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 = ( K 3 1) e/ kT + (l 3 K 3 ) e dT kT 2
/ kT

according to which d B /dT = 0 for T and also for an intermediate temperature Tm : Tm = k ln + K3 1 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. 721

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 49.8 34.3 24.9 22.1 161.9 119.1 106.1 95.0 98.3 270.3

f (el) 0 0 0 0 0 0 0 0.143 0.263 0.806

f (ind) 0 0.008 0.088 0.188 0.008 0.096 0.205 0.087 0.151 0.052

f (disp) 1.000 0.992 0.912 0.812 0.992 0.904 0.795 0.770 0.586 0.142

f (el)/ f (disp) 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 disulde 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 (g) Chloroform/n-hexane is NA/NP. Hence, G , H , and S .
E E E

, HE

, 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 denition, i j 2 Bi j
1 2

Bii + B j j

At normal temperature levels, intermolecular attractions prevail, and the second virial coefcients are negative. (See Sec. 16.2 for a discussion of the connection between intermolecular forces and the second virial coefcient.) If interactions between unlike molecular pairs are weaker than interactions between pairs of molecules of the same kind, | Bi j | < 1 | Bii + B j j | 2 722

and hence (since each B is negative) i j > 0. If unlike interactions are stronger than like interactions, | Bii + B j j | | Bi j | > 1 2 Hence i j < 0. For identical interactions of all molecular pairs, Bi j = Bii = B j j , and i j = 0 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. 16.8 The magnitude of Henrys constant Hi is reected through Henrys law in the solubility of solute i in a liquid solvent: The smaller Hi , the larger the solubility [see Eq. (10.4)]. Hence, molecular factors that inuence solubility also inuence Hi . In the present case, the triple bond in acetylene and the double bond in ethylene act as proton acceptors for hydrogen-bond formation with the donor H in water, the triple bond being the stronger acceptor. No hydrogen bonds form between ethane and water. Because hydrogen-bond formation between unlike species promotes solubility through smaller values of G E and i than would otherwise obtain, the values of Hi are in the observed order. 16.9 By Eq. (6.70), H = T S . For the same temperaature and pressure, less structure or order means larger S . Consequently, S sl , S l v , and S s v are all positive, and so therefore are H sl , H l v , and H s v . 16.11 At the normal boiling point: Therefore H R ,l = H R ,v H l v H v H l = ( H v H ig ) ( H l H ig ) = H R ,v H R ,l H lv

At 1(atm), H R ,v should be negligible relative to H l v . Then H R ,l H l v . Because the normal boiling point is a representative T for typical liquid behavior, and because H R reects intermolecular forces, H l v has the stated feature. H l v (H2 O) is much larger than H l v (CH4 ) because of the strong hydrogen bonding in liquid water.
R ,l R ,l , where C P is the residual heat capacity for the liquid phase. 16.12 By denition, write C lP = C P +C P ig R ,l = ( H R ,l / T ) P . By assumption (modest pressure levels) C P C v Also by denition, C P P. ig

Thus,
R ,l

C lP C v P +

H R ,l T

For liquids, H is highly negative, becoming less so as T increases, owing to diminution of interR ,l molecular forces (see, e.g., Fig. 6.5 or Tables E.5 and E.6). Thus C P is positive, and C lP > C v P. 16.13 The ideal-gas equation may be written: Vt = N RT n RT = P NA P Vt RT = N NA P

The quantity V t / N is the average volume available to a particle, and the average length available is about: V t 1/3 RT 1/3 = N NA P V t 1/3 83.14 cm3 bar mol1 K1 300 K = = 34.6 1010 m or 34.6 A N 6.023 1023 mol1 1 bar 106 cm3 m3 For argon, this is about 10 diameters. See comments on p. 649 with respect to separations at which attractions become negligible.
1/3

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