Chemical Kinetic 2

Chemical Kinetics (Note -2)
The Arrhenius Equation:
The Arrhenius equation is an expression that provides a relationship between the rate constant
(of a chemical reaction), the absolute temperature, and the A factor (also known as the pre-
exponential factor). The expression of the Arrhenius equation is:
Arrhenius Equation
Where,
 k denotes the rate constant of the reaction

 A denotes the pre-exponential factor which, in terms of the collision theory, is the
frequency of correctly oriented collisions between the reacting species
 e is the base of the natural logarithm (Euler’s number)
 Ea denotes the activation energy of the chemical reaction (in terms of energy per mole)
 R denotes the universal gas constant
 T denotes the absolute temperature associated with the reaction (in Kelvin)
If the activation energy is expressed in terms of energy per reactant molecule, the universal gas
constant must be replaced with the Boltzmann constant (k B) in the Arrhenius equation.
Arrhenius Plot
When logarithms are taken on both sides of the equation, the Arrhenius equation can be written
as follows:
ln k = ln(Ae-Ea/RT)
Solving the equation further:
ln k = ln(A) + ln(e-Ea/RT)
ln k = ln(A) + (-Ea/RT) = ln(A) – (Ea/R)(1/T)
Since ln(A) is a constant, the equation corresponds to that of a straight line (y = mx + c) whose
slope (m) is -Ea/R. When the logarithm of the rate constant (ln K) is plotted on the Y-axis and the
inverse of the absolute temperature (1/T) is plotted on the X-axis, the resulting graph is called an
Arrhenius plot.
Arrhenius Plot
The Arrhenius plot for the decomposition of nitrogen dioxide is illustrated above.
Arrhenius Equation for a reaction taking place at two different temperatues

Considering a chemical reaction at two different temperatures T 1 and T2, whose corresponding
rate constants are k1 and k2 respectively, the logarithmic form of the Arrhenius equation is:
ln k1 = ln(A) – Ea/RT1
ln k2 = ln(A) – Ea/RT2
Subtracting eqn (2) from eqn (1)
𝐸 𝐸
ln(𝑘1 ) − ln(𝑘2 ) = 𝑎⁄𝑅𝑇 − 𝑎⁄𝑅𝑇
2 1
𝑘1 𝐸
ln ⁄𝑘 = 𝑎⁄𝑅 [1⁄𝑇 − 1⁄𝑇 ]
2 2 1
Arrhenius Equation and the Pre-Exponential Factor (A)

The symbol ‘A’ in the Arrhenius equation denotes the pre-exponential factor or the frequency
factor. This factor deals with the collisions between molecules and can be thought of as the
frequency of correctly oriented collisions between molecules that have sufficient energy to spark
a chemical reaction.
The pre-exponential factor is often represented by the following equation:
A = ⍴Z
Where Z is the frequency factor (frequency of collisions) and ⍴ is the steric factor (deals with
orientation of molecules).
The value of A must be determined experimentally since it assumes different values for different
reactions. It is also dependent on the temperature at which the reaction is taking place. The units
of A are dependent on the order of the reaction. For example, the value of ‘A’ for a second-order
rate constant is expressed in L.mol-1.s-1 (or M-1s-1 , since M = mol.L-1) and that of a first-order
rate constant is expressed in s-1.
Collision Theory:
According to this theory, for chemical reaction to occur, there must be collisions between the
reactant molecules. However all the collisions between molecules are not effective. Only those
collisions in which the colliding molecules are associated with a certain minimum energy called
the threshold energy result in chemical reaction.
A certain minimum energy which the colliding molecules must acquire to undergo a
chemical reaction is called Threshold Energy. However most of the molecules have much lesser
Kinetic energy than the threshold energy. The excess energy that the reactant molecules having
energy less than the threshold energy must acquire in order to react to yield products is known as
activation energy.
Thus,
Activation Energy=Threshold Energy – Energy actually possessed by molecules
From the Kinetic theory of gases, the number of bimolecular collisions per second per cm3
8𝜋𝐾𝑇 1/2
among molecules of one species is given by 𝑍 = 2𝑛2 𝑑 2 ( )
𝜇
For a reaction n involving two different gases A and B, the rate of bimolecular collisions
8𝜋𝐾𝑇 1/2
between unlike molecules per second unit voliume is given by 𝑍𝐴𝐵 = 𝑛𝐴 𝑛𝐵 (𝑑𝑎𝑣 )2 ( )
𝜇
𝑛𝐴 and 𝑛𝐵 are the numbers of A and B molecules, respectively and 𝑑𝑎𝑣 is the average collision
(𝑑𝐴 +𝑑𝐵 )⁄ 𝑀𝐴 𝑀𝐵
diameter defined as 2 and 𝜇 is the reduced mass defined as 𝜇 = (𝑀𝐴+𝑀𝐵 ). In terms
of molar masses 𝑀𝐴 and 𝑀𝐵
2
(𝑀𝐴 + 𝑀𝐵 )8𝜋𝑟𝑇 1/2
𝑍𝐴𝐵 = 𝑛𝐴 𝑛𝐵 (𝑑𝑎𝑣 ) [ ]
𝑀𝐴 𝑀𝐵
Activated Complex Theory (ACT) of Bimolecular Reactions:

