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Solvent Polarity of Cyclic Ketone (cyclopentanone, cyclohexanone) – Alcohol (methanol, ethanol) Renewable Mixed-Solvent Systems for Applications in Pharmaceutical and Chemical Processing Alif Duereh, Haixin Guo, Tetsuo Honma, Yuya Hiraga, Yoshiyuki Sato, Richard Lee Smith, and Hiroshi Inomata Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b00689 • Publication Date (Web): 14 May 2018 Downloaded from http://pubs.acs.org on May 15, 2018

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Industrial & Engineering Chemistry Research

Solvent

Polarity

of

Cyclic

Ketone

(cyclopentanone,

cyclohexanone) – Alcohol (methanol, ethanol) Renewable Mixed-Solvent Systems for Applications in Pharmaceutical and Chemical Processing

Alif Duereh,† Haixin Guo, ‡ Tetsuo Honma,§ Yuya Hiraga‡, Yoshiyuki Sato,† Richard Lee Smith Jr.*†, ‡ and Hiroshi Inomata†

†

Graduate School of Engineering, Research Center of Supercritical Fluid

Technology, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan ‡

Graduate School of Environmental Studies, Research Center of Supercritical

Fluid Technology, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan §

Material and Biological Engineering Course, Department of Industrial

System Engineering, National Institute of Technology, Hachinohe College, 16-1 Uwanotai, Tamonoki-Aza, Hachinohe, 039-1192, Japan.

*Corresponding Author Tel (Fax): +81-22-795-5863, e-mail: [email protected]

1 ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract Kamlet-Taft (KT) parameters were measured for four nonaqueous hydrogen bond donor (HBD)-hydrogen bond acceptor (HBA) solvent-pair mixtures: methanol-cyclopentanone, methanol-cyclohexanone, ethanol-cyclopentanone and ethanol-cyclohexanone to define their solvent polarity as a function of composition. KT mixed-solvent polarities differed greatly from molar average property values. The preferential solvation (PS) model was used to correlate solvent polarity and showed that local compositions of 1:1 (HBD-HBA) complex molecules were highly-asymmetric. Trends of KT parameters of both cyclohexanone and cyclopentanone mixtures were similar, although the specific hydrogen bonding interactions of HBD-HBA complex molecules in cyclohexanone mixtures were stronger than those of cyclopentanone mixtures according to density functional theory calculations, infrared spectroscopy, and solution macroscopic properties.

Application of the PS model to

pharmaceuticals showed that the solvent-pair mixtures have wide-working composition ranges (~0 < xHBA 0.5, both VE and x12L (Fig. 3) decreased and approached zero with



increasing bulk composition, implying that high local concentrations of CPN molecules ( x 2L ) compete with the 1:1 complex HBD-HBA molecules ( x12L ) for hydrogen bonds, since CPN prefers to have self-complex CPN association through C-H hydrogen bonding31, 52. These results for self-complex CPN associations are consistent with the red shift of the C=O stretching spectra (peak 2, Fig. 3b). Figures 3e-3h show IR spectral shifts, fH, VE, and local compositions for the EtOH-CPN mixed-solvent system. Addition of CPN to pure EtOH caused the breaking of self-complex EtOH molecules that exhibited a blue shift for the alcohol νOH (Fig. 3e) and formed complex HBD-HBA molecules as shown by the red shift for the ketone νC=O (Fig. 3f), negative VE values (Fig. 3g), and almost symmetric x12L values (Fig. 3h). These results are in accordance with previous discussion for the MeOH-CPN mixed-solvent system (Fig. 3a-3d). However, hydrogen bonding strength in the EtOH-CPN mixture (Fig. 3e-3h) was weaker than that in the MeOH-CPN mixture (Fig. 3a-3d) according to lower fH and negative VE values and lack of skewness in the x12L values, as expected because longer alkyl chain length alcohols (e.g. ethanol, n-propanol, n-butanol) in solutions have been shown to have weaker interactions than shorter alkyl chain length alcohols.24, 46, 59, 60 Trends of the properties of the other HBD-HBA mixtures studied in this work with bulk composition (Fig. S12) were similar to those of the MeOH-CPN and EtOH-CPN mixedsolvent system (Fig. 3). The order of hydrogen bonding strength of the four HBD-HBA mixed-solvent systems is qualitatively compared by considering macroscopic (VE and η) and microscopic (fH and x12L ) properties in the following sections.

4.3 Macroscopic properties


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Experimental ρ and η data for pure solvents and HBD-HBA mixed-solvent systems used in this work are tabulated in Tables S10-S14 (Supporting Information). Figure S5 shows residual deviations (∆ρ = ρExp – ρCal) calculated from data measured in this work that were in accordance with literature values within the experimental uncertainties provided in Table S10. Figure S6 shows percent relative deviation in viscosity (∆η (%) = 100(η

Exp

/ ηCal-1 )

calculated from data measured in this work that were in accordance with literature values within experimental uncertainties, except for MeOH (Fig. S6).

MeOH had the highest

relative deviation in viscosity (± 2.6 %) compared with the literature61 that also had a relatively high uncertainty (± 2.0 %). Figure S7 shows comparisons of density data for the MeOH-CHN, EtOH-CHN, MeOH-CPN mixtures studied in this work that were consistent with literature24, 31 within the experimental uncertainties (± 1 kg⋅m-3). Figure 4 shows comparisons of VE and η for all mixed-solvent systems. The VE of the mixtures (Fig. 4a) were negative over entire composition ranges, except for EtOH-CPN mixtures at high CPN mole fractions due to self-complex CPN association as mentioned in Section 4.2. For the viscosity of the mixed-solvent systems (Fig. 4b), as the mole fraction of HBA increased, η of the mixtures exhibited a monotonic increase, except for EtOH-CPN mixture that showed broad minima in viscosity. Minima in η for other mixtures of EtOH with 1,4-dioxane62, carbon tetrachloride63, and dimethyl sulfoxide64 have been reported in the literature and the reason is probably due to breaking of self-associated EtOH structures.

