Bangladesh University

of Engineering and
Technology

Department of Chemistry

Course Title:
Chemical Kinetics & Solution
Thermodynamics
Code: Chem-6107
Study Team
Anila Anwar Sharmi

Md.Moniruzzaman

Keya Chowdhury

Maharun
Mojumder
Table of content
• Unimolecular Surface Reactions.
• Inhibitions.
• Activation Energies.
• Bimolecular Surface Reactions.
Unimolecular Surface Reactions:
Examples of Unimolecular Surface
Reaction
 Inhibition

• A complication in surface reactions arises when a

substance other than reactant is adsorbed on the
surface. This reduces the effective surface area, and
therefore rate. If the fraction of the surface covered
by the reactant A and a nonreacting substance I,
Known as an inhibitor or a poison-
We have ,𝜃 =1+k
kA [A]
----------
A A +K I [I]

------------------------------- (i)
Where k A and K I are the adsorption constant for A and I
Again, The rate of reaction = K𝜃
When the surface is covered only sparsely by the
reactant but is covered fairly by the inhibitor , then
K I [I] >>1 + k A A ………………. …(iii)
𝐾kA [A]
And , the rate is then =
KI [I]
………………………………..(iv)
From the equation (iv)we can get the fact that since
the surface is covered sparsely by [A],the coverage is
proportional to [A],since it is covered almost fully by
I,the bare fraction is inversely proportional to [I]
An example of a reaction obeying from equation (iv) is the decomposition of
ammonia on platinum, inhibited by hydrogen.
The rate equation is ,
𝐾 [NH3 ]
= ………………………(v)
[H2 ]
Since hydrogen is a product of reaction there is progressive inhibition as
reaction proceeds.
Definition of activation energy
A common example
Summary
Energy Diagram of a Reaction
Potential Energy Curve: Endothermic
Potential Energy Curve: Exothermic
Arrhenius Equation
Activation energies of Adsorption
Activation energies of Adsorption
Activation energies of Adsorption
Activation energies of Adsorption
Reaction between two adsorb molecules :
Two special cases are of interest:
References

Principal of physical chemistry.

Chemical_Kinetics-Laidler

http://vallance.chem.ox.ac.uk/pdfs/KineticsAtSurfaces.pdf

https://www.personalas.ktu.lt/~julivan/chemistry