期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 25, 期 59, 页码 13500-13503出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201903485
关键词
acidity scale; ionic liquids; linear free energy relationships; pH window; proton hole
资金
- JSPS KAKENHI [JP26410157, JP19H01168, JP18H03392]
In order to investigate the proton solvation state in protic ionic liquids (PILs), ten acid dissociation enthalpies and entropies of eight compounds were determined in ethylammonium nitrate (EAN). Regardless of the nature of the compound, 24 kJ mol(-1) larger enthalpy and 65 J mol(-1) K-1 larger entropy than those in water, respectively, were observed. These values were reasonably explained by the differences in the proton solvation structure in EAN and water. Namely, protons in EAN exist as HNO3, having a higher reaction energy than that of H3O+ in water, undergo entropic stabilization as a result of the less-structured solvation. As such, the entropic effect of the proton solvation structure on the acid-base property is possibly applicable to all PILs. In addition, based on these proton thermodynamics, enthalpy and entropy windows were proposed as a novel perspective for the characterization of solvents. Use of this concept enabled the visualization of similarities and differences between EAN and water.
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