MM2015 : Thermodynamics of Materials

Quiz 1 dated 10th September 2018

Instructions: Write your answers in this bundle itself. You can use extra sheets for rough work but
copy the final solution into this bundle for it to be evaluated. Submit your A4 sheet of formulas, any
rough sheets along with this bundle. All your answers will be evaluated. The question paper is for
30 marks but the maximum for this exam is capped at 25. State and make any assumptions you need
to. All questions carry 5 marks each.

Marks:

Q1 Q2 Q3 Q4 Q5 Q6 Total

[Q1] Consider a model in which the available energy levels are linearly spaced along the energy
axis: where the symbol n refers to the energy level. Compare the two systems
listed below.
n 0 1 2 3 4 5 6 7 8 9
System A 0 1 2 1 4 2 2 0 0 0
System B 0 2 3 1 2 2 0 0 1 1

Do the two systems belong to the same macro state? [Yes/No]

Which is the entropy of system A in units of Boltzmann constant?

Which is the entropy of system B in units of Boltzmann constant?

Which system is more likely to be observed?

[Q2] Each of the following statements are true. Give your justification for these in the space
provided.

The phase with the highest heat capacity is the one that is most stable at high temperatures.

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Enthalpy of an ideal gas is independent of the pressure of the gas.

In a system with two levels, the ratio of the particles occupying the two levels tends to unity as the
temperature is increased to large values.

[Q3] In the diagram below, using the axes as indicated, plot a schematic pressure (P in bar) –
temperature (T in K) phase diagram of a pure material, such as silicon. Label the melting point,
boiling point, triple point and regions of the P-T space as relevant. Label the slopes assuming ideal
gas behavior of the vapor phase.

Log(P)

0.001 0

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[Q4] One mole of a metal block at 900 K is dropped into a large reservoir of liquid at 1200 K. The
metal block eventually attains the temperature of the reservoir. The heat capacity of the metal block
as a function of temperature is given by . Calculate the following quantities and
give the answers with correct units.

Entropy change for the metal block

Heat gained by the metal block

Entropy change for the surroundings

[Q5] Use the following definitions for this problem.

Prove the following:

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[Q6] Gibbs energy of 1 mole of binary regular solution is plotted below at a temperature of 1000 K.
The x-axis shows the mole fraction of B increasing towards the right. The y-axis shows the Gibbs
energy in J/mol. Estimate the following quantities to the best accuracy possible using the scale
provided along with the plot. Label the quantities L, M, N and Q on the plot.

Quantity Meaning Value

L Gibbs energy of pure A

M Gibbs energy of a mechanical mix of 30% A + 70% B

N Gibbs energy of the solution containing 30% A + 70% B

P An estimate of regular solution parameter

Q Chemical potential of the component A for the alloy 30% A + 70% B

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 MM2015 : Thermodynamics of Materials
Quiz 2 dated 24th October 2018
Instructions: Write your answers in this bundle itself. You can use extra sheets for rough work but
copy the final solution into this bundle for it to be evaluated. Submit your A4 sheet of formulas, any
rough sheets along with this bundle. All your answers will be evaluated. The question paper is for
30 marks but the maximum for this exam is capped at 25. State and make any assumptions you need
to. All questions carry 5 marks each.
Name: Roll Number:

Q1 Q2 Q3 Q4 Q5 Q6 Total

[Q1] The molar excess Gibbs energy of formation of solid solutions in the system Au-Ni can be
represented by the following expression. The units are in Joules.

Calculate the following for the alloy with mole fraction of Nickel of 0.5 and at 1330 K.

Expression to be used
for
Activity coefficient of Ni

Activity of Ni

Activity coefficient of Au

Activity of Au

[Q2] Each of the following statements are true. Give your justification for these in the space
provided.

For a binary alloy, in the composition range where the solute exhibits Henrian behavior, the
solvent exhibits Raoultian behavior.

Page 1 of 5
Activity coefficient of B decreases with increasing temperature for a binary solution A-B with a
positive deviation from ideal behavior.

If a gas mixture contains a constant number of moles in all states along the reaction coordinate,
then the equilibrium constant Kp is independent of pressure.

[Q3] One mole each of hydrogen, iodine vapor and HI gas are allowed to react at 1500 K and 1 atm
pressure. Calculate the mole fractions of H2, I2 and HI in the equilibrium mixture.

For the reaction given above, in Joules. Assume the universal gas
constant to be 8.314 J/(mol.K).

Condition of reaction
equilibrium

Equilibrium constant

Fraction of H2 reacted at equilibrium

Mole fraction of H2 in the gas mixture at equilibrium

Mole fraction of HI in the gas mixture at equilibrium

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[Q4] Binary phase diagram of Silver – Copper system is shown below. At 900 oC, plot
schematically the Gibbs energy versus composition diagram. Indicate the common tangent locations
by mapping them onto the phase diagram appropriately.

Page 3 of 5
[Q5] Consider a binary system A-B exhibiting an isomorphous phase diagram as shown below. The
temperature marked are in Kelvin. Plot the activity of the species B as a function of mole fraction of
B at 1100 K in the box given below. Label the transition in the slopes by comparing with
appropriate locations in the phase diagram. Indicate the standard chosen for the activity.

1500

1400
Liquid
1300
L+S
1200

Solid
1100

1000

A B

1
Activity

0
0 1
Mole fraction of B

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[Q6] Consider the following two hypothetical reactions:

How do the reaction equilibrium conditions of these two reactions differ?

