Micellar medium effects on the hydrolysis of phenyl chloroformate in ionic, zwitterionic, nonionic, and mixed micellar solutions

✍ Scribed by María Muñoz; Amalia Rodríguez; María Del Mar Graciani; María Luisa Moyá

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: English
• Weight: 139 KB
• Volume: 34
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.10067

✦ Synopsis

Abstract

The spontaneous hydrolysis of phenyl chloroformate was studied in various anionic, nonionic, zwitterionic, and cationic aqueous micellar solutions, as well as in mixed anionic–nonionic micellar solutions. In all cases, an increase in the surfactant concentration results in a decrease in the reaction rate and micellar effects were quantitatively explained in terms of distribution of the substrate between water and micelles and the first‐order rate constants in the aqueous and micellar pseudophases. A comparison of the kinetic data in nonionic micellar solutions to those in anionic and zwiterionic micellar solutions makes clear that charge effects of micelles is not the only factor responsible for the variations in the reaction rate. Depletion of water in the interfacial region and its different characteristics as compared to bulk water, the presence of high ionic concentration in the Stern layer of ionic micelles, and differences in the stabilization of the initial state and the transition state by hydrophobic interactions with surfactant tails can also influence reactivity. The different deceleration of the reaction observed in the various micellar solutions studied was discussed by considering these factors. Synergism in mixed‐micellar solutions is shown through the kinetic data obtained in these media. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 445–451, 2002