Solubility Parameter of Ionic Liquids: A Comparative Study of Inverse

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Solubility Parameter of Ionic Liquids: A Comparative Study of Inverse Gas Chromatography and Hansen Solubility Sphere Li Zhao, Qiang Wang, and Kongjun Ma ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b01093 • Publication Date (Web): 17 May 2019 Downloaded from http://pubs.acs.org on May 20, 2019

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ACS Sustainable Chemistry & Engineering

Solubility Parameter of Ionic Liquids: A Comparative Study of Inverse Gas Chromatography and Hansen Solubility Sphere Li Zhao†,‡, Qiang Wang*,†,‡, KongJun Ma‡ †Center

for Physical and Chemical Analysis, Xinjiang University, Shengli Road, Urumqi 14, 830046, Xinjiang, China

‡ Key

Laboratory of Coal Cleaning Conversion and Chemical Engineering Process,

Xinjiang Uyghur Autonomous Region, College of Chemistry and Chemical Engineering, Xinjiang University, Shengli Road, Urumqi 14, 830046, Xinjiang, China E-mail: [email protected]

1

ACS Paragon Plus Environment

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ABSTRACT: The solubility parameters of four ionic liquids (ILs), 1-ethyl-3methylimidazolium methyl sulfate ([EMIM][MeSO4]), 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO4]), 1-hexyl-3-methylimidazolium methyl sulfate ([HMIM][MeSO4])

and

1-octyl-3-methylimidazolium

methyl

sulfate

([OMIM][MeSO4]), were estimated using two complementary methods. The first is an inverse gas chromatography (IGC) method, which determined the Hildebrand solubility parameters of four ILs based on a series of formulaic calculations. The second is the Hansen solubility sphere method, which determined the Hansen solubility parameters (HSPs) of the four ILs based on solubility testing of four ILs in 30 pure solvents. The results showed that the Hansen solubility sphere method provides higher values of the solubility parameters, while the IGC method presents lower values. In addition, the miscibilities of ILs in various solvents were evaluated by the method of IGC, and the results exhibit good agreement with those derived from the Hansen solubility sphere method. It is confirmed that the IGC and Hansen solubility sphere methods can be used to determine the solubility parameters of the ILs and were useful for solvent selection. KEYWORDS: Ionic liquid, Inverse gas chromatography, Hansen solubility sphere, Solubility parameters, Miscibility

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INTRODUCTION As green solvents, ionic liquids (ILs) are molten salts composed entirely of ions that have melting points below 373.15 K.1 Recently, ILs have received significant attention due to their unusual physicochemical properties, such as nonvolatility, negligible vapor pressure, high polarities, high ionic conductivity, and high thermal stability.2,3 They have been widely used in many applications, including as electrolytes,4 in catalysis,5 as reaction media,6 in extraction and separation processes,7 as lubricants,8 and in gas separation.9 The most distinct feature is possibly that their physical and chemical properties can be fine-tuned through slight structural modifications of the cation and anion, which allows the design of task-specific ILs intended for a specific application and makes them potentially useful as “designer solvents.”10 Knowledge about the thermophysical properties of each ionic liquid is essential to design new ILs and scale up promising applications. Among the many physicochemical properties, solubility parameters have been most widely studied due to high significance and are often used to predict and characterize the miscibility between the solvent /ionic liquid system.11 To date, more reports have appeared in the literature about calculating the Hildebrand solubility parameters of ionic liquids.1,12,13 However, the Hildebrand solubility parameters make no distinction based on the type of interactions (polar or nonpolar).14 Therefore, we introduced the Hansen solubility parameters (HSPs), which were first introduced by Hansen, who divided the Hildebrand solubility parameter into three

3



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components which represent the specific type of interaction, namely, dispersion interactions (δD), polar interactions (δP) and hydrogen bonds (δH), respectively.15 The theory of HSPs has been extensively used in classes of materials such as nanoparticles and pigments,16 organic semiconductors,17 polymers,18 in artwork conservation,19 and in solid phase extraction.20 However, there are few researchers in the field of ILs.21 In this study, the Hansen solubility sphere method was used to calculated the HSPs of four ILs by solubility testing. To obtain the Hansen solubility sphere of four ILs, the data processing software package Hansen Solubility Parameter in Practice (HSPiP), presented by Hansen, was used. In addition, a widely used inverse gas chromatography (IGC) method is proposed to calculate the Hildebrand solubility parameter of four ILs and perform a comparative study, with the results derived from the Hansen solubility sphere. THEORETICAL CALCULATIONS Theory of IGC. IGC technique is often used to characterize the thermodynamic properties of ILs. In IGC theory, specific retention volume Vg0 is used to characterize the elution behavior of probes in a column, which can be expressed as,22 Vg0 

273.15 Po  Pw 3 ( Pi / Po ) 2 - 1 F (tr  t0 ) mTa Po 2 ( Pi / Po )3 - 1

(1)

where m is the mass of the ILs on the column packing, Ta is room temperature, F is the flow rate of carrier gas, t r  t 0 is the net retention time of the probes, Pw is the saturated vapor pressure of water, and Pi and Po are the pressure of the column inlet and outlet, respectively. 4


