Intermolecular interaction of organic solutes with protic [MIM][NO3] and aprotic [EMIM][NO3] ionic liquids

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Intermolecular interaction of organic solutes with protic [MIM][NO3] and aprotic [EMIM][NO3] ionic liquids Artashes A. Khachatrian a,⁎, Ilnaz T. Rakipov a, Boris N. Solomonov a, Sergey P. Verevkin b a b

Department of Physical Chemistry, Kazan Federal University, Kremlevskaya 18, Kazan 420008, Russia Department of Physical Chemistry, University of Rostock, 18059 Rostock, Germany

a r t i c l e

i n f o

Article history: Received 4 October 2019 Received in revised form 21 November 2019 Accepted 28 November 2019 Available online xxxx Keywords: Ionic liquid Solvophobic effect Activity coefficients Solution enthalpy Hydrogen bond enthalpy

a b s t r a c t Intermolecular interactions of organic solutes with a protic ionic liquid (1-methylimidazolium nitrate [MIM] [NO3]) have been in focus of this work. Activity coefficients at infinite dilution of organic compounds in [MIM] [NO3] were measured by gas-liquid chromatography at different temperatures between 303.15 and 343.15 K. Based on activity coefficients at infinite dilution of organic compounds in [MIM][NO3] the solution enthalpies were obtained. The solvophobic effect in protic ionic liquids was analyzed. It was shown the contribution of solvophobic effect on the solvation enthalpy in protic [MIM][NO3] is negligible. The hydrogen bond enthalpies of organic solutes in protic [MIM][NO3] and aprotic [EMIM][NO3] were calculated. The hydrogen bond enthalpies of organic solutes in the protic [MIM][NO3] and aprotic [EMIM][NO3] ionic liquids were compared. The hydrogen bond enthalpies of proton acceptor molecules in [MIM][NO3] and [EMIM][NO3] ionic liquids were analyzed. © 2019 Elsevier B.V. All rights reserved.

1. Introduction Ionic liquids (ILs) are commonly defined as salts with low melting points. Admittedly, the most unique properties of ILs are their thermal stability and the negligible vapor pressure even at elevated temperatures. These properties made ILs an alternative to volatile solvents currently used in industry. Ionic liquids can be divided into a two large subgroups: aprotic and protic ILs. The AILs have already found some interesting industrial applications. Physical-chemical and thermodynamic properties of aprotic ILs (AILs) have been intensively studied last two decades. Surprisingly, systematic thermodynamic studies of protic ionic liquids (PILs) have been launched only recently [1–5] in spite of significant practical interest. For example, PILs are already used in separation and extraction processes [6,7], as protein stabilizers [8,9] or antitumor drugs [10,11], as well as in the petroleum industry [12,13]. Thermodynamic data on PILs are indispensable for development and optimization of their practical applications. Moreover, thermodynamic data are helpful from the theoretical point of view in order to understand the specific and intensity of intermolecular interactions solute/ solvent in PILs and AILs. This knowledge is essential for prediction of solvation properties of both types of ionic liquids. ⁎ Corresponding author. E-mail address: [email protected] (A.A. Khachatrian).

Activity coefficients at infinite dilution (γ∞ 1, 3) of solutes (index 1) in ionic liquids (index 3) are considered as a convenient thermodynamic tool for interpretation of intermolecular interactions between solute (any volatile compound) and solvent (IL in this work). A proper comparison of solute/solvent properties of PILs and AILs are very seldom in the literature. Domanska et al. [14] demonstrated that the acidic and basic properties of PILs are significantly higher than those for AILs. Comparison of hydrogen bond enthalpies of different solutes in PIL ([MIM][NTf2]) and AIL ([BMIM][NTf2]) was reported in our recent work [15]. It has turned out, that in contrast to an AIL, molecules of a PIL having an acidic hydrogen atom are structured in the liquid phase through a hydrogen bond network like those in the similarly shaped molecular solvents. Quantification of intermolecular interactions of in the self-associated solvents is a challenging task. A suitable approach based on enthalpy of solvation was developed just recently [16,17] and it was applied for to the organic solute/AILs systems successfully [18]. A linear correlation between hydrogen bond enthalpy of methanol in different AILs with an IR-frequence shift of methanol OH-group was established [19]. Moreover, we have revealed that that a contribution of the solvophobic effect to the solvation enthalpy of a solute in AILs can be considered as negligible [20]. Is the solvophobic effect also negligible in PILs? In this current study, the enthalpic contribution of solvophobic effect in the protic ionic liquid 1-methylimidazolium nitrate ([MIM][NO3])

