Abstract
The acid-base and complexation equilibria of rifampicin with H+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, and Pb2+were studied by means of potentiometry. The stoichiometric equilibrium constants were determined in 50% (v/v) methanol-water medium at different temperatures and constant ionic strength (0.05 M KCl). It was established that rifampicin has two proton-binding sites. The distribution diagram of the corresponding ionic species as a function of pH is given and indicated that rifampicin exists predominantly in the zwitterionic form at pH [Formula: see text] 5. The thermodynamic parameters of protonation and complexation were derived and discussed. The formation of the complexes is spontaneous, more favourable at lower temperatures, entropically unfavourable, and an enthalpy-driven process. The order of the changes in Gibbs energy and enthalpy accompanying the complexation was found to be Mn2+< Co2+< Ni2+< Cu2+> Pb2+> Zn2+> Cd2+> Hg2+in accordance with the well-known sequence of Irving and Williams. The transition series contraction energy (Er(Mn-Zn)), and the ligand field stabilization energy (δH) were calculated from the enthalpy changes.Key words: rifampicin, thermodynamics, potentiometry, and complexation.
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