Distribution thermodynamics of 1,10-phenanthroline in non-ionic surfactant Triton X-100 micelles

Abstract

The distribution thermodynamics of 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmphen) in micelles of the non-ionic surfactant Triton X-100 were studied by potentiometry and titration calorimetry at 298 K. Both of these ligands form HL⁺ and HL₂⁺ (L = phen and dmphen) in acidic solution. Their formation constants were determined in aqueous solutions containing various concentrations of Triton X-100, and were found to decrease with increasing concentration of the surfactant. The decrease is explained in terms of accommodation of neutral phenanthrolines in micelles by taking into account the surfactant solution as a heterogeneous solvent mixture. The case in which the surfactant is treated as the third reactant was also examined, and thermodynamic parameters for the interaction between the surfactant and phenanthrolines, i.e. the Gibb's energies, enthalpies and entropies of transfer of phenanthrolines from aqueous solution to a micellar pseudo-phase, were obtained. The Gibb's energies of transfer of the neutral ligand L are − 8.2 and − 11.7 kJ mol⁻¹ for L = phen and dmphen, respectively. The corresponding enthalpies of transfer are both small and negative, implying that these neutral 1,10-phenanthrolines are still strongly hydrated in micelles, as well as in water, through the hydrophilic nitrogen sites.