Vapor Pressure Osmometry Studies of Aqueous Ionic Liquid-Carbohydrate Systems

Article abstract of DOI:10.1021/acs.jced.7b00719

Precise vapor pressure osmometry (VPO) measurements at 308.15 K were conducted for solutions of three ILs, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF₄]), 1-butyl-3-methylimidazolium bromide ([Bmim][Br]), and 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim][HSO₄]), in aqueous solutions of three carbohydrates, sucrose, maltose, and maltitol, as well as for solutions of the carbohydrates in aqueous solutions of these ILs. Because of the unfavorable IL-carbohydrate interactions, all the investigated IL + carbohydrates aqueous systems show the soluting-out effect and vapor-liquid equilibria behavior of these systems in the monophasic region show the negative deviation from the semi-ideal behavior (a_w + 1 < a_wIL° + a_wC° and δp < δp_IL° + δp_C°). For a certain carbohydrate and at the same molality of IL, the magnitude of the departures for the investigated ILs follows the order: [Bmim][BF₄] > [Bmim][HSO₄] [Bmim][Br]. In the case of [Bmim][BF₄]/carbohydrate aqueous systems, which have a phase separation capability, the soluting-out power of the carbohydrates on [Bmim][BF₄] in aqueous solutions (or negative deviation from the semi-ideal behavior) reduced by decreasing the hydrophilicity of the carbohydrates. Aqueous [Bmim][Br]/carbohydrate and [Bmim][HSO₄]/carbohydrate systems are unable to form the ABS, and the soluting-out effect of the ILs on the aqueous carbohydrate solutions appears in the form of precipitation of sugars from the aqueous solutions.

Full text of DOI:10.1021/acs.jced.7b00719

Article
Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX
pubs.acs.org/jced
Vapor Pressure Osmometry Studies of Aqueous Ionic Liquid−
Carbohydrate Systems
Bahman Jamehbozorg and Rahmat Sadeghi*
Department of Chemistry, University of Kurdistan, Sanandaj, Iran 66135
*
S Supporting Information
ABSTRACT: Precise vapor pressure osmometry (VPO) measurements at
08.15 K were conducted for solutions of three ILs, 1-butyl-3-
3
methylimidazolium tetrafluoroborate ([Bmim][BF ]), 1-butyl-3-methylimi-
4
dazolium bromide ([Bmim][Br]), and 1-butyl-3-methylimidazolium hydro-
gen sulfate ([Bmim][HSO ]), in aqueous solutions of three carbohydrates,
4
sucrose, maltose, and maltitol, as well as for solutions of the carbohydrates
in aqueous solutions of these ILs. Because of the unfavorable IL−
carbohydrate interactions, all the investigated IL + carbohydrates aqueous
systems show the soluting-out effect and vapor−liquid equilibria behavior of
these systems in the monophasic region show the negative deviation from
the semi-ideal behavior (a + 1 < a ° + a ° and Δp < Δp ° + Δp °). For
w
wIL
wC
IL
C
a certain carbohydrate and at the same molality of IL, the magnitude of the
departures for the investigated ILs follows the order: [Bmim][BF ] >
4
[
Bmim][HSO ] ≫ [Bmim][Br]. In the case of [Bmim][BF ]/carbohydrate
4
4
aqueous systems, which have a phase separation capability, the soluting-out power of the carbohydrates on [Bmim][BF ] in
4
aqueous solutions (or negative deviation from the semi-ideal behavior) reduced by decreasing the hydrophilicity of the
carbohydrates. Aqueous [Bmim][Br]/carbohydrate and [Bmim][HSO ]/carbohydrate systems are unable to form the ABS, and
4
the soluting-out effect of the ILs on the aqueous carbohydrate solutions appears in the form of precipitation of sugars from the
aqueous solutions.
1
. INTRODUCTION
difference between vapor−liquid equilibria (VLE) data for a
certain aqueous ternary IL−carbohydrate system and its
corresponding aqueous binary IL and carbohydrate solutions
can provide some valuable information about soluting effect
produced by addition of one solute to aqueous solution of
another solute and therefore explain phase-forming ability of
After introducing the aqueous biphasic systems (ABS) and their
applications in bioseparation processes by Albertson, a lot of
1
work has been conducted to introduce the new ABSs, to obtain
thermodynamic information about the soluting effect phenom-
enon, and effective applications of ABS in biotechnology. ABS
are formed of two aqueous A-rich and B-rich phases and both
the phases have a water content above 70% that can provide the
gentle environment for biomolecules. These systems are
categorized based on ionic liquid/salt, ionic liquid/polymer,
polymer/salt, polymer/amino acid, polymer/carbohydrate,
or ionic liquid/amino acid compositions. These systems can be
used for the extraction and purification of different types of
3
,6,14,15
these systems.
The activity coefficient, osmotic coef-
ficient, water activity, and Gibbs energy of transfer can be
obtained from different technics such as direct vapor pressure
measurements, isopiestic method, membrane osmometry,
electromotive force measurements, headspace chromatography,
2
3
6
4
5
16
7
and vapor pressure osmometry (VPO). In this work, we used
the VPO method because of its reliability, performance at
ambient pressure, easier and cheaper, and shorter time
measurements. In recent years various thermodynamic studies
have been conducted on the aqueous solutions containing some
7
−9
valuable materials from biomolecules to metal ions.
