Chemical Kinetics
Rate of a Chemical Reaction
For RP
Average & Instantaneous Rate
For 2HI(g) → H2(g) + I2(g)
Rate law / Rate equation /
Rate expression
For aA + bB → cC + dD
Differential Rate Equation
Order of a Reaction
Elementary reactions
Unit of rate constant
Molecularity of a Reaction
Rate Determining Step
Half-life (t1/2)
Zero Order Reactions
(Integrated Rate Equation)
First Order Reactions
(Integrated Rate Equation)
Dependence of t1/2 on [R]0
Example of Zero Order
Reactions
Radioactive decay
Pseudo First Order
Reaction
Activation Energy
Arrhenius equation
e -Ea /RT
If k1 and k2 are rate constants at
T1 and T2
Action of catalyst
Collision frequency (Z)
Change in concentration of a reactant or product in unit time. Unit => mol L -1s–1
Rate of reaction =
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.
The rate expression for this reaction is :
Rate α [A]x [B]y => Rate = k [A]x [B]y k is the Rate const. (x , y from expts)
The sum of powers of the concentration of the reactants in the rate law expression is
called the order of that chemical reaction.
If Rate = k [A]x [B]y Order = x + y
The reactions taking place in one step are called Elementary Reactions
For n th order reaction : mol1-n Ln-1 s-1
The number of reacting species taking part in an elementary reaction, which must
collide simultaneously in order to bring about a chemical reaction is called
molecularity of a reaction (values are limited from 1 to 3)
The overall rate of the reaction is controlled by the slowest step in a reaction called
the rate determining step
The half-life of a reaction is the time in which the concentration of a reactant is
reduced to one half of its initial concentration. It is represented as t 1/2.
For zero order : t1/2 α [R]0. For first order reaction t1/2 is independent of [R]0
The decomposition of gaseous ammonia on a hot platinum surface is a zero order
reaction at high pressure. Rate = k [NH3]0 = k
All natural and artificial radioactive decay of unstable nuclei take place by first order
kinetics
When one of two reactants is present in large excess. During the hydrolysis of 0.01
mol of ethyl acetate with 10 mol of water The concentration of water does not get
altered much during the course of the reaction and the reaction behaves as first order
reaction. Such reactions are called pseudo first order reactions.
Activation energy is given by the energy difference between activated complex and
the reactant molecules
k = A e -Ea /RT (exponential form)
ln k = – Ea/RT + ln A (logarithmic form)
A is the Arrhenius factor or the frequency factor or pre-exponential factor
The factor e -Ea /RT corresponds to the fraction of molecules that have kinetic energy
greater than Ea
Catalyst provides an alternate pathway or reaction mechanism
by reducing the activation energy between reactants and products and hence lowering
the potential energy barrier
The number of collisions per second per unit volume of the reaction mixture.
For A + B → Products Rate = P.ZAB e−Ea/ RT P is probability or steric factor ZAB is
collision frequency of reactants, A and B