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THERMODYNAMICS OF MATERIALS

Time : Three hours

any four from the rest.

1.

i)

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)

iii)

U

T for

V

iv)

a) an ideal gas

b) a real gas.

3

dU

and

dT

( H )

for chemical reactions

T

3

v)

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

vi)

2

[ Turn Over ]

( 2 )

vii)

( 7 )

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

temperatures.

3

viii)

dealing with the impossibility of processes / cycles. 3

xi)

considered to vary with temperature as follows :

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.

4

x)

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)

fixed composition system, prove that

dU=Tdspdv

xii)

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

constants.

3

xiii)

GB

1

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

2 2

ii)

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)

9

3.

i)

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

sublimation of zinc are as follows :

Zn (l) = Zn (v) ; G = 118, 114 100 T J

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

H 298, S 298, and the equilibrium CO / CO2 ratio at

298 K for the following reaction :

= 65.3).

9

cm3, which are assumed to be insenstive to pressure and

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

8

i)

p = pO2

p = pO2

Find

i) the normal melting point of zinc

p CO / p CO2

0.826

0.990

C(s) +

4.

a.

b.

taken with oxygen in a constant T, constant p system.

Find which phases will be present in the system at

equilibrium, when

5.

i)

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

[ Turn Over ]

( 3 )

( 6 )

B.

find the free energy of mixing and excess free energy.

2.

i)

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)

Z=

6.

i)

gas in terms of the given data. Note air contains 80% N2

and 20% O2.

6

pV

= 1+ 5 x 104 p

RT

ii)

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

CO

CO2

H2O (g)

26, 420

94, 050

57, 800

8, 450

13, 360

10, 385

[ Turn Over ]

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