(4 pts) a. Is heat independent of path? How does your answer relate to the First Law of thermodynamics?
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1 Part I: Thermodynamics: First Law 1. Concept Questions. Try to be concise, and correct! (4 pts) a. Is heat independent of path? How does your answer relate to the First Law of thermodynamics? (3 pts) b. How does enthalpy change with temperature? (3 pts) c. How does enthalpy change with entropy? 2
2 2. Heat & Work. Suppose that you have an unknown chemical reaction in which the reactants are solvated in 5.83L of water, and the liquid is inside a LARGE container with an inert gas at 4.55 atm of pressure, and 300 K. (5 pts) a. If the reaction produces.345 moles of H 2 gas, how much work does the system do on the environment? Answer: (5 pts) b. If the temperature change in the water is measured to be C, how much heat did the the reaction give to the water solvent? (HINT: The heat capacity of water is 1.0 cal g 1 C 1.) Answer: (5 pts) c. What is U for this reaction? (Assume that the inert gas has negligible heat capacity.) (5 pts) d. What is H for this reaction? (Assume that the inert gas has negligible heat capacity.) 3
3 Part II: Thermodynamics: Second & Third Law 3. Concept Questions. Try to be concise, and correct! (5 pts) a. Use the Second Law of thermodynamics to explain why a Carnot Cycle is not 100% efficient. (5 pts) b. How is Gibbs energy relevant to calculating the coexistence curve between the gas and liquid phases of water? 4
4 4. Physical transformation of pure substances. (8 pts) a. Draw a P-V diagram of a material that exhibits solid, liquid and gas phases. Make sure to identify as many features of the diagram as possible. (6 pts) b. The vapor pressure of a liquid in the temperature range from K to K was found to fit the expression ln(p/torr) = ( K)/T. Calculate the enthalpy of vaporization of the liquid. Answer: (6 pts) c. Suppose that the gas of this substance satisfies the ideal gas law as long as it is a gas. Using the expression in part (b), derive an expression for the gas-side of the coexistence curve on a V-P diagram in the temperature range between K and K. Answer: 5
5 Part III: The Thermodynamics of Chemical Systems 5. Concept Questions. Try to be concise, and correct! (5 pts) a. In general chemistry you learned that the equilibrium constant can be written in terms of pressures and concentrations. Under what conditions was this statement not true, and how do you correct it using the tools that you ve learned in this course? (5 pts) b. What are colligative properties of a liquid? Justify how such properties do or do not depend on the nature of a solute. 6
6 6. Equilibrium and Mixtures (5 pts) a. The vapor pressure of two pure solvents, A and B, at 30.0 C is 353 torr and 241 torr, respectively. Assuming Raoult s Law at all concentrations, what is the total pressure of the gas in equilibrium with a liquid mixture of 80% A and 20% B? Answer: (5 pts) b. In addition to the properties provided in part (a), now suppose that the Henry s Law constant for A and B at 30.0 C is 175 torr and 165 torr, respectively. If Raoult s Las is no longer correct at all concentrations, but using other reasonable assumptions, what is the total pressure of the gas in equilibrium with a liquid mixture of 80% A and 20% B? Answer: 7
7 (5 pts) c. The pk a of acetic acid (CH 3 COOH) is 4.76 at 298K. What is the molar Gibbs energy of reaction of Acetic Acid to its conjugate base? Answer: (5 pts) d. Suppose that an equilibrium mixture containing 1.25M acetic acid is at a ph of Assuming ideality, what is the concentration of the conjugate base? Answer: 8
8 Part IV: Kinetics & Beyond 7. Concept Questions. Try to be concise, and correct! (5 pts) a. How is collision rate relevant to the gas-phase reaction rate? And what other terms might also be relevant? JUSTIFY! (5 pts) b. How is collision rate relevant to the liquid-phase reaction rate? And what other terms might also be relevant? JUSTIFY! 9
9 8. Molecular Motion and Reactivity Consider the following reversible elementary reaction: A k 1 B + C k2 Suppose that an equilibrium mixture of this system has been measured to have concentrations of mol L 1, mol L 1, and mol L 1 for A, B, and C, respectively. (4 pts) a. What is the equilibrium constant for this reaction? Answer: (9 pts) b. Provide three distinct examples of how this system might be driven out of equilibrium. JUSTIFY each! 10
10 (7 pts) c. Now suppose that an increase in the concentration of A by the amount x is found to relax back to equilibrium in 2.75µsec. What is the value of k 1? Answer: 11
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