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Compatible Mechanism for a Simultaneous Description of the Roebuck, Dushman, and Iodate-Arsenous Acid Reactions in an Acidic Medium.

The iodine-arsenous acid (Roebuck), iodide-iodate (Dushman), and iodate-arsenous acid reactions have been studied simultaneously by a stopped-flow technique by monitoring the absorbance-time profiles at the isosbestic point of the I2/I3(-) system (468 nm). Using the well-accepted rate coefficients of iodine hydrolysis, we have proven that iodine is the kinetically active species of the iodine-arsenous acid reaction. Strong iodide inhibition of this system is explained by a rapidly established equilibrium between iodine and arsenous acid to produce an iodide ion, a hydrogen ion, and a short-lived intermediate H2AsO3I, which is shifted far to the left. Taking into consideration the generally accepted kinetic model of the Dushman reaction where I2O2 plays a key role to account for all of the most important observations in this subsystem and a sequence of simple formal oxygen-transfer reactions between arsenous acid and iodic acid as well as iodous acid and hypoiodous acid, we propose a 13-step comprehensive kinetic model, including seven rapidly established equilibria with only six fitted parameters, that is able to explain all of the most important characteristics of the kinetic curves of all of the title systems both individually and simultaneously.