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JUNIORCOLLEGE
ANDERSON
CHEMISTRY
PHYSICAL
KINETICS
REACTION
Contenfs
'1
2

Introduction
Rate of reaclion
(a) Average reactionrate
(b) Instantaneousreactionrate
(c) Initialreactionrate
Rate Law / Equation
(a) Order of reaction
(b) Rate constant
Determinationof Order of Reaction
I
ExperimentalProcedure
(a) For analysisusing rate curve,half-lifemethod
(b) For analysisusing initialrate method
ll
Analysisof experimentaldata
(a) Zero-orderreaction
(b) Firslorder reaction
(c) Second-orderreaction

ReaclionMechanism
(a) Molecularity
(b) Ratedetermining
step
(c) Proposingmechanism
TheTheories
(a) TheCollisionTheory
(b) TheTransitionStateTheory
Factorsaffeclingrale of reaction
(a) Concentration
(b) Temperature
(c) Catalysts

Objectives
Candidatesshouldbe able to:
(a)
(b)

(c)

(d)
i"i
<O
iS)
(h)
0

0)

(k)

explain and use the terms: rate of reactiontrate equation:order of reaction; rate constant;halflife of a
reaction;rate-determiningstep; activalionenergy;catalysis
construct and use rate equationsof the form rate = ktAl'[Bl" (limited to simple cases of single step
reactions and of multi-stepprocesseswith a ratedetermining step, for which m and n are 0, 1, 2),
including:
(i)
deducingthe order of a reaclionby the initial rates method
justifying, for zero- and firsl-order reactions, the order of reaction from concentration-time
(i0
graphs
(iiD
veriryingthat a suggesledreac{ionmechanism is consislenlwith the obseNed kinetics
predictingthe order that would result ftom a given reaclionmechanism
(iv)
(v)
calculatingan initialrale using concentrationdata
(i)
show understandingthat the half-lifeof a first-orderreaclionis
independentof concenlration
(iD
use the half-lifeof a frst-order reaclion in calculalions
calculatea rate constantusingthe initialrates method
techniquefor studying the rate of a reaclion,from given information
devise a suitableexperimential
explain qualitarively,in ierms of collisions,the effect of mncentrationchanges on the rate of a reaction
show underslanding,includingreferenceto the Boltzmann distribution,of what is meant by the term
activationenergy
explain qualitatively,in terms both of the Boltzmann distributionand of collision frequency,the effect of
the temperalurechange on a rate @nstant(and, hence, on lhe rate) of a reaction
(D
explain that, in the presenceof a catalyst, a reactionhas a differenl
mechanism,i.e. one of lower activationenergy, giving a largerrate constanl
(ii)
.interpretthis catalyticefiect on a rate constant in terms of the Boltzmanndistribution
outline $ie differentmodes of action of homogeneousand heterogeneouscatalysis,including:
(i)
the Haber Process
the catalyticremovalof oxidesof nitrogenin the exhaust gases from car engines
iiU
the catalyticremovalof almosphericoxides of nilrogen in the oxidationof atmosphericsulphur
iiiU
dioxide
(iv)
catalyticrole of Fe3tin the l- / SzOe2'reaction
describeenzymesas biologicalcatalysts(proteins)which may have specilic activity

References:
Chemistr)4Ann & PatrickFullick
Chemistryin ContexCHill and Holman
Chemistryin Actbn; MichaelFreemantle
Chemistry - The Central Science; Brorvn, Lemay and Bursten
Chemistry- The MolecularScience;Olmsted& Wlliam
I|nderstanding Chemistry for Advanced Level; Ted Lislet & Janet Renshaw

I
krr/kin<'r
it's2U01/.1

INTRODUCTION

Reactionkineticsis a studyof the ralesof chemicalreactionsand the factorsthat intluence


them.
Ratesof reactionsvaryimmenselyfrom reactionto reaction:
- explosions:reactantsare usedup and productsare formedso fast that theyare
instantaneous
- fermenlationol grape juice to form wine is a processthat can take many months to
complete
Factorsaffectingthe rateof chemicalreactionsare :
(i)
(ii)
(iii)

of reactantsI
Concentration
Temperature
I Seesection
Presenceof catalysts
)

(iv)

Natureand surfaceareaof reactants


- the largerthe surfacearea, the fasterthe rateof reactionof a heterogenous
reactioninvolvino
a solid

RATE OF REACTION
describesthe speedat whichreactantsare convertedto products
representedas the changein concentration
of eitherthe reactantsor productswithtime :
(a) Averagereactionrate
(b) Instantaneous
reactionrate
(c) Initialreactionrate
.

The rateof reactiongenerallydecreaseswithtimesincereactantsare graduallyusedup

[0".,.n,,,., 1.^liunl=) Dr,,,"i','!"rlt,i

1
kw/kinetics2004/J I

vi,l-

\ i.(1,r.

r
J

^t

(o)
.

ArterooeReoctionRote
a reactant
orproductItrrerilF

oflFFGGot
Measursment
Averagerate=

J l'cerbtl

- Alaectoi]

\v', cF0o6l tolocr A rrg,+-tt

b1

dt

+)tr'vl,,61

Average rate=

lr

The rate at which a reactantis used up is IppA


reactantdecreases

since concentrauon
of

The rate at whicha productis formedis IlfFEIfif


increases

sinceconcentration
of product

Example: Hydrolysisot an ester- methylethanoate


CH3COOCHst CHgCOOH+ CHOH

Time/ min
festerl/ mol dm'
UFIsGUUH / mol dmo

0
0.500
0

10
0.375
0.125

20

30

0.3(n

0.216

o.2u

0.200

Forthefirst10mins:

0.t75-0'500

-,

alats

ln

0. 115 - O
lo

4l

ff

=
Averagerateof formationof CHsCOOH

.l .*tv

Atw. 1tt .d,dr'.'


ttLt h{1n

Averagerateof disappearance
of ester=

- s. gtt!- -c lAa'l;r-r
t |

otattt8ct

41C,tl

tt|

tu*rral

I 0.0rr3 nt *,4 *:l

Asthe reacfionratecfianges
wih time,the
continuousv
acqir$ rab dffifrilod
tremrt0otrh
A moreaccurateindbatbnof rateof reaciionis instantaneous
rate

Lilkinetics2004/Jl

/f

,,

\-

(b)

fnstontoreous Reoctrbl Rote

Measurement
of tde d qffin
&e

Instantaneous
rate=EraiFfrilhtthetangentto thecurveat specifiedlime

of a reactantor p.odrrctaf lllsGm

Concntration
o fA

t1

Instantianeous
rateat time,h = nrlar ar rl. tarP*
Instantianeous
rateat time,t2= qalrr a+ I

+.ft

tava

+ro1n +. 'lt,

{.

a1

tr .

