Abstract
The iron-catalyzed Belousov-Zhabotinsky (BZ) oscillating reaction was investigated in an unstirred reactor by combining Br K-edge X-ray absorption and UV-vis spectroscopies. The experimental data were analyzed through an integrated approach based on principal component analysis, multivariate curve resolution, and ab initio theoretical X-ray absorption spectroscopy (XAS), providing quantitative insights into the properties of the key reaction bromine species while contextually tracking the Fe(2+) to Fe(3+) oscillatory transformation. The high-quality XAS experimental data supported by the multivariate and theoretical analyses provide clear-cut evidence of the conversion of bromate, initially predominant in the reaction mixture, to the brominated derivative of the employed allylmalonic acid substrate. The described interdisciplinary method was proven to be valuable to monitor the fate of the main BZ reaction brominated species, which are silent to conventional spectroscopic methods of detection, and the developed approach may support future mechanistic investigations of other oscillatory systems.