pH oscillations in the hemin-hydrogen peroxide-sulfite reaction

Oscillatory behaviour in the pH value has been observed during the oxidation of sulfite by hydrogen peroxide mediated by hemin, a well known enzyme model compound, in a continuous-flow stirred tank reactor. The dynamics of this reaction has been studied for a variety of flow rates of the reactants. As the flow rates increase, the oscillations evolve from relaxation oscillations to more complex shapes, displaying, among others, bursting behaviour. A reaction mechanism is proposed that involves the autocatalytic oxidation of HSO3- by H2O2, while slow equilibria between different pH-dependent forms of hemin account for the feedback loop which gives rise to oscillatory dynamics. It is shown in experiments that no participation of CO2 is required for oscillations to occur.