Therateofreaction

ChemicalKinetics
Therateofareactionisthespeedwithwhichthe
concentrationsofthemoleculespresentchange.Therate
isgivenbythegradientofaconcentrationvs timegraph.

Therateofreaction
dependson(among
otherfactors)...
Chem11021B

Chem11021B

Concentrationofsomeorallof
themoleculespresent
Temperature
Thepresenceofacatalyst

DecompositionofH2O2

DecompositionofH2O2

TherateofremovalofH2O2 isnot
constant.
ThelowertheconcentrationofH2O2
theslowertherate.
Therateisdependenton
concentration.

2H2O2 (aq) 2H2O(l)+O2 (g)

After10s[H2O2]=0.983M
Timeintervalt=10.0s

Time
s

t s

[H2O2] [H2O2]
M
M

400
400

1200
1600

2400

3.8

-0.11

2.8

0.28
400

Time

Chem11021B

The Rate Law

Therateofreactionateverypointonthecurveis
directlyproportionalto[A]atthatmomentintime,i.e.

15
Rate
7.5

Rate=k[A]

[A]

0.00
0

0.007

2.5

k=therateconstant.

[A] (mol L-1)

Rateconstant=constantofproportionality.
Rateconstant=gradient(slope)ofaboveplot.
Rateconstant=Rate/[A].

Theproportionalityconstant,

Chem11021B

Chem11021B

Rate (mol L-1 s-1)

4.8

-0.15
0.39

400
2800

The Rate Constant

6.3

-0.19
0.54

400

8.0

-0.25
0.73

400
2000

low rate

10.5

-0.32
0.98

400

Toavoidnegativerates.
Rateisdefinedas[reactant]/t

15.0

-0.42
1.30

400

high
rate

-0.60
1.72

800

Concentration

Reaction
rate
x 10-4
M s-1

2.32
400

=Rateofchangeof[H2O2]
=[H2O2]/ t
= 0.017/10.0 =1.7x103 Ms1

Rateofreaction

2H2O2 (aq) 2H2O(l)+O2 (g)

0
Chem11021B

Start1.000MH2O2
[H2O2]= 0.017M

TheRateEquation

Example

Thisrelatestherateofreactiontotheconcentrationtermswhichaffectit.

Forthegeneralreaction:
aA +bB mM +nN
d[A]/dt = k [A]x[B]y

ThisreactionisfirstorderwithrespecttoH2,firstorderwith
respecttoICl andsecondorderoverall.
Question:
Forthereaction:2NO2 (g)+F2 (g) 2NO2F(g)

Rate =k[NO2][F2]
WhatistheorderofreactionwithrespecttoNO2,F2 andtheoverall
8
orderofreaction?

DeterminetheRateEquation

DeterminetheRateEquation

O2(g)+2NO(g) 2NO2(g)
[NO]/M
1.30x102
1.30x102
2.60x102
1.30x102

InitialRate/Ms1
3.21 x103
6.40 x103
12.8 x103
9.60 x103

Rate=k[O2]x [NO]y

1
2
3
4

[NO]/M
1.30x102
1.30x102
2.60x102
1.30x102

InitialRate/Ms1
3.21 x103
6.40 x103
12.8 x103
9.60 x103

Rate =k[O2]x [NO]y

keeponeconcentrationconstant,alterotherconcentrationandsee
whathappenstorate.

doubledouble thereforex=1(2=(2)1)

10

DeterminetheRateEquation

DeterminetheRateEquation

O2(g)+2NO(g) 2NO2(g)
[NO]/M
1.30x102
1.30x102
2.60x102
1.30x102

InitialRate/Ms1
3.21 x103
6.40 x103
12.8 x103
9.60 x103

Rate =k[O2]1 [NO]y

fourtimes

1
2
3
4

[O2]/M
1.10x102
2.20x102
1.10x102
3.30x102

[NO]/M
1.30x102
1.30x102
2.60x102
1.30x102

InitialRate/Ms1
3.21 x103
6.40 x103
12.8 x103
9.60 x103

Chem11021B

[O2]/M
1.10x102
2.20x102
1.10x102
3.30x102

O2(g)+2NO(g) 2NO2(g)

