synopsisThe quantitative theory of the f-radical mechanism in emulsion polymerization is reexamined. A mechanism involving desorption and reabsorption of radicals is discuased.The average number of radicals per particle has been calculated as a function of three parameters. A simplified, approximate solution for the average number of radicals per particle is given for cases where this number is low.

A stable algorithm for reducing a symmetric, non-definite matrix of order n to tridiagonal form, involving about n3/6 additions and multiplications is presented. L m 3 J

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Expressions for calculating the stationary state distribution of radicals in compartmentalized systems with a constant number of reaction loci containing an oil‐soluble initiator are given. Besides pairwise formation of radicals in the particles, desorption and reabsorption, water phase termination, solubility of the initiator in the aqueous phase, and the possibility of formation of a single radical species are taken into consideration. The calculation is based on a probabilistic analysis leading to a third‐order recurrence relation solved using confluent, hypergeometric Kummer functions. Some calculated curves illustrating the de‐pendence of the average number of radicals per particle on various relevant parameters are included. © 1995 John Wiley & Sons, Inc.

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