Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity Setup
The dynamical properties of four protic ionic liquids, based on the ethyltriazolium ([C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></seman...
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MDPI AG
2023-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/13/5147 |
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| author | Eduardo Maurina Morais Alexander Idström Lars Evenäs Anna Martinelli |
| author_facet | Eduardo Maurina Morais Alexander Idström Lars Evenäs Anna Martinelli |
| author_sort | Eduardo Maurina Morais |
| collection | DOAJ |
| description | The dynamical properties of four protic ionic liquids, based on the ethyltriazolium ([C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>HTr<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>124</mn></msub></semantics></math></inline-formula>]) and the ethylimidazolium ([C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>HIm]) cation, were investigated. The associated anions were the triflate ([TfO]) and the bistriflimide ([TFSI]). Ionic conductivity values and self-diffusion coefficients were measured and discussed, extending the discussion to the concept of fragility. Furthermore, in order to allow the measurement of the ionic conductivity of very small volumes (<0.5 mL) of ionic liquid under an inert and dry atmosphere, a new setup was developed. It was found that the cation nature strongly affected the transport properties, the [C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>HTr<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>124</mn></msub></semantics></math></inline-formula>] cation resulting in slower dynamics than the [C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>HIm] one. This was concluded from both conductivity and diffusivity measurements while for both properties, the anion had a lesser effect. By fitting the conductivity data with the Vogel–Fulcher–Tammann (VFT) equation, we could also estimate the fragility of these ionic liquids, which all fell in the range of very fragile glass-forming materials. Finally, the slower dynamics observed in the triazolium-based ionic liquids can be rationalized by the stronger interactions that this cation establishes with both anions, as deduced from the frequency analysis of relevant Raman signatures and density functional theory (DFT) calculations. |
| first_indexed | 2024-03-11T01:33:34Z |
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| language | English |
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| spelling | doaj.art-bc346e03ba984ad6902be777c5ba25792023-11-18T17:08:52ZengMDPI AGMolecules1420-30492023-06-012813514710.3390/molecules28135147Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity SetupEduardo Maurina Morais0Alexander Idström1Lars Evenäs2Anna Martinelli3Department of Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Gothenburg, SwedenDepartment of Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Gothenburg, SwedenDepartment of Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Gothenburg, SwedenDepartment of Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Gothenburg, SwedenThe dynamical properties of four protic ionic liquids, based on the ethyltriazolium ([C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>HTr<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>124</mn></msub></semantics></math></inline-formula>]) and the ethylimidazolium ([C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>HIm]) cation, were investigated. The associated anions were the triflate ([TfO]) and the bistriflimide ([TFSI]). Ionic conductivity values and self-diffusion coefficients were measured and discussed, extending the discussion to the concept of fragility. Furthermore, in order to allow the measurement of the ionic conductivity of very small volumes (<0.5 mL) of ionic liquid under an inert and dry atmosphere, a new setup was developed. It was found that the cation nature strongly affected the transport properties, the [C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>HTr<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>124</mn></msub></semantics></math></inline-formula>] cation resulting in slower dynamics than the [C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>HIm] one. This was concluded from both conductivity and diffusivity measurements while for both properties, the anion had a lesser effect. By fitting the conductivity data with the Vogel–Fulcher–Tammann (VFT) equation, we could also estimate the fragility of these ionic liquids, which all fell in the range of very fragile glass-forming materials. Finally, the slower dynamics observed in the triazolium-based ionic liquids can be rationalized by the stronger interactions that this cation establishes with both anions, as deduced from the frequency analysis of relevant Raman signatures and density functional theory (DFT) calculations.https://www.mdpi.com/1420-3049/28/13/5147protic ionic liquidsimidazoliumtriazoliumself-diffusionionic conductivityfragility |
| spellingShingle | Eduardo Maurina Morais Alexander Idström Lars Evenäs Anna Martinelli Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity Setup Molecules protic ionic liquids imidazolium triazolium self-diffusion ionic conductivity fragility |
| title | Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity Setup |
| title_full | Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity Setup |
| title_fullStr | Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity Setup |
| title_full_unstemmed | Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity Setup |
| title_short | Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity Setup |
| title_sort | transport properties of protic ionic liquids based on triazolium and imidazolium development of an air free conductivity setup |
| topic | protic ionic liquids imidazolium triazolium self-diffusion ionic conductivity fragility |
| url | https://www.mdpi.com/1420-3049/28/13/5147 |
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