
b t
c t
d t

 Unitsofreactionratesare
molL1s1(ormolL1min1,etc.)
Reactionratesareusuallydefinedintermsof
concentrations
Ratescanalsobedefinedintermsofmolesofreactants
andproducts:
1 n A
1 nB 1 nC 1 nD
rate =
=
=
=
a t
b t c t d t

Theunitsaremols1inthatcase.

RXN:AB
nA=(0.741.00)
=0.26mol
t=10.0min

initialrate=nA/t=(0.26mol)/(10.0min)
=0.026molmin1
Note:rateasreactiongoestocompletion:
finalrate=nB/t=(0.840.78)mol/(10.0min)
=0.006molmin1

C4H9Cl(aq)+H2OC4H9OH(aq)+HCl(aq)
Instantaneousratescanbe
foundfromagraphby
drawingatangentatthe
pointofinterest
Thisisthegraphical
equivalenttotakingthe
derivativeofafunction
e.g.Therateat600s(blue
triangle)is:
d[C4H9Cl ]
(0.0170.042
)molL1
rate=
=
dt
400s
=6.2x105molL1s1

CPS:RateofReaction
Usingthedatainthetable,determinethecalculated
rateofthereaction2SO2(g)+O2(g) 2SO3(g).
Time,s[SO2],M[O2],M[SO3],M
3000.02700.05000.0072
7200.01940.04620.0148

7.6x106M/s
8.5x106M/s
9.0x106M/s
9.4x106M/s

CPS:RateofReaction
Usingthedatainthetable,determinethecalculated
rateofthereaction2SO2(g)+O2(g) 2SO3(g).
Time,s[SO2],M[O2],M[SO3],M
3000.02700.05000.0072
7200.01940.04620.0148
Rate=[SO2]/2t=(0.01940.0270)/{2(720300)}
=9.0106M/s

ReactionRatesandConcentration
Ratesofreactiontendtofallasreactantsareconsumed
Generalformofratelawexpressionsis:
rate=k[A]m[B]n
WhereAandBarereactants,kistherateconstant
mandnaregeneralexponentsdeterminedbyexperiment
(notthestoichiometriccoefficients)
e.g.CHCl3+Cl2CCl4+HClrate=k[CHCl3][Cl2]0.5
mandnarecalledthereactionorders,andthesumofall
theexponentsiscalledtheoverallreactionorder

CPS:DefiningRateLaws
Thereaction2H2(g)+2NO(g)2H2O(g)+N2(g)is
firstorderinH2andsecondorderinNO.Whichisthe
ratelaw?
A. k[H2][NO]
B. k[H2][NO]2
C. k[H2]2[NO]2
D. k[H2]3[NO]3

HowareReactionOrdersMeasured?
NH4+(aq)+NO2(aq)N2(g)+2H2O(l)
Observeinitialreactionratesasconcentrationsof
reactantsarevaried

Rateincreaseslinearlywith[NH4+]and[NO2]
Therefore,rate=k[NH4+][NO2]

Findingk
Onceweknowthereactionorders,wecanfindtherate
constantusingtheratedata

rate=k[NH4+][NO2]
k=rate/([NH4+][NO2])
k=(21.5x107M/s)/[(0.200M)(0.0400M)]
=2.69x104M1s1(unitsdependonrxnorder)

CPS:RateConstants
Sulfurylchloride,SO2Cl2,decomposestoSO2andCl2bythe
reactionSO2Cl2(g) SO2(g)+Cl2(g).Usingthedatainthe
tableat320C,calculatetherateconstantforthereaction.
Experiment[SO2Cl2]0,MInitialRate,M/s
10.00501.10x107

20.00751.65x107

30.01002.20x107

k=1.3x105s1

k=2.2x105s1

k=3.1x105s1

k=4.0x105s1

CPS:RateConstants
Sulfurylchloride,SO2Cl2,decomposestoSO2andCl2
bythereactionSO2Cl2(g) SO2(g)+Cl2(g).Using
thedatainthetableat320C,calculatetherate
constantforthereaction.
Experiment[SO2Cl2]0,MInitialRate,M/s
10.00501.10x107

20.00751.65x107

30.01002.20x107
k=rate/[SO2Cl2](datashowsthatitisfirstorder)
=1.10107/0.0050
=2.2105

