CHEMICAL KINETICS

Section A: QUICK REVISION OF THE CHAPTER

6L INTRODUCTION: INSTANTANEOUS RATE OF REACTION:
Chemlcal Kinetics is a branch ofphysicalchemistry A is defined as the rate of chemical reaction
thatdenls with the ate of reactiop, factors.affecting measured at a specific tinstant
the ratc of reaction, and the mcchanism by which,a Explanation: A+B 2C
reaction takes place Tnstantaneous rate of reaction:
E RATE OF REACTIONS d[A) d(B] 1 dËc
Mate of reaction: The change in the molar dt dt 2 dt
concentration of the reactant or product per unit NoterTheehange in SIgn áto din the rate equation.
time is cailed the rate of reaction. N, + 3H, 2NH,
Change in the nolar Instantaneous rate
concentration of reactant/product 1d[H,l 1d[NH,
lte of reaction Time taken for the change
d|N,I
dt 3 dt 2 dt
Aplanation:Consider a hypothetical reaction
B
Refe of disappearance (consumption) of A
Decrease in molar concentration of reactant
Time taken |For reactant
Rate atf
Nslope of fangent at t Rateoduct
slope oftangent at f
ORRate of formation of B
Increase in molar concentration of product B
Time taken t, time t time
a|B) Determination of instantaneous rate
At 6.3 RATE LAW
The negative and positive sign indicates that The rate law is defined as 'an experimentally
concentration decreases and increases respectively. determined equation which expresses the rateof
A|A] A|B| a chemicalreaction in tems ofthe molar concentration
Aus, Rate of reaction = At At
of the reactants
Explanation: Consider the general reaction,
Units ofLrate of reaction aA + b B c C dD
M timel OR mol L- time.
AeTage rate of reaction:Itis defined as the change Rate = k(AJB|
According to rate law, expression can be written as
in the concentration of reactant or product divided R JAJ"B
by time interval over which the change occurs.
Average rate of reaction can be determined 1 I n the above rate law equation, x and y are
determined experimentallyand they may or may not
graphicaly. be equal to a.and b (stoichiometric coeficient).
Jtrage rate At
2H,O210 2H,0O
The rate of reaction is experimentally found to be
proportional to the concentration of H,0,
. Rate - k(H,0,]
Note: The x and y which are experimentally
determined may be simple whole number, zero or
fraction.
ORDER OF REACTION:
The overall order of reaction is defined as the sum of
exponents (powers) to which concentration terms in
the rate law expression is raised.
Explanation: Considera general reaction,
time (t) r bB cC+ dD
Average rate of reaction is not a true rate of According to rate law expression, R = AB|P
reaction because as reaction proceeds, the molar Overall of reaction with respect to A is x and that of
concentration of reactant decreases, and the rate B is y.
also decreases. 2H,0,
(47)
 UTTAM' XI Chemintry Pape Sok
erty of Tit is the property ot e
Uperimentally determined rate law, pH s the pu elementary mactions
Rate kH.OA compleK actions apd ha no meaning B
1he reaction is o first order Icompleeaction
tion
Characteristics of Order Of ea INTEGRATED RATE LAW
eGment 63
The equation obtained by n t e n differe
fraction or cven tero. eaw that een
er lt can not beOedicted from the stoichiometric vs and the time in cal
concentrat
balanccd equatign
ithexperimental conditions. ented catr law
7 t may change teation of erated rate law for frst order reaction :
t is dehncgs
Consider frst order reaction.
1 Orderin anplicablc to clementanS well aS Complex Aproduct
reactio The differential rate law is.
VLARITY
4 MOLECULA OF ELENENTARY REACTION
d|A
7ementasy r e a c t i o n : R o n Rate
P a c e i e a l eeactions
Complex reaction:A chemicalrcaction thatollaes dA. -kdt
sumple rate laxc bytROcCurs in multiple steps Integrating the above equation with the limits
Reaction intermediate The adstitional spscics AAL at Oand [A] Al, at tt,
other than the reactants and noducts formed
in the reaction mechanism is.calledthe rcacbon A
-kfdt
Ane Tetermining Step: he slowest aten naE
reaction mechanism is called rate determmining step where. JA, is the initial concentration of Aat t *h
Explanation: Consider the reaction, and JA, is the concentration of Aremain unreacin
2NO, C L 2 N O C
The reaction takes place in two steps
() NO,CNOC (slow, unimoleculari AL
In|A,- InlA],- kt
12) NO,C +C NOC AI
(fast, bimolecular) njA-kt
Overall reacton
2NO,C2NOCle k lnIAL
() ttis a complex reaction
(u) Each step in a complex reaction is an elementary Converting it to logSio We get
( ) It can be seen that Ci is formed in the irst step
12.303 A
and consumed in the second. Hence it is reaction
intermediate 2.303
(iv) The first step is slower than second: it is the
rate determining Step
Rate law can also be written as
(v) The rate lasw predicted from the slow step
kNO,C
oleculariKate meatary reaction: It is
k

