Chapter 16 - Section B - Non-Numerical Solutions

16.1 The potential is displayed as follows. Note that K is used in place of k as a parameter to avoid
confusion with Boltzmanns constant.

Combination of the potential with Eq. (16.10) yields on piecewise integration the following expression
for B:





2
B = N A d 3 1 + (K 3 1) 1 e/kT (l 3 K 3 ) e/kT 1
3
From this expression,


1 
dB
3
/kT
3
3
/kT
=
(K

1)
e
+
(l

K
)e
dT
kT 2

according to which d B/dT = 0 for T and also for an intermediate temperature Tm :

Tm =

+

  3
K 1
k ln
 l3 K 3

That Tm corresponds to a maximum is readily shown by examination of the second derivative d 2 B/dT 2 .
16.2 The table is shown below. Here, contributions to U (long range) are found from Eq. (16.3) [for U(el)],
Eq. (16.4) [for U(ind)], and Eq. (16.5) [for U(disp)]. Note the following:
1. As also seen in Table 16.2, the magnitude of the dispersion interaction in all cases is substantial.
2. U(el), hence f (el), is identically zero unless both species in a molecular pair have non-zero
permanent dipole moments.
3. As seen for several of the examples, the fractional contribution of induction forces can be substantial for unlike molecular pairs. Roughly: f (ind) is larger, the greater the difference in polarity
of the interacting species.
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Molecular Pair
CH4 /C7 H16
CH4 /CHCl3
CH4 /(CH3 )2 CO
CH4 /CH3 CN
C7 H16 /CHCl3
C7 H16 /(CH3 )2 CO
C7 H16 /CH3 CN
CHCl3 /(CH3 )2 CO
CHCl3 /CH3 CN
(CH3 )2 CO/CH3 CN

C6 /1078 J m6

f (el)

f (ind)

f (disp)

f (el)/ f (disp)

49.8
34.3
24.9
22.1
161.9
119.1
106.1
95.0
98.3
270.3

0
0
0
0
0
0
0
0.143
0.263
0.806

0
0.008
0.088
0.188
0.008
0.096
0.205
0.087
0.151
0.052

1.000
0.992
0.912
0.812
0.992
0.904
0.795
0.770
0.586
0.142

0
0
0
0
0
0
0
0.186
0.450
5.680

16.3 Water (H2 O), a highly polar hydrogen donor and acceptor, is the common species for all four systems;
in all four cases, it experiences strong attractive interactions with the second species. Here, interactions
between unlike molecular pairs are stronger than interactions between pairs of molecules of the same
kind, and therefore H is negative. (See the discussion of signs for H E in Sec. 16.7.)
16.4 Of the eight potential combinations of signs, two are forbidden by Eq. (16.25). Suppose that H E is
negative and S E is positive. Then, by Eq. (16.25), G E must be negative: the sign combination G E ,
H E , and S E is outlawed. Similar reasoning shows that the combination G E , H E , and S E 
is inconsistent with Eq. (16.25). All other combinations are possible in principle.
16.5 In Series A, hydrogen bonding occurs between the donor hydrogens of CH2 Cl2 and the electron-rich
benzene molecule. In series B, a charge-transfer complex occurs between acetone and the aromatic
benzene molecule. Neither cyclohexane nor n-hexane offers the opportunity for these special solvation
interactions. Hence the mixtures containing benzene have more negative (smaller positive) values of
H E than those containing cyclohexane and n-hexane. (See Secs. 16.5 and 16.6.)
16.6 (a) Acetone/cyclohexane is an NA/NP system; one expects G E , H E , and S E .
(b) Acetone/dichloromethane is a solvating NA/NA mixture. Here, without question, one will see
G E , H E , and S E .
(c) Aniline/cyclohexane is an AS/NP mixture. Here, we expect either Region I or Region II behavior:
G E and H E , with S E or . [At 323 K (50 C), experiment shows that S E is for this
system.]
(d) Benzene/carbon disulfide is an NP/NP system. We therefore expect G E , H E , and S E .
(e) Benzene/n-hexane is NP/NP. Hence, G E , H E , and S E .
(f ) Chloroform/1,4-dioxane is a solvating NA/NA mixture. Hence, G E , H E , and S E .
(g) Chloroform/n-hexane is NA/NP. Hence, G E , H E , and S E .
(h) Ethanol/n-nonane is an AS/NP mixture, and ethanol is a very strong associator. Hence, we expect
Region II behavior: G E , H E , and S E .



16.7 By definition,
i j 2 Bi j 12 Bii + B j j
At normal temperature levels, intermolecular attractions prevail, and the second virial coefficients are
negative. (See Sec. 16.2 for a discussion of the connection between intermolecular forces and the
second virial coefficient.) If interactions between unlike molecular pairs are weaker than interactions
between pairs of molecules of the same kind,
|Bi j | < 12 |Bii + B j j |
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and hence (since each B is negative) i j > 0. If unlike interactions are stronger than like interactions,
|Bi j | > 12 |Bii + B j j |
and hence i j < 0.
i j = 0

If interactions are identical for all molecular pairs,

Bi j = Bii = B j j , and

The rationalizations of signs for H E of binary liquid mixtures presented in Sec. 16.7 apply approximately to the signs of 12 for binary gas mixtures. Thus, positive 12 is the norm for NP/NP, NA/NP, and
AS/NP mixtures, whereas 12 is usually negative for NA/NA mixtures comprising solvating species.
One expects 12 to be essentially zero for ideal solutions of real gases, e.g., for binary gas mixtures of
the isomeric xylenes.

619