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Solubility of inorganic salts in pure ionic liquids

Article  in  The Journal of Chemical Thermodynamics · December 2012


DOI: 10.1016/j.jct.2012.06.007

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J. Chem. Thermodynamics 55 (2012) 29–36

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Solubility of inorganic salts in pure ionic liquids


A.B. Pereiro ⇑, J.M.M. Araújo, F.S. Oliveira, J.M.S.S. Esperança, J.N. Canongia Lopes, I.M. Marrucho,
L.P.N. Rebelo ⇑
Instituto de Tecnologia Química e Biológica,1 Universidade Nova de Lisboa, Av. da República, 2780-157 Oeiras, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: The solubility of different conventional salts in several room-temperature ionic liquids – containing
Received 14 March 2012 ammonium, phosphonium or imidazolium cations combined with acetate, sulfate, sulfonate, thiocyanate,
Received in revised form 1 June 2012 chloride, tetracyano-borate, tris(pentafluoroethyl)trifluoro-phosphate, L-lactate, bis(trifluoromethylsul-
Accepted 8 June 2012
fonyl)imide or trifluoromethylsulfonate anions – were screened using a visual detection method. The
Available online 17 June 2012
most promising mixtures were then re-measured using an ATR–FTIR (Attenuated Total Reflection Fourier
Transform Infra Red) spectroscopy technique in order to accurately and quantitatively determine the cor-
Keywords:
responding solubility at 298.15 K.
Ionic liquids
Inorganic salts
Ó 2012 Elsevier Ltd. All rights reserved.
Solubility
Ionicity

1. Introduction systems, 1-ethyl-3-methylimidazolium ethylsulfate/acetate


([C2C1Im][C2SO4], [C2C1Im][OAc]), combined with ammonium thio-
The unique and diverse nature of ionic liquids (ILs) [1–6] has led cyanate, [NH4][SCN]. This approach represents a simple and effec-
to many scientific and technological advances in this novel and tive manner to boost the charge density of the system and the
multidisciplinary area of knowledge [7]. In recent years, several magnitude of the electrostatic interactions while preserving the li-
authors have debated the concept of the ionicity of ionic liquids quid nature of the ionic mixture. As a result, a new sub-class of io-
[8,9], i.e. the relationship between ion concentration and ion nic liquids – High Ionicity Ionic Liquids (HIILs) – can be produced
mobility in a fluid medium. Ionicity is controlled and serves as and characterized.
an effective way to probe the balance between different interactive To the best of our knowledge, research merging ILs and ISs has
forces – electrostatic, dispersive, hydrogen-bonding, p–p interac- mainly focused on developing systems for batteries, and, as a re-
tions – present in the ionic liquid. The ionicity concept can also sult, the characterization of their structure and physical properties
be used to analyse the ionic liquid structure since the association have concentrated on mixtures based on the bistriflamide anion
of ions as ion pairs or other charged/non-charged aggregates will [13–21]. The earliest of these studies, 1994, was performed by
also impact the effectiveness of ion mobility via altered conductiv- Wilkes et al. and focused on the physical properties, solid-liquid
ity and diffusion coefficients. Other properties such as vapour pres- equilibria and X-ray analysis of chloroaluminate-based ILs with
sure and hydrogen acceptor or hydrogen donor character can also distinct ISs [20,21]. Rosol et al. published the first studies address-
be correlated to the ionicity concept [10]. ing the solubility behaviour of lithium salts in four imidazolium-
In this context, many ionicity studies have focused on the effect based ILs with distinct anions and its effect on viscosity and ionic
of increasing the van der Waals contributions to the inter-ionic conductivity [13]. Only one paper [22] has reported observations
interactions through the increase in the alkyl chain present in of 1-ethyl-4-(methoxycarbonyl)pyridinium iodide (Kosower’s salt)
the IL ions [5]. Other studies have introduced hydrogen bonding in six different ionic liquids. However, due to the similar nature
between ions by functionalizing the alkyl chains [11]. In contrast, and size of the ions no exceptional trends were observed. Besides,
only one previous work [12] has analysed, in a broad sense, the in- the solubility of different commercial sodium salts has been stud-
crease of IL ionicity via the solubilization of inorganic salts (ISs) in ied by AlNashef [23] for their potential use in the production of
the ionic milieu. This study proved the increase ionicity in two IL/IS sodium metal by electrochemical processes in ILs.
In this work, we have tested the solubility of different inorganic
salts in a wide variety of ILs including those with ammonium,
1 phosphonium or imidazolium cations combined with acetate,
www.itqb.unl.pt.
⇑ Corresponding authors. Tel.: +351 214469414; fax: +351 214411277. sulfate, sulfonate, thiocyanate, chloride, tetracyano-borate,
E-mail addresses: anab@itqb.unl.pt (A.B. Pereiro), luis.rebelo@itqb.unl.pt tris(pentafluoroethyl)trifluoro-phosphate, L-lactate, bis(trifluoro-
(L.P.N. Rebelo). methylsulfonyl)imide or trifluoromethylsulfonate anions. The

