CHEMICAL KINETICS

CHEMICAL KINETICS

INTRODUCTION 1.2 Instantaneous rate

Chemical Kinetics Rate of change of concentration of any one of the reactants

(Kinesis : Movement) or products at that particular instant of time is called
The branch of chemistry which deals with the study of the instantaneous rate.
rates of chemical reactions, the factors affecting the rates d [R] d [P]
of the reactions and the mechanism by which the reactions As 't o 0 or rinst
dt dt
proceed is called Chemical Kinetics.
Classification of reactions IMPORTANT :

On the basis of rates : Rate of a reaction is always positive.

x Very fast reactions Since, ' [R] is a negative quantity (as concentration of
reactants is decreasing), it is multiplied with –1 to make
e.g. precipitation of AgCl
the rate of the reaction a positive quantity.
x Very slow reactions
1.3 Units of rate of a reaction
e.g. rusting of iron
x Reactions taking place at moderate speeds Units of rate are concentration time–1

e.g. hydrolysis of starch e.g. mol L–1s–1; atm s–1 (for gaseous reactions)

1.4 Overall rate of a reaction

1. RATE OF A CHEMICAL REACTION
The rate of a reaction can be defined as the change in
concentration of a reactant or a product in unit time.
1.1 Average rate
The rate of reaction measured over a definite time interval
is called average rate of a reaction.
Consider a hypothetical reaction,
R P
Average rate of reaction = (Decrease in concentration of R)
/ (Time taken)
When there are several reactants and products the
individual rates of the various components may differ as
they would depend on the stoichiometric coefficients.
For a reaction,
A + 2B 3C + 4D
Rate of disappearance of B = 2 × Rate of disappearance of
A (2:1)
Rate of formation of C = 3 × Rate of disappearance of A
(3:1)
Rate of formation of D = 4 × Rate of disappearance of A
(4:1)

= ['R] / 't To define a unique value for the overall rate of the reaction
we divide the individual rates by the respective coefficients
Or = (Increase in concentration of P) / (Time taken)
and equate their signs.
[ 'P] / 't Overall Rate = – 'A / 't = (–1/2) 'B / 't = (+1/3) 'C / 't
= (+1/4) 'D / 't
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Remember!!! 2.2 Order of a Reaction

aA + bB cC + dD
aA + bB cC + dD
Overall Rate = (–1/a) 'A / 't = (–1/b) 'B / 't
Rate = k [A]x [B]y
= (+1/c) 'C / 't = (+1/d) 'D / 't
Sum of these exponents, i.e., x + y gives the overall order of
Instantaneous Rate = (–1/a)dA/dt = (–1/b) dB/dt a reaction where x and y represent the order with respect to
the reactants A and B respectively.
= (+1/c) dC/dt = (+1/d) dD/dt
Hence, the sum of powers of the concentration of the
2. DEPENDENCE OF RATE ON CONCENTRATION reactants in the rate law expression is called the order of
that chemical reaction.
Factors Influencing Rate of a Reaction Order of a reaction can be 0, 1, 2, 3 and even a fraction.
x concentration of reactants (pressure in case of gases),
2.3 Units of rate constant
x temperature and
x catalyst. Rate = k [A]x [B]y
Dependence on Concentration :
Rate concentration 1
k u
2.1 Rate law [A]x [B]y time (concentration)n

Consider a general reaction

Reaction Order Units of rate constant
aA + bB cC + dD
The rate expression for this reaction is mol L1 1
Zero order reaction 0 u
Rate D [A]x [B]y s (mol L1 )0
where exponents x and y may or may not be equal to the
= mol L–1 s–1
stoichiometric coefficients (a and b) of the reactants.
Rate = k [A]x [B]y mol L1 1
First order reaction 1 u s 1
– d>R@dt = k >$@x >%@y s (mol L1 )1

Above equation is known as differential rate equation,

mol L1 1
k is a proportionality constant called rate constant. Second order reaction 2 u
s (mol L1 )2
Rate law is the expression in which reaction rate is given
in terms of molar concentration of reactants with each = mol–1 L s–1
term raised to some power, which may or may not be same
as the stoichiometric coefficient of the reacting species in
a balanced chemical equation. 3. INTEGRATED RATE EQUATIONS

IMPORTANT 3.1 Zero order reaction

Rate law for any reaction cannot be predicted by merely
looking at the balanced chemical equation, i.e., The rate of the reaction is proportional to zero power of the
theoretically but must be determined experimentally. concentration of reactants.

e.g 2NO(g) + O2(g) o 2NO2 (g) Rate = k [NO]2[O2] Ro P

CHCl3 + Cl2 o CCl4 + HCl Rate = k [CHCl3] [Cl2]1/2 Rate = –>dR@dt = kR0
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k = ([R]0  [R])/t

e.g.

x The decomposition of gaseous ammonia on a hot platinum

surface at high pressure.