4.4 Microscopic properties Figure 5 shows trends of fH and local complex HBD-HBA composition ( x12L ) for all mixed-solvent systems. The fH of the mixtures (Fig. 5a) rapidly decreased at x 2bulk < 0.1 and changed only slightly at 0.1 < x 2bulk < 0.5 probably due to complex molecule HBD-HBA



formation that leads to skewness in x12L (Fig. 5b). EtOH-CPN mixtures had the least negative VE (Fig. 4a), and showed the presence of a minimum in η (Fig. 4b), and the lowest x12L values (Fig. 4d), implying that hydrogen bonding strength of the EtOH-CPN mixture was weaker than that of the other HBD-HBA mixtures. Figure 6 shows the DFT-optimized geometries for 1:1 complexes (HBD solvent molecule: HBA solvent molecule) for all HBD-HBA mixed-solvent systems. The hydrogen bonding strengths of molecular pairs of the mixed-solvent systems are compared with DFT calculations in the next section.

4.5 H-bond strength Table 2 provides a tabulation of binding energies (Be), the H-bond distance and dipole moment of the 1:1-complexes and selected properties along with molar excess enthalpies taken from literature.59, 65 The MeOH-CHN system (Table 2) had the highest value of Be and the highest values in -VE, G12, fH and x12L , whereas the EtOH-CPN system had the lowest values of Be and lowest values in -VE, G12 and x12L . The EtOH-CHN complex (Table 2) had an intermediate value of Be and intermediate value in -VE, G12, fH and x12L . Thus, H-bond strengths of the alcohols with cyclohexanone (CHN) evaluated from fH, x12L and Be values (Table 2) were stronger than that those of cyclopentanone (CPN) in the order of: MeOH-CHN > EtOH-CHN > MeOH-CPN > EtOH-CPN, and consistent with the G12 values that are related to steric hindrance of the complexes. In addition, the effect of steric hindrances on the order of H-bond strengths can interpreted with available literature on dielectric spectra. Dielectric relaxation times and reorientation activation free energies of MeOH-CHN mixtures obtained from the literature66 are higher than those of mixtures of MeOH with aliphatic ketones (acetone, 2-butanone, and 3-pentanone, Table S16) that is attributed to the 18 ACS Paragon Plus Environment

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effect of steric hindrance in the cyclic structures60,

66

that make stronger H-bond in the

mixtures. The IR results of MeOH-CHN mixtures and propanol-2-butanone mixtures in Figure S13 (Supporting Information) were in accordance with trends of the literature dielectric relaxation results.

4.6 Comparison with aqueous mixtures Complex HBD-HBA formation in non-aqueous systems (alcohol-ketone) can be compared with complexes formed in aqueous systems (water-ketone).

Water-acetone

mixtures can be discussed because the system exhibits complete miscibility. Figure 7 shows HE, η, λmax and local mole fractions for water-acetone (Fig. 7 (a)-(d)) and MeOH-CPN (Fig. 7 (e)-(h)) mixtures. For water-acetone mixtures that can form 1:1 to 1:3 complexes,28, 67 a water hydration shell surrounding the complex forms at water-rich compositions ( x 2b u lk < 0.5).27

The

hydration shell formation in the aqueous system leads to: (i) negative HE values (Fig. 7a, x 2b u lk < 0.5) because the exothermic enthalpy for formation of the complexes and the

hydration shell is higher than the endothermic enthalpy of breaking of water self-associated structures, (ii) maxima in viscosity (Fig. 7b, x 2bulk ≈ 0.15) due to bulky complex structures and the hydration shell28, and (iii) maxima in λmax values (Fig. 7c, x 2bulk ≈ 0.10) since the hydration shell has higher polarity and basicity than that of pure water so that local mole fractions of the complexes ( x12L , Fig. 7d) are highly skewed in the dilute HBA solvent region ( x 2bulk < 0.1). On the other hand, although 1:1 complex formation can occur in non-aqueous systems (e.g. MeOH-CPN, Fig. 7h), the MeOH-CPN mixtures do not show negative HE values, they have HE values that are almost symmetric (Fig. 7e) and they do not show maxima in η (Fig. 7f), and only have a weak maximum in the λmax values (Fig. 7g) probably due to the lack of an



alcohol solvation shell surrounding the complexes. Comparison of the local composition of complexes between MeOH-CPN (Fig. 7h) and water-acetone (Fig. 7d) shows a lack of skewness in the MeOH-CPN system, which is further evidence for the absence of an alcohol solvation shell. For other nonaqueous systems, although alcohol-chlorinated mixtures68 show high synergism in λmax values due to complex formation, they do not exhibit a maximum in mixture viscosity,63 except for methanol-chloroform mixtures69 that has a weak maximum in viscosity due to weak hydrogen bonding network.70 The results in this study show that complex molecules in alcohol-cyclic ketone systems do not have long-range influence on the alcohol solvation shell.

4.7 Application to pharmaceuticals Solvent mixture working compositions for twelve API (Table 3) were determined based on favorable KT solvent polarities by using the intersection of values that satisfy the KT * * windows ( π window , β window , α window ). The π window , β window , α window values for 12 APIs evaluated

from solubility data in pure solvents and solvent mixtures reported in the literature13 are tabulated in Table 3. Paracetamol is used as an example for discussion and had KT windows * of π window ≥ 0.35, β window ≥ 0.62, and α window ≤ 0.75 (Table 3).

Figures 8 and 9 show plots of the KT parameters for EtOH-CPN and MeOH-CPN systems, respectively. The intersections of KT windows of paracetamol (Table 3) provide range of actual working compositions ( x2actual , yellow-hatched regions, Fig. 8) and ideal working compositions ( x 2ideal , gray-shaded regions, Figs. 8-9) of the EtOH-CPN and MeOHCPN solvent mixtures, respectively.