0021-9614/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jct.2012.06.007
30 A.B. Pereiro et al. / J. Chem. Thermodynamics 55 (2012) 29–36

TABLE 1
Description of the ionic liquids and inorganic salts used in the solubility screening of inorganic salts in a wide range of ionic liquids.

Formal name Structure Abbreviation Supplier and purity %


Ionic liquids

1-Ethyl-3-methylimidazolium acetate [C2C1Im][OAc] Iolitec 95%

[C2C1Im][SCN] Iolitec 98%


1-Ethyl-3-methylimidazolium thiocyanate

1-Ethyl-3-methylimidazolium ethylsulfonate [C2C1Im][C2SO3] Prepared according to


reference [24] 99%

1-Ethyl-3-methylimidazolium ethylsulfate [C2C1Im][C2SO4] Iolitec 99%

1-Ethyl-3-methylimidazolium [C2C1Im][NTf2] Iolitec 99%


bis(trifluoromethylsulfonyl)imide

1-Ethyl-3-methylimidazolium [C2C1Im][OTf] Iolitec 99%


trifluoromethanesulfonate

Solvent Innovation 98%


1-Ethyl-3-methylimidazolium tetracyano-borate [C2C1Im][B(CN)4]

1-Ethyl-3-methylimidazolium [C2MIM][(C2F5)3PF3] Solvent Innovation 98%


tris(pentafluoroethyl)trifluoro-phosphate

Trihexyl(tetradecyl)phosphonium [P66614][NTf2] Iolitec 99%


bis(trifluoromethylsulfonyl)imide

Trihexyl(tetradecyl)phosphonium L-lactate [P66614][L-Lactate] Prepared by QUILL 98%

Trihexyl(tetradecyl)phosphonium [P66614][OTf] Iolitec 98%


trifluoromethanesulfonate

Trihexyl(tetradecyl)phosphonium chloride [P66614]Cl Cytec 96%


A.B. Pereiro et al. / J. Chem. Thermodynamics 55 (2012) 29–36 31

TABLE 1 (continued)

Formal name Structure Abbreviation Supplier and purity %


Tributylmethylphosphonium methylsulfate [P4441][C1SO4] Cytec 98.6%

2-Hydroxyethyl(trimethyl) ammonium L-lactate [Ch][L-Lactate] Prepared by QUILL 98%

Ethyl(2-hydroxyethyl)dimethyl ammonium [EtCh][NTf2] Prepared according to


bis(trifluoromethylsulfonyl)imide reference [25] 99%

Inorganic salts
Sodium thiocyanate Na[SCN] Fluka 98%

Sodium cyanate Na[OCN] Sigma–Aldrich 96%

Sodium chloride NaCl Sigma–Aldrich 99.5%

Sodium sulfate Na2[SO4] Fluka 99%

Sodium acetate Na[OAc] Sigma–Aldrich 99%

Sodium lactate Na[Lactate] Fluka 99%

Sodium bis(trifluoromethylsulfonyl)imide Na[NTf2] Prepared according to


reference [26]

Calcium chloride CaCl2 Sigma–Aldrich 97%

Ammonium chloride [NH4]Cl Sigma–Aldrich 99.5%

Ammonium thiocyanate [NH4][SCN] Sigma–Aldrich 97.5%

Cesium bis(trifluoromethylsulfonyl)imide Cs[NTf2] Prepared according to


reference [26]