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According to Flory-Huggins theory, the interaction parameter χ12 can be calculated as follows,23

χ12  ln(273.15 RV2 / P10Vg0V1 )  1  P10 ( B11  V1 ) / RT

(2)

where R denotes the universal gas constant, V 1 represents the molar volume of the probes, V2 is the specific volume of the ILs in the stationary phase, T is the column temperature, P10 is the saturated vapor pressure of the probes, M 1 represents the molecular weight of the solvent, and B11 is the second virial coefficient, which can be expressed through eq 3.24 The detailed B11 values of the solvents used in this study are listed in Table S1 in the Supplementary Material (SM). 2

B11 / V c  0.430  0.886(T c / T )  0.694 (T c / T )  0.0375(n  1) (T c / T )

4.5

(3)

where n is the number of carbon atoms in the solvent, Vc is the critical molar volume of the solvent, and Tc is the critical temperature of the solvent. The Hildebrand solubility parameter δ2 can be computed according to the following equation,25 (

δ12 χ 2δ δ2  12 )  ( 2 )δ1  2 RT V1 RT RT

(4)

In this expression, δ1 represents the solubility parameters of the solvents which can be found from the literature.26 The detailed δ1 values of the solvents are presented in Table S2. According to eq 4, the δ2 is obtained from a straight line with a slope of

2 2 / RT . Theory of HSPiP. The Hansen solubility parameters are given by the following equation,27 5



δt2  δD2  δP2  δH2

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(5)

where δt, δD, δP and δH are the total solubility parameter, the dispersion solubility parameter, the polar solubility parameter and the hydrogen bonding solubility parameter, respectively. For the four solubility parameter values mentioned in eq 5, a calculated value Ra is defined to evaluate the difference of solubility for both substances.

Ra2  4(δ1D  δ 2D)2  (δ1P  δ 2P)2  (δ1H  δ 2H)2

(6)

A small Ra value indicates similar interaction force between the substances, which have a higher miscibility for each other. The concept of HSPs can be quantified by plotting the values of δD, δP and δH in a three dimensional figure known as the Hansen solubility sphere. In the solubility sphere, good solvents exist inside the region of the sphere, while poor solvents are outside the area of sphere. The HSP of the desired substance is represented at the center of the sphere, and the radius of the sphere is called the interaction radius R0.28 Another very useful parameter is the relative energy difference (RED) value given by eq 7,

RED  Ra / R0

(7)

RED ≤ 1.0 indicates good solvents, while progressively higher RED values imply poor solvents.15 EXPERIMENTAL SECTION Materials. The four ILs used in this investigation were 1-ethyl-3-methylimidazolium methyl sulfate ([EMIM][MeSO4]), 1-butyl-3-methylimidazolium methyl sulfate 6


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([BMIM][MeSO4]), 1-hexyl-3-methylimidazolium methyl sulfate ([HMIM][MeSO4]) and 1-octyl-3-methylimidazolium methyl sulfate ([OMIM][MeSO4]), and the details of each IL are presented in Table 1. All ILs were acquired from Chengjie Chemical Co. Ltd., China. Before use, ILs were subjected to vacuum evaporation at 353.15 K over 24 h to remove water and volatile chemicals. The content of water in ionic liquids was measured using the Karl Fischer titration, all of which were less than 4×10-4. All of the solvents were obtained from J&K Scientific Ltd. and were used without further purification; the details are presented in Table S3. Table 1. IGC method. The column preparation and packing method used in this work is consistent with the method described by Ban.29 A stainless steel column with 1.2 m length and 2 mm inner diameter was used. The ionic liquid coated silicon alkylation 102 monomer as the stationary phase, which was prepared using dichloromethane as the dissolving solvent and rotary evaporation allows, the IL to be uniformly spread onto the surface of the monomer. The mass fraction of the ionic liquid in the stationary phase was 20%. The prepared column was heated under nitrogen for 12 h at 393.15 K before the experiment. The Shimadzu QP2010 gas chromatograph equipped with a flame ionization detector (FID) was used in this experiment. The obtained data were collected and processed using GC solution (version. 2.30.00). The experiments were carried out with the column temperature ranging from 313.15 to 353.15 K, and the temperatures of injector and detector were set at 523.15 K. High-purity nitrogen was used as carrier 7



gas. The flow rate of the carrier gas was 20 mL/min, which was determined by the soap bubble flowmeter. The volume of the solvents injected into the column for infinite dilution measurements was approximately 0.5 μL.. At each temperature, the dead time was determined by methane. Each experiment was repeated three times to ensure repeatability. HSPiP method. We employed 30 pure solvents to simulate the Hansen solubility sphere for four ionic liquids based on the solubility test. For each solubility experiment, 10 mL solvent was added to 2 mL ILs and then stirred for 24 h at room temperature. The solution was allowed to stand for two days, then the solubility state was recorded. If phase separation was observed in the solubility test, then the solvent was determined to be a poor solvent (score 0), while uniform solutions were considered to be good solvents (score 1). The commercial software package HSPiP (version 4.1.07) was adopted to process the data and create the Hansen solubility parameter sphere, based on the solubility test scores of 0 or 1. RESULTS AND DISCUSSION Flory-Huggins interaction parameter. The Flory-Huggins interaction parameter χ12 is often used to assess thermodynamic miscibility for solvent-solute systems. In this regard, some rules have been previously presented in the literature for estimating solute-solvent system miscibility.30 Theoretically, χ12 < 0.5, indicates good solvents,

