The Briggs-Rauscher reaction containing malonic acid may undergo a sudden transition from low (state I) to high iodide and iodine (state II) concentration states after a well-defined and strongly reproducible oscillatory period. This study clearly shows that even though the time-dependent behavior of the oscillatory state is reproducible, the time lag necessary for the appearance of the state I to state II transition after the system leaves the oscillatory state becomes irreproducible for an individual kinetic run. This crazy clock behavior of the state I to state II transition is identified by repeated experiments in which stirring rate is taken as a control parameter and all other parameters such as initial conditions, temperature, vessel surface, and the age of solution were kept constant. Surprisingly, a better stirring condition does not make the transition reproducible; it simply does not allow the transition to happen at all. The proposed mechanism, additional explanations, and proposals for this irreproducibility of state I to state II transition have been presented. Considering the fact that the number of crazy clock reactions is only a few, this study may contribute to a better understanding of fundaments of this phenomenon.
The differences in the mechanism of the halogenate reactions with the same oxidizing/reducing agent, such as H 2 O 2 contribute to the better understanding of versatile halogen chemistry. The reaction between iodate, bromate, and chlorate with hydrogen peroxide in acidic medium at 60 °C is investigated by using the electron paramagnetic resonance (EPR) spin trapping technique. Essential differences in the chemistry of iodate, bromate, and chlorate in their reactions with hydrogen peroxide have been evidenced by finding different radicals as governing intermediates. The reaction between KIO 3 and H 2 O 2 is supposed to be the source of IO 2• radicals. The KBrO 3 and H 2 O 2 reaction did not produce any EPR signal, whereas the KClO 3 −H 2 O 2 system was found to be a source of HO • radical. Moreover, KClO 3 dissolved in sulfuric acid without hydrogen peroxide produced HO • radical as well. The minimal-core models explaining the origin of obtained EPR signals are proposed. Current findings suggested the inclusion of IO 2• and HOO • radicals, and ClO 2• and HO • radicals in the particular kinetic models of iodate−hydrogen peroxide and chlorate−hydrogen peroxide systems, as well as possible exclusion of BrO 2• radical from the kinetic scheme of the bromate−hydrogen peroxide system. Obtained results may pave the way for understanding more complex, nonlinear reactions of these halogen-containing species.
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