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QOOH radicals are key species in autoignition, produced by internal isomerizations of RO 2 radicals, and are central to chain branching reactions in low-temperature combustion. The kinetics of QOOH radical decomposition and reaction with O 2 have been determined as a function of temperature and pressure, using observations of OH radical production and decay following H-atom abstraction from  -butyl hydroperoxide ((CH 3 ) 3 COOH) by Cl atoms to produce QOOH (CH 2 (CH 3 ) 2 COOH) 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 O 2 have been investigated as a function of temperature (251-304 K) and pressure (10-100 Torr) in He and N 2 . 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 O 2 was determined to be (5.6 ± 1.7) × 10 -13 cm 3 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 cm 3 s -1 and E  a = -(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.

the journal of physical chemistry a

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O2: Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH3)3COOH