r05221803 Metallurgical Thermodynamics

Code No: R05221803 Set No.
1
II B.Tech II Semester Supplimentary Examinations, Aug/Sep 2007
METALLURGICAL THERMODYNAMICS
(Metallurgy & Material Technology)
Time: 3 hours Max Marks: 80
Answer any FIVE Questions
All Questions carry equal marks
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1. (a) Discuss Fick’s laws of diffusion. Write stepwise expressions to explain them.
(b) Explain about the following:
i. Pipe diffusion
ii. Lattice diffusion
iii. Entharpy of motion. [7+9]
2. (a) Explain the various factors that affect activation energy.

(b) Explain the mechanism of diffusion in Ionic compounds with suitable examples
and figures. [8+8]
3. (a) Calculate the equilibrium constant for the reaction

N iO + H2 = N i + H2 Oat750o C
from the following data:
Ni + 1/2 O2 = NiO ∆Go = −58, 450 + 2355T cal
H2 + 1/2O2 = H2 O ∆Go = −58900 + 13.1T cal
(b) Calculate the CO/CO2 ratio in equilibrium with Carbon at 727o C assuming
that the total pressure to be 2 atm. 2C + O2 = 2CO ∆ Go 1000 = -95.3
kcal
C + O2 = CO2 ∆ Go 1000 = -94.0 kcal [8+8]
4. (a) Define and explain the terms Cp and Cv and derive the thermodynamic rela-
tionship betweent them.
(b) Explain why Dulag-pesit law is not applicable at low temperatures.
(c) Define and explain the term molar heat. What are units in which it is ex-
pressed. [8+4+4]
5. (a) Discuss the significance of knowing specific heat, thermal conductivity and
melting point of a solid. What factors influence the thermal conductivity of
solids? Explain them.
(b) A copper rod of 50 mm diameter has to be fitted into a circular hole in a 70
cu-30 zinc brass plate of diameter 49.98 mm. To what temperature the brass
plate has to be heated so that the copper rod just fits into the hole in the
brass plate. Assume room temperature to be 30o C and α = 20 × 106 o C −1 .
[10+6]
6. (a) State and explain Sievert’s law.
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Code No: R05221803 Set No. 1
(b) Define activity of a substance. Indicate the relationship between activity and
mole fraction for an ideal solution. [6+10]
7. (a) What is the significance of phase rule? Discuss its applications and limitations.
(b) Explain the differences between a liquidus line and solidus line. Explain how
the liquidus line is obtained for an eutectic system. [8+8]
8. (a) Derive an expression for Gibb’s-Helmholtz equation to galvanic cells.

(b) What do you understand by thermodynamics of electrochemical cells? Explain
briefly. [8+8]
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1. (a) Explain the engineering importance of diffusion. State and Explain Fick’s first
and second law.
(b) Explain the phenomenon of diffusion in all states of matter.
(c) Distinguish between thermal energy; kinetic energy and activation energy.
[5+5+6]
2. Distinguish between the following.
(a) Steady state and unsteady state of diffusion.

(b) Diffusivity and permeability. [8+8]
3. (a) Discuss the derivation and uses of the oxygen nomographic scale in Richard-
sons diagram.
(b) Discuss in detail about the properties of a single standard free energy change/temperature
line. [8+8]
4. (a) Define and explain the terms Cp and Cv and derive the thermodynamic rela-
tionship betweent them.
(b) Explain why Dulag-pesit law is not applicable at low temperatures.
(c) Define and explain the term molar heat. What are units in which it is ex-
pressed. [8+4+4]
5. (a) What are the differences between lattice thermal conductivity effects and
thermo electric effects of solids.
(b) The volume of a cubical block of metal changes by 0.15%. When its tempera-
ture is raised by 30o C compute the coefficient of linear expansion of the metal.
[8+8]
6. (a) What do you mean by ‘activity’ of a component? How it can explain the
behavior of a solution? Also explain about ‘activity coefficient’ with suitable
example.
(b) Derive gibb’s-Duhem equation N1 dG1 + N2 dG2 =0 from first principles. [9+7]
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8. (a) Differentiate between electrochemical cells & electrolytic cells.
(b) Explain in detail about the concentration cells. [8+8]
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1. Define and explain the following:
(a) Diffusion
(b) Solid state diffusion
(c) Self diffusion
(d) Hetero diffusion. [4X4=16]
2. (a) Describe the mechanism of diffusion from a limited source of dopants.