χ12 > 1, denotes poor solvents, and 0.5 < χ12 < 1 corresponds to moderate solvents. Therefore, we applied the Flory-Huggins theory to predict the interaction between ILs

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and solvents. The results of χ12 ranging from the temperatures of 313.15 to 353.15 K for four ILs are presented in Table S4. From Table S4, the values of χ12 for n-alkanes (n-C6 to n-C12), cyclopentane, cyclohexane, aromatic hydrocarbons, alkenes and butyl ether are relatively large, while the values are small for dichloromethane, 1,4dioxane, acetone and alcohols. Based on the above theory, good solvents, poor solvents and intermediate solvents of the four ionic liquids were determined according to χ12 , and the results are listed in Table 2. For a binary solvent-solute system, this parameter depends on temperature. We can see from Table S4 that, with an increase of the temperature, a decrease in χ12 is observed for most of the solvents including nalkanes, cyclopentane, cyclohexane, benzene, toluene, p-xylene, ethylbenzene, 1,4dioxane, alkenes, acetone, butyl ether and alcohols. However, for dichloromethane and ethyl propionate, the trend with temperature is the opposite. The interaction parameter χ12 has been considered as a Gibbs free energy parameter and allows division into entropy χ s and enthalpy χ H components.31 The χ s contribution is related to the free volume of the solvent, which increased with increasing temperature. The χ H contribution is related to the intermolecular forces between materials and solvents, which decreased with increasing temperature. For dichloromethane and ethyl propionate, this means that the χ s contribution plays a major role, while the χ H contribution is greater than the χ s for other probes. Table 2. [δ12/(RT)- 12 /V1] values versus δ1 were

Hildebrand solubility parameter. The

plotted and fitted by eq 4 to determine the Hildebrand solubility parameters of ILs at 9



different temperatures. Figure 1 shows the fitted curve for [δ12/(RT)- 12 /V1] in terms of δ1 for ionic liquid [EMIM][MeSO4] at five temperatures, and the plots of other ILs are shown in Figures S1-S3 in the SM. The Hildebrand solubility parameters of the four ILs were obtained from the slopes of the respective fitted curves at various temperatures, and the results are listed in Table 3. As is shown in Table 3, the increase in temperature from 313.15 to 353.15 K shows the decrease of the Hildebrand solubility parameter of four ILs varying within the ranges of 23.06-22.76 (J·cm-3)0.5, 22.52-22.02 (J·cm-3)0.5, 22.42-22.76 (J·cm-3)0.5 and 22.20-21.63 (J·cm-3)0.5. The Hildebrand solubility parameter exhibits a slight decrease with increasing temperature, which confirms the previous works.1,29,32,33 The trends of Hildebrand solubility parameters with respect to the temperature for the four ILs are shown in Figure 2. The regression equations and correlation coefficients (> 0.961) associated with the lines of four ILs are presented in Table 4. To obtain the Hildebrand solubility parameter of the ILs at room temperature, we used the extrapolation method based on the relationship curve of Figure 2. The δ2 values of four ILs (at 298.15 K) obtained from the equations are 23.16, 22.73, 22.58, and 22.43 (J·cm-3)0.5. In addition, the ionic liquid structure is a critical factor in influencing the value of the Hildebrand solubility parameter. Ionic liquids which have different types of anion and cation have different polarities and possess different molecular interaction forces.34 In this study, the effect of alkyl chain-length of cation and anion structures on the Hildebrand solubility parameters of imidazolium-based ILs has also been

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investigated. We found that the Hildebrand solubility parameter decreases with increasing alkyl chain-length on the imidazolium ring at the same temperature, which is in agreement with the results of Marciniak35 and Alavianmehr.11 In other words, enhanced aliphatic character of the imidazolium cation leads to the lower solubility parameters. Figure 1. Table 3. Figure 2. Table 4. Solubility test for ILs. The solubility test results of each ionic liquid in 30 pure solvents are summarized in Table 5. As Table 5 demonstrates, for the four ILs, nalkanes (n-C6 to n-C12), cyclopentane, cyclohexane, ethylbenzene, hexene, cyclohexene, octene and butyl ether are poor solvents, while dichloromethane, acetone, methanol, alcohol, propanol, isopropanol, butanol and isobutanol are good solvents. This result is essentially consistent with that derived from the method of IGC based on χ12 . Four ILs have the same anionic group but different alkyl chainlengths on the imidazolium ring, which leads to solubility differences: the ionic liquids [BMIM][MeSO4], [HMIM][MeSO4] and [OMIM][MeSO4] dissolve in 1,4dioxane, butanone and 2-butanol, but the ionic liquid [EMIM][MeSO4] does not. Benzene

