Solvation of ion

Entry 4 shows that reaction of a secondary 2-octyl system with the moderately good nucleophile acetate ion occurs wifii complete inversion. The results cited in entry 5 serve to illustrate the importance of solvation of ion-pair intermediates in reactions of secondary substrates. The data show fiiat partial racemization occurs in aqueous dioxane but that an added nucleophile (azide ion) results in complete inversion, both in the product resulting from reaction with azide ion and in the alcohol resulting from reaction with water. The alcohol of retained configuration is attributed to an intermediate oxonium ion resulting from reaction of the ion pair with the dioxane solvent. This would react until water to give product of retained configuratioiL When azide ion is present, dioxane does not efiTectively conqiete for tiie ion-p intermediate, and all of the alcohol arises from tiie inversion mechanism. ... 

Certainly these approaches represent a progress in our understanding of the interfacial properties. All the phenomena taken into account, e.g., the coupling with the metal side, the degree of solvation of ions, etc., play a role in the interfacial structure. However, it appears that the theoretical predictions are very sensitive to the details of the interaction potentials between the various species present at the interface and also to the approximations used in the statistical treatment of the model. In what follows we focus on a small number of basic phenomena which, probably, determine the interfacial properties, and we try to use very transparent approximations to estimate the role of these phenomena. 

The interaction between a solute species and solvent molecules is called solvation, or hydration in aqueous solution. This phenomenon stabilizes separated charges and makes possible heterolytic reactions in solution. Solvation is, therefore, an important subject in solution chemistry. The solvation of ions has been most thoroughly studied. 

Selective Solvation of Ions and Competition Between Solvation and Ion Association. 

Preferential solvation of ions in binary mixed solvents. S. Janardhanau and C. Kalidas, Rev. Inorg. Chem., 1984, 6, 101,(91). 

The published experimental estimates of the surface potentials of various organic solvents have been derived mainly from the data on the real, asi, and chemical, gSi, energies of solvation of ions ... 

Neutron scattering has been used for studying the state of solvation of ions in aqueous solution (Enderby et al., 1987 Salmon, Neilson Enderby, 1988). These studies have shown that a distinct shell of water molecules of characteristic size surrounds each ion in solution. This immediate hydration shell was called zone A by Frank Wen (1957) they also postulated the existence of a zone B, an outer sphere of molecules, less firmly attached, but forming part of the hydration layer around a given ion. The evidence for the existence of zone B lies in the thermodynamics of... 

Girault and Schiffrin [4] proposed an alternative model, which questioned the concept of the ion-free inner layer at the ITIES. They suggested that the interfacial region is not molecularly sharp, but consist of a mixed solvent region with a continuous change in the solvent properties [Fig. 1(b)]. Interfacial solvent mixing should lead to the mixed solvation of ions at the ITIES, which influences the surface excess of water [4]. Existence of the mixed solvent layer has been supported by theoretical calculations for the lattice-gas model of the liquid-liquid interface [23], which suggest that the thickness of this layer depends on the miscibility of the two solvents [23]. However, for solvents of experimental interest, the interfacial thickness approaches the sum of solvent radii, which is comparable with the inner-layer thickness in the MVN model. 

If a substance is to be dissolved, its ions or molecules must first move apart and then force their way between the solvent molecules which interact with the solute particles. If an ionic crystal is dissolved, electrostatic interaction forces must be overcome between the ions. The higher the dielectric constant of the solvent, the more effective this process is. The solvent-solute interaction is termed ion solvation (ion hydration in aqueous solutions). The importance of this phenomenon follows from comparison of the energy changes accompanying solvation of ions and uncharged molecules for monovalent ions, the enthalpy of hydration is about 400 kJ mol-1, and equals about 12 kJ mol-1 for simple non-polar species such as argon or methane. 

Parker, A. J., Solvation of ions—enthalpies, entropies and free energies of transfer, Electrochim. Acta, 21, 671 (1976). 

The main classes of plasticizers for polymeric ISEs are defined by now and comprise lipophilic esters and ethers [90], The regular plasticizer content in polymeric membranes is up to 66% and its influence on the membrane properties cannot be neglected. Compatibility with the membrane polymer is an obvious prerequisite, but other plasticizer parameters must be taken into account, with polarity and lipophilicity as the most important ones. The nature of the plasticizer influences sensor selectivity and detection limits, but often the reasons are not straightforward. The specific solvation of ions by the plasticizer may influence the apparent ion-ionophore complex formation constants, as these may vary in different matrices. Ion-pair formation constants also depend on the solvent polarity, but in polymeric membranes such correlations are rather qualitative. Insufficient plasticizer lipophilicity may cause its leaching, which is especially undesired for in-vivo measurements, for microelectrodes and sensors working under flow conditions. Extension of plasticizer alkyl chains in order to enhance lipophilicity is only a partial problem solution, as it may lead to membrane component incompatibility. The concept of plasticizer-free membranes with active compounds, covalently attached to the polymer, has been intensively studied in recent years [91]. 

A route to the resolution of this conundrum is provided by the photoactivation of the donor-acceptor complex to the ion-radical pair, as described in equation (98). In this case, the close interrelationship between the photochemi-cally-produced or vertical (nonadiabatic) ion pair formed in equation (98) and the thermally accessed or contact (adiabatic) ion pair in equation (99) is illustrated in Scheme 28, where the asterisk identifies the contact ion-pair in the gas phase and s represents the solvation of ion-radical pair. According to... 

As defined earlier, the lattice energy is positive while the solvation of ions is strongly negative. Therefore, the overall heat of solution may be either positive or negative depending on whether it requires more energy to separate the lattice into the gaseous ions than is released when the ions are solvated. Table 7.7 shows the heats of hydration, AH °hy(, for several ions. 

Calculations on dynamics of solvation shells are still in their infancy. However, very recent papers on this subject, show that in most examples we cannot expect a realistic picture of solvent shells from a purely static approach. Most probably, molecular dynamics calculations and Monte Carlo methods will produce a variety of interesting data and will improve our knowledge on solvation of ions substantially. 

Figure 1. Thermochemical cycle for the solvation of ions from the gas phase into aqueous solution.

Also, the dielectric constant of a solvent near an ion may differ from that of the bnlk hqnid. Althongh the Born equation is only an approximation, it does indicate that free energies of solvation of ions will be larger as the solvent dielectric constant increases. 

Apparently, solvation of ion-pairs is not very much different from solvation of activated complex. 

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