In
recent years, ionic liquids gained attention for their interesting
properties such as negligible vapor pressures, nonflammability,
and good thermal and electrochemical stabilities. Rogers and
co-workers in 2003 established that these electrolytes are
3
,17−25
imidazolium based ILs or carbohydrates.
However, as far
as we know there is very limited information about the ternary
11,13,26−30
10
aqueous carbohydrate−IL solutions in the literature.
capable of ABS formation in the presence of the salts. In
007, Zhang et al. reported the ability of carbohydrates to
In ternary aqueous IL + solute solutions, ILs can act as both
soluting-out agent and a component that is soluted-out from
the solution depending on the hydrophilicity differences
2
11
solute-out ionic liquids from aqueous solution. Carbohydrates
are nontoxic, renewable feedstock and biodegradable organic
molecules and use of them in the formation of IL/carbohydrate
ABS has various advantages.
ternary solute A + solute B solutions resulted from the quality
12,13
The soluting effect in aqueous
Received: August 8, 2017
Accepted: January 9, 2018
of solute-water and solute A−solute B interactions. The
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.jced.7b00719
J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data
Article
Table 1. Specification of Chemicals Used in this Work
chemical
source
CAS registry number
mass fraction purity
water content (mass fraction)
maltitol
sucrose
Alfa Aesar
Merck
585-88-6
≥0.97
≥0.98
≥0.99
≥0.995
≥0.97
≥0.99
≥0.98
>0.99
≥0.98
≥0.98
57-50-1
maltose monohydrate
NaCl
Merck
6363-53-7
7647-14-5
13755-29-8
616-47-7
Merck
sodium tetrafluoroborate
Merck
1
1
-methylimidazole
-bromobutane
Merck
Merck
109-65-9
[
[
[
Bmim][HSO4]
IoLiTec
262297-13-2
<0.003
<0.003
<0.001
3
3
3
Bmim][Br]
synthetic
synthetic
3
Bmim][BF4]
Scheme 1. Chemical Structures of the Carbohydrates and Ionic Liquids Studied
between the IL and the secondary solute. In order to study
both situations, we chose three ILs and three sugars that their
2.1.1. Synthesis of Ionic Liquids. Ionic liquids [Bmim][Br]
and [Bmim][BF ] were synthesized and purified according to
standard procedures described in the literature.
4
33
hydrophilicity powers follow the order: [Bmim][HSO ] >
4
31,32
Synthesis of [Bmim][Br]. Equimolar quantities of butyl
bromide (slightly excess) and 1-methylimidazole with an
appropriate amount of ethyl acetate as solvent were added to
a round-bottomed flask connected to a reflux condenser for 48
h at 70 °C with stirring until two phases formed. The reaction
was conducted under an argon atmosphere. The top phase,
containing unreacted starting materials along with ethyl acetate,
was decanted and fresh ethyl acetate was again added, this
process was repeated six times. Finally the bottom phase was
vacuum-dried at 90 °C for 3 h to remove the traces of ethyl
acetate. Yield of reaction was 95%. The ionic liquid was
[
Bmim][Br] ≥ carbohydrates ≫ [Bmim][BF4].
Therefore,
[
Bmim][BF ], which is more hydrophobic than the selected
4
carbohydrates, and [Bmim][HSO ] and [Bmim][Br], which
4
are more hydrophilic than the investigated carbohydrates, were
selected. In order to study the effects of some parameters, such
as number of hydroxyl groups, stereochemical properties of
carbohydrate molecules, and anion of ionic liquids, on the
vapor−liquid equilibria behavior of these systems, three ionic
liquids mentioned above and three carbohydrates including
disaccharides maltose and sucrose and a polyol (maltitol) were
selected and the thermodynamic properties of their ternary
aqueous systems were studied at 308.15 K.
1
13
analyzed by FT-IR and H NMR and C NMR spectroscopy.
The FT-IR spectrum of the synthesized IL contains the peaks at
−1
ν/cm 3076 Br, 2960 (s, aliphatic C−H stretch), 1628 (w,
CC), 1568 (s, sym. ring stretch), 1463 (s, sym ring stretch),
2. EXPERIMENTAL SECTION
1
1
114 (w, sym. ring stretch), 1380 (m, CH bending vibration),
168 (s, C−N vibration). H NMR spectrum contains peaks at
3
1
2.1. Materials. The properties of chemicals used in this
δ(ppm): 0.53 (t, J = 7.3, 3H), 0.89−1.03 (m, 2H), 1.44−1.56
work were listed in Table 1. Sodium chloride was dried in an
electrical oven at 383.15 K for 24 h prior to use. The water
content of the ionic liquids were determined by Karl Fischer
titration. The purities of the ILs were determined by Karl
Fischer titration and NMR spectroscopy. Double distilled and
deionized water were used for the preparation of the solutions.
The structures of studied carbohydrates and ionic liquids have
been presented in Scheme 1.
(
1
1
m, 2H), 3.72 (s, 3H), 3.95 (t, J = 7.13, 2H), 7.3 (s, 1H), 7.4 (s,
H), 9.82 (s, 1H). 13C NMR: 13, 19, 31.8, 36.3, 49.4, 122,
23.6, 136.6.