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Due to complex HBD-HBA formation that causes non-ideality, the actual working compositions ( x2actual ) of the EtOH-CPN solvent mixtures (yellow-hatched regions, Fig. 8) for paracetamol are narrower than ideal working compositions ( x 2ideal gray-shaded regions, Fig. 8). For example, actual working compositions ( x2actual ) of EtOH-CPN for paracetamol (yellowhatched regions, Fig. 8) were 0.33 ≤ x2actual ≤ 0.67 (Table 3), while ideal working compositions ( x 2ideal gray-shaded regions, Fig. 8) were 0.27 ≤ x 2ideal ≤ 0.76 (Table S17, Supporting Information). As shown in Figure 9, the MeOH-CPN solvent mixture is not applicable to paracetamol as a favorable solvent due to its high acidity parameter, however, this solvent mixture could be applied as an anti-solvent. Thus, actual KT parameters of the mixtures are essential to solvent selection and can provide precise identification of working composition ranges. The estimated (actual) working compositions ( x2actual ) of the alcohol-ketone HBD-HBA solvent mixtures for 12 APIs are tabulated in Table 3.

Table S17 provides working

compositions assuming the lack of measured mixture KT values. Among 12 APIs, actual working compositions ( x2actual ) for piroxicam and sulfamethoxypyridazine (Table 3) were much

more

narrower

than

those

for

other

APIs,

because

piroxicam

and

sulfamethoxypyridazine have sulfonyl functional group (O=S=O) that promote strong solutesolute interactions. Benzoic acid-derivative APIs (e.g. aspirin, p-amino benzoic acid, salicylic acid in Table 3) had wide ranges of working compositions for the alcohol-ketone systems studied in this work because there are a fewer number of HBD or HBA functional groups and they have simpler molecular structures than piroxicam or sulfamethoxypyridazine.



4.8 Application to chemical processing For the alcohol-ketone mixtures studied in this work, several applications to chemical processing can be considered as follows: (i) exfoliation, (ii) fractionation, (iii) reactive extraction and (iv) organosolv lignin processing. Since bio-based Cyrene shows potential uses in exfoliation of metal–organic frameworks (MOFs)71 and graphene72, the alcohol-cyclic ketone mixtures can be chosen to have comparable KT values with Cyrene, since cyclic ketones are favorable solvents for graphene dissolution.8 Aqueous (HBD-HBA) mixtures of N,N-dimethylformamide showed efficient fractionation of carbazole from anthracene18 and give maximum selectivity at xHBA ≈ 0.4 (α ≈ 0.45 and β ≈ 0.66) and thus the alcohol-cyclic ketone mixtures can be used to separate anthracene from carbazole due to differences in molecular interactions. Methyl isobutyl ketone (MIBK) is an effective solvent for extraction of gallic acid from aqueous solutions73 and for separation of organosolv lignin from phenolic monomers.74 Pure cyclic ketones or alcohol-cyclic ketone mixtures can be expected to have higher efficiency than MIBK due to control of solvent mixture polarity that can be higher than that of pure MIBK.

5. Conclusions Kamlet-Taft (KT) parameters of four HBD-HBA mixed-solvent systems (MeOH-CHN, MeOH-CPN, EtOH-CHN, EtOH-CPN) show non-ideality in physical and chemical properties due to formation of 1:1 complex HBD-HBA molecules. The complex molecules were confirmed with spectroscopic techniques and theoretical DFT calculations. Binding energies and fractions of hydrogen bonding in the cyclohexanone mixtures (MeOH-CHN and EtOHCHN) were higher than those in the cyclopentanone mixtures (MeOH-CPN and EtOH-CPN)


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and thus the orders of hydrogen bonding strength of 1:1 HBD-HBA complex structures in the mixtures including their steric factors are MeOH-CHN > EtOH-CHN > MeOH-CPN > EtOHCPN. Working compositions of the mixtures for API processing evaluated from actual KT values are narrower than those from ideal KT values due to complex HBD-HBA formation. The cyclic ketone-alcohol solvent mixtures studied in this work have wide application to chemical processing when especially nonaqueous solvents are required.

6. Acknowledgment The authors acknowledgement partial financial support of this research from a JSPS Grant in Aid Scientific Research (B), contract No. 25289272 (Japan).

7. Supporting Information Section A tabulates Kamlet-Taft parameters of solvent mixtures (Tables S1-S7 and Figs. S1-S4). Section B provides densities and dynamic viscosities of pure solvent and solvent mixtures (Tables S8-S14 and Figs. S5-S7). Section C gives IR spectral shifts and working compositions of solvent mixtures (Table S15-S17 and Figs. S8-S13). 8. Abbreviations and symbols Abbreviations Be

binding energy

CHN

cyclohexanone

CPN

cyclopentanone

DFT

density functional theory

d(–H)

hydrogen-bonding distance

EtOH

ethanol

∆F

reorientation activation free energy



HBA

hydrogen-bond acceptor solvent (component 2)

HBD

hydrogen-bond donor solvent (component 1)

KT

Kamlet-Taft solvatochromic parameters

MeOH

methanol

MIBK

methyl isobutyl ketone

Latin symbols f2/1

preferential solvation parameter, according to eq. (9)

f12/1


f12/2


fH

fraction of hydrogen bonding, according to eq. (18)

G12

i-j binary interaction parameter, according to eq. (16)

