Bangladesh University of Engineering and Technology

Department of Chemistry
Course Title:
Chemical Kinetics & Solution Thermodynamics
Code: Chem-6107

Topic : Theories of Reaction Rate

GROUP C
MEMBER OF THE GROUP:
1. Keya Chowdhury
2. Anila Anwar Sharmi
3. Md.Moniruzzaman
4. Maharun Mojumder
Table of content

• Application of conventional Transition-state Theory.

• Reaction Between Atoms.
• Reaction Between Molecules.
• Example.
Reaction Between Atoms
Considering a reaction between two atoms A and B to form a diatomic molecule AB
via an activated complex.

𝐴 + 𝐵 → 𝑋 ≠ → AB

Here, 𝑋≠ = Activated complex

Reaction Between Atoms
By the methods of Conventional Transitional State Theory, the rate equation for
the reaction is,
Here, k = Boltzman constant
𝑘𝑇 𝑞≠ 𝐸
− 0 T = Temperature
𝑘𝑎 = 𝑒 𝑅𝑇
h = Plank constant
ℎ 𝑞𝐴 𝑞𝐵
𝑞≠ = Partition function of the
activated complex
𝑞𝐴 = Partition function of the atom A
𝑞𝐴 = Partition function of the atom B
E = Activation energy
R = Molar gas constant
Reaction Between Atoms
As A and B are atoms, they will only have transition partition function.
3
(2𝜋𝑚𝐴 𝑘𝑇)2
𝑞𝐴 = 𝑚𝐴 =Atomic Mass of A
ℎ3
3
(2𝜋𝑚𝐵 𝑘𝑇)2
𝑞𝐵 = 𝑚𝐵 =Atomic Mass of B
ℎ3
As activated complex, X = A……B, that means it is a diatomic molecule, so it
should have three types of partition function. Considering all the partition
function together we can write,
3
[2𝜋(𝑚𝐴 +𝑚𝐵 )𝑘𝑇]2 8𝜋2 𝐼𝑘𝑇
𝑞≠ = Here, I = Deceiver inertia
ℎ3 ℎ2
Reaction Between Atoms
In activated complex, the distance between A and B is d
So we can write,
2 𝑚𝐴 𝑚𝐵 2
Deceiver Inertia= 𝐼 = 𝜇𝑑𝐴𝐵 = 𝑑𝐴𝐵
𝑚𝐴 +𝑚𝐵
Here,
𝑚𝐴 𝑚𝐵
Reduced Mass =𝜇 =
𝑚𝐴 +𝑚𝐵
Reaction Between Atoms
Now from the rate equation,
𝐸 0
𝑘𝑇 𝑞≠ − 𝑅𝑇
𝑘𝑎 = 𝑒
ℎ 𝑞𝐴 𝑞𝐵
3
𝐸
𝑘𝑇 [2𝜋(𝑚𝐴 +𝑚𝐵 )𝑘𝑇]2 8𝜋2 𝐼𝑘𝑇 ℎ3 ℎ3 0
− 𝑅𝑇
= 3 3 𝑒
ℎ ℎ3 ℎ2
(2𝜋𝑚𝐴 𝑘𝑇)2 (2𝜋𝑚𝐵 𝑘𝑇)2
3
𝐸
𝑘𝑇 [2𝜋(𝑚𝐴 +𝑚𝐵 )𝑘𝑇]2 8𝜋2 𝑘𝑇 𝑚𝐴 𝑚𝐵 2 ℎ3 ℎ3 0
− 𝑅𝑇
= 𝑑𝐴𝐵 3 3 𝑒
ℎ ℎ3 ℎ 2 𝑚𝐴 +𝑚𝐵
(2𝜋𝑚𝐴 𝑘𝑇)2 (2𝜋𝑚𝐵 𝑘𝑇)2
Reaction Between Atoms
After solving the equation we got:
8𝜋𝑘𝑇 1 2
𝐸
− 0
𝑘𝑎 = ( )2 𝑑𝐴𝐵 𝑒 𝑅𝑇
𝜇

And from this equation, we can see that the result from the
Conventional Transition State Theory is same as the Collision Theory.
Reaction Between Molecules.
Let us consider a complex reaction,

𝐴 + 𝐵 → 𝑋#

Where, A is the nonlinear# molecule having 𝑁𝐴 atoms ,B is the nonlinear molecule

having 𝑁𝐵 atoms and 𝑋 is the nonlinear molecule having (𝑁𝐴 + 𝑁𝐵 ) atoms.

