Insights into the absorption of hydrocarbon gases in phosphorus-containing ionic liquids

Sam McCalmont; Inês C. M. Vaz; Hanne Oorts; Zheng Gong; Leila Moura; Margarida Costa Gomes

doi:10.1021/acs.jpcb.2c08051

Insights into the absorption of hydrocarbon gases in phosphorus-containing ionic liquids

Sam McCalmont, Inês C. M. Vaz, Hanne Oorts, Zheng Gong, Leila Moura^*, Margarida Costa Gomes^*

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

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

2 Citations (Scopus)

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Abstract

The solubility of ethane, ethylene, propane, and propylene was measured in two phosphorus-containing ionic liquids, trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate, [P6,6,6,14][DiOP], and 1-butyl-3-methylimidazolium dimethylphosphate, [C4C1Im][DMP], using an isochoric saturation method. The ionic liquid [C4C1Im][DMP] absorbed between 1 and 20 molecules of gas per 1000 ion pairs, at 313 K and 0.1 MPa, while [P6,6,6,14][DiOP] absorbed up to 169 molecules of propane per 1000 ion pairs under the same conditions. [C4C1Im][DMP] had a higher capacity to absorb olefins than paraffins, while the opposite was true for [P6,6,6,14][DiOP], with the former being slightly more selective than the later. From the analysis of the thermodynamic properties of solvation, we concluded that in both ionic liquids and for all of the studied gases the solvation is ruled by the entropy, even if its contribution is unfavorable. These results, together with density measurements, 2D NMR studies, and self-diffusion coefficients suggest that the gases’ solubility is ruled mostly by nonspecific interactions with the ionic liquids and that the looser ion packing in [P6,6,6,14][DiOP] makes it easier to accommodate the gases compared to [C4C1Im][DMP].

Original language	English
Pages (from-to)	3402-3415
Number of pages	14
Journal	Journal of Physical Chemistry B
Volume	127
Issue number	15
Early online date	03 Mar 2023
DOIs	https://doi.org/10.1021/acs.jpcb.2c08051
Publication status	Published - 20 Apr 2023

Bibliographical note

Funding Information:
The authors thank Pauline Lefebvre and Nicolas Scaglione for their help with some of the gas absorption measurements. M.C.G. and I.C.M.V. ackowledge the IDEX-LYON for financial support (Programme Investissements d’Avenir ANR-16-IDEX-0005). L.M. acknowledges support from the Royal Academy of Engineering in the form of a research fellowship (RF\201718\17111). S.H.M. thanks the EPSRC for his standard research studentship (ref 2374580). The authors thank Professor John Holbrey for supplying ionic liquid [P6,6,6,14][DiOP] and Professor Panagiotis Manesiotis for his help in setting and interpreting the 2D NMR results.

Funding Information:
The authors thank Pauline Lefebvre and Nicolas Scaglione for their help with some of the gas absorption measurements. M.C.G. and I.C.M.V. ackowledge the IDEX-LYON for financial support (Programme Investissements d’Avenir ANR-16-IDEX-0005). L.M. acknowledges support from the Royal Academy of Engineering in the form of a research fellowship (RF \201718 \17111). S.H.M. thanks the EPSRC for his standard research studentship (ref 2374580). The authors thank Professor John Holbrey for supplying ionic liquid [P ][DiOP] and Professor Panagiotis Manesiotis for his help in setting and interpreting the 2D NMR results. 6,6,6,14

Publisher Copyright:
© 2023 American Chemical Society.