The raterelationship
amongthe speciesis givenby theirstoichiometric
coefficients
in
thechemical
equation
Example: Fora generalreaction
: aA +bB) cC+dD
ratioof ratesfor differentspecies= ratio oJstoichiometriccoefficients
rateof disapperance
of A _ 4
rateof disapperarEe
of B
b

rateof frormation
ol C
rateof foramtionof D

Example:2NO2
) 2NO+ 02
Forevery2 molesof NO2consumed,
2 molesof NOand 1 moleof 02 are produced
Rateof consumPtron
of NOz= rateof pfoductionOfNO= 2 x rateof pfoductionof 02

.t

'a

961. ,

lc'n'/ki neti cs2004/J I

It

12

t_to)
tt

,-. 3

(C)

Inifiol Reoction Rqte

or productat thefrilutEl
Measurement
of rateol afr|0F o[ concenbafonof a reactiant
=0
otad?,mtadl
tffim i.e.attime

= gradient
at thetangsntto lhecurveat time= 0
Initial161s

* o'o. . tuFt !

Reactant

RATE LAW' RATE EQUATION


An expressionthat relatesthe concentrationof reactants,raisedto the appropriate
power,to the rateof a chemicalreaction
Rate= k lXl'Nl'
[X],m
m, n
k

.
(o)

: concentration
of reactantin thechemicalreaction
: oder of reac{ion
: rateconstant

Unitsof rate: .olI,r.-3: -l

r,.crd--3-4.-t

Order of r"ecction

Givesthe FtFEndsflce

n =0 , 1,2,3.....

(seeSection4) and S[
Mustbe determinedexperimentally
thechemical
equation

(D

of theF

onthe llrentration of the reactant

fromthe stoichiometry
of

Reactioninvolvinoonereactant

Example:

xA ) products
(.ot -- hfdn

kw/kinctics2004/JI

p.. otlr

r.b.AYt

. ..t

ta-!.

Whenn =0

Rate=x[r]i= a
Rateof the reactionis

lFaro

Hence rate ol reactionis

fii.r*

qrlcv

withrespectto the concentration


of A

and

-j!:tg!!ts-

on the concentrationof A

W h e n n =1

p61s =" t [ l l

- r[r1

Rateof the reactionis

{rtrt

r.lcr

withrespectto the concentration


of A

Hencerateot reactionis

to the concentration
of A

Ro! a frl

i.e.

Wh e n n =2
Rate= k [42
qaol

Rateof the reactionis

withrespectto the concentration


of A

c,lr,/

i.e. ndr o[ fl] "


.b

(iD

tut

c's,A'ta

L|

sli.

, r.i

j.rcr

+ a.-.r

Reactioninvolvinotworeactants
x A +y B )

Example:

pr o d u c t s

R & = l fA J "[Dl"

rr' lr
n *!

m is the orderot reactionwithrespectto [4


n is the orderof reactionwithrespectto [B]
Overallorderof reactionis the sumof the powercof the concentration
termsin the rate
equation:
t h, + tl
0wrall ev&v rl certfb rr

(b)

Rcte constont. k

lt is r-

for a givenreaclionrlfFnilIre

unitswlls5tetrtodr.dt!8ros-tid6

kw/kinetics
2004/JI

Ur*s 4 r dr
U\ilJ

6l

t U*rr 4

o,,.ttt1nsltoe)

Overall order of
reaction

Rate law

Zeroorder

gsls = k [A]o
=k

Firstorder

Rate = k [A]1

Unit of k

3s-l
rof L-l
rcl d--3"
-*"tJJ
Mo,l dri

psls = k [A]2

n th order

-J

'
=

(rol /r,- 3) -rs


Mol

Or'.

S -t

/t'

L a*' n *' ^t'o


co ,
I

Rate= k [A]'

DETERMINATION OF ORDEROF REAGTION

E(PERIMENTAL PROCEDURE

o-l

---:----:--:tii
(,*rr t* /

Secondorder
Rate=klAl[B]

Chemicaland physicalmethodscan be used dependingon the natureof the reactionto


be carriedout
.

Physicalmethods
colour
Volumeof gas evolved,gas pressure,electricalconductivity,

Chemicalmethod: titrimetricmethodto determineconcentration

on whichmethodis usedto analysethedata


is carriedoutdepends
llav an experiment
obtained
(o)
method
.

Changesin a certainpropertyof the reactionis followedcontinuouslyover a sufficiently


long periodof time at varioustimeintervals

(i) Volume measurement


reactionwitha gaseousproduct
This methodis suitablelor a heterogeneous
The volumeol gas evolvedat varioustime intervalscan be monitoredwith the use of a gas
syringe

hv/kinct ics2004/JI

Experimentalprocedure :
(1) Reactantsmixed togetherin a stopperedtlask and stoFwatchstarted simultaneously
(flaskis immersedin a waterbathmaintainedat constanttemperature)
(2) At various time intervals,the volume of gas producedis read off the syringe and
recorded
(3) A volumevs time graphcan thenbe plotted
| !{F
r .d-.

r,(Fr.'e('td
t6
4-c ltr

l r a '{i /tf{r !a v.

E.N. Famsden
A-LevelChemisty (2d Edition)
Pg 260 Fig 14.2

ll-lit

. f6rd.

rrbE

Examples:
Mg (s) + 2HCl(aq) ) H, (g) + MgCl,(aq)
2HrO,(aq) ) 2HrO0) + oz (g)

(iil Titrimetricanalvsis
This methodis suitablefor reactionsin solutionswith eithera reactantor oroductwhose
concentration
can be analysedby meansof a titration
Experimentalprocedure :
(1) Knownquantitiesof reactantsare mixedtogetherin a flaskand a stopwatchis started
(flaskis immersedin a waterbathmaintained
simultaneously
at a constanttemperature)
(2) At suitabletime intervals,a small sampleof the reactionmixtureis removedusing a
pipetteand then quenchedby transferring
quickly:
) into a largevolumeof ice-coldwater(thedilutionand coolingeffectreduces
the reactionrateto almostzero)
.' or a suitablequenchingagent(to reactwith one of the reactantsto stopthe
reactioncompletely)

(3) Theconcentration
of the remaining
reactantor productformedin the sampleof reaction
mixtureis thentitratedwitha suitable
reagent 'ji
{1
^ +
(4) A concentration
graph
vs time
canthenbe plotted "I {
[
nr/

wl

Nore:

Y c t\r..

