Infinite dilution activity coefficients of solutes dissolved in anhydrous alkyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide ionic liquids containing functionalized- and nonfunctionalized-alkyl chains

Infinite dilution activity coefficients of solutes dissolved in anhydrous alkyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide ionic liquids containing functionalized- and nonfunctionalized-alkyl chains

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    Infinite dilution activity coefficients of solutes dissolved in anhydrous alkyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide ionic liquids containing functionalized- and nonfunctionalized-alkyl chains Fabrice Mutelet, Dominique Alonso, Sudhir Ravula, Gary A. Baker, Bihan Jiang, William E. Acree Jr. PII: DOI: Reference:

S0167-7322(16)31254-5 doi: 10.1016/j.molliq.2016.07.012 MOLLIQ 6026

To appear in:

Journal of Molecular Liquids

Received date: Revised date: Accepted date:

19 May 2016 17 June 2016 2 July 2016

Please cite this article as: Fabrice Mutelet, Dominique Alonso, Sudhir Ravula, Gary A. Baker, Bihan Jiang, William E. Acree Jr., Infinite dilution activity coefficients of solutes dissolved in anhydrous alkyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide ionic liquids containing functionalized- and nonfunctionalized-alkyl chains, Journal of Molecular Liquids (2016), doi: 10.1016/j.molliq.2016.07.012

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ACCEPTED MANUSCRIPT Infinite Dilution Activity Coefficients of Solutes Dissolved in Anhydrous Alkyl(dimethyl)isopropylammonium bis(Trifluoromethylsulfonyl)imide Ionic Liquids

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Containing Functionalized- and Nonfunctionalized-Alkyl Chains

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Fabrice MUTELETa, Dominique ALONSOa, Sudhir RAVULA,b Gary A. BAKERb, Bihan

a

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JIANGc, William E. ACREE, Jr.c

Universite de Lorraine, Laboratoire de Reactions et Genie des Procedes (UPR CNRS 3349), 1

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rue Grandville, BP 20451 54001 NANCY, FRANCE.

Department of Chemistry, University of Missouri-Columbia, COLUMBIA, MISSOURI 65211.

c

Department of Chemistry, 1155 Union Circle #305070, University of North Texas, DENTON,

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b

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Abstract

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TEXAS 76203-5017.

hexyl(dimethyl)isopropylammonium

bis(trifluoromethylsulfonyl)imide,

2-hydroxyethyl(dimethyl)isopropylammonium

bis(trifluoromethylsulfonyl)imide,

cyanomethyl(dimethyl)isopropylammonium

Infinite dilution activity coefficients and gas-to-liquid partition coefficients have been determined for at least 42 different organic solutes of varying polarity and hydrogen-bonding character dissolved in anhydrous ionic liquids comprising propyl(dimethyl)isopropylammonium bis(trifluoromethyl-sulfonyl)imide,

bis(trifluoromethylsulfonyl)imide,

and

N,N,N’,N’-tetramethyl-N,N’-diisopropyl-1,9-

nonanediaminium di[bis(trifluoromethylsulfonyl)imide]. The measured gas-to-liquid partition coefficient data were converted to water-to-liquid partition coefficients using standard thermodynamic relationships. Abraham model predictive correlations were developed from both

1

ACCEPTED MANUSCRIPT sets of partition coefficients.

The derived correlations describe the observed partitioning

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behavior to within 0.14 (or fewer) log units.

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KEY WORDS AND PHRASES: Ionic liquid solvents; activity coefficients at infinite dilution;

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partition coefficients; predictive methods; chemical separations

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________________________________________________________________________

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*To whom correspondence should be addressed. (E-mail: [email protected])

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ACCEPTED MANUSCRIPT Introduction Ionic liquids (ILs) have emerged as a new solvent class possessing properties that can be

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fine-tuned and modulated by judicious alteration of the cation-anion combination or introduction

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of task-specific polar and/or hydrogen-bonding functional groups onto the pendant chains attached to the cation. Task-specific ionic liquids have been designed for distinct purposes, such

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as sorbents for greenhouse gas and acidic gas capture in natural gas and post-combustion

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treatments, stationary phase materials for gas-liquid chromatographic separations, extraction solvents/additives for the selective removal of metal ions from aqueous solution [1-3],

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components of aqueous two-phase systems for the enantiomeric separation of racemic amino acids [4], and more recently, for the dissolution and fractionation of cellulose, hemicellulose, and

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lignin in biomass processing [5-8]. Amine-functionalized ILs have been shown to exhibit increased carbon dioxide sorption efficiency [9-11], whereas hydroxyl-functionalized ILs

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provide an efficient means for sorbing ammonia gas [12]. Nitrile-terminated alkyl chains are reported [13] to afford improved CO2/N2 and CO2/CH4 solubility selectivity when compared to their non-functionalized alkyl-chain counterparts. ILs containing acetate, formate, and chloride anions have been found to be especially effective in dissolving cellulose [14].

The fore-

mentioned examples represent just a few of the many disparate applications involving ILs in practical industrial and manufacturing processes.

Expanded utilization of ILs in chemical

synthesis and chemical separation processes requires both the experimental determination of chemical and physical properties of additional ILs, as well as the development of predictive methods that allow for the estimation of IL properties in the absence of direct measured values. Our contribution towards facilitating the use of IL solvents has focused on physical property measurements [15,16] and on determining the solubilizing ability of ILs as reflected by

3

ACCEPTED MANUSCRIPT the infinite dilution activity coefficients of organic solutes dissolved in anhydrous ILs. In terms of activity coefficient measurements, we have previously studied a series of ILs containing the cation

[17-28],

the

tetraalkylammonium

cation

[22,29],

the

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1,3-dialkylimidazolium

dialkylpyridinium

cation

[26],

the

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tetraalkylphosphonium cation [30,31], the 1,1-dialkylpyrrolidinium cation [32-35], the 1,41,1-dialkylpiperidinium

cation

[34,35],

the

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alkylquinuclidinium cation [36], and several dicationic [27] and tricationic [37] ILs.

The

The results of our

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specific ILs studied are listed in Table 1 according to cation type.

1-

experimental activity coefficient measurements have led to the development of IL-specific

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Abraham model correlations for the various IL studied, as well as the calculation of ionicspecific equation coefficients for the Abraham model [38-41] and the determination of group

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fragment values [42,43] for predicting both gas-to-liquid partition coefficients and infinite dilution activity coefficients for solutes dissolved in ILs. The ion-specific equation coefficients

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and fragment group values that we have obtained during the course of our studies can be used to make predictions for many ILs that have not yet been synthesized nor studied. As a continuation of our past experimental efforts, we have measured the infinite dilution activity coefficients and gas-to-liquid partition coefficients of 40 to 47 organic solutes dissolved in

anhydrous

propyl(dimethyl)isopropylammonium

bis(trifluoromethylsulfonyl)imide

([PM2iPAm]+ [Tf2N]–), hexyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide ([HM2iPAm]+

[Tf2N]–),

bis(trifluoromethylsulfonyl)imide cyanomethyl(dimethyl)isopropylammonium

2-hydroxyethyl(dimethyl)isopropylammonium ([EtOHM2iPAm]+[Tf2N]–), bis(trifluoromethyl-sulfonyl)imide

([CNMeM2iPAm]+[Tf2N]–), and N,N,N’,N’-tetramethyl-N,N’-diisopropyl-1,9-nonanediaminium di[bis(trifluoromethylsulfonyl)imide] ([C1,9(M2iPAm)2]2+[Tf2N]–2). The chemical structures of

4

ACCEPTED MANUSCRIPT these five ionic liquids are given in Figure 1. The measured experimental partition coefficient data will be used to derive Abraham model correlations for each of the five individual ionic

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liquids, as well as ionic-specific equation coefficients for the five different tetraalkylammonium

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cations. As an informational note, the tetraalkylammonium ILs that we have studied thus far have contained only non-functionalized linear alkyl chains. This represents that first time that

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we have studied tetraalkylammonium cations containing either branched alkyl chains or

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functionalized alkyl chains. The experimental partition coefficient data determined during this study will be available to us when we decide to update our existing functional group values for

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the fragment group version of the Abraham model. Our fragment group method does not have a

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2. Experimental Methods

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numerical value for the tertiary carbon atom group, -C(H)<.

2.1. Preparation of Alkyl(dimethyl)isopropyl ammonium bis(trifluoromethylsulfonyl)imide ionic liquids

Propyl(dimethyl)isopropylammonium bromide, ([PM2iPAm]+[Br]–): In a 500 mL roundbottomed flask, 78.32 g of N,N-dimethylisopropylamine (≥99%, 0.898 mol) and 150 mL of ethyl acetate (EtOAc) were taken and the solution flask chilled in an ice bath for 30 min. Chilled 1bromopropane (118.17 g; 99%, 0.944 mol) was added slowly via a dropping funnel to the reaction mixture over a period of 45 min. This reaction mixture was stirred in an ice bath for 30 min and then at room temperature for two days. The obtained white solid was filtered, washed with EtOAc (3 × 150 mL) and dried under vacuum overnight at 60 °C to obtain the desired product ([PM2iPAm]+[Br]–) as a pristinely white solid (ca. 20% yield) suitable for spec-grade

5

ACCEPTED MANUSCRIPT applications. 1H-NMR (300 MHz, D2O): δ 3.80-3.63 (m, 1H), 3.33-3.27 (m, 2H), 2.98 (s, 6H), 1.88-1.71 (m, 2H), 1.38 (dd, J = 1.8, 6.6 Hz, 3H), 0.98 (m, 6H). bis(trifluoromethylsulfonyl)imide

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Propyl(dimethyl)isopropylammonium

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([PM2iPAm]+[Tf2N]–): A solution of 35.9 g (0.171 mol) of [PM2iPAm]+[Br]– was dissolved in

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30 mL of 18.2 MΩ cm NANOpure water and added dropwise to a solution prepared by dissolving 51.6 g (0.180 mol) of lithium bis(trifluoromethylsulfonyl)imide [LiTf2N] in 30 mL of

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NANOpure water. The cloudy mixture was stirred for a few hours and then allowed to settle

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down. The aqueous phase was decanted and the lower phase then washed multiple times (6 × 30 mL) with NANOpure water until no residual halide was detected in the aqueous phase using

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concentrated silver nitrate. The resultant liquid was dried under high vacuum at 60 °C for two

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days, resulting a viscous colorless IL with a yield of 53.5 g (76%). 1H-NMR (300 MHz, CDCl3): δ 3.80-3.62 (m, 1H), 3.26-3.12 (m, 2H), 3.0 (s, 3H), 2.93 (s, 3H), 1.88-1.67 (m, 2H), 1.42 (d, J =

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6.6 Hz, 3H), 1.47-1.30 (d, J = 6.6 Hz, 3H), 1.1-0.92 (m, 3H). Hexyl(dimethyl)isopropylammonium bromide, ([HM2iPAm]+[Br]–): The halide precursor ([HM2iPAm]+[Br]–) was synthesized following the same procedure used for [PM2iPAm]+[Br]–. The slow reaction of 18.0 g of N,N-dimethylisopropylamine (≥99%, 0.206 mol) and 36.33 g of 1bromohexane (99%, 0.217 mol) in 150 mL of EtOAc yielded 56% of the desired product ([HM2iPAm]+[Br]–) after two days. 1H-NMR (300 MHz, D2O): δ 3.80-3.63 (m, 1H), 3.37-3.20 (m, 2H), 2.98 (s, 6H), 1.84-1.68 (m, 2H), 1.46-1.23 (m, 12H), 0.97-0.80 (m, 3H). Hexyl(dimethyl)isopropylammonium

bis(trifluoromethylsulfonyl)imide,

([HM2iPAm]+[Tf2N]–): Ion exchange was performed as for the [PM2iPAm]+[Br]– salt described above. The colorless viscous [HM2iPAm]+[Tf2N]– IL was obtained with a yield of 89%.

