Effect of Cation Structure in Quinolinium-Based Ionic Liquids on the Solubility in Aromatic Sulfur Compounds or Heptane: Thermodynamic Study on Phase Diagrams
Abstract
:1. Introduction
2. Results and Discussion
3. Materials and Methods
3.1. Materials
3.2. Karl–Fischer Analysis
3.3. Phase Equilibria Apparatus and Measurements
3.4. Correlation with NRTL Equation
4. Conclusions and Future Perspectives
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Samples of the compounds [BQuin][NTf2], [HQuin][NTf2] and [OQuin][NTf2]) are available from the authors. |
x1 | TSLE/K | γ1 | x1 | TSLE/K | γ1 |
---|---|---|---|---|---|
[BiQuin][NTf2] (1) + thiophene (2) | |||||
1.0000 | 321.5 | 1.00 | 0.5139 | 297.8 | 0.48 |
0.9527 | 320.2 | 0.99 | 0.4904 | 295.7 | 0.44 |
0.8930 | 318.0 | 0.95 | 0.4541 | 292.5 | 0.38 |
0.8515 | 316.5 | 0.92 | 0.4106 | 287.9 | 0.32 |
0.8008 | 314.5 | 0.87 | 0.3808 | 284.2 | 0.27 |
0.7746 | 313.3 | 0.83 | 0.3514 | 280.5 | 0.23 |
0.7328 | 311.3 | 0.78 | 0.3347 | 277.9 | 0.20 |
0.7105 | 310.1 | 0.75 | 0.3066 | 273.3 | 0.16 |
0.6664 | 307.8 | 0.69 | 0.2808 | 269.4 | 0.13 |
0.6153 | 305.1 | 0.62 | 0.2543 | 264.8 | 0.10 |
0.5665 | 302.2 | 0.55 | 0.2231 | 258.7 | 0.06 |
[BQuin][NTf2] (1) + thiophene (2) | |||||
1.0000 | 329.6 | 1.00 | 0.6235 | 311.4 | 0.62 |
0.9807 | 329.2 | 1.00 | 0.5497 | 305.8 | 0.51 |
0.9664 | 328.8 | 0.99 | 0.4948 | 300.6 | 0.42 |
0.9476 | 328.3 | 0.99 | 0.4499 | 296.3 | 0.35 |
0.9106 | 327.0 | 0.97 | 0.4094 | 291.0 | 0.29 |
0.8736 | 325.6 | 0.94 | 0.3621 | 284.5 | 0.22 |
0.8415 | 324.2 | 0.91 | 0.3279 | 278.8 | 0.16 |
0.8216 | 323.1 | 0.89 | 0.3080 | 275.2 | 0.14 |
0.7919 | 321.5 | 0.85 | 0.2542 | 264.5 | 0.07 |
0.7309 | 317.9 | 0.78 | 0.2226 | 255.2 | 0.04 |
0.6972 | 316.0 | 0.73 | |||
[HQuin][NTf2] (1) + thiophene (2) | |||||
1.0000 | 317.9 | 1.00 | 0.5226 | 299.0 | 0.42 |
0.9431 | 316.8 | 0.98 | 0.4878 | 296.5 | 0.36 |
0.8968 | 315.5 | 0.95 | 0.4625 | 294.8 | 0.32 |
0.8472 | 313.7 | 0.90 | 0.4144 | 290.7 | 0.25 |
0.8091 | 312.4 | 0.85 | 0.3633 | 285.6 | 0.18 |
0.7695 | 311.1 | 0.80 | 0.3367 | 282.2 | 0.15 |
0.7284 | 309.4 | 0.74 | 0.2917 | 276.1 | 0.09 |
0.6662 | 306.8 | 0.64 | 0.2638 | 271.5 | 0.07 |
0.6292 | 305.2 | 0.58 | 0.2398 | 267.0 | 0.05 |
0.5830 | 302.7 | 0.51 | 0.2146 | 262.5 | 0.03 |
