Lecture 3

Fluid-solid catalytic reactions: Mechanism

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Steps in a Catalytic Reaction

A photograph of different types and sizes of catalyst is shown in Figure 5a. A schematic diagram
of a tubular reactor packed with catalytic pellets is shown in Figure 5b.

Fig. 5. (a) Different shapes and sizes of catalyst (b) Catalytic packed-bed reactor-schematic

For a catalytic reaction occurring in a porous catalyst pellet (the traditional case in chemical
engineering applications), we can envision the overall reaction as a series of sequential steps:

(1) Transport of reactants to the exterior surface of the catalyst pellet.

(2) Transport of reactants to active sites inside the pores.
(3) Adsorption of reactants onto the surface at active sites.
(4) Reaction on the surface.
(5) Desorption of products from the surface.
(6) Transport of products out of the pores to the pellet surface.
(7) Transport of products from the pellet surface to the bulk fluid.
For the generic catalytic reaction A → B, this can be illustrated schematically as

We will first focus on steps 3, 4, and 5 – which we might call the reactive steps, as opposed to
steps 1, 2, 6, and 7, which involve only transport and not chemical transformations. In subsequent
lectures, we will consider the effects of transport limitations that can be both external (steps 1 and
7) and internal (steps 2 and 6) to the catalyst pellet. For situations other than heterogeneous
catalysis with a porous pellet catalyst, some of these steps may be missing. In a CVD reactor, for
example, the surface is generally flat, smooth, and nonporous. Then, the transport steps can be
simplified or eliminated, but the reactive steps remain essentially the same.

Adsorption of gases on solid surfaces is often classified as chemisorption or physisorption,

depending on the strength of interaction between the surface and the adsorbed molecule.

Physisorption is characterized by interaction energies comparable to heats of vaporization

(condensation). The adsorbate is held to the surface by relatively weak van der Waals forces.
Multiple layers may be adsorbed with approximately the same heat of adsorption (∆H for the
reaction written as A + surface → adsorbed A). The heat of adsorption for physisorption is at most
a few kcal/mole.

Chemisorption is characterized by interaction energies between the surface and adsorbate

comparable to the strength of chemical bonds (tens of kcal/mole). The adsorbate forms a chemical
bond to a surface atom (or atoms). The adsorbate may dissociate or otherwise react upon
adsorption. Generally only a single molecular layer can be adsorbed. The heat of adsorption is
tens of kcal/mole.

Of course, this is a somewhat arbitrary distinction, but it has proven to be a useful one. In general,
physisorption behaves like condensation, while chemisorption behaves like chemical reaction. For
a surface-catalyzed reaction to occur, chemical bonds must be made and broken, so we will focus
primarily on chemisorption.

Adsorption Isotherms:
Because chemisorption is usually a necessary part of a catalytic process, we shall discuss
it before treating catalytic reaction rates. The letter S will represent an active site; alone, it
will denote a vacant site, with no atom, molecule, or complex adsorbed on it. 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. Species A can be an atom, molecule, or some other atomic combination, depending
on the circumstances. Consequently, the adsorption of A on a site S is represented by

A + S ↔ A·S

The 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 labeled Ct (mol/g cat).
The molar concentration of vacant sites, Cv, is the number of vacant sites per unit mass of
catalyst divided by Avogadro's number. In the absence of catalyst deactivation, we assume that
the total concentration of active sites remains constant. Some further definitions include
Pi = partial pressure of species i in the gas phase, (atm or kPa)
Ci.s = surface concentration of sites occupied by species i, (mol/g cat)

A conceptual model depicting species A and B on two sites is shown in Figure 6.

A + S ↔ A·S

Fig. 6. Vacant and occupied sites

For the system shown, the total concentration of sites is

Ct = Cv + CA.S + CB.S (1)

This equation is referred to as a site balance. Now consider the adsorption of a nonreacting gas
onto the surface of a catalyst. Adsorption data are frequently reported in the form of adsorption
isotherms. Isotherms portray the amount of a gas adsorbed on a solid at different pressures but at
one temperature. First, 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 data, the model may reasonably describe what is
occurring physically in the real system. If the predicted curve does not agree with the
experimental data, the model fails to match the physical situation in at least one important
characteristic and perhaps more. To illustrate the difference between molecular adsorption and
dissociative adsorption, we will postulate two models for the adsorption of carbon monoxide on
metal surfaces. In one model, CO is adsorbed as molecules, CO,

as is the case on nickel

In the other, carbon monoxide is adsorbed as oxygen and carbon atoms instead of molecular CO.
as is the case on iron

The former is called molecular or nondissociated adsorption (e.g., CO) and the latter is
called dissociative adsorption (e.g., C and O). Whether a molecule adorbs nondissociatively or
dissociatively depends on the surface.