and

pentanone

dissolved

ionic

liquids

11


[HMIM][MeSO4]

and


[OMIM][MeSO4], while toluene, p-xylene and ethyl propionate dissolved only ionic liquid [OMIM][MeSO4]. Table 5. HSPs of the ILs. On the basis of the solubility test results, Figure 3 shows the Hansen solubility parameter spheres of four ILs. The largest green sphere with a small green solid dot in the middle represents the solubility parameter sphere of ionic liquid, the symbol “●” indicates a good solvent and the symbol “■” indicates a poor solvent. Table 6 lists the HSP values and interaction radii of the four ionic liquids. We found that the total solubility parameter decreases with increasing alkyl chain length, which confirms the observation of the IGC method. The different alkyl chain length on the imidazolium ring largely changed the Hansen sphere radius, R0. The range of R0 is ca. 7.6-11.8 (J·cm-3)0.5, which reflects the difference in HSPs allowed for good solvents for each ionic liquid. Morimoto also found the same results when studying asphaltene model compounds.36 Therefore, additional good solvents should be available for ionic liquid [OMIM][MeSO4], which has the Hansen solubility sphere with the largest R0 = 11.8 (J·cm-3)0.5. Among the selected 30 solvents, there are 17 solvents that can be dissolved in ionic liquid [OMIM][MeSO4], which is the greatest number among the four ionic liquids. It should be added that the solubility parameters of four ILs obtained by the Hansen solubility sphere are higher than those derived from the method of IGC. However, the results obtained by both methods were within an error range of 0.12-0.57 (J·cm-3)0.5. The harmony between the calculated and experimental values of the solubility parameters is remarkable. The IGC method calculates the 12


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Hildebrand solubility parameter through a series of formulas, which is a theoretical value, while the Hansen solubility sphere method is based on solubility testing to obtain the HSPs of ionic liquids, which is an experimental value closer to the true value. In practical applications, we should comprehensively consider two methods according to our own needs to obtain more suitable solubility parameter values. The RED values between 30 pure solvents and each IL are also shown in Table 5, which were calculated by eq 7. We found that the good and poor solvents determined from the RED values are consistent with those of the previous solubility experiments and the χ12 values. Thus, it would be useful to select suitable solvents using both IGC and Hansen solubility sphere methods. Figure 3. Table 6. CONCLUSIONS It is essential to know the solubility parameters of ionic liquids. In the current study, we have successfully calculated the Hildebrand solubility parameters of four ionic liquids using the IGC method, and the HSPs have been precisely determined for them using the Hansen solubility sphere method based on solubility testing with various pure solvents. It was found that the solubility parameter decreases with increasing alkyl chain length, but it depends slightly on temperature. At the same temperature, the Hildebrand solubility parameters of the four ILs were obtained as δ2([EMIM][MeSO4]) = 23.16 (J·cm-3)0.5, δ2([BMIM][MeSO4]) = 22.73 (J·cm-3)0.5, δ2([HMIM][MeSO4]) = 22.58 (J·cm-3)0.5 13



and δ2([OMIM][MeSO4]) = 22.43 (J·cm-3)0.5. The Hansen solubility sphere results showed that δt([EMIM][MeSO4]) = 23.65 (J·cm-3)0.5, δt([BMIM][MeSO4]) = 23.30 (J·cm-3)0.5, δt([HMIM][MeSO4]) = 22.87 (J·cm-3)0.5 and δt([OMIM][MeSO4]) = 22.55 (J·cm-3)0.5, which were slightly higher values than those obtained by the IGC method; however, only small errors covered the range of 0.12 to 0.57 (J·cm-3)0.5. In addition, the miscibilities of ionic liquids in various solvents were successfully determined using χ12 values and solubility testing, and the results obtained by both methods were essentially consistent. ASSOCIATED CONTENT Supporting Information Solvent description table , B11 and δ1 values of the 30 solvents at different  temperatures, and Flory-Huggins interaction parameter χ12 between solvents and four

ILs at various temperatures (PDF) AUTHOR INFORMATION Corresponding Author *E-mail:

[email protected]. Tel.:+86 991 8582966. Fax: +86 991 8582966.

ORCID Qiang Wang: 0000-0002-5248-6466 Notes The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grants No. 21566036 and 21868037).