0.5523 | 300.8 | 0.46 | 0.1860 | 256.3 | 0.02 |
[OQuin][NTf2] (1) + thiophene (2) | |||||
1.0000 | 322.3 | 1.00 | 0.4361 | 297.1 | 0.29 |
0.9436 | 321.4 | 0.98 | 0.4093 | 294.6 | 0.25 |
0.8762 | 319.3 | 0.93 | 0.3762 | 291.0 | 0.20 |
0.7590 | 314.7 | 0.79 | 0.3319 | 285.0 | 0.14 |
0.6824 | 311.3 | 0.68 | 0.3028 | 280.7 | 0.10 |
0.6244 | 308.4 | 0.59 | 0.2694 | 275.0 | 0.07 |
0.5934 | 306.8 | 0.54 | 0.2345 | 268.5 | 0.04 |
0.5319 | 303.5 | 0.44 | 0.2093 | 263.0 | 0.02 |
0.5061 | 301.9 | 0.40 | 0.1861 | 256.3 | 0.01 |
0.4734 | 300.0 | 0.35 |
x1 | TSLE/K | γ1 | x1 | TSLE/K | γ1 |
---|---|---|---|---|---|
[BiQuin][NTf2] (1) + benzothiophene (2) | |||||
1.0000 | 321.5 | 1.00 | 0.5960 | 304.7 | 0.64 |
0.9175 | 319.6 | 0.98 | 0.5495 | 301.1 | 0.56 |
0.8633 | 317.9 | 0.96 | 0.5153 | 297.7 | 0.49 |
0.8325 | 316.8 | 0.94 | 0.4704 | 293.4 | 0.40 |
0.7910 | 315.0 | 0.90 | 0.4332 | 288.6 | 0.33 |
0.7337 | 312.8 | 0.84 | 0.4052 | 283.6 | 0.27 |
0.6469 | 307.9 | 0.72 | |||
[BQuin][NTf2] (1) + benzothiophene (2) | |||||
1.0000 | 329.6 | 1.00 | 0.4839 | 298.7 | 0.37 |
0.9185 | 326.8 | 0.98 | 0.4419 | 292.3 | 0.29 |
0.8200 | 322.7 | 0.90 | 0.4002 | 286.0 | 0.22 |
0.7509 | 319.6 | 0.82 | 0.3675 | 280.7 | 0.16 |
0.6885 | 315.3 | 0.73 | 0.3481 | 275.4 | 0.13 |
0.6181 | 310.9 | 0.62 | 0.3166 | 275.2 | |
0.5674 | 307.1 | 0.53 | 0.2786 | 275.2 | |
0.5261 | 303.0 | 0.45 | |||
[HQuin][NTf2] (1) + benzothiophene (2) | |||||
1.0000 | 317.9 | 1.00 | 0.6037 | 302.4 | 0.48 |
0.9559 | 316.7 | 0.99 | 0.5493 | 299.5 | 0.39 |
0.9112 | 315.3 | 0.96 | 0.4990 | 295.8 | 0.30 |
0.8650 | 313.7 | 0.91 | 0.4586 | 291.4 | 0.24 |
0.8277 | 312.4 | 0.86 | 0.4112 | 286.5 | 0.17 |
0.7619 | 310.0 | 0.76 | 0.3797 | 282.4 | 0.13 |
0.7205 | 308.3 | 0.69 | 0.3481 | 277.5 | 0.09 |
0.6521 | 305.1 | 0.57 | |||
[OQuin][NTf2] (1) + benzothiophene (2) | |||||
1.0000 | 322.3 | 1.00 | 0.5573 | 304.0 | 0.45 |
0.9439 | 320.9 | 0.99 | 0.5180 | 301.6 | 0.38 |
0.9160 | 320.0 | 0.97 | 0.4763 | 298.4 | 0.31 |
0.8591 | 318.1 | 0.92 | 0.4415 | 295.4 | 0.25 |
0.8276 | 316.9 | 0.88 | 0.4137 | 292.7 | 0.21 |
0.8039 | 315.8 | 0.85 | 0.3790 | 288.3 | 0.15 |
0.7693 | 314.3 | 0.80 | 0.3418 | 282.3 | 0.10 |
0.7239 | 312.4 | 0.74 | 0.3069 | 275.0 | 0.07 |
0.6591 | 309.5 | 0.63 | 0.2683 | 264.8 | 0.03 |
0.6028 | 306.5 | 0.53 |