H

molar enthalpy

Mw

molecular weight

x

mole fraction

V

molar volume

Greek symbols

Kamlet-Taft acidity

β

Kamlet-Taft basicity

Kamlet-Taft acidity

λmax

maximum absorption wavelength

v m ax

maximum absorption wavenumber

η

dynamic viscosity

π*

Kamlet-Taft dipolarity/polarizability

τ

dielectric relaxation time


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µ

dipole moment

Superscript Actual

actual working composition

bulk

bulk composition

x2ideal

ideal working composition

L

local composition

Subscript 1

HBD solvent

2

HBA solvent

12

complex HBD-HBA solvent molecule pair

mix

mixture property

window

KT windows

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24. Tsierkezos, N. G.; Molinou, I. E.; Filippou, A. C., Thermodynamic Properties of Binary Mixtures of Cyclohexanone with n-Alkanols (C1–C5) at 293.15 K. J. Solution Chem. 2005, 34, 1371-1386. 25. Max, J.-J.; Chapados, C., Infrared Spectroscopy of Acetone-Methanol Liquid Mixtures: Hydrogen Bond Network. J. Chem. Phys. 2005, 122, 014504. 26. Duereh, A.; Sato, Y.; Smith, R. L.; Inomata, H., Analysis of the Cybotactic Region of Two Renewable Lactone–Water Mixed-Solvent Systems that Exhibit Synergistic Kamlet– Taft Basicity. J. Phys. Chem. B 2016, 120, 4467-4481. 27. Laage, D.; Elsaesser, T.; Hynes, J. T., Water Dynamics in the Hydration Shells of Biomolecules. Chem. Rev. 2017, 117, 10694-10725. 28. Duereh, A.; Sato, Y.; Smith, R. L.; Inomata, H.; Pichierri, F., Does Synergism in Microscopic Polarity Correlate with Extrema in Macroscopic Properties for Aqueous Mixtures of Dipolar Aprotic Solvents? J. Phys. Chem. B 2017, 121, 6033-6041. 29. Yu, I. K. M.; Tsang, D. C. W.; Chen, S. S.; Wang, L.; Hunt, A. J.; Sherwood, J.; De Oliveira Vigier, K.; Jérôme, F.; Ok, Y. S.; Poon, C. S., Polar Aprotic Solvent-Water Mixture as the Medium for Catalytic Production of Hydroxymethylfurfural (HMF) from Bread Waste. Bioresour. Technol. 2017, 245, 456-462. 30. Bosch, E.; Rived, F.; Roses, M., Solute-Solvent and Solvent-Solvent Interactions in Binary Solvent Mixtures. Part 4. Preferential Solvation of Solvatochromic Indicators in Mixtures of 2-Methylpropan-2-ol with Hexane, Benzene, Propan-2-ol, Ethanol and Methanol. J. Chem. Soc., Perkin Trans. 2 1996, 2177-2184. 31. Zhang, Y.-F.; Huang, R.-Y.; Wang, J.-W.; Geng, T.-M.; Zhao, S.-P.; Wu, G.-H., Experimental and Computational Investigation of Intermolecular Interactions in Cyclopentanone with Methanol Mixture. Chem. Phys. Lett. 2014, 612, 223-228. 32. Varfolomeev, M. A.; Rakipov, I. T.; Solomonov, B. N.; Lodowski, P.; Marczak, W., Positive and Negative Contributions in the Solvation Enthalpy due to Specific Interactions in Binary Mixtures of C1–C4 n-Alkanols and Chloroform with Butan-2-one. J. Phys. Chem. B 2015, 119, 8125-8134. 33. Duereh, A.; Sato, Y.; Smith, R. L.; Inomata, H., Spectroscopic Analysis of Binary Mixed-Solvent-Polyimide Precursor Systems with the Preferential Solvation Model for Determining Solute-Centric Kamlet–Taft Solvatochromic Parameters. J. Phys. Chem. B 2015, 119, 14738-14749. 34. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A., et al., Gaussian 09 , revision C.01; Gaussian, Inc.: Wallingford, CT, 2009. 35. Becke, A. D., Density Functional Thermochemistry. III. The Role of Exact Exchange. J. Chem. Phys. 1993, 98, 5648-5652. 36. Frisch, M. J.; Pople, J. A.; Binkley, J. S., Self-Consistent Molecular Orbital Methods 25. Supplementary Functions for Gaussian Basis Sets. J. Chem. Phys. 1984, 80, (7), 32653269. 37. Cancès, E.; Mennucci, B.; Tomasi, J., A New Integral Equation Formalism for The Polarizable Continuum Model: Theoretical Background and Applications to Isotropic and Anisotropic Dielectrics. J. Chem. Phys. 1997, 107, 3032-3041. 38. Boys, S. F.; Bernardi, F., The Calculation of Small Molecular Interactions by the Differences of Separate Total Energies. Some procedures with reduced errors. Mol. Phys. 1970, 19, 553-566 39. Dennington R.; Keith T.; Millam J., GaussView, Version 5, Semichem Inc., Shawnee Mission, KS, 2009.



