Kinetics of Catalytic Reactions

After a catalyst is selected for the reaction under consideration, the next step is
to determine the intrinsic kinetics, which is discussed in Chapter 3. There are
many aspects of kinetics that should be investigated before and in conjunction
with this determination. This chapter considers some of the aspects that are
reievant to reactor design.
The Chemical transformation on the catalyst surface takes place in an orderly,
sequential manner. A catalytic reaction is initiated by the interaction of
reactant(s) with the active sites on the catalyst surface, usually in the form of
chemisorption. This causes a Chemical transformation on the surface, with the
transformed species then leaving the surface. Although the exact nature of the
sequence is quite difficult to identify in many cases, this sequence of surface
reactions is in general applicable to any catalytic reaction. This framework
provides a basis on which rate expressions that typically lead to LangmuirHinshelwood kinetic forms can be derived. On the other hand, the kinetics based
on a postulated mechanism often do not represent the true picture, and a
correlation, usually in a power-law form, may describe observed kinetics equally
well. Nevertheless, Langmuir-Hinshelwood kinetics based on some levei of
mechanistic understanding are much more desirable than brute- force kinetic
correlations. The rate expressions resulting from postulated mecha- nisms can be
checked for self-consistency by using some thermodynamic concepts. Consider,
first, surface reactions.
2-

1 SURFACE REACTIONS

The Chemical transformation of reactants on catalyst surfaces take place

sequentially in several steps. For the simple example of an isomerization
reaction, A ?= B, which takes place on a surface containing only one type of
active site, S, these individual steps are:
A + S ^=t A ' S
AS^B-S

(2.1)

BSB+S
The first step in this sequence represents the adsorption of A onto the surface;
the second, the surface reaction of adsorbed gas molecule A - S to B S; and the
third, the desorption of product B from the surface, which frees the active site S
for subsequent reactions. As indicated in the sequence for the isomerization
reaction, the precursor to any surface reaction is chemisorption, which involves a
specific interaction between surface and gas molecule (adsorbate), and thus is a
Chemical reaction in itself. Although the chemisorption was treated in Chapter 1,
it is exam- ined here in some detail for the surface reactions under consideration.
To derive an expression for the rate of adsorption, consider the process of
molecular effusion (Moore 1955) (Figure 2.1), which is the effusion of gas
molecules from a vessel of gas under pressure through a tiny orificean opening
so small that the distribution of the velocities of the gas molecules remaining in
the vessel is not affected in any way. The number of molecules escaping in unit
time is then equal to the number of molecules that, in their random motion,

happen to hit the orifice. This number is proportional to the average molecular
speed. If an incremental area, ds, of the catalyst surface is regarded as an orifice
and if there are n molecules per unit volume, the number striking the surface is
ncds, provided that all the molecules are movng directly perpendicular to the
surface at a mean speed of c. For unit surface area, the number of collisions
would be nc if all the molecules were moving perpendicular to the surface.
Actually, the number of collisions is only a fraction of nc since molecules move
randomly. If the direction of the molecules is no longer normal to the wall