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Article
Fructose and glucose dissolution in ionic
liquids: solubility and thermodynamic modeling
Aristides P Carneiro, Oscar Rodriguez, and Maria Eugnia Rebello Almeida Macedo
Ind. Eng. Chem. Res., Just Accepted Manuscript DOI: 10.1021/ie3024752 Publication Date (Web): 04 Feb 2013
Downloaded from http://pubs.acs.org on February 5, 2013
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1

Fructose and glucose dissolution in ionic liquids: solubility and 1
thermodynamic modeling 2
3
Aristides P. Carneiro, Oscar Rodrguez, Eugnia A. Macedo* 4
5
LSRE - Laboratory of Separation and Reaction Engineering - Associate Laboratory 6
LSRE/LCM 7
Faculdade de Engenharia, Universidade do Porto 8
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal 9
10
11
* To whom correspondence should be addressed. Tel.: +351 22 5081653. Fax: +351 22 508 1674. E-mail: 12
eamacedo@fe.up.pt. 13
14
15
16
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Abstract 17
18
Biorefining has shown the potential as an alternative source of feedstock 19
instead of crude oil. In parallel, ionic liquids have proved to be adequate solvents for 20
biomass processing. Thus, phase equilibrium between carbohydrates and ionic liquids 21
is critical for process design and optimization in biorefineries. In this work, the 22
solubility of glucose and fructose in six ILs were measured in the temperature range 23
288 K - 339 K. An isothermal method with quantification by HPLC analysis was used. 24
Modeling of solubility was carried out using excess Gibbs energy models (NRTL and 25
UNIQUAC). Experimental data were also compared with literature data. The 26
thermodynamic functions of dissolution the process were calculated from the 27
experimental solubilities. 28
29
30
31
32
33
Keywords 34
35
Ionic liquids 36
Carbohydrates 37
Dissolution 38
Dynamics 39
Thermodynamic models 40
Phase equilibria 41
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42
43
1. Introduction 44
45
Modern lifestyle and continuous population growth pushes towards to an 46
increasing consumption of fossil resources for the production of energy and materials. 47
This causes a great impact in the planets management. Meanwhile, a threat begins to 48
be seriously taken into account: a future shortage of fossil resources
1
. Fortunately, a 49
concern on the importance of renewable sources of energy and materials to face these 50
troubles, have introduced new milestones and rules for the future (United Nations, 51
Agenda 21). One aspect of extremely relevance is the integrated use of biomass as 52
feedstock for both materials and energy. This is the goal of the modern biorefining 53
concept
2
. Present in a great diversity of plants, wood and residues from industries 54
such as agriculture, biomass is indeed the major source of renewable carbon in 55
nature, being ready available to be converted into materials and energy. Its main 56
compounds, biopolymers such as cellulose, hemicellulose, starch and lignin can be 57
independently processed, to strategically produce fuels, added-value chemicals and 58
energy
3
. The most promising route to achieve this concerted biorefining is through the 59
platform of sugars present in biomass. Cellulose, hemicellulose and starch can be 60
hydrolyzed or depolymerized into their sugar monomers. Depending on the biomass' 61
nature, many different sugars can be obtained from the depolymerization: glucose, 62
fructose, xylose, galactose, sucrose, maltose, lactose, etc. Being highly functionalized 63
chemicals, these sugars are likely to be transformed in derivatives through many 64
reactional routes
4
. Sugar derivatives, such as dicarboxylic acids, sugar alcohols and 65
furan compounds are high potential chemicals whether to be used directly as 66
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additives in food, medicines and package materials or used as intermediate building 67
blocks for the production of commodity chemicals and added valued products
5
. Even 68
though the biorefining concept seems to be a suitable alternative to the petrochemical 69
industry, processing biomass is actually an extremely challenging task. After the 70
biomass' harvest, their biopolymers need to be separated. Conventional pre-treatment 71
processes
6
usually involve high temperatures, large amounts of water and the use of 72
corrosive chemicals such as strong acids and caustic soda. The nature of this standard 73
processes would turn a large scale integrated biorefinery, unfeasible due to very high 74
operating costs (wastewater, energy) and the investment in processing equipment 75
would be over costly. 76
Room temperature ionic liquids, ILs, are a recently explored class of materials 77
that have been an important investigation topic in the last decade. Briefly defined as 78
liquid salts at room temperature, their unique and unusual properties
7-9
such as non- 79
volatility, high thermal stability and versatility to dissolve polar, non-polar and 80
polymeric chemicals, have made them, potential solvents to a wide range of 81
applications, not only in reaction engineering
10-12
and separation technology
13-15
but 82
also in tribology
16
and electrochemistry
17
. Another key feature of these novel solvents, 83
is their tunability, i.e. the ILs properties can be strategically tuned by small change 84
either in the cation or in the anion in order to suit a specific application. The ability of 85
ILs as suitable solvents for biomass processing has already been demonstrated
18-19
. 86
Either acting as simple solvents to dissolve biomass biopolymers or as catalysts to 87
yield their monomers and transform them into building blocks for biorefining, the 88
ionic liquids' nature could permit biomass treatment/conversion processes to run 89
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with a lower energetic demand, water consumption and with a lower investment in 90
process equipment
20-21
. Nevertheless, ILs recycling has to be maximized to maintain 91
economical feasibility of such processes, due to the actual price of the ionic liquids. 92
The capacity of the ionic liquids to dissolve carbohydrates is primarily associated to 93
strong hydrogen bonding between ionic liquid's anion and the hydrogen atoms of 94
hydroxyl groups
22
. Playing a secondary role, the cation has also an effect in the affinity 95
with the carbohydrates, but apart from the hydrophobicity effect and the inclusion of 96
ether functional groups in the alkyl chains, a better elucidation of the entire role of the 97
cation in these interactions, needs more experimental and theoretical support
23
. 98
The phase equilibria knowledge of IL mixtures with carbohydrates is of 99
extremely relevance for process design and optimization purposes. Therefore, 100
solubility of carbohydrates in ionic liquids is an important parameter in reaction 101
engineering (kinetic studies and reactor sizing) as well as in separation technology 102
where it could be useful to design and optimize liquid-liquid extractions as well as 103
selective precipitations. Some data regarding this phase equilibria is already available 104
in the literature
23-25
. However, on one hand, this data are mostly focused in cellulose 105
and glucose, being the data for other carbohydrates very scarce. On the other hand, 106
the available data do not cover, for the same system, several measurements in a 107
representative temperature range, which difficult the application of existent or the 108
development of new thermodynamic models to describe the phase equilibrium. 109
Providing such modeling treatment will also support the issues concerning with 110
process design and optimization. Our previous works
26-27
, present both solubility data 111
for several carbohydrates and derivatives in ILs, as well as modeling of their phase 112
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equilibrium through thermodynamic models. In this work, in a similar perspective, the 113
solubility of glucose and fructose in six ionic liquids were measured at several 114
temperatures in the range from 288 K to 339 K, using an isothermal approach and 115
quantification by HPLC. Four dicyanamide ILs were tested in this work: 1-ethyl-3- 116
methylimidazolium dicyanamide, [emim][DCA], 1-butyl-3-methylimidazolium 117
dicyanamide, [bmim][DCA], Aliquat

