Use of Phase Transition Curves for Testing Models of the pH-Oscillatory Hydrogen Peroxide-Thiosulfate-Sulfite Reaction

Abstract

The reaction system hydrogen peroxide-thiosulfate-sulfite in diluted sulfuric acid (HPTS) displays strongly nonlinear dynamics when operated in a continuous-flow stirred tank reactor. Due to a crucial role of hydrogen ion during the reaction, this system is a prime example of an inorganic pH-oscillator. Under specific external conditions the system exhibits multiple steady states, periodic oscillations and chaotic behavior. We focus on evaluating alternative kinetic models by exploring phase resetting of the periodic oscillatory regime caused by a single-pulse perturbation with various reacting species. Phase transition curve (PTC), the plot of phase after the resetting against the phase of perturbation, is a convenient characteristic of the oscillatory dynamics adopted as a major tool in this work. Experimental results for hydrogen ions, hydroxide ions, thiosulfate ions, sulfite ions, and hydrogen sulfite ions used as perturbants are systematically compared with calculations under corresponding conditions using two available reaction mechanisms. In addition, we use the stoichiometric network analysis to identify possible core oscillatory subnetworks in the models and choose the one that corresponds best to the measured PTCs.

The Key Heterolysis Selectivity of Divalent Sulfur–Sulfur Bonds for a Unified Mechanistic Scheme in the Thiosulfatolysis and Sulfitolysis of the Pentathionate Ion

“…A wide range of “exotic” kinetic phenomena can be displayed in thiosulfate oxidation reactions, and the detailed mechanisms of the reactions are so complicated that no successful attempt has been made to unravel the complete mechanism in the whole system range , . Pentathionate can be formed as an intermediate of the oxidation reaction of thiosulfate and in detectable amounts during kinetic studies of hydrogen peroxide–thiosulfate, chlorite–thiosulfate, and hypochlorous acid–thiosulfate systems.…”