Exam : KCET

2023 – 24
Class : 11
CHEMICAL KINETICS

Rate of a Chemical Reaction :

• Speed of a reaction or the rate of a reaction can be defined as the change in concentration of a reactant or product
in unit time.
• Average rate of a reaction, 𝒓𝒓𝒂𝒂𝒂𝒂 : Average rate depends upon the change in concentration of reactants or products
and the time taken for that change to occur.
• units of rate are concentration time–1.
• Instantaneous rate : It is obtained when we consider the average rate at the smallest time interval say dt (i.e.
when ∆𝑡𝑡 approaches zero).
• Hence, mathematically for an infinitesimally small dt instantaneous rate is given by
−∆[R] ∆[P]
𝑟𝑟𝑎𝑎𝑎𝑎 = =
∆𝑡𝑡 ∆𝑡𝑡
−𝑑𝑑 [R] 𝑑𝑑 [P]
As ∆𝑡𝑡 → 0 or 𝑟𝑟inst = =
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
• Reaction where stoichiometric coefficients of the reactants and products are same.
Hg(l) + Cl2 (g) → HgCl2 (s)
∆[Hg] ∆[Cl2 ] ∆[HgCl2 ]
Rate of reaction = =− =−
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
• Reaction where stoichiometric coefficients of reactants or products are not equal to one
2HI(g) → H2 (g) + I2 (g)
1 ∆[HI] ∆[H2 ] ∆[I]
Rate of reaction = = =
2 ∆𝑡𝑡 ∆𝑡𝑡 ∆𝑡𝑡

Factors Influencing Rate of a Reaction :

• Concentration of the reactants : Rate of a reaction is proportional to the concentration i.e., greater the
concentration, faster is the reaction.
• Temperature : The rate of reaction increases (as the temperature increase) because large number of molecules
cross the energy barrier.
• Presence of catalyst : Catalyst alters the activation energy of reaction and hence changes the rate of reaction.
• Surface area of the reactants : Greater the surface area, faster is the reaction.
• Presence of light : For many reactions, light provides the necessary activation energy to initiating the reaction.
(ex : photochemical reactions).
• Rate Expression and Rate Constant :
 Consider a general reaction
aA + bB → CC + dD
where 𝑎𝑎, 𝑏𝑏, 𝑐𝑐 and 𝑑𝑑 are the stoichiometric coefficients of reactants and products.
The rate expression for this reaction is
 Rate ∝ [A]𝑥𝑥 [B]𝑦𝑦
Rate = 𝑘𝑘[A]𝑥𝑥 [B]𝑦𝑦
𝑑𝑑 [R]
or − = 𝑘𝑘 [A]𝑥𝑥 [B]𝑦𝑦
𝑑𝑑𝑑𝑑
(𝑥𝑥 and 𝑦𝑦 may or may not be equal to the stoichiometric coefficient)
𝑘𝑘 is a proportionality constant called rate constant.
 Rate law is the expression in which reaction rate is given in terms of molar concentration of reactants with
each 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.
 Rate law for any reaction cannot be predicted by merely looking at the balanced chemical equation, i.e.,
theoretically but must be determined experimentally.

• Order of a Reaction : The sum of powers of the concentration of the reactants in the rate law expression is called
the order of that chemical reaction.
Order of a reaction can be 0, 1, 2, 3 and even a fraction.
 The reactions taking place in one step are called elementary reactions.
 When a sequence of elementary reactions (called mechanism) gives us the products, the reactions are
called complex reactions.

Units of Rate Constant :

Units of Rate Constant
Reaction Order Units of Rate Constant
Zero order reaction 0 molL−1 1
× = molL−1 s −1
s (molL−1 )0
First order reaction 1 molL−1 1
× = s −1
s (molL−1 )1
Second order reaction 2 molL−1 1
× = mol−1 Ls −1
s (molL−1 )2

