Tunable hydrophobic eutectic solvents based on terpenes and monocarboxylic acids

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1 Supporting Information Tunable hydrophobic eutectic solvents based on terpenes and monocarboxylic s Mónia A. R. Martins 1-4, Emanuel A. Crespo 1,5, Paula V. A. Pontes 4, Liliana P. Silva 1, Mark Bülow 5,Guilherme J. Maximo 4, Eduardo A. C. Batista 4, Christoph Held 5, Simão P. Pinho 2,3, and João A. P. Coutinho 1,* 1 CICECO Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Aveiro, Portugal 2 Associate Laboratory LSRE-LCM, Department of Chemical and Biological Technology, Polytechnic Institute of Bragança, Bragança, Portugal 3 Mountain Research Center CIMO, Polytechnic Institute of Bragança, Bragança, Portugal 4 Faculty of Food Engineering, University of Campinas, Campinas, Brazil 5 Laboratory of Thermodynamics, Department of Biochemical and Chemical Engineering, TU Dortmund, Dortmund, Germany *Corresponding author: João A. P. Coutinho, address: jcoutinho@ua.pt, Phone: , Fax: Number of pages: 33 Number of tables: 14 Number of figures: 14 S1

2 Caprylic L( )-menthol Capric Lauric Thymol Myristic Palmitic Stearic Figure S1. Structures of the compounds investigated in this work. Menthol + Lauric , 5, , 8 CHCl 3 OH TMS S2

3 Menthol Lauric Menthol + Lauric Thymol + Myristic 1, CHCl TMS S3

4 Figure S2. 1 H spectra of pure menthol, thymol, lauric and myristic ; and the mixtures menthol + lauric and thymol + myristic at a composition close to the eutectic point and at room temperature. 360 T/ K Stearic Palmitic Myristic Lauric Capric Caprylic x monocarboxylic S4

5 360 T/ K Stearic Palmitic Myristic Lauric Capric Caprylic x monocarboxylic Figure S3. Solid-liquid phase diagrams of mixtures composed of monocarboxylic s and terpenes L( )-menthol or thymol. Symbols represent the experimental data measured in this work while the solid lines represent the ideal solubility curves. γ 1.20 γ x Caprylic Acid x Capric Acid S5

6 γ 1.10 γ γ x Lauric Acid 1.20 γ x Myristic Acid x Palmitic Acid x Stearic Acid Figure S4. Activity coefficients of mixtures composed of monocarboxylic s and L( )- menthol. Legend:, experimental; - -, Ideal;, PC-SAFT. γ 1.10 γ x Caprylic Acid x Capric Acid S6

7 γ 1.10 γ γ x Lauric Acid 1.20 γ x Myristic Acid x PalmiticAcid x Stearic Acid Figure S5. Activity coefficients of mixtures composed of monocarboxylic s and thymol. Legend:, experimental; - -, Ideal;, PC-SAFT. S7

8 T/ K x Lauric Acid Figure S6. SLE of binary mixtures composed of lauric and terpenes. Symbols represent experimental data measured in this work while solid lines depict the PC- SAFT results. Legend:, L( )-menthol;, thymol ρ/ g cm a) T/ K L( )-menthol L( )-menthol_caprylicacid L( )-menthol_capricacid L( )-menthol_lauricacid L( )-menthol_myristicacid L( )-menthol_palmiticacid L( )-menthol_stearicacid S8

9 ρ/ g cm b) T/ K Thymol Thymol_CaprylicAcid Thymol_CapricAcid Thymol_LauricAcid Thymol_MyristicAcid Thymol_PalmiticAcid Thymol_StearicAcid Figure S7. Density of eutectic mixtures involving monocarboxylic s and: a) L( )- menthol or b) thymol. Symbols represent experimental density data measured in this work while dashed lines represent PC-SAFT modelling results. S9

10 0.1 V m E / cm 3 mol T/ K L( )-menthol_caprylicacid L( )-menthol_capricacid L( )-menthol_lauricacid L( )-menthol_myristicacid L( )-menthol_palmiticacid L( )-menthol_stearicacid 0.6 V m E / cm 3 mol T/ K Thymol_CaprylicAcid Thymol_CapricAcid Thymol_LauricAcid Thymol_MyristicAcid Thymol_PalmiticAcid Thymol_StearicAcid Figure S8. Excess molar volumes, V m E, versus temperature for the binary mixtures investigated in this work. S10

