( 6 ) Ex/MET/T/224/87/2008

Data (assorted) : INTER ENGG. (METALLURGICAL) EXAMINATION, 2008

i) 1
Fe(s) + – O2(g) = FeO(s); ∆G° = –259,600 + 62.55 T J (2nd Semester)
2
THERMODYNAMICS OF MATERIALS
ii) 1
C(s) + – O2(g) = CO(g); ∆G° = – 111,700 – 87.65 T J
2

iii) C(s) + O2(g) = CO2(g); ∆G° = – 394,100 – 0.84 T J Time : Three hours Full Marks : 100

iv) ∆G°Cu S, 900K = – 103,350 J/mol Answer question no. 1 and any four from the rest.
2

v) ∆G°H S, 900K = – 45,850 J/mol 1. i) Give the conditions under which the relation δq = dH is
2
valid. Do you think the relation is still valid when the
system involved a non-mechanical work δ w / ? 3

ii) How will you explain the fact that heat capacities of
solids do not conform to CV = 3R at low temperatures ?
—————×—————
How did Einstein address this problem and what
expression of heat capacity he arrived at ? What
correction Debye incorporate into Einstein’s theory and
what relationship of CV and T for low temperatures he
obtained ? 5

iii) How will you justify the following statement in terms of

G which is a state function, not a path function :
dGP,T ≤ – δ w / (< refers to irreversible path
= refers to reversible path) 2

iv) The vapor pressure of water is given by

log p (atm) = – 2900/T – 4.65 log T + 19.732

At what temperature does water boil at the top of Mount
Everest ? Data : Mount Everest is 29028 ft high. Assume

[ TURN OVER ]
 ( 2 ) ( 5 )

that the air temperature at the top and the bottom of the Calculate the corresponding expression for the composition
mountain are equal. 5 dependence of Iog γ cd , and hence calculate acd in the
v) Find whether the following statements are TRUE or xcd = 0.5 alloy at 435°C. 15
FALSE ; give justifications. 4
6. i) FeO is heated in a mixture of 54.3% CO – 45.7% CO2.
(a) for solids : (∂H/∂P)T > (∂H/∂V)T
At what temperature metallic iron is formed ? 5
(b) for ideal gas : (∂S/∂P)T = 0
ii) The partial pressure of oxygen in equilibrium with
(c) (∂ G/∂P)T is greater for solids than for gases pure liquid lead and pure liquid PbO at 1200 K is
∂H 3.83 × 10–9 atm. If SiO 2 is added to the liquid PbO
(d) for solids, T = ( ∂S )P such that the equilibrium pO2 for the pure Pb-liquid
PbO – SiO 2 solution couple is decreased to
vi) 50 gms of aluminum at the temperature T are placed
9.58 × 10–10 atm, calculate the activity of PbO in the lead
in 100 gms of water which is adiabatically contained
silicate melt. 4
at 298 K. Find out
iii) Which of the following processes releases more heat ?
(a) an equation relating the final temperature of the
system T /, with T (T varies in the range 298–773 K). a) the oxidation of graphite to CO at 1000 K.

(b) an equation relating ∆Suniv with T. b) the oxidation of diamond to CO at 1000 K.

Data : Given :
–2
CP,H = 75.44 J/K.mol Cp(diamond) = 9.12 + 13.2 × 10–3T – 6.19 × 105T J/mol.K
2O(l)

CP, Al = 16.3 J/K.mol –2

Cp(graphite) = 17.2 + 4.27 × 10–3T – 8.79 × 105T J/mol.K
MW of H2O = 18, MW of Al = 27 8
for C(graphite) = C(diamond) , ∆H298 = 1900 J/mol 6
vii) A mixture of A(s), AO2(s), B(s), and BO(s), and O2(g)
at 10–3 atm are taken in a constant pressure system
at 1000 K. Using the following, Ellingham reaction data,
find which phases will be present at equilibrium.
[ TURN OVER ]
 ( 4 ) ( 3 )

More specifically, the proposed process involves treating A(s) + O2(g) = AO2(s), ∆G°1000 = – 60 kJ
one mole Cu2S with six moles H2 to produce 2 moles Cu
2B(s) + O2(g) = 2BO(s), ∆G°1000 = – 50 kJ 4
and an H2S/H2 product gas. The temperature is 900 K and
ptotal = 1 atm, at all times. viii) The Virial equation for hydrogen is given as

(a) Find ∆G for the proposed process of H2 reduction of pV

Z = RT = 1 + 6.4 × 10–4 p. 4
Cu2S, in joules per mole of Cu2S.

b) Is this process thermodynamically feasible ? Explain. Calculate :

c) Find the minimum moles of H2 which must be fed to the a) the fugacity of hydrogen at 500 atm and 298 k,
copper-making reactor per 2 moles Cu produced. b) the pressure at which the fugacity is twice the pressure.
Note : the minimum is neither 1 nor 6. 15 ix) The integral molar excess free energy of a regular
solution A–B is given by
4. i) The vapor pressure of liquid gallium varies with
Gxs = 2000 xA xB , J
temperature as follows :
Determine γA and γB in a xA = 0.6 solution at 1000 K.
T, °C 1029 1154 1350
5
p, mm Hg 0.01 0.1 1.0

Calculate ∆ H, ∆ S, and ∆ G for the equilibrium 2. A gas consisting of 30% CO2, balance CO, is cooled at a
vaporization of liquid gallium at 1154°C. 7 constant total pressure of 1.37 atm from 1150 K to 950 K.

ii) Consider the phase transformation M(L) = M(V). Given, At what temperature does carbon begin to soot out from the
–2
gas, and at 950 K, how many moles of carbon have sooted
CP,M(V) – CP,M(L) = ∆a + ∆bT + ∆cT . Express In pM(V) as
out per mole of gas cooled ? 15
a function of T. 8
3. It has been proposed to make copper powder from the
Cu2S (chalcocite) using H2 as reducing agent, according to
5. The activity coefficient of Zn in liquid Cd – Zn alloys at
the reaction
435°C can be represented by
Cu2S(s) + H2(g) = 2Cu(s) + H2S(g).
In γzn = 0.38 xcd
2 3
– 0.13 xcd .

[ TURN OVER ]