1. A container of volume V contains N molecules of a gas.

We assume that the gas is

dilute so that the position of any one molecule is independent of all other molecules.
Although the density is uniform on the average, there are fluctuations in the density.
(a) What is the probability that n molecules are in a part of the vessel of volume v ? (b)
What is the average number of molecules in volume v ? (c) What are the relative
fluctuations of the number of molecules in volume v ? (d) Show that when N and n are
both large the probability distribution is approximately Gaussian. (e) What will be the
form of the distribution if the volume element v is very small compared to V?

2. Suppose there are two systems A and B in thermal contact with a heat bath at
temperature T and there exists some mechanism enabling the two systems to exchange
particles. Obtain the expression for the probability of having a distribution P(NA, NB)
of particles into A and B in terms of the partition functions QA(NA, VA , T) and QB(NB,
VB, T), and derive the condition for finding the most probable distribution.

3. Show, in general, that the chemical potential (N, V, T) is given by

[
μ ( N ,V , T )=k B T ln
]
Q ( N −1 ,V , T )
Q ( N , V ,T )
where Q(N-1,V,T) is the canonical partition

function for an N-1 particle system.

4. Show that the partition function Q(N, V, T) of a canonical ensemble satisfies the
following relation: N (
∂ ln Q
)
∂ N V ,T
+V (
∂ ln Q
∂ V N ,T )
=ln Q. It is assumed for simplicity that
the system is a one-component system made up of N particles.

5. Consider an adsorbent surface having N sites each of which can adsorb one gas
molecule. Suppose that it is in contact with an ideal gas with the chemical potential 
(determined by the pressure p and the temperature T). Assuming that an adsorbed
molecule has energy -0 compared to one in a free state, determine in this case the
covering ratio  (the ratio of adsorbed molecules to adsorbing sites). (Use the grand-
canonical ensemble.) Find, in particular, the relation between  and p in the case of
monatomic molecules.

6. Consider a collection of N three-dimensional classical harmonic oscillators of

frequency . Show that the total energy of the system is equal to 3NkBT and the

[(
entropy is given by S=3 N k B ln
2 π kB T
hω
+1) ]
7. Prove for an ideal classical gas obeying the grad-canonical distribution, N 2−N 2=N .

8. Consider a box containing an ideal classical gas at pressure p and temperature T. The
walls of the box have N0 adsorbing sites, each of which can adsorb one molecule of
the gas. Let  be the energy of an adsorbed molecule. (a) Show that the fugacity of

( )
2 3/2
−5 /2 h
the gas is given by ζ = p ( k B T ) (b) Show that the mean number of
2 πm
N0
adsorbed molecules is given by ⟨ N ⟩= 3/ 2 .
1+ ( 2 πm/h 2 ) p−1 ( k B T ) e− βε
5/ 2
9. Consider a system of N distinguishable independent particles in which each of which
can exist in one of two states separated by an energy . Find S(E,N) and examine the
behavior of 1/T as a function of E/N. Show that for some values of E/N, 1/T can be
negative.

10. Suppose that the following explicit formula for the partition function were found: (a)
2
N 5 N /2 N 3N /2 aN /V k T
Q=V ( 2 πmk B T ) (b) Q= (V −Nb ) ( 2 πmk B T ) e . For both cases
B

calculate the equation of state and the specific heat at constant volume. From the
results identify the systems described by these partition functions.

11. If the energy of the microscopic states changes by the addition of a constant which is
independent of the state, Ej  Ej + C, how do the partition function, the average
energy, and the free energy change?

12. By what factor does the number of states increase if 1 Joule of heat energy is added to
a system at room temperature (295 K)?

13. Consider two isolated systems of non-interacting spins with N A = 4 and NB = 16.
Their initial energies are E A =−2 μB∧E B=−2 μB . (a) What is the total number of
microstates available to the composite system? (b) If the two systems are now allowed
to exchange energy with one another, what is the probability that system A has energy
EA? (c) What is the mean value of EA and its relative fluctuations of EA? Calculate the
analogous quantities for system B. (d) What is the most probable macrostate for the
composite system?

