Comparing Composition- and Temperature-Dependent Viscosities of

Article pubs.acs.org/jced

Comparing Composition- and Temperature-Dependent Viscosities of Binary Systems Involving Ionic Liquids Abdolhossein Haghani,† David R. Saeva,‡,# Hossein Iloukhani,† and Markus M. Hoffmann*,‡ †

Department of Physical Chemistry, Faculty of Chemistry, Bu-Ali Sina University Hamedan, 65178-38695, Iran The College at Brockport, State University of New York, Brockport, New York 14420, United States

‡

S Supporting Information *

ABSTRACT: More than 200 composition- and temperature-dependent viscosity datasets for binary systems involving ionic liquids are analyzed with the Arrhenius model to inspect the composition dependence of the Arrhenius fit parameters activation energy, Ea, and y-intercept, ln A. The analysis also includes a new viscosity dataset for the binary system 1-hexyl-3methylimidazolium bis(trifluoromethylsulfonyl)amide−trichloromethane. The majority of the binary systems show linear dependence of Ea and ln A with mole fraction, either over the entire range of composition or over a wide range of compositions, typically between 0.2 < xIL < 1.0. These findings are useful for estimating unknown viscosities for binary systems involving ILs. As a side-outcome from the Arrhenius analysis and careful comparisons between datasets, a number of datasets are identified that are suspect of experimental inaccuracies.

■

INTRODUCTION Because ionic liquids (ILs) are salts, they are completely composed of ions. Unlike mineral salts, not only are their melting points very low, by definition below 100 °C,1 but depending on the particular structures of cation and anion, they may also be completely miscible with molecular solvents, even with very nonpolar solvents. In fact, the ability of ILs to dissolve a wide variety of substances is one major reason for their extensive exploitation as a neoteric solvent for chemical synthesis2 and chemical processing such as extraction.3 Consequently, there has been a need for physical property data of binary and multicomponent systems involving ILs. Since it is practically impossible to measure physical properties of every conceivable combination of IL and molecular solvent, any predictive models and schemes for these are highly desirable. However, as pointed out by Jiang et al.,4 especially binary systems with nonpolar molecular solvents constitute fairly unexplored systems that are not well understood because ordinary mineral salts do not dissolve in nonpolar molecular solvents. The dependence of the viscosity for binary IL−molecular solvent systems with respect to composition and temperature (and even with respect to pressure5) has been the subject of many studies that include works where 3D representations are given.6−9 Blahušiak and Schlosser have recently summarized nicely the most common models for correlating the temperature and the composition dependence of viscosity.10 They point out that it has been noted that the Arrhenius equation generally describes well the temperature dependence for neat ILs with asymmetric cation structure, which represents the majority of IL cation structures, while ILs with symmetric cations tend to show non-Arrhenius behavior, and the Vogel− Fulcher−Tammann (VFT) equation is more suitable.10 In this © XXXX American Chemical Society

study, we solely focus on the Arrhenius equation, the simplest model, for the meta-analysis of the composition- and temperature-dependent viscosity data, η(xIL, T), where we will specifically inspect the IL mole fraction composition dependence of the activation energy, Ea(xIL), and preexponential factor, A(xIL), as shown in eq 1 η−1(x IL , T ) = A(x IL)e−Ea(xIL)/(RT )

(1)

where R is the gas constant. Equation 1 expresses the inverse viscosity, generally referred to as the fluidity, for easier comparison with the Arrhenius analysis of other physical properties such as self-diffusion coefficients or conductivity as we have done, for example, in prior work.11,12 Other, more complicated approaches of correlating viscosity to both composition and temperature include the Jouyban−Acree model,8,13 and the Eyring−Patel−Teja model, which requires however knowledge of critical temperatures, pressures, and densities for the neat components as well as the acentric factor for the binary system.14 We might add that the viscosity composition dependence (at constant temperature) for several binary systems with ammonium- and sulfonium-based ILs has been very well fit with the Jones−Dole equation.15,16 The reason why we focus in this study on the composition dependence of Ea(xIL) and A(xIL) is that we made a peculiar observation in a prior work for the particular binary system 1ethyl-3-methylimidazolium methanesulfonate ([C2 mim][MeSO3])−water.11 When fitting the temperature dependencies of self-diffusion coefficients of cation, anion, and water, as well as the fluidity and the 1H NMR T1-relaxation time of Received: June 16, 2015 Accepted: October 15, 2015

A

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

heated slightly in a microwave to at least partially remove dissolved gas that can compromise viscosity (and density) measurements at elevated temperatures. Overall, the expanded uncertainty at the 95 % level (k = 2) of the solution compositions is estimated to be within 0.005 mole fraction units. The viscosities were measured with an AMVn automated microviscometer rolling ball viscometer from Anton Paar. The densities were measured in parallel with a DMA 4100 vibrating tube density meter with internal sample viscosity compensation, also from Anton Paar, and have already been reported as part of another study.23 Both instruments are temperature controlled to within 0.02 °C by Peltier systems. Viscosities were measured in at least six repetitions, typically 12 or 18 with 6 repetitions for each set angle of capillary tilt that was chosen to anticipate ball rolling times around 1 min. The results reported in Table 2 are the averages of the measurements and their corresponding standard deviations. For xIL = 0.074 and 0.186 solutions the capillary used was of 1.6 mm and was calibrated against water (ultrapure water, Anton Paar lot 1012).24 For the samples 0.2 < xIL < 0.8 a 1.8 mm capillary was used and the remaining samples were measured with a 3.0 mm capillary. The 1.8 mm and 3.0 mm capillaries were calibrated against a viscosity standard purchased from Kohler covering calibration ranges of 105 mPa·s to 45 mPa·s and 30 mPa to 103 mPa, respectively. Realizing that the measured viscosities especially at the higher temperatures fell outside the calibration range for some samples, the viscosities for the 0.418 mol·kg−1 sample was also measured with the 3.0 mm capillary and the results agreed within 1.5 % even for the highest temperature. Also, in prior work we compared viscosity measurements for the 1.6 mm and 1.8 mm capillaries and agreement was within 3 %.17 The accuracy of the viscosity measurements was checked against reported viscosity measurements for pure [C6mim][NTf2] as presented in the Results and Discussion section in Table 2. When calculating relative standard deviations from the reported standard deviations in Table 2, they amount to values typically (well) below 1 % except for a few cases in which likely shorter ball rolling times contributed to the larger measurement uncertainty. Overall, the relative expanded uncertainty at the 95 % level (k = 2) for the reported viscosity data is estimated to be 2 % for the samples exceeding xIL = 0.2 and 3 % for samples below xIL = 0.2.

water with the Arrhenius equation for each mixture composition, the resulting activation energies were found to be all linear with respect to mole fraction composition and to be very similar, if not identical.11 We recently followed up on this peculiar finding for the related binary system 1-butyl-3methylimidazolium methanesulfonate ([C4mim][MeSO3])− water and observed a more differentiated behavior of the mole fraction dependence of these activation energies.17 We have also been studying the binary system 1-hexyl-3methylimidazolium bis(trifluoromethanesulfonyl)amide ([C6mim][NTf2])−trichloromethane (chloroform, HCCl3), initially only at low concentrations (and as deuterated chloroform) to investigate ion pair formation and aggregation.18 We include in this report new data for the temperature and composition dependence of the viscosity for this binary system. As we will show, we observe some deviation from a linear mole fraction dependence for the activation energy. A linearity of the activation energy with respect to mole fraction was also observed for the binary systems 1-butyl-3-methylimidazolium hexafluorophosphate−N,N-dimethylformamide19 and ethylammonium nitrate with dimethyl carbonate as well as formamide,20 while Gong et al. were using a second order polynomial for the mole fraction dependence of the activation energy.21 This raises the question of how far a linear dependence for the viscosity activation energy can be found in other binary IL−molecular solvent systems. However, except for these cited works, this aspect has generally not been inspected even though there are numerous temperature- and composition-dependent viscosity studies of binary IL−molecular solvent systems. We thus embarked in a very thorough literature search for binary IL−molecular solvent viscosity datasets and meta-analyzed these to discern which types of binary IL−molecular solvent systems would display a linear relationship between activation energy and the composition expressed in mole fraction and which not. A total of 215 binary IL−molecular solvent systems are included in this study covering publication dates up to and including the year 2014. Yu et al. also completed a thorough search on IL viscosity data up to 2009.22 Although they included binary (and ternary) datasets, their presented observations and quantitative structure−property analysis was focused only on neat ILs.

■

EXPERIMENTAL SECTION New viscosities are reported for the [C6mim][NTf2]−CHCl3 binary system. The specifications of the chemicals are summarized in Table 1. The [C6mim][NTf2] was of clear

■

RESULTS AND DISCUSSION New Viscosity Measurements and Data Analysis. Table 2 lists our new viscosity measurements for the binary system [C6mim][NTf2]−CHCl3 at ambient pressure. Viscosities for neat [C6mim][NTf2] are compared with two literature sources25,26 that were deemed reliable in a critical review on physical property measurements of neat [C6mim][NTf2], which has been chosen as a reference IL.27 The agreement is within 1 % for 298.15 K to 318.15 K and at about 2 % for 288.15 K. The viscosity of the neat IL is very sensitive to the presence of water that decreases the viscosity.26 The good agreement of the neat IL viscosities with the values from the two literature sources confirms that the water content of less than 150 ppm was at similar levels as reported for the measurements in the two literature sources (200 ppm and 7 ppm to 117 ppm). We now turn to the Arrhenius analysis of our new viscosity measurements for the binary system [C6mim][NTf2]−CHCl3. Figure 1 shows the Arrhenius plots according to eq 2,

Table 1. Specifications of Chemicals chemical

CAS no.

vendor

mass fraction puritya

trichloromethane [C6mim][NTf2]c

67-66-3 382150-50-7

Acros Io-Li-Tec

0.998b > 0.99

a

Chemicals were opened and stored under nitrogen atmosphere in glovebox. Purity represents initial and final purity. bIndicated purity is excluding 0.005 to 0.010 ethanol as stabilizer that was not removed. c1hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide.

and colorless appearance and contained a mass fraction of smaller than 1.5 × 10−4 of water as determined by Karl Fischer titration. Solution preparation was done by mass using an analytical balance in an inert atmosphere glovebox where the chemicals were stored. Before filling the capillary tubes and the density meter, each of the prepared sample vials was briefly B

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 2. Viscosity, η, in mPa·s and Arrhenius Analysis for the Binary System [C6mim][NTf2]−CHCl3 at Ambient Pressure (p = 0.101 ± 0.005 MPa)a xIL b

1.000 1.000c 1.000 0.906 0.805 0.707 0.651 0.565 0.511 0.418 0.266 0.186 0.074

T/K = 288.2

T/K = 298.2

T/K = 308.2

T/K = 318.2

Ea/kJmol−1

115.4 ± 1.2 116.3 ± 1.2 117.8 ± 0.1 95.7 ± 0.5 78.4 ± 0.4 60.6 ± 0.2 50.6 ± 0.2 38.0 ± 0.4 30.16 ± 0.13 20.36 ± 0.02 8.57 ± 0.07 4.556 ± 0.003 1.701 ± 0.015

70.1 ± 0.7 70.6 ± 0.7 70.4 ± 0.1 59.1 ± 0.3 49.6 ± 0.7 38.9 ± 0.2 33.3 ± 0.1 25.55 ± 0.05 20.92 ± 0.13 14.63 ± 0.09 6.63 ± 0.06 3.667 ± 0.006 1.462 ± 0.011

45.6 ± 0.5 45.9 ± 0.5 45.4 ± 0.1 39.5 ± 0.3 33.7 ± 0.4 26.6 ± 0.1 23.1 ± 0.4 18.18 ± 0.02 15.19 ± 0.14 10.96 ± 0.10 5.25 ± 0.01 3.002 ± 0.011 1.265 ± 0.007

31.3 ± 0.3 31.5 ± 0.3 31.23 ± 0.03 27.7 ± 0.2 24.0 ± 0.2 19.16 ± 0.09 16.97 ± 0.18 13.58 ± 0.04 11.49 ± 0.13 8.50 ± 0.11 4.29 ± 0.02 2.500 ± 0.004 1.104 ± 0.001

33.2 33.2 33.8 31.5 30.0 29.2 27.8 26.2 24.5 22.2 17.6 15.3 11.0

± ± ± ± ± ± ± ± ± ± ± ± ±

ln (A/mPa−1·s−1)

R2

σ

± ± ± ± ± ± ± ± ± ± ± ± ±

0.999 0.999 0.998 0.998 0.999 0.999 0.999 0.998 0.999 0.999 0.999 1.000 1.000

1.4 1.4 1.8 1.3 1.0 0.76 0.58 0.45 0.26 0.16 0.044 0.008 0.002

0.8 0.8 1.0 0.9 0.8 0.8 0.7 0.7 0.5 0.5 0.3 0.1 0.1

9.1 9.1 9.3 8.6 8.2 8.1 7.7 7.3 6.8 6.3 5.2 4.9 4.1

0.3 0.3 0.4 0.4 0.3 0.3 0.3 0.3 0.2 0.2 0.1 0.1 0.1

a

Indicated are the standard deviations from at least six viscosity measurement repetitions. The relative expanded uncertainty at the 95 % level (k = 2) for the listed viscosity data is estimated to be 2 % for the samples exceeding xIL = 0.2 and 3 % for samples below xIL = 0.2. Expanded uncertainties at the 95 % level (k = 2) of temperature and xIL are respectively, 0.02 K and 0.005. See Experimental Section for further detail. bFrom Widegren and Magee.25 cFrom Kandil et al.26

Figure 1. Arrhenius plots at ambient pressure for [C6mim][NTf2]− CHCl3 binary system for different IL mole fraction, xIL, at 1.000 (●), 0.906 (○), 0.805 (▼), 0.707 (△), 0.651 (■), 0.565 (□), 0.511 (⧫), 0.418 (◊), 0.266 (▲), 0.186 (▽), and 0.074 (⬢). The parameters of the least linear square fits (solid lines) are included in Table 2.

ln(η−1(x IL , T )) = ln(A(x IL)) − (Ea(x IL))/RT

Figure 2. (a) Activation energy, Ea, and (b) y-intercept, ln A, as a function of IL mole fraction, xIL, for binary systems [C6mim][NTf2]− CHCl3 (this work, ○) and [C6mim][NTf2]−CDCl3 (ref 7, □) obtained from the Arrhenius analysis of the viscosity data shown in Table 2. The solid lines connect the values of Ea ln A for neat chloroform and neat IL.

