The Neutral Hydrolysis of the Methyl Halides

The rate of hydrolysis of methyl chloride, methyl bromide and methyl iodide have been measured in water over a wide range of temperature by a conductance method. The tempera­ture dependence of the rate was shown to conform to an equation of the general form log10 k = A/T + B log10 T + C within exper...

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Bibliographic Details
Published in:Proceedings of the Royal Society of London. Series A, Mathematical and physical sciences Mathematical and physical sciences, 1959-09, Vol.252 (1269), p.273-285
Main Authors: Heppolette, R. L., Robertson, R. E.
Format: Article
Language:English
Subjects:
Bromides
Chlorides
Enthalpy
Halides
Hydrolysis
Iodides
Ionization
Molecules
Solutes
Solvation
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Summary:The rate of hydrolysis of methyl chloride, methyl bromide and methyl iodide have been measured in water over a wide range of temperature by a conductance method. The tempera­ture dependence of the rate was shown to conform to an equation of the general form log10 k = A/T + B log10 T + C within experimental error. This implies that d∆Cp/dT = 0. By combining thermodynamic parameters derived from these data for the activation process with the corresponding terms for the gas-solution process and those for the gas phase, ‘absolute’ parameters for the transition state have been determined. A re-examination of the probable mechanism of hydrolysis is made in terms of a hypo­thetical gaseous ionization and the probable contribution of interaction of the water with the quasi-ionic transition state.
ISSN:1364-5021
0080-4630
1471-2946
2053-9169
DOI:10.1098/rspa.1959.0152