x1 | TSLE/K | γ1 | x1 | TSLE/K | γ1 |
---|---|---|---|---|---|
[BiQuin][NTf2] (1) + 2-methylthiophene (2) | |||||
1.0000 | 321.5 | 1.00 | 0.5601 | 302.0 | 0.56 |
0.9665 | 320.5 | 1.00 | 0.5204 | 299.1 | 0.50 |
0.9334 | 319.4 | 0.99 | 0.4646 | 295.1 | 0.43 |
0.8815 | 317.7 | 0.96 | 0.4359 | 292.5 | 0.39 |
0.8280 | 315.6 | 0.91 | 0.4083 | 290.0 | 0.35 |
0.7882 | 314.1 | 0.87 | 0.3813 | 287.4 | 0.32 |
0.7505 | 312.5 | 0.82 | 0.3434 | 283.6 | 0.28 |
0.7082 | 310.5 | 0.77 | 0.3135 | 280.4 | 0.24 |
0.6620 | 308.2 | 0.71 | 0.2865 | 277.4 | 0.22 |
0.6081 | 305.0 | 0.63 | 0.2576 | 274.0 | 0.19 |
x1 | TSLE/K | x1 | TSLE/K | TLLE/K |
---|---|---|---|---|
[BiQuin][NTf2] (1) + heptane (2) | ||||
1.0000 | 321.51 | 0.9684 | 321.49 | 324.54 |
0.9833 | 321.49 | 0.9640 | 321.49 | 337.15 |
0.9490 | 321.49 | 361.29 | ||
[BQuin][NTf2] (1) + heptane (2) | ||||
1.000 | 329.6 | 0.967 | 328.4 | 333.3 |
0.988 | 329.0 | 0.956 | 328.4 | 355.6 |
0.975 | 328.4 | 0.967 | 328.4 | 333.3 |
[HQuin][NTf2] (1) + heptane (2) | ||||
1.000 | 317.9 | 0.958 | 314.0 | 321.3 |
0.985 | 316.8 | 0.946 | 314.0 | 348.0 |
0.971 | 315.3 | |||
[OQuin][NTf2] (1) + heptane (2) | ||||
1.000 | 322.3 | 0.942 | 318.0 | 326.0 |
0.982 | 321.4 | 0.923 | 318.0 | 360.1 |
0.961 | 320.5 |
System | NRTL Parameters | RMSD | ||
---|---|---|---|---|
[BiQuin][NTf2] (1) + thiophene (2) | −4591.78 | −2579.41 | 0.78 | 0.64 |
[BQuin][NTf2] (1) + thiophene (2) | −5915.62 | −2776.95 | 0.71 | 0.45 |
[HQuin][NTf2] (1) + thiophene (2) | −5797.59 | −3159.81 | 0.62 | 0.56 |
[OQuin][NTf2] (1) + thiophene (2) | −6318.13 | −3125.06 | 0.62 | 0.69 |
[BiQuin][NTf2] (1) + benzothiophene (2) | −8888.07 | −2032.34 | 0.46 | 0.55 |
[BQuin][NTf2] (1) + thiophene (2) | −11,775.80 | −2937.43 | 0.45 | 0.78 |
[HQuin][NTf2] (1) + thiophene (2) | −11,068.53 | −3916.45 | 0.45 | 0.80 |
[OQuin][NTf2] (1) + thiophene (2) | −12,273.10 | −3527.76 | 0.45 | 1.05 |
[BiQuin][NTf2] (1) + 2-methylthiophene (2) | −2000.44 | −4000.62 | 0.20 | 0.85 |
Structure | Name, Abbreviation, CAS No. |
---|---|
N-butylisoquinolinium bis(trifluoromethylsulfonyl)imide, [BiQuin][NTf2] M = 466.42 g·mol−1 CAS No. 957763-47-2 | |
N-butylquinolinium bis(trifluoromethylsulfonyl)imide, [BQuin][NTf2] M = 466.42 g·mol−1 CAS No. 1289382-58-6 | |
