Solvent volume, effect, stability

Suppose we have a physical system with small rigid particles immersed in an atomic solvent. We assume that the densities of the solvent and the colloid material are roughly equal. Then the particles will not settle to the bottom of their container due to gravity. As theorists, we have to model the interactions present in the system. The obvious interaction is the excluded-volume effect caused by the finite volume of the particles. Experimental realizations are suspensions of sterically stabilized PMMA particles, (Fig. 4). Formally, the interaction potential can be written as... 

Chlorofonn is too non-polar to dissolve the phenolic compounds under study, but it dissolves many of the monoterpenes, at least to some extent. Because the solubility of some monoterpenes into chloroform was low, different solvent/ solid ratios were tested. These were 50,20,10 and 5 1/kg of dry phloem. The extracts were bright yellow and the strongest colour was with the smallest solvent/solid ratio (51/kg). The colour of the solvent indicated that the solubility of the extractable compounds was not restricting the reaction even with the smallest solvent volume. The taste of the dry samples was evaluated by comparing them to the original phloem sample. The results showed that the mildest taste was in the phloem extracted with a solvent/solid ratio of 50 1/kg and 20 1/kg also had some effect on the taste. The taste of the chloroform-extracted phloem was stabile and it was the same after a week. 

Since n-alkanes are good solvents for poly (dimethylsiloxane), the adjacent dimethylsiloxane chains may not interpenetrate, as a result of excluded volume effect. Thus, the shape of a dimethylsiloxane chain may be represented by a prolate ellipsoid with y as the minor axis. The major axis h may be calculated by equating the volume of ellipsoid to (y/2)2(h/2) to (s2)3/2. The h value so calculated agreed reasonably well with the value of <5. Therefore, the shape of the stabilizing dimethylsiloxane chain should be close to an ellipsoid. 

The mixing of surfactant and polymer in the porous medium occurs due to both dispersion and the excluded volume effect for the flow of polymer molecules in porous media, which in turn could lead to the phase separation. Figure 16 illustrates the schematic explanation of the surfactant-polymer incompatibility and concomittant phase separation. We propose that around each micelle there is a region of solvent that is excluded to polymer molecules. However, when these micelles approach each other, there is overlapping of this excluded region. Therefore, if all micelles separate out then the excluded region diminishes due to the overlap of the shell and more solvent becomes available for the polymer molecules. This effect is very similar to the polymer depletion stabilization (55). Therefore, this is similar to osmotic effect where the polymer molecule tends to maximize the solvent for all possible configurations. ... 

The emulsifying effect of a copolymer can be characterized by determining the type of emulsion (DMF in hexane or hexane in DMF), its stability, its viscosity, and the particle size of the dispersed phase. These characteristics of oil-in-oil emulsions obtained with PS-PI block copolymers were studied as functions of solvent volume ratio, molecular weight, composition, and structure of the copolymer (5). Although Bancroft s rule was established for conventional oil-water emulsions, it appears to apply also to oil-in-oil emulsions—the continuous phase of the emulsion is preferentially formed by the solvent having the best solubility for the emulsifier (6, 7). Thus, block or graft copolymers can be prepared giving hexane/DMF, DMF/hexane, or both types of emulsions. 

The presence of solution can dramatically alter the chemical reactions. This is clearly present in the electrochemical processes. Water has been considered critical to the performance of electrocatalysts [3-8], which may effectively stabilize both the protons and the reaction intermediates in various important electrochemical reactions (Fig. 1). Water/catalyst interfaces were described by optimizing a cluster or an ice-like solvent stmcture on the catalyst surfaces, partially or completely filling the volume between... 

The volumetric ratio of the two liquid phases (j6 = Forg/ Faq) can affect the efficiency of substrate conversion in biphasic media. The biocatalyst stability and the reaction equilibrium shift are dependent on the volume ratio of the two phases [29]. In our previous work [37], we studied the importance of the nonpolar phase in a biphasic system (octane-buffer pH 9) by varying the volume of solvent. The ratio /I = 2/10 has been the most appropriate for an improvement of the yield of the two-enzyme (lipase-lipoxygenase) system. We found that a larger volume of organic phase decreases the total yield of conversion. Nevertheless, Antonini et al. [61] affirmed that changes in the ratios of phases in water-organic two-phase system have little effect upon biotransformation rate. 

These experiments demonstrate the importance of proton transfer processes during hole transfer through DNA. S. Steenken has already remarked that a proton shift between the G C bases stabilizes the positive charge [23]. If such a proton shift is coupled with the hole shift, a deuterium isotope effect should arise. Actually, H/D isotope effects are described by V. Shafiro-vich, M.D. Sevilla as well as H.H. Thorp in their articles of this volume. Experiments with our assay [22] also demonstrate (Fig. 16) that hole transfer in protonated DNA (H20 as solvent) is three times more efficient than in deuterated DNA (D20 as solvent). If this reflects a primary isotope effect, it shows that the charge transfer is coupled with a proton transfer. 

Besides temperature and addition of non-solvent, pressure can also be expected to affect the solvency of the dispersion medium for the solvated steric stabilizer. A previous analysis (3) of the effect of an applied pressure indicated that the UCFT should increase as the applied pressure increases, while the LCFT should be relatively insensitive to applied pressure. The purpose of this communication is to examine the UCFT of a nonaqueous dispersion as a function of applied pressure. For dispersions of polymer particles stabilized by polyisobutylene (PIB) and dispersed in 2-methylbutane, it was observed that the UCFT moves to higher temperatures with increasing applied pressure. These results can qualitatively be rationalized by considering the effect of pressure on the free volume dissimilarity contribution to the free energy of close approach of the interacting particles. 

Extreme cases were reactions of the least stabilized, most reactive carbene (Y = CF3, X = Br) with the more reactive alkene (CH3)2C=C(CH3)2, and the most stabilized, least reactive carbene (Y = CH3O, X = F) with the less reactive alkene (1-hexene). The rate constants, as measured by LFP, were 1.7 x 10 and 5.0 X lO M s, respectively, spanning an interval of 34,000. In agreement with Houk s ideas,the reactions were entropy dominated (A5 —22 to —29e.u.). The AG barriers were 5.0 kcal/mol for the faster reaction and 11 kcal/ mol for the slower reaction, mainly because of entropic contributions the AH components were only —1.6 and +2.5 kcal/mol, respectively. Despite the dominance of entropy in these reactive carbene addition reactions, a kind of de facto enthalpic control operates. The entropies of activation are all very similar, so that in any comparison of the reactivities of alkene pairs (i.e., ferei)> the rate constant ratios reflect differences in AA//t, which ultimately appear in AAG. Thus, car-benic philicity, which is the pattern created by carbenic reactivity, behaves in accord with our qualitative ideas about structure-reactivity relations, as modulated by substiment effects in both the carbene and alkene partners of the addition reactions. " Finally, volumes of activation were measured for the additions of CgHsCCl to (CH3)2C=C(CH3)2 and frani-pentene in both methylcyclohexane and acetonitrile. The measured absolute rate constants increased with increasing pressure Ayf ranged from —10 to —18 cm /mol and were independent of solvent. These results were consistent with an early, and not very polar transition state for the addition reaction. 

DN. The dinitro general contact weed killers are usually formulated with some oil. In these, the oil serves as both solvent and filming agent. The emulsifier is usually also incorporated to stabilize the emulsion and give wetting properties. To lower costs and conserve oil, it is desirable to use the minimum effective volume in these sprays. Possibly some of the penetrating oils may fit into this n ed. No research is known that is designed specifically to find the best oil for this purpose. 

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