Temperature dependence of the rate constants for the reactions O(3P) + 2,3-dimethyl-2-butene and O(3P) + NO + M determined by a phase shift technique

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Abstract
Absolute values of the rate constant k2 for the reaction of O(3P) atoms with 2,3-dimethyl-2-butene are determined over the temperature range 298–481 °K using modulated photosensitized decomposition of N2O to generate O(3P) atoms. The rate constants obtained from the phase shift measurements fit the Arrhenius expression, k2 = (1.24±0.12) ×1010 exp(774±76 cal mole−1/RT) in units of l mole−1⋅sec−1. The indicated uncertainties are least squares standard deviations. Possible explanations for the negative Arrhenius activation energy are reviewed. Also, the rate constant k3 for the reaction O(3P) + NO + M is redetermined for M=N2O. Over the temperature range 298–473 °K, the results fit the Arrhenius expression, k3 = (6.12±0.45) ×109 exp(1230±55 cal mole−1/RT), where the units are l2 mole−2⋅sec−1 and the uncertainties are the least squares standard deviations.

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