CHAPTER-4 CHEMICAL KINETICS

Chemical Branch of chemistry which deals with study of chemical reaction, Mechanism of chemical reaction and
Kinetics their mechanism
Types of  Very Fast or Instantaneous Reaction:-Reaction takes 10-14 to 10-16 Second for completion.For
reaction Example :-Ionic reaction
 (AgNO3 + NaClAgCl + NaNO3 ,
 BaCl2 + H2SO4 BaSO4 + 2HCl ,
 HCl + NaOHNaCl + H2O)
 Very Slow Reaction:-Reaction takes place very slowly For Example:-
 Rusting of iron,
 Reaction between H2 and O2 intheabscence of catalyst and
 CO +H2 CH3OH(At roomTemperature)
 Moderate Reaction:-Reaction which proceed with measurable rate of reaction
 Decompositon ofH2O2(2H2O2 2H2O + O2),
 Decompositionof N2O5(2N2O5 4NO2 +O2)
 Hydrolysis of Ester(CH3COOC2H5 + NaOH CH3COONa + C2H5OH)
 Inversion of cane sugar in aqueous solution
 Reaction of NO with chlorine(NO + Cl2  NOCl2)
RATE OF The change in concentration of either reactant or product per unit time.
REACTION

dc = change in concentration in a small interval dt.

[–] sign is used when we refer to reactant concentration.
[+] sign is used when we refer to product concentration.
Example : N2 + 3H2 - 2NH3

Average Rate The change in concentration of reactant or product Over a certain measureable period for a reaction
Of Reaction AB
rAv =
The change in concentration of reactant or product at any particular instant during reaction
Instantaneous
rate ofreaction

Rate of reactionin form of stoichiometry of a chemical reaction

Unit of rate Mol L-1time-1 or mol L-1 S-1

of reaction
Determinatio
n of rate of
reaction

Rate Law The expression of rate of reaction in term of concentration of reactant

aA + bB Product Rate=K[A]x[B]y
Rate Constant Rate of reaction when concentration are taken as unity Rate=K[A]x[B]y [A]=1 [B]=1 Rate=K
Specific Rate
of reaction
Unit of rate
constatnt
Order of The sumof powerof concentration of reactant inrate law expression
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reaction aA + bB Product Rate=K[A] [B] Order of reaction = x+y
x y

It may be Zero,Positive or Negative or in fraction.It is experimental quantity.

Mechanism of Elementary reaction:-Chemical reaction complete in single step and have exponant in rate law
Reaction expression equal to their stochiometric cofficient.Zero order reactioncan not be an elementry
reaction.Fraction order cannot be possible
Complex Reaction:- For the complex reaction,The overall reaction is controlled by the slowest step
In the rate law expression,rate of reaction depends on concentration of reactant of slowest step
which must be free from intermediate.
Example:1

Example-2

Molecularity  The total no. Of molecules,atom or ions participating inan elementry reaction
 It is a theoretical quantity.It can be aninteger but cannot be zero,negative or fractional
 For elementry reaction, it is equal to its order
 Incomplex reaction,molecularity of slowest step is same as order of reaction which can consider
as molecularity of reaction.(Except when slowest step contain intermediate)
 Maximum value of molecularity or order of reaction is 3 because chance of effective collosion of
more than three molecule is rare.

Diffrance
between
molecularity
and order of
reaction

Pseudo Achemical reaction which seemsto be higher order but actually they are of first order
firstorder  For these reaction,Order of reaction is one but molecularity is more than one Example :-
reaction Hydrolysis of ester in acedic medium,
CH3COOC2H5 + H2O CH3COOH + C2H5OH Rate =K[CH3COOC2H5][ H2O]
When water is in excess then K’[CH3COOC2H5]
Inversion of cane sugar inacidic medium C12H22O11 + H2O --- C6H12O6 + C6H12O6
Rate =K[C6H12O6][ H2O]
When water is in excess then K’[C6H12O6]

INTEGRATED Zero Order of Reaction:-Reaction in which rate of reaction is directly proportional to zero power
RATE of the reactant in rate law expression.
EQUATION
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First order Reaction in which the rate of reaction is directly proportional to concentration of reactant
reaction
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GENERAL
INTEGRATIO
N RATE
EQUATION
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Example of
second order

