Step Involved in

Catalytic Reaction

1. Mass transfer (diffusion of the reactants) (e.g.. species A) from the bulk
fluid to the external surface of the catalyst pellet.
2. Diffusion of the reactant from the pore mouth through the catalyst pores
to the intermediate vicinity of the internal catalytic surface.
3. Adsorption of reactant A onto the catalyst surface.
4. Reaction on the surface of the catalyst (e.g. A

B)

5. Desorption of the products (e.g. B) from the surface.

6. Diffusion of the products from the interior of the pellet to the pore mouth
at the external surface.
7. Mass transfer of the products from the external pellet surface to the bulk
fluid.

Reaction takes
place on the
surface, but the
species involved in
reaction must get to
and from the
surface

Steps in heterogeneous catalytic reaction

 The overall rate of reaction is equal to the rate of the slowest

step in the mechanism.
When the diffusion steps (1,2,6, and 7) are very fast
compared with the reaction steps (3, 4. and 5), the
concentrations in the immediate vicinity of the active sites are
indistinguishable from those in the bulk fluid. In this situation,
the transport or diffusion steps do not affect the overall rate
of the reaction.
Reaction steps are very fast compared with the diffusion
steps, mass transport does affect the reaction rate.

Step I Overview: Diffusion from the

Bulk to the External Transport

Bulk concentration CAb must travel through the boundary layer of

thickness to the external surface of the pellet where the concentration
is CAS as shown in Figure. Rate of transfer:

Kc: mass transfer coefficient

Rate

Low Velocities
Boundary layer is thick
Long time for A to travel to the surface
Small mass transfer coefficient kc.
Mass transfer across the boundary layer is slow
and limits the rate of the overall reaction.

Very high velocities

Boundary layer is so small it no longer
offers any resistance to the diffusion
across the boundary layer.
External mass transfer no longer limits the
rate of reaction.

External resistance also decreases as the particle size is decreased.

As the fluid velocity increases and/or the particle diameter decreases,

the mass transfer coefficient increases until a plateau is reached.

Step 2 Overview: Internal Diffusion

As A diffuses into the interior of the pellet, it reacts with catalyst deposited on
the sides of pore walls.

For large pellets, it takes a long time for the reactant A to diffuse into interior
compared to the time it takes for the reaction to occur on the interior pore
surface. Under these circumstances, the reactant is only consumed at the
exterior surface of the pellet and the catalyst near the centre of the pellet is
wasted catalyst.

For very small pellets it takes very little time to diffuse into and out of pellet
interior and, as a result, internal diffusion no longer Limits the rate of reaction

Rate of Reaction

At small particle sizes internal diffusion is no longer the slow

step
Surface reaction sequence of adsorption, surface reaction desorption (Steps
3, 4, and 5) limit the overall rate of reaction

A model system is proposed and then the isotherm obtained

from the model is compared with the experimental data shown
on the curve.

If the curve predicted by the model agrees with the

experimental one, the model may reasonably describe what is
occurring physically in the real system.

If the predicted curve does not agree with data obtained

experimentally, the model fails to match the physical situation in
at least one important characteristic and perhaps more.

Adsorption Isotherms

Isotherms portray the amount of a gas adsorbed On a solid at different

pressures but at one temperature.

A physical phenomena

Adsorption Isotherms

S : an active site; alone it will denote a vacant site,

The combination of S with another Letter (e.g., A.S) will mean that one
unit of species A will be adsorbed on the site S.

The adsorption of A on a site S is represented by

total molar concentration of active sites

per unit mass of catalyst is equal to the
number of active sites per unit mass
divided by Avogadro's number and will
be labelled C, (mol/g .cat).

Absence of catalyst deactivation: total concentration of active sites

remains constant.

Pi

Ci.s surface concentration of sites occupied by species i, rnol/g cat

partial pressure of species i in the gas phase. atm or kPa.

A conceptual mode1 depicting species A and B on two sites

For the system shown, the total concentration of sites is

Site balance

Adsorption of carbon monoxide on

metal surfaces
molecular or non-dissociated adsorption
dissociative adsorption

C O + S

C O + 2 S

Adsorption of carbon monoxide

molecules
C O + S
rate of attachment of the carbon
monoxide molecules to the active proportional
site on the surface

(1)
number of collisions that these
molecules make with a surface
active site per second

a specific fraction of the molecules that

strike the surface become adsorbed

Carbon monoxide partial pressure, Pco

Concentration of vacant sites, Cv

(2)

Detachment of carbon monoxide molecules from the surface is usually

directly proportional to the concentration of sites occupied by the
adsorbed molecules

The net rate of adsorption is equal to the rate of molecular attachment to the
surface minus the rate of detachment from the surface.

(3)
adsorption equilibrium
constant

(4)

Because carbon monoxide is the only material adsorbed on the

catalyst the site balance gives
(5)

At equilibrium, the net rate of adsorption equals to zero from equation 4

From equation 5 &

6

Rearranging

(6)

adsorption isotherm
Langmuir isotherm

Langmuir-Hinshelwood (LH) mechanism :

The adsorbed species are held onto definite points of attachment on the
surface. Each site can accommodate only one adsorbed species.

