Solvent cohesive energy density

The value of kd was obtained from the determination of triplet lifetimes by measuring the decay of phosphorescence and found to be insensitive to changes in solvent polarity. The k2 values derived from Eqs. 10 and 11 were correlated with solvent parameters using the linear solvation energy relationship described by Abraham, Kamlet and Taft and co-workers [18] (Eq. 12), which relates rate constants (k) to four different solvation parameters (1) or the square of the Hildebrand solubility parameter (solvent cohesive energy density), (2) n or solvent dipolarity or polarizability, (3) a, or solvent hydrogen bond donor acidity (solvent electrophilic assistance), and (4) or solvent hydrogen bond acceptor basicity (solvent nucleophilic assistance). 

Often referred to as the solvent cohesive energy density, the Hildebrand solubility parameter is considered to be a measure of the solvent contribution to the cavity term, and is used as a correction factor in the - solvatochromic equation. It is related to the general definition of London cohesive energy between two interacting species ... 

Tfaeie have been a number of attempts to develop solvent parameter scales that could be used to correlate ttiermodynamic and kinetic results in terms of these patametois. Gutmann s Donor Numbers, discussed previously, are sometimes used as a solvent property scale. Kamlet and Taft and co-workers developed the solvatochromic parameters, Uj, B, and n that are related to the hydrogen bonding acidity, basicity and polarity, respectively, of the solvent. Correlations with these parameters also use the square of tte Hildebrand solubility parameter, (5, that gives the solvent cohesive energy density. Parameters for some common solvents are collected in Table 3.6. 

Table 8.2 Values of the Cohesive Energy Density (CED) for Some Common Solvents and the Solubility Parameter 6 for These Solvents and Some Common Polymers...

The polarity of the polymer is important only ia mixtures having specific polar aprotic solvents. Many solvents of this general class solvate PVDC strongly enough to depress the melting temperature by more than 100°C. SolubiUty is normally correlated with cohesive energy densities or solubiUty parameters. For PVDC, a value of 20 0.6 (J/cm (10 0.3 (cal/cm ) has been estimated from solubiUty studies ia nonpolar solvents. The value... 

Thermodynamic Properties The variation in solvent strength of a supercritical fluid From gaslike to hquidlike values may oe described qualitatively in terms of the density, p, or the solubihty parameter, 6 (square root of the cohesive energy density). It is shown For gaseous, hquid, and SCF CO9 as a function of pressure in Fig. 22-17 according to the rigorous thermodynamic definition ... 

The polymer has a low cohesive energy density (the solubility parameter 5 is about 16.1 MPa ) and would be expected to be resistant to solvents of solubility parameter greater than 18.5 MPa. Because it is a crystalline material and does... 

The internal pressure is a differential quantity that measures some of the forces of interaction between solvent molecules. A related quantity, the cohesive energy density (ced), defined by Eq. (8-35), is an integral quantity that measures the total molecular cohesion per unit volume. - p... 

Table 8-6. Internal Pressure and Cohesive Energy Density (ced) of Solvents...

The liquid-liquid interface is not only a boundary plane dividing two immiscible liquid phases, but also a nanoscaled, very thin liquid layer where properties such as cohesive energy, density, electrical potential, dielectric constant, and viscosity are drastically changed along with the axis from one phase to another. The interfacial region was anticipated to cause various specific chemical phenomena not found in bulk liquid phases. The chemical reactions at liquid-liquid interfaces have traditionally been less understood than those at liquid-solid or gas-liquid interfaces, much less than the bulk phases. These circumstances were mainly due to the lack of experimental methods which could measure the amount of adsorbed chemical species and the rate of chemical reaction at the interface [1,2]. Several experimental methods have recently been invented in the field of solvent extraction [3], which have made a significant breakthrough in the study of interfacial reactions. 

TABLE 1.2 Internal Pressures and Cohesive Energy Densities for Some Common Solvents (25° C)9... 

The study of the recombination (kc) and the disproportionation (/tdis) of ethyl radicals proved the dependence of the ratio kdis/kc on the solvent [230-232], Stefani [231] found that log( dis/ c) is a linear function of the solubility 8S, which is equal to the square root of the cohesive energy density of the solvents (Dce) ... 

Volumes of activation can be unambiguously determined only from the pressure dependence of the rate constants. Attempts to obtain volumes of activation from the correlation of rate constants with the solubility parameter 22 or the cohesive energy density parameter (ced)23, which are related to the internal pressure of solvents, have not led to clear-cut results. 

These block copolymers can act as effective steric stabilizers for the dispersion polymerization in solvents with ultralow cohesion energy density. This was shown with some polymerization experiments in Freon 113 as a model solvent. The dispersion particles are effectively stabilized by our amphi-philes. However, these experiments can only model the technically relevant case of polymerization or precipitation processes in supercritical C02 and further experiments related to stabilization behavior in this sytem are certainly required. 

The cohesive pressure (c) of a solvent, otherwise known as cohesive energy density (CED), is a measure of the attractive forces acting in a liquid, including dispersive, dipolar and H-bonding contributions, and is related to the energy of vaporization and the molar volume (Equation 1.1) ... 

The second important solvent effect on Lewis acid-Lewis base equilibria concerns the interactions with the Lewis base. Since water is also a good electron-pair acceptor129, Lewis-type interactions are competitive. This often seriously hampers the efficiency of Lewis acid catalysis in water. Thirdly, the intermolecular association of a solvent affects the Lewis acid-base equilibrium242. Upon complexation, one or more solvent molecules that were initially coordinated to the Lewis acid or the Lewis base are liberated into the bulk liquid phase, which is an entropically favourable process. This effect is more pronounced in aprotic than in protic solvents which usually have higher cohesive energy densities. The unfavourable entropy changes in protic solvents are somewhat counterbalanced by the formation of new hydrogen bonds in the bulk liquid. 

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