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The reaction of CH3C(O)CH2O2 with HO2 has been studied at 296 K and 700 Torr using long path FTIR spectroscopy, during photolysis of Cl2/acetone/methanol/air mixtures. The branching ratio for the reaction channel forming CH3C(O)CH2O, OH and O2 (reaction (3b)) was investigated in experiments in which OH radicals were scavenged by addition of benzene to the system, with subsequent formation of phenol used as the primary diagnostic for OH radical formation. The observed prompt formation of phenol under conditions when CH3C(O)CH2O2 reacts mainly with HO2 indicates that this reaction proceeds partially by channel (3b), which forms OH both directly and indirectly, by virtue of secondary generation of CH3C(O)O2 (from CH3C(O)CH2O) and its reaction with HO2 (reaction (6c)). The secondary generation of OH radicals was confirmed by the observed formation of CH3C(O)OOH, a well-established product of the CH3C(O)O2 HO2 reaction (via channel (6a)). A number of delayed sources of OH also contribute to the observed phenol formation, such that full characterisation of the system required simulations using a detailed chemical mechanism. The dependence of the phenol and CH3C(O)OOH yields on the initial peroxy radical precursor reagent concentration ratio, [methanol]0/[acetone]0, were well described by the mechanism, consistent with a small but significant fraction of the reaction of CH3C(O)CH2O2 with HO2 proceeding via channel (3b). This allowed a branching ratio of k3b/k3 = 0.15 ± 0.08 to be determined. The results therefore provide strong indirect evidence for the participation of the radical-forming channel of the title reaction. [ABSTRACT FROM AUTHOR]

FTIR smog chamber techniques and ab initio calculations have been used to investigate the kinetics and mechanism of the reaction of Cl atoms with i-propanol in 700 Torr of N2 at 296 K. The reaction is observed to proceed with a rate constant of k1 = (8.28 ± 0.97) × 10−11 cm3 molecule−1 s−1 and gives CH3C(OH)CH3 and CH3CH(OH)CH2 radicals in yields of 85 ± 7 and 15 ± 7%, respectively. Calculations indicate that abstraction of the secondary H can proceed through a lower energy pathway than the primary. Rapid decomposition of the chlorination product CH3CCl(OH)CH3 complicates its direct detection, likely due to heterogeneous chemistry. IR spectra for the chlorides CH3CCl(OH)CH3 and CH3CH(OH)CH2Cl were inferred experimentally and assignments confirmed via comparison with ab initio computed spectra. [ABSTRACT FROM AUTHOR]

The reaction of CH3C(O)O2 with HO2 has been investigated at 296 K and 700 Torr using long path FTIR spectroscopy, during photolysis of Cl2/CH3CHO/CH3OH/air mixtures. The branching ratio for the reaction channel forming CH3C(O)O, OH and O2 (reaction (3c)) has been determined from experiments in which OH radicals were scavenged by addition of benzene to the system, with subsequent formation of phenol used as the primary diagnostic for OH radical formation. The dependence of the phenol yield on benzene concentration was found to be consistent with its formation from the OH-initiated oxidation of benzene, thereby confirming the presence of OH radicals in the system. The dependence of the phenol yield on the initial peroxy radical precursor reagent concentration ratio, [CH3OH]0/[CH3CHO]0, is consistent with OH formation resulting mainly from the reaction of CH3C(O)O2 with HO2 in the early stages of the experiments, such that the limiting yield of phenol at high benzene concentrations is well-correlated with that of CH3C(O)OOH, a well-established product of the CH3C(O)O2 + HO2 reaction (via channel (3a)). However, a delayed source of phenol was also identified, which is attributed mainly to an analogous OH-forming channel of the reaction of HO2 with HOCH2O2 (reaction (17c)), formed from the reaction of HO2 with product HCHO. This was investigated in additional series of experiments in which Cl2/CH3OH/benzene/air and Cl2/HCHO/benzene/air mixtures were photolysed. The various reaction systems were fully characterised by simulations using a detailed chemical mechanism. This allowed the following branching ratios to be determined: CH3C(O)O2 + HO2→ CH3C(O)OOH + O2, k3a/k3 = 0.38 ± 0.13; → CH3C(O)OH + O3, k3b/k3 = 0.12 ± 0.04; → CH3C(O)O + OH + O2, k3c/k3 = 0.43 ± 0.10: HOCH2O2 + HO2→ HCOOH + H2O + O2, k17b/k17 = 0.30 ± 0.06; → HOCH2O + OH + O2, k17c/k17 = 0.20 ± 0.05. The results therefore provide strong evidence for significant participation of the radical-forming channels of these reactions, with the branching ratio for the title reaction being in good agreement with the value reported in one previous study. As part of this work, the kinetics of the reaction of Cl atoms with phenol (reaction (14)) have also been investigated. The rate coefficient was determined relative to the rate coefficient for the reaction of Cl with CH3OH, during the photolysis of mixtures of Cl2, phenol and CH3OH, in either N2 or air at 296 K and 760 Torr. A value of k14 = (1.92 ± 0.17) × 10−10 cm3 molecule−1 s−1 was determined from the experiments in N2, in agreement with the literature. In air, the apparent rate coefficient was about a factor of two lower, which is interpreted in terms of regeneration of phenol from the product phenoxy radical, C6H5O, possibly via its reaction with HO2. [ABSTRACT FROM AUTHOR]