1

H-

6

ACCEPTED MANUSCRIPT NMR (300 MHz, DMSO-d6): δ 3.73-3.54 (m, 1H), 3.27-3.08 (m, 2H), 2.92 (s, 6H), 1.74-1.53 (m, 2H), 1.40-1.12 (m, 12H), 0.94-0.75 (m, 3H). bromide,

([EtOHM2iPAm]+[Br]–):

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2-hydroxyethyl(dimethyl)isopropylammonium

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[EtOHM2iPAm]+[Br]– was synthesized according to previously reported procedures [16]. 1H-

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NMR (300 MHz, D2O): δ 4.12-4.03 (m, 2H), 3.89-3.73 (m, 1H), 3.49 (t, J = 5.4 Hz, 2H), 3.08 (s,

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6H), 1.42 (d, J = 6.6 Hz, 6H). 2-hydroxyethyl(dimethyl)isopropylammonium

bis(trifluoromethylsulfonyl)imide,

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([EtOHM2iPAm]+[Tf2N]–): Ion exchange was performed as for the [PM2iPAm]+[Br]– salt described earlier. A colorless viscous [EtOHM2iPAm]+[Tf2N]– IL was obtained with a yield of

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50%. 1H-NMR (300 MHz, DMSO-d6): δ 5.26 (t, J = 4.8 Hz, 1H), 3.89-3.67 (m, 3H), 3.35 (t, J =

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5.4 Hz, 2H), 2.98 (s, 6H), 1.29 (d, J = 6.6 Hz, 6H).

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Cyanomethyl(dimethyl)isopropylammonium bromide, ([CNMeM2iPAm]+[Br]–): The halide precursor [CNMeM2iPAm]+[Br]– was synthesized using a procedure similar to that for [PM2iPAm]+[Br]–. The reaction of 30.0 g of N,N-dimethylisopropylamine (≥99%, 0.344 mol) with 27.39 g of chloroacetonitrile (99%, 0.361 mol) in 150 mL of EtOAc afforded 89% of the desired product ([HM2iPAm]+[Br]–). 1H-NMR (300 MHz, DMSO-d6): δ = 5.07 (s, 2H), 3.983.82 (m, 1H), 3.17 (s, 6H), 1.36 (d, J = 6.3 Hz, 6H). Cyanomethyl(dimethyl)isopropylammonium

bis(trifluoromethylsulfonyl)imide,

([CNMeM2iPAm]+[Tf2N]–): Ion exchange was performed as for the [PM2iPAm]+[Br]– salt described already. A colorless viscous [CNMeM2iPAm]+[Tf2N]– IL was obtained with a yield of 63%. 1H-NMR (300 MHz, DMSO-d6): δ = 4.81 (s, 2H), 3.82-3.76 (m, 1H), 3.12 (s, 6H), 1.35 (d, J = 6.6 Hz, 6H).

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ACCEPTED MANUSCRIPT N,N,N’,N’-tetramethyl-N,N’-diisopropyl-1,9-nonanediaminium

dibromide,

([C1,9(M2iPAm)2]2+[Br]–2): In a typical synthesis, 9.18 g of N,N-dimethylisopropylamine

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(≥99%, 0.105 mol), 10 g of 1,9-dibromononane (≥99 %, 0.034 mol), and 25 mL of EtOAc were

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combined in a 60 mL pressure tube (Ace Glass, Inc.) equipped with a FETFE® O-ring and sealed. The reaction mixture was allowed to react at 90 °C overnight. The obtained white solid

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was filtered, washed with EtOAc (3 × 120 mL) and dried under vacuum for overnight at 60 °C to

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obtain 70% of the desired dicationic product ([C1,9(M2iPAm)2]2+[Br]–2). 1H-NMR (300 MHz, D2O): δ 3.85-3.67 (m, 2H), 3.40-3.24 (m, 4H), 3.02 (s, 12H), 1.91-1.72 (m, 4H), 1.54-1.32 (m,

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22H).

N,N,N’,N’-tetramethyl-N,N’-diisopropyl-1,9-nonanediaminium

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di[bis(trifluoromethylsulfonyl)imide], ([C1,9(M2iPAm)2]2+[Tf2N]–2): In a typical preparation, 9.40 g (0.021 mol) of [C1,9(M2iPAm)2]2+[Br]–2 was dissolved in 20 mL of NANOpure water and

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then added to 11.78 g (0.041 mol) of lithium bis(trifluoromethylsulfonyl)imide [LiTf2N] predissolved within 15 mL of NANOpure water, giving a slightly yellow solid precipitate. To this mixture was added 100 mL of EtOAc, followed by stirring for a few hours. The aqueous phase was removed using a separatory funnel. The organic layer was washed multiple times (6 × 30 mL) with NANOpure water until no residual halide was detectable in the aqueous phase (AgNO3 test). The solvent was removed in vacuo and the resultant yellowish glassy material dried under high vacuum at 60 °C for two days, yielding 6.0 g (51%) of product. 1H-NMR (300 MHz, DMSO-d6): δ 3.73-3.56 (m, 2H), 3.26-3.13 (m, 4H), 2.91 (s, 12H), 1.73-1.57 (m, 4H), 1.44-1.15 (m, 22H). 2.2 Chromatographic instrumentation and experimental procedures.

8

ACCEPTED MANUSCRIPT The experimental procedures used for the determination of activity coefficients were described in previous works [4-8]. A Bruker 450 gas chromatograph equipped with a heated on-

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column injector and a thermal conductivity detector (TCD) detector was used for the

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measurements. The GC operating conditions are given in Table 1. The dead time of the packed column was determined using air. Helium carrier gas flow rate was measured using an Alltech

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Digital Flow Check Mass Flowmeter. The temperature of the oven was measured with a Pt 100

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probe and controlled within 0.1 K. Data were collected and treated with Galaxie software (Varian).

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The preparation of columns was described in detail in our previous publications [4-8]. Packed columns of 1-m length containing between 30 to 40% IL stationary phase coated onto a

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60–80 mesh Chromosorb WHP support material were prepared by a rotary evaporation method. Briefly, the desired IL was dissolved in ethanol in the presence of a precise mass of Chromosorb

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WHP. Ethanol was then removed from the mixture using rotary evaporation. The support was equilibrated at 343 K under vacuum during 6 h. Then, the conditioning of the packed columns was performed at 373 K over 12 h using a gas flow rate of 20 cm3 min–1. 2.3. Density measurements

Densities of ILs were measured using an Anton Paar DMA 60 digital vibrating-tube densimeter, with a DMA 512P measuring cell in the temperature range from 293.15 to 343.15 K at atmospheric pressure. The detailed procedure was given in our previous work [32]. All experimental data are given in Table 3.

3. Results and Discussion

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ACCEPTED MANUSCRIPT 3.1. Activity coefficients and selectivity at infinite dilution Activity coefficients at infinite dilution for model solutes in [Tf2N]– based ILs studied in

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this work were calculated using the theoretical basis described in our previous researches [29) and gas-to-IL partition

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32]. The uncertainties in infinite dilution activity coefficients (

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coefficients (K) were less than 3% [29-32]. All experimental data measured in this work are presented in Tables 4–13.

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The solubility of n-alkanes is related to the alkyl chain length; that is, an increase of the

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chain length leads to an increase of solubility. Nevertheless, the solubility of n-alkanes in typical ILs remains low. Functionalized ILs containing cyano or hydroxyl groups have the tendency to

of

alkanes

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coefficients

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increase repulsive forces between alkanes and IL. Experimental data show that activity increase

according

. In most cases,

with an increase of temperature. Some exceptions can be found.

to

values decrease

Indeed, the solubility of

aromatics, 1,4-dioxane, pentanone, and chloroform slightly decrease with increasing temperature. Not surprisingly, the best solubility for alcoholic solutes is obtained with the alcohol-bearing IL [EtOHM2iPAm]+[Tf2N]–. Similar results were observed with 1-(4sulfobutyl)-3-methylimidazolium based ILs [44]. Ab initio calculations have shown that the anion will then associate with the hydroxyl group of the cation as well as with the alcohols. This leads to a decrease in the disruption of the cation/anion interaction and a better solubility for the alcohol in functionalized ILs than in non-functionalized dialkylimidazolium based ILs. Numerous [Tf2N]– based ILs were characterized by gas chromatography and large data sets of activity coefficients at infinite dilution can be found in the literature. We have found that most selected organic compounds studied in this work have better solubility in ILs based on the 110

ACCEPTED MANUSCRIPT alkylquinuclidinium cation than tetraalkylammonium or dialkylpyrrolidinium analogs. Solute interactions with the dicationic [C1,9(M2iPAm)2]2+[Tf2N]– were also found to be quite similar to

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those observed with its monocat tetraalkylammonium analogs.

) and infinite dilution capacity (

) values using the

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through the calculation of selectivity (

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The performance of the ILs as extractant media for separation problems can be evaluated

(1)

and

(2)

correspond to the infinite dilution activity coefficients of solutes 1 and 2,

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where

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following expressions:

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respectively, within the IL of interest. The performance of selected [Tf2N]– based ILs was

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evaluated for hexane/benzene, hexane/pyridine, hexane/thiophene, and heptane/thiophene separations at 323.15 K and compared to N-methyl-2-pyrrolidone (NMP) and sulfolane. Results for different separation problems are compiled in Table 14, along with the references [32,33,36,45-51] from which the data used to calculate the selectivities and capacity factors were drawn. In the case of the hexane/benzene separation problem, numerous ILs present larger capacities than sulfolane or NMP. Five ILs with better performance than sulfolane can be identified:

N,N,N’,N’-tetramethyl-N,N’-diisopropyl-1,9-nonanediaminium

di[bis(trifluoromethylsulfonyl)imide],

1-ethyl-3-methylimidazolum

bis(trifluoromethylsulfonyl)imide, 1-methyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,

4-methyl-N-butylpyridinium

bis(trifluoromethylsulfonyl)imide,

and

1-propyl-1-

methylpiperidinium bis(trifluoromethylsulfonyl)imide. The IL 1-propyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide presents a hexane/benzene selectivity comparable to sulfolane 11

ACCEPTED MANUSCRIPT but with a better capacity. In addition, the ILs propyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide,

1-butyl-3-methylimidazolium and

1-butyl-3-methylpyrrolidinum

PT

bis(trifluoromethylsulfonyl)imide,

) are larger.