(2)

the logarithmic form of eq 1, for each of the studied compositions. The values for Ea, and ln A obtained from least linear square fits and their uncertainties are included in Table 2. It is fair to say that the data in Figure 1 are well fit by the Arrhenius model. We include in Table 2 the standard deviation of the viscosities to the Arrhenius fit of eq 2 for each composition. However, because the viscosity changes so much in value over the temperature range, the absolute deviations are larger than the values listed in Table 2 for low temperatures and smaller for high temperatures. Inspecting the relative deviation (not shown) of each data point to the Arrhenius fit, these are 2.2% or less (mostly between 1% and 1.5%). Figure 2 displays Ea(xIL) and ln A(xIL) and includes data from our prior work on the same system but with deuterated chloroform rather than CHCl3.18 To guide the eye, a linear line is shown connecting Ea and ln A for the lowest and highest xIL. It is evident that Ea(xIL) shows a positive deviation from linearity while nonlinearity, if indeed present, is smaller for ln A(xIL). In fact, in our prior work with CDCl3 at low IL concentrations we noted a linearity of Ea with mass fraction rather than mole fraction.18 Nevertheless, when we attempted a

linear fit through the data points in Figure 2 (not shown) we obtained for Ea in units of kJ·mol−1 Ea(x IL) = 28.76x IL + 7.85

(3)

−1 −1

and for ln(A/mPa ·s ) ln A(x IL) = 6.19x IL + 3.43

(4)

2

with R -value of 0.977 and 0.991 for Ea(xIL) and ln A(xIL), respectively, and corresponding standard deviations to the fit of 1.5 kJ·mol−1 and 0.20. These standard deviations to the linear fits are about as large as the standard deviations for the Ea and ln (A) values listed in Table 2, thus not allowing a conclusive judgment if Ea(xIL) and ln A(xIL) are indeed nonlinear. General Comments to the Meta-Analysis of Reported Viscosities for Binary System Data. We meta-analyzed with the Arrhenius equation a total of 215 datasets of binary systems with IL and present for each dataset in the Supporting Information section tables and figures similar to that shown in Table 2 and Figures 1 and 2. It has clearly been shown that especially over large temperature ranges the viscosities of the C

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 3. Identification of ILs abbreviation [C2mim]Cl [C4mim]Cl [C6mim]Cl [C8mim]Cl [N8,8,8,1]Cl [C2OHMe3N]Cl [C3mPyr]Br [C4mPyr]Br [C5mPyr]Br [C4mim][SCN] [N0,0,0,0][SCN] [C4mPyr][SCN] [C4-4-mPy][SCN] [C8mim][NO3] [N4,0,0,0][NO3] [Pyr][NO3] [C2mim][N(CN)2] [C4mim][N(CN)2] [C4mPyr][N(CN)2] [C4mPip][N(CN)2] [C2mim][C(CN)3] [C4mim][C(CN)3] [C4mPyr][C(CN)3] [C2mim][BF4] [C4mim][BF4] [C6mim][BF4] [C8mim][BF4] [C3dmim][BF4] [C4dmim][BF4] [C2OHmim][BF4] [C4Py][BF4] [C8Py][BF4] [C4-3-mPy][BF4] [C4-4-mPy][BF4] [C4mim][PF6] [C5mim][PF6] [C6mim][PF6] [N1,1,1,0][DHP] [N2,2,2,0][DHP] [C1mim][DMP] [C2mim][DMP] [C4mim][DMP] [(C2OH)2NC1H] [C0CO2] [C0mim][C1CO2] [C2mim][C1CO2] [C4mim][C1CO2] [N4,0,0,0][C1CO2] [N2,2,0,0][C1CO2] [N1,1,1,0][C1CO2] [N2,2,2,0][C1CO2] [C2mim][TFA] [C2Pip][C2CO2] [C2OHN(C1)3] [lact]

name 1-ethyl-3-methylimidazolium chloride 1-butyl-3-methylimidazolium chloride 1-hexyl-3-methylimidazolium chloride 1-octyl-3-methylimidazolium chloride trioctylmethylamonium chloride choline chloride N-propyl-N-methylpyrrolidinium bromide N-butyl-N-methylpyrrolidinium bromide N-pentyl-N-methylpyrrolidinium bromide 1-butyl-3-methylimidazolium thiocyanate ammonium thiocyanate 1-butyl-1-methylpyrrolidinium thiocyanate 1-butyl-4-methylpyridinium thiocyanate 1-octyl-3-methylimidazolium nitrate N-butylammonium nitrate pyrrolidinium nitrate 1-ethyl-3-methylimidazolium dicyanamide 1-butyl-3-methylimidazolium dicyanamide 1-butyl-1-methylpyrrolidinium dicyanamide 1-butyl-1-methylpiperidinium dicyanamide 1-ethyl-3-methylimidazolium tricyanomethanide 1-butyl-3-methylimidazolium tricyanomethanide 1-butyl-1-methylpyrrolidinium tricyanomethanide 1-ethyl-3-methylimidazolium tetrafluoroborate 1-butyl-3-methylimidazolium tetrafluoroborate 1-hexyl-3-methylimidazolium tetrafluoroborate 1-methyl-3-octylimidazolium tetrafluoroborate 1-propyl-2,3-dimethylimidazolium tetrafluoroborate 1-butyl-2,3-dimethylimidazolium tetrafluoroborate 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate 1-butylpyridinium tetrafluoroborate 1-octylpyridinium tetrafluoroborate 1-butyl-3-methylpyridinium tetrafluoroborate 1-butyl-4-methylpyridinium tetrafluoroborate 1-butyl-3-methylimidazolium hexafluorophosphate 1-pentyl-3-methylimidazolium hexafluorophosphate 1-hexyl-3-methylimidazolium hexafluorophosphate trimethylammonium dihydrogen phosphate triethylammonium dihydrogen phosphate 1,3-dimethylimidazolium dimethylphosphate 1-ethyl-3-methylimidazolium dimethylphosphate 1-butyl-3-methylimidazolium dimethylphosphate bis(2-hydroxyethyl)methylammonium formate

abbreviation

name

[TMG][lact] [Im][C7CO2] [C4mim][Gly] [C4mim][Ala] [Bu3PC3NH2][Ala]

1,1,3,3-tetramethylguanidinium lactate imidazolium octanoate 1-butyl-3-methylimidazolium glycine acid 1-butyl-3-methylimidazolium alanine acid (3-aminopropyl) tributylphosphonium L-αaminopropionic acid salt (3-aminopropyl) tributylphosphonium L-αaminoisovaleric acid salt (3-aminopropyl) tributylphosphonium L-α-amino-4methylvaleric acid salt 1-butyl-3-methylimidazolium glutamic acid 1-ethyl-3-methylimidazolium methylsulfonate 1-butyl-3-methylimidazolium methylsulfonate diethyl-methylammonium methylsulfonate 1-ethyl-3-methylimidazolium ethylsulfonate 1-ethyl-3-methylimidazolium trifluoromethanesulfonate 1-butyl-3-methylimidazolium hydrogensulfate diethylammonium hydrogen sulfate trimethylammonium hydrogen sulfate triethylammonium hydrogen sulfate 1-ethyl-3-methylimidazolium methyl sulfate 1-propyl-3-methylimidazolium methyl sulfate 1-butyl-3-methylimidazolium methyl sulfate 1-methylpyridinium methyl sulfate 1-ethyl-3-methylimidazolium ethyl sulfate 2-ethoxy-1-ethyl-1,1-dimethyl-2-oxoethanamonium ethyl sulfate 1-ethyl-1-methylpyrrolidinium ethyl sulfate 1-ethyl-1-methylmorpholinium ethyl sulfate 1-ethylpyridinium ethyl sulfate 1-ethyl-3-methylpyridinium ethyl sulfate 1-butyl-1-methylpyrrolidinium butyl sulfate 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl)amide 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl)amide 1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl)amide trimethylammonium bis(trifluoromethylsulfonyl)amide butyltrimethylammonium bis(trifluoromethylsulfonyl) amide lithium diethanolamine bis(trifluoromethylsulfonyl) amide 1-ethyl-1,4-dimethylpiperazinium bis (trifluoromethylsulfonyl)amide 1-n-pentyl-1,4-dimethylpiperazinium bis (trifluoromethylsulfonyl)amide 1-butylpyridinium bis(trifluoromethylsulfonyl)amide N-butyl-N-methylpyrrolidinium bis (trifluoromethylsulfonyl)amide N-hexyl-N-methylpyrrolidinium bis (trifluoromethylsulfonyl)amide 1-ethyl-4-methylpyridinium bis (trifluoromethylsulfonyl)amide 1-octylisoquinolinium bis(trifluoromethylsulfonyl) amide trimethylsulfonium bis(trifluoromethylsulfonyl)amide

[Bu3PC3NH2][Val] [Bu3PC3NH2][Leu] [C4mim][Glu] [C2mim][C1SO3] [C4mim][C1SO3] [N2,2,1,0][C1SO3] [C2mim][C2SO3] [C2mim][TfO] [C4mim][C0SO4] [N2,2,0,0][C0SO4] [N1,1,1,0][C0SO4] [N2,2,2,0][C0SO4] [C2mim][C1SO4] [C3mim][C1SO4] [C4mim][C1SO4] [C1Py][C1SO4] [C2mim][C2SO4] [EtMe2NAcOEt] [C2SO4] [C2mPyr][C2SO4] [C2mMor][C2SO4] [C2Py][C2SO4] [C2-3-mPy][C2SO4] [C4mPyr][C4SO4] [C2mim][NTf2] [C4mim][NTf2] [C6mim][NTf2] [N1,1,1,0][NTf2] [N4,1,1,1][NTf2] [LiChelate][NTf2] [C2dmPip][NTf2] [C5dmPip][NTf2] [C4Py][NTf2] [C4mPyr][NTf2]

1-methylimidazolium acetate 1-ethyl-3-methylimidazolium acetate 1-butyl-3-methylimidazolium acetate N-butylammonium acetate diethylammonium acetate trimethylammonium acetate triethylammonium acetate 1-ethyl-3-methylimidazolium trifluoroacetate N-ethyl piperazinium propionate choline lactate

[C6mPyr][NTf2] [C2-4-mPy][NTf2] [C8iQuin][NTf2] [Me3S][NTf2]

neat surfactants are more accurately fit with the VFT equation.28 However, from inspecting the tables and figures in the Supporting Information section, the simpler Arrhenius equation actually fits the temperature dependence of each

composition quite well for all the datasets inspected in this study resulting in R2 values very close to 1 in nearly all instances. In fact, the R2 values are so consistently near a value of 1 that R2 values significantly lower than 1 indicate the D

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 4. Solvent−IL Binary Systems That Show Linear Ea(xIL) and ln A(xIL) over the Entire Composition Range with Corresponding Fit Parameters for Slope m, Intercept b, and Standard Deviation σ of the Linear Fit to the Data. A Is in Units of mPa−1·s−1 Ea(xIL) dataset

solvent

S43 S102 S58 S40 S141 S214 S44 S211 S20 S107 S199 S47 S50 S78 S68 S108 S59 S60 S61 S62 S200 S48 S51 S79 S69 S83 S193 S195 S109 S80 S70 S194 S120 S121 S154

H2O H2O H2O H2O H2O H2O H2O H2O C1OH C1OH C1OH C1OH C1OH C1OH C1OH C2OH C2OH C2OH C2OH C2OH C2OH C2OH C2OH C2OH C2OH C2OH C2OH C2OH C3OH C3OH C3OH C3OH C4OH C6OH PEG 200

S155 S153 S156 S33 S210 S96 S116 S179 S18 S205 S180 S73 S182 S15 S17 S158 S122 S159 S145 S160

PEG 200 PEG 400 MPEG 350 MMA GBL PC PC C1CN C1CN DMF DMA NMP NMP DMSO DMSO toluene C6H6C2OH pyridine thiophene thiophene

T-range

mEa

K

kJ·mol−1

IL [C8mim]Cl [C2mim][N(CN)2] [C6mim][BF4] [C3dmim][BF4] [C2OHN(C1)3][lact] [C2mim][C1SO3] [C2mim][C2SO4] [C2mPip][C2SO4] [C4mim][SCN] [N4,0,0,0][NO3] [C1mim][DMP] [C2mim][DMP] [C4mim][DMP] [N4,0,0,0][C1CO2] [C2Pip][C2CO2] [N4,0,0,0][NO3] [C2mim][BF4] [C4mim][BF4] [C6mim][BF4] [C8mim][BF4] [C1mim][DMP] [C2mim][DMP] [C4mim][DMP] [N4,0,0,0][C1CO2] [C2Pip][C2CO2] [C2mim][NTf2] [C2dmPip][NTf2] [C5dmPip][NTf2] [C4,0,0,0][NO3] [C4,0,0,0][C1CO2] [C2pip][C2CO2] [C2dmPip][NTf2] [C8iQuin][NTf2] [C8iQuin][NTf2] [EtMe2NAcOEt] [C2SO4] [C5mim][PF6] [C4mim][PF6] [C2mim][BF4] [C4mim][PF6] [C4mim][NTf2] [Pyr][NO3] [C4mim][NTf2] [C4mim][BF4] [C4dmim][BF4] [C4mim][BF4] [C4mim][BF4] [C4mim][BF4] [C4mim][BF4] [C4mim][BF4] [C4dmim][BF4] [C8iQuin][NTf2] [C8iQuin][NTf2] [C8iQuin][NTf2] [C2mim][C(CN)3] [C8iQuin][NTf2]

bEa

ln A(xIL) σEa

kJ·mol−1 kJ·mol−1

R2Ea

mln A

bln A

σln A

R2ln A

ref.

298.15 298.15 288.15 293.15 293.15 215.15 293.15 298.15 298.15 293.15 293.15 293.15 293.15 298.15 298.15 293.15 288.15 288.15 288.15 288.15 293.15 293.15 293.15 298.15 298.15 278.15 293.15 293.15 293.15 293.15 278.15 293.15 298.15 298.15 293.15

to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to

343.15 343.15 318.15 323.15 353.15 353.15 303.15 343.15 328.15 313.15 323.15 333.15 333.15 313.15 313.15 313.15 318.15 318.15 318.15 318.15 323.15 333.15 333.15 313.15 313.15 338.15 323.15 323.15 313.15 313.15 308.15 323.15 338.15 338.15 328.15

57.93 17.26 22.70 24.60 82.49 22.32 14.97 36.55 21.07 21.63 37.23 35.79 40.79 36.73 47.99 16.95 12.21 21.61 26.72 31.22 35.16 29.13 36.10 31.74 44.12 4.33 28.05 35.94 11.95 27.22 39.82 24.96 23.54 20.83 23.08

13.80 21.45 17.35 15.99 47.77 16.33 17.50 18.33 8.20 9.56 7.41 8.41 9.51 9.60 9.93 13.69 12.67 13.18 12.71 12.89 10.25 12.26 13.09 13.66 12.77 7.50 15.11 16.03 17.80 17.01 15.93 8.11 20.46 23.24 28.04

9.37 8.58 5.22 4.94 17.86 3.32 3.43 9.19 2.27 1.82 2.38 1.46 2.96 3.01 2.23 2.01 3.41 5.63 3.78 3.24 5.79 2.54 2.12 3.82 2.20 2.38 2.51 2.77 2.82 5.66 2.80 1.97 2.04 2.16 4.21

0.98 0.82 0.94 0.97 0.96 0.98 0.96 0.94 0.99 0.99 1.00 1.00 0.99 1.00 1.00 0.99 0.89 0.94 0.98 0.99 0.98 0.99 1.00 0.99 1.00 0.79 0.99 1.00 0.96 0.97 1.00 1.00 0.99 0.99 0.97

14.30 3.09 4.26 4.44 27.65 4.34 1.92 8.12 4.08 3.60 9.01 8.36 9.65 8.02 13.49 2.40 1.45 4.46 5.80 7.04 8.58 6.28 8.33 6.63 12.48 −1.63 6.24 8.65 1.35 5.42 11.30 5.53 4.83 4.21 5.56

4.59 7.11 6.41 5.92 17.78 5.78 6.25 6.19 3.57 4.04 2.88 3.33 3.68 4.00 3.84 5.10 4.95 4.90 4.77 4.73 3.58 4.39 4.68 5.11 4.67 2.88 5.54 5.79 6.09 6.01 5.54 6.30 6.80 7.53 7.57

3.48 1.54 2.00 2.00 6.12 0.98 1.16 2.54 0.98 0.49 2.00 1.18 0.84 1.51 0.57 1.11 1.37 2.28 1.68 1.58 2.89 1.72 1.32 2.07 1.25 0.96 1.11 0.89 0.78 2.49 1.50 0.89 0.59 0.72 1.47

0.95 0.82 0.79 0.85 0.96 0.96 0.77 0.92 0.96 0.98 0.96 0.97 0.99 0.98 1.00 0.83 0.42 0.81 0.93 0.96 0.91 0.90 0.97 0.93 0.99 0.76 0.98 0.99 0.76 0.87 0.98 0.98 0.99 0.97 0.94

47 14 48 49 50 11 47 51 52 53 54 21 21 55 56 53 57 57 57 57 54 21 21 55 56 58 59 59 53 55 56 59 60 60 61

293.15 293.15 293.15 283.15 293.15 283.15 293.15 303.15 293.15 303.15 303.15 278.15 303.15 293.15 293.15 298.15 298.15 298.15 298.15 298.15

to to to to to to to to to to to to to to to to to to to to

353.15 353.15 353.15 353.15 323.15 353.15 333.15 333.15 343.15 333.15 333.15 318.15 333.15 353.15 353.15 348.15 338.15 348.15 348.15 348.15

