Molecular dynamics study of imidazolium ionic liquids and molecular solvents: insights into microstructure and transport phenomena
Binary mixtures composed of room-temperature ionic liquids and aprotic dipolar solvents are widely used in the modern electrochemistry. While these systems exhibit maximum electroconductivity and other changes in diluted solutions, as confirmed by NMR and vibrational spectroscopic data, there is cur...
Saved in:
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
V. N. Karazin Kharkiv National University
2024-09-01
|
| Series: | Вісник Харківського національного університету: Серія xімія |
| Subjects: | |
| Online Access: | https://periodicals.karazin.ua/chemistry/article/view/24305 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1841549964506824704 |
|---|---|
| author | Dmytro Dudariev Yaroslav Kolesnik Abdenacer Idrissi Oleg Kalugin |
| author_facet | Dmytro Dudariev Yaroslav Kolesnik Abdenacer Idrissi Oleg Kalugin |
| author_sort | Dmytro Dudariev |
| collection | DOAJ |
| description | Binary mixtures composed of room-temperature ionic liquids and aprotic dipolar solvents are widely used in the modern electrochemistry. While these systems exhibit maximum electroconductivity and other changes in diluted solutions, as confirmed by NMR and vibrational spectroscopic data, there is currently no theory that can fully explain these phenomena. In current work twelve mixtures of ionic liquids (ILs), in particular 1-butyl-3-methylimdazolium (C4mim+) with tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), trifluoromethanesulfonate (TFO-) and bis(trifluoromethane)sulfonimide (TFSI-) with molecular solvents such as acetonitrile (AN), propylene carbonate (PC) or gamma butyrolactone (γ-BL) were studied by the molecular dynamics simulation technique. The local structure of the mixtures was studied in the framework of radial distribution functions (RDFs) and running coordination numbers (RCNs) that showed the particular behavior in AN and TFSI- systems. For TFSI- system the presence of two peaks on the RDFs with similar intensities were observed. The mutual arrangement of cation and anion corresponding to observed on the RDFs interatomic distances were investigated: they represent the position when the nitrogen atom of the anion is close to the imidazolium ring and when nitrogen atom of TFSI- not directly interacting with the ring, but instead the oxygen atoms do. The cation-anion coordination numbers changed for mixtures with AN from ~1.2 to ~3.6, for PC – from 0.6 to 3.0 and for γ-BL – from 0.8 to 3.1 with the increasing mole fraction of the ILs. Also, the association analysis was conducted using two different distance criteria. The results showed the formation of large clusters at approximately 0.15, 0.20, and 0.25 IL mole fractions for AN, PC, and γ-BL, respectively, based on the first criterion. However, this criterion tends to overestimate the extent of aggregation. In contrast, the second, stricter criterion indicates that the formation of large aggregates begins at IL mole fractions similar to where the experimental conductivity curves reach their maximum. To analyze the transport properties the diffusion coefficients of all the components and shear viscosity for all binary mixtures were obtained. The diffusion coefficients show good agreement with experimental data. |
| format | Article |
| id | doaj-art-d9ce9af07f234c1ebfbe0f88d9a0d195 |
| institution | Kabale University |
| issn | 2220-637X 2220-6396 |
| language | English |
| publishDate | 2024-09-01 |
| publisher | V. N. Karazin Kharkiv National University |
| record_format | Article |
| series | Вісник Харківського національного університету: Серія xімія |
| spelling | doaj-art-d9ce9af07f234c1ebfbe0f88d9a0d1952025-01-10T11:27:05ZengV. N. Karazin Kharkiv National UniversityВісник Харківського національного університету: Серія xімія2220-637X2220-63962024-09-01416–246–2410.26565/2220-637X-2023-41-0124305Molecular dynamics study of imidazolium ionic liquids and molecular solvents: insights into microstructure and transport phenomenaDmytro Dudariev0Yaroslav Kolesnik1Abdenacer Idrissi2Oleg Kalugin3V. N. Karazin Kharkiv National University, 4 Svobody sq., Kharkiv, 61022, UkraineV. N. Karazin Kharkiv National University, 4 Svobody sq., Kharkiv, 61022, UkraineUniversity of Lille, CNRS UMR 8516 -LASIRe - Laboratoire Avancé de Spectroscopie pour les Interactions la Réactivité et l'environnement, 59000 Lille, FranceV. N. Karazin Kharkiv National University, 4 Svobody sq., Kharkiv, 