(continued on next page)


32 A.B. Pereiro et al. / J. Chem. Thermodynamics 55 (2012) 29–36

TABLE 1 (continued)

Formal name Structure Abbreviation Supplier and purity %

Lithium bis(trifluoromethylsulfonyl)imide Li[NTf2] Iolitec 99%

3]
5)
2F

]
4]

te
4]
3]

N)

3 (C

t e]
2 SO

2]

cta
O

O
]
]

]
Ac

CN

Tf
Tf

(C

4]
2S

ta
f2 ]

2]
F

La

O
] [O

][O

f
][C

][C

][N

Tf
][B

][P
][S

ac
OT
NT

1S
(a)

L-

[N
-L
1 Im
1 Im

1 Im

1 Im

1 Im

1 Im

1 Im

[C
1 Im

4 ][
4 ][

4 ][

h]
[L
41 ]
2C
2C
2C

2C

2C

2C

2C

2C

61

61

61

tC
h]
44
66

66

66
[C

[C
[C

[C

[C

[C
[C

[C

[C

[E
[P

[P

[P

[P
Na[SCN]

Na[OCN]

Inorganic Salts
NaCl

Na2[SO4]

CaCl2

[NH4]Cl

[NH4][SCN]

Ionic Liquids
N]
e]
ta t

SC
2]
]

2]
]

2]
CN

l
Ac

(b)
Tf

4 ]C
ac

Tf

Tf
4 ][
2
[O

[N

Cl

Cl
[L

[N
[S

[N
H

H
Ca
Na

Na

Na
Na

Na

[N

Cs
[N

Li

[C2C1Im][OAc
Im][OAc]]

[C2C1Im][SCN]
Ionic Liquids

[C2C1Im][NTf2]

[EtCh][NTf
EtCh][NTf2]

[P66614][L
][L-Lactate]
Lactate]

[P66614]Cl

Inorganic Salts
FIGURE 1. (a) Matrix of the ionic liquid plus inorganic salt binary mixtures studied. (b) Matrix of the binary mixtures with a common ion. : solubility tests using a visual
detection method; : solubility tests also using a spectroscopic method. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

inorganic salts were chosen to map a substantial part of the Hof- 2. Experimental section
meister series, both in terms of the cation and the anion. A visual
detection method served to screen solubility initially. The binary 2.1. Materials
systems of ionic liquid + inorganic salt with the highest solubilities
underwent further testing, and their accurate solubilities at All ionic liquids and inorganic salts used in this study are de-
298.15 K were accurately determined by Attenuated Total Reflec- scribed in table 1, including their source and purity. Ionic liquids
tion Fourier Transform Infra Red (ATR-FTIR) spectroscopy. prepared at QUILL were characterized by a combination of 1H
A.B. Pereiro et al. / J. Chem. Thermodynamics 55 (2012) 29–36 33

0.4 0.4
Na[SCN] (a) CaCl2
(b)
Mass fraction of inorganic salt

Mass fraction of inorganic salt


[NH4][SCN] [NH4]Cl
0.3 0.3

0.2 0.2

0.1 0.1

0.0 a b c d e f g h i j l m n
0.0
k a b c d a b c d e f g h i j k l m n a b c d e f g h i j k l m n
Ionic Liquids
Ionic Liquids a [C2C1Im][OAc]
0.4 b [C2C1Im][SCN]
NaCl
(c) c [C2C1Im][C2SO3]
Mass fraction of inorganic salt

Na2[SO4]
Na[OCN]
d [C2C1Im][C2SO4]
0.3
e [C2C1Im][NTf2]
f [C2C1Im][OTf]
0.2 g [C2C1Im][B(CN)4]
h [C2C1Im][PF3(C2F5)3]
i [P66614][NTf2]
0.1
j [P66614][L-Lactate]
k [P66614][OTf]
0.0 l [P4441][C1SO4]
a b c d e f g h i j k l m n a b c d e f g h i j k l m n a b c d e f
m [Ch][L-Lactate]
Ionic Liquids n [EtCh][NTf2]

FIGURE 2. Solubilities of different inorganic salt solutes in several ionic liquid solvents obtained by the visual method: (a) solubility of sodium and ammonium thiocyanate;
(b) solubility of calcium and ammonium chloride; (c) solubility of sodium chloride, sulphate and cyanate. The systems selected for further spectroscopic tests are highlighted.