10.33 7.57 8.45 33.64 18.64 6.38 15.50 27.60 41.09 25.20 24.36 24.29 22.50 19.65 33.78 34.42 15.93 34.42 9.85 34.49

29.86 32.73 26.02 6.37 11.36 15.61 13.70 5.62 4.90 8.12 9.63 12.20 11.79 13.62 12.32 10.28 27.85 10.28 9.36 10.84

2.09 3.06 2.14 0.81 2.91 1.84 2.20 2.03 3.43 1.60 0.94 0.67 1.37 0.68 1.14 3.48 1.71 3.48 1.52 5.19

0.96 0.85 0.95 0.99 0.98 0.92 0.98 1.00 0.99 1.00 1.00 1.00 1.00 0.99 1.00 0.99 0.99 0.99 0.97 0.98

2.42 1.98 1.82 7.47 4.33 0.07 3.39 5.58 9.19 5.39 5.19 5.85 5.02 4.08 7.92 8.19 2.96 8.19 1.17 8.12

8.15 8.60 7.03 2.80 3.67 5.19 4.29 2.92 2.74 3.23 3.67 4.18 3.96 4.50 4.09 3.50 8.69 3.50 3.69 3.71

1.08 1.08 0.80 1.62 0.71 0.62 0.49 1.46 0.56 0.99 0.59 0.21 0.49 0.41 0.42 0.97 0.94 0.97 0.30 1.61

0.84 0.76 0.85 0.96 0.98 0.01 0.98 0.94 0.97 0.97 0.99 0.99 0.99 0.99 1.00 0.99 0.92 0.99 0.92 0.97

61 62 61 63 64 65 66 67 68 69 67 70 67 68 68 71 60 71 71 72

E

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 4. continued Ea(xIL) dataset

solvent

S183 S149 S175 S176 S190 S191 S192 S169 S170 S177 S52

benzothiophene [C2mim][N(CN)2] [C2mim][BF4] [C4mim][BF4] [C4mim][BF4] [C4Py][BF4] [C4Py][BF4] [C4mim][PF6] [C6mim][PF6] [C4mim][C1SO4] [C4Py][NTf2]

T-range

mEa

K

kJ·mol−1

IL [C4mPyr][CCN)3] [C2-4-mpy][NTf2] [C6mim][BF4] [C6mim][BF4] [C2OHmim][BF4] [C2OHmim][BF4] [C4mim][BF4] [C4mim][BF4] [C6mim][BF4] [C4mim][BF4] [C4Py][BF4]

308.15 293.15 298.15 298.15 293.15 293.15 293.15 293.15 293.15 298.15 293.15

to to to to to to to to to to to

358.15 353.15 308.15 308.15 343.15 343.15 343.15 333.15 333.15 308.15 353.15

3.75 4.83 16.27 4.77 1.10 −3.54 −4.61 2.73 2.72 −4.59 35.94

bEa

ln A(xIL) σEa

kJ·mol−1 kJ·mol−1 18.14 19.32 26.87 37.29 33.39 37.84 38.38 43.64 49.82 42.30 19.39

2.24 1.35 2.47 1.67 0.78 1.11 0.09 2.58 2.84 2.37 4.21

R2Ea

mln A

bln A

σln A

R2ln A

ref.

0.68 0.93 0.98 0.91 0.68 0.92 1.00 0.55 0.50 0.83 0.98

−0.36 1.13 4.82 1.27 0.38 −1.04 −1.42 1.45 1.34 −1.17 7.38

5.68 5.01 7.21 10.37 8.83 10.19 10.38 12.08 14.19 11.68 6.09

0.29 0.40 0.86 0.65 0.26 0.38 0.03 1.04 1.19 0.91 0.75

0.54 0.90 0.98 0.83 0.69 0.89 0.03 0.68 0.58 0.68 0.99

73 74 75 75 76 76 76 77 77 75 78

experimental datasets) are. The linear fit coefficients mEa, bEa, and mln A, bln A in Tables 4 to 8 represent the slopes (m) and intercepts (b) for Ea(xIL) and ln A(xIL), respectively. The standard deviations of the linear fits to Ea(xIL) and ln a(xIL) are also provided in Tables 4 to 8 using the symbols σEa and σln A, respectively. In contrast to the composition and temperature dependence of VE, where we observed in a prior study a much stronger dependence on the molecular solvent rather than the identity of the IL,23 Wang et al. showed that the viscosity of [C4mim][BF4] displays very similar composition dependence with the molecular solvents acetonitrile, dichloromethane, 2-butanone, and N,N-dimethylformamide.30 Nevertheless, the wealth of dataset entries in Tables 4 to 8 is organized first by molecular solvent, then IL anion, and last IL cation in the order as shown in Tables S1 to S3. The viscosity was measured more than once only for a couple of binary systems. Except for some difference in the Ea values for the neat IL, datasets S73 and S182 are in reasonable agreement and both show linear Ea(xIL) and ln A(xIL) for the binary system N-methyl-2-methy-2-pyrrolidone−[C4mim][BF4]. Datasets S162 and S200 for the binary system ethanol−[C1mim][DMP] show activation energies in reasonable agreement even though the viscosity measurements themselves differ. For dataset S200 the viscosities are by about 10 % lower than for dataset S162 for xIL = 0.2 and xIL = 0.4 but about 25 % higher for xIL = 0.8 and 5 % to 10 % higher for the neat IL. Possibly, the xIL values for dataset S200 are somewhat inaccurate, which might explain the slight S-shape in the Ea(xIL) graph that is even more accentuated in the ln A(xIL) graph. As just illustrated, plots of the obtained Ea(xIL) and ln A(xIL) can serve indeed as a quick quality check revealing questionable datasets even if their R2 values for the Arrhenius temperature dependences at each mole fraction are all close to 1. Notably, datasets by Kavitha et al. published in two articles31,32 tend to show very large scatter for Ea(xIL) (see datasets S88 to S91 and S164 to S167). Datasets S93 and S105 also show large scatter with one particular clear outlier in dataset S105. Finally, we note that datasets S63−S65 have only precision to 1 mPa·s in their reported viscosity values, which approaches the measurement values themselves for the waterrich compositions of the binary system IL−water systems especially at higher temperatures. IL and Water. The viscosity temperature dependence of neat water33 shows slight non-Arrhenius behavior and therefore activation energies vary between 14.3 kJ·mol−1 and 17.7 kJ·

presence of outliers as observed in the following datasets (see dataset tables in Supporting Information): S2 for xIL = 0.1, 0.3, and 0.4; S3 for xIL = 0.2), S30 for xIL = 0.0083, 0.0374 and 0.0770; and S136 for xIL = 0.1022. The general Arrhenius behavior could certainly be attributed to the relatively limited temperature range of typically less than 50 K over which the viscosities were investigated. However, there are (only) two datasets (datasets S143 and S144) where clearly non-Arrhenius behavior is indicated both of which were reported by Guo et al. and involve methylbenzene (i.e., toluene) as the molecular solvent with [C4mim][BF4] and [C4mim][BF6].29 One additional dataset (S148) also shows poor R2 values but in this case this may be due to experimental error as only three temperatures were investigated and the reported viscosities show inconsistent changes with increasing temperature, decreasing by about one-third of the value from 298.15 K to 303.15 K but then by much less from 303.15 K to 308.15 K. It is interesting that the Arrhenius behavior holds also very well for the viscosity temperature dependence of binary molecular solvent−IL systems with IL cations that are very symmetric such as datasets S1 to S4 for imidazolium octanoate, S97 to S100 for 1-methylimidazolium based ILs, S123 to S125 for trimethylammonium based ILs, S126 to S130 for trimethylammonium bis(trifluoromethylsulfonyl)amide, and S161, S162, and S199 to S202 for 1,3-dimethylimidazolium dimethylphosphate. It was pointed out that the viscosity temperature dependence of ILs with symmetric cations would tend to deviate from Arrhenius behavior compared to asymmetric ILs.10 Apparently, this is not generally true in the case of binary systems. In Tables S1 to S3 are shown the chemical structures and identifications of molecular solvent, anion, and cation, and Table 3 lists the full names of the ILs. Tables 4 to 8 summarize the Arrhenius analysis results. Binary systems where Ea(xIL) and ln A(xIL) appear to be linear over the entire composition range are listed in Table 4, and linear for the measured (limited) composition range in Table 5. Table 6 lists those binary systems where Ea(xIL) and ln A(xIL) are found to be linear only over a limited composition range, and the range of compositions is included in Table 6. Table 7 lists those binary systems that clearly do not show linear Ea(xIL) and ln A(xIL), and Table 8 lists those systems for which a classification determination was not possible because of a limited composition range and/or too large scatter. We nevertheless included also in Tables 7 and 8 the Arrhenius analysis results to provide some sense of how poor the resulting fits (or F

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 5. Solvent−IL Binary Systems That Show Linear Ea(xIL) and ln A(xIL) over Investigated xIL-Range with Corresponding Fit Parameters for Slope m, Intercept b, and Standard Deviation σ of the Linear Fit to the Data. A Is in Units of mPa−1·s−1 Ea(xIL) T-range Dataset

Solvent

IL

S106

H2O

[N4,0,0,0][NO3]

S13

H2O

S14

H2O

S161

H2O

[C4mim] [N(CN)2] [C4mim] [C(CN)3] [C0mim][DMP]

S65

H2O

[C2mim][TFA]

S64

H2O

[C2mim][TfO]

S67

H2O

[N2,2,1,0][C1SO3]

S9

H2O

S11

H2O

S10

H2O

S12

H2O

S212

H2O

S97

C1OH

S111

C1OH

[C4mim] [C0SO4] [C2mim] [C1SO4] [C4mim] [C1SO4] [C2mim] [C2SO4] [C2mMor] [C2SO4] [C0mim] [C1CO2] [C4mPyr][NTf2]

S53

C2OH

[C8mim][NO3]

S162

C2OH

[C0mim][DMP]

S98

C2OH

S54

C3OH

[C0mim] [C1CO2] [C8mim][NO3]

S99

C3OH

S55

C4OH

[C0mim] [C1CO2] [C8mim][NO3]

S118

TFE

[C4mim][NTf2]

S112

CH3CN

[C4mPyr][NTf2]

S206

DMF

[C2mim]Cl

S207

DMF

[C4mim]Cl

S208

DMF

[C6mim]Cl

S209

DMF

[C8mim]Cl

S19

DMF

[C6mPyr][NTf2]

S86

uracil

S143

toluene

[C2mim] [C1CO2] [C4mim][BF4]

S144

toluene

[C4mim][PF6]

S87

adenine

S134

[C2mim] [C2SO3]

[C2mim] [C1CO2] [N0,0,0,0][[SCN]

K 293.15 to 313.15 278.15 to 358.15 278.15 to 358.15 298.15 to 323.15 278.15 to 348.15 278.15 to 348.15 278.15 to 288.15 293.15 to 313.15 278.15 to 338.15 293.15 to 343.15 283.15 to 343.15 298.15 to 343.15 293.15 to 313.15 288.15 to 308.15 283.15 to 333.15 298.15 to 323.15 293.15 to 313.15 283.15 to 333.15 293.15 to 313.15 283.15 to 333.15 278.15 to 333.15 288.15 to 308.15 288.15 to 318.15 288.15 to 318.15 288.15 to 318.15 288.15 to 318.15 300.15 to 325.15 298.15 to 313.15 298.15 to 338.15 298.15 to 338.15 298.15 to 313.15 298.15 to 323.15

mEa xIL-range 0.10 to 1.00 0.52 to 1.00 0.44 to 1.00 0.25 to 1.00 0.07 to 1.00 0.06 to 1.00 0.29 to 0.63 0.10 to 0.99 0.11 to 1.00 0.10 to 1.00 0.10 to 1.00 0.00 to 0.81 0.05 to 0.90 0.21 to 0.71 0.13 to 1.00 0.20 to 1.00 0.05 to 0.89 0.13 to 1.00 0.05 to 0.90 0.15 to 1.00 0.13 to 0.91 0.19 to 0.82 0.00 to 0.18 0.00 to 0.15 0.00 to 0.72 0.00 to 0.59 0.30 to 1.00 0.00 to 0.22 0.67 to 0.95 0.60 to 0.95 0.00 to 0.21 0.00 to 0.30

kJ·mol−1

bEa

ln A(xIL) σEa

kJ·mol−1 kJ·mol−1

R2Ea

mln A

bln A

σln A

R2ln A

ref.

15.03

14.99

1.65

0.99

1.94

5.40

0.99

0.75

53

9.08

17.21

0.32

0.99

1.46

5.55

0.24

0.88

79

8.93

17.97

1.25

0.94

1.79

5.72

0.44

0.84

79

14.41

30.36

1.24

0.92

3.29

9.07

0.40

0.86

80

13.87

12.37

1.88

0.97

3.42

3.50

0.54

0.96

7

16.72

8.48

0.60

1.00

4.18

2.19

0.36

0.99

7

15.17

20.24

0.09

1.00

2.80

6.31

0.02

1.00

81

35.94

19.39

4.21

0.98

7.38

6.09

0.75

0.99

82

13.83

18.44

1.07

0.99

2.06

6.17

0.69

0.87

82

19.11

20.05

1.38

0.99

3.58

6.52

0.46

0.98

82

14.63

18.57

1.24

0.99

2.43

6.11

0.81

0.87

82

36.55

18.33

9.19

0.94

8.12

6.19

2.54

0.92

51

13.82

10.66

0.63

1.00

3.21

4.49

0.30

0.99

83

22.26

13.85

0.64

0.99

4.71

5.03

0.09

1.00

84

40.06

9.64

3.21

0.99

10.12

3.30

1.44

0.97

85

33.38

10.48

0.76

0.99

8.91

3.08

0.31

0.99

80

8.73

14.04

0.93

0.98

1.71

5.46

0.47

0.91

83

37.48

11.82

4.47

0.98

9.47

3.79

1.95

0.94

85

6.03

16.86

0.89

0.97

1.11

6.18

0.39

0.85

83

37.12

12.13

3.38

0.99

9.50

3.78

1.42

0.97

85

15.59

14.87

0.88

0.99

2.94

5.16

0.54

0.93

86

29.95

7.10

0.57

1.00

7.18

2.98

0.05

1.00

84

32.44

8.81

0.82

0.99

5.86

3.73

0.36

0.93

87

45.48

8.64

1.46

0.97

10.41

3.63

0.58

0.92

87

47.55

8.97

3.68

0.99

11.82

3.60

1.41

0.98

87

40.77

9.52

2.40

0.99

10.17

3.70

0.78

0.98

87

23.16

7.93

2.70

0.97

5.28

2.49

0.79

0.95

9

103.73

37.22

0.42

1.00

30.76

10.20

0.14

1.00

88

62.33

48.52

1.00

1.00

22.62

18.03

0.36

1.00

89

98.07

35.48

2.35

0.99

35.72

13.21

0.85

0.99

89

105.23

37.12

0.16

1.00

31.91

10.18

0.07

1.00

88

−1.40

42.70

0.40

0.50

−2.60

11.90

0.20

0.90

90

G

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 6. Solvent−IL Binary Systems That Show Linear Ea(xIL) and ln A(xIL) over Parts of the Investigated xIL-Range As Indicated with Corresponding Fit Parameters for Slope m, Intercept b, and Standard Deviation σ of the Linear Fit to the Data. A Is in Units of mPa−1·s−1 Ea(xIL) T-range Dataset

Solvent

IL

K 298.15 to 343.15 298.15 to 343.15 298.15 to 343.15 298.15 to 343.15 298.15 to 338.15 298.15 to 348.15 298.15 to 338.15 298.15 to 343.15 298.15 to 343.15 298.15 to 343.15 293.15 to 308.15 293.15 to 353.15 303.15 to 328.15 215.15 to 358.15 298.15 to 343.15 278.15 to 348.15 313.15 to 343.15 293.15 to 323.15 298.15 to 343.15 298.15 to 343.15 298.15 to 328.15 298.15 to 328.15 298.15 to 328.15 298.15 to 348.15 293.15 to 323.15 298.15 to 328.15 298.15 to 328.15 293.15 to 323.15 293.15 to 323.15 298.15 to 328.15 293.15 to 353.15 293.15 to 318.15

