Complex dynamical behavior in the oxidation of hydroxylamine by bromate

Complex dynamical behavior has been observed in the oxidation of hydroxylamine by bromate in acidic sulfate medium. The reaction shows clock type kinetics in closed conditions and an aperiodic oscillations if gaseous products are removed from the system with a constant flow‐rate. The reduction kinetics of bromate ions with excess hydroxylamine has been studied in the presence of allyl alcohol. The observed pseudo‐first‐order rate constant kobs has been found to follow the expression \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{{\rm obs}} = \frac{{kK_1 \left[{{\rm H}^ +} \right]\left[{{\rm hydroxylamine}} \right]}}{{\left({1 + {\rm K}_{\rm 1} \left[{{\rm H}^ +} \right]} \right){\rm K}_{\rm 2}}} $$\end{document} where [hydroxylamine] is total initial hydroxylamine concentration, K1 = 0.5 M−1, K2 = 106 M−1, and k = 2.57 × 103 M−1 s−1 at 298.15 K and I = 2.0 M. The rate constant for the bromine oxidation of hydroxylamine in sulfuric aqueous solution has been determined. © 1994 John Wiley & Sons, Inc.