Solvent dielectric

This is no longer the case when (iii) motion along the reaction patir occurs on a time scale comparable to other relaxation times of the solute or the solvent, i.e. the system is partially non-relaxed. In this situation dynamic effects have to be taken into account explicitly, such as solvent-assisted intramolecular vibrational energy redistribution (IVR) in the solute, solvent-induced electronic surface hopping, dephasing, solute-solvent energy transfer, dynamic caging, rotational relaxation, or solvent dielectric and momentum relaxation. 

Onsager s original reaction field method imposes some serious lunitations the description of the solute as a point dipole located at the centre of a cavity, the spherical fonn of the cavity and the assumption that cavity size and solute dipole moment are independent of the solvent dielectric constant. 

The solvent dielectric constant, ionic strength and temperature are chosen to fit the conditions of the experimental studies. The protein dielectric constant is assigned some small value, e.g. 4. The PB calculations are currently carried out with the atomic charges and radii of the PARSE parameter set, developed by Honig and coworkers [17] or that for CHARMM [12]. The PARSE parameter set... 

A parameter used to characterize ER fluids is the Mason number, Af, which describes the ratio of viscous to electrical forces, and is given by equation 14, where S is the solvent dielectric constant T q, the solvent viscosity 7, the strain or shear rate P, the effective polarizabiUty of the particles and E, the electric field (117). 

The effect of temperature on Mv has been studied by a number of workers (Table 8) and in all cases, a decrease in temperature increased PIB molecular weight. Since solvent dielectric constant increases with decreasing temperatures, molecular weights also areexpected to decrease. Apparently such effect is small as shown by the increase in Mv s with decreasing temperature. At very low temperatures, Mv suddenly drops as shown above. This was explained4 by assuming a reduced rate of initiation leading to an increase in transfer to initiator. 

In order to go further into the experimental check we constructed Arrhenius plots of the fluorescence quantum yield of BMPC in a few solvents (methanol, ethanol, propanol, hexanol and methylene chloride), all of which showed good linearity. The activation energies and A/kp ratios, calculated from the slopes and intercepts of those plots, are collected in Table 1. The smooth increase of both parameters in the alcohol series is mainly associated with the increase of solvent viscosity. On the other hand, decrease of the solvent dielectric constant from 32.7 (methanol) to 8.9 (dichloromethane) causes a small but significant increase of the activation energy also, this increase is probably somewhat compensated by the decrease of the viscous-flow... 

Table 1. Activation energies and ratios of the preexponential factors to the radiative rate constants (A/kp) for the photoisomcrization of BMPC in several solvents. Solvent dielectric constants at room temperature, e [65], and viscous flow activation energies, Eri [66], are shown too.

The successive equilibria are characterized by K12 and K23, respectively, and when Kl2 (often denoted K0) cannot be directly determined, it may be estimated from the Fuoss equation (3), where R is the distance of closest approach of M2+ and 1/ (considered as spherical species) in M OH2 Um x) +, e is the solvent dielectric constant, and zM and zL are the charges of Mm+ and Lx, respectively (20). Frequently, it is only possible to characterize kinetically the second equilibrium of Eq. (2), and the overall equilibrium is then expressed as in Eq. (4) (which is a general expression irrespective of mechanism). Here, the pseudo first-order rate constant for the approach to equilibrium, koba, is given by Eq. (5), in which the first and second terms equate to k( and kh, respectively, when [Lx ] is in great excess over [Mm+]. When K0[LX ] <11, koba - k,K0[Lx ] + k.it and when K0[LX ] > 1, fc0bs + k l. Analogous expressions apply when [Mm+] is in excess. 

Solvent Dielectric constant Boiling point (°C) Closed-vessel temperature (°C)... 

Solvent (dielectric constant) ethyl butyl tributyl... 

Fig. 46. Influence of solvent dielectric constant (logarithm (In) values) on (a) phenol hydroxyla-tion [data taken from Thangaraj et al. (266)] and (b) epoxidation of allyl alcohol catalyzed by TS-1 [data from Wu and Tatsumi (229)].

The next question to be discussed was already mentioned in Section 2.1, namely, since the electrostatic problem, with its sharp boundary and its homogeneous solvent dielectric constant, already represents a somewhat unrealistic idealization of the true molecular situation, how important is it to solve that problem by exact electrostatics We would answer that this is not essential. Although it presumably can t hurt to solve the electrostatics accurately, except perhaps by raising the computer time, it may be unnecessary to do so in order to represent the most essential physics, and a simpler model may be more manageable, more numerically stable, and even more interpretable. This is the motivation for the GB approximation and COSMO. 

Another type of ternary electrolyte system consists of two solvents and one salt, such as methanol-water-NaBr. Vapor-liquid equilibrium of such mixed solvent electrolyte systems has never been studied with a thermodynamic model that takes into account the presence of salts explicitly. However, it should be recognized that the interaction parameters of solvent-salt binary systems are functions of the mixed solvent dielectric constant since the ion-molecular electrostatic interaction energies, gma and gmc, depend on the reciprocal of the dielectric constant of the solvent (Robinson and Stokes, (13)). Pure component parameters, such as gmm and gca, are not functions of dielectric constant. Results of data correlation on vapor-liquid equilibrium of methanol-water-NaBr and methanol-water-LiCl at 298.15°K are shown in Tables 9 and 10. 

Figure 2. Solvent-averaged potential for charged hard-sphere ions in a dipolar hard-sphere solvent. MC approximation by Patey and Valleau (16) and LHNC approximation by Levesque, Weis, and Patey (11). Also shown are the primitive model functions for solvent dielectric constants 9.6 and 6.

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