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The polymerization of acrylamide initiated by ceric nitrate and 3‐chloro‐1‐propanol was studied in aqueous solution at 25°C. At constant hydrogen ion and nitrate ion concentration, the rate of polymerization was found to be independent of the ceric ion concentration. The molecular weight of the polymer was very low. To explain the data, a kinetic scheme is proposed whereby ceric ions are responsible for both initiation and termination. The rate constant for oxidative termination was found to be of the order of 105 l. mole−1 sec.−1 and varied with the hydrogen ion and the nitrate ion concentrations.

The rate of reaction of ceric nitrate with the 1,2‐glycol units and the alcohol units of polyvinyl alcohol was determined at 20°C. It was found that the glycol units are oxidized much faster than the alcohol units even though they are outnumbered about one hundred to one in the polymer chain. Under the conditions studied, at least 83 glycol units reacted per 100 hours oxidized. Since the oxidation of the glycol units is accompanied by chain splitting, the free radicals are produced predominantly at the fragments end.

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