Investigation of glycerol hydrogen-bonding networks in choline chloride/glycerol eutectic-forming liquids using neutron diffraction

John Holbrey, Adam Turner

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Abstract

The structure of choline chloride/glycerol (ChCl:Gly) mixtures at two mole fractions (the eutectic χChCl = 0.33 (1:2), and a higher χChCl = 0.50 (1:1) composition) in the liquid state at 333 K and 1 atm. has been investigated using neutron diffraction coupled with hydrogen/deuterium isotopic substitution. Modelling using the empirical potential structure refinement (EPSR) technique, constrained to the experimental neutron diffraction data, produced structural models at both compositions consistent with the experimental data with an extensive, persistent homo-molecular glycerol hydrogen bonding network at χChCl = 0.33 similar to that present in pure glycerol and suggests that persistence of the latent glycerol hydrogen bonding network is key to formation of the ChCl:Gly deep eutectic solvent. In the choline chloride-rich χChCl = 0.50 composition, significant domain segregation is observed with a dramatic reduction in the extent of the homo-molecular glycerol hydrogen bond network which is replaced by a more homogeneous system-wide hydrogen bonded network incorporating glycerol, Cl-, and choline cations.
Original languageEnglish
Pages (from-to)21782-21789,
Number of pages8
JournalPhysical Chemistry Chemical Physics (PCCP)
Volume21
Early online date19 Sep 2019
DOIs
Publication statusEarly online date - 19 Sep 2019

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choline
Neutron diffraction
glycerols
Choline
eutectics
Glycerol
Eutectics
neutron diffraction
Hydrogen bonds
chlorides
Liquids
hydrogen
liquids
Hydrogen
Chemical analysis
Deuterium
Cations
deuterium
Substitution reactions
substitutes

Cite this

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title = "Investigation of glycerol hydrogen-bonding networks in choline chloride/glycerol eutectic-forming liquids using neutron diffraction",
abstract = "The structure of choline chloride/glycerol (ChCl:Gly) mixtures at two mole fractions (the eutectic χChCl = 0.33 (1:2), and a higher χChCl = 0.50 (1:1) composition) in the liquid state at 333 K and 1 atm. has been investigated using neutron diffraction coupled with hydrogen/deuterium isotopic substitution. Modelling using the empirical potential structure refinement (EPSR) technique, constrained to the experimental neutron diffraction data, produced structural models at both compositions consistent with the experimental data with an extensive, persistent homo-molecular glycerol hydrogen bonding network at χChCl = 0.33 similar to that present in pure glycerol and suggests that persistence of the latent glycerol hydrogen bonding network is key to formation of the ChCl:Gly deep eutectic solvent. In the choline chloride-rich χChCl = 0.50 composition, significant domain segregation is observed with a dramatic reduction in the extent of the homo-molecular glycerol hydrogen bond network which is replaced by a more homogeneous system-wide hydrogen bonded network incorporating glycerol, Cl-, and choline cations.",
author = "John Holbrey and Adam Turner",
year = "2019",
month = "9",
day = "19",
doi = "10.1039/C9CP04343H",
language = "English",
volume = "21",
pages = "21782--21789,",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "The Royal Society of Chemistry",

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TY - JOUR

T1 - Investigation of glycerol hydrogen-bonding networks in choline chloride/glycerol eutectic-forming liquids using neutron diffraction

AU - Holbrey, John

AU - Turner, Adam

PY - 2019/9/19

Y1 - 2019/9/19

N2 - The structure of choline chloride/glycerol (ChCl:Gly) mixtures at two mole fractions (the eutectic χChCl = 0.33 (1:2), and a higher χChCl = 0.50 (1:1) composition) in the liquid state at 333 K and 1 atm. has been investigated using neutron diffraction coupled with hydrogen/deuterium isotopic substitution. Modelling using the empirical potential structure refinement (EPSR) technique, constrained to the experimental neutron diffraction data, produced structural models at both compositions consistent with the experimental data with an extensive, persistent homo-molecular glycerol hydrogen bonding network at χChCl = 0.33 similar to that present in pure glycerol and suggests that persistence of the latent glycerol hydrogen bonding network is key to formation of the ChCl:Gly deep eutectic solvent. In the choline chloride-rich χChCl = 0.50 composition, significant domain segregation is observed with a dramatic reduction in the extent of the homo-molecular glycerol hydrogen bond network which is replaced by a more homogeneous system-wide hydrogen bonded network incorporating glycerol, Cl-, and choline cations.

AB - The structure of choline chloride/glycerol (ChCl:Gly) mixtures at two mole fractions (the eutectic χChCl = 0.33 (1:2), and a higher χChCl = 0.50 (1:1) composition) in the liquid state at 333 K and 1 atm. has been investigated using neutron diffraction coupled with hydrogen/deuterium isotopic substitution. Modelling using the empirical potential structure refinement (EPSR) technique, constrained to the experimental neutron diffraction data, produced structural models at both compositions consistent with the experimental data with an extensive, persistent homo-molecular glycerol hydrogen bonding network at χChCl = 0.33 similar to that present in pure glycerol and suggests that persistence of the latent glycerol hydrogen bonding network is key to formation of the ChCl:Gly deep eutectic solvent. In the choline chloride-rich χChCl = 0.50 composition, significant domain segregation is observed with a dramatic reduction in the extent of the homo-molecular glycerol hydrogen bond network which is replaced by a more homogeneous system-wide hydrogen bonded network incorporating glycerol, Cl-, and choline cations.

U2 - 10.1039/C9CP04343H

DO - 10.1039/C9CP04343H

M3 - Article

VL - 21

SP - 21782-21789,

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

ER -