PG/Chem/4th Sem/21 (CBCS)

2021

CHEMISTRY
Paper - CHEM 403

( Physical Chemistr y Theor y )

(CB CS )

Full Marks : 40 Time : Two Hours

The figures in the margin indicate full marks.

Candidates are required to give their answers
in their own words as far as practicable.
Question No. 1 is compulsory and answer any three questions from the rest.

1. Answer any five of the following : 2×5=10

(a) Show that for a Boltzmann distribution the lower level is always more
populated at any finite temperature.

(b) Write how entropy is related to thermodynamic probability. What is the

minimum value of entropy ?

(c) State the law of equipartition of energy and hence calculate the average
energy of a He atom.

(d) Explain the terms: Fermi function and Fermi energy.

(e) Explain what is thermal de-Broglie wave length.

(f) Define Brillouin zone; draw the first Brillouin zone for a 1-D lattice and
mark different high symmetry points.

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 (g) What is a coupling phenomenon ? Explain with example.
(h) What is the Onsager symmetry rule for the cross phenomenological
coefficients ?

2. (a) Express Cv in terms of molecular partition function. 3

(b) State and prove the equipartition theorem. 7

3. (a) Define Z, the canonical ensemble partition function. Find an expression of

Z for an ideal monatomic gas. 5
(b) Arrive at Sackur Tetrode equation. 5

4. (a) Explain the terms bosons and fermions. Show that the chemical potential
of a Bose gas is negative. 5
(b) Derive Planck equation using Bose statistics. 5

5. (a) Define reciprocal lattice for a given bravais lattice. Show that reciprocal
lattice is also a bravais lattice. 4
(b) Show that reciprocal lattice of BCC is a direct lattice of FCC. 3
(c) What is hexagonal closed pack (hcp) structure ? Prove that the ideal c/a
ration for hcp structure is 1.633. 3

6. (a) What are the characteristic features of local equilibrium ? 3

(b) State the Curie-Prigogine principle and illustrate it. 2
(c) Two compartments a and b with same gas and constant volumes at
temperatures T and T  T and pressures p and p  p, respectively
are connected through a small orifice (or a rigid membrane). For the
transfer of heat (dq) and matter (dn), derive the rate of entropy production
equation and phenomenological equations of the system. 5
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