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Solute–solvent interaction effects on second‐order rate constants of reaction between 1‐chloro‐2,4‐dinitrobenzene and aniline in alcohol–water mixtures
Author(s) -
Harati M.,
Gholami M. R.
Publication year - 2005
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.20041
Subject(s) - chemistry , aniline , aqueous solution , reaction rate constant , solvent , solvent effects , mole fraction , methanol , alcohol , hydrogen bond , reaction rate , nucleophilic substitution , polarizability , computational chemistry , medicinal chemistry , organic chemistry , kinetics , molecule , catalysis , physics , quantum mechanics
The second‐order rate coefficients for aromatic nucleophilic substitution reaction between 1‐chloro‐2,4‐dinitrobenzene and aniline have been measured in aqueous solutions of ethanol and methanol at 25°C. The plots of rate constants versus mole fraction of water show a maximum in all‐aqueous solutions. The effect of four empirical solvent parameters including hydrogen bond donor acidity (α) dipolarity/polarizability (π * ) normalized polarity ( E N T ) and solvophobicity ( Sp ) has been investigated. This investigation has been carried out by means of simple and multiple regression models. A dual‐parameter equation of log k 2 versus Sp and α was obtained in all‐aqueous solutions ( n = 41, r = 0.962, s = 0.053, p = 0.0000). This equation shows that solvophobicity and hydrogen bond donor acidity are important factors in the occurrence of the reaction and they have opposite effects on reaction rate. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 37: 90–97, 2005