1130K
2NH3 (g) 
Pt catalyst
o N2 (g)  3H 2 (g)

Rate = k [NH3]0 = k

x Thermal decomposition of HI on gold surface

3.2 First order

Consider the reaction,
RoP The rate of the reaction is proportional to the first power of
the concentration of the reactant R.
d [R]
Rate =  k [R]0
Rate = – d>R@dt k>R@
dt

d [R]
Rate =  k u1
dt
d [R] = – k dt
Integrating both sides
[R] = – k t + I
where, I is the constant of integration.
At t = 0, the concentration of the reactant R = [R]0, where
[R]0 is initial concentration of the reactant.
Substituting in equation
[R]0 = – k × 0 + I
[R]0 = I
Substituting the value of I in the equation
[R] = –kt + [R]0

Ro P

d [R]
Rate  k [R]
dt

d [R]
or  kdt
[R]

Integrating this equation, we get

In [R] = –kt + I ........ (1)

Again, I is the constant of integration and its value can be

determined easily.
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When t = 0, R = [R]0, where [R]0 is the initial concentration The first order rate equation (3) can also be written in the
of the reactant. form
Therefore, equation can be written as
2.303 [R]0
k log
In [R]0 = – k × 0 + I t [R]
In [R]0 = I
[R]0 kt
Substituting the value of I in equation log
[R] 2.303
In [R] = –kt + ln [R]0 ......... (2)

Rearranging this equation

[R]
ln  kt
[R]0

1 [R]0
or k ln ......... (3)
t [R]

At time t1 from equation (2)

In [R]1 = – kt1 + ln [R]0

At time t2 e.g.

ln [R]2 = – kt2 + ln [R]0 x Hydrogenation of ethane,

where, [R]1 and [R]2 are the concentrations of the reactants C 2 H 4 (g)  H 2 (g) o C 2 H 6 (g)
at time t1 and t2 respectively. Rate = k [C2H4]
Subtracting x Decomposition of N2O5 and N2O
ln [R]1 – ln [R]2 = – kt1 – (–kt2)
3.3 Half-Life of a Reaction
[R]1
ln [R] k (t 2  t1 ) The half-life of a reaction is the time in which the
2
concentration of a reactant is reduced to one half of its
1 [R]1 initial concentration.
k= ln
(t 2 - t1 ) [R]2 Represented as : t1/2.
Comparing equation (2) with y = mx + c, if we plot In [R] x For a zero order reaction, rate constant is given by equation.
against t, we get a straight line with slope = –k and intercept
[R]0  [R]
equal to ln [R]0 k
t

1
At t = t1/2, [R] = [R]0
2
The rate constant at t1/2 becomes

[R]0  1/ 2 [R]0
k
t1/ 2

[R]0
t1/ 2
2k
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x For the first order reaction,

3.5 Practical Analysis of First Order Reactions
2.303 [R]0
k log Case - 1 : In gaseous phase reactions we prefer to measure
t [R]
the pressure of the gases or volume. For example the
at t1/2 following reactions :

[R]0 x For a first order gas phase reaction of the type :

[R]
2 A(g) B(g) + C(g)
So, the above equation becomes
Let pi be the initial pressure of A and pt the total pressure at
time ‘t’.
2.303 [R]0
k log
t1/ 2 [R]/ 2 Integrated rate equation for such a reaction can be derived
as :
2.303
or t1/ 2 log 2 Total pressure pt = pA + pB + pC (pressure units) pA, pB and
k
pC are the partial pressures of A, B and C, respectively.
2.303
t1/ 2 u 0.301 If x atm be the decrease in pressure of A at time t and one
k
mole each of B and C is being formed, the increase in
pressure of B and C will also be x atm each.
0.693
t1/ 2
k
A(g) o B(g)  C(g)
At t 0 pi atm 0 atm 0 atm
3.4 Pseudo First Order Reactions
At time t (pi  x) atm x atm x atm