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however, their capacity values (

) than sulfolane;

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bis(trifluoromethylsulfonyl)imide have slightly lower selectivity values (

3.2. Development of Abraham Model Correlations for Solute Partition Coefficients

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Selectivities and capacity factors can be calculated for any pair of organic compounds for Activity

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which infinite dilution activity coefficients have been experimentally determined.

coefficient measurements can be very time consuming. This is particularly the case in studies

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involving many organic solutes dissolved in a series of IL solvents or select organic solutes

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dissolved in many different IL solvents of varying polarity and hydrogen-bonding character as

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would be needed to solve practical chemical separation problems. Predictive methods based on linear free energy relationships (LFERs) or quantitative structure-property relationships (QSPRs) can reduce the number of experimental measurements required to make informed decisions. The Abraham solvation parameter is among the more versatile of the LFERs that have been developed for predicting solute properties in both traditional organic solvents and ILs. The method is capable of predicting the logarithm of the water-to-ionic liquid and gas-to-ionic liquid partition coefficients, log P and log K, respectively [28-36]: log P = cp,il + ep,il·E + sp,il·S + ap,il·A + bp,il·B + vp,il·V

(3)

log K = ck,il + ek,il·E + sk,il·S + ak,il·A + bkil·B + lk,il·L

(4)

as well as the solubility of organic nonelectrolyte solutes dissolved in anhydrous ILs: log (CS,organic/CS,water) = cp,il + ep,il·E + sp,il·S + ap,il·A + bp,il·B + vp,il·V

(5)

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ACCEPTED MANUSCRIPT log (CS,organic/CS,gas) = ck,il + ek,il·E + sk,il·S + ak,il·A + bkil·B + lk,il·L

(6)

where (CS,organic/CS,water) and (CS,organic/CS,gas) denote the solute’s molar solubility ratios, with the

PT

subscripts indicating the phase to which the solute molar concentrations pertain. Partition

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coefficients predicted through Eqns. (3) and (4) can be converted to infinite dilution activity

RT 

o

 solute Psolute Vsolvent

)

(7)

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log K  log P  log K W  log (

SC

coefficients, γsolute∞, using standard thermodynamic relationships (see Eqn. (7)):

and a prior knowledge of the solute’s gas-to-water partition coefficient, Kw. In Eqn. (7), R is the

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universal constant law constant, Vsolvent is the molar volume of the IL solvent, Psoluteo is the vapor pressure of the solute at the system temperature, and T is the system temperature.

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The Abraham model describes the various solute–solvent interactions that are believed to be present in solution in terms of products of solute properties (called solute descriptors) and

AC CE P

solvent properties (called equation or process coefficients). The solute properties are denoted by the capitalized alphabetical letters on the right-hand side of Eqns. (3) to (6), while the solvent properties are denoted by the lowercase alphabetical characters. Solute descriptors are available for more than 5,000 different organic and inorganic compounds, and are defined as follows: the solute excess molar refractivity in units of (cm3 mol–1)/10 (E), the solute dipolarity/polarizability (S), the overall or summation hydrogen-bond acidity and basicity (A and B, respectively), the McGowan volume in units of (cm3 mol–1)/100 (V), and the logarithm of the gas-to-hexadecane partition coefficient at 298 K (L). Solvent/process coefficients describe the complimentary solvent property and, when combined with the appropriate solute descriptor, the product describes a particular type of molecular interaction. For example, the lowercase characters ail and bil refer to the hydrogen-bond basicity and hydrogen-bond acidity of the dissolving solvent

13

ACCEPTED MANUSCRIPT medium. The products ail·A and bil·B describe the hydrogen-bonding interactions that occur between the acidic sites on the solute molecule and the basic site(s) of the solvent (ail·A), and that

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occur between the basic sites on the solute molecule and acidic sites on the solvent molecule

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(bil·B), respectively. To date, Abraham model correlations have been reported for more than 60 different ILs. The derived correlations allow one to predict log K and log P values for solutes

SC

dissolved in anhydrous ILs at 298.15 K.

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The numerical log K (at 298.15 K) values used in the present study were calculated from the standard thermodynamic log K versus 1/T linear relationship based on the measured values at

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323.15 K and 333.15 K, as these were the two lowest temperatures studied for each IL. The linear extrapolation should be valid as the measurements were performed at temperatures not too

D

far removed from the desired temperature of 298.15 K (within ca. 35 K in the worst case). The

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calculated log K and log P values for [PM2iPAm]+[Tf2N]– are given in Table 15, along with the

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numerical solute descriptor values of the organic compounds studied in the present communication. Partition coefficient data for [HM2iPAm]+[Tf2N]–, [EtOHM2iPAm]+[Tf2N]–, [CNMeM2iPAm]+[Tf2N]–, and [C1,9(M2iPAm)2]2+[Tf2N]–2 are displayed in Tables S1 to S4 of the Supporting Information. Each partition coefficient determination contained experimental data for a minimum of 37 different organic solutes of varying polarity and hydrogen bonding character. Analysis of the experimental log P and log K values in Table 14 in accordance with Eqns. (3) and (4) of the Abraham model gave the following two IL-specific correlations: log P (298 K)= –0.378(0.118) + 0.115(0.114) E + 0.723(0.117) S – 1.061(0.178) A –4.594(0.109) B + 3.388(0.094) V

(8)

(SD = 0.113, N = 44, R2 = 0.996, and F = 1889)

14

ACCEPTED MANUSCRIPT and log K (298 K) = –0.702(0.071) + 2.532(0.064) S + 2.578(0.139) A + 0.331(0.083) B (9)

RI

(SD = 0.096, N = 46, R2 = 0.985, and F = 654.2)

PT

+ 0.682(0.017) L

SC

where the standard error in each calculated equation coefficient is given in parenthesis immediately after the respective coefficient. The statistical information associated with each

NU

correlation includes the standard deviation (SD), the number of experimental data points used in

MA

the regression analysis (N), the squared correlation coefficient (R2) and the Fisher F-statistic (F). The regression analyses used in deriving Eqns. (8) and (9) were performed using IBM SPSS

D

Statistics 22 commercial software.

TE

The Abraham model correlations given by Eqns. (8) and (9) are statistically very good with standard deviations of less than 0.12 log units. Figure 2 compares the observed log K

AC CE P

values against the back-calculated values based on Eqn. (9). The experimental data covers a range of approximately 2.78 log units, from log K = 1.066 for 2-methylpentane to log K = 3.842 for tetradecane. A comparison of the back-calculated versus measured log P data is depicted in Figure 3. As expected, the standard deviation for the log P correlation is slightly larger than that of the log K correlations because the log P values contain the additional experimental uncertainty in the gas-to-water partition coefficients used in the log K to log P conversion. There are insufficient experimental data to permit a training set and test set assessment of the predictive ability of Eqns. (8) and (9) by randomly splitting the entire database in half. The log P and log K data sets for [HM2iPAm]+[Tf2N]–, [EtOHM2iPAm]+[Tf2N]–, [CNMeM2iPAm]+[Tf2N]–, and [C1,9(M2iPAm)2]2+[Tf2N]–2 were analyzed in similar fashion. Numerical values of the equation coefficients and the associated statistical information are

15

ACCEPTED MANUSCRIPT compiled in Table 16. Each derived correlation provides a very good mathematical description of the observed partition coefficient data, as evidenced by the low standard deviations and near

PT

unity values for the squared correlation coefficients. Based on our past experience, we would

RI

expect each derived expression to provide reasonably accurate predictions for additional organic compounds dissolved in the given IL, provided that the solute descriptor values of the additional

SC

compounds fall within the range of values used in deriving each respective log K and log P

NU

correlation. The predicted log K and log P values can be converted first to activity coefficients and then to selectivity values for use in solving chemical separation problems. The derived

MA

expressions are specific to the given IL solvent, however, and cannot be used to predict activity coefficients for solutes in other IL solvents per se.

TE

D

The ion-specific equation coefficient version of the Abraham model [38-41]: log P = cp,cation + cp,anion + (ep,cation + ep,anion) E + (sp,cation + sp,anion) S + (ap,cation + ap,anion) A

AC CE P

+ (bp,cation + bp,anion) B + (vp,cation + vp,anion) V

(10)

log K = ck,cation + ck,anion + (ek,cation + ek,anion) E + (sk,cation + sk,anion) S + (ak,cation + ak,anion) A + (bk,cation + bk,anion) B + (lk,cation + lk,anion) L

(11)

and fragment-group version of the Abraham model [42]:

n

log P 

i

c p ,i 

group

e

p ,i

ni E 

group

s

p ,i

ni S 

group

a

p ,i

ni A 

group

b

p ,i

ni B   v p ,i ni V 

group

group

(c p ,anion  e p ,anion E  s p ,anion S  a p ,anion A  bp ,anion B  v p ,anion V) log K 

n

i

group

ck ,i 

e

k ,i

group

ni E 

s group

k ,i

ni S 

a group

k ,i

ni A 

b

k ,i

group

(ck ,anion  ek ,anion E  sk ,anion S  ak ,anion A  bk ,anion B  lk ,anion L)

(12)

ni B   lk ,i ni L  group

(13)

have been developed for predicting partition coefficients of solutes into those IL solvents whenever one does not have an IL-specific correlation equation. In Eqns. (12) and (13), ni

16

ACCEPTED MANUSCRIPT denotes the number of times that the given fragment group appears in the cation and the summations extend over all fragment groups contained in the IL under consideration. Thus far,

PT

ion-specific equation coefficients have been derived for 43 different cations and 17 different anions (Eqns. (10) and (11)), with numerical group values for 12 cation fragments (CH3–, –CH2– +

RI

+

+

, –O–, –O-Ncyclic, –OH, CH2cyclic, CHcyclic, Ccyclic, Ncyclic, >N< , >P< , and >S– ) and 9 individual

SC

anions (Tf2N–, PF6–, BF4–, EtSO4–, OcSO4–, SCN–, CF3SO3–, AcF3–, and (CN)2N–) (Eqns. (12)

NU

and (13)). The 43 different cation-specific and 17 different anion-specific equation coefficients can be combined to permit the estimation of log P and log K values for solutes in a total of 731

MA

different ILs. The number of ion-specific equation coefficients and fragment group values is expected to increase as additional experimental data become available for functionalized IL

TE

D

solvents.