0.6
a Na[NTf2] (a) 1.1 0.025
Mass fraction of inorganic salt

(a)
ATR units ([C2C1Im][C2SO3])

[C2C1Im][C2SO3]
0.5 b Cs[NT2] c

ATR units ([NH4][SCN])


[NH4][SCN]
c Li[NTf2] 0.020
0.8
0.4
b c
b
0.015
0.3 0.6
a 0.010
0.2 a
0.3
0.1 0.005

0.0 0.0 0.000


[C2C1Im][NTf2] [EtCh][ NTf2] 4000 3150 2300 1450 600
Wavenumber / cm-1
0.6
a Na[OAc] 0.6
(b) 0.6
w[NH ][SCN] = 0
4
Mass fraction of inorganic salt

b Na[SCN]
0.5 c [NH ][SCN] y = 1.2103 x
R2 = 0.9979
(b) w[NH ][SCN] = 0.0195
4
ATR units

4
0.3
w[NH ][SCN] = 0.0399
d Na[Lactate] 0.4 4

0.4 e NaCl w[NH ][SCN] = 0.0549


4

f CaCl2 0.0 w[NH ][SCN] = 0.0597


4
0.00 x [NH4][SCN] 0.50
0.3 g [NH4]Cl 0.3 w[NH ][SCN] = 0.0726
4

w[NH ][SCN] = 0.0826


4

0.2 w[NH ][SCN] = 0.0915


4

b 0.2 w[NH ][SCN] = 0.1006


c 4

a w[NH ][SCN] = 0.1379


0.1 f 4

w[NH ][SCN] = 0.1895


d e g 0.0 4

0.0 2100 2080 2060 2040 2020


-1
[C2C1Im][OAc] [C2C1Im][SCN] [P6 6 6 14][Lactate] [P6 6 6 14]Cl Wavenumber cm

FIGURE 3. Solubilities of different inorganic salt solutes in several ionic liquid FIGURE 4. (a) Representative ATR-FTIR spectra of pure [C2C1Im][C2SO3] (IL) and of
solvents with a common ion obtained visually: (a) Systems including the bis(tri- pure [NH4][SCN] (IS); (b) ATR-FTIR spectra of [NH4][SCN] plus [C2C1Im][C2SO3]
fluoromethylsulfonyl)imide anion; (b) Systems including the acetate, thiocyanate, mixtures in the range of the C–N bond stretching vibration of the inorganic salt
lactate and chloride anions. The systems selected for further spectroscopic tests are anion. The inset shows the calibration of the absolute peak intensity in the range of
highlighted. the C–N bond stretching vibration as a function of [NH4][SCN] concentration.
34 A.B. Pereiro et al. / J. Chem. Thermodynamics 55 (2012) 29–36

1.1 0.50 safe–lock micro test tubes are conical at the bottom, it was impor-
[C2C1Im][NTf2] (a) tant to add the solid at the end of the process to guarantee efficient
ATR units ([C2C1Im][NTf2])

Cs[NTf2]

ATR units (Cs[NTf2])


equilibrium. A study of the amount of inorganic salt solubilized in
0.8 0.38
the ionic liquid over time ensured that the equilibrium was
achieved. Before sampling, each solution was centrifuged
0.6 0.25 (30 min) to enhance the physical separation of the liquid and solid
phases. Triplicates of each sample were always measured.
Attenuated Total Reflection Fourier Transform Infra Red
0.3 0.13 (ATR–FTIR) spectroscopy quantitatively evaluated the amount of
inorganic salt in the ionic liquid. This procedure allows for an accu-
rate measurement of the solubility of the inorganic salt in the ionic
0.0 0.00
4000 3150 2300 1450 600 liquid. The infrared spectra of the neat IL/IS and the selected solu-
Wavenumber / cm-1 tions were recorded by means of an IFS–66/S FTIR spectrometer
from Bruker (Bruker Daltonics, MA, USA) using a single reflection
0.10 0.10
ATR cell (DuraDisk). Acquisition was accomplished in the DTGS–
(b) wCs[NTf ] = 0
2
detection mode using an accumulation rate of 258 scans at a reso-
0.09
wCs[NTf ] = 0.1354 lution of 8 cm 1 at room temperature in the spectral range of
0.08 2

