The Rate Constants for H and D-Atom Additions to O2, NO, Acetylene, and 1,3-Butadiene

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Abstract
Pulse radiolysis has been combined with Lyman-α absorption spectroscopy for the measurement of absolute rate constants for the addition reactions of H and D-atoms to oxygen, nitrogen monoxide, acetylene-d0 and -d2, and 1,3-butadiene at room temperature. The rate constants obtained with O2 and NO were in good agreement with the results previously reported and no H/D isotope effect was found. With acetylenes and 1,3-butadiene, the following rate constants were obtained (units of cm3 molecule−1 s−1): (3.8±0.4)×10−13 for H+C2H2; (2.6±0.2)×10−13 for D+C2H2; (3.8±0.2)×10−13 for H+C2D2; (2.5±0.2)×10−13 for D+C2D2; (8.5±1.5)×10−12 for H+1,3-C4H6; (7.5±0.6)×10−12 for D+1,3-C4H6. These results are compared to previous studies, and the H/D isotope effect discussed.