4

CHAPTER

CHEMICAL
KINETICS

Syllabus
 Rate of a reaction (Average and instantaneous), factors affecting rate of reaction: concentration, temperature,
catalyst; order and molecularity of a reaction, rate law and specific rate constant, integrated rate equations and
half-life (only for zero and first order reactions), concept of collision theory (elementary idea, non mathematical
treatment). Activation energy, Arrhenius equation.

Trend Analysis
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D/OD D OD D OD
Rate of reaction, Rate law, Rate 1Q 1Q 1Q
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constant and Numericals (2 marks) (2 marks) (1 mark)
1Q 2Q
Order of reaction, Integrated rate
(2 marks) (1 mark) 3Q
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(3 marks)

TOPIC-1 TOPIC - 1

Rate of a Chemical Reaction and Rate of a Chemical Reaction and

Factors Affecting Rate of Reactions
Factors Affecting Rate of Reactions .... P. 99

TOPIC - 2
Revision Notes Order of a Reaction, Integrated Rate
Equations and Half-life of a Reaction
 Chemical Kinetics : It is the branch of physical chemistry which .... P. 106
deals with study of the rate of chemical reaction and the mechanism
by which the reaction occurs. TOPIC - 3
 Rate of Reaction : The rate of reaction is the change of concentration Concept of Collision Theory,
of any reactant or product with time, for a reaction. Activation Energy and Arhenius
A+B→C equation .... P. 117
Decrease in concentration of A −∆[ A ]
Rate of reaction, A = =
Time taken ∆t
−∆[ B ]
Similarly, B=
∆t
D [C ]

and for product C=
Dt
where, [A], [B] and [C] are molar concentrations of the reactants and the product respectively.
 Unit of rate of reaction : mol L–1 s–1 or mol L–1 min–1 (in liquid), atm s–1 or atm min–1 (in gaseous form)
 Instantaneous rate of reaction : Instantaneous rate is defined as the rate of change in concentration of any one of
the reactant or product at a particular time.
 dx -d[ A] -d[ B] +d[C ]
Instantaneous rate = = = =
dt dt dt dt
 Average rate of reaction : The rate of reaction measured over a long time interval is called
Dx
average rate of a reaction. Average rate = , where, Dx = change in concentration in given
Dt
time and Dt = time taken.

 Factors affecting the rate of a chemical reaction :

(i) Concentration of reactants : Rate of reaction is directly proportional to the concentration of the reactants.
Thus, to increase the rate of a reaction the concentration of the reactants has to be increased.
(ii) Temperature : The rate of a reaction increases with the increase in temperature. Increase in temperature
increases the kinetic energy of the molecules which results in the increase in rate of reaction.
(iii) Pressure : Pressure affects the rate of only gaseous reactions. Increase in pressure decreases volume and
increases concentration. Increase in concentration increases the rate of reaction.
(iv) Presence of catalyst : The rate of many reactions is greatly affected by the presence of a catalyst. In the
presence of a catalyst, the activation energy of a reaction decreases due to which the reaction proceeds at a
faster rate.
(v) Nature of the reactants : In a chemical reaction, some bonds are broken while some new bonds are formed.
Thus, if the molecules are simpler, then less bonds will rupture and the rate of reaction becomes fast while in
complex molecules, more bonds will rupture and consequently the rate of reaction decreases.
(vi) Surface area of the reactants : In some heterogeneous reactions, the reaction takes place at the surface of
the reactant. Thus in such reactions, the reaction rate is greatly affected by the surface area. Marble powder
reacts faster than marble chips.
(vii) Effect of radiations : The reactions which are initiated by the radiations of particular wavelengths are
termed as photochemical reactions. These reactions generally proceed at a faster rate than normal thermal
reactions.
Concentration

Product
(moles/litre)

Reactant

Time ( t )

(viii) Effect of physical state : Rate of reaction depends upon physical state of the reactant, e.g.,
I2(g) reacts faster than I2(s). AgNO3(aq) reacts with NaCl but AgNO3(s) does not react with NaCl.
 Rate Law : Rate law or rate equation is the expression which relates the rate of reaction with concentration of the
reactants. The constant of proportionality ‘k’ is known as rate constant. The rate law states that the rate of reaction
is directly proportional to the product of molar concentration of reactants and each concentration is raised to
some power which may or may not be equal to stoichiometric coefficients of reacting species.
Rate = k[A]m [B]n
 Rate Constant : Rate constant is also called specific reaction rate. When concentration of both reactants are unity
(one), then the rate of reaction is known as rate constant. It is denoted by ‘k’.
 Molecularity : Total number of atoms, ions or molecules of the reactants involved in the reaction is termed as
molecularity. It is always a whole number. It is never more than three. It cannot be zero.
Example :
NH4NO2 → N2+2H2O (Unimolecular reaction)
2HI → H2 + I2 (Bimolecular reaction)
2NO+ O2 → 2NO2 (Trimolecular reaction)
 Elementary Reaction : An elementary reaction is a chemical reaction in which one or more of the chemical species
react directly to form products in a single reaction step and with a single transition state.
 For a complex reaction generally, molecularity of the slowest step is same as the order of the overall reaction.
 Initial rate of reaction : The rate at the beginning of the reaction when the concentrations have not changed
appreciably is called initial rate of reaction.
 Rate Determining Step : The slowest step in the reaction mechanism is called rate determining step.
 Rateof
(ii) Rate of dissociation
dissociation of of N
N 2O O5 (iii) Rate of dissociation of N2O5 = 2 × Rate of
1
2 5
formation of O2
1
== 2 ´´ Rate
Rateofof formation
formation of
of NO
NO2
2 Rate of formation of O2
2
Rate of dissociation of NO
Rate of dissociation of NO22 1
= ´ Rate of dissociation of N 2O5
==22 ´´ Rate
Rateofof formation
formation of
of NN 2O
2
O5
5
2
= 2 ´ 5.65 ´ 10 -5
-5 1
= 2 ´ 5.65 ´ 10 = ´ 5.65 ´ 10 -5
10--55mol
molLL--11ss--11 2
==11.3
11.3 ´´10 [1]
 [1]
= 2.825 ´ 10 -5 mol L-1s -1

TOPIC-2
Order of a Reaction, Integrated Rate Equations and
Half-life of a Reaction

Revision Notes
 Order of reaction : Order is defined as the sum of powers of concentration of the reactants
in the experimentally derived rate equation or rate law expression. Order of reaction is
experimentally determined and is not written from the balanced chemical equation. Order of
reaction can be whole number, zero or fractional.
 Zero order reaction : The rate of reaction does not change with the concentration of the
reactants.
i.e. Rate = k [A]0,
[ A]0 - [ A] , where ‘k’ is rate constant, [A] is initial concentration of reactant.
k= 0
t
Unit of the rate constant k is mol L–1 s–1. This reaction will be zero order reaction. Decomposition of gaseous
ammonia on hot platinum, thermal decomposition of HI on gold surface and photochemical reaction between
hydrogen and chlorine are examples of zero order reaction.
 First order reaction : The rate of reaction is directly proportional to the first power of the concentration of reacting
substance. Rate constant of the first order reaction is
2.303 a
k= log
t a - x

⇒ k = 2.303 log [A 0 ] ,
t [ A]

where ‘a’ is initial concentration and (a – x) is the concentration after time ‘t’.
Unit of ‘k’ is s–1 or min–1.
Decomposition of N2O5 and N2O are examples.
 Pseudo first order reaction : If a reaction is not truly of the first order but under certain conditions becomes
reaction of first order is called pseudo first order reaction, e.g., acidic hydrolysis of ester (ethyl acetate).
H+

CH3COOC2H5 + H2O  CH3COOH + C2H5OH
 Second order reaction : The reaction in which sum of powers of concentration terms in rate law or rate equation
is equal to 2.
dx
\ = k[A] [B]
dt
Unit of rate constant is mol–1 L s–1 or M–1 s–1, where M is molarity.
Reaction Order Unit of rate constant Example

Zero order 0 mol–1 L–1 s–1 Sunlight

H2 + Cl2 → 2HCl
First order 1 s–1 2N2O5 → 4NO2 + O2

Pseudo first order 1 s–1 H+

C12H22O11 + H2O 
→ C6H12O6 + C6H12O6
Second order 2 mol–1 L s–1 H2 + I2 → 2HI
  Equation for typical first order gas phase reaction : A(g) → B(g) + C(g)
2.303 p
k= log i
t pA
2.303 pi
or k= log
t (2pi − pt )

where pi is the initial pressure of A at time, t = 0 and pt is the total pressure at time t.
 Half-life of a reaction : The time taken for a reaction when half of the initial value has reacted is called half-life of
a reaction.
[A]0
For zero order reaction, t1/2 = ,
2k
0
where [A] is initial and last concentration of reaction it means there is no change in concentration and ‘k’ is rate
constant.
0.693
For 1st order reaction, t1/2 =
k
 nth order reaction : In general for nth order reaction of the type
dx
A → products, where, = k[A]n
dt
1  1 1 
kn =  n −1 − 
t(n − 1) [ A] [ A]0 n−1 
where [A]0 is initial concentration, [A] is final concentration after time t and n can have all the values except 1.
 Half-life of a reaction of nth order :
1
t1/2 µ
[ A]n-
0
1

t1/2 µ [A] for zero order

t1/2 is independent of [A] for 1st order
1
t1/2 µ for 2nd order
[A]
1
t1/2 µ for 3rd order
[A]2
[A]0
Amount of substances left after n half-lives =
2n

 Integrated rate laws for the reactions of zero and first order :

Reaction Differential rate Straight line

Order Integrated rate law Half Life Units of k
type law plot
d[ A] [ A]0
0 A→P =–k kt = [A]0 – [A] [A] vs. t conc. time–1
dt 2k
[A] = [A]0 e–kt
d[ A] 2
1 A→P = – k[A] ln[ A]0 ln [A] vs. t ln time–1
dt kt = k
[ A]
 Life time : The time in which 98% of the reaction is completed is called life time.

Mnemonics

• Concept: Zero order

• Mnemonics : ZOR don’t CCR
• Interpretation : In zero order reaction, the rate of reaction does not change with
concentration of the reactants.
Know the Formulae
 Integrated Rate Equations :
(i) For a zero order reaction :
[ R]0 − [ R] [ R]0
t = and t[½] =
k 2k
(ii) For a first order reaction :
2.303 [ R] 0.693
t = log 0 and t[½] =
k [ R] k
k ( T + 10 )
 Temperature coefficient =
k ( T)

Objective Type Questions (1 mark each)

[A] MULTIPLE CHOICE QUESTIONS : -k

(a) (b) –k
2.303
Q. 1. In a chemical reaction X → Y, it is found that the
+k
rate of reaction doubles when the concentration of (c) (d) +k
X is increased four times. The order of the reaction 2.303
(where [R] is the final concentration of reactant)
with respect to X is [CBSE, Delhi Set-2, 2020]
(a) 1 (b) 0  R [CBSE Outside Delhi Set-3, 2020]
(c) 2 (d) 1/2 Ans. Correct option : (b)
Explanation :
Ans. Correct option : (d)
Explanation : X → Y
Rate(r) ∝ [X]n [Where n = Order of reaction]
If the concentration X is increased by 4 times

X’ = 4X
Then, Rate(r’) ∝ [X’]n
r ' [ 4X ]
n

= =2
r [X ]n Q. 4. A first order reaction is 50% completed in
r’ is new rate, X’ is a new concentration 1.26 × 1014 s. How much time would it take for
[4]n = 2 100% completion ? U
1 (a) 1.26 × 1015 s (b) 2.52 × 1014 s
\n = (c) 2.52 × 1028 s (d) Infinite
2
Ans. Correct option : (d)
1 Explanation : The reaction will be 100% complete
Order of reaction = 
2 only after infinite time.
Q. 2. The half-life period for a zero order reaction is Q. 5. Consider a first order gas phase decomposition
equal to
reaction given below :
0.693 (b) 2k
(a) A(g) B(g) + C(g)
k [R ]0
The initial pressure of the system before
2.303 [R ]0
(c) (d) decomposition of A was ‘pi’. After lapse of time
k 2k
‘t’, total pressure of the system increased by x
(where [R]0 is initial concentration of reactant and
units and became ‘pt’. The rate constant k for the
k is rate constant).
 R [CBSE Outside Delhi Set-2, 2020] reaction is given as :
Ans. Correct option : (d) 2.303 pi
(a) k = log
Explanation : Half life period of a zero order t pi - x
[R]0
reaction = 2.303 pi
2k (b) k = log
Where [R]0 = initial concentration of reactant t 2 pi - pt
k = Rate constant 2.303 pi
Q. 3. For a zero order reaction, the slope in the plot of (c) k = log
t 2 pi + pt
[R] vs. time is
 2.303 2.303 2.303
= × 0.3010 [1] = log 10 = [1]
1800 k k
2.303 a STEP 3 : By putting the value of k here, we get
STEP 2 : and t = log
k (a − x) 2.303 × 1800
⇒ t =
2.303 100 2.303 × 0.3010
= log = 5.98 × 103 s [1]
k 100 − 90

