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Along the diagonal line on Fig 164, S E = 0 In regions to the right of the diagonal (V, VI, and I), S E is positive; for regions to the left of the diagonal (11,111, and IV), sE negative is Lines of constant nonzero S E are parallel to the diagonal Convenience in modeling and rationalizing the behavior of GE suggests a focus on enthalpic (energetic) and entvopic contributions, a separation suggested by Eqs (1183) and (1625) According to these equations, GE can be positive or negative if H E and S E have the same sign If H E and S E are positive and if GE is also positive, then H E > T S and ~ "enthalpy dominates"; If H E and sE positive and GE is negative, then T S > H E and are ~ "entropy dominates" Similar reasoning applies when both H E and sEare negative, leading to the identification of Regions I and IV on Fig 164 as regions of enthalpy domination, and of Regions I11 and VI as regions of entropy domination The notions of enthalpy and entropy domination can be helpful for explaining the molecular origins of observed mixture-property behavior Abbott et al classify binary organic and aqueous/organic mixtures by a simple scheme based on hydrogen-bonding concepts (Sec 165) A pure species is categorized as nonpolar ("NP": eg, benzene, carbon tetrachloride, or n-heptane); polar but nonassociating ("NA": eg, acetone, chloroform, or diethylether); or polar and associating ("'AS": eg, acetic acid, ethanol, or water) With these categories for pure species, there are then six binary mixture types: NPINP (eg, benzeneln-heptane); NANP [eg, chloroformln-heptane, Fig 114(a)]; ASINP [eg, ethanolln-heptane,Fig 114(d)];NAJNA [eg, acetone/chloroform,Fig 114(c)];ASINA [eg, ethanol/chloroform, Fig 114(e)]; and ASIAS [eg, ethanollwater, Fig 114(f)] Figure 165 is a G E /RT vs H ~ / R T of data for 135 different binary mixtures at plot 29815 K(25"C), with systems distinguished according to t h e N P M A S classificationscheme For clarity, we mainly omit data for which the three principal excess properties are very small The figure appears chaotic at first glance, but on inspection important patterns emerge We list here a few; statistics, where given, apply to the full data set analyzed by Abbott et al About 85% of all mixtures exhibit positive GE or positive H E (Regions I, 11,111,and VI); about 70% have positive GE and positive H E (Regions I and 11)Thus positive G E and positive H E are the "norms" About 60% of all mixtures fall in Regions I and IV, with only about 15% in Regions I11 and VI Thus the enthalpy is more likely to dominate solution behavior than is the entropy.

62 1

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NPINP mixtures (the open circles on Fig 165) tend to concentrate in Regions I and VI: for such mixtures, H E and sEare normally positive When GE is positive (enthalpy domination), G E / R rarely exceeds about 02 If G E is negative (entropy domination), ~ G ~ / R T rarely less than -02 is NA/NP mixtures (the filled circles) usually fall in Region I, with occasional significant excursions into Region 11 Thus, G E and H E are positive, as is (normally) sE Both G E and H~ can be large ASNP mixtures (the open triangles) invariably occupy Region I or 11, with Region 1 1 behavior (negative S E ) favored when the polar species is a very strong associator, such as an alcohol or a carboxylic acid In the latter case, G E can be extremely large owing to the reinforcing effects of positive H E and negative sE [Eq (1 183)] Mixtures containing two polar species exhibit a diversity of behaviors Perhaps the easiest class to categorize involves pure solvation, in which one species is a nonassociating hydrogen donor and the other a nonassociating hydrogen acceptor Here, unless one of the species has extremely high effective polarity (eg, acetonitrile), Region IV behavior obtains: G E , H E , and sE all negative (enthalpy dominates) Examples are represented are by the open squares on Fig 165 For AS/NA and ASIAS mixtures (the filled triangles on Fig 165), a variety of hydrogen-bonding possibilities is available (see Table 165), and it is impossible to make easy generalizations We note however that these are the mixture types with significant representation in Region 111; here, both H E and sEare negative, but entropy dominates

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Figure 165 Equimolar excess properties for 135 binary mixtures at 29815 K (25 C)

NAINP mixtures; A ASINP mixtures; A AS/NA and AS/AS mixtures;

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Not much to that code, is there So, here s how it works. When you encounter an error in some routine, the in-effect error handler calls the central GeneralError method.

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