As a basis for understanding emulsion polymerization, the kinetics of free radical reactions in isolated loci is discussed subject to the condition that the free radicals are supplied to the loci from an external source. Three cases of interest are considered: that in which the average number of free radicals per locus is small compared with unity, that in which this number approximates one-half, and that in which the number is large. Of these three possibilities, the second, in which the free radicals per locus approximate one-half, is by far the most interesting as it explains in a satisfactory manner the characteristic features of styrene emulsion polymerization. For this case the average rate of reaction per locus is independent of the size of the locus, since this rate is simply one-half the rate of polymerization of a single free radical. Thus the rate of emulsion polymerization, the concentration of monomer in the loci, and the number of loci present provide the information needed for calculating the chain propagation constant for the monomer. A simplified treatment is given for approximating the number of reaction loci (polymer particles) produced in emulsion polymerization when the rate of polymerization per locus is constant (see case 2 above). The law obtained indicates that the number of particles should increase with the soap concentration (3/5ths power) and with the rate of formation of free radicals (2/5ths power), but should decrease with increasing rate of growth of the free radicals (−2/5ths power).

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The theory of scattering by an inhomogeneous dielectric medium has been extended so as to account for the turbidimetric behavior of polymer solutions in solvent-precipitant mixtures. It is predicted by this theory and verified by experiment that correct values of molecular weight are obtained by the usual interpretation of turbidity measurements if and only if the solvent and precipitant have the same refractive index. The practical utility of turbidimetry in high polymer solutions is shown to be greatly increased by the proper use of solvent-precipitant mixtures. If the solvent and precipitant have different refractive indices, scattering measurements give information about the extent of selective absorption of solvent by the polymer.

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