Homework 1 Physical Chemistry II, Semester 2014-1 Due Date: Mon, 03/03, 4:OO PM, in my spot

9. A cup of water at 278 K (the system) is placed in a microwave oven and the oven is turned on for 1 minute during which it begins to boil. Which of q, w, and U are positive, negative, or zero?

10. What is wrong with the following statement?: Burns caused by steam at 100C can be more severe than those caused by water at 100C because steam contains more heat than water. Rewrite the sentence to convey the same information in a correct way. 11. 3.00 moles of an ideal gas at 27.0C expands isothermally from an initial volume of 20.0 dm3 to a final volume of 60.0 dm3. Calculate w for this process a) for expansion against a constant external pressure of 1.00 105 Pa and b) for a reversible expansion. 12. 3.00 moles of an ideal gas are compressed isothermally from 60.0 to 20.0 L using a constant external pressure of 5.00 atm. Calculate q, w, U, and H. 13. For 1 mol of an ideal gas, Pexternal = P = 200 103 Pa. The temperature is changed from 100C to 25.0C, and CV,m = 3/2R. Calculate q, w, U, and H. 14. 3.50 moles of an ideal gas is expanded from 450 K and an initial pressure of 5.00 bar to a final pressure of 1.00 bar, and CP,m = 5/2R. Calculate w for the following two cases.

a) The expansion is isothermal and reversible. b) The expansion is adiabatic and reversible. Without resorting to equations, explain why the result to part (b) is greater than or less than the result to part (a). 15. An ideal gas described by Ti = 300 K, Pi = 1.00 bar, and Vi = 10.0 L is heated at constant volume until P = 10.0 bar. It then undergoes a reversible isothermal expansion until P = 1.00 bar. It is then restored to its original state by the extraction of heat at constant pressure. Depict this closed-cycle process in a P-V diagram. Calculate w for each step and for the total process. What values for w would you calculate if the cycle were traversed in the opposite direction? 16. A nearly flat bicycle tire becomes noticeably warmer after it has been pumped up. Approximate this process as a reversible adiabatic compression. Take the initial pressure and temperature of the air before it is put in the tire to be Pi = 1.00 bar and Ti = 298 K. The final volume of the air in the tire is Vf = 1.00 L and the final pressure is Pf = 5.00 bar. Calculate the final temperature of the air in the tire. Assume that CV,m =5/2R. 17. Because U is a state function, . Using this relationship, show that for an ideal gas.

18. Obtain an expression for the isothermal compressibility 19. if

for a van der Waals gas.

express as a function of and Vm for an ideal gas, and as a function of b, , and Vm for a van der Waals gas. 20. The Joule coefficient is defined as

Calculate the Joule coefficient for an ideal gas and for a van der Waals gas. 21. Use the relation

the cyclic rule, and the van der Waals equation of state to derive an equation for C P,m - C V ,m in terms of Vm and the gas constants R, a, and b.

22. Because the change in enthalpy of a gas expanded at constant temperature can be calculated. In order to do so, the functional dependence of on P must be known. Treating Ar as a van der Waals gas, calculate H when 1 mol of Ar is expanded from 400 bar to 1.00 bar at 300 K. Assume that is independent of pressure and is given by

for Ar. What value would H have if the gas exhibited ideal gas behavior? 23. Calculate Hreaction and reaction U at 298.15 K for the following reactions: a) 4NH3(g) + 6NO(g) 5 N2(g) + 6H2O(g) b) 2NO(g) + O2(g) 2NO2(g) c) TiCl4(l) + 2H2O(l) TiO2(s) + 4HCl(g) d) 2 NaOH(aq) + H2SO4(aq) Na2SO4(aq) + 2H2O(l) Assume complete dissociation of NaOH, H2SO4, and Na2SO4 e) CH4(g) + H2O(g) CO(g) + 3H2(g) f) CH3OH(g) + CO(g) CH3COOH(l) 24. Several reactions and their standard reaction enthalpies at 25C are given here. H (kJ mol1) CaC2(s) + 2H2O(l) Ca(OH)2(s) + C2H2(g) 127.9 Ca(s) + O2(g) CaO(s) 635.1 CaO(s) + H2O(l) Ca(OH)2(s) 65.2 The standard enthalpies of combustion of graphite and C2H2(g) are 393.51 and 1299.58 kJ mol1, respectively. Calculate the standard enthalpy of formation of CaC2(s) at 25C. 25. Use the following data at 25C to complete this problem: H H2(g) + O2(g) OH(g) H2(g) + O2(g) H2O(g) H2(g) 2H(g) O2(g) 2O (g) Calculate Hreaction for a) OH(g) H(g) + O(g) b) H2O(g) 2H(g) + O(g) c) H2O(g) H(g) + OH(g) Assuming ideal gas behavior, calculate H reaction and U reaction for all three reactions (kJ mol-1) 38.95 241.814 435.994 498.34

reaction