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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 $ie differentmodes of action of homogeneousand heterogeneouscatalysis,including:
(i)
the Haber Process
the catalyticremovalof oxidesof nitrogenin the exhaust gases from car engines
iiU
the catalyticremovalof almosphericoxides of nilrogen in the oxidationof atmosphericsulphur
iiiU
dioxide
(iv)
catalyticrole of Fe3tin the l- / SzOe2'reaction
describeenzymesas biologicalcatalysts(proteins)which may have specilic activity
References:
Chemistr)4Ann & PatrickFullick
Chemistryin ContexCHill and Holman
Chemistryin Actbn; MichaelFreemantle
Chemistry - The Central Science; Brorvn, Lemay and Bursten
Chemistry- The MolecularScience;Olmsted& Wlliam
I|nderstanding Chemistry for Advanced Level; Ted Lislet & Janet Renshaw
I
krr/kin<'r
it's2U01/.1
INTRODUCTION
of reactantsI
Concentration
Temperature
I Seesection
Presenceof catalysts
)
(iv)
RATE OF REACTION
describesthe speedat whichreactantsare convertedto products
representedas the changein concentration
of eitherthe reactantsor productswithtime :
(a) Averagereactionrate
(b) Instantaneous
reactionrate
(c) Initialreactionrate
.
1
kw/kinetics2004/J I
vi,l-
\ i.(1,r.
r
J
^t
(o)
.
ArterooeReoctionRote
a reactant
orproductItrrerilF
oflFFGGot
Measursment
Averagerate=
J l'cerbtl
- Alaectoi]
b1
dt
+)tr'vl,,61
Average rate=
lr
since concentrauon
of
sinceconcentration
of product
Time/ min
festerl/ mol dm'
UFIsGUUH / mol dmo
0
0.500
0
10
0.375
0.125
20
30
0.3(n
0.216
o.2u
0.200
Forthefirst10mins:
0.t75-0'500
-,
alats
ln
0. 115 - O
lo
4l
ff
=
Averagerateof formationof CHsCOOH
.l .*tv
Averagerateof disappearance
of ester=
- s. gtt!- -c lAa'l;r-r
t |
otattt8ct
41C,tl
tt|
tu*rral
Asthe reacfionratecfianges
wih time,the
continuousv
acqir$ rab dffifrilod
tremrt0otrh
A moreaccurateindbatbnof rateof reaciionis instantaneous
rate
Lilkinetics2004/Jl
/f
,,
\-
(b)
Measurement
of tde d qffin
&e
Instantaneous
rate=EraiFfrilhtthetangentto thecurveat specifiedlime
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. ,
It
12
t_to)
tt
,-. 3
(C)
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
.
(o)
: concentration
of reactantin thechemicalreaction
: oder of reac{ion
: rateconstant
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
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
fii.r*
qrlcv
and
-j!:tg!!ts-
on the concentrationof A
W h e n n =1
p61s =" t [ l l
- r[r1
{rtrt
r.lcr
Hencerateot reactionis
to the concentration
of A
Ro! a frl
i.e.
Wh e n n =2
Rate= k [42
qaol
c,lr,/
(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 *!
(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
'
=
Or'.
S -t
/t'
Rate= k [A]'
E(PERIMENTAL PROCEDURE
o-l
---:----:--:tii
(,*rr t* /
Secondorder
Rate=klAl[B]
Physicalmethods
colour
Volumeof gas evolved,gas pressure,electricalconductivity,
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\
r.,
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)
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) )
\ f
/
.}
,"",
,.J'n'
I O I
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
(o)
.
-
bw/kinctics2004/J I
l0
(i)
[AL,
IAt
.
w6 -z.vo
tAl
nzldirz slott '
, with a
toltlt
lnltial ratemethod
(ii)
..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
tAllmoldm'
0.40
0.30
cor:ta"t
Tlme,s
30
n l? ,
1 lo *,t *t
I tu,rt ,tw
' &, .-..u}ntrl
,r
.(b)
.
,.dbL
Iot/kinetics2004/JI
=+
Rate c [A]
ll
(D
Ratecurue rredrod
[d,
[6,
lAlr. [4t,
[A] vs time gph :
cuv{s
(iD
nrgativr. s lon,
with a
, passingthrough ovtht^
trdadt
t.Fd+-ery
Delinition:
rt,oliovt-
|etiEfrlilfrFFhtriti
ffird\
Concentration
- timegraphis an exponential
decaycurvewithdecreasingslope
tAl
(^1,
dhorartr*e)
bg 1
+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
-
== e-
: -r+1I^e
l"l
lnt-
.r.--
v+-
lcilkinetics2004/J I
\n 2 ' lctr
Lir
lrna e
-k*r
12
(iii)
.
) Directcomoarisionof data
E x a m p l e : A+ B )
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.
o. * _
o 9o -
t
2
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
0
30
40
20
P61sc, 1
Recall:
&
(vxr)
ott *.Vi'*l"
I l r, 0,A av
+
w\,ri
ti,rr
kw/kinetics2004/J I
..a.g+aql
$r-
lsi
o"l,' y rc*{ic
,' o
,
t*.9.c*l
'r6.+t*'
'arp 7. t ( r 03
I.'