TimeDependenceofConcentration
Firstorderreactions:e.g.ABrate=k[A]

d[A ]
rate
k[A]
dt

Rearrangeandintegratetofind[A](t)

d[A] t
=kdt

[ A ]0 [A]
0
[ A ]t

[A ]t
ln
=kt
[A ]0

lnA
[ ]t =kt+ln[A ]0

y(t)=mx+b
or:

[A ]t =[A ]0 ekt

e.g.CH3NC(g)CH3CN(g)
rate=k[CH3NC]

Slopeofthislineisk,sorateconstant
iseasilyobtainedfromgraph:
k=(5.03.4)/31,000s=5.2x105s1

HalfLife
Halflife,t1/2,isthetimerequiredtoconsumehalfofthe
reactantavailableattimezero,[A]0
Firstorderratelaw:
Att1/2:

[A ]t
ln
=kt
[A ]0
(1 2)[A ]0
ln
=kt1/2
[A ]0
ln 2
t1/2 =
k

Forthepreviousreaction,k=5.2x105s1,so
t1/2=1.3x104s=3.7h

 Inafirstorderreaction,t1/2isconstant

t1/2forSecondOrderReactions
d[A ]
2
rate=
=k[A ]
dt
1
1
=kt+
[A ]t
[A ]0

y=mx+b

att1/2,

1
t1 2 =
k [ A] 0

t1/2ofa2ndorderrxn
dependson[A]0

CPS:HalfLife
Inafirstorderreactionthehalflifeis116minutes.What
istherateconstantkins1?
A.
B.
C.
D.

1.0105
1.0104
6.0103
3.6

CPS:HalfLife
Inafirstorderreactionthehalflifeis116minutes.What
istherateconstantkins1?
ln 2
t1/2 =
k
ln2
k=
116 60

k=9.959105=1.0104

OrderofNO2(g)NO(g)+1/2O2(g)
Time(s)
0.0
50.0
100.0
200.0
300.0

[NO2](M)
0.01000
0.00787
0.00649
0.00481
0.00380

ln[NO2]
4.610
4.845
5.038
5.337
5.573

1/[NO2]
0.235
0.193
0.299
0.236

100
127
154
208
263

27
27
54
55

1stOrder

ln[A ]t =kt+ln[A ]0

ln[A]linearwitht

2ndOrder

1
1
=kt+
[A ]t
[A ]0

1/[A]linearwitht

KineticPlots

FirstOrder

SecondOrder

Temperature,Energy,andRates

Arrheniusequationforrateconstant:
Ea

k =Aexp
RT

frequencyfactor
effectivecollisionsgeometry
smallTdependence(negligible)

CPS:ActivationEnergy
Acertainreactionhasanactivationenergyof10kJand
H=200kJ.Whatistheactivationenergyofthe
reversereaction?
A.
B.
C.
D.

10kJ
190kJ
200kJ
210kJ

CPS:ActivationEnergy
Acertainreactionhasanactivationenergyof10kJand
H=200kJ.Whatistheactivationenergyofthe
reversereaction?
Answer:Theenergyofthetransitionstateisthesame,so
210kJworthofenergymustbeinputtotheproducts
toreacthetransitionstate.

Plottingk(T)
AlinearformoftheArrhenius
equationcanbeobtainedby
takingthenaturallogarithm:

E a 1
lnk = +lnA
R T

y=mx+b

Slope=Ea/R
yint=lnA

EstimatingEa
WhatisEaforareactionifkis2.52x105s1at189.7Cand
6.30x104s1at230.3C?
Ea 1
lnk1 = +lnA
R T1
k2
Ea 1 1
ln =
k1
R T2 T1

Ea 1
lnk2 = +lnA
R T2

Rln(k2 k1)
Ea =
1 1

T2 T1

ConverttemperaturestoKanduseR=8.314J/K/mol
Ea=154kJ/mol

ReactionMechanisms
1.ElementaryProcesses:reactionoccursinasingleeventorstep
Unimolecular

N
H3CNCH3CH3CCN
C

Bimolecular
CH3Cl(aq)+OH(aq)CH3OH(aq)+Cl(aq)
HO-

H
C
H H

Cl-

Termolecularandhigherorderarerare.Involvesingle
collisionof3ormoreparticles

2.MultistepMechanisms:reactionoccursinaseriesof
elementarysteps
e.g.NO2(g)+CO(g)NO(g)+CO2(g)
step1:2NO2(g)NO3(g)+NO(g)
step2:NO3(g)+CO(g)NO2(g)+CO2(g)
Thetotalreactionforamultistepmechanismmustbethe
sumofallthesteps
Asubstance,suchasNO3above,thatisformedinone
elementaryprocessandconsumedinthenext,iscalled
anintermediate

