title: Linear free energy study of ring-substituted aniline ozonation for developing treatment of aniline-based pesticide wastes.
abstract: The relative rate constants for the reaction of ozone were determined for several substituted anilines in aqueous solutions at pH 6.5 and 1.5. At pH 6.5, with the exception of m- and p-nitroaniline, the rate constants obey Hammett's equation: log(k(X)/k(H)) = rho sigma. The departure of m- and p-nitroaniline may be explained by direct conjugation of the reaction center. The commonly used sigma(p)(-) value of 1.27, which extends the range of applicability of the Hammett equation, was insufficient to account for the conjugation effects on ozonation of p-nitroaniline; rho = -1.48 (R = 0.973). Use of amine group atomic charge determinations significantly improved correlations: (k(X)/k(H)) = 48.7 delta - 18.2 (R = 0.996). A linear plot of Hammett constants versus relative rate data at pH 1.5 showed poor correlation: rho = 0.72 (R = 0.572). Poor correlation was similarly observed for amine group atomic charge determinations, suggesting varied reaction mechanisms.
authors.affiliation: Environmental Engineering Program, Department of Civil and Environmental Engineering, University of Maryland, College Park, Maryland 20742, USA.
authors.forename: A C
authors.initials: AC
authors.lastname: Pierpoint
authors.forename: C J
authors.initials: CJ
authors.lastname: Hapeman
authors.forename: A
authors.initials: A
authors.lastname: Torrents
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry*; D002273:Carcinogens; D002626:Chemistry, Pharmaceutical; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D010126:Ozone / Q000737:chemistry*; D010573:Pesticide Residues; D014866:Waste Products
chemical_list: D000814:Aniline Compounds; D002273:Carcinogens; D010573:Pesticide Residues; D014866:Waste Products; D010126:Ozone; C023650:aniline