Abstract
Photoactivation of methane has been kinetically studied in the CH4–NH3–H2O mixture, and the radical intermediates measured by the spin trap (PBN, α-phenyl-N-tert-butylnitrone)–EPR method. The trapped radicals were CH3O˙(aN= 1.35, aHβ= 0.20 mT), ˙CH2NH2(aN= 1.46, aHβ= 0.26 mT), and ˙CHNH (aN= 1.48, aHβ= 0.62 mT). It was suggested that ˙CH2NH2 was mainly provided by H abstraction from methylamine and the photolysis of CH3NH2 to CH3NH˙ and ˙CH2NH2 was low. The coupling of ˙CH2NH2 led to the formation of ethylenediamine, while CH3NH˙ decayed to CH2NH from which the ˙CHNH radical was generated by the H elimination. The water photolysis proceeded with a quantum yield of 0.06 in the gas mixture.
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