INDIAN INSTITUTE OF TECHNOLOGY, BOMBAY Department of Metallurgical Engineering and Materials Science MM 202: THERMODYNAMICS of MATERIALS Assignment No.

2 (SOLVE ANY 15) Submission Date: 14.02.2014 One should rid of the prejudice that an arithmetical mistake or a mistake in conversion is less serious than a mistake in analysis. In engineering practice, a numerical mistake leads to consequences, which may be as serious as those of a mistake in analysis. Furthermore, an engineer should cultivate a critical feel for orders of magnitude. Kestin Please submit all assignments in A4 sized sheets. Please submit the assignments during the class on the date mentioned above. Evaluation is based on the serious effort one puts into to solve the problems. Remember that you learn more when you are on the wrong tract and then correct yourselves. Do not therefore bother about what is the correct answer. Solve them yourself. It pays to solve problems, even in terms of grades! Where data is not given, use data from : Kubaschewskii: Materials Thermochemistry, (Pergamon Press. Cite the edityion of the book and page numbers correctly. __________________________________________________________________ 1. When the reference junction of a thermocouple is kept at the ice point and the test junction at the Celsius temperature t, the emf E of the thermocouple is given by E = t + t2, where = 0.20 mV/C and = -5.0xl0-4 mV/deg2. Suppose that the emf E is taken as the thermometric property, and a temperature t* is defined by the linear equation t* = a E +b, and that t* = 0 at the ice point and t* = 100 at the steam point. Find the numerical value of a and b. Find the values of t* at t = -100 C, 200 C, 300 C and 400 C. Draw a graph of t vs. t*. 2. With numerical examples show difference between two states of values and the ratios of energies are not. that in the same a gravitational body only is field, potential meaningful; the energy absolute

3. A strong capillary tube fully filled with mercury and closed at 0C is heated to 10C. Assuming the volume of the capillary remains constant, calculate the resulting pressure. For mercury near room temperature the expansion coefficient is 18x10 -5 per degree and the compressibility is 3.7x10 -6 per atmosphere. [you need to find ( P/ T) V] 4. If you put some salts, like ammonium chloride, into water, the solution cools down? Why? Dont I have to do some work, like in a refrigerator, to cool anything? 5. (a) Derive an expression similar to the statement dE= q -P.dV for the application of a unidimensional stress to a metal bar of length l . How do the signs account for the two cases of extension and compression? (b) Evaluate the work done in the equation derived in (a) for the process in which the stress on a wire of cross-section A is increased from 1 to 2 at constant temperature. Youngs Modulus: = . Neglect changes in Y, l and A.

6. An imperfect gas obeys the equation:

/ =

Where a = 8x10 -3 N.m4 .mol-2 and b = 3x10 -5 m3 .mol-1 -1. Calculate the work required to compress 0.3 moles of this gas isothermally from a volume of 5x10 -3 m3 to 2x10 -3 m3 at 300K. 7. 10 liters of a monatanic gas at 25 o C and 10 atm. are expanded to a final pressure of 1 atm. =

and is independent of pressure and temperature. Calculate final states, the work done, the heat absorbed and the change in E and H if the processes are carried out: (a) Reversibly and isothermally (b) adiabatically and reversibly Having determined the final state of the gas after the reversible adiabatic expansion, verify that the change in E for the process is independent of the path taken between the initial and final states by considering the process to be carried out as (i) (ii) (iii) (iv) (v) isothermal process and a constant volume process constant vol. process and an isothermal process isothermal process followed by a constant pressure process constant vol. process followed by a constant pressure process constant pressure process and a constant volume process

8. 1 kmol of CO (assume ideal, C P = 29.3 J/ mol K) at 2.758 MPa and 700K (state 1) is subjected to the following process: (i) (ii) (iii) (iv) (v) Expand isothermally to 0.552 MPa (state 2) Cool at constant volume to 437.5K (state 3) Cool at constant pressure to 350K (state 4) Compress adiabatically to 2.758 MPa (state 5) Heated at constant pressure to 2.758 MPa (state 1)

Compute Q, W, H, E for the system for each step if all the processes are conducted reversibly. State also which of the values will change if reversibility is not ensured. 9. Derive from the first law of thermodynamics the equation:

10. Show from the first law that :

11. (a) 18.02 g of liquid water is enclosed under a frictionless weightless piston at 100C and 1 atm. pressure. The pressure above the piston is lowered infinitesimally below 1 atm and the water allowed to vaporize isothermally until all vaporized. For this process, q=40,710 joules. The specific volume of water at 100C is 1.043 cm3 /g, and the specific volume of steam is 1677 cm3 /g at 100C and 1 atm. Calculate the work attending this vaporization and E and for the process. (b)Find the values of , H, and q for the process where pressure above the piston is zero and the water is allowed to vaporize freely and isothermally into an evacuated space of such volume that the pressure finally builds upto 1 atm. when all the water vaporized. 12. Complete the following tabular summary for various processes with an ideal gas in terms of C V, C P and R. Process Constant V Constant P Constant T Adiabatic Initial State Final State E H V 1 , T1 V 1 , T2 C V(T 2 -T 1 ) C P (T 2 -T 1 ) P1, T1 P1, T2 T1, P1 T1, P2 T1, P1 T 2, P 2 q ln -