Synthesis of [Bmim][BF ]. In total, 0.1 mol (22 g) of
Bmim][Br] and an appropriate amount of acetone (about 100
4
[
mL) as solvent were added to the single-mouth flask connected
to a reflux condenser until the IL was dissolved completely.
Then 0.1 mol (11 g) of NaBF was added to the obtained IL
4
B
DOI: 10.1021/acs.jced.7b00719
J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data
Article
a
Table 2. Experimental Water Activity, a , and vapor pressure, p, against IL Molality, m , for Ternary Solutions of the ILs in
Aqueous Solution of 1 mol kg of the Carbohydrates at 308.15 K
w
IL
−1
m /(mol kg−1)
aw
p/(kPa)
m /(mol kg−1)
aw
p/(kPa)
m /(mol kg−1)
aw
p/(kPa)
IL
IL
IL
[
Bmim][BF ] in sucrose
[Bmim][BF ] in maltose
[Bmim][BF ] in maltitol
4
4
4
0
0
0
1
2
2
2
3
.0000
.4772
.9290
.5150
.0601
.6400
.7012
.2435
0.9811
0.9680
0.9609
0.9551
0.9524
0.9526
0.9526
0.9520
5.520
5.446
5.406
5.375
5.359
5.360
5.360
5.356
0.0000
0.2571
0.5665
1.0799
1.5394
1.8066
1.8117
2.0676
0.9818
0.9738
5.524
5.479
5.440
5.397
5.377
5.374
5.377
5.375
5.370
0.0000
0.2561
0.3863
0.7878
1.3730
1.5135
2.0728
0.9813
0.9731
0.9698
0.9623
0.9561
0.9565
0.9559
5.521
5.475
5.456
5.414
5.379
5.382
5.378
0.9668
0.9593
0.9556
0.9552
0.9557
0.9553
2.5288
0.9544
[
Bmim][Br] in sucrose
[Bmim][Br] in maltose
0.9829
[Bmim][Br] in maltitol
0
0
0
0
.0000
.3095
.5262
.7610
0.9814
5.522
5.472
5.439
5.407
0.0000
0.3292
0.5639
0.7710
5.530
5.477
5.442
5.414
5.385
5.328
0.0000
0.3053
0.5183
0.7629
0.9813
0.9725
0.9668
0.9608
5.521
5.471
5.439
5.406
0.9725
0.9735
0.9668
0.9673
0.9609
0.9623
0
1
.9929
.4629
0.9571
0.9470
[
Bmim][HSO ] in sucrose
[Bmim][HSO ] in maltose
[Bmim][HSO ] in maltitol
4
4
4
0
0
1
1
2
.0000
.3440
.1305
.9503
.7635
0.9813
0.9678
0.9418
0.9175
0.8954
5.521
5.445
5.299
5.162
5.038
0.0000
0.3351
0.6151
1.2209
1.8604
0.9816
0.9690
0.9594
0.9400
0.9210
0.9016
5.523
5.452
5.398
5.289
5.182
5.073
0.0000
0.9814
0.9591
0.9430
0.9425
0.9307
0.9023
5.522
5.396
5.306
5.303
5.237
5.077
0.6116
1.1172
1.1335
1.5263
2.5753
2.6014
a
mIL (ionic liquid molality) = the number of moles of IL per kilogram of water.The standard uncertainty in the measurement of water activity,
−4
−3
−3
−1
temperature, vapor pressure, and molality were found to be 2 × 10 , 5 × 10 K, 1 × 10 kPa, and 0.01 mol kg , respectively.
solution and then stirred for 48 h at 55 °C. Because of the
presence of white precipitate, the reaction mixture was filtered
and vacuum distilled. Dichloromethane as the extraction
solvent was added to the residue liquid (in order to removal
of the bromide salt), and the white precipitated NaBr salt was
obtained. Then, the solid precipitate was separated by filtration
and the product solution was dissolved in an excess amount of
dichloromethane and was washed 3−5 times with deionized
water to ensure complete removal of the bromide salt. Aqueous
2) placed in an airtight cell which measure resistance changes
aroused from the changes in temperature. The cell temperature
was controlled electronically within ±1 × 10− K. Initially, a
droplet of pure water is placed on each thermistor, and after
equilibration (about 5 min), the reading is adjusted to zero.
Then, the pure water on the thermistor 1 is replaced by the
under study solution. Because of the heat of condensation of
water from the vapor phase into the solution droplet, the
thermistor 2 will be warmed until the vapor pressure of the
droplet on the thermistor 2 equals that of the pure water
droplet. Generally, the times of 4−8 and 15−20 min suffice to
reach this steady state, respectively, for monophasic and
biphasic samples. In this steady state, a bridge circuit measures
the resistance differences aroused from the temperature
difference between the two thermistors. Before analysis of the
samples, the apparatus was calibrated with the help of reference
aqueous NaCl solutions in the proper concentration range,
resulting a function which correlates the panel readings to the
corresponding concentrations of the sodium chloride aqueous
solutions (Figure S5 of the Supporting Information). The
following relation was used to correlate instrument panel
reading (signal, SI) and NaCl molality (mNaCl):
3
phase was tested with a saturated solution of AgNO . The
3
product was dried for more than 5 h under vacuum conditions
at 120 °C to remove the traces of dichloromethane and water.