.J

l\

V' -------..aL I Y"

r.,

To investigatethe rate of reactiondue to the changein concentrationof a particular


- reactiant(e.S.A), the concentration
of the otherreactantsmustbe usedin largeexcess
This
helps
to
minimize
any changes in rate of reaction due to the change in
concentrations
of the otherreactants
) so that any changesin the rateobservedcan be considered
to be solelydue to A

kw/kinetics2004/JI

(b)
Differentsets of experimentsof the samereactionare preparedand conducted
(i)
ExperimentalProcedure:
(1) Differentsets of experimentsof the samereactionareprepareo
the procedureusedis describedabove(see4aii)
tzi For e"cn set of experiment,
canthen be plotted
isi e ;oni"ntrution vs time graphlor eachset of experiment
from tangentsdrawnat time = o
i+i iniii"r iate of eachset oiexperimentcan be determined
curves
for eachconcentration-time
Examples:
.
-

of hydrogenperoxide
Determineorderof reactionin decomposition
known amt of HzOz+ small amt boiate buffer(maintainconstantpH) + small amt of
reaction)
KMnO,(reactswith H2O2to produceMnO2whichcatialyses
Quenchingagent: fixedvolumeof diluteHzSOa
Titrant: standardsolutionof KMnO4(RemainingHOz reactswith KMnO4)
usedvs time
OR volumeof KMnO+
vs time
Plot: [H2O2]

. Alkalinehydrolysis
of bromoethane
w.r.t.hydroxideions
reaction
of
Determineorder
(in excess)+ knownamtof NaOH
- knownamt of bromoethane
- Quenchingagent: largeexcessof ice-coldwater
NaOHreactswithHCI)
- Titrant: stlndard solutionof acid (e.g.HCI)(Remaining
vs
OR volumeo{ acidused time
- Plot: [NaOHlvs time
Determineorderof reactionw.r.t.bromoethane
+ constant[NaOH]
- Repeataboveexperimentusingditferentlbromoethane]
- Plot : INaOH]vs time for each[bromoethane]
. Reactionbetweeniodineand propanonein the presenceof an acid
Determineorderol reactionw.r.t.iodine
- knownamts of propanone+ diluteHCI+ iodine
... ^ ^ ,.\
- Quenchingagent: lixed amtsof aqueoussodiumhydrogencarbonate
with
szos'')
(emaining
lz
reacts
thiosulphate
sodium
of
solution
:
standard
Titrant
vs
voiumeof SzOs2- time
OB
- Plot : 2lvs time
Determineorderof reactionw.r.t.propanone
+ constant[12]and [HCl]
- Repeataboveexperimentusingdifferent[propanone]
- Plot : [2] vs timetor eachlpropanone]
Determineorderof reactionw.r.t.acid
Repeataboveexpe mentusingdifierent[acid]+ constant[l2land lpropanone]
- Plot : [2] vs time for each[acidl

kv'/kinctics2004iJI

(ii)

Measuretime for reactlonto proceedto the sameextent

Theory:
The rate of a reactionis inverselyproportionalto the time taken for the reactionto be
completed

?-+,Oli;Experimentalprocedure:
(1) Differentsets of experiments
of the samereactionare preparedwherethe concentration
of a particularreactantis variedwhile the concentration
oI the other reactantsare kept
constant
(2) For each set of experiment,a stopwatchis startedsimultaneously
on additionof last
reactantinto reactionmixture
(3) When the reaction has reached a certain point (depends on the nature of the
experiment),the stopwatchis stoppedandthe timetakenis recorded
(4) The product(v x t) or (f x t) is thencalculatedfor eachset of experiment

Example:S.O32'(aq)
+ 2H'(aq) )

2S(s) + SOz(aq)+ HzO(l)

A yettowprecipitateof sutphuris formed.

\ f
/

.}
,"",

,.J'n'
I O I

For eachset of experiment,


the reactionis assumedto havereachedthe sameextentwhen
s u f f i c i e n t s u |p h u rh a sfo rme d to @ p|acedbe|owthe
reactionmixture.

Expt Vol of HCI/cm" Vol of thiosulphate/ cmr Vol of water/ cm' Time/ s
No.
v
t
1
a

20
20
20

60
30
20

0
30
40

10
20
30

Note :
ln the aboveexample,the concentration
of the reactantis directlyproporfrbnal
to the volume
usedas the total volumeof the reactionmixturein eachset of experimentis keptconstant.
haa"*\

&

rdd

,'actl.4

vtd.

II

ANALYSISOF SPERIMENTAL DATA

(o)

Zero - order reoction

.
-

Recaff: rateof reaction


is constantand independent
ontheconcentration
of the
reactant
R ate=k l A l o=k

bw/kinctics2004/J I

l0

Rate curve method

(i)

Concentrationvs time graph : gradientof curve = te of reac{ion

[AL,

IAt
.

[A] vs time graph

Ratevs [A] graph

w6 -z.vo

tAl
nzldirz slott '

, with a

toltlt

lnltial ratemethod

(ii)

the gradientsof each concentration-time


For differentinitial reactantconcentrations,
graphs afe

..r.t+rtt
* F,, * ka

tAt
[Al = 0.40
tAI= 0.30

= c(,!lddt

qp/lr./t

tn qv.d a'
aF

thQ *
ct to

'trtel

lAl = 0'20

Timefor eachset of experimentto proceedto the sameextentis also


Expt No.

tAllmoldm'

0.40
0.30

fBl / mol dm0.10


0.10

cor:ta"t

Tlme,s
30

n l? ,

1 lo *,t *t
I tu,rt ,tw
' &, .-..u}ntrl
,r

.(b)
.

,.dbL

First - order rcoction


Recalf: Rate of reactionis dlredly prcrp'rtional to the concentrationof A
g61s= k [A]'

Iot/kinetics2004/JI

=+

Rate c [A]
ll

(D

Ratecurue rredrod

[d,
[6,

lAlr. [4t,
[A] vs time gph :

cuv{s

Rate vs [A] graph : _-hgrr_

(iD

Half - fife meffiod e a\

nrgativr. s lon,

with a

with a i6^ -r.'o


qplaut

, passingthrough ovtht^

trdadt

t.Fd+-ery

Delinition:

rt,oliovt-

|etiEfrlilfrFFhtriti

ffird\

Concentration
- timegraphis an exponential
decaycurvewithdecreasingslope
tAl
(^1,

dhorartr*e)

bg 1

easta'* twl - l*e E

+r|1.
t(+rrq

{
-

time

66

o'AvL

t+ a ,

fi'tl.uq" ,*&ln
rl s+ ,a+,& ,
- *", SlS qq +rr F r.
,ry+ ly* o.b
I
-

Fora first- orderdecayexponentiat


curve: EStrlFilPi
Initialconcentration
of A= [A]o;ott= tn: concenhation
of A= [A]e= ]6 [tr]o
_ ,r !r1. =.f11. g-n.t
I

== e-

: -r+1I^e

l"l
lnt-

.r.--

v+-

lcilkinetics2004/J I

\n 2 ' lctr

Lir

lrna e

-k*r

12

(iii)
.

lnitial rate method


lf initialrateof eachset of experimentis given:

) Directcomoarisionof data
E x a m p l e : A+ B )

Initlal [A] / mol dm{

Initial [B] / mol dm{

Initlal rate/ mol dm'3dl


a'4kt1'
r'. t {ve' +w
!s'l 'svd !'
^.

ComDarinoexperiments1 and 2 :
Luu.d

When [A] is

/ increasesbY
-+.""

A*.ts

Hencereactionis

{i'st

, the initialrateJ!g!!1-

t,"o ti,",,r

/ increasedby

o'&Y

with respectto A.