[DCA] and trihexyltetradecylphosphonium 118

dicyanamide, [P6,6,6,14][DCA]. In addition Aliquat

[NO3] and 1-ethyl-3- 119

methylimidazolium trifluoroacetate, [emim][TFA] were also used. The ionic liquids 120
with Aliquat's cation were synthesized in this work as well as the [emim][TFA]. The 121
stirring time to attain the equilibrium was obtained for the studied systems and 122
solubility data were modeled with excess Gibbs energy models NRTL and UNIQUAC 123
was performed. Comparison with available literature data was carried out and the 124
dissolution's thermodynamic functions were obtained from the experimental data. 125
126
127
2. Theory 128
129
2.1. Solubility 130
131
The equilibrium equation that allows calculating the solubility of a solid solute in a 132
liquid, is usually derived through a thermodynamic cycle, under some assumptions
28
: 133
i) There are not solvent molecules in the solid phase. 134
ii) A hypothetical subcooled liquid state is assumed for fugacity of pure solute. 135
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iii) The solute's triple-point is not much different from the normal melting 136
temperature,Ts,fus. 137
iv) Solute's heat capacity difference between pure liquid and solid state, 138
S L
Ps
C

, is considered temperature independent. 139
140
Therefore, the expression used in this work to calculate solubilities,
L
s
x , from 141
thermodynamic models is: 142
143

, , ,
,
( )
( )
( ) 1 1 ln
S L
fus s s fus s fus s fus L L Ps
s s
s fus
H T T T
C
ln x
RT T R T T

( | | | | | |
= +
( | | |
\ \ \
(1) 144
145
where fusHs

and Ts,fus account for the melting enthalpy and melting temperature of 146
the pure solute, respectively. T is the equilibrium temperature, R the ideal gas 147
constant and
L
s
the solute's activity coefficient of the solute in the liquid phase. 148
149
2.2. Activity coefficients 150
In order to compute the activity coefficients, two local composition models were 151
applied in this work. These models are explicit in terms of excess Gibbs free energy, 152
g
E
, and the activity coefficient is calculated through fundamental thermodynamic 153
relationships
28
. In this work we considered two well-known models: the non-random- 154
two-liquid model, NRTL
29
and the UNIQUAC model
30
UNIQUAC structural parameters 155
ri and qi for each pure compound are usually calculated using the group-contribution 156
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values of Bondi
31
. However, for ILs other methodologies are needed and in this work 157
we used an empirical model proposed by Domanska and Mazurowska
32
was used: 158
0.029281
i
M
r

= (2) 159

( ) 2 1
2
i
i i
l
z
q r
z z

= + (3) 160
In the above expressions, z and li stand for the coordination number and bulk 161
factor and assume the values of 10 and 1, respectively. M is the molar mass of the ionic 162
liquid in gmol
-1
and , the density at 298.15 K in gcm
-3
. 163
2.3. Data correlation 164
The parameters for each model were obtained by fitting to the experimental data, 165
through minimization of the following objective function: 166

2
,
exp.
1 ,
1
p
N Model
s i
i s i
obj
p
F
N

=
| |

|
|
\
=

(4) 167
with, Np representing the number of experimental points and the experimental 168
activity coefficients,
exp.
, s i
, calculated through eq.1 according to: 169

, , , exp.
,
, ,
( )
( ) 1
exp 1 1 ln
L
S L
fus s s fus s fus s fus
Ps
s i
s i s fus i i i
H T T T
C
x RT T R T T

| | ( | | | | | |
= + |
( | | |
|
\ \ \ \
(5) 170
After fitting the adjustable parameters, the quality of the data correlation was 171
evaluated by means of the average absolute relative deviation, AARD: 172
( )
,exp. ,mod
,exp.
, ,
1
,
100
%
L L el p
L
N
s i s i
i
p s i
x x
AARD
N x
=

(6) 173
2.4. Thermodynamic functions of dissolution 174
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The approach to calculate the thermodynamic functions of dissolution proposed by 175
Krug and co-workers
32
was adopted in this work. The dissolution enthalpy is 176
calculated through a modified Vant Hoff equation and it is obtained from the slope of 177
the linear representation of ln(xs) vs. (1/T - 1/Thm): 178

0
.
ln
1 1
s
diss
hm
P
x
H R
T T
(
(

(
=
(
| |

(
|
(
\
(7) 179
In this approach, the harmonic average temperature, Thm is calculated from the 180
experimental data: 181

1
1
p
p
hm N
i i
N
T
T
=
=

(8) 182
The intercept of the linear representation, k, represents the logarithm of the 183
solubility at Thm, and it is used to calculate the Gibbs free energy of dissolution: 184

0
. diss hm
G RT k = (9) 185
Finally, the dissolution entropy is calculated from the definition of Gibbs free 186
energy: 187

0 0
0 . .
.
diss diss
diss
hm
H G
S
T

= (10) 188
189
190
3. Materials and Methods 191
3.1. Materials 192
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D-(-)-fructose and D-(+)-glucose supplied by Merck with purity > 0.99. Sodium 193
dicyanamide, NaN(CN)2, (>0.97, Acros Organics) and sodium nitrate, NaNO3, (>0.99, 194
Sigma) were used in the synthesis of Aliquat

[DCA] and Aliquat

[NO3], respectively. 195

Aliquat

336 supplied by Acros organics with 0.0386 of water mass fraction 196
(measured by Karl-Fisher titration) and with a molar mass of 442 gmol
-1
, n-heptane 197
(> 0.99, BDH Prolabo) and acetone (>0.999, Labsolve) were also used in the 198
preparation of these two ionic liquids. 1-Methylimidazole (>0.99, Merck) and ethyl 199
trifluoroacetate (>0.999, Merck) were used for the preparation of [emim][TFA]. The 200
ionic liquids [emim][DCA] (>0.99), [bmim][DCA] (>0.98) and [P6,6,6,14][DCA] (>0.95) 201
were purchased from Iolitec GmbH and used as received. Silver nitrate, AgNO3 (Ph. 202
Eur, Merck) was used for quantification of chloride anion content in Aliquat

