Chapter 4

Chemical Kinetics
tnal chffnicol ~ the three important factors to be determined are feasibility of reaction, extent of reaction
ond spttd of R'OC'OOn..
Chemical ltiMtics is the study of rates of chemical reactions with the elucidation of the mechanisms by which they
pnx:ttd On the m.sis of rates of reactions, chemical reactions are of three type :
(1) lnstllaueous or Ve,y Fast Reactions: Ionic reactions come under this category.
(2)-, Slow Reactions : Such reactions are completed in few days and months, e.g., rusting of iron.
(3) lilodetall: Reactions : Such reactions have moderate speeds. Rate of such reactions are determined by comroori
laboratory methods. 41~ hydrolysis of esters, decomposition of H2 0 2 etc.

R:i~ ~• a Chemical Reaction

lb.te of a reaction can be defined as the change in concentration of any one of the reactants or products per unit ~
~a~~ reaction :
R----+ p
in •ilich one molie of the reactant · R' produces one mole of·P. Thus,
Rate of reaction = Decrease in concentration of R =Increase in concentration of P
Tune taken Tune taken
If (R1 ) and. (PJ are the initial concentr2tions of R and P respectively at time t 1 and (R:z] and (P:z] are their respec:tm
wOC.d!ll.tion:s at time t2- tt»en ~ = =: - l1, (R] = [Rzl - [Rll and ~Pj =[Pz] - [PJ

Rate o.f!!"e.2COOo = -~(R] = -~[P]

~ .1t

~ ~ b.ot..i.&:s ~ m e ~ a.re ~ concentrations.. The n::ga:twe ~ in thf: cxmcem:r.;:oon oo rei('l!a:Ff,

~ me cia:rese oi m:::ca::_ =.tiuJ af re2-02Dc:s ;,im time. T.:iis rate ~ a!so caI!:ed me zc.~ rn.e of ; r ~
~ ~'"'1:i=;,\e :

~ {_g) --+ ~ (B) - Clz(2)

R.:le oire.aOlion = - ~) = - ~ J= - ~Ozj

~ .l: ..l.!

A,c..--a-_ge .::;,_a~e a.nc i..n.st2!1.::a..··,eocs R.a:e

\ \ ~ ~ ~ ei ll"Pal'tfc:;n iis o 'i/, ·la a:il oc c\:£5 c..:.::::erl ful.7- .a ca ,~·--, ,~ o f ~ ,.-tm m l " ~ !.."l ~~ d
re-1SiCCS or- ~ i s ~ as~ a.eag,:: ,-...:: oi reaafm. h ~ be- a<=?c:SE'Si":ed as
- ~RJ
rL"' = .l.:
- .l.{Pj
--=--
~
Chemical Kinetics 93

-( A1:]) =-d[R] and (A[P]) =d[PJ

M ➔o dt M .1t ➔ 0 dt

Thus, 'inst = - d[R] = +d[P]

dt dt
Graphically, the two rates ofreaction can be represented In the following Fig. 4.1.

i [R]o
tilP)
final .. _::!:...l • slope

J!l
C
i
~::,
di

~ (R1J T'
~ 6[R) ~
c.. [P2) ·•···•······•
o [R:zl -·*··· - -··· 0
5 - d[R) j P)
-.:, .--.......-- r1nst =-d-- = - slope
1 _g (P1) ·
_g
C C

8 ~
C

8 8
nme- nme-
(a) (b)

Fig. 4.1. Instantaneous and average rate of a reaction

Dependence of Relative Rates of Reaction on Coefficients in the Reaction

of
For reactions in which the stoichiometr ic coefficients of the reactants and products are same as in the decompositi on
thionyl chloride (S0 2 Cl 2), the rate of disappearan ce of any of the reactants is same as the rate of appearance of the products.
SOzClz (g) ----+ SOz (g) + Clz (g)

Rate ofreaction = A[SOzClz] = A[SOz) = A[Clz]

M M M

But in certain reactions, the stoichiometr ic coefficients of the reactants and products are not the same. For example :
2N 20 5 (g) ----+ 4N02 (g) + 0 2 (g)
by
For expressing such reactions, the rate of appearance of any reactant or rate of formation of any product is divided
their respective stoichiomet ric coefficients.
1 A[N 20 5) 1 A[N02 ] A(02)
Rate of reaction = ---=-"'""" =+ -----'=-- =- -
2 M 4 M M

