Using thermodynamics to assess the molecular interactions of tetrabutylphosphonium carboxylate-water mixtures

Transcription

1 /CH18481_AC CSIRO 2019 Australian Journal of Chemistry Supplementary Material Using thermodynamics to assess the molecular interactions of tetrabutylphosphonium carboxylate-water mixtures Darius J. Yeadon, A,E Johan Jacquemin, A,B,E Natalia V. Plechkova, A Margarida Costa Gomes, C and Kenneth R. Seddon A,D A QUILL Research Centre, Queen s University Belfast, David Keir Building, Stranmillis Road, Belfast BT9 5AG, Northern Ireland, UK. B Université de Tours, Laboratoire PCM2E, Parc de Grandmont 37200, Tours, France. C Laboratoire de Chimie, Ecole Normale Supérieure de Lyon and CNRS, 46 allée d'italie, Lyon Cedex 07, France. D Deceased. E Corresponding authors. dyeadon01@qub.ac.uk; jj@univ-tours.fr

2 General chemical characterisation of selected ionic liquids Tetrabutylphosphonium ethanoate: 1 H NMR (d 6 -dmso, 400 MHz, K) /ppm = 0.53 (t, 12H, (CH 2 CH 3 ) 4 ); 1.05 (m, 8H, (CH 2 CH 2 CH 3 ) 4 ); 1.19 (m, 8H, (CH 2 CH 2 CH 3 ) 4, s, 3H, CH 3 -COO); 2.21 (m, 8H, P(CH 2 ) 4 ). 13 C NMR (d 6 - dmso, 101 MHz, K) /ppm = ((CH 2 CH 2 CH 3 ) 4 ); (d, P-CH 2 ); (d, (CH 2 CH 2 CH 3 ) 4 ); (d, (CH 2 CH 2 CH 3 ) 4 ); (CH 3 COO); (COO). 31 P NMR (PO 4 (CH 3 ) 3, 162 MHz, K) /ppm = (s, P(CH 2 CH 2 CH 2 CH 3 ) 4 ). MS ES+ m/z (% rel. Intensity): 259 M + (100). Calc. for [P ] , found MS ES- m/z (% rel. Intensity): 377 M - (100). Calc. for [{P }{C 1 COO} 2 ] , found Tetrabutylphosphonium propanoate: 1 H NMR (d 6 -dmso, 400 MHz, K) /ppm = 0.50 (t, 3H, CH 3 CH 2 COO); 0.52 (t, 12H, (CH 2 CH 2 CH 3 ) 4 ); 1.05 (m, 8H, (CH 2 CH 2 CH 3 ) 4 ); 1.16 (m, 8H, (CH 2 CH 2 CH 3 ) 4 ); 1.41 (q, 2H, CH 3 CH 2 COO); 2.20 (m, 8H, P(CH 2 ) 4 ). 13 C NMR (d 6 -dmso, 101 MHz, K) /ppm = (CH 3 CH 2 COO); ((CH 2 CH 2 CH 3 ) 4 ); (d, P(CH 2 ) 4 ); (d, (CH 2 CH 2 CH 3 ) 4 ); (d, (CH 2 CH 2 CH 3 ) 4 ); (CH 3 CH 2 COO); (COO). 31 P NMR (PO 4 (CH 3 ) 3, 162 MHz, K) /ppm = (s, P(CH 2 CH 2 CH 2 CH 3 ) 4 ). MS ES+ m/z (% rel. Intensity): 259 M + (100). Calc. for [P ] , found MS ES- m/z (% rel. Intensity): 405 M - (100). Calc. for [{P }{C 2 COO} 2 ] , found Tetrabutylphosphonium octanoate: 1 H NMR (d 6 -dmso, 400 MHz, K) /ppm = 0.46 (t, 3H, CH 3 (CH 2 ) 6 COO); 0.54 (t, 12H, (CH 2 CH 2 CH 3 ) 4 ); 0.86 (m, 10H, (CH 3 (CH 2 ) 5 CH 2 COO); 1.08 (m, 8H, (CH 2 CH 2 CH 3 ) 4 ); 1.18 (m, 8H, (CH 2 CH 2 CH 3 ) 4 ); 1.45 (t, 2H, CH 2 COO); 2.25 (P(CH 2 ) 4 ). 13 C NMR (d 6 -dmso, 101 MHz, K) /ppm = ((CH 2 CH 2 CH 3 ) 4 ); (CH 3 (CH 2 ) 5 CH 2 COO); (d, P(CH 2 ) 4 ); (CH 3 CH 2 (CH 2 ) 5 COO); (d, (CH 2 CH 2 CH 3 ) 4 ); (d, (CH 2 CH 2 CH 3 ) 4 ); (CH 3 CH 2 CH 2 (CH 2 ) 4 COO); (CH 3 (CH 2 ) 2 CH 2 (CH 2 ) 3 COO); (CH 3 (CH 2 ) 3 CH 2 (CH 2 ) 2 COO); (CH 3 (CH 2 ) 4 CH 2 CH 2 COO); (CH 3 (CH 2 ) 5 CH 2 COO); (COO). 31 P NMR (PO 4 (CH 3 ) 3, 162 MHz, K) /ppm = (s, P(CH 2 CH 2 CH 2 CH 3 ) 4 ). MS ES+ m/z (% rel. Intensity): 259 M + (100). Calc. for [P ] , found MS ES- m/z (% rel. Intensity): 143 M - (100). Calc. for [C 7 COO] , found S2

