Batch pH Oscillations in the Belousov-Zhabotinsky Reaction.

No single-phase system has been previously reported to give significant pH oscillations in a closed (batch) reactor. We report here sustained pH oscillations in batch for the Belousov-Zhabotinsky reaction using much lower [H+]0 and much higher [BrO3-]0 than in traditional studies of this reaction. In fact, pH oscillations were obtained in the presence of only BrO3-, malonic acid (MA), and Mn2+. The amplitude, frequency, and duration of oscillations tend to depend primarily on the ratio of [BrO3-]0 to [MA]0. A critical part of the proposed mechanism involves the reversible formation of a manganese(III) complex with bromomalonic acid, followed by two-electron oxidation to tartraric acid and Mn2+. Estimates of the corresponding rate constant values for these reactions have been obtained by simulation. It is suggested that the presence of a supercatalytic reaction in H+ may be a sufficient, if not necessary, requirement for the occurrence of pH oscillations in a batch system.