ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of the gas-phase reaction of CH3F with I2 have been studied spectrophotometrically from 629 to 710 K, and were determined to be consistent with the following mechanism: A least-squares analysis of the kinetic data taken in the initial stages of reaction resulted in \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_4 (M^{ - 1} \cdot s^{ - 1}) = (11.3 \pm 0.1) - (30.8 \pm 0.2)/\theta $$\end{document} where θ = 4.575T/1000 kcal/mol. The errors represent one standard deviation. The experimental activation energy E4 = 30.8 ± 0.2 kcal/mol was combined with the assumption E3 = 1 ± 1 kcal/mol and estimated heat capacities to obtain \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta H_r^\circ (4,g,298K) = 30.0 \pm 1{\rm kcal}/{\rm mol} $$\end{document} The enthalpy change at 298 K was combined with selected thermochemical data to derive \documentclass{article}\pagestyle{empty}\begin{document}$$ DH^\circ ({\rm CH}_{\rm 2} {\rm F} - {\rm H}) = 101.2 \pm 1{\rm kcal/mol} $$\end{document} The kinetic studies of ĊHF2 and CH2F2 have been reevaluated to yield \documentclass{article}\pagestyle{empty}\begin{document}$$ DH^ \circ \left( {{\rm CHF}_{\rm 2} - {\rm H}} \right) = 103.2 \pm 1\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}} $$\end{document} These results are combined with literature data to yield the C—H, C—F, and C—Cl bond dissociation energies in their respective fluoromethanes, and the effect of α-fluorine substitution is discussed.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550150607
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