The adsorption of carbon monoxide molecules will be considered first. Because the carbon
monoxide does not react further after being adsorbed, we need only to consider the
adsorption process:

In obtaining a rate law for the rate of adsorption, the above reaction can be treated as an
elementary reaction. The rate of attachment of the carbon monoxide molecules to the active site
on the surface is proportional to the number of collisions that these molecules make with a
surface active site per second. In other words, a specific fraction of the molecules that strike
the surface become adsorbed. The collision rate is, in turn, directly proportional to the carbon
monoxide partial pressure, PCO. Because carbon monoxide molecules adsorb only on vacant
sites and not on sites already occupied by other carbon monoxide molecules, the rate of
attachment is also directly proportional to the concentration of vacant sites, Cv. Combining
these two facts means that the rate of attachment of carbon monoxide molecules to the surface
is directly proportional to the product of the partial pressure of CO and the concentration of
vacant sites; that is,

(2)
The rate of detachment of molecules from the surface can be a first-order process; that is, the
detachment of carbon monoxide molecules from the surface is usually directly proportional
to the concentration of sites occupied by the adsorbed molecules (e.g., Cco·s):
(3)
The net rate of adsorption is equal to the rate of molecular attachment to the surface minus the rate
of detachment from the surface. If kA and k-A are the constants of proportionality for the attachment
and detachment processes, then
(4)
The ratio KA = kA/k-A is the adsorption equilibrium constant. Using KA to rearrange above equation
gives

(5)

The adsorption rate constant, kA, for molecular adsorption is virtually independent of
temperature, while the desorption constant, k-A, increases exponentially with increasing
temperature. Consequently, the equilibrium adsorption constant KA decreases exponentially with
increasing temperature.

Because carbon monoxide is the only material adsorbed on the catalyst, the site balance gives

(6)

At equilibrium, the net rate of adsorption equals zero, i.e. rAD ≡ 0. Setting the left-hand side of
Equation (5) equal to zero and solving for the concentration of CO adsorbed on the surface,
we get

(7)

Using Equation (7) to give Cv in terms of CCO·S and the total number of sites Ct we can
solve for the equilibrium value of CCO·S in terms of constants and the pressure of carbon
monoxide:

(8)
Rearranging gives us

(9)

This equation thus gives the equilibrium concentration of carbon monoxide adsorbed on the
surface, CCO·S, as a function of the partial pressure of carbon monoxide, and is an equation
for the adsorption isotherm. This particular type of isotherm equation is called a Langmuir
isotherm.

Figure 7 shows the Langmuir isotherm for the amount of CO adsorbed per unit mass of catalyst
as a function of the partial pressure of CO.

Fig. 7. Langmuir isotherms for (a) molecular adsorption (b) dissociative adsorption of CO.

One method of checking whether a model (e.g., molecular adsorption versus dissociative
adsorption) predicts the behavior of the experimental data is to linearize the model's equation
and then plot the indicated variables against one another. For example, Equation (9) may be
arranged in the form

(10)

and the linearity of a plot of PCO/CCO·S as a function of PCO (Fig. 8) will determine if the data
conform to a Langmuir single-site isotherm.

Fig. 8. Molecular adsorption

Next, we derive the isotherm for carbon monoxide disassociating into separate atoms as it adsorbs
on the surface, i.e.

When the carbon monoxide molecule dissociates upon adsorption, it is referred to as the
dissociative adsorption of carbon monoxide. As in the case of molecular adsorption, the rate of
adsorption is proportional to the pressure of carbon monoxide in the system because this
rate is governed by the number of gaseous collisions with the surface. For a molecule to
dissociate as it adsorbs, however, two adjacent vacant active sites are required, rather than
the single site needed when a substance adsorbs in its molecular form. The probability of two
vacant sites occurring adjacent to one another is proportional to the square of the concentration of
vacant sites. These two observations mean that the rate of adsorption is proportional to the
product of the carbon monoxide partial pressure and the square of the vacant-site
concentration, PCOCv2.