) Comoarisionof ratioof initialratesto ratioof initialconcentrations


1=
initialratein experiment
2
initialratein experiment

o. * _
o 9o -

Since ratio of initial rates is the

t
2

as the ratioof initial

s ord

1 = g:
in experiment
initialconcentration
2
in experiment
o,ro
initialconcentration

concentrations,
then the reaction
with
is
/r's+ - o'e'

resDectto A-

is notgiven:
lf intialrateof eachsetoJexperiment

wheretimeis measured
forreaction
to orooress
to thesame
) Forexoeriments
extent
+ 2H*(aq) ) 25 (s) + SOz(aQ)+ HO (l)
Example: S2O32'(aq)
Expt Vol of HCI /cmo Vol of S2O3''/ cmo
V
No.
20
20
20

2
3

60
30

'a'h

\
2 4"V
concentrationcr,volume

flme

'

Vxt
600
600
600

"otq7.,t

d volu-r

9v..

oa =ffi

w\!'n

Time / s
t
10
20
30

Sincerate crconcentration and


+

0
30
40

20

P61sc, 1

Recall:

Vol of water / cm"

&

(vxr)

ott *.Vi'*l"

I l r, 0,A av
+

w\,ri

ti,rr

kw/kinetics2004/J I

..a.g+aql

$r-

lsi

o"l,' y rc*{ic

,' o
,

t*.9.c*l

'r6.+t*'
'arp 7. t ( r 03

I.'

) For exoerimentswhereconcentration
of a oarticularreactantis measuredat
varioustimeintervals
l)*

Ex a m p l e : A+ B )

Expt Initial [Al /

lnitial[B]-/
mol dm-"

mol dm-3

1
2
3

0.20
0.40
0.40

g
htc.l co"Vat"aa
a.a'?onis.y\ol t dio l

aialNS

[A] / mol dm'" at each time


interval (min)
5
10 15 20 25 30

Initial rate
/ mol dm-3 s-l

o.20

R1

0.20
0.40

Ra

R.

rAl

tAl

tA

4L

?-l

l i me

trme

lime

Concentration
- timegraphsareplottedfor eachsetof experiment
= gradientat thetangentt = 0
graph
Foreach
: Initial121s
Resuftsare tabulatedand analysiscan be carriedout usingdirectcomparisionof dataol
comparisonof the ratio of the initial rates to the ratio of the initial concentrations

(c)
.

(i)

Second - order reoction


Recall :

Rate = k [A]2

rate 0 [A]2

Ratecurve method

lAlr. lAlr r
[A] vs time graph :

curvc

Rate vs [A]2graph:

lVr rv

with a
with

/vgatir

<'lS
, passingthrough ontr v'

kw/kinetics2004/J
I

t4

(ii)

lnitial rate method


Methodof analysisis similarto firstorderreaction
lf initialrate is givenfor eachset of experiment:

of data
) Directcgmoarison
A+ B) C
Example:
Inltial [A] / mol dm

Initial [B] / mol dm'3 lnitlal rate / mol dm{ s'l


clra.5

1 and 2 :
ComoarinoexDeriments

vhj'l

t""

/ increasesby
ee,na, - ot&t

Hencereactionis

clrt a.t .

t-o tivz.r

, increasesby

when [A] is -@!3luadrapLs

cot' fEJ ia

, the initial rate

S-rl
with respectto A.

) Comparisonof ratioof initialratesto ratioof (initialconcentrations)2


Since ratio of initial rates is the
sav(
as the ratio of (initial

1
inexoeriment
initialrate
2
initialratein exoeriment
1F
(o,ro)t
(nitialconcentration
inexperiment
lo,{o)r
(nitialconcentration
2f
in experiment
"t

hA fa h
.

'6rya.rd' &

the
concentrations)2,then
reactionis
s' (a1t ' o'L v
with respectto A.

)d o,&,

lf initialrateis notgiven:

of timefor eachexperimentto progressto the sameextent


) for measurement

Recall:

Rateo#

\ \ :^y_f**

and
Sincerate cr(concentration)2
=

. a*c or (vohrre)"

('a*$"ot#
(hh\,

= rorlel+

)a x uar
k

kw/kinetics2004/J I

c volume
concentration

"

2aL -ot&t

l)

Example 1 :
The followingtablegivesthe valuesof initialratesmeasuredfor the reaction:
2 A + B) C+D

Experament [A] / mol dm'


0.150
0.150
0.075
0.075

3
4

(a)

[B] / mol dm'


0.25
0.50
0.50

o.25

Initial rate
/ mol dm'3mln-1
1.4 x 10-"
5.6x 10'
2.8 x 10-'
7.0x 10'

Find the orderwith respectto A, the orderwith respectto B and the overallorder of
the reaction. E- .42
Writethe ratelaw,forthis reaction.
Findthe valueof the rateconstant.
Findthe initialrateof the reactionwhen
and
[AL = 0.120moldm'3
IBL = 0.220moldm-'

(b)
(c)
(d)

a) z"*p.r r vt 2 I 3 : ra'u FAf , cons+ar* fs f


voro' fl]

atro ih.rrrrA

\
f.vd - o'tr"

.'. ft4rtrbvr lr

t ?r

&nporr 6(d
rCur. trJ
i,6l
ralt

2 tuo

ihOt.r) b9 a

c&

) $r.s

rr

,a'".+

A.

cot{qr.

Fr]

fio..r o, tS +o o,5 ,.otJ-- i ,


{atS *.r,, t../rx,o-r t 6 L* to' 5

Srz.r'J -o'Aav

*t

r.9x r"3 lo 5. 6 r rdS

to."

I r alt fs] , a"sl..r

',sot tt:

:, .r 4.+gr
Oaoll

o.o:}s +. o ' t5o not Ari3,

i,<err ht 5 tiwa , !*

ilrnd relr

rr.v,'t

gl

}+ :
? /,

6)

o)

Rarr- r5ql[sl'
drng

e.p* r l qrus{,lr! ir# .arr .4rttir^


I,r1kt0 ''.
K to.rioYo,ri)a
l'4xlo-s

,', X 3

t, qq t lo-t

_
6)

f^lo = o.rzo

.g{bn'lv*

'.

( g' Eo ) ( 0, t r ) '

"ol

ft

a.,,-3

? O ,r> a .n l Ab

,6n

(t,+4 r ;e-J)(e.rzo) ( o. r ro)'

g.Lg x lo-6

kw/kinetics2004/J I

,,.o1Jr 3*r--l

16

Example2 :
A study of the rate of reactionbetweenNO and Oz at constanttemperaturegave the
tollowingresultsfor3 ditlerentsetsof experimenls.
Experiment
1

2
3
(a)
(b)
(c)

Initial partial
pressuneof No / atm
0.30
0.30

lnitial partial
Plessure of O, / atm
0.70

0.60

2.10

1.zl0

lnitial rate of
reaction / amt s'l
0.80
1.60
9.60

Find the order of reactionwith respectto NO and the order ol reactionwith respectto
Oz.
Findthe overallorderof reaction.
write the ratelaw for this reaction.

nh'
Pr.
'dfiot rdt

e <n"rrs *on
,,.cra3(J \
'r
146g
b! 2 {fr{
*lso

, ' , t ttu tm a

6"eqn

tr

l r.t

o ,L '

.rF a. b.

Pd.

at|' sa

.a..bf

, I

vd

u rd.l.t

.)

