Abstract
QOOH radicals are key species in autoignition, produced by internal isomerizations of RO2 radicals, and are central to chain branching reactions in low-temperature combustion. The kinetics of QOOH radical decomposition and reaction with O2 have been determined as a function of temperature and pressure, using observations of OH radical production and decay following H-atom abstraction from t-butyl hydroperoxide ((CH3)3COOH) by Cl atoms to produce QOOH (CH2(CH3)2COOH) radicals. The kinetics of QOOH decomposition have been investigated as a function of temperature (251–298 K) and pressure (10–350 Torr) in helium and nitrogen bath gases, and those of the reaction between QOOH and O2 have been investigated as a function of temperature (251–304 K) and pressure (10–100 Torr) in He and N2. Decomposition of the QOOH radical was observed to display temperature and pressure dependence, with a barrier height for the decomposition of (44.7 ± 4.0) kJ mol–1 determined by master equation fitting to the experimental data. The rate coefficient for the reaction between QOOH and O2 was determined to be (5.6 ± 1.7) × 10–13 cm3 s–1 at 298 K, with no significant dependence on pressure, and can be described by the Arrhenius parameters A = (7.3 ± 6.8) × 10–14 cm3 s–1 and Ea = −(5.4 ± 2.1) kJ mol–1 in the temperature range of 251–304 K. This work represents the first measurements of any QOOH radical kinetics as a function of temperature and pressure.