Baesman, S.M., and Miller, L.G., 2005, Laboratory determination of the carbon kinetic isotope effects (KIEs) for reactions of methyl halides with various nucleophiles in solution: Journal of Atmospheric Chemistry, v. 52, no. 2, p. 203-219.

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).