Accepted Manuscript

Liquid-liquid separation of hexane/hex-1-ene and cyclohexane/cyclohexene by

dicyanamide-based ionic liquids

Monika Karpińska, Michał Wlazło, Maciej Zawadzki, Urszula Domańska

PII: S0021-9614(17)30333-6
DOI: http://dx.doi.org/10.1016/j.jct.2017.09.014
Reference: YJCHT 5213

To appear in: J. Chem. Thermodynamics

Received Date: 8 July 2017

Revised Date: 9 September 2017
Accepted Date: 11 September 2017

Please cite this article as: M. Karpińska, M. Wlazło, M. Zawadzki, U. Domańska, Liquid-liquid separation of hexane/
hex-1-ene and cyclohexane/cyclohexene by dicyanamide-based ionic liquids, J. Chem. Thermodynamics (2017),
doi: http://dx.doi.org/10.1016/j.jct.2017.09.014

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J. Chem. Thermodyn.

Liquid-liquid separation of hexane/hex-1-ene and cyclohexane/cyclohexene

by dicyanamide-based ionic liquids

Monika Karpińskaa, Michał Wlazłoa , Maciej Zawadzkia, Urszula Domańskaa,b*

a
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology,
Noakowskiego 3, 00-664 Warsaw, Poland

b
Thermodynamic Research Unit, School of Chemical Engineering, University of KwaZulu-
Natal, Howard College Campus, King George V Avenue, Durban 4001, South Africa.

Keywords:
Literature review
Experimental LLE measurements
Ionic liquids with [DCA]- anion
Selectivity, Solute distribution ratio

NRTL correlation

*Corresponding author at Department of Physical Chemistry, Faculty of Chemistry, Warsaw

University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland. Tel.:+48 22 6213115; fax: +48
22 6282741. E-mail address: ula@ch.pw.edu.pl (U. Domańska).

1
ABSTRACT

The work presented focused on the experimental liquid-liquid phase equilibrium

measurements in ternary systems {ionic liquid (1) + hex-1-ene (2) + hexane (3)} and (ionic

liquid (1) + cyclohexene (2) + cyclohexane (3)} at temperature T = 298.15 K and ambient

pressure. The dicyanamide-based ionic liquids (ILs) were discussed as solvents for two types

of separation problems of hexane/hex-1-ene and cyclohexane/cyclohexene. The objective of

this work was to explore the feasibility of six ILs, namely N-ethyl-N-methylmorpholinium

dicyanamide, [EMMor][DCA], (3-hydroxypropyl)-1-methylmorpholinium dicyanamide, [N-

C3OHMMor][DCA], 1-(3-hydroxypropyl)-3-methylimidazolium dicyanamide, [N-

C3OHMIM][DCA], 1-(3-hydroxypropyl)pyridinium dicyanamide, [N-C3OHPy][DCA], (3-

cyanopropyl)pyridinium dicyanamide, [N-C3CNPy][DCA] and (3-

cyanopropyl)methylpyrrolidinium dicyanamide,[N-C3CNMPyr][DCA]. The separating ability

of the investigated ILs was compared with the previously measured by us in ternary LLE ILs

for these chosen separation problems. The effect of cation for the same anion was examined

with respect to the selectivity and solute distribution ratio in these processes. The separation

effectiveness of the [N-C3CNMPyr][DCA] in comparison with other ILs used in this work is

the best for hex-1-ene/hexane separations but lower than those presented by us earlier for

[EMIM][DCA], however with better solute distribution coefficient. The experimental tie-lines

were correlated with the non-random two liquid NRTL model. The proposed [N-

C3CNMPyr][DCA] may be used as an alternative solvent for the separation of alkenes from

alkanes and [EMMor][DCA] for cyclohexene/cyclohexane separation.

2
1. Introduction

The conventional separation technique of alkane/alkene is a distillation process, which

involves large energetic and technological efforts. Other technologies, such as an use of

membranes, or adsorption processes, achieve a poor separation selectivity. This work focuses

on a simple liquid-liquid phase separation, which is feasible, economical and technologically

an easy alternative. In recent years ionic liquids (ILs) have been widely promoted as non-

volatile solvents with high thermal and chemical stability, with potential recoverability and

design possibility. ILs may be used as an attractive replacement for harmful volatile organic

solvents in many fields of chemistry, chemical engineering and industry [1-3]. The literature

review for the hexane/hex-1-ene separation process, based on activity coefficients at infinite

dilution was presented by our team earlier [4-8]. The selectivity ( S12∞ = γ 1∞ / γ 2∞ ) as well as the

capacity ( k 2∞ = 1 / γ 2∞ ) for separation for hexane (1)/hex-1-ene (2) at T = 323.15 K are

discussed in our papers for different ILs. The best results, as for the separation of the

aromatic/aliphatic hydrocarbons, or the thiophene/alkane are observed for thiocyanate, [SCN]-

anion [9-12]. ILs such as 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN] [10], or 1-

butyl-1-methylpiperidinium thiocyanate, [BMPIP][SCN] [12] reveal selectivity of

hexane/hex-1-ene separation higher than three at T = 323.15 K. The second best anion for the

hexane/hex-1-ene separation is dicyanamide anion ([DCA]-). The selectivities higher than two

are observed for 1-ethyl-3-methylimidazolium dicyanamide, [EMIM][DCA] [13], for 1-butyl-

1-methylpyridinium dicyanamide, [BMPY][DCA] [14], for 1-(3-

cyanopropyl)methylimidazolium dicyanamide, [N-C3CNMIM][DCA] [15] and all [DCA]-

based ILs in works [6-8]. High selectivities were also observed for the tricyanomethanide,

[TCM]--based ILs [7,16]. Unfortunately, for all mentioned ILs the capacity is much lower

3
than one ( k 2∞< 0.1). The larger capacity was observed for almost all phosphonium-based ILs,

( k 2∞>1) with average selectivity close to 1.2 [see data in Ref. 5].

The 1-(3-hydroxypropyl)pyridynium dicyanamide [N-C3OHPY][DCA] [6], 1-benzyl-

3-methylimidazolium dicyanamide, [BzMIM][DCA] [8] and 1-allyl-3-methylimidazolium

dicyanamide, [AMIM][DCA] [17] were presented by us in limiting activity coefficients

measurements as an efficient solvents in separation for cyclohexane/cyclohexene process.

