Formation of H and D atoms in pyrolysis of 1,3‐butadiene and 1,3 butadiene‐1,1,4,4,‐d4 behind shock waves

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Abstract
Highly dilute mixtures of 1,3‐butadiene and 1,3‐butadiene‐1,1,4,4‐d4 were pyrolyzed behind reflected and incident shock waves, respectively. Concentrations of H and D atoms were measured by resonance absorption spectroscopy. In the early stages of the reaction, nearly equal amounts of H and D were formed from CD2CHCHCD2, indicating that loss of H from C2 followed by loss of D from C1 is a more important reaction than breaking of the central CC bond. Overall, rate constants for atom‐forming reactions are much slower than rate constants for disappearance of butadiene in earlier experiments, suggesting that most of the butadiene disappears by processes that do not involve H or D atoms or by radicals that produce them rapidly.