61022, UkraineBinary mixtures composed of room-temperature ionic liquids and aprotic dipolar solvents are widely used in the modern electrochemistry. While these systems exhibit maximum electroconductivity and other changes in diluted solutions, as confirmed by NMR and vibrational spectroscopic data, there is currently no theory that can fully explain these phenomena. In current work twelve mixtures of ionic liquids (ILs), in particular 1-butyl-3-methylimdazolium (C4mim+) with tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), trifluoromethanesulfonate (TFO-) and bis(trifluoromethane)sulfonimide (TFSI-) with molecular solvents such as acetonitrile (AN), propylene carbonate (PC) or gamma butyrolactone (γ-BL) were studied by the molecular dynamics simulation technique. The local structure of the mixtures was studied in the framework of radial distribution functions (RDFs) and running coordination numbers (RCNs) that showed the particular behavior in AN and TFSI- systems. For TFSI- system the presence of two peaks on the RDFs with similar intensities were observed. The mutual arrangement of cation and anion corresponding to observed on the RDFs interatomic distances were investigated: they represent the position when the nitrogen atom of the anion is close to the imidazolium ring and when nitrogen atom of TFSI- not directly interacting with the ring, but instead the oxygen atoms do. The cation-anion coordination numbers changed for mixtures with AN from ~1.2 to ~3.6, for PC – from 0.6 to 3.0 and for γ-BL – from 0.8 to 3.1 with the increasing mole fraction of the ILs. Also, the association analysis was conducted using two different distance criteria. The results showed the formation of large clusters at approximately 0.15, 0.20, and 0.25 IL mole fractions for AN, PC, and γ-BL, respectively, based on the first criterion. However, this criterion tends to overestimate the extent of aggregation. In contrast, the second, stricter criterion indicates that the formation of large aggregates begins at IL mole fractions similar to where the experimental conductivity curves reach their maximum. To analyze the transport properties the diffusion coefficients of all the components and shear viscosity for all binary mixtures were obtained. The diffusion coefficients show good agreement with experimental data.https://periodicals.karazin.ua/chemistry/article/view/243051-butyl-3-methylimdazoliumionic liquidsaprotic dipolar solventslocal structuretransport propertiesionic aggregation |
| spellingShingle | Dmytro Dudariev Yaroslav Kolesnik Abdenacer Idrissi Oleg Kalugin Molecular dynamics study of imidazolium ionic liquids and molecular solvents: insights into microstructure and transport phenomena Вісник Харківського національного університету: Серія xімія 1-butyl-3-methylimdazolium ionic liquids aprotic dipolar solvents local structure transport properties ionic aggregation |
| title | Molecular dynamics study of imidazolium ionic liquids and molecular solvents: insights into microstructure and transport phenomena |
| title_full | Molecular dynamics study of imidazolium ionic liquids and molecular solvents: insights into microstructure and transport phenomena |
| title_fullStr | Molecular dynamics study of imidazolium ionic liquids and molecular solvents: insights into microstructure and transport phenomena |
| title_full_unstemmed | Molecular dynamics study of imidazolium ionic liquids and molecular solvents: insights into microstructure and transport phenomena |
| title_short | Molecular dynamics study of imidazolium ionic liquids and molecular solvents: insights into microstructure and transport phenomena |
| title_sort | molecular dynamics study of imidazolium ionic liquids and molecular solvents insights into microstructure and transport phenomena |
| topic | 1-butyl-3-methylimdazolium ionic liquids aprotic dipolar solvents local structure transport properties ionic aggregation |
| url | https://periodicals.karazin.ua/chemistry/article/view/24305 |
| work_keys_str_mv | AT dmytrodudariev moleculardynamicsstudyofimidazoliumionicliquidsandmolecularsolventsinsightsintomicrostructureandtransportphenomena AT yaroslavkolesnik moleculardynamicsstudyofimidazoliumionicliquidsandmolecularsolventsinsightsintomicrostructureandtransportphenomena AT abdenaceridrissi moleculardynamicsstudyofimidazoliumionicliquidsandmolecularsolventsinsightsintomicrostructureandtransportphenomena AT olegkalugin moleculardynamicsstudyofimidazoliumionicliquidsandmolecularsolventsinsightsintomicrostructureandtransportphenomena |