For desorption to occur, two occupied sites must be adjacent, meaning that the rate of desorption
is proportional to the product of the occupied-site concentration, (C·S)×(O·S). The net rate of
adsorption can then be expressed as

(11)

Factoring out kA, the equation for dissociative adsorption is

(12)
Where
For dissociative adsorption, both kA and k_A increase exponentially with increasing temperature,
while KA decreases with increasing temperature.

At equilibrium, rAD = 0, and

(13)

(14)

Substituting for CC.S and CO.S in a site balance Equation (1),

(15)

This value may be substituted into Equation (10) to give an expression that can be solved
for the equilibrium value of CCO·S. The resulting equation for the isotherm shown in Figure 9 is

(16)

Taking the inverse of both sides of the equation, then multiplying through by (PCO)1/2, yields

(17)

If dissociative adsorption is the correct model, a plot of (PCO1/2/CO.S) versus (PCO)1/2 should be
linear with slope (2/Ct).

Fig. 9. Dissociative adsorption

When more than one substance is present, the adsorption isotherm equations are somewhat
more complex. The principles are the same, though, and the isotherm equations are easily derived.
It is left as an exercise to show that the adsorption isotherm of A in the presence of another
adsorbate B is given by the relationship

(18)

When the adsorption of both A and B are first-order processes, the desorption are also first
order, and both A and B are adsorbed as molecules.

Instead of using the surface concentrations (CA-S) as the concentration variable, it is often
preferable to use the fractional coverage, defined by θA = CA-S/Ct. In terms of the fractional
coverage of A, the Langmuir isotherm is

K A PA
A  (19)
1  K A PA  K B PB

This adsorption isotherm (in terms of dimensionless variables) looks like

Fig. 10. Langmuir adsorption isotherm

The derivations of other Langmuir isotherms are relatively easy. The Langmuir isotherm is based
on 3 primary assumptions:

(1) The solid surface is made up of a uniform array of energetically identical adsorption sites.
(2) A maximum of one monolayer (one adsorbate molecule per site) can be adsorbed.
(3) There are no interactions between the adsorbed molecules.

In obtaining the Langmuir isotherm equations, several aspects of the adsorption system were
presupposed in the derivations. The most important of these, and the one that has been subject
to the greatest doubt, is that a uniform surface is assumed. In other words, any active site has
the same attraction for an impinging molecule as does any other active site. Isotherms different
from the Langmuir isotherm, such as the Freundlich isotherm, may be derived based on various
assumptions concerning the adsorption system, including different types of nonuniform surfaces.
Two other isotherms are the Freundlich isotherm and the Temkin isotherm.

The Freundlich isotherm is

(20)

where α and β are generally taken as fitting parameters. It has 2 parameters, which is one more
than the Langmuir isotherm, so it can often be made to fit adsorption data better over a limited
range.

The Temkin isotherm can be written as

(21)

where H ad0
is the heat of adsorption at zero coverage, and α is a fitting parameter. This isotherm
is derived by assuming that the heat of adsorption varies linearly with surface coverage, that is

Had  Had
0
(1   A ) (22)

There are, of course, many more sophisticated means of treating adsorption, but those listed above
are the most common. An important advantage of the Langmuir isotherm is that it can be simply
extended to competitive adsorption, dissociative adsorption, etc. while the other isotherms
mentioned here cannot be easily extended to these more complex situations.

Surface Reaction
The rate of adsorption of species A onto a solid surface,
A+ S ↔ A·S
is given by

After a reactant has been adsorbed onto the surface, i.e., A·S, it is capable of reacting in a
number of ways to form the reaction product. Three of these ways are:
Desorption

In each of the preceding cases, the products of the surface reaction adsorbed on the surface
are subsequently desorbed into the gas phase. For the desorption of a species (e.g., C),
C·S ↔ C + S

the rate of desorption of C is

where KDC is the desorption equilibrium constant. Now let’s look at the above adsorption from
right to left. We note that the desorption step for C is just the reverse of the adsorption step.
Consequently, the rate of desorption of C, rDC, is just opposite in sign to the rate of adsorption of
C, rADC:

In addition, we see that the desorption equilibrium constant KDC is just the reciprocal of
the adsorption equilibrium constant for C, KC:

in which case the rate of desorption of C can be written

(23)
In the material that follows, the form of the equation for the desorption step that we will
use to develop our rate laws will be similar to Equation (23).