Interphase partitioning

Miertus, S., Jakus, V. (1990) Theoretical interpretation of interphase partition of the series polychlorinated biphenyls. Chem. Pap. 44(6), 793-804. 

Trends in CFSE data derived from the absorption spectral measurements described in chapter 5 may be used to predict or interpret element partitioning involving AT3 cations between coexisting aluminosilicate minerals. In many cases, however, the CFSE data represent average values for cations in several Al3+ sites in individual crystal structures. Nevertheless, the stabilization energies are applicable to interphase partitioning trends based on bulk chemical data for coexisting minerals. 

Indeed, the atmospheric input of PCBs into Lake Michigan has been found to exceed that from landfills (Hornbuckle et al. 1995), so that important interphase partitions should be taken into account. Atmospheric deposition and transport of toxaphene into sediments in the Great Lakes are dominant, although during the more recent 10-year period there is some increase in the hepta- and hexachlorinated congeners that suggests a slow transformation by dechlorination with an estimated half-life > 50 years (Pearson et al. 1997). Attention has been drawn in Chapter 2, Sections 2.4.1.3, 2.4.2.1, and 2.5 to analytical problems with toxaphene, and specifically to the presence of isomeric enantiomers. 

As discussed above, differences in reactivity ratios can lead to drift in the copolymer composition from that of the starting materials. Noel et al. [39] studied a unique set of monomers, namely VAc, vinyl 2,2-dimethylpropionate and vinyl 2-ethylhexanoate, and determined their reactivity ratios with methyl acrylate. Their work led to the conclusion that the three vinyl esters can be described with one set of reactivity data. This greatly simplifies any potential for compositional drift since only one variable must now be dealt with, namely interphase partitioning of the monomer. Copolymers or terpolymers produced with VAc and vinyl esters have the potential to outperform VAc/acrylic copolymers due to the mote random copolymerization of VAc with other vinyl ester monomers compared with acrylic monomers [40], as is discussed in Section 16.9. 

From this point on, two reaction loci are present, the relative importance of which is the result of a complex interplay of different factors such as interphase partitioning and transport rates of the reactants and reaction rates. 

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