CHEM 131

FINAL EXAM

F. Paesani Winter 2011

NAME

STUDENT ID

1. /25 5. /20

2. /10 6. /15

3. /12 7. /13

4. /8 8. /12

TOTAL FINAL /115

NOTE: Your REASONING and ANSWERS MUST be clear to me. Guesswork,

or apparent guesswork, will not earn credit.

TOTAL NUMBER OF PAGES INCLUDING THIS COVER PAGE: 21.

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1. 25 points
This problem has five parts, one part for each of Chapters 6-10. YOU NEED ONLY
ANSWER T OR F. Correct choice = 1 points, no choice = 0 points, incorrect choice
= -0.25 points. Be careful: pure guessing is a very bad idea because you lose
points for incorrect choices.

Chapter 6 - Reaction Equillbirum in Ideal Gas Mixtures.

The chemical potential of ideal gas i in an ideal gas mixture

at temperature T and partial pressure Pi equals the chemical
potential of pure gas i at temperature T and pressure Pi .

µ of a pure ideal gas goes to −∞ as P → 0

and goes to +∞ as P → ∞.

The entropy of a mixture of N2 and O2 gases (assumed ideal)

is equal to the sum of the entropies of the pure gases,
each at the same temperature and volume as the mixture.

When the ideal-gas reaction A + B ⇋ C + D has reached

equilibrium, it must hold that nC + nD = nA + nB .

For an ideal-gas reaction KP◦ for the reverse reaction

is the negative of KP◦ for the forward reaction.

KP◦ for a particular ideal-gas reaction is a function of temperature

but is independent of pressure and of the initial composition
of the reaction mixture.

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Chapter 7 - One Component Phase Equilibrium.

Since the three possible phases are solid, liquid, and gas, the maximum
possible value of the number of phases p in the phase rule is 3.

The number of degrees of freedom f is the number of variables needed

to specify the thermodynamic state of a system.

The normal boiling point is the temperature at which the vapor pressure
of a liquid equals 1 atm.

The enthalpy of vaporization of a liquid becomes zero at the critical

point.

When three phases coexist in equilibrium in a one-component system,

one must be a gas, one must be a liquid, and one must be a solid.

For a one-component system, the most stable phase at a given T

and P is the phase with the lowest Gm .

Chapter 8 - Real Gases.

The parameters a and b in the van der Waals equation for CO2
have the same values as in the Redlich-Kwong equation for CO2 .

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Chapter 9 - Solutions.

The volume of a solution at T and P equals the sum of the volumes of

its pure components at T and P .

µi is a partial molar quantity.

Intermolecular interactions are negligible in an ideal solution.

If B is a component of a solution, µB cannot be greater than µ∗B .

For equilibrium between an ideal solution and an ideal vapor, the

mole fraction xB of component B in the solution must be equal to the
mole fraction yB of B in the vapor.

In an ideally dilute solution, µi = µ∗i + RT ln xi for all components.

Chapter 10 - Nonideal Solutions.

When a solution component is in its standard state, its activity is 1.

ai and γi are extensive properties.

For a solute in a solution, γII,B = γI,B .

The activity ai is never negative.

Activity coefficients may be positive or negative.

The ionic charge z+ in an electrolyte solution does not affect the value
of the mean ionic activity coefficient γ± .

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2. 10 points - Problems about ideal gas equilibria

(a) 5 points
For the gas-phase reaction 2SO2 + O2 ⇋ 2SO3 , observed mole fractions for a
certain equilibrium mixture at 1000 K and 1767 torr are xSO2 = 0.310, xO2 =
0.250, and xSO3 = 0.440. Find Kp0 and ∆G0 at 1000 K, assuming ideal gases.
(R = 8.314 J/mol-K, 1 bar = 0.987 atm = 750 torr.)

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(b) 5 points
For the ideal-gas reaction A + B ⇋ 2C + 2D, it is given that ∆G0500 = 1250
cal/mol. If 1.000 mol of A and 1.000 mol of B are placed in a vessel at 500 K and
P is held fixed at 1200 torr, find the equilibrium amounts ni of all the components.
R = 1.987 cal/mol-K. If ∆H 0 = 2000 cal/mol, calculate Kp0 at 800 K when P is
held fixed at 1200 torr (∆H 0 can be assumed to be constant in this temperature
range). Will the equilibrium amount of C be larger than at 500 K?
(1 bar = 750 torr.)

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3. 12 points - Problems about one-component phase equilibria

(a) 4 points
At the normal melting point of Hg, -38.9 ◦ C, its enthalpy of fusion is 2.82 cal/mol,
the density of the solid is 14.193 g/cm3 , and the density of the liquid is 13.690
g/cm3 . Find the melting point of Hg at 500 atm.
(R = 1.987 cal mol−1 K−1 = 82.06 cm3 atm mol−1 K−1 ).

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(b) 4 points
The normal boiling point of diethyl ether is 34.5◦C and its ∆vap Hm at the normal
boiling point is 6.38 kcal/mol. Find the vapor pressure of ether at 25.0◦ C using
appropriate approximations. (R = 1.987 cal mol−1 K−1 , 1 atm = 760 torr.)

