Rates of Bimolecular Heterogeneous

L. Glasser
Rhodes University
Grahamstown, 6140, South Africa
Reactions following the

Langmuir- Hinshelwood Mechanism

The Langmuir-Hinshelwood equation is fundamental to does the maximal rate indeed occur when
the study of heterogeneous catalysis.1'2 Since it is derived from KaPa= KbPb
an idealized model of bimolecular surface-mediated reactions,
This may be verified by substitution of the above conditional
it involves certain considerable limitations in its application statement on the pressure into the Langmuir-Hinshelwood
to real systems; nevertheless, it deserves some attention be-
equation, followed by differentiation and solution for the
cause this model forms a basis to the study of such reaction
maximum. The result corresponds to the maximum possible
rates. number of A-B interactions on the catalyst surface.
The model assumes a uniform solid surface with no inter-
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Figure 1 depicts the reaction rate as a function of KaPa (or

action between adsorbed species (other than reaction!), re- of p a) with Kbp b a parameter (i.e., it is maintained constant
,

quires equilibrium between gas and adsorbed species at all

times, and permits of no adsorption of reaction products. The
reactants (A, B) are each regarded as adsorbing on the catalyst
surface, following the Langmuir isotherm
qA _
K.\Pa_
1 + KaPa + KbPb
where 0 a fraction of surface sites occupied by the A species;
=

Ka, Kb Langmuir adsorption coefficients; and Pa, Ph

= =

equilibrium pressures in the volume phase. The second and

third terms in the denominator result from competitive ad-
sorption of A and of B, respectively, onto surface sites, which
are assumed to be available to either species.
The rate of the bimolecular reaction on the surface is pro-
portional to the product of the fractions of surface covered by
the two reacting species, viz.,
rate =
k iiOaUb
Figure 1. Reaction rate according to the Langmuir-Hinshelwood mechanism as

11
. AapaKbPb a function of KApA. with KbPb as a parameter (increasing at equal intervals of
(1 + KaPa + AbPb)2 5 from the value 2, from left- to right-most curves). Maxima in the rate occur when
where An is the bimolecular rate constant. This is the Lang- KApA = KbPb + 1. with the values
muir-Hinshelwood equation. fdi KbPb
The variation in reaction rate with pressure is not easily 4(1 + KaPa)
visualized because of the presence of the two independent
variables (pa.Pb), and recourse is normally had to consider-
ation of limiting behavior to illustrate this variation. Thus,
if Pb is maintained constant then, at sufficiently low values
of pA
rate =* A’hAaAbpb A
(1 + KbPb)2

i.e., the rate is first-order in A. The same result follows if A is

weakly adsorbed, i.e., if K\ is sufficiently small. At sufficiently
high values of pa, with pe kept constant
rate (knKbPbKa_i)/pa
^

i.e., the rate is of order in A. Hence, the rate passes through

—1
a maximum as pa is varied, attaining that maximum when
AaPa AbPb + 1; conversely, if p a is kept constant and pn
=

varied, a maximum rate is attained when KbPb KaPa + 1. =

These conditions for maximal rates are found by partial dif-

ferentiation of the rate expression with respect to the variable
pressure and setting the results equal to zero. Many texts
mistakenly assert that maximal rates are found when KaPa
-

AbPB' However, only if p\ and pb are not independent, so

that
Kapa + KbPb const =

Figure 2. Contour diagram of reaction rate as a function of KApA and of KapB;

Thomas, J. M., and Thomas, W. J., “Introduction to the Principles
1
the scales along each axis are equal, and the contours are plotted at equal in-
of Heterogeneous Catalysis,” Academic Press, London, 1967. tervals of 0.02 Kn, increasing from 0.04 KM tor the contour nearest the origin.
2
Thomson, S. J., and Webb, G., “Heterogeneous Catalysis,” Oliver Lines representing the conditions: KbPb = constant; KApA = KBps; and KApA
& Boyd Ltd., Edinburgh, 1968. + KbPb = constant, are indicated on the figure.

22 / Journal of Chemical Education

at successive values). The appearance of a maximum in the
rate is obvious; it has the value

rate (max) =
ku KhPh
4 (1 +Kbpb)
and rises towards a saturation value, corresponding to com-
plete surface coverage, as po (and pA) increases: viz.
rate -*
ku/4
If both pressures are varied simultaneously and indepen-
dently then, at low pressures (or small values of Ka and KB,
corresponding to weak adsorption
rate e* (ktiKaFb)paPb

i.e., the rate is second-order overall, and first-order in each

reactant.
These limiting results and orders, though quantitative and
descriptive, may not be readily assimilable. Their significance
is more easily appreciated with the aid of the following two
diagrams of the Langmuir-Hinshelwood equation. Figure 2
is a contour plot of the equation surface, the variables being
KaPa and KBpB with rate as a parameter. The contours are
plotted at equal increments of rate. The approach to a plateau
at high pressure is apparent, as is the first-order kinetics at
low pressures. The mirror symmetry about the line KaPa =
KbPb is evident.
Figure 3 displays the same surface in three dimensions,
where the various lines represent pressure variation of one
component at constant pressure of the other, and thus cor-
respond to the curves in Figure 1. Saturation of the adsorption
sites at high pressure explains, as before, the slow increase in
rate with pressure at high reactant pressures.
rate
Figure 3. Surface diagram of reaction rate as a function of KApA and of KbPb.
The two sets of lines (vertical sections through the surface) represent variation
of KApA at constant values of KBpB {cf. Fig. 1) and vice versa. The ridge from
the front of the figure lies on the line KApA = KbPb: the maxima in the vertical
sections at KApA = KBpa = 1 are clearly visible. Figure 2 corresponds to a pfan
view of the region of this figure near its origin.
Acknowledgment
The computer plotting programs used in the preparation
of the accompanying figures were provided by Dr. P. D. Terry,
adapted from available contour (J. Snowden, Ohio State
University) and surface3 plotting programs.
s
Watkins, S. L., Comnutn. Assoc. Compt. Mach., 17(a), 570
(1974).

Volume 56, Number 1, January 1979 / 23