defined ber of reactant molecmcS Taking antilog on both the sides,

involvedin the rcactior
cg Brye28r Unimolcular
Ht 2HI Bimolecular
DISTINCTION BETWEEN
MOLECULARITy orE ORDE
R AND
IALIA,er
RTY OF A REACTI Ifthe initial concentration ofA be 'a' mol/ dn and
Order eculartt '*'mole/dm' has reacted during time then the
t is sum of exponents to Itis the nunber of reactant concentration of Athat remains unreacted is (a- N
which the concentration molecules involved in an 2.303 a
terms in the rate law is
Men k
elementary reaction
aised
YIE is a purely experimnental It is a theoretical property PUnit of rate constant for the first order eactios
AJ
IAI is a ratio, it has no unit
is
ean integer, zero It is always an integer
Lor afraction.
l tmay change with Tit doesn t change with Hence, the units of k will be time ie. s, min
espernimental conditions lexperimental conditions. or hour
 49
ChemicalKinetics
HALF-LIFE AND RATE CONSTANT OF
THE FIRST ORDER REACTION (t,n):
The half life of a reaction is defined as the time
required for a reactant concentration to become half
of its initial value or concentration.
2.303 (Alo log 1o.Alo
Ao
k
t
Initial concentration,loß10|Al, A
A, Concentration after timet.

Ahen t 2 (A, Concentration

2.303 [Alo (3Y Agraph of log,olA), versus tyilds astraight line, with
thy2 -1oB10 JAJo/2 -k
slope a03 and and y- axis intercept as log,o [AJo:

2.3031og10
2.303 x 0.3010

ty2 log 1oAl,

0.693
/2
0.693
Time t
k
The above equation indicates that half life of the 2.303 [Alo
frst order reaction is independent of initial reactant t
concentration.
kt
GRAPHICAL REPRESENTATION OF 2.303 - logo [AJo - log,o [Al,
FIRST ORDER REACTION: k
The differential rate law for the first order reaction, 1og,o [A), = 2.303 + log,o [AJo
= mx
d[A]
Rate = = k-(A], +0
dt ZERO-ORDER REACTION:
Rate = k-{AJ, (y= mx+ c) The reactions whose rate is independent of the
When the rate of reaction is plotted against reactant concentration and remains constant
concentration A, astraight line is obtained. throughout the reaction is called zero order reaction.
Slope of the line gives the value ofk Examples:
(1) Decomposition of NH M on hot platinum surface
under high pressure.
1103 K
2NHale N2e
Pt. catalyst
(ii) Decomposition of PHae on hot tungsten at high
pressure.
(iüi) Decomposition of N,O to N, and O, on platinum
catalyst.
2N,O2Nag)+ Ozjg
Initial Concentration Note: All catalytic reactions are generally zero order
reaction.
2.303 IAlo
k
kt
t 1oB10[Alk Differentialrate law of zero order reaction:
Consider a general reaction
2.303 A- +product
kt d[A]
- log,o [Alo - log,o [Al, Rate = k(A10 = k
i.2.303 k Rate= k
dt

