CH302H

Problem Set 4

February 28, 2012

Due March 6, 2012

1. For each of the following processes, identify the system and the surroundings. For each spontaneous process below, identify a constraint that has been removed to enable the process to occur. (You may add needed information to the brief description of the process that is given here or state needed assumptions, in order to answer the question precisely.) a) b) c) d) e) A solution of hydrochloric acid reacts with a solution of sodium hydroxide. Zinc pellets dissolve in aqueous hydrochloric acid. A rubber band is slowly extended by a hanging weight. The gas in a chamber is rapidly compressed by a weighted piston. A tray of water freezes in the 0oC freezer compartment of an ele refrigerator.

2. Suppose a volume is divided into three equal parts. a) How many microstates can be written for all possible ways of distributing four molecules among the three parts? b) What is the probability that all four molecules are in the left-most one-third of the volume at the same time? 3. The two gases BF3(g) and BCl3(g) are mixed in equal molar amounts. All B-F bonds have about the same bond energy, as do all B-Cl bonds. Explain what drives the mixture to react to form a mixture of BF2Cl(g) and BCl2F(g). 4. Tetraphenylgermane, (C6H5)4Ge, has a melting point of 232.5C, and its enthalpy increases by 106.7 J g-1 during fusion. Calculate the molar enthalpy of fusion and molar entropy of fusion of tetraphenylgermane. 5. Suppose 60.0 g hydrogen bromide, HBr(g), is heated reversibly from 300 to 500 K at a constant volume of 50.0 L, and then allowed to expand isothermally and reversibly until the original pressure is reached. Using cP(HBr(g)) = 29.1 J K-1 mol-1, calculate U, q, w, H, and S for this process. Assume that HBr is an ideal gas under these conditions. 6. Suppose 1.00 mol of water at 25C is flash-evaporated by allowing it to fall into an iron crucible maintained at 150C. Calculate S for the water, S for the iron crucible, and Stot, if cP(H2O(l)) = 75.4 J K-1 mol-1 and cP(H2O(g)) = 36.0 J K-1 mol-1. Take Hvap = 40.68 kJ mol-1 for water at its boiling point of 100C. (Hint: First outline the described physical process and identify the various values of q and T that are needed for your calculation, before trying to put in numbers.)

7. (a) Use data from Appendix D to calculate the standard entropy change at 25C for the reaction. CH3COOH(g) + NH3(g) CH3NH2(g) + CO2(g) + H2(g) (b) Suppose that 1.00 mol each of solid acetamide, CH3CONH2(s), and water, H2O(l), react to give the same products. Will the standard entropy change be expected to be larger or smaller than that calculated for the reaction in part (a)? EXPLAIN the reasoning for your answer 8. Quartz, SiO2(s), does not spontaneously decompose to silicon and oxygen at 25C in the reaction SiO2(s) Si(s) + O2(g) even though the standard entropy change of the reaction is large and positive (S = 182.02 J K-1). Explain. 9. A quantity of ice is mixed with a quantity of hot water in a sealed, rigid, insulated container. The insulation prevents heat exchange between the icewater mixture and the surroundings. The contents of the container soon reach equilibrium. State whether the total internal energy of the contents decreases, remains the same, or increases in this process. Make a similar statement about the total entropy of the contents. Explain your answers. 10. One mole of a monatomic ideal gas begins in a state with P = 1.00 atm and T = 300 K. It is expanded reversibly and adiabatically until the volume has doubled; then it is expanded irreversibly and isothermally into a vacuum until the volume has doubled again; and then it is heated reversibly at constant volume to 400 K. Finally, it is compressed reversibly and isothermally until a final state with P = 1.00 atm and T = 400 K is reached. Calculate Ssys for this process. (Hint: There are two ways to solve this problem an easy way and a hard way. Think until you identify the easy way, to save a lot of trouble and time.) 11. The N2O molecule has the structure N-N-O. In an ordered crystal of N2O, the molecules are lined up in a regular fashion, with the orientation of each determined by its position in the crystal. In a random crystal (formed on rapid freezing), each molecule has two equally likely orientations. (a) Calculate the number of microstates available to a random crystal of NA (Avogadros number) of molecules. (b) Calculate S when 1.00 mol of a random crystal is converted to an ordered crystal.