From a eutectic mixture to a deep eutectic system via anion selection: Glutaric acid + tetraethylammonium halides

Adriaan van den Bruinhorst, Laura J.B.M. Kollau, Mark Vis, Marco M.R.M. Hendrix, Jan Meuldijk, Remco Tuinier (Corresponding author), A. Catarina C. Esteves

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Samenvatting

In pursuit of understanding structure-property relationships for the melting point depression of binary eutectic mixtures, the influence of the anion on the solid-liquid (S-L) phase behavior was explored for mixtures of glutaric acid + tetraethylammonium chloride, bromide, and iodide. A detailed experimental evaluation of the S-L phase behavior revealed that the eutectic point is shifted toward lower temperatures and higher salt contents upon decreasing the ionic radius. The salt fusion properties were experimentally inaccessible owing to thermal decomposition. The data were inter- and extrapolated using various models for the Gibbs energy of mixing fitted to the glutaric-acid rich side only, which allowed for the assessment of the eutectic point. Fitting the experimental data to a two-parameter Redlich-Kister expansion with Flory entropy, the eutectic depth could be related to the ionic radius of the anion. The anion type, and in particular its size, can therefore be viewed as an important design parameter for the liquid window of other acid and salt-based deep eutectic solvents/systems.

Originele taal-2Engels
Artikelnummer014502
Aantal pagina's11
TijdschriftJournal of Chemical Physics
Volume155
Nummer van het tijdschrift1
DOI's
StatusGepubliceerd - 7 jul. 2021

Bibliografische nota

Publisher Copyright:
© 2021 Author(s).

Financiering

We are grateful to Sietske de Louw and Mégane Maignan for their experimental efforts in constructing the S–L phase diagrams and Professor G. de With for discussions on the thermodynamic modeling. AvdB would like to thank Dr. ir. P. J. T. Verheijen for his help with the numerical fitting procedures. Financial support from the Netherlands Organization for Scientific Research (NWO) and the company Paques B.V. (Balk, The Netherlands) is gratefully acknowledged. This work is part of the research program “MES meets DES” with Project No. STW–Paques 12999.

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