y = -0.0796x+0.0979 wCs[NTf ] = 0.2080


2
4000–600 cm 1 and was processed using the Opus software pack-
age (Bruker) with a wave number accuracy of 0.1 cm 1. Any inter-
ATR units

2
R = 0.9996 wCs[NTf ] = 0.2346
0.07 2
0.00 x Cs[NTf2] 0.30
0.05 wCs[NTf ] = 0.2731
2
ference due to water vapour and CO2 was avoided by purging the
wCs[NTf ] = 0.2901
2
sample and detector compartments with N2, at a flow rate of
wCs[NTf ] = 0.2958 18 L  min 1. The uncertainty of the composition resulted in an
0.03 2

wCs[NTf ] = 1
2
estimation of ±0.0045 in mass fraction.

0.00
1640 1615 1590 1565 1540 3. Results and discussion
Wavenumber cm-1
Screening of the solubility of inorganic salts in a wide variety of
FIGURE 5. (a) Representative ATR-FTIR spectra of pure [C2C1Im][NTf2] (IL) and of
pure Cs[NTf2] (IS); (b) ATR-FTIR spectra of Cs[NTf2] plus [C2C1Im][NTf2] mixtures in ILs was performed in order to establish the most promising ionic
the range of the C–N bond stretching vibration of the imidazolium cation. The inset liquids – in terms of IS solubility range – for use as HIILs. Figure
shows the calibration of the absolute peak intensity in the range of the C–N bond 1 shows the matrix of the inorganic salt + ionic liquid systems
stretching vibration as a function of Cs[NTf2] concentration.
studied for mapping the general behaviour of these binary systems.
In figure 1a, the screened ionic liquids included cations as diverse
NMR, 13C NMR, electrospray ionization mass spectrometry, halide
as ammonium, phosphonium or imidazolium and anions such as
content determination, CHN elemental analysis, and water content
acetate, sulfate, sulfonate, thiocyanate, chloride, tetracyano-borate,
assay techniques. Typical halide content was always less than 0.1%.
tris(pentafluoroethyl)trifluoro-phosphate, L-lactate, bis(trifluoro-
To reduce water and other volatile substances, vacuum
methylsulfonyl)imide or trifluoromethylsulfonate. The screened
(3  10 2 Torr) and moderate temperature (ca. 318.15 K) were al-
ISs mapped a significant portion of the Hofmeister series, both in
ways applied to samples of both ionic liquid and inorganic salt for
terms of the chosen cation and anion.
several days prior to use. The final water mass fraction was mea-
The solubility results obtained are displayed in figure 2. The
sured by Karl Fischer coulometric titration (Metrohm 831 KF Coulo-
behaviour is largely dependent on the cation/anion of both the io-
meter). The dried ionic liquids contained less than: 100 ppm of
nic liquid and the inorganic salt present in the mixture. In general,
water for [C2C1Im][NTf2], [C2C1Im][OTf], [C2C1Im][PF3(C2F5)3],
binary mixtures containing ammonium thiocyanate yielded higher
[P66614][NTf2] and [EtCh][NTf2]; 200 ppm of water for [C2C1Im]-
solubilities. On the other hand, inorganic salts with a divalent atom
[C2SO3], [C2C1Im][C2SO4], [C2C1Im][B(CN)4], [P66614][OTf] and
(Na2[SO4] and CaCl2) exhibit lower solubilities in the IL. The highly
[P4441][C1SO4]; 500 ppm of water for [C2C1Im][SCN], [P66614][L-Lac-
viscous ([C2C1Im][OAc] plus CaCl2) mixture is an exception to this
tate] and [P66614][Cl]; and 1500 ppm of water for [C2C1Im][OAc] and
rule. The combination of two divalent atoms (for instance Ca[SO4])
[Ch][L-Lactate]. The purity of all ionic liquids was checked by 1H
was not tested due to the high viscosity of the resulting mixtures.
NMR.
The effect of increasing the alkyl side chains present in the ionic li-
quid was also studied: a comparison between the cations [C2C1Im]+
2.2. Apparatus and procedure and [P66614]+ cations demonstrates that larger alkyl chains hinder
the solubility of inorganic salts in the ionic liquid.
Screening of the solubility of inorganic salts in a wide variety of A specific study of the solubility of inorganic salts in ILs with a
ILs was accomplished using a visual detection method. The solubil- common anion was also carried out. Figure 1b illustrates the ma-
ity was detected by the appearance of a precipitate as a conse- trix of the corresponding binary mixtures. Figure 3 displays the re-
quence of repeated addition of 1–2 mg of inorganic salt to sults from this specific screening. Binary systems which contained
approximately 1 g of IL, with continuous stirring, at room tempera- the common bis(trifluoromethylsulfonyl)imide anion were those
ture and atmospheric pressure, between 24–48 h after the addition. that yielded higher solubilities. It must be stressed that this partic-
A Thermomixer Comfort (Eppendorf) provided a precise quanti- ular anion only shows high solubility in common anion binary
tative measure of the solubility of a given inorganic salt in an ionic mixtures. For all other binary mixtures presented in figure 2, the
liquid for each binary mixture selected from the initial screening solubility of different ISs in the ionic liquid [C2C1Im][NTf2] exhibits
tests. The solubility measurements were carried out at 298.15 K, the lowest values. In terms of systems with a common anion, the
whilst stirring at up to 1400 rmin 1. Approximately 0.250 g of best results were obtained for the lithium cation, which shows sol-
ionic liquid was placed inside the safe–lock micro test tubes and ubilities higher than the cesium ion.
an excess amount of the inorganic salt was added at constant The [NH4]+, [NTf2] , and [SCN] inorganic salt ions – that in gen-
temperature. The uncertainty in this variable is ±0.1 K. Since the eral yielded higher solubilities in different ionic liquids – are clas-
A.B. Pereiro et al. / J. Chem. Thermodynamics 55 (2012) 29–36 35