Keywords

gases
hydrocarbons
salts
solubility
solvents
ionic liquid
separation

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

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This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acs.jpcb.2c08051Licence: Unspecified

Insights into the absorption of hydrocarbon gases in phosphorous-containing ionic liquids
Copyright 2023 American Chemical Society. This work is made available online in accordance with the publisher’s policies. Please refer to any applicable terms of use of the publisher.
Accepted author manuscript, 712 KBLicence: Unspecified

Designing ionic liquids to enhance ethylene/ethane separations
McCalmont, S. (Author), Holbrey, J. (Supervisor) & Moura, L. (Supervisor), Dec 2024
Student thesis: Doctoral Thesis › Doctor of Philosophy

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Cite this

@article{7c1bc742211e4050887bc870564c1937,

title = "Insights into the absorption of hydrocarbon gases in phosphorus-containing ionic liquids",

abstract = "The solubility of ethane, ethylene, propane, and propylene was measured in two phosphorus-containing ionic liquids, trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate, [P6,6,6,14][DiOP], and 1-butyl-3-methylimidazolium dimethylphosphate, [C4C1Im][DMP], using an isochoric saturation method. The ionic liquid [C4C1Im][DMP] absorbed between 1 and 20 molecules of gas per 1000 ion pairs, at 313 K and 0.1 MPa, while [P6,6,6,14][DiOP] absorbed up to 169 molecules of propane per 1000 ion pairs under the same conditions. [C4C1Im][DMP] had a higher capacity to absorb olefins than paraffins, while the opposite was true for [P6,6,6,14][DiOP], with the former being slightly more selective than the later. From the analysis of the thermodynamic properties of solvation, we concluded that in both ionic liquids and for all of the studied gases the solvation is ruled by the entropy, even if its contribution is unfavorable. These results, together with density measurements, 2D NMR studies, and self-diffusion coefficients suggest that the gases{\textquoteright} solubility is ruled mostly by nonspecific interactions with the ionic liquids and that the looser ion packing in [P6,6,6,14][DiOP] makes it easier to accommodate the gases compared to [C4C1Im][DMP].",

keywords = "gases, hydrocarbons, salts, solubility, solvents, ionic liquid, separation",

author = "Sam McCalmont and {M. Vaz}, {In{\^e}s C.} and Hanne Oorts and Zheng Gong and Leila Moura and {Costa Gomes}, Margarida",

note = "Funding Information: The authors thank Pauline Lefebvre and Nicolas Scaglione for their help with some of the gas absorption measurements. M.C.G. and I.C.M.V. ackowledge the IDEX-LYON for financial support (Programme Investissements d{\textquoteright}Avenir ANR-16-IDEX-0005). L.M. acknowledges support from the Royal Academy of Engineering in the form of a research fellowship (RF\201718\17111). S.H.M. thanks the EPSRC for his standard research studentship (ref 2374580). The authors thank Professor John Holbrey for supplying ionic liquid [P6,6,6,14][DiOP] and Professor Panagiotis Manesiotis for his help in setting and interpreting the 2D NMR results. Funding Information: The authors thank Pauline Lefebvre and Nicolas Scaglione for their help with some of the gas absorption measurements. M.C.G. and I.C.M.V. ackowledge the IDEX-LYON for financial support (Programme Investissements d{\textquoteright}Avenir ANR-16-IDEX-0005). L.M. acknowledges support from the Royal Academy of Engineering in the form of a research fellowship (RF \201718 \17111). S.H.M. thanks the EPSRC for his standard research studentship (ref 2374580). The authors thank Professor John Holbrey for supplying ionic liquid [P ][DiOP] and Professor Panagiotis Manesiotis for his help in setting and interpreting the 2D NMR results. 6,6,6,14 Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = apr,

day = "20",

doi = "10.1021/acs.jpcb.2c08051",

language = "English",

volume = "127",

pages = "3402--3415",

journal = "Journal of Physical Chemistry B",

issn = "1520-6106",

publisher = "American Chemical Society",

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T1 - Insights into the absorption of hydrocarbon gases in phosphorus-containing ionic liquids

AU - McCalmont, Sam

AU - M. Vaz, Inês C.