Nowadays, the liquid-liquid extraction with ILs is the most studied technique and

solvents for different separation processes. Recently, ten ILs have been studied in our laboratory

for thehexane/hex-1-ene and cyclohexane/cyclohexene separation. The ILs studied were as

follow: 1-butyl-3-methyl-imidazolium dicyanamide, [BMIM][DCA] [18], 1-butyl-3-methyl-

imidazolium tricyanomethanide, [BMIM][TCM] [18], 1-butyl-4-cyanopyridinium

bis{(trifluoromethyl)sulfonyl}imide, [BCN4PY][NTf2] [18], 1-allyl-3-methylimidazolium

bis{(trifluoromethyl)sulfonyl}imide, [AMIM][NTf2] [19], [AMIM][DCA] [19], 1-benzyl-3-

methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [BzMIM][NTf2] [19],

[BzMIM][DCA] [19], 1-ethyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide,

[EMIM][NTf2] [20], 1-ethyl-3-methylimidazolium dicyanamide, [EMIM][DCA] [20], and 1-

ethyl-3-methylimidazolium tricyanamide, [EMIM][TCM] [20].The best selectivities were

obtained with the [DCA]-based ILs, such as [EMIM][DCA], [AMIM][DCA] or

[BzMIM][DCA], which confirmed our earlier study of limiting activity coefficients.

In this work we continue the measurements of the LLE in 12 ternary systems with the

following ILs:N-ethyl-N-methylmorpholinium dicyanamide, [EMMor][DCA], (3-

hydroxypropyl)-1-methylmorpholinium dicyanamide, [N-C3OHMMor][DCA], 1-(3-

hydroxypropyl)-3-methylimidazolium dicyanamide, [N-C3OHMIM][DCA], 1-(3-

hydroxypropyl)pyridinium dicyanamide, [N-C3OHPy][DCA], (3-cyanopropyl)pyridinium

dicyanamide, [N-C3CNPy][DCA] and (3-cyanopropyl)methylpyrrolidinium dicyanamide, [N-

4
C3CNMPyr][DCA]. The discussion on the separation of hexane/hex-1-ene and

cyclohexane/cyclohexene is provided. The comparison with previously-published data for the

[DCA]-based ILs is presented to show the ability of a new solvents in the discussed separation

processes.

2. Experimental

2.1. Materials and sample preparation

All ILs investigated in this work were synthesized in our laboratory and their

structures, names, abbreviations of name, molar masses (M), purification methods, water

content and purities are presented in Table 1 [6,21]. Three of them were not published yet

and the synthesis is described below. The samples of ILs were dried for 24 h at 320 K with

stirring under reduced pressure to remove volatile impurities and trace water. The solvents,

purchased from POCh, Aldrich and Fluka, were purified with molecular sieves of type 4Å

(4×10 -8 cm) (Union Carbide) and GC analysis as is described in Table 1.

2.1.1. Synthesis of N-ethyl-N-methylmorpholiniumdicyanamide, [EMMor][DCA]

To a 336.42 g of N-methylmorpholine (3.326 mol, Sigma-Aldrich 99%, used as

received) 402.29 g of bromoethane (3.692 mol, 11% excess, Sigma-Aldrich 98%, used as

received) in 400 cm3 of acetonitrile (POCh) was added. The mixture was stirred at room

temperature for 24 h. White crystals form within the mixture. Afterwards solution was

recrystallized from the acetonitrile. After cooling to room temperature, 500 cm3 of ethyl

acetate were added crystals were filtered washed with ethyl acetate and dried in vacuum at T

5
= 348 K. A total of 674.38 g of white crystalline powder of N-ethyl-N-methylmorpholinium

bromide was obtained. Reaction yield 96.5%.

1
H NMR: δH(400 MHz; D2O): 1.457 (3 H, tt, 3JH,H = 7.2 Hz, 5JH,H = 2.0 Hz NCH2CH3), 3.243

(3 H, s, NCH3), 3.561 (4 H, m,N(CH2CH2)2O),3.633 (2 H, q, 3JH,H = 7.2 Hz, NCH2CH3),4.123

(4 H, m, N(CH2CH2)2O).

13
C NMR: δC(100 MHz; D2O): 7.350, 46.860, 59.806, 61.148, 61.557.

To a solution of 53.52 g N-ethyl-N-methylmorpholinium bromide (0.2547 mol, synthesized)

in 500 cm3 of water 51.22 g of silver dicyanamide (0.2945 mol, 1.16 equivalent, synthesized

by addition of equimolar amounts of sodium dicyanamide (Io-Li-Tec 97%) and sodium nitrate

(Alfa Aesar 99%) followed by filtration, washing with water and drying) were added. Mixture

was stirred at the temperature T = 323K for 1 hour. Afterwards the solution was filtered on a

column with 5 g of silica gel 60 (Machery Nagel for column chromatography). Water was

removed by evaporation and the oil was further dried in vacuum for 3 days at T = 373K.

Finally, 47.49 g of oil was obtained (0.2420mol, Yield 95.01%). Purity estimated from NMR

analysis: > 96% wt. Bromide content estimated by X-ray fluorescence XRF (Rigaku NEX QC

equipment) was below 30 x 10-6 mass fraction.

1
H NMR: δH(500 MHz; D2O): 1.41 (3H, tt, 3JH,H = 7.34 Hz, JH,H = 1.96 Hz), 2.40 (3H, s), 3.48

(4H, m), 3.56 (2H, quartet, 3JH,H = 7.34 Hz), 4.06 (4H, m).

13
C NMR: δC(100 MHz; D2O): 6.76, 46.29, 59.32, 60.59, 61.05, 120.04.

2.1.2. Synthesis of (3-cyanopropyl)pyridinium dicyanamide, [N-C3CNPy][DCA]

6
 Preparation of N-(3-cyanopropyl)pyridinium chloride was as follows: to a 24.69 g of

pyridine (0.3121 mol, Sigma-Aldrich 99.9%, used as received) 37.57 g of 4-

chlorobutyronitrile (0.3628 mol, 1.16 eq, Sigma-Aldrich 97%, used as received) in 50 cm3 of

acetonitrile (POCh) were added. The mixture was stirred in an oil bath at temperature T =

383.2 K for 96h. After cooling down to room temperature, the solution crystallized. The

crystals were filtered and re-crystallized from the acetonitrile. The mixture was filtered and

washed with ethyl acetate and dried in vacuum at T = 348 K. The 52.52 g of white crystalline

powder was obtained. The reaction yield was 92.13% with purity estimated from NMR

analysis : >95% wt.