TABLE 2
Fitting parameters used in the ATR-FTIR/concentration linear regressions (y = mx + B) and corresponding solubility of ISs (component 2) in ILs (component 1) at 298.15 K and
atmospheric pressure.

Binary mixture m B R2 Solubility


Molar fraction of ISs Mass fraction of ISs
[C2C1Im][C2SO4] (1) + [NH4][SCN] (2) 1.1132 0 0.9983 0.6479 ± 0.0036a 0.3722 ± 0.0037
[C2C1Im][C2SO3] (1) + [NH4][SCN] (2) 1.2103 0 0.9979 0.4137 ± 0.0046 0.1960 ± 0.0030
[C2C1Im][OAc] (1) + [NH4][SCN] (2) 1.4520 0 0.9996 0.4035 ± 0.0046a 0.2322 ± 0.0034
[C2C1Im][C2SO4] (1) + Na[SCN] (2) 0.9218 0 0.9977 0.2371 ± 0.0038 0.0964 ± 0.0018
[C2C1Im][SCN] (1) + Na[SCN] (2) 0.1235 0.2705 0.9968 0.2462 ± 0.0015 0.1353 ± 0.0009
[C2C1Im][C2SO3] (1) + [NH4]Cl (2) 0.2525 0 0.9978 0.2529 ± 0.0031 0.0760 ± 0.0012
[C2C1Im][OAc] (1) + [NH4]Cl (2) 0.2517 0 0.9985 0.3755 ± 0.0016 0.1590 ± 0.0009
[C2C1Im][NTf2] (1) + Li[NTf2] (2) 0.0785 0.0966 0.9961 0.4331 ± 0.0036 0.3592 ± 0.0033
[EtCh][NTf2] (1) + Li[NTf2] (2) 0.0522 0.0834 0.9994 0.5603 ± 0.0027 0.4787 ± 0.0028
[C2C1Im][NTf2] (1) + Cs[NTf2] (2) 0.0796 0.0979 0.9996 0.2999 ± 0.0034 0.3114 ± 0.0035
[EtCh][NTf2] (1) + Cs[NTf2] (2) 0.0491 0.0835 0.9994 0.3223 ± 0.0044 0.3302 ± 0.0045
a
From reference [12].