[DCA] 203
and Aliquat

[NO3]. A sample description of the ionic liquids and the sugars is 204
provided in table 1, and the chemical structures of the ions present in the ionic liquids 205
are presented in Figure 1. All purities are given in mass fraction. 206
207
3.2. Methods 208
3.2.1. Synthesis of ionic liquids 209
210
Aliquat

[NO3] 211
212
The preparation of this IL was carried out according to a procedure available in 213
literature
33
and applying the improvements in purification as described in a previous 214
work
27
. About 58 % in excess of NaNO3 was dissolved in deionized water. Aliquat

336 215
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at 373 K was added dropwise to the aqueous solution with 10 mL of acetone to 216
improve phase separation. The mixture was stirred at room temperature for six hours, 217
and then two liquid phases were formed. The IL-rich phase was washed with 218
deionized water to remove sodium chloride and unreacted sodium nitrate, whereas 219
the separation of unreacted Aliquat

336 was carried out through extraction with n- 220

heptane. Finally, the IL was dried under vacuum and moderate temperatures (343 - 221
353 K) for 48 h to remove the volatile compounds. The water content of the final IL in 222
mass fraction was 0.0184 (measured by Karl-Fisher titration) whereas the chloride 223
anion content was 0.008 in mass fraction (measured with Mohr's Method
34
). Cations 224
chemical structure was checked by
1
H-NMR in a Bruker Avance III 400 spectrometer, 225
operated at 400 MHz
27
. 226
227
Aliquat

[DCA] 228
229
This synthesis was performed based on a procedure available in the 230
literature
35
. 200 g of Aliquat

336 were dissolved in 300 mL of dichloromethane and 231

50 g of sodium dicyanamide, NaN(CN)2, were added forming a suspension which was 232
stirred for 48 hours at room temperature. The unreacted dicyanamide salt and the 233
sodium chloride formed in the reaction were filtered and then the dichloromethane 234
was distilled in a rotary evaporator (IKA

RV 10 D S40). Extractions with water and n- 235

heptane were carried out, in order to remove the salts dissolved in Aliquat

[DCA]. 236
Finally, the ionic liquid was dried under vacuum at 353 K to remove all the volatile 237
compounds. Approximately 100 g of Aliquat

[DCA] were obtained with 500 ppm of 238

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water (measured by Karl-Fisher titration) and with chloride anion content < 1300 239
ppm (measured by Mohr's method). The IL chemical structure was checked by
1
H- 240
NMR and
13
C-NMR in a Bruker Avance III 400 spectrometer, operated at 400 MHz. 241
242
1-ethyl-3-methylimidazolium trifluoroacetate, [emim][TFA] 243
244
This ionic liquid was produced trough a one-pot reaction in a solvent-free 245
system according to the literature
36
. A 28 mL cylindrical stainless steel reactor, was 246
used in this synthesis. The reaction mixture, approximately 9 g of 1-methylimidazole 247
and 16 g of ethyl trifluoroacetate, was stirred at 373 K for 24 hours in closed system. 248
To maintain a constant temperature, the reactor was immersed in an oil bath. After 249
that, the excess of ethyl trifluoroacetate was removed by distillation in a rotary 250
evaporator and recycled to be used in the next batch. Four identical batches were run 251
to produce the needed amount of ionic liquid. After drying under vacuum at 353 K for 252
72 hours, approximately 72 g of [emim][TFA] was obtained, with 1200 ppm of water 253
(measured by Karl-Fisher titration). The chemical structure of the IL was verified by 254
1
H-NMR in a Bruker Avance III 400 spectrometer, operated at 400 MHz. H (400 MHz, 255
CDCl3) 1.502 (3H, t, NCH2CH3), 3.954 (3H, s, NCH3), 4.258 (2H, q, NCH2CH3), 7.401 (2H, 256
m, C(4,5)H), 10.006 (1H, s, C(2)H). 257
All NMR experiments were carried out using a Bruker Avance III 400 258
spectrometer, operating at 400 MHz and available at CEMUP, University of Porto. The 259
water contents in the ionic liquids were measured in a Metrohm

870 KF Titrino Plus 260

titrator. Chloride anion content was measured using the Mohr's method. Acetone was 261
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added to obtain a homogeneous aqueous solution of the hydrophobic ionic liquids. 262
Titration was carried out with a 0.01 mol/kg of AgNO3 aqueous solution. Preliminary 263
experiments to validate this procedure for ILs were carried out. 264
265
3.2.2. Solubility determination 266
267
268
The same isothermal technique adopted in previous works
26-27
was applied 269
here. Approximately 10 g of IL were placed in jacketed equilibrium cells, where water 270
from a JULABO F12-ED recirculation bath, was used to maintain a constant 271
temperature with a precision of 0.1 K. After the desired temperature was achieved, 272
the sugars, added in a slight excess, were magnetically stirred for the period of time 273
needed to attain the saturation, as discussed in section 4.1. This time was determined 274
by successive samplings over time, until no significant increase on solute's 275
concentration in the IL was observed. After phase separation (solute sedimentation), 276
samples of the clear liquid phase were withdrawn in triplicate and analyzed by HPLC 277
for quantification. A 2504 mm HPLC column with Purospher

