Changes of dissolved oxygen in aqueous solutions of caffeine oxidized by photo-Fenton reagent

ABSTRACT Formation of oxygen in the caffeine aqueous solutions occurs through self-decomposition reactions of the hydrogen peroxide, used as an oxidant in the photo-Fenton treatment. The total concentration of hydrogen peroxide used in the treatment would be the contribution of the stoichiometric concentration that reacts with the organic matter ([H₂O₂]₀= 2.0 mM) and the excess of oxidant that decomposes to oxygen, through radical mechanisms, according to a ratio of 0.8164 mmol H₂O₂ mg^-1 O₂. When operating at concentrations lower than [H₂O₂]₀= 2.0 mM, oxygen is not released because there is no excess of oxidant. Moreover, it is verified that the ferrous ion catalyst is oxidized to ferric ion and its subsequent regeneration to ferrous ion. Working at concentrations higher than [H₂O₂]₀= 2.0 mM, oxygen is released in the water, verifying that the catalyst remains as ferric species, which does not regenerate. The reaction time in which oxygen evolution happpens depends on the concentration of catalyst used in the oxidation, verifying that the highest oxygen generation rates are obtained when applying [Fe]₀= 10.0 mg L^-1. Once generated in the water, the maximum concentration of oxygen begins to decrease as the hydrogen peroxide is consumed, until reaching a constant value. The stages of formation and decrease of oxygen are adjusted to zero-order kinetics, estimating the kinetics constants as a function of the catalyst concentration: k _f= 29.48 [Fe]₀ ^-1.25 (mg O₂ L^-1 min^-1) and k _d= -0.006 [Fe]₀ ^2.0 + 0.244 [Fe]₀-3.69 (mg O₂ L^-1 min^-1).