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TD5 Statistical Physics (M1)

Sublimation of a Solid and Surface Adsorption

Exercise 1: Sublimation.
In this exercise, we will study the sublimation of a crystalline solid, with a simple
microscopic model.
In a box with volume V, and temperature T, coexist a crystalline solid with its
monoatomic gas. The mass of the atoms is m. They have no spin. The volume of
the solid is negligible in comparison with the volume occupied by the gas. The
vapor is considered as a classical perfect gas.
The total number of atoms is N, with Ng atoms in the gas phase, and Ns=N-Ng
atoms in the solid phase.

1) Gas. Give the expression of the partition function Zg(Ng) of the gas, its
free energy, its pressure, its chemical potential, its entropy.

2) Solid. In the solid, the atoms are positioned at the nodes of a crystalline
lattice. The atoms are supposed to be independent from each other and
behave as a 3D harmonic oscillator, as in the Einsteins model. The energy
of each atom is thus given by three quantum numbers n x, ny and nz:
n x ,n y ,n z o n x n y n z

where o and are characteristic constants of the crystal.

2-a) What do represent o and ? Give an order of magnitude for these


2-b) Give the expression of the partition function Zs(Ns) of the solid, its
free energy and its chemical potential.

3) Equilibrium condition between solid and vapor.

The number of atoms in the gas phase, Ng, can take a priori every value
between 0 and N. In this question, we will determine its value at a given

3-a) Give the partition function of the total system (solid + gas) as a
function of Zg and Zs.

3-b) Give the probability P(Ng=Ng o), where Ngo is a given value of Ng, as a
function of Zg and Zs.

3-c) Check that the most probable value Ng m of Ng is given by the equality
of the chemical potentials of the gas phase and of the solid phase.

3-d) At a given temperature, how does Ng m depend on the volume V? At a

given N and T, prove that the solid-vapor equilibrium is possible only if
V<Vo. Determine the volume Vo. What happens if V>Vo?
We will now consider only the case where V<Vo.

4) Equilibrium pressure.
4-a) Compute the pressure for a given volume V<Vo and at a given
temperature T. Prove that it is proportional to the average number <Ng>
of atoms in the gas phase.

4-b) Considering that for a large system <Ng>Ng m, prove that the
pressure P depends only on T, and on parameters characteristics of the
solid phase, but is independent on V.

Exercise 2: Adsorption of a gas on a solid surface.

We consider in this exercise a gas in contact with a solid surface containing M
sites that can get gas molecules. The gas quantity is sufficiently large for the gas
not to be disturbed by adsorption of some molecules on the solid surface.

I. We consider first that each of the M sites can get only one
molecule at maximum.
The energy of each site is =0 when it is empty, and =-1 (1>0) when it gets one
The distance between the sites is supposed to be sufficiently large for the
adsorbed molecules not to interact. When n molecules are adsorbed, the energy
of adsorption is thus E=-n1.

1) Chemical potential of the gas. The gas is a classical perfect gas. The
mass of the molecules in the gas, is m. The molecules have no internal
degree of freedom. They are confined in a volume V.

1-a) Compute the grand-canonical partition function, and the grand-

potential of the gas.

1-b) Find the equation of state PV=<N>kBT

1-c) Prove that the chemical potential of a molecule in the gas can be
o T k B T ln P / Po

P is the pressure of the gas, P o is a reference pressure, for example

Po=1 bar, o(T) is called standard chemical potential.
o T k B T. ln f T
with f(T) a function of temperature T.

2) Solid. What imposes the equilibrium condition for the chemical

potential of the molecules adsorbed at the solid surface?

3) Adsorption sites. Write first the grand-canonical partition function for

a given site on the solid surface, and then the grand-canonical function
for the M adsorption sites. What is the corresponding grand-potential?

4) Coverage ratio. Compute the average number <n> of adsorbed

molecules and the coverage ratio =<n>/M as a function of 1, T, .
Compute and draw (T,P) as a function of the temperature T and of the
pressure P in the gas. These curves are called Langmuirs isotherms.

II. Lets now consider the case where each site can get many
This case corresponds to the case of successive adsorption layers.
On each site, the energy of adsorption for the first molecule is still equal to 1.
The energy of adsorption for the following molecules are equal to -2 (0<2<1).
We suppose now that the number of molecules that can be adsorbed on a given
site is unlimited. As previously, the chemical potential of the adsorbed molecules
is given by the equilibrium condition with the surrounding gas.

1) Compute the grand-canonical partition function for the adsorption


2) Compute the coverage ratio =<n>/M as a function of the temperature

T and of the pressure P in the gas. Prove that

(1 x cx )(1 x )

where x=P/P1(T) and c=exp[(1-2)] with P1(T)=Po.exp[-(2+o(T))].

3) When c>>1, (T,P) is shown in Figure 1. What does represent the

elbow in the beginning of the figure?
(T,P) is called the Brunauer-Emmett-Teller adsorptions isotherms
(B.E.T. isotherms). It is used to measure the effective surface of divided
solids (like powders).