Excess Molar Volumes, Excess Molar Isentropic ... - ACS Publications

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Excess Molar Volumes, Excess Molar Isentropic Compressibilities, Viscosity Deviations, and Activation Parameters for 1‑Ethyl-3-methylimidazolium Trifluoro-methanesulfonate + Dimethyl Sulfoxide and/ or Acetonitrile at T = 298.15 to 323.15 K and P = 0.1 MPa Naushad Anwar and Riyazuddeen* Department of Chemistry, Aligarh Muslim University, Aligarh 202002, U.P., India S Supporting Information *

ABSTRACT: The densities, ρ, speeds of sound, u, and dynamic viscosities, η, of pure 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, ([EMIM][CF3SO3]), dimethyl sulfoxide, (DMSO), acetonitrile, (ACN), and their binary and ternary mixtures have been measured experimentally over the entire composition range and at temperatures of 298.15, 303.15, 308.15, 313.15, 318.15, and 323.15 K and at a pressure of 0.1 MPa. The excess molar volume, VE, excess molar isentropic compressibility, Ks,mE, viscosity deviations, Δη, Gibbs energy of activation, ΔG*, and excess Gibbs energy of activation, ΔG*E have been calculated using the experimental ρ, u, and η values of pure [EMIM][CF3SO3], DMSO, ACN, and their binary/ternary mixtures at the studied temperatures and pressure. The excess/deviations properties for the studied binary/ternary systems have been fitted to Redlich−Kister equation. The variations of these parameters with composition and temperature are discussed in terms of ion−ion, ion−dipole, and dipole−dipole interactions prevailing in these mixtures. The excess molar volumes of each binary system have also been correlated to the Prigogine−Flory−Patterson (PFP) theory. Some semiempirical models for correlation/prediction of experimental dynamic viscosity data for studied binary and VE, Ks,mE, Δη, and ΔG*E for ternary mixtures have been applied. ionic liquid.8 Dimethyl sulfoxide (DMSO) was chosen because of its wide range of applicability as a solvent in chemical and biological processes, in pharmaceutical applications, in veterinary medicine, and in microbiology.15,16 Acetonitrile (ACN) is an excellent solvent for many organic compounds as well as some inorganic compounds. ACN was chosen because of its range of applicability as a solvent in pharmaceuticals, agrochemicals.17 A number of researchers18−30 have reported the experimental ρ, u, and η values of pure [EMIM][CF3SO3] and its mixtures with various organic solvents at different temperatures and pressure but no study on the thermophysical properties of binary [EMIM][CF3SO3] + DMSO/ACN and ternary [EMIM][CF3SO3] + DMSO + ACN mixtures has been reported yet at our studied temperature range and pressure. The main focus of this study is to obtain original and highly accurate data on ρ, u, and η of ionic liquid, organic solvents, and of their binary and ternary mixtures as functions of mole fraction and temperature as these studies are helpful in understanding about the molecular interactions between the various

1. INTRODUCTION Ionic liquids (ILs) are a new class of solvent with potential applications in various fields, such as catalysis, lubricants, electrically conductive liquids in electrochemistry, synthesis, protein stability, and polymers conformation.1−3 In addition, ILs gained honor as novel fluids due to their unique chemical and physical properties, such as stability on exposure to air and moisture, a high solubility power, extremely low vapor pressure, nonflammability, high ionic conductivity, thermal and electrochemical stability, and the ability of dissolution and extraction of inorganic and organic components.4−8 Due to these features together with tunable properties of ionic liquids they are considered to be perfect “designed” and “green solvents” replacing volatile organic solvents, catalysts for organic and organometallic synthesis, extraction media for separation processes and entrainers for extractive distillation.9−12 Thermophysical properties, such as volumetric, acoustic and viscometric, are of utmost importance for the design of new ILs to meet specific requirements. Since the variations of ion pair give rise to a great number of ILs with a wide variety of properties, an understanding of solute−solvent interactions is necessary.13,14 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][CF3SO3]) is hydrophilic and a thermally stable © XXXX American Chemical Society

Received: May 13, 2017 Accepted: December 11, 2017

A

DOI: 10.1021/acs.jced.7b00429 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Compounds with Their CAS Number, Molar Mass, Source, Purification Method, Mass Fraction Purity, and Water Content mass fraction puritya

water content

Sigma-Aldrich without further purification

>0.98

0.014% (Karl Fischer)

78.13

Merck

without further purification

>0.99

0.99

0.98), dimethyl sulfoxide (DMSO, purity >0.99), and acetonitrile (ACN, purity >0.99) used in this work are listed in Table 1. 2.2. Methods. 2.2.1. Sample Preparation. Water content of pure [EMIM][CF3SO3] was measured by Karl Fischer E



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Table 5. Experimental Values of Viscosities, η/mPa·s, at Temperature T = 298.15 to 323.15 K and Mole Fraction, x1, for the Binary Mixtures [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3](1) + ACN(2), and DMSO(1) + ACN(2) at Pressure P = 0.1 MPaa

DMSO, ACN, and of their binary and ternary mixtures were experimentally measured at temperature range of 298.15 to 323.15 K with an interval of 5 K and pressure of 0.1 MPa using an Anton Paar DSA 5000 M digital vibratingtube densimeter (ultrasound transducer frequency of 3 MHz) which has an accuracy of 0.001 kg·m−3 for density and 0.01 m·s−1 for speed of sound. The standard uncertainty in the temperature measurements was found to be 0.01 K. Before each series of measurements, the instrument was calibrated at temperatures of 298.15, 303.15, 308.15, 313.15, 318.15, and 323.15 K with the triply distilled water and dry air. Taking into account the purity of the chemicals and calibration, the combined expanded uncertainties (level of confidence = 0.95, k = 2) in density and speed of sound measurements were found to be 5 × 10−4 g·cm−3 and 0.5 m·s−1, respectively. 2.2.3. Viscosity Measurements. The dynamic viscosities of the pure [EMIM][CF3SO3], DMSO, ACN and of their binary and ternary mixtures were experimentally measured at temperature range of 298.15 to 323.15 K with an interval of 5 K and pressure of 0.1 MPa with an Anton-Paar Lovis 2000 M falling ball automated viscometer. The viscosities were measured using different combinations of ball/capillary of different diameters, which allow determination in the viscosity interval from 1.0 to 1700 mPa·s. The microviscometer was calibrated at temperatures of 298.15, 303.15, 308.15, 313.15, 318.15 and 323.15 K by standards and capillaries with diameters of 1.59, 1.8, and 2.5 mm. The combined expanded uncertainties (level of confidence 0.95, k = 2) in the viscosity measurements were found to be as Uc(η) < 1 mPa·s = 0.20 mPa·s, Uc(η) (1−10 mPa·s) = 0.60 mPa·s, Uc(η) (11−50 mPa·s) = 0.80 mPa·s, respectively. The standard uncertainty in the temperature measurements was found to be 0.01 K.

T (K) x1

298.15

303.15

[EMIM][CF3SO3] + DMSO 0.0000b 2.03 1.84 0.1068 3.65 3.26 0.2015 5.35 4.72 0.3077 7.89 6.90 0.4023 11.82 10.20 0.4933 16.26 13.93 0.6022 21.05 17.95 0.6993 26.12 22.18 0.7929 31.96 27.03 0.9008 38.88 32.74 1.0000 45.67 38.31 [EMIM][CF3SO3] + ACN 0.0000 0.34 0.32 0.1026 0.85 0.80 0.2053 1.88 1.82 0.3044 2.99 2.74 0.3948 4.51 4.13 0.4980 7.44 6.64 0.5950 10.90 9.46 0.6936 15.92 13.80 0.8010 24.05 20.32 0.9005 33.72 27.94 1.0000 45.67 38.31 DMSO + ACN 0.0000 0.34 0.32 0.0995 0.42 0.40 0.2061 0.52 0.49 0.2936 0.57 0.53 0.4055 0.72 0.67 0.5051 0.86 0.81 0.6001 1.06 0.97 0.7006 1.27 1.17 0.8072 1.54 1.42 0.8947 1.76 1.60 1.0000b 2.03 1.84

