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Ex/MET/T/224/91/2010

BACHELOR OF METALLURGICAL ENGG. EXAMINATION, 2010

(2nd Year, 2nd Semester)

THERMODYNAMICS OF MATERIALS
Time : Three hours

Full Marks : 100

Answer question no. 1 and


any four from the rest.
1.

i)

Consider n moles of an ideal gas is expanded along an


a) isothermal path and b) adiabatic path. Will the
following two statements apply to each case ?
3
U = f (T, V)
State = f (T, V)

ii)

Prove that for an ideal gas, ( U / T)P = Cv .

iii)

Is there any difference between the derivatives

U
T for

V
iv)

a) an ideal gas

b) a real gas.

3
dU
and
dT

( H )
for chemical reactions
T

Write an expression for P

in terms of molar volumes V and thermal expansivity .


3
v)

Explain how a chemical reaction such as M (s) + O2 (g)


= MO 2 (s) can be reversibly carried out.

vi)

Write the formation reaction for the compound Ca2SiO4.


2
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( 2 )
vii)

( 7 )

Explain why the electronic heat capacity of metals are

moles of the gas mixture are required to reduce 302 gm


of SnO2 ? pt = 1 atm. The reduction furnace consists of

best detected at either high temperatures or very low


temperatures.
3
viii)

Write three statements of the 2nd law of thermodynamics


dealing with the impossibility of processes / cycles. 3

xi)

The molar free energy of a metal, at 1 atm pressure, is


considered to vary with temperature as follows :

a tube filled with SnO2, through which is passed the gas


mixture.
Data :
(i) SnO2 (s) = Sn (l) + O2 (g) ; G = 575, 290 198.5 T, J
(ii) C(s) +

G = 30,000 + 175 T 25 T ln T
Find the molar entropy S and molar heat capacity CP of
the metal at 500 K.
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x)

The total free energy of a system comprising of three


gases A, B, and C is a function of different state
variables, as follows :
G = f (T, p, nA, nB, nC , )
Does this functionality hold good a) when the three gases
enter into a chemical reaction, b) for a fixed mass of the
gas mixture ?
4

xi)

For an irrerersible process carried out with a fixed mass,


fixed composition system, prove that
dU=Tdspdv

xii)

Find an expression for (dG / dT)V for n moles of an ideal


gas in the form of a + bs, where both a and b are
constants.
3

xiii)

Plot schematically the variation of

GB

with XB, at a given

temperature and pressure, in a binary system A B.

1
O (g) = CO (g) ; G = 111, 700 87.65 T, J
2 2

(iii) C(s) + O2 (g) = CO2 (g) ; G = 394, 100 0.84 T, J

ii)

Comment on the nature of three binary (A B) solutions,


whether ideal, real (regular), or real (nonregular), from
their following solution parameter () values :
Solution 1 : = 0
Solution 2 : = 10,000 J
Solution 3 : = 10,000 0.1 T J
Find, also Hm and SXS for each solution, with xB = 0.5.
8

( 4 )

Hf , 298 K
H2
N2
O2

( 5 )
H1400 H298
7, 905
8, 355
8, 835

ii)
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3.

i)

According to Darken and Gurry (Table 9 2, p. 219), iron


and magnetite (Fe3O4) are in equilibrium with CO / CO2
mixtures, as follows :
Temperature, K
700
811

ii)

c.

p =

B / BO
A / AO

= 103 atm
= 104 atm

pO2 = 0.5 x 103 atm

The standard free - energy changes for vaporization and


sublimation of zinc are as follows :
Zn (l) = Zn (v) ; G = 118, 114 100 T J

ii) the saturated vapor pressures of solid and liquid zinc


iii) the melting point of zinc at 1000 atm total pressure.

Using these data and assuming C P = 0, calculate


H 298, S 298, and the equilibrium CO / CO2 ratio at
298 K for the following reaction :

(Given, the molar volumes of solid and liquid zinc at the

(Fe3O4 (S)+ 4 CO (g) = 3 Fe (S) + CO2 (g)4.

small changes in temperature. The atomic weight of Zn


= 65.3).
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normal melting point are, respectively, 9.60 cm3 and 9.88


cm3, which are assumed to be insenstive to pressure and

A gas mixture containing 50% argon and 50% CO2 is


passed through a bed of carbon at 1100 K. pt = 1 atm.
Calculate the mol% of CO and CO2 in the exit gas. Given,

1
O (g) = CO (g) ; G = 111, 700 87.65 T, J
2 2
C(s) + O2(g) = CO2 (g) ; G = 394, 100 0.84 T, J
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i)

p = pO2
p = pO2

Zn (s) = Zn (v) ; G = 125, 436 110.6 T J


Find
i) the normal melting point of zinc

p CO / p CO2
0.826
0.990

C(s) +

4.

a.
b.

Four chemical species, A , A O2, B and BO, all solids are


taken with oxygen in a constant T, constant p system.
Find which phases will be present in the system at
equilibrium, when

5.

i)

Refer to the binary eutectic phase diagram A B, given


in Figure 1. The following data are obtained with respect
to the vapor pressure of B in the solution A B, at 1000K.
pB = 0.01 atm
pB (at xB = 0.5) = 7 x 103 atm
pB (at xB = 0.7) = 8 x 103 atm
a) Find the activity of B in the solution at the state
Y (xB = 0.7, T = 1000 K), with respect to
(i) pure solid B as the standard state
(ii) pure liquid B as the standard state
(iii) 1 atm B (gas) as the standard state
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( 3 )

( 6 )

Given, GA and GB are standard free energies of A and

b) If 1 mole of pure B is mixed with a large quantity of

B.

the solution with xB = 0.5, at 1000 K and 1 atm pressure,


find the free energy of mixing and excess free energy.
2.

i)

One mole of methane and the stoichiometic amount of


air are introduced at 298 K in a constant volume,
adiabatic reactor. The following combustion reaction
takes place :
CH4 (g) + 2O2 (g) = CO2 (g) + 2H2O (g)
If the internal energies of formation of CO2, H2O and CH4
are a, b and c respectively, and the constant - volume
molarheat capacities of CO2, H2O and N2 are d, e and f

ii)

The virial equation for H2 is given as


Z=

6.

i)

respectively, find the final temperature Tf of the resulting


gas in terms of the given data. Note air contains 80% N2
and 20% O2.
6

pV
= 1+ 5 x 104 p
RT

ii)

A fuel gas 50% CO and 50% H2 (by moles) is completely


burned with just the theoretical moles of air in a melting

Calculate
a) The fugacity of hydrogen at 400 atm and 298 K.
b) The pressure at which the fugacity is twice the

furnace. Gas and air enter at 298 K. The heat loss from
the furnace is 20% of the heat input from the combustion
reactions. The gaseous products of combustion leave the

pressure.
c) The free - energy change (G) resulting from the
compression of 1 mole of hydrogen at 298 K from 1 atm

furnace at 1400 K.
What percentage of the calorific power of the fuel is
available within the furnace for heating and melting the

to 400 atm.
What is the magnitude of the contribution to C. arising
from the nonideality of hydrogen ?
9+6

furnace charge ?
Given thermodynamic data in calories / mole :
Hf , 298 K
H1400 H298

A reducing gas mixture of 80% CO 20% Ar is being

CO
CO2
H2O (g)

used to reduce SnO2 to metallic tin at 1000 K. How many

26, 420
94, 050
57, 800

8, 450
13, 360
10, 385
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