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The relations between excess properties and property changes of mixing (Sec 123) facilitate discussion of the molecular phenomena which give rise to observed excess-property behavior An essential connection is provided by Eq (1233), which asserts the identity of H E and AH Thus we focus on the mixing process (and hence on A H ) for explaining the behavior of H E The sign and magnitude of A H roughly reflect differences in the strengths of intermolecular attractions between pairs of unlike species on the one hand, and pairs of like species on the other In the standard mixing process (Fig 1210) interactions between like species are disrupted, and interactions between unlike species are promoted If the unlike attractions are weaker than the average of those between species of the same kind, then in the mixing process more energy is required to break like attractions than is made available by formation of unlike attractions In this case AH(= H E ) is positive, ie, the mixing process is endothermic If the unlike attractions are stronger, then A H is negative, and the mixing process is exothermic In Secs 161 and 165 we identify intermolecular attractive interactions of four kinds: dispersion, induction, direct electrostatic, and quasichemical A summary list of important points follows:

Of the four attractive interactions, the dispersion force is always present It dominates when interacting molecules are nonpolar or slightly polar (See Table 162 and the accompanying discussion) The induction force requires that at least one of the interacting species be polar It is normally the weakest of the "physical" intermolecular attractive forces (Table 162) For neutral molecules, the simplest and normally the strongest direct electrostatic force is that operating between two permanent dipoles This force can dominate "physical" attractive interactions if the molecules have high effective polarity, ie, if they are small and have large permanent dipoles Quasichemicalforces, when present, can be the strongest of the four attractiveinteractions However, their existence requires special chemical make-up of the interacting molecules Hydrogen bonding is the most important interaction of this type, although charge-transfer complexing can play a major role in some kinds of systems

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Public Sub SomeRoutine( ) On Error GoTo ErrorHandler ' ----- Lots of code here. Return ErrorHandler: GeneralError("SomeRoutine", Err.GetException( )) Resume Next End Sub

With these notions in mind, we offer some rationalizations of the observed signs and magnitudes of HE(= AH) for binary liquid mixtures of the kinds discussed in Sec 166 H E of N P N P Mixtures Here, dispersion forces are usually the only significant attractive intermolecular forces Thus H E reflects energetic effects associated with disruption of dispersion interactions between like species, and simultaneous promotion of dispersion interaction betweenunlike species Molecular theory19 suggests that dispersion forces between unlike species are weaker than the average of dispersion forces between like species (This is the molecular basis of the "like prefers like" rule of elementary chemistry) Here, then, one expects H~ to be positive This is what is usually observed for NPINP mixtures (Fig 165) H E of NA/NP Mixtures For this class of mixtures, interactions between molecules of like species are different in kind for the two species In particular, two molecules of the polar species experience a directelectrostatic interaction and a (usually weak) induction interaction, in addition to the usual dispersion interaction; here, the attractive forces are stronger than would be observed for a nonpolar species of similar size and geometry Interaction between unlike species, on the other hand, involves only the dispersion and (weak) induction forces One therefore expects H E to be positive, only more so than for otherwise similar NPNP mixtures Experiment bears this out, on average (Fig 165) H E of ASATP Mixtures As for NPNP and NAINP mixtures, one expects positive H E ; this is what Fig 165 shows However, H E is often observed to be only modest in magnitude, frequently less than H E for

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19see,eg, J M Prausnitz, R N Lichtenthaler, and E G de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria, 2d ed, sec 44, Prentice Hall, Englewood Cliffs, NJ, 1986

otherwise similar NA/NP mixtures The reason for this is the unusual strength of the like interactions for the associating polar species Here, hydrogen-bonded complexes for the polar species can persist in solution up to rather high dilution, thus mitigating the otherwise very large positive values of H E expected from simple disruption/promotion arguments

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