-rr,

(;r,tial.o+l),

r [^,0],"far],

(i{rtrrr

k r"tiJ f0,l

'r)o

9r-

o ..,t

Q1 ercor'

| ."1 3,

o,:t0 {o t.+0 d'ta


'
(rr,
o, }0 to 1.5g

) r6to cl vrt c4t

l'
I
I

(o .h )" to .1 !)
(o .a !)' { } .rD )

0 .t0
q ,h

+.Gr
n -- f
'
2Z

r.)

utl.tq.

Qy6qn o.&r

.\ efu .

.t

e<tnaA -o.\"

.tir+G

kfNoJ![o;]

kw/kinetics2004/JI

,,r,t

&,

= l+z = ?

/,

l7

REACTION MECHANISM

A chemicalreactionmay involvea sequenceof individualreactionsteftsrivhereatoms,


rearrange
andrecombine.
ionsandmolecules
This sequenceof reactionstepsis calledthe reaction mechanism.

consistof morethan one step.


Mostreactionmechanisms

Thus an overallreactiondoes not representthe individualsteps by which.the reaction


occurs;it onlydescribesthe startingreactantsand the linal products.

The numberof speciestaking part in a particularstep of the reactionmechanismis


of thatstep.
calledthe molecularity

(o)
.

/lAoleculority
rulav
urniw,ok

reactantspecies only in that Step.

step involvesJ,!_

to a newisomer ey A ''+ c
or rearrange
- singlemoleculemayfragment
.

stepinvolves i.,o

b{r'.eL
t rrar

reactantspeciesin thatstep.

of chemical
two molecules,atomsor ions collideand resultsin a rearrangement

LrI, A.b

bonds

A _ter,*t
-

stepinvolves3[

Rote determininq step


One of the stepsin a reactionmechanismis muchslowerthanthe others
) This sloweststeois calledthe

reactantspeciesin thatstep. 1,4,r)

threechemicalspeciescollidesimultaneously
termolecularreactionsare rarebecausethe threeoarticleshaveto collideat the same
time and in exactlythe rightorientationto form the products
a.4- c + o + s . E

(b)
.

,rtc"_

_-, c

rdle

Aefoni['r{

$, I

The overallrateof a reactioncannotexceedthe rateof the sloweststep


)

lluu , ro+t

l&",1y,i^sO tu7

btl,ai:

lw

.!er alt ratt

ol a

cho,nxal equatlw

The overall order of reactionthat appearin the rate equationis an indicationof the
- molecularityoI the rate-determining
step
-)

thr

o"&.r rl 441{ror. rr +h
L.fAtqn. aa
'at
.t6ct,'l
cp..Jer '6 *C rab tra,p.'l ,1q ttrp

\t

kw/kinetics2004/./ I

o<vilfr*+t *

l8
)

(c)

ProPosinqmechonism

:
Someguidelines
.Th e su m otthei ndi v i dua| s tep s in t h e m e c h a n is m m u s t g iv e t h e o v e r a | | b a |a n ce d
equation
chemical
ratelawequation
withtheexperimental
mustbein agreement
Thereactionmechanism
sb'o gttp
ih

111

xoc{aa*s

{r

c qrclmo

tat

qda'

v':ll

ll;

The overallorderof the reactionis that of the sloweststep


j itre orOersof reactionsof the reactantsin the rate law/equationwill appear as the
step
in the rate-determining
coefticients
stoichiometric

SinqlestePmechanism

(i)
.

Somereactionsinvolveonlyone step

'

Then,the ratedeteminingstep= overallchemicalequation


in overallchemicaleqn = orderof reactionin rateeqn
coetficients
stoichiometric
l,tlv* arl h ? stoi't';t"it'

reaction ,
Fora sinsle-step

a,((te"'+:

A^L?:"W

(aq) + Br (aq)
(aq) + OH-(aq)) CH3CHzOH
Example:CHgCHzBT
fls1s= k [cH3cHrBr]'[oH']l

(ii)
.

Multi steP mechanism


E.gHaOz(aq) + 2H*(aq) + 2l-(aq) )

(l)
l, (aq) + 2H'1O

=Btu'o'1'r';-l'
" ] R.d
""if;xi3.#i1,1?i'["Jx5?i"ii8:i'
- first order with respectto [l-l
)

l'+.
tnr
ia.+. 's'ib\

Mechanism ,

Step1 : Hzoz(aq)+ l'1aq1-!!9a I- lo'(aq) + Hro (l)


Step2 : lO' (aq) + H- (aq) rast > HtO(aq)
Step3 : HIO(aq) + l'(aq) + H. (aq)--J99!-1
+zu'*>L1
Overalf: A,o,

kw/kinctics2004/JI

T,

HrO(l) + l, (aq)

+ lrlr0

l9

Example3 :
At very hightemperatures,NO2decomposesinto nitrogenmonoxideand molecularoxygen:
2No, (g) t 2NO (S) + O, (S)
Given that the experimentalrate law is Rate = k [NOr]', which one ot the following
mechanismis plglgl$lwith the observedkineticsof the reaction?
1:
Mechanism
(slow)
Stepl:NOzl(9) ) No(g) + o(g)
Step2 : O (g) + NOz(g) ) Oz(g) NO (S) (fas0
2:
Mechanism
(slow)
(fast)

Step 1 : 2NOr'(g) ) NO3(g) + NO (g)


Step2 : NO3(g) ) O, (g) + NO (g)
fnr'

c1n I ^yo.&v 'l .r4. teh


.a riaArt r.rlar .i0fr.s'r ,{

rut

't

f,

ir

,.&,

,r..z.t

r.ror.

ih 3L,J s+t9 tt 2 '


^ro '
..r"U" r,lrfr. p+1" ;|vv :q 1fu alt

) .'dL..ra' .+ .r0!
t{ f{,i,r,t
S+r?.

tlrrnu, r". rha;la

+ 2'l

ro,rriit r{ "hL -{r

l4'hr{t' s

'l

4fi

norlxn

Example4 :
Giventhat the proposedmechanismis :
NO3(g)+ NO(g) (slow)

Stepl:NO2(g) + NOr(g) )

NO, (g) + CO, (g) (fast)

Step2 : lIO3(g) + CO (g) )


(a)
(b)
(c)

Writethe overallequationfor the reaction.