Chem11021B

1
2
3
4

[O2]/M
1.10x102
2.20x102
1.10x102
3.30x102

Chem11021B

[O2]/M
1.10x102
2.20x102
1.10x102
3.30x102

O2(g)+2NO(g) 2NO2(g)

Chem11021B

1
2
3
4

=d[H2]/dt =k[H2][ICl](byexperiment)
Chem11021B

Therateequationcanonlybedeterminedbyexperiment,notfromthe
stoichiometric equation.
Rateconstant,k,dependsontemperature.
Orderofthereactionisgivenbyx+y.
xistheorderwithrespecttoA,yistheorderwithrespecttoBetc.
Thereisnorelationshipbetweenaandx,bandy.
Themolecularity isgivenbytheorderofthereaction.

Rate

Chem11021B

H2 (g)+2ICl (g) 2HCl (g)+I2 (s)

Rate =k [O2]1 [NO]2 substitutevaluestogetk

double thereforey=2(4=(2)2)

3.21x103=k(1.10x102)(1.30x102)2
11

Rate=1.73x103 [O2][NO]2

12

Question:

IntegratedRateEquation

Determinetherateequationandvalueoftherateconstantforthe
reaction:
NO2 (g)+CO(g) NO(g)+CO2 (g)

Eg N2O5 NO3 +NO2Rate= d[N2O5]/dt =k [N2O5]1

Chem11021B

1
2
3

[CO]/MInitialRate/Ms1
0.10
0.0050
0.10
0.080
0.20
0.0050

Chem11021B

[NO2]/M
0.10
0.40
0.10

Analysingacurveisdifficult;muchbetterto
convertthedatatoastraightlineplot.

IntegratetogiveLn[A]=Ln[A]okt
AndplotLn[A]vs t

Rate = k[NO2

]2

k = 0.5 s-1 M-1

13

14

IntegratedRateEquation
Order=
Molecularity

Integrated
RateEquation
conc/time

Plot

Thehalflifeofareactionisthetimerequiredfortheconcentration
tofalltohalfitsinitialvalue.Forfirstorderreactionsthisisa
constant.

[A]vs t
Ln[A]vs t
1/[A]vs t

FirstOrderReactions
t1/2 =Ln 2 / k

Chem11021B

Rate=k [A]=[A]okt
Rate=k [A]
Ln[A]=Ln[A]okt
Rate=k [A]2
1/[A]=1/[A]o+kt

1/2

Chem11021B

0
1
2

Differential
RateEquation
rate/conc

HalfLife,t

15

Example

Theradioactiveisotope15Oisusedinmedicalimagingandhasahalflife
of122.2seconds.Whatpercentageisleftafter10minutes?
Usek=Ln2/t andLn[A]=Ln[A]okt
Note:Ln{[A]/[A]o }=ktand[A]/[A]o isamountleft.
k=Ln2/t=0.693/122.2=5.67x103 s1

Chem11021B

Threehalflives=xx=1/8

Question

Chem11021B

Anantibioticbreaksdowninthebodywithafirstorderrate
constantofk =1.9x102 min1.Howlongdoesittakeforthe
concentrationtodropto1/8th theinitialvalue?
t =Ln 2/k =0.693/1.9x102 min1
=36min

16

Ln{[A]/[A]o }=kt=(5.67x103 s1)(10x60s)=3.40

Timeofthreehalflivesis3x36min=109min

[A]/[A]o=0.0334so%usedafter10minutesis3.34%
17

18

ReactionMechanisms

ReactionMechanisms
Aratedeterminingstepinareactionmechanismisanelementary
processthatisthesloweststepinthemechanism

Abalancedchemicalequationdescribestheoverallchemical
reaction
e.g.
2NO2 (g)
+
F2 (g)
2NO2F(g)

e.g.Step1

e.g.

