ISSN:
0894-3230
Keywords:
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The kinetics of the oxidation of six substituted phenethyl alcohols by sodium N-chlorobenzenesulphonamide or chloramine-B (CAB) in the presence of HCl was studied at 35°C. The rate shows a first-order dependence on [CAB]0 and [H+] and is fractional order in [PEA]0 and [Cl-]. Ionic strength variations, addition of reaction product of benzenesulphonamide and variation of the dielectric constant of the medium have no effect on the rate. The solvent isotope effect k1H2O/k1D2O ≅ 0·78. Proton inventory studies were made in H2O-D2O mixtures. The rates correlate satisfactorily with the Hammett linear free energy relationship. The reaction constant ρ was -3 · 5 for electron-releasing and -0·30 for electron-withdrawing groups at 35°C. Activation parameters ΔH*, ΔS*, ΔG* and log A were calculated for the reaction. An isokinetic relationship is observed with β = 338 K, indicating enthalpy as a controlling factor.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
