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PHYSCHEM4

1. The document discusses several examples involving the second law of thermodynamics and calculations of changes in entropy, heat, work, and temperature. 2. Key concepts covered include isothermal and adiabatic processes, heat capacities, phase changes, and heat engines. 3. Ten problems are presented involving calculations for entropy changes, heats, works, and temperatures for systems involving gases, solids, liquids and their phase changes under different conditions.

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Nikki Byrne
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© Attribution Non-Commercial (BY-NC)
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2K views

PHYSCHEM4

1. The document discusses several examples involving the second law of thermodynamics and calculations of changes in entropy, heat, work, and temperature. 2. Key concepts covered include isothermal and adiabatic processes, heat capacities, phase changes, and heat engines. 3. Ten problems are presented involving calculations for entropy changes, heats, works, and temperatures for systems involving gases, solids, liquids and their phase changes under different conditions.

Uploaded by

Nikki Byrne
Copyright
© Attribution Non-Commercial (BY-NC)
Available Formats
Download as DOC, PDF, TXT or read online on Scribd
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Second Law of Thermodynamics 1.

The heat capacity of chloroform (trichloromethane, CHCl3) in the range 240 K to 330 K is given by Cpm/J K-1 mol-1 = 91.47 + 7.5 x 10 2 (T/K). In a particular experiment, 1.00 mol CHCl3 is heated from 273 K to 300 K. Calculate the change in molar entropy of the sample. Ans: +11 J/K 2. A block of copper of mass 2.00 kg (Cp,s = 0.385 J K-1 mol-1) and temperature 0 oC is introduced into an insulated container in which there is 1.00 mol H2O (g) at 100 oC and 1.00 atm. (a) Assuming all the steam is condensed to water, what will be the final temperature of the system, the heat transferred from water to copper, and the entropy change of the water, copper, and the total system? In fact, some water vapour is present at equilibrium. From the vapour pressure of water at the temperature calculated in (a), and assuming that the heat capacities of both gaseous and liquid water are constant and given by their values at that temperature, obtain an improved value of the final temperature, the heat transferred, and the various entropies. (Hint. You will need to make plausible approximations.) Ans: (a) 57.0 oC, -43.9 kJ, +146 J/K, +28 J/K; (b) 53.5 oC. Consider a perfect gas contained in a cylinder and separated by a frictionless adiabatic piston into two sections A and B. All changes in B are isothermal; that is, a thermostat surrounds B to keep its temperature constant. There is 2.00 mol of the gas in each section. Initially TA=TB= 300 K, VA=VB= 2.00L. Heat is added to Section A and the piston moves to the right reversibly until the final volume of Section B is 1.00L. Calculate (a) SA and SB (b) S of the total system and its surroundings. If numerical values cannot be obtained, indicate whether the values should be positive, negative, or zero or are indeterminate from the information given. (Assume Cv,m = 20 J K-1 mol-1) Ans: (a) + 50.74 J/K, -11.5 J/K; (b) +39.2 J/K, -39.2 J/K

3.

4. 1.00 mol of perfect gas at 27 oC is expanded isothermally from an initial pressure of 3.00 atm to a final pressure of 1.00 atm in two ways: (1) reversibly, and (2) against constant external pressure of 1.00 atm. Calculate the final temperature and q, w, H, S, S, and Stot for each path. Take Cv,m = 3/2 R. Ans: Path 1: w = -2.74 kJ, q = +2.74 kJ, U = 0, H = 0, S = +9.13 J/K, Ssur = -9.13 J/K, Stot =0; Path 2: w = -1.66 kJ, q = +1.66 kJ, U = 0, H = 0, S = +9.13 J/K, Ssur = -5.53 J/K, Stot = +3.60 J/K 5. The standard molar entropy of NH3 (g) is 192.45 J K-1 mol-1 at 298 K. Calculate the standard molar entropy at (a) 100 oC and (b) 500 oC. Ans: (a) 200.7 J K-1 mol-1 (b) 232.0 J K-1 mol-1 6. A block of copper of mass 500 g and initially at 293 K is in thermal contact with an electric heater of resistance 1.00 k and negligible mass. A current

of 1.00 A is passed for 15.0 s. Calculate the change in entropy of the copper, taking Cp,m = 24.4 J K-1 mol-1. The experiment is then repeated with the copper immersed in a stream of water that maintains its temperature at 293 K. Calculate the change in entropy of the copper and the water in this case. Ans: +45.4 J/K, +51.2 J/K. 7. Calculate (a) the maximum work and (b) the maximum non-expansion work that can be obtained from the freezing of supercooled water at 5 oC and 1.0 atm. The densities of waater and ice are 0.999 and 0.917 g/ cm 3 respectively at 5 oC. Ans: (a) 0.11 kJ/mol (b) 0.11 kJ/mol 8. Suppose that an internal combustion engine runs on octane, for which the enthalpy of combustion is 5512 kJ/mol and take the mass of 1 gallon of fuel as 3 kg. What is the maximum height, neglecting all forms of friction, to which a 1000-kg car can be driven on 1 gallon of fuel given that the engine cylinder temperature is 2000 oC and the exit temperature is 800 oC. Ans: 7.8 km. 9. From standard enthalpies of formation, standard entropies, and standard heat capacities, calculate the standard enthalpies and entropies at 298 K and 398 K for the reaction CO2 (g) + H2 (g) CO (g) + H2O (g). Assume that the heat capacities are constant over the temperature range involved. Ans: At 298 K: +41.16 kJ/mol, +42.08 J K-1 mol-1; at 398 K: +40.84 kJ/mol, +41.05 J K-1 mol-1. 10. Calculate the minimum work needed to reduce the temperature of a 1.0-g block of copper form 1.10 K to 0.10 K, the surroundings being at 1.20 K. Proceed by supposing that the heat capacity remains constant at 39 J K-1 mol-1 and that the coefficient of performance can be evaluated at the mean temperature of the block. Then go on to do a more realistic calculation in which Cp,m = AT3 + BT, with A = 48.2 J K-1 mol-1 and B = 688 J K-1 mol-1, and taking into account the variation of the coefficient of performance with temperature. Ans: 0.61 J, 6.7 J

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