Kinetics of the reactions of unsaturated hydrocarbon free radicals (vinyl, propargyl, and allyl) with molecular bromine (original) (raw)

1993, The Journal of Physical Chemistry

It is of some interest to note that in the limits of cB = 1 and 03, the 6-coefficients for the cavity field are zero and 2, respectively, and for the reaction field, 3 and zero. For the solvent range of usual interest, say, eB from 10 to 80, the former coefficient ranges from 0.8 to 1.4 and the latter from 1.8 to 0.9. What has been obtained are nonanalytic, albeit tractable, expressions for the potential and fields of probable interest corresponding to a dielectric function, eq A3, which is continuous at the cavity boundary, and has as its' recognizable limit the Onsager-Born form. To complete the development as regards application to free energies of solvation, where the solvent is (in the limit of vanishing 1987, 91, 1873-1877 1873 6) homogeneous in the region r = a to m The energies may be obtained from tabulations of X , quantities or from the sum which is relatively rapidly converging for all media of interest. E.g., for eB = 120, only one sum term is required for better than 1 part in 1000 accuracy for AAG,' with 6 = 0.001 and five terms if 6 = 0.01; for cB = 10 to the same accuracy, one and three terms, respectively, are required with these &values. Similar but slightly more complicated expressions can also be derived for multiregion solvents with each or some regions approaching homogeneity in the limit of vanishing 6.