STAR RP-18e (5m) as 278

stationary phase and an isocratic method with water as eluent at 0.7 mLmin
- 1
was 279
used. Sugar detection was made with refractive index at 313 K. More details of the 280
procedure are available elsewhere
26
. 281
282
3.2.3. Density measurements and dehydration product identification 283
284
285
Densities of glucose dissolved in [emim][DCA] were measured using an Anton 286
Paar DMA 4500M densimeter with precision of 0.00001 gcm
-3
. 5- 287
hydroxymethylfurfural, a dehydration product of fructose was identified by HPLC 288
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with an isocratic method in which the eluent composed by 80% (v/v) of a 5 wt. % 289
aqueous solution of acetic acid and 20 %(v/v) methanol flowed at 1.0 mLmin
-1
290
through the same column used for solubility determinations. In this case, detection 291
was performed by UV absorption at 285 nm. 292
293
294
4. Results and discussion 295
296
297
4.1. Stirring time 298
299
The viscosity of the ionic liquids used in this work varies greatly. Higher viscosity 300
reduces the diffusivity of the solute from the solid phase to the bulk liquid mixture, 301
representing a higher resistance to mass transfer. Due to this limitation, the more 302
viscous the IL, the longer will be the step to attain the saturation of the solution. 303
Therefore, the stirring time to apply in the solubility experiments will vary from 304
system to system and it should be assessed as often as possible when determining 305
solubility data. Magnetic stirrers were used and so, the speed had to be adjusted 306
sometimes due to fluctuations in viscosity during the dissolution processes. 307
Preliminary experiments near room temperature, allowed to conclude that for all the 308
studied systems, 48 h is enough to attain equilibrium with good accuracy. Moreover, 309
in the case of ionic liquids with lower viscosity, such as [emim][DCA], [bmim][DCA] 310
and [emim][TFA], 24-hour stirring was sufficient. Thus, solubility determinations 311
were carried out, considering these time constants, according to the system in study 312
(low or high viscosity). 313
314
4.2. Measured solubility data 315
316
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The solubility data obtained in this work are presented in Tables 2 and 3. The 317
reported relative uncertainty was calculated as an average of all the experimental 318
measurements, using the conventional error propagation theory. The experimental 319
data are also plotted in Figures 2 and 3. Herein the data are presented in molar 320
fractions instead of mass fractions used in our previous works
26-27
. This choice is due 321
to differences in the molar mass of the ionic liquids used here (Table 4), being the 322
molar basis more suitable for comparison purposes. Fructose and glucose are very 323
similar in terms of chemical structure (structural isomerism). This causes specific 324
interactions with the ILs to have the same order of magnitude for both of them. 325
However, different carbon skeletons give to fructose a more stable and low energetic 326
structure, causing its melting temperature and enthalpy (378.15 K and 26.030 kJmol
-
327
1
) to be lower than for glucose
37
(423.15 K and 32.432 kJmol
-1
). According to eq.1 the 328
solubility is affected essentially by these two contributions (specific interactions and 329
solute melting properties). Consequently, the solubility in the selected ionic liquids is 330
higher for fructose, as observed from the measured solubility data (Table 2). The 331
major solubility differences between fructose and glucose occurred for hydrophobic 332
ILs: Aliquat

[NO3], Aliquat

[DCA] and [P6,6,6,14][DCA], where the solubility of 333

fructose is in average, 2.9, 4.3 and 2.4-fold the solubility of glucose, respectively. 334
Whereas, for the hydrophilic ILs: [emim][DCA], [bmim][DCA] and [emim][TFA] these 335
mean ratios are 1.8, 1.9 and 1.2, respectively. One possible reason for this fact is that 336
hydrophilic ILs interact more strongly with the carbohydrates through specific 337
interactions (such as hydrogen bonds) which causes the effect of the melting 338
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properties to be somehow hidden in contrast to the hydrophobic ILs (where specific 339
interactions are reduced). 340
The water content in the mixture can slightly oscillate during the solubility 341
experiments, caused by water uptake in sampling procedures or loss by evaporation 342
when submitted to moderate temperatures. Controlling this parameter is essential to 343
ensure reliability of the experimental data. Table 4 shows the water content before 344
and after the solubility determination for each system. Apart from the dissolution of 345
fructose in [emim][TFA], in which water content rose considerably due to solute's 346
degradation (section 4.3), the variations on water content in the other systems were 347
sufficiently small to be considered negligible possible changes in ILs properties during 348
solubility experiments. 349
The ability of ionic liquids with dicyanamide anion to dissolve carbohydrates, has 350
been recognized
38
and it is mainly attributed to its capacity for hydrogen bonding 351
with hydroxyl groups. However, the structure and nature of the cation can 352
dramatically change this. As it is clear from the obtained data, hydrophobic ionic 353
liquids are much less able to dissolve these highly polar solutes. They are barely 354
soluble in [P6,6,6,14][DCA] (maximum solubility obtained was 0.055 for fructose) even 355
with a higher water content than in Aliquat

[DCA]. The quaternary ammonium was 356

able to dissolve up to 0.13 (molar fraction) of fructose, showing more affinity with 357
sugars than the phosphonium IL. The later is slightly more bulky, which partially 358
explains the difference. In addition, the central atom could also play a role affecting 359
the solubility: a more electronegative central atom (nitrogen) could attract more 360
electrons from the surrounding atoms to the cation's core, which causes the positive 361
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charge to be less effective, reducing the cation-anion interactions. A reduced ion-ion 362
interaction could give more freedom to the anion to establish hydrogen bonds with 363
the carbohydrates' hydroxyl groups, and therefore higher solubilities could be 364
achieved. The alkyl chain length in imidazolium cations has also a negative impact in 365
the solubility capacity, being the [emim][DCA] more able to dissolve sugars than 366
[bmim][DCA]. 367
ILs with acetate-based anions are also known as efficient to dissolve 368
carbohydrates
39
. The IL used in this work, [emim][TFA], has also a further advantage: 369
low viscosity. The three fluor atoms decrease the viscosity to 32 mPas at 298 K
40
370
while the viscosity with the non-fluorinated acetate anion is 4.5 times higher, 143 371
mPas at the same temperature
41
. [emim][TFA] has clearly a higher affinity with 372
glucose and fructose in the whole range of temperature studied compared to 373
[emim][DCA]. The higher Lewis basicity of trifluoroacetate anion (ability to accept 374
hydrogen bonds) due to a larger concentration of free electron pairs, plays herein an 375
important role. 376
Two ionic liquids with the Aliquat

cation were also used in this work, with nitrate 377

and dicyanamide anions. In this case, the differences in solubility can be attributed 378
mainly to different water contents. Whereas Aliquat

[DCA] was used almost dried 379

(0.05 wt.% of water), the Aliquat

[NO3], needing a certain amount of water to be 380

liquid with a reasonable viscosity, was used with 1.8 wt.% of water. Once solubility of 381
glucose and fructose in water is much higher than in these hydrophobic ILs, the effect 382
of the anion is somehow hidden. A more realistic comparison between nitrate and 383
dicyanamide anions would only be possible using the Aliquat

[DCA] with the same 384

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water content as the Aliquat

[NO3]. Therefore, solubility of glucose and fructose in 385

Aliquat

[DCA] with 1.9 wt.% of water was measured at 323.15 K for comparison 386
purposes (see filled symbols in Fig. 2 and 3). This proves that even with the same 387
water content, the Aliquat

[DCA] is indeed less able to dissolve these solutes, 388

compared with Aliquat

[NO3]. Figures 2 and 3 also show the comparison with the 389
solubility of the two sugars in water. In molar fraction basis, the three hydrophilic ILs 390
present higher values of glucose and fructose solubility than water, following the 391
series: [emim][TFA]>[emim][DCA]>[bmim][DCA]. Solubility in the hydrophobic ILs is 392
much lower than in water, following the series: Aliquat

