The temperature dependence of the rate coefficients for β-hydroxyperoxy radical self reactions

A laser-flash photolysis/UV absorption technique has been used to study the temperature dependence (from T = 300 - 470 K) of the self-reaction kinetics of representative primary secondary and tertiary β-hydroxyperoxy radicals The following Arrhenius expressions were derived for the rate coefficients of reactions (1)-(3) (in cm³ molecule ⁻¹s⁻¹) and for the product branching ratios of reactions (1) and (2) as a function of temperature (all errors 1σ) The calculated rate coefficients for reactions (1)-(3) at 298 K are therefore (in 10⁻¹³ cm³molecule ⁻¹s ⁻¹ 23 ± 2, 6.7 ± 1.3, and 0.040 ± 0.012, respectively which compare well with the values measured elsewhere at this temperature using a similar technique. The product branching ratios and the Arrhenius parameters are compared with those for other substituted and unsubstituted peroxy radical self reactions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 323–331, 1997