Problems 111

Problems
4.1. Show that the entropy of a system in the grand canonical ensemble can be written as
X
S = k Pr,s ln Pr,s ,
r,s

where Pr,s is given by equation (4.1.9).

4.2. In the thermodynamic limit (when the extensive properties of the system become infinitely large,
while the intensive ones remain constant), the q-potential of the system may be calculated by
taking only the largest term in the sum

X
zNr QNr (V , T ).
Nr =0

Verify this statement and interpret the result physically.

4.3. 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 (1N)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 .
N!
4.4. The probability that a system in the grand canonical ensemble has exactly N particles is given by
zN QN (V , T )
p(N) = .
Q(z, V , T )
Verify this statement and show that in the case of a classical, ideal gas the distribution of particles
among the members of a grand canonical ensemble is identically a Poisson distribution. Calculate
the root-mean-square value of (1N) for this system both from the general formula (4.5.3) and from
the Poisson distribution, and show that the two results are the same.
4.5. Show that expression (4.3.20) for the entropy of a system in the grand canonical ensemble can also
be written as
 

S=k (Tq) .
T ,V

4.6. Define the isobaric partition function

1
Z
YN (P, T ) = QN (V , T )ePV dV .
3 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 PV = NkT . [The
factor of the cube of the thermal deBroglie wavelength, 3 , serves to make the partition function
dimensionless and does not contribute to the Gibbs free energy in the thermodynamic limit.]
4.7. Consider a classical system of noninteracting, diatomic molecules enclosed in a box of volume V
at temperature T . The Hamiltonian of a single molecule is given by
1 1
H(r 1 , r 2 , p1 , p2 ) = (p2 + p22 ) + K |r 1 r 2 |2 .
2m 1 2
2 i on T .
Study the thermodynamics of this system, including the dependence of the quantity hr12
112 Chapter 4 . The Grand Canonical Ensemble

4.8. Determine the grand partition function of a gaseous system of magnetic atoms (with J = 12 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 off by
the system when the magnetic field is reduced from H to zero at constant volume and constant
temperature.
4.9. Study the problem of solidvapor equilibrium (Section 4.4) by setting up the grand partition
function of the system.
4.10. A surface with N0 adsorption centers has N( N0 ) gas molecules adsorbed on it. Show that the
chemical potential of the adsorbed molecules is given by

N
= kT ln ,
(N0 N)a(T )

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.]
4.11. Study the state of equilibrium between a gaseous phase and an adsorbed phase in a single-
component system. Show that the pressure in the gaseous phase is given by the Langmuir
equation

Pg = (a certain function of temperature),
1
where is the equilibrium fraction of the adsorption sites that are occupied by the adsorbed
molecules.
4.12. Show that for a system in the grand canonical ensemble
 
U
{(NE) N E} = (1N)2 .
N T ,V

4.13. Define a quantity J as

J = E N = TS PV .

Show that for a system in the grand canonical ensemble

(  )2
2 U
(1J)2 = kT CV + (1N)2 .
N T ,V

4.14. Assuming that the latent heat of vaporization of water Lv = 2260 kJ/kg is independent of
temperature and the specific volume of the liquid phase is negligible compared to the specific
volume of the vapor phase, vvapor = kT /P (T ), integrate the ClausiusClapeyron equation (4.7.7)
to obtain the coexistence pressure as a function of temperature. Compare your result to the
experimental vapor pressure of water from the triple point to 200 C. The equilibrium vapor
pressure at 373 K is 101 kPa = 1 atm.
4.15. Assuming that the latent heat of sublimation of ice Ls = 2500 kJ/kg is independent of temperature
and the specific volume of the solid phase is negligible compared to the specific volume of the
vapor phase, vvapor = kT /P (T ), integrate the ClausiusClapeyron equation (4.7.7) to obtain the
coexistence pressure as a function of temperature. Compare your result to the experimental vapor
pressure of ice from T = 0 to the triple point. The equilibrium vapor pressure at the triple point is
612 Pa.
4.16. Calculate the slope of the solid-liquid transition line for water near the triple point T = 273.16 K,
given that the latent heat of melting is 80 cal/g, the density of the liquid phase is 1.00 g/cm3 , and
the density of the ice phase is 0.92 g/cm3 . Estimate the melting temperature at P = 100 atm.
 Problems 113

4.17. Show that the ClausiusClapeyron equation (4.7.7) guarantees that each of the coexistence curves
at the triple point of a material points into the third phase; for example, the slope of the
solidvapor coexistence line has a value in-between the slopes of the the the solidliquid and
liquidvapor coexistence lines.
4.18. Sketch the PV phase diagram for helium-4 using the sketch of the PT phase diagram in
Figure 4.3.
4.19. Derive the equivalent of the ClausiusClapeyron equation (4.7.7) for the slope of the coexistence
chemical potential as a function of temperature. Use the fact that the pressures P(, T ) in two
different phases are equal on the coexistence curve.
4.20. Sketch the PT and PV phase diagrams of water, taking into account the fact that the mass
density of the liquid phase is larger than the mass density of the solid phase.