[NO3]> Aliquat

[DCA]> 393
[P6,6,6,14][DCA]. In addition to water solubility, ideal solubility of glucose and fructose 394
are also plotted in Fig. 2 and 3. This clearly shows that in hydrophilic ionic liquids, the 395
solutions have negative deviations (solute < 1) relative to an ideal solution (no 396
interactions between carbohydrate and IL), while in hydrophobic ILs, positive 397
deviations to the ideal solubility (solute > 1) were observed from the solubility data. 398
Moreover, glucose and fructose water solubility is closer to the ideal solubility than 399
solubilities in any IL. In accordance to this fact, the IL with higher water content, 400
Aliquat[NO3], is the one in which solubility of the sugars are closer to ideal 401
solubility. 402
Glucose solubility data in [bmim][DCA] are available in literature. A comparison 403
with the results obtained in this work, is presented in Figure 4. Data from references
38,
404
42
were determined in gL
-1
. Direct comparison with the data obtained in this work 405
with those data, would only be possible if the density of the saturated solution were 406
known. Therefore, in this work and to enable proper conversion of these literature 407
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data to molar fractions, the density of mixtures of glucose and [bmim][DCA] were 408
measured at five different concentration and four temperatures, as it is shown in 409
Table 5. From the knowledge of the concentrations in mole fraction, density of the 410
solutions, , and the molar mass, M, of the two components, one could calculate the 411
correspondent concentration in gL
-1
is calculated as follows: 412
413

( )
( )
1
1
[ ][ ]
glucose glucose
1
1 1
emim DCA
g mL
C g mL
M
M x

=
| || |
+
| |
| |
\ \
(11) 414
415
Then, the correspondence between the two concentrations can be achieved 416
through linear regression of the calculated values, as shown in Figure 5. 417
This linear regression gave a slope of 0.9711, an intercept of 5.1310
-3
and a 418
correlation coefficient of 0.9991, which represents a good correlation despite some 419
dispersion observed due to density variation with temperature. With this relation, the 420
literature data
38, 42
could be converted into molar fraction and therefore compared 421
with the data measured in this work as presented in Figure 4. Clearly, solubility data 422
measured in [bmim][DCA] are in good agreement with the literature. However 423
comparing solubilities of glucose at 308 K in Aliquat

[DCA] and in [P6,6,6,14][DCA] with 424

those measured by Rosatella et al.
25
, the same agreement was not achieved (Table 6). 425
Several reasons could be behind these differences. First, these two ILs are usually 426
prepared from the IL with chloride anion. In this work, a purification step to remove 427
unreacted Aliquat

[Cl] from Aliquat

[DCA] was carried out to decrease the chloride 428

content to approximately 0.1 wt.%. In the work of Rosatella et al.
25
, the authors do not 429
provide information about the halide content, which could affect IL properties and 430
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increase solubility of carbohydrates (once chloride anion is likely to establish strong 431
hydrogen bonds with the hydrogen atoms of hydroxyl groups). In the case of 432
[P6,6,6,14][DCA], the supplier is not the same and once again the content of [P6,6,6,14][Cl] 433
could differ from this work and produce the observed differences. Furthermore, and 434
as the solubilities in this IL are remarkable small, difficulties regarding experimental 435
technique (stirring time, phase separation, sampling and analysis) could also be 436
related to the differences observed in the comparison. 437
The work published by Rosatella et al.
25
presents solubility of glucose at 308 K 438
in 28 different ILs. These data are represented in Figure 6, together with the data 439
measured in this work for glucose at the same temperature, and those presented in a 440
previous work
26
for comparison and to study the effect of the different cations and 441
anions. Some solubility data presented in Figure 6 are associated to significant water 442
content, which are the cases of ILs with acetate anion, some ILs with phosphonium 443
cation and with the guanidinium cation, (C3O)4DMG. This causes solubility to be 444
higher than it would be in the dried IL, and comparing ILs with very different water 445
contents does not allow to explain the role of different cations and anions in glucose 446
solubility. Nevertheless, some ILs were used sufficiently dried to assume water had 447
little effect on solubility. Some of the ILs studied in this work are among the most able 448
to dissolve glucose: [emim][DCA] and [emim][TFA]. Connecting this capacity with the 449
relative low viscosity for both of them, they are undoubtedly, two promising ILs to be 450
used in carbohydrate processing. Higher solubilities with low water contents are 451
associated to hydrophilic ILs with imidazolium-based cations: [emim] and 452
[moeomim]. Solubility of glucose is slightly higher in [moeomim][DCA] than in 453
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[emim][DCA], which is in agreement with the fact that oxygen atoms in the alkyl 454
chains of imidazolium cations give extra ability to interact with carbohydrates, as it 455
was already demonstrated elsewhere
38
. 456
457
4.3. Solute degradation 458
459
Some ILs are known to be acidic catalysts for the dehydration of hexoses
43-44
. 460
Whereas glucose is hardly ever dehydrated in pure IL media, fructose is easier to be 461
converted into dehydration products (water, furfural, 5-hydroxymethylfurfural, 462
formic acid, levullinic acid, humims, etc.) without any additional catalyst
45-46
. Even 463
though, this phenomenon occurs in many acidic ILs, only above a relatively high 464
temperature (353-373 K) is observed a significant conversion of fructose. In our 465
laboratory, during the solubility experiments, degradation products are identified by 466
observation of yellow to brown color in the solutions, as well as by identification of 5- 467
hydroxymethyl furfural by HPLC. When degradation has a significant impact on the 468
conversion of fructose, the concentration of fructose begins to decrease (instead of 469
increase) with temperature. This happened with the ionic liquid [emim][TFA], which 470
seemed to convert significant amounts of fructose above 308 K. This effect is clearly 471
illustrated in Figure 7. For that reason, it was not possible to measure the solubility at 472
higher temperatures, and only three solubilities were measured for this system. 473
Another indicator of fructose dehydration is the high water content in the solution, 474
compared to other systems (Table 4). 475
476
4.4. Modeling 477
478
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As done in our previous works
26-27
, Gibbs energy models NRTL and UNIQUAC 479
were applied to correlate the measured solubility data. As the number of solubility 480
points is usually relatively small in SLE, the non-randomness parameter in NRTL, , 481
was set to a value within the range of 0.20-0.30, as recommended in the literature
47
. 482
UNIQUAC structural parameters r and q were obtained from the literature for glucose 483
and fructose, and estimated for ILs through an empirical model also available in 484
literature
48
. The binary interaction parameters for each model were then fitted to the 485
experimental data, minimizing the differences between the activity coefficients 486
experimentally obtained and those calculated through the model (NRTL or UNIQUAC). 487
It should be mentioned that the water content in the ILs was not taken into account in 488
the modeling of the solubility data. As a result, binary parameters for systems with 489
higher water mass fractions (Aliquat[NO3] and [P6,6,6,14][DCA], see table 4) are rather 490
"apparent" parameters which also account for the effect of water in the solubility. 491
With the obtained parameters, the melting properties
26
for glucose (fusH=32.432 492
kJmol
-1
and Tfus=423.15 K) and fructose (fusH=26.030 kJmol
-1
and Tfus=378.15 K) 493
and their solid-liquid heat capacity difference (Cp
S-L
=120
49
and 99
50
Jmol
-1
K
-1
for 494
glucose and fructose, respectively), eq.1 was applied to compute the solubility for each 495
system. The models accuracy to correlate the solubility data was measured by the 496
average absolute relative deviation, AARD, as described in eq.6. Table 7 presents the 497
results for the correlation obtained with these two models. In Table 8, the structural 498
parameters for all the compounds used in this work are also presented. The values of 499
the parameter in NRTL were almost all set to 0.30, according to the 500
recommendations in the literature. However, for systems with Aliquat

