Kinetics of oxidative degradation of methyl orange using the “Sonoperoxate” process
Abstract
Disadvantages of photocatalytic and Fenton-like advanced oxidation processes of dyes are high energy consumption and long duration, which is due to the formation of only one main reactive species – hydroxyl radicals. To increase the degradation rate of azo dyes, in particular methyl orange (MO), it is proposed for the first time to use the “Sonoperoxate” advanced oxidation process (ultrasound/H2O2/KIO4), during the implementation of which a complex of reactive species is formed, which includes both radicals (iodyl, periodyl, hydroxyl) and a highly active compound of molecular type (singlet oxygen – 1O2). Rational conditions for the oxidative degradation of MO are established: the initial concentration of MO in its aqueous solution is 76.5·10-6 mol/L; the molar ratio of MO:H2O2:KIO4=1:50:10; the pH value of the reaction medium – 3.00; the temperature of the medium – 293 K; the specific power of ultrasonic cavitation treatment is 68.0 W/L. The oxidative degradation rate constant of MO, which under rational conditions is equal to 2.883·10-3 s-1, is determined. The negative value (-19472 J/mol) of the effective activation energy of the oxidative degradation of MO using the “Sonoperoxate” advanced oxidation process is associated with the multistage nature of this process. The synergistic effect, which is due to the combination of the action of ultrasonic cavitation and the H2O2/KIO4 process, is characterized by the value of the synergistic coefficient, which is equal to 1.62. Based on the results of UV/Vis and IR spectroscopy, the destruction of the azo bond in molecules of MO and the dye degradation are confirmed. According to the results of the identification of the functional groups of intermediates by the IR spectroscopy method, a possible pathway of oxidative degradation of MO using the “Sonoperoxate” process is proposed, which sequentially includes breaking the azo bond, demethylation of primary amines, deamination of amino derivatives of benzene, opening of the benzene ring with the formation of linear compounds, and their mineralization
Keywords
azo dyes; oxidative degradation; rate constant; ultrasonic cavitation; periodate; UV/Vis spectroscopy; IR spectroscopy
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