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Title: Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains

Abstract

X-ray diffraction and molecular dynamics simulations were used to probe the structures of two families of ionic liquids containing oligoether tails on the cations. Imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)amide ILs with side chains ranging from 4 to 10 atoms in length, including both linear alkyl and oligo-ethylene oxide tails, were prepared. Their physical properties, such as viscosity, conductivity and thermal profile, were measured and compared for systematic trends. Consistent with earlier literature, a single ether substituent substantially decreases the viscosity of pyrrolidinium and imidazolium ILs compared to their alkyl congeners. Remarkably, as the number of ether units in the pyrrolidinium ILs increases there is hardly any increase in the viscosity, in contrast to alkylpyrrolidinium ILs where the viscosity increases steadily with chain length. Viscosities of imidazolium ether ILs increase with chain length but always remain well below their alkyl congeners. To complement the experimentally determined properties, molecular dynamics simulations were run on the two ILs with the longest ether chains. The results point to specific aspects that could be useful for researchers designing ILs for specific applications.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
NSFNIH
OSTI Identifier:
1372236
Resource Type:
Journal Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 8; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; conductivity; ether; h-bonding; imidazolium; molecular dynamics; pyrrolidinium; structure; viscosity; x-ray

Citation Formats

Lall-Ramnarine, Sharon I., Zhao, Man, Rodriguez, Chanele, Fernandez, Rahonel, Zmich, Nicole, Fernandez, Eddie D., Dhiman, Surajdevprakash B., Castner, Edward W., and Wishart, James F. Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains. United States: N. p., 2017. Web. doi:10.1149/2.0371708jes.
Lall-Ramnarine, Sharon I., Zhao, Man, Rodriguez, Chanele, Fernandez, Rahonel, Zmich, Nicole, Fernandez, Eddie D., Dhiman, Surajdevprakash B., Castner, Edward W., & Wishart, James F. Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains. United States. doi:10.1149/2.0371708jes.
Lall-Ramnarine, Sharon I., Zhao, Man, Rodriguez, Chanele, Fernandez, Rahonel, Zmich, Nicole, Fernandez, Eddie D., Dhiman, Surajdevprakash B., Castner, Edward W., and Wishart, James F. Sun . "Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains". United States. doi:10.1149/2.0371708jes.
@article{osti_1372236,
title = {Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains},
author = {Lall-Ramnarine, Sharon I. and Zhao, Man and Rodriguez, Chanele and Fernandez, Rahonel and Zmich, Nicole and Fernandez, Eddie D. and Dhiman, Surajdevprakash B. and Castner, Edward W. and Wishart, James F.},
abstractNote = {X-ray diffraction and molecular dynamics simulations were used to probe the structures of two families of ionic liquids containing oligoether tails on the cations. Imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)amide ILs with side chains ranging from 4 to 10 atoms in length, including both linear alkyl and oligo-ethylene oxide tails, were prepared. Their physical properties, such as viscosity, conductivity and thermal profile, were measured and compared for systematic trends. Consistent with earlier literature, a single ether substituent substantially decreases the viscosity of pyrrolidinium and imidazolium ILs compared to their alkyl congeners. Remarkably, as the number of ether units in the pyrrolidinium ILs increases there is hardly any increase in the viscosity, in contrast to alkylpyrrolidinium ILs where the viscosity increases steadily with chain length. Viscosities of imidazolium ether ILs increase with chain length but always remain well below their alkyl congeners. To complement the experimentally determined properties, molecular dynamics simulations were run on the two ILs with the longest ether chains. The results point to specific aspects that could be useful for researchers designing ILs for specific applications.},
doi = {10.1149/2.0371708jes},
journal = {Journal of the Electrochemical Society},
issn = {0013-4651},
number = 8,
volume = 164,
place = {United States},
year = {2017},
month = {1}
}

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