[NO3], the non- 501

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randomness parameter were optimized to 0.22, obtaining a significant decrease in its 502
AARD values. Apart from this exception, alpha equal to 0.30 presented the lower 503
values of AARD for all the other systems. 504
The solid lines in Figures 2 and 3 represent the solubility calculated with 505
UNIQUAC model, representing satisfactorily the experimental data. Nevertheless, 506
deviations were too high for systems with very low solubility (Table 7). The solubility 507
of fructose in [P6,6,6,14][DCA] has shown a high increase from 318 to 328 K. This 508
unexpected behavior was confirmed by repeating the experiments for the same 509
system at 328 K. Modeling the solubility in this system, was found to be very sensitive 510
to initial guess of the parameters, and also to the starting values of xs
L
to solve eq.1, 511
probably due to very low solubility values. In addition, using UNIQUAC model, the 512
experimental point at the highest temperature had to be neglected in order to obtain 513
reasonable binary parameters and a satisfactory solubility correlation. The ILs with 514
lower carbohydrate solubility were those which produced higher values of ARD in 515
solubility. This is due, in part, to the larger experimental uncertainty in this range of 516
solubility. Apart from [P6,6,6,14][DCA] and Aliquat

[DCA], the correlation with NRTL 517

and UNIQUAC was very satisfactory, with deviations (AARD) lower than 3.5 % in all 518
cases. 519
520
4.5. Thermodynamic functions of dissolution 521
522
The procedure based on a modified Vant Hoff equation described by eqs. (7 to 10) 523
and which was already applied by Panteli and Voutsas
51
and more recently by our 524
research team
26-27, 52
, was also applied here to obtain the thermodynamic functions of 525
dissolution(enthalpy, Gibbs energy and entropy) from the experimental data. Table 9 526
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shows these functions calculated for all the binary systems.All values presented for 527
the thermodynamic functions are positive, which means that the dissolution of 528
glucose and fructose in the studied ionic liquids is endothermic, non-spontaneous and 529
entropically favorable. The lowest values of dissolution enthalpy and Gibbs energy are 530
associated to the systems that exhibited the highest values of solubility. These systems 531
require less energy to break intermolecular interactions and establish new solute- 532
solvent interactions, being able to dissolve larger amounts of solute. In addition, 533
positive dissolution entropy reveals that the final state (solute dissolved in the ionic 534
liquid) gives a higher degree of freedom to the molecule's and ionic pairs' movement 535
than before the solute is dissolved (initial state). 536
537
5. Conclusions 538
539
540
Solubility data measured in this work reveal that fructose is more soluble than 541
glucose, which is due to lower melting temperature and enthalpy of the former. 542
Dicyanamide ILs used in this work exhibited a wide range of solubilities depending on 543
the nature of the cation. The hydrophilic dicyanamide ILs were much able to dissolve 544
the highly polar solutes. Besides, shorter alkyl chain in [emim][DCA], improves the 545
dissolution of the monosaccharides. Among the hydrophobic ILs, the more bulky 546
(more hydrophobic) [P6,6,6,14][DCA] was less capable to dissolve the sugars, when 547
compared with Aliquat

[DCA]. Trifluoroacetate anion, having more free electron pairs 548

to establish hydrogen bonds, has shown higher ability to interact with the 549
carbohydrates than the dicyanamide anion. Dissolving fructose in [emim][TFA] 550
caused significant degradation of the solute, observable at 308 K. A dehydration 551
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product (5-hydroxymethylfurfural) was identified by HPLC. High increase of water in 552
the mixture was also observed, confirming this reaction. The NRTL and UNIQUAC 553
models were successfully used to correlate the experimental data. AARDs obtained 554
were in general < 3.5 %. Nevertheless, problems were found for systems with lowest 555
solubility (Aliquat

[DCA] and [P6,6,6,14][DCA]). The thermodynamic functions of 556

dissolution, calculated from the experimental data, proved all the processes are non- 557
spontaneous, endothermic and entropically favorable. Low dissolution enthalpies and 558
Gibbs energies are related to systems with the highest solubilities. 559
560
Nomenclature 561
562
C concentration (gL
-1
) 563
Fobj Objective function 564
g Gibbs free energy (kJmol
-1
) 565
k y-axis intercept 566
l bulk factor 567
M Molar mass (gmol
-1
) 568
n Number of moles 569
Np Number of points 570
P Pressure 571
q UNIQUAC structural parameter of area 572
r UNIQUAC structural parameter of volume 573
R Ideal gas constant (8.314 Jmol
-1
K
-1
) 574
T Temperature (K) 575
u uncertainty 576
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x molar fraction 577
578
Greek letters 579
580
non-randomness parameter 581
activity coefficient 582
Cp Heat capacity difference (Jmol
-1
K
-1
) 583
G Gibbs free energy variation (kJmol
-1
) 584
H Enthalpy variation (kJmol
-1
) 585
S Entropy variation (Jmol
-1
K
-1
) 586
density (gmL
-1
) 587
standard deviation 588
589
Subscripts 590
591
diss. Dissolution 592
fus Fusion 593
i Compound i 594
ij Interaction i-j 595
IL Ionic liquid 596
j Compound j 597
hm harmonic mean 598
s solute 599
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600
601
Superscripts 602
603
0 Standard 604
exp. Experimental 605
E Excess 606
L Liquid 607
Model Referent to model 608
S-L Phase transition from solid to liquid 609
610
Abbreviations 611
612
AARD Average absolute relative deviation 613
HPLC High performance liquid chromatography 614
ILs Ionic Liquids 615
NRTL Non-random-two-liquid 616
UNIQUAC Universal quasichemical 617
618
Acknowledgements 619
620
This work is partially supported by project PEst-C/EQB/LA0020/2011, financed 621
by FEDER through COMPETE - Programa Operacional Factores de Competitividade 622
and by FCT - Fundao para a Cincia e a Tecnologia. A.C. and O.R. acknowledge 623
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financial support (Grant SFRH/BD/62105/2009) and Programme Cincia 2007, 624
respectively, from Fundao para a Cincia e a Tecnologia (FCT, Portugal). Authors 625
also acknowledge CEMUP, University of Porto by performing the NMR analysis needed 626
for this work. 627
628
629
630
631
632
References 633
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Figure Captions 781
Figure 1 Chemical structures of the involved anions and cations 782
Figure 2. Solubility of glucose in the studied ionic liquids and in water. 783
[emim][TFA]:;[emim][DCA]:;[bmim][DCA]:; water
54-55
: *; 784
Aliquat