According to Activated Complex Theory (ACT) or Transition State Theory (TST), the
bimolecular reaction between two molecules A2 and B2 progresses through the formation of the
so-called activated complex which then decomposes to yield the product AB, as illustrated below
A2 + B2 ⇌ (𝐴2 B2 )≠ →2AB
𝐴−𝐴 𝐴 … .𝐴 𝐴 𝐴
or, + ⇌ ⋮ ⋮ → ∣ + ∣
𝐵−𝐵 𝐵 … .𝐵 𝐵 𝐵
(1)The activated complex is regarded as a separate entity and ut is always equilibrium

with the reactant molecules.
A+ B⇋X
𝑐𝐴 𝑐𝐵 𝑐≠
𝐶≠
The equilibrium constant 𝑘 ≠ = 𝐶
𝐴 𝐶𝐵
𝑐 ≠ = 𝑘 ≠ 𝑐𝐴 𝑐𝐵
(2)The activation energy (E) of the reaction is the additional energy which the reactant
molecules acquire to form the activated complex (X)
(3) The activated complex must have one of uts vibrational degrees of freedom which
would be quite unstable. The frequency of such vibration will be low and the average energy will
be of the order of kT. If 𝑣 be the frequency of this vibration
ℎ𝑣 = 𝑘𝑇
𝑘𝑇
𝑣=
ℎ
This frequency would give the rate at which complex would break up into products
𝑟𝑎𝑡𝑒 = 𝑣𝑐 ≠
𝑟𝑎𝑡𝑒 = 𝑣𝑘 ≠ 𝑐𝐴 𝑐𝐵
If k1 is the rate constant of the reaction
𝑟𝑎𝑡𝑒 = 𝑘1 𝑐𝐴 𝑐𝐵
Comparing the above two equations
𝑘𝑇 ≠
𝑘1 = 𝑣𝑘 ≠ = 𝑘
ℎ
𝑘 ≠ can be expressed in terms of thermodynamic quantities
𝑅𝑇𝑙𝑛𝑘 ≠ = ∆𝐺 ≠
∆𝐺 ≠⁄ (∆𝐻 ≠ −𝑇∆𝑆 ≠ )⁄
𝑘≠ = 𝑒− 𝑅𝑇 = 𝑒− 𝑅𝑇
∆𝑆 ≠⁄ ∆𝐻 ≠⁄
=𝑒 𝑅 𝑒− 𝑅𝑇
𝑘𝑇 ≠ 𝑘𝑇 ∆𝑆 ≠⁄ −∆𝐻 ≠⁄
𝑘1 = 𝑘 = 𝑒 𝑅 𝑒 𝑅𝑇
ℎ ℎ

Chemical Kinetic 2

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Chemical Kinetics (Note -2)

The Arrhenius Equation:

 k denotes the rate constant of the reaction

Arrhenius Equation for a reaction taking place at two different temperatues

Arrhenius Equation and the Pre-Exponential Factor (A)

Activated Complex Theory (ACT) of Bimolecular Reactions:

(1)The activated complex is regarded as a separate entity and ut is always equilibrium

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