3 Table S1. Elemental analysis and water content: Ionic Liquid %C %H Calc. Exp. Calc. Exp. Water content / ppm [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] Table S2. Thermal gravimetric analysis: Ionic Liquid T d (exp)/ C T d (lit.)/ C [P ][C 1 COO] [1] [P ][C 2 COO] [2] [P ][C 8 COO] [1] C 80 Weight / % T / C Figure S1. TGA trace for [P ][C 1 COO] at a heating rate of 10 C min -1. S3

4 C 80 Weight / % T / C Figure S2. TGA trace for [P ][C 2 COO] at a heating rate of 10 C min C 80 Weight / % T / C Figure S3. TGA trace for [P ][C 7 COO] at a heating rate of 10 C min -1. S4

5 Table S3. Differential scanning calorimetry heating: Ionic Liquid Glass transitions T g / C Solid-solid transitions T sol / C H sol / kj mol -1 Melting T m / C H f / kj mol -1 T g T g lit. T sol H T m H f T m lit. [P ][C 1 COO] [1] [P ][C 2 COO] [P ][C 7 COO] [1] Table S4. Differential scanning calorimetry cooling: Crystallisation Ionic Liquid T c / C H / kj mol -1 T c H c T c H c [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] C C 0.0 Heat Flow / W g C C Exo Down T / C Figure S4. DSC trace of [P ][C 1 COO] at a standard heating and cooling rate of 5 C min -1. S5

6 C C(I) Heat Flow / W g C C C Exo Down T / C Figure S5. DSC trace of [P ][C 2 COO] at a standard heating and cooling rate of 5 C min C(I) 0.5 Heat Flow / W g Exo Down T / C Figure S6. DSC trace of [P ][C 7 COO] at a standard heating and cooling rate of 5 C min -1. S6

7 Table S5. Densities,, of the dry [P ][C n COO] ILs as a function of temperature, K. [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] H2O: 140ppm 180ppm 120ppm T / K / g cm Experimental uncertainties: u( ) = g cm -3 ; u(t) = K; u( ) = S7

8 Table S6. Densities,, of [P ][CnCOO] as a function of temperature, K, and mole fraction of water, K K K K K K K K K K K / g cm -3 [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] u( ) = g cm -3 ; u(t) = K; u( ) = S8

9 Table S7. Molar volume,, excess molar volumes,, apparent molar volumes,, and partial molar volumes,,, for [P ][C1COO]-water mixtures as a function of water mole fraction,, and temperature, K K / cm 3 mol -1 / cm 3 mol -1 / cm 3 mol -1 / cm 3 mol -1, / cm 3 mol -1, / cm 3 mol K K S9