Factors Influencin g Rates of Chemical Reactions

1. Nature of the Reactants
A chemical reaction involves the rearrangeme nt of atoms between the reacting molecules to form products. Different
in
reactants require different energies to undergo collision to form products. Hence, the rate of reaction is different
different types of reactants.
2. Concentra tion of the Reactants
Concentratio n of the reactants is directly proportional to the rate of reaction.
3. Temperatu re
an
In most cases, the rate of a reaction in a homogeneou s reaction mixture is approximate ly doubled or even tripled by
increase of temperature of 10°C. It means the rate ofreaction is temperature dependent.

4. Surface Area of the Reactants

Finely divided reactants because of their larger surface area react more rapidly than larger specimens of the same
substance.
.
5. Catalysts
VATSAL ISC Handbook of Chemistry Xn

Many reactions are accelerated in the presence of small amount of substance known as catalysts and their action is
specific for a particular reaction.
6. Radiations
Photochemical reactions are affected in the presence of ultraviolet light. For example,
H2(B) + Cl2(g)---. 2HCI (g)

Dependence of Reaction Rate on Concentration (Law of Mass Action)

According to this law, "At a given temperature, the rate of a chemical reaction is directly proportional to the product of
the mola r conce ntrations of the reactants with each term raised to the power equal to its stoichiometric coefficient as ,
represented by the balanced chemical equation". Here the molar concentration of the reactant is also called active mass.
Suppose in the following reaction,
aA + bB---. cC + dD
Rate (r) ex. [AJ 0 [B]b = k [A]° [B]b
where k is the rate constant.
The above rate expression is according to law of mass action. This expression is based upon theoretical fact and is written
for complete balanced equ ation which includes all the steps together. i
Rate Law Expression
It tells about the actual dependence of the rate of reaction on the concentrations of various reacting species. It is based
upon the experimental fact and is always written for the slowest step or rate determining step in the mechanism of a
I
reaction. For example :
1. 2N 20 5 (g ) ---+ 4N02 (g) + 0 2 (g)
Rate expression according to law of mass action,

Mechanism of the Reaction

Slow
~

Fast
N20 5 + N03 ~ 3N02 + 02

r=k[N2 0 5] 1 (For slow step)

The above expression is rate law expression or rate equation.
2. 2N0 2(g) + F2 (g) ---+ 2N02F(g)

Rate expression according to the Jaw of mass action,

2
r = k[N02] [F 2]
Mechanism of the Reaction
N02

N02
+ F2

+ F
~
~ N02 F
N02F + F
I
l
1
r = k [N0 2] [F2] 1 (For slow step)
The above expression is rate law expression or rate equation.

Order of a Reaction I
The orde:, of a reaction is ~efined as, "The sum of the powers to which the concentration terms are raised in the rate laW /I
equation . Order of a reaction cannot exceed three. It can be negative fracf I
Thus, for a reaction, ' tona or zero. /
aA + bB+ cC~ Products
The rate law may be given as
dx
Rate = - - = k[A]P[Bf [Ct
dt
 95
Chemical Kinetics
Then order of reaction is ( n) = p + q + r
where p, q and rare the orders with respect to individual reactants.

Examples of Different Orders

(a) zero Order
2NH 3 Platinum)
1130K
0
r= k (NH 3 ]

(b) First Order

NH 4 N02 ~ N2 + 2H 20
r = k (NH 4 N0 2J1
(c) Second Order
2N02 ~ 2NO + 02
2
r = k [N0 2]

Units of Reaction Rate Constants

In general, the units for the rate <::onstant for the reaction of nth order are :
Rate= k [At

molL- l =k(molL- 1 t or, k = (molL- 1 )1- ntime- 1

time
-1 -]
For zero order; k = moI L time
1
For first order; k = time -
1
For second order; k = L mol- time- l
1
For gaseous phase reactions, mol L- is replaced by atm or bar.

