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

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Abstract

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).

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  1. U.S. Geological Survey, Menlo Park, CA, 94025, USA

    Shaun M. Baesman & Laurence G. Miller

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  1. Shaun M. Baesman
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Correspondence to Laurence G. Miller.

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Baesman, S.M., Miller, L.G. Laboratory Determination of the Carbon Kinetic Isotope Effects (KIEs) for Reactions of Methyl Halides with Various Nucleophiles in Solution. J Atmos Chem 52, 203–219 (2005). https://doi.org/10.1007/s10874-005-1904-0

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  • DOI: https://doi.org/10.1007/s10874-005-1904-0

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