Photochemical Primary Process in Biacetyl Vapor at 4358 A

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Abstract
At 4358 A at room temperature the quantum yield for the primary dissociation of biacetyl increases with intensity. It is thus implied that the primary process is second order in some active species. By use of the rotating sector it is shown that the species responsible for this effect has a mean life close to that ascribed to an excited triplet state for biacetyl. At higher temperatures this intensity effect disappears and one of the products strongly inhibits both the phosphorescence and the primary dissociation. At these temperatures the data may best be treated by assuming that the triplet state of biacetyl undergoes a unimolecular dissociation with an activation energy of about 15 kcal.