40. Kamlet, M. J.; Abboud, J. L.; Taft, R. W., The Solvatochromic Comparison Method. 6. the .Pi.* Scale of Solvent Polarities. J. Am. Chem. Soc. 1977, 99, 6027-6038. 41. Kamlet, M. J.; Taft, R. W., The Solvatochromic Comparison Method. I. the Beta. Scale of Solvent Hydrogen-Bond Acceptor (HBA) Basicities. J. Am. Chem. Soc. 1976, 98, 377-3833. 42. Taft, R. W.; Kamlet, M. J., The Solvatochromic Comparison Method. 2. the. Alpha. Scale of Solvent Hydrogen-Bond Donor (HBD) Acidities. J. Am. Chem. Soc. 1976, 98, 28862894. 43. Marcus, Y., The Properties of Organic Liquids that Are Relevant to Their Use as Solvating Solvents. Chem. Soc. Rev. 1993, 22, 409-416. 44. Wyatt, V. T.; Bush, D.; Lu, J.; Hallett, J. P.; Liotta, C. L.; Eckert, C. A., Determination of Solvatochromic Solvent Parameters for the Characterization of GasExpanded Liquids. J. Supercrit. Fluids 2005, 36, 16-22. 45. Jessop, P. G.; Jessop, D. A.; Fu, D.; Phan, L., Solvatochromic Parameters for Solvents of Interest in Green Chemistry. Green Chem. 2012, 14, 1245-1259. 46. Kohantorabi, M.; Salari, H.; Fakhraee, M.; Gholami, M. R., Surfactant Binary Systems: Ab Initio Calculations, Preferential Solvation, and Investigation of Solvatochromic Parameters. J. Chem. Eng. Data 2016, 61, 255-263. 47. Navarro, A. M.; García, B. a.; Hoyuelos, F. J.; Peñacoba, I. A.; Leal, J. M., Preferential Solvation in Alkan-1-ol/Alkylbenzoate Binary Mixtures by Solvatochromic Probes. J. Phys. Chem. B 2011, 115, 10259-10269. 48. Khupse, N. D.; Kumar, A., Delineating Solute−Solvent Interactions in Binary Mixtures of Ionic Liquids in Molecular Solvents and Preferential Solvation Approach. J. Phys. Chem. B 2011, 115, 711-718. 49. Roses, M.; Buhvestov, U.; Rafols, C.; Rived, F.; Bosch, E., Solute-Solvent and Solvent-Solvent Interactions in Binary Solvent Mixtures. Part 6. A Quantitative Measurement of the Enhancement of the Water Structure in 2-Methylpropan-2-Ol-Water and Propan-2-olWater Mixtures by Solvatochromic Indicators. J. Chem. Soc., Perkin Trans. 2 1997, 13411348. 50. Grunberg, L.; Nissan, A. H., Mixture Law for Viscosity. Nature 1949, 164, 799-800. 51. Fang, S.; He, C.-H., A New One Parameter Viscosity Model for Binary Mixtures. AIChE J. 2011, 57, 517-524. 52. Vaz, P. D.; Ribeiro-Claro, P. J. A., Strong Experimental Evidence of CH···O Hydrogen Bonds in Cyclopentanone: The Splitting of the ν(CO) Mode Revisited. J. Phys. Chem. A 2003, 107, 6301-6305. 53. Gupta, R. B.; Brinkley, R. L., Hydrogen-Bond Cooperativity in 1-Alkanol + n-Alkane Binary Mixtures. AIChE J. 1998, 44, 207-213. 54. Davis, R. E.; Kim, K. S., Fermi Resonance in the Carbonyl Band of Cyclopentanone. Theor. Chem. Acc. 1972, 25, 89-96. 55. Cataliotti, R.; Jones, R. N., Further Evidence of Fermi Resonance in the C-O Stretching Band of Cyclopentanone. Spectrochim. Acta, Part A 1971, 27, 2011-2013. 56. Shikata, T.; Yoshida, N., Dielectric Behavior of Some Small Ketones as Ideal Polar Molecules. J. Phys. Chem. A 2012, 116, 4735-4744. 57. Moita, M.-L. C. J.; Santos, Â. F. S.; Silva, J. F. C. C.; Lampreia, I. M. S., Polarity of Some [NR1R2R3R4]+[Tf2N]− Ionic Liquids in Ethanol: Preferential Solvation Versus Solvent–Solvent Interactions. J. Chem. Eng. Data 2012, 57, 2702-2709.


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58. Ohno, K.; Shimoaka, T.; Akai, N.; Katsumoto, Y., Relationship between the Broad OH Stretching Band of Methanol and Hydrogen-Bonding Patterns in the Liquid Phase. J. Phys. Chem. A 2008, 112, 7342-7348. 59. Iloukhani, H.; Fattahi, M., Correlation of Excess Molar Enthalpies of Cyclopentanone (1)+1-Alkanols (C1–C5) (2) by Peng–Robinson–Stryjek–Vera Equation of State and ERASmodel. J. Mol. Liq. 2012, 171, 37-42. 60. González, J. A.; Mediavilla, Á.; García de la Fuente, I.; Cobos, J. C.; Alonso Tristán, C.; Riesco, N., Orientational Effects and Random Mixing in 1-Alkanol + Alkanone Mixtures. Ind. Eng. Chem. Res. 2013, 52, 10317-10328. 61. Xiang, H. W.; Laesecke, A.; Huber, M. L., A New Reference Correlation for the Viscosity of Methanol. J. Phys. Chem. Ref. Data 2006, 35, 1597-1620. 62. Omrani, A.; Rostami, A. A.; Mokhtary, M., Densities and Volumetric Properties of 1,4-Dioxane with Ethanol, 3-Methyl-1-Butanol, 3-Amino-1-Propanol and 2-Propanol Binary Mixtures at Various Temperatures. J. Mol. Liq. 2010, 157, 18-24. 63. Lang, Z. H.; Jun, H. S., Interaction Studies from Viscometric and Volumetric Behaviour of Binary Systems of Chlorinated Methanes with Normal Alkanols at 303.15 K. Phys. Chem. Liq. 1996, 31, 49-62. 64. Nikam, P. S.; Jadhav, M. C.; Hasan, M., Density and Viscosity of Mixtures of Dimethyl Sulfoxide + Methanol, +Ethanol, +Propan-1-ol, +Propan-2-ol, +Butan-1-ol, +2Methylpropan-1-ol, and +2-Methylpropan-2-ol at 298.15 K and 303.15 K. J. Chem. Eng. Data 1996, 41, 1028-1031. 65. Chao, J. P.; Dai, M., Excess Enthalpies of (an Alkan-1-ol + Tetrahydrofuran or Cyclohexanone) at 298.15 K. J. Chem. Thermodyn. 1989, 21, 977-983. 66. Madhurima, V.; Viswanathan, B.; Murthy, V. R. K., Effect of Steric Hindrance of Ketones in the Dielectric Relaxation of Methanol + Ketone Systems. Phys. Chem. Liq. 2006, 44, 563-569. 67. Liao, D.-W.; Mebel, A. M.; Chen, Y.-T.; Lin, S.-H., Theoretical Study of the Structure, Energetics, and the n−π* Electronic Transition of the Acetone + nH2O (n = 1−3) Complexes. J. Phys. Chem. A 1997, 101, 9925-9934. 68. Gupta, S.; Rafiq, S.; Kundu, M.; Sen, P., Origin of Strong Synergism in Weakly Perturbed Binary Solvent System: A Case Study of Primary Alcohols and Chlorinated Methanes. J. Phys. Chem. B 2012, 116, 1345-1355. 69. Kadam, U. B.; Hiray, A. P.; Sawant, A. B.; Hasan, M., Densities, Viscosities, and Ultrasonic Velocity Studies of Binary Mixtures of Trichloromethane with Methanol, Ethanol, Propan-1-ol, and Butan-1-ol at T=(298.15 and 308.15)K. J. Chem. Thermodyn. 2006, 38, 1675-1683. 70. Gupta, S.; Mukherjee, P.; Sengupta, B.; Sen, P., Dynamical Response in Methanol– Chloroform Binary Solvent Mixture over fs–µs time regime. Phys. Chem. Liq. 2017, 1-12. 71. Zhang, J.; White, G. B.; Ryan, M. D.; Hunt, A. J.; Katz, M. J., Dihydrolevoglucosenone (Cyrene) As a Green Alternative to N,N-Dimethylformamide (DMF) in MOF Synthesis. ACS Sustainable Chem. Eng. 2016, 4, 7186-7192. 72. Salavagione, H. J.; Sherwood, J.; De bruyn, M.; Budarin, V. L.; Ellis, G. J.; Clark, J. H.; Shuttleworth, P. S., Identification of High Performance Solvents for the Sustainable Processing of Graphene. Green Chem. 2017, 19, 2550-2560. 73. Pandey, S.; Kumar, S., Reactive Extraction of Gallic Acid using Aminic and Phosphoric Extractants Dissolved in Different Diluents: Effect of Solvent’s Polarity and Column Design. Ind. Eng. Chem. Res. 2018, 57, 2976-2987