Elementary and Complex Reactions

Reactions which take place in one step are called elementary reactions. For such reactions order of reaction is equal to its
molecularity represented by balanced chemical equation.
For example: H2 + 1 2 --➔ 2HI is an elementary reaction and order of reaction is 1 + 1 = 2.
· Reactions which take place in two or more steps are called complex reactions. Each step of a complex reaction is an
elementary reaction and the slowest elementary step is the rate determining step. Complex reactions cannot be identified
just by looking at the balanced chemical equation.
For example :
(i) H2 + Br2 ~ 2HBr
(ii) SBr- + Br03+ 64H+--➔ 3Br 2 + 3H20
Many complex reactions involve side and reverse reactions.

First Order Reactions

A reaction is said to be first order; if its reaction rate is determined by the variation of one co ncentration term only.

Integrated Rate Expression for First Order Reactions

For First Order Kinetics
A --➔ Product
Initially a 0
After time 't' (a-x) ,Y

dx
- cx: (a-x)
dt
dx
- = k(a - x)
dt
 VATSAL LSC Handbook of Chem.- y );l
~ "ulhl WMtant.. lntegnnnc above equation.~ art'
I~
fo- .r)
:a Jtdc
t
Rate
- ln(a - t}= kr ~ I
Whtf"t I lJ tht l f t ~lt<,n comun t
AU • 0 . .t • O
l'W dof t.
- In (o - t) 1, kt - In a
0
lcr .. ,n -
(o x)
I o 2.30 3 a
k • - ln- - or k = - -lo a-
r (a - x) t (a - .r)
If (Alo 1, the Initi al con cent rllll on and
the con ccnt r.itlo n ;,ftt r Umc 'c' l!I IAI. The abo ve equ atio n bec ome s
10R l1i
L 2.303
11 • -
C IA)
Vnlt of Ir IJ Uml' _, for Ont ordl'r reaction
.
lnt ~gr ite d Rat e Equation for First Ord
er Gas Phase Reactio n
Comidff ~ general ftrst ps pha se reac
tion :
A(g) _ . B(g ) + C(g )
P0 atm 0 0
~~ da ws ·r (Po - PJ P.1tm Pnm
Total pressure of the reac tion mix ture afte
r time r.
Pr :a (Po - P) + P + P = P0 + P atm
P= Pr - Po
Prft'SUff ol A after time r. (P,4) = P
0 - P= Po - (Pr - Po) = 2Po - P,
Subldnmn.a these valu es In the first orde . 2.303 [Ak)
r rate equ atlo n. k = - - log - . we get
C [A)
2.30 3 Po
k = - - 1og -- -
1 ZP0 - P,
Hall-Lile (r11 ) for First Order React ion
H.aJHIJe pcn od nuy ~ deflnNI u
the time requ ired for half of the Initi
rex unL Whffl r • o/2 and r • r rz•then
1
al amo unt to 1 .....__ _ A_rst.:.......;.01_rde_ ·l_ _
2.303 1112
- 1os-0 • -0,69-3
L
.. - -
r, 11 af2 cl/?
It • 0 .693
,,,z
fl ~ \Ml IMllf•II~ pl'ti od of ftrs1 orde r rt
acti on Is Inde pen den t of con cen trati
on term . Fig ·U P ,:-• I, '" .:JS rM
{ ~ I A> )- - - - - - -- - - -- - - -- C.J ne ~(/ , •. afff ' ¢Jr

- - -__,:!.=::
'Md._-_ ~
TM ._.. .... (f 111> ol I rnc: tion ~
on u~ lnlttaJ ex>nanmtkln of the reac tant (A)
tMordiffafr'NCtion 0 in the totlowing ~ whe re 'r,' 11

l
f1,i ~ - -
(Ai: - l

J
Chemical Kinetics 97
Evaluation of k of First Order Reaction
1. First Method
For different time-interval if the value of (a - x) and the initial concentration of reactant is known, the value of k can be
calculated and if the value of kin each case comes out to be constant, the reaction is said to be of first order.
2. second (Graphical) Method
_
kt
2 303
=loga-log(a-x) f
>< f k
I log a slope = 2.303
-kt (U a-x
log(a-x)=--+log a
2.303 j

3. Third Method
·-
(a) ·-
(b)

Fig. 4.4. Graphical melhod for the determination of k for first order reaction

When the-initial concentration of the reactants is not known, k can be calculated as follows :
2.303 a
t1 =-k- 1og ) ...(i)
(a-x 1
2.303 a
t2 = - - l o g - - - ... (ii)
k (a-x2 )
2.303
(t2 -tiJ=-k-[log(a-x1 )-log(a-x2)]