1
H NMR: δH(400 MHz; D2O): 2.355 (2 H, pent, 3JH,H = 7.34 Hz, NCH2CH2CH2OH), 2.591 (2

H, t, 3JH,H = 7.34 Hz, NCH2 CH2CH2OH),4.680 (2 H, t, 3JH,H = 7.34 Hz, NCH2CH2CH2OH),

8.031 (2 H, t, 3JH,H = 6.85 Hz), 8.510 (1 H, tt, 3JH,H = 7.83Hz, 3JH,H = 1.43), 8.834 (2 H, m)

13
C NMR: δC(100 MHz; D2O): 13.80, 26.10, 60.15, 119.94, 126.61, 144.5, 146,29.

To a solution of 52.53 g N-(3-cyanopropyl)-pyridiniumchloride (0.2876 mol,

synthesized) in 150 cm3 of water 26.92 g of sodium dicyanamide (0.3024 mol, 1.05 eq, Io-Li-

Tec 98%) were added. The mixture was stirred at room temperature for 2 hours. The water

was removed by rotary evaporation, and the mixture was further dried by addition of ethanol

and evaporation by rotary evaporator. The mixture was further dried at T= 373.2 K in vacuum

for 24 h. To this mixture 150 cm3 of dry acetone (P.O.Ch cz.d.a) and 3 g of activated charcoal

were added. The mixture was stirred for 2 h at room temperature. Afterwards, the solution

was filtered on a column with 5 g of silica gel 60 (Machery Nagel for column

chromatography). The acetone was removed by rotary evaporation and the mixture was

placed in a vacuum oven at T = 353.2 K for 48h. A total of 55.31 g of oil was obtained

(0.2594mol, Yield 90.19%) with p Purity estimated from NMR analysis: >95% wt. The

7
chloride content was estimated by X-ray fluorescence XRF (Rigaku NEX QC equipment) and

was below 30 x 10 -6 mass fraction.

1
H NMR: δH(400 MHz; D2O): 2.487 (2 H, pent, 3JH,H = 7.34 Hz, NCH2CH2CH2OH), 2.723 (2

H, t, 3JH,H = 7.34 Hz, NCH2CH2CH2OH), 4.800 (2 H, t, 3JH,H = 7.34 Hz, NCH2CH2CH2OH),

8.177 (2 H, t, 3JH,H = 6.85 Hz), 8.655 (1 H, t(m), 3JH,H = 7.83Hz), 8.953 (2 H, m)

13
C NMR: δC(100 MHz; D2O): 14.05, 26.38, 60.34, 119.90, 120.06, 126.82, 144.65, 146.48.

2.1.3. Synthesis of (3-cyanopropyl)methylpyrrolidinium dicyanamide, [N-C3CNMPyr][DCA]

The chloride salt needed for further reaction was synthesized according to a well-

known path [22,23]. To a 25.26 g of N-methylpyrrolidine (0.2967 mol, Sigma-Aldrich 98%,

used as received), 33.73 g of 4-chlorobutyronitrile (0.2570 mol, 1.1 equivalent, Sigma-

Aldrich 98%, used as received) in 100 cm3 of acetonitrile (POCh) were added. The mixture

was stirred in an oil bath at 353 K for 48 h. The solvents were removed by evaporation. The

product was crystallized from acetonitrile, washed with ethyl acetate, and dried in vacuum to

give 48.97 g of crystalline powder with reaction yield 87.47%.

1
H NMR: δH(500 MHz; D2O): 2.16 (6 H, m), 2.56 (2 H, t, 3JH,H = 6.85 Hz), 3.01 (3 H, s), 3.41

(2 H, m), 3.49 (4 H, m).

To a solution of 41.03 g of N-(3-cyanopropyl)-N-methylpyrrolidinium chloride

(0.2174 mol, synthesized) in water 19.86 g of sodium dicyanamide ( 0.2231 mol, 1.03

equivalent, Io-Li-Tec 98%, used as received) were added. The mixture was stirred at room

temperature for 2 hours. Afterwards water was removed by evaporation, and the oil obtained

was further dried in vacuum at T = 383K for 1 day. To the oil obtained, 150 cm3 of acetone

(P.O.Ch cz.d.a) and 1 g of activated charcoal (Sigma-Aldrich powder) were added and the

mixture was stirred at room temperature for 2 h. Afterwards the solution was filtered on a

8
column with 5 g of silica gel 60 (Machery Nagel for column chromatography). Solvents were

removed by evaporation and the product obtained was further dried in vacuum for 3 days at T

= 373K. The 44.09 g of product was obtained in the form of oil (0.2011 mol, yield 92.48%).

The purity was estimated from NMR analysis: > 97% wt and chloride content estimated via

X-ray fluorescence (XRF) to be below 30 x 10 -6 mass fraction.

1
H NMR: δH(500 MHz; D2O): 2.28 (6 H, m), 2.70 (2 H, t, 3JH,H = 6.85 Hz), 3.12 (3 H, s), 3.50

(2 H, m), 3.61 (4 H, m).

13
C NMR: δC(100 MHz; D2O): 14.28, 19.80, 21.59, 48.47, 62.56, 64.93, 120.01, 120.14.

All NMR spectra are shown in Figures 1S-3S in the SupplementaryMaterial (SM).

2.2. Water content

The water content was analysed by the Karl-Fischer titration technique (method

TitroLine KF). The sample of IL, or solvent was dissolved in methanol and titrated with steps

of 0.0025 cm3. The error on the water content was ± 10 × 10 -6 for the 3 cm3 injected IL. The

value of the water content in ILs and solvents used is presented in Table 1.

2.3. Procedure in ternary system

The mixtures of two, or three compounds with compositions inside the immiscible

region of the ternary system were introduced into a jacketed glass cell with

a volume of 10 cm3. The vessel was properly closed to avoid losses by evaporation or to

pickup of moisture from the atmosphere. The jackets were connected to a thermostatic water

bath (LAUDA Alpha) to maintain a constant temperature of T = 298.15±0.1K. The mixtures

9
were stirred for 4 h to reach the thermodynamic equilibrium and after getting the phase

separation for a minimum of 12 h were analysed. The samples of about 0.1-0.3·10-3 cm3 were

taken from both phases using glass syringes with coupled stainless steel needles. Sample of

the phase was placed in an ampoule with a capacity of 2×10 -3 cm3. The ampoule was closed

with a septum cap. Next, acetone (1.0 cm3) was added to the samples to avoid phase splitting

and to maintain a homogeneous mixture. Methyl acetate was used as internal standard for the

GC-analysis of hexane and hex-1-ene and ethyl acetate was used for the analysis of

cyclohexane and cyclohexene. The remaining content of the third component, the IL (low

vapour pressure), was determined by subtracting the mole fractions of the two other

components from one.

