CHRONOPOTENTIOMETRIC MEASUREMENTS OF CHEMICAL REACTION RATES .2. KINETICS AND MECHANISM OF DEHYDRATION OF P-HYDROXYPHENYLHYDROXYLAMINE

Current-reversal chronopotentiometry, chronoamperometry, and chronocoulometry have been applied to the elucidation of the kinetics and mechanism of the dehydration of p-hydroxyphenylhydroxylamine, the reactive intermediate in the p-nitrosophenol system which enjoys widespread use as a model system for verification of ECE theories. Specific acid and general base catalysis were established for the system. Solvent studies, substituent effects, and thermodynamic activation parameters deduced from the temperature dependence of the reaction provided evidence for mechanisms proposed here.