Finally, a colorless to pale yellow liquid with a yield of 75% was
1
obtained. The compound was analyzed by FT-IR, H NMR,
1
3
and C NMR spectroscopy. The FT-IR spectrum of
−1
[
Bmim][BF ] contains the peaks at ν/cm 2938 and 2876
4
(
aliphatic asymmetric and symmetric (C−H) stretching
vibrations), 1171 and 1059 (inplane bending vibrations for
methyl groups), a broad peak at 3122−3162 (for quaternary
amine salt formation with tetrafluoroborate), 1657 (stretching
CC), 1466 (stretching CN), 757 and 623 (stretching
1
vibration C−N). H NMR spectrum contains peaks at δ(ppm):
0
.89 (t, J = 7.1, 3H), 1.25−1.36 (m, 2H), 1.77−1.89 (m, 2H),
.91 (s, 3H), 4.17 (t, J = 7.3, 2H), 7.44 (s, 2H), 8.67 (s, 1H).
C NMR: 13, 19, 31.6, 35.8, 49.4, 122.3, 123.6, 135.8. The
2
3
mNaCl = a + a SI + a SI + a SI
(1)
0
1
2
3
3
1
3
where a , a , a , and a are calibration constants and their values
0
1
2
3
NMR spectra of both the synthesized ILs are presented in the
along with the standard deviation are reported in Table S1 of
the Supporting Information. For a certain aqueous solution
which has the same instrument reading as a sodium chloride
solution with molality m , the water activity, a , was obtained
Supporting Information (Figures S1−S4).
2.2. Experimental Procedures. All the solutions were
prepared freshly by mass using a Sartorius CP124S balance
NaCl
w
−
7
34
precise to within ±1.10 kg. The VPO measurements
performed with the help of an Osmomat K-7000 (Knauer
Inc.) at 308.15 K. The instrument has two thermistors (1 and
according to
aw = exp(−0.001νNaClmNaClΦ
NaCl
M )
w
(2)
C
DOI: 10.1021/acs.jced.7b00719
J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data
Article
a
Table 3. Experimental Water Activity, a , and Vapor Pressure, p, against Carbohydrate Molality, m , for Ternary Solutions of
w
C
the Carbohydrates in Aqueous Solution of the ILs at 308.15 K
m /(mol kg−1)
aw
p/(kPa)
m /(mol kg−1)
aw
p/(kPa)
m /(mol kg−1)
aw
p/(kPa)
C
C
C
carbohydrates in aqueous solution of 1 mol kg− of [Bmim][Br]
1
sucrose
maltose
maltitol
0
0
1
2
.0000
.5116
.5644
.5600
0.9737
0.9630
0.9398
0.9165
5.478
5.418
5.288
5.157
0.0000
0.5843
0.8966
1.1163
0.9737
0.9616
0.9552
0.9509
5.478
5.410
5.375
5.350
0.0000
0.7093
0.8365
1.1777
0.9737
0.9588
0.9559
0.9482
0.9453
0.9312
5.478
5.394
5.378
5.335
5.319
5.239
1
1
.3042
.9174
crbohydrates in aqueous solution of 1 mol kg− of [Bmim][HSO4]
1
sucrose
maltose
maltitol
0
0
0
0
1
.0000
.2070
.6429
.8307
.1873
0.9697
0.9631
0.9510
0.9463
0.9361
5.456
5.418
5.351
5.324
5.267
0.0000
0.1627
0.4920
0.7948
1.1258
0.9697
0.9659
0.9584
0.9516
0.9443
5.456
5.435
5.392
5.354
5.313
0.0000
0.1735
0.5318
0.9077
0.9697
0.9658
0.9574
0.9484
5.456
5.434
5.387
5.336
−1
crbohydrates in aqueous solution of 1.5 mol kg of [Bmim][BF4]
maltose
sucrose
maltitol
0
0
0
1
1
2
.0000
.2608
.7540
.2818
.5832
.0081
0.9786
0.9727
0.9623
0.9500
0.9446
0.9371
5.506
5.473
5.414
5.345
5.315
5.272
0.0000
0.4289
0.7778
1.2022
1.3889
1.7899
0.9786
0.9683
0.9609
0.9517
0.9500
0.9445
5.506
5.448
5.407
5.355
5.345
5.314
0.0000
0.4292
0.8164
1.1046
1.6086
1.9741
0.9786
0.9678
0.9591
0.9544
0.9477
0.9396
5.506
5.445
5.396
5.370
5.332
5.287
a
m (carbohydrate molality) = the number of moles of carbohydrate per kilogram of water. The standard uncertainty in the measurement of water
C
−4
−3
−3
−1
activity, temperature, vapor pressure, and molality were found to be 2 × 10 , 5 × 10 K, 1 × 10 kPa, and 0.01 mol kg , respectively.
where νNaCl is the stoichiometric number of reference
electrolyte and M is the molar mass of water. Φ is the
the used maltose was in a monohydrate form, in the case of
solutions of maltose in aqueous IL solutions, because of the
water molecules released from maltose monohydrate crystals,
the molality of the ILs in the solutions cannot be constant and
in fact it slightly decreases by increasing molality of maltose.