• Molecularity of a Reaction : The number of reacting species (atoms, ions or molecules) taking part in an
elementary reaction, which must collide simultaneously in order to bring about a chemical reaction is called
molecularity of a reaction.
• The overall rate of the reaction is controlled by the slowest step in a reaction called the rate determining step.
Difference between order of reactions and Molecularity
Order Molecularity
Order of a reaction is an experimental quantity. It Molecularity cannot be zero or a non-integer.
can be zero and even a fraction.
Order is applicable to elementary as well as Molecularity is applicable only for elementary reactions.
complex reactions. For complex reaction molecularity has no meaning.
For complex reaction, order is given by the slowest Molecularity of the slowest step is same as the order of the
step. overall reaction.
Integrated Rate Equations :
• Zero Order Reactions : Rate of the reaction is proportional to zero power of the concentration of reactants.
𝑑𝑑 [R]
Rate = − = 𝑘𝑘 [R]0
𝑑𝑑𝑑𝑑
𝑑𝑑 [R] = −𝑘𝑘 𝑑𝑑𝑑𝑑
Integrating both sides
[R] = −𝑘𝑘 𝑡𝑡 + I; At 𝑡𝑡 = 0, R = [R]0 ,
Substituting in equation
[R]0 = −𝑘𝑘 × 0 + I; [R]0 = I.
Substituting the value of I in the equation
[R] = −𝑘𝑘 𝑡𝑡 + [R]0

Variation in the concentration vs time plot for a zero order reaction

• First Order Reactions :

 The rate of the reaction is proportional to the first power of the concentration of the reactant R.
𝑑𝑑 [R]
Rate = = 𝑘𝑘[R]
𝑑𝑑𝑑𝑑
 The first order rate equation can written in the form
2.303 [R]0
𝑘𝑘 = log
𝑡𝑡 [R]
  All natural and artificial radioactive decay of unstable nuclei take place by first order kinetics.
226
88Ra → 42He + 222
86Rn

Rate = 𝑘𝑘[Ra]
 Decomposition of N2 O5 and N2 O are some more examples of first order reactions.
 Consider a typical first order gas phase reaction.
A(g) → B(g) + C(g)
Integrated rate equation for such a reaction can be
2.303 𝑝𝑝𝑖𝑖
𝑘𝑘 = � � �log �
𝑡𝑡 𝑝𝑝A
2.303 𝑝𝑝𝑖𝑖
= log
𝑡𝑡 (2𝑝𝑝𝑖𝑖 − 𝑝𝑝𝑡𝑡 )
Where, 𝑝𝑝𝑖𝑖 = Initial pressure
𝑝𝑝A = Portial pressure of A
𝑝𝑝𝑡𝑡 = total pressure (𝑝𝑝𝐴𝐴 + 𝑝𝑝𝐵𝐵 + 𝑝𝑝𝐶𝐶 )
• Half-Life of a Reaction :
 For a zero-order reaction,
[R]0
𝑡𝑡1/2 =
2𝑘𝑘
 For the first order reaction,
2.303 [R]0
𝑘𝑘 = log
𝑡𝑡 [R]
[R]0 0.693
at 𝑡𝑡1/2 [R] = ∴ 𝑡𝑡1/2 =
2 𝑘𝑘
 For zero order reaction 𝑡𝑡1/2 ∝ [R]0 and for first order reaction 𝑡𝑡1/2 is independent of [R]0 .

Integrated Rate Laws for the Reactions of Zero and First Order
Order Reaction Differential Integrated rate law Straight line plot Half-life Units of 𝒌𝒌
type rate law
0 R→P 𝑑𝑑 [R] 𝑘𝑘𝑘𝑘 = [R]0 − [R] [R] vs 𝑡𝑡 [R]0 conc. time–1 or
= −𝑘𝑘
𝑑𝑑𝑑𝑑 2𝑘𝑘 molL–1s–1
1 R→P 𝑑𝑑 [R] [R] = [R]0 𝑒𝑒 −𝑘𝑘𝑘𝑘 or ln[R] vs 𝑡𝑡 ln 2 time–1 or s–1
= −𝑘𝑘 [R]
𝑑𝑑𝑑𝑑 [R]0 𝑘𝑘
𝑘𝑘𝑘𝑘 = ln � �
[R]

Pseudo First Order Reaction :