The composition was analyzed by gas chromatography (PerkinElmer Clarus 580 GC

equipped with auto sampler and FID and TCD detectors). The capillary column of the

chromatograph was protected with an pre-column to avoid the non-volatile IL reaching the

column in case of leak from the glass wool in the liner. The TotalChrom Workstation

software was used to obtain the chromatographic areas for the substances and external

standard. Samples were injected three times, and the average value was calculated. Details of

the operational conditions of the apparatus are reported in our previous work [20,Tables 3 and

4]. The estimated uncertainty in the determination of mole fraction compositions is u(x) =

±0.003.

3. Results and discussion

The experimental tie-line ends measurements were performed to determine the selectivity (S)

and the solute distribution ratio (β ), which are defined as follow:

10
 x2II ⋅ x3I
S= (1)
x2I ⋅ x3II

x2II
β= (2)
x 2I

where x is the mole fraction; superscripts I and II refer to aromatic hydrocarbon–rich phase

and IL–rich phase, respectively. Subscripts 2 and 3 refer to hex-1-ene, or cyclohexene

compounds and hexane, or cyclohexane compounds, respectively. The extraction process is

the best for the large selectivity and large solute distribution ratio. Unfortunately, usually

entrainer with high capacity presents low selectivity and opposite.

The experimental data for twelve ternary systems are presented in this work: six for (hex-1-ene /

hexane) separation and six for (cyclohexene / cyclohexane) separation at T = 298.15 K and ambient

pressure. The mole fraction compositions of tie-lines are reported in Tables 2 and 3 and are plotted in a

form of the Gibbs triangles in Figures and in Figures 4S-8S in the SM for hex-1-ene/hexane as well as

in Figure 2 and Figures 9S-13S in the SM for cyclohexene/cyclohexane separation. The tie-line slope

of these ternary systems is very similar to the reported by us earlier ternary systems with using

[DCA]–based ILs such as [EMIM][DCA], [BMIM][DCA], [AMIM][DCA], and [BzMIM][DCA] [18-

20]. The ternary plots for all systems indicates negative sloping of the tie lines, which implies low

selectivities for the two chosen systems.

3.1. Ternary systems {IL (1) + hex-1-ene (2) + hexane (3)}

Figures 1 and 4S-8S show that the picture of the immiscibility in ternary systems is almost the

same for all ILs. The solubility of hexane in the used ILs is very low; in a range of 0.002 to 0.007 in

mole fraction and increases in order [N-C3CNMPy][DCA] < [N-C3OHMPy][DCA] = [N-

11
C3OHMIM][DCA] < [EMMor][DCA < [N-C3OHMMor][DCA] = [N-C3CNMPyr][DCA]. The

solubility of hex-1-ene in the IL is expected as high as possible. In binary systems presented here it is

in a range of 0.006 to 0.016 in mole fraction and increases in order: [N-C3CNMPy][DCA]<[N-

C3OHMPy][DCA] < [N-C3OHMIM][DCA] = [EMMor][DCA] < [N-C3CNMPyr][DCA] <

[N-C3OHMMor][DCA]. The effect of the cation for the same anion of the IL was examined with

respect to the selectivity and solute distribution ratio of hex-1-ene extraction. These data are listed in

Tables 2 and 3 in the studied ternary systems. The average values SAv and βAvfor tested ILs are

presented in Table 4. The introduction of OH group to morpholinium-based cation decreases the

SAvfrom 1.91 to 1.67. The [N-C3OHMIM][DCA]cation reveals better SAv than [N-

C3OHMPy][DCA] (2.48 versus 2.29). Changing OH substituent for CN substituent in the

pyridinium-based cation decreases S Av from 2.29 to 1.96. Changing pyridinium-based cation with CN

substituent for pyrrolidinium-based cation with the same CN substituent has increased selectivity

from S Av = 1.96 ([N-C3CNMPy][DCA]) to SAv = 3.52 ([N-C3CNMPyr][DCA]). This is the best

selectivity (S Av = 3.52) with quite high average solute distribution ratio, (β Av= 0.010). The highest SAv,

observed in our earlier work was for [EMIM][DCA] (SAv = 3.90) but with very low solute distribution

ratio (βAv= 0.001) [20], for [AMIM][DCA] (SAv = 2.47, β Av= 0.017) [19] and for [BMIM][DCA] (S Av

= 2.46, β Av= 0.038) [18]. The comparison of the selectivity and solute distribution ratio, obtained in

this work and in the literature as a function of the mole fraction of hex-1-ene in the hydrocarbon-rich

phase for the ternary systems (IL + hex-1-ene + hexane) at T = 298.15 K is presented in Figures 3,4

and 14S and 15S in the SM.

3.2. Ternary systems {IL (1) + cyclohexene (2) + cyclohexane (3)}

Figures 2, and 9S-13S in the SM show the ternary systems with cyclohexane. The solubility of

cyclohexane in used ILs is about three times larger than that of hexane and increases in order: [N-

C3CNMPy][DCA] < [EMMor][DCA] = [N-C3OHMMor][DCA] < [N-C3OHMPy][DCA] <

[N-C3CNMPyr][DCA] < [N-C3OHMIM][DCA]. The solubility of cyclohexane in the ILs is in

the range of 0.006 to 0.013 in mole fraction. The solubility of cyclohexene in the tested ILs
12
increases in order: [N-C3OHMMor][DCA] < [N-C3CNMPy][DCA] < [EMMor][DCA] < [N-

C3OHMIM][DCA] < [N-C3OHMPy][DCA] < [N-C3CNMPyr][DCA]. From this point of view

the [N-C3CNMPyr][DCA] (x2 = 0.032) should show the best extraction properties. The best

solubility of cyclohexene in the IL at T = 298.15 K was observed by us earlier in [BzMIM][NTf2 ] (x2 =

0.198) [19]. The S and β values depend on the concentrations of cyclohexene in the IL-layer and are

changing across the tie-lines. The average selectivity for cyclohexene/cyclohexane separation process

is in order: [N-C3OHMMor][DCA] (S Av = 1.97) < [N-C3CNMPyr][DCA] (S Av = 2.48) < [N-

C3OHMIM][DCA] (SAv = 2.68) < [N-C3OHMPy][DCA] (SAv = 2.82) < [N-C3CNMPy][DCA]

(SAv = 3.10) < [EMMor][DCA] (SAv = 3.25). The Gibbs triangle for the best IL, [EMMor][DCA] is

presented as an example in Figure 2. The best value for this separation process was observed in our

earlier work for [AMIM][DCA] (SAv = 2.77) with the solute distribution ratio (β Av= 0.017) [19]. The

comparison of the selectivity and solute distribution ratio, obtained in this work and in the literature as

a function of the mole fraction of cyclohexene in the hydrocarbon-rich phase for the ternary systems

{IL + cyclohexene + cyclohexane} at T = 298.15 K is presented in Figures 5 and 6 as well as in

Figures 16S and 17S in the SM.