Then the partition function may be given as,

3𝑁 −6
𝑄𝐴 =𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣 𝐴
3𝑁𝐵 −6
𝑄𝐵 =𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣
3(𝑁𝐴 + 𝑁𝐵 )−7
𝑄# =𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣
The absolute reaction rate in the case, We know from Eyring equation,

𝑘𝑇 𝑄#
𝑘′ = 𝑒 − 𝐸0 /𝑅𝑇 …………………….(i)
ℎ 𝑄𝐴 𝑄𝐵
Putting the value of 𝑄𝐴 , 𝑄𝐵 , 𝑄 # equation (i) then we get,

𝑘𝑇 𝑄#
𝑘′ = 𝑒 − 𝐸0 /𝑅𝑇
ℎ 𝑄𝐴 𝑄𝐵

𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣
(
3 𝑁𝐴 + 𝑁𝐵 )−7
𝑘𝑇
= 𝑒 − 𝐸0 /𝑅𝑇
ℎ 𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣 3𝑁𝐴 −6 𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣 3𝑁𝐵 −6
 𝑞𝑣
(
3 𝑁𝐴 + 𝑁𝐵 )−7
𝑘𝑇
𝑘′ = 𝑒 − 𝐸0 /𝑅𝑇
ℎ 𝑞𝑣 3𝑁𝐴 −6 𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣 3𝑁𝐵 −6

𝑘𝑇 𝑞 5
∴ 𝑘′ = 𝑣
𝑒 − 𝐸0/𝑅𝑇
ℎ 𝑞𝑇 3 𝑞𝑟 3

′ 𝑘𝑇 𝑞𝑟 2 𝑞𝑣 5
or, 𝑘 = 𝑒 − 𝐸0 /𝑅𝑇
ℎ 𝑞𝑇 3 𝑞𝑟 5

′ 𝑘𝑇 𝑞𝑟 2 𝑞𝑣 5 − 𝐸 /𝑅𝑇
∴𝑘 = 𝑒 0
ℎ 𝑞𝑇 3 𝑞𝑟
………………………….(ii)
Equation (ii) shows that,
The rate constant for a molecular reaction differs
𝑞𝑣 5
from that obtained in simple atomic reaction by a factor of .This
𝑞𝑟
factor may link to steric factor p.
𝑞𝑣 5
∴𝑝=
𝑞𝑟
Example.
 𝑞𝑣
(
3 𝑁𝐴 + 𝑁𝐵 )−7 𝑞𝑣
(
3 𝑁𝐴 + 𝑁𝐵 ) /𝑞7
𝑣
• 3𝑁𝐴 −6 3 3 3𝑁𝐵 −6 = 3(𝑁𝐴 +𝑁𝐵 ) −12
𝑞𝑣 𝑞𝑇 𝑞𝑟 𝑞𝑣 𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣

𝑞𝑣
3 𝑁𝐴( + 𝑁𝐵 ) /𝑞 7 𝑞𝑣
(
3 𝑁𝐴 + 𝑁𝐵 ) /𝑞 7
𝑣 𝑣
• = 3 3 3𝑁𝐴 −6 3𝑁𝐵 −6 = 3(𝑁𝐴 +𝑁𝐵 )
𝑞𝑇 𝑞𝑟 𝑞𝑣 𝑞𝑣 𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣 /𝑞𝑣 12

𝑞𝑣
(
3 𝑁𝐴 + 𝑁𝐵 ) /𝑞 7 (
3 𝑁𝐴 + 𝑁𝐵 )
𝑣 1 𝑞𝑣
• = 3 3 3𝑁𝐴 −6+3𝑁𝐵 −6 =𝑞 3 3 𝑞𝑣 7
×
𝑞𝑇 𝑞𝑟 𝑞𝑣 𝑇 𝑞𝑟
𝑞𝑣 12
3(𝑁𝐴 +𝑁𝐵 )
𝑞𝑣

𝑞𝑣
3 𝑁𝐴( + 𝑁𝐵 ) /𝑞 7
𝑣 1 1
• = 3(𝑁𝐴 +𝑁𝐵 ) −12 = 3 3
𝑞𝑇 𝑞𝑟
× 𝑞𝑣 12−7 =
𝑞𝑇 3 𝑞𝑟 3
× 𝑞𝑣 5
𝑞𝑇 3 𝑞𝑟 3 𝑞𝑣