2.303 (a-xi)
( t 2 -t1 ) = - - 1og-~~
k (a-x2 )
Pseudo First Order Reactions : Those reactions which appear to be of second order but are actually of first order reaction
under certain conditions are termed as pseudo uni molecular or pseudo first order reactions, e.g., Hydrolysis of ester.
CH 3COOC2H5 + H20 ~ CH 3COOH + C2H5 0H
excess

r = k' [CH 3COOC 2H5] [H 20]

The concentration of water does not change much during the reaction and term [H 20J can be taken as constant. The
equation may be written as

wherek=k' [H 20J
In hydrolysis of ester, rate of reaction is affected only by changing the concentration of ester, not by changing the
concentration of water because it is taken in large excess.
Note
Those .reactions which occur in single step, they have rate expression according to law of mass action similar to rate law
expression.
Complex reactions are completed in various steps but all the steps are individually known as elementary reactions .

.Rate law equation for reactions involving parallel reactions:

In general,

kz : B (Main reaction)
A------1
,.....________ C (Side reaction)
98 VATIAL ISC Handliook of Chemistry Xi
Rate = - d IAI = kJIAI + k;ilA] -= (k + k2)IAI
dt 1

k1
Percenta ge yield of B ";. - -- and percentag e yield of C = - ki
kl ·I k2 ,, l 1 1<2

Determination of Order of Reaction by Various Methods

1. Integration Method
For Zero Order Reactions
(A] =- kt+(A]o
For First Order Reactions
k = Z.303 10g _ a_
t (a - x)
For Second Order Reactions

k=tl { (A]l - [Alo

1 }

2. Graphical Method

t
Cl>
t
Q)
~
t
iii iii ro
a:: er::: a::

[A] - - 1 2
[A] -- [A) --
Zero order First order Second order
Fig. 4.5. Differential rate law method for testing the order ot a reaction graphically

3. Initial Rate Method

ft is used to find the order of a reaction with respect to one reactant at a time. The total order
of the reaction is then equal
to the sum of the orders of reaction for individual reactants expression which tells us about
Lhe actual dependence of rate
of reaction on molar concentr ations of each reactant.

Molecularity of a Reaction
ft may be defined as the total number of reactant molecules which take part in a particula
r step or in rate determining
step of a chemical reaction.
Table. 4.1 Dllfcrenccs between order and molecularlty of reactions

S.No. Order Molecularity

t. Order is the sum of exponents in the rate law equation. Molecularity is the total number of molecules of reactant.I
taking part In a particular step of reaction.
z. Order of reaction may have fractional values or it may be There is always a whole number
other than zero.
zero.
3. For complex reaction, the overall rate of the reaction depends There is no significance of overall
molecularity for a compleJ
on the slowest step and the overall order is also determined reaction. It is expressed for each
elementary step.
by the slowest step.
4. Order of reaction is determined experimentally. Molecularity is determined theoretically.
S. Order of a reaction can change with change in temperature, Molecularity of a reaction in invariable
.
pressure, etc.
Chemical Kinetics 99
Temperature Depende nce of the Rate of a Reaction
Most of the chemical reactions are accelerated by increase in temperature. For example, potassium permanganate
is decolourised faster at a higher temperature than that a lower temperature. For a chemical reaction with rise in
temperature by 10°, the rate constant is almost doubled.

Temperature coefficient(µ) "7 Rate of constant at (T+lO)°C

Rate constant at T°C

According to the collision theory of chemical reactions, the rate of reaction depends upon collision frequency (z) i.e.,
the number of collisions taking place per second per unit volume of the reaction mixture and the fraction of effective
collisions(/) i.e., the molecules which after collision actually produce the products. Effective collisions take place only in
those molecules which 'have threshold energy and proper orientation.
Increase in rate of reaction with temperature is brought out by either of two or a combination of both factors discussed
below :
(i) Increase in Collision Frequency: Every 10° rise in temperature increases the kinetic energy by 3% only.
(ii) Effective Collisions : From the figure it is clear that the fraction of molecules capable of effective collision gets doubled
on 10° rise in temperature. So that rate of reaction gets doubled.

