Study of the Kinetics and Mechanisms of Alkoxy Radical Reactions in the Gas Phase (￥°). Arrhenius Parameters for t-Butoxy Radical Reactions with Isobutane and Cyclohexane

摘要

The relative Arrhenius parameters for t-butoxy radical decomposition (log Ad, Ed) and hydrogen abstraction of t-butoxy radical from hydrogen donor (log Aa, Ea) by competitive method were obtained as follows: for cyclohexane; log Aa/Ad = -4.17 mole/l and Ed - Ea = 9.01 kcal/mole, for isobutane; log Aa/Ad = -5.70 mole/l and Ee - Ea = 11.0 kcal/moIe. From the reported Arrhenius parameters for t-Butoxy radical decomposition reactions the parameters for t-Butoxy radical reactions with isobutane and cyclohexane are estimated to be log A(l/mol·sec) = 8.4, Ea = 4.3 kcal/mol and log A (l/mol·sec)= 9.9, Ea = 6.3 kcal/mol, respectively.