Characterization of a manganese-catalyzed bromate-driven oscillator within the < sup> 1 H NMR framework

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The oscillating behavior of Mn2+ in a manganese-catalyzed bromate-driven oscillator with methylmalonic acid as the organic substrate is shown to induce corresponding oscillations in the following NMR parameters: chemical shift, line width, and the spin-lattice relaxation rate of the solvent water protons. The induction period and period lengths derived from such NMR experiments are found to be in qualitative agreement with results obtained by potentiometric measurements. One major advantage with the NMR technique is the potential of monitoring the NMR absorption of the organic species to follow the degradation of methylmalonic acid to bromomethylmalonic acid and acetic acid in situ as the oscillations proceed. The sum of the concentrations of these three species is found to be constant, as suggested by earlier measurements. A value for the enolization rate constant of methylmalonic acid is determined ((4.87 ± 0.29) × 10-5 s-1) and found to be in agreement with previous values. © 1989 American Chemical Society.

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Journal of Physical Chemistry