• The reactions which appears to be second order reactions but follows first order kinetics.
e.g.: hydrolysis of ester, inversion of cane sugar.
H+
CH3 COOC2 H5 + H2 O �⎯⎯⎯� CH3 COOH + C2 H5 OH
• The concentration of water does not get altered much during the course of the reaction. So, the reaction behaves
as first order reaction.
Rate = 𝑘𝑘 ′ [CH3 COOC2 H5 ][H2 O]
 The term [H2 O] can be taken as constant
Rate = 𝑘𝑘[CH3 COOC2 H5 ]
Where 𝑘𝑘 = 𝑘𝑘 ′ [H2 O]

Temperature Dependence of the Rate of a Reaction :

• Most of the chemical reactions are accelerated by increase in temperature.
• For a chemical reaction with rise in temperature by 10°, the rate constant is nearly doubled.
• The temperature dependence of the rate of a chemical reaction can be accurately explained by Arrhenius equation
𝑘𝑘 = A 𝑒𝑒 −E𝑎𝑎/RT where A is the Arrhenius factor or the frequency factor. It is also called pre-exponential factor.
• R is gas constant and E𝑎𝑎 is activation energy measured in joules/mole (J mol–1).
• Consider following reaction H2 (g) + I2 (g) → 2HI(g).
• According to Arrhenius, this reaction can take place only when a molecule of hydrogen and a molecule of iodine
collide to form an unstable intermediate. It exists for a very short time and then breaks up to form two molecules
of hydrogen iodide.

Diagram showing plot of potential energy vs reaction coordinate

• The energy required to form unstable intermediate or activated complex is called activation energy.
• Plot of fraction of molecules vs Kinetics energy :
 The peak of the curve corresponds to most probable kinetic energy. i.e., the kinetic energy possessed by
maximum fraction of molecules.

Distribution curve showing energies among gaseous molecules

  Increasing temperature, increases the fraction of molecules.

Distribution curve showing temperature dependence of rate of a reaction

 Taking natural logarithm of both sides of Arrhenius equation

E𝑎𝑎
ln 𝑘𝑘 = − + ln A
RT

A plot between 𝐥𝐥𝐥𝐥 𝒌𝒌 and 𝟏𝟏/𝐓𝐓

 If 𝑘𝑘1 and 𝑘𝑘2 are the values of rate constants at temperatures T1 and T2 respectively.
𝑘𝑘2 E𝑎𝑎 T2 − T1
log = � �
𝑘𝑘1 2.303 R T1 T2

• Effect of Catalyst :
 A catalyst is a substance which increases the rate of a reaction without itself undergoing any permanent
chemical change.
Catalyst MnO2
2KClO3 �⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯� 2KCl + 3O2
 When the added substance reduces the rate of reaction. The substance is then called inhibitor.

Effect of catalyst on activation energy

  It is believed that the catalyst provides an alternate pathway or reaction mechanism by reducing the
activation energy between reactants and products and hence lowering the potential energy barrier.
 A small amount of the catalyst can catalyse a large amount of reactants.
 A catalyst does not alter Gibbs energy, ∆G of a reaction.
 It catalyses the spontaneous reactions but does not catalyse non- spontaneous reactions.
 It is also found that a catalyst does not change the equilibrium constant of a reaction rather, it helps in
attaining the equilibrium faster.
 It catalyses the forward as well as the backward reactions to the same extent.

Collision Theory of Chemical Reactions :

 According to this theory, the reactant molecules are assumed to be hard spheres and reaction is postulated to
occur when molecules collide with each other.
 The number of collisions per second per unit volume of the reaction mixture is known as collision frequency (Z).
 For a bimolecular elementary reaction
A + B → Products
Rate of reaction can be expressed as
Rate = ZAB 𝑒𝑒 −Ea /RT
where, ZAB represents the collision frequency of reactants, A and B and 𝑒𝑒 − E𝑎𝑎 /RT represents the fraction of
molecules with energies equal to or greater than E𝑎𝑎 .
 The collisions in which molecules collide with sufficient kinetic energy (called threshold energy*) and proper
orientation, so as to facilitate breaking of bonds between reacting species and formation of new bonds to form
products are called as effective collisions.

 To account for effective collisions, another factor P, called the probability or steric factor is introduced.
Rate = RZAB 𝑒𝑒 −E𝑎𝑎 /RT
In collision theory activation energy and proper orientation of the molecules together determine the criteria for an
effective collision and hence the rate of a chemical reaction.

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