Abstract

An investigation has been made of the mercury (3P1) photosensitized reactions of ethylene. In addition to hydrogen and acetylene the main products are butene, butane and hexenes. The variation of the rate with the pressure of ethylene suggests that a deactivation process is involved, the initial process being of the type C2H4+Hg(3P1)→C2H4*+Hg(1S0)followed by C2H4*+C2H4→2C2H4.or C2H4*→C2H2+H2.Polymerization arises largely by a free radical mechanism and butane is formed by the reactionsH2+Hg(3P1)→2H+Hg(1S0)H+C2H4→C2H52C2H5→C4H10.The mechanism is shown to be consistent with the value found for the quantum yield.

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