A Comparative Kinetic Study on the Efficacious Permanganate Oxidation of Fluorenes in Perchloric and Sulfuric Acid Media

Oxidation kinetics of fluorene (Fl) and its halogenated derivatives, namely, 2,7-dichlorofluorene (Fl-Cl), 2,7-dibromofluorene (Fl-Br) and 2,7-diiodofluorene (Fl-I), by permanganate ion in both perchloric and sulfuric acid media have been investigated using conventional spectrophotometric technique. In both acidic media, the reactions manifested first order kineticsin [permanganate] and less than unit order each in [reductants] and [acid]. Increasing ionic strength had no effect on the oxidation rates. Oxidation rates of fluorenes in perchloric acid were higher than those in sulfuric acid and the order of the oxidation rates was: Fl > Fl-I > Fl-Br > Fl-Cl. Final oxidation products were identified by GC/MS and FT-IR analyses in all cases as 9H-fluorenone derivatives. Reaction constants as well as activation parameters of the second order rate constants were also evaluated.