S41

H2O

[C4mim]Cl

S196

H2O

[C3mPyr]Br

S197

H2O

[C4mPyr]Br

S198

H2O

[C5mPyr]Br

S137

H2O

[C4mim][SCN]

S139

H2O

[C4mPyr][SCN]

S138

H2O

[C4-4-mPy][SCN]

S115

H2O

S114

H2O

S101

H2O

[C4mPyr][N (CN)2] [C4mPip][N (CN)2] [C2mim][C1CO2]

S105

H2O

[N4,0,0,0][C1CO2]

S140

H2O

S74

H2O

[C2OHN(C1)3] [lact] [TMG][lact]

S215

H2O

[C4mim][C1SO3]

S5

H2O

[C2mim][C2SO4l

S63

H2O

[C2mim][C2SO4]

S213

H2O

[C2mPyr][C2SO4]

S3

C1OH

[Im][C7CO2]

S104

C2OH

S103

C2OH

[C2mim][N (CN)2] [C2mim][C1CO2]

S7

C2OH

[C2Py][C2SO4]

S6

C2OH

S29

C3OH

[C2-3-mPy] [C2SO4] [C8mim][Cl]

S22

C3OH

[C4mim][SCN]

S201

C3OH

[C1mim][DMP]

S8

C3OH

[C2Py][C2SO4]

S31

C3OH

[C2mim][C2SO4]

S4

C8OH

[Im][C7CO2]

S202

[C1mim][DMP]

S152

2propanol 2propanol PEG 200

S178

PC

[C4mpyr][NTf2]

S32

[C2mim][C2SO4] [C4mPyr][C4SO4]

mEa xIL-range

bEa

ln A(xIL) σEa

kJ·mol−1 kJ·mol−1 kJ·mol−1

R2Ea

mln A

bln A

σln A

R2ln A

ref

0.04 to 0.43

46.01

16.07

1.04

1.00

8.52

6.04

0.45

0.98

47

0.10 to 0.35

45.11

21.12

0.44

1.00

8.66

7.63

0.27

0.97

91

0.09 to 0.33

57.97

19.14

0.72

1.00

12.67

6.96

0.24

0.99

91

0.09 to 0.45

53.31

20.87

0.97

1.00

11.32

7.43

0.31

0.99

91

0.28 to 1.00

9.96

17.71

1.48

0.96

1.56

5.66

0.68

0.71

92

0.13 to 1.00

9.53

20.66

0.72

0.99

0.60

6.73

0.51

0.51

92

0.23 to 1.00

14.85

17.72

0.97

0.99

3.07

5.60

0.51

0.95

92

0.16 to 1.00

0.91

20.64

0.87

0.51

−1.24

6.34

0.60

0.80

93

0.09 to 1.00

12.02

20.49

1.52

0.98

1.78

6.42

0.54

0.91

93

0.19 to 1.00

11.88

25.11

1.23

0.99

2.31

7.64

0.81

0.85

14

0.06 to 1.00

26.93

21.35

12.82

0.81

4.95

6.95

4.94

0.50

94

0.30 to 1.00

17.96

27.39

1.56

0.98

3.82

8.05

0.26

0.99

50

0.19 to 1.00

64.73

27.79

1.30

1.00

18.46

8.53

0.28

1.00

8

0.20 to 0.44

19.10

19.68

0.25

0.99

2.43

6.38

0.09

0.96

17

0.21 to 1.00

14.67

21.28

0.91

0.99

2.73

6.68

0.50

0.95

95

0.23 to 1.00

19.00

14.28

0.79

1.00

4.78

3.96

0.28

0.99

7

0.35 to 1.00

6.95

22.97

0.45

0.99

0.24

6.83

0.13

0.49

51

0.40 to 1.00

32.39

0.63

0.27

1.00

10.31

−1.29

0.20

1.00

96

0.82 to 1.00

8.12

10.88

0.63

0.99

0.97

3.89

0.39

0.83

14

0.25 to 1.00

29.78

7.48

1.22

1.00

7.78

2.29

0.70

0.99

14

0.20 to 1.00

20.94

10.65

2.26

0.98

4.24

3.64

0.91

0.93

95

0.30 to 1.00

29.06

7.69

1.30

1.00

7.48

2.28

0.65

0.98

95

0.28 to 1.00

79.03

−1.36

5.47

0.99

22.28

−0.82

2.05

0.98

97

0.25 to 0.93

11.49

14.37

0.61

0.99

2.06

4.66

0.25

0.96

52

0.20 to 1.00

34.42

10.52

2.07

0.99

9.47

2.82

0.94

0.98

54

0.20 to 1.00

18.12

13.11

1.61

0.99

3.51

4.22

0.73

0.93

95

0.20 to 1.00

19.55

12.65

1.19

0.99

4.26

4.05

0.64

0.96

98

0.10 to 1.00

14.23

19.11

0.93

0.99

3.41

5.67

0.40

0.98

96

0.20 to 1.00

33.08

13.14

2.89

0.99

9.03

3.64

1.19

0.97

54

0.28 to 1.00

18.90

13.45

0.94

0.99

4.26

4.13

0.55

0.96

98

0.00 to 0.41

7.05

28.61

0.40

0.97

0.83

7.64

0.11

0.86

99

0.21 to 1.00

15.80

17.04

1.60

0.99

3.69

5.37

0.39

0.99

100

H

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 6. continued Ea(xIL) T-range Dataset

Solvent

IL

S125

DMSO

[N1,1,1,0][DHP]

S124

DMSO

[N1,1,1,0][C0SO4]

S147

DMSO

[N1,1,1,0][DHP]

S146

DMSO

[N1,1,1,0][C1CO2]

S148

DMSO

[N1,1,1,0][C0SO4]

K 298.15 to 313.15 298.15 to 313.15 298.15 to 308.15 298.15 to 308.15 298.15 to 308.15

mEa xIL-range

bEa

ln A(xIL) σEa

kJ·mol−1 kJ·mol−1 kJ·mol−1

R2Ea

mln A

bln A

σln A

R2ln A

ref

0.23 to 1.00

5.01

16.64

1.12

0.95

1.03

5.65

0.34

0.90

101

0.20 to 1.00

15.06

8.87

0.64

1.00

5.47

2.49

0.36

1.00

101

0.11 to 1.00

14.18

5.50

1.47

0.99

3.16

0.51

0.72

0.96

102

0.36 to 1.00

3.23

27.65

0.50

0.96

−0.07

9.30

0.09

0.26

102

0.42 to 1.00

3.76

37.23

0.73

0.91

−0.29

11.38

0.17

0.52

102

mol−1 depending on the investigated temperature range. However, upon close inspection of the binary IL−water datasets there are several datasets showing viscosities for water that increasingly deviate from known values at higher temperatures.33 Specifically, viscosities of datasets S114 to S115, S137 to S139, and S211 to S213 are increasingly larger by up to about 15 %, then accepted values resulting in activation energies lower by about 3 kJ·mol−1. Nevertheless, even for these datasets a general behavior becomes apparent that Ea(xIL) and ln A(xIL) only deviate clearly from linearity for xIL less than about 0.2 (datasets S5, S44, S101 to S102, S105, S114 to S115, S137 to S140, S161, S196 to S198, S214) or are, within data scatter, completely linear over the entire (investigated) composition range (datasets S9 to S14, S40, S43 to S44, S58, S102, S106, S141, S211, S212 to S213). For datasets S42, S66, S74 to S77, S94 to S95, S142, S163 there are unfortunately either too few compositions measured over a limited xIL range or the data is too scattered to clearly discern any trends. Dataset S72 investigates the highly dilute region, 0 < xIL < 0.03, but the activation energies are more than 6 kJ·mol−1 smaller than the Ea value of 14.9 kJ·mol−1 for pure water over the measured temperature range. Dataset S67 is also measured over a limited xIL-range but is clearly linear in Ea(xIL) and ln A(xIL). Dataset S213 shows large scatter for Ea(xIL) and ln A(xIL) for 0 < xIL < 0.2 but appears to be linear at higher xIL. Datasets S63 to S65, which have been measured with precision of only 1 mPa·s, also appear to be clearly linear Ea(xIL) and ln A(xIL) (for S64 when xIL > 0.2), but extrapolating visually to xIL = 0 results in viscosity activation energies for neat water that are clearly too low. Similar can be said for dataset S142 and finally, dataset S41 has one value for Ea of 11.4 kJ·mol−1 at xIL = 0.0115 that is below the Ea value of 14.9 kJ·mol−1 for pure water over the measured temperature range. Thus, notwithstanding the possible presence of erroneous data points in some of the just discussed datasets for water−IL binary systems, Ea(xIL) and ln A(xIL) appear to be generally linear over a wide range of xIL, typically at least as low as xIL = 0.2 if not the entire concentration range regardless of IL cation or anion structure. This may reflect what has been noted in other works that the addition of water to ILs does not change significantly the principle structural architecture of the IL until very high amounts of water are present.11,34,35 Also, ILs with long aliphatic side chains in their cation are essentially cationic surfactants that are known to form micelles at a particular critical micelle concentration (cmc) in aqueous solutions. The cmc manifests itself in a well-defined trend change in spectroscopic or physical properties including the solution

viscosity as shown in several works for aqueous IL solutions.36−38 There are, however, a few types of ILs that show different behavior. ILs with the less polar octanoate (C7CO2−, dataset S1), dimethyl phosphate (DMP, datasets S46 and S49) and the bis(trifluoromethylsulfonyl)amide (NTf2]−, dataset S184) anions show positive deviation from linearity for Ea(xIL) and ln A(xIL). With respect to this behavior, it is important to note that viscosities of binary systems at experimental conditions of composition and temperature near a critical point of phase separation are enhanced due to fluctuations in the mode coupling wavenumber. This criticality effect has been studied by the Schröer group for the binary system [C6mim][BF4]−1pentanol.39 It is quite possible that the binary systems of datasets S1, S46, S49, and S184 are near a miscibility gap because, for example, [NTf2]− type ILs are generally more hydrophobic, and Heintz et al. observed upper consulate temperatures for this IL with much less polar alcohols: 340 K for 1-pentanol, 320 K for 1-butanol, and 293 K 1-propanol.40 Larger viscosity values due to the criticality effect would result in a much steeper reduction of viscosity with temperature and correspondingly larger activation energies as is observed for these datasets. This leaves datasets S56 and S57 with [BF4]− ILs that are the only binary water−IL dataset with a slight but distinct negative deviation from linearity for Ea(xIL) and ln A(xIL), while such negative deviation is much more frequently observed in other IL−molecular solvent systems including IL−methanol systems we discuss in the next subsection. These deviations from linearity for Ea(xIL) and ln A(xIL) seem to become less from [C2mim][BF4] in dataset S56 to [C4mim][BF4] in dataset S57 and diminished for [C6mim][BF4] in dataset S58. IL−Methanol Binary Systems. Using the critically reviewed and evaluated viscosity data for pure methanol published by Xiang, pure methanol follows very closely the Arrhenius equation resulting in an activation energy of about 10.5 kJ·mol−1.41 Datasets S20, S47, S50, S68, S78, S107, S131, and S199, report viscosity values for pure methanol that slightly deviate from the recommended values leading to activation energies that are typically lower than 10.5 kJ·mol−1. Of these datasets, the graphs of Ea(xIL) and ln A(xIL) for dataset S131 in the Supporting Information are particularly peculiar showing an abrupt, seemingly unphysical increase between neat methanol and xIL = 0.05 and then a relatively flat xIL-dependence at about 45 kJ·mol and 14, respectively. A larger portion of the IL−methanol binary systems than for the IL−water systems shows within data scatter linearity for Ea(xIL) and ln A(xIL) over the entire xIL-range: datasets S20, I

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 7. Solvent−IL Binary Systems That Show Nonlinear Ea(xIL) and ln A(xIL) with Corresponding Fit Parameters for Slope m, Intercept b, and Standard Deviation σ of the Linear Fit to the Data. A Is in Units of mPa−1·s−1 Ea(xIL) dataset

solvent

IL

S56 S57 S46 S49 S1 S184 S27 S181 S34 S36 S38 S174 S131 S30 S21 S28 S35 S37 S39 S132 S45 S168 S133 S171 S71 S100 S172 S173 S23 S24 S25 S26 S16 S187 S188 S189 S203 S151 S150 S113 S82 S123

H2O H2O H2O H2O H2O H2O C1OH C1OH C1OH C1OH C1OH C1OH C1OH C1OH C2OH C2OH C2OH C2OH C2OH C2OH C2OH C3OH C3OH C4OH C4OH C4OH C5OH C6OH C7OH C8OH C9OH C10OH EG 1,2-C3diol 1,2-C4diol 2,3-C4diol acetone Me2NH formamide MDEA NMP DMSO

[C2mim][BF4] [C4mim][BF4] [C2mim][DMP] [C4mim][DMP] [Im][C7CO2] [LiChelate][NTf2] [C8mim]Cl [C4mim][BF4] [C4Py][BF4] [C4-3-mPy][BF4] [C4-4-mPy][BF4] [C4-4-mPy][BF4] [(C2OH)2NC1H][C0CO2] [C2mim][C2SO4] [C4mim][SCN] [C8mim][Cl] [C4Py][BF4] [C4-3-mPy][BF4] [C4-4-mPy][BF4] [(C2OH)2NC1H][C0CO2] [C2mim][C2SO4] [C6mim][BF4] [(C2OH)2NC1H][C0CO2] [C4mim][SCN] [C2Pip] [C0mim][C1CO2] [C4mim][SCN] [C4mim][SCN] [C4mim][SCN] [C4mim][SCN] [C4mim][SCN] [C4mim][SCN] [C4mim][BF4] [N4,1,1,1][NTf2] [N4,1,1,1][NTf2] [N4,1,1,1][NTf2] [C4mim][BF4] [N8,8,8,1]Cl [N8,8,8,1]Cl [C4mim][C1CO2] [C2mim][NTf2] [N1,1,1,0][C1CO2]

ln A(xIL)

T-range

mEa

bEa

σEa

K

kJ·mol−1

kJ·mol−1

kJ·mol−1

R2Ea

mln A

bln A

σln A

R2ln A

ref

10.07 18.95 52.04 30.64 16.40 32.17 67.79 23.49 26.03 31.70 31.58 30.67 11.24 12.63 11.69 71.28 25.35 27.17 27.67 10.17 18.90 13.47 9.22 9.84 21.24 5.67 9.01 7.22 5.60 4.28 3.59 2.80 4.31 −7.29 −10.80 −10.80 28.74 46.16 33.35 8.48 6.43 6.99

14.38 15.96 19.45 22.36 18.98 37.60 5.08 7.85 11.94 7.34 8.49 9.21 37.02 15.87 14.89 8.13 11.58 11.74 12.47 38.02 12.41 21.82 38.76 16.61 39.35 18.05 17.56 19.52 21.19 22.75 23.66 25.05 25.29 30.75 34.71 34.71 4.19 11.72 25.58 34.40 6.40 9.68

4.58 4.36 7.55 10.71 5.24 49.09 13.65 4.80 6.54 10.16 8.12 6.46 34.26 18.26 10.43 14.04 6.00 9.14 6.71 28.32 4.38 3.86 24.26 4.38 24.98 2.00 4.18 3.49 3.62 3.08 2.47 2.94 5.20 5.70 4.38 4.38 5.06 8.10 11.90 6.01 1.46 8.89

0.84 0.96 0.88 0.85 0.91 0.39 0.98 0.96 0.96 0.94 0.96 0.96 0.14 0.40 0.62 0.97 0.97 0.93 0.96 0.16 0.96 0.76 0.18 0.86 0.44 0.86 0.86 0.85 0.77 0.71 0.71 0.55 0.38 0.64 0.84 0.84 0.97 0.97 0.87 0.58 0.96 0.56