The changes in the molalities of ILs for maltose +
w
NaCl
osmotic coefficient for aqueous solutions of NaCl with molality
35
mNaCl calculated from the correlation of Clarke and Glew.
From the water activity values, the vapor pressures of aqueous
solutions, p, were determined according to
[
Bmim][BF ], maltose + [Bmim][Br], and maltose + [Bmim]-
4
0
0
0
w
⎛
⎜
⎞
⎠
(
B − V )(p − p )
p
w
w
[HSO ] systems were in the range of 1.5000−1.4517, 0.9997−
0
of aqueous [Bmim][BF ]/sugar systems, with the ability to
form ABS, the water activity and vapor pressure data were
obtained in both mono and biphasic regions. However, for
4
⎟
⎟
ln(a ) = ln⎜
+
−1
w
0
.9796, and 0.9998−0.9795 mol kg , respectively. In the case
p
RT
⎝
(3)
w
4
where B 0 and Vw are the second virial coefficient and molar
volume of pure water, respectively. pw is the vapor pressure of
pure water calculated using the Saul and Wagner’s equation of
state. By taking into account all the factors (X) affecting the
quantity Y, such as repeatability of instrument, purity of sample,
composition, and temperature, the combined uncertainty in
quantity Y was obtained by u(Y) = Σ(u(X )∂Y/∂X ), in which
u(Y) is the combined uncertainty and u(X ) is the experimental
0
w
0
[Bmim][Br]/carbohydrate and [Bmim][HSO ]/carbohydrate
4
3
6
systems that cannot form ABS, the vapor−liquid equilibria
behavior was studied only in the monophasic region.
Tables 2 and 3 present the experimental water activity and
vapor pressure values of the investigated systems. In Figure 1,
the experimental values of water activities for solutions of
sucrose in aqueous solutions of 1 mol kg− [Bmim][Br] have
i
2
i
i
2
i
1
uncertainty in the measured quantity Xi.
27
been compared with the literature values. As can be seen,
there is a good agreement between our experimental water
activity data and those taken from the literature.
3
. RESULTS AND DISCUSSION
In order to study of relation between the VLE behavior and the
soluting effect phenomenon in aqueous IL/carbohydrate
systems, VPO measurements were conducted for aqueous
In order to study the soluting effect occurring in a ternary A
+
B + water solution, we consider deviations from the following
15,37
ideal behavior equations:
[Bmim][BF ]/sucrose, [Bmim][BF ]/maltose, [Bmim][BF ]/
4 4 4
0
0
maltitol, [Bmim][Br]/sucrose, [Bmim][Br]/maltose, [Bmim]-
Br]/maltitol, [Bmim][HSO ]/sucrose, [Bmim][HSO ]/mal-
(a + 1) − (a + a ) = 0
(4)
w
wA
wB
[
4
4
0
0
tose, and [Bmim][HSO ]/maltitol systems at 308.15 K. The
experimental water activity and vapor pressure data were
obtained for solutions of the ILs in aqueous solutions 1 mol
4
Δp − (Δp + Δp ) = 0
A B
(5)
where a and Δp = p − p*, respectively, are the water activity
w
−
1
kg
of the carbohydrates and for solutions of the
and vapor pressure depression in the aqueous ternary A + B
−1
carbohydrates in aqueous solutions 1 mol kg of [Bmim][Br]
solution with solute molalities m and m . In these equations
A
B
−1
and [Bmim][HSO ] and 1.5 mol kg of [Bmim][BF ]. Since
a ° and Δp ° = p ° − p*, respectively, are the water activity and
4
4
i
i
i
D
DOI: 10.1021/acs.jced.7b00719
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Journal of Chemical & Engineering Data
Article
with water molecules becomes weaker in the presence of the
other solute. Therefore, water molecules released from the
hydration shell of solutes to the bulk state and more free water
molecules would be available with respect to the semi-ideal
behavior in which the solute−water interactions in the ternary
solution are the same as those in the binary solutions and
therefore Δa > 0 and Δπ > 0 (positive deviation). In these
w
w
systems, the activity coefficient of solute A in aqueous solution
38
is lowered by the presence of solute B. On the other hand, for
A + B + water systems which show the soluting-out effect,
because of the unfavorable A−B interactions, the interaction of
each solute with water becomes stronger in the presence of
another solute, and therefore, in these ternary systems, less free
water molecules would be available with respect to the semi-
ideal behavior, and then these systems show negative
departures from eqs 4 and 5 (Δa < 0 and Δπ < 0). Because
w
w
of the unfavorable A−B interactions, they exclude themselves
from the vicinity of each other due to their preferential
hydration. At higher concentrations, this exclusion will increase,
and ultimately, the system could reach a state where, for
entropic reasons, phase formation would become favorable and
these systems separate into an A-rich aqueous phase and a B-
rich aqueous phase. By phase separation, the partial
dehydration of solutes leads to increasing the free water
molecules in systems and therefore increasing the entropy of
system.
Figure 1. Plot of a against carbohydrate molality, m , for solutions of
sucrose in aqueous solutions of 1 mol kg [Bmim][Br]. ●, This work
at T = 308.15 K; ○, ref 27 at T = 298.15 K.
w
C
−1
vapor pressure depression in the binary i + water solutions with
the same solute molalities as the aqueous ternary solution.
