<?xml version='1.0' encoding='utf-8'?>
<oai_dc:dc xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:oai_dc="http://www.openarchives.org/OAI/2.0/oai_dc/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xsi:schemaLocation="http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd">
  <dc:contributor>L.G. Miller</dc:contributor>
  <dc:creator>S.M. Baesman</dc:creator>
  <dc:date>2005</dc:date>
  <dc:description>&lt;p class="Para"&gt;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 H&lt;sub&gt;2&lt;/sub&gt;O (neutral hydrolysis) or Cl&lt;sup&gt;−&lt;/sup&gt;&lt;span&gt;&amp;nbsp;&lt;/span&gt;(halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ± 6%&lt;sub&gt;0&lt;/sub&gt;&lt;span&gt;&amp;nbsp;&lt;/span&gt;for MeBr and 38 ± 8%&lt;sub&gt;0&lt;/sub&gt;&lt;span&gt;&amp;nbsp;&lt;/span&gt;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&lt;sup&gt;−&lt;/sup&gt;. 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&lt;sup&gt;−&lt;/sup&gt;&lt;span&gt;&amp;nbsp;&lt;/span&gt;and MeCl substitution with Br&lt;sup&gt;−&lt;/sup&gt;&lt;span&gt;&amp;nbsp;&lt;/span&gt;(57 ± 5 and 60 ± 9%&lt;sub&gt;0&lt;/sub&gt;, respectively). The KIE for halide exchange of MeI was lower overall (33 ± 8%&lt;sub&gt;0&lt;/sub&gt;) and was greater for substitution with Br&lt;sup&gt;−&lt;/sup&gt;&lt;span&gt;&amp;nbsp;&lt;/span&gt;(46 ± 6%&lt;sub&gt;0&lt;/sub&gt;) than with Cl&lt;sup&gt;−&lt;/sup&gt;&lt;span&gt;&amp;nbsp;&lt;/span&gt;(29 ± 6%&lt;sub&gt;0&lt;/sub&gt;).&lt;/p&gt;</dc:description>
  <dc:format>application/pdf</dc:format>
  <dc:identifier>10.1007/s10874-005-1904-0</dc:identifier>
  <dc:language>en</dc:language>
  <dc:publisher>Springer</dc:publisher>
  <dc:title>Laboratory determination of the carbon kinetic isotope effects (KIEs) for reactions of methyl halides with various nucleophiles in solution</dc:title>
  <dc:type>article</dc:type>
</oai_dc:dc>