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Solvent and substituent effects on the electrochemical oxidation of para‐ and meta‐substituted anilines
Author(s) -
Bhuvaneshwari D. S.,
Elango K. P.
Publication year - 2007
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20242
Subject(s) - chemistry , substituent , reactivity (psychology) , electrochemistry , solvent , sulfuric acid , supporting electrolyte , solvent effects , electrolyte , organic chemistry , reaction rate constant , medicinal chemistry , inorganic chemistry , kinetics , electrode , medicine , alternative medicine , pathology , physics , quantum mechanics
Electrochemical oxidation of 15 para‐ and meta‐substituted anilines in different mole fractions of water in 2‐methylpropan‐2‐ol has been investigated in the presence of 0.1 M sulfuric acid as a supporting electrolyte. The oxidation potential data of anilines correlate well with the Brown–Okamoto's substituent constants affording a negative reaction constant. The effect of para‐ and meta‐substituents on the oxidation potential confirms to Swain's F and R , affording negative reaction constants. The oxidation potential values also correlate satisfactorily with macroscopic solvent parameter such as relative permittivity, ε r . The results of Kamlet–Taft multiple correlation analysis show that specific solute–solvent interactions play a dominant role in governing the reactivity. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 289–297, 2007