Abstract
PREVIOUS work on the photolysis of ozone has led to the conclusion that a simple atom-chain mechanism is incapable of explaining the experimental facts. The existence of an energy chain involving excited oxygen molecules has gained wide acceptance due to the work of Schumacher1, Heidt and Forbes2, and Ritchie3. The nature of the excitation involved in the energy chain was not known, however, most workers assuming it to be the 1σ+g state of the oxygen4. Experiments on the flash photolysis of ozone5 have enabled us to show that the excitation is purely vibrational, the oxygen being formed in the ground electronic state with up to 16 quanta of vibrational energy, by reaction (1) which is exothermic to the extent of 93 kcal./mole for O(3P) and 138 kcal./mole for O(1D).
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References
Schumacher, J. Amer. Chem. Soc., 52, 2377 (1930).
Heidt and Forbes, J. Amer. Chem. Soc., 56, 2365 (1934).
Ritchie, Proc. Roy. Soc., A, 146, 848 (1934).
Noyes and Leighton, “The Photochemistry of Gases” (Reinhold Publishing Corp., New York, 1941).
McGrath and Norrish, Proc. Roy. Soc., A, 242, 265 (1957).
Lipscomb, Norrish and Thrush, Proc. Roy. Soc., A, 233, 455 (1956).
McKinley, Garvin and Boudart, J. Chem. Phys., 23, 784 (1955).
Benson, J. Chem. Phys., 20, 1351 (1957).
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McGRATH, W., NORRISH, R. Production of Vibrationally Excited Oxygen Molecules in the Flash Photolysis of Ozone. Nature 180, 1272–1273 (1957). https://doi.org/10.1038/1801272b0
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DOI: https://doi.org/10.1038/1801272b0
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