RateLawsandMechanism
Ratelawsdependdirectlyontheelementarystepsofthe
mechanism
Ratelawsdonotdependonthestoichiometryunlessthe
reactionoccursinoneelementarystep:
unimolecular:
AP
rate=k[A]
bimolecular:
A+AP
rate=k[A]2
bimolecular:
A+BP
rate=k[A][B]
Formechanismsthatinvolvemorethanoneelementary
step,ratelawdependsontheslowestelementarystep,
calledtheratedeterminingstep

MultistepRateLaws
Firststepisslow:
e.g.NO2(g)+CO(g)NO(g)+CO2(g)
Step1:2NO2NO3+NOrateconst=k1
Step2:NO3+CONO2+CO2rateconst=k2
Rate1=k1[NO2]2slow
Rate2=k2[NO3][CO]fast
Rate1<<Rate2;therefore,step1isabottleneckforthe
reaction
Ratelawforentirereaction=Rate1=k1[NO2]2

Firststepisfast
2NO(g)+Br2(g)2NOBr(g)
NO+Br2 1(rev) NOBr2
k1(fwd)andk
Step1:
Step2:NOBr2+NO2NOBrk2(slow)
Inthefirststep,equilibriumisachievedrapidly,anda
steadystateconcentrationofNOBr2isavailable

Theslowstep2isratelimiting
Fortheoverallreaction,Rate=k2[NOBr2][NO]
BUT:NOBr2isanintermediate,notareactant
Howdowefind[NOBr2]?

FindanexpressionfortherateofformationofNOBr
d[NOBr2]/dt=k1[NO][Br2]k1[NOBr2]k2[NOBr2][NO]
Forward
reaction,
Step1

Reverse
reaction,
Step1

Step2

Step2isslow,sothethirdtermisnegligible
Atsteadystate,theratesofappearanceanddisappearance
ofNOBr2areequalandso:
d[NOBr2]/dt=0=k1[NO][Br2]k1[NOBr2]
[NOBr2]=(k1/k1)[NO][Br2]
Therefore,therateoftheoverallreactionis:
Rate=k2(k1/k1)[NO]2[Br2]

CPS:RateDeterminingStep
Thecompletemechanismforareactionoccursintwo
steps:A+BC+D(slow)
A+CE+F(fast)
Whatistheratelawexpressionfortheoverallreaction?
A.
B.
C.
D.

k[A][B]
k[A][B][C]
k[A]2[B]
k[A]2[B][C]

Catalysis
Acatalystisasubstancethatenhancestherateofa
chemicalreactionwithoutundergoingapermanentchange
Thecatalystmaybeconsumedinonestepofthereaction,
butisregeneratedinasubsequentstep
Acatalystneverappearsintheoverallstoichiometric
equation
Thereactionrateisenhancedbecausetheactivation
energy,Ea,forthereactioninvolvingthecatalystis
smallerthanthatoftheuncatalysedreaction

HomogeneousCatalysis
Thecatalystispresentinthesamephaseasthereactants

HomogeneousCatalysisContinued

HeterogeneousCatalysis
Thecatalystandreactantsareindifferentphases
Catalystisusuallysolid
metalsormetaloxides
Reactantsareusuallygasorliquidsolution
Reactantsadsorbontothesurfaceofthecatalyst
adsorptionisachemicalreaction
Surfaceareatovolumeratioofcatalystmustbelarge
forlargenumberofactivesites
powders,nanocrystals
Poisons(e.g.S)deactivateactivesites

e.g.Hydrogenation
C2H4(g)+H2C2H6(g)H=137kJ

Summary
ReactionrateconstantsdependonEaandTaccordingto
theArrheniusequation
Ratesdependonconcentrationsofreactants
For1storderreactions,ln[A]islinearwitht
For2ndorderreactions,1/[A]islinearwitht
Reactionordersdependontheelementarystepsofthe
mechanism
Knowterminology:unimolecular,bimolecular,
termolecular,elementarystep,ratedeterminingstep,etc.
CatalystsincreaseratesbydecreasingEa