Limited ionicity in poor protic ionic liquids: Association Gibbs energies
| Autor: | Devin O. Klapatiuk, Shawn L. Waugh, Abdulrahman A. Mukadam, Allan L. L. East |
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| Rok vydání: | 2023 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 158:034507 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/5.0124900 |
| Popis: | Protic ionic liquids (PILs), made from anhydrous mixtures of Bronsted acids HA and bases B (HA + B → BH++ A−), occasionally suffer from limited ionicity. In cases of “poor” PILs (A(and thus the association constants KA) as functions of three fundamental properties: the acid/base mixing ratio (n = xA/xB), the HA-to-B proton-transfer strength (ΔpKa,ε=78), and the dielectric constant (relative permittivity) of the mixture (ε). Parameter values were obtained from fits to constant-dielectric quantum chemistry data (obtained and presented here). These ΔGAfunctions were then used to predict ΔGionizvalues for the net ion-generating (autoionization) equilibrium in carboxylic acid/amine mixtures: [Formula: see text], where n = xA/xBand d = degree of disproportionation. The agreement with experiment was excellent, demonstrating that these equations could have useful predictive power. |
| Databáze: | OpenAIRE |
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