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(c) 4 points
The vapor pressure of water at 25◦ C is 23.76 torr. Suppose that 0.360 g of
H2 O is placed in an empty rigid container at 25◦ C. What phase(s) are present
at equilibrium if the volume of the container is V = 10.0 L? What phase(s) are
present at equilibrium if the volume of the container is V = 20.0 L? Assume the
vapor to be an ideal gas. Make sure I understand how you get your answers.
(R = 82.06 cm3 atm mol−1 K−1 , 1 atm = 760 torr.)

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4. 8 points - Problem about real gases

For ethane, Pc = 48.2 atm and Tc = 305.4 K. Calculate the pressure exerted by 74.8 g
of C2 H6 (molar mass = 30 g/mol) in a 200-cm3 vessel at 37.5 ◦ C using
(a) 3 points
the ideal-gas law

(b) 5 points
the van der Waals equation
RT a
P = − 2
Vm − b Vm

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5. 20 points total
Throughout this problem the temperature is kept at T = 308K. Also, I
want numerical answers for all parts. A container is divided into two separate
compartments. One contains liquid acetone (A) in equilibrium with its vapor. The
vapor pressure is 347 torr. The other compartment contains liquid chloroform (C) in
equilibrium with its vapor at 273 torr. (R = 8.314 J/mol-K.)
(a) 3 points
We now remove the partition so that the liquids mix. The composition of the
resulting solution in mole fractions is 80% acetone and 20% chloroform, xA = 0.8
and xC = 0.2. If this were an ideal solution, what would be the partial vapor
pressures of each component and the total vapor pressure in equilibrium with the
liquid solution?

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(b) 3 points
Suppose that the vapor also behaves ideally. What are the mole fractions of
acetone and chloroform in the vapor?

(c) 3 points
Calculate the molar free energy of mixing of the ideal solution. R = 8.314 J/mol-
K.

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(d) 3 points
The solution with 80% acetone and 20% chloroform is not really ideal. Instead, it
is better described as ideally dilute. The Henry’s Law constant for chloroform is
K = 165 torr. Calculate the partial vapor pressures of each component and the
total vapor pressure in equilibrium with the liquid solution.

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(e) 4 points
Calculate the molar free energy of mixing of this ideally dilute solution.

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(f) 4 points
Alas, the solution is neither ideal nor ideally dilute, since one observes non-
negligible deviations from both behaviors. The actual ratio of partial pressure to
Henry’s constant for the chloroform in this solution is pc /K = 0.21 and the ratio of
the partial pressure to the vapor pressure of pure liquid acetone is pA /p∗A = 0.72.
Calculate the activity coefficients for acetone and for chloroform in this solution
according to convention II (for the chloroform, use the mole fraction convention,
i.e., don’t change to molality units).

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6. 15 points - Problems about real solutions (nonelectrolytes)

At 35◦ C the vapor pressure of chloroform is 295.1 torr and that of ethanol is 102.8 torr.
A chloroform-ethanol solution at 35◦ C with xeth = 0.200 has a vapor pressure of 304.2
torr and a vapor composition of yeth = 0.138. R = 8.314 J/mol-K.

(a) 5 points
Calculate γI and aI for chloroform and for ethanol in this solution.

(b) 5 points
Calculate µi − µ∗i for each component in this solution in J/mol.

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(c) 5 points
Calculate ∆G for the mixing of 0.200 mol of liquid ethanol and 0.800 mol of liquid
chloroform at 35◦ C.

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7. 13 points - Problems about real solutions (electrolytes)

Consider the strong electrolyte MgCl2 .

(a) 4 points
Give the following numerical values (rather than a formula) for this electrolyte:
ν+ , ν− , z+ , z− , ν± .

(b) 4 points
Express γ± in terms of γ+ and γ− , and ai in terms of γ± and mi , exhibiting explicit
exponents and coefficients.

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(c) 5 points
Calculate the ionic strength of a 0.2-mol/kg aqueous solution of MgCl2 at 25 ◦ C
knowing that the fraction of Mg2+ ions that associate with Cl− ions to form ion
pairs is 1 − α = 0.35. Note that the ion pair is charged.
Useful equation for this problem:
1X 2
Im = z mj
2 j j

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8. 12 points total
Short unrelated questions.
(a) 4 points
Suppose that the ideal-gas reaction A+B ⇌ C+D has reached equilibrium. All
quantities below are the values at equilibrium. Only two of the following relations
are true. Tell me which ones. (1) nC + nD = nA + nB ; (2) PC + PD = PA + PB ;
(3) nA = nB ; (4) nC = nA ; (5) nC = nD ; (6) if only A and B are present initially,
then nC = nA ; (7) if only A and B are present initially, then nC = nD ; (8) if only
A and B are present initially, then nC + nD = nA + nB ; (9) µA + µB = µC + µD .

(b) 4 points
Which has the higher vapor pressure at -20◦C, ice or supercooled liquid water?
Explain using quantitative arguments.

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(c) 4 points
Consider an aqueous solution of the weak acid HCN. The system has five chemical
species, H2 O, HCN, H+ , OH− , and CN− , and two independent reactions:

H2 O ⇋ H+ + OH−

HCN ⇋ H+ + CN−
Find the number of degrees of freedom f for this system, and tell me which
intensive variables you would use to specify the state of the system. I must
understand your reasoning.

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