NO2 +
NO2 +
2NO2 +

F2
F
F2

NO2F +F
NO2F
2NO2F

Step1
Step2
Overall

Reactionorder

(slow)

Insimplereactions,theexponentsintherateequationarethe
sameasthecoefficientsofthemoleculesoftheratedetermining
elementaryprocess.Sointhiscase,

Notetheoverallreactionis:2NO2(g)+F2(g) 2NO2F(g)

20

ExtraNotes

Letslookatthekineticsofaclassicsubstitutionreaction.

Rate=k[CH3Br][OH]

Br

i.e.firstorderinCH3BrandfirstorderinOH.
21

ReactionProfile SN2

Ratelaw (definition):anexpressionrelatingtherateof
reactiontotherateconstantandtheconcentrationsofthe
reactants
Onecancalculatetherateofreactionatanypointgiven
thevaluesofk,xandyaswellas[A]and[B]
Reactionorder:atermusedtodefinetheoverallpowerof
aratelaw.
Note thatRate=k[F2][ClO2]sameask[F2]1[ClO2]1
Otherexample:IftheratelawwasRate=k[A]2[B]1,then
order=3(3rdorderreaction)
Considerlastexample,reactioniszeroorderinA(ie.
independentoftheconcentrationofA).Thereactionis
zeroorderinA,butfirstorderinBandfirstorderoverall. 22

Chem11021B

Chem11021B

H
H C OH
H

NO2F +F

Rate=k[NO2][F2]
19

H
H C Br + OH
H

+F2

Chem11021B

Chem11021B

Areactionmechanismisaseriesofelementaryreactionstepsthat
adduptogiveadetaileddescriptionofachemicalreaction.

NO2

Reactionorder
Nowletslookatthekineticsofarelatedsubstitution
reaction.
CH3
H3C C OH
CH3

Br

Rate=k[(CH3)3CBr]

Chem11021B

CH3
H3C C Br + OH
CH3

i.e.firstorderin(CH3)3CBronly.
Onceagain,thereisnorelationshipbetweenstoichiometry
andtheratelaw.Theratelawcanonlybedetermined
experimentally.
Chem11021B

24

23

Reactionorder

ExtraNotes

Fromtheratelaw,itcannotproceedinasinglestep.
Rate=k[(CH3)3CBr].

First,theBr isdissociatedintoapairofions.Thecationicchargeat
thecentralcarbonatomisstabilised bytheelectrondonating
methylgroups.

CH3
H3C C Br
CH3

CH3
H3C C+
CH3

Br

Chem11021B

Chem11021B

Infact,thereactionoccursintwodistinctsteps.

Experimentaldatanormallyobtainedforrateequationsusing
spectroscopicmeasurements(eg,UVvis)orpressure
measurements(forgases)
Whenreactioninvolvesmorethanonereactant:needtouse
isolationmethod.
Isolationmethod;thisistheprocedureoffixingconcentrationof
onereactantandalteringconcentrationoftheother.(Aneveryday
methodreally:e.g.,investigatingcauseofallergyindiet,may
systematicallyremoveonecomponentwhilekeepingothers
constants)
Isolationmethodyieldsfollowing:
Rate [A]2 andRate [B],combinedgivesRate=k[A]2[B]
i.e.,athirdorderreactionwhichis2ndorderinAandfirstorderin
B

25

26

Example:NO2 +CO NO+CO2

Reactionorder
Second, the (CH3)3C+ cation quickly reacts with hydroxide ion:

NO2+CO

NO+CO2 overall

Chem11021B

Chem11021B

The second step is much faster than the first, and the overall
rate of the reaction approximates the rate of the first step due
to a bottleneck.

Theexpt determinedrateequationisRate=k[NO2]2
Showtherateexpressionisconsistentwiththemechanism:
2NO2
N2O4
fastequilibrium
N2O4
NO+NO3 slow
NO3 +CO
NO2 +CO2 fast

Rate=k2[N2O4]
butk1[NO2]2 =k1[N2O4]

or

[N2O4]=k1/k1 [NO2]2

27

28

soRate=(k2 k1/k1)[NO2]2orRate=k[NO2]2

Question

ActivationEnergy
Theactivationenergy,Ea,ofareactionistheminimumamount
ofenergythatthereactingmoleculesmustpossessifthe
reactionistobesuccessful.