sified according to the Hofmeister series as weakly hydrated ions. 0.6


However, whereas the ammonium cation has a rather localized po-

Mass fraction of inorganic salt


Li[NTf2]
sitive charge and a high degree of symmetry, the anions are char- 0.5
acterized by a negative charge delocalized asymmetrically among [NH4][SCN]
several atoms of the molecular framework, thus being structurally 0.4 Cs[NTf2]
similar to the anions characteristic of ionic liquids. In order to fully
0.3
appreciate the changes taking place during solubilization, we must
now consider the asymmetry present in the IL/IS binary mixtures, 0.2 [NH4]Cl
namely the different roles played by the cation and anion of the IS. Na[SCN]

This asymmetry may explain structural changes during the addi- 0.1
tion of inorganic salt to the IL, including the ultimate precipitation
of the salt from the IL/IS saturated mixture. In the most highly con- 0.0

2]
[C [C 4 ]

c]

c]

h] f2 ]
m 3]

m O4 ]

m O3 ]
]

h] 2 ]
2]
N
centrated IL solution, the inorganic salt ions can be easily accom-

Tf
O
O

Tf

tC Tf
A

tC T
C
1 Im 2 S

][O

][O
2S

2S

2S

[N
[E ][N

[E ][N
[N
][S
][C

[C ][C

C
modated within the local charge–ordered structure of the IL.

m
[C ][

m
]
Im

1I

1I
1 Im

1 Im

1I
1I

1I
2C

2C

2C
2C

2C
1
C
2C

2C

2C
When the concentration of inorganic salt is increased, the small

[C

[C
2
[C
[C

[C

size and high-charge density of the IS cation will start to out-com- [C Ionic Liquids
pete the interactions between the IL cation and the anions and the
FIGURE 6. Solubilities of different inorganic salt solutes in several ionic liquid
polar network of the IL/IS mixture will start to contract relative to solvents determined by an ATR-FTIR spectroscopic method at 298.15 K.
the original IL structure [12]. The size, shape and charge dispersion
of the IL cation probably allow it to find new orientations and
accommodate itself inside this new shrinking ionic fluid network tration, as illustrated in figure 5b. This same peak was used to
– at least up to a certain IS concentration, beyond which the sepa- calibrate the following binary mixtures: [C2C1Im][SCN] + Na[SCN],
ration of an IS precipitate from a saturated IL/IS solution will occur. [C2C1Im][C2SO3] or [C2C1Im][OAc] + [NH4]Cl and [C2C1Im][NTf2] +
The binary systems with the highest inorganic salt solubility Li[NTf2]. For the binary mixtures containing the cation ethyl(2-
(mole fraction higher than 0.20) were subjected to accurate solu- hydroxyethyl)dimethyl ammonium, [EtCh][NTf2] + Li[NTf2] and
bility measurements using ATR-FTIR spectroscopy. These systems [EtCh][NTf2] + Cs[NTf2], the linear calibration functions were
are highlighted in figures 2 and 3. Two examples of different cali- obtained using the peak at 1484 cm 1, which can be attributed
brations using ATR-FTIR spectroscopy for the binary mixtures to the interaction of the –CH2 groups with the quaternary ammo-
[C2C1Im][C2SO3] + [NH4][SCN] and [C2C1Im][NTf2] + Cs[NTf2] are nium ion [30]. The fitting parameters of the linear calibrations
illustrated in figures 4 and 5. The spectra of [NH4][SCN] and are given in table 2 together with the coefficient R2.
[C2C1Im][C2SO3] are depicted in figure 4a. The vibration modes of A study of the amount of inorganic salt solubilized in the ionic
the ammonium thiocyanate in the region between 2100 and liquid over time was carried out during continual stirring to ensure
2015 cm 1 are attributed mainly to the C–N bond stretching mo- that equilibrium was achieved. The time needed to achieve equilib-
tions [27,28], where the IL does not show any particular absor- rium at 298.15 K for the studied systems varied from around 24 h
bance. A linear calibration was obtained by means of the for the binary mixtures with Na[SCN] or [NH4][SCN] to around
absolute peak intensity of this characteristic band versus the 240 h (10 days) for the binary mixtures with [NH4]Cl. Samples
[NH4][SCN] concentration. figure 4b pictures the ATR-FTIR spectra were analysed until the difference in solubility between two con-
of this band and calibration as a function of inorganic salt concen- secutive samples was less than 0.8%.
tration. This same peak was used to calibrate the following binary The results obtained for the mixtures analysed using ATR-FTIR
mixtures: [C2C1Im][C2SO4] or [C2C1Im][OAc] + [NH4][SCN] and spectroscopy are depicted in figure 6, where it can be seen that
[C2C1Im][C2SO4] + Na[SCN]. For the mixtures with a common ion, the systems including the bis(trifluoromethylsulfonyl)imide com-
the system [C2C1Im][NTf2] + Cs[NTf2] has been used as an example. mon anion or the ammonium thiocyanate inorganic salt are those
The spectra of Cs[NTf2] and [C2C1Im][NTf2] appear in figure 5a The showing the largest solubility of the inorganic salt in the ionic li-
band observed at 1574 cm 1 can be attributed to the C–N bond quid. From the solubility data in table 2, the system [EtCh][NT-
stretching vibration in the imidazolium ring of the IL [29]. Since f2] + Li[NTf2] seems to be particularly adequate in terms of the
this inorganic salt does not show any absorbance at this frequency, formation of a high-ionicity ionic liquid (HIIL), since it shows a
linear calibration functions were obtained at the maximum absor- mass percentage of inorganic salt above 50%. In other words, these
bance value of the characteristic band versus the Cs[NTf2] concen- mixtures are the most promising for increasing the ionicity of ionic
36 A.B. Pereiro et al. / J. Chem. Thermodynamics 55 (2012) 29–36

