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Thermophysical Properties of Furfural Compounds


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Impact Factor: 2.04 DOI: 10.1021/je400783h

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Article
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Thermophysical Properties of Furfural Compounds


Laura Lomba, Beatriz Giner,*, Ma Carmen Lopez, Luis Aldea, and Carlos Lafuente

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
*

ABSTRACT: A physicochemical study of 5-methylfurfural and tetrahydrofurfuryl alcohol (density,


speed of sound, refractive index, surface tension, static permittivity, and viscosity) has been carried
out under atmospheric pressure at temperatures from (278.15 to 338.15) K, while the vapor
pressure was determined over a temperature range from (303.15 to 453.15) K. Furthermore, the
pT behavior has also been assessed over a temperature range from (283.15 to 338.15) K and a
pressure range from (0.1 to 60.0) MPa. Results indicate that although values of speed of sound,
molar free volume, and viscosity of tetrahydrofurfuryl alcohol are higher than for the rest of the
furfural family, the free volume/molar volume ratio is smaller for 5-methylfurfural, indicating a
better packing. Furthermore, VOC character of the studied compounds is smaller than some
traditional solvents.

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

prepared from carbohydrate resources and is a key derivative for


the production of important chemicals that cannot be obtained
from petroleum.6,7 The chemistry of furfural has been developed
during the past years.7 One important chemical coming from
furfural is furfuryl alcohol which presents several applications
in the chemical industry such as lubricants, adhesives, and
precursor. Moreover, it is mainly used in the manufacture of
resins, as a starting material for the production of tetrahydrofurfuryl alcohol, and it is also an important chemical
intermediate for the manufacture of fragrances, vitamin C, and
lysine.8 On the other hand, 5-methylfurfural can be obtained
from traditional balsamic vinegar which is produced from acetic
acid fermentation under specic conditions.9 This chemical can
give an especial avor to this product. However, its presence in
this vinegar is regulated in order to evaluate its organoleptic
properties and potential fraudulent commercial use.9
Nevertheless, the use of these chemicals is very limited due
to the poor knowledge about them, and for this reason it is
important to know as much information as possible about their
molecular behavior and how these types of molecules interact
with other chemicals. In addition, through the study of several
physicochemical properties, the applicability of these chemicals
in dierent industrial processes can be assessed; moreover, the
thermophysical properties will probably validate the goodness
of these compounds from an environmental point of view and as
a potential substitute for traditional solvents.
A review of the literature shows that the thermophysical
properties of furfural derivatives are not complete. Regarding
Received: August 29, 2013
Accepted: December 23, 2013

dx.doi.org/10.1021/je400783h | J. Chem. Eng. Data XXXX, XXX, XXXXXX

Journal of Chemical & Engineering Data

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

mixtures of 5-methylfurfural and other chemicals, the activity


coecients of water in 5-methylfurfural at innite dilution have
been measured, while the azeotropic information for the system
5-methylfurfural water has also been studied.10 Furthermore, in
the case of tetrahydrofurfuryl alcohol, there is a report in which
the density and refractive index at T = 293.2 K has been
published.11 Nevertheless, as far as we know, 5-methylfurfural or
furfuryl alcohol has not been studied within all its perspectives. In
view of that, we have completed the available information for this
family of chemicals through a comprehensive thermophysical
study. To achieve this objective, density, speed of sound,
refractive index, surface tension, static permittivity, and dynamic
viscosity of 5-methylfurfural and tetrahydrofurfuryl alcohol have
been obtained at atmospheric pressure from (278.15 to 338.15)
K, while the vapor pressure was determined over a temperature
range from (303.15 to 453.15) K. Furthermore, