TOPIC-1 Rate of a Chemical Reaction and Factors Affecting Rate of Reactions

Concepts Covered
 Rate of chemical reaction  Factors affecting it  Rate constant and molecularity

Revision Notes reaction. Average rate = ∆x , where, Dx = change in

Chemical Kinetics: It is the branch of physical chemistry
  ∆t
concentration in given time and Dt = time taken.
which deals with study of the rate of chemical reaction
and the mechanism by which the reaction occurs.  Factors affecting the rate of a chemical reaction:

Rate of Reaction: The rate of reaction is the change of

   [Board 2023]
(i) Concentration of reactants: Rate of reaction is directly
concentration of any reactant or product with time, for a
proportional to the concentration of the reactants.
reaction. [Board 2023] Thus, to increase the rate of a reaction the concentration
A+B→C of the reactants has to be increased.
Rate of reaction, (ii) Temperature: The rate of a reaction increases with
Decrease in concentration of A the increase in temperature. Increase in temperature
Rate of disappearance of A =
Time taken increases the kinetic energy of the molecules which
− ∆ [A] results in the increase in rate of reaction.
=
∆t (iii) Pressure: Pressure affects the rate of only gaseous
− ∆ [ B] reactions. Increase in pressure decreases volume and
Similarly, Rate of disappearance of B =
∆t increases concentration. Increase in concentration
∆ [C] increases the rate of reaction.
and for product Rate of appearance of C = (iv) Presence of catalyst: The rate of many reactions
∆t
is greatly affected by the presence of a catalyst. In
where, [A], [B] and [C] are molar concentrations of the the presence of a catalyst, the activation energy of a
reactants and the product respectively. reaction decreases due to which the reaction proceeds
–1 –1 –1 –1
 Unit of rate of reaction: mol L s or mol L min (in at a faster rate.
liquid), atm s–1 or atm min–1 (in gaseous form). (v) Nature of the reactants: In a chemical reaction, some
 Instantaneous rate of reaction: Instantaneous rate is bonds are broken while some new bonds are formed.
defined as the rate of change in concentration of any Thus, if the molecules are simpler, then less bonds will
one of the reactant or product at a particular time. rupture and the rate of reaction becomes fast while
dx in complex molecules, more bonds will rupture and
Instantaneous rate = consequently the rate of reaction decreases.
dt
−d [A] (vi) Surface area of the reactants: In some heterogeneous
= reactions, the reaction takes place at the surface of the
dt
= −d [B] reactant. Thus in such reactions, the reaction rate is
greatly affected by the surface area. Marble powder
dt
reacts faster than marble chips.
+d[C]
= (vii) Effect of radiations: The reactions which are initiated
dt by the radiations of particular wavelengths are termed
 Average rate of reaction: The rate of reaction measured as photochemical reactions. These reactions generally
over a long time interval is called average rate of a proceed at a faster rate than normal thermal reactions.
 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’. [Board 2023]
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.
(viii) Effect of physical state: Rate of Example:
reaction depends upon physical N2O4 → 2NO2 (Unimolecular reaction)
state of the reactant, e.g., I2(g) reacts 2HI → H2 + I2 (Bimolecular reaction)
faster than I2(s). AgNO3(aq) reacts 2NO+ O2 → 2NO2 (Trimolecular reaction)
 Elementary Reaction: An elementary reaction is a
with NaCl but AgNO3(s) does not
chemical reaction in which one or more of the chemical
react with NaCl.
species react directly to form products in a single
 Rate Law: Rate law or rate equation reaction step and with a single transition state.
is the expression which relates the  For a complex reaction, generally, molecularity of the
rate of reaction with concentration of the reactants. The slowest step is same as the order of the overall reaction.
constant of proportionality ‘k’ is known as rate constant.  Initial rate of reaction: The rate at the beginning of the
The rate law states that the rate of reaction is directly reaction when the concentrations have not changed
proportional to the product of molar concentration of appreciably is called initial rate of reaction.
reactants and each concentration term is raised to some  Rate Determining Step: The slowest step in the reaction
power which may or may not be equal to stoichiometric mechanism is called rate determining step.
coefficients of reacting species. [Board 2023]
m n KEY TERM
Rate = k[A] [B]
Catalyst: The substance that can alter the rate of reaction.


 Rate of formaation of NO2
= 2 × Rate of dissociation of N 2O5
= 2 × 5.65 × 10 −5
= 11.3 × 10 −5 mol L−1s −1

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

Concepts Covered
 Order of reaction  Zero order  First -order  Pseudo first order  Second order  Half life  Integrated rate laws.
ammonia on hot platinum, thermal decomposition
Revision Notes of HI on gold surface and photochemical reaction
Order of reaction: Order is defined as
  between hydrogen and chlorine are examples of zero
the sum of powers of concentration order reaction.
of the reactants in the experimentally
  irst order reaction: The rate of reaction is directly
F
derived rate equation or rate law proportional to the first power of the concentration
expression. Order of reaction is of reacting substance. Rate constant of the first order
experimentally determined and reaction is [Board 2023]
is not written from the balanced 2.303 a
chemical equation. Order of reaction k = log
can be whole number, zero or fractional. t a-x
 Zero order reaction: The rate of reaction does not 2.303 [A ]
change with the concentration of the reactants. ⇒k = log 0 ,
t [ A]
i.e., Rate = k [A]o,
[ A]o - [ A] where ‘a’ is initial concentration and (a – x) is the
 k= , where ‘k’ is rate constant, [A]o is concentration after time ‘t’.
t
Unit of ‘k’ is s–1 or min–1.
initial concentration of reactant.
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
Unit of the rate constant k is mol L–1 s–1. This reaction of powers of concentration terms in rate law or rate
will be zero order reaction. Decomposition of gaseous equation is equal to 2.

This Question is for practice and their solution is given at the end of the chapter.
 dx KEY TERM
\ = k[A] [B]
dt Thermal Decomposition is a reaction wherein a
Unit of rate constant is mol–1 L s–1 or M–1 s–1, where M is chemical substance decomposes into simpler substance
molarity. when heat is imparted on it.

Reaction Order Unit of rate constant Example

–1 –1
Zero order 0 mol L s 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
th
Equation
  for typical first order gas phase reaction: n
  order reaction: In general for nth order reaction of
the type
A(g) → B(g) + C(g)
dx
2.303 p A → products, where, = k[A]n
k= log i dt
t pA
2.303 pi 1  1 1 
or k= log kn = −
t (2pi − pt ) t(n - 1)  [ A]n − 1 [ A]on − 1 
where pi is the initial pressure of A at time, t = 0 and pt
where, [A]o is initial concentration, [A] is final concentra-
is the total pressure at time t.
tion after time t and n can have all the values except 1.
Half-life of a reaction: The time taken for a reaction
  th
 Half-life of a reaction of n order:
when half of the initial value has reacted is called half-
life of a reaction. [Board 2023] 1
t1/2 ∝
For zero order reaction, [ A]n-
o
1

[A] t1/2 ∝ [A] for zero order

t1/2 = o ,
2k t1/2 is independent of [A] for 1st order
where [A]o is initial and final concentration of reaction it
1
means there is no change in concentration and ‘k’ is rate t1/2 ∝ for 2nd order
constant. [A]
0.693 1
For 1st order reaction,   t1/2 = t1/2 ∝ for 3rd order
k [A]2
[A]
Amount of substances left after n half-lives = no
2
Integrated
  rate laws for the reactions of zero and first order:
Reaction Differential Integrated Straight line
Order Half Life Units of k
type rate law rate law plot

d[ A] [ A]o
0 A→P =–k kt = [A]o – [A] [A] vs. t conc. time–1
dt 2k
[A] = [A]o e–kt
d[ A] 2
1 A→P = – k[A] ln[ A]o ln [A] vs. t ln time–1
dt kt = k
[ A]
 Half life : The time in which 98% of the reaction is completed is called half life time.

SUBJECTIVE TYPE QUESTIONS

 TOPIC-3 Concept of Collision Theory, Activation Energy and Arrhenius Equation
Concepts Covered
 Collision theory  Activation energy  Threshold energy  Arrhenius equation  Catalyst

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.  
Those collisions which lead to the formation of product
Activation energy: It is an extra energy which must
  molecules are called effective collisions.
be possessed by reactant molecules so that collision  Rate of reaction = f × Z,
between reactant molecules is effective and leads to the where, ‘Z’ is collision frequency and ‘f ’ is fraction of
formation of product molecules. collisions which are effective.
 [Board 2023]  The number of collisions that take place per second per
 
Activation energy (Ea) for a reaction cannot be zero. It unit volume of the reaction mixture is called collision
is not possible that every collision between molecules frequency. It is represented by ‘Z’.
will be effective. Ea cannot have negative value.  Activated complex is defined as unstable intermediate
formed between reacting molecules. It is highly
 Threshold energy: The minimum energy that the unstable and readily changes into product.
reacting species must possess in order to undergo  According to the collision theory, rate of reaction
effective collision to form product molecules is called depends on the collision frequency and effective
threshold energy. collisions.
Activation theory (Ea) = Threshold energy (ETh) –  Rate = Z AB e − Ea / RT ,
Average energy of the reactions (ER) 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 colliding
molecules that contributes to effective collision,
 k = PZ AB e − Ea / RT

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.
 [Board 2023]
 k = Ae − Ea / RT
where, k = Rate constant Catalyst:
  A catalyst is a substance that alters the rate
 A = Frequency factor (Arrhenius factor) of reaction without itself undergoing any chemical
Ea = Activation Energy. change at the end of reaction.
Intermediate complex theory:
 R = Gas constant
T = Temperature in Kelvin
 ln k = ln A – Ea / RT
Ea
 log k = log A −
2.303 RT
A plot of log k with 1/T gives a straight line with  Intermediate complex
Ea
slope = − Characteristics of catalyst:
2.303 R (i) Catalyzes only the spontaneous reaction.
If k2 and k1 are rate constants at temperature T2 and T1 (ii) Does not change the equilibrium constant.
respectively, then [APQ Set-1, 2023-24]
(iii) Catalyzes both the forward and backward reactions.
k E a  T2 − T1  (iv) Does not alter the free energy change (ΔG) of a reaction.
log 2 = −  
k1 2.303 R  T1T2  (v) A small amount of the catalyst can catalyse large

amount of reactions.