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M. C. Lpez
Carlos Lafuente
University of Zaragoza
University of Zaragoza
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Article
pubs.acs.org/jced
Grupo de investigacion GIMACES, Facultad de Ciencias de la Salud, Universidad San Jorge, Villanueva de Gallego, 50830,
Zaragoza, Spain
Departamento de Qumica Fsica, Facultad de Ciencias, Universidad de Zaragoza, 50009, Zaragoza, Spain
S Supporting Information
*
1. INTRODUCTION
One of the Green Chemistry principles described by Anastas and
Warner1 is related to solvents, because they are greatly used in
the chemical industry not only for many chemical reactions but
also for cleaning equipment, regulating temperatures, isolating
and purifying compounds by recrystallization or extractions, and
assisting structural characterization. However, it is well-known
that some of these solvents can result in serious environmental
and health problems. Accordingly, it is important to develop new
less toxic and hazardous solvents.2
A good alternative to traditional harmful solvents would be
processes without solvent use, especially when one of the
substrates or the product is a liquid that can be used as the solvent
of the reaction. Nevertheless, this is not possible in most cases
because solvents are still really important in the vast majority of
reactions. For this reason, it is necessary to look for dierent
kinds of environmentally friendly solvents. There are some
candidates for alternates to traditional solvents, for example
solvents from biomass, which have received much attention as
renewable organic resources.2,3
Biomass is dened as any organic matter that is available on a
renewable basis, including dedicated energy crops and trees,
aquatic plants, animal wastes, agricultural food and feed crop
residues, wood and wood residues, and other waste materials.4
With the use of biomass, some solvents can be obtained by
fermentation, enzymatic, or esterication processes. These kinds
of compounds are classied as green solvents and can be used for
a variety of industrial processes. Some of these chemicals are fatty
acid esters, furfural, levulinic acid, terpenes, glycols and their
esters, low molecular weight alcohols, and lactates.5
Furfural is an important compound accessible from biomass
because it is the only unsaturated large-volume organic chemical
XXXX American Chemical Society
Article
dry air. The nal uncertainty of density and speed of sound can
be estimated in 5106 gcm3 and 0.05 ms1 respectively.
Refractive indices at 589.3 nm sodium D wavelength, nD, were
measured using a high precision automatic refractometer
Abbemat-HP from DR. Kernchen, whose temperature was
internally controlled at 0.01 K. The uncertainty of the
measurements is 5106.
Previous results of density and refractive index of tetrahydrofurfuryl alcohol11 corroborates our results; deviation of
0.07 % for density and 0.06 % for refractive index.
Surface tensions, , were determined using a drop volume
tensiometer Lauda TVT-2.17 The temperature was kept constant within 0.01 K by means of an external Lauda E-200
thermostat. The uncertainty of the surface tension measurement
is 0.05 mNm1.
Kinematic viscosities, , were measured using an Ubbelohde
viscosimeter with a Schott-Gerate automatic measuring unit
model AVS-440. The temperature was kept constant at 0.01K
by means of a Ct52 Schott-Gerate thermostat. The viscosimeter
was calibrated with ultrapure water supplied by SH Calibration
service GmbH. The estimated uncertainty of kinematic viscosity
determinations, expressed as percentages, is 1 %. Kinetic
energy corrections were applied to the experimental data. The
dynamic viscosity, = v, has been obtained from density and
kinematic viscosity measurements, and the estimated uncertainty
in dynamic viscosity is 1%.
Static permittivities, , at a frequency of 2 MHz were
obtained using a capacitive measurement method, the
capacitances were measured by means of an Agilent 4263BA
precision LCR meter connected to a four terminal Agilent
16452A liquid dielectric test xture through Agilent 16048A
test leads. The uncertainty of permittivity measurements is less
than 0.5 %. During all measurements, the temperature of the
cell was controlled at 0.01 K by means of a CT52 SchootGerate thermostat.
Vapor pressures were determined using an all-glass dynamic
recirculating still, Fischer-Labodest which was equipped with
a Cottrell pump. The temperatures were measured by means
of a thermometer model F25 with a PT100 probe from
Automatic Systems Laboratories, and the pressures in the still
were measured with a Digiquartz 735-215A-102 pressure
transducer from Paroscientic equipped with a Digiquartz 735
display unit. The uncertainty in the temperature and pressure
equilibrium measurement in the still is 0.01 K and 50 Pa,
respectively.