Reactions which are not truly of the first order but under
where, pi is the initial pressure at time t = 0.
certain conditions become reactions of the first order.
pt = (pi – x) + x + x = pi + x
e.g.
x = (pt – pi)
H
CH 3COOC2 H 5  H 2O o CH 3COOH  C2 H 5OH
pA = pi – x = pi – (pt – pi)
Rate = k [CH3COOC2H5] [H2O] = 2pi – pt
The concentration of water does not get altered much during
the course of the reaction. So, in the rate equation the term
§ 2.303 · § pi ·
[H2O] can be taken as constant. k ¨ ¸ ¨ log ¸
© t ¹ © pA ¹
Rate = k c [CH3COOC2H5]

where k c = k [H2O] 2.303

log
pi
t (2pi  p t )
H 
C12 H 22O11  H 2O  
o C6 H12 O6  C6 H12O6
Cane Sugar Glu cose Fructose
x For a first order gas phase reaction of the type :
Rate = k [C12H22O11]
A(s) o B(s)  C(g)
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The data given to us is:

analysis the expression would have been same for the
Time Pressure of gas C/Total Pressure following reactions as well as the constants will cancel out.

0 0 A(s) o B(s) + 2C(g)

t Pt
A(s) o 2B(g) + C(g) (if total pressure is given)
f Pf
And the results will be same if the similar data is given in
If we have to find the expression for k or verify that its a terms of volume.
first order reaction then we will use the expression for k:
Case 2 : If one of reactants is titrated with a red/ox reagent:

a Suppose we have a reaction of the type:

ln kt
ax
AoB+C
But we don’t know the values for a or a – x but we can find
the above ratio by relating the given data with concentration And suppose we detect the amount of A left by titrating it
values. with some reagent and volume of that reagent reacting with
the left over A is given at different time intervals:
For gases, P v number of moles
Time Volume of the reagent
A(s) o B(s) + C(g)
0 V0
t=0 a 0 0
t Vt
t=t a–x x x
Now the volume of the reagent will be proportional to the
t= f 0 a a moles of A present. Therefore:

Now we can write: V0 v a

Pt v x Vt v a – x

Pf v a We can evaluate k:

kt = ln (V0/Vt)
Pf – Pt v a – x
If the same reagent reacts with all the reactants and
a/(a –x) = Pf /( Pf – Pt) products:

V0 v a
Now we can substitute this into the expression for k.
Vt v a + x
k = (1/t) ln [ Pf /( Pf – Pt)]
2V0 – Vt v a – x
The above expression can be used to evaluate the value of
k from the pressure data and also verify that the reaction is kt = ln (V0/2V0 – Vt)
of first order by checking 2-3 data points. In the above
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Reaction Expression for rate constant

1 2.303 Vf
N 2O5 o 2NO2  O2a k log
2 t Vf  Vt
Here V t = volume of O 2 after time t and V f
volume of O2 after infinite time.
NH4 NO2 (aq) o 2H2O + N2 Same as above, here Vt and Vf are volumes
of N2 at time t and at infinite time respectively.
1 .303 V
H 2O 2 o H 2 O  O 2 k log 0
2 t Vt
Here V o and V t are the volumes of KMnO 4
solution used for titration of same volume
of reaction mixture at zero time (initially)
and after time t.
2.303 V  V0
H
CH 3 COOC 2 H 5  H 2 O  

o CH 3COOH k log f
t Vf  Vt
C2H5 OH Here V 0 ,V t and V f are the volumes of NaOH
solution used for titration of same volume
of reaction mixture after time, 0, t and
infinite time respectively.
 2.303 r r
H
C12 H 22 O11  H 2 O  
o C6 H12 O 6  C6 H12 O 6 k log 0 f
d sucrose d Glucose A  Fructose t rt  rf
(After the reaction is complete the Here, r 0,r t and r f are the polarimetric
equimolar mixture of glucose and fructose readings after time 0, t and infinity
obtained is laevorotatory) respectively.

3.6 Practical Methods of determining order of a reaction

i. Initial Rate Data Method:

We take different set of initial concentration and measure
the initial rate. Then by keeping the concentration of one
of the reactants constant and varying the other one we can
study the effect on the rate and hence find out the order.
ii. Logarithmic data method:
For any order, be it fractional or integral, if we plot log (rate)
vs log (concentration) graph it will always be a straight line
for the reactions of the type:
A o products iii. Half Life Method:

