Thermodynamics study of the dimerization equilibria of rhodamine B and 6G in different ionic strengths by photometric titration and chemometrics method

The dimerization constants of rhodamine B and 6G have been determined by studying the dependence of their absorption spectra on the temperature in the range 20-80 degrees C at different total concentrations of rhodamine B (5.89 x 10(-6) to 2.36 x 10(-4) M) and rhodamine 6G (2.34 x 10(-5) to 5.89 x 10(-4) M) and in different concentrations of LiCl, NaCl and KCl salts as supporting electrolytes. The monomer-dimer equilibrium of rhodamine B and 6G have been determined by chemometrics refinement of the absorption spectra obtained by thermometric titrations performed at different ionic strengths. The quantitative analysis of the data of undefined mixtures, was carried out by simultaneous resolution of the overlapping spectral bands in the whole set of absorption spectra. The dimerization constants are varied by changing the ionic strength and the degree of dimerization are decreased by increasing of the ionic strength of the medium. The enthalpy and entropy of the dimerization reactions were determined from the dependence of the equilibrium constants on the temperature (van't Hoff equation). From the thermodynamic results the T Delta S degrees-Delta H degrees plot was sketched. It shows a fairly good positive correlation which indicates the enthalpy-entropy compensation in the dimerization reactions (compensation effect). (c) 2005 Elsevier B.V. All rights reserved.