Values of log P have been calculated using the ALOGPS 2.1
method (available on http://www.vcclab.org/lab/alogps/).1214
2. EXPERIMENTAL SECTION
5-Methylfurfural and tetrahydrofurfuryl alcohol have been
provided by Sigma with a mass purity of 99 %. Information of
the studied chemicals is summarized in Table 1. These purities
Table 1. Purities and Source of the Solvents
chemical name
CAS
source
purity/mass fraction
5-methylfurfural
tetrahydrofurfuryl alcohol
620-02-0
97-99-4
Sigma
Sigma
99 %
99 %
3. RESULTS
The density values as a function of temperature and pressure
were collected and are detailed in Table 2. The experimental
values of density, refractive index, speed of sound, surface
tension, kinematic and dynamic viscosity, static permittivity,
vapor pressure, and derived properties such as molar refraction,
isentropic compressibility, and enthalpy of surface formation
for the studied chemicals were gathered and presented in Table 3.
Moreover experimental values of vapor pressure are listed in
Table 4.
The measured densities have been correlated with temperature and pressure using the three-dimensional pT correlating
model TRIDEN.18 In this model the Tait equation19 for isothermal compressed densities was combined with a modied
Rackett equation20 for isothermal compressed densities. For the
B
Article
0.1 MPa
2.5 MPa
5.0 MPa
283.15
288.15
293.15
298.15
303.15
308.15
313.15
318.15
323.15
328.15
333.15
338.15
1118.02
1113.09
1108.15
1103.20
1098.25
1093.29
1088.32
1083.33
1078.33
1073.32
1068.30
1063.25
1119.83
1114.82
1110.03
1104.82
1100.71
1095.01
1090.31
1085.42
1080.39
1075.43
1070.05
1065.43
1121.37
1116.39
1111.50
1106.62
1101.81
1096.90
1092.06
1087.05
1082.17
1077.24
1072.29
1067.33
283.15
288.15
293.15
298.15
303.15
308.15
313.15
318.15
323.15
328.15
333.15
338.15
1062.84
1058.59
1054.34
1050.06
1045.78
1041.48
1037.17
1032.83
1028.47
1024.08
1019.68
1015.24
1064.37
1060.15
1055.94
1051.72
1047.47
1043.19
1038.92
1034.57
1030.30
1025.88
1021.52
1017.04
1065.68
1061.47
1057.30
1053.11
1048.90
1044.66
1040.41
1036.11
1031.87
1027.49
1023.18
1018.75
7.5 MPa
10.0 MPa
20.0 MPa
5-Methylfurfural
1122.65
1124.02
1129.41
1117.87
1119.23
1124.75
1112.96
1114.40
1120.15
1108.34
1109.63
1115.43
1103.11
1104.89
1110.81
1098.15
1100.06
1106.17
1093.64
1095.27
1101.50
1088.71
1090.41
1096.72
1083.95
1085.56
1092.07
1079.03
1080.70
1087.38
1074.10
1075.84
1082.66
1069.06
1070.99
1077.96
Tetrahydrofurfuryl Alcohol
1066.97
1068.24
1073.16
1062.80
1064.09
1069.11
1058.64
1060.00
1065.10
1054.48
1055.84
1061.08
1050.31
1051.69
1057.06
1046.09
1047.48
1052.96
1041.89
1043.41
1048.93
1037.62
1039.11
1044.81
1033.41
1034.93
1040.79
1029.13
1030.63
1036.60
1024.84
1026.39
1032.49
1020.45
1022.06
1028.31
30.0 MPa
40.0 MPa
50.0 MPa
60.0 MPa
1134.53
1129.99
1125.46
1120.97
1116.44
1111.86
1107.37
1102.74
1098.22
1093.64
1089.10
1084.52
1139.44
1134.99
1130.57
1126.15
1121.72
1117.24
1112.86
1108.39
1104.01
1099.55
1095.12
1090.69
1144.14
1139.79
1135.40
1131.12
1126.87
1122.38
1118.10
1113.73
1109.47
1105.14
1100.86
1096.51
1148.58
1144.31
1140.08
1135.84
1131.66
1127.34
1123.12
1118.89
1114.68
1110.48
1106.23
1102.02
1077.84
1073.88
1069.97
1066.04
1062.11
1058.12
1054.21
1050.15
1046.28
1042.20
1038.22
1034.16
1082.28
1078.41
1074.62
1070.75
1066.94
1063.05
1059.19
1055.24
1051.44
1047.50
1043.64
1039.68
1086.55
1082.72
1078.97
1075.22
1071.49
1067.61
1063.91
1060.12
1056.41
1052.52
1048.73
1044.89
1090.57
1086.83
1083.18
1079.49
1075.79
1072.09
1068.44
1064.68
1061.07
1057.30
1053.60
1049.83
Standard uncertainties u are u(T) = 0.01 K, u(p) = 0.050 MPa, and the combined expanded uncertainty Uc is Uc() = 0.1 kgm3 with 0.95 level of
condence (k 2).
