Effects of Methylating Imidazolium-Based Ionic Liquids on Viscosity: New Insights from the Compensated Arrhenius Formalism

Allison M. Fleshman; Allison M. Goldman; Wesley J. Hetcher; Stefan L. Debbert; Chi Linh Do-Thanh; Shannon M. Mahurin; Sheng Dai

doi:10.1021/acs.jpcb.3c02057

Effects of Methylating Imidazolium-Based Ionic Liquids on Viscosity: New Insights from the Compensated Arrhenius Formalism

Allison M. Fleshman, Allison M. Goldman, Wesley J. Hetcher, Stefan L. Debbert, Chi Linh Do-Thanh, Shannon M. Mahurin, Sheng Dai

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Methylation of the C(2) carbon on imidazolium-based room temperature ionic liquids (RTILs) causes an unexpected increase in viscosity when paired with the anion bis(trifluoromethylsulfonamide) [Tf₂N]⁻, but the viscosity decreases when the methylated imidazolium is paired with a tetracyanoborate [B(CN)₄]⁻ anion. This paper investigates these different observations in viscosity using the compensated Arrhenius formalism (CAF) for fluidity (inverse viscosity), which assumes fluidity to be a thermally activated process. CAF activation energies are determined for imidazolium [Tf₂N]⁻ and methylated imidazolium [Tf₂N]⁻ and compared to imidazolium [B(CN)₄]⁻ and methylated imidazolium [B(CN)₄]⁻. The results show that the activation energy increases with methylation for [Tf₂N]⁻, but it decreases with methylation for [B(CN)₄]⁻. The CAF results also yield information concerning the entropy of activation, which are compared for the two systems.

Original language	English
Pages (from-to)	6136-6143
Number of pages	8
Journal	Journal of Physical Chemistry B
Volume	127
Issue number	27
DOIs	https://doi.org/10.1021/acs.jpcb.3c02057
State	Published - Jul 13 2023

Funding

C.D. and S.D. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, for synthesis of ionic liquids. S.M. was sponsored by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. A.F was supported by the Oak Ridge Science Semester through the Associated Colleges of the Midwest and the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS), under the Visiting Faculty Program (VFP). W.H was funded by the Lawrence University Excellence in Science Fund.

Funders	Funder number
Lawrence University Excellence in Science Fund
Oak Ridge Science Semester
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Workforce Development for Teachers and Scientists
Division of Materials Sciences and Engineering
Chemical Sciences, Geosciences, and Biosciences Division

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title = "Effects of Methylating Imidazolium-Based Ionic Liquids on Viscosity: New Insights from the Compensated Arrhenius Formalism",

abstract = "Methylation of the C(2) carbon on imidazolium-based room temperature ionic liquids (RTILs) causes an unexpected increase in viscosity when paired with the anion bis(trifluoromethylsulfonamide) [Tf2N]−, but the viscosity decreases when the methylated imidazolium is paired with a tetracyanoborate [B(CN)4]− anion. This paper investigates these different observations in viscosity using the compensated Arrhenius formalism (CAF) for fluidity (inverse viscosity), which assumes fluidity to be a thermally activated process. CAF activation energies are determined for imidazolium [Tf2N]− and methylated imidazolium [Tf2N]− and compared to imidazolium [B(CN)4]− and methylated imidazolium [B(CN)4]−. The results show that the activation energy increases with methylation for [Tf2N]−, but it decreases with methylation for [B(CN)4]−. The CAF results also yield information concerning the entropy of activation, which are compared for the two systems.",

author = "Fleshman, {Allison M.} and Goldman, {Allison M.} and Hetcher, {Wesley J.} and Debbert, {Stefan L.} and Do-Thanh, {Chi Linh} and Mahurin, {Shannon M.} and Sheng Dai",

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doi = "10.1021/acs.jpcb.3c02057",

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AU - Fleshman, Allison M.

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AU - Hetcher, Wesley J.

AU - Debbert, Stefan L.

AU - Do-Thanh, Chi Linh

AU - Mahurin, Shannon M.

AU - Dai, Sheng

PY - 2023/7/13

Y1 - 2023/7/13

N2 - Methylation of the C(2) carbon on imidazolium-based room temperature ionic liquids (RTILs) causes an unexpected increase in viscosity when paired with the anion bis(trifluoromethylsulfonamide) [Tf2N]−, but the viscosity decreases when the methylated imidazolium is paired with a tetracyanoborate [B(CN)4]− anion. This paper investigates these different observations in viscosity using the compensated Arrhenius formalism (CAF) for fluidity (inverse viscosity), which assumes fluidity to be a thermally activated process. CAF activation energies are determined for imidazolium [Tf2N]− and methylated imidazolium [Tf2N]− and compared to imidazolium [B(CN)4]− and methylated imidazolium [B(CN)4]−. The results show that the activation energy increases with methylation for [Tf2N]−, but it decreases with methylation for [B(CN)4]−. The CAF results also yield information concerning the entropy of activation, which are compared for the two systems.

AB - Methylation of the C(2) carbon on imidazolium-based room temperature ionic liquids (RTILs) causes an unexpected increase in viscosity when paired with the anion bis(trifluoromethylsulfonamide) [Tf2N]−, but the viscosity decreases when the methylated imidazolium is paired with a tetracyanoborate [B(CN)4]− anion. This paper investigates these different observations in viscosity using the compensated Arrhenius formalism (CAF) for fluidity (inverse viscosity), which assumes fluidity to be a thermally activated process. CAF activation energies are determined for imidazolium [Tf2N]− and methylated imidazolium [Tf2N]− and compared to imidazolium [B(CN)4]− and methylated imidazolium [B(CN)4]−. The results show that the activation energy increases with methylation for [Tf2N]−, but it decreases with methylation for [B(CN)4]−. The CAF results also yield information concerning the entropy of activation, which are compared for the two systems.

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Effects of Methylating Imidazolium-Based Ionic Liquids on Viscosity: New Insights from the Compensated Arrhenius Formalism

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