Unimolecular Decomposition of Chemically Activated sec-Deuterobutyl Radicals from D Atoms plus cis-Burene-2

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Abstract
Chemically activated sec‐deuterobutyl radicals were produced at 25°C by the reaction of D atoms with cis‐butene‐2. These vibrationally excited species contain an increment of energy above that of the corresponding light radicals as formed from H plus cis‐butene‐2 in a previous study [B. S. Rabinovitch and R. W. Diesen, J. Chem. Phys. 30, 735 (1959)]. Apparent rate constants for the unimolecular decomposition to propylene of the deuterobutyl radicals were obtained as a function of pressure, relative to the collision induced stabilization process. Theoretical values for the rate constants at the limits of high and low pressures were calculated using a direct count for the density of vibrational energy levels. The calculated and experimental results are compared with one another, and with the results of the previous study of the sec‐butyl radical decomposition. The expected energy effect is observed; the deuterobutyl radicals appear slightly more monoenergetic than the equivalent nondeuterated species.

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