10 Table S8. Molar volume,, excess molar volumes,, apparent molar volumes,, and partial molar volumes,,, for [P ][C2COO]-water mixtures as a function of water mole fraction,, and temperature, K K / cm 3 mol -1 / cm 3 mol -1 / cm 3 mol -1 / cm 3 mol -1, / cm 3 mol -1, / cm 3 mol K K K K S10

11 Table S9. Molar volume,, excess molar volumes,, apparent molar volumes,, and partial molar volumes,,, for [P ][C7COO]-water mixtures as a function of water mole fraction,, and temperature, K K / cm 3 mol -1 / cm 3 mol -1 / cm 3 mol -1 / cm 3 mol -1, / cm 3 mol -1, / cm 3 mol K K K K K S11

12 K K K K K S12

13 Table S10. Excess molar volume,, and partial molar volume,,, fitting parameters obtained from least squares test T / K A0 A1 A2 A3 AAD / % [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] Table S11. Viscosities,, of dry [P ][CnCOO] ILs, as a function of temperature, K. T / K ƞ / mpa s [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] [P ][C1COO] and [P ][C2COO]: ur( ) = 0.35 %; u(t) = K [P ][C7COO]: ur( ) = 0.1 %; u(t) = K S13

14 Table S12. Viscosities,, of binary [P ][CnCOO]-water mixtures as a function of temperature, K K K K K K K K K K K K / mpa s [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] ur( ) = 0.1 %; u(t) = K; u( ) = S14

15 Table S13. Fitting parameters from the Vogel-Fulcher-Tammann equation for viscosities,, of binary [P ][CnCOO]-water mixtures as a function of temperature, K. / mpa s B / K / K 10 4 AAD / % [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] Table S14. Excess Gibbs free energy of viscous flow, for binary [P ][C1COO]-water mixtures as a function of temperature, K K K K / kj mol Table S15. Excess Gibbs free energy of viscous flow, for binary [P ][C2COO]-water mixtures as a function of temperature, K K K K K / kj mol S15

16 Table S16. Excess Gibbs free energy of viscous flow, for binary [P ][C7COO]-water mixtures as a function of temperature, K K K K K K K K K K K K / kj mol S16

17 Table S17. Stoichiometric data and heat effects of the calorimetry experiments with [P ][C1COO] + water at K. The subscript c and d mean cell (or container) and dispenser (or syringe) respectively., / mol, / mol, / mol / J 9.32E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E u( ) = 10 mj; u(t) = 50 µk S17

18 Table S18. Stoichiometric data and heat effects of the calorimetry experiments with [P ][C2COO] + water at K. The subscript c and d mean cell (or container) and dispenser (or syringe) respectively., / mol, / mol, / mol / J 8.25E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E u( ) = 10 mj; u(t) = 50 µk S18

19 Table S19. Stoichiometric data and heat effects of the calorimetry experiments with [P ][C7COO] + water at K. The subscript c and d mean cell (or container) and dispenser (or syringe) respectively., / mol, / mol, / mol / J 1.10E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E u( ) = 10 mj; u(t) = 50 µk Table S20. Fitting parameters obtained for the partial excess enthalpies of water,, with the Redlich-Kister equation IL water mixture / kj mol -1 / kj mol -1 / kj mol -1 AAD / % [P ][C 1 COO] [P ][C 2 COO] [P ][C 7 COO] References [1] Q. Yang, D. Xu, J. Zhang, Y. Zhu, Z. Zhang, C. Qian, et al. Long-Chain Fatty Acid-Based Phosphonium Ionic Liquids with Strong Hydrogen-Bond Basicity and Good Lipophilicity: Synthesis, Characterization, and Application in Extraction. ACS Sustainable Chem. Eng. 2015, 3, 309. [2] Y. Cao, T. Mu. Comprehensive Investigation on the Thermal Stability of 66 Ionic Liquids by Thermogravimetric Analysis. Ind. Eng. Chem. Res. 2014, 53, S19