Will the values depend on whether or not the processes are carried out reversibly? 13. A cylinder contains 0.1 kg of water at 15C. A piston increases the pressure on the water isothermally and reversibly from 1 atm to 100 atm. Find (a) (b) (c) (d) The work done on the water by the piston, Heat removed from the water, and Change in internal energy of the water, What would be the change in the temp. of water if the increase in pressure were made adiabatically? For water at 15C, the coefficient of thermal volume expansion =1.5 * 10-4/K and the isothermal compressibility =4.9 * 10-12/Pa. Take density of water at 1 atm and 15C to be 1000 kg/m3, and CP = 4.18 kJ/ kg.K. 14. One mole of an ideal gas at 25C and 1 atm undergoes the following reversibly conducted process: a. Isothermal expansion to 0.5 atm, followed by b. Isobaric expansion to 100C, followed by c. Isothermal compression to 1 atm, followed by d. Isobaric compression to 25C. The system then undergoes the following cyclic process: a. Isobaric expansion to 100C, followed by b. A decrease in pressure at constant volume to P atm, followed by c. An isobaric compression at P atm to 24.5 liters, followed by d. An increase in pressure at constant volume to 1 atm. Calculate the value of P which makes the work done on the gas in the first cycle equal to the work done by the gas in the second cycle.

15. A mixture of steam and oxygen at 1000K and 1 atm. reacts with a column of graphite at 1000K to yield a mixture of H 2 and CO at the same temperature. Calculate the composition of the CO/H 2 mixture, if the above isothermal process is also adiabatic (i.e. no heat effect). Data: Enthalpy of formation at 1000K: H 2 O: -247,857 J/mol.; CO: -111,983 J/mol. 16. 1 mole of supercooled tin is adiabatically contained at 495 K at constant pressure. If it spontaneously freezes, what is the final temperature? What fraction of tin freezes? Calculate S for the system and surrounding for this process?
= 7070

. = 505 : : 34.7 9.210 J/mol.K : 18.5 2610 -3 T J/mol.K

17. Zinc is produced by the reduction of ZnO with carbon, the product Zn being distilled out in vapour form. (You may be surprised to know that one can find thousands of retorts which were used almost two thousand years ago in a place called Zaver in Rajasthan). If the temperature of the reactants is 298K and the final products, Zn vapour and CO, should be at 1273K, what is the minimum heat to be supplied to the retort? 18. What is the adiabatic flame temperature when propane (C 3 H 8 ) at 300K is burnt with stoichiometric amount of pure oxygen at 300K? Take 1 Nm3 propane as basis. Present results in tabular form. 19. A 50:50 (by volume) mixture of CO and CH 4 at 500K is burnt with 20% excess air (20% in excess of what is needed for complete combustion) at 298K. What is the adiabatic flame temperature? Use the following data:
, J/mol 36.6T - 16400 61.0T - 30500 47.4T - 22200 46.2T - 13800 36.4T - 16500 36.2T - 13500

CO CO 2 H 2 O(g) CH 4 N2 O2

, J/mol -111000 -394000 -242000 -75000 -

Present your results as mass and heat balance tables.

20. Blast furnaces producing liquid iron use heat generated by blowing preheated air (79:21 by volume) to a bed of coke. It is necessary to calculate the temperature at the combustion zone to predict the behavior of the furnace. The following points may be noted/ assumed: (i) Because of high temperature and the availability of excess carbon, the product of combustion is almost pure CO and H 2 .

(ii) Coke bed may be assumed to be pure carbon (no ash in coke) and to be at the combustion H 2 zone temperature itself. That is, coke is at the same temperature as the product gases CO, H 2 and N 2 . (iii) Rate of generation of heat is so large compared to rate of heat loss that adiabatic conditions may be assured. Calculate the combustion zone temperature for one such furnace blowing a) Dry air at 1200K b) Moist air ( 15g H 2 O/) 1200K. c) Moist air as above with additionally 0.05 Nm3 CH 4 / Nm3 of dry air Solve the problem by completing the following tables.

input

Mass balance : Basis 1 kg carbon kg Output

kg

Heat Balance : Basis : all materials at 298 K have zero enthalpy Input kJ Output Sensible heats Sensible heats

kJ

Reaction heat (-H) Total Sensible heats are enthalpy above 298K :( HT-H298) Total