:. logso [A), = 2.303 t +log,o lAlo Jntegrated rate law for zero order reaction:
mx + C Consider a general reaction
A - > product
The graph of log,oA(Al versus t yields a straight line d[A)
Rate= dt -k(AJ0= k
with slope- a03and y-axis intercept as log,o [Alo:
 UTTAM's Xl Chemistry Papera Sol,
50 Rate k(CH,COOCH,J|H,O)
On rearranging yhe equation. concentration of H,0, is Large excess,
chanec in itcODCentration
concentraton.gigibHence
lyStDa
1A-kdt
its initial
prtgrating the above equation between limits Comparcd to
remainscanstant.
A-JAL at tO and JA|A at t- t, we get constant k
Aate iCH,COOCH,]
-kját k(CH,COOCHJ
A Aaus, reaction is of first order.
vdroysis of cane sugar is
LHydr pseudo- first Gtty
- ktt) eaction,
RpH,Oyent H,Ofexcess) C,H,,O, C,H,0
lglucose) (fructose
6.6 COLLISION THEORY OF BIMOLECULAR
Jkt AL-A
REACTIONS
taits of kt i Collisions between reactant molecules: Dae
al dmP tt (sec, min or hour) a chemical reactiohrefore, t mav h Teact
REACTION:
molecuies tue etion is equal to theApecte
HALE LIPE OF ZERO ORDER collisions between the molecules. However, it k
been found that rate of reaction is much lowerth
JAJ-(AL the rate of collisions
It follows therefore, all the collisions between
[AJ reactant molecule do not result in the formatine
2 product.
IA- (Al,/2 Aetvt energy: Ithyis the
the minimum energy
reactantmocenes
haYe colisions between them.
A, Note:Areaction can only occur if the kinetic ene
of reactant molecules is equal to or greater than t
activation energy.
(S) Orientation of reactant molecules t In reactions
Thus, hai He ofzero order reaction is proportional o involving complex to occur. ion
to the initin concenimtipn ofreacnnt eaction to
boting suficient energy. the colliding molecules
Graphical representation: must have proper orientations
Consider the reaction
AB A,B AB, tA
No ractie

Tme
IA, - - kt Alg Raactaats Colinlom
ResctantsColiaR aprope
plot of [A), versus tis astraight line.
SThe 3tope o tie linc is- k and its intercept on (iv) Potential energy barrier:
y-aXIS 1s AJ During a chemical reaction,
The a of zero order reaction is directiy molecules react to form
proportional to [Alo an tntermediate or

7PSEUDO-FIRST ORDER REACTIONS: an activated comnlex

Arcaction which in.cxpected to follow higher order The energy provided is
true rate Iaw. but follows first order kinctics are
GRUcp8cudoiratorderrcaction. kinetic energy which is
converted to potential energy
YConsider the hydrolysis of methyl acetate. Due to high energy activated cornplex is highy
unstable and decomposed to product
CH,CO0CHH,On To forman activated complex, the reactant molecul
dl HCL CH,COOHCH,OH must climb the energy barrier (refer above igue
 51
Chemical Kinetics
only those molecules havina ht anetic With its intercept being
Thulliding with proper result in Jaj The slope of line is-
formation of a product ToRnA
temperaure,
R7 TEMPERATURE DEPENDENCE OP REACTION 1 scen that with an increase in
RATES the rate of reaction increases
ARRHENIUS EQUATION GRAPHICAL REPRESENTATION OF
Arrhenius suggested that the rate of reaction varies EPPECT OF TEMPERATURE
increases witn
with temperature as The kinetic energy of molecules of molecules
Ae-k/RT temperature. As a result, the fraction
possessing minimum energy BA inCrcascs_W
InA-PT temperature The fraction of molect
n increase
nettc energy B also increases
ogoklogA 2.303 RT
wherc,
A Rate constant at absolute temperature
VE Energy of activation
Molar gas constant
Frequency factor or pre-exponential factor
I Temperature in Kelvin.
DETERMINATION OF ACTIVATION ENERGY:
For two temperatures T and Ta

Aogo k lo8oA 2.303 RT,

ERT,.
Sogoky - logA- 2.303
ubtogoadann
bth
Kinetic energy
of fraction of molecules
at T, and T,
activatea
6.8 EFFECT OF CATAYLST ON THE RATE OF
E. E,
Loerok, - lo%,ok 2303 RT,*2303RT REACTION
A catalyst is a substance. Whcn d to the
E h e l e e stne rate of reaction
JoBo ky -log,ok, 2.303 RT,2.303 RT,
It enters the reaction but doesn't appear in the
balanced equation.
It provides an alternative path (mechanism) for
the reaction to take place having lwer activation
energy.
The potential energy barriers for catalyzed reaction
GRAPHICAL DETERMINATION OF is much lower than that of uncatalyzed reaction.
ACTIVATION ENERGY:

In the presence
DTt InA of catalyst
Belore use
E, 1
2.303 RT logA of catalyst
Fraction of
xc molecules

L The plot of log ok verses isa straight line.

Comparison of fraction of molecules for catalyzed
uncatalyzed reactions
According to Arrhenius equation,
kAe-R/ RT
At constant Tand for the same concentration
E/RT -E/RT -ela/KT k
decreases decreases increasee inereases increascs

5cET