11 60 a) 40 η/ mpa s T/ K L( )-menthol L( )-menthol_caprylicacid L( )-menthol_capricacid L( )-menthol_lauricacid L( )-menthol_myristicacid L( )-menthol_palmiticacid L( )-menthol_stearicacid b) η/ mpa s T/ K Thymol Thymol_CaprylicAcid Thymol_CapricAcid Thymol_LauricAcid Thymol_MyristicAcid Thymol_PalmiticAcid Thymol_StearicAcid S11

12 Figure S9. Experimental viscosity of eutectic mixtures involving monocarboxylic s and: a) L( )-menthol or b) thymol. Lines correspond to the Vogel Tammann Fulcher correlations. η/ mpa s L( )-menthol_caprylicacid Thymol_CaprylicAcid Caprylic Acid L( )-menthol Thymol η/ mpa s L( )-menthol_capricacid Thymol_CapricAcid CapricAcid L( )-menthol Thymol T/ K T/ K L( )-menthol_lauricacid Thymol_LauricAcid LauricAcid L( )-menthol Thymol L( )-menthol_myristicacid Thymol_MyristicAcid MyristicAcid L( )-menthol Thymol η/ mpa s η/ mpa s T/ K T/ K L( )-menthol_palmiticacid Thymol_PalmiticAcid PalmiticAcid L( )-menthol Thymol L( )-menthol_stearicacid Thymol_StearicAcid StearicAcid L( )-menthol Thymol η/ mpa s 9 6 η/ mpa s T/ K T/ K S12

13 Figure S10. Comparison between the viscosity of pure compounds and their mixtures H-Bond Donor Region Non-polar Region H-Bond Acceptor Region p(σ) d) σ/e nm -2 Water Thymol L(-)-menthol Figure S11. Sigma profiles of the terpenes used in this work computed by COSMO-RS ((COnductor-like Screening MOdel for Real Solvents, BP_TZVP_C30_1401, COSMOconfX v3.0, COSMOlogic GmbH & Co KG. Leverkusen, Germany). S13

14 Table S1. Experimental (x 2, T) a and calculated (γ i ) data of the SLE of systems involving L( )-menthol. x 2 T / K γ 1 x 2 T / K γ 2 Solid Phase: L( )-menthol (1) Solid Phase: Monocarboxylix Acid (2) Caprylic Acid Capric Acid Lauric Acid Myristic Acid Palmitic Acid Stearic Acid S14

15 a Standard uncertainties, u, are u(t) = 0.1 K and u r (x) = Table S2. Experimental (x 2, T) a and calculated (γ i ) data of the SLE of systems involving thymol. x 2 T / K γ 1 x 2 T / K γ 2 Solid Phase: Thymol (1) Solid Phase: Monocarboxylix Acid (2) Caprylic Acid Capric Acid Lauric Acid Myristic Acid Palmitic Acid S15

16 Stearic Acid a Standard uncertainties, u, are u(t) = 0.1 K and u r (x) = Table S3. Binary parameters applied within the PC-SAFT model and average absolute deviations (AAD / K) for each system investigated. System k ij_eps AAD / K (Ideal) AAD / K (PC-SAFT) L( )-menthol Caprylic Acid Capric Acid Lauric Acid Myristic Acid Palmitic Acid Stearic Acid Thymol Caprylic Acid Capric Acid Lauric Acid Myristic Acid Palmitic Acid Stearic Acid Table S4. Eutectic points calculated using PC-SAFT and considering an ideal behavior for the systems investigated in this work. x E Ideal T E Ideal x E PC-SAFT T E PC-SAFT x E Ideal T E Ideal x E PC-SAFT T E PC-SAFT L( )-menthol Thymol Caprylic Acid Capric Acid Lauric Acid Myristic Acid Palmitic Acid Stearic Acid S16

17 Table S5. Experimental density results, ρ, at 0.1 MPa as a function of temperature, for the mixtures of L( )-menthol and monocarboxylic s. The mole fraction of the (x ) is provided. a L( )-menthol + x Caprylic Capric Lauric ρ / g cm -3 Myristic Palmitic Stearic T / K a Uncertainties are u(t) = 0.02 K, u(ρ) = g cm -3 and u r (p) = Table S6. Experimental density results, ρ, at 0.1 MPa as a function of temperature, for the mixtures of thymol and monocarboxylic s. The mole fraction of the (x ) is provided. a Thymol + x Caprylic Capric Lauric ρ / g cm -3 Myristic Palmitic Stearic T / K S17