308.15

313.15

318.15

323.15

1.67 2.94 4.20 6.08 8.91 12.06 15.48 19.05 23.08 27.81 32.38

1.53 2.66 3.76 5.42 7.85 10.52 13.47 16.52 19.91 23.88 27.68

1.41 2.42 3.39 4.85 6.96 9.26 11.82 14.45 17.32 20.68 23.86

1.30 2.22 3.08 4.37 6.22 8.23 10.45 12.72 15.19 18.05 20.75

0.31 0.75 1.65 2.52 3.76 5.95 8.41 12.08 17.54 23.87 32.38

0.30 0.72 1.54 2.34 3.46 5.37 7.51 10.66 15.27 20.58 27.68

0.29 0.68 1.42 2.16 3.17 4.87 6.75 9.46 13.39 17.89 23.86

0.28 0.65 1.38 2.01 2.91 4.43 5.96 8.27 11.66 15.49 20.75

0.31 0.39 0.46 0.52 0.64 0.75 0.91 1.08 1.29 1.47 1.67

0.30 0.37 0.44 0.49 0.60 0.71 0.85 1.00 1.19 1.35 1.53

0.29 0.35 0.42 0.47 0.57 0.67 0.79 0.94 1.10 1.24 1.41

0.28 0.34 0.40 0.45 0.54 0.63 0.75 0.87 1.03 1.15 1.30

3. RESULTS AND DISCUSSION 3.1. Binary Systems. 3.1.1. Densities, Speeds of Sound, and Viscosities. The experimentally measured ρ, u, and η values of pure [EMIM][CF3SO3], DMSO, ACN, and of their binary mixtures [EMIM][CF3SO3] + DMSO, [EMIM][CF3SO3] + ACN, and DMSO + ACN are reported in Tables 2, 3, 4, and 5, respectively. The measured density, speed of sound, and viscosity values of pure [EMIM][CF3SO3], DMSO, and ACN have been compared with the literature values20−30,47−70 and are listed in Table 2. We have found an infinitesimal deviation in our data and reported literature data. Figure 1a−c shows the percent deviations at different temperatures between experimental and literatures data for density, speed of sound, and viscosity of pure IL, DMSO, and ACN. The ρ, u, and η values decrease with an increase in temperature for pure components as well as for binary mixtures. A linear increase has been observed for ρ, u, and η values with temperature whereas exponential increase is observed with concentrations. These trends of variation show that molecular interactions exist in the studied binary mixtures at all temperatures. The cause of molecular interactions between like/unlike molecules of liquid mixtures depends on many factors, such as nature and structural conformations of the components. The density, speed of sound, and viscosity values increase with an increase in x1 of [EMIM][CF3SO3] in [EMIM][CF3SO3](1) + DMSO/ACN(2) as well as x1 of DMSO in DMSO(1) + ACN(2) studied binary systems. The increasing trends of variation of ρ, u, and η seem due to the corresponding increase in ion−dipole interactions between [EMIM]+/[CF3SO3]− and DMSO/ACN while decreasing trend with an increase in temperature may

a

Standard uncertainties u: u(T) = 0.01 K, u(P) = 10 kPa, combined expanded uncertainties Uc: Uc(x) = 2 × 10−4, Uc(η) < 1 mPa·s = 0.20 mPa·s, Uc(η) (1−10 mPa·s) = 0.60 mPa·s, Uc(η) (11−50 mPa·s) = 0.80 mPa·s (level of confidence = 0.95, k = 2). bOur earlier published work (reference 42).

coulometric titrator (C20, Metller Toledo), and the mass fraction was found to be 0.014%. The binary mixtures [EMIM][CF3SO3] + DMSO, [EMIM][CF3SO3] + ACN, DMSO + ACN, and ternary mixtures [EMIM][CF3SO3] + DMSO + ACN of different mole fractions were prepared by weighing on a New Classic MS Mettler Toledo electronic digital balance with a precision of 1 × 10−4 g. All the binary and ternary mixtures were freshly prepared and kept at the desired temperature for some hours to ensure complete miscibility. The combined expanded uncertainty in mole fractions of all the samples was estimated less than 2 × 10−4. 2.2.2. Density and Speed of Sound Measurements. The density, ρ, and speeds of sound, u, of the pure [EMIM][CF3SO3], F



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Figure 1. Relative percent deviations {100·[(Ylit−Yexp)/Ylit] (Y = ρ, u and η)} at T = 298.15 to 323.15 K of experimental values of pure components with literature (a) ρ for [EMIM][CF3SO3]: black ●, ref 20; black ▲, ref 21; black ▼, ref 22; black ⧫, ref 23,24; black ◀, ref 25; black ▶, ref 26; light blue ▲, ref 27; light blue ▼, ref 28; light blue ▶, ref 29. For DMSO: red ●, ref 47; red ▲, ref 48; red ▼, ref 49; red ⧫, ref 50; red ◀, ref 51; red ▶, ref 52; yellow ■, ref 53; yellow ●, ref 54; yellow ▲, ref 55; light green ■, ref 56; light green ●, ref 57; light green ▲, ref 59; light green ▼, ref 60; light green ⧫, ref 61; light green ◀, ref 62; light green ▶, ref 63 For ACN: blue ●, ref 54; blue ▲, ref 55; blue ▼, ref 56; blue ⧫, ref 57; blue ◀, ref 59; blue ▶, ref 60; pink ■, ref 66; pink ●, ref 67; pink ▲, ref 68; pink ▼, ref 69; pink ⧫, ref 70. (b) u for [EMIM][CF3SO3]: red ●, ref 20; light green▲, ref 22; blue ▼, ref 23,24. For DMSO: pink ●, ref 56; yellow ▲, ref 57; hunter green ▼, ref 60; blue ⧫, ref 64; purple ◀, ref 65 For ACN: hunter green ●, ref 56; turquoise ▲, ref 57; dark blue ▼, ref 60; light purple ⧫, ref 64; pink ◀, ref 69. (c) η for [EMIM][CF3SO3]: red ●, ref 25; light green ▲, ref 26; blue ▼, ref 27; light blue ⧫, ref 28; pink ◀, ref 29; yellow ▶, ref 30. For DMSO: blue ●, ref 47; purple ▲, ref 51; dark red ▼, ref 53; hunter green ⧫, ref 54; turquoise ◀, ref 56; dark blue ▶, ref 61; hunter green ⬢, ref 62; dark blue ★, ref 63 For ACN: red ⬡, ref 54; light green △, ref 56; blue ▽, ref 58; light blue ◊, ref 66; pink ◁, ref 67; pink ▷, ref 70; and binary mixture of DMSO + ACN as function of x1 with literature: (d) ρ values with Grande et al.:54 black ■, 298.15 K; green ■, 303.15 K; blue ■, 308.15 K; light blue ■, 313.15 K; pink ■, 318.15 K. Zarei et al.:55 blue ▲, 303.15 K; hunter green ▲, 313.15 K; dark red ▲, 323.15 K. Oswal et al.:56 light blue ▼, 303.15 K. Namakura et al.:60 red ●, 298.15 K. (e) u values with Oswal et al.:56 black ■, 303.15 K. Namakura et al.:60 red ●, 298.15 K. (f) η values with Grande et al.:54 black ■, 298.15 K; light green ▲, 303.15 K; blue ▼, 308.15 K; light blue ⧫, 313.15 K; pink ◀, 318.15 K. Oswal et al.:56 red ●, 303.15 K. G



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Figure 2. Experimental values of excess molar volume as a function of mole fraction x1 for the binary systems (a) [EMIM][CF3SO3] + DMSO, (b) [EMIM][CF3SO3] + ACN, and (c) DMSO + ACN at black ■, 298.15 K; red ●, 303.15 K; light green ▲, 308.15 K; dark blue ▼, 313.15 K; light blue ⧫, 318.15 K; and pink ◀, 323.15 K. Symbols represent the experimental values while the solid lines present the results calculated from the Redlich−Kister equation (eq 3).

