| Abstract: | The reactions of OH radical with Cl?, Br?, I?, and F? ions have been studied by entrapping the product radicals as polymer endgroup which have been detected and estimated by the sensitive dye partition technique. The rate constants of the reactions with Br?, Cl?, and F? ions have been determined to be 1.51 × 109, 1.32 × 109, and 0.92 × 109 L mol?1 s?1, respectively at 25°C and pH 1.00. Oxidation of I? ions liberates I, which inhibits the polymerization and the reaction could not be followed by polymer endgroup analysis. The observed order of reactivity Br? > Cl? > F? is in accordance with the electron affinities of the halide ions. The acidity of the reaction medium has a strong influence on the rate of reaction. With Br? ions, the rate constant of the reaction falls from 1.51 × 109 to 0.75 × 109 L mol?1 s?1 at 25°C as the pH is raised from 1.0 to 2.8. The method is simple and accurate and can be applied to study very reactive radicals. |