AU - Oorts, Hanne

AU - Gong, Zheng

AU - Moura, Leila

AU - Costa Gomes, Margarida

N1 - Funding Information: The authors thank Pauline Lefebvre and Nicolas Scaglione for their help with some of the gas absorption measurements. M.C.G. and I.C.M.V. ackowledge the IDEX-LYON for financial support (Programme Investissements d’Avenir ANR-16-IDEX-0005). L.M. acknowledges support from the Royal Academy of Engineering in the form of a research fellowship (RF\201718\17111). S.H.M. thanks the EPSRC for his standard research studentship (ref 2374580). The authors thank Professor John Holbrey for supplying ionic liquid [P6,6,6,14][DiOP] and Professor Panagiotis Manesiotis for his help in setting and interpreting the 2D NMR results. Funding Information: The authors thank Pauline Lefebvre and Nicolas Scaglione for their help with some of the gas absorption measurements. M.C.G. and I.C.M.V. ackowledge the IDEX-LYON for financial support (Programme Investissements d’Avenir ANR-16-IDEX-0005). L.M. acknowledges support from the Royal Academy of Engineering in the form of a research fellowship (RF \201718 \17111). S.H.M. thanks the EPSRC for his standard research studentship (ref 2374580). The authors thank Professor John Holbrey for supplying ionic liquid [P ][DiOP] and Professor Panagiotis Manesiotis for his help in setting and interpreting the 2D NMR results. 6,6,6,14 Publisher Copyright: © 2023 American Chemical Society.

PY - 2023/4/20

Y1 - 2023/4/20

N2 - The solubility of ethane, ethylene, propane, and propylene was measured in two phosphorus-containing ionic liquids, trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate, [P6,6,6,14][DiOP], and 1-butyl-3-methylimidazolium dimethylphosphate, [C4C1Im][DMP], using an isochoric saturation method. The ionic liquid [C4C1Im][DMP] absorbed between 1 and 20 molecules of gas per 1000 ion pairs, at 313 K and 0.1 MPa, while [P6,6,6,14][DiOP] absorbed up to 169 molecules of propane per 1000 ion pairs under the same conditions. [C4C1Im][DMP] had a higher capacity to absorb olefins than paraffins, while the opposite was true for [P6,6,6,14][DiOP], with the former being slightly more selective than the later. From the analysis of the thermodynamic properties of solvation, we concluded that in both ionic liquids and for all of the studied gases the solvation is ruled by the entropy, even if its contribution is unfavorable. These results, together with density measurements, 2D NMR studies, and self-diffusion coefficients suggest that the gases’ solubility is ruled mostly by nonspecific interactions with the ionic liquids and that the looser ion packing in [P6,6,6,14][DiOP] makes it easier to accommodate the gases compared to [C4C1Im][DMP].

AB - The solubility of ethane, ethylene, propane, and propylene was measured in two phosphorus-containing ionic liquids, trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate, [P6,6,6,14][DiOP], and 1-butyl-3-methylimidazolium dimethylphosphate, [C4C1Im][DMP], using an isochoric saturation method. The ionic liquid [C4C1Im][DMP] absorbed between 1 and 20 molecules of gas per 1000 ion pairs, at 313 K and 0.1 MPa, while [P6,6,6,14][DiOP] absorbed up to 169 molecules of propane per 1000 ion pairs under the same conditions. [C4C1Im][DMP] had a higher capacity to absorb olefins than paraffins, while the opposite was true for [P6,6,6,14][DiOP], with the former being slightly more selective than the later. From the analysis of the thermodynamic properties of solvation, we concluded that in both ionic liquids and for all of the studied gases the solvation is ruled by the entropy, even if its contribution is unfavorable. These results, together with density measurements, 2D NMR studies, and self-diffusion coefficients suggest that the gases’ solubility is ruled mostly by nonspecific interactions with the ionic liquids and that the looser ion packing in [P6,6,6,14][DiOP] makes it easier to accommodate the gases compared to [C4C1Im][DMP].

KW - gases

KW - hydrocarbons

KW - salts

KW - solubility

KW - solvents

KW - ionic liquid

KW - separation

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DO - 10.1021/acs.jpcb.2c08051

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SN - 1520-6106

VL - 127

SP - 3402

EP - 3415

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

IS - 15

ER -

Insights into the absorption of hydrocarbon gases in phosphorus-containing ionic liquids

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

UN SDGs

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Student theses

Designing ionic liquids to enhance ethylene/ethane separations

Cite this