From the chromatographic analysis made after the LLE experiment, the absence of the IL in the

hexane or cyclohexane layer was noted. Thus, the raffinate phase is free from any IL (within the

experimental error). The possible application of the IL in the new technology of separation must

assume easy recovery for the IL for the further process.

4. Data correlation

The experimental tie-line data in ternary LLE systems were correlated using the non-random

model, (NRTL) [24]. The equations and algorithms used for the calculation of the compositions in

both phases followed the method described by Walas [25]. The objective function F(P), was used to

minimize the difference between the experimental and calculated compositions:

13
 n 2

[ ] [
2
] [ ] [
2
]
F ( P) = ∑ x 2I exp − x2Icalc (PT ) + x3I exp − x3Icalc (PT ) + x 2II exp − x 2IIcalc (PT ) + x3II exp − x3IIcalc (PT )
2

i =1
(3)

where P is the set of parameters vector, n is the number of experimental points, x2I exp , x 3I exp and

x2Icalc (PT ) , x 3Icalc (PT ) are the experimental and calculated mole fractions of one phase and x 2II exp ,

x 3II exp and x 2IIcalc ( PT ) , x 3IIcalc ( PT ) are the experimental and calculated mole fractions of the second

phase. The binary parameters of each constituent were regressed by minimizing the square of the

differences between the experimental and calculated mole fractions of each component of both liquid

phases for each ternary system. These binary parameters were obtained for all data together (binaries

and ternaries). The value for the non-randomness parameter, α ij was optimized in order to obtained

the best fit model. The binary interaction parameters for all systems are given in Tables 5 and 6 along

with the root mean square deviations (RMSD) for the ternary systems {IL (1) + hex-1-ene (2) +

hexane (3)} and (IL (1) + cyclohexene (2) + cyclohexane (3)}, respectively. The RMSD values,

which can be taken as a measure of the precision of the correlation, were calculated according to the

equation:

1/ 2
 
RMSD =  ∑∑∑ xilm
exp
[
calc 2
− xilm / 6k  ] (4)
 i l m 

where x is the mole fraction and the subscripts i, l, and m designate the component, phase, and tie-line,

respectively. The results of the correlation are presented in all figures with Gibbs triangles (Figure 1

and 2 as well as Figures 4S-13S in the SM). The experimental and calculated tie-lines agreed

relatively well. The average RMSD values are lower than 0.003, which is the experimental mole

fraction error for all systems.

14
5. Conclusions

The ternary liquid–liquid phase equilibrium diagrams of (IL + hex-1-ene + hexane), and (IL +

cyclohexene + cyclohexane)were analytically determined at temperature T = 298.15 K at ambient

pressure using GC for the composition analysis. Liquid-liquid equilibrium measurements

demonstrated that new ILs, namely[EMMor][DCA], [N-C3OHMMor][DCA], [N-

C3OHMIM][DCA], [N-C3OHMPy][DCA], [N-C3CNMPy][DCA] and [N-

C3CNMPyr][DCA]present good performance as separation agents of hex-1-ene/hexane and

cyclohexene/cyclohexane processes in comparison with many other ILs tested earlier. High selectivity

and acceptable solute distribution ratio for hex-1-ene/hexane process was achieved with [N-

C3CNMPyr][DCA] and for cyclohexene/cyclohexane process with [EMMor][DCA]. The

[DCA]-based ILs are the most powerful solvents in comparison with other listed in literature.

The cross contaminations of the IL and hydrocarbon in both the phases were nearly zero. The

experimental data were correlated using the NRTL activity coefficient model and binary interaction

parameters. The non-random two liquid NRTL model successfully described the experimental tie-lines

with the parameter α ij = 0.1 or α ij = 0.2.

Acknowledgement

Funding for this research was provided by the Warsaw University of Technology,

Faculty of Chemistry, Warsaw, Poland.

References

[1] H. Passos, M.G. Freire, J.A.P. Coutinho, Green Chem. 16 (2014) 4786-4815.

[2] A.R. Hansmeir, G.W. Meindersma,A.B. De Haan, Green Chem. 13 (2011) 1907-1913.

[3] U. Domańska, M. Wlazło, Fuel, 134 (2014) 114-125.

[4] A. Marciniak, Fluid Phase Equilib. 294 (2010) 213-233.

15
[5] U. Domańska, M. Wlazło, M. Karpińska, Fluid Phase Equilib. 417 (2016) 50-61.

[6] U. Domańska, M. Wlazło, M. Karpińska, M. Zawadzki, J. Chem. Thermodyn. 110 (2017)

227-236.

[7] M. Karpińska, M. Wlazło, U. Domańska, J. Molec. Liq. 225 (2017) 382-390.

[8] M. Karpińska, M. Wlazło, D. Ramjugernath, P. Naidoo, U. Domańska, RSC Adv. 7

(2017) 7092-71-07.

[9] U. Domańska, A. Marciniak, J. Chem. Thermodyn. 40 (2008) 860-866.

[10] U. Domańska, M. Laskowska, J. Chem. Thermodyn. 41 (2009) 645-650.

[11] U. Domańska, M. Królikowska , J. Phys. Chem. B 114 (2010) 8460-8466.

[12] U. Domańska, M. Królikowska, J. Chem. Eng. Data 56 (2011) 124-129.

[13] F. Mutelet, A.L-. Revelli, J.-N. Jaubert, L.M. Sprunger, W.E. Acree Jr., G.A. Baker, J.

Chem. Eng. Data 55 (2010) 234-242.

[14] M. Królikowski, M. Królikowska, J. Chem. Thermodyn. 68 (2014) 138-144.

[15] A.L-. Revelli, F. Mutelet, J.-N. Jaubert, M. Garcia-Martinez, L.M. Sprunger, W.E. Acree

Jr., G.A. Baker, J. Chem. Eng. Data 55 (2010) 2434-2443.

[16] U. Domańska, E. V. Lukoshko, J. Chem. Thermodyn. 68 (2014) 53-59.

[17] M. Wlazło, J. Gawkowska, U. Domańska, Ind. Eng. Chem. Res. 55 (2016) 5054-5056.

[18] M. Karpińska, M. Wlazło, U. Domańska, J. Chem. Thermodyn. 108 (2017) 127-137.

