Mechanism of Persulfate Activation by Phenols

Abstract

The activation of persulfate by phenols was investigated to further the understanding of persulfate chemistry for in situ chemical oxidation (ISCO). Phenol (pKa = 10.0) activated persulfate at pH 12 but not at pH 8, suggesting activation occurred only via the phenoxide form. Evaluation of the phenoxide activation mechanism was complicated by the concurrent activation of persulfate by hydroperoxide anion, which is generated by the base catalyzed hydrolysis of persulfate. Therefore, phenoxide activation was investigated using pentachlorophenoxide at pH 8.3, midway between the pKa of pentachlorophenol (pKa = 4.8) and that of hydrogen peroxide (pKa = 11.8). Of the two possible mechanisms for phenoxide activation of persulfate (reduction or nucleophilic attack) the results were consistent with reduction of persulfate by phenoxide with oxidation of the phenoxide. The concentration of phenoxide required for maximum persulfate activation was low (1 mM). The results of this research document that phenoxides activate persulfate via reduction; phenolic moieties ubiquitous to soil organic matter in the subsurface may have a significant role in the activation of persulfate during its injection into the subsurface for ISCO. Furthermore, the results provide the foundation for activation of persulfate by other organic anions without the toxicity of phenols, such as keto acids.