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Structure-property relationships in protic ionic liquids: a thermochemical study.

Joshua E S J Reid1, Filipe Agapito, Carlos E S Bernardes

  • 1York Structural Biology Laboratory, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. seishi.shimizu@york.ac.uk.

Physical Chemistry Chemical Physics : PCCP
|July 20, 2017
PubMed
Summary
This summary is machine-generated.

Cation functionality impacts intermolecular interactions in protic ionic liquids (PILs). Enthalpy measurements reveal cation modification influences cohesive energies predictably, following a group additivity rule.

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Area of Science:

  • Physical Chemistry
  • Materials Science

Background:

  • Protic ionic liquids (PILs) are salts that are liquid at ambient temperatures.
  • Understanding intermolecular interactions is key to designing PILs with specific properties.

Purpose of the Study:

  • To investigate how cation functionality affects intermolecular interactions in protic ionic liquids.
  • To quantify the energetic contributions of cation structure to PIL properties.

Main Methods:

  • Calvet-drop microcalorimetry and solution calorimetry were used to determine enthalpies.
  • Ab initio calculations complemented experimental data.
  • Standard molar enthalpies of vaporization and formation were measured for PILs and precursor amines.

Main Results:

  • Protic ionic liquids were observed to vaporize as their neutral acid and base precursors.
  • A strong correlation was found between the enthalpy of vaporization of PILs and their precursor amines.
  • Cation modification's influence on cohesive energies followed a group additivity rule.

Conclusions:

  • The cohesive energies of these protic ionic liquids are predictable based on cation structure.
  • Intermolecular interactions in these PILs are strongly influenced by the precursor amine's properties.
  • Proton transfer extent, based on pKa differences, did not correlate with enthalpy measurements.