[19] U. Domańska, M. Karpińska, M. Wlazło, J. Chem. Thermodyn. 105 (2017) 375-384.

[20] U. Domańska, M. Karpińska, M. Wlazło, Fluid Phase Equilib. 427 (2016) 421-428.

16
[21] M. Karpińska, M. Wlazło, M. Zawadzki, U. Domańska, J. Chem. Thermodyn. (2017)-

submitted.

[22] B. Hitchcock, K.R. Seddon, T. Welton, J. Chem. Soc. Dalton Trans. (1993) 2639.

[23] W.A. Herrmann, L.J. Goossen, M. Spiegler, Organometallics 17 (1998) 2162-2165.

[24] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135-144.

[25] S.W. Walas, Phase Equilibria in Chemical Engineering, Butterworth Publishers: Boston, (1985).

17
 Table 1. Properties of the ionic liquids investigated: structure, name, abbreviation of name,

supplier, molar mass (M), mass fraction purity, water content and purification method.

Structure Name, abbreviation, M/(g· mol-1) Mass fraction Purification

purity/water method/method of
supplier content(mass analysis
fraction)

O N-ethyl-N- 196.25 >0.96/ Low pressure

methylmorpholiniumdicyan 24h 320K
351x10-6
amide, 1
N
+ H NMR and
CH3 13
H3C [EMMor][DCA] C NMR, ChA

N- Synthesis

N N

(3-hydroxypropyl)-1- 226.27 >0.980/ Low pressure

methylmorpholinium 24h 320K
dicyanamide, 358x10-6
1
H NMR and
13
[N-C3OHMMor][DCA] C NMR, Ch.A.

Synthesis [21]
N-

N N

1-(3-hydroxypropyl)-3- 207.23 >0.980/ Low pressure

methylimidazolium 24h 320K
429x10-6
dicyanamide, 1
H NMR and
13
[N-C3OHMIM][DCA] C NMR, Ch.A.
N-
Synthesis [21]
N N

1-(3- 204.23 >0.980/ Low pressure

+
N OH hydroxypropyl)pyridiniumd 24h 320K
456 x10-6
icyanamide, 1
H NMR and
13
[N-C3OHPy][DCA] C NMR,Ch.A.

N- Synthesis [6]

N N

+
CN (3- 213.24 >0.95/ Low pressure
N
cyanopropyl)pyridiniumdic 24h 320K
495x10-6
yanamide, 1
H NMR and

18
 13
N- [N-C3CNPy][DCA] C NMR, Ch.A.

Synthesis
N N

(3- 219.29 >0.97/ Low pressure

cyanopropyl)methylpyrroli 24h 320K
+
N 495x10-6
CN diniumdicyanamide, 1
H3C H NMR and
13
[N-C3CNMPyr][DCA] C NMR, Ch.A.
N-
Synthesis
N N

Hexane 86.18 >0.990 Molecular

sieves, GC
CAS: 110-54-3 75x10-6

Fluka

Hex-1-ene 84 .16 >0.980 Molecular

sieves, GC
CAS: 592-41-6 34x10-6

Sigma Aldrich

Cyclohexane 84.16 >0.995 Molecular

sieves, GC
CAS: 110-82-7 45x10-6

POCh

Cyclohexene 82.14 >0.995 Molecular

sieves, GC
CAS: 110-83-8 60x10-6

FLUKA

19
Table 2. Compositions of experimental tie lines selectivity, S and solute distribution ratios, β for

ternary systems {IL (1) + hex-1-ene (2) + hexane (3)} at T = 298.15 K, p =101 kPa.

Hydrocarbon – rich phase IL – rich phase S β

x1HC x2HC x1IL x2IL
[EMMor][DCA]

0.000 1.000 0.991 0.009 – 0.009

0.000 0.913 0.990 0.009 1.80 0.010

0.000 0.835 0.991 0.009 2.07 0.010

0.000 0.746 0.991 0.008 2.07 0.010

0.000 0.620 0.992 0.006 1.80 0.009

0.000 0.497 0.993 0.004 1.83 0.009

0.000 0.425 0.994 0.003 1.41 0.007

0.000 0.306 0.995 0.002 1.77 0.008

0.000 0.212 0.995 0.002 1.86 0.008

0.000 0.142 0.995 0.001 2.04 0.008

0.000 0.078 0.996 0.001 2.51 0.010

0.000 0.000 0.996 0.000 – –

[N-C3OHMMor][DCA]

0.000 1.000 0.984 0.016 – 0.016

0.000 0.957 0.984 0.016 1.04 0.016

0.000 0.904 0.984 0.015 1.45 0.017

0.000 0.837 0.984 0.014 2.00 0.017

0.000 0.734 0.986 0.012 1.73 0.016

0.000 0.608 0.988 0.009 1.66 0.015

0.000 0.477 0.990 0.006 1.58 0.013

0.000 0.356 0.991 0.004 1.56 0.012

20
 0.000 0.260 0.991 0.003 1.63 0.012

0.000 0.107 0.992 0.002 2.78 0.018

0.000 0.055 0.993 0.000 1.26 0.009

0.000 0.000 0.993 0.000 – –

[N-C3OHMIM][DCA]

0.000 1.000 0.991 0.009 – 0.009

0.000 0.965 0.992 0.008 1.66 0.009

0.000 0.873 0.992 0.008 1.86 0.009

0.000 0.814 0.992 0.008 2.37 0.009

0.000 0.701 0.992 0.007 3.25 0.011

0.000 0.619 0.992 0.007 3.76 0.011

0.000 0.522 0.992 0.006 2.67 0.011

0.000 0.412 0.993 0.004 2.71 0.011

0.000 0.324 0.995 0.003 1.95 0.008

0.000 0.235 0.995 0.002 1.72 0.007

0.000 0.112 0.996 0.001 2.57 0.010

0.000 0.043 0.996 0.000 2.76 0.010

0.000 0.000 0.997 0.000 – –

[N-C3OHPy][DCA]

0.000 1.000 0.993 0.007 – 0.007

0.000 0.935 0.993 0.007 2.04 0.007

0.000 0.871 0.993 0.007 2.35 0.008

0.000 0.784 0.993 0.006 2.73 0.008

0.000 0.710 0.993 0.006 2.48 0.008

0.000 0.626 0.994 0.005 3.10 0.009

0.000 0.529 0.994 0.005 2.81 0.009

21
 0.000 0.470 0.994 0.004 2.23 0.008

0.000 0.376 0.995 0.002 1.59 0.006

0.000 0.295 0.995 0.002 1.86 0.007

0.000 0.219 0.996 0.002 2.06 0.007

0.000 0.120 0.996 0.001 2.40 0.008

0.000 0.049 0.996 0.000 1.80 0.006

0.000 0.000 0.997 0.000 – –

[N-C3CNPy][DCA]

