Charge-transfer complex (CTC) formation between tioconazole (TCZ) as an n-electron donor and 7, 7, 8, 8-tetracyanoquinodimethane (TCNQ) as a π-acceptor was studied spectrophotometrically with an accompanying kinetic and thermodynamic investigation. Multivariate data analysis via a set of experimental designs was executed for this purpose. A 23 - two-level full factorial design (FFD) was used for inspecting the proposed variables while a face-centered central composite design (FCCCD) was used to adjust the levels of variables proved to be significant. Two responses were quantified as a result of this interaction; complex I (Y1, measured at 743 nm) and complex II (Y2, measured at 842 nm). Derringer's function and overlaid contour plots were used to concurrently optimize both responses. Benesi–Hildebrand equation was applied to determine of formation constant (K), and the molar absorptivity (Ɛ) of the formed complex. Different thermodynamic parameters; the standard Gibbs free energy change (∆G°), the standard enthalpy of formation (∆H°) and the standard entropy change (∆S°) were determined for the reaction product. The proposed method was validated regarding the linearity, intra-, and inter-day precision and accuracy, limit of detection, limit of quantification and following the ICH standards. The proposed method was also applied for the determination of TCZ in its pharmaceutical preparations. Having a higher molar absorptivity and higher formation constant, complex II was of choice for all subsequent measurements. Application of Benesi–Hildebrand equation supported the formation of 1: 1 CTC. Thermodynamic study revealed the endothermic characters and the spontaneity of formation of the CTC at high temperature.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy – Elsevier
Published: Sep 5, 2018
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