Temperature and pressure dependence of the rate coefficient for the reaction between ClO and CH3O2 in the gas-phase.

A temperature and pressure kinetic study for the CH(3)O(2) + ClO reaction has been performed using the turbulent flow technique with a chemical ionisation mass spectrometry detection system. An Arrhenius expression was obtained for the overall rate coefficient of CH(3)O(2) + ClO reaction: k(10)(T) = (1.96(−0.24)(+0.28)) × 10(-11) exp[(-626 ± 35)/T] cm(3) molecule(-1) s(-1) where the uncertainty associated with the rate coefficient is given at the one standard deviation level. Over a range of pressure (100-200 Torr) and temperature (298-223 K) no pressure dependence is observed. The smaller rate coefficients measured at lower temperatures compared with both previous low temperature studies are believed to arise through the reduction of secondary chemistry and greater sensitivity in terms of reactant detection (hence much lower initial concentrations were employed). These new data reduce the effectiveness of ozone loss cycles involving reaction of CH(3)O(2) + ClO in the polar stratosphere by around a factor of 1.5 and restrict the importance of the reaction to the tropical and extra-tropical clean marine environments in the troposphere.

Ozonolysis of organic compounds and mixtures in solution. Part I: Oleic, maleic, nonanoic and benzoic acids.

In this paper, infrared spectroscopic and mass spectrometric studies of the ozonolysis of some simple proxies of precursors to organic materials found in atmospheric aerosols is reported. Oleic and maleic acids are used as proxies of reactive material, containing unsaturation which is amenable to ozonolysis. Nonanoic acid and benzoic acid are utilised as co-reactants which, although not likely to undergo direct ozonolysis themselves, are potential reaction partners to the Criegee radical intermediates formed from oleic and maleic acid ozonolysis. The precursor species are studied as single components in solution, followed by co-reaction studies. The products of the ozonolysis are followed by mass spectrometry and infrared spectroscopy. The product distributions from oleic and maleic acid are broadly in agreement with those observed in other studies. In the co-reaction studies, new evidence for cross-reaction products is obtained. Furthermore, the nature of some of the products does not fully comply with the widely accepted Ziemann scheme.