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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 Boltzmann’s constant.

Combination of the potential with Eq. (16.10) yields on piecewise integration the following expression for B : 2 B = π N A d 3 1 + ( K 3 − 1) 1 − e−ξ/ kT − (l 3 − K 3 ) e / kT − 1 3 From this expression, 1 dB = −( K 3 − 1)ξ e−ξ/ 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 +ξ K3 − 1 l3 − K 3

ξ

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

Here. (b) Acetone/dichloromethane is a solvating NA/NA mixture. [At 323 K (50◦ C).770 0. H ⊕. in all four cases. it experiences strong attractive interactions with the second species. without question. G E must be negative: the sign combination G E ⊕.3 f (el) 0 0 0 0 0 0 0 0. δi j ≡ 2 Bi j − 1 2 Bii + B j j At normal temperature levels. H E ⊕.5 In Series A.088 0. G ⊕. (16. one will see G E .] (d) Benzene/carbon disulfide is an NP/NP system.6 (a) Acetone/cyclohexane is an NA/NP system. Hence. and S E is inconsistent with Eq. we expect either Region I or Region II behavior: G E ⊕ and H E ⊕.0 98.188 0.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 /10−78 J m6 49. All other combinations are possible in principle.9 119. two are forbidden by Eq. and S E ⊕. (c) Aniline/cyclohexane is an AS/NP mixture.912 0. In series B.1 95.087 0.795 0. and S E ⊕.7.4-dioxane is a solvating NA/NA mixture. Hence.904 0.9 22.263 0. H E ⊕.000 0.8 34.806 f (ind) 0 0.2 for a discussion of the connection between intermolecular forces and the second virial coefficient.3 Water (H2 O). Here.586 0. intermolecular attractions prevail. and S E ⊕ is outlawed. 16. is the common species for all four systems.7 By definition. G E (g) Chloroform/n-hexane is NA/NP. a charge-transfer complex occurs between acetone and the aromatic benzene molecule. we expect Region II behavior: G E ⊕.1 161. a highly polar hydrogen donor and acceptor. H E .5 and 16. and the second virial coefficients are negative.6.680 16. Suppose that H E is negative and S E is positive. E E E .) If interactions between unlike molecular pairs are weaker than interactions between pairs of molecules of the same kind. Similar reasoning shows that the combination G E . and S E . Hence. Hence. and S E .25).25).) 16. 16. 16. with S E ⊕ or . H E ⊕.186 0. experiment shows that S E is ⊕ for this system. (See the discussion of signs for H E in Sec.151 0.205 0. (See Secs. hydrogen bonding occurs between the donor hydrogens of CH2 Cl2 and the electron-rich benzene molecule. H E ⊕.992 0. one expects G E ⊕.25). HE . (h) Ethanol/n-nonane is an AS/NP mixture. (16.052 f (disp) 1. (e) Benzene/n-hexane is NP/NP.143 0.3 270.450 5.008 0.) 16.008 0. (16. H E ⊕. G E ⊕.4 Of the eight potential combinations of signs. and S ⊕. (See Sec.812 0. Here. interactions between unlike molecular pairs are stronger than interactions between pairs of molecules of the same kind. We therefore expect G E ⊕. Then.142 f (el)/ f (disp) 0 0 0 0 0 0 0 0. 16. and S E ⊕. (f ) Chloroform/1. by Eq. Hence the mixtures containing benzene have more negative (smaller positive) values of H E than those containing cyclohexane and n-hexane. | Bi j | < 1 | Bii + B j j | 2 722 . and S E . and therefore H is negative. and ethanol is a very strong associator.992 0.096 0. H E . 16. Neither cyclohexane nor n-hexane offers the opportunity for these special solvation interactions.3 24.1 106.

H l v (H2 O) is much larger than H l v (CH4 ) because of the strong hydrogen bonding in liquid water. less structure or order means larger S . H αβ = T S αβ ..l molecular forces (see. and AS/NP mixtures. See comments on p.6 × 10−10 m or 34. NA/NP. Thus. (6. 16. | Bii + B j j | | Bi j | > 1 2 Hence δi j < 0.v − H l v ≡ H v − H l = ( H v − H ig ) − ( H l − H ig ) = H R .14 cm3 bar mol−1 K−1 × 300 K ˚ = = 34.l H lv At 1(atm). S l v .l ∂T P For liquids.9 By Eq. 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. and H s v . positive δ12 is the norm for NP/NP. e. Because the normal boiling point is a representative T for typical liquid behavior. 1/3 723 . (10.5 and E. Because hydrogen-bond formation between unlike species promotes solubility through smaller values of G E and γi than would otherwise obtain.l = H R .v − H R . for binary gas mixtures of the isomeric xylenes. In the present case. owing to diminution of interR . 16. If unlike interactions are stronger than like interactions. the triple bond being the stronger acceptor. and because H R reflects intermolecular forces.. For identical interactions of all molecular pairs. H R .70).4)]. the larger the solubility [see Eq. R . 16. No hydrogen bonds form between ethane and water.g. H is highly negative. Thus C P is positive.8 The magnitude of Henry’s constant Hi is reflected through Henry’s law in the solubility of solute i in a liquid solvent: The smaller Hi . molecular factors that influence solubility also influence Hi . C P P. 649 with respect to separations at which attractions become negligible.l . S sl . whereas δ12 is usually negative for NA/NA mixtures comprising solvating species.g.l = (∂ H R . 16. Fig. 6. where C P is the residual heat capacity for the liquid phase. and the average length available is about: V t 1/3 RT 1/3 = N NA P V t 1/3 83. For the same temperaature and pressure. By assumption (modest pressure levels) C P ≈ C v Also by definition. and so therefore are H sl .l /∂ T ) P . becoming less so as T increases. Then H R . 16. e. write C lP = C P +C P ig R .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. 16. One expects δ12 to be essentially zero for ideal solutions of real gases. this is about 10 diameters. H l v .7 apply approximately to the signs of δ12 for binary gas mixtures.6).6 A N 6. and C lP > C v P.11 At the normal boiling point: Therefore H R .023 × 1023 mol−1 × 1 bar × 106 cm3 m−3 For argon. Hence.l ≈ − H l v . Bi j = Bii = B j j .and hence (since each B is negative) δi j > 0.12 By definition. H l v has the stated feature.l C lP ≈ C v P + ∂ H R . and S s v are all positive. Consequently. ig Thus. and δi j = 0 The rationalizations of signs for H E of binary liquid mixtures presented in Sec. R . the values of Hi are in the observed order.l R .5 or Tables E.v should be negligible relative to H l v .