The experimental partition coefficient data that we have measured for solutes dissolved in [PM2iPAm]+[Tf2N]–,

AC CE P

anhydrous

[HM2iPAm]+[Tf2N]–,

[EtOHM2iPAm]+[Tf2N]–,

[CNMeM2iPAm]+[Tf2N]–, and [C1,9(M2iPAm)2]2+[Tf2N]–2 can be used to calculate ion-specific equation coefficients for an additional five cations. At the time that Eqns. (10) and (11) were proposed, provisions were made for calculating equation coefficients for additional cations and anions from newly measured experimental data without having to perform a regression analysis on the entire log K (or log P) dataset. The proposed methodology allows one to retain the numerical values of the ion-specific equation coefficients that have already been calculated. For example, ion-specific equation coefficients of a new cation could be obtained as the difference in the calculated IL-specific equation coefficient minus the respective anion-specific equation coefficient (e.g., ck,cation = ck,il - ck,anion, ek,cation = ek,il - ek,anion, sk,cation = sk,il - sk,anion, ak,cation = ak,il ak,anion, bk,cation = bk,il - bk,anion, lk,cation = lk,il - lk,anion), provided of course that the anion-specific

17

ACCEPTED MANUSCRIPT equation coefficients are known. The five ILs studied in the current communication all contain the [Tf2N]– anion, and the equation coefficients for this particular anion are all equal to zero.

PT

The IL-specific equation coefficients in the Abraham model always represent the sum of a

RI

cation-specific plus an anion-specific contribution. It is impossible to compute numerical values for individual ions unless one sets a reference point. This is analogous to calculating chemical

SC

potentials for single ions or calculating ionic limiting molar conductances for individual ions. In

NU

each case, one must define a reference state from which all single-ion values are calculated. Thus, with the defined [Tf2N]–-anion reference point, the coefficients in Eqns. (10) and (11)

MA

represent the ion-specific values for the [PM2iPAm]+ cation. This is also the case with the equation coefficients for the other four ILs we investigate here. Hence, the coefficients provided

solvent.

AC CE P

4. Conclusion

TE

D

in Table 15 pertain to both the specific IL as well as the respective cation that comprises the IL

Infinite dilution activity coefficients and gas-to-liquid partition coefficients are reported for more than 42 different organic solutes of varying polarity and hydrogen-bonding character dissolved in anhydrous propyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide, hexyl(dimethyl)isopropylammonium

bis(trifluoromethylsulfonyl)imide,

hydroxyethyl(dimethyl)isopropylammonium

2-

bis(trifluoromethylsulfonyl)imide,

cyanomethyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide, and N,N,N’,N’tetramethyl-N,N’-diisopropyl-1,9-nonanediaminium

di[bis(trifluoromethylsulfonyl)imide]

as

determined by inverse gas chromatography in the temperature range from 323.15 K to 363.15 K. The measured gas-to-anhydrous IL partition coefficient data were converted to water-toanhydrous IL partition coefficient data using standard thermodynamic relationships and 18

ACCEPTED MANUSCRIPT published gas-to-water partition coefficient data. Both sets of partition coefficient data were analyzed in terms of the Abraham general solvation model and a modified version of the Equation coefficients were

PT

Abraham model containing ion-specific equation coefficients.

RI

calculated for the five additional cations: namely, propyl(dimethyl)isopropylammonium, hexyl(dimethyl)isopropylammonium,

2-hydroxyethyl(dimethyl)isopropylammonium,

The five newly calculated cation-specific equation coefficients that are

NU

nonanediaminium.

SC

cyanomethyl(dimethyl)isopropylammonium, and N,N,N’,N’-tetramethyl-N,N’-diisopropyl-1,9-

reported in the present communication can be combined with our previously published values for

MA

17 IL anions [41, 52] to enable one to predict log K, log P, and infinite dilution activity coefficients of solutes dissolved in an additional 85 ILs, bringing the total number of ILs for

TE

D

which such predictions can be made to 816. Based on our past experience, Abraham model correlations obtained by combining cation-specific and anion-specific equation coefficients

AC CE P

should be able to predict the partitioning behavior of solutes dissolved in additional anhydrous ILs to within 0.14 log units, provided that the solute descriptors fall within the range of values used in deriving the respective ion-specific equation coefficients. Acknowledgement

Bihan Jiang thanks the University of North Texas’s Texas Academy of Math and Science (TAMS) program for a summer research award.

19

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27

ACCEPTED MANUSCRIPT Table 1. List of Ionic Liquids Studied ______________________________________________________________________________

1,3-Dialkylimidazolium cation:

RI

1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

PT

Ionic Liquid Ref. ______________________________________________________________________________

SC

1-ethyl-3-methylimidazolium dicyanamide

[20] [22] [21]

1-(methylethylether)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[21]

NU

1,3-dimethoxyimidazolium bis(trifluoromethylsulfonyl)imide

[21]

1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate

[24]

MA

1-ethanol-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[24]

1,3-didecyl-2-methylimidazolium bis(trifluoromethylsulfonyl)imide

[24]

1-ethyl-3-methylimidazolium methanesulfonate

[24]

D

1-butyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide

TE

1-(3-cyanopropyl)-3-methylimidazolium dicyanamide

[21] [28]

1-ethyl-3-methylimidazolium methylphosphonate

[25]

AC CE P

1-ethyl-3-methylimidazolium tetracyanoborate

1,3-dimethylimidazolium methylphosphonate

[25]

1-ethanol-3-methylimidazolium tetrafluoroborate

[17]

1-ethanol-3-methylimidazolium hexafluorophosphate

[17]

1,3-dimethylimidazolium dimethylphosphate

[17]

1-ethyl-3-methylimidazolium diethylphosphate

[17]

1-butyl-3-methylimidazolium tetrafluoroborate

[23]

1-hexadecyl-3-methylimidazolium tetrafluoroborate

[19]

1-butyl-3-methylimidazolium hexafluorophosphate

[20]

1-butyl-3-methylimidazolium octyl sulfate

[18]

1-methyl-2-propoxymethylimidazolium bis(trifluoromethylsulfonyl)imide

[27]

1-methyl-3-propoxymethylimidazoilum tetrafluoroborate

[27]

1-methyl-3-propoxymethylimidazolium dicyanmide

[27]

2-methyl-1-octyl-3-propoxymethylimidazolium bis(trifluoromethylsulfonyl)imide

[27]

2-methyl-1-octyl-3-propoxymethylimidazolium dicyanmide

[27] 28

ACCEPTED MANUSCRIPT [27]

1-benzyl-3-propoxymethylimidazolium tetrafluoroborate

[27]

1-benzyl-3-propoxymethylimidazoium dicyanmide

[27]

1-ethyl-3-methylimidazolium tosylate

[18]

PT

1-benzyl-3-propoxymethylimidazolium bis(trifluoromethylsuflonyl)imide

1-butyl-3-methylimidazolium tricyanomethanide

RI

Tetraalkylammonium cation:

SC

trimethyl(hexyl)ammonium bis(trifluoromethylsulfonyl)amide

[26]

[22] [29]

methyl(tributyl)ammonium bis(trifluoromethylsulfonyl)imide

[29]

NU

decyl(trimethyl)ammonium bis(trifluoromethylsulfonyl)imide

[29]

tetraoctylammonium bis(trifluoromethylsulfonyl)imide

[29]

MA

octyl(trimethyl)ammonium bis(trifluoromethylsulfonyl)imide

Tetraalkylphosphonium cation:

[30]

trihexyl(tetradecyl)phosphonium L-lactate

[31]

D

trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide

[31]

1-butyl-1-methylpyrrolidinium thiocyanate

[34]

TE

trihexyl(tetradecyl)phosphonium (1S)-(+)-10-camphorsulfonate

AC CE P

1,1-Dialkylpyrrolidinium cation:

1-butyl-1-methylpyrrolidinium tetracyanoborate

[35]

1-propyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

[32]

1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

[32]

1-pentyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

[32]

1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

[33]

1-octyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

[33]

1-decyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

[33]

1,4-Dialkylpyridinium cation: 1-butyl-4-methylpyridinium tricyanomethanide

[26]

1,1-Dialkylpiperidinium cation: 1-propyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide

[34]

1-butyl-1-methylpiperdidinium bis(trifluoromethylsulfonyl)imide

[35]

1-Alkylquinuclidinium cation: 1-hexylquinuclidinium bis(trifluoromethylsulfonyl)imide

[36] 29

ACCEPTED MANUSCRIPT 1-octylquinuclidinium bis(trifluoromethylsulfonyl)imide

[36]

Miscellaneous dicationic: [27]

3,3'-[1,7-(2,6-dioxaheptane)]bis(2-methyl-1-octylimidazolium) tetrafluoroborate

[27]

3,3'-[1,7-(2,6-dioxaheptane)]bis(2-methy-1-octylimidazolium) dicyanamide

[27]

3,3'-[1,7-(2,6-dioxaheptane)]bis(1-benzylimidazolium) dicyanamide

[27]

RI

PT

3,3'-[1,7-(2,6-dioxaheptane)]bis(1-methylimidazolium) dicyanamide

SC

1,1'-[1,7-(2,6-dioxaheptane)]bis(4-dimethylaminopyridinium) bis(trifluoromethylsulfonyl)imide

[27]

bis(trifluoromethylsulfonyl)imide

MA

Miscellaneous tricationic:

NU

3,3'-[1,7-(2,6-dioxaheptane)]bis(2-methy-1-octylimidazolium)

[27]

3,3',3''-[1,2,3-propanetriyltris(oxymethylene)]tris[1-methylimidazolium] bis(trifluoromethylsulfonyl)imide

[37]

D

3,3',3''-[1,2,3-propanetriyltris(oxymethylene)]tris[1-(phenylmethyl)imidazolium]

TE

bis(trifluoromethylsulfonyl)imide

[37]

1,1',1'-[1,2,3-propanetriyltris(oxymethylene)]tris[4-(dimethylamino)pyridinium]

AC CE P

bis(trifluoromethylsulfonyl)imide

[37]

3,3',3''-[1,2,3-propanetriyltris(oxymethylene)]tris[1-methylimidazolium] dicyanamide

[37]

3,3',3''-[1,2,3-propanetriyltris(oxymethylene)]tris[2-methyl-1-octyl-imidazolium] bis(trifluoromethylsulfonyl)imide

[37]

3,3',3''-[1,2,3-propanetriyltris(oxymethylene)]tris[2-methyl-1-octylimidazolium] tetrafluoroborate

[37]

30

ACCEPTED MANUSCRIPT Table 2 GC operating conditions for activity coefficient measurements.

PT

Injector Temperature 250 °C Helium

Flow rate

10 mL min–1

Column Oven

Isothermal (323 K - 363 K)

Detector Type

TCD

MA

NU

SC

RI

Carrier Gas

AC CE P

TE

D

Detector Temperature 250 °C

31

ACCEPTED MANUSCRIPT

Table 3

PT

Densities (ρ) for the Alkyl(dimethyl)isopropylammonium bis(Trifluoromethylsulfonyl)imide ILs as a function of temperature at P = 101.33 kPa. a

+

ρ/ (kg. m–3)

RI

T/K

–

([CNMeM2iPAm] [Tf2N] )

NU

SC

293.15 303.15 313.15 323.15 333.15 343.15

1493.4 1479.2 1472.2 1468.0 1465.1 1463.1

293.15 303.15 313.15 323.15 333.15 343.15

D TE AC CE P

293.15 303.15 313.15 323.15 333.15 343.15

MA

([PM2iPAm]+ [Tf2N]–) 1397.0 1381.6 1373.8 1369.2 1366.1 1363.9

([HM2iPAm]+ [Tf2N]–) 1318.0 1299.5 1290.3 1284.3 1281.0 1278.4 ([EtOHM2iPAm]+[Tf2N]–)

323.15 333.15 343.15

1450.9 1449.4 1448.3 ([C1,9(M2iPAm)2]2+[Tf2N]–2)

323.15 1382.2 333.15 1379.9 343.15 1378.3 a –3 Standard uncertainties are u(ρ) = 0.0001 g·cm , u(T) = 0.1 K, u(P) = ±0.1 kPa.

