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PY3104 Statistical thermodynamics: Assignment 5

Due in class March 26

1. Thermal ionization of hydrogen. Consider the formation of atomic hydrogen from

a proton and an electron, i.e. according to the reaction
e + H + H.
Show that the equilibrium concentration of the reactants is
ne nH +
= nQ,e exp(I/ ),
where I is the energy required to ionize atomic hydrogen; ne , nH + and nH are the
concentrations of electrons, protons and hydrogen, respectively; and nQ,e = (m /2~2 )3/2
is the quantum concentration of electrons. To account for the internal degrees of freedom
of all the particles (electrons, protons and hydrogen atoms), assume that they have only
the ground state. Neglect the spin of the particles. (5/20)
2. Gas-solid equilibrium. (a) Consider a solid in equilibrium with a gas. The solid
can be modelled as a three-dimensional harmonic oscillator, whose energy levels are (nx +
ny + nz )~ 0 , where ~ is Plancks constant, 0 is the binding energy of atoms, and nx ,
ny and nz can be any non-negative integer number (nx , ny , nz = 0, 1, 2, ...). Neglecting the
volume of the solid, show that the chemical potential of the solid is given as

exp(o / )
s = log
(1 exp(~/ ))3
Use the expression:


xn =

if x < 1.

(b) Assume that the gas phase behaves as an ideal classical gas with the chemical potential g = log(n/nQ ) (n is the gas concentration, and nQ is the quantum concentration)

and the pressure p = n . Find the vapor-pressure equation of the solid-gas mixture. (2/20)
3. Latent heat of melting. Consider a substance which can exist in either one of two
phases, labeled A and B. If the number of molecules is N , the heat capacity of the A phase
at fundamental temperature is
CA = N 3 ,
while the heat capacity of the B phase is
CB = N .

(a) Find the entropies A and B of the two phases at temperature . (1.5/20)
(b) Suppose that, for both the A phase and the B phase, the internal energy is U0 = N 0
at zero temperature. Find the internal energies UA and UB of the two phases at finite
temperature . (1.5/20)
(c) Find the Helmholtz free energies and the chemical potentials of the two phases.
(d) Which phase is favored at low temperature? At what melting temperature m does
a transition occur to the other phase? (1.5/20)
(e) At the melting temperature, how much heat must be added to transform the
low-temperature phase to the high-temperature phase? (1.5/20)