Plot for both the reactions on an Ellingham diagram and illustrate the differences. Assume that
the Enthalpy of both the reactions is negative and that the metal X tends to oxidize more readily
than metal M.

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 MM2015: Thermodynamics of Materials
End Semester Examination, 19-Nov-2018, 09:00 - 12:00 Hrs, NAC204/205

Name: Roll Number:

Instructions
1. Maximum mark for this question paper is 50. All questions carry 6 marks except the first one.
2. Write your name and roll number all the sheets you have and hand them over along with your answer
sheet. This includes the question paper, A4 sheet of formulas your brought along and the handouts that
came along with the question paper.
3. In case of any doubt, state and make suitable assumptions and proceed.

1. Derive the following Maxwell’s equation. [2 Marks]

   
∂S ∂V
=−
∂p T ∂T p

2. Consider in a binary system a solid solution that exhibits a regular solution behavior with Ω as
the regular solution parameter. Determine the critical temperature TC above which the solution
is expected to be homogeneous for all compositions. Based on this information construct a
function for Gibbs energy of mixing GM such that the critical temperature is 1000 K. Determine
the partial molar Gibbs energy of mixing for the component A at equi-molar composition.

3. In the Figure 1 given along in a separate sheet, enthalpy of reactants is plotted using dashed line
and enthalpy of the products is plotted using bold continuous line for a hypothetical reaction
aA + bB = cC + dD. Mark the following on the figure.

(a) Locate the sum of enthalpies of reactants at T1

(b) Locate the sum of enthalpies of products at T3
(c) Indicate the change in enthalpy of products when the temperature is changed from T1 to
T2
(d) Indicate the change in enthalpy of reactants when the temperature is changed from T2 to
T3
(e) Indicate the heat of reaction at T2
(f) Comment on the plot itself if the reaction is exothermic or endothermic at T2

4. The volume (in cm3 ) of a dilute solution of KCl of molality m (m moles of KCl in 1 kg of water)
is given by the following equation.

V = 1003 + 27.15 m + 1.7444 m2

(a) Calculate the partial molar volume of KCl at m = 0.5 (b) Calculate the partial molar volume
of KCl at the infinitely dilute solution

5. Consider a system consisting of the following species: Fe(s) , FeO(s) , Fe3 O4 (s) , CO(g) and CO2 (g) .
It is known that CO reduces Fe3 O4 first to FeO with a ∆Gr = 29200 − 26.26 T and then FeO
to Fe with a ∆Gr = −17900 + 22.74 T . Both the affinities are given in Joules per mole of CO.
(a) Determine the number of degrees of freedom in this system. (b) Determine the temperature
at which all the five species exist together in equilibrium (c) Determine the partial pressures of
CO and CO2 at a total pressure of 1 atm.

6. Using the Richardson-Ellingham diagram provided along, answer the following to the best of the
accuracy you are able to read off the diagrams. Mark these on the diagram for partial credit.

1
 (a) What is the partial pressure of oxygen in equilibrium with nickel and its oxide at 1200 o C
(b) What is the partial pressure of oxygen below which titanium metal can be free of oxide at
1500 o C.
(c) What is the ratio of partial pressures of CO and CO2 above which MnO could be reduced
at 1200 o C.
(d) At the ratio of partial pressures of hydrogen and water vapor of about 104 , what would be
the temperature when Mn and its oxide will be at equilibrium?

7. Pidgeon’s process is one in which Dolomite (CaO.MgO) reacts with Ferro silicon (Fe.Si) to form
silicate slag (CaO.SiO2 .FeO) and magnesium vapor. Rationalize the feasibility of reduction of
MgO at temperatures as low as 1200 o C from what you know about the way Ellingham diagrams
change due to activity changes of the species involved. Use schematic plots to illustrate and
comment on the change of slopes clearly.

8. The vapor pressures of zinc have been written in the following two expressions. The pressures
are given in atm.
15780
A : ln p = − − 0.755 ln T + 19.25
T
15250
B : ln p = − − 1.255 ln T + 21.79
T
Which of these two expressions is for solid zinc and which one is for liquid zinc? What is your
estimate of the melting point of zinc? Show the calculation process.

9. Draw schematically a simple binary phase diagram of a binary system A-B with the following
observations. Metal A has limited solid solubility with B forming the phase α. Element B has
negligible solid solubility with A. There is a eutectic reaction between α and B at xA = 0.2. At a
temperature slightly below the eutectic, draw a schematic Gibbs energy versus composition plot
showing all the relevant parameters. Express the equilibrium condition (analytically) between
α and the liquid alloy at a temperature slightly above the eutectic temperature.

10. The boiling point of a liquid A is elevated by adding a solute B to it that forms a liquid
solution A+B. For the same liquid A, the freezing point got depressed upon adding solute B
to it. Illustrate this possibility using a chemical potential versus temperature diagram. Using
concepts of phase equilibrium, derive a relationship for the extent of change in the freezing /
boiling points.

11. Alloys of Cu-Zn are called brasses. Figure 2 given along in a separate sheet shows Cu-Zn phase
diagram drawn for at 1 atm pressure. Answer the following briefly.

(a) Apply Gibbs phase rule for a point (40 wt% Zn, 600 o C) and comment on the degrees of
freedom.
(b) For an equi-atomic binary alloy in this system, at 800 o C, apply Gibbs phase rule and
comment on the degrees of freedom.
(c) What is the composition range of gamma brasses? What is the composition range for
duplex or two phase (α + β) brasses?
(d) Locate a point that has no degrees of freedom.
(e) At a temperature 1000 o C, draw a schematic Gibbs energy versus composition diagram [2
Marks].