South African Journal of Chemistry
On-line version ISSN 1996-840X
Print version ISSN 0379-4350
HASANI, Masoumeh and SHARIATI-RAD, Masoud. Kinetic and thermodynamic studies of charge-transfer complex formation between imipramine and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (ddq) in acetonitrile and dichloromethane solutions. S.Afr.j.chem. (Online) [online]. 2015, vol.68, pp.208-214. ISSN 1996-840X. http://dx.doi.org/10.17159/0379-4350/2015/v68a28.
Spectro-kinetic studies revealed the formation of charge-transfer (CT) complex of Imipramine as an electron donor with π acceptor 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in acetonitrile and dichloromethane solutions. The resulted CT complexes exhibit spectra that were remarkably different from those of the donor and acceptor. The stoichiometry of the resulting complex was found to be 1:1 by the method of Job's continuous variation. The formation constants and thermodynamic parameters of the resulting electron-donor-acceptor (DA) complexes were determined by Benesi-Hildebrand and van't Hoff equations, respectively. The time-dependent spectra recorded after mixing donor and acceptor has been related to an immediate formation of DA complex, which is followed by two relatively slow consecutive reactions. The pseudo-first-order rate constants for the formation of the ionic intermediate and the final product have been evaluated at various temperatures by computer fitting of the absorbance-time data to appropriate equations. The activation parameters, i.e. activation energy, enthalpy, and entropy of activation were computed from temperature dependence of the rate constants. The observed results afford evidence concerning the critical role of solvent polarity on the kinetics and stability of the resulting charge transfer complexes. The ionization potential of the donor in the two solvents was estimated and compared with the theoretical values.
Keywords : Charge-transfer complex; imipramine; DDQ; ionization potential; kinetic; thermodynamic.