0.000 1.000 0.994 0.006 – 0.006

0.000 0.949 0.994 0.006 1.73 0.006

0.000 0.899 0.994 0.005 1.36 0.006

0.000 0.743 0.995 0.005 1.97 0.006

0.000 0.567 0.995 0.004 1.90 0.006

0.000 0.390 0.995 0.003 2.09 0.007

0.000 0.227 0.996 0.001 2.19 0.006

0.000 0.089 0.997 0.001 2.50 0.006

0.000 0.032 0.997 0.000 1.96 0.005

0.000 0.000 0.998 0.000 – –

[N-C3CNMPyr][DCA]

0.000 1.000 0.990 0.010 – 0.010

0.000 0.969 0.990 0.010 6.03 0.010

0.000 0.902 0.990 0.009 6.94 0.010

0.000 0.805 0.991 0.009 4.27 0.011

0.000 0.714 0.991 0.008 3.06 0.011

0.000 0.544 0.992 0.006 2.54 0.010

0.000 0.425 0.993 0.004 2.21 0.010

22
 0.000 0.298 0.994 0.003 2.17 0.009

0.000 0.211 0.995 0.002 2.34 0.009

0.000 0.107 0.996 0.001 3.15 0.011

0.000 0.046 0.996 0.000 2.48 0.009

0.000 0.000 0.997 0.000 – –

Standard uncertainties u are u(x) = ±0.003, u(S) = 4%, u(β) = 10%, u(T) = 0.1 K, u(p) = 1 kPa.

23
Table 3. Compositions of experimental tie lines, selectivity, S and solute distribution ratios, β for

ternary systems {IL (1) + cyclohexene (2) + cyclohexane (3)} at T = 298.15 K, p =101 kPa.

Hydrocarbon – rich phase IL – rich phase S β

x1HC x2HC x1IL x2IL

[EMMor][DCA]

0.000 1.000 0.977 0.023 – 0.02

0.000 0.924 0.977 0.023 5.38 0.02

0.000 0.865 0.977 0.022 3.69 0.03

0.000 0.774 0.978 0.021 3.89 0.03

0.000 0.659 0.979 0.018 3.10 0.03

0.000 0.554 0.980 0.016 3.01 0.03

0.000 0.453 0.983 0.013 3.15 0.03

0.000 0.338 0.985 0.009 2.99 0.03

0.000 0.229 0.987 0.006 2.61 0.02

0.000 0.129 0.989 0.003 2.56 0.02

0.000 0.058 0.990 0.001 2.15 0.02

0.000 0.000 0.991 0.000 – –

[N-C3OHMMor][DCA]
0.000 1.000 0.981 0.019 – 0.02

0.000 0.910 0.981 0.018 1.93 0.02

0.000 0.839 0.982 0.017 2.05 0.02

0.000 0.731 0.982 0.016 2.83 0.02

0.000 0.613 0.982 0.015 3.65 0.02

0.000 0.479 0.986 0.009 1.64 0.02

0.000 0.357 0.987 0.006 1.69 0.02

0.000 0.271 0.988 0.005 1.76 0.02

24
 0.000 0.189 0.989 0.003 1.48 0.01

0.000 0.103 0.990 0.002 1.65 0.02

0.000 0.054 0.991 0.001 1.05 0.01

0.000 0.000 0.991 0.000 – –

[N-C3OHMIM][DCA]

0.000 1.000 0.972 0.028 – 0.03

0.000 0.962 0.973 0.027 2.60 0.03

0.000 0.878 0.973 0.026 4.08 0.03

0.000 0.758 0.973 0.024 3.19 0.03

0.000 0.677 0.974 0.022 3.14 0.03

0.000 0.588 0.976 0.019 2.75 0.03

0.000 0.541 0.977 0.017 2.67 0.03

0.000 0.434 0.980 0.013 2.21 0.03

0.000 0.355 0.980 0.012 2.62 0.03

0.000 0.290 0.982 0.009 2.56 0.03

0.000 0.211 0.984 0.006 2.20 0.03

0.000 0.153 0.984 0.005 2.44 0.03

0.000 0.063 0.986 0.001 1.70 0.02

0.000 0.000 0.987 0.000 – –

[N-C3OHPy][DCA]

0.000 1.000 0.971 0.029 – 0.03

0.000 0.914 0.972 0.027 3.19 0.03

0.000 0.806 0.974 0.024 3.07 0.03

0.000 0.722 0.976 0.022 3.13 0.03

0.000 0.633 0.977 0.019 3.02 0.03

0.000 0.516 0.980 0.015 2.64 0.03

25
 0.000 0.411 0.983 0.011 2.41 0.03

0.000 0.323 0.984 0.009 2.53 0.03

0.000 0.228 0.986 0.006 2.73 0.03

0.000 0.150 0.987 0.004 2.67 0.03

0.000 0.065 0.989 0.002 2.84 0.03

0.000 0.000 0.990 0.000 – –

[N-C3CNPy][DCA]

0.000 1.000 0.979 0.021 – 0.02

0.000 0.949 0.979 0.021 3.11 0.02

0.000 0.890 0.979 0.020 2.86 0.02

0.000 0.790 0.981 0.017 2.18 0.02

0.000 0.598 0.983 0.014 2.98 0.02

0.000 0.458 0.986 0.010 2.59 0.02

0.000 0.274 0.989 0.006 2.77 0.02

0.000 0.109 0.992 0.002 3.19 0.02

0.000 0.047 0.992 0.002 5.14 0.03

0.000 0.000 0.994 0.000 – –

[N-C3CNMPyr][DCA]

0.000 1.000 0.968 0.032 – 0.03

0.000 0.965 0.969 0.030 1.39 0.03

0.000 0.913 0.969 0.030 2.27 0.03

0.000 0.807 0.970 0.028 3.12 0.03

0.000 0.629 0.973 0.022 3.00 0.04

0.000 0.434 0.977 0.014 2.27 0.03

0.000 0.274 0.982 0.008 1.93 0.03

0.000 0.123 0.984 0.005 2.94 0.04

26
 0.000 0.043 0.987 0.002 2.93 0.04

0.000 0.000 0.988 0.000 – –

Standard uncertainties u are u(x) = ±0.003, u(S) = 4%, u(β) = 10%, u(T) = 0.1 K, u(p) = 1 kPa.

