Abstract
This paper reports how free radicals generated in a liquid phase cross the boundary to an adjacent immiscible liquid phase as a function of the concentration of added surfactant. The yields of this crossing process are evaluated. If non-ionic free radicals are generated in the organic phase, this yield decreases with increasing occupation of the interphase by the surfactant, without vanishing however at saturation point. On the other hand, if ionic radicals are generated in an aqueous phase containing surfactant, transfer occurs generating non-ionic free radicals which, in turn, cross the interface more easily being insensitive to the Helmholtz electric double layer. If the organic phase contains styrene, the crossing free radicals form polystyrene which appears to be a mixture of two types of product, viz, a normal product for which DP is calculable in a classical kinetic manner, and another with very small DP which may result from the combination of growing polystyrene chains having their — OSO 3K ends bound at the interface.
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