Predictthe orderof reactionwith respectto NOzand CO.
Writethe ratelaw for the reaction.
! {$r?plf
0,tuall t1p

a)

a co ( q'l +
No: l{)
u) 6t

gfip 2)

^ro

c) RA = r flrl.lr

t3) + rrr (r)

(ua ;a
lh

-L'

Eco:r
^'

;r trro )

3etrr.;u1 stp 6L'a *;) l


" 'rL
r.r$":rn+ .f }o? it 2 '
'ti.\'!{t.rc
+ r-ln ol aa1&' .ir atYa 1o t$t t ) , 7

c0.
)

dqr
ulu

r.ll

.pProt

4 tr.+lor.

kwy'kinetics2004/JI

1'^ r'l't
r!.r,+

aa

(at Pzraor\)
;\

4'o

/l

20

THE THEORIES

(o)
Basedon threemaiorpostulates:
(1) ,.sl<roto ,.ur+ c" lhl.
(2) Su<trsil

*tclditn -lo

.{are plae

b(.!1'. v"fren n olzr,rlrt roll & *i$

6ilc;ori

ra

.o'

"o-)p
a

(o,

1t9

'
t-

+/G:)

- ^ln Yb-

(,

(o,

(3) A.r.s.rlul ,"llnh"


rr.i*a Y r

Oc cat't

Or\

c^tkd w

ttYrtg

oito1.7.?Jivt

fo)
- -/-/.'/
to}

( o +{

o&

flo!.. !.6.1r tlx imronanceol ntob,A o.itxua6


dqiio : collisim.Ihc collision9m h (r) rdl nol
p.odue.. @cri6. blt rhatrhM ii Oj ,elti in lt'c

a.", ct

&

colt&
"lobol<s
-:tl
a&tva,lw.
7v"tr,$1t , ^
,*ten

atlow

The rateof a reactionthereforedependson the @


>

'fw
{dr/

+h

rhr

foJat

rltcasP.,l

tr,.u\ry'o[

+lr

caltir.-all occurr;n6

g.co" |

(*.

'

of nr ctt^toy1

tol c

(b)
particles
: whenreactant
collidein a particular
orientation,
thebond-making
Postulate
processes
and bond-braking
are not instantaneous,
but occurconlinuously
andsimultaneously
.

happens
Providesan explanationof whatactually
duringa collision
'-------\

/|
:\_/

{^I

._/

\.-r

'-")
B

/z\

( c )-

\__,

- - {^ l,-f-\ B I

lc

-_\__/

\lt

at

2-

\.
-,

t l"l'
\
}A-Level Chemistry
E.N. Ramsden
Pg 273 Flg 14.9

.\-

kw/kinetics2004/J I

,,-1-

-7'--\'1

\--l-

-\-^---l/

(^)

!_.'i

(.) T$ .roreint
mol-lk oli{k.
Th. ddd
ch{& do nd i.(6Fdd.

}_

\-./_-

l cl

\.-r
tb) Trc knrvt
r.larild.o&d..
r@
rtF,rtt
drrdt,
ad adr.
.ldldr
inrdF6d..
Th; hrd. ro.<iE

.' I

When two moleculescollide,the kinetic energy can be used to stretch, bend and
ultimatelybreakbonds,leadingto a chemicalreaction
lf the moleculeshavetoo littlekineticenergy,theymerelybounceoff one anotherwithout
reactingdue to the repulsionot the electronclouds
Hencethe collidingmoleculesmust havea lotal kineticenergyequal or greaterthan a
minimumenergyrequiredto initiatea reaction- knownas activationenergy
moleculescollide,they havea lot of kineticenergyand are ableto
Whentwo fast moving.
repulsionof the electronclouds and to approacheach other
forces
of
overcomethe
closely
of the electroncloudsthat occurspermitsa rearrangementof the
The interpenetration
valenceelectrons,withthe breakingo{ old bondsandthe formationof new bonds
into products,can be represented
The energychanges,as the reactantsare transformed
profile
diagram
in the form of an energy/ enthalpy
I

the moleculararrangementat the pointof Jgt^.+


profile diagram is known as an
trandn'on st72

in the enthalpy

"r{tliatEudh.tr

t*'dt

the energy difference betvveenthe reactants and activated complex is the


ac{fsibn ew.E.l , 9n
The ditterence between the energy of reactants and products is the
4fl
cdhl
EndothermicReaction

ExothermicReaction

E
,t=
L reactar{s \ L prodtrcts

Er eaaanls > Epr odc r s


Epr ouuc t s - E65e1q65 ( o

+AH<o
)

E producl s-E 16acr6d5

('rcgafivr)

aare1ir ral..t d.

+AH

<O

eft[

)o

( p:rl'.r)
atso'V l.

kw/kinetics2004/J I

22

thereis morethanone activation


For reactionstakingplacevia a reactiveintermediate,
energyandtransitionstiate
: (CHg)gCBr
of tertiaryhalogenoalkane
Example: Hydrolysis

Tro.dtloar dole I

E dr = oe,OYo{ oc{volto.l of lbf .bp


Rescli krtoflrdiLia

Rdctonts

ol o"t rcno.t of tco.rd dop

E . ' *,tgv

AH-

Reoctlrn coordlnote

FACTORSAFFECTINGRATE OF REACTION

Recall: The rateof a reactionthereforedependson thefrequencyof successful


collisions
persecond,the
occurring
collisions
) Thegreaterthenumberof succebsful
greatertherateof reaction.

(o)
.

Concentrotion
Increase
intheconcentraton
ofa reactant
edr.br' *

hurrrLr- al

)
'

*,

S '+l
)

+lv

l^c/ry{.r

lvlc,

1.71,|p1rtprif
+
rr l.,thn

.t

ln$u,A
ral.

Q4l *l

fs

atlb,

hrrarrl

Vv

a,lfrcb*

oUP :l. cna,

o..or

oucrrr& I

gatt|W

uirt ru urr

qq!

.A

.'q1L+

ok''l.*^

colbsw' ',1^Cnaf4r

',r\t#.

lncrease in the concentrationof a reactiantdoes not changethe rate c9nstant,k,


providedall otherconditionsremainconslant

lilkinetics2004/J I

23

(b)
.

TemDerofure
Fotr

rr*.to".

'$<tl*o|.\

.,1'rtt tl rrprretuz,

An increasein temperatureincreasesthe averagekineticenergyof the reactantparticles


and hencecollidesmorefrequently

For an increasein temperatureof 10"C, the averagespeed of the reactantparticles


increaseby a factorof 1.016.
But the rateof reactionincreasesby about100times!

Reactionrates increasesgreatlywith temperaturebecausea larger proportionof the


collidingreactantmoleculeshavethe minimumactivationenergyneededto react

Explanationusinq Maxwell-BoltzmannDistributioncurve :

*(i)

g
f

oo
Y <lt
OC

b.>

Lowertenperafure

ci,)

H'lghertemperafure

c{'")

Eo

o (q
o _-

Mini(I{an efle.gy
requi(sd fo( raction

(L }

Collisiondnergy

At any temperature,the numberof moleculeswith a givenenergyis distributedover a


wide range
The shadedarea underthe curve,for a particulartemperature,
representsthe proportion
of moleculespossessingenergiesgreaterthanor equalto Ea
As the temperatureincreases, ( f' > f , )
rhok.rlar

p,* ht6b.v

ri.orr

r..ba, uf .,"r.r&.l / c$t.+,v r,ililtrr

ltrl

\or'rt

dt

kw/kinetics2004/JI

'.oyt

grqov'{nvr

dro

,t

sFedc

w4zr.,dtt

a^l

havr

hevr

{4r

a'l a t|$rv

V\wn

Y$r+tL .wvt\rt

r;nilre.^ ttv?d n y*A

b*p,1ha

:u,xa*t

l1y nt**4>t

6qtlu*.

ivrceetr'
-eJraq6..

24

.'f

(ii) Relatlonshlobetrveenternoeratureand ratEconstant : Antenltrs Eouadon


.

