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Sample 12

1. This document provides information about thermodynamic properties and equilibrium constants for various substances. It includes two tables: one listing standard enthalpies, Gibbs free energies, and heat capacities; and one listing enthalpies of fusion and vaporization. 2. Several problems are presented involving calculations of equilibrium constants, partition functions, heat capacities, and other thermodynamic quantities for gases, liquids, and solids using the data and equations provided. 3. The maximum translational, vibrational, and rotational degrees of freedom for a gaseous NH3 molecule is asked. Heat capacities at various temperature limits are also requested.

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Charles Taft
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82 views2 pages

Sample 12

1. This document provides information about thermodynamic properties and equilibrium constants for various substances. It includes two tables: one listing standard enthalpies, Gibbs free energies, and heat capacities; and one listing enthalpies of fusion and vaporization. 2. Several problems are presented involving calculations of equilibrium constants, partition functions, heat capacities, and other thermodynamic quantities for gases, liquids, and solids using the data and equations provided. 3. The maximum translational, vibrational, and rotational degrees of freedom for a gaseous NH3 molecule is asked. Heat capacities at various temperature limits are also requested.

Uploaded by

Charles Taft
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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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

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