vb.net barcode freeware Introduction to Molecular Thermodyluzmics in Software

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CHAPTER 16 Introduction to Molecular Thermodyluzmics
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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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H E of Solvating NANA Mixtures
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These mixtures are the major occupants of Region IV in Fig 165 Since neither species associates by hydrogen bonding, attractions between like species result from dispersion, induction, and dipoleldipole interactions The same kinds of interaction obtain for unlike molecules, but in addition there is superposed a strong attraction owing to the formation of a hydrogen-bonded solvation complex The net effect is a negative value for H ~the system is exothermic ;
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H~ of ASNA and AS/AS Mixtures
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All four types of attractive interaction occur between unlike species, and for at least one of the pure species Thus the sign and magnitude of H E reflect a balance between competing effects of dipoleldipole interactions, association, and solvation Qualitative prediction of enthalpic behavior is difficult, except by analogy Figure 165 suggests the diversity of behavior observed for such mixtures
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Excess Entropy
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The excess entropy is related to AS through Eqs (1238) and (1235) Thus,
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where
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= -R
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xi Inxi
(1235)
An ideal solution is one comprising molecules of identical size and shape, and for which intermolecular forces are the same for all molecular pairs, whether like or unlike For such a hypothetical solution, the entropy change of mixing, given by Eq (1235), is always positive In a real mixture, molecules of different species have different sizes andlor shapes, and the intrinsic strengths of molecular interactions are different for different molecular pairs As a result, AS for a real mixture may be greater or less than a s i d , and by Eq (1626), sE may be positive or negative The behavior of S E is most conveniently rationalized by separate consideration of size/shape effects on the one hand and structural effects on the other (The word "structure" refers to the order brought about at the molecular level by intermolecular forces) Pure sizelshape effects result in a AS greater than AS", and hence provide a positive contribution to sEPrausnitz et a1" discuss the relative roles of size and shape, and give references to the relevant literature If size effects alone are considered, an approximate upper bound to this contribution to S E is given by the Flory-Huggins equation:
sE= -R
xi In Xi
where
Q I =
xi Vi -
C xj vj
Here, Qi is the apparent volume fraction, and V, is molar volume of the pure species
205 M Prausnitz, R N Lichtenthaler, and E G de Azevedo, op cit, sec 74
167 Molecular Basisfor Mixture Behavior
Structural contributions to AS (hence to S E ) reflect primarily the relative strengths of competing intermolecular attractions Consider the mixing of a nonassociating polar species (eg, acetone) with a nonpolar species (eg, n-hexane) Energetically, the net result of the mixing process is determined primarily by the energy associated with disruption of dipoleldipole interactions, as discussed earlier with respect to H E for NANP mixtures With respect to entropy, this is a structure-breaking process wherein molecular aggregates promoted by a strong dipoleldipole interaction are broken up by mixing Consider instead the mixing of two nonassociating polar species, one a hydrogen donor and the other a hydrogen acceptor [eg, chloroform/acetone,Fig 1 14(c)]Energetically, the net result of the mixing process is determined primarily by the energy associated with formation of a solvation complex, as discussed earlier regarding H E for solvating NA/NA mixtures This is a structure-making process, wherein molecular aggregates promoted by a strong quasichemical interaction are formed on mixing Structure breaking implies a positive contribution to S E (AS > a s i d ) , and structure making a negative contribution to S" (AS < n s i d ) When used in conjunction with sizelshape arguments, these simple notions help to explain observed signs for s E By way of example, we consider again binary liquid mixtures of the kinds discussed in Sec 166
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