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Specific Rate Coefficients from Vibrational Overtone Activation of 1-Methylcyclopropene.
BOWLING GREEN STATE UNIV OH CENTER FOR PHOTOCHEMICAL SCIENCES
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Laser vibrational overtone activation has been used to investigate the reaction channel competition in the isomerization of 1-methylcyclopropene MCPene. The vibrational overtone activation of three types of CH stretches methyl, methlenic and olefinic in the 5v sub CH and 6v sub CH transitions was initiated and all three products 2-butyne, 1,3-butadiene and 1,2-butadiene were detected by gas chromatography. Stern Volmer plots were constructed for the appearance of each individual product and the derived experimental specific rate coefficients were compared to those of RRKM theory. The rate coefficients at high energy were 10 higher than predicted and those at low energy were 60 to 80 high. Product ratios of 1 ,3-butadiene to 2-butyne were independent of pressure. These ratios were compared to the RRKM ratios. The product yield ratio for the lowest energy photolysis compared well with the RRKM ratio but the two higher energy product yield ratios were approximately 35 lower than the RRKM ratio. The implications of these comparisons are discussed.
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