14. A physical system is composed of N distinguishable spins assuming two possible

values ±1. These two values correspond to the energy levels ± , respectively.
Compute the total energy E using the Boltzmann formula and the microcanonical
ensemble. Finally, compute the results with those in the canonical ensemble.

15. Assuming that the entropy S and the statistical number  of a physical system are
related through an arbitrary functional form S=f ( Ω ) , show that the additive character
of S and the multiplicative character of  necessarily require that the function f ( Ω ) be
of the form k ln Ω.

16. Show that for a system in a canonical ensemble,

⟨ ( E− ⟨ E ⟩ ) ⟩=( E−E ) =k
3 3 2
B {( )
T
4 ∂C V
∂T V
3
}
+2T CV . Show that, in particular for an ideal

( E−E )3 8
gas of N monatomic particles 3
= 2
.
E 9N

17. Consider a lattice gas model of a system in which there are N sites, each of which can
be empty or occupied by one particle, the energy being 0 for no particles on a site and
ε for one particle. Each particle has a magnetic moment μ which in the presence of a
magnetic field B leads to a shift in energy into either μB or -μB. What is the partition
function of the system? Evaluate the mean energy of the lattice gas.
18. Consider an adsorbent surface having N sites each of which can adsorb one gas
molecule. Suppose that it is in contact with an ideal gas with the chemical potential 
(determined by the pressure p and the temperature T). Assume that an adsorbed
molecule has energy - compared to one in a free state. (a) Find the fugacity z=e βμ of
the gas in terms of temperature and pressure. (b) Find the covering ratio  (the ratio of
mean number of adsorbed molecules to adsorbing sites) and investigate its low and
high pressure limit. (Note that, the resulting equation for  is known as Langmuir’s
isotherm).

19. The energy of a system described by the canonical ensemble fluctuates, because the
system is able to exchange energy with a heat bath, and the size of these fluctuations
can be characterized by ⟨ ( ∆ E )2 ⟩C =⟨ E 2 ⟩C −⟨ E ⟩C , where the subscript C denotes the
2

canonical ensemble. For a system described by the grand canonical ensemble, both
energy and particle number fluctuate, and variances ⟨ ( ∆ E )2 ⟩G ∧⟨ ( ∆ N )2 ⟩G can be
defined in a corresponding manner. One might suppose that particles exchanged with
a reservoir would carry energy and, for this reason, that ⟨ ( ∆ E )2 ⟩G > ⟨ ( ∆ E )2 ⟩ C . Express
⟨ ( ∆ E )2 ⟩G and ⟨ ( ∆ E )2 ⟩C in terms of derivatives of appropriate thermodynamic functions.
In the thermodynamic limit, assume that ⟨ E ⟩C =⟨ E ⟩G= E and ⟨ N ⟩G =N and use

[( ) ]
2
∂E
thermodynamic reasoning to show that ⟨ ( ∆ E ) ⟩G −⟨ ( ∆ E ) ⟩C =⟨ ( ∆ N ) ⟩ G
2 2 2
.
∂N T ,V

20. Consider a system of classical ideal gas of indistinguishable particles (by taking the
classical limit of quantum ideal gases), and let  be the chemical potential of the gas
particles. (a) Compute the grand canonical partition function,  of the gas. Assume
that the mass of a gas particle is m. (b) Find the internal energy and the pressure as a
function of chemical potential . (c) Find the chemical potential  as a function of ⟨ N ⟩
and T, where ⟨ N ⟩ is the average number of gas particles in the system.

21. A single particle system has three non-degenerate energy levels 0, 0.5  and 0.8. It is
in thermal equilibrium with a heat reservoir of absolute temperature T = /kB.
Calculate for each level the probability that the particle is in that level. Calculate also
the partition function and the mean energy of the single particle system.

22. Consider a system of one particle in equilibrium with a heat bath. The particle has two
microstates of energy 1 = 0 and 2 = . Find the probabilities p1 and p2 when the mean
energy of the system is 0.2, 0.4, 0.5, and 0.6, respectively.