[NO3]:; Aliquat

[DCA]: and (with 1.9 wt% of water, see text for 785
details);[P6,6,6,14][DCA]:;UNIQUAC : ; ideal solubility: . 786
*experimental data not modeled, dash-dot line is just to guide the eye 787
788
Figure 3. Solubility of fructose in the studied ionic liquids and in water. 789
[emim][TFA]:;[emim][DCA]:;[bmim][DCA]:; water
54-55
: *; 790
Aliquat

[NO3]:; Aliquat

[DCA]: and (with 1.9 wt% of water, see text for 791
details);[P6,6,6,14][DCA]:;UNIQUAC: ; ideal solubility: . 792
*experimental data not modeled, dash-dot line is just to guide the eye 793
794
Figure 4 - Comparison of glucose solubility in [bmim][DCA] with literature data. This 795
work - ; Ref. 25 - ; Ref. 42 - ; Ref. 38 - . 796
797
Figure 5 - Concentration correspondence for the system glucose+[bmim][DCA] 798
799
Figure 6 Comparison of glucoses solubility at 308 K with literature data. 800
801
Figure 7 Degradation of fructose in [emim][TFA] 802
803
804
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Figures 805
806
807
Figure 1 808
809
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Temperature / K
290 300 310 320 330 340
S
o
l
u
b
i
l
i
t
y

/

m
o
l
e

f
r
a
c
t
i
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0.05
0.15
0.25
0.35
0.00
0.10
0.20
0.30
0.40
811
Figure 2 812
813
814
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815
Temperature / K
280 290 300 310 320 330 340 350
S
o
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b
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y

/

m
o
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e

f
r
a
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0.15
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0.45
0.00
0.10
0.20
0.30
0.40
0.50
816
Figure 3 817
818
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Temperature / K
280 290 300 310 320 330 340 350 360
S
o
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/

m
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Figure 4 821
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glucose concentration / gmL
0.00 0.05 0.10 0.15 0.20 0.25 0.30
m
o
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Figure 5 824
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38

Ionic Liquids
[
C
l
]
[
D
C
A
]
[
S
A
C
]
[
A
C
E
S
]
[
S
C
N
]

[
C
l
]

[
D
C
A
]

[
S
A
C
]

[
A
C
E
S
]

[
S
C
N
]
[
A
C
E
T
]


[
C
l
]


[
D
C
A
]


[
S
A
C
]


[
A
C
E
S
]


[
S
C
N
]


[
A
C
E
T
]
[
N
T
f
2
]



[
D
C
A
]
*



[
A
C
E
T
]




[
A
C
E
T
]
E
t
S
O
4
*
*






[
D
C
A
]
*
[
T
F
A
]
*



[
C
l
]




[
D
C
A
]
*






[
A
C
E
T
]




[
C
l
]
*
*





[
D
C
A
]
*







[
A
C
E
T
]
[
N
O
3
]
*
S
o
l
u
b
i
l
i
t
y

/

m
o
l
a
r

f
r
a
c
t
i
o
n
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Solubility
water content
[MOEOEMIM] [(C
3
O)
4
DMG] [(di-h)
2
DMG] [BMIM] [EMIM] [P
6,6,6,14
] Aliquat

W
a
t
e
r

c
o
n
t
e
n
t

/

m
a
s
s

f
r
a
c
t
i
o
n
826
*data measured in this work 827
**data measured in a previous work (Carneiro et al., 2012a) 828
Figure 6 829
830
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39

Temperature / K
280 290 300 310 320 330 340
S
o
l
u
b
i
l
i
t
y

o
f

f
r
u
c
t
o
s
e

/

m
o
l
a
r

f
r
a
c
t
i
o
n
0.35
0.36
0.37
0.38
0.39
0.40
0.41
0.42
831
Figure 7 832
833
834
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835
List of Tables 836
Table 1- Sample description table of the chemicals used 837
838
Chemical Name Source Initial Purity
Purification
Method
Final
Purity
Analysis Method
[emim][DCA] Iolitec 0.99 - 0.99 -
[bmim][DCA] Iolitec 0.98 - 0.98 -
[P6,6,6,14][DCA] Iolitec 0.95 - 0.95 -
[emim][TFA] Synthesized Not measured Distillation 0.999
Karl-Fisher Titration, HPLC and
1
H-NMR
Aliquat

[DCA] Synthesized Not measured

Extraction and
distillation
0.998
Karl-Fisher Titration, Mohr
method, HPLC and
1
H-NMR
Aliquat

[NO3] Synthesized Not measured

Extraction and
distillation
0.974
Karl-Fisher Titration, Mohr
method, HPLC and
1
H-NMR
D-(-)-fructose Merck 0.99 - 0.99 -
D-(+)-glucose Merck 0.999 - 0.999 -
839
840
841
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Table 2. Experimental solubility data of glucose in the ionic liquids 842
843
Aliquat

[NO3]

Aliquat

[DCA]

[P6,6,6,14][DCA]
T / K xs
*
10
2
T / K xs 10
2
T / K xs 10
2

299.95 0.0078 0.07 298.37 0.0018 0.09
307.75 0.0393 0.05 307.72 0.0114 0.05 308.29 0.0024 0.02
318.19 0.053 0.1 317.93 0.01759 0.004 318.43 0.00365 0.003
328.05 0.0691 0.03 328.8 0.0215 0.08 329.51 0.0048 0.04
339.75 0.0865 0.02 339.74 0.03230 0.006
u

(xs)/xs u(xs)/xs u(xs)/xs

0.01 0.009 0.03
[emim][TFA] [emim][DCA] [bmim][DCA]
T / K xs 10
2
T / K xs 10
2
T / K xs 10
2