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Table 1. Fitting parameters (f2/1, f12/1 and v12 ) from the preferential solvation model (eq. (5)) with solvent mixtures of hydrogen bond (1, HBD) donor solvents and hydrogen bond (2, HBA) acceptor solvent using experimental maximum absorption wavenumbers ( vmax , kK) data in Fig. 1 (a)-(c) at 25 °C. HBD solvents are methanol (MeOH) and ethanol (EtOH). HBA solvents are cyclopentanone (CPN) and cyclohexanone (CHN). Indicator R2 f2/1 f12/1 f12/2 %AAD v1 v2 v12 (HBD(1)-HBA(2)) Indicator 1 (N,N-dimethyl-4-nitroaniline) for dipolarity/polarizability (π*) MeOH-CHN 25.68 25.51 25.40 3.26 4.21 1.29 0.022 0.986 MeOH-CPN 25.68 25.49 25.31 1.55 2.15 1.39 0.015 0.995 EtOH-CHN 25.90 25.51 25.44 2.10 3.38 1.61 0.026 0.994 EtOH -CPN 25.90 25.49 25.48 2.23 4.19 1.88 0.024 0.994 Indicator 2 (4-nitroaniline) for basicity (β) MeOH-CHN 26.95 27.15 26.82 7.52 12.28 1.63 0.036 0.964 MeOH-CPN 26.95 27.12 26.80 7.96 9.65 1.21 0.014 0.995 EtOH-CHN 26.85 27.15 26.80 3.49 8.43 2.42 0.027 0.990 EtOH-CPN 26.85 27.12 26.83 1.97 2.82 1.43 0.018 0.990 Water-acetone 26.32 27.30 25.97 50.87 49.32 0.97 0.131 0.987 Indicator 3 (2,6-diphenyl-4-(2,4,6-triphenylpyridinio) phenolate)for acidity (α) MeOH-CHN 19.29 14.01 18.45 0.93 6.61 7.09 0.085 0.999 MeOH-CPN 19.29 13.99 18.32 0.53 4.86 9.26 0.200 0.999 EtOH-CHN 18.08 14.01 17.44 0.20 1.25 6.31 0.126 0.999 EtOH-CPN 18.08 13.99 17.65 0.18 1.26 7.01 0.106 0.999 %AAD = (1/ N )

∑ (v

Cal

− vExp ) / vExp ×100


Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47

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Table 2. Molar excess volume (VE), binary interaction parameter (G12) obtained from fitting with dynamic viscosity data (eq. (16)), molar L

excess enthalpy (HE), maximum in local mole fractions of complex HBD-HBA molecule ( x12 , Fig. 5a), fraction of H-bond (fH) from IR spectroscopic analysis (Fig. 5b) at

x 2b ulk

= 0.50, and binding energy (Be), hydrogen-bonding distance (d(–H)) and dipole moment (µ) from

DFT calculations on the 1:1-complexes of hydrogen bond donor (HBD) solvent molecule and hydrogen bond acceptor (HBA) 25 ºC. HBD solvent are methanol (MeOH) and ethanol (EtOH). HBA solvent are cyclohexanone (CHN) and cyclopentanone (CPN).

Mixed-solvent system (HBD(1)-HBA(2)) MeOH-CHN MeOH-CPN EtOH-CHN EtOH -CPN

Molar excess volume x 2bulk - V mEax (-) (cm3⋅mol-1) 0.39 0.67 0.38 0.27 0.36 0.19 0.36 0.10

Macroscopic property Dynamic Molar excess viscosity enthalpy G12 Ref. x 2bulk H mE ax -1 (-) (-) J·mol 0.091 0.55 953.0 [65] -0.282 0.55 883.6 [59] -0.954 0.49 1195.2 [65] -0.956 0.55 1262.2 [59]

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UV-Vis Bulk Local x 2bulk

x1L2 , m a x

(-) 0.27 0.26 0.35 0.42

(-) 0.69 0.63 0.69 0.50

Microscopic property IR DFT calculation fH Be d(–H) µ (-) kJ·mol-1 (Å) (D) 0.78 0.50 0.68 0.52

