Tutorial-1 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017

Date: 12.01.17 Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class; backside
of this sheet can also be used for presenting the solution to problem

1. An ideal gas at T=25oC having a volume of 10 litre at a pressure of 10 atm has been
expanded to reach a final pressure of 1 atm. Calculate the work done, the heat flown, and
the changes in internal energy (U) and enthalpy (H), for the when the gas expansion was
carried
(i) as an reversible isothermal process
(ii) as an reversible adiabatic process

For the above two cases, determine the final state of the system.

Following data may be used; for ideal gas, = R, and =

Tutorial-2 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

1. An adiabatic container at a temperature of 300 K is filled with 5 moles of ideal gas at a

pressure of 50 atm. When the pressure has been reduced suddenly to 10 atm, the gas
expanded irreversibly and performed a work of 4000 joules. Calculate the following
(i) final values of state variables (T, P and V) for the above described irreversible expansion.
Indicate the final and initial states in PV diagram
(ii) final values of state variables when the same process of expansion has been conducted
reversibly. Indicate the final and initial state in PV diagram
(iii) Calculate the entropy produced during irreversible expansion

Following data may be used; for ideal gas, = R, and =

Tutorial-3 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

Isotopic composition of lead in atomic percent is as follows

Isotope atomic weight Atomic % of isotope
204 1.5
206 23.6
207 22.6
208 52.3

Calculate the molar configurational entropy (J/K) of lead. Do the calculation after taking the
system to a total of 1 mole and use the Stirlings approximation.
Tutorial-4 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

Derive the following expressions;

dU TdS pdV dH TdS Vdp dA SdT pdV dG SdT Vdp

Write down the four Maxwells expressions.

Tutorial-5 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem during this week Fridays lecture;
backside of this sheet can also be used for presenting the solution to problem

1. A mixture of Fe2O3 and Al, present in the molar ratio 1:2, is placed in an adiabatic
container at 298 K, and the Thermit reaction 2Al + Fe O 2Fe + Al O proceeds until
completion, i.e., no reactants will be left at the end of reaction. Calculate the state (i.e.,
liquid/solid or partly liquid and partly solid) and the temperature of the reaction products
utilizing the following thermodynamic data
, = 1675700 /
, = 1328330 /

, ,
= 118 + 10 J/K in the range 298-2325 K

, ( ) = 37 + 6 10 J/K in the range 298-1187K

, ( ) = 24 + 9 10 J/K in the range 1187-1664K

, ( ) = 37 + 6 10 J/K in the range 1664-1809K

Tutorial-5 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem during this week Fridays lecture;

2. Vapor pressure-temperature relationships for CaF2(), CaF2(), and CaF2(liquid) are

as follows

Calculate the temperatures and pressures of the triple points for the equilibria CaF2()
CaF2()CaF2(vapor) and CaF2()CaF2(liquid)CaF2(vapor). Also calculate the molar latent
heat of melting of CaF2().
Tutorial-6 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

Calculate the values of , at 800K for the following reaction at constant pressure of 1 atm
+3 3 ( ) +2

Calculate the percentage error in if it is assumed that for reaction is zero.

Given data: ( ) = 910900

( ) = 744800

( ) = 41.5

( ) = 113
( ) = 191.5
( ) = 205.1

( ) = 27.87 + 4.27 10

( ) = 29.96 + 4.18 10 1.67 10

( ) = 43.89 + 10 6.02 10

( ) = 70.54 + 98.74 10
Tutorial-7 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

1. Nitrogen gas behaves as a van der Walls gas with a = 1.39 l2. atm/mol2 and b = 39.1
cm3/mol. Calculate the change in Gibbs energy when one mole of nitrogen gas has
been expanded isothermally, at 400 K, from 1 l (litre) to 2 l (litre).
Tutorial-7 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

2. The virial equation of state for n-butane at 460K is Z= 1+ A/V + B/V2 with A= -265
cm3/g.mole and B= 30250 cm6/g.mole2. calculate the change in Gibbs energy when
the volume of one mole of butane is decreased from 400 cm 3 to 200 cm3 at 460K.
Tutorial-8 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

One hundred moles of hydrogen gas at 298 K has been reversibly and isothermally compressed
from 30 to 10 liters. The van der Waals constants for hydrogen are a=0.2461 liters2atm mole-
2 and b=0.02668 l/mole, and in the range of pressure 01500 atm, the virial equation for

hydrogen is PV=RT (1+ 6.4 x 10-4 P). Calculate the work that must be done on the system to
effect the required change in volume for the following cases
(1) hydrogen behaves as a van der Waals gas,
(2) hydrogen behaves as an ideal gas
(3) hydrogen gas expansion given by virial equation of state
Tutorial-8 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