32

ACCEPTED MANUSCRIPT Table 4

15.493 13.698 22.888 22.597 33.299 52.125 67.816 97.310 133.28 188.17 263.12 10.063 10.000 13.766 1.104 1.535 2.334 2.191 2.179 2.001 8.617 3.338 4.814 0.549 0.932 0.872 0.750 1.258 1.631 1.999 1.862 2.350 2.573 2.728 6.728 0.960 0.755

D

RI

17.043 15.145 24.982 24.767 36.510 57.877 75.442 109.57 150.64 219.93 300.89 10.731 10.811 14.813 1.092 1.515 2.316 2.168 2.171 1.976 9.069 3.384 4.870 0.593 0.918 0.849 0.743 1.362 1.767 2.196 2.021 2.586 2.865 2.733 6.981 0.930 0.719

343.15 K 353.15 K 363.15 K 14.083 12.583 20.908 20.868 30.300 46.837 61.587 86.637 119.68 167.71 230.10 9.449 9.169 12.690 1.110 1.557 2.352 2.214 2.184 2.032 8.174 3.297 4.722 0.508 0.942 0.892 0.756 1.161 1.493 1.834 1.717 2.151 2.318 2.718 6.554 0.990 0.776

NU

SC

T/K 333.15 K

TE

AC CE P

Hexane 3-Methylpentane Heptane 2,2,4-Trimethylpentane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Dichloromethane

323.15 K

MA

Solutes

PT

) for organic solutes in [PM2iPAm]+[Tf2N]–. a

Activity coefficients at infinite dilution (

13.197 11.822 19.106 19.492 28.068 42.662 56.897 78.857 108.12 151.62 203.48 9.025 8.585 11.705 1.119 1.576 2.368 2.234 2.192 2.061 7.776 3.244 4.665 0.482 0.960 0.922 0.760 1.099 1.396 1.682 1.597 2.017 2.174 2.712 6.360 1.028 0.813

12.138 10.897 17.701 18.088 25.884 38.929 52.075 71.195 97.853 134.62 181.23 8.536 7.992 10.956 1.126 1.595 2.384 2.254 2.198 2.085 7.436 3.209 4.603 0.450 0.971 0.941 0.766 1.025 1.298 1.556 1.489 1.861 1.980 2.705 6.188 1.055 0.839 33

ACCEPTED MANUSCRIPT

PT RI

)=3%, u(T) = 0.1 K.

2.888 0.515 0.574 0.795 8.638 0.654 0.990 0.655 1.005

2.889 0.516 0.566 0.798 8.373 0.660 0.998 0.857 1.010

2.889 0.515 0.558 0.801 8.130 0.667 1.005 0.773 1.014

TE

D

MA

NU

Standard uncertainties u are u(

2.888 0.515 0.583 0.790 9.015 0.645 0.982 0.810 1.003

AC CE P

a

2.888 0.515 0.593 0.787 9.253 0.639 0.973 0.799 0.996

SC

Tetrachloromethane Acetonitrile Nitromethane 1-Nitropropane Triethylamine Pyridine Thiophene Tetrahydrofuran Ethyl acetate

34

ACCEPTED MANUSCRIPT Table 5 Logarithm of the partition coefficient (log K) for organic solutes in [PM2iPAm]+[Tf2N]–.a

0.671 0.647 0.915 0.912 1.162 1.407 1.652 1.896 2.140 2.386 2.629 0.885 1.020 1.152 1.931 2.214 2.415 2.493 2.479 2.615 0.836 1.337 1.596 2.134 2.345 2.336 2.411 1.680 1.809 2.061 1.824 2.187 2.344 0.919 1.000 1.720 1.467 1.466 2.288

RI

SC

0.757 0.732 1.022 1.019 1.287 1.551 1.818 2.076 2.342 2.608 2.863 0.985 1.114 1.258 2.069 2.371 2.587 2.669 2.655 2.795 0.937 1.468 1.739 2.283 2.505 2.496 2.573 1.802 1.945 2.220 1.973 2.354 2.513 1.029 1.117 1.859 1.580 1.596 2.426

NU

0.852 0.820 1.142 1.131 1.427 1.711 1.997 2.275 2.557 2.835 3.121 1.094 1.222 1.380 2.219 2.541 2.770 2.861 2.843 2.989 1.047 1.608 1.895 2.442 2.678 2.671 2.748 1.937 2.099 2.388 2.137 2.536 2.700 1.148 1.239 2.007 1.706 1.736 2.574

D TE

AC CE P

Hexane 3-Methylpentane Heptane 2,2,4-Trimethylpentane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Dichloromethane Tetrachloromethane Acetonitrile

MA

Solutes

PT

T/K 323.15 K 333.15 K 343.15 K 353.15 K 363.15 K 0.582 0.560 0.817 0.810 1.041 1.269 1.493 1.723 1.953 2.177 2.411 0.787 0.926 1.054 1.802 2.069 2.255 2.331 2.312 2.450 0.744 1.215 1.459 1.987 2.189 2.181 2.260 1.557 1.675 1.913 1.685 2.026 2.174 0.816 0.893 1.588 1.351 1.345 2.158

0.508 0.489 0.723 0.720 0.933 1.143 1.352 1.569 1.781 1.995 2.209 0.700 0.843 0.960 1.681 1.935 2.106 2.184 2.156 2.298 0.656 1.099 1.330 1.863 2.046 2.041 2.117 1.450 1.555 1.773 1.557 1.887 2.032 0.720 0.794 1.468 1.246 1.233 2.037 35

ACCEPTED MANUSCRIPT 2.539 2.844 1.165 2.682 2.038 1.964 1.937

PT

2.688 3.021 1.291 2.850 2.181 2.001 2.081

2.399 2.681 1.043 2.527 1.905 1.728 1.803

2.270 2.529 0.927 2.382 1.782 1.660 1.679

AC CE P

TE

D

MA

NU

SC

RI

Nitromethane 2.848 1-Nitropropane 3.213 Triethylamine 1.432 Pyridine 3.028 Thiophene 2.334 Tetrahydrofuran 2.146 Ethyl acetate 2.237 a Standard uncertainties u are u(K)=3%, u(T) = 0.1 K.

36

ACCEPTED MANUSCRIPT Table 6 ) for organic solutes in [HM2iPAm]+[Tf2N]–. a

Activity coefficients at infinite dilution (

MA

7.379 6.552 9.889 9.902 13.246 19.302 23.656 31.691 41.302 55.343 71.605 4.955 4.916 6.306 6.294 0.831 1.109 1.578 1.519 1.513 1.404 4.599 2.153 2.899 0.395 0.676 0.642 0.643 1.128 1.342 1.514 1.442 1.667 1.780 0.771 0.629 1.961 0.500 0.565 0.670

RI

SC

7.843 6.948 10.465 10.318 14.142 20.908 25.705 34.606 45.043 62.064 79.489 5.246 5.157 6.685 6.682 0.828 1.093 1.562 1.496 1.500 1.400 4.762 2.177 2.910 0.425 0.664 0.621 0.636 1.213 1.422 1.651 1.549 1.820 1.934 0.750 0.609 1.963 0.502 0.576 0.670

NU

8.164 7.288 11.178 10.900 15.124 22.511 27.855 37.685 48.892 67.463 87.988 5.489 5.468 7.032 7.085 0.815 1.071 1.535 1.475 1.478 1.352 4.921 2.190 2.921 0.457 0.649 0.602 0.629 1.316 1.507 1.815 1.701 1.998 2.143 0.727 0.585 1.964 0.503 0.588 0.670

D TE

AC CE P

Hexane 3-Methylpentane Heptane 2,2,4-Trimethylpentane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Cycloheptane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Chloroform Dichloromethane Tetrachloromethane Acetonitrile Nitromethane 1-Nitropropane

PT

T/K 323.15 K 333.15 K 343.15 K 353.15 K 363.15 K

Solutes

7.057 6.437 9.450 9.432 12.713 18.183 22.458 29.549 38.515 51.362 67.129 4.814 4.704 6.071 6.040 0.854 1.152 1.624 1.578 1.542 1.465 4.501 2.144 2.889 0.377 0.694 0.669 0.658 1.064 1.274 1.406 1.348 1.582 1.679 0.803 0.655 1.960 0.498 0.559 0.670

6.841 6.047 8.919 8.942 12.027 16.923 21.123 27.632 36.014 47.108 61.879 4.576 4.530 5.807 5.763 0.865 1.181 1.642 1.623 1.540 1.509 4.463 2.118 2.879 0.361 0.702 0.689 0.664 1.001 1.193 1.288 1.272 1.478 1.575 0.820 0.673 1.958 0.496 0.548 0.670 37

ACCEPTED MANUSCRIPT

PT

4.745 0.530 0.777 0.416 0.606 0.763 3.244

4.674 0.546 0.805 0.423 0.630 0.789 2.871

4.613 0.556 0.822 0.430 0.641 0.804 2.614

RI

4.908 4.821 0.518 0.521 0.759 0.765 0.405 0.410 0.586 0.594 0.739 0.747 4.144 3.560 )=3%, u(T) = 0.1 K.

