Studies on solubility and solubility-related processes.

Abstract

A general description is given of solubility and solubility related processes, including the solubility of gases and vapours in liquids, and the partition of solutes between two condensed phases. Particular attention is devoted to gas-liquid chromatography (GLC) and reverse-phase high performance liquid chromatography (RP-HPLC). Theories of solubility are surveyed, including Hildebrand's theory, the scaled particle theory, and theories based on linear regression analysis. The latter requires a knowledge of characteristic parameters of solutes (solvation parameters), and solvents (solvatochromic parameters), and the determination of these is discussed. It is shown that the method of multiple linear regression analysis is very useful in the study of solution and solubility related processes, and the aim of the work in the thesis is to set out characteristic solute parameters, and apply them to a wide range of processes. Methods are given for the determination of solute solvation parameters based on experimental procedure. A collection of parameters (R2 - an excess molar refraction, x*2 - dipolarity, αH2-hydrogen bond acidity, βH2-hydrogen bond basicity, log - Ostwald solubility coefficient on n-hexadecane, Vx - size parameter) is assembled for a wide range of solutes. The construction of a solute parameter database, and its associated programs is also discussed. A thermodynamically consistent set of explanatory variables, all related to Gibbs energy are determined. New scales of multifunctional solvation parameters reflecting real solubility situations are developed and EΣH2)- These, and the older parameters, above, are applied to various processes using equations 1 and 2 (where SP is the dependant solute variable); log SP(gas condensed phase) = c + r.R2 + S.ΣxH2 + a.ΣαH2 + b.ΣβH2 + l.logL16 [1] log SP (within condensed phase) = c + r.R2 + S.ΣxH2 + a.ΣαH2 + b.ΣβH2 [2] Equations 1 and 2 are shown to be extremely useful for the prediction of physicochemical and biochemical data, and for the interpolation of factors influencing solubility and solubility related processes

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