Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
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:
3
n x ,n y ,n z o n x n y n z
2
2-b) Give the expression of the partition function Zs(Ns) of the solid, its
free energy and its chemical potential.
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.
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.
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
molecule.
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-c) Prove that the chemical potential of a molecule in the gas can be
written:
o T k B T ln P / Po
II. Lets now consider the case where each site can get many
molecules.
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.