AC CE P

TE

D

MA

NU

SC

Triethylamine Pyridine Thiophene Acetone Tetrahydrofuran Ethyl acetate Water a Standard uncertainties u are u(

38

ACCEPTED MANUSCRIPT Table 7 Logarithm of the partition coefficient (log K) for organic solutes in [HM2iPAm]+[Tf2N]–.a

D

RI

0.910 0.888 1.197 1.194 1.479 1.749 2.025 2.290 2.559 2.825 3.094 1.123 1.248 1.413 1.672 2.014 2.318 2.546 2.614 2.596 2.733 1.044 1.479 1.767 2.200 2.446 2.436 2.438 1.650 1.812 2.102 1.858 2.256 2.416 1.787 1.516 1.595 2.263 2.503 2.887

SC

1.010 0.985 1.320 1.317 1.617 1.905 2.197 2.483 2.770 3.048 3.341 1.226 1.359 1.530 1.801 2.151 2.476 2.718 2.793 2.775 2.907 1.152 1.611 1.915 2.351 2.610 2.601 2.602 1.776 1.963 2.261 2.011 2.423 2.594 1.923 1.630 1.725 2.398 2.651 3.060

NU

1.129 1.096 1.449 1.445 1.768 2.078 2.387 2.696 3.003 3.306 3.601 1.343 1.476 1.661 1.943 2.304 2.649 2.906 2.986 2.967 3.111 1.271 1.754 2.075 2.513 2.786 2.778 2.777 1.909 2.126 2.429 2.170 2.606 2.784 2.071 1.753 1.861 2.542 2.810 3.240

TE

AC CE P

Hexane 3-Methylpentane Heptane 2,2,4-Trimethylpentane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Cycloheptane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Chloroform Dichloromethane Tetrachloromethane Acetonitrile Nitromethane 1-Nitropropane

MA

Solutes

PT

T/K 323.15 K 333.15 K 343.15 K 353.15 K 363.15 K 0.811 0.782 1.081 1.083 1.342 1.597 1.854 2.107 2.359 2.605 2.850 1.017 1.144 1.297 1.546 1.876 2.162 2.377 2.440 2.423 2.555 0.939 1.353 1.623 2.052 2.288 2.278 2.280 1.528 1.672 1.949 1.716 2.089 2.244 1.652 1.403 1.471 2.130 2.358 2.712

0.715 0.703 0.979 0.984 1.223 1.462 1.701 1.938 2.173 2.408 2.634 0.929 1.047 1.193 1.432 1.753 2.023 2.226 2.284 2.268 2.397 0.836 1.237 1.492 1.917 2.144 2.135 2.137 1.418 1.549 1.813 1.582 1.945 2.090 1.535 1.300 1.359 2.011 2.227 2.564 39

ACCEPTED MANUSCRIPT 1.237 2.566 1.956 1.854 1.819 1.868 1.679

PT

1.366 2.730 2.101 1.983 1.955 2.014 1.795

1.131 2.419 1.827 1.736 1.699 1.737 1.562

AC CE P

TE

D

MA

NU

SC

RI

Triethylamine 1.665 1.516 Pyridine 3.077 2.900 Thiophene 2.400 2.246 Acetone 2.252 2.116 Tetrahydrofuran 2.238 2.119 Ethyl acetate 2.325 2.166 Water 2.064 1.935 a Standard uncertainties u are u(K)=3%, u(T) = 0.1 K.

40

ACCEPTED MANUSCRIPT Table 8 ) for organic solutes in [EtOHM2iPAm]+[Tf2N]–. a

PT

40.828 60.579 142.96 212.46 307.44 447.14 643.37 15.856 15.661 22.632 22.103 1.546 2.275 3.599 3.447 3.284 3.159 13.609 5.030 7.732 0.414 0.826 0.811 0.546 0.739 0.925 1.218 1.057 1.580 1.653 2.363 5.975 1.415 0.982 4.413 0.419 0.546 1.570 1.323 0.355

SC

44.932 70.570 162.42 243.51 351.67 520.01 737.27 16.993 16.826 24.944 24.428 1.547 2.273 3.614 3.452 3.290 3.158 14.451 5.168 7.992 0.438 0.802 0.777 0.525 0.764 0.956 1.274 1.081 1.650 1.732 2.328 5.854 1.384 0.953 4.513 0.414 0.550 1.475 1.311 0.344

343.15 K 353.15 K 363.15 K

RI

T/K 333.15 K

MA

51.122 78.739 185.89 281.77 404.47 605.69 845.65 19.139 18.982 27.909 27.280 1.548 2.271 3.636 3.456 3.297 3.159 16.014 5.389 8.238 0.462 0.776 0.746 0.506 0.793 0.994 1.334 1.119 1.755 1.880 2.298 5.740 1.370 0.922 4.645 0.412 0.556 1.355 1.300 0.333

D

AC CE P

2,2,4-Trimethylpentane Octane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Cycloheptane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Dichloromethane Tetrachloromethane Acetonitrile Nitromethane Triethylamine Thiophene Acetone

323.15 K

TE

Solutes

NU

Activity coefficients at infinite dilution (

36.752 54.725 125.58 188.27 273.54 396.82 563.26

33.216 47.529 110.61 162.64 236.67 343.27 486.82

13.987 20.425 20.224 1.545 2.278 3.584 3.442 3.278 3.158 12.579 4.833 7.532 0.400 0.856 0.852 0.573 0.727 0.908 1.175 1.036 1.536 1.599 2.385 6.050 1.448 1.013 4.319 0.425 0.542 1.659 1.334 0.371

12.828 18.224 1.544 2.280 3.572 3.438 3.274 3.157 11.660 4.596 7.159 0.386 0.864 0.875 0.584 0.699 0.874 1.099 0.999 1.475 1.528 2.400 6.130 1.461 1.021 4.217 0.427 0.540 1.812 1.339 0.375 41

ACCEPTED MANUSCRIPT 0.569 0.594 0.862 0.878 1.463 1.359 )=3%, u(T) = 0.1 K.

0.618 0.900 1.294

0.651 0.935 1.233

0.661 0.954 1.179

AC CE P

TE

D

MA

NU

SC

RI

PT

Tetrahydrofuran Ethyl acetate Water a Standard uncertainties u are u(

42

ACCEPTED MANUSCRIPT Table 9 Logarithm of the partition coefficient (log K) for organic solutes in [EtOHM2iPAm]+[Tf2N]–.a

0.718 0.959 1.437 1.676 1.918 2.165 2.414 0.756 0.886 0.998 1.279 1.922 2.200 2.395 2.478 2.477 2.606 0.710 1.276 1.517 2.379 2.568 2.544 2.726 2.017 2.175 2.414 2.207 2.505 2.683 1.091 1.151 1.697 1.476 1.400 2.519 2.711 2.075 2.056 2.228

0.619 0.859 1.284 1.504 1.728 1.958 2.180 0.658 0.785 0.898 1.167 1.786 2.047 2.227 2.305 2.304 2.431 0.613 1.151 1.380 2.220 2.399 2.375 2.550 1.874 2.015 2.237 2.033 2.319 2.488 0.983 1.038 1.563 1.363 1.280 2.375 2.558 1.966 1.919 2.087

353.15 K 363.15 K

SC

RI

PT

343.15 K

NU

0.815 1.092 1.603 1.862 2.126 2.393 2.670 0.841 0.976 1.102 1.399 2.066 2.363 2.572 2.662 2.659 2.787 0.798 1.403 1.665 2.547 2.749 2.725 2.913 2.170 2.347 2.603 2.392 2.702 2.881 1.221 1.322 1.837 1.596 1.528 2.669 2.874 2.265 2.207 2.378

D TE

AC CE P

2,2,4-Trimethylpentane Octane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Cycloheptane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Dichloromethane Tetrachloromethane Acetonitrile Nitromethane Triethylamine Thiophene Acetone

323.15 K

MA

Solutes

T/K 333.15 K

0.531 0.749 1.147 1.343 1.548 1.757 1.967

0.454 0.667 1.023 1.208 1.396 1.586 1.778

0.712 0.811 1.061 1.658 1.901 2.069 2.140 2.140 2.263 0.533 1.040 1.249 2.065 2.237 2.213 2.380 1.734 1.860 2.067 1.871 2.143 2.305 0.870 0.913 1.437 1.254 1.169 2.240 2.410 1.792 1.777 1.950

0.635 0.972 1.542 1.771 1.928 1.928 1.981 2.115 0.459 0.941 1.136 1.928 2.094 2.071 2.233 1.614 1.724 1.922 1.728 1.986 2.143 0.770 0.803 1.325 1.159 1.067 2.117 2.278 1.577 1.655 1.835 43

ACCEPTED MANUSCRIPT 1.987 1.983 2.234

1.845 1.834 2.087

1.726 1.703 1.921

AC CE P

TE

D

MA

NU

SC

RI

PT

Tetrahydrofuran 2.291 2.139 Ethyl acetate 2.298 2.137 Water 2.556 2.394 a Standard uncertainties u are u(K)=3%, u(T) = 0.1 K.

44

ACCEPTED MANUSCRIPT Table 10 ) for organic solutes in [CNMeM2iPAm]+[Tf2N]–. a

MA

102.16 176.76 252.44 388.45 561.42 834.34 1174.3 25.430 24.400 37.470 2.196 3.343 5.479 4.997 4.918 4.495 21.151 8.022 13.089 0.547 1.148 1.062 1.150 1.633 2.263 2.067 3.035 3.194 4.781 15.538 2.210 1.332 7.352 0.481 0.591 1.040 21.332 0.796 1.878 0.461

RI

118.05 210.46 293.82 457.04 657.33 969.46 1350.3 27.607 27.489 42.844 2.217 3.350 5.541 5.028 4.961 4.504 24.346 8.483 13.784 0.585 1.131 1.029 1.225 1.757 2.458 2.226 3.291 3.484 4.827 16.938 2.210 1.294 7.655 0.475 0.591 1.040 21.434 0.791 1.883 0.464

PT

T/K 333.15 K 343.15 K 353.15 K 363.15 K

NU

139.66 244.01 341.68 503.47 744.83 1097.7 1524.3 31.737 31.360 48.968 2.253 3.357 5.605 5.080 5.032 4.513 24.792 9.048 14.525 0.628 1.112 1.000 1.319 1.916 2.720 2.441 3.661 3.931 5.004 16.873 2.211 1.273 8.106 0.473 0.591 1.040 21.555 0.771 1.882 0.453

D

159.91 288.03 393.98 565.01 884.70 1285.6 1643.4 37.396 36.934 57.070 2.291 3.363 5.681 5.133 5.073 4.523 29.129 9.607 15.279 0.652 1.100 0.964 1.426 2.097 2.971 2.703 4.118 4.575 5.337 18.874 2.211 1.224 8.577 0.474 0.591 1.040 21.770 0.746 1.883 0.437

AC CE P

Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Dichloromethane Tetrachloromethane Acetonitrile Nitromethane 1-Nitropropane Triethylamine Pyridine Thiophene Acetone

313.15 K 323.15 K

TE

Solutes

SC

Activity coefficients at infinite dilution (

92.020 149.45 220.38 334.78 495.15 734.01 1036.6 23.074 21.648 33.622 2.165 3.337 5.471 4.958 4.881 4.486 20.109 7.879 12.434 0.521 1.170 1.105 1.093 1.530 2.088 1.924 2.846 2.986 4.574 14.838 2.208 1.362 7.146 0.488 0.591 1.040 21.115 0.825 1.884 0.474

82.715 134.69 198.58 296.57 443.28 631.22 893.87 20.497 19.243 29.799 2.139 3.331 5.417 4.914 4.836 4.482

11.692 0.502 1.180 1.131 1.039 1.420 1.938 1.872 2.696 2.804 14.133 2.208 6.763 0.497 0.591 1.040 20.905 0.848 1.883 0.478 45

ACCEPTED MANUSCRIPT 1.167 2.103

1.215 1.954

1.220 1.709

AC CE P

TE

D

MA

NU

SC

RI

PT

Ethyl acetate 1.119 1.138 1.152 Water 2.858 2.453 2.281 a Standard uncertainties u are u( )=3%, u(T) = 0.1 K.

