Kinetics and mechanisms of the sonolytic destruction of non-volatile organic compounds: investigation of the sonochemical reaction zone using several OH [rad] monitoring techniques

Abstract

This study investigates the sonolytic degradation mechanism of non-volatile organic compounds and reaction sites for its degradation using various tools that allow OH to be monitored, such as: the spin-trapping method of OH detection using non-volatile nitrone trap 5,5-dimethyl-1-pyrroline- N-oxide (DMPO), the hydrogen peroxide analytical methods and the p-chlorobenzoic acid (pCBA)-probe method. These methods can successfully monitor OH produced during sonochemical processes, and identify the major reaction sites involving OH of the three proposed reaction zones––within the cavity, in the bulk solution, and at the gas–liquid interfacial (shell) region. The patterns of hydrogen peroxide accumulation under the various conditions suggest that peroxides pre-form at the interfacial region, but the self-scavenging reaction by hydrogen peroxide simultaneously takes place in the same region. The simultaneously measured peroxide concentration, in the absence and presence of DMPO, and that of the DMPO–OH adduct indicated the peroxide production and DMPO–OH adduct formation reaction occur at the shell region. The sonolytic destruction efficiency of ultrasound coupled with Fe(II) has been also investigated. The coupled Fe(II)/ultrasound process was found to enhance the OH production rate by 70% compared to the ultrasound process alone due to the reaction of Fe(II) with sonochemically produced hydrogen peroxide (Fenton’s reaction). This accelerated reaction was also found to occur at the shell region rather than in the bulk solution. The enhancement effect of Fe(II)/ultrasound was also examined using pCBA as a probe. 2.8-fold and 3.6-fold increases of the pCBA degradation rate were observed at Fe(II) concentrations of 10 and 20 μM, respectively.