Mutual Effects of Ions and Solvents

The effect of changing the dielectric constant is shown for ions of radius 4.0A in Figure 5, where the values of D correspond to those for the solvents methanol, water, and N-methylpropionamide. The upward turn of log y at higher concentrations is exaggerated when D is low, which is again in qualitative agreement with some experimental observations (2) the effect is attributed to mutual polarization of ions, which is more effective when the permittivity is low. On an intuitive basis it might have been expected, erroneously, that the polarization would lower the activity coefficients, which could be the reason why ionic polarization has received so little attention in interionic theory. 

In conclusion, it can be said that the electrostatic theory of solvent effects is a most useful tool for explaining and predicting many reaction patterns in solution. However, in spite of some improvements, it still does not take into account a whole series of other solute/solvent interactions such as the mutual polarization of ions or dipoles, the specific solvation etc., and the fact that the microscopic relative permittivity around the reactants may be different to the macroscopic relative permittivity of the bulk solvent. The deviations between observations and theory, and the fact that the relative permittivity cannot be considered as the only parameter responsible for the changes in reaction rates in solution, has led to the creation of different semiempirical correlation equations, which correlate the kinetic parameters to empirical parameters of solvent polarity (see Chapter 7). 

In almost all theoretical studies of AGf , it is postulated or tacitly understood that when an ion is transferred across the 0/W interface, it strips off solvated molecules completely, and hence the crystal ionic radius is usually employed for the calculation of AGfr°. Although Abraham and Liszi [17], in considering the transfer between mutually saturated solvents, were aware of the effects of hydration of ions in organic solvents in which water is quite soluble (e.g., 1-octanol, 1-pentanol, and methylisobutyl ketone), they concluded that in solvents such as NB andl,2-DCE, the solubility of water is rather small and most ions in the water-saturated solvent exist as unhydrated entities. However, even a water-immiscible organic solvent such as NB dissolves a considerable amount of water (e.g., ca. 170mM H2O in NB). In such a medium, hydrophilic ions such as Li, Na, Ca, Ba, CH, and Br are selectively solvated by water. This phenomenon has become apparent since at least 1968 by solvent extraction studies with the Karl-Fischer method [35 5]. Rais et al. [35] and Iwachido and coworkers [36-39] determined hydration numbers, i.e., the number of coextracted water molecules, for alkali and alkaline earth metal... 

In general, MS performance should not be compromised by a static magnetic field. Many factors such as the design of ion optics, selection of interface, and type of MS analyzer should be considered with regard to the construction and configuration of the double hyphenated system. The optimum design should overcome some of the mutual incompatibilities of LC-NMR and LC-MS systems. For LC-MS, ionization propensities vary considerably depending upon solvent, ionization source type, and complex matrix effects. Most NMR analyses, however, are not affected by variations... 

Solvent effects in electrochemistry are relevant to those solvents that permit at least some ionic dissociation of electrolytes, hence conductivities and electrode reactions. Certain electrolytes, such as tetraalkylammonium salts with large hydrophobic anions, can be dissolved in non-polar solvents, but they are hardly dissociated to ions in the solution. In solvents with relative permittivities (see Table 3.5) s < 10 little ionic dissociation takes place and ions tend to pair to neutral species, whereas in solvents with 8 > 30 little ion pairing occurs, and electrolytes, at least those with univalent cations and anions, are dissociated to a large or full extent. The Bjerrum theory of ion association, that considers the solvent surrounding an ion as a continuum characterized by its relative permittivity, can be invoked for this purpose. It considers ions to be paired and not contributing to conductivity and to effects of charges on thermodynamic properties even when separated by one or several solvent molecules, provided that the mutual electrostatic interaction energy is < 2 kBT. For ions with a diameter of a nm, the parameter b is of prime importance ... 

A system of an ionic amphiphile contains in its simplest form three entities the solvent water, an amphiphilic ion, and a hydrophilic counterion. The properties of the total system can then be understood as the effects of the mutual interactions between these three species. A comprehensive treatment of all the interactions on a molecular level is not at present feasible. However, the development of methods for determining intermolecular potentials and for making statistical mechanical simulations292-294 should change this in the not too distant future. 

A common feature of self-ionizing solvents are the amphoteric properties of the solvent molecules, since they may act both as EPD and as EPA (27). It appears therefore that outer-sphere effects, similar to those existing between polarized solvent molecules of solvated ions, occur in the pure liquids resulting in mutual polarization of solvent molecules within associated units. From the functional point of view this is described in the following way ... 

Though ionic polymerization resembles free-radical polymerization in terms of initiation, propagation, transfer, and termination reactions, the kinetics of ionic polymerizations are significantly diflFerent from free-radical polymerizations. In sharp contrast to free-radical polymerizations, the initiation reactions in ionic polymerizations have very low activation energies, chain termination by mutual destruction of growing species is nonexistent, and solvent effects are much more pronounced, as the nature of solvent determines whether the chain centers are ion pairs, free ions, or both. No such solvent role is encountered in free-radical polymerization. The overall result of these features is to make the kinetics of ionic polymerization much more complex than the kinetics of free-radical polymerization. 

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