Thermodynamic dissociation constants of benzoic and nitrobenzoic acids in mixtures of ethanol and 1-propanol with water at 25�C

Gibbs energies of transfer of the proton from water into mixtures of water with chain multiple ethers: Equilibria involving changes of solvation of the proton

“…(6), producing high percentage conversions in eqn. (2) as found by eqns. ( 9) and (10) at low x 2 (Fig.…”

“…[3][4][5] Equilibrium (2) moves sharply to the left as the number of hydroxy groups in S increases 3,4,6 in accordance with the effect of multiple electron attracting hydroxyl groups on the basic site. However, no sharp movement of equilibrium (2) occurs between S ¼ tetrahydrofuran and S ¼ dioxane. 3,6,7 To investigate the effect of multiple -O-groups on the free energy of transfer of H + , we now report the investigation of equilibrium (2) using the dimethyl ethers of diethylene glycol and triethylene glycol.…”

“…A reliable knowledge of the change in the stability of single ions with solvent composition in water + co-solvent mixtures relative to that in water is of considerable interest when interpreting the effect of gradual changes in solvent composition on, for example, kinetic processes 1 and equilibria. 2 The method of assessing these changes in the stability of ions with gradual changes in solvent composition based on determining the changes in the solvation of the proton uses eqn. (1) for the free energy of transfer of protons from water into the mixtures.…”

“…DG D is the Gibbs energy of transfer of the spherical aquaproton arising from the difference in the relative permittivities of water and the mixture, DG cav is the difference between the Gibbs energy of cavity formation in the mixture and that of the cavity collapse in water and DG RE is the Gibbs energy of the subsequent change in the solvent re-arrangement around the proton in the mixture of water with S as in eqn. (2).…”

Molecular Heteroconjugation Equilibria in (n-Butylamine + Acetic Acid) Systems in Binary (Dimethyl Sulfoxide + 1,4-Dioxane) Solvent Mixtures

“…The most frequently studied systems in this respect are (water + alcohol) mixtures [8]. Some authors [9,10] describe the relationships between pK a of acids and relative dielectric constants (ε −1 ), as being almost linear, while others [11,12] consider these relationships as being non-linear. Far less attention has been given to binary systems consisting of non-aqueous solvents.…”