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REFERENCES (1) Weerachanchai, P.; Chen, Z.; Leong, S. S. J.; Chang, M. W.; Lee, J. M. Hildebrand solubility parameters of ionic liquids: Effects of ionic liquid type, temperature and DMA fraction in ionic liquid. Chem. Eng. J. 2012, 213 (12), 356−362, DOI 10.1016/j.cej.2012.10.012. (2) Huang, Y.; Zhang, X.; Zhao, Y.; Zeng, S.; Dong, H.; Zhang, S. New models for predicting thermophysical properties of ionic liquid mixtures. Phys. Chem. Chem. Phys. 2015, 17 (40), 26918−26929, DOI 10.1039/C5CP03446A. (3) Yongsheng, Z.; Ying, H.; Xiangping, Z.; Suojiang, Z. A quantitative prediction of the viscosity of ionic liquids using S(σ-profile) molecular descriptors. Phys. Chem. Chem. Phys. 2015, 17 (5), 3761−3767, DOI 10.1039/C4CP04712E. (4) Abbott, A. P.; Frisch, G.; Ryder, K. S. Electroplating Using Ionic Liquids. Annu. Rev. Mater. Res. 2013, 43 (1), 335−358, DOI 10.1146/annurev-matsci-071312121640. (5) Olivier-Bourbigou, H.; Magna, L.; Morvan, D. Ionic liquids and catalysis: Recent progress from knowledge to applications. Appl. Catal. A 2010, 373 (1), 1−56, DOI 10.1016/j.apcata.2009.10.008. (6) Cybulski, J.; Wiśniewska, A.; Kulig-Adamiak, A.; Dąbrowski, Z.; Praczyk, T.; Michalczyk, A.; Walkiewicz, F.; Materna, K.; Pernak, J. Mandelate and prolinate

16


Page 16 of 35

Page 17 of 35 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


ionic liquids: synthesis, characterization, catalytic and biological activity. Tetrahedron Lett. 2011, 52 (12), 1325−1328, DOI 10.1016/j.tetlet.2011.01.069. (7) Hoogerstraete, T. V.; Onghena, B.; Binnemans, K. Homogeneous Liquid-Liquid Extraction of Metal Ions with a Functionalized Ionic Liquid. J. Phys. Chem. Lett. 2013, 4 (10), 1659−1663, DOI 10.1021/jz4005366. (8) Kheireddin, B. A.; Lu, W.; Chen, I. C.; Akbulut, M. Inorganic nanoparticle-based ionic

liquid

lubricants.

Wear.

2013,

303

(1-2),

185−190,

DOI

10.1016/j.wear.2013.03.004. (9) Switzer, J. R.; Ethier, A. L.; Flack, K. M.; Biddinger, E. J.; Gelbaum, L.; Pollet, P.; Eckert, C. A.; Liotta, C. L. Reversible Ionic Liquid Stabilized Carbamic Acids: A Pathway Toward Enhanced CO2 Capture. Ind. Eng. Chem. Res. 2013, 52 (36), 13159−13163, DOI 10.1021/ie4018836. (10) Batista, M. L. S.; Neves, C. M. S. S.; Carvalho, P. J.; Rafiqul, G.; Coutinho, J. O. A. P. Chameleonic behavior of ionic liquids and its impact on the estimation of solubility parameters. J. Phys. Chem. B 2011, 115 (44), 12879−12888, DOI 10.1021/jp207369g. (11) Alavianmehr, M. M.; Hosseini, S. M.; Mohsenipour, A. A.; Moghadasi, J. Further property of ionic liquids: Hildebrand solubility parameter from new molecular thermodynamic

model.

J.

Mol.

Liq.

2016,

10.1016/j.molliq.2016.02.032. 17


218,

332−341,

DOI


Page 18 of 35

(12) Li, X.; Wang, Q.; Li, L.; Deng, L.; Zhang, Z.; Tian, L. Determination of the thermodynamic parameters of ionic liquid 1-hexyl-3-methylimidazolium chloride by inverse gas chromatography. J. Mol. Liq. 2014, 200 (1), 139−144, DOI 10.1016/j.molliq.2014.10.015. (13) Chen, Y.; Wang, Q.; Zhang, Z.; Tang, J. Determination of the Solubility Parameter of Ionic Liquid 1-Hexyl-3-methylimidazolium Hexafluorophosphate by Inverse Gas Chromatography. Ind. Eng. Chem. Res. 2012, 51 (46), 15293−15298, DOI 10.1021/ie301924y. (14) Süß, S.; Sobisch, T.; Peukert, W.; Lerche, D.; Segets, D. Determination of Hansen parameters for particles: A standardized routine based on analytical centrifugation.

Adv.

Powder

Technol.

2018,

29

(7),

1550−1561,

DOI

10.1016/j.apt.2018.03.018. (15) Tripathi, A.; Parsons, G. N.; Khan, S. A.; Rojas, O. J. Synthesis of organic aerogels with tailorable morphology and strength by controlled solvent swelling following Hansen solubility. Sci. Rep. 2018, 8 (1), 1−2, DOI 10.1038/s41598-01819720-4. (16) Petersen, J. B.; Jeevan, M.; Randle, J. S.; Cross, W. M.; Kellar, J. J. Hansen solubility parameters of surfactant-capped silver nanoparticles for ink and printing technologies. Langmuir. 2014, 30 (51), 15514−15519, DOI 10.1021/la502948b.

18


Page 19 of 35 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


(17) Machui, F.; Abbott, S.; Waller, D.; Koppe, M.; Brabec, C. J. Determination of Solubility Parameters for Organic Semiconductor Formulations. Macromol. Chem. Phys. 2011, 212 (19), 2159−2165, DOI 10.1002/macp.201100284. (18) Liu, G.; Hoch, M.; Wrana, C.; Kulbaba, K.; Liu, S.; Bi, W.; Zhao, S. Investigation of the swelling response and quantitative prediction for hydrogenated nitrile

rubber.