Equations 4 and 5 are established for the ternary semi-ideal
solutions that the A−B interactions can be either mutually self-
canceled or neglected. In such systems the A−water and B−
water interactions in the ternary solutions are the same as those
in the corresponding binary solutions.
The plots of Δa
and Δπ
against solutes molality for the
] + carbohydrate + water systems are
w
w
investigated [Bmim][BF
4
Departures from eqs 4 and 5, Δa and Δπ are calculated
shown in Figures 2 and 3. In these systems since the
carbohydrates are more hydrophilic than the IL, the IL is
soluted out by the carbohydrates and the soluting-out effect
appears with ABS formation (visual observation).
w
w
from the following equations:
0
0
Δa = a + 1 − (a + a )
(6)
(7)
w
w
wA
wB
0
0
B
As can be seen from these figures, for aqueous [Bmim][BF
carbohydrate systems, which are capable of phase separation,
the slopes of the plots of Δa and Δπ against solute molality
4
]
Δπ = Δp − (Δp + Δp )
w
A
+
The water activity and vapor pressure of the investigated
w
w
in the before and after of phase separation points are negative
and positive, respectively. In fact, all of these plots showed a
shape of two lines, respectively, with negative and positive
slopes intersecting at the break point, which corresponds to a
point on the binodal curve. Comparison of parts a and b of
Figure 2 for [Bmim][BF4]−sugars systems shows that in the
binary carbohydrate−water and IL−water solutions were
19,30
obtained from the our previous work.
The soluting effect
phenomenon, which resulted from the quality of A−B and
solute−solvent interactions, leads to the negative or positive
deviations from the semi-ideal behavior. This effect can increase
and decrease the mutual solubilities of each solute in the
presence of another solute which, respectively, is known as the
soluting-in and soluting-out effects. For A + B + water systems
which show the soluting-in effect, as a consequence of
preferential A−B interactions, the interaction of each solute
case of solutions of [Bmim][BF ] in aqueous solution of the
4
sugars (Figure 2a), the break point of the maltose containing
system is close to that of the maltitol containing system.
However, in the case of solutions of carbohydrates in an
Figure 2. Plot of Δa against solute molality, m or m , for [Bmim][BF ] + carbohydrate + water systems at 308.15 K. (a) [Bmim][BF ] in aqueous
w
IL
C
4
4
−1
−1
solution of 1 mol kg of carbohydrates and (b) carbohydrates in aqueous solution of 1.5 mol kg of [Bmim][BF ]. ●, maltitol; ○, maltose; ▲,
4
sucrose.
E
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Article
Figure 3. Plot of Δπ against solute molality, m or m , for [Bmim][BF ] + carbohydrate + water systems at 308.15 K. (a) [Bmim][BF ] in aqueous
w
IL
C
4
4
−1
−1
solution of 1 mol kg of carbohydrates and (b) carbohydrates in aqueous solution of 1.5 mol kg of [Bmim][BF ]. ●, maltitol; ○, maltose; ▲,
4
sucrose.
−1
Figure 4. Plots of Δa (a) and Δπ (b) against carbohydrate molality, m , for solutions of the carbohydrates in aqueous solutions of 1 mol kg
w
w
C
[
Bmim][HSO ] at T = 308.15 K. ●, maltitol; ○, maltose; ▲, sucrose.
4
aqueous solution of [Bmim][BF ] (Figure 2b), the break point
reducing magnitude of departure from the semi-ideal behavior.
As can be seen from Figure 2, at each solute molality in the
monophasic region, the magnitude of the negative departure
follows the order: maltitol > maltose > sucrose. This trend is
quite in agreement with the liquid−liquid equilibria behavior of
4
of the maltose containing system is close to that of sucrose
containing system (the phase separation occurs in the higher
concentration of maltose in relative to those we expect from
Figure 2a). As mentioned above, in the IL + maltose systems in
which maltose acts as solute, the molality of [Bmim][BF ] is
aqueous [Bmim][BF ]−carbohydrate systems in which the
4
4
not constant and decreases with increasing the molality of
maltose. Therefore, a higher concentration of maltose is needed
for phase separation.
biphasic region decreases in the order: maltitol > maltose >
sucrose.
The observed trend for the magnitude of the negative
In the monophasic region, the large negative deviation from
departure from the semi-ideal behavior shows that the
the semi-ideal behavior was observed (soluting-out effect).
