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PreprintCC BY-NC-NDChemRxiv

Weak Anion Hydration Drives LCST Behaviour in Ionic Liquid–Water Mixtures: Insights from Calorimetry and Neutron Diffraction

  • Sanskrita Madhukailya1
  • Guillaume Depraetère2
  • Nithavong Cam2
  • Tristan G. A. Youngs3,4
  • James P. Tellam3,4
  • Margarida Costa Gomes2
  • Leila Moura1
  • John D. Holbrey1
4 affiliations
  1. 1School of Chemistry and Chemical Engineering, Queen’s University Belfast, David Keir Building, Stranmillis Road, Belfast, UK, BT9 5AG
  2. 2ENS Lyon, CNRS and Université de Lyon, 46 allée d’Italie, Lyon, France, 69364
  3. 3Rutherford Appleton Laboratory
  4. 4Harwell Science & Innovation Campus
Open at sourceDOICite

Abstract

Isothermal titration calorimetry (ITC) combined with neutron diffraction and isotopic substitution (NDIS) has been used to elucidate the molecular origins of lower critical solution temperature (LCST) behaviour in the tetrabutylphosphonium 5-phenyltetrazolate/water ([P4444][Ph−tet]/H2O) system. Comparison with the structurally similar but fully water-miscible analogue, tetrabutylphosphonium benzoate ([P4444][Bz]) reveals a much smaller negative enthalpy of mixing with water. This is indicative that weaker solvation of the [Ph−tet]–anion drives an entropy-dominated desolvation process upon heating, leading to phase separation into IL-rich and water-rich domains and is supported by observation from NDIS that the [Ph−tet]–anion is only weakly hydrated by water.

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Cite

BibTeXRIS
BibTeX
@misc{madhukailya2026weak,
  title = {{Weak Anion Hydration Drives LCST Behaviour in Ionic Liquid–Water Mixtures: Insights from Calorimetry and Neutron Diffraction}},
  author = {Sanskrita Madhukailya and Guillaume Depraetère and Nithavong Cam and Tristan G. A. Youngs and James P. Tellam and Margarida Costa Gomes and Leila Moura and John D. Holbrey},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008428/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008428/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Weak Anion Hydration Drives LCST Behaviour in Ionic Liquid–Water Mixtures: Insights from Calorimetry and Neutron Diffraction
AU  - Sanskrita Madhukailya
AU  - Guillaume Depraetère
AU  - Nithavong Cam
AU  - Tristan G. A. Youngs
AU  - James P. Tellam
AU  - Margarida Costa Gomes
AU  - Leila Moura
AU  - John D. Holbrey
PY  - 2026
DA  - 2026/09/07
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008428/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008428/v1
AB  - Isothermal titration calorimetry (ITC) combined with neutron diffraction and isotopic substitution (NDIS) has been used to elucidate the molecular origins of lower critical solution temperature (LCST) behaviour in the tetrabutylphosphonium 5-phenyltetrazolate/water ([P4444][Ph−tet]/H2O) system. Comparison with the structurally similar but fully water-miscible analogue, tetrabutylphosphonium benzoate ([P4444][Bz]) reveals a much smaller negative enthalpy of mixing with water. This is indicative that weaker solvation of the [Ph−tet]–anion drives an entropy-dominated desolvation process upon heating, leading to phase separation into IL-rich and water-rich domains and is supported by observation from NDIS that the [Ph−tet]–anion is only weakly hydrated by water.
ER  -