Figure 3. Experimental values of excess molar isentropic compressibility as a function of mole fraction x1 for the binary systems (a) [EMIM][CF3SO3] + DMSO, (b) [EMIM][CF3SO3] + ACN, and (c) DMSO + ACN at black ■, 298.15 K; red ●, 303.15 K; light green ▲, 308.15 K; dark blue ▼, 313.15 K; light blue ⧫, 318.15 K; and pink ◀, 323.15 K. Symbols represent the experimental values while the solid lines present the results calculated from the Redlich−Kister equation (eq 3).

be caused by the corresponding decrease in ion−dipole interactions.

In the case of the DMSO + ACN binary mixtures, density, speed of sound, and viscosity results have been compared H



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Table 6. Values of Enthalpy of Activation, ΔH*/kJ·mol−1, and Entropy of Activation, ΔS*/kJ·mol−1, at Mole Fraction, x1, for the Binary Mixtures [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3](1) + ACN(2), and DMSO(1) + ACN(2) at Pressure P = 0.1 MPa x1

ΔH*/kJ·mol−1

[EMIM][CF3SO3] + DMSO 0.0000 14.1291 0.1068 15.2840 0.2015 17.1322 0.3077 18.3657 0.4023 20.0175 0.4933 21.3343 0.6022 21.9342 0.6993 22.5421 0.7929 23.3530 0.9008 24.1072 1.0000 24.8070 [EMIM][CF3SO3] + ACN 0.0000 4.8032 0.1026 7.7151 0.2053 10.0701 0.3044 12.0387 0.3948 13.4271 0.4980 16.0258 0.5950 18.4314 0.6936 20.2212 0.8010 22.4487 0.9005 24.1348 1.0000 24.8070 DMSO + ACN 0.0000 4.8032 0.0995 5.8681 0.2061 6.8002 0.2936 7.1260 0.4055 8.0486 0.5051 9.4144 0.6001 10.3279 0.7006 11.1569 0.8072 12.3621 0.8947 12.7519 1.0000 14.1291

ΔS*/kJ·mol−1 −0.1855 −0.1837 −0.1857 −0.1856 −0.1869 −0.1880 −0.1871 −0.1867 −0.1871 −0.1874 −0.1879 −0.1721 −0.1724 −0.1720 −0.1735 −0.1737 −0.1772 −0.1813 −0.1833 −0.1866 −0.1888 −0.1879 −0.1721 −0.1735 −0.1737 −0.1757 −0.1758 −0.1784 −0.1796 −0.1806 −0.1828 −0.1828 −0.1855

with those of available literature data and discussed in terms of absolute average percent deviation. The absolute average pern cent deviation ⎡⎣AAD% = 100/n·∑i = 1 (Ylit − Yexp)/Ylit ⎤⎦ between our experimental density and literature data from Grande et al.54 at T = 298.15, 303.15. 308.15, 313.15, and 318.15 K were 0.89, 0.88, 0.93, 0.90, 0.94%, from Zarei et al.55 at T = 303.15, 313.15, and 323.15 K were 0.20, 0.21, 0.21%, from Oswal et al.56 at T = 303.15 K was 0.12%, from Namakura et al.60 at T = 298.15 K was 0.16%, respectively. The absolute average percent deviation between our experimental speed of sound and literature data from Oswal et al.56 at T = 303.15 K was 0.35%, and from Namakura et al.60 at T = 298.15 K was 0.62%. The absolute average percent deviation between our experimental viscosity and literature data from Grande et al.54 at T = 298.15, 303.15. 308.15, 313.15, and 318.15 K were 5.54, 6.82, 9.31, 11.26, 14.01%, from Oswal et al.56 at T = 303.15 K was 4.06%. Figure 1d−f describes the percent deviation versus x1 for density, speed of sound and viscosity values of binary mixture of DMSO + ACN. The larger variations in percent and absolute

Figure 4. Experimental values of viscosity deviation as a function of mole fraction x1 for the binary systems (a) EMIM][CF3SO3] + DMSO, (b) [EMIM][CF3SO3] + ACN, and (c) DMSO + ACN at black ■, 298.15 K; red ●, 303.15 K; light green ▲, 308.15 K; dark blue ▼, 313.15 K; light blue ⧫, 318.15 K; and pink ◀, 323.15 K. Symbols represent the experimental values while the solid lines present the results calculated from the Redlich−Kister equation (eq 3). I



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average percent deviations for the comparison data of pure components and binary mixture with existing literature in case of viscosities may be due to either variation in the purity of the samples or to the use of a different experimental set up. 3.1.2. Excess Molar Volumes. The excess molar volumes, VE, of binary mixtures [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3](1) + ACN(2), and DMSO(1) + ACN(2) have been calculated from the experimental density values of pure and binary mixtures of IL and solvents using the standard equation reported earlier.32,41 The measured values of VE for all the three studied binary systems have been reported in Table S1 and the plots have been shown in Figure 2a−c. The VE values have been found to be negative for the studied binary mixtures [EMIM][CF3SO3](1) + DMSO(2)/ACN(2) and DMSO(1) + ACN(2) over the entire range of compositions and at all temperatures and decrease with an increase in temperature. The VE values mainly depend on the ion−dipole, ion−ion, and dipole−dipole interactions between components of the mixtures and on the packing of components due to the differences in size and shape of molecules. The negative VE values of [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3](1) + ACN(2), and DMSO(1) + ACN(2) binary mixtures may be attributed to strong ion−dipole interactions between ILs and solvent and dipole−dipole interactions in solvent−solvent system. The VE values are more negative in case of IL + ACN system at a temperature. This phenomenon may be due to the occupation of voids created by larger IL molecules by ACN molecule and, thereby, reducing the volume of the mixture to a larger extent, resulting in more negative VE values with increase in temperature. 3.1.3. Excess Molar Isentropic Compressibilities. The excess molar isentropic compressibilities, Ks,mE, of the studied [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3](1) + ACN(2), and DMSO(1) + ACN(2) systems have been calculated using the standard equations reported earlier.32 The measured values of Ks,mE for all the three studied binary systems have been reported in Table S2 and the graphs have been plotted in Figure 3a−c, respectively. The Ks,mE values have been found to be negative over the whole range of compositions, and the whole region of experimental temperatures in all the three studied binary mixtures [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3](1) + ACN(2), and DMSO(1) + ACN(2) and decrease with an increase in temperature in all studied binary systems. The negative value of Ks,mE for studied binary systems indicate that these mixtures are less compressible than the ideal mixtures, suggesting the corresponding decrease of free volume due to specific interactions and interstitial accommodation of components. The Ks,mE of IL + DMSO system is more negative than that of IL + ACN system at a temperature. This trend may be attributed to the interactions of DMSO molecules with IL molecules, thereby, reducing the volume of the mixture to a larger extent, resulting in more negative Ks,mE values with increase in temperature. 3.1.4. Viscosity Deviations. The viscosity deviations, Δη of studied binary mixtures [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3](1) + ACN(2), and DMSO(1) + ACN(2) have been calculated from the experimental viscosity values of pure components and binary mixtures using standard equation reported earlier.41,42 The calculated values of Δη for all the three studied binary systems have been reported in Tables S3 and the graphs have been plotted in Figure 4a−c, respectively. The values of Δη have been found to be negative at whole concentration range and all

Figure 5. Experimental values of excess Gibbs energy of activation as a function of mole fraction x1 for the binary systems (a) [EMIM][CF3SO3] + DMSO, (b) [EMIM][CF3SO3] + ACN, and (c) DMSO + ACN at black ■, 298.15 K; red ●, 303.15 K; light green ▲, 308.15 K; dark blue ▼, 313.15 K; light blue ⧫, 318.15 K; and pink ◀, 323.15 K. Symbols and lines both represent the experimental values.

temperatures and increase with an increase in temperature for the studied binary systems. The Δη values increase with temperature J