liquids via the solubilization of inorganic salts in the ionic milieu, a J. Ferguson, Dr. K.R. Seddon and QUILL for their contributions in
process which can be achieved at very low cost and where the the synthesis of ionic liquids.
magnitude of the electrostatic interactions in the ionic mixture is
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A.B. Pereiro acknowledges Marie Curie Actions Intra-European
7329–7337.
Fellowships (IEF) for a contract under FP7-PEOPLE-2009-IEF – [25] A.J.L. Costa, M.R.C. Soromenho, K. Shimizu, I.M. Marrucho, J.M.S.S. Esperança,
252355 – HALOGENILS. J.M.M. Araújo and F.S. Oliveira gratefully J.N.C. Lopes, L.P.N. Rebelo, ChemPhysChem 13 (2012) 1–9.
acknowledge the financial support of FCT/MCTES (Portugal) [26] J.P. Leal, M.E. Minas da Piedade, J.N. Canongia Lopes, A.A. Tomaszowska,
J.M.S.S. Esperanca, L.P.N. Rebelo, K.R. Seddon, J. Phys. Chem. B 113 (2009)
through the Post-Doc Grant SFRH/BPD/65981/2009 and through 3491–3498.
the PhD fellowship SFRH/BD/73761/2010. J.M.S.S. Esperança and [27] C. Guha, J.M. Chakraborty, S. Karanjai, B. Das, J. Phys. Chem. B 107 (2003)
I.M. Marrucho acknowledge FCT/MCTES (Portugal) for a contract 12814–12819.
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para a Ciência e Tecnologia through Projects: PTDC/QUI/72903/ [30] S. Mukherjee, M. Chakraborty, A.K. Panda, S.C. Bhattacharya, S.P. Moulik,
2006, PTDC/QUI/71331/2006, PTDC/EQU-EPR/104554/2008, Colloid. Surf. A 388 (2011) 1–11.
PTDC/EQU-FTT/116015/2009 and PTDC/EQU-FTT/118800/2010. In
addition, the authors wish to acknowledge M.R.C. Soromenho, JCT 12-165

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