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PH 304: Assignment 5 (Grand-Canonical Ensemble)

1. Consider an ultra-relativistic gas contained in a volume V. The Hamiltonian for a


single ultra-relativistic particle of momentum P~ is H = c|~p|. Using the grand canonical
ensemble, evaluate the chemical potential (T, P ).
2. A classical ideal gas is contained in a box of fixed volume V whose walls have N0
absorbing sites. Each of the sites can absorb at most two particles, the energy of each
absorbed particle being . The total number of particles N is fixed and greater than
2N0 . Using the grand canonical ensemble, find the average number of free particles
and the average number of absorbed particles. Then using the consstraint on the total
number of particles N, obtain the equation of state of the gas in the presence of the
absorbing walls, and find the average number of adsorbed particles in the limits T 0
and T .
3. Consider a system of non-interacting, identical but distinguishable particles. Using
both the canonical and grand-canonical ensembles, find the partition function, and
the thermodynamic functions of Internal Energy (U (T, V, N )), Entropy (S(T, V, N ))
and Helmholtz free energy (F (T, V, N )), where T is the temperature, V is the volume
and N is the number of particles in terms of the single-particle partition function
Z1 (T, V ). Verify that the internal energies obtained in the two ensembles are the same,
i.e. UG = UC . If s is the entropy per particle, show that (sG sC )/k (ln N )/N , in
the limit of large N .
4. Consider a 3-dimensional classical gas of independent and indistinguishable particles
with a single particle Hamiltonian H(~p, ~q) = F (~p), where p~ and ~q are the momentum
and position of the single particle. Prove that in the grand canonical ensemble, the
probability to have N molecules
z N ZN (T, V, N )
P (N ) =
Q(T, V, z)
is a Poisson distribution (Hint: Calculate the average number of particles < N > and
express P (N ) in terms of < N >). Here, z(= e ) is the fugacity, and ZN and Q are
the canonical and grand canonical partition functions respectively.

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