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?

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(3 pts) b. How does enthalpy change with temperature?

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(3 pts) c. How does enthalpy change with entropy?

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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 H2 gas, how much work does the
system do on the environment?

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(5 pts) b. If the temperature change in the water is measured to be 10.15◦ 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 .)

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(5 pts) c. What is ∆U for this reaction? (Assume that the inert gas has negligible
heat capacity.)

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(5 pts) d. What is ∆H for this reaction? (Assume that the inert gas has negligible
heat capacity.)

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 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.

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(5 pts) b. How is Gibbs energy relevant to calculating the coexistence curve between
the gas and liquid phases of water?

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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.

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(6 pts) b. The vapor pressure of a liquid in the temperature range from 200.0 K
to 300.0 K was found to fit the expression ln(p/Torr) = 15.212 − (1430.1 K)/T .
Calculate the enthalpy of vaporization of the liquid.

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(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
200.0 K and 300.0 K.

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 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?

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(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.

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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?

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(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, respec-
tively. 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?

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(5 pts) c. The pKa of acetic acid (CH3 COOH) is 4.76 at 298K. What is the molar
Gibbs energy of reaction of Acetic Acid to its conjugate base?

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(5 pts) d. Suppose that an equilibrium mixture containing 1.25M acetic acid is at a

pH of 4.76. Assuming ideality, what is the concentration of the conjugate base?

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 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!

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(5 pts) b. How is collision rate relevant to the liquid-phase reaction rate? And what
other terms might also be relevant? JUSTIFY!

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8. Molecular Motion and Reactivity
Consider the following reversible elementary reaction:

k1
* B+C
A )
k2

Suppose that an equilibrium mixture of this system has been measured to have
concentrations of 1.98×10−13 mol L−1 , 4.57×10−3 mol L−1 , and 2.47×10−2 mol L−1
for A, B, and C, respectively.
(4 pts) a. What is the equilibrium constant for this reaction?

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(9 pts) b. Provide three distinct examples of how this system might be driven out of
equilibrium. JUSTIFY each!

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(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 k1 ?

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