Weak Anion Hydration Drives LCST Behavior in Ionic Liquid-Water Mixtures: Insights from Calorimetry and Neutron Diffraction.
- 1The QUILL Research Centre, School of Chemistry and Chemical Engineering, Queen's University Belfast, David Keir Building, Stranmillis Road, BelfastBT9 5AG, U.K.
- 2Laboratoire de Chimie, ENS Lyon, CNRS and Université de Lyon , 46 allée d'Italie, 69364Lyon, France.
- 3ISIS Neutron and Muon Source, Rutherford Appleton Laboratory, Harwell Science & Innovation Campus, Didcot, OxfordshireOX11 0QX, U.K.
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) behavior 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.
Related
- Weak Anion Hydration Drives LCST Behaviour in Ionic Liquid–Water Mixtures: Insights from Calorimetry and Neutron Diffraction
- Temperature-dependent deformation behavior of the additively manufactured Al0.75CrFeNi2.1 alloy using in-situ high energy X-ray diffraction
- Stick–Slip Behavior of Ethenzamide-Based Binary Powder Mixtures Evaluated Using the Shear Cell Method: φCSL as a Robust State Parameter
- Rheological Insights: The Role of Divalent Ions on the Stability and Phase Behavior of Oil–Water Emulsions
- The Investigation of Thermal Stability of Na3V2(PO4)2F3/Hard Carbon Cylindrical Cells Using Accelerating Rate Calorimetry
BibTeX
@article{madhukailya2026weak,
title = {{Weak Anion Hydration Drives LCST Behavior 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},
journal = {The journal of physical chemistry. B},
year = {2026},
month = oct,
doi = {10.1021/acs.jpcb.6c04727},
url = {https://europepmc.org/article/MED/42910874},
note = {CC BY},
}
RIS
TY - JOUR
TI - Weak Anion Hydration Drives LCST Behavior 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 - 2026/10/01
JO - The journal of physical chemistry. B
DO - 10.1021/acs.jpcb.6c04727
UR - https://europepmc.org/article/MED/42910874
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) behavior 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.
SN - 1520-6106
SN - 1520-5207
ER -