ENCH 421 – Dr.

Hector De la Hoz Siegler

Catalysis
A Catalyst is a substance that affects the rate of chemical reaction but
emerges from the process unchanged.

A catalyst changes the reaction mechanism, providing a new path for

the reaction. The formation of a catalyst-reactant complex results in a
change in the reaction activation energy, which –frequently– means a
faster rate of reaction. Note that ∆GR and Keq are thermodynamic
properties and consequently are not affected by the reaction path
followed. A catalyst will not change ∆GR and Keq.

Steps in a heterogeneous catalytic reaction

1. Transport of reactants from the bulk mixture to
the catalyst particle
2. Transport of reactants in the pores of the catalyst
particles to an active site
3. Adsorption of the reactants to the active site
4. Reaction of reactants to form an adsorbed
product
5. Desorption of the product from the active site
6. Transport of the products in the pores of the
catalytic particle out of the particle
7. Transport of the products from the particle to the
bulk of the mixture

The Langmuir adsorption isotherm

Basic assumptions
• surface uniform (∆Hads does not vary with coverage)
• monolayer adsorption
• no interaction between adsorbed molecules, and
• adsorbed molecules immobile

Case I - single molecule adsorption

Cs B0 P
A(g) + M(surface site) D AM θ= =
C∞ 1+ B0 P

II - single molecule adsorbed dissociatively on one site

A-B(g) + M(surface site) D A-M-B Cs ( B0 PAB )1/2

θ= =
C∞ 1 + ( B0 PAB )1/2
III - two molecules adsorbed on two sites
Cs , A B0, A PA
A(g) + B(g) + 2M(surface site) D A-M θA = =
C∞ 1 + B0, A PA + B0, B PB
Cs , B B0, B PB
θB = =
C∞ 1 + B0, A PA + B0, B PB