a
1
RMSDr (%) = 100
n
AR
BR [1 + (1 T /C R )DR ]
0
B +p
1 C T ln B T + p
T 0
T 3
T 2
T
BT = b0 + b1 + b2 + b3
ET
ET
ET
i ,corr
i ,exp
i ,exp
i=1
1/2
(4)
(1)
(2)
(3)
Y = AT + B
(5)
Article
Table 3. Experimental and Calculated Physicochemical Properties at Atmospheric Pressure as a Function of Temperaturea
T
kgm3
ms1
TPa1
278.15
280.65
283.15
285.65
288.15
290.65
293.15
295.65
298.15
300.65
303.15
305.65
308.15
310.65
313.15
315.65
318.15
320.65
323.15
325.65
328.15
330.65
333.15
335.65
338.15
1122.936
1120.495
1118.023
1115.557
1113.091
1110.623
1108.153
1105.676
1103.203
1100.728
1098.250
1095.770
1093.288
1090.804
1088.316
1085.822
1083.329
1080.833
1078.332
1075.829
1073.322
1070.811
1068.296
1065.776
1063.252
1521.03
1511.82
1502.55
1493.23
1483.97
1474.72
1465.52
1456.28
1447.02
1437.84
1428.70
1419.57
1410.46
1401.41
1392.34
1383.28
1374.29
1365.29
1356.09
1347.33
1338.36
1329.45
1320.54
1311.63
1302.77
384.92
390.47
396.18
402.03
407.96
414.01
420.16
426.46
432.91
439.44
446.08
452.86
459.77
466.79
473.97
481.31
488.75
496.35
504.28
512.05
520.14
528.38
536.79
545.40
554.15
278.15
280.65
283.15
285.65
288.15
290.65
293.15
295.65
298.15
300.65
303.15
305.65
308.15
310.65
313.15
315.65
318.15
320.65
323.15
325.65
328.15
330.65
333.15
335.65
338.15
1067.066
1064.958
1062.839
1060.717
1058.593
1056.467
1054.338
1052.201
1050.064
1047.925
1045.782
1043.633
1041.480
1039.327
1037.166
1034.999
1032.828
1030.650
1028.467
1026.279
1024.084
1021.883
1019.676
1017.463
1015.243
1556.44
1547.59
1538.61
1529.70
1520.76
1511.85
1503.00
1494.16
1485.32
1476.53
1467.78
1459.02
1450.27
1441.56
1432.84
1424.13
1415.43
1406.75
1398.06
1389.40
1380.75
1372.13
1363.47
1354.83
1346.20
386.85
392.06
397.44
402.89
408.46
414.12
419.86
425.70
431.66
437.71
443.85
450.12
456.51
463.00
469.63
476.39
483.28
490.29
497.46
504.75
512.19
519.77
527.53
535.44
543.51
nD
Rm
cm3mol1
mNm1
mNm1
mm2s1
mPas
43.02
42.75
42.37
42.13
41.80
41.46
41.20
40.90
40.61
40.22
39.95
39.66
39.32
39.04
38.75
38.44
38.13
37.78
37.51
37.26
36.91
36.54
36.21
35.92
35.57
77.34
77.38
77.31
77.37
77.35
77.32
77.37
77.38
77.40
77.31
77.35
77.37
77.34
77.37
77.39
77.38
77.38
77.34
77.38
77.44
77.40
77.34
77.31
77.33
77.29
2.8176
2.6537
2.4718
2.3559
2.1949
2.0685
1.9630
1.8594
1.7654
1.6835
1.6000
1.5281
1.4615
1.4000
1.3424
1.2913
1.2417
1.1950
1.1510
1.1171
1.0720
1.0370
1.0038
0.9745
0.9426
3.164
2.974
2.764
2.628
2.443
2.297
2.175
2.056
1.948
1.853
1.757
1.674
1.598
1.527
1.461
1.402
1.345
1.292
1.241
1.202
1.151
1.110
1.072
1.039
1.002
45.2
44.5
43.7
43.0
42.3
41.6
40.9
40.2
39.4
38.7
38.0
37.2
36.4
35.8
35.1
34.4
33.7
33.6
32.4
31.7
31.1
30.4
29.8
29.1
28.4
39.54
39.29
39.03
38.78
38.53
38.27
38.02
37.77
37.51
37.26
37.01
36.75
36.50
36.25
35.99
35.74
35.48
35.23
34.98
34.72
34.47
34.22
33.96
33.71
33.46
67.75
67.76
67.72
67.75
67.76
67.72
67.77
67.72