t
<I)
Q)
t
<I)
Q)
Energy of
activation
a
Q)
a
Q)
This area
shows
0 0
E E fraction of
'i5 'i5 additional
C: C:
0
molecules
0
n n which react
ti! ti! at (t + 10)
u. Most probable kinetic energy LL

Kinetic energy - Kinetic energy -

Fig. 4 .6. Distribution curve showing energies among Fig. 4.7. Distribution curve showing temperature dependence
gaseous molecules of rate of a reaction

Concept of Activation Energy and Transition State Theory

We know that all the chemical reactions do not take place at room Activated complex
temperature. Some extra energy has to be supplied to the reactions (A....B ....B)

to bring their energy equal to the threshold energy to carry out the
reaction. This excess energy which must be supplied to the reactants to
Energy barrier
undergo chemical reactions is called activation energy (Ea). (activation energy)
Activation energy (E0 ) = Threshold energy
- Average kinetic energy of the reacting molecules Energy of the
or E, A; B~-(E~)-- -------;- reaction
~H

Fast reactions have low activation energies whereas slow reactions Ep --- - - -- - - - -- ----- - t_ ---------
AB+ B (Ep)
have high activation energies.
Progress of reaction -
Activated complex or transition state is an intermediate complex which
Fig. 4.8. Progress of a reaction
is highly unstable due to high energy.
· For a reversible reaction, the activation energies are different for forward and backward reactions. These have been
represented below for exothermic and endothermic reactions.
 VATSAL ISC Handbook ofChell'listry ~
Exothermic reaction Endothermic reaction
t.H • - ve
---------------- f -
t.H = + ve

1 ----------------1-·
t Ea (forward)
I ---!~-------
! H --- _l -----t-- •• l""kw•HIJ
H,
_________l _______, __
, t.H

- . t -------- -·
Hp

Progress of reaction - Progress of reaction - - +

(a) (b)
Fig. 4.9. Acllvation energies for the forward and backward reactions in case of
(a) exothermic and (b) endothermic reactions

~rrhenius Equation
Arrhenius equation proposes a quantitative relationship between the rate constant and temperatu re as
k = Ae- Ea/RT
where k is the rate constant, 'A' is the Arrhenius or frequency or pre exponential factor. Ea is the activation
energy. Ris gas
constant (11\ 1 mol- 1) and temperatu re is in kelvin. The value of A does not depend upon the temperatu
re and catalyst
The two quantities 'A' and Ea are collectively called "Arrhenius parameters". The factor e-Ea/RT gives
the fraction ol
molecules having energy equal to or greater than the activation energy and it is called Boltzmann factor.
lnk=lnAEa --
RT
E0
logic= logA-
2.303RT
For two different reactions :
logk1 = log A-
Ea
2.303RT1 ...(i
E
logk2 =logA - a
2.303RT2
Subtracting equation (i) from equation (ii), we get

(logkz - logki)=(lo gA - Ea )-(togA - Ea )

2.303RT2 2.303RT1
kz Ea (
log k = 2.303R T - T
1
1 1)
1 2
From this given equation; Ea can be calculated.

Calculation of Activation Energy by Graphical Method

logk =
- Ea
+ log A
2.303RT
From the slope of the graph, Ea can be calculated. logk
t
Effect of Catalyst on Reaction Rates I
The substances which affect the rate of reaction and can be recovered ch~mically ur-
unchanged in mass and composition after the reaction are called catalysts. It provides
. . . tll
an entirely new path for the reaction in which the reactants are converted into products Fig. 4·1°· Determinatio
n of actJVoda
quickly. It d oes no t s h'ft
I
th e pos1·ti·on o f equ1·1·b ·
1 num. They are h'1ghly specific in nature energy by graphical meth
 Chemical Kinetics 10'
and does not change M (or Ml) and l:!.G (Gibbs energy) of the reaction.
Without catalyst

_l_________ ---------- ------ ~=~:~,...,

E8 (f) = for forward reaction
ei lE'.(f) / \ E.(b) E8 (b) = for backward reaction
~ / \ E8 = for uncatalysed reaction
w
- - (/--- ··••
~

Reactants With catalyst -.,,••••• E'• = for catalysed reaction

Products

Progress of reaction -
Fig. 4 .11 . Progress of an uncatalysed and catalysed reaction. Addition of a catalyst
provides a path of lower activation energy (shown dotted)

Effect of Catalyst on Activation Energy

(i) Let the rate constant of reaction in the absence and presence of catalyst be k and k2 respectively. As the catalyst
1
lowers the activation energy, therefore, E1 > E2 and k2 > k 1 at constant temperature (T). So that

logkz = E1 -Ez or, logkz = M

k1 2.303RT k1 2.303RT
(ii) Let Ea be the activation energy of a reaction at higher temperature T1 and E~ be the decrease in the activation energy
barrier after adding catalyst at lower temperature T2 . Then,
Ea = Ea - E~
T1 T2

T1 and T2 should be in kelvin.

