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ADDITION OF OXYGEN AS A DIAGNOSTIC TEST IN MERCURY 6 (3P1) PHOTOSENSITIZATION

Abstract— Mercury in contact with oxygen is rapidly removed from the gas phase when irradiated with the 253.7 run resonance line. The final, steady‐state concentration of mercury depends on the total pressure, the mol % of oxygen, and the presence (or absence) of mercury droplets in the reaction cell. The effect of oxygen on the mercury photosensitized formation of allene from methylenecyclobutane and trans‐2‐butene from cis‐2‐butene at room temperature was investigated. After correction for competitive quenching, collisional deactivation of the excited methylenecyclobutane, and decreased absorption (due to mercury depletion), the maximum decrease in the allene yield was only 12.3%. This decrease could be caused by the reaction of oxygen atoms or ozone with the product allene. In most of the experiments with mercury‐oxygen‐cis‐2‐butene mixtures, the corrected quantum yield of the trans‐isomer is unchanged from the yield in the absence of oxygen (0.50). Thus oxygen cannot be used to detect the participation of triplet state molecules in mercury photosensitized reactions.