CH 353 Spring 2014

Professor A. Campion
Name: _____________________

Exam 3
CH 353 52950 Spring 2014
May 2, 2014
Professor Campion

Check to ensure that your exam has 6 questions on 4 pages. Carefully read all the problems
before beginning to work on them; they are not necessarily written in order of increasing
difficulty. Please organize your work and write clearly.
Useful information
R = 8.314 J K-1 mol-1
lnK 2 lnK1 =

r H0 1 1
( )
R T2 T1

F = 96,500 C mol-1
E 0cell = E 0 cathode E 0 anode

r G 0 = nFE 0cell

I certify that I have worked the following exam without the help of others, and that the work
I am turning in is my own.

Signed:

-----------------------------------------------------------Signature

Date

CH 353 Spring 2014

Professor A. Campion

1. (6 pts) Sketch a phase diagram for a typical one-component system, as well as one for
water, which is atypical. Identify chemical potential relationships between phases at a
point, on a line, and in a region for either phase diagram, and explain what determines the
slopes of the phase boundaries. In doing so, comment on the physical origin of the
difference between the two phase diagrams.

The figure on the left (Atkins 4.8) is a typical one-component phase diagram with a
positive S-L coexistence curve slope, and the figure on the right (Atkins 4.9) is the phase
diagram for water. At the triple point (I meant for you to understand that this was the
point I was referring to), the chemical potentials of all three phases are equal. On any
line, the chemical potentials of the phases separated by that line are equal. In the region
that a certain phase is located, the chemical potential of that phase is lower than the
other phases. The slopes of phase boundaries are determined by the values of p and T
necessary to maintain equilibrium. More specifically, the Clapeyron equation is used to
determine these slopes. The difference between the two phase diagrams is that the S-L
coexistence curve for water has a negative slope. This is due to the fact that waters
volume strangely increases on freezing (like the time I shattered a glass jar in the
freezer).

CH 353 Spring 2014

Professor A. Campion

2. (5 pts) Write an expression for the chemical potential of an ideal, pure gas at a pressure
other than 1 bar. (Hint: recall one of the two fundamental partial derivative equations that
Dr. Campion has mentioned over and over). Use this result to find a general expression
for the Gibbs free energy of mixing for two ideal gases at constant temperature. Your
final result should contain the mole fractions of the two species. What does this
expression imply about the spontaneity of mixing and why?

This comes directly out of Atkins:

Since xA and xB are less than 1, Gmixing < 0, and the mixing of ideal gases occurs
spontaneously.

CH 353 Spring 2014

Professor A. Campion

3. (5 pts) Sketch a plot of the Gibbs free energy G versus extent of reaction , identifying
conditions under which the reaction (as written moving from left to right) is spontaneous,
nonspontaneous, or at equilibrium. What criteria did you choose to identify these
regions? Locate

G o on this graph and explain its meaning.

I did not specify that the forward reaction was favorable or that there were no
intermediates or transition states, so I was grading this one loosely, but I just wanted
something simple like this (modified Figure 6.1 of Atkins):

Go

When the Gibbs reaction energy, rG is positive, the reaction is spontaneous in the
forward direction. When it is negative, the reaction is spontaneous in the reverse
direction. When it is equal to zero, the reaction is at equilibrium. Go is just the
difference between the Gibbs energies of 100% reactant and 100% product when they
are in their standard states.

CH 353 Spring 2014

Professor A. Campion

4. (4 pts) The ammonia synthesis reaction is

N 2 (g) + 3H 2 (g) 2 NH 3 (g)

The standard Gibbs free energy of formation is

Gfo = 33 kJ mol1 of reaction as

G for this reaction using the following partial pressures:

= 100 atm, p N2 = 10 atm, p H 2 = 10 atm . Is the reaction spontaneous or

written. Calculate

p NH3

nonspontaneous at 298.15 K under these conditions?

Note that the Gibbs energy of reaction is equal to the Gibbs energy of formation here.
G = G o + RT ln Q
= 33kJ mol 1 + 8.314 J K 1mol1 (298 K) ln

100 2
10 *103

= 33 kJ mol 1 + 0

Since G < 0, the reaction is spontaneous under these conditions.

5. (3 pts) K for the ammonia synthesis reaction at 298.15 K is 6.1 x 105. What is K at 500 K
o

for this reaction given that H f = 46.1kJ mol ? Is this result consistent with your
expectations and why or why not?

Use the vant Hoff equation from the front page.

H0 1 1
lnK 2 lnK1 = r ( )
R T2 T1
ln K 2 = ln (6.1*105 ) +

46,100 1
1
(

)
8.314 500 298

K 2 = e5.8 330
This decrease in K2 on going to a higher temperature is expected since the reaction is
exothermic. In accord with Le Chatliers principle, when a perturbation such as a
temperature increase occurs and products are releasing heat, the chemical equilibrium
will shift in order to offset the perturbation, so less products will be formed.

CH 353 Spring 2014

Professor A. Campion

6. (4 pts) Given that the standard reduction potentials for Cu+ and Fe3+ are 0.52 V and 0.77
V, is the following redox reaction spontaneous in the forward or reverse direction?
Fe2+ + Cu +
Cu 0 + Fe3+
Determine the maximum amount of work that could be obtained from this reaction when
it is run in the appropriate direction.

As written, copper is being reduced, so set E0cathode = 0.52 V. Without changing the sign,
set E0anode = 0.77 V. The standard cell potential is given by the equation on the front
page:
E 0cell = E 0cathode E 0anode
= 0.52 V 0.77 V = 0.25 V
The cell potential is negative, so the reaction above is spontaneous in the reverse
direction. The maximum amount of electrical work that can be done is equal to the
change in Gibbs free energy for the process.
r G 0 = nFE 0cell

= 1mol of electrons (96, 500 C mol1 )(0.25 V)

= 24 kJ