0.60 3.48 9.67 6.51 3.72 5.32 16.95 4.43 5.11 7.24 7.08 6.48 0.23 0.17 1.07 18.09 5.43 6.09 6.05 0.00 3.15 1.00 −0.21 1.01 4.57 1.20 1.00 0.56 0.17 −0.14 −0.19 −0.39 −0.05 −3.72 −4.95 −4.95 5.93 10.14 7.77 5.40 −0.16 2.48

5.59 5.91 6.99 7.64 5.89 12.84 2.52 3.44 5.11 3.32 3.78 4.15 12.48 6.43 5.65 3.37 4.49 4.53 4.86 12.70 4.69 8.07 12.85 5.68 14.11 6.45 5.79 6.31 6.71 7.12 7.25 7.62 7.71 9.10 10.48 10.48 2.46 4.34 7.69 10.28 1.70 3.08

2.15 2.03 1.28 2.08 1.39 15.30 5.68 2.32 2.66 4.26 3.41 2.95 10.47 7.51 4.09 5.20 2.26 3.60 2.65 8.56 2.29 1.61 7.41 1.93 9.08 0.74 1.82 1.50 1.58 1.34 1.12 1.39 1.49 1.88 1.38 1.38 2.62 2.98 2.67 1.84 0.19 3.96

0.72 0.80 0.90 0.87 0.88 0.15 0.94 0.80 0.86 0.82 0.87 0.84 0.00 0.00 0.08 0.94 0.90 0.82 0.89 0.00 0.74 0.09 0.00 0.25 0.22 0.66 0.29 0.15 0.02 0.01 0.03 0.09 0.00 0.81 0.92 0.92 0.85 0.92 0.88 0.86 0.45 0.45

48 48 21 21 96 103 97 67 104 104 104 105 106 98 52 97 104 104 104 106 47 107 106 108 56 83 108 108 109 109 109 109 68 110 110 110 69 111 111 6 112 101

288.15 288.15 293.15 293.15 293.15 313.15 298.15 303.15 293.15 293.15 293.15 298.15 293.15 298.15 298.15 298.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 298.15 278.15 293.15 298.15 298.15 298.15 298.15 298.15 298.15 293.15 323.15 323.15 323.15 393.15 298.15 298.15 293.15 278.15 298.15

to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to

318.15 318.15 333.15 333.15 323.15 333.15 328.15 333.15 323.15 323.15 323.15 323.15 323.15 328.15 348.15 328.15 323.15 323.15 323.15 323.15 303.15 333.15 323.15 348.15 308.15 313.15 348.15 348.15 348.15 348.15 348.15 348.15 353.15 353.15 353.15 353.15 323.15 318.15 318.15 353.15 338.15 313.15

S84 shows too much scatter to allow any classification and datasets S135 to S136 include several questionable data points at low xIL where in particular for dataset S135 for xIL = 0.2 an unphysical negative activation energy is obtained. IL−Ethanol Binary Systems. Just like neat methanol, the viscosity temperature dependence of neat ethanol is also following closely the Arrhenius equation resulting in a value of 13.8 kJ·mol−1.24 A number of datasets that include viscosity measurements of neat ethanol show noticeably higher values (datasets S3, S79, S83, S103 to S104, S108, S193, and S195). A majority of the IL−ethanol binary datasets is showing within data scatter linear Ea(xIL) and ln A(xIL) over the entire xIL-range (datasets S48, S51, S57, S59 to S62, S69, S79, S83, S108, S193, S195, and S200) or at least over a wide xIL-range

S47, S50, S68, S78, S107 and S199, and this includes all ILs with DMP as the anion (datasets S47, S50, and S199). Datasets S97 and S111 also show linearity for Ea(xIL) and ln A(xIL) over the measured xIL-range. All [BF4]− ILs show either negative deviation from linearity for Ea(xIL) and ln A(xIL) (datasets S36, S38, S174, and S181) or an S-shape (dataset S34). Negative deviation from linearity for Ea(xIL) and ln A(xIL) is also observed for dataset S27, the only IL with chloride as anion, and dataset S30, the only IL with ethyl sulfate ([C2SO4]−) as anion, except that dataset S30 is plagued by three clear outliers in the low xIL-range. The negative deviations from linearity might indicate that for these systems interactions between IL and methanol are sufficiently strong to break up or at least lessen the IL−IL and methanol−methanol interactions. Dataset J

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 8. Datasets of Solvent−IL Binary Systems Where Classification of Ea(xIL) and ln A(xIL) Is Undetermined with Corresponding Fit Parameters for Slope m, Intercept b, and Standard Deviation σ of the Linear Fit to the Data. A Is in Units of mPa−1·s−1 Ea(xIL) dataset

solvent

IL

S42 S142 S94 S95 S66 S75 S76 S77 S72 S163 S84 S135 S136 S110 S93 S117 S119 S129 S126 S130 S127 S2 S128 S92 S165 S167 S164 S88 S89 S166 S90 S91 S185 S186 S157 S85

H2O H2O H2O H2O H2O H2O H2O H2O H2O H2O C1OH C1OH C1OH C4OH 2-butanol TFE TFE GBL GBL PC PC C1CN C1CN AP NMP NMP NMP NMP NMP NMP NMP NMP Benzene Benzene Benzene C6H6C1OH

[C6mim]Cl [C2OHN(C1)3]Cl [C4Py][BF4] [C8Py][BF4] [C2mim][C1CO2] [Bu3PC3NH2][Ala] [Bu3PC3NH2][Val] [Bu3PC3NH2][Leu] [C3mim][C1SO4] [C2mim][NTf2] [C4mim][Ala] [C4mim][Glu] [C4mim][Gly] [C4,0,0,0][NO3] [C6mim][BF4] [C4mim][BF4] [C4mim][PF6] [N1,1,1,0][NTf2] [Me3S][NTf2] [N1,1,1,0][NTf2] [Me3S][NTf2] [Im][C7CO2] [Me3S][NTf2] [C6mim][BF4] [N1,1,1,0][DHP] [N2,2,2,0][DHP] [N1,1,1,0][C1CO2] [N2,2,0,0][C1CO2] [N2,2,2,0][C1CO2] [N1,1,1,0][C0SO4] [N2,2,0,0][C0SO4] [N2,2,2,0][C0SO4] [C4mim][SCN] [C4mim][N(CN)2] [C8iQuin][NTf2] [C4mim][Ala]

ln A(xIL)

T-range

mEa

bEa

σEa

K

kJ·mol−1

kJ·mol−1

kJ·mol−1

R2Ea

mln A

bln A

σln A

R2ln A

ref

55.93 30.62 20.19 13.47 11.60 5.83 8.10 11.72 −107.38 15.31 27.48 49.38 8.92 8.76 8.67 13.88 17.49 22.50 28.75 −5.06 7.06 32.84 −18.24 1.91 −14.44 1.81 2.86 10.28 16.23 −2.82 −38.63 −75.39 37.01 9.71 36.33 14.37

16.09 13.58 14.29 24.17 25.00 41.55 33.94 36.47 8.70 8.94 14.12 −7.04 34.14 20.88 26.44 14.87 15.61 14.07 15.52 23.84 23.85 −1.46 23.98 35.57 28.96 31.86 14.71 12.52 8.12 28.62 62.55 92.86 20.75 18.72 9.73 21.72

10.20 2.09 3.75 4.70 0.60 0.56 0.39 0.60 3.44 1.03 9.70 11.57 4.04 5.54 8.73 3.92 1.65 4.77 5.86 3.47 3.06 18.29 3.65 1.65 15.52 25.21 8.20 4.44 15.03 10.70 88.49 163.19 11.74 5.37 8.47 4.81

0.97 0.93 0.92 0.79 0.96 0.89 0.98 0.94 0.54 0.80 0.90 0.92 0.74 0.73 0.50 0.74 0.94 0.70 0.79 0.14 0.43 0.76 0.59 0.64 0.29 0.00 0.05 0.91 0.69 0.03 0.27 0.29 0.87 0.68 0.96 0.91

13.50 1.47 3.95 2.69 1.89 0.61 1.56 2.03 −64.31 4.28 6.49 15.09 −0.85 0.12 −0.27 1.49 2.15 5.65 7.40 −6.16 −1.49 8.22 −15.13 −1.01 −6.32 −2.77 0.85 1.76 4.31 −1.47 −18.36 −35.42 10.21 0.07 8.08 3.09

5.59 5.57 5.08 7.22 7.62 11.78 9.49 10.23 3.75 1.98 5.63 −2.96 13.65 7.21 9.15 5.57 5.83 5.10 5.70 8.94 8.91 −0.37 10.69 11.05 9.40 12.11 4.89 4.41 2.67 9.83 23.25 36.31 8.65 7.89 3.88 7.14

3.78 0.91 1.43 1.69 0.31 0.12 0.07 0.10 1.34 0.41 3.33 4.37 1.62 2.24 3.67 1.43 0.59 1.87 2.35 1.52 1.38 8.19 1.69 0.63 6.75 9.83 3.67 2.03 6.47 4.06 37.17 66.97 4.32 1.86 2.05 1.82

0.93 0.14 0.77 0.54 0.73 0.68 0.98 0.94 0.74 0.65 0.81 0.88 0.14 0.00 0.01 0.20 0.66 0.49 0.61 0.56 0.14 0.50 0.82 0.77 0.29 0.04 0.02 0.59 0.46 0.06 0.32 0.34 0.78 0.00 0.95 0.76

47 50 113 113 81 114 114 114 115 116 58 117 117 53 118 86 86 16 16 16 16 96 16 118 31 31 31 32 32 31 32 32 119 119 71 58

298.15 293.15 283.15 283.15 293.15 298.15 298.15 298.15 298.15 303.15 298.15 298.15 298.15 293.15 303.15 278.15 278.15 298.15 298.15 298.15 298.15 293.15 298.15 303.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 293.15 293.15 298.15 298.15

to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to to

343.15 353.15 343.15 343.15 353.15 343.15 343.15 343.15 328.15 323.15 313.15 313.15 313.15 313.15 308.15 333.15 333.15 343.15 343.15 343.15 343.15 323.15 343.15 308.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 333.15 333.15 348.15 313.15

IL−Propanol Binary Systems. The majority of IL−1propanol binary systems is also showing linear Ea(xIL) and ln A(xIL) either over the entire xIL-range (datasets S70, S80, S109, and S194) or for 0.2 < xIL < 1.0 (datasets S8, S22, S29, S31, and S201) where the deviations from linearity at xIL < 0.2 tend to be positive, which is just the opposite behavior to what is observed for IL−water binary systems. The deviations from linearity at xIL < 0.2 to larger values is also observed for the two binary datasets with 2-propanol (datasets S32 and S202). The datasets S54 and S99 do not cover the entire xIL-range but appear to be linear at least for high xIL values. This leaves two datasets S133 and S168 that do not show linearity for Ea(xIL) and ln A(xIL) but both datasets are questionable. Dataset S133 shows the same peculiar graphs as discussed for S131 and S132 in the IL−methanol and IL−ethanol subsections, and dataset S168 shows an activation energy for neat 1-propanol of 26.04 kJ·mol−1 while all other 1-propanol containing datasets are showing activation energy values for neat 1-propanol close to

typically for 0.2 < xIL < 1.0 (datasets S6 to S7, S45, S53 S98, S103 to S104, and S162). For datasets S3 and S83 the scatter in the Ea(xIL) and ln A(xIL) graphs is large at low xIL but Ea(xIL) and ln A(xIL) appear to be linear at least over a wide range at high xIL. Datasets S79 and S200 could still be classified as having linear Ea(xIL) and ln A(xIL) although some slight negative deviations from linearity might be present. The binary systems with [BF4]− ILs show again negative deviation from linearity in Ea(xIL) and ln A(xIL) for datasets S37 and S39 or Sshaped deviation for S35 although possibly inaccurate data points for xIL = 0.05 and xIL = 0.10 in this particular dataset make this distinction difficult. Negative deviation from linearity in Ea(xIL) and ln A(xIL) is also indicated for the IL−ethanol binary systems with [C8mim]Cl (datasets S28), [C2mim][C2SO4] (S45) and possibly [C4mim][SCN] (S21) although this dataset is plagued by a couple of clear outliers. This leaves dataset S132, which has that same peculiar behavior as discussed for dataset S131 in the IL−methanol binary system subsection. K

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

the expected value of 18.2 kJ·mol−1 based on established viscosity data for 1-propanol.24 IL Binary Systems with Butanol and Longer Chained Alcohols. For the IL binary systems with 1-butanol and longer chained alcohols there seems to be a stronger differentiation between the anion type of the ILs. ILs with acetate (datasets S81, S100) and thiocyanate (datasets S23 to S26 and S171 to S173) show at least a slight negative deviation from linearity for Ea(xIL) and ln A(xIL), regardless of cation alkyl chain length, while ILs with the [NTf2]− anion show linearity over the entire composition range (datasets S120 to S121). ILs with nitrate also appear to display linear Ea(xIL) and ln A(xIL) over a wide range of xIL (dataset S55). Dataset S4 for imidazolium octanoate and octanol also shows linearity for Ea(xIL) and ln A(xIL) for all data points except that of the neat octanol, which however shows an Ea value by about 5 kJ·mol−1 higher than expected from accepted viscosities from the literature of 24.6 kJ·mol−1.24 Dataset S71 is the only dataset that shows very large positive deviations from linearity for Ea(xIL) and ln A(xIL). Dataset S93 and dataset S110 for a binary system with 2butanol and 1-butanol, respectively, are too scattered for any classification. IL Binary Systems with Diols or Polyethylene Glycols. For diols (datasets S16, S187 to S189), which are fairly viscous molecular solvents, Ea(xIL) and ln A(xIL) tend to show a slight negative curvature, but PEG 200 and PEG 400 systems (datasets S153 to S155) as well as MPEG 350 (dataset S156) seem to be more linear again except for dataset S152, which shows linearity in the Ea(xIL) and ln A(xIL) at low xIL but then shows an unusual behavior of large negative deviation from linearity between 0.4 < xIL < 1.0. IL Binary Systems with Ketone Type Solvents. Linear Ea(xIL) and ln A(xIL) over the entire composition range are indicated for binary systems with methyl methacrylate (dataset S33), butanone (dataset S204) and for one of the three binary systems with gamma-butyrolactone (dataset S210), while two other datasets (S126 and S129) with this molecular solvent only measured compositions for xIL < 0.5 that appear to show linear Ea(xIL) and ln A(xIL) except that extrapolation to the xIL = 0 would result in much larger values than Ea(xIL) and ln A(xIL) for the neat molecular solvent. Therefore, a classification is too uncertain. Dataset S203 with acetone shows some negative deviation from linearity for Ea(xIL) and ln A(xIL). ILs−Propylene Carbonate Binary Systems. The datasets S127 and S130 for propylene carbonate systems are problematic insofar that viscosities of neat propylene carbonate disagree significantly from literature42 as well as the other propylene carbonate datasets (S96, S116, and S178) making their measurements possibly unreliable. Datasets S96 and S116 show largely linear Ea(xIL) and ln A(xIL) within experimental scatter while some deviation from linearity to lower values are observed near neat propylene carbonate for dataset S178. ILs−Acetonitrile Binary Systems. For acetonitrile there are two datasets of binary systems showing linearity for Ea(xIL) and ln A(xIL) over the entire xIL-range except for some minor deviations near neat acetonitrile (S18, S179) and one dataset showing linear Ea(xIL) and ln A(xIL) for the entire measured xIL-range (S112). In contrast, the two binary systems S2 and S128 show deviations from linearity for the acetonitrile-rich compositions. However, both of these datasets appear to be erroneous at these acetonitrile rich compositions showing Ea values of 11.86 kJ·mol−1 and 26.27 kJ·mol−1 for neat

