Interaction favorable location

The macroscopic property of interest, e.g., heat of vaporization, is represented in terms of some subset of the computed quantities on the right side of Eq. (3.7). The latter are measures of various aspects of a molecule s interactive behavior, with all but surface area being defined in terms of the electrostatic potential computed on the molecular surface. Vs max and Fs min, the most positive and most negative values of V(r) on the surface, are site-specific they indicate the tendencies and most favorable locations for nucleophilic and electrophilic interactions. In contrast, II, a ot and v are statistically-based global quantities, which are defined in terms of the entire molecular surface. II is a measure of local polarity, °fot indicates the degree of variability of the potential on the surface, and v is a measure of the electrostatic balance between the positive and negative regions of V(r) (Murray et al. 1994 Murray and Politzer 1994). 

Zeolites are somewhat like silica in their surface characteristics. Ketones and hydroxy-1,4-biradicals have very polar groups which can interact favorably with metal cations located along zeolite walls. The potential effect of the metal ions on the position of the reacting ketones is twofold. First, the cations may force a ketone molecule into a conformation or a site which it would normally not occupy based solely upon free-volume considerations. Second, the diffusion coefficient of a ketone or a hydroxy-1,4-biradical is probably much more than an order of magnitude smaller than that of benzene [289] so that the residence time of a ketone and its Norrish II intermediates in a zeolite site with at least one metal ion is expected to be closer to 100 ns than to 1 ns. 

Amphiphilic molecules contain a polar and an apolar part. As a result, such molecules have an ambiguous (amphi) affinity (philos) for water. The apolar parts behave hydrophobically the water molecules tend to escape from contact with these parts. The polar parts are hydrophilic. They interact favorably with water. The consequence of the amphiphilic character is that the molecules are preferably located at interfaces with water, where the polar parts are exposed to the aqueous phase and the apolar parts to the nonaqueous phase. Low-molecular-weight, amphiphilic compounds are often called surfactants. Well-known examples of surfactants are the classical soaps (single-chain fatty acids), phospholipids, cholesterol, bile acids, lung surfactant, and so on. In Figure 7.1, the chemical structures showing the polar and apolar parts of some of these surfactants are given. Monolayers may also be formed by polymers, polyelectrolytes, and proteins that contain polar and apolar parts. 

The important yet unexpected result is that in NR-s-SBR (solution) blends, carbon black preferably locates in the interphase, especially when the rubber-filler interaction is similar for both polymers. In this case, the carbon black volume fraction is 0.6 for the interphase, 0.24 for s-SBR phase, and only 0.09 in the NR phase. The higher amount in SBR phase could be due to the presence of aromatic structure both in the black and the rubber. Further, carbon black is less compatible with NR-cE-1,4 BR blend than NR-s-SBR blend because of the crystallization tendency of the former blend. There is a preferential partition of carbon black in favor of cis-1,4 BR, a significant lower partition coefficient compared to NR-s-SBR. Further, it was observed that the partition coefficient decreases with increased filler loading. In the EPDM-BR blend, the partition coefficient is as large as 3 in favor of BR. 

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