The kinetics of oxygen evolution on warming the trapped products (at −196 °C) from water or hydrogen peroxide vapor dissociated in a glow discharge were studied by the manometric method. Under closely controlled conditions it was possible to distinguish clearly the decomposition of the two intermediates, H2O3 and H2O4. The latter begins to decompose measurably following crystallization of the glassy solid at about −115°; the trioxide decomposes readily between −50 and −35°. Typically, the yields of H2O3 from dissociated water vapor were of the order of 3 to 5 mol%; those of H2O4, only about one-tenth as much. Varying the distance between the microwave discharge and the cold trap was found to affect differently the yields of the various products. Those of water and peroxide showed a simple, direct correlation; the minor constituents H2O3 and H2O4 followed entirely different patterns. Only a small fraction of the peroxide is formed via the H2O4 intermediate in these systems. Less water, and more of the higher oxides, were obtained from dissociated hydrogen peroxide than from water vapor.The deuterated systems showed some unusual isotope effects. The yields of D2O3 were always higher (up to twice and even more) than those of H2O3 under similar conditions. The other products showed little or no such effect, except for occluded oxygen and ozone which decreased by about half. Finally, the deuterium polyoxides decompose at slightly higher temperatures (10 to 15°) than their hydrogen analogs. Mechanisms are proposed for the formation and decomposition of the polyoxides.