unfavorability of interactions of [Bmim][BF ] with the
4
Because of the unfavorable [Bmim][BF ]−carbohydrate
investigated carbohydrates follows the order: maltitol > maltose
> sucrose. It was shown that the solubility of monosaccharides
4
interactions, the solutes in ternary solutions exclude themselves
by strengthening their interactions with water molecules, and
therefore, the solute−water interaction in the ternary solutions
is stronger than those in the corresponding binary solutions
with the same molalities. This phenomenon reduces the
amount of free water molecules in the bulk state compared to
the semi-ideal solution, and therefore a + 1 < awIL° + a °
39,40
in pure [Bmim][BF4]
follows the order: fructose > glucose,
and therefore the [Bmim][BF ]−maltose (which contains two
4
glucose molecules) interaction is more unfavorable than
[Bmim][BF ]−sucrose (which contains two monosaccharides
4
glucose and fructose) interaction, and consequently maltose has
a higher soluting-out power than sucrose. The magnitude of
negative deviation for maltitol is larger than maltose. Maltitol,
which has one additional hydroxyl group instead of etheric
oxygen, has more capability for hydrogen bounding with water
molecules and therefore shows a higher strength for phase
separation. There is two different and quit reverse orders for
magnitude of Δa and Δπ in the mono and biphasic regions
w
wC
(
Δa < 0) and Δp < Δp ° + Δp ° (Δπ < 0). By increasing
w
IL
C
w
the concentration of the solutes, the extent of the exclusion
zone increases and thus the entropy of the system decreases,
and eventually above a critical concentration, phase separation
occurs and an aqueous biphasic system is formed. In fact by
phase separation, the extent of the exclusion zones decreases
and then the entropy of system increases. In other words,
entropy increase is the driving force for ABS formation. By
phase separation, the solutes in each phase is slightly
dehydrated that leads to increasing of water activity and
vapor pressure of the aqueous biphasic solution and therefore
w
w
of [Bmim][BF ]−carbohydrate aqueous systems: maltitol >
4
maltose > sucrose, in the monophasic region, and sucrose >
maltose > maltitol, in the biphasic region. In the case of systems
which have more unfavorable IL−carbohydrate interactions,
more partial dehydration occurs by ABS formation.
F
DOI: 10.1021/acs.jced.7b00719
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Article
Figure 5. Plots of Δaw (a) and Δπw (b) against IL molality, m , for solutions of [Bmim][Br] in aqueous solutions of 1 mol kg− different
1
IL
carbohydrates at T = 308.15 K. ●, maltitol; ○, maltose; ▲, sucrose.
follows the order: HSO − > Br > BF , and therefore BF
−
−
−
The plots of Δa and Δπ against solutes molality for the
w
w
4 4 4
investigated [Bmim][HSO ] + carbohydrate + water and
anion is less hydrated than the other anions (Table 4). In the
4
[
Bmim][Br] + carbohydrate + water systems are shown in
Figures 4 and 5, respectively. Figure 4 shows that the
magnitude of the departures from the semi-ideal behavior for
Table 4. Values of Gibbs Free Energies of Hydration
43
42
(ΔGhyd) and the Hydrogen Bond Accepting Strength (β)
[
Bmim][HSO ]−carbohydrate systems follows the order:
of the Various Anions
4
sucrose ≫ maltitol ≅ maltose. As can be seen from Figure 5,
for [Bmim][Br]−carbohydrate systems the negative departures
are very small and the VLE behavior of these systems are close
to the semi-ideal behavior. In these systems, the magnitude of
the deviations are equal for all the [Bmim][Br]−carbohydrate
systems. The small hydrophilicity differences between [Bmim]-
anion
ΔGhyd/kJ mol−
1
β
−
BF
−190
−315
−330
0.55
0.87
4
−
Br
−
HSO4
[
Br] and the investigated carbohydrates and favorable
−
interactions between Br and the hydroxyl groups of
carbohydrates lead to reducing the soluting-out effect of
−
4
1
case of HSO , protonation/deprotonation equilibria leads to
4
2
−
the production of SO4 , which forms the more stable
hydration complexes with water molecules. On the other
hand, the hydrophilicity power of the investigated carbohy-
[
Bmim][Br] on the aqueous solutions of the carbohydrates.
Figure 6 shows that the magnitude of the negative departure
from the semi-ideal behavior for a certain carbohydrate and at
drates and ILs obey the order: [Bmim][HSO ] > [Bmim][Br]
4
≥
carbohydrates ≫ [Bmim][BF ]. This trend explains the
4
observed negative departures from the semi-ideal behavior
soluting-out effect) for all investigated IL−carbohydrate
systems. In aqueous [Bmim][Br]/carbohydrate and [Bmim]-
HSO ]−carbohydrate systems, the ILs (more hydrophilic
(
[
4
solutes) act as the soluting-out agent and they reduce the
solubility of carbohydrates (more hydrophobic solutes) in
aqueous solutions. In fact, in these systems the soluting-out
effect appears with solid−liquid equilibria formation. In the case
of [Bmim][Br] and [Bmim][HSO ] + carbohydrate + water
4
systems, in the concentration range studied in this work, there
is no any solid−liquid equilibria observation. In fact, the
solubility of the carbohydrates in the aqueous solutions of these
ILs is higher than the concentration range studied here.
Figure 6. Plots of Δa , against IL molality, m , for solutions of
w
IL
−1
[Bmim][HSO ] is more hydrophilic than [Bmim][Br] and
4
different ILs in aqueous solutions of 1 mol kg of maltose at T =
thereby shows the larger deviation from the semi-ideal
3
08.15 K.●, [Bmim][BF ]; ○, [Bmim][HSO ]; ▲, [Bmim][Br].
4
4
32
behavior. From the solubility data, it was found that for a
certain carbohydrate, [Bmim][HSO ] has a stronger soluting-
4
the same molality of IL follows the order: [Bmim][BF ] >
out power than [Bmim][Br]. However, for the IL−carbohy-
4
[
Bmim][HSO ] ≫ [Bmim][Br]. For the other IL−carbohy-
drate systems including the most hydrophobic IL in this work
4
drate systems, similar behaviors were obtained.