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Table 7. Values of Coefficients of the Redlich−Kister Equation for Excess Molar Volumes, VE/cm3·mol−1, Excess Molar Isentropic Compressibilities, Ks,mE/m3·mol−1·Pa−1, Viscosity Deviations, Δη/mPa·s, and their Standard Deviations (σ) at Temperature T = 298.15 to 323.15 K for the Binary Mixtures [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3] (1) + ACN(2), and DMSO(1) + ACN(2) at Pressure P = 0.1 MPa T/K [EMIM][CF3SO3] + DMSO VE 298.15 303.15 308.15 313.15 318.15 323.15 [EMIM][CF3SO3] + ACN VE 298.15 303.15 308.15 313.15 318.15 323.15 DMSO + ACN VE 298.15 303.15 308.15 313.15 318.15 323.15 [EMIM][CF3SO3] + DMSO KEs,m 298.15 303.15 308.15 313.15 318.15 323.15 [EMIM][CF3SO3] + ACN KEs,m 298.15 303.15 308.15 313.15 318.15 323.15 DMSO + ACN KEs,m 298.15 303.15 308.15 313.15 318.15 323.15 [EMIM][CF3SO3] + DMSO Δη 298.15 303.15 308.15 313.15 318.15 323.15 [EMIM][CF3SO3] + ACN Δη 298.15 303.15 308.15 313.15 318.15 323.15 DMSO + ACN Δη 298.15

A0

A1

A2

B1

σ

−2.4377 −2.5925 −2.7957 −2.9865 −3.2047 −3.3996

3.2913 3.3985 3.5931 3.6845 3.8263 3.9963

−1.6014 −1.6531 −1.7220 −1.7522 −1.7265 −1.7997

−0.8349 −0.8254 −0.8216 −0.8030 −0.7904 −0.7848

0.0051 0.0060 0.0101 0.0171 0.0230 0.0300

−3.4840 −3.6622 −3.8261 −4.0282 −4.2097 −4.4462

0.5578 0.6573 0.5834 0.5453 0.5248 0.3186

2.1470 1.9402 1.6649 1.5654 1.4110 1.5405

0.9353 0.9033 0.8877 0.8790 0.8731 0.8920

0.0222 0.0166 0.0196 0.0175 0.0150 0.0144

−1.3230 −1.4104 −1.5051 −1.6005 −1.7114 −1.8056

2.0506 2.1583 2.2702 2.3863 2.5280 2.6721

−0.5138 −0.5143 −0.5157 −0.5265 −0.5018 −0.5303

−1.2433 −1.2425 −1.2382 −1.2318 −1.2459 −1.2479

0.0231 0.0224 0.0223 0.0215 0.0206 0.0211

−10.7025 −11.0792 −11.4711 −11.8361 −12.1186 −12.4543

−0.0456 −0.0519 −0.0459 −0.0653 −0.0245 −0.0131

−0.0211 −0.0112 −0.0182 −0.0137 −0.0243 −0.0366

0.4343 0.4342 0.4327 0.4329 0.4284 0.4260

0.0005 0.0004 0.0005 0.0005 0.0004 0.0004

−120.4317 −126.3804 −132.5607 −139.8941 −145.6909 −152.6682

−0.0592 −0.0631 −0.0778 −0.0913 −0.1057 −0.1210

0.0112 0.0178 0.0303 0.0387 0.0483 0.0611

0.6152 0.6148 0.6144 0.6139 0.6134 0.6127

0.0004 0.0005 0.0004 0.0006 0.0007 0.0007

−53.1536 −56.0652 −59.0846 −62.3156 −65.9004 −69.5369

0.2506 0.5956 0.6962 0.8494 0.7044 0.7433

−0.0811 −0.1720 −0.2006 −0.2389 −0.2056 −0.2200

0.2448 0.2395 0.2386 0.2371 0.2409 0.2413

0.0011 0.0011 0.0012 0.0014 0.0014 0.0013

−31.2181 −25.1092 −20.2279 −16.5445 −13.6089 −11.2927

−79.1227 −63.5232 −50.3610 −40.5449 −32.4670 −26.5737

10.1673 9.4901 9.0947 8.7413 8.4011 7.7734

2.6521 2.6644 2.6530 2.6452 2.6192 2.6146

0.1933 0.2021 0.1714 0.1355 0.1111 0.0988

−62.8062 −51.0136 −41.8009 −34.6413 −28.9664 −24.6377

144.7873 −11.3705 −10.1660 −3.8555 −0.0154 0.3483

69.4775 −0.0659 −0.7717 1.0491 1.8028 1.3489

−2.7097 −0.2118 −0.1721 −0.2880 −0.3797 −0.4203

0.1554 0.1389 0.1067 0.0881 0.0724 0.0941

−1.4465

−3.0243

−0.4964

1.9407

0.0156

K



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Table 7. continued T/K

A1

A2

B1

σ

−1.0835 −1.1146 −0.9633 −0.8378 0.9238

0.1674 −0.0008 0.0021 −0.0230 0.2098

0.6980 0.8992 0.9043 0.8890 −1.4461

0.0157 0.0098 0.0086 0.0097 0.0086

A0 −1.3135 −1.0838 −0.9478 −0.8264 −0.7279

303.15 308.15 313.15 318.15 323.15

Table 8. Values of Interaction Parameters and Standard Deviations σ for Grunberg−Nisaan (G−N), G12, Tamura−Kurata(T−K), T12, Hind−Ubbelohde(H−U), H12, Katti−Chaudhary(K−C), Wvis/RT, Arrhenius (Ar), and Kendall−Monroe(K−M) at Temperature T = 298.15 to 323.15 K for the Binary Mixtures [EMIM][CF3SO3](1) + DMSO(2), [EMIM][CF3SO3](1) + ACN(2), and DMSO(1) + ACN(2) at Pressure P = 0.1 MPa G−N T/K

G12

[EMIM][CF3SO3] + DMSO 298.15 1.88 303.13 1.74 308.15 1.80 313.15 1.76 318.15 1.73 323.15 1.70 [EMIM][CF3SO3] + ACN 298.15 2.88 303.13 2.89 308.15 2.82 313.15 2.79 318.15 2.74 323.15 2.69 DMSO + ACN 298.15 0.13 303.13 0.10 308.15 0.20 313.15 0.18 318.15 0.15 323.15 0.16

T−K

H−U

Ar

K−M

σ

Wvis/RT

σ

σ

σ

8.21 7.38 6.85 6.30 5.82 5.37

0.46 0.41 0.37 0.33 0.31 0.28

5.39 5.25 5.30 5.27 5.24 5.20

1.00 0.75 0.74 0.64 0.56 0.49

0.52 0.48 0.43 0.41 0.39 0.38

1.58 1.49 1.41 1.33 1.24 1.15

0.77 0.66 0.55 0.37 0.23 0.18

−8.63 −6.88 −5.10 −3.77 −2.77 −2.25

0.33 0.22 0.17 0.11 0.10 0.08

6.72 6.71 6.62 6.59 6.53 6.47

0.98 0.88 0.77 0.50 0.35 0.20

0.58 0.49 0.46 0.41 0.37 0.32

1.42 1.39 1.34 1.31 1.29 1.28

0.04 0.05 0.04 0.04 0.04 0.04

0.51 0.45 0.51 0.50 0.47 0.46

0.03 0.03 0.02 0.02 0.01 0.01

0.36 0.35 0.37 0.36 0.36 0.36

0.06 0.05 0.05 0.05 0.04 0.04

0.04 0.04 0.03 0.02 0.02 0.01

0.13 0.11 0.10 0.09 0.07 0.06

σ

T12

σ

0.62 0.43 0.42 0.34 0.28 0.24

−1.73 −0.81 0.03 0.57 0.96 1.21

0.84 0.64 0.48 0.36 0.27 0.21

1.76 1.76 1.44 1.28 1.09 1.05

−3.13 −2.59 −2.07 −1.68 −1.37 −1.17

0.02 0.02 0.02 0.01 0.01 0.03

0.37 0.32 0.32 0.31 0.30 0.28

H12

where V1 and V2 are the molar volume of pure components. η are the dynamic viscosities of binary mixtures and ηi are for pure components i. The values of activation parameters ΔH* and ΔS* for the studied binary mixtures have been listed in Table 6 and the calculated values of ΔG* and ΔG*E for all the three studied binary systems have been reported in Tables S4 and S5 and the plot of ΔG*E have been shown in Figure 5a−c. The ΔG* and ΔG*E values of the studied systems are positive and increase with an increase in temperature. The positive values of ΔG* and ΔG*E indicates that stronger interactions between component of mixtures in the studied binary systems. The values of ΔS* of the studied binary systems are in relation with the reforming of solvent in the bulk of solution from ground state to transition state. 3.1.6. Redlich−Kister Equation. The values of VE, Ks,mE, and Δη for the studied binary systems have been fitted to the Redlich−Kister polynomial equation31,32

may be attributed to the decreasing effects of the ion-dipole interactions between IL and DMSO/ACN and also between DMSO and ACN. 3.1.5. Gibbs and Excess Gibbs Free Energies of Activation. The values of activation parameters can be explained in terms of the relative effect of solute on the ground and transition state of solvents. From the energy point of view, difference between these two states is the activation energy requires for the molecules to overcome the attraction free of each other. Using the standard thermodynamic Gibbs equation and graphical method, the thermodynamic activation parameters of binary mixtures including Gibbs free energy of activation, ΔG*, enthalpy of activation, ΔH*, and entropy of activation, ΔS*, for the viscous flow for each studied binary system have been calculated using Eyring equation71 η=

