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The kinetics and pressure dependence of the reactions of NO, with CH, and CH,O have been investigated in the gas phase at 298 K, at pressures from 1 to 10 Torr. A low-pressure discharge-flow laser-induced fluorescence (LIF) technique was used. In a consecutive process, CH, reacted with NO, to form CH,O, CH, + NO, + CH,O + NO (l), which further reacted with NO, to form products, CH30 + NO, + products (2). Reaction (1) displayed Paper 3/04404A;

We have determined the rate constants for the reactions IO + CH3O2 --> Products (1) and IO + CF3O2 --> Products (2) using a discharge-flow tube equipped with off-axis cavity-enhanced absorption spectroscopy (CEAS) for the detection of IO. NO2, produced from the titration of RO2 with NO, was also detected using the CEAS system. The rate constants obtained were k1 = (6.0 +/- 1.3) x 10(-11) cm3 molecule(-1) s(-1) and k2 = (3.7 +/- 0.9) x 10(-11) cm3 molecule(-1) s(-1) at T = 295 +/- 2 K and P = 2.5 +/- 0.3 Torr; this is the first determination of these rate constants. The possible products and the atmospheric implications of reaction (1) are discussed.

Concern has been expressed over the use of the halogenated anaesthetics halothane (CF3CClBrH), enflurane (CF2HOCF2CFClH) and isoflurane (CF2HOCHClCF3) because of their potential for stratospheric ozone destruction. Halogenated species also contribute to global warming. The significance of the anaesthetics in stratospheric ozone loss or in 'greenhouse' heating depends on their atmospheric lifetimes. Because reaction with hydroxyl (OH) radicals is likely to be the main homogeneous sink for these species in the troposphere, we have measured absolute rates of reaction with OH. Comparison with a one-dimensional model indicates that the lifetimes of halothane, enflurane and isoflurane with respect to this reaction are 2, 6 and 5 years, respectively. Thus the small production of the anaesthetics is not offset by anomalously long atmospheric lifetimes to give a large atmospheric burden of the compounds. The anaesthetics will contribute at most a fraction of approximately 5 x 10(-4) to the total atmospheric content of chlorine-containing species.