https://doi.org/10.1016/j.molliq.2019.112243 0167-7322/© 2019 Elsevier B.V. All rights reserved.

Please cite this article as: A.A. Khachatrian, I.T. Rakipov, B.N. Solomonov, et al., Intermolecular interaction of organic solutes with protic [MIM] [NO3] and aprotic [EMIM][NO3] ionic liquids..., Journal of Molecular Liquids, https://doi.org/10.1016/j.molliq.2019.112243

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was analyzed and compared with those in the similarly shaped aprotic ionic liquid 1-ethyl-3-methylimidazolium nitrate ([EMIM][NO3]). Molecular structures of both ILs are given in Fig. 1. The hydrogen bond enthalpies of different solutes (proton donors as well as proton acceptor) in the protic ionic liquid [MIM][NO3] were derived from activity coefficients at infinity dilution measured in this work. The hydrogen bond enthalpies of solutes in protic ([MIM][NO3]) and aprotic ([EMIM][NO3]) ionic liquid having the same anion were compared. These comparisons contributed to general understanding of cation and anion influence on PILs and AILs properties. 2. Experimental part 2.1. Materials Ionic liquid [MIM][NO3] was purchased by IoLiTec-Ionic Liquids Technologies GmbH with mass fraction purity higher than 0.98 and was used without further purification. All organic solutes were of commercial origin (see Table S1) with mass fraction purities higher than 0.99 and they also were used without purification. Details on purity of samples are given in Table S1. 2.2. Gas chromatography (GC): activity coefficients at infinite dilution of organic solutes in [MIM][NO3] The ionic liquid (solvent) was used as a stationary phase covering solid support packed in a column of 1 m length. Solid support (Chromosorb W/AW-DMCS 100/120 mesh) coated with the ionic liquid was obtained by dispersing a well-defined amount of the chromosorb in the solution of the ionic liquid in dichloromethane followed by slow evaporation of the solvent. The amount of [MIM][NO3] on the solid support is equal to 1.576 × 10−3 mol. Different volatile organic solutes were injected in the GC column. The experimental measurements were performed with a Hewlett-Packard gas chromatograph equipped with a flame-ionization detector. Nitrogen as a carrier gas was used. Small amount of organic solutes (0.5 to 2) μL were injected into the GC column. The retention times were recorded and corrected for the dead time (methane retention time in this work). The retention times were reproducible within 0.01–0.03 min. The temperature of the GC column was constant within ±0.1 K. The detailed description of the GC measurement procedures was published elsewhere [21,22]. The thermal stability of [MIM][NO3] along the GC experiments was systematically checked by measuring the retention time of n-decane at 303.15 K.

steps) between 303.15 K and 343.15 K. Temperature dependences of γ∞ 1, 3 values for each solute were approximated by the linear regression: ln γ∞i ¼ a þ

b T

ð1Þ

Primary experimental data on γ∞ 1, 3 of solutes in [MIM][NO3] at each temperature are collected in the Supporting information in Table S2. From our experiences, the γ∞ 1, 3-values in a homologous series are linearly increasing with the growing chain [22]. The linear correlation between lnγ∞ i values and the chain length in n-alkanes and in aliphatic alcohols is apparent from Fig. 2. This fact can be considered as a prove of consistency for data measured in this work for these series of solutes. The values of the partial molar excess enthalpy at infinite dilution ΔsolnHA/IL solutes in [MIM][NO3] were calculated from temperature dependences of activity coefficients according to the following equation:
 ∂ ln γ∞i Δ HA=IL ¼ soln R ∂ð1=T Þ

