Kinetics and Mechanism of Counterionic Salt-Catalysed Piperidinolysis of Anionic Phenyl Salicylate in the Presence of Cationic–Nonionic Mixed Micelles

Abstract

The quantitative correlation of counterion-affinity to aqueous hexadecyltrimethylammonium bromide (HDAB, cationic micelles/nanoparticles) and the counterion-induced HDAB micellar growth, in the presence of different amounts of poly(ethylene glycol hexadecyl ether) (C16E20, nonionic surfactant), was achieved by the use of a semi-empirical kinetic (SEK) method. The values of the ratio of cationic HDAB, as well as mixed HDAB–C16E20, micellar binding constants of X and Br, KX/KBr (= KXBr or RXBr) for X = 4-ClC6H4CO2-, were obtained by the SEK method. The concentration range (0.006–0.015 M) of pure HDAB was found to have no influence on the values of KXBr or RXBr. These observations were also recorded upon addition of a nonionic surfactant, C16E20, in an aqueous solution of HDAB. The mean value of KXBr or RXBr obtained in the presence of pure HDAB (KXBr or RXBr = 50.3) is 2.3 times larger than that in the presence of mixed HDAB–C16E20 (mKXBr or mRXBr = 21.7). From rheometric measurements of aqueous HDA+/4-ClC6H4CO2- with 0.015 M HDAB, single symmetric maxima (at both 25 and 35 °C) were obtained at [4-ClC6H4CO2Na] = 0.03 M. This is evidence for the existence of wormlike micelles/nanoparticles. However, the absence of a maximum in rheometric data for aqueous HDA+/C16E20/4-ClC6H4CO2- with 0.015 M HDAB and 0.006 M C16E20 at various [4-ClC6H4CO2Na] revealed the existence of spherical micelles.