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

Autor:	D. L. Singleton, S. Furuyama, R. J. Cvetanović, Robert S. Irwin
Rok vydání:	1975
Předmět:	Arrhenius equation Chemistry Analytical chemistry General Physics and Astronomy Thermodynamics Entropy of activation Activation energy Atmospheric temperature range Decomposition Least squares Arrhenius plot symbols.namesake Reaction rate constant symbols Physical and Theoretical Chemistry
Zdroj:	The Journal of Chemical Physics. 63:1003-1007
ISSN:	1089-7690 0021-9606
Popis:	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.
Databáze:	OpenAIRE
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