27
 Table 4. The average selectivity, SAv and average solute distribution ratios, βAv for ternary systems

{IL (1) + hex-1-ene (2) + hexane (3)} and {IL (1) + cyclohexene (2) + cyclohexane (3)} at

T = 298.15 K, p =101 kPa.

IL SAv βAv

{IL (1) + hex-1-ene (2) + hexane (3)}

[EMMor][DCA] 1.91 0.009

[N-C3OHMMor][DCA] 1.67 0.013

[N-C3OHMIM][DCA] 2.48 0.009

[N-C3OHPy][DCA] 2.29 0.007

[N-C3CNPy][DCA] 1.96 0.006

[N-C3CNMPyr][DCA] 3.52 0.010

{IL (1) + cyclohexene (2) + cyclohexane (3)}

[EMMor][DCA] 3.25 0.025

[N-C3OHMMor][DCA] 1.97 0.018

[N-C3OHMIM][DCA] 2.68 0.030

[N-C3OHPy][DCA] 2.82 0.030

[N-C3CNPy][DCA] 3.10 0.020

[N-C3CNMPyr][DCA] 2.48 0.033

28
 Table 5. Values of binary parameters for the NRTL equation for the ternary systems {IL (1)

+ hex-1-ene (2) + hexane (3)} at T = 298.15 K, p =101 kPa.

IL ij gij/J·mol–1 gji/J·mol–1 αij σx

[EMMor][DCA] 12 2703 19216 0.1 0.0005

13 4656 20248

23 -1310 566.9

[N-C3OHMMor][DCA] 12 1317 21092 0.1 0.0005

13 3215 21288

23 -493.1 -741.2

[N-C3OHMIM][DCA] 12 2758 21184 0.1 0.0005

13 5224 20736

23 -59.19 955.6

[N-C3OHPy][DCA] 12 3092 25486 0.1 0.0004

13 5476 17848
23 2618 -2033

[N-C3CNPy][DCA] 12 3698 25156 0.1 0.0001

13 6160 18151

23 5248 -3509

[N-C3CNMPyr][DCA] 12 2489 21324 0.1 0.0002

13 4996 20795

23 1002 -686.3

29
 Table 6. Values of binary parameters for the NRTL equation for the ternary systems {IL (1)

+ cyclohexene (2) + cyclohexane (3)} at T = 298.15 K, p =101 kPa.

IL ij gij/J·mol–1 gji/J·mol–1 αij σx

[EMMor][DCA] 12 5249 15322 0.2 0.0005

13 8186 21173

23 8734 -4248

[N-C3OHMMor][DCA] 12 5952 17314 0.2 0.0005

13 7814 19521

23 11566 -5408

[N-C3OHMIM][DCA] 12 5454 20603 0.2 0.0006

13 7202 20298

23 8656 -4411

[N-C3OHPy][DCA] 12 4820 15866 0.2 0.0003

13 7748 20758
23 8040 -4780

[N-C3CNPy][DCA] 12 5712 18266 0.2 0.0004

13 9093 22437

23 1130 -509.4

[N-C3CNMPyr][DCA] 12 4672 17024 0.2 0.0007

13 6821 16306

23 104.8 513.2

30
Captions to the figures

Figure 1. Plot of the experimental versus NRTL correlations for the composition tie lines of the

ternary system {[N-C3CNMPyr][DCA] (1) + hex-1-ene (2) + hexane (3)} at T = 298.15 K; (×― ×)
×)

experimental data, (+---+, red lines) NRTL correlation.

Figure 2. Plot of the experimental versus NRTL correlations for the composition tie lines of the

ternary system {[EMMor][DCA] (1) + cyclohexene (2) + cyclohexane (3)} at T = 298.15 K; (•― •))

experimental data, (+---+, red lines) NRTL correlation.

Figure 3. Plot of the selectivity, S as a function of the mole fraction of hex-1-ene in the hydrocarbon-

rich phase for the ternary systems {IL + hex-1-ene + hexane} at T = 298.15 K: (♦) [EMMor][DCA];

(•)) [[N-C3OHMMor][DCA]; (•)) [[N-C3OHMIM][DCA]; (□) [N-C3OHPy][DCA]; (•)) [[N-

4
C3CNPy][DCA]; (•)) [[N-C3CNMPyr][DCA]; (+) [BCN Py][NTf2] [18].

Figure 4. Plot of the solute distribution ratio, β as a function of the mole fraction of hex-1-ene in the

hydrocarbon-rich phase for the ternary systems { IL + hex-1-ene + hexane } at T = 298.15 K: (♦)

[EMMor][DCA]; (•)) [[N-C3OHMMor][DCA]; (•)) [[N-C3OHMIM][DCA]; (□) [N-C3OHPy][DCA]; (•))

4
[N-C3CNPy][DCA]; (•)) [N-C3CNMPyr][DCA]; (+) [BCN Py][NTf2] [18].

Figure 5. Plot of the selectivity, S as a function of the mole fraction of cyclohexene in the

hydrocarbon-rich phase for the ternary systems {IL + cyclohexene + cyclohexane} at T = 298.15 K:

(♦) [EMMor][DCA]; (•)) [[N-C3OHMMor][DCA]; (•)) [[N-C3OHMIM][DCA]; (□) [N-C3OHPy][DCA];

4
(•)) [[N-C3CNPy][DCA]; (•)) [[N-C3CNMPyr][DCA]; (+) [BCN Py][NTf2] [18].

Figure 6. Plot of the solute distribution ratio, β as a function of the mole fraction of cyclohexene in

the hydrocarbon-rich phase for the ternary systems {IL + cyclohexene + cyclohexane} at

T = 298.15 K: (♦) [EMMor][DCA]; (•)) [[N-C3OHMMor][DCA]; (•)) [[N-C3OHMIM][DCA]; (□) [N-

4
C3OHPy][DCA]; (•)) [[N-C3CNPy][DCA]; (•)) [[N-C3CNMPyr][DCA]; (+) [BCN Py][NTf2] [18].

31
Figures

Figure 1.

32
Fig 2.

33
Figure 3.

34
Figure 4.

35
Figure 5.

36
Figure 6.

37
HIGHLIGHTS

> Synthesis of six ionic liquids: [EMMor][DCA], [N-C3OHMMor][DCA], [N-C3OHMIM][DCA],

[N-C3OHPy][DCA], [N-C3CNPy][DCA], [N-C3CNMPyr][DCA]. > Measurements of LLE in ternary

systems at T = 298.15 K. > Large selectivity and solute distribution ratio for hexane/hex-1-ene and

cyclohexane/cyclohexene separation processes.

38