⎛ ΔH * hN ΔS* ⎞ exp⎜ − ⎟ V R ⎠ ⎝ RT

(1)

where h, N, and V are Plank constant, Avogadro constant, and molar volume, respectively. On the basis of the theory of absolute reaction rate, the excess Gibbs free energy of activation for viscous flow ΔG*E for each studied binary system have also been calculated by the following equation71 ⎡ ⎛N ⎞⎤ ΔG*E = RT ⎢lnηV − ⎜⎜∑ xi lnηiVi ⎟⎟⎥ ⎢⎣ ⎝ i=1 ⎠⎥⎦

K−C

m

Y = x1(1 − x1)

∑i = 0 Ai (2x1 − 1)i n

1 + ∑ j = 1 Bj (2x1 − 1) j

(3)

where Y = VE or Ks,mE or Δη; Ai and Bj are adjustable parameters; m and n are the degree of polynomial; and x1 is the mole fraction of [EMIM][CF3SO3] in [EMIM][CF3SO3] + DMSO/ACN as well as DMSO in DMSO + ACN binary systems, respectively.

(2) L



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regression method. In each case, the optimum number of coefficients is ascertained from an examination of standard deviation (σ) values. The standard deviation, σ has been calculated using the relation defined as follows ⎡ p ⎤1/2 2 σ(Y ) = ⎢∑ (Ycal − Yexp) /(p − (m + n + 1))⎥ ⎢⎣ i = 1 ⎦⎥

(4)

where p is the number of experimental data points; m and n are the number of numerical coefficients in the equation. The values of the parameters Ai, Bj and standard deviations have been listed in the Table 7. 3.1.7. Prediction of Viscosity: Fitting Models. The Arrhenius,34 Kendall−Monroe,35 Grunberg and Nissan,36 Tamura and Kurata,37 Hind−Ubbelohde,38 Katti−Chaudhary,39 and Heric40 semiempirical models for viscosity correlation were used for the evaluation of theoretical η values and some interactional parameters of corresponding models alongwith their standard deviations(σ) between experimental and theoretical η for the studied binary systems. The interaction parameters G12, T12, H12, and Wvis/RT along with their standard deviations71 between ηexp vs ηcal at T = 298.15 to 323.15 K are reported in Table 8. The values of ηexp and ηcal for above-mentioned model equations at entire mole fraction range and at T = 298.15 K have been listed in Table S6 and the comparative plots are shown in Figure 6a−c, respectively. It can be seen from Table 8 that the minimum standard deviation has been found in the case of Arrhenius model for the studied binary mixtures and therefore the Arrhenius model is more suitable for predicting the η values. 3.1.8. Prigogine−Flory−Patterson Theory. The Prigogine− Flory−Patterson (PFP) theory has been used to correlate the excess thermodynamic properties of different kinds of binary mixtures, including both nonpolar and polar components. A number of authors19,20,41,42 have applied the PFP theory to correlate the excess molar volumes of IL + organic solvent binary systems at different temperatures. In this work, the PFP theory has been applied for the correlation of the VE values of all the three studied binary systems [EMIM][CF3SO3] + DMSO/ACN and DMSO + ACN at T = 298.15 to 323.15 K with an interval of 5 K. According to PFP theory, VE is considered as the sum of three contributions (i) an interactional contribution, V(int)E, which is proportional to the only interaction parameter, χ12; (ii) a free volume, V(fv)E; and (iii) internal pressure contribution, V(ip)E. The following form of PFP theory has been used to estimate the VE values in the present study19,20,41,42 E

E

E

V(ip) V(int) V(fv) VE = + + * * * * * * * x1V1 + x 2V 2 x1V1 + x 2V 2 x1V1 + x 2V 2 x1V1 + x 2V 2* =

(Ṽ

1/3

− 1)Ṽ

2/3

Ψ1θ2χ12

−1/3 − 1]P1∗ [(4/3)Ṽ −1/3

− (V1̃ − V2̃ )2 ((14/9)Ṽ − 1)ΨΨ 1 2 −1/3 ̃ − 1]Ṽ [(4/3)V (Ṽ − V2̃ )(P1∗ − P2∗)ΨΨ 1 2 + 1 P2*Ψ1 + P1∗Ψ2 +

Figure 6. Experimental and theoretical η values for (a) [EMIM][CF3SO3] + DMSO, (b) [EMIM][CF3SO3] + ACN, and (c) DMSO + ACN as a function of x1 at T = 298.15 K: , experimental η; symbols black ■, Arrhenius; red ●, Kandall−Monroe; light green ▲, Grunberg− Nissan; blue ▼, Tamura−Kurata; light blue ⧫, Hind−Ubbelohde; pink ◀, Katti−Chaudhary.

(5)

where xi, Vi*, Vi, Ṽ i, ϕi, Ψi, θi, Si, Pi*, and kTi are the mole fractions, characteristic volumes, molar volumes, reduced volumes, hard-core volume fraction, molecular contact energy fraction, molecular surface fraction, molecular surface/volume ratio, characteristic pressure, and the isothermal compressibility of pure components. Ṽ is the reduced volume of the mixtures.

The adjustable parameters, Ai and Bj have been obtained by fitting the eq 3 to the experimental data using a least-squares M



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Table 9. Values of Flory’s Parameters for Pure [EMIM][CF3SO3], DMSO, and ACN at Temperature T = 298.15 to 323.15 K and at Pressure P = 0.1 MPa T/K

104α/K−1

[EMIM][CF3SO3] 298.15 6.04 303.15 6.06 308.15 6.08 313.15 6.10 318.15 6.11 323.15 6.13 DMSO 298.15 9.08 303.15 9.12 308.15 9.16 313.15 9.21 318.15 9.25 323.15 9.29 ACN 298.15 14.16 303.15 14.26 308.15 14.36 313.15 14.47 318.15 14.57 323.15 14.68

104kT/MPa−1

V*/cm3·mol−1

V/cm3·mol−1

Ṽ /cm3·mol−1

P*/J·cm−3

CP/(J·mol−1·K−1)

4.05 4.13 4.21 4.29 4.37 4.46

162.50 162.60 162.70 162.81 162.90 163.00

188.63 189.20 189.78 190.36 190.94 191.52

1.160 1.163 1.166 1.169 1.172 1.175

598.51 602.11 605.15 607.58 611.09 613.58

381.072 382.072 383.072 384.072 385.072 386.072

5.22 5.36 5.50 5.65 5.81 5.96

58.02 58.09 58.17 58.24 58.31 58.39

71.311 71.64 71.97 72.30 72.64 72.97

1.229 1.233 1.237 1.241 1.245 1.249

783.49 784.31 784.83 784.92 785.52 785.45

151.561 152.261 152.961 153.761 154.761 155.661

11.35 11.78 12.24 12.71 13.21 13.73

39.82 39.92 40.02 40.13 40.24 40.36

52.85 53.22 53.60 53.99 54.38 54.788

1.327 1.333 1.339 1.345 1.351 1.357

655.23 652.21 648.85 644.98 641.21 636.92

90.9373 91.2873 91.6673 92.0773 92.5073 92.9673

Table 10. Values of Experimental Excess Molar Volumes, V(expt)E, Calculated Excess Molar Volumes, V(PFP)E, Interactional Parameter, χ12, Interactional, V(int)E, Free Volume, V(fv)E, and Internal Pressure, V(ip)E at Temperature T = 298.15 to 323.15 K and Mole Fraction x1 = 0.4 for [EMIM][CF3SO3](1) + DMSO(2), at Mole Fraction x1 = 0.3 for [EMIM][CF3SO3](1) + ACN(2), and Mole Fraction x1 = 0.4 for DMSO(1) + ACN(2) at Pressure P = 0.1 MPa T/K

