Acetonyl Peroxy and Hydro Peroxy Self- and Cross-Reactions: Kinetics, Mechanism, and Chaperone Enhancement from the Perspective of the Hydroxyl Radical Product.

Pulsed laser photolysis coupled with infrared (IR) wavelength modulation spectroscopy and ultraviolet (UV) absorption spectroscopy was used to study the kinetics and branching fractions for the acetonyl peroxy (CH3C(O)CH2O2) self-reaction and its reaction with hydro peroxy (HO2) at a temperature of 298 K and pressure of 100 Torr. Near-IR and mid-IR lasers simultaneously monitored HO2 and hydroxyl, OH, respectively, while UV absorption measurements monitored the CH3C(O)CH2O2 concentrations. The overall rate constant for the reaction between CH3C(O)CH2O2 and HO2 was found to be (5.5 +/- 0.5) X 10(-12) cm(3) molecule(-1) s(-1), and the branching fraction for OH yield from this reaction was directly measured as 0.30 +/- 0.04. The CH3C(O)CH2O2 self-reaction rate constant was measured to be (4.8 +/- 0.8) X 10(-12) cm(3) molecule(-1) s(-1), and the branching fraction for alkoxy formation was inferred from secondary chemistry as 0.33 +/- 0.13. An increase in the rate of the HO2 self-reaction was also observed as a function of acetone (CH3C(O)CH2O2 ) concentration which is interpreted as a chaperone effect, resulting from hydrogen-bond complexation between HO2 and CH3C(O)CH3. The chaperone enhancement coefficient for CH3C(O)CH2O2 was determined to be k(A)'' = (4.0 +/- 0.2) x 10(-29) cm(6) molecule(-2) s(-1), and the equilibrium constant for HO2 center dot CH3C(O)CH2O2 complex formation was found to be k(c)(R14) = (2.0 +/- 0.89) X 10(-18) cm(3) molecule(-1); from these values, the rate constant for the HO2 + HO2 center dot CH3C(O)CH3 reaction was estimated to be (2 +/- 1) X 10(-11) cm(3) molecule(-1) s(-1). Results from UV absorption cross-section measurements of CH3C(O)CH2O2 and prompt OH radical yields arising from possible oxidation of the CH3C(O)CH3-derived alkyl radical are also discussed. Using theoretical methods, no likely pathways for the observed prompt OH radical formation have been found and the prompt OH radical yields thus remain unexplained.