Solvent Effects on Protonation Constants of Betanin in Different Aqueous Solutions of Methanol at T = 25 ºC

The protonation constants of the betanin (pKa1, pKa2, and pKa3) were determined in mixed solvent of water and methanol containing 0, 10, 20, 30, 40, 50, 60, 70, and 80 % (v/v) methanol, using a combination of the spectrophotometric and potentiometric methods at T = 25 ºC and constant ionic strength (0.1 mol.dm-3 NaClO4). The obtained protonation constants were analyzed using Kamlet, Abboud, and Taft parameters. KAT parameters are α (hydrogen-bond donor acidity), β (hydrogen-bond acceptor basicity), and π* (dipolarity/polarizability). In this study, a good linear relationship was obtained between protonation constants (on the logarithmic scale) and dielectric constant (ɛ) of the water-methanol mixed solvents. It was found that the dual-parameter correlation between log10K,s and π*, β give us the best result in various volume fractions of methanol for water-methanol mixed solvent. Finally, the results are discussed in terms of the effect of the solvent on the protonation constants. Resumen. Las constantes de protonación de la betanina (pKa1, pKa2 y pKa3) se determinaron en un disolvente mixto de agua y metanol que contenía metanol al 0, 10, 20, 30, 40, 50, 60, 70 y 80% (v / v), utilizando una combinación de los métodos espectrofotométricos y potenciométricos a T = 25 ºC y fuerza iónica constante (0,1 mol.dm-3 NaClO4). Las constantes de protonación obtenidas se analizaron utilizando los parámetros de Kamlet, Abboud y Taft. Los parámetros KAT son α (acidez del donante de enlaces de hidrógeno), β (basicidad del aceptor de enlaces de hidrógeno) y π* (dipolaridad / polarizabilidad). En este estudio, se obtuvo una buena relación lineal entre las constantes de protonación (en la escala logarítmica) y la constante dieléctrica (ɛ) de los disolventes mixtos agua-metanol. Se encontró que la correlación de doble parámetro entre log10K, s y π*, β nos da el mejor resultado en varias fracciones de volumen de metanol para el disolvente mixto agua-metanol. Finalmente, los resultados se discuten en términos del efecto del solvente en las constantes de protonación.

Intermolecular interactions upon carbon dioxide capture in deep-eutectic solvents

An increase in hydrogen bond acceptor basicity (β) and a decrease in hydrogen bond donor acidity (α) simultaneously promotes higher CO2 uptake in deep eutectic solvents.

Kinetic analysis of tautomer forms of aromatic-urea compounds with acetate ions: solvent effect of excited state intermolecular proton transfer

The tautomer form of an anthracene-urea compound in the excited state is stabilized by hydrogen bond acceptor basicity.

Hydrolysis of dimethylphenyltin(IV) and triphenyltin(IV) chlorides in different aqueous ethanol solutions

The hydrolysis of [(Me)2(Ph)Sn(IV)]+ and [(Ph)3Sn(IV)]+ has been investigated at 25 °C and different aqueous solutions of ethanol, using a combination of spectrophotometric and potentiometric techniques. The species formed together with their formation constants have been determined using the computer program Squad over a wide pH range of 1 to 11. The hydrolysis constants in different media were analyzed in terms of Kamlet and Taft parameters. Single-parameter correlation of the formation constants, K11 and K12, versus α (hydrogen-bond donor acidity), β (hydrogen-bond acceptor basicity), and π* (dipolarity/polarizability) for both cases are relatively poor in all solutions, but multiparameter correlation represents significant improvement with regard to the single-parameter models. In this work, we have also used the normalized polarity parameter, ETN, alone and in combination with the Kamlet–Taft parameter to find a better correlation of the formation constants in different aqueous ethanol solutions.Key words: dimethylphenyltin(IV) chloride, triphenyltin(IV) chloride, hydrolysis constant, aqueous ethanol solutions, solvent effect.