(b) Explain the factors that affect the diffusion rate in solid metal crystals. [8+8]
3. (a) Explain the condition of equillibrium of two-phase mixture of a pure substance

in terms of free energy.
(b) Explain the effect of temperature on equillibrium constant.
(c) Distinguish between Gibb’s and Helmholtz free energies. What is their signif-
icance? [6+4+6]
4. (a) Describe ‘Debye’s theory’ of specific heats of solids. Explain the concept of
Debye’s temperature.
(b) Discuss the merits and defects of Debye’s model in comparision with Einstein’s
model in explaining specific heats of solids. [8+8]
5. (a) Why does thermal expansion occur in a material? What are the effects of
potential energy and the temperature on the magnitude of thermal expansion
in important engineering metals?
(b) The coefficients of expansion of a rock crystal in three orthogonal directions are
13 × 10−7 /0o C; 146 × 10−7 /0o C and 231 × 10−7 /0o C. Calculate its coefficient
of cubical expansion. [9+7]

7. (a) Explain the concept of chemical potential and derive the expressions related
there in. Show that for any heterogeneous system of equillibrium, the chemical
potential of each component has identical values in all the phases.
(b) Disucss the graphical method of valuation of partial molal quantities from the
molal quantity. [9+7]
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8. (a) Explain about the Galvanic cell its sign convention & representation.
(b) What are the reversible and irreversible cells, Explain about any one cell in
detail. [8+8]
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1. (a) Explain the generalized laws of diffusion to include kirkendall effect as pro-
posed by DARKEN.
(b) We find that 10h are required to successfully carburize a batch of 500 steel
gears at 900o C, where the iron has the FCC structure. We find that it costs
Rs.1000 per hour to operate the carburizing furnace at 900o C AND Rs.1500
per hour to operate the furnace at 1000o C. Find out whether it is economical
to increase the carburizing temperature to 1000o C? [8+8]
2. (a) Explain the various factors that affect the diffusion coefficient.
(b) The diffusivity of aluminium in Cu is 2.6 × 10−17 m2 /sec at 500o C and 1.6 ×
10−12 m2 /sec at 1000o C.
i. Determine the values of Do , Q for this diffusion couple.
ii. What is the diffusivity at 750o C. [6+10]
3. (a) What is the importance of equilibrium constant & how this can be calculated
from standard free energy changes?
(b) Define equilibrium constant & how this can be influenced on the extraction
process. [8+8]
4. (a) Give the mathematical expression for specific heat capacity at constant volume
below Debye’s characteristic temperature. Explain about the expression and
discuss the terms involved in it.
(b) Explain why the contribution by the electrons to specific het is significant even
at room temperatures. [8+8]
5. (a) For metals, it is expected that thermal conductivity will be relatively insensi-
tive to temperature if the electrical resistivity increases linearly with temper-
ature. Justify this statement andcite its limitations.
(b) Explain the limitations of Dulong-petit’s law.
(c) Give the expression for the electronic contribution to the heat capacity. Ex-
plain it’s significance. Discuss various terms in the expression. [6+4+6]

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8. (a) Differentiate between electrochemical cells & electrolytic cells.

(b) Explain in detail about the concentration cells. [8+8]
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Code No: R05221803 Set No.

2. (a) Explain the various factors that affect activation energy.

3. (a) Calculate the equilibrium constant for the reaction

6. (a) State and explain Sievert’s law.

8. (a) Derive an expression for Gibb’s-Helmholtz equation to galvanic cells.

2. Distinguish between the following.

(a) Steady state and unsteady state of diffusion.

1. Define and explain the following:

2. (a) Describe the mechanism of diffusion from a limited source of dopants.

3. (a) Explain the condition of equillibrium of two-phase mixture of a pure substance

6. (a) State and explain Sievert’s law.

6. (a) State and explain Sievert’s law.

8. (a) Differentiate between electrochemical cells & electrolytic cells.

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