ð2Þ

where R is the universal gas constant. Experimental results of γ∞ i for different solutes in the [MIM][NO3]: temperature ranges, coefficients of A/IL Eq. (1), γ∞ values derived from Eq. (2) are coli at 298.15 K, and ΔsolnH lected in Table 1. As can be seen from Table 1, the solution enthalpies of alcohols in [MIM][NO3] are exothermic. It is due to that the interaction alcohol-IL does not compensate a disruption of the alcohol-alcohol hydrogen bond network. The solution enthalpies of proton acceptor molecules in [MIM][NO3] are less exothermic in comparison to proton donor molecules hydrogen bonds network is absent. Experimental ΔsolnHA/IL-values were used for interpretation of intermolecular interactions between solutes and solvents (ionic liquids [MIM][NO3] and [EMIM][NO3]) as described below. In general, a solvation enthalpy of a solute A in a solvent S (ΔsolvHA/S) can be separated into few contributions as defined by Eq. (3) [23]: Δsolv H A=S ¼ ΔsolvðnonspÞ H A=S þ Δ intðspÞ H A=S þ Δse H A=S

ð3Þ

where Δ solv(nonsp) H A/S is a non-specific solvation enthalpy, Δ int(sp) H A/S is a specific interaction enthalpy (in this case hydrogen bond), and ΔseHA/S is an enthalpy of solvophobic effect. The evaluation of Δ se H A/S for organic solutes in [MIM][NO 3 ] was performed with help of an approach based on the Gibbs energy of solvation [23]. This approach utilizes the linear correlation between

3. Results and discussion Activity coefficients at infinite dilution γ∞ 1, 3 of different solutes in [MIM][NO3], as well as partial molar excess enthalpies at infinite dilution, ΔsolnHA/IL, were derived from retention times temperature dependences. The experiments were carried out at five temperatures (in five

Fig. 1. Molecular structures of 1-methylimidazolium nitrate ([MIM][NO3], left) and 1ethyl-3-methylimidazolium nitrate ([EMIM][NO3], right) studied in this work.

Fig. 2. Dependencies of lnγ∞ i -values at T = 298.15 K on the number of carbon atoms n in the alkyl chain of n-alkanes (■) and aliphatic alcohols (●).

Please cite this article as: A.A. Khachatrian, I.T. Rakipov, B.N. Solomonov, et al., Intermolecular interaction of organic solutes with protic [MIM] [NO3] and aprotic [EMIM][NO3] ionic liquids..., Journal of Molecular Liquids, https://doi.org/10.1016/j.molliq.2019.112243

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Table 1 Experimental results of γ∞ i measurements for different solutes in the [MIM][NO3]: solute i, A/IL temperature ranges, coefficients of Eq. (1), γ∞ i adjusted to T = 298.15 K, and ΔsolnH values derived from Eq. (2). Solute i

Temperature range/K

a

b/K

γ∞a ΔsolnHA/ILb i (298.15 K) /kJ·mol−1

n-Octane n-Nonane n-Decane n-Undecane n-Dodecane Methanol Ethanol Propanol-1 Propanol-2 Acetone Acetonitrile Ethyl acetate Tetrahydrofuran Dichloromethane Trichloromethane

303–333 303–343 303–343 303–343 303–343 313–343 313–343 313–343 313–343 303–343 303–343 303–333 303–343 303–343 303–343

−2.77 −2.80 −2.92 −3.26 −3.23 −0.46 −1.01 −0.71 −0.61 0.45 0.16 −0.29 −1.22 2.01 3.99

