Thermodynamics of Complexation of 18-Crown-6 with NH4+ Ion in Water-Dioxane Mixtures

The stability constants of 1 : 1 complexes of ammonium ion with 18-crown-6 in water and aqueous dioxane (dioxane weight fraction 0.2, 0.4, 0.6, and 0.8) in the range 283-318 K were determined electrometrically, and the thermodynamic parameters of the complexation were calculated. The stability of the complexes is determined by the enthalpy factor. The contributions from the Gibbs energy of solvation of NH₄ ⁺ ion, 18-crown-6·NH₄ ⁺ complex, and free 18-crown-6 to stabilization of the complex with increasing content of dioxane in the mixed solvent were estimated. The thermodynamics of complexation of ammonium, sodium, and potassium ions with 18-crown-6 in aqueous-organic solvents, such as water-2-propanol, water-acetone, and water-dioxane, were compared considering the effects of reactant solvation. The variations of the conformational component of the Gibbs energy of solvation of 18-crown-6 and the parameters of selective solvation of the reactants were evaluated. The influence of the dielectric permittivity and donor-acceptor properties of mixed aqueous-organic solvents on the Gibbs energy of complexation and solvation of the cations and 18-crown-6 was subjected to correlation analysis.