Long-Lasting Complex Reaction Behavior in a Closed Ferroin-Bromate-Hydroxybenzenesulfonate System

The bromate-phenolsulfonate reaction was found to exhibit spontaneous oscillations in a batch reactor, where the addition of small amounts of ferroin would result in nonoscillatory behavior. As the ferroin concentration was increased, the system produced very rich nonlinear behavior, including three isolated oscillatory regimes that were separated by as long as 48 h nonoscillatory period. The long-lasting nonlinear behavior may be attributed to the slow desulfonation of phenolsulfonate in an acidic solution, forming phenol-like intermediates. However, unlike the bromate-phenol oscillator, oxygen was found to greatly influence the reaction, and various complex oscillations could be observed by tuning the oxygen concentration. Mechanistic studies performed through employing ¹H NMR spectroscopy and mass spectrometry to measure intermediate species at different stages of the reaction were able to identify 1,4-benzoquinone, 2-bromo-1,4-benzoquinone, 2,6-dibromo-1,4-benzoquinone, and 2,4,6-tribromophenol as major components during the reaction.