2160 2210 2327 2470 2535 48 261 316 295 −392 −301 72 −49 −514 −774

87 100 132 152 194 0.7 0.9 1.4 1.4 0.4 0.4 0.9 0.2 1.3 4.0

17.9 18.4 19.2 20.5 21.1 0.4 2.2 2.6 2.5 −3.3 −2.5 0.6 −0.4 −4.3 −6.4

Standard uncertainties u are u(γ∞ i ) = 3%. The uncertainties of ΔsolnHA/IL are estimated to be not higher than ±10% due to the ∞ small slope of lnγi versus 1/T plots and taking the experimental uncertainty of the γ∞ i values into account. a

b

enthalpies of solvation and Gibbs energies of solvation of n-alkanes in various solvents were developed in our previous work [23]. The solvation Gibbs energy or solvation enthalpy at T = 298.15 K can be calculated according to Eq. (4). Δsolv f

A=S

¼ Δsoln f

A=S

−Δvap f

A

ð4Þ

where, ΔsolvfA/S is solvation thermodynamic function (Gibbs energy or enthalpy), Δ soln fA/S solution thermodynamic function, Δ vap fA is enthalpy of vaporization. The data for calculation solvation Gibbs energy and enthalpy were taken from work [23]. The results of calculations of Gibbs energies of solvation and solvation enthalpies of n-alkanes in [MIM][NO 3 ] are collected in Table 2. Using the data collected in Table 2, a linear correlation between Gibbs energies of solvation and solvation enthalpies for the series of n-alkanes in [MIM][NO3] at T = 298.15 K was derived (see Fig. 3). Δsolv GA=S ¼ ð0:597  0:013Þ  Δsolv H A=S þ 15:3  0:4Þ −1 ¼ 0:16 kJ mol R2 ¼ 0:99

σ ð5Þ

where σ is a standard error of the regression. This correlation is specific for the protic ionic solvent [MIM][NO3 ]. Is this correlation derived for ionic solvent, different from correlation derived for the molecular solvents? Indeed, in our recent study [23] we have obtained a common correlation Gibbs energies and solvation enthalpies of n-alkanes at T = 298.15 K in different nonsolvophobic (non-self-associated) solvents (acetone, acetonitrile,

Table 2 Solvation enthalpies (ΔsolvHA/S) and Gibbs solvation energies (ΔsolvGA/S) of n-alkanes in [MIM][NO3] at T = 298.15 K and 0.1 MPa. Solute

ΔsolvHA/S/a kJ·mol−1

ΔsolvGA/S/a kJ·mol−1

n-Octane n-Nonane n-Decane n-Undecane n-Dodecane

−23.8 −28.0 −31.7 −35.9 −39.7

1.2 −1.5 −3.9 −6.2 −8.3

a

Calculated according to Eq. (4) by using data reported in [23].

Fig. 3. Correlation between solvation Gibbs energies and solvation enthalpies of n-alkanes in [MIM][NO3] at T = 298.15 K.

pyridine, 1,4-dioxane etc. with all together 978 experimental points). The following correlation was established [24]: Δsolv GA=S ¼ 0:627  Δsolv HA=S þ 16:3

σ ¼ 1:6 kJ mol

−1

ð6Þ

It is obvious that coefficients of Eqs. (5) and (6) are indistinguishable within combined experimental uncertainties. As a consequence, the protic ionic liquid [MIM][NO3] should be also considered as definitely not solvophobic ionic solvent. To our surprise, this conclusion contradicts our expectations, based on our previous study of molecular solvents [23]. Indeed, for the series of self-associated molecular solvents (alcohols, formamide, water, ethylene glycol) we demonstrated the presence of solvophobic effects in terms of Gibbs solvation energy. In contrast, in ionic solvent [MIM] [NO3], containing in the structure both acceptor (anion of PIL) and donor groups (hydrogen atoms on the imidazolium cation) the solvophobic effect is practically absent, as it is shown above. Quantitative studies of hydrogen bond enthalpies ΔHBHA/IL between different classes of molecular solutes and ionic solvents are one of our long standing goals [15]. In the frame of the current study it is interesting to perform a systematic comparison of ΔHBHA/AL-values for a selected set of molecular solutes (see Table 3) in the protic [MIM][NO3] and in aprotic [EMIM][NO3] ionic solvents. A general procedure for quantification of hydrogen bond enthalpies at T = 298.15 K has been already described in details [18]. This procedure was carefully validated for different pairs solute/ILs [20]. The main idea was to separate the Table 3 Hydrogen bond enthalpies of organic solutes in [MIM][NO3] and [EMIM][NO3] at T = 298.15 K and 0.1 MPa. Solute i

