HIGH CONCENTRATION-RATIO TECHNIQUE: ISOTOPE FRACTIONATION AT THE METHYL CARBON IN THE REACTION OF CYANIDE ION AND METHYL IODIDE. ISOTOPE EFFECT UNDER CONDITIONS OF EQUAL REAGENT CONCENTRATIONS
The C/sup 13/ isotope effect for the methyl carbon atom was measured in the cyseization of methyl iodide in water solution between 11.4 and 58.0 deg . As a check on these results and those previously reported for isotope fractionation at the cyanide carbon atom, experiments were carried out also in which the reagents were present at equal concentrations instead of one being in large- excess; the check experiments yield data of considerably higher quality than either set obtained under high concentrationratio conditions. There is general agreement among the three sets of results, but it is not sufficiently close to permit detailed speculations concerning the nature of the reaction coordinate motion in tests of simple models. The methyl carbon isotope effect in the cyanization is much linser than that observed in the related hydrolysis, a fact which cannot be explained unless account is taken of the details of activation changes in C-H bonding. (auth)
- Research Organization:
- Illinois. Univ., Urbana. Noyes Lab. of Chemistry
- NSA Number:
- NSA-14-022808
- OSTI ID:
- 4166540
- Report Number(s):
- TID-6344
- Country of Publication:
- United States
- Language:
- English
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