N-hexylquinolinium bis(trifluoromethylsulfonyl)imide, [HQuin][NTf2] M = 494.47 g·mol−1 CAS No. 1263302-30-2 | |
N-octylquinolinium bis(trifluoromethylsulfonyl)imide, [OQuin][NTf2] M = 522.52 g·mol−1 CAS No. 868671-34-5 |
Sample | Source | Initial Mole Fraction Purity (wt%) | Purification Method | Final Mole Fraction Purity (wt%) | Analysis Method | Water Content/ppm |
---|---|---|---|---|---|---|
[BiQuin][NTf2] | own synthesis | - | crystallization, vacuum heating | 97.0 | Karl–Fischer, 1H-NMR | 290 |
[BQuin][NTf2] | own synthesis | - | crystallization, vacuum heating | 97.0 | Karl–Fischer, 1H-NMR | 280 |
[HQuin][NTf2] | own synthesis | - | crystallization, vacuum heating | 97.0 | Karl–Fischer, 1H-NMR | 280 |
[OQuin][NTf2] | own synthesis | - | crystallization, vacuum heating | 97.0 | Karl–Fischer, 1H-NMR | 250 |
heptane | Sigma-Aldrich b | 99.0 | - | 99.0 | - | 50 |
thiophene | Sigma-Aldrich b | 99.0 | - | 99.0 | - | 70 |
2-methylthiophene | Sigma-Aldrich b | 98.0 | - | 98.0 | - | 110 |
benzothiophene | Sigma-Aldrich b | 98.0 | - | 98.0 | - | 150 |
Ionic Liquid | Tg,1/K | ΔCp(g),1/J mol−1 K−1 | Tfus/K | ΔfusH/kJ mol−1 |
---|---|---|---|---|
[BiQuin][NTf2] [19] | 217.9 | 332.4 | 321.0 | 46.13 |
[BQuin][NTf2] [18] | 199.2 | 105.9 | 329.1 | 44.14 |
[HQuin][NTf2] [20] | 219.3 | 317.7 | 317.2 | 63.54 |
[OQuin][NTf2] [22] | 219.4 | 423 | 321.3 | 62.91 |
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Królikowska, M.; Królikowski, M.; Domańska, U. Effect of Cation Structure in Quinolinium-Based Ionic Liquids on the Solubility in Aromatic Sulfur Compounds or Heptane: Thermodynamic Study on Phase Diagrams. Molecules 2020, 25, 5687. https://doi.org/10.3390/molecules25235687
Królikowska M, Królikowski M, Domańska U. Effect of Cation Structure in Quinolinium-Based Ionic Liquids on the Solubility in Aromatic Sulfur Compounds or Heptane: Thermodynamic Study on Phase Diagrams. Molecules. 2020; 25(23):5687. https://doi.org/10.3390/molecules25235687
Chicago/Turabian StyleKrólikowska, Marta, Marek Królikowski, and Urszula Domańska. 2020. "Effect of Cation Structure in Quinolinium-Based Ionic Liquids on the Solubility in Aromatic Sulfur Compounds or Heptane: Thermodynamic Study on Phase Diagrams" Molecules 25, no. 23: 5687. https://doi.org/10.3390/molecules25235687