ΔHBHA/[MIM][NO3]/a kJ·mol−1

ΔHBHA/[EMIM][NO3]/b kJ·mol−1

Methanol Ethanol Propanol-1 Propanol-2 Acetone Acetonitrile Ethyl acetate Tetrahydrofuran Dichloromethane Trichloromethane

−13.0 ± 1.0 −13.0 ± 1.0 −13.0 ± 1.0 −14.0 ± 1.0 −3.0 ± 1.0 −3.0 ± 1.0 −0.3 ± 1.0 −1.0 ± 1.0 −6.0 ± 1.0 −11.0 ± 1.0

−14.0 ± 1.0 −14.0 ± 1.0 −13.0 ± 1.0 −13.0 ± 1.0 −3.0 ± 1.0 −3.0 ± 1.0 −1.0 ± 1.0 0.5 ± 1.0 −6.21 ± 1.0 −10.0 ± 1.0

a b

Calculated in this work using Eq. (7). Calculated in this work using Eq. (7) and experimental data from [25].

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solvation enthalpy into the two terms: non-specific solvation enthalpy (van-der-Waals interactions) and the specific interaction enthalpy (hydrogen bonding) between the solute and solvent according to the following equation [18]:
qffiffiffiffiffiffiffiffiffiffiffiffiffi   S C H S ΔHB H A=S ¼ Δsoln HA=S −Δsoln HA=C6 H12 − δcav h −δcav h 6 12  V Ax − aR þ bR δcav h  h    i SR C6 H12 A=SR A=C6 H12 A − δcav h −δcav h  Vx ; −Δsoln H  Δsoln H

ð7Þ where ΔsolnHA/S is solution enthalpy of a solute A (molecular solutes in this work) in a solvent S (ionic solvents in this work), ΔsolnHA/SR is solution enthalpy of a solute A in the reference solvent R, and ΔsolnHA/C6H12 is solution enthalpy of a solute A in cyclohexane, respectively. Values δcavhSR and δcavhC6H12 are referred to the specific relative cavity formation enthalpies for the reference solvent and cyclohexane, respectively. Value VAx is a characteristic volume of the solute. Details on the procedure and the numerical values of all required contributions can be found elsewhere [18]. Hydrogen bond enthalpies of ten selected solutes (divided in series of proton donors and proton acceptors) in [MIM][NO3] were calculated according to Eq. (7) and they are collected in Table 3. Hydrogen bond enthalpies of the same set of solutes in [EMIM][NO3] were derived from data reported in work [25]. They are also given in Table 3 for comparison. A correlation between hydrogen bond enthalpies of organic solutes in protic [MIM][NO3] and in aprotic [EMIM][NO3] is given in Fig. 4. As can be seen from this figure, except for tetrahydrofuran, the hydrogen bond enthalpies of proton donors and proton acceptors correlate linearly. The outlying of points does not exceed 2 kJ mol−1. Following, the hydrogen bond enthalpies of proton donor molecules in protic [MIM][NO3] and in aprotic [EMIM][NO3] are similar. 4. Conclusions In current study, the activity coefficients at infinite dilution of organic solutes in [MIM][NO3] at five temperatures were measured. The solution enthalpies were calculated from temperature dependence of activity coefficients at infinity dilution. It was shown that [MIM][NO3] does not have solvophobic contribution. The hydrogen bond enthalpies of solutes in protic [MIM][NO3] and in aprotic [EMIM][NO3] ionic liquids were calculated from solution enthalpies.