Forthereaction:2NO(g)+Br2(g) 2NOBr(g)
Aproposedmechanismconsistsoftwoelementaryreactions:
fastequilibrium
slow

Energy

Confirmthismechanismisconsistentwiththestoichiometry of
thereactionandtheobservedratelawof
Rate=k[NO]2[Br2]
29

activation
energy

exothermic
reaction

Chem11021B

NOBr2
2NOBr

Chem11021B

NO+Br2
NOBr2 +NO

Reaction coordinate
30

ActivationEnergy

ArrheniusEquation

Athighertemperatures,moremoleculeshavethe
minimumrequiredenergy(Ea)andhencethefaster
thereaction.

S. Arrhenius
(1859 1927)
1903
Chemistry
Nobel prize

TheArrheniusequationdescribesthetemperature
dependenceoftherateconstantthatisexponentially
relatedtotheactivationenergy,Ea(Aisthepre
exponentialfactor,ortheAfactor).

k =AeEa/RT
where:T=temperature(K)
R=universalgasconstant (8.314JK1mol1)
A =Arrheniusconstantorpreexponentialfactor
(reactionefficiency)
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31

ActivationEnergy

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32

k =AeEa/RT orLnk =LnA Ea/RT

Whydoesanactivationbarrierexistforchemicalreactions?

Iftherateconstantismeasured,atleast,attwodifferenttemperatures,the
activationenergymaythenbedetermined.

Moleculeshavetocollidewithsufficientenergy.
Moleculeshavetocollidewiththecorrectorientation.

Forexample:
and

atT1
atT2

Ln k1
Ln k2

Chem11021B

ln k1 ln k 2 ln

k1 Ea

k2
R

=Ln A Ea /RT1
=Ln A Ea /RT2

1 1
T T
2
1

Example:Ifareactionhasarateconstantof2.0x105 s1 at20Cand7.3x105
s1 at30C,whatistheactivationenergy?
Ln {(2.0x105)/(7.3x105)}= (Ea/8.314){1/293 1/303}
Ea =96kJmol1

33

Chem11021B

Question

Catalysis

Therateconstantofaparticularreactiontripleswhenthetemperatureis
increasedfrom25Cto35C.Calculatetheactivationenergy,Ea,forthis
reaction.

Acatalystprovidesanalternative
reactionpathwayoflower
activationenergy.

Ln (k1)/(k2 = Ea/R(1/T1 1/T2 )

Inthiscasemoremoleculeshavethe
minimumenergyrequiredfor
successfulreactionandthe
reactionproceedsatafasterrate.

Chem11021B

= Ea(1.310x105)

Chem11021B

Ln (1/3)= (Ea /8.314)(1/298 1/308)

1.099

34

Ea =83800Jmol1 or83.8kJmol1

35

36

Catalysis

Catalysis

Fourcriteriamustbemetbycatalysts:

LetslookatthedecompositionofH2O2 again.

Catalystsincrease therateofreaction.

2H2O2(aq)

2H2O(l) +O2(g)

Catalystsarenotconsumed bythereaction.

Thepositionofequilibrium forthereactionremains
unchanged.
37

Catalyst
None
I
Pt
Catalase

Ea (kJmol1)Rel.rateofreaction
75.3
1
56.5
2.0x103
49.0
4.1x104
8.0
6.3x1011

Chem11021B

Chem11021B

Asmallquantity ofcatalystaffectsthereactionrate
foralargeamountofreactant.

38

Summary - Chemical Kinetics

Determine rate law from experimental data

Determine reaction order from rate law
Use integrated rate law (1st order)
Half life
Activation Energy
Arrhenius Equation
Catalysis what is it and how does it work?

Chem11021B

39