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Volume 14, Issue 3, Pages 99-107

Proton transfer equilibria, temperature and substituent effects on hydrogen bonded complexes between chloranilic acid and anilines

Gamal A. Gohar1 and Moustafa M. Habeeb2

1Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt
2Chemistry Department, Faculty of Education, Alexandria University, Alexandria, Egypt

Copyright © 2006 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


The proton transfer equilibrium constants (KPT) for 1 : 1 complex formation between Chloranilic Acid (CA) and a series of p- and m‒substituted anilines have been measured in 1,4-dioxane spectrophotometrically. The results supported the concept of amine-solvent hydrogen bond formation (short range solvation effect). Beside, this effect, the KPT values were apparently affected by the electron donation power of the aniline ring substituent, which was transmitted to the interaction center via resonance and inductive effects. Linear relationships between KPT and σ-Hammett substituent constants, or pK values for m and p anilines,were obtained verifying the above conclusions. The solute-solvent hydrogen bond formation might increase the reactivity of the aniline nitrogen than would the inductive effect of the alkyl group, in case of CA-N-alkyl aniline complexes. The thermodynamic parameters for the proton transfer complex formation were estimated and it was indicated that the solvent–aniline hydrogen bond formation was preferred in the case of p-substituted aniline complexes more than in the case of the corresponding m‒isomer. It has been found that the proton transfer process was enthalpy and entropy controlled.