Fig. 4. Comparison between hydrogen bond enthalpies of proton donors (squares) and proton acceptors (circles) in [MIM][NO3] and [EMIM][NO3] at T = 298.15 K. (1 – propanol-2; 2 – ethanol; 3 – methanol; 4 – propanol-1; 5 – trichloromethane; 6 – dichloromethane; 7 – acetonitrile; 8 – acetone; 9 – ethyl acetate; 10 – tetrahydrofuran).

CRediT authorship contribution statement Artashes A. Khachatrian:Investigation, Validation, Writing - original draft.Ilnaz T. Rakipov:Formal analysis.Boris N. Solomonov:Conceptualization.Sergey P. Verevkin:Writing - review & editing. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments The financial support of this work by the Russian Science Foundation (Project No 19-73-10131) is gratefully acknowledged. Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi. org/10.1016/j.molliq.2019.112243. References [1] S.P. Verevkin, D.H. Zaitsau, B. Tong, U. Welz-Biermann, New for old. Password to the thermodynamics of the protic ionic liquids, Phys. Chem. Chem. Phys. 13 (2011) 12708–12711. [2] J.T. Reilly, M.A. Coats, M.M. Reardon, A. Mirjafari, Study of biocatalytic activity of histidine ammonia lyase in protic ionic liquids, J. Mol. Liq. 248 (2017) 830–832. [3] K. Kopczynski, A. Gabryelczyk, M. Baraniak, B. Legosz, J. Pernak, P. Kedzior, G. Lota, The effect of the substituent length in protic ionic liquid additive on the corrosion process in the lead-acid battery, Int. J. Electrochem. Sci. 13 (2018) 4390–4400. [4] Y. Oba, M. Okuhata, T. Osakai, T. Mochida, Solvate and protic ionic liquids from azacrown ethers: synthesis, thermal properties, and LCST behavior, Phys. Chem. Chem. Phys. 20 (2018) 3118–3127. [5] E.C. Achinivu, Protic ionic liquids for lignin extraction—a lignin characterization study, Int. J. Mol. Sci. 19 (2018) 428. [6] M.F. Volia, E.E. Tereshatov, V. Mazan, C.M. Folden III, M. Boltoeva, Effect of aqueous hydrochloric acid and zwitterionic betaine on the mutual solubility between a protic betainium-based ionic liquid and water, J. Mol. Liq. 276 (2019) 296–306. [7] N. Patsos, K. Lewis, F. Picchioni, M.N. Kobrak, Extraction of acids and bases from aqueous phase to a pseudoprotic ionic liquid, Molecules (2019) https://doi.org/10. 3390/molecules24050894. [8] T. Takekiyo, K. Miyazaki, Y. Watanabe, Y. Uesugi, S. Tanaka, Y. Ishikawa, Y. Yoshimura, Solubilization and recovery of heat-aggregated cytochrome c using alkylammonium nitrate, J. Mol. Liq. 291 (2019), 111239. [9] I. Jha, P. Attri, P. Venkatesu, Unexpected effects of the alteration of structure and stability of myoglobin and hemoglobin in ammonium-based ionic liquids, Phys. Chem. Chem. Phys. 16 (2014) 5514–5526. [10] J. Stoimenovski, P.M. Dean, E.I. Izgorodina, D.R. MacFarlane, Protic pharmaceutical ionic liquids and solids: aspects of protonics, Faraday Discuss. 154 (2012) 335–352. [11] Z. Wojnarowska, K. Grzybowska, L. Hawelek, A. Swiety-Pospiech, E. Masiewicz, M. Paluch, W. Sawicki, A. Chmielewska, P. Bujak, J. Markowski, Molecular dynamics studies on the water mixtures of pharmaceutically important ionic liquid lidocaine HCl, Mol. Pharm. 9 (2012) 1250–1261. [12] Q. Wang, T. Zhang, S. Zhang, Y. Fan, B. Chen, Extractive desulfurization of fuels using trialkylamine-based protic ionic liquids, Sep. Purif. Technol. 231 (2020), 115923. [13] Z. Ren, L. Wei, Z. Zhou, F. Zhang, W. Liu, Extractive desulfurization of model oil with protic ionic liquids, Energy Fuel 32 (2018) 9172–9181. [14] U. Domańska, M. Królikowski, W.E. Acree Jr., G.A. Baker, Physicochemical properties and activity coefficients at infinite dilution for organic solutes and water in a novel bicyclic guanidinium superbase-derived protic ionic liquid, J. Chem. Thermodyn. 58 (2013) 62–69. [15] A.A. Khachatrian, Z.I. Shamsutdinova, I.T. Rakipov, M.A. Varfolomeev, B.N. Solomonov, S.P. Verevkin, Hydrogen bonding of molecular solutes in protic and aprotic ionic liquids, J. Mol. Liq. 271 (2018) 815–819. [16] B.N. Solomonov, V.B. Novikov, M.A. Varfolomeev, N.M. Mileshko, A new method for the extraction of specific interaction enthalpy from the enthalpy of solvation, J. Phys. Org. Chem. 18 (2005) 49–61. [17] B.N. Solomonov, V.B. Novikov, A simple method for determining the enthalpy of specific solute-solvent interaction, Russ. J. Gen. Chem. 74 (2004) 694–700. [18] M.A. Varfolomeev, A.A. Khachatrian, B.S. Akhmadeev, B.N. Solomonov, Thermodynamics of hydrogen bonding and van der Waals interactions of organic solutes in solutions of imidazolium based ionic liquids: “structure-property” relationships, Thermochim. Acta 633 (2016) 12–23. [19] A.A. Khachatrian, Z.I. Shamsutdinova, I.T. Rakipov, M.A. Varfolomeev, The ability of ionic liquids to form hydrogen bonds with organic solutes evaluated by different experimental techniques. Part I. Alkyl substituted imidazolium and sulfonium based ionic liquids, J. Mol. Liq. 265 (2018) 238–242.

