Partitioning dielectric constant

When the reaction times for Step 1 are 5 min or longer, the samples severely crack, curl, or dissolve. These results suggest that substantial reaction is occurring in the bulk of the polymer. Significant hydrophilization can occur with reaction times as short as 5 s with RTD concentrations of 0.2-0.5 M. However, 0.002-0.02 M solutions of MeTD or PhTD do not allow sufficient reaction rates for surface hydrophilization at the shorter reaction times. Thus, diffusion of MeTD and PhTD into the polymer must occur readily from the acetonitrile solutions. Acetonitrile was used because it does not swell or dissolve the polymer or RTD-polymer adduct, and the RTDs are soluble and stable in it. This solvent is quite polar (dielectric constant, 38) (25), and this is probably a major factor in the partitioning of the relatively nonpolar RTDs between the polydiene film and the solvent. As noted below, more polar RTDs show less tendency to diffuse into the polymer. 

Extraction processes that proceed according to the model of ion-pair extraction are described by a formalism different from that presented in section 16.4.2, and are based on partition of single ions and their association in the organic phase [76] (see also section 2.6). The Born equation has been widely used to describe the transfer of an ion of the charge q and radius r from vacuum to the liquid (water) of the dielectric constant e ... 

Table 1.4 Solvent descriptors of organic solvents commonly used for biocatalysis. Sw/o (solubility of water in solvent, wt%) So/w (solubility of solvent in water, wt%) and e (dielectric constant) values from [78], log P (P = partition coefficient between octanol and water), ET (empirical polarity parameter by Reichardt-Dimroth) and HS (Hildebrand solubility parameter, )l, cm J, ) from [79].

It is important to point out that sorption of simple ions is not affected only by charge non-uniformity. The non-homogeneity of the dielectric constant in the membrane is also significant. This becomes particularly evident in the case of uncharged hydrophobic membranes of the type commonly used for water desalination by reverse osmosis, where dielectric exclusion of the electrolyte from the membrane phase is the only sorption mechanism in operation 127). If the swollen membrane is treated as a homogeneous phase, the ionic partition coefficient Sj is expected to be... 

Each ion M+ N+ X and Y will generally have different energies in water and in an organic phase an ester such as dioctyladipate (low dielectric constant). The partition free energy... 

Omitted from this elementary theory are effects of plasticizer and ion pairing. Ion pair formation constants in the organic phase increase with decreasing dielectric constants of the plasticizer, in the absence of specific bonding effects. In the more general theory the single ion partition coefficients are replaced by the product of partition coefficient and ion pair formation constant. 

In an influential early investigation, correlation of biocatalytic activity data of aerobic and anaerobic whole-cell biocatalysis with solvent properties resulted in the strongest correlation for the partition coefficient log P, whereas both Hildebrand s solubility parameter 6 and the dielectric constant e showed either a weak correlation with activity data or none at all (Laane, 1985,1987) (Figure 12.2). 

Pratt and co-workers have proposed a quasichemical theory [118-122] in which the solvent is partitioned into inner-shell and outer-shell domains with the outer shell treated by a continuum electrostatic method. The cluster-continuum model, mixed discrete-continuum models, and the quasichemical theory are essentially three different names for the same approach to the problem [123], The quasichemical theory, the cluster-continuum model, other mixed discrete-continuum approaches, and the use of geometry-dependent atomic surface tensions provide different ways to account for the fact that the solvent does not retain its bulk properties right up to the solute-solvent boundary. Experience has shown that deviations from bulk behavior are mainly localized in the first solvation shell. Although these first-solvation-shell effects are sometimes classified into cavitation energy, dispersion, hydrophobic effects, hydrogen bonding, repulsion, and so forth, they clearly must also include the fact that the local dielectric constant (to the extent that such a quantity may even be defined) of the solvent is different near the solute than in the bulk (or near a different kind of solute or near a different part of the same solute). Furthermore... 

The compatibility of electrochemical detection with the various modes of liquid chromatography is limited. For all practical purposes, electrochemical detection is not suitable for use with normal phase adsorption or partition chromatography due to the solvents of low dielectric constant used as the mobile phase. On the other hand, reverse-phase adsorption and partition (including ion-exchange or ion-pairing systems) are highly com-... 

Another approach used in the empirical characterization of liquid polarity is the study of the outcome of a chemical reaction. Earle et al. [216] report a preliminary study of the keto-enol tautomerization of pentane-2,4-dione, and create an empirical correlation between the degree of tautomerization and the dielectric constant of molecular liquids. They then predict dielectric constants for a series of ILs based on the observed keto-enol equilibrium the values range from 40 to 50, slightly higher than those of short-chain alcohols. A more detailed study by Angelini et al. [217] considers the tautomerization of a nitroketone complex in a series of five imidazolium-based ILs. The results, parameterized as a linear free energy analysis of the behavior of the equilibrium constant, indicates an overall polarity comparable to that of acetonitrile, consistent with the partitioning and spectroscopic studies referenced above. 

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