46

ACCEPTED MANUSCRIPT Table 11

RI

0.741 0.948 1.185 1.408 1.652 1.900 2.156 0.550 0.678 0.768 1.769 2.035 2.214 2.312 2.301 2.445 0.489 1.066 1.285 2.258 2.424 2.427 1.817 1.916 2.134 1.899 2.211 2.384 0.785 0.719 1.500 1.348 1.176 2.464 2.685 2.905 0.918 2.764

SC

NU

0.848 1.089 1.344 1.616 1.866 2.140 2.420 0.627 0.763 0.864 1.908 2.198 2.389 2.494 2.481 2.633 0.614 1.184 1.424 2.420 2.598 2.603 1.954 2.067 2.299 2.058 2.388 2.566 0.889 0.859 1.634 1.461 1.291 2.614 2.853 3.095 1.068 2.950

MA

0.985 1.238 1.526 1.836 2.082 2.390 2.729 0.703 0.847 0.963 2.059 2.376 2.577 2.693 2.676 2.838 0.688 1.313 1.574 2.592 2.780 2.796 2.102 2.231 2.483 2.231 2.582 2.756 0.990 0.961 1.780 1.590 1.418 2.773 3.033 3.301 1.226 3.153

D

AC CE P

Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Dichloromethane Tetrachloromethane Acetonitrile Nitromethane 1-Nitropropane Triethylamine Pyridine

T/K 323.15 K 333.15 K 343.15 K 353.15 K 363.15 K

313.15 K

TE

Solutes

PT

Logarithm of the partition coefficient (log K) for organic solutes in [CNMeM2iPAm]+[Tf2N]–.a

0.637 0.833 1.042 1.248 1.472 1.692 1.924 0.459 0.598 0.685 1.638 1.885 2.051 2.142 2.130 2.273 0.427 0.954 1.156 2.104 2.262 2.263 1.687 1.773 1.973 1.747 2.041 2.208 0.677 0.628 1.375 1.236 1.064 2.321 2.529 2.731 0.776 2.599

0.528 0.728 0.908 1.098 1.295 1.496 1.707 0.382 0.527 0.599 1.518 1.746 1.895 1.988 1.968 2.115 0.334 0.833 1.036 1.956 2.107 2.105 1.563 1.639 1.823 1.607 1.880 2.039 0.593 0.528 1.259 1.130 0.955 2.185 2.384 2.569 0.644 2.433

0.431 0.607 0.774 0.953 1.129 1.327 1.520 0.323 0.464 0.528 1.406 1.619 1.753 1.849 1.817 1.969

0.929 1.819 1.965 1.965 1.447 1.519 1.681 1.460 1.729 1.884 0.438 1.150 0.867 2.056 2.248 2.419 0.520 2.281 47

ACCEPTED MANUSCRIPT 1.901 2.103 2.024 2.174

1.763 1.979 1.876 2.029

1.632 1.849 1.726 1.892

1.512 1.735 1.601 1.792

AC CE P

TE

D

MA

NU

SC

RI

PT

Thiophene 2.213 2.051 Acetone 2.412 2.250 Ethyl acetate 2.357 2.183 Water 2.480 2.337 a Standard uncertainties u are u(K)=3%, u(T) = 0.1 K.

48

ACCEPTED MANUSCRIPT Table 12

AC CE P

TE

D

343.15 K 353.15 K 363.15 K

SC

18.349 16.535 27.426 28.820 40.003 62.400 83.176 119.48 167.05 239.35 334.68 11.221 11.018 15.384 14.811 1.112 1.567 2.433 2.273 2.271 2.041 9.848 3.755 5.460 0.604 1.036 0.971 0.790 1.331 1.750 2.175 2.074 2.594 2.778 3.103 7.805 1.016 3.134 0.566

NU

MA

21.057 18.687 29.935 32.329 44.094 69.918 92.629 134.68 187.64 275.78 382.97 12.655 12.360 17.027 16.319 1.089 1.548 2.411 2.215 2.254 1.918 10.549 3.837 5.526 0.656 1.020 0.947 0.775 1.440 1.919 2.386 2.267 2.876 3.101 3.199 7.935 0.989 3.173 0.567

PT

T/K 323.15 K 333.15 K

Solutes Hexane 3-Methylpentane Heptane 2,2,4-Trimethylpentane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Cycloheptane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Tetrachloromethane Acetonitrile

) for organic solutes in [C1,9(M2iPAm)2]2+[Tf2N]–2. a

16.977 14.701 24.502 25.988 35.502 56.512 74.602 107.20 150.21 214.31 297.41 10.360 10.090 14.139 13.673 1.133 1.608 2.480 2.319 2.290 2.101 9.179 3.705 5.402 0.568 1.058 1.006 0.802 1.247 1.618 2.002 1.919 2.398 2.554 3.016 7.637 1.035 3.113 0.565

RI

Activity coefficients at infinite dilution (

15.188 13.244 22.092 22.943 32.489 51.539 69.364 98.641 137.84 193.99 269.75 9.748 9.333 13.088 12.682 1.160 1.667 2.520 2.406 2.308 2.201 8.871 3.665 5.356 0.541 1.082 1.046 0.822 1.188 1.539 1.858 1.794 2.247 2.398 2.951 7.518 1.093 3.080 0.565

14.358 12.594 19.981 20.717 29.981 45.396 60.814 85.762 122.06 168.76 236.30 9.150 8.666 11.978 11.644 1.184 1.692 2.545 2.460 2.328 2.242 8.164 3.615 5.307 0.511 1.107 1.075 0.823 1.092 1.397 1.693 1.682 2.093 2.212 2.876 7.363 1.127 3.064 0.564 49

ACCEPTED MANUSCRIPT

PT

0.624 0.882 8.089 0.648 1.000 0.530 0.740 1.143 2.899

RI

0.643 0.628 0.883 0.883 7.389 7.672 0.632 0.638 0.972 0.990 0.530 0.530 0.734 0.736 1.129 1.138 3.637 3.195 )=3%, u(T) = 0.1 K.

0.624 0.883 8.357 0.676 1.011 0.530 0.904 1.187 2.711

0.616 0.883 8.665 0.685 1.028 0.530 0.750 1.223 2.286

AC CE P

TE

D

MA

NU

SC

Nitromethane 1-Nitropropane Triethylamine Pyridine Thiophene Acetone Tetrahydrofuran Ethyl acetate Water a Standard uncertainties u are u(

50

ACCEPTED MANUSCRIPT Table 13 Logarithm of the partition coefficient (log K) for organic solutes in [C1,9(M2iPAm)2]2+[Tf2N]–2.a

RI

0.548 0.537 0.803 0.775 1.051 1.283 1.526 1.761 1.999 2.237 2.475 0.803 0.936 1.062 1.335 1.880 2.157 2.350 2.430 2.414 2.558 0.744 1.244 1.495 2.042 2.252 2.241 2.343 1.607 1.731 1.981 1.733 2.098 2.259 0.832 0.891 1.658 1.395 2.208

SC

0.641 0.608 0.901 0.871 1.165 1.431 1.687 1.945 2.201 2.461 2.716 0.896 1.029 1.168 1.456 2.023 2.320 2.526 2.611 2.595 2.744 0.836 1.374 1.642 2.230 2.417 2.407 2.397 1.736 1.872 2.141 1.884 2.269 2.437 0.944 1.010 1.791 1.521 2.360

NU

MA

0.718 0.687 1.021 0.973 1.303 1.586 1.866 2.143 2.419 2.694 2.974 0.980 1.122 1.277 1.581 2.171 2.489 2.710 2.791 2.784 2.938 0.939 1.511 1.798 2.355 2.590 2.581 2.687 1.870 2.021 2.310 2.045 2.447 2.623 1.038 1.086 1.938 1.653 2.489

D TE

AC CE P

Hexane 3-Methylpentane Heptane 2,2,4-Trimethylpentane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Cycloheptane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Tetrachloromethane Acetonitrile

PT

T/K 323.15 K 333.15 K 343.15 K 353.15 K 363.15 K

Solutes

0.478 0.468 0.712 0.697 0.935 1.145 1.365 1.583 1.805 2.028 2.246 0.711 0.847 0.963 1.223 1.743 2.002 2.181 2.257 2.239 2.379 0.644 1.120 1.356 1.894 2.095 2.084 2.183 1.481 1.590 1.828 1.592 1.937 2.089 0.744 0.778 1.519 1.271 2.076

0.393 0.384 0.628 0.619 0.826 1.034 1.242 1.446 1.643 1.854 2.052 0.628 0.765 0.879 1.126 1.625 1.867 2.035 2.104 2.088 2.224 0.574 1.017 1.239 1.765 1.958 1.947 2.044 1.380 1.480 1.694 1.461 1.794 1.942 0.638 0.663 1.397 1.165 1.955 51

ACCEPTED MANUSCRIPT 2.314 2.594 0.973 2.474 1.857 1.748 1.662 1.690 1.704

RI

PT

2.460 2.762 1.152 2.643 1.845 1.875 1.869 1.839 1.844

2.184 2.444 0.857 2.328 1.729 1.640 1.631 1.642 1.620

AC CE P

TE

D

MA

NU

SC

Nitromethane 2.771 2.613 1-Nitropropane 3.120 2.941 Triethylamine 1.386 1.319 Pyridine 2.991 2.812 Thiophene 2.293 2.145 Acetone 2.138 2.003 Tetrahydrofuran 2.140 2.000 Ethyl acetate 2.141 1.983 Water 2.121 1.982 a Standard uncertainties u are u(K)=3%, u(T) = 0.1 K.

