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Cairo University 2nd Year Metallurgy

Faculty of Engineering Physical Chemistry

Department of Mining, Petroleum Final Examination
and Metallurgy Engineering Time Allowed :3hours
2010/2011 (1st Term)
Attempt All Questions (Number of pages =3)
The First Question
a. Discuss the following:
1. reversible and irreversible processes (2)
2. Lewis and Randall considerations (2)
 U 
3. Joule’s experiment that proved   0 (2)
 V T
b. The theoritical calculation of Cv dependence on temperature had been attempted
by Einstein and then developed by Debye. Discuss this statement in detail writing
down the Cv – T relation developed by Einstein and then the relation developed by
Debye. Show also the Debye T3 Law for low-temperature heat capacities, and the
high temperature relation. (7)
T2 P2

c. Show that: S   CP d ln T   VdP for a fixed – phase closed system undergoing

T1 P1

a change of T and P where  is the coefficient of thermal expansion given by:

T2 P2
1  V 
  .
V  T  P
Show also that for an ideal gas system: S   CP d ln T  R  d ln P (6)
T1 P1

The Second Question

a. One mole of an ideal gas at 25C and 1 atm undergoes the following reversibly
cyclic processes:
a.isothermal expansion to 0.5 atm; followed by,
b.isobaric expansion to 100C; followed by,
c.isothermal compression to 1atm; followed by,
d.isobaric compression to 25C.
The system then undergoes the following reversibly cyclic processes;
a. isobaric expansion to 100C; followed by,
b. a decrease in pressure at constant volume to P atm; followed by,
c. an isobaric compression at P atm to 24.46 liters; followed by,
d. an increase in pressure at constant volume to 1 atm.
Schematically draw each cycle; then, calculate the value of P which makes the
work done on the gas in the first cycle equal to the work done by the gas in the
second cycle. Calculate also  S for each step of the second cycle, and  A and
 G for only two steps you choose of the first cycle .
Tabulate your results. (18)

The Third Question
a. For one component homogenous system that contains very large number of
particles, prove that: U = KT ln Ω + nKT ln P, where P is the partition function of
the system. (8)
b. Calculate the entropy increase when 10 grams of gold are mixed with 20 grams of
silver to form an ideal homogenous alloy. The atomic weights of Au and Ag are
197 and 108, respectively. (7)
The Fourth Question
a. For sulfur dioxide gas, Tcrit = 430.7K and Pcrit = 77.8 atm. Calculate:
i. the van der Weals constants for the gas, (5)
ii. the critical volume of van der Waals SO2, and (5)
iii. the pressure exerted by 1 mole of SO2 occupying a volume of
500 cm at 500K. Compare this with the pressure which would be exerted by
an ideal gas having the same temperature, comment on your results. (5)

The Fifth Question

a. Show that: (∂ Cp / ∂ P)T = - T (∂2 V/∂ T2)P (4)

b. A solid metal M can form two oxides, MO and M3O4. The metal can exist in
equilibrium with one of these oxides at low temperatures and can exist in
equilibrium with the other oxide at high temperatures. The standard free energies
of formation of these oxides are:

M + 0.5 O2(g)  MO ΔG°(R) = - 62,050 + 14.95 T cal/mole

3M + 2 O2(g)  M3O4 ΔG°(R) = - 260,700 + 74.75 T cal/mole

Determine which of the two oxides is in equilibrium with the metal at room
temperature, and the maximum temperature at which this oxide is in equilibrium
with M. (14)
The Sixth Question
a. Small droplets of gold have been observed to supercool by a maximum amount of
approximately 230 °C. What is the entropy change associated with the isothermal
solidification of 1 gm atom of such supercooled droplets of gold? What is the
entropy change of the surrounding if its temperature remains at the same
temperature of the supercooled gold? Also, calculate the total entropy change;
given that: (10)
ΔH°(fus) of Au = 3,050 cal/(gm atom)
Cp (Au)s = 5 cal/ (deg-gm atom)
Cp (Au)l = 7 cal/ (deg-gm atom)
Melting point of gold = 1063 °C

b. The rate constants k for the leaching of galena in an aqueous medium containing
ammonite acetate under constant oxygen pressure at different temperatures are
listed below:
log k -10.9 -11.1 -11.2 -11.5 -12.1 -12.6
(1/T) x 10 2.3 2.35 2.38 2.45 2.61 2.75
2 -4 -1
where k in mole .cm .min and T in K. Calculate the activation energy of the
leaching process. (10)



Good Luck
Prof. Dr. Fawzi A.