Rate, r = k[A]n If we take various concentrations of reactant and measure

half life for all of them then we can find out the order of the
log r = log k + n log [A]
reaction by mere observation or with the help of some
We can take various data points and convert them to log calculations.
values and plot them. We will obtain a straight line after
t1/2 v [A]01-n
curve-fitting with slope n and intercept log k. And hence
we can find out the order and rate constant from the graph.
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If simple observation is not possible then we can calculate x Bimolecular reactions : involve simultaneous collision
the order of the reaction by taking two data points and between two species, for example, dissociation of hydrogen
using log for calculating n. iodide.
iv. By integrated rate Equations: 2HI o H2 + I2
If we have simple data of concentration and time we can x Trimolecular or termolecular reactions : involve
use the integrated rate equations to find out the order. For
simultaneous collision between three reacting species, for
this we will have to try and fit the data into the equation at
example,
various intervals and calculate the value of rate constants.
If the values come out to be the same in all intervals then 2NO + O2 o 2NO2
the data fits into the equation taken and we will know the
order. For example, we have the following data: Reactions with molecularity greater than three are very
rare.
Time: 0 t1 t2 t3 ....... t 4.2 Mechanism

Conc: A0 A1 A2 A3.......At The reactions taking place in one step are called elementary
reactions.
And if we assume that it can be of first order then we will
calculate the values of k at minimum three data points by When a sequence of elementary reactions (called
using the equation for first order: mechanism) gives us the products, the reactions are called
(1/t) ln (A0/At) = k complex reactions.

Let these values be k1, k2 and k3. If k1 = k2 =k3 then it means
that this data fits into the above equation hence the order
is 1. If it doesn’t we will have to try other equations as well.
v. Isolation method:
In this method we try and eliminate one of the two reactants
from the rate equation by taking it in excess. What happens
is when the amount of a reactant is in excess its effect on
the rate becomes marginal or negligible and then we can
vary the concentration of the other reactant and observe
its effect on rate and find out the order.
4. MOLECULARITY AND MECHANISM
4.1 Molecularity
The different steps in which the complex reaction takes
place is called the mechanism of the reaction.
Rate determining step :
The overall rate of the reaction is controlled by the slowest
step in a reaction called the rate determining step.
A complex reaction can be represented as a series of
elementary steps.
For example
2NO2(g) + F2(g) o 2NO2F(g)
Experimentally, Rate of reaction = k[NO2][F2]
Probable mechanism :

The number of reacting species (atoms, ions or molecules) Step-1:

taking part in an elementary reaction, which must collide NO2 + NO2 o NO + NO3 (slow)
simultaneously in order to bring about a chemical reaction
is called molecularity of a reaction. Step-2 :

Classification of reactions on the basis of Molecularity : NO3 + CO o NO2 + CO2 (fast)

x Unimolecular reactions : when one reacting species is Slow step : bimolecular

involved, Hence, a bimolecular reaction.
for example, decomposition of ammonium nitrite.

NH4NO2 o N2 + 2H2O
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Reaction intermediates : Threshold energy = Activation energy + Energy possessed

There are some species which are formed during the course by the reactants
of the reaction but do not appear in the overall reaction.
Less is the activation energy, faster is the reaction.
They are called reaction intermediates.
In order that the reactants may change into products, they
e.g. NO3 in the above example.
have to cross an energy barrier (corresponding to threshold
Distintion between Order and Molecularity of a reaction
energy). Reactant molecules absorb energy and form an
Order
intermediate called activated complex which immediately
1. Order is the sum of the powers of the concentration of the
reactants in the rate law expression. dissociates to form the products.

2. It can be zero and even a fraction. e.g.

3. It is applicable to elementary as well as complex reactions.
4. It can be determined experimentally only and cannot be
calculated.
5. For complex reaction, order is given by the slowest step.
Reaction profile of an exothermic reaction
Molecularity
1. Molecularity is the number of reacting species taking part
in an elementary reaction, which must collide
simultaneously in order to bring about a chemical reaction.
2. It cannot be zero or a non integer.
3. It is applicable only for elementary reactions. For complex
reaction molecularity has no meaning.
4. It can be calculated by simply adding the molecules of the
slowest step.
5. Generally, molecularity of the slowest step is same as the
order of the overall reaction.

5. TEMPERATURE DEPENDENCE Reaction profile of an endothermic reaction

5.1 Activation Energy

According to collision theory, a reaction takes place

because the reactant molecules collide with each other.

The minimum energy which the colliding molecules must

have in order that the collision between them may be
effective is called threshold energy.