52

ACCEPTED MANUSCRIPT

TABLE 14 and capacity

values at infinite dilution for different separation problems at T = 323.15 K using [Tf2N]– based ILs.

anion

Cation

hexane/benzene hexane/pyridine hexane/thiophene heptane/thiophene reference 15.60/0.92

26.67/1.56

17.51/1.02

22.87/1.02

This work

hexyl(dimethyl)isopropylammonium

10.02/1.23

3.49/0.43

4.78/0.43

This work

N,N,N’,N’-tetramethyl-N,N’-diisopropyl-1,9-nonanediaminium

19.33/0.92

33.32/1.58

21.66/1.03

30.80/1.03

This work

1-hexylquinuclidinium

10.17/1.51

13.76/2.05

11.25/1.67

14.92/1.67

[36]

PT ED

1-propyl-1-methylpyrrolidinium 1-butyl-1-methylpyrrolidinium 1-pentyl-1-methylpyrrolidinium 1-hexyl-1-methylpyrrolidinium

1-butyl-3-methylimidazolium 4-methyl-N-butylpyridinium N-octylisoquinolinium

CE

1-propyl-1-methylpiperidinium 1-ethyl-3-methylimidazolium

20.69/1.88

7.58/1.81

9.69/2.31

8.08/1.93

10.21/1.93

[36]

16.69/1.01

26.2/1.59

19.23/1.16

27.95/1.16

[32]

15.2/1.10

23.64/1.69

17/1.22

24.01/1.22

[32]

14.3/1.22

22.13/1.89

15.8/1.35

20.39/1.35

[32]

10.2/1.32

14.88/1.92

MA

1-octylquinuclidinium

1-methyl-3-methylimidazolium

NU

propyl(dimethyl)isopropylammonium

AC

[Tf2N]

–

/

SC

ILs

RI

PT

Selectivity

20.5/1.06

11.1/1.43 23.14/1.19

[33] 30.19/1.19

[45]

24.85/0.73

[46]

20/0.83

[46]

14.06/1.11

18.29/1.43

22.14/1.43

[46], [47]

18.2/1.37

20.70/1.56

27.01/1.56

[48]

6.71/1.62

7.48/1.81

8.91/1.81

[49]

N-methyl-2-pyrrolidone (NMP)

10.38/0.95

Sulfolane

16.86/0.43

[50] 34.61/0.88

[51]

53

ACCEPTED MANUSCRIPT TABLE 15 Logarithm of gas-to-IL partition coefficients, log K, and logarithm of water-to-IL partition

B

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.225 0.310 0.244 0.610 0.601 0.613 0.623 0.613 0.663 0.080 0.166 0.160 0.166 0.143 0.154 0.289 0.329 0.278 0.246 0.236 0.212 0.217 0.224 0.041 –0.063 0.425 0.390 0.458 0.237

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.100 0.100 0.060 0.520 0.520 0.510 0.520 0.520 0.560 0.080 0.220 0.230 0.700 0.680 0.660 0.520 0.750 0.440 0.420 0.420 0.360 0.390 0.420 0.250 0.170 0.490 0.570 0.380 0.900

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.100 0.090 0.000 0.000 0.000 0.000 0.000 0.430 0.370 0.370 0.330 0.370 0.370 0.000 0.000 0.150 0.100 0.000 0.070

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.140 0.140 0.150 0.160 0.160 0.160 0.070 0.120 0.100 0.510 0.510 0.510 0.480 0.640 0.470 0.480 0.480 0.560 0.480 0.480 0.450 0.570 0.020 0.050 0.000 0.320

NU

MA

D

L

V

RI

A

2.668 2.581 3.173 3.106 3.677 4.182 4.686 5.191 5.696 6.200 6.705 2.907 2.964 3.319 2.786 3.325 3.778 3.839 3.839 3.939 2.572 2.510 3.000 2.287 2.755 2.811 2.636 2.892 0.970 1.485 2.031 1.764 2.413 2.601 2.015 2.501 2.480 2.019 2.823 1.739

SC

S

AC CE P

Hexane 3-Methylpentane Heptane 2,2,4-Trimethylpentane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Methylcyclopentane Cyclohexane Methylcyclohexane Benzene Toluene Ethylbenzene m-Xylene p-Xylene o-Xylene 1-Hexene 1-Hexyne 1-Heptyne 2-Butanone 2-Pentanone 3-Pentanone Tetrahydrofuran 1,4-Dioxane Methanol Ethanol 1-Propanol 2-Propanol 2-Methyl-1-propanol 1-Butanol Diethyl ether Diisopropyl ether Chloroform Dichloromethane Carbon tetrachloride Acetonitrile

E

TE

Solute

PT

coefficients, log P, for solutes dissolved in anhydrous [PM2iPAm]+[(Tf)2N]– at 298.15 K

0.9540 0.9540 1.0949 1.2358 1.2358 1.3767 1.5176 1.6590 1.7994 1.9400 2.0810 0.8454 0.8454 0.9863 0.7164 0.8573 0.9982 0.9982 0.9982 0.9982 0.9110 0.8680 1.0089 0.6879 0.8288 0.8288 0.6220 0.6810 0.3082 0.4491 0.5900 0.5900 0.7309 0.7309 0.7309 1.0127 0.6167 0.4943 0.7390 0.4042

Log K

log P

1.118 1.066 1.479 1.446 1.819 2.156 2.497 2.828 3.158 3.468 3.842 1.399 1.526 1.719 2.640 3.015 3.283 3.396 3.369 3.532 1.357 1.997 2.331 2.886 3.159 3.158 2.551 3.236 2.312 2.528 2.858 2.595 3.045 3.223 1.481 1.582 2.421 2.059 2.128 2.987

2.938 2.906 3.439 3.566 3.929 4.306 4.817 5.208 5.688

2.569 2.426 2.969 2.010 2.365 2.703 2.786 2.779 2.872 2.517 2.207 2.771 0.156 0.579 0.658 0.001 –0.474 –1.428 –1.145 –0.702 –0.885 –0.255 –0.237 0.311 0.532 1.631 1.099 2.318 0.137

54

ACCEPTED MANUSCRIPT 0.060 0.000 0.000 0.000 0.000 0.000

0.310 0.310 0.790 0.520 0.150 0.450

1.892 2.894 3.040 3.022 2.819 2.314

0.4237 0.7055 1.0538 0.6753 0.6411 0.7470

PT

0.950 0.950 0.150 0.840 0.570 0.620

3.294 3.747 1.828 3.527 2.764 2.675

0.344 1.297 –0.532 0.087 1.724 0.515

TE

D

MA

NU

SC

RI

0.313 0.242 0.101 0.631 0.687 0.106

AC CE P

Nitromethane 1-Nitropropane Triethylamine Pyridine Thiophene Ethyl acetate

55

ACCEPTED MANUSCRIPT

TABLE 16

PT

Equation Coefficients for Log P and Log K Abraham Model Correlations for [PM2iPAm]+[Tf2N]–, [HM2iPAm]+[Tf2N]–,

([HM2iPAm]+[(Tf)2N]–) Log P Log K

([EtOHM2iPAm]+[Tf2N]–) Log P Log K

([CNMeM2iPAm]+[Tf2N]–) Log P Log K

–0.378 (0.118) –0.702 (0.071)

0.115 (0.114)

0.723 (0.117) 2.532 (0.064)

–0.340 (0.129) –0.531 (0.077)

b

v

–1.061 (0.178) 2.578 (0.139)

–4.594 (0.109) 0.331 (0.083)

3.388 (0.094)

0.582 (0.115) 2.232 (0.091)

–1.194 (0.183) 2.297 (0.137)

–4.631 (0.118) 0.344 (0.100)

3.640 (0.104)

–0.669 (0.143) –0.934 (0.075)

0.236 (0.129) 0.200 (0.088)

0.617 (0.138) 2.361 (0.086)

–0.850 (0.178) 2.695 (0.115)

–3.356 (0.123) 1.532 (0.086)

3.270 (0.109)

–1.001 (0.151) –1.344 (0.114)

–0.459 (0.198) 3.118 (0.174)

–4.191 (0.120) 0.819 (0.129)

3.529 (0.117)

–0.140 (0.122)

1.512 (0.126) 3.283 (0.116)

SC

a

MA

NU

s

PT ED

Log K

e

–0.124 (0.092)

CE

([PM2iPAm]+[(Tf)2N]–) Log P

c

AC

Ionic Liquid/Property

RI

[EtOHM2iPAm]+[Tf2N]–, [CNMeM2iPAm]+[Tf2N]–, and [C1,9(M2iPAm)2]2+[Tf2N]–2 at 298.15 K l

0.682 (0.017)

0.736 (0.018)

0.641 (0.017)

0.735 (0.025)

N

SD

R2

F

44

0.113

0.996

1889

46

0.096

0.985

654.2

45

0.125

0.996

2527

47

0.099

0.980

407.8

41

0.122

0.994

1188

43

0.086

0.986

538.2

40

0.134

0.994

1341

42

0.126

0.978

316.6

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ACCEPTED MANUSCRIPT

–4.438 (0.156) 0.492 (0.103)

3.429 (0.110)

PT

–1.034 (0.190) 2.544 (0.116)

RI

0.798 (0.142) 2.533 (0.086)

0.690 (0.015)

45

0.131

0.995

1511

47

0.086

0.988

684.7

PT ED

MA

NU

SC

0.225 (0.127) 0.175 (0.082)

CE

Log K

–0.606 (0.137) –0.894 (0.064)

AC

([C1,9(M2iPAm)2]2+[Tf2N]–2) Log P

57

ACCEPTED MANUSCRIPT

SC

RI

PT

Figure 1.

[EtOHM2iPAm]+[Tf2N]–

[CNMeM2iPAm]+[Tf2N]–

TE

D

MA

NU

[HM2iPAm]+[Tf2N]–

Figure

1.

AC CE P

[PM2iPAm]+[Tf2N]–

Molecular

[C1,9(M2iPAm)2]2+[Tf2N]–2

structures

of

cations

in

the

IL

solvents

propyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide ([PM2iPAm]+[Tf2N]–), hexyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide ([HM2iPAm]+[Tf2N]–), 2-hydroxyethyl(dimethyl)isopropyl-ammonium ([EtOHM2iPAm]+[Tf2N]–),

bis(trifluoromethylsulfonyl)imide cyanomethyl(dimethyl)isopropylammonium

bis(trifluoromethylsulfonyl)imide ([CNMeM2iPAm]+[Tf2N]–), and N,N,N’,N’-tetramethyl-N,N’diisopropyl-1,9-nonanediaminium

di[bis(trifluoromethyl-sulfonyl)imide]

([C1,9(M2iPAm)2]2+[Tf2N]–2).

58

ACCEPTED MANUSCRIPT

AC CE P

TE

D

MA

NU

SC

RI

PT

Figure 2

Figure 2. Comparison between the observed log K data and calculated log K values based on Eqn. (9) for the 46 organic solutes dissolved in [PM2iPAm]+[Tf2N]– at 298.15 K.

59

ACCEPTED MANUSCRIPT

AC CE P

TE

D

MA

NU

SC

RI

PT

Figure 3

Figure 3. Comparison between the observed log P data and calculated log P values based on Eqn. (10) for the 44 organic solutes dissolved in [PM2iPAm]+[Tf2N]– at 298.15 K.

60

ACCEPTED MANUSCRIPT HIGHLIGHTS Infinite Dilution Activity Coefficients of Solutes Dissolved in Anhydrous

PT

Alkyl(dimethyl)isopropylammonium bis(Trifluoromethylsulfonyl)imide Ionic Liquids

RI

Containing Functionalized- and Nonfunctionalized-Alkyl Chains

SC

Fabrice MUTELETa, Dominique ALONSOa, Sudhir RAVULA,b Gary A. BAKERb, Bihan

a

NU

JIANGc, William E. ACREE, Jr.c

Universite de Lorraine, Laboratoire de Reactions et Genie des Procedes (UPR CNRS 3349), 1

MA

rue Grandville, BP 20451 54001 NANCY, FRANCE.

Department of Chemistry, University of Missouri-Columbia, COLUMBIA, MISSOURI 65211.

c

Department of Chemistry, 1155 Union Circle #305070, University of North Texas, DENTON,



AC CE P

TEXAS 76203-5017.

TE

D

b

Infinite dilution activity coefficients of organic solutes measured in five [R4N]+[Tf2N]ionic liquids



Gas-liquid partition coefficients of organic solutes measured in five [R4N]+[Tf2N]- ionic liquids



Abraham model correlations developed for predicting gas-liquid partition coefficients of solutes in ionic liquids

61