| Abstract: | The kinetics of oxidation of ethanolamines, monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA), by sodium N‐bromobenzenesulfonamide or bromamine‐B (BAB) in alkaline buffer medium (pH 8.7–12.2) has been studied at 40°C. The three reactions follow identical kinetics with first‐order in oxidant] and fractional‐order each in substrate] and OH?]. Under comparable experimental conditions, the rate of oxidation increases in the order: DEA > TEA > MEA. The added reaction product, benzenesulfonamide, retards the reaction rate. The addition of halide ions and the variation of ionic strength of the medium have no significant effect on the rate. The dielectric effect is negative. The solvent isotope effect k′(H2O)/k′(D2O) ≈ 0.92. Activation parameters for the composite reaction and for the rate‐limiting step were computed from the Eyring plots. Michaelis‐Menten type of kinetics is observed. The formation and decomposition constants of ethanolamine‐BAB complexes are evaluated. An isokinetic relationship is observed with β = 430 K indicating that enthalpy factors control the rate. For each substrate, a mechanism consistent with the kinetic data has been proposed. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 480–490, 2001 |