Polym.

Test.

2014,

34

(4),

72−77,

DOI

10.1016/j.polymertesting.2013.12.013. (19) Fardi, T.; Stefanis, E.; Panayiotou, C.; Abbott, S.; Loon, S. V. Artwork conservation materials and Hansen solubility parameters: A novel methodology towards critical solvent selection. Journal of Cultural Heritage. 2014, 15 (6), 583−594, DOI 10.1016/j.culher.2013.11.006. (20) Bielicka-Daszkiewicz, K.; Voelkel, A.; Pietrzyńska, M.; Héberger, K. Role of Hansen solubility parameters in solid phase extraction. J. Chromatogr. A 2010, 1217 (35), 5564−5570, DOI 10.1016/j.chroma.2010.06.066. (21) Agata, Y.; Yamamoto, H. Determination of Hansen Solubility Parameters of Ionic Liquids Using Double-Sphere Type of Hansen Solubility Sphere Method. Chem. Phys. 2018, 513, 165−173, DOI 10.1016/j.chemphys.2018.04.021. (22) Boutboul, A.; Lenfant, F.; Giampaoli, P.; Feigenbaum, A.; Ducruet, V. Use of inverse gas chromatography to determine thermodynamic parameters of aroma–starch

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interactions. J. Chromatogr. A 2017, 969 (1), 9−16, DOI 10.1016/s00219673(02)00208-x. (23) Mutelet, F.; Butet, V.; Jaubert, J. N. Application of Inverse Gas Chromatography and Regular Solution Theory for Characterization of Ionic Liquids. Ind. Eng. Chem. Res. 2005, 44 (11), 4120−4127, DOI 10.1021/ie048806l. (24) Kozłowska, M. K.; Domańska, U.; Lempert, M.; Rogalski, M. Determination of thermodynamic properties of isotactic poly(1-butene) at infinite dilution using density and inverse gas chromatography. J. Chromatogr. A 2005, 1068 (2), 297−305, DOI 10.1016/j.chroma.2005.01.090. (25) Yazici, O.; Sakar, D.; Cankurtaran, O.; Karaman, F. Thermodynamical Study of Poly(n-hexyl methacrylate) with Some Solvents by Inverse Gas Chromatography. J. Appl. Polym. Sci. 2011, 122 (3), 1815−1822, DOI 10.1002/app.34288. (26) Barton, A. F. M. Solubility parameters. Chem. Rev. 1975, 75 (9), 731−753, DOI 10.1021/cr60298a003. (27) Huth, M.; Chen, C. W.; Köhling, J.; Wagner, V. Influence of Hansen solubility parameters on exfoliation of organophilic fluoromica. Appl. Clay Sci. 2018, 161, 412−418, DOI 10.1016/j.clay.2018.04.036. (28) Sato, T.; Araki, S.; Morimoto, M.; Tanaka, R.; Yamamoto, H. Comparison of Hansen Solubility Parameter of Asphaltenes Extracted from Bitumen Produced in

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Different Geographical Regions. Energy Fuels. 2014, 28 (2), 891−897, DOI 10.1021/ef402065j. (29) Tao, B.; Cai-Lian, L.; Qiang, W. Determination of the solubility parameter of allyl imidazolium-based ionic liquid using inverse gas chromatography and Hansen solubility parameter in practice. J. Mol. Liq. 2018, 271, 265−273, DOI 10.1016/j.molliq.2018.08.095. (30) Yazıcı, D. T.; Aşkın, A.; Bütün, V. GC Investigation of the Solubility Parameters of Water-Soluble Homopolymers and Double-Hydrophilic Diblock Copolymers. Chromatographia. 2008, 67 (9-10), 741−747, DOI 10.1365/s10337-008-0561-2. (31) Strzemiecka, B.; Voelkel, A.; Hinz, M.; Rogozik, M. Application of inverse gas chromatography in physicochemical characterization of phenolic resin adhesives. J. Chromatogr. A 2014, 1368, 199−203, DOI 10.1016/j.chroma.2014.09.069. (32) Moganty, S. S.; Baltus, R. E. Regular Solution Theory for Low Pressure Carbon Dioxide Solubility in Room Temperature Ionic Liquids: Ionic Liquid Solubility Parameter from Activation Energy of Viscosity. Ind. Eng. Chem. Res. 2010, 49 (12), 5846−5853, DOI 10.1021/ie901837k. (33) Pan, X.; Chen, Y.; Deng, L.; Wang, Q. Determination of Infinite Dilution Activity Coefficients of Several Organic Solutes in N-Butylpyridinium Nitrate/NOctylpyridinium Nitrate by Blend Inverse Gas Chromatography. J. Chem. Eng. Data. 2017, 62, 3095−3104, DOI 10.1021/acs.jced.7b00244. 21



Page 22 of 35

(34) Lee, S. H.; Lee, S. B. The Hildebrand solubility parameters, cohesive energy densities and internal energies of 1-alkyl-3-methylimidazolium-based room temperature

ionic

liquids.

