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Ultraslow Phase Transitions in an Anion-Anion Hydrogen-Bonded Ionic Liquid
Journal article   Peer reviewed

Ultraslow Phase Transitions in an Anion-Anion Hydrogen-Bonded Ionic Liquid

Luiz F. O. Faria, Thamires A. Lima, Fabio F. Ferreira and Mauro C. C. Ribeiro
The journal of physical chemistry. B, v 122(6), pp 1972-1980
15 Feb 2018
PMID: 29360380
url
http://doi.org/10.1021/acs.jpcb.7b09497View
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Abstract

Chemistry Chemistry, Physical Physical Sciences Science & Technology
A Raman spectroscopy study of 1-ethyl-3-methylimidazolium hydrogen sulfate, [C(2)C(1)im][HSO4], as a function of temperature, has been performed to reveal the role played by anion-anion hydrogen bond on the phase transitions of this ionic liquid. Anion-anion hydrogen bonding implies high viscosity, good glass forming ability, and also moderate fragility of [C(2)C(1)im][HSO4] in comparison with other ionic liquids. Heating [C(2)C(1)im][HSO4] from the glassy phase results in cold crystallization at similar to 245 K. A solid-solid transition (crystal I -> crystal II) is barely discernible in calorimetric measurements at typical heating rates, but it is clearly revealed by Raman spectroscopy and X-ray diffraction. Raman spectroscopy indicates that crystal I has extended ([HSO4](-))(n) chains of hydrogen-bonded anions but crystal II has not. Raman spectra recorded at isothermal condition show the ultraslow dynamics of cold crystallization, solid-solid transition, and continuous melting of [C(2)C(1)im][HSO4]. A brief comparison is also provided between [C(2)C(1)im][HSO4] and [C(4)C(1)im][HSO4], as Raman spectroscopy shows that the latter does not form the crystalline phase with extended anion-anion chains.

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Chemistry, Physical
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