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Homework 2 Physical Chemistry II, Semester 2014-1 Due Date: Tue, 03/18, 1:OO PM, in class 1.

Under what conditions is dG 0 a condition that defines the spontaneity of a process? 2. Under what condition is KP = Kx? 3. It is found that KP is independent of T for a particular chemical reaction. What does this tell you about the reaction? 4. Calculate G for the isothermal expansion of 2.50 mol of an ideal gas at 350 K from an initial pressure of 10.5 bar to a final pressure of 0.500 bar. 5. A sample containing 2.50 mol of an ideal gas at 298 K is expanded from an initial volume of 10.0 L to a final volume of 50.0 L. Calculate G and A for this process for (a) an isothermal reversible path and (b) an isothermal expansion against a constant external pressure of 0.750 bar. Explain why G and A do or do not differ from one another. 6. Calculate reaction Greaction for the reaction CO(g) + 1/2 O2(g) CO2(g) at 298.15 K. Calculate reaction Greaction at 650 K assuming that reaction Hreaction is constant in the temperature interval of interest. 7. Consider the equilibrium C2H6(g) C2H4(g) + H2(g). At 1000 K and a constant total pressure of 1 atm, C2H6(g) is introduced into a reaction vessel. At equilibrium, the composition of the mixture in mole percent is H2(g): 26%, C2H4(g): 26%, and C2H6(g): 48%. 8. If the reaction Fe2N(s) + 3/2 H2(g) 2Fe(s) + NH3(g) comes to equilibrium at a total pressure of 1 atm, analysis of the gas shows that at 700 and 800 K,

and 1.083, respectively, if only H2(g) was initially present in the gas phase and Fe2N(s) was in excess. a) Calculate KP at 700 and 800 K. b) Calculate reaction Sreaction at 700 and 800 K and , Hreaction assuming that it is independent of temperature. c) Calculate reaction Greaction for this reaction at 298.15 K. 9. Show that

Write a procedure that would allow you to relate A at two temperatures. 10. A sample containing 2.25 mol of He (1 bar, 298 K) is mixed with 3.00 mol of Ne (1 bar, 298 K) and 1.75 mol of Ar (1 bar, 298 K). Calculate Gmixing and Smixing. 11. Calculate the degree of dissociation of N2O4 in the reaction N2O4(g) 2NO2(g) at 250 K and a total pressure of 0.500 bar. Do you expect the degree of dissociation to increase or decrease as the temperature is increased to 550 K? Assume that reaction Hreaction is independent of temperature. 12. A sample containing 2.00 moles of N2 and 6.00 mol of H2 are placed in a reaction vessel and brought to equilibrium at 20.0 bar and 750 K in the reaction 1/2 N2(g) + 3/2 H2(g) NH3(g).

a) Calculate KP at this temperature. b) Set up an equation relating KP and the extent of reaction c) Using Mathematica, calculate the number of moles of each species present at equilibrium. 13. As Ca(HCO3)2(s) decomposes at elevated temperatures according to the stoichiometric equation Ca(HCO3)2(s) CaCO3(s) + H2O(g) + CO2(g). a) If pure Ca(HCO3)2(s) is put into a sealed vessel, the air is pumped out, and the vessel and its contents are heated, the total pressure is 0.115 bar. Determine KP under these conditions. b) If the vessel initially also contains 0.225 bar H2O(g), what is the partial pressure of CO2(g) at equilibrium? 14. Express the rate of reaction with respect to each species in the following reactions:

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