The surface is completely uniform so that there is the same probability

of adsorption on all sites. Attractive or repulsive forces between
adjacent adsorbed molecules are taken to be negligible.

Amount of CO adsorbed per unit mass of catalyst as a

function of the partial pressure of CO

Isotherm for carbon monoxide

adsorption
adsorbed as atomsDissociative
(
)
C O + 2 S

For a molecule to dissociate as it adsorbed, two adjacent vacant

active sites are required rather than the sing site needed when a
substance adsorbs in its molecular form
Probability of two vacant sites occurring adjacent to one another
is proportional to the square of the concentration of vacant sites

For desorption to occur, two occupied sites must be adjacent

Factoring out kA, the equation for dissociative adsorption is

-

)
Please write
down the
steps ???

Langmuir
isotherm for
adsorption as

When more than one substance is

present

Home Assignment
??????

Surface
The rate of adsorption of species A onto a solid surface,
Reaction
A + S
-

After a reactant has been adsorbed onto the surface, it is capable

of reacting in a number of ways to form the reaction products.

Reaction Mechanism
Single site:

only the site on which the reactant is adsorbed is

involved

Dual site:

adsorbed reactant interacts with another site

reaction between two adsorbed species
reaction of two species adsorbed on different types of
sites

Eley-Rideal:

the reaction between an adsorbed molecule and a

molecule in

the gas phase

Single site

only the site on which the reactant is adsorbed is involve

an adsorbed molecule of A may isomerize (or perhaps decompose)

directly on the site to which it is attached.

A . S

Because in each step the reaction mechanism is elementary, the

surface reaction rate law is
-

Dual site

adsorbed reactant interacts with another site (either unoccupied or

occupied) to form the product

A.S
+S

corresponding surface reaction rate law

-

)
dehydration of butanol

Dual site

Reaction between two adsorbed species

A . S + B . S
surface reaction rate law
-

Dual site

the reaction of two species adsorbed on different types of sites

A.S
+ B.S

surface reaction rate law

-

Eley-Rideal

the reaction between an adsorbed molecule and a molecule in the gas

phase.

A . S + B ( g )
surface reaction rate law
-

propylene and benzene

Desorption

the products of the surface reaction adsorbed on the surface are

subsequently desorbed into the gas phase

C . S
The rate of desorption of
C
-

KDC is the desorption equilibrium constant

The Rate-Limiting Step

When heterogeneous reactions are carried out at steady state. the rates
of each of the three reaction steps in series (adsorption, surface reaction
and desorption) are equal to one another.

One particular step in the series is usually found to be rare-limiting or

rate-controlling.

if we could make this particular step go faster, the entire reaction would
proceed at an accelerated rate.

In writing this sequence. one must choose among such

mechanisms as molecular or atomic adsorption, and singleor dual-site reaction. Next, rate Iaws are written for the
individual steps as shown in the preceding section,

synthesis of ammonia from hydrogen

and nitrogen (adsorption-limited)

Rapid

Rate Limiting

Rapid

Two noxious automobile exhaust

products CO and NO (Surface-limiting )

Rapid

Rate
Limiting

Rapid

Synthesizing a Rate Law, Mechanism,

and Rate-Limiting Step

decomposition of cumene to form benzene and propylene

platinum
catalyzed
reaction

Steps in Langmuir-Hinshelwood
Kinetic Mechanism
(22)

(23)

(24)

Rate of adsorption of cumene

(25)

Surface reaction: Adsorbed benzene and propylene in gas phase

(26)

rate of benzene desorptian

(28)

Desorption is just the reverse of the adsorption of

benzene

Rate of desorption may be written as:

Because there is no accumulation of reacting species on the

surface

By assuming that this (or any other) step is

rate-limiting, we are considering that the
reaction rate constant of this step (in this

Is the Adsorption of Cumene RateLimiting?

(25
)

Need to express CV, and CC,S in terms of PC , PB and PP

For adsorption limited reactions, kA is small and kS and kD are large.

Consequently, the ratios rS/kS and rD/kD are very small (approximately
zero), whereas he ratio rAD/kA is relatively large.

Surface reaction rate law

(31)

For adsorption-limited reactions the surface specific reaction rate k S is

large by comparison
(32)

(33)

For adsorption-limited reactions, kD is large by comparison

(34)

By (33) & (35)

(35)

(36)

Replacing CC.S in the rate equation by Equation (36) and then factoring C V

(37)

by setting rAD = 0, the term (KS KC/KB) is simply the overall partial pressure
equilibrium constant, KP for the reaction

Cv, can be eliminated from Equation (37) by utilizing the site balance

Cumene reaction rate law if adsorption were the limiting

step

No products are
present; consequently,
PP = PB = 0. The initial
rate is given by

Is the Surface Reaction Rate-Limiting?

rate of surface reaction

kA and kD, are very large by comparison with kS

rAD/kA = 0 = rD/kD and site balance

Initial rate

At low pressure

At high
pressure

Is the desorption Rate-Limiting?

Actual initial rate as a function of partial pressure of cumene

Surface limited reaction mechanism is consistent with the

experimental data

If we were to have an adsorbing inert in the feed

Inert would not participate in the reaction but would occupy sites on
the catalyst surface

Rate law For surface reaction control when an adsorbing inert is present