18 a Uncertainties are u(t) = 0.02 K, u(ρ) = g cm -3 and u r (p) = Table S7. Average absolute relative deviations (ARD / %) of the densities calculated with PC-SAFT and the ones measured experimentally for each system investigated. System L( )-menthol Thymol Caprylic Acid Capric Acid Lauric Acid Myristic Acid Palmitic Acid Stearic Acid Table S8. Experimental viscosity results, η, at 0.1 MPa and as a function of temperature, for the mixtures of L( )-menthol and monocarboxylic s. The mole fraction of the (x ) is provided. a η / mpa s L( )-menthol + - Caprylic Capric Lauric Myristic Palmitic Stearic x T / K S18

19 a Uncertainties are u(t) = 0.02 K, u r (η) = 0.35% and u r (p) = Table S9. Experimental viscosity results, η, at 0.1 MPa and as a function of temperature, for the mixtures of thymol and monocarboxylic s. The mole fraction of the (x ) is provided. a η / mpa s Thymol + - Caprylic Capric Lauric Myristic Palmitic Stearic x T / K S19

20 a Uncertainties are u(t) = 0.02 K, u r (η) = 0.35% and u r (p) = Table S10. Kamlet-Taft solvatochromic parameters of pure components and mixtures investigated in this work at K, along with the standard deviations, and of other common solvents 1 (standard temperature and pressure). β π* α Terpenes L( )-menthol 0.66 ± ± Monocarboxylic s Caprylic Acid 0.14 ± ± Capric Acid 0.17 ± ± Lauric Acid 0.26 ± ± Other solvents 1 Water Ethanol Methanol Acetone Heptane Cyclohexane o-xylene Mixtures L( )-menthol + Caprylic Acid 0.43 ± ± Capric Acid 0.45 ± ± Lauric Acid 0.54 ± ± Myristic Acid 0.50 ± ± Palmitic Acid 0.57 ± ± Stearic Acid 0.64 ± ± Thymol + Caprylic Acid 0.05 ± ± Capric Acid 0.05 ± ± Lauric Acid 0.02 ± ± Myristic Acid 0.02 ± ± Palmitic Acid 0.01 ± ± S20

21 Stearic Acid 0.05 ± ± Table S11. Solubility of water in the eutectic mixtures, x w, and solubility of thymol (+ monocarboxylic s), x thymol, in water at K. x w x w 10 5 x thymol L( )-menthol Thymol Caprylic Acid ± ± ± Capric Acid ± ± ± Lauric Acid ± ± ± Myristic Acid ± ± ± Palmitic Acid - a - a ± Stearic Acid - a - a ± a Solid at K. S21

22 PC-SAFT EoS SAFT-type equations are written as a sum of free energy terms, each of them mimicking a specific interaction, yielding the system s residual Helmholtz energy, res A. For classical PC-SAFT, which was used in this work, the residual Helmholtz energy can be expressed as: res A Nk T B hc disp assoc A A A = + + (S1) Nk T Nk T Nk T B B B where res, hc, disp and assoc refer to residual, hard-chain reference fluid, dispersive and associative interactions, respectively. N and k B stand for number of molecules and the Boltzmann constant, respectively. For non-associating molecules, three pure- seg component parameters are required: the number of segments in the chain ( m i ), the diameter of the segments ( σ i ) and the dispersive energy between segments ( u i / kb). The extension to mixtures requires the value of the unlike size and energy parameters for which the conventional Lorentz-Berthelot combining rules are commonly applied and whenever required, one adjustable binary interaction parameter, k ij, for adjustment of the cross-dispersion energy can be used: ij ( σ σ ) 1 σ = + 2 i j (S2) ij ( ij) uiu j u = 1 k (S3) When dealing with self-associating components as those studied in this work, a proper association scheme, establishing the number and type of association sites and the interactions between them, needs to be specified a priori based on the structure and knowledge of the molecule and its interactions. Furthermore, the inclusion of the association term in a SAFT-type equation ( assoc A in Equation S1) requires two AiBi additional pure-component parameters related to the association energy ( ε ) and AiBi association volume ( κ ). S22

