Brønsted acids in ionic liquids: how acidity depends on the liquid structure

Phys Chem Chem Phys. 2014 Nov 14;16(42):23233-43. doi: 10.1039/c4cp03217a.

Abstract

Gutmann Acceptor Number (AN) values have been determined for Brønsted acid-ionic liquid mixtures, over a wide compositional range. Four systems of general formula [C2mim][A]-HA (A(-) = bistriflamide, [NTf2](-); triflate, [OTf](-); mesylate, [OMs](-); or acetate, [OAc](-), [C2mim](+) = 1-ethyl-3-methylimidazolium cation) were studied. A library of Brønsted acidic systems of varying acidity was constructed and the AN parameter was found to be a convenient approach for quantifying their acidity. HOAc, HOMs and HOTf, when dissolved in ionic liquids, were found to associate with the respective anions to form hydrogen-bonded anionic clusters, [A(HA)x](-). In contrast, HNTf2 was solubilised as a discrete, undissociated molecule. AN values were sensitive to the presence of anionic clusters; acidity could be buffered to a particular AN by binding the solubilised acid in the anionic cluster form. Overall, a simple way to manipulate and quantify the Brønsted acidity of acid-ionic liquid mixtures was demonstrated, and measured AN values were related to liquid speciation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acids / chemistry*
  • Crystallography, X-Ray
  • Hydrogen Bonding
  • Ionic Liquids / chemistry*
  • Models, Molecular
  • Molecular Structure

Substances

  • Acids
  • Ionic Liquids