1

On the Gas Adsorption and Surface Diffusion

Mohammad Kazemi
The molecules at solid surface experience a different environment compared to those which
are in the solid bulk. The interior molecules are bounded with similar molecules in all
directions and therefore, the net force on them is zero. In contrary, the molecules at the
surface see this only on one side of the interface and consequently, they have excess energy
in which they try to minimize it by adsorbing the molecules from the adjacent phase (for
example gases).
The adsorption on solid surfaces is usually categorized in two types; physisorption and
chemisorption. In physisorption, the bonding type is of weak Van der Waals type and
kj
. On the other hand,
usually happens when the heat of adsorption is less than 40-50 mol
the chemisorption forms the strong covalent, metallic, or ionic type of bonding and is often
irreversible. Rexer et al. (2014) calculations of methane-kerogen heat of adsorption (11-18
kj
) shows that the adsorption of methane to the kerogen is more likely physisorption.
mol
The surface of solids can be considered as a two dimensional potential energy landscape,
dotted with wells of varying depths corresponding to adsorption sites. The thermal fluctuations tend to drive back the adsorbed molecules into the gas phase but there is another
possibility that the molecules move from one well to another well. The adsorbed molecules
tend to minimize the free energy of the surface and therefore, they move from one adsorption site to another (surface diffusion). The energy barrier to this motion (Em ) is typically
smaller than the heat of adsorption (5 20%) (Zangwill, 1988). When the adsorption is
physical, the adsorption energy is less than kB T and the adsorbed molecules are highly
mobile. In chemisorption, the adsorption involves chemical bonding and the adsorption
energy is much more than kB T . Hence, the adsorbed molecules are much less mobile, but
instead are said to hop from one site to another (Cussler, 2009). There is no priori bias
for molecules to jump to the left or right. Therefore, the surface diffusion is a completely
random; also called random walk.

Mathematical Description
Consider a two-dimensional square lattice with lattice constant l where the molecule is
located at (x, y) site with probability P (x, y, t). The molecule may jump into the four
neighboring lattices after time ,
1
1
1
1
P (x, y, t + ) = P (x + l, y, t) + P (x l, y, t) + P (x, y l, t) + P (x, y + l, t)
4
4
4
4

Figure 1. Depending on the particle energy and the particle-wall potential, the particle
may reflect or adsorbed.
which can be rewritten
P (x, y, t + ) P (x, y, t) =

l2
[P (x l, y, t) 2P (x, y, t) + P (x + l, y, t)]+
4l2
l2
[P (x, y l, t) 2P (x, y, t) + P (x, y + l, t)]
4l2

Dividing the above equation by and letting both l and approaches zero in such a way
l2
that D = 4
remains finite, the familiar diffusion equation for the probability function is
derived.
P
= D2 P
t
This shows that D is different from chemical diffusion coefficient (Dc ) which occurs in
diffusion equation for the adsorbate particle density n(r) at finite coverage (Ficks law).
n
= Dc 2 n
t
The P (x, y, t) describes the probability distribution function for diffusion of a single particle, where n(r) describes the transport of total flux. It can be proved that the diffusion
coefficient can be related to the chemical diffusion coefficient through the Darken equation
as follow (Mazenko et al., 1981),
Dc

=
(
)
D
ln kB T
where is the surface coverage, is the chemical potential, and T is the temperature. It
should be mentioned that the Darken equation is valid for simple cases where the surface
is homogeneous (Zgrablich, 1997).

References
Cussler, E. L. (2009). Diffusion: mass transfer in fluid systems. Cambridge university
press.
Mazenko, G., J. Banavar, and R. Gomer (1981). Diffusion coefficients and the time autocorrelation function of density fluctuations. Surface Science 107 (2), 459468.
Rexer, T. F., E. J. Mathia, A. C. Aplin, and K. M. Thomas (2014). High-pressure methane
adsorption and characterization of pores in posidonia shales and isolated kerogens.
Energy & Fuels 28 (5), 28862901.
Zangwill, A. (1988). Physics at surfaces. Cambridge University Press.
Zgrablich, G. (1997). Surface diffusion of adsorbates on heterogeneous substrates. Studies
in Surface Science and Catalysis 104, 373449.