Chem.

Commun.

2005,

27,

3469−3471,

DOI

10.1039/b503740a. (35) Marciniak, A. The hildebrand solubility parameters of ionic liquids-part 2. Int. J. Mol. Sci. 2011, 12 (6), 3553−3575, DOI 10.3390/ijms12063553. (36) Morimoto, M.; Fukatsu, N.; Tanaka, R.; Takanohashi, T.; Kumagai, H.; Morita, T.; Tykwinski, R. R.; Scott, D. E.; Stryker, J. M.; Murray, G. R. Determination of Hansen Solubility Parameters of Asphaltene Model Compounds. Energy Fuels. 2018, 32, 11296−11303, DOI 10.1021/acs.energyfuels.8b02661.

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Table Captions Table 1. ILs description table. Table 2. Solvent classification. Table 3. Hildebrand solubility parameters of four ILs at varied temperatures for the hypothetical liquid at zero pressure. Table 4. Regression equations and correlation coefficients of four ILs. Table 5. Solubility test results. Table 6. HSPs of four ILs.

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Table 1. ILs description table. ILs

CAS

Source

Mole fraction purity

Purification method

Analysis method

[EMIM][MeSO4]

516474-01-4

Chengjie Chemical Co. Ltd.

0.99

Low pressure, 8 h, 363 K

﹤4×10-4

[BMIM][MeSO4]

-


0.99


﹤4×10-4

[HMIM][MeSO4]

-


0.99


﹤4×10-4

[OMIM][MeSO4]

-


0.99


﹤4×10-4

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Table 2. Solvent classification. Solvent

Solvent classification [EMIM][MeSO4]

[BMIM][MeSO4]

[HMIM][MeSO4]

[OMIM][MeSO4]

n-Hexane

poor

poor

poor

poor

n-Heptane

poor

poor

poor

poor

n-Octane

poor

poor

poor

poor

n-Nonane

poor

poor

poor

poor

n-Decane

poor

poor

poor

poor

n-Undecane

poor

poor

poor

poor

n-Dodecane

poor

poor

poor

poor

Cyclopentane

poor

poor

poor

poor

Cyclohexane

poor

poor

poor

poor

Benzene

poor

moderate

good

good

Toluene

poor

poor

moderate

good

p-Xylene

poor

poor

poor

moderate

Ethylbenzene

poor

poor

poor

moderate

Dichloromethane

good

good

good

good

1,4-Dioxane

moderate

good

good

good

Hexene

poor

poor

poor

poor

Cyclohexene

poor

poor

poor

poor

Octene

poor

poor

poor

poor

Acetone

moderate

good

good

good

Butanone

poor

moderate

good

good

Pentanone

poor

moderate

moderate

moderate

Butyl ether

poor

poor

poor

poor

Ethyl propionate

poor

poor

poor

moderate

Methanol

good

good

good

good

Alcohol

good

good

good

good

Propanol

good

good

good

good

Isopropanol

good

good

good

good

Butanol

moderate

good

good

good

2-Butanol

poor

good

good

good

Isobutanol

moderate

good

good

good

25



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Table 3. Hildebrand solubility parameters of four ILs at varied temperatures for the hypothetical liquid at zero pressure. ILs

δ2 /(J·cm-3)0.5 313.15 K

323.15 K

333.15 K

343.15 K

353.15 K

[EMIM][MeSO4]

23.06

22.98

22.87

22.79

22.76

[BMIM][MeSO4]

22.52

22.43

22.29

22.11

22.02

[HMIM][MeSO4]

22.42

22.33

22.28

22.05

22.76

[OMIM][MeSO4]

22.20

22.09

21.93

21.81

21.63

Standard uncertainties are as follow: u(T)=±0.5 K, u(δ2)=0.02

(J·cm-3)0.5

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Table 4. Regression equations and correlation coefficients of four ILs. ILs

Regression equation

R2

δ2

[EMIM][MeSO4]

Y=-0.0079X+25.5238

0.9612

23.16a

[BMIM][MeSO4]

Y=-0.0132X+26.6175

0.9827

22.73a

[HMIM][MeSO4]

Y=-0.0102X+25.6301

0.9621

22.58a

[OMIM][MeSO4] a: at 298.15 K

Y=-0.0142X+26.6872

0.9937

22.43a

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Page 28 of 35

Table 5. Solubility test results. Solvent

HSP/(J·cm-3)0.5

[EMIM][MeSO4]

[BMIM][MeSO4]

[HMIM][MeSO4]

[OMIM][MeSO4]

