r050211802 Thermodynamics and Kinetics

Code No: R050211802 Set No.
1
II B.Tech I Semester Supplementary Examinations, February 2007
THERMODYNAMICS AND KINETICS
(Metallurgy & Material Technology)
Time: 3 hours Max Marks: 80
Answer any FIVE Questions
All Questions carry equal marks
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1. (a) Prove the following for a closed system .

For constant volume process Q = mCv (T2 − T1 )
For constant pressure process Q =mCp (T2 − T1 )
(b) Differentiate between intensive and extensive properties with examples. [12+4]
2. (a) State and explain HESS’s law of heat summation.

(b) Explain the conclusion that are drawn from Joule - Thomson experiment.
(c) Derive an expression for the work done in isothermal expansion of an ideal
gas. [5+5+6]
3. (a) From the Consideration of the variation of entropy and heat content with tem-
perature, pressure and volume , derive the general thermodynamic equation
of state and comment on them.
(b) Calculate the differences in entropy of 0.5kg of liquid water at 00 C and 1 × 105
N/m2 Pressure and 0.5kg of water vapour at 1000 C and 1 atm pressure. The
latent heat of vaporization at 1000 C is 530kcal /gm. [16]
4. (a) Why free energy is called a thermodynamic work function or thermodynamic

driving force? Explain.
(b) Define Gibb’s free energy and Helmholtz free energy and differentiate
(c) What do you understand by the term spontaneous thermodynamic process
and non-spontaneous thermodynamic process? [16]
5. (a) What do you know about thermo chemical data. [8]

(b) Discuss the use of third law of thermodynamics in evolution of ∆S O of a
reaction [8]
6. (a) Define equilibrium constant and what is its role in metallurgical processes.
(b) Calculate the equilibrium constant for the reaction
ZrO2 = Zr + O2 ∆GO = 259, 940 + 4.33 T log T-59. 12TCal at 1727O C. [16]
7. (a) Say true or false the following statements with suitable Explanation. Activity
of component can never be greater then unity in a system under equilibrium.
(b) State and explain Troutons rule. [16]
8. (a) Derive an expression for half life of a first order reaction.
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Code No: R050211802 Set No. 1
(b) What is a catalyst? What is the importance of catalyst in a chemical reaction?
[16]
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1. (a) State whether the following statements are true or false and justify your answer
in brief.
i. Internal energy of a gas does not depend upon its pressure and tempera-
ture.
ii. If f is negative , a reaction will definitely will be spontaneous .
(b) The properties of a closed system undergoes change following the relation PV
=4 and P isin bar and V in metre cube . Calculate the work done, when P
increases from 2.5 bar to 8 bar. [8+8]
2. With the help of first law of thermodynamics equation calculate internal energy for
isobaric process and isothermal process. [16]
3. (a) what is entropy? What are the deferent types of entropies? Give the entropy
criterion for spontaneity of a process.
(b) Calculate the strand enthalpy and entropy changes at 250 C for the reaction.
2Cu + 1/2 O2 →< Cu2 O >
∆G0 = - 40,500- 3.92 Tlog T + 29.5 T Cal. [16]
4. (a) What do you understand by the term free energy of a system. what is its
Significance?
(b) From the first principles, derive the equations for the Gibbs free energy ∆G =
∆H − T ∆S
(c) How can free energy change of a reaction determine experimentally. [16]
5. (a) state the third law of thermodynamics and explain how it rationalize the
thermo chemical data [6]
(b) What is the meaning of thermodynamically possible process [5]
(c) What are he important deductions of third law of thermodynamics [5]
6. Define the following and explain [16]
(a) Fugacity
(b) Activity
(c) Equilibrium Constant
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(d) Raoult’s law
8. (a) Comment on the following statement: A catalyst increases the rate of reaction,
but it is not consumed because it does not participate in the reaction.
(b) Why does not a catalyst appear in the overall chemical equation for a reaction?
(c) What effect does a catalyst have on the rate, mechanism and activation energy
of a chemical reaction?
(d) Distinguish between homogeneous catalyst and heterogeneous catalyst and
give an example for each. [16]
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1. (a) State whether the following statements are true or false and justify your answer
in brief.
i. Internal energy of a gas does not depend upon its pressure and tempera-
ture.
ii. If f is negative , a reaction will definitely will be spontaneous .
(b) The properties of a closed system undergoes change following the relation PV
=4 and P isin bar and V in metre cube . Calculate the work done, when P
increases from 2.5 bar to 8 bar. [8+8]
2. (a) Define the following :

i. Heat
ii. Work
iii. Internal Energy.
iv. Heat capacity.
(b) State and explain the first law of thermodynamics and its applications. [8+8]
3. Explain the application of a thermodynamic equation of state to the equation of

state to the elastic compression or Expansion of a solid. [16]
4. (a) What do you mean by spontaneity based on free energy?

