Document type
Journal articles
Document subtype
Full paper
Title
Structure–property relationships in protic ionic liquids: a thermochemical study
Participants in the publication
Joshua E. S. J. Reid (Author)
Filipe Agapito (Author)
Carlos E. S. Bernardes (Author)
Dep. Química e Bioquímica
Dep. Química e Bioquímica
CQB
Filomena Martins (Author)
Dep. Química e Bioquímica
CQB
Adam J. Walker (Author)
Seishi Shimizu (Author)
Manuel E. Minas da Piedade (Author)
Dep. Química e Bioquímica
CQB
Summary
How does cation functionality influence the strength of intermolecular interactions in protic ionic liquids (PILs)? Quantifying the energetics of PILs can be an invaluable tool to answer this fundamental question. With this in view, we have determined the standard molar enthalpy of vaporization, delta vap Hºm, and the standard molar enthalpy of formation, delta f Hºm, of three tertiary ammonium acetate PILs with varying cation functionality, and of their corresponding precursor amines, through a combination of Calvet-drop microcalorimetry, solution calorimetry, and ab initio calculations. The obtained results suggest that these PILs vaporize as their neutral acid and base precursors. We also found a strong correlation between delta vap Hºm of the PILs and of their corresponding amines. This suggests that, within this series of PILs, the influence of cation modification on their cohesive energies follows a group additivity rule. Finally, no correlation between the delta vap Hºm of PILs and the extent of proton transfer, as estimated from the difference in aqueous pKa between the precursor acid and the conjugate acid of the precursor base, was observed
Date of Submisson/Request
2017-04-06
Date of Acceptance
2017-07-10
Date of Publication
2017-07-10
Institution
FACULDADE DE CIÊNCIAS DA UNIVERSIDADE DE LISBOA
Where published
Physical Chemistry Chemical Physics
Publication Identifiers
ISSN - 1463-9076
Publisher
Royal Society of Chemistry (RSC)
Number of pages
9
Starting page
19928
Last page
19936
Document Identifiers
DOI -
https://doi.org/10.1039/c7cp02230a
URL -
http://dx.doi.org/10.1039/c7cp02230a
Rankings
SCOPUS Q1 (2017) - 1.686 - Physical and Theoretical Chemistry
Web Of Science Q2 (2017) - 3.906 - CHEMISTRY, PHYSICAL - SCIE
Web Of Science Q1 (2017) - 3.906 - PHYSICS, ATOMIC, MOLECULAR & CHEMICAL - SCIE
SCIMAGO Q1 (2017) - 1.686 - Physical and Theoretical Chemistry