) For exoerimentswhereconcentration
of a oarticularreactantis measuredat
varioustimeintervals
l)*
Ex a m p l e : A+ B )
lnitial[B]-/
mol dm-"
mol dm-3
1
2
3
0.20
0.40
0.40
g
htc.l co"Vat"aa
a.a'?onis.y\ol t dio l
aialNS
Initial rate
/ mol dm-3 s-l
o.20
R1
0.20
0.40
Ra
R.
rAl
tAl
tA
4L
?-l
l i me
trme
lime
Concentration
- timegraphsareplottedfor eachsetof experiment
= gradientat thetangentt = 0
graph
Foreach
: Initial121s
Resuftsare tabulatedand analysiscan be carriedout usingdirectcomparisionof dataol
comparisonof the ratio of the initial rates to the ratio of the initial concentrations
(c)
.
(i)
Rate = k [A]2
rate 0 [A]2
Ratecurve method
lAlr. lAlr r
[A] vs time graph :
curvc
Rate vs [A]2graph:
lVr rv
with a
with
/vgatir
<'lS
, passingthrough ontr v'
kw/kinetics2004/J
I
t4
(ii)
of data
) Directcgmoarison
A+ B) C
Example:
Inltial [A] / mol dm
1 and 2 :
ComoarinoexDeriments
vhj'l
t""
/ increasesby
ee,na, - ot&t
Hencereactionis
clrt a.t .
t-o tivz.r
, increasesby
cot' fEJ ia
S-rl
with respectto A.
1
inexoeriment
initialrate
2
initialratein exoeriment
1F
(o,ro)t
(nitialconcentration
inexperiment
lo,{o)r
(nitialconcentration
2f
in experiment
"t
hA fa h
.
'6rya.rd' &
the
concentrations)2,then
reactionis
s' (a1t ' o'L v
with respectto A.
)d o,&,
lf initialrateis notgiven:
Recall:
Rateo#
\ \ :^y_f**
and
Sincerate cr(concentration)2
=
. a*c or (vohrre)"
('a*$"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
3
4
(a)
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)
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]
Srz.r'J -o'Aav
*t
to."
',sot tt:
:, .r 4.+gr
Oaoll
i,<err ht 5 tiwa , !*
ilrnd relr
rr.v,'t
gl
}+ :
? /,
6)
o)
Rarr- r5ql[sl'
drng
,', 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
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,
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
(o)
.
/lAoleculority
rulav
urniw,ok
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[
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{
$, I
lluu , ro+t
l&",1y,i^sO tu7
btl,ai:
lw
ol a
cho,nxal equatlw
The overall order of reactionthat appearin the rate equationis an indicationof the
- molecularityoI the rate-determining
step
-)
thr
o"&.r rl 441{ror. rr +h
L.fAtqn. aa
'at
.t6ct,'l
cp..Jer '6 *C rab tra,p.'l ,1q ttrp
\t
kw/kinetics2004/./ I
o<vilfr*+t *
l8
)
(c)
ProPosinqmechonism
:
Someguidelines
.Th e su m otthei ndi v i dua| s tep s in t h e m e c h a n is m m u s t g iv e t h e o v e r a | | b a |a n ce d
equation
chemical
ratelawequation
withtheexperimental
mustbein agreement
Thereactionmechanism
sb'o gttp
ih
111
xoc{aa*s
{r
c qrclmo
tat
qda'
v':ll
ll;
SinqlestePmechanism
(i)
.
Somereactionsinvolveonlyone step
'
reaction ,
Fora sinsle-step
a,((te"'+:
A^L?:"W
(aq) + Br (aq)
(aq) + OH-(aq)) CH3CHzOH
Example:CHgCHzBT
fls1s= k [cH3cHrBr]'[oH']l
(ii)
.
(l)
l, (aq) + 2H'1O
=Btu'o'1'r';-l'
" ] R.d
""if;xi3.#i1,1?i'["Jx5?i"ii8:i'
- first order with respectto [l-l
)
l'+.
tnr
ia.+. 's'ib\
Mechanism ,
kw/kinctics2004/JI
T,
HrO(l) + l, (aq)
+ lrlr0
l9
Example3 :
At very hightemperatures,NO2decomposesinto nitrogenmonoxideand molecularoxygen:
2No, (g) t 2NO (S) + O, (S)
Given that the experimentalrate law is Rate = k [NOr]', which one ot the following
mechanismis plglgl$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)
rut
't
f,
ir
,.&,
,r..z.t
r.ror.
) .'dL..ra' .+ .r0!
t{ f{,i,r,t
S+r?.
+ 2'l
l4'hr{t' s
'l
4fi
norlxn
Example4 :
Giventhat the proposedmechanismis :
NO3(g)+ NO(g) (slow)
Stepl:NO2(g) + NOr(g) )
a)
a co ( q'l +
No: l{)
u) 6t
gfip 2)
^ro
c) RA = r flrl.lr
(ua ;a
lh
-L'
Eco:r
^'
;r trro )
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
6ilc;ori
ra
.o'
"o-)p
a
(o,
1t9
'
t-
+/G:)
- ^ln Yb-
(,
(o,
Oc cat't
Or\
c^tkd w
ttYrtg
oito1.7.?Jivt
fo)
- -/-/.'/
to}
( o +{
o&
a.", ct
&
colt&
"lobol<s
-:tl
a&tva,lw.