67.74
67.72
67.73
67.72
67.79
67.85
67.88
67.81
67.78
67.75
67.68
67.70
67.63
67.80
67.74
67.74
67.77
9.7379
8.9079
8.1709
7.5147
6.9286
6.4036
5.9322
5.5076
5.1242
4.7773
4.4625
4.1763
3.9155
3.6774
3.4594
3.2597
3.0762
2.9074
2.7518
2.6081
2.4752
2.3521
2.2380
2.1319
2.0332
10.391
9.487
8.684
7.971
7.335
6.765
6.254
5.795
5.381
5.006
4.667
4.359
4.078
3.822
3.588
3.374
3.177
2.996
2.830
2.677
2.535
2.404
2.282
2.169
2.064
15.2
15.0
15.0
14.9
14.8
14.7
14.6
14.5
14.4
14.4
14.3
14.2
14.1
14.0
13.9
13.8
13.8
13.6
13.5
13.5
13.4
13.3
13.2
13.1
13.0
5-Methylfurfural
1.536401
30.729
1.535291
30.744
1.533931
30.746
1.532694
30.755
1.531443
30.763
1.530189
30.771
1.528904
30.778
1.527652
30.786
1.526400
30.794
1.525132
30.801
1.523855
30.808
1.522567
30.815
1.521298
30.822
1.520000
30.829
1.518716
30.835
1.517421
30.842
1.516145
30.849
1.514857
30.856
1.513565
30.863
1.512288
30.870
1.510996
30.877
1.509721
30.885
1.508422
30.892
Tetrahydrofurfuryl Alcohol
1.456462
1.455486
1.454522
1.453559
1.452588
1.451616
1.450627
1.449652
1.448668
1.447686
1.446715
1.445720
1.444730
1.443746
1.442742
1.441757
1.440721
1.439698
1.438711
1.437718
1.436683
1.435673
1.434661
26.144
26.148
26.152
26.157
26.161
26.166
26.169
26.174
26.177
26.182
26.186
26.190
26.194
26.198
26.202
26.207
26.209
26.212
26.216
26.221
26.224
26.228
26.232
Standard uncertainty u is u(T) = 0.01 K. and the combined expanded uncertainties Uc are Uc() = 0.05 kgm3. Uc(u) = 0.05 ms1. Uc(nD) = 5
105. Uc() = 0.05 mNm1. Uc() = 1 %. Uc() = 0.5 % with 0.95 level of condence (k 2).
Article
p/kPa
5-methylfurfural
tetrahydrofurfuryl alcohol
303.15
308.15
313.15
318.15
323.15
328.15
333.15
338.15
343.15
348.15
353.15
358.15
363.15
368.15
373.15
378.15
383.15
388.15
393.15
398.15
403.15
408.15
413.15
418.15
423.15
428.15
433.15
438.15
443.15
448.15
453.15
0.10
0.15
0.20
0.30
0.40
0.54
0.74
0.97
1.30
1.66
2.17
2.76
3.52
4.40
5.52
6.79
8.43
10.20
12.31
15.00
18.00
21.27
25.33
30.01
34.95
40.57
47.43
55.14
63.39
72.37
83.40
0.09
0.15
0.21
0.31
0.43
0.63
0.86
1.15
1.55
2.11
2.72
3.53
4.51
5.72
7.22
9.11
11.18
13.68
16.64
20.17
24.22
28.63
34.22
40.19
47.32
56.31
65.02
74.02
84.98
97.93
nD
u/ms1
s/mNm1
h/mPas
p/kPa
e
nD
u/ms1
s/mNm1
h/mPas
p/kPa
e
5-methylfurfural
tetrahydrofurfuryl alcohol
771.51
0.73780
354.68395
0.94211
0.07842
344.6906
12.23527
53.31163
8.33967
103.69167
0.00582
662.54
0.71555
421.02707
0.79258
0.07490
279.9662
34.36228
39.36321
4.77683
90.97230
0.00317
nD2 + 2
Vm
149.31
190.15
117.68
152.464
RMSDr/%
0.00
0.03
0.08
0.29
0.87
0.30
0.00
0.02
0.08
0.06
0.87
0.12
S =
T p
(8)
H = T
T p
(9)
Experimental values of surface tension have a linear dependence with temperature; for this reason, entropy of surface formation per unit surface area is constant in this range of temperature. The entropy of surface formation values at T = 313.15 K
are collected in Table 7.