:
Equation
Arrhenius

rate constant
Anfienius constant(relatedto collisiontrequoncy
and molec-ular'oriedaton)
activationenergy
gas cmstant,8.31J mol'' K''
temperalurein Kelvin

k
A

g - [ .roLe"/cr)

Ea
R
T

:
FromAnheniusequation

{- Enlcl)

lr<vra3e.r

ih calrt{a

lc rrr oagFa

('

T increases

- :i

tvrsr.osca

grp ('Eo larl r a c.,|,ra

exporur*all$'

where[reactantlis a constant
Fromratelaw : Rate= k [reac{ant]n

= r r^J'
l1

vcatt4l

,db,

it Cra.tat

exponentially
rateincreases
incroases,
Hence,whentemperature
energy,Ea:
of activation
Determination
: k = A exp(nD
Arrhenius
equation
ln K = ;, f.s ,*rGe.lertt
lnP '

1n A -

(g ' / e r)

t,a r = [- * J f "'. q
Hence,by plottingIn k vs 1ff, a straightline graphwill be obtainedwhere

$ - i,rttrt.r+
= lr^A

I
lcw/kinetics2004/J

- E" lp .

25

(c)
.

Cotolysts
Catalyst : I arutanc
h,

Lr

{u+ 4lt c {gr"erelg


p+

rr.c'rrrt) .rL rrl rl

rrec-trbn

41co+ rtr Tct | .l- {rr po,lr.u

the end of the reaction (but it may undergo a


A catalyst is thgfrtffitqmtitlGat
changea physicalchange)
in a subsequentstep
+ it is consumedin one reactionstepand regenerated

usua y Wfffit
) may increasethe rateof one reactionbut not increasethe rateof a similar
reaction

UsuallylFilqtrr;f#\which
reactionrate

is sufficientto bring about a great change in


)

ReactionMechanismof a catalvst :
.

A catalyst providesan fifilffiltlttrfiCl


thetFf,gtie

p6[l9tet] with a lmPdrrtion

eflcry than

Er - rclivrtiro co.lE| oa
udcrtdy$d rc..ii6
E = ..rivdiod a.rE/ of
cafdyt.d rcr.ttoo

Rcrc&n coordidc

Arrhenius
equation:k=A exp(.@

Eadecreases
=e F natl',$

-*

v,,qtrt

g.g ( - arfi)

\u.".4t t

?lp6.tilth

Fromratelaw: Rate= k [reactant]'where


is a,constant
[reactang
Pirntrlat

ldkinetics2004/J I

's{t rr,r.rqCel

26

curve:
distribution
From Maxwell-Boltzmann
F>

:E5

e'
qt .gy,"q.,t.od F4 fot'tXtl)
Mi.{mu.n
radcdon

fo( cataF

MLftvnn oney .'qdmd


lor dr:latvsad radrxr

E. q
\/

Coltsioo oo.Ey

ft a^+r[ard natffo^

far o

lc'*

I Ft t

ar'{tre't'or^ er(-$

llqc,

rr*n\v
-

B o

.e

,i
nUl.l,

.rot

'dr c,lrr

s6,q

T,.ltt'!

"o+at!xl\

&

a,...,st t

.dhro,": , 4a

cdliarors iercd?.t,J

rHtttit
ra+r

rr{h *lfoa'+

''l.,unv'

.,hau,rr c"rf,.,r,r io
,

>. 6^Aa*t)
- (tw, , nvwbr ol *olrr,l o
^'ltt chd6
tk ,r.ctc.l#I
Ca.+b'^- (fw

at' otl*xd|,i

,Jlt;.

Recall: shadedarearepresentsnumberof moleculeswithenergy> Ea

a7,a{.lo* i NeoJaJ

Tvpe of catalvsts
(i)

Homooeneouscatalvst

Catalystand reactantsare in the

Reactantand catalystcombineto torma reactiveintermediate

'

thenbreaksdownto givethe productsand regeneratesthe catalyst


The intermediate

sa,'e

&a '

phaseb*u thh)

alfratVr

orl aS 'l

1l6lalal9tl

Fr,) I ar.trvahYr avrJ

F6y I aq*i@o

ul

orroJ

act&n '
4rr{ +l,trtrlt u

4 $l

Reactant
ftL L
lthtq&a

Product
Reactioncoordinate

I
L:uy'kinerics2004/J

ftlt

tar'r xrp' slct

Examole1:
Catalyticoxidationof SO2to SOsby attnosphericoxidesot nifogon (contibutesto the
formationol acidrain)
Uncatalysed
reaction:2so2+ O, t 2Sq

Activation
enerry,F.

Catalysedreaction: 2SO2+ 02 ) 2SOs

Activationenergy,E"'

:
Proposedmechanism
stgp 1

t0r'

step 2

.b,

0, + ,$
r

rlo,

-t

--t

SinceEr and E2< Ea

tot

Fr

NOr b,tr.<lou)

5{1, + AtO

:e

e,

Eo' i lryt

"I

jlu

raLf ,
-)

2: Gr'.7't)
I Examole
Reaction
iodideandperoxodisulphate
ionscatal!,sed
betweenaqueous
by iron(lll)ions
2l-(aq) + SzOsz-(aq)
) l, (aq) + 2SOca(aq)
Proposed
mechanism
:
Step1 : lron(lll) ionsllI|m,
2Fe$ (aq) + 2t-(aq) )

itselfis reduced
to iron(ll) ions
2Fe2.(aq) + l, (aq)

Step2 : The
ffi

of catalyst
- regoneration
2Fe& (aq) + SOe2- (aq) )

2Fe* (aq) + 2SO1'?'(aq)

ExplanatiOn : - Tb qtdg/{lo /&E{hyr :}{o lwr rlc ,othrt^ bt*rrr ;or r * llrc paC
ctq4 ;o o ;rV t+V '
q f4rn" bri;
d" fiq,n*\
&,qt6 iort,.
' Ta crd1r.|
bnr I
*s0. d*ra <a. oIp
d.
^.{+b,
- Hou .diy,,ln N8,
1* rh rc I f e .a go.h bw +,6. 11n
qrgfl\r^ rr1{
at {h utva'l.orlyl a+t/o,

Note :
lron (ll) ions can also act as a catalyst and the mec,hanismoccurs in the rverseorder
describedabove.
Lt+rCI +hr. .rrp r l

lcvv/kinctics2004/JI

28

(ii)

Heterooeneouscatalvst
Catalystand reactantsare in

ilFlcvrnt

phases

catalysisinvolvesthe formationot an intermediatebut most take


Some heterogeneous
placeon the surfaceof the solidcatalyst
+ Adsorptiontheory
catalystsare moreeffectivewith largersurfacearea (finelydivided
Solid heterogeneous
powder
form) as this providesmore surfacearea for adsorptionof reactant
or in
molecules
Adsorption theorv
Example1 : Synthesisof ammoniain the Habe/s Processusingfinelydividedironcatalyst
(cow,orr9- arld)

(D-fN)
- l-

G}__+ff')
v

1'Jractivesites

Step 1 : Diffusion
The reactantgas moleculesdiffusetowardsthe
solidcatalystsurface

Step 2: Adsorption
Reactantmoleculesareadsorbedon activesiteson solid
catalyst.
Physicaladsorption: boundby weakvan der Waalsforces
Chemicaladsorption: boundby strongerchemicalbonds

Step 3: Chemicalreaction
Adiacentreactantas moleculesreactto form
the oroduct

Step 4 llesorption
Productmoleculesformedare firstchemisorbed
on the solidsurface.
Theythenbecomephysicallyadsorbedand
finallybreakfreefromthe surface.

