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Statistical Mechanics

Homework 3
(Due date: October 20, 2017)
1. (Prob.3.6 in the text book)
(a) Assuming that the total number of microstates accessible to a given statistical system
is , show that the entropy of the system, as given by equation (3.3.13), is maximum when
all states are equally likely to occur.
(b) If, on the other hand, we have an ensemble of systems sharing energy (with mean
value E), then show that the entropy, as given by the same formal expression, is maximum
when Pr exp(Er ), being a constant to be determined by the given value of E.
(c) Further, if we have an ensemble of systems sharing energy (with mean value E) and
also sharing particles (with mean value N ), then show that the entropy, given by a similar
expression, is maximum when Pr,s exp(Nr Es ), and being constants to be
determined by the given values of N and E.
2. (Prob.3.29 in the text book)
The potential energy of a one-dimensional, anharmonic oscillator may be written as

V (q) = cq 2 gq 3 f q 4 , (1)

where c, g, and f are positive constants; quite generally, g and f may be assumed to be
very small in value. Show that the leading contribution of anharmonic terms to the heat
( 2
)
capacity of the oscillator, assumed classical, is given by 32 k 2 cf2 + 5g
4c3 T and, to the same
3gkT
order, the mean value of the position coordinate q is given by 4c2
.
3. (Prob.3.35 in the text book)
(a) Consider a gaseous system of N noninteracting, diatomic molecules, each having an
electric dipole moment , placed in an external electric field of strength E. The energy of
such a molecule will be given by the kinetic energy of rotation as well as translation plus
the potential energy of orientation in the applied field:
{ 2 }
p2 p p2
= + + E cos , (2)
2m 2I 2I sin2

where I is the moment of inertia of the molecule. Study the thermodynamics of this system,
including the electric polarization and the dielectric constant. Assume that (i) the system
is a classical one and (ii) |E| kT .

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(b) The molecule H2 O has an electric dipole moment of 1.85 1018 e.s.u. Calculate,
on the basis of the precediing theory, the dielectric constant of steam at 100o C and at
atmospheric pressure.
4. (Prob.4.3 in the text book)
A vessel of volume V (0) contains N (0) molecules. Assuming that there is no correlation
whatsoever between the locations of the various molecules, calculate the probability P (N, V )
that a region of volume V (located anywhere in the vessel) contains exactly N molecules.
(a) Show that N = N (0) p and (N )r.m.s = {N (0) p(1 p)}1/2 , where p = V /V (0) .
(b) Show that if both N (0) p and N (0) (1 p) are large numbers, the function P (N, V )
assumes a Gaussian form.
(c) Further, if p 1 and N N (0) , show that the function P (N, V ) assumes the form
of a Poisson distribution:
(N )N
P (N ) = eN . (3)
N!
5. (Prob.4.6 in the text book)
Define the isobaric partition function

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YN (P, T ) = 3 QN (V, T )eP V dV. (4)
0

Show that in the thermodynamic limit the Gibbs free energy (4.7.1) is proportional to
ln YN (P, T ). Evaluate the isobaric partition function for a classical ideal gas and show that
P V = N KT . [The factor of the cube of the thermal deBroglie wavelength 3 serves to make
the partition function dimensionless and dose not contribute to the Gibbs free energy in the
thermodynamic limit.]
6. (Prob.4.8 in the text book)
Determine the grand partition function of a gaseous system of magnetic atoms (with
J = 1/2 and g = 2) that can have, in addition to the kinetic energy, a magnetic potential
energy equal to B H or B H, depending on their orientation with respect to an applied
magnetic field H. Derive an expression for the magnetization of the system, and calculate
how much heat will be given o by the system when the magnetic field is reduced from H
to zero at constant volume and constant temperature.
7. (Prob.4.10 in the text book)
A surface with N0 adsorption centers has N ( N0 ) gas molecules adsorbed on it. Show
N
that the chemical potential of the adsorbed molecules is given by = kT ln (N0 N )a(T )
,

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where a(T ) is the partition function of a single adsorbed molecule. Solve the problem by
constructing the grand partition function as well as the partition function of the system.
[Neglect the intermolecular interaction among the adsorbed molecules.]