acetonitrile while Ea should be near 7 kJ·mol−1 based on published viscosity data of acetonitrile.43 Therefore, a classification of these two datasets is not possible with the available data. IL Binary Systems with Formamide and Related Molecular Solvents. For binary systems with formamide and related solvents, linear Ea(xIL) and ln A(xIL) over the entire composition range or the entire measured composition range are indicated for all binary systems with N,N-dimethylformamide (S19 and S205 to S209), N,N-dimethylacetamide (dataset S180), and uracil (dataset S86). Only dataset S150 for formamide shows deviations from linearity for xIL < 0.2. IL−N-Methyl-2-pyrrolidone Binary Systems. Unfortunately, most of the available datasets (datasets S88 to S91 and S164 to S167) are of poor quality and unreliable as pointed out in the above general comments subsection. This only leaves three datasets, two of which clearly show linear Ea(xIL) and ln A(xIL) (datasets S73 and S182, both for the same IL). Dataset S82 seems to deviate from linearity especially at lower xIL values except that the dataset S82 may be inaccurate because the Ea value for neat N-methyl-2-pyrrolidone is with 5.53 kJ· mol−1 significantly below the value of about 12 kJ·mol−1 one obtains from other published viscosities of the neat molecular solvent.43 IL−Dimethyl Sulfoxide Binary Systems. Eight datasets are reported with dimethyl sulfoxide. Unfortunately, only datasets S15 and S17 for [BF4]− type ILs cover a wide temperature range, and these two show linear Ea(xIL) and ln A(xIL) over the entire composition range. Datasets S123 to S125 cover a temperature range of 15 K with four measurements for binary systems with trimethyammonium ILs with varying anion. Differentiated behavior by the IL anion is indicated. In the case of dihydrogen phosphate and hydrogen sulfate linear Ea(xIL) and ln A(xIL) are observed between 0.2 < xIL < 1 but Ea(xIL) and ln A(xIL) deviate to higher values for xIL < 0.2 for hydrogen sulfate (dataset S124) but to lower values for dihydrogen phosphate (dataset S125). In the case of acetate (dataset S123), negative deviation from linearity for Ea(xIL) and ln A(xIL) is observed. The same authors reporting datasets S123 to S125 also measured viscosities for the corresponding triethylammoniom ILs (datasets S146 to S148) but unfortunately at only three temperatures over a narrow range of 10 K, which hampers accuracy for Ea(xIL) and ln A(xIL) especially for dataset S148 where viscosities decrease substantially from 298.15 K to 303.15 K but then only slightly from 303.15 K to 308.15 K. Nevertheless, linear Ea(xIL) and ln A(xIL) is only indicated for high xIL values for datasets S146 to S148. IL Binary Systems with Aromatic Solvents. Linear Ea(xIL) and ln A(xIL) within data scatter are indicated for IL binary system with thiophene (datasets S145 and S160), benzothiophene (dataset S183), pyridine (S159), toluene (S142 and within shown xIL-ranges datasets S143 to S144), 2 phenylethanol (dataset S122), and adenine (within shown xILrange dataset S87). Dataset S85 with phenyl methanol and all three datasets with benzene (S157, S185, S186) show too much scatter to clearly discern linearity for Ea(xIL) and ln A(xIL), although at least for datasets S85 and S157 this seems to be indicated. IL Binary Systems with Other Molecular Solvents. For the three datasets S117−S119 with trifluoroethanol differentiation by the anion is observed. For the binary system with [C4mim][NTf2] (dataset S118) Ea(xIL) and ln A(xIL) are linear over the measured composition range of 0.12 < xIL < 0.91, L

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

[C4mim][SCN] with a homologue series of aliphatic alcohols has also been investigated all the way up to decanol (datasets S20 to S26 and S171 to S173). As the alcohol alkyl chain length increases, the polarity of the alcohol decreases, while the increase in molecular weight causes the viscosity and concurrently the activation energy to increase. For decanol the activation energy is as large as for the neat IL, which results in relatively flat functions of Ea(xIL) and ln A(xIL). It can also be observed that a negative deviation of linearity for Ea(xIL) and ln A(xIL) at both ends, that is, small and large xIL, develops for the first members of the homologue series that then persists for the higher members. This could be explained with the disruption of like−like interactions when adding the IL into the alcohol as well as the alcohol into the IL. Dataset S185 for [C4mim][SCN] with benzene has only five data points preventing any deeper interpretation. The viscosity of binary systems with [C4mim][BF4] has been studied with a wide variety of solvents as well as with other ILs, which are already discussed in subsection “Binary Systems with Two ILs”. Besides the binary systems with two ILs, linear Ea(xIL) and ln A(xIL) are also observed with ethanol, acetonitrile, DMF, DMA, NMP, DMSO, and toluene (Datasets S60, S179, S205, S180, S73, S182, S15, and S143, respectively) and deviations from linearity for Ea(xIL) and ln A(xIL) are observed with H2O, C1OH, EG, and acetone (datasets, S56, S181, S16, and S203, respectively). Interestingly, the latter are oxygen-rich compounds with three of them being hydrogen bonding donors and acceptors. On the other hand, Ea(xIL) and ln A(xIL) are linear for [C4mim][BF4] with ethanol as well as for [C6mim][BF4] with water (dataset S58) and [C6mim][BF4] with ethanol (dataset S61), making it inconclusive if these [Cnmim][BF4]-type ILs tend to show deviations from linearity for Ea(xIL) and ln A(xIL) in binary systems with molecular solvents that are hydrogen-bonding donors and acceptors. Finally, there is the case of binary systems with Noctylisoquinolinium bis(trifluoromethylsulfonyl)amide as the IL. All seven different molecular solvents (datasets S120 to S122 and S157 to S160) display linearity in Ea(xIL) and ln A(xIL) with this particular IL. However, five of seven molecular solvents contain an aromatic ring, a feature we noted earlier that tends to result in linear Ea(xIL) and ln A(xIL).

while [C4mim][BF4] (dataset S117) and [C4mim][PF6] (datasets S119) appear to show nonlinear Ea(xIL) and ln A(xIL), although indication of linearity to high xIL, which has not been measured, is present, and a clear classification is therefore presently not possible with the available data. This leaves three datasets with amines. Dataset S151 concerning dimethylamine shows deviation from linearity for Ea(xIL) and ln A(xIL) to smaller values except that the values of Ea and ln A for the neat dimethylamine are significantly higher than at xIL = 0.02 the lowest composition measured. Dataset S92 concerning 3amino-1-propanol shows significant scatter especially at smaller xIL compositions making a classification too difficult although Ea(xIL) and ln A(xIL) appear to be linear over the entire composition range. Finally, dataset S113 concerning Nmethydiethanolamine, which is a very viscous substance on its own, shows substantial negative deviation from linearity for Ea(xIL) and ln A(xIL). Binary Systems with Two ILs. There are several studies that have investigated the viscosities of mixed ILs or ILs mixed with mineral salt. The datasets of these mixtures of IL with another IL (datasets S52, S149, S169, S170, S175 to S177, 190 to S192) are all very linear in Ea(xIL) and ln A(xIL), and the same can be said for the mixture of IL with a salt over the investigated composition range (dataset S134). Thus, for mixtures of ILs it appears that viscosities can be correlated from just knowing Ea and ln A for the neat ILs, although of course additional systems should be studied to verify this observation. IL Point of View. To begin with a general comment, it has been noted that the solubility of ILs in other traditional organic solvents is largely influenced by the nature of the anion, where ILs with soft, large anions tend to be hydrophobic, while ILs with hard, small anions tend to be hydrophilic.44,45 Consequently, for example ILs with the soft anion [NTf2]− are found in Tables 4 to 8 mostly with more nonpolar solvents, while ILs with for example the hard chloride as anion are frequently found in combination with water. When perusing Tables 4 to 8 one can find entries for ILs with same anion or with same cation generally in any of Tables 4 to 8. In other words a pattern that an IL with particular anion or particular cation always or never shows linearity for Ea(xIL) and ln A(xIL) in binary system with a molecular solvent is not indicated. This leaves as only hope to discover any structure− property relationships the inspection of same specific ILs with varying solvents. Unfortunately, the viscosity of only a few ILs was investigated with more than a handful of varying molecular solvents, which we will discuss in the following one IL at a time. [C4mim][SCN] with water (dataset S137) shows some positive deviations from linearity for Ea(xIL) and ln A(xIL) for xIL below about 0.4, while with methanol the deviations from linearity appear to be only for xIL below 0.1. The [SCN]− ion has been characterized as a water structure breaker 46 (chaotropic), which should lead to a decrease and not an increase of the activation barrier for viscous shear. However, [C4mim][SCN] is after all miscible with water and the [SCN]− ion might still more strongly interact with the water rather than with the cation, which would shift equilibrium from the paired ion to freely dissociated ions at dilute concentrations. The necessary reorganization of the water solvent around the cation and ion could explain the higher activation energies at low xIL. When the IL is dissolved in the less polar solvent methanol, equilibrium is expected to be shifted toward ion pairing, which would explain why the observed effect is significantly lessened.

■

CONCLUSION The careful inspection of more than 200 datasets with respect to the temperature and composition dependence of viscosity for binary IL containing systems allows the following conclusions. The viscosity temperature dependence at fixed composition in all but a couple of binary systems followed closely Arrhenius-type behavior. The functions of Ea(xIL) and ln A(xIL) were found to be linear over the entire composition range for a large number of binary systems. For those binary systems in which deviations from linearity is observed, these tend to occur mostly for mole fractions of less than 0.2. Even for systems that clearly showed nonlinearity in Ea(xIL) and ln A(xIL), the deviations are not overly excessive. Therefore, for situations where only the viscosity temperature dependence for the neat components is known, at least a reasonable first estimate of Ea and ln A can be obtained for the viscosity of mixtures from the mole fraction weighed Ea and ln A of the neat components. However, this approach should not be tried for binary systems with miscibility gaps because of criticality effects on the mixture’s viscosity. For desired viscosity measurements of binary IL−solvent systems of interest a lot M

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

of measurement time could be saved by first measuring at compositions of xIL = 0.2 and xIL = 0.5 to see if the obtained values of Ea and ln A are close to linearity with the values of Ea and ln A of both neat components or only the IL neat component or neither of them. Only in the latter case more measurements may be warranted. While inspecting carefully the more than 200 datasets, it became also unfortunately apparent that a number of published binary datasets are suspect of containing inaccurate data points. It seems therefore to be a good recommendation to analyze obtained composition- and temperature-dependent viscosity datasets as presented here as a way to check the quality of the obtained datasets. Especially viscosity measurements of very fluid systems may be more challenging and require more care. Calibrations with neat components of established literature values should be done for the range of temperatures to be investigated not only at standard 298.15 K. Especially when dealing with very volatile components, one might consider analyzing for example by spectroscopic methods the sample composition post-measurement to confirm sample composition and purity. With the presented meta-analysis we hope that readers will be encouraged to adopt these experimental precautions in their own research, if they have not already.

■

Determined by the Falling-Ball Method. J. Chem. Eng. Data 2011, 56, 2379−2385. (6) Haghtalab, A.; Shojaeian, A. Volumetric and Viscometric Behaviour of the Binary Systems of N-Methyldiethanolamine and Diethanolamine with 1-Butyl-3-Methylimidazolium Acetate at Various Temperatures. J. Chem. Thermodyn. 2014, 68, 128−137. (7) Rodríguez, H.; Brennecke, J. F. Temperature and Composition Dependence of the Density and Viscosity of Binary Mixtures of Water + Ionic Liquid. J. Chem. Eng. Data 2006, 51, 2145−2155. (8) Tian, S.; Ren, S.; Hou, Y.; Wu, W.; Peng, W. Densities, Viscosities and Excess Properties of Binary Mixtures of 1,1,3,3-Tetramethylguanidinium Lactate + Water at T = (303.15 to 328.15) K. J. Chem. Eng. Data 2013, 58, 1885−1892. (9) Comminges, C.; Barhdadi, R.; Laurent, M.; Troupel, M. Determination of Viscosity, Ionic Conductivity, and Diffusion Coefficients in Some Binary Systems: Ionic Liquids + Molecular Solvents. J. Chem. Eng. Data 2006, 51, 680−685. (10) Blahušiak, M.; Schlosser, Š. Physical Properties of Phosphonium Ionic Liquid and Its Mixtures with Dodecane and Water. J. Chem. Thermodyn. 2014, 72, 54−64. (11) Stark, A.; Zidell, A. W.; Hoffmann, M. M. Is the Ionic Liquid 1Ethyl-3-Methylimidazolium Methanesulfonate [emim][MeSO3] Capable of Rigidly Binding Water? J. Mol. Liq. 2011, 160, 166−179. (12) Stark, A.; Zidell, A. W.; Russo, J. W.; Hoffmann, M. M. Composition Dependent Physicochemical Property Data for the Binary System Water and the Ionic Liquid 1-Butyl-3-Methylimidazolium Methanesulfonate ([C4mim][MeSO3]). J. Chem. Eng. Data 2012, 57, 3330−3339. (13) Jouyban, A.; Soleymani, J.; Jafari, F.; Khoubnasabjafari, M.; Acree, W. E. Mathematical Representation of Viscosity of Ionic Liquid + Molecular Solvent Mixtures at Various Temperatures Using the Jouyban-Acree Model. J. Chem. Eng. Data 2013, 58, 1523−1528. (14) Quijada-Maldonado, E.; van der Boogaart, S.; Lijbers, J. H.; Meindersma, G. W.; de Haan, A. B. Experimental Densities, Dynamic Viscosities and Surface Tensions of the Ionic Liquids Series 1-Ethyl-3Methylimidazolium Acetate and Dicyanamide and Their Binary and Ternary Mixtures with Water and Ethanol at T = (298.15 to 343.15 K). J. Chem. Thermodyn. 2012, 51, 51−58. (15) Haldar, P.; Das, B. Viscosities of Some Tetraalkylammonium Bromides in 2-Ethoxyethanol at 308.15, 313.15, 318.15, and 323.15 K. Can. J. Chem. 2005, 83 (5), 499−504. (16) Couadou, E.; Jacquemin, J.; Galiano, H.; Hardacre, C.; Anouti, M. A Comparative Study on the Thermophysical Properties for Two Bis[(trifluoromethyl)sulfonyl]imide-Based Ionic Liquids Containing the Trimethyl-Sulfonium or the Trimethyl-Ammonium Cation in Molecular Solvents. J. Phys. Chem. B 2013, 117, 1389−1402. (17) Hoffmann, M. M.; Sylvester, E. D.; Russo, J. W. On the Temperature Dependence of Several Physicochemical Properties for Aqueous Solutions of the Ionic Liquid 1-Butyl-3-Methylimidazolium Methanesulfonate ([C4mim][MeSO3]. J. Mol. Liq. 2014, 199, 175− 183. (18) Scharf, N. T.; Stark, A.; Hoffmann, M. M. Ion Pairing and Dynamics of the Ionic Liquid 1-Hexyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)amide ([C6mim][NTf2]) in the Low Dielectric Solvent Chloroform. J. Phys. Chem. B 2012, 116, 11488−11497. (19) Geng, Y.; Wang, T.; Yu, D.; Peng, C.; Liu, H.; Hu, Y. Densities and Viscosities of the Ionic Liquid [C4mim][PF6]+ N,N-Dimethylformamide Binary Mixtures at 293.15 to 318.15 K. Chin. J. Chem. Eng. 2008, 16, 256−262. (20) Litaeim, Y.; Dhahbi, M. Measurements and Correlation of Viscosity and Conductivity for the Mixtures of Ethylammonium Nitrate with Organic Solvents. J. Mol. Liq. 2010, 155, 42−50. (21) Gong, Y.; Shen, C.; Lu, Y.; Meng, H.; Li, C. Viscosity and Density Measurements for Six Binary Mixtures of Water (Methanol or Ethanol) with an Ionic Liquid ([BMIM][DMP] or [EMIM][DMP]) at Atmospheric Pressure in the Temperature Range of (293.15 to 333.15) K. J. Chem. Eng. Data 2012, 57, 33−39.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b00503. Chemical structures of involved solvents, IL anions and cations are provided and the referenced meta-analyzed viscosity datasets are tabulated and plotted(PDF)

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: mhoff[email protected]. Tel.: 585-395-5598. Fax: 585-395-5805. Present Address #

D.R.S.: [email protected], University of Maryland at Baltimore.

