1.

In the famous reaction A B + C with equilibrium constant K, the extent of reaction depends on the
total pressure as:
2
ptotal
K=
1 2
(a) Assuming that K = 1 and ptotal = 1, what is the equilibrium value of ?
(b) Assume again that K = 1 but now that ptotal = 0.5, what now is the equilibrium value of ?
2. Consider the partition function for one type of gas made up of interacting particles:
Q(N, V, ) =

1
N!

2m
h2

3N/2

(V N b)N eaN

/V

where = 1/kT and a and b are constants.

Compute the expected value hpi of the energy for this gas.
3. What is the maximum number of translational, vibrational, and rotational freedom can a gaseous NH3
molecule have?
4. An electron can exist in two states. In a magnetic field these states have different energies. Denote these
energies by 0 and .
Now consider a system of non-interacting fixed spins. The partition function for such a system is:
Q = qN
There is no N ! since the spins are fixed in place. Find an expression for q and use it to compute both the
expected energy hEi and the corresponding heat capacity CV .
5. Given the vibrational partition function for a diatomic ideal gas molecule:

CV,vib = R

vib
T

2

eV,vib /T
(1 eV,vib /T )2

find the values reached by CV,vib as T goes to zero and as T goes to infinity.
6. Work out an expression for the equilibrium constant as a function of both the extent of the reaction and
the total pressure P for the gas phase reaction:
2A B + C
7. Find the fraction of H2 molecules in excited states at 300 K and again at 1000 K.
HINT: The text has a discussion of this sort of thing in Chapter 18.
8. Do Problem 18-38 in the text on page 761.
9. Do Problem 17-12 in the text on page 718.
10. Compute the heat capacity of an ideal gas of chlorine atoms and compare it to the value given in the
attached table.

Table 1: Thermodynamic Properties of Selected Substances

Species
Ag+ (aq)
AgCl (s)
Br2 (g)
HBr (g)
Ca2+ (aq)
CaCO3 (s, ara)
C (s, graphite)
CO (g)
CO2 (g)
CO2
3 (aq)
C2 H5 OH (l)
C2 H5 OH (g)
C6 H6 (l)
C6 H6 (g)
C6 H5 CH3 (g)
C12 H22 O11 (s)
Cl (g)
Cl2 (g)
Cl (aq)
Fe(s)
Fe2 O3 (s)
Fe3 O4 (s)
H2 (g)
H+ (aq)
HCl (aq)
HI (g)
H2 O(l)
H2 O(g)
O2 (g)
OH (aq)

MW (g/mol)
107.87
143.32
159.82
90.92
40.08
100.09
12.011
28.011
44.010
60.01
46.07
46.07
78.12
78.12
92.14
342.30
35.453
70.906
35.453
55.845
159.69
231.54
2.016
1.008
36.461
127.91
18.015
18.015
31.996
17.007

f H kJ/mol
105.58
127.07
30.9
36.3
542.83
1207.1
0
110.53
393.51
677.14
277.69
235.10
49.0
82.93
50.0
1543.
121.679
0
167.16
0
824.2
1118.4
0
0
167.16
26.5
285.83
241.82
0
229.99

f G kJ/mol
77.11
109.79
3.1
53.4
553.58
1127.8
0
137.17
394.36
527.81
174.78
169.49
124.3
129.72
122.0
2222.
105.680
0
131.23
0
742.2
1015.4
0
0
131.23
1.70
237.13
228.57
0
157.24

Cp J/mol-K
21.8
50.79
36.0
29.1
81.88
8.527
29.14
37.11
111.46
65.44
136.1
81.67
103.6
21.840
33.907
136.4
25.10
103.85
143.43
28.824
0
136.4
29.2
75.291
33.58
37.69
148.5

Table 2: Enthalpies of Fusion and Vaporization at

the Transition Temperature
Species
Ag
Cu
H2 O
NH3
C2 H5 OH
C6 H 6

Tf (K)
1234
1357
273.15
195.4
156.
278.61

f kJ/mol
11300
29800
6.008
5.652
4.60
10.59

Tb (K)

373.15
239.7
352.
353.2

v kJ/mol

40.656
23.35
43.5
30.8

31 Mar 12