23 The extension to mixtures requires the evaluation of the cross-association parameters for which the mixing rules proposed by Wolbach and Sandler 2 are considered: AiBi AjBj ( ε + )(1 k ) AiBj 1 ε = ε ij _ eps (S4) ( ) 2 σ ii σ AiBj AiBi AjBj jj κ = κ κ (S5) σ + ii σ jj In order to account for deviations from the value calculated through the selected mixing rules, a binary interaction parameter, k ij_eps, for correction of the crossassociation energy can be applied when required for an accurate description of the data. PC-SAFT Pure-Component Parameters As previously mentioned, within the framework of PC-SAFT, a total of five purecomponent parameters are required to model each associating compound. To better describe the thermodynamic behavior of real substances, these parameters are usually regressed from experimental data on thermodynamic properties and/or phase equilibria, preferably of the pure substance. The molecular parameters regressed in this work are reported in Table S12 along with the average relative deviation (%ARD) values for the thermodynamic properties considered in the fitting procedure (for those regressed in this work): calc exp N 1 X i X i % ARD = 100 (S6) exp N X exp i= 1 i where N exp is the total number of experimental points and X i calc and X i exp are the calculated and the experimental values of the physical property being evaluated. The PC-SAFT modelling of systems involving monocarboxylic s was addressed by several authors 3 6 with the 2B association scheme (according to the nomenclature of Huang and Radosz 7 ) as being the most appropriate for long-chain monocarboxylic S23

24 s. Therefore, PC-SAFT pure-component parameters are available in the literature for the monocarboxylic s investigated in this work except for caprylic, which are here regressed from experimental liquid densities (at 1 atm) and vapor pressures as depicted in Figure S12 and reported in Table S12. ρ/ kg m ³ a) ln(p/pa) b) T / K / T / K ¹ ρ/ kg m ³ c) ln(p/pa) d) T / K / T / K ¹ S24

25 ρ/ kg m ³ e) ln(p/pa) f) T/ K / T/ K ¹ Figure S12. Liquid densities (at 1 atm) and vapor pressures of: a,b) caprylic ; c,d) thymol; and e,f) L( )-menthol. The symbols represent experimental data 8 10 while the lines depict the PC-SAFT results with the parameters proposed here (solid lines) and those of Okuniewski et al. 11 (dashed lines). As depicted in Figure S12a) and S12b), PC-SAFT is able to provide a good description of the experimental density and vapor pressure data of the caprylic. Moreover, following the procedure applied in our previous work, 6 the association volume was kept constant and equal to 0.02 decreasing the number of parameters used in the fitting procedure without any loss of accuracy. This supports the idea that the associative behavior in pure carboxylic s is induced by the presence of a carboxylic group and thus not strongly influenced by the compounds chain length. Concerning the consistency of the non-associative parameters proposed here for caprylic when compared to those reported in previous works, 4,6 correlations as a function of the s molecular weight M w_ can be drawn for the whole homologous series with coefficients of determination (R 2 ) very close to one: m _ , R 2 = (S7) = M w 3 mσ , R 2 = (S8) = 1 M w _ mε _ , R 2 = (S9) = M w S25

26 Regarding the terpenes, Okuniewski et al. 11 used the PC-SAFT EoS to describe the solidliquid equilibria (SLE) phase diagrams of binary mixtures: [L( )-menthol or thymol] + [1- decanol, benzyl alcohol, n-decane or 2-cyclohexanethanol]. A 2B association scheme was used to take into account the hydrogen bonding character of the hydroxyl group present in the terpene s structure as previously done for other hydroxyl containing compounds. 4,5 Although Okuniewski et al. 11 proposed pure-component parameters for the terpenes here investigated, a new set of parameters was proposed in this work for L( )-menthol and thymol as those from the literature were found to provide an unsatisfactory description of the terpene s liquid densities as depicted in Figure S12c) 2e). Furthermore, the new parameters not only provide a better description of the liquid densities (without loss of accuracy on the vapor pressures) but also allow the model to produce a good and consistent description of the SLE data reported in this work using no more than one binary, temperature independent interaction parameter, as will be shown below. Table S12. PC-SAFT pure-component parameters used in this work. The 2B association scheme is considered for all compounds. Compound seg m i σ i / Å AiBi u / k / K ε / K i B AiBi κ %ARD(ρ L ) %ARD(p*) Thymol L( )-menthol Caprylic Capric Lauric Myristic Palmitic Stearic S26