V(expt)E/cm3·mol−1

[EMIM][CF3SO3] + DMSO 298.15 −0.6560 303.15 −0.6929 308.15 −0.7419 313.15 −0.7824 318.15 −0.8269 323.15 −0.8740 [EMIM][CF3SO3] + ACN 298.15 −1.1421 303.15 −1.1967 308.15 −1.2546 313.15 −1.3145 318.15 −1.3682 323.15 −1.4267 DMSO + ACN 298.15 −0.3614 303.15 −0.3819 308.15 −0.4045 313.15 −0.4269 318.15 −0.4505 323.15 −0.4739

V(PFP)E/cm3·mol−1

δ%

χ12/J·cm−3

V(int)E/cm3·mol−1

V(fv)E/cm3·mol−1

−0.6607 −0.6973 −0.7474 −0.7889 −0.8312 −0.8807

0.72 0.64 0.74 0.83 0.52 0.77

−42.13 −43.57 −45.76 −47.56 −49.49 −51.72

−0.9205 −0.9509 −0.9955 −1.0320 −1.0671 −1.1103

−0.1707 −0.1770 −0.1834 −0.1898 −0.1966 −0.2034

0.4305 0.4306 0.4315 0.4329 0.4324 0.4330

−1.1486 −1.1983 −1.2562 −1.3162 −1.3728 −1.4304

0.57 0.13 0.13 0.13 0.33 0.26

−40.53 −40.99 −41.71 −42.28 −42.39 −42.42

−0.6589 −0.6539 −0.6563 −0.6598 −0.6526 −0.6471

−0.7610 −0.7886 −0.8170 −0.8459 −0.8758 −0.9063

0.2713 0.2442 0.2171 0.1895 0.1556 0.1230

−0.3637 −0.3837 −0.4062 −0.4287 −0.4516 −0.4743

0.64 0.46 0.43 0.41 0.25 0.09

2.2703 1.9089 1.2013 0.6653 0.2778 0.0282

0.0134 0.0111 0.0070 0.0038 0.0016 0.0002

−0.1694 −0.1760 −0.1828 −0.1898 −0.1971 −0.2046

−0.2077 −0.2188 −0.2304 −0.2427 −0.2561 −0.2699

The methods for calculation of Vi*, Vi, Ṽ i, ϕi, Ψi, θi, Si, Pi*, and kTi terms are given in our previous work.41,42 The methods of calculations of isobaric thermal expansion coefficient, αi values of pure components [EMIM][CF3SO3], DMSO, and ACN is also given in our previous work.41,42 The data of molar heat capacity, Cp for pure [EMIM][CF3SO3], DMSO, and ACN have been taken from the literature.61,72,73 Flory’s interaction parameters used in the current calculation for the pure components are reported in Table 9. The interactional parameter, χ12 which is the only adjustable parameter in

V(ip)E/cm3·mol−1

PFP theory, for all three binary mixtures can be calculated from experimental values of HE or VE. In this study, due to unavailability of the experimental HE, χ12 were obtained from the experimental VE and reported in Table 10 at T = 298.15 to 323.15 K. The experimental and correlated values of VE along with all the three PFP contributions to VE at x1 = 0.4 for [EMIM][CF3SO3](1) + DMSO(2), x1 = 0.3 for [EMIM][CF3SO3](1) + ACN(2), and x1 = 0.4 for DMSO(1) + ACN(2) systems at the same temperatures owing to their minimum VE values have also been reported in Table 10. The experimental and correlated values of N



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PD ≈ 0.64% for DMSO(1) + ACN(2) system, respectively at 298.15 K. The experimental and PFP correlated VE at T = 298.15 K and at entire mole fraction range for [EMIM][CF3SO3] + DMSO/ ACN and DMSO + ACN are plotted in Figure 7a−c. Thus, the experimental and correlated VE values for the studied systems are quite close to each other. The data reported in Table 10 reveals that the cross-interaction parameter, χ12, is negative for both [EMIM][CF3SO3] + DMSO and [EMIM][CF3SO3] + ACN systems which is responsible for the extent of strong intermolecular interactions between IL and organic solvents due to the increased void volume between the ILs molecules with temperature while positive for DMSO + ACN system which indicate a weak intermolecular interactions between the molecules of organic solvents. The χ12 values show a decreasing trend with an increase in temperature for all three systems. The free volume, V(fv)E, also contributes negative and decrease with increasing temperature for all the three systems. It seems that the thermal effect is more pronounced than that of interactional contribution in both IL + organic solvent and also in solvent−solvent systems. The contribution due to internal pressure, V(ip)E, does not seem to play a dominant role in deciding the sign and magnitude of the excess molar volume because it is positive for both [EMIM][CF3SO3] + DMSO and [EMIM][CF3SO3] + ACN systems at all the temperatures and decreases when the temperature increases whereas negative for DMSO + ACN system and also decreases with an increase in temperature.

4. TERNARY SYSTEM 4.1. Experimental and Correlation of Thermophysical Properties. The measured ρ, u, and η of ternary mixture [EMIM][CF3SO3] + DMSO + ACN have been reported in Tables 11, 12, and 13, respectively. Like binary systems, it has been found that the density, speed of sound and viscosity values of [EMIM][CF3SO3] + DMSO + ACN ternary system decreases with an increase in temperatures. The excess molar volumes, excess molar isentropic compressibilities, viscosity deviations and excess Gibbs free energy of activation at 298.15 to 323.15 K with an interval of 5 K and pressure 0.1 MPa for the studied ternary system have been evaluated by the known equations19,20,33,71,74 and reported in Tables S7−S10, respectively. The plot of VE, Ks,mE, Δη, and ΔG*E are shown in Figures 8, 9, 10, and 11, respectively at 298.15 K. The calculated VE and Ks,mE values have been found to be negative at studied concentration and temperature range and decrease with an increase in temperature. The values of Δη have also been found to be negative at studied concentration and temperatures and increase with an increase in temperature whereas the values of ΔG*E are positive for the studied ternary system over studied composition range and all temperatures and also increase with increase in temperature. The negative VE could be ascribed to the packing effect of DMSO/ACN in the interstices of [EMIM][CF3SO3] and the ion-dipole interactions between [EMIM]+/[CF3SO3]− and DMSO/ACN. In view of these, the negative/positive values of all the parameters for the studied ternary system may ascribe the strong/weak interactions between the components of mixtures. On comparison the binary and ternary systems it is observed that the third component modifies the nature and degree of molecular interaction of binary systems. The VE, Ks,mE, and Δη values of the studied ternary system were fitted to the following Redlich−Kister polynomial equation31,33

Figure 7. ■, Experimental excess molar volumes; and calculated with the PFP theory: solid line, excess molar volume; dash line, interactional contribution; dotted line, free volume contribution; dash-dotted line, internal pressure contribution for (a) [EMIM][CF3SO3] + DMSO, (b) [EMIM][CF3SO3] + ACN, and (c) DMSO + ACN as a function of mole fraction and at T = 298.15 K.