21.80 20.68 21.29 19.76

1.859 1.862 1.867 1.875

4.548 4.335 4.466 4.086

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Table 3. Kamlet-Taft (KT) windows ( π w* indow , β window , α window ) for active pharmaceutical ingredient (API) dissolution13, actual working compositions ( x2actual ) of hydrogen bond (HBD) donor and hydrogen bond (HBA) acceptor mixed-solvent systems. HBD solvents are methanol (MeOH) and ethanol (EtOH). HBA solvents are cyclopentanone (CPN) and cyclohexanone (CHN). API Aspirin Benzoic acid Ibuprofen Naproxen Niflumic acid p-amino benzoic acid Paracetamol p-hydroxy benzoic acid Piroxicam Salicylic acid Sulfamethoxy pyridazine Temazepam

KT windows [13] π w* indow

β window

α window

≥ 0.47 ≥ 0.48 ≥ 0.00 ≥ 0.49 ≥ 0.24 ≥ 0.50 ≥ 0.35 ≥ 0.40 ≥ 0.49 ≥ 0.49 ≥ 0.49 ≥ 0.55

≥ 0.42 ≥ 0.37 ≥ 0.00 ≥ 0.37 ≥ 0.37 ≥ 0.37 ≥ 0.62 ≥ 0.48 ≥ 0.37 ≥ 0.42 ≥ 0.37 ≥ 0.32

≤ 1.00 ≤ 0.90 ≤ 1.00 ≤ 0.50 ≤ 1.00 ≤ 1.00 ≤ 0.75 ≤ 1.00 ≤ 0.50 ≤ 1.00 ≤ 0.50 ≤ 0.90

Actual working composition ( x2actual ) of HBD (1)-HBA (2) for API dissolution MeOH -CHN MeOH -CPN EtOH-CHN EtOH-CPN 0.04-1.00 0.04-1.00 0.00-1.00 0.00-1.00 0.18-0.95 0.20-1.00 0.00-0.90 0.00-1.00 0.04-1.00 0.04-1.00 0.00-1.00 0.00-1.00 0.84-1.00 0.86-1.00 0.76-1.00 0.76-1.00 0.04-1.00 0.04-1.00 0.00-1.00 0.00-1.00 0.04-1.00 0.04-1.00 0.00-1.00 0.00-1.00 0.53-0.56 None 0.27-0.67 0.33-0.67 0.04-0.93 0.04-1.00 0.00-0.93 0.00-1.00 0.84-1.00 0.86-1.00 0.76-1.00 0.76-1.00 0.04-1.00 0.04-1.00 0.00-1.00 0.00-1.00 0.84-0.93 0.86-1.00 0.76-0.93 0.76-1.00 0.26-1.00 0.43-1.00 0.15-1.00 0.27-1.00

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0.9

26.0

(d)

(a)

25.9

0.8

25.8 25.7

0.7

25.6 25.5

0.6

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(b)

(e)

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19

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14

0.0 0.0

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0.6

0.8

0.0

1.0

0.2

0.4

0.6

0.8

1.0

bulk 2

x

x2bulk

Figure 1. Experimental maximum absorption wavenumbers ( vmax ) of indicators and KamletTaft parameters (π*, β, α) for solvent mixtures calculated from modified methods (Table 1) for methanol-cyclohexanone ( ethanol-cyclohexanone (

MeOH-CHN), methanol-cyclopentanone (

EtOH-CHN), ethanol-cyclopentanone (

MeOH-CPN),

EtOH-CPN) mixed-

solvent systems at 25 °C as a function of bulk mole fraction of component 2 ( x 2b u lk , CHN or CPN): (a) N,N-dimethyl-4-nitroaniline (indicator 1), (b) 4-nitroaniline (indicator 2), (c) 2,6diphenyl-4-(2,4,6-triphenylpyridinio) phenolate (indicator 3), (d) dipolarity/polarizability (π*), (e) basicity (β) and (f) acidity (α). Lines ((a)-(c)) were correlated with eq. (5) with preferential solvation parameters (f2/1 and f12/1) in Table 1. Lines ((d)-(f)) were correlated with eqs. (6)-(8) with f2/1 and f12/1 parameters in Table S6 (Section A, Supporting Information).


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(a)

Abs

0.45

0.30

Peak 1

Peak 2 0.15

0.00

(b)

Abs

0.45

0.30

0.15

0.00

(c)

Abs

0.45

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Abs

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0.30

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0.00

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0.45

Abs

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.30

0.15

0.00 1760

1740

1720

1700

Wavenumber (cm-1) 35 ACS Paragon Plus Environment


Figure 2. Deconvolution of IR spectra of C=O stretching for methanol (1) –cyclopentanone (2) mixed-solvent systems using Voigt profile at: (a) x2 = 0.2, (b) x2 = 0.4, (c) x2 = 0.6, (d) x2 = 0.8, (e) x2 = 1.0. Red-solid line (

), experimental IR spectra. Black-dashed line (-----),

cumulative IR spectra obtained from deconvolution. Magenta-dashed line (-----), peak 1 for hydrogen-bonding carbonyl. Blue-dashed line (-----), peak 2 for free carbonyl.


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1.0

3520

3520

3480

3480

3440

3440

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3400

3360

3360

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3320

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(e)

(b)

(f)

(c)

(g)

(d)

(h)

fH

0.8

0.6

0.4

1748

νC=O (cm-1)

1746 1744 1742 1727 1726 1725 0.0

VE (cm3⋅mol-1)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


νOH (cm-1)

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-0.2

-0.4

-0.6

1.0 0.8 0.6 0.4 0.2 0.0 0.0

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0.6

0.8

1.0 1.00.0

0.2

bulk 2

0.4

0.6

0.8

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bulk 2

x

x

Figure 3. Mixed-solvent systems of cyclopentanone (2, HBA) with methanol (1, HBD, (a)(d)) and with ethanol (1, HBD, (e)-(f)) as a function of bulk mole fraction of component 2 ( x 2b u lk ) at 25 °C showing: IR wavenumber of OH stretching (νOH), fraction of H-bond (fH), IR spectral of C=O stretching (νC=O) for hydrogen-bonding carbonyl ( , peak 1) and free carbonyl ( , peak 2 ), molar excess volume (VE) and local mole fractions, x1L ( , HBD L L solvent), x 2 ( ,HBA solvent), and x12 (-----, complex molecule HBD-HBA solvent) around central 4-nitroaniline indicator molecule (indicator 2) that are calculated with preferential solvation model using eqs. (12)-(15) with preferential solvation parameters (f2/1 and f12/1) in Table 1.