TOPIC-3
Concept of Collision Theory, Activation Energy and
Arrhenius Equation
Revision Notes
 The rate of reaction is dependent on temperature. This is expressed in terms of temperature coefficient.
Rate constant at 308 K
Temperature coefficient =
Rate constannt at 298 K
It is observed that for a chemical reaction with rise in temperature by 10°C, the rate constant is nearly doubled.
 Activation energy : It is an extra energy which must be possessed by reactant molecules so that collision between
reactant molecules is effective and leads to the formation of product molecules.
 Activation energy (Ea) for n reaction can not be zero. It is not possible that every collision between molecules will
be effective. Ea can not have negative value.
 Threshold energy : The minimum energy that the reacting species must possess in order to undergo effective
collision to form product molecules is called threshold energy.
Activation theory (Ea) = Threshold energy (ET) – Average energy of the reactions (ER)

 Arrhenius equation : Activated complex is defined as unstable intermediate formed between reacting molecules.
It is highly unstable and readily changes into product. Arrhenius equation gives the relation between rate of
reaction and temperature.
k = Ae − Ea / RT
where k =Rate constant
A = Frequency factor (Arrhenius factor) Ea = Activation Energy.
R =Gas constant T = Temperature in Kelvin
ln k = ln A – Ea / RT
Ea
log k = log A −
2.303 RT
Ea
A plot of log k with 1/T gives a straight line with slope = −
2.303 R
If k2 and k1 are rate constants at temperature T2 and T1 respectively, then
k Ea T2 − T1
log 2 = −
k1 2.303 R T1 − T2

log k

1
  Those collisions which lead to the formation of product molecules are called effective collisions.
Rate of reaction = f × z,
where ’z’ is collision frequency and ‘f’ is fraction of collisions which are effective.
 The number of collisions that take place per second per unit volume of the reaction mixture is called collision
frequency. It is represented by ‘Z’.
 Activated complex is defined as unstable intermediate formed between reacting molecules. It is highly unstable
and readily changes into product.
 According to the collision theory, rate of reaction depends on the collision frequency and effective collisions.
Rate = Z AB e − Ea / RT ,

where ZAB represents the collision frequency of reactants A and B. e − Ea / RT represents the fraction of molecules
with energies equal to or greater than Ea.
 According to collision theory, another factor P which is called steric factor refers to the orientation of molecules
which collide, is important and contributes to effective collision,
k = PZ AB e − Ea / RT

 Catalyst : A catalyst is a substance that alters the rate of reaction without itself undergoing any chemical change
at the end of reaction.
Intermediate complex theory :
A+B + X →A B → A→B+ X
Reactants Catalyst Product Catalyst

X
       Intermediate complex
Characteristics of catalyst :
(i) Catalyzes only the spontaneous reaction.
(ii) Does not change the equilibrium constant.
(iii) Catalyzes both the forward and backward reactions.
(iv) Does not alter the free energy change (ΔG) of a reaction.
(v) A small amount of the catalyst can catalyse large amount of reactions.

Mnemonics

• Concept: Effect of Collision

• Mnemonics : ECFPM
• Interpretation : Effective collisions lead to formation of product molecules.
• Concept: Catalyst
• Mnemonics : CAR
• Interpretation : A catalyst alters the reaction

Know the Formulae

Rate constant at (T+10)°
 Temperature coefficient =
Rate constant at T°
 Rate of reaction = f × Z
where Z is the collision frequency, f is the fraction of collisions.
 Arrhenius equation : k = Ae − Ea / RT

 Rate = PZe − Ea / RT