Large Amplitude pH Oscillation in the Oxidation of Hydroxylamine by Iodate in a Continuous-Flow Stirred Tank Reactor

Article abstract of DOI:10.1021/j100379a038

Large amplitude pH oscillation occurs in the iodate oxidation of hydroxylamine in a continuous-flow tank reactor (CSTR) in a narrow range of flow rates and input concentrations.In addition to pH, the redox potential, the iodide ion concentration, the rate of gas (N2O) formation, and the color of the solution (I2) change periodically.The oscillatory period is extremely long, 2-6 h.The dynamical behaviour of the reaction was modeled by a scheme that takes into account the following component processes: the protonation equilibrium of NH2OH, the dissociation of water,the direct redox reaction between IO3^- and NH3OH⁺, the Dushman reaction between IO3^- and I^-, the autoinhibitory reaction between I2 and NH3OH⁺, the fast dimerization of NOH to N2O, the reaction of NOH with NH2OH, and the volatility of iodine.Empirical rate laws of the component reactions were used successfully to calculate the kinetic behaviour in a closed system, as well as in the CSTR.