Funding

This report is based upon work supported by the National Science Foundation under RUI-Grant No. 0842960. A.H. was supported by an exchange visiting research program of the Iranian Ministry of Science, Research and Technology. Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Wilkes, J. S. A Short History of Ionic Liquids - from Molten Salts to Neoteric Solvents. Green Chem. 2002, 4, 73−80. (2) Chaturvedi, D. Ionic Liquids, a Class of Versatile Green Reaction Media for the Syntheses of Nitrogen Heterocycles. Curr. Org. Synth. 2011, 8, 438−471. (3) Ho, T.-D.; Canestraro, A. J.; Anderson, J. L. Ionic Liquids in Solid-Phase Microextraction: A Review. Anal. Chim. Acta 2011, 695, 18−43. (4) Jiang, Y.; Nadolny, H.; Käshammer, S.; Weibels, S.; Schröer, W.; Weingärtner, H. The Ion Speciation of Ionic Liquids in Molecular Solvents of Low and Medium Polarity. Faraday Discuss. 2012, 154, 391−407. (5) Qiao, Y.; Yan, F.; Xia, S.; Yin, S.; Ma, P. Densities and Viscosities of [Bmim][PF6] and Binary Systems [Bmim][PF6] + Ethanol, [Bmim][PF6] + Benzene at Several Temperatures and Pressures: N

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

(22) Yu, G.; Zhao, D.; Wen, L.; Yang, S.; Chen, X. Viscosity of Ionic Liquids: Database, Observation, and Quantitative Structure-Property Relationship Analysis. AIChE J. 2012, 58, 2885−2899. (23) Cade, E. A.; Saeva, D. R.; Hoffmann, M. M. Comparing Composition- and Temperature-Dependent Excess Molar Volumes of Binary Systems Involving Ionic Liquids. J. Chem. Eng. Data 2014, 59, 1892−1914. (24) Lide, D. R. CRC Handbook of Chemistry and Physics, 83rd ed.; Lide, D. R., Ed.; CRC Press: Boca Raton, 2003. (25) Widegren, J. A.; Magee, J. W. Density, Viscosity, Speed of Sound, and Electrolytic Conductivity for the Ionic Liquid 1-Hexyl-3Methylimidazolium Bis(trifluoromethylsulfonyl)imide and Its Mixtures with Water. J. Chem. Eng. Data 2007, 52, 2331−2338. (26) Kandil, M. E.; Marsh, K. N.; Goodwin, A. R. H. Measurement of the Viscosity, Density, and Electrical Conductivity of 1-Hexyl-3Methylimidazolium Bis(trifluorosulfonyl)imide at Temperatures between (288 and 433) K and Pressures below 50 MPa. J. Chem. Eng. Data 2007, 52, 2382−2387. (27) Chirico, R. D.; Diky, V.; Magee, J. W.; Frenkel, M.; Marsh, K. N. Thermodynamic and Thermophysical Properties of the Reference Ionic Liquid: 1-Hexyl-3-Methylimidazolium Bis[(trifluoromethyl)sulfonyl]amide (including Mixtures). Part 2. Critical Evaluation and Recommended Property Values (IUPAC Technical Report). Pure Appl. Chem. 2009, 81, 791−828. (28) Tokuda, H.; Tsuzuki, S.; Susan, M. A. B. H.; Hayamizu, K.; Watanabe, M. How Ionic Are Room-Temperature Ionic Liquids? An Indicator of the Physicochemical Properties. J. Phys. Chem. B 2006, 110, 19593−19600. (29) Guo, B.; Song, Y.; Liang, W. Z.; Zhang, D. D.; Han, W.; Song, W. Viscosity of Methylbenzene in [Bmim][BF4] and [Bmim][PF6] Ionic Liquids. Adv. Mater. Res. 2013, 864−867, 125−130. (30) Wang, J.; Tian, Y.; Zhao, Y.; Zhuo, K. A Volumetric and Viscosity Study for the Mixtures of 1-N-Butyl-3-Methylimidazolium Tetrafluoroborate Ionic Liquid with Acetonitrile, Dichloromethane, 2Butanone and N,N-Dimethylformamide. Green Chem. 2003, 5, 618− 622. (31) Kavitha, T.; Attri, P.; Venkatesu, P.; Rama Devi, R. S.; Hofman, T. Influence of Temperature on Thermophysical Properties of Ammonium Ionic Liquids with N-Methyl-2-Pyrrolidone. Thermochim. Acta 2012, 545, 131−140. (32) Kavitha, T.; Attri, P.; Venkatesu, P.; Rama Devi, R. S.; Hofman, T. Temperature Dependence Measurements and Molecular Interactions for Ammonium Ionic Liquid with N-Methyl-2-Pyrrolidone. J. Chem. Thermodyn. 2012, 54, 223−237. (33) Thermophysical Properties of Fluid Systems. http://webbook. nist.gov/chemistry/fluid/ (accessed Jun 5, 2015). (34) Zhang, L.; Xu, Z.; Wang, Y.; Li, H. Prediction of the Solvation and Structural Properties of Ionic Liquids in Water by TwoDimensional Correlation Spectroscopy. J. Phys. Chem. B 2008, 112, 6411−6419. (35) Hanke, C. G.; Lynden-Bell, R. M. A Simulation Study of WaterDialkylimidazolium Ionic Liquid Mixtures. J. Phys. Chem. B 2003, 107, 10873−10878. (36) Tantry, H. I.; Sheikh, F. A.; Bhat, P. A. Micellization Behavior of Dodecylethyldimethylammonium Bromide as a Function of Temperature and Concentration. J. Mol. Liq. 2013, 183, 79−84. (37) Gómez-Díaz, D.; Navaza, J. M.; Sanjurjo, B. Density, Kinematic Viscosity, Speed of Sound, and Surface Tension of Tetradecyl and Octadecyl Trimethyl Ammonium Bromide Aqueous Solutions. J. Chem. Eng. Data 2007, 52, 2091−2093. (38) Sheikh, F. A.; Bhat, P. A. Effect of Temperature and Concentration on Density, Apparent Molar Volume, Ultrasound Velocity, Isoentropic Compressibility, Viscosity, and Conductivity of Hexadecyldimethylethylammonium Bromide. J. Chem. Eng. Data 2012, 57, 3368−3374. (39) Wagner, M.; Stanga, O.; Schröer, W. Critical Viscosity near the Liquid-Liquid Phase Transition in the Solution of the Ionic Liquid 1Methyl-3-Hexylimidazolium Tetrafluoroborate in 1-Pentanol. Phys. Chem. Chem. Phys. 2004, 6, 1750−1757.

(40) Heintz, A.; Lehmann, J. K.; Wertz, C. Thermodynamic Properties of Mixtures Containing Ionic Liquids. 3. Liquid-Liquid Equilibria of Binary Mixtures of 1-Ethyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)imide with Propan-1-Ol, Butan-1-Ol, and Pentan-1-Ol. J. Chem. Eng. Data 2003, 48, 472−474. (41) Xiang, H. W.; Laesecke, A.; Huber, M. L. A New Reference Correlation for the Viscosity of Methanol. J. Phys. Chem. Ref. Data 2006, 35, 1597−1620. (42) Barthel, J.; Neueder, R.; Roch, H. Density, Relative Permittivity, and Viscosity of Propylene Carbonate + Dimethoxyethane Mixtures from 25 to 125 °C. J. Chem. Eng. Data 2000, 45, 1007−1011. (43) Dortmund Data Bank Software & Separation Technology GmbH (DDBST). http://www.ddbst.com/en/EED/PCP/PCPindex. php (accessed Jun 5, 2015). (44) Stark, A.; Ajam, M.; Green, M.; Raubenheimer, H. G.; Ranwell, A.; Ondruschka, B. Metathesis of 1-Octene in Ionic Liquids and Other Solvents: Effects of Substrate Solubility, Solvent Polarity and Impurities. Adv. Synth. Catal. 2006, 348, 1934−1941. (45) Scharf, N. T.; Stark, A.; Hoffmann, M. M. Calorimetric Study on the Ion Pairing and Aggregation of 1-Ethyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)amide ([C2mim][NTf2]) and Related Ionic Liquids in the Low-Dielectric Solvent Chloroform. J. Solution Chem. 2013, 42, 2034−2056. (46) Zhao, H. Are Ionic Liquids Kosmotropic or Chaotropic? An Evaluation of Available Thermodynamic Parameters for Quantifying the Ion Kosmotropicity of Ionic Liquids. J. Chem. Technol. Biotechnol. 2006, 81, 877−891. (47) Gómez, E.; González, B.; Calvar, N.; Tojo, E.; Domínguez, Á . Physical Properties of Pure 1-Ethyl-3-Methylimidazolium Ethylsulfate and Its Binary Mixtures with Ethanol and Water at Several Temperatures. J. Chem. Eng. Data 2006, 51, 2096−2101. (48) Rilo, E.; Vila, J.; Pico, J.; Garcia-Garabal, S.; Segade, L.; Varela, L. M.; Cabeza, O. Electrical Conductivity and Viscosity of Aqueous Binary Mixtures of 1-Alkyl-3-Methyl Imidazolium Tetrafluoroborate at Four Temperatures. J. Chem. Eng. Data 2010, 55, 639−644. (49) Ge, M.-L.; Ren, X.-G.; Song, Y.-J.; Wang, L.-S. Densities and Viscosities of 1-Propyl-2,3-Dimethylimidazolium Tetrafluoroborate + H2O at T= (298.15 to 343.15) K. J. Chem. Eng. Data 2009, 54, 1400− 1402. (50) Francisco, M.; González, A. S. B.; García de Dios, S. L.; Weggemans, W.; Kroon, M. C. Comparison of a Low Transition Temperature Mixture (LTTM) Formed by Lactic Acid and Choline Chloride with Choline Lactate Ionic Liquid and the Choline Chloride Salt: Physical Properties and Vapour−liquid Equilibria of Mixtures Containing Water and Ethanol. RSC Adv. 2013, 3, 23553−23561. (51) Królikowska, M.; Lipiński, P.; Maik, D. Density, Viscosity and Phase Equilibria Study of {ethylsulfate-Based Ionic Liquid+water} Binary Systems as a Function of Temperature and Composition. Thermochim. Acta 2014, 582, 1−9. (52) Domańska, U.; Laskowska, M. Temperature and Composition Dependence of the Density and Viscosity of Binary Mixtures of {1Butyl-3-Methylimidazolium Thiocyanate + 1-Alcohols}. J. Chem. Eng. Data 2009, 54, 2113−2119. (53) Xu, Y.; Chen, B.; Qian, W.; Li, H. Properties of Pure NButylammonium Nitrate Ionic Liquid and Its Binary Mixtures of with Alcohols at T = (293.15 to 313.15) K. J. Chem. Thermodyn. 2013, 58, 449−459. (54) Zhang, Z.; Zhou, Q.; Lu, X.; Qiao, C.; Zhang, S. Densities and Viscosities of Binary Mixtures Containing 1,3-Dimethylimidazolium Dimethylphosphate and Alcohols. J. Chem. Eng. Data 2014, 59, 2377− 2388. (55) Xu, Y.; Yao, J.; Wang, C.; Li, H. Density, Viscosity, and Refractive Index Properties for the Binary Mixtures of NButylammonium Acetate Ionic Liquid + Alkanols at Several Temperatures. J. Chem. Eng. Data 2012, 57, 298−308. (56) Shao, D.; Lu, X.; Fang, W.; Guo, Y.; Xu, L. Densities and Viscosities for Binary Mixtures of the Ionic Liquid N-Ethyl Piperazinium Propionate with N-Alcohols at Several Temperatures. J. Chem. Eng. Data 2012, 57, 937−942. O

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Methylimidazolium Tricyanomethanide with Thiophene. Colloids Surf., A 2013, 436, 504−511. (73) Domańska, U.; Królikowska, M.; Walczak, K. Density, Viscosity and Surface Tension of Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Tricyanomethanide with Benzothiophene. J. Solution Chem. 2014, 43, 1929−1946. (74) Larriba, M.; Navarro, P.; García, J.; Rodríguez, F. Separation of Toluene from N-Heptane, 2,3-Dimethylpentane, and Cyclohexane Using Binary Mixtures of [4empy][Tf2N] and [emim][DCA] Ionic Liquids as Extraction Solvents. Sep. Purif. Technol. 2013, 120, 392− 401. (75) Navia, P.; Troncoso, J.; Romaní, L. Viscosities for Ionic Liquid Binary Mixtures with a Common Ion. J. Solution Chem. 2008, 37, 677− 688. (76) Song, D.; Chen, J. Densities and Viscosities for Ionic Liquids Mixtures Containing [eOHmim][BF4], [bmim][BF4] and [bpy][BF4]. J. Chem. Thermodyn. 2014, 77, 137−143. (77) Khupse, N. D.; Kurolikar, S. R.; Kumar, A. Temperature Dependent Viscosity of Mixtures of Ionic Liquids at Different Compositions. Indian J. Chem. 2010, 49A, 727−730. (78) Larriba, M.; García, S.; Navarro, P.; García, J.; Rodríguez, F. Physical Characterization of an Aromatic Extraction Solvent Formed by [bpy][BF4] and [4bmpy][Tf2N] Mixed Ionic Liquids. J. Chem. Eng. Data 2013, 58, 1496−1504. (79) Carvalho, P. J.; Regueira, T.; Santos, L. M. N. B. F.; Fernandez, J.; Coutinho, J. A. P. Effect of Water on the Viscosities and Densities of 1-Butyl-3-Methylimidazolium Dicyanamide and 1-Butyl-3-Methylimidazolium Tricyanomethane at Atmospheric Pressure. J. Chem. Eng. Data 2010, 55, 645−652. (80) He, Z.; Zhao, Z.; Zhang, X.; Feng, H. Thermodynamic Properties of New Heat Pump Working Pairs: 1,3-Dimethylimidazolium Dimethylphosphate and Water, Ethanol and Methanol. Fluid Phase Equilib. 2010, 298, 83−91. (81) Romich, C.; Merkel, N. C.; Valbonesi, A.; Schaber, K.; Sauer, S.; Schubert, T. J. S. Thermodynamic Properties of Binary Mixtures of Water and Room-Temperature Ionic Liquids: Vapor Pressures, Heat Capacities, Densities, and Viscosities of Water + 1-Ethyl-3Methylimidazolium Acetate and Water + Diethylmethylammonium Methane Sulfonate. J. Chem. Eng. Data 2012, 57, 2258−2264. (82) Bhattacharjee, A.; Varanda, C.; Freire, M. G.; Matted, S.; Santos, L. M. N. B. F.; Marrucho, I. M.; Coutinho, J. A. P. Density and Viscosity Data for Binary Mixtures of 1-Alkyl-3-Methylimidazolium Alkylsulfates + Water. J. Chem. Eng. Data 2012, 57, 3473−3482. (83) Qian, W.; Xu, Y.; Zhu, H.; Yu, C. Properties of Pure 1Methylimidazolium Acetate Ionic Liquid and Its Binary Mixtures with Alcohols. J. Chem. Thermodyn. 2012, 49, 87−94. (84) Geppert-Rybczyńska, M.; Lehmann, J. K.; Heintz, A. Physicochemical Properties of Two 1-Alkyl-1-Methylpyrrolidinium Bis[(trifluoromethyl)sulfonyl]imide Ionic Liquids and of Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Bis[(trifluoromethyl)sulfonyl]imide with Methanol or Acetonitrile. J. Chem. Thermodyn. 2014, 71, 171−181. (85) Mokhtarani, B.; Sharifi, A.; Mortaheb, H. R.; Mirzaei, M.; Mafi, M.; Sadeghian, F. Densities and Viscosities of Pure 1-Methyl-3Octylimidazolium Nitrate and Its Binary Mixtures with Alcohols at Several Temperatures. J. Chem. Eng. Data 2010, 55, 3901−3908. (86) Salgado, J.; Regueira, T.; Lugo, L.; Vijande, J.; Fernández, J.; García, J. Density and Viscosity of Three (2,2,2-trifluoroethanol+1Butyl-3-Methylimidazolium) Ionic Liquid Binary Systems. J. Chem. Thermodyn. 2014, 70, 101−110. (87) Yan, X.-J.; Li, S.-N.; Zhai, Q.-G.; Jiang, Y.-C.; Hu, M.-C. Physicochemical Properties for the Binary Systems of Ionic Liquids [Cnmim]Cl + N,N-Dimethylformamide. J. Chem. Eng. Data 2014, 59, 1411−1422. (88) Araujo, J. M. M.; Pereiro, A. B.; Alves, F.; Marrucho, I. M.; Rebelo, L. P. N. Nucleic Acid Bases in 1-Alkyl-3-Methylimidazolium Acetate Ionic Liquids: A Thermophysical and Ionic Conductivity Analysis. J. Chem. Thermodyn. 2013, 57, 1−8.

