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Thermal Decomposition of Hydrogen Peroxide in the Vapour Phase


Baker and Ouellet1 reported that when they boiled 98 per cent hydrogen peroxide solution at 100° C. and passed the vapour at pressures varying between 3 and 18 cm. of mercury through a wide Pyrextube heated to 335° C., they got no explosion even when they passed an electric discharge along the tube or caused a piece of cotton to burn in the gas. We find that, in a 3-cm. diameter Pyrexâtube at 100° C., thermal decomposition flames and explosions are very readily initiated by a hot wire or a spark when the pressure is about 2 cm. of mercury or higher. At atmospheric pressure the explosion is very violent and is initiated by catalytic spots on imperfectly cleaned glass. The minimum temperature to which a wire must be heated to cause immediate ignition of the gas at atmospheric pressure has been roughly determined to be about 600° C. Thus, hydrogen peroxide seems similar in its behaviour in the vapour phase to the di-alkyl peroxides with which Harris2 obtained thermal explosions. These compounds, unlike hydrogen peroxide, decompose entirely homogeneously below 170° C., the temperature around which the explosions occur. The results of the latest workers with hydrogen peroxide are not in complete agreement on this point. Giguére3 reports no slow thermal decomposition at temperatures as high as 420° C.; but Mackenzie and Ritchie4 are of the opinion that their results may indicate an appreciable gas-phase reaction in the upper part of their temperature range (namely, 82–137° C.).

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  1. Baker and Ouellet, Can. J. Res., 23 B, 167 (1945).

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  2. Harris, Proc. Roy. Soc., A, 175, 254 (1940).

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  3. Giguére, Can. J. Res., 25 B, 135 (1947).

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  4. Mackenzie and Ritchie, Proc. Roy. Soc., A, 185, 207 (1946).

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  5. Midard, C.R. Acad. Sci., Paris, 222, 1491 (1946).

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HART, A. Thermal Decomposition of Hydrogen Peroxide in the Vapour Phase. Nature 163, 876–877 (1949).

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