Journal of Atmospheric Chemistry

, Volume 52, Issue 2, pp 203-219

First online:

Laboratory Determination of the Carbon Kinetic Isotope Effects (KIEs) for Reactions of Methyl Halides with Various Nucleophiles in Solution

  • Shaun M. BaesmanAffiliated withU.S. Geological Survey
  • , Laurence G. MillerAffiliated withU.S. Geological Survey Email author 

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Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H2O (neutral hydrolysis) or Cl (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ± 6%0 for MeBr and 38 ± 8%0 for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl and MeCl substitution with Br (57 ± 5 and 60 ± 9%0, respectively). The KIE for halide exchange of MeI was lower overall (33 ± 8%0) and was greater for substitution with Br (46 ± 6%0) than with Cl (29 ± 6%0).


abiotic fractionation kinetic isotope effects methyl halides