Solvation and Solvent Phenomena

The role of solvents in chemical reactions has been well docnmented. It may be characterized as a carrier for another snbstance, as a medinm for condncting a chemical reaction, or as a means of extracting or separating other snbstances. Whatever the precise definition used, solvents are a ubiquitous feature of modem chemical research, industry and everyday life. 

A change of solvents or the use of different solvating media entirely can alter the rate of the chemical process, can shift the product mixture, and can significantly change the economics of the chemical process. The critical role that solvents play in chemistry (intentionally and inadvertently) is undisputed. An initial understanding of the basic chemistry involved is necessary. 

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Solvation and Solvent Phenomena 59 Table 3.7. Donor numbers of some solvents. 

Earlier analyses making use of AH vs. AS plots generated many p values in the experimentally accessible range, and at least some of these are probably artifacts resulting from the error correlation in this type of plot. Exner s treatment yields p values that may be positive or negative and that are often experimentally inaccessible. Some authors have associated isokinetic relationships and p values with specific chemical phenomena, particularly solvation effects and solvent structure, but skepticism seems justified in view of the treatments of Exner and Krug et al. At the present time an isokinetic relationship should not be claimed solely on the basis of a plot of AH vs. A5, but should be examined by the Exner or Krug methods. 

Solvation and especially hydration are rather complex phenomena and little is known about them. Depending on the kind of molecular groups, atoms or ions interacting with the solvent, one can differ between lyo- or hydrophilic and lyo-or hydrophobic solvation or hydration. Due to these interactions the so-called liquid structure is changed. Therefore it seems to be unavoidable to consider, at least very briefly, the intermolecular interactions and the main features of liquids, especially water structure before dealing with solvation/hydration and their effects on the formation of ordered structures in the colloidal systems mentioned above. 

Short-lived organic radicals, electron spin resonance studies of, 5, 53 Small-ring hydrocarbons, gas-phase pyrolysis of, 4, 147 Solid state, tautomerism in the, 32, 129 Solid-state chemistry, topochemical phenomena in, 15, 63 Solids, organic, electrical conduction in, 16, 159 Solutions, reactions in, entropies of activation and mechanisms, 1, 1 Solvation and protonation in strong aqueous acids, 13, 83 Solvent effects, reaction coordinates, and reorganization energies on nucleophilic substitution reactions in aqueous solution, 38, 161 Solvent, protic and dipolar aprotic, rates of bimolecular substitution-reactions in,... 

In this contribution we have presented some specific aspects of the quantum mechanical modelling of electronic transitions in solvated systems. In particular, attention has been focused on the ASC continuum models as in the last years they have become the most popular approach to include solvent effects in QM studies of absorption and emission phenomena. The main issues concerning these kinds of calculations, namely nonequilibrium effects and state-specific versus linear response formulations, have been presented and discussed within the most recent developments of modern continuum models. 

Developments in experimental and computational science have shed light on phenomena in bioenvironments and condensed phases that pose significant challenges for theoretical models of solvation [27]. Tapia [22] raises the important distinction between solvation theory and solvent effects theory. Solvation theory is concerned with direct evaluation of solvation free energies this is extensively covered by recent reviews [16,17]. Solvent-effect theory concerns changes induced by the medium onto electronic structure and molecular properties of the solute. Solvent-effect theory is concerned with molecular properties of the solvated molecule relative to the properties in vacuo as such it focuses on chemical features suitable for studying systems at the microscopic level [23]. Extensive reviews of different computational methods are given in a book by Warshel [24]. 

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