Micellar-catalyzed alkaline hydrolysis of 2,4-dinitrochlorobenzene in a cationic gemini surfactant

Micellar-catalyzed alkaline hydrolysis of 2,4-dinitrochlorobenzene (DNCB) in the presence of a conventional cationic surfactant CTAB or a cationic gemini surfactant 1,2-ethane bis(dimethyldodecylammonium bromide) (12-2-12) were studied spectrophotometrically at 25 °C. It was found that both CTAB and 12-2-12 micelles accelerated the alkaline hydrolysis of DNCB, and the binding constant of the substrate to the micelle, KS, for 12-2-12 (KS = 310 M−1) was larger than that for CTAB (85 M−1), which suggested that DNCB molecules bound with gemini micelles more easily than with CTAB. However, the second-order rate constant in micellar pseudophase (kM = 1.22 × 10−3 s−1) for 12-2-12 was lower than kM for CTAB (4.01 × 10−3 s−1) because the substrate may enter the interior of the 12-2-12 micelles. It was found also that 12-2-12 had a similar catalysis mechanism to CTAB when the concentration of 12-2-12 was relatively low (ca. <5 mM). However, above this concentration, higher microviscosity and significant increases in aggregation number and micelle size with increased surfactant concentration may remarkably influence the hydrolysis reaction.