The experiments of Baxendale, Evans and Park5 on the initiation of vinyl polymerization by ferrous ions and hydrogen peroxide provide good evidence for the participation of OH radicals, but steps (2) and (a) have not had similar experimental confirmation.The present experimental investigation of the iron + H,O, system which we now report has revealed several new features incompatible with the details of the Haber and Weiss chain mechanism. A short account of our work has been given elsewhere.6 We conclude that the reaction producing oxygen is not that of HO, with hydrogen peroxide but HO, or 0,' with the ferric ion, and we propose a new chain mechanism with OH, HO, and ferrous ion as carriers. The same chain mechanism interprets sa.tisfactorily many aspects of the ferric ion catalyzed decomposition of hydrogen peroxide, as will be shown in Pa.rt I1 of this work.

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