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The TiO 2  photoassisted oxidation and ultimate mineralization of the cationic benzyldodecyldimethylammonium chloride (BDDAC) and the anionic sodium dodecylsulfate (DoS) surfactants in aqueous media were re-visited as part of our systematic examination of their cationic/anionic binary BDDAC/DoS complexes of variable compositions. The processes were monitored by surface tension measurements, by total organic carbon (TOC) assays, carbon dioxide evolution, and HPLC analyses. Some hydroxylated intermediates of the BDDAC system were identified by time-of-flight mass spectral (TOF-MS) techniques. Oxidative degradation of the anionic surfactant was significant involving prior adsorption of the species on the positively charged metal-oxide particle surface. By contrast, the degradation of the cationic surfactant was rather limited owing to a lesser extent of adsorption on the TiO 2  surface under otherwise identical conditions. The mineralization yield assayed by CO 2  evolution was ca. 80% for DoS and 47% for BDDAC after 180 min of UV irradiation. Evolution of CO 2  gas for DoS was 4-fold faster (k = 1.2 × 10 -2  min -1 ) than for BDDAC (k = 0.31 × 10 -2  min -1 ). Mineralization of the binary mixed system was also faster (k = 0.52 × 10 -2  min -1 ) than for the BDDAC systemalone, but 2-fold slower than for DoS alone. Initial intermediates identified by TOF-MS techniques were the mono-, di-, and tri-hydroxylated BDDAC species followed by several other intermediates with m/z greater than and less than the mass peaks of the two surfactant substrates.

Binary Cationic BDDAC/Anionic DoS Surfactant Systems of Variable Compositions.Mineralization by an Advanced Oxidation Process in Aqueous Dispersions