The dynamic viscosity of the studied compounds as a function of
temperature is shown in Figure 4. The values for this property decrease
as temperature increases. The temperature dependence of dynamic
viscosity values reveals convex shape functions, therefore, the data have
been tted using the VogelFulcherTamman equation:2224
= 0 exp[B /(T T0)]
(10)
Rm =
5-Methylfurfural
5.16096104
1.681017
3.63968
2532.59
0.12338
77.36
0.084
467.5
6.205
1585.824
3101
123.046
Tetrahydrofurfuryl Alcohol
3.96282104
1.568766
3.50178
2529.74
0.10142
67.75
0.027
953.0
5.797
1246.500
4102
25.077
AR/kgm3
BR
CR/K
DR
CT
b0/MPa
b1/MPa
b2/MPa
b3/MPa
ET/K
RMSDr/%
property
T/K
2 =
(6)
2
2
9TM ( nD)(2 + nD)
4NA
(nD2 + 2)2
(11)
Article
Figure 1. Density, , isobaric expansibility, p, and isothermal compressibility, T, as a function of temperature and pressure for 5-methylfurfural: ,
experimental densities; , calculated values using TRIDEN equation.
Figure 2. Density, , isobaric expansibility, p, and isothermal compressibility, T, as a function of temperature and pressure for tetrahydrofurfuryl
alcohol: , experimental densities; , calculated values using TRIDEN equation.
5-methylfurfural
tetrahydrofurfuryl alcohol
p/kK1
T/TPa1
Ss/mNm1K1
/D
Hvap/kJmol1
log P
0.9145
626.25
0.123
4.21
49.73
0.69
0.8357
590.85
0.101
2.69
49.98
0.28
4. DISCUSSION
In this section, a comparison of the thermophysical behavior of
furfural compounds (furfural, 5-methylfurfural, furfuryl alcohol,
and tetrahydrofurfuryl alcohol) has been carried out.16,26 Some
values for several thermophysical properties analyzed beforehand
have been collected and are presented in Table S3 of the
Supporting Information.16,26 To assist in the understanding of
Article
Figure 3. Refractive index, nD, molar refraction, Rm, speed of sound, u, and isentropic compressibility, S, as a function of temperature for the studied
solvents: , furfural; , furfuryl alcohol; , 5-methylfurfural; , tetrahydrofurfuryl alcohol.
Article
Figure 4. Surface tension, , dynamic viscosity, , and static permitivitty, , as a function of temperature for the studied solvents: , furfural; , furfuryl
alcohol; , 5-methylfurfural; , tetrahydrofurfuryl alcohol.
Article
5. CONCLUSIONS
New data about the physicochemical behavior of 5-methylfurfural and tetrahydrofurfuryl alcohol (density, speed of sound,
refractive index, surface tension, static permittivity, and dynamic
viscosity) have been measured as well as pT behavior, while the
vapor pressure has also been determined. All these values
obtained for 5-methylfurfural and tetrahydrofurfuryl alcohol
have been compared with other chemicals of the furfural family
such as furfural and furfuryl alcohol which have been reported
before. The results give information about several important
characteristics of these compounds and their potential
applications as green chemicals. For instance, tetrahydrofurfuryl
alcohol shows lower values of density, surface tension, and dipole
moment than the rest of chemicals within the family, while values
of properties such as speed of sound and viscosity are higher. The
study concludes that molar free volume for this chemical is the
highest within the family. However, the free volume/molar
volume ratio is smaller for 5-methylfurfural.
Regarding some environmental characteristics, the results
indicate that the vapor pressures for the studied chemicals are
much lower than that for some traditional solvents; therefore,
these chemicals should have a lower VOC character.
ASSOCIATED CONTENT
* Supporting Information
S
AUTHOR INFORMATION
Corresponding Author
Research groups GIMACES (Grupo Consolidado de Investigacion Aplicada, E02) and PLATON (Grupo Consolidado,
E54), acknowledge nancial support by Gobierno de Aragon and
Fondo Social Europeo Construyendo Europa desde Aragon.
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