Example of
third order

Factor Affacting  1.Nature of reactant:-

rate of reaction (a)Physical state of reactant:-Increasing order of rate of reaction-Solid<Liqid<Gas
(b)Size of particle:-Rate of reaction α Surface area α I/Physical size
(c)Chemical Nature of Reactant:-Reaction having less value of activation energy will takes place faster
 2.Concentration of Reactant:- Rate of reaction α Concentration of Reactant
 3.Pressure:-Effect of pressure is negligible when reactant are solid or liquid but reactant are in
gaseous state than rate of reaction increases on increasing pressure because no. of effective collision
increases.
 4.Temperature:-On increasing temperature, rate of reaction increases weather the reaction is
exothermic or endothermic because KE of molecule increase on increases temperature which led to
increasing activated molecule.
 Relation between rate constant and temperature
(a)Generally it isfound that for every 10 0C rise in temperature rate of reaction become 2 to 3 times
Temperature Cofficient:-It is defined as ratio of rate of a reaction at two different temperature which
will bediffer by 10 0C

 5.Presence of catalyst:-In the presence of catalyst, Ea(Activation energy) decreases therefore rate of
reaction increases

 6.Exposure of radiation:-Rate of some reaction increases on exposure of radiation. These reaction are
called photochemical reaction
For Example:-
QuantumYield

ARRHENIUS Arrhenius derived a mathematical expression to give a quantitative relationship between rate constant
EQUATION :
and temperature. K= A.e—Ea /RT (Here, A = frequency factor; Ea = activation energy ;

Limitation of
collosion theory
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Collision theory
of chemical
reaction
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ILLUSTRATION FOR RATE OF CHEMICAL REACTION

E x . 1 What should be (a) the rate of disappearance of B and (b) the rate of formation of C, if the rate of disappearance
of A for the reaction A + B  2C is 10–2 mole/litre/second at a particular temperature ?

ILLUSTRATION FOR ORDER OF REACTION

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ILLUSTRATION FOR FIRST ORDER OF REACTION

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NUMERICAL BASED ON ARRHENIUS EQUATION

Question :1.Ethylene oxide is decomposed into CH4 and CO. Rate constant for this reaction may be described by the
equation log k (s–1) = 14.34 - –

(i) What will be the energy of activation of this reaction ?

(ii) What will be the value of k at 670 K ?

(iii) At what temperature will its half-life period be 25.6 minutes ?

Solution:-
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Question :-2.The rate constant of forward reaction a reaction increases by 6% when the temperature of the reaction is

increased from 300 to 301 K, whereas equilibrium constant increases by 2%. Calculate the activation energy

for the forward as well as backward reaction.

Question:-Value of rate constant for a first order reaction at 500 K is 1.60 × 10–5 second–1, whereas at 600 K, it is

6.36 × 10–3 second–1. Find out the activation energy of the reaction.
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OBJECTIVE QUESTION FOR RATE OF CHEMICAL REACTION

OBJECTIVE FOR ORDER OF REACTION

OBJECTIVE FOR FIRST ORDER OF REACTION

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OBJECTIVE FOR ARRHEBIUS EQUATION REACTION

–1. If energy change (ΔE) during the

reaction is – 20kJ, then the activation energy for the reverse reaction is

[A] –30kJ [B] 20 kJ [C] 50 kJ [D] 10 kJ

–1 of A. If energy change of the

reaction is y kJ, the activation energy of reverse reaction is

[A] – x [B] x – y [C] x + y [D] y – x Ans. [B]

3.Which of the following relations is correct ?

[A] k = A eEa/RT [B] ln k – ln A =Ea/RT [C] ln A – ln k =Ea/RT [D] ln A – ln k = –Ea/RT Ans. [C]

4.Which of the following expression give the effect of temperature on the rate constant ?

[A] ln A = RT ln Ea – ln k [B] ln k = ln A – Ea/RT [C] k = AEa /RT [D] None of these Ans. [B]

5.The plot of log k vs 1/T helps to calculate

[A] Energy of activation [B] Rate constant of the reaction

[C] Order of the reaction [D] Energy of activations as well as the frequency factor