288.47 0.261 0.2 288.25 0.171 0.1 288.15 0.1330 0.01
298.29 0.292 0.2 298.25 0.207 0.6 298.35 0.165 0.1
308.25 0.314 0.2 308.15 0.229 0.3 308.05 0.192 0.2
318.05 0.3294 0.04 318.15 0.2548 0.06 318.15 0.2095 0.03
329.07 0.349 0.6 328.25 0.281 0.2 328.45 0.236 0.2
u(xs)/xs u(xs)/xs u(xs)/xs
0.005 0.003 0.005
*
standard deviation 844

uncertainty (u(T)=0.01 K) 845

**relative uncertainty: (

)/

846
847
848
849
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Table 3. Experimental solubility data of fructose in the ionic liquids 850
851
Aliquat

[NO3]

Aliquat

[DCA]

[P6,6,6,14][DCA]
T / K xs
*
10
2
T / K xs 10
2
T / K xs 10
2



299.95 0.032 0.5

298.37 0.00276 0.004
307.75 0.131 0.1

307.72 0.054 0.1

308.29 0.0070 0.05
318.15 0.158 0.4

317.93 0.0716 0.07

318.43 0.011 0.1
328.05 0.185 0.2

328.8 0.1017 0.04

329.51 0.0552 0.04
339.75 0.218 0.4

339.74 0.130 0.3


u

(xs)/xs u(xs)/xs u(xs)/xs

0.01 0.02 0.04

[emim][TFA] [emim][DCA] [bmim][DCA]
T / K xs 10
2
T / K xs 10
2
T / K xs 10
2

288.05 0.355 0.3

288.25 0.333 0.1

288.15 0.281 0.1
297.75 0.398 0.4

298.25 0.360 0.1

298.35 0.310 0.4
308.30 0.415 0.2

308.15 0.394 0.5

308.05 0.340 0.2


318.15 0.440 0.3

318.15 0.378 0.1


328.25 0.495 0.2

328.45 0.41 1
u(xs)/xs u(xs)/xs u(xs)/xs
0.01 0.008 0.01
*
standard deviation 852

uncertainty (u(T)=0.01 K) 853

**relative uncertaity (

)/

854
855
856
857
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Table 4. Molar mass of the ionic liquids and water contents before and after solubility 858
measurements 859
Ionic Liquid M / gmol
-1

Water / wt.%
Before
After
Glucose Fructose
Aliquat

[NO3] 468.55 1.84 1.34 1.34

Aliquat

[DCA] 472.59 0.05 0.17 0.24

[emim][DCA] 177.21 0.16 0.16 0.26
[bmim][DCA] 205.26 0.18 0.35 0.22
[P6,6,6,14][DCA] 549.90 0.52 0.51 0.50
[emim][TFA] 224.18 0.12 0.23 1.44
860
861
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Table 5 - Density of mixtures of glucose and [bmim][DCA] 862
xGlucose
(mole fraction)
*/gmL
-1

298 K 313 K 328 K 343 K
0.0000 1.06059 1.05106 1.04167 1.03241
0.0313 1.06937 1.05985 1.05046 1.04120
0.0937 1.08722 1.07772 1.06837 1.05912
0.1849 1.11565 1.10609 1.09664 1.08729
0.2280 1.12902 1.11944 1.10987 1.10036
0.2474 1.13733 1.12781 1.11830 1.10889
* uncertainty in density, u()=0.00001 gmL
-1
863
864
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Table 6 - Comparison of solubility of glucose at 308 K with literature data 865
866
Ref. \ IL Aliquat

[DCA] [P6,6,6,14][DCA]
This work 0.0114 0.0024
25 0.0321 0.0151
867
868
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869
Table 7 Results for solubility data correlation with NRTL and UNIQUAC 870
Solute Ionic Liquid
NRTL UNIQUAC

g12/R
(K)
g21/R
(K)
AARD
(%)

u12/R
(K)
u21/R
(K)
AARD
(%)
Glucose [emim][DCA] 0.30 -828.7 901.6 2.5 -230.5 156.2 2.4
[bmim][DCA] 0.30 -732.4 836.5 3.3 -243.0 234.4 3.3
[emim][TFA] 0.30 -974.8 1848.9 2.0 -82.3 -119.7 2.0
Aliquat

[DCA] 0.30 1144.5 -359.7 7.7 165.0 -25.2 6.7

Aliquat

[NO3] 0.30 -118.7 482.6 2.9 -73.6 171.1 2.7

[P6,6,6,14][DCA] 0.30 976.2 4122.6 2.9 61.2 272.6 2.9
Fructose [emim][DCA] 0.30 -806.9 1357.5 0.8 -334.3 442.9 0.6
[bmim][DCA] 0.30 -610.7 2449.5 0.6 -343.7 644.5 1.1
[emim][TFA] 0.30 -836.5 1769.7 1.9 -363.3 531.7 1.9
Aliquat

[DCA] 0.30 250.9 310.8 10.0 95.1 15.5 8.6

Aliquat

[NO3] 0.22 -250.0 3162.6 1.2 -236.5 699.0 1.4

[P6,6,6,14][DCA] 0.30 1770.9 -394.4 31.6 277.0 -32.6 38.8
871
872
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Table 8 UNIQUAC models structural parameters 873
Compound r q Source
Glucose 5.80 4.84
56

Fructose 5.80 4.92
57

[emim][DCA] 4.71 3.77
a
[bmim][DCA] 5.67 4.53
a
[emim][TFA] 5.08 4.07
a
Aliquat

[DCA] 15.53 12.43

a
Aliquat

[NO3] 15.04 12.03

a
[P6,6,6,14][DCA] 17.90 14.32
a
a
estimated in this work 874
875
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Table 9 - Thermodynamic functions of dissolution calculated from experimental data 876
solute Ionic Liquid Thm / K

0
diss. H
(kJmol
-1
)

0
diss. G
(kJmol
-1
)

0
diss. S
(Jmol
-1
)
Glucose [emim][DCA]
307.6 9.5 3.8 18.5
[bmim][DCA]
307.6 11.0 4.3 21.5
[emim][TFA]
298.1 5.5 3.1 8.0
Aliquat

[DCA]
318.2 29.1 10.9 57.2
Aliquat

[NO3]
323.0 21.6 7.6 43.5
[P6,6,6,14][DCA] 313.2 26.3 15.2 35.7
Fructose [emim][DCA] 307.6 7.8 2.3 17.7
[bmim][DCA] 307.6 7.5 2.8 15.3
[emim][TFA] 298.1 5.6 2.3 11.0
Aliquat

[DCA] 318.2 28.7 7.1 67.9

Aliquat

[NO3] 323.0 13.9 4.8 28.2

[P6,6,6,14][DCA] 308.2 53.3 13.2 130.1
877
878
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