VE at x1 ≈ 0.40, are −0.6560, −0.6607 with PD ≈ 0.72% for [EMIM][CF3SO3](1) + DMSO(2) and at x1 ≈ 0.30, are −1.1421, −1.1486 with PD ≈ 0.57% for [EMIM][CF3SO3](1) + ACN(2) systems and at x1 ≈ 0.40 are −0.3614, −0.3637 with

Y123 = Y12 + Y13 + Y23 + x1x 2x3[A + B(x1 − x 2) + C(x1 − x3) + D(x 2 − x3) + E(x1 − x 2)2 + ... ... .... ] O

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Table 11. Experimental Values of Densities, ρ/g·cm−3, at Temperature T = 298.15 to 323.15 K and Mole Fraction, x1, for the Ternary Mixture [EMIM][CF3SO3](1) + DMSO(2) + ACN(3) at Pressure P = 0.1 MPaa T/K x1

x2

298.15

303.15

308.15

313.15

318.15

323.15

0.0313 0.0628 0.0996 0.1328 0.1693 0.2065 0.2333 0.2695 0.3091 0.3343 0.3610 0.4096 0.4353 0.4741 0.5094 0.5368 0.5656 0.5961 0.6284 0.6565 0.6860 0.7058 0.7476

0.8985 0.8526 0.8035 0.7578 0.7074 0.6555 0.6152 0.5629 0.5059 0.4656 0.4229 0.3523 0.3096 0.2498 0.1935 0.1703 0.1458 0.1200 0.0927 0.0845 0.0760 0.0663 0.0458

1.10945 1.12867 1.14923 1.16697 1.18445 1.20043 1.21106 1.22413 1.23680 1.24367 1.25062 1.26316 1.26827 1.27636 1.28300 1.28968 1.29624 1.30281 1.30967 1.31634 1.32336 1.32739 1.33569

1.10447 1.12409 1.14476 1.16246 1.18004 1.19603 1.20666 1.21961 1.23228 1.23938 1.24620 1.25876 1.26396 1.27194 1.27845 1.28524 1.29181 1.29848 1.30516 1.31194 1.31896 1.32299 1.33132

1.09961 1.11934 1.14040 1.15809 1.17559 1.19159 1.20219 1.21527 1.22783 1.23492 1.24186 1.25444 1.25954 1.26755 1.27403 1.28080 1.28754 1.29399 1.30066 1.30750 1.31451 1.31863 1.32697

1.09478 1.11483 1.13577 1.15361 1.17124 1.18712 1.19773 1.21081 1.22337 1.23045 1.23749 1.25005 1.25513 1.26312 1.26956 1.27647 1.28317 1.28968 1.29630 1.30309 1.31014 1.31429 1.32258

1.08988 1.11007 1.13128 1.14911 1.16677 1.18253 1.19302 1.20635 1.21892 1.22599 1.23324 1.24578 1.25083 1.25888 1.26524 1.27208 1.27862 1.28526 1.29193 1.29866 1.30582 1.30999 1.31823

1.08486 1.10531 1.12679 1.14473 1.16239 1.17804 1.18840 1.20185 1.21454 1.22171 1.22872 1.24147 1.24639 1.25445 1.26079 1.26756 1.27422 1.28089 1.28750 1.29425 1.30143 1.30561 1.31388

a Standard uncertainty u: u(T) = 0.01 K, u(P) = 10 kPa, combined expanded uncertainties Uc(x) = 2 × 10−4, Uc: Uc(ρ) = 5 × 10−4 g·cm−3 (level of confidence = 0.95, k = 2).

Table 12. Experimental Values of Speeds of Sound, u/m·s−1, at Temperature T = 298.15 to 323.15 K and Mole Fraction, x1 for the Ternary Mixture [EMIM][CF3SO3](1) + DMSO(2) + ACN(3) at Pressure P = 0.1 MPaa T/K x1

x2

298.15

303.15

308.15

313.15

318.15

323.15

0.0313 0.0628 0.0996 0.1328 0.1693 0.2065 0.2333 0.2695 0.3091 0.3343 0.3610 0.4096 0.4353 0.4741 0.5094 0.5368 0.5656 0.5961 0.6284 0.6565 0.6860 0.7058 0.7476

0.8985 0.8526 0.8035 0.7578 0.7074 0.6555 0.6152 0.5629 0.5059 0.4656 0.4229 0.3523 0.3096 0.2498 0.1935 0.1703 0.1458 0.1200 0.0927 0.0845 0.0760 0.0663 0.0458

1496.30 1484.52 1472.03 1461.96 1452.15 1443.52 1438.15 1431.97 1426.59 1423.88 1421.59 1418.87 1418.13 1417.85 1418.36 1419.20 1420.45 1422.10 1424.13 1426.06 1428.17 1429.60 1432.50

1480.31 1468.82 1456.66 1446.88 1437.38 1429.05 1423.89 1417.96 1412.84 1410.28 1408.15 1405.67 1405.05 1404.92 1405.56 1406.49 1407.82 1409.55 1411.67 1413.66 1415.85 1417.33 1420.35

1464.38 1453.19 1441.37 1431.88 1422.67 1414.63 1409.66 1403.98 1399.12 1396.71 1394.73 1392.53 1392.04 1392.10 1392.91 1393.96 1395.41 1397.27 1399.50 1401.60 1403.89 1405.44 1408.59

1448.54 1437.66 1426.18 1416.97 1408.06 1400.30 1395.52 1390.09 1385.48 1383.23 1381.40 1379.46 1379.11 1379.36 1380.33 1381.50 1383.08 1385.06 1387.43 1389.63 1392.02 1393.64 1396.92

1432.21 1421.91 1411.01 1402.26 1393.78 1386.39 1381.83 1376.67 1372.31 1370.19 1368.49 1366.75 1366.49 1366.87 1367.95 1369.21 1370.87 1372.94 1375.40 1377.68 1380.17 1381.85 1385.26

1417.15 1406.85 1396.02 1387.39 1379.09 1371.93 1367.56 1362.66 1358.59 1356.67 1355.18 1353.80 1353.72 1354.36 1355.65 1357.06 1358.87 1361.08 1363.67 1366.05 1368.63 1370.36 1373.88

a Standard uncertainties u: u(T) = 0.01 K, u(P) = 10 kPa, combined expanded uncertainties Uc: Uc(x) = 2 × 10−4, Uc(u) = 0.5 m·s−1 (level of confidence = 0.95, k = 2).

where Y123 represents VE, Ks,mE, and Δη for the ternary system and A, B, C, D, and E are the adjustable parameters. The Y12, Y13, and

Y23 are the contribution of the excess properties of the constituent binary mixtures evaluated by the Redlich−Kister eq 3. P



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Table 13. Experimental Values of Viscosities, η/mPa·s, at Temperature T = 298.15 to 323.15 K and Mole Fraction, x1 for the Ternary Mixture [EMIM][CF3SO3](1) + DMSO(2) + ACN(3) at Pressure P = 0.1 MPaa T/K x1

x2

298.15

303.15

308.15

313.15

318.15

323.15

0.0313 0.0628 0.0996 0.1328 0.1693 0.2065 0.2333 0.2695 0.3091 0.3343 0.3610 0.4096 0.4353 0.4741 0.5094 0.5368 0.5656 0.5961 0.6284 0.6565 0.6860 0.7058 0.7476

0.8985 0.8526 0.8035 0.7578 0.7074 0.6555 0.6152 0.5629 0.5059 0.4656 0.4229 0.3523 0.3096 0.2498 0.1935 0.1703 0.1458 0.1200 0.0927 0.0845 0.0760 0.0663 0.0458

3.10 3.13 3.15 3.18 3.30 3.52 3.73 4.11 4.65 5.07 5.58 6.68 7.36 8.53 9.74 10.78 11.98 13.37 14.97 16.48 18.19 19.41 22.28

2.76 2.79 2.82 2.87 3.00 3.20 3.40 3.75 4.23 4.59 5.03 5.98 6.57 7.56 8.59 9.47 10.50 11.60 13.00 14.20 15.70 16.70 19.00

2.53 2.55 2.56 2.63 2.75 2.95 3.13 3.44 3.87 4.19 4.57 5.39 5.90 6.75 7.63 8.37 9.23 10.20 11.40 12.40 13.60 14.50 16.40

2.29 2.31 2.34 2.40 2.52 2.70 2.87 3.15 3.53 3.82 4.15 4.88 5.31 6.05 6.81 7.45 8.19 9.03 10.00 10.90 11.90 12.70 14.30

2.08 2.10 2.14 2.21 2.33 2.50 2.66 2.91 3.25 3.51 3.81 4.44 4.82 5.46 6.12 6.68 7.32 8.04 8.88 9.65 10.50 11.20 12.60

1.88 1.91 1.96 2.03 2.15 2.32 2.46 2.69 3.00 3.23 3.50 4.06 4.40 4.96 5.54 6.03 6.58 7.22 7.94 8.61 9.37 9.91 11.10

Standard uncertainties u: u(T) = 0.01 K, u(P) = 10 kPa, combined expanded uncertainties Uc: Uc(x) = ± 2 × 10−4, Uc(η) < 1 mPa·s = 0.20 mPa·s, Uc(η) (1−10 mPa·s) = 0.60 mPa·s, Uc(η) (11−50 mPa·s) = 0.80 mPa·s (level of confidence = 0.95, k = 2).

a

Figure 9. 3D mesh plot for excess molar isentropic compressibilities of [EMIM][CF3SO3] + DMSO + ACN as a function of mole fraction and at T = 298.15 K.