([Bmim][BF ]), the extreme departure is due to the soluting-
4
All the investigated aqueous IL−carbohydrate systems
out effect of carbohydrates (more hydrophilic solutes) on the
IL in aqueous solutions. In this case, the soluting-out effect
appears with liquid−liquid equilibria formation.
(
capable or not of ABS formation) show the negative departure
from the semi-ideal behavior and therefore soluting-out effect
has been observed in these systems. The investigated ILs in this
work are different in their anions. The values of hydrogen bond
ΔG is the free energy change of the water in the following
process: a solution of m moles of IL in 1 kg of water is mixed
IL
42
accepting (HBA) strength β and Gibbs free energies of
isothermally with a solution of m moles of carbohydrate in 1
C
43
hydration (ΔGhyd) for the anions of the investigated ILs show
kg of water; then 1 kg of liquid water is isothermally separated
44
that the ability of these anions to create hydration complexes
via an osmotic membrane. This quantity can be defined as
G
DOI: 10.1021/acs.jced.7b00719
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Figure 7. Plots of ΔG against carbohydrate molality, m , for solutions of different carbohydrates in aqueous solution of the investigated ILs at T =
C
3
08.15 K: (a) [Bmim][BF ] + carbohydrate + water, (b) [Bmim][HSO ] + carbohydrate + water, and (c) [Bmim][Br] + carbohydrate + water
4
4
systems. ●, maltitol; ○, maltose; ▲, sucrose.
⎛
ΔG = 55.5RT ln⎜
⎝
⎞
⎟
⎠
that maltose has a glucose unit instead of fructose and therefore
has more negative values of Δaw and Δπw than sucrose.
However, for the other investigated systems, the magnitude of
aw
a
0
0
a
wIL wC
(8)
deviations were smaller than that of [Bmim][BF ]−carbohy-
4
In this equation, a , a ° and a ° have been defined
w
wIL
wC
drate systems and for a certain carbohydrate follow the order:
previously. As it can be seen from Figure 7, in the monophasic
region of the [Bmim][BF ]−carbohydrate systems, the values
[
Bmim][HSO ]−carbohydrate ≫ [Bmim][Br]−carbohydrate,
4
4
which is in agreement with hydrophilicity of ILs. The soluting-
of ΔG are negative and become more negative by increasing
the concentration and soluting-out power of the carbohydrates.
For these systems, the magnitude of ΔG become smaller after
ABS formation. Above the critical concentration, since the
aqueous solution of each solute is an unsuitable cosolvent for
another solute, the mixing process becomes a more undesirable
process and therefore values of ΔG become less negative. ΔG
out effect of [Bmim][HSO ] on aqueous solutions of
4
carbohydrates follows the order: sucrose ≫ maltitol ≅ maltose,
but in the case of [Bmim][Br] no significant difference was
found between sugars. For [Bmim][BF ]−carbohydrate
4
systems, the carbohydrates act as soluting-out agent and the
soluting-out effect appears with liquid−liquid equilibria
formation, and in aqueous [Bmim][Br]−carbohydrate and
for [Bmim][Br]−carbohydrate and [Bmim][HSO ]−carbohy-
drate systems have the same trend as that observed in Figures 4
and 5 for deviations from eqs 4 and 5.
4
[
Bmim][HSO ]−carbohydrate systems, the ILs act as soluting-
4
out agent and the soluting-out effect is appears with solid−
liquid equilibria formation.
4
. CONCLUSION
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jced.7b00719.
■
Vapor−liquid equilibria behavior of aqueous ternary IL +
carbohydrate (sucrose, maltose, and maltitol) systems were
studied at 308.15 K by means of the VPO method. The results
show that, in the case of aqueous solutions of [Bmim][BF4]
*
S
1H and 13C NMR spectra, calibration plot of VPO
instrument, and calibration coefficients of eq 1with
standard deviation of correlation (PDF)
(
the most hydrophobic IL)−carbohydrate systems which form
ABSs, because of the unfavorable IL−carbohydrate interactions,
the interaction of each solute with water becomes more
favorable in the presence of the other solute and therefore
reduces the amount of free water molecules in the bulk state in
AUTHOR INFORMATION
Corresponding Author
Phone: +98 8733624133. Fax: +98 8733660075. E-mail:
rahsadeghi@yahoo.com and rsadeghi@uok.ac.ir.
■
*
compared to the semi-ideal solution and thus a + 1 < awIL° +
w
a ° and Δp < Δp ° + Δp ° (negative deviation). The
wC
IL
C
magnitude of deviations in the monophasic region increases by
increasing the concentration and soluting-out power of the
carbohydrates (maltitol > maltose > sucrose) and decreases by
ABS formation. Maltose and sucrose are structural isomers so
ORCID
Rahmat Sadeghi: 0000-0002-5560-5993
H
DOI: 10.1021/acs.jced.7b00719
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Journal of Chemical & Engineering Data
Article
Notes
(19) Ebrahimi, N.; Sadeghi, R. Osmotic Properties of Carbohydrate
The authors declare no competing financial interest.
Aqueous Solutions. Fluid Phase Equilib. 2016, 417, 171−180.
(20) Shekaari, H.; Zafarani-Moattar, M. T. Osmotic Coefficients of
Some Imidazolium Based Ionic Liquids in Water and Acetonitrile at
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