VE (cm3⋅mol-1)

0.0 -0.2 -0.4

(a)

-0.6 -0.8

2.1 1.8

η (mPa⋅s)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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1.5

(b)

1.2 0.9 0.6 0.0

0.2

0.4

0.6

0.8

1.0

x2bulk Figure 4. Macroscopic properties of methanol-cyclohexanone ( , MeOH-CHN), methanolcyclopentanone ( , MeOH-CPN), ethanol-cyclohexanone ( , EtOH-CHN), ethanolcyclopentanone ( ,EtOH-CPN) mixed-solvent systems as a function of bulk mole fraction of component 2 (

x 2b u lk

) at 25°C showing: (a) molar excess volume (VE) and (b) dynamic

viscosity (η). Lines show correlations with VE data using Redlich-Kister model (eq. 17) and with η data using Grunberg-Nissan viscosity model (eq. (16)).


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1.0

0.8

fH

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.6

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1.0 0.8 0.6

(b)

0.4 0.2 0.0 0.0

0.2

0.4

0.6

0.8

1.0

bulk 2

x

Figure 5. Microscopic properties of methanol-cyclohexanone ( ,

, MeOH-CHN),

methanol-cyclopentanone ( ,-----, MeOH-CPN), ethanol-cyclohexanone ( , CHN), ethanol-cyclopentanone ( ,

, EtOH-

, EtOH-CPN) mixed-solvent systems as a function of

bulk mole fraction of component 2 ( x 2b u lk ) at 25°C showing: (a) fraction of H-bond (fH) from IR spectroscopic analysis and (b) local mole fractions of complex HBD-HBA molecule ( x12L ) around central 4-nitroaniline molecule (indicator 2) that are calculated with preferential solvation model using eqs. (12)-(15) with preferential solvation parameters (f2/1 and f12/1) in Table 1.



Figure 6. Optimized geometries of 1:1 complexes of hydrogen bond donor (HBD) solvent molecule and hydrogen bond acceptor (HBA) solvent molecule as (a) methanolcyclohexanone, (b) methanol-cyclopentanone, (c) ethanol-cyclohexanone and (d) ethanolcyclopentanone. Distances between HBD molecule and HBA molecule in Å.


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Page 41 of 45

HE (J⋅mol-1)

900 600 300 0

(e)

(a)

-300

η (mPa⋅s)

-600 1.4

1.4

1.2

1.2

1.0

1.0

0.8

(b)0.8

0.6

0.6

0.4

0.4

(f)

384

λmax (nm)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


380 376 372

(c)

(g)

(d)

(h)

368

1.0 0.8 0.6 0.4 0.2 0.0 0.0

0.2

0.4

0.6

0.8

1.00.0

0.2

0.4

bulk 2

0.6

0.8

1.0

bulk 2

x

x

Figure 7. Aqueous system of water (1)-acetone (2) mixture ( , (a)-(d)) and non-aqueous systems of methanol (1)-cyclopentanone (2) mixture ( , (e)-(h)) as a function of bulk mole fraction of component 2 ( x 2b u lk ) at 25°C showing: molar excess enthalpy (HE), dynamic viscosity (η), maximum UV wavelength (λmax) of 4-nitroaniline indicator (indicator 2) and local mole fractions,

x 1L

(

, HBD solvent),

x 2L

(

,HBA solvent), and

x12L

(-----,

complex molecule HBD-HBA solvent) around central the 4-nitroaniline indicator molecule 41 ACS Paragon Plus Environment


that are calculated with preferential solvation model using eqs. (12)-(15) with preferential solvation parameters (f2/1 and f12/1) in Table 1. The HE data of water-acetone mixture75 and methanol-cyclopentanone mixtures59 were taken from literature and correlated with RedlichKister. The η and λ data of water-acetone mixture taken from literature.28 McAllister model76 was used to correlate aqueous-system viscosity data. Grunberg-Nissan model (eq. (16)) was used to correlate non aqueous-system viscosity data.


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x2ideal x2actual 0.80

0.75

π ∗ 0.70

∗ π window

0.65

0.9

β

0.8

β window

0.7

0.6

1.0 0.8

α

0.6

α window

0.4 0.2 0.0 0.0

0.2

0.4

x

0.6

0.8

1.0

bulk 2

Figure 8. Kamlet-Taft parameters versus hydrogen bond acceptor (HBA) solvent mole fraction for the ethanol-cyclopentanone system. Gray shading and yellow-hatched regions are the intersection working composition range of the solvent mixture for having high solubility of paracetamol that obtained from ideal Kamlet-Taft parameter (linear) and non-ideal KamletTaft parameter of solvent mixtures, respectively. Symbols represent experimental data. Solid lines were correlated with eqs. (6)-(8) with preferential solvation parameters (f2/1 and f12/1) in Table S6 (Section A, Supporting Information).



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x2ideal 0.80

∗ π window

0.75

π∗

0.70

0.65

0.8

β

0.7

β window

0.6

1.0 0.8

α

0.6

α window

0.4 0.2 0.0 0.0

0.2

0.4

0.6

0.8

1.0

x 2bulk Figure 9. Kamlet-Taft parameters versus hydrogen bond acceptor (HBA) solvent mole fraction for the methanol-cyclopentanone system. Gray shading and yellow-hatched regions are the intersection working composition range of the solvent mixture for having high solubility of paracetamol that obtained from ideal Kamlet-Taft parameter (linear) and nonideal Kamlet-Taft parameter of solvent mixtures, respectively. Symbols represent experimental data. Solid lines were correlated with eqs. (6)-(8) with preferential solvation parameters (f2/1 and f12/1) in Table S6 (Section A, Supporting Information).


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Solvent Polarity of Cyclic Ketone - ACS Publications - American

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