LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034
M.Sc. DEGREE EXAMINATION – CHEMISTRY
SUPPLEMENTARY EXAMINATION – JUNE 2007
CH 2810 - THERMODYNAMICS AND STATISTICAL MECHANICS
Date & Time: 26/06/2007 / 9:00 - 12:00
Dept. No.
Max. : 100 Marks
PART A
Answer ALL the questions.
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10.
(10 x 2 = 20 Marks)
The density of N2 at 00C and 1 atm is 1.25 g/l. Estimate its fugacity at 00C and
100 atm.
Show that i (Chemical potential) = (E/ni)S,V,nj
The mean ionic activity coefficient for In2(SO4)3 in 0.1 m solution at 250C is
0.13. Find m and a
State any one of the formulations of Konowaloff’s rule.
What are the phenomenological coefficients in Onsager’s theory?
What is thermodynamic probability?
Calculate the number of ways of distributing 4 particles among 5 energy levels if
they are Bosons.
What is the significance of free energy function?
Calculate the ratio of translational partition function of He to Ne at 270C 1 atm
pressure.
What is meant by ‘distinguishable’ particles?
PART – B
Answer ANY EIGHT questions
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(8 x 5 = 40 Marks)
Explain the use of Ellingham Diagram in the extraction of metals.
The virial equation of state for N2(g) at 1000C is PV= RT – 0.656 x 10-2 P +
3.3835 x 10-5 P2 where P is in atm and V is in litres. Find the fugacity of N2 at
1000C and 100 atm pressure.
For the reaction 2SO2(g) + O2(g)  2SO3 (g), it has been found that variation of
equilibrium constant with temperature can be expressed as, log KP = 9888/T 9.346, calculate H0298 K, G0298 K and S0298 K.
Explain with diagram the isobaric fractional distillation of an ideal binary solution.
Explain the EMF method for the determination of activity coefficient of a strong
electrolyte.
Write a note on entropy production in chemical reactions using the principles of
non-equilibrium thermodynamics.
Derive an expression for translational partition function
At what temperature will qvib = 10 for N2(g)? ( = 2355 cm-1)
19.
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22.
What is the approximate value of S0 for the gaseous reaction, 35Cl35Cl +
37 37
Cl Cl 35Cl37Cl. Assume that any difference in the molar masses, moment of
inertia and vibrational energy levels are negligible for the isotopes.
Compare the three statistical distributions.
How is equilibrium constant of a reaction evaluated using statistical mechanics?
Show that the vibrational contribution to CV for a diatomic gas approaches R as T

PART – C
Answer ANY FOUR questions
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28.
(4 x 10 = 40 Marks)
a) How will you apply the Nernst distribution law for the determination of the
activity of a solute?
(5)
b) The apparent molar heat capacity C of an aqueous solution of glucose as a
function of molality is given by C = 633.9 + 4.728 m – 0.195 m2 J K-1 mol-1
Calculate the partial molar heat capacity of glucose in 1 molal
(5)
a) State the postulates of irreversible thermodynamics.
(3)
b) How will you verify Onsager’s reciprocal relationship experimentally using
Elecrokinetic effects?
(7)
a) Calculate the pressure of oxygen over a sample of NiO(s) at 250C given that
G0 = 211.7 kJ for the reaction, NiO(s)  Ni(s) + ½ O2(g).
(5)
b) Draw and explain the phase diagram of a three component system involving
two solids (B and C) and a liquid (A) with the formation of a double salt
(BmCn). (5)
a) Derive the Sackur-Tetrode equation and explain.
b) How are the partition functions separated?
Derive any two of the following:
a) Debye’s theory of heat capacity of solids (No derivation needed)
b) Application of Bose-Einstein Statistics.
c) Electronic partition function
Mention the postulates of Maxwell-Boltzmann distribution and hence derive an
expression from most probable distribution.
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