#4
I
kw/kinetics2004/J

Step 5 : Diffusion
The productgas moleculesditluseawayfrom
the catalystsurface,makingroomfor fresh
reactantmoleculesto be adsorbed.

29

Adsorptionof reactantmoleculeson the solidcatalystsurface


) h\'r +o ra.a,kdz *r. t&o,'t
)
.

A.fvc

ir.trars ln#"\

C*.r

*ltilrtr

',rkciet

*,"en*l',1

etc+a.t

alh,$ons.
th

vaq'tht

{l

co,act

62

/ ci<"+ali0, .

*,.r+$

Examole2 : Catalyticcrackingof petroleum


are brokendownintosmallermoleculesin a laterstage of
Large,high-boilinghydrocarbons
petroleum
refining.
Crackingis performedat high temperaturein the presenceof a heterogeneouscatalyst
com0osedof SiOzand AlzOs.

sioz / Alzo:

-----:

C,, and hiqher

5oo"c

(ieroseni)

Csto Cro
alkanes,alkenes

Example3 :

usinga nickel
oilsto formmargarine
Hydrogenationof alkenesto alkanesor unsaturated
catalyst
r'ri

cAn.A t

ar'lr{a

---+

i.Examole4 : catalyticconverter
The combustionprocessoccurringin a car enginegeneratesundesiredproducts
(C,.Hy),
oxidesof nitrogen(NO,NO, or NO,)
e.g. CO, unburnthydrocarbons
A mixtureof catalysts(platinum,palladiumand rhodiummetalstogetherwithoxidessuch as
CUOand CrzOs)convertsthesepollutantsintoharmlessproducts
e.g.co2, Hzo,Nz

co, c,Hy

catalvst

i"*

b<.loo^z

No, No2 cat?lvst>


e6 + lo7
CtA5 M,

bw/kinetics2004/J I

ovt

con

/a2 + A1a

tt{o
:NO:

<ot"bt +
ct*aitli

Nrl
,

o.

0r + )O> ,

30

(iii)
.

Autocatalvsis

A productof a chemicalreactionwhich functionas a catalysisfor the reactionis an


autocatalyst
:r

(a) kattov.

(b) .f9-'

i'riiallX-

sbo
r!

[-ftl4

gcdr.r

Sqtra

.o

-tlv adoct"tSr+ ) , 4, ,oh V6'rt

(g

r,^<

o)
c
o

(c) n4

orl

ri,re

.4

.qf'; d lg

qa.1<s

Psl r^c+ / arr*. a,rall:1

(d)
Reactionco-ordinale

{o

,h ' I
I r.:1,
4 inway'

yirt^+ , +te

n 6rlru6

;,

4J

eV,h

tr.gta

ttr

ir.,t6

&.taA..

,1talr+ls p.owo

^r

-?

-lb

.aL

rlor

L.-.
b4.rq t^nC"rr6.

AQ

"g.',"

as

11{ r.ca4 rlr

(Vll)andethanedioate
Example: Reactionbetweenaqueousmanganate
ions
2MnOa-+ C;Oa2-+ 16H. )

2Mn2*+ 10COz+ SHzO

Mn2*producedis an autocatalyst
for this reaction

Whena dropof MnOa'is first addedto an acidifiedsolutionof ethandioate(heatedto


60'C),the pinkcolourof MnO4'decolourises
slowly

With subsequentaddilionof MnO4-,the pink colourdecolourisesmore rapidlyas


moreautocatalyst,
Mn2*,is formed

Test for autocatalvst


Add the catalvstat the startol the reaction
e.g. add Mn2ito the reactionmixtureof MnOa'and GOr2t Dueto the presenceof the autocatalyst,
the reactionwill nowbe very rapidat the startof
the reaction
i.e. decolourisation
of MnOawill nowbe rapidat the startol the reaction

(iv)

Enzvmecatalvst

Large protein moleculeswhichac;tas biologicalcatalysts

Temperaturesensitive
) an optimumtemperature
at whichenzymeactivityis highest
(usually
) at hightemperatures
>45"C),they are denaturedand deactivated

kw/kinetic.s2004/JI

.),ta ,'"* ou-1',


.r+{*.. C&4 aa,,,r,t_

3I

pH sensitive
) an optimumpH at whichenzymeworksbest

pii"l.iiii"o""is
) workswelloveranarrow

toa) [du"+*l 16r'r+|'rrragrl

Veryspecificin the reactionstheycatalyse


) will usuallycatalyseone particularreactionor one particulartype of reaction
) highlyspecilicactionis due to its proteinstructureand is relatedto howenzymes
worK

Mechanismof enzvmeaction: Lock- and - kev hvDothesis


.

Catalyticreactionoccurson a specificlocationon the enzymecalledthe a(fv. stt'

The moleculeswhichthe enzymeactsuponis calledthe

in whichonlycertainsubstratemolecules
configuration
The activesite has a distinctive
canfit

At the end of the catalyticreaction,the productsare releasedand the activesite is free


molecule
for yet anothersubstrate

t"bt n+e

(l ) Withinihe rtru.ture ol achnzyme6 an


areaknown.s the a.iive site. lt may involve
onl yarm.l l numberol .mi no acds. l thasa
ve.yspecilicshape.whi(h giveseachenzyme
ilr rpdl.cny,asonly one rubnrateo. type ol
tubrtratwill lii inio lhe gap

5ile

(2) He.ewe (an 5eelhe diflerencbetlveen


the rhapeof lhe enzymesubskareand
anolherbiologicalmole(ule.Oolya
mole(uleof the righr sh.pe(an be a
substrat,orlhen2yme
(l) Thenrymeandsubslraterlor togerher
to lolm a (omple! asa keyfils into a lock.
In lhis (omplexthe rubnratis enabledto
read at d loweraclivaiionenergy Thismay
be due to bond5within binqde{ormed
't
and siressd
in the compler.
to makingthem

0)
tnzyme^ubsirate

'o'

J)

Produdr.L-,//

6-\
.-/

Q Q-/

(4)Oncethe reactionhasbeen(alalyied,the
produc6are no longe.the right shapto
ltay in lhe activiite and rhecomplexbreals
up, releasingthe prod!,ct5and freeing the
enzymelor further catalyl;caction.

Examplesof enzvmesandtheirroles

Enryme

..Role

Rennin

Coagulatesmilkproteincaseinto producecheese

Pectinase

Preventschilledfruitdrinkslrom becomingcloudy

Papain

Tenderizesmeat by breakingdown large moleculesresponsible


for touqhness
Fermentation
of glucoseto ethanol

zymase(yeast)

\u/kinetics2004/JI

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