Hydrogen solvation

Meot-Ner M 1984 Ionic hydrogen bond and ion solvation 2. Solvation of onium ions by 1-7 water molecules. Relations between monomolecular, specific and bulk hydration J. Am. Chem. Soc. 106 1265-72... 

Hydrogen-bonded clusters are an important class of molecular clusters, among which small water clusters have received a considerable amount of attention [148, 149]. Solvated cluster ions have also been produced and studied [150, 151]. These solvated clusters provide ideal model systems to obtain microscopic infonnation about solvation effect and its influence on chemical reactions. 

Ionisations 2, 3 and 5 are complete ionisations so that in water HCI and HNO3 are completely ionised and H2SO4 is completely ionised as a monobasic acid. Since this is so, all these acids in water really exist as the solvated proton known as the hydrogen ion, and as far as their acid properties are concerned they are the same conjugate acid species (with different conjugate bases). Such acids are termed strong acids or more correctly strong acids in water. (In ethanol as solvent, equilibria such as 1 would be the result for all the acids quoted above.) Ionisations 4 and 6 do not proceed to completion... 

Evidence for the solvated electron e (aq) can be obtained reaction of sodium vapour with ice in the complete absence of air at 273 K gives a blue colour (cf. the reaction of sodium with liquid ammonia, p. 126). Magnesium, zinc and iron react with steam at elevated temperatures to yield hydrogen, and a few metals, in the presence of air, form a surface layer of oxide or hydroxide, for example iron, lead and aluminium. These reactions are more fully considered under the respective metals. Water is not easily oxidised but fluorine and chlorine are both capable of liberating oxygen ... 

Mavri, J., Berendsen, H.J.C., Van Gunsteren, W.F. Influence of solvent on intramolecular proton transfer in hydrogen malonate. Molecular dynamics study of tunneling by density matrix evolution and nonequilibrium solvation. J. Phys. Chem. 97 (1993) 13469-13476. 

Solvation can have a profound effect on the results of a chern ical calculation, Th is is especially true wh en tti e solute an d solven t are polar or when they can participate in hydrogen honding. The solvent effect is expressed in several ways, including these ... 

Solvation increases solubility above predicted values. When the components of a solution possess an abnormally large attraction for each other, solvates are formed. Thus certain oxygen-containing compounds have a great tendency to form hydrates, thus contributing to increased water solubility hydrogen bondir also plays an important role. 

FIGURE 8 4 Solvation of a chloride ion by hydrogen bonding with water... 

Once m the organic phase cyanide ion is only weakly solvated and is far more reactive than It IS m water or ethanol where it is strongly solvated by hydrogen bonding Nude ophilic substitution takes place rapidly... 

Names follow the lUPAC Nomenclature. Solvates are listed under the entry for the anhydrous salt. Acids are entered under Hydrogen and acid salts are entered as a subentry under hydrogen. 

This reaction can be violent partiy because of the heat Hberated in the solvation of the hydrogen chloride. The hydrolysis can be moderated by adding PCl to a saturated solution of HCI Subsequentiy, the water and hydrogen chloride are boiled until the temperature reaches 180°C. On cooling, phosphonic acid crystallizes from the melt. 

A significant advance in the synthesis of monoorganotin trihaHdes was the preparation of P-substituted ethyl tin trihaHdes in good yield from the reaction of stannous chloride, hydrogen haHdes, and a,P-unsaturated carbonyl compounds, eg, acryHc esters, in common solvents at room temperature and atmospheric pressure (153,154). The reaction is beHeved to proceed through a solvated trichlorostannane intermediate (155) ... 

The dissolution of polar molecules in water is favored by dipole—dipole interactions. The solvation of the polar molecules stabilizes them in solution. Nonpolar molecules are soluble in water only with difficulty because the relatively high energy cost associated with dismpting and reforming the hydrogen-bonded water is unfavorable to the former occurring. 

Modem understanding of the hydrophobic effect attributes it primarily to a decrease in the number of hydrogen bonds that can be achieved by the water molecules when they are near a nonpolar surface. This view is confirmed by computer simulations of nonpolar solutes in water [15]. To a first approximation, the magnimde of the free energy associated with the nonpolar contribution can thus be considered to be proportional to the number of solvent molecules in the first solvation shell. This idea leads to a convenient and attractive approximation that is used extensively in biophysical applications [9,16-18]. It consists in assuming that the nonpolar free energy contribution is directly related to the SASA [9],... 

The free energy difference is mainly governed by the subtle balance of the two energetic components, the formation energies of hydrogen halides and the solvation ener-... 

Solvent effects on chemical equilibria and reactions have been an important issue in physical organic chemistry. Several empirical relationships have been proposed to characterize systematically the various types of properties in protic and aprotic solvents. One of the simplest models is the continuum reaction field characterized by the dielectric constant, e, of the solvent, which is still widely used. Taft and coworkers [30] presented more sophisticated solvent parameters that can take solute-solvent hydrogen bonding and polarity into account. Although this parameter has been successfully applied to rationalize experimentally observed solvent effects, it seems still far from satisfactory to interpret solvent effects on the basis of microscopic infomation of the solute-solvent interaction and solvation free energy. 

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