Additional Informations
Rate Law Equation for Reversible Reaction
k1
For example : H2(B) + I 2 (g) ~ 2Hl(g)

Rate of reaction = .! d [HI] = k 1 [H 2][1 2 ] - k2 [HI] 2

2 dt
:. Rate of formation of HI,
d [Hij = 2k1 [H2][12J- 2kz[H1]2
dt
Dependence of Rate on the Species other than Reactants
For example : CH3COCH 21 + HI
d[l ]
Rate = - - 2- = k [CH 3 COCH 3 ][H + ]
dt
Negative Order w .r.t . Reactant/Produc t
For example : . 203 ---+ 302
Mechanism : (i) 03 ~ 02 + 0 (fast)

l_
 VATSAL ISC Handb ook of Chemistry XII
102
(ii) 0 + 03 ~ 202 (slow)

For s low step : Rate= k [O3J [OJ

From mecha nism (i),

kequ = [Oz J [~J or [OJ= kequ [03 J / [Oz J

[03

Hence,

The order w.r.t. 0 2 is - 1.

IQUESTIONS
A. Fill in the Blank s (1 mark )
while the . ........ increas es with both increase
1. The race constan t of a reaction .. ... ... . only with increase in temper ature (1997)
in temper ature and increase in concen tration of reactan ts.
2. A catalyst .. ....... the accivatio·n energy of the reacting molecules.
...... ... .
3. The inversion of cane sugar is a .. .. ..... reaction though its molecularity is
collisions, so that the produc ts are formed is
4. The minimum energy that the reactan t molecules must possess before
known as ........ .
5. The hydrolysis of ethyl acetate in .. .... ... medium is .... .... . order reactio n.
temper atures differin g by ...... .. ..
6. The temper ature coefficient of a reaction is the ratio of the rate constan ts at
.. . . . .. .. the efficiency of catalyst.
7. A catalytic promot er . . ... .. .. the efficiency of a catalys t wherea s a catalytic poison
tration of reactan ts is expres sed in the form
8. The experimentally observ ed depend ence of the reaction rate on the concen
of .. ... ... ..
9. The unit of race constan t for a first order reaction is .... ... . . .
n is .. . .. ... ..
10. The slope of the line obtaine d on plotting log 10 IAI vs t for a first order reactio
of the reactan t. (2008, 13)
11 . The half-life period of a ............ order reaction is ........... of the concen tration
. (20111
12. For a first reaction, the unit of rate is ............. and that of rate consta nt is ...........
becom es ............. times but for ............. order
13. When the concen tration of a reactan t of first order is double d, the rate (2016, 19)
reaction, the rate remains same.
Answers
I. increases, rate 2. lowers 3. first order, two
4. thresho ld energy s.acidic, first 6. 100 7. increas es, decrea ses
8. rille law 1
9. time- 10. -k/2.3 03 11. first, indepe ndent
1
12. moI L- I s - I , s - 13. two, zero

f ·Multiple Choice Questions (1 mark) I

1. Diazoniurn salt decomp oses as
C6HsN{ c1 - ~ C6H5 ct + N2
I
• .. ~I
At O' C. the evoluti on of N become s tw t'Imes c:,aster w h en the m1t1 al concen tration of the salt is double d. Therefore I
is : 2 o

(a) a first order reaction

I
(b) a second order reactio n
(c) indepe ndent of the initial concen tration of salt (d) a zero order reactio n !
1f111
In a reactio n A ➔ B. the rate of reactio n increas es two . . . ·
2. times on mcreas mg the co'ncen tration of reactan ts four times. 1
order of reaction is : I
i
(a) 0 (b) 2 (c) 1/2 (d ) 4