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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
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( 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.
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)
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
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 .
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