1. The virial equation of state for n-butane at 460K is Z= 1+ A/V + B/V2 with A= -265
cm3/g.mole and B= 30250 cm6/g.mole2. calculate the change in Gibbs energy when
the volume of one mole of butane is decreased from 400 cm 3 to 200 cm3 at 460K.
Tutorial-9 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

Copper (Cu) and gold (Au) form complete ranges of regular solid solutions at between 410C
and 889C, and, at 600C, the excess molar Gibbs free energy of formation of the solid
solutions is given by = 28280 / . Calculate the partial pressures of Au
and Cu exerted by the solid solution of XCu= 0.6 at 600C.
For a regular binary solution: = , ln = and = =
The saturated vapor pressure for solid copper is given by
40920
( )= 0.86 ln + 21.67
The saturated vapor pressure for solid gold is given by

45650
( )= 0.306 ln + 10.81
Tutorial-9 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____
Tutorial-10 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

Using the given Ellingham diagram answer the following questions; marks 7 x 1 = 7
1. Give the values of the standard enthalpy change (with in accuracy of 20 kJ/mol) for
the oxidation of Ti, Ti + O = TiO , at temperatures of 600oC and 400oC.

2. The elemental Si can be used to produce elemental Ti from TiO2? Answer True or
False.

3. Slopes of Ellingham lines for most metal oxidation reactions are positive due to
positive values of entropy change for the metal oxidation reactions. Answer True or
false

4. Indicate, in the given Ellingham diagram, the equilibrium partial pressure of O 2 at

800oC for the equilibrium between Mn and MnO.

5. Indicate, in the given Ellingham diagram, the equilibrium CO/CO2 partial pressure
ratio at 1600oC for the equilibrium between Ti and TiO2

6. Can we produce elemental Si from SiO2 at 1200oC by maintaining the H2/H2O partial
pressure ratio of 100? Answer yes or No

7. Can we produce elemental Fe from FeO by maintaining the partial pressure of

oxygen at 10-20
Tutorial-10 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____
Tutorial-11 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

For binary Ge-Si system, at constant pressure of 1 atm, assuming that both solid-solution and liquid-
solution behave ideally over the entire range of composition, calculate the composition of solid-
solution and liquid-solution at 1473K. Given data: (i) melting temperatures of Si and Ge are 1685 K
and 1210 K, respectively, (ii) enthalpies of melting of Si and Ge are 50200 J/mol and 36900 J/mol.
Use the equations on back side of this page for calculation. Assume that the specific heats of pure
solid and liquid phases are equal.
Tutorial-11 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____
Tutorial-12 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Student must submit this sheet with the solution of the problem at the end of tutorial class;
backside of this sheet can also be used for presenting the solution to problem

Standard Gibbs energy change ( ) for dissociation of gaseous ammonia ( ) according to the
reaction, 2 ( ) = ( )+3 ( ) is = 87030 25.8 31.7 .
Calculate the composition of gas (partial pressures of ammonia, hydrogen and nitrogen in gas
mixture at equilibrium) at 673 K for the conditions (i) total pressure is constant at 1 atm and (ii) total
.
volume is constant. Use the relation = ln . For the given reaction =

Procedure for answering question (i): Represent the partial pressures of all components of gas with
one unknown according to the stoichiometry of the given reaction. If we assume that at equilibrium
the number of moles of are x, then from the stoichiometry of reaction at equilibrium the number
of moles of must be 3x. If we start the reaction with one mole of , then the number of moles
of ammonia at equilibrium (i.e., after the reaction reaches equilibrium state) must be 1-2x. Accordingly
the total number of moles of gaseous molecules at equilibrium must be 3x+x+1-2x=1+2x. From the
known amounts of molecules of each gas and the total number of moles of gas molecules in the system
calculate the partial pressures of all three gases for a total pressure of 1 atm. For example, = .

Calculate x first and then using x calculate the partial pressures of all gas species. Finally calculate the
percentage of ammonia in the final gas mixture.
Tutorial-12 MT-102 Metallurgical Thermodynamics and kinetics Spring-2017
Date: __________ Student name: _____________________ Enroll. No. __________ Batch:_____

Procedure for answering question (ii): total volume constant

As reaction results in increased amount of moles from initial 1 mole to final 1+2x moles, when the
volume is kept constant the total pressure increases, which means the reaction equilibrium shifts to
left from the case of constant total pressure of 1 atm. Assume that the gas behaves ideally. For initial
one mole of ammonia at pressure P, the volume of gas is V= RT/P. as volume is constant, the final
pressure p is given as V=(1+2x)RT/P which implies that P=(1+2x)P. for initial pressure of 1 atm,
P=1+2x. Using this as total pressure, calculate the partial pressures of all gases in this case. For
example, = = 3 . From here on follow the same procedure as in the previous case and
finally calculate the percentage of ammonia in the gas mixture when the volume is kept constant.