(57) Rilo, E.; Vila, J.; García, M.; Cabeza, O. Viscosity and Electrical Conductivity of Binary Mixtures of CnMIM-BF4 with Ethanol at 288 K, 298 K, 308 K, and 318 K. J. Chem. Eng. Data 2010, 55, 5156−5163. (58) Yu, Z.; Gao, H.; Wang, H.; Chen, L. Densities, Viscosities, and Refractive Properties of the Binary Mixtures of the Amino Acid Ionic Liquid [bmim][Ala] with Methanol or Benzylalcohol at T = (298.15 to 313.15) K. J. Chem. Eng. Data 2011, 56, 2877−2883. (59) Lu, X.; Cao, Q.; Wu, X.; Xie, H.; Lei, Q.; Fang, W. Conformational Isomerism Influence on the Properties of Piperazinium Bis(trifluoromethylsulfonyl)imide. J. Phys. Chem. B 2014, 118 (30), 9085−9095. (60) Domańska, U.; Zawadzki, M.; Lewandrowska, A. Effect of Temperature and Composition on the Density, Viscosity, Surface Tension, and Thermodynamic Properties of Binary Mixtures of NOctylisoquinolinium Bis{(trifluoromethyl)sulfonyl}imide with Alcohols. J. Chem. Thermodyn. 2012, 48, 101−111. (61) Wu, T.-Y.; Chen, B.-K.; Hao, L.; Lin, Y.-C.; Wang, H. P.; Kuo, C.-W.; Sun, I.-W. Physicochemical Properties of Glycine-Based Ionic Liquid [QuatGly-OEt][EtOSO3] (2-Ethoxy-1-Ethyl-1,1-Dimethyl-2Oxoethanaminium Ethyl Sulfate) and Its Binary Mixtures with Poly(ethylene Glycol) (MW = 200) at Various Temperatures. Int. J. Mol. Sci. 2011, 12, 8750−8772. (62) Wu, T.-Y.; Chen, B.-K.; Hao, L.; Peng, Y.-C.; Sun, I.-W. Effect of Temperature on the Physico-Chemical Properties of a Room Temperature Ionic Liquid (1-Methyl-3-Pentylimidazolium Hexafluorophosphate) with Polyethylene Glycol Oligomer. Int. J. Mol. Sci. 2011, 12, 2598−2617. (63) Fan, W.; Zhou, Q.; Sun, J.; Zhang, S. Density, Excess Molar Volume, and Viscosity for the Methyl Methacrylate + 1-Butyl-3Methylimidazolium Hexafluorophosphate Ionic Liquid Binary System at Atmospheric Pressure. J. Chem. Eng. Data 2009, 54, 2307−2311. (64) Vraneš, M.; Papović, S.; Tot, A.; Zec, N.; Gadžurić, S. Density, Excess Properties, Electrical Conductivity and Viscosity of 1-Butyl-3Methylimidazolium Bis(trifluoromethylsulfonyl)imide + Γ-Butyrolactone Binary Mixtures. J. Chem. Thermodyn. 2014, 76, 161−171. (65) Pires, J.; Timperman, L.; Jacquemin, J.; Balducci, A.; Anouti, M. Density, Conductivity, Viscosity, and Excess Properties of (pyrrolidinium Nitrate-Based Protic Ionic Liquid+propylene Carbonate) Binary Mixture. J. Chem. Thermodyn. 2013, 59, 10−19. (66) Vraneš, M.; Zec, N.; Tot, A.; Papović, S.; Dožić, S.; Gadžurić, S. Density, Electrical Conductivity, Viscosity and Excess Properties of 1Butyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)imide+propylene Carbonate Binary Mixtures. J. Chem. Thermodyn. 2014, 68, 98− 108. (67) Wu, J.-Y.; Chen, Y.-P.; Su, C.-S. Density and Viscosity of Ionic Liquid Binary Mixtures of 1-N-Butyl-3-Methylimidazolium Tetrafluoroborate with Acetonitrile, N,N-Dimethylacetamide, Methanol, and NMethyl-2-Pyrrolidone. J. Solution Chem. 2015, 44, 395−412. (68) Ciocirlan, O.; Croitoru, O.; Iulian, O. Densities and Viscosities for Binary Mixtures of 1-Butyl-3-Methylimidazolium Tetrafluoroborate Ionic Liquid with Molecular Solvents. J. Chem. Eng. Data 2011, 56, 1526−1534. (69) Wu, J.-Y.; Chen, Y.-P.; Su, C.-S. The Densities and Viscosities of a Binary Liquid Mixture of 1-N-Butyl-3-Methylimidazolium Tetrafluoroborate, ([Bmim][BF4]) with Acetone, Methyl Ethyl Ketone and N,N-Dimethylformamide, at 303.15 to 333.15K. J. Taiwan Inst. Chem. Eng. 2014, 45, 2205−2211. (70) Tian, S.; Hou, Y.; Wu, W.; Ren, S.; Pang, K. Physical Properties of 1-Butyl-3-Methylimidazolium Tetrafluoroborate/N-Methyl-2-Pyrrolidone Mixtures and the Solubility of CO2 in the System at Elevated Pressures. J. Chem. Eng. Data 2012, 57, 756−763. (71) Domańska, U.; Zawadzki, M.; Krolikowski, M. Heat Capacity, Excess Molar Volumes and Viscosity Deviation of Binary Systems of N-Octylisoquinolinium Bis{(trifluoromethyl)sulfonyl}imide Ionic Liquid. Z. Phys. Chem. 2013, 227, 217−238. (72) Domańska, U.; Królikowska, M.; Walczak, K. Effect of Temperature and Composition on the Density, Viscosity Surface Tension and Excess Quantities of Binary Mixtures of 1-Ethyl-3P

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

(106) Kurnia, K. A.; Abdul Mutalib, M. I.; Murugesan, T.; Ariwahjoedi, B. Physicochemical Properties of Binary Mixtures of the Protic Ionic Liquid Bis(2-Hydroxyethyl)methylammonium Formate with Methanol, Ethanol, and 1-Propanol. J. Solution Chem. 2011, 40, 818−831. (107) Kermanpour, F.; Sharifi, T. Thermodynamic Study of Binary Mixture of x1[C6mim][BF4]+x2 1-Propanol: Measurements and Molecular Modeling. Thermochim. Acta 2012, 527, 211−218. (108) Domańska, U.; Laskowska, M. Effect of Temperature and Composition on the Density and Viscosity of Binary Mixtures of Ionic Liquid with Alcohols. J. Solution Chem. 2009, 38, 779−799. (109) Domańska, U.; Krolikowska, M. Density and Viscosity of Binary Mixtures of {1-Butyl-3-Methylimidazolium Thiocyanate + 1Heptanol, 1-Octanol, 1-Nonanol, or 1-Decanol}. J. Chem. Eng. Data 2010, 55, 2994−3004. (110) Domańska, U.; Papis, P.; Szydłowski, J.; Królikowska, M.; Królikowski, M. Excess Enthalpies of Mixing, Effect of Temperature and Composition on the Density, and Viscosity and Thermodynamic Properties of Binary Systems of {Ammonium-Based Ionic Liquid + Alkanediol}. J. Phys. Chem. B 2014, 118, 12692−12705. (111) Litaiem, Y.; Dhahbi, M. Measurements and Correlations of Viscosity, Conductivity and Density of an Hydrophobic Ionic Liquid (Aliquat 336) Mixtures with a Non-Associated Dipolar Aprotic Solvent (DMC). J. Mol. Liq. 2012, 169, 54−62. (112) Yao, H.; Zhang, S.; Wang, J.; Zhou, Q.; Dong, H.; Zhang, X. Densities and Viscosities of the Binary Mixtures of 1-Ethyl-3Methylimidazolium Bis(trifluoromethylsulfonyl)imide with N -Methyl-2-Pyrrolidone or Ethanol at T = (293.15 to 323.15) K. J. Chem. Eng. Data 2012, 57, 875−881. (113) Mokhtarani, B.; Sharifi, A.; Mortaheb, H. R.; Mirzaei, M.; Mafi, M.; Sadeghian, F. Density and Viscosity of Pyridinium-Based Ionic Liquids and Their Binary Mixtures with Water at Several Temperatures. J. Chem. Thermodyn. 2009, 41, 323−329. (114) Wang, Z.; Fu, L.; Xu, H.; Shang, Y.; Zhang, L.; Zhang, J. Density, Viscosity, and Conductivity for the Binary Systems of Water + Dual Amino-Functionalized Ionic Liquids. J. Chem. Eng. Data 2012, 57, 1057−1063. (115) Shekaari, H.; Armanfar, E. Physical Properties of Aqueous Solutions of Ionic Liquid, 1-Propyl-3-Methylimidazolium Methyl Sulfate, at T = (298.15 to 328.15) K. J. Chem. Eng. Data 2010, 55, 765−772. (116) Husson, P.; Pison, L.; Jacquemin, J.; Gomes, M. F. C. Influence of Water on the Carbon Dioxide Absorption by 1-Ethyl-3Methylimidazolium Bis(trifluoromethylsulfonyl)amide. Fluid Phase Equilib. 2010, 294, 98−104. (117) Yu, Z.; Gao, H.; Wang, H.; Chen, L. Thermodynamic Properties of Binary Mixtures of the Amino Acid Ionic Liquids [Bmim][Glu] or [Bmim][Gly] with Methanol at T = 298.15 to 313.15 K. J. Solution Chem. 2012, 41, 173−186. (118) Kermanpour, F.; Niakan, H. Z. Measurement and Modeling the Excess Molar Properties of Binary Mixtures of {[C6mim][BF4]+3Amino-1-Propanol} and {[C6mim][BF4]+isobutanol}: Application of Prigogine−Flory−Patterson Theory. J. Chem. Thermodyn. 2012, 48, 129−139. (119) Gonfa, G.; Bustam, M. A.; Moniruzzaman, M.; Murugesan, T. Volumetric Properties of Binary Mixtures of Benzene with CyanoBased Ionic Liquids. In AIP Conference Proceedings; AIP Publishing: 2014; Vol. 1621, pp 256−260.

(89) Guo, B.; Song, Y.; Liang, W. Z.; Zhang, D. D.; Han, W.; Song, W. Viscosity of Methylbenzene in [Bmim][BF4] and [Bmim][PF6] Ionic Liquids. Adv. Mater. Res. 2014, 864−867, 125−130. (90) Oliveira, F. S.; Pereiro, A. B.; Araújo, J. M. M.; Bernardes, C. E. S.; Canongia Lopes, J. N.; Todorovic, S.; Feio, G.; Almeida, P. L.; Rebelo, L. P. N.; Marrucho, I. M. High Ionicity Ionic Liquids (HIILs): Comparing the Effect of Ethylsulfonate and Ethylsulfate Anions. Phys. Chem. Chem. Phys. 2013, 15, 18138−18147. (91) Zawadzki, M.; Królikowska, M.; Lipiński, P. Physicochemical and Thermodynamic Characterization of N-Alkyl-N-Methylpyrrolidinium Bromides and Its Aqueous Solutions. Thermochim. Acta 2014, 589, 148−157. (92) Domańska, U.; Królikowska, M. Density and Viscosity of Binary Mixtures of Thiocyanate Ionic Liquids + Water as a Function of Temperature. J. Solution Chem. 2012, 41, 1422−1445. (93) Królikowska, M.; Zawadzki, M.; Królikowski, M. Physicochemical and Thermodynamic Study on Aqueous Solutions of Dicyanamide − Based Ionic Liquids. J. Chem. Thermodyn. 2014, 70, 127−137. (94) Xu, Y. Volumetric, Viscosity, and Electrical Conductivity Properties of Aqueous Solutions of Two N-Butylammonium-Based Protic Ionic Liquids at Several Temperatures. J. Chem. Thermodyn. 2013, 64, 126−133. (95) González, B.; Calvar, N.; Gómez, E.; Domínguez, I.; Domínguez, Á . Synthesis and Physical Properties of 1-Ethylpyridinium Ethylsulfate and Its Binary Mixtures with Ethanol and 1-Propanol at Several Temperatures. J. Chem. Eng. Data 2009, 54, 1353−1358. (96) Anouti, M.; Jacquemin, J.; Lemordant, D. Volumetric Properties, Viscosities, and Isobaric Heat Capacities of Imidazolium Octanoate Protic Ionic Liquid in Molecular Solvents. J. Chem. Eng. Data 2010, 55, 5719−5728. (97) González, E. J.; Alonso, L.; Domínguez, Á . Physical Properties of Binary Mixtures of the Ionic Liquid 1-Methyl-3-Octylimidazolium Chloride with Methanol, Ethanol, and 1-Propanol at T = (298.15, 313.15, and 328.15) K and at P = 0.1 MPa. J. Chem. Eng. Data 2006, 51, 1446−1452. (98) González, E. J.; González, B.; Calvar, N.; Domínguez, Á . Physical Properties of Binary Mixtures of the Ionic Liquid 1-Ethyl-3Methylimidazolium Ethyl Sulfate with Several Alcohols at T = (298.15, 313.15, and 328.15) K and Atmospheric Pressure. J. Chem. Eng. Data 2007, 52, 1641−1648. (99) Wu, T.-Y.; Hao, L.; Chen, P.-R.; Liao, J.-W. Ionic Conductivity and Thermophysical Properties of 1-Butyl-1-Methylpyrrolidinium Butyl Sulfate and Its Binary Mixtures with Poly (ethylene Glycol) at Various Temperatures. Int. J. Electrochem. Sci. 2013, 8, 5067−5085. (100) Zarrougui, R.; Dhahbi, M.; Lemordant, D. Effect of Temperature and Composition on the Transport and Thermodynamic Properties of Binary Mixtures of Ionic Liquid N-Butyl-N-Methylpyrrolidinium bis(Trifluoromethanesulfonyl)imide and Propylene Carbonate. J. Solution Chem. 2010, 39, 921−942. (101) Govinda, V.; Reddy, P. M.; Attri, P.; Venkatesu, P.; Venkateswarlu, P. Influence of Anion on Thermophysical Properties of Ionic Liquids with Polar Solvent. J. Chem. Thermodyn. 2013, 58, 269−278. (102) Govinda, V.; Madhusudhana Reddy, P.; Bahadur, I.; Attri, P.; Venkatesu, P.; Venkateswarlu, P. Effect of Anion Variation on the Thermophysical Properties of Triethylammonium Based Protic Ionic Liquids with Polar Solvent. Thermochim. Acta 2013, 556, 75−88. (103) Shen, M.; Che, S.; Zhang, Y.; Yao, J.; Li, H. Effect of the Temperature and Coordination Atom on the Physicochemical Properties of Chelate-Based Ionic Liquids and Their Binary Mixtures with Water. J. Chem. Eng. Data 2014, 59, 3960−3968. (104) Garcia-Mardones, M.; Gascon, I.; Lopez, M. C.; Royo, F. M.; Lafuente, C. Viscosimetric Study of Binary Mixtures Containing Pyridinium-Based Ionic Liquids and Alkanols. J. Chem. Eng. Data 2012, 57, 3549−3556. (105) Heintz, A.; Klasen, D.; Lehmann, J. K. Excess Molar Volumes and Viscosities of Binary Mixtures of Methanol and the Ionic Liquid 4Methyl-N-Butylpyridinium Tetrafluoroborate at 25, 40, and 50 °C. J. Solution Chem. 2002, 31, 467−476. Q

DOI: 10.1021/acs.jced.5b00503 J. Chem. Eng. Data XXXX, XXX, XXX−XXX