27 Densities Isobaric thermal expansion coefficients The experimental density data was further correlated according to a linear dependency on the temperature (equation S10, parameters available in Table S13), and the isobaric thermal expansion coefficient, α p, which considers the volumetric changes with temperature, derived from equation S11. No temperature dependence was assigned to this property. Figure S13 illustrates the results obtained as a function of the monocarboxylic. ln ρ = + AT (S10) A0 1 1 ρ α p = ρ T p lnρ = T p = A 1 (S11) where ρ is the density, and A 0 and A 1 are fitting parameters. Table S13. Estimated parameters of Equation S10, A 0 and A 1, for the studied mixtures. a Expanded uncertainty with approximately 95% level of confidence. Mixture Experimental PC-SAFT (A 0 ± σ) a 10 4 (A 1 ± σ) a / K -1 (A 0 ± σ) a 10 4 (A 1 ± σ) a / K -1 L( )-menthol + Caprylic Acid ± ± ± ± Capric Acid ± ± ± ± Lauric Acid ± ± ± ± Myristic Acid ± ± ± ± Palmitic Acid ± ± ± ± Stearic Acid ± ± ± ± Thymol + Caprylic Acid ± ± ± ± Capric Acid ± ± ± ± Lauric Acid ± ± ± ± Myristic Acid ± ± ± ± S27

28 Palmitic Acid ± ± ± ± Stearic Acid ± ± ± ± α p L( )-menthol L( )-menthol PC-SAFT Thymol Thymol PC-SAFT -9.5 Caprylic Capric Lauric Myristic Palmitic Stearic Figure S13. Experimental and predicted thermal expansion coefficients of eutectic mixtures of L( )-menthol or thymol and monocarboxylic s. S28

29 Viscosity Energy barrier The viscosity (η) describes the internal resistance of a fluid to a shear stress and can be correlated through the Vogel Tammann Fulcher (VTF) model, 12 B η η( T ) = Aη exp (S12) T Cη where A η, B η, and C η are adjustable parameters estimated from experimental data. The energy barrier (E) can be estimated based on the viscosity dependence with temperature using the following equation, 13 E = R ( ln[ η( T) ]) ( 1/ T) (S13) Experimental viscosity values were fitted using the VTF equation and the estimated parameters are listed in Table S14 together with the energy barrier, E, calculated from equation S13 at K. This temperature was chosen because it is the lowest temperature at which all mixtures are liquid. The energy barrier for the various mixtures and the terpenes studied is represented in Figure S14. Table S14. Fitting coefficients of the VTF equation and derived energy barrier, E, of mixtures involving L( )-menthol or thymol and monocarboxylic s at K and 0.1 MPa. a Expanded uncertainty with an approximately 95% level of confidence. Mixture 10 2 (A η ± σ) a / mpa s (B η ± σ) a / K (C η ± σ) a / K (E ± σ) a / kj mol -1 L( )-menthol + Caprylic Acid 3.06 ± ± ± ± 0.24 Capric Acid 2.85 ± ± ± ± 0.13 Lauric Acid 2.79 ± ± ± ± 0.24 Myristic Acid 2.67 ± ± ± ± 0.34 Palmitic Acid 2.77 ± ± ± ± 0.76 Stearic Acid 2.72 ± ± ± ± 0.56 S29

30 Thymol + Caprylic Acid 4.98 ± ± ± ± 0.23 Capric Acid 5.33 ± ± ± ± 0.46 Lauric Acid 5.41 ± ± ± ± 0.57 Myristic Acid 5.61 ± ± ± ± 0.80 Palmitic Acid 5.53 ± ± ± ± 1.28 Stearic Acid 5.69 ± ± ± ± E( K) / kj mol Caprylic Capric Lauric Myristic Palmitic Stearic Figure S14. Energy barrier of the eutectic mixtures investigated at K as a function of the monocarboxylic used. Legend:, L( )-menthol mixtures;, thymol mixtures; ---, pure L( )-menthol;, pure thymol. S30

31 Kamlet Taft Solvatochromic Parameters The dipolarity/polarizability, π*, and the hydrogen-bond acceptor basicity, β, solvatochromic parameters were determined from the experimental measurements according with the following equations: π ν * N, N ( mixture) N, N ( cyclohexane) = (S14) ν N, N ( DMSO) ν ν N, N ( cyclohexane) ( ν ν ) N, N ( mixture) N, N ( cyclohexane ) β = (S15) ν ν N, N ( DMSO) N, N ( cyclohexane ) ν = ν (S16) N, N ν 4N 1 4 ν = 10 (S17) λ max probe where ν is the experimental wavenumber and λ max probe is the maximum wavelength of the probe. Subscripts N,N and 4N represent the probes N,N-diethyl-4-nitroaniline and 4-nitroaniline, respectively. The subscripts cyclohexane and DMSO indicate the corresponding reference values for these solvents. The hydrogen-bond donor ity, α, was estimated using the 13 C NMR chemicals shifts, δ(c i ) (in ppm), of the carbons atoms of pyridine-n-oxide in positions i = 2 and 4: α = 0.15 d (S18) where d 24 = δ 4 δ S31

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