Figure 8. 3D mesh plot for excess molar volumes of [EMIM][CF3SO3] + DMSO + ACN as a function of mole fraction and at T = 298.15 K.

The Redlich−Kister adjustable parameters A, B, C, D, and E and standard deviations obtained by least-squares regression have been reported in Table 14. The experimental and correlated values using Redlich−Kister equation for VE, Ks,mE, and Δη for the studied ternary system show an agreement with correlated values. 4.2. Prediction of Excess Molar Volumes, Excess Molar Isentropic Compressibilities, Viscosity Deviations and Excess Gibbs Free Energies of Activation. The predictive

methods are classified into symmetric and asymmetric, depending on whether the assumption of the three binary mixtures contributing equally to the ternary mixture magnitude is accepted or not. The VE, Ks,mE, Δη, and ΔG*E for the studied ternary system have been predicted from the Jacob and Fitzner43 and Kohler44 models which are symmetric, and Tsao−Smith45 and Rastogi46 models which are asymmetric geometrical solution models. The standard deviations have been determined for the Q



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above models using the standard equation22,41 and are reported in Table S11. It can be seen that from Table S11 at T = 298.15 to 323.15 K that the standard deviations are minimum for VE in the case of Tsao−Smith model whereas the standard deviations are found to be minimum for Ks,mE and Δη in the case of Jacob and Fitzner model. The standard deviations are found to be minimum for ΔG*E in the case of Kohler model. By comparing the standard deviation values for all the four fitting models, it may be concluded that Tsao−Smith is best fitting model for predicting VE, whereas Jacob−Fitzner model for Ks,mE and Δη and Kohler model for ΔG*E.

5. CONCLUSION The values of VE and Ks,mE have been found to be negative at all compositions and temperatures and decrease with an increase in temperature for each binary [EMIM][CF3SO3] + DMSO and [EMIM][CF3SO3] + ACN and DMSO + ACN and ternary [EMIM][CF3SO3] + DMSO + ACN systems. Similarly, the values of Δη have also been found to be negative at all compositions and temperatures and increase with an increase in temperature for each binary system and ternary system. The ΔG* and ΔG*E values have been found to be positive at all compositions and temperatures and also increase with an increase in temperature for the studied binary/ternary systems. The dependence of the excess/deviation properties on temperature for binary and ternary mixtures indicates that the temperature has a great influence on intermolecular interactions in the studied systems. The VE, Ks,mE, and Δη values for each binary and only the ternary system have been fitted to Redlich− Kister polynomial equation. We have applied a number of semiempirical models, such as Arrhenius, Kendall−Monroe, Grunberg−Nissan, Tamura−Kurata, Hind−Ubbelohde, Katti−Chaudhary, and Heric for the correlation/prediction of dynamic viscosity data and to evaluate some interactional parameters of studied binary mixtures. The comparative plots between η vs x1 show an agreement between the experimental and theoretical values of dynamic viscosities. The Prigogine−Flory−Patterson theory is found to be applicable to correlate the excess molar volumes of [EMIM][CF3SO3] with DMSO/ACN and DMSO + ACN binary mixtures despite using one fitting parameter. Thus, the PFP theory is suitable for correlating excess molar volume values of mixtures of [EMIM][CF3SO3] with molecular organic solvents like DMSO and ACN. The VE, Ks,mE, Δη, and ΔG*E values of ternary system have also been predicted by a number of empirical expressions, such as Jacob and Fitzner and Kohler as symmetric, and Tsao−Smith and Rastogi as asymmetric geometrical solution models using the

Figure 10. 3D mesh plot for viscosity deviations of [EMIM][CF3SO3] + DMSO + ACN as a function of mole fraction and at T = 298.15 K.

Figure 11. 3D mesh plot for excess Gibbs energy of activation of [EMIM][CF3SO3] + DMSO + ACN as a function of mole fraction and at T = 298.15 K.

Table 14. Coefficients of the Redlich−Kister Equation for Excess Molar Volumes, VE/cm3·mol−1, Excess Molar Isentropic Compressibilities, Ks,mE/m3·mol−1·Pa−1, Viscosity Deviations, Δη/mPa·s, and the Standard Deviations (σ) at Temperature T = 298.15 to 323.15 K for the Ternary Mixture [EMIM][CF3SO3](1) + DMSO(2) + ACN(3) at Pressure P = 0.1 MPa T/K

VE123

298.15

303.15

[EMIM][CF3SO3] + DMSO + ACN A 38.9474 35.3711 B 418.3360 182.3731 C −198.5697 −165.0149 D −8776.7838 −9795.4902 E 7634.1886 7194.2683 σ 0.0074 0.0044 [EMIM][CF3SO3] + DMSO + ACN A 25.3635 67.5899

308.15

313.15

318.15

323.15

20.7175 −926.7703 −942.4755 −9283.2781 5424.9335 0.0064

24.3823 110.1860 −137.9707 −8486.2628 6854.7391 0.0064

25.1652 −324.4598 −917.0592 −13214.9960 6923.4715 0.0089

51.2961 343.5288 −245.2926 −14081.8665 10392.7107 0.0081

38.8153

65.9733

79.6069

75.5358

R



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Table 14. continued T/K KEs,m123

Δη

298.15

303.15

B 71.0916 82.8553 C −59.3356 −199.0913 D −27.9075 −55.6124 E −57.7854 35.2931 σ 0.0702 0.0611 [EMIM][CF3SO3] + DMSO + ACN A 55.9803 9.9772 B −18.5850 −201.2033 C 282.3217 530.0334 D 342.0258 166.1689 E −79.7508 −114.7948 σ 0.0004 0.0003

308.15

313.15

240.1295 −288.4106 165.6827 8.3591 0.0543

−12.3998 −92.1678 −133.8938 32.9839 0.0434

86.1630 −321.5210 −159.5795 106.3117 0.0421

104.7282 −294.1984 −100.6421 84.2491 0.0398

28.6972 −70.0867 268.7257 198.8275 −56.9842 0.0003

15.2097 −16.6625 206.6040 228.6377 −54.3208 0.0002

4.3414 −111.0647 283.7736 105.3480 −46.7850 0.0001

−12.9458 −42.6158 269.2021 205.4914 −79.2668 0.0001

data for the corresponding values of VE, Ks,mE, Δη, and ΔG*E of studied binary systems.

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ASSOCIATED CONTENT

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.7b00429. The equations used for the calculation of excess molar volumes, isentropic, and excess molar isentropic compressibilities and viscosity deviations; calculated values of excess molar volumes, excess molar isentropic compressibilities, viscosity deviations, Gibbs free energy of activation, excess Gibbs free energy of activation, and Flory’s parameters for the studied binary systems as functions for mole fraction and temperature; excess molar volumes, excess molar isentropic compressibilities, viscosity deviations, and excess Gibbs free energy of activation as functions for mole fraction and temperature for the studied ternary system; and model equations for the prediction of excess properties for the binary and ternary systems (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: rz1@rediffmail.com. ORCID

Riyazuddeen: 0000-0002-2745-0592 Notes

The authors declare no competing financial interest. Funding

Financial support from the UGC (Major Research Project) F. No. 41-240/2012(SR) scheme is acknowledged.

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ACKNOWLEDGMENTS The authors are thankful to the Chairman, Department of Chemistry, A.M.U., Aligarh for providing the necessary facility for the compilation of this work.

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S Supporting Information *

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