δD

δP

δH

δt

Score

RED

Score

RED

Score

RED

Score

RED

n-Hexane

14.90

0.00

0.00

14.90

0

2.21

0

1.95

0

1.72

0

1.28

n-Heptane

15.30

0.00

0.00

16.00

0

2.19

0

1.93

0

1.69

0

1.26

n-Octane

15.50

0.00

0.00

15.50

0

2.17

0

1.92

0

1.68

0

1.25

n-Nonane

15.70

0.00

0.00

15.70

0

2.16

0

1.91

0

1.66

0

1.24

n-Decane

15.70

0.00

0.00

15.70

0

2.16

0

1.91

0

1.66

0

1.24

n-Undecane

16.00

0.00

0.00

16.00

0

2.15

0

1.89

0

1.65

0

1.23

n-Dodecane

16.00

0.00

0.00

16.00

0

2.15

0

1.89

0

1.65

0

1.23

Cyclopentane

16.40

0.00

1.80

16.50

0

1.94

0

1.71

0

1.49

0

1.10

Cyclohexane

16.80

0.00

0.20

20.33

0

2.10

0

1.85

0

1.61

0

1.19

1

1.08a

Benzene

18.40

0.00

2.00

18.50

0

1.93

0

1.71

1

1.46a

Toluene

18.00

1.40

2.00

18.10

0

1.81

0

1.59

0

1.35

1

0.99

p-Xylene

17.80

1.00

3.10

18.10

0

1.72

0

1.51

0

1.29

1

0.95

Ethylbenzene

17.80

0.60

1.40

17.90

0

1.93

0

1.70

0

1.46

0

1.07

Dichloromethane

17.00

7.30

7.10

19.81

1

0.86

1

0.71

1

0.54

1

0.37

1,4-Dioxane

17.50

1.80

9.00

19.80

0

1.11

1

0.99

1

0.84

1

0.63

Hexene

14.70

1.10

3.00

15.04

0

1.84

0

1.62

0

1.42

0

1.06

Cyclohexene

17.20

1.00

2.00

17.30

0

1.83

0

1.61

0

1.38

0

1.01

Octene

15.30

1.00

2.40

15.52

0

1.86

0

1.64

0

1.43

0

1.06

Acetone

15.50

10.40

7.00

19.90

1

0.99

1

0.81

1

0.69

1

0.50

Butanone

16.00

9.00

5.10

19.05

0

1.15

1

0.95

1

0.79

1

0.56

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Pentanone

15.80

7.60

4.70

18.15

0

1.22

0

1.03

1

0.86

1

0.62

Butyl ether

15.20

3.40

3.20

15.90

0

1.63

0

1.41

0

1.22

0

0.90

Ethyl propionate

15.50

6.10

4.90

17.36

0

1.27

0

1.08

0

0.92b

1

0.67

1

1.34a

1

1.37a

1

1.12a

Methanol

14.70

12.30

22.30

29.41

1

1.43a

Alcohol

15.80

8.80

19.40

26.52

1

0.88

1

0.86

1

0.93

1

0.78

Propanol

16.00

6.80

17.40

24.60

1

0.69

1

0.69

1

0.76

1

0.64

Isopropanol

15.80

6.10

16.40

23.60

1

0.67

1

0.66

1

0.72

1

0.60

Butanol

16.00

5.70

15.80

22.52

1

0.63

1

0.62

1

0.67

1

0.56

0

0.60b

1

0.57

1

0.61

1

0.51

2-Butanol

15.80

5.70

14.50

22.19

Isobutanol 15.10 5.70 15.90 22.19 1 0.79 1 0.75 1 0.80 1 a Worry in, which mean that the HSPiP software prediction should be out the sphere, contrary to the experimental result. b

Worry out, which mean that the HSPiP software prediction should be in the sphere, contrary to the experimental result.

29


0.66


Page 30 of 35

Table 6. HSPs of four ILs. ILs

δ /(J·cm-3)0.5

R0

δD

δP

δH

δt

[EMIM][MeSO4]

17.31

8.96

13.40

23.65

7.60

[BMIM][MeSO4]

17.20

9.20

12.75

23.30

8.40

[HMIM][MeSO4]

17.51

9.01

11.63

22.87

9.10

[OMIM][MeSO4]

17.59

8.94

10.92

22.55

11.80

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Figure Capions Figure 1. Relation of between δ1 and [δ12/(RT)- 12 /V1] for [EMIM][MeSO4] (a) 313.15 K; (b) 323.15 K; (c) 333.15 K; (d) 343.15 K; (e) 353.15 K. Figure 2. Relation of between δ2 and T for four ILs. Figure 3. Hansen solubility sphere for four ILs (a) [EMIM][MeSO4]; (b) [BMIM][MeSO4]; (c) [HMIM][MeSO4]; (d) [OMIM][MeSO4].

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Figure 1. Relation of between δ1 and [δ12/(RT)- 12 /V1] for [EMIM][MeSO4] (a) 313.15 K; (b) 323.15 K; (c) 333.15 K; (d) 343.15 K; (e) 353.15 K.

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Figure 2. Relation of between δ2 and T for four ILs.

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Figure 3. Hansen solubility sphere for four ILs (a) [EMIM][MeSO4]; (b) [BMIM][MeSO4]; (c) [HMIM][MeSO4]; (d) [OMIM][MeSO4].

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Graphical abstract

Synopsis IGC and Hansen Solubility Sphere methods are used to determine the solubility parameters of ILs and predict the miscibility of solvents and ionic liquids.

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Solubility Parameter of Ionic Liquids: A Comparative Study of Inverse

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