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A.A. Khachatrian et al. / Journal of Molecular Liquids xxx (xxxx) xxx [20] A.A. Khachatrian, T.S. Batukaev, I.T. Rakipov, M.A. Varfolomeev, B.N. Solomonov, Solvation thermochemistry of aromatic hydrocarbons and their halogen derivatives in imidazolium-based ionic liquids, J. Mol. Liq. 289 (2019), 111105. [21] A. Ostonen, J. Bervas, P. Uusi-Kyyny, V. Alopaeus, D.H. Zaitsau, V.N. Emel’yanenko, C. Schick, A.W.T. King, J. Helminen, I. Kilpeläinen, A.A. Khachatrian, M.A. Varfolomeev, S.P. Verevkin, Experimental and theoretical thermodynamic study of distillable ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate, Ind. Eng. Chem. Res. 55 (2016) 10445–10454. [22] A. Heintz, D.V. Kulikov, S.P. Verevkin, Thermodynamic properties of mixtures containing ionic liquids. Activity coefficients at infinite dilution of polar solutes in 4-

5

methyl-N-butyl-pyridinium tetrafluoroborate using gas-liquid chromatography, J. Chem. Thermodyn. 34 (2002) 1341–1347. [23] I.A. Sedov, М.А. Stolov, B.N. Solomonov, Solvophobic effects and relationships between the Gibbs energy and enthalpy for the solvation process, J. Phys. Org. Chem. 24 (2011) 1088–1094. [24] I.A. Sedov, М.А. Stolov, B.N. Solomonov, Solvophobic effects: qualitative determination and quantitative description, J. Struct. Chem. 54 (2013) 262–270. [25] M. Sobota, V. Dohnal, P. Vrbka, Activity coefficients at infinite dilution of organic solutes in the ionic liquid 1-ethyl-3-methyl-imidazolium nitrate, J. Phys. Chem. B 113 (2009) 4323–4332.

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