7v"tr,$1t , ^
,*ten
atlow
'fw
{dr/
+h
rhr
foJat
rltcasP.,l
tr,.u\ry'o[
+lr
caltir.-all occurr;n6
g.co" |
(*.
'
of nr ctt^toy1
tol c
(b)
particles
: whenreactant
collidein a particular
orientation,
thebond-making
Postulate
processes
and bond-braking
are not instantaneous,
but occurconlinuously
andsimultaneously
.
happens
Providesan explanationof whatactually
duringa collision
'-------\
/|
:\_/
{^I
._/
\.-r
'-")
B
/z\
( c )-
\__,
- - {^ l,-f-\ B I
lc
-_\__/
\lt
at
2-
\.
-,
t l"l'
\
}A-Level Chemistry
E.N. Ramsden
Pg 273 Flg 14.9
.\-
kw/kinetics2004/J I
,,-1-
-7'--\'1
\--l-
-\-^---l/
(^)
!_.'i
(.) T$ .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
in the enthalpy
"r{tliatEudh.tr
t*'dt
ExothermicReaction
E
,t=
L reactar{s \ L prodtrcts
+AH<o
)
('rcgafivr)
aare1ir ral..t d.
+AH
<O
eft[
)o
( p:rl'.r)
atso'V l.
kw/kinetics2004/J I
22
Tro.dtloar dole I
Rdctonts
E . ' *,tgv
AH-
Reoctlrn coordlnote
FACTORSAFFECTINGRATE OF 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$u,A
ral.
Q4l *l
fs
atlb,
hrrarrl
Vv
a,lfrcb*
o..or
oucrrr& I
gatt|W
uirt ru urr
qq!
.A
.'q1L+
ok''l.*^
colbsw' ',1^Cnaf4r
',r\t#.
lilkinetics2004/J I
23
(b)
.
TemDerofure
Fotr
rr*.to".
'$<tl*o|.\
.,1'rtt tl rrprretuz,
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
p,* ht6b.v
ri.orr
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
b*p,1ha
:u,xa*t
l1y nt**4>t
6qtlu*.
ivrceetr'
-eJraq6..
24
.'f
:
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
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
rrec-trbn
usua y Wfffit
) may increasethe rateof one reactionbut not increasethe rateof a similar
reaction
UsuallylFilqtrr;f#\which
reactionrate
ReactionMechanismof a catalvst :
.
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
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
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;.
a7,a{.lo* i NeoJaJ
Tvpe of catalvsts
(i)
Homooeneouscatalvst
'
sa,'e
&a '
phaseb*u thh)
alfratVr
orl aS 'l
1l6lalal9tl
F6y I aq*i@o
ul
orroJ
act&n '
4rr{ +l,trtrlt u
4 $l
Reactant
ftL L
lthtq&a
Product
Reactioncoordinate
I
L:uy'kinerics2004/J
ftlt
Examole1:
Catalyticoxidationof SO2to SOsby attnosphericoxidesot nifogon (contibutesto the
formationol acidrain)
Uncatalysed
reaction:2so2+ O, t 2Sq
Activation
enerry,F.
Activationenergy,E"'
:
Proposedmechanism
stgp 1
t0r'
step 2
.b,
0, + ,$
r
rlo,
-t
--t
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) )
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
(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
A.fvc
ir.trars ln#"\
C*.r
*ltilrtr
',rkciet
*,"en*l',1
etc+a.t
alh,$ons.
th
vaq'tht
{l
co,act
62
/ ci<"+ali0, .
*,.r+$
sioz / Alzo:
-----:
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
bw/kinetics2004/J I
ovt
con
/a2 + A1a
tt{o
:NO:
<ot"bt +
ct*aitli
Nrl
,
o.
0r + )O> ,
30
(iii)
.
Autocatalvsis
(a) kattov.
(b) .f9-'
i'riiallX-
sbo
r!
[-ftl4
gcdr.r
Sqtra
.o
(g
r,^<
o)
c
o
(c) n4
orl
ri,re
.4
.qf'; d lg
qa.1<s
(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
(Vll)andethanedioate
Example: Reactionbetweenaqueousmanganate
ions
2MnOa-+ C;Oa2-+ 16H. )
Mn2*producedis an autocatalyst
for this reaction
(iv)
Enzvmecatalvst
Temperaturesensitive
) an optimumtemperature
at whichenzymeactivityis highest
(usually
) at hightemperatures
>45"C),they are denaturedand deactivated
kw/kinetic.s2004/JI
3I
pH sensitive
) an optimumpH at whichenzymeworksbest
pii"l.iiii"o""is
) workswelloveranarrow
in whichonlycertainsubstratemolecules
configuration
The activesite has a distinctive
canfit
t"bt n+e
5ile
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
zymase(yeast)
\u/kinetics2004/JI