(b) Calculate the standard free energy change for the following reaction at 25O C.
NiO + H2 = Ni + H2 O Given data
NiO = Ni + 1/2 O2 ∆H298O =50,786Cal
H2 + 1/2 O2 = H2 O ∆H298O =54,996Cal [16]
5. (a) State and explain the third law of thermodynamics .what is its importance.
[6]
(b) Derive an expression to show variation of equilibrium constant with tempera-
ture. [10]
6. Calculate the equilibrium constant and equilibrium partial pressure of oxygen for
the reaction.
ZrO2 → Zr + O2
∆GO = 259940 + 4.33TlogT - 59.12T cal, at 1727O C.
Also predict the possibility of decomposing a pure Zirconium crucible under a
vaccum of 10−5mm Hg at that temperature. [16]
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8. (a) Derive an expression for rate of rate constant of a second order equation A+B
→ product.
(b) Explain how does the temperature affect the rate of a reaction. [16]
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1. (a) Write the statement for four laws of thermodynamics.

(b) Define and explain the standard state of a substance.
(c) Equation of state. [8+4+4]
2. (a) State and explain Le-chatlier principle.

(b) Derive Kirchoff’s equation.
(c) Define and explain joule - Thomson coefficient and derive an equation for it
in terms of Vanderwalls constants [5+5+6]
3. (a) Define entropy and explain its importance.

(b) Calculate standard entropy change for the reaction at 250 C.
Cr2 O3 + 3C = 2Cr + 3CO
Given Data:
O
S298<Cr2O3> = 19.4 cal/deg/mole
O
S298<C> = 1.36 cal/deg/mole
O
S298<Cr> = 5.68 cal/deg/mole
O
S298(Co) = 47.3 cal/deg/mole [4+12]
4. (a) What are the various factors on which the free energy of substance of a fixed
mass depends? Explain them.
(b) Derive all T ds equations from thermodynamic relations. [16]
5. (a) What do you know about thermo chemical data. [8]

(b) Discuss the use of third law of thermodynamics in evolution of ∆S O of a
reaction [8]
6. (a) Discuss the importance of sigma function in evalution of fugacity.

(b) Explain the effect of temperature on equilibrium constant.
(c) How is equilibrium constant determined at any time? [16]
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8. (a) explain the standard free energy change for any reaction. [6]
(b) Determine the equilibrium constant at 250 c for the reaction
CH4 (g) + H2 O(l) → CO(g) + 3H2 (g)
Data: [10]
COMPONENT ∆0 G at 250 c
CO(g) -137.8 KJ/mole
CH4 (g) -50.09 KJ/mole
H2 O (1) -238.0 KJ/mole
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Code No: R050211802 Set No.

1. (a) Prove the following for a closed system .

2. (a) State and explain HESS’s law of heat summation.

4. (a) Why free energy is called a thermodynamic work function or thermodynamic

5. (a) What do you know about thermo chemical data. [8]

8. (a) Derive an expression for half life of a first order reaction.

2Cu + 1/2 O2 →< Cu2 O >

∆G0 = - 40,500- 3.92 Tlog T + 29.5 T Cal. [16]

6. Define the following and explain [16]

2. (a) Define the following :

3. Explain the application of a thermodynamic equation of state to the equation of

4. (a) What do you mean by spontaneity based on free energy?

1. (a) Write the statement for four laws of thermodynamics.

2. (a) State and explain Le-chatlier principle.

3. (a) Define entropy and explain its importance.

Cr2 O3 + 3C = 2Cr + 3CO

5. (a) What do you know about thermo chemical data. [8]

6. (a) Discuss the importance of sigma function in evalution of fugacity.

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