The minimum extra amount of energy absorbed by the

reactant molecules so that their energy becomes equal to
threshold value is called activation energy.
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The area under the curve remains constant since total

5.2 Temperature Dependence of the Rate of a Reaction
For a chemical reaction with rise in temperature by 10°,
the rate constant is nearly doubled.
Temperature coefficient = (Rate constant at T + 100) / (Rate
Arrhenius equation
constant at T0)
Explanation :
At a particular temperature, if fractions of molecules are
plotted versus corresponding kinetic energies, a graph of
the type shown is obtained. The peak of the curve
represents the kinetic energy possessed by the maximum
fraction of molecules and is called most probable kinetic
energy.
probability must be one at all times. At (t + 10), the area
showing the fraction of molecules having energy equal to
or greater than activation energy gets doubled leading to
doubling the rate of a reaction.
Quantatively, the temperature dependence of the rate of a
chemical reaction can be explained by Arrhenius equation
k Ae Ea / RT
where A is the Arrhenius factor or the frequency factor or
pre-exponential factor. R is gas constant and Ea is activation
energy measured in joules/mole.
The factor e Ea / RT corresponds to the fraction of molecules
that have kinetic energy greater than Ea.

Thus, it has been found from Arrhenius equation that

increasing the temperature or decreasing the activation
energy will result in an increase in the rate of the reaction
and an exponential increase in the rate constant.

Taking natural logarithm of both sides of equation

Ea
ln k   ln A
Distribution curve showing energies among gaseous RT
molecules The plot of ln k vs 1/T gives a straight line with slope
Ea
 and intercept = ln A.
R
At temperature T1, equation

Ea
ln k1  ln A
RT1

At temperature T2, equation is

Ea
Distribution curve showing temperature dependence of rate of ln k 2  ln A
RT2
a reaction
(since A is constant for a given reaction)
With increase in temperature :
k1 and k2 are the values of rate constants at temperatures T1
(i) maximum of the curve moves to the higher energy value and T2 respectively.
i.e., most probable kinetic energy increases
Substracting equation form, we obtain
(ii) the curve spreads to the right i.e., there is a greater
proportion of molecules with much higher energies. Ea E
ln k 2  ln k1  a
RT1 RT2
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Important characteristics of catalyst :

k2 Ea ª 1 1 º
ln k «  »  A small amount of the catalyst can catalyse a large amount
1 R ¬ T1 T2 ¼
of reactants.
 A catalyst does not alter Gibbs energy, 'G of a reaction.
k2 Ea ª1 1º
log «  »  It catalyses the spontaneous reactions but does not
k1 2.303R ¬ T1 T2 ¼
catalyse non-spontaneous reactions.
 A catalyst does not change the equilibrium constant of a
k E a ª T2  T1 º
log 2 « » reaction rather, it helps in attaining the equilibrium faster.
k1 2.303R ¬ T1T2 ¼
7. COLLISION THEORY OF CHEMICAL REACTIONS
6. EFFECT OF CATALYST
According to this theory, the reactant molecules are
A catalyst is a substance which alters the rate of a reaction assumed to be hard spheres and reaction is postulated to
without itself undergoing any permanent chemical change. occur when molecules collide with each other.

e.g. Rate of reaction depends on the number of effective

collisions which in turn depends on :
MnO2
2KClO3 o 2 KCl  3O 2 (i) Energy factor : colliding molecules must have energy more
than threshold energy.
Action of the catalyst
(ii) Steric or probability factor (P) : colliding molecules must
According to intermediate complex theory, reactants first
have proper orientations at the time of collision.
combine with catalyst to form intermediate complex which
then decomposes to form the products and regenerating Thus, the Arrhenius equation is modified to
the catalyst.
k = PZ AB e  Ea /RT

8. IMPORTANT FORMULAE

8.1 Rate of Reactions

Effect of catalyst on activation energy
(aA + bB o cC + dD)

1 dA 1 dB 1 dc 1 dD
Instantaneous Rate = – =– = =
a dt b dt c dt d dt
1 'A 1 'B 1 'C 1 'D
Average Overall Rate =  
a 't b 't c 't d 't

8.2 Arrhenius Equation

Ea

k Ae RT
.

Catalyst provides an alternate pathway by reducing the

activation energy between reactants and products and
hence lowering the potential energy barrier.
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Zero-Order First Order Second Order nth-Order

d[A] d[A ] d[ A] d[A ]

Rate Law  k  k[A ]  k[ A]2  k[A ]n
dt dt dt dt

1 1 1 1
Integrated [A] = [A]0 – kt [A] = [A]0e–kt  kt  (n  1)kt
[A ] [ A]0 [A ]n 1 [A]0n 1

Rate Law (Except first Order)

M 1 1 1
Units of Rate M.s n 1
s s M .s

Constant (k)

1 1
Linear Plot to [A] vs. t ln([A]) vs. t vs. t vs. t
[A ] [A ]n 1

determine k (Except first Order)

[ A ]0 ln(2) 1 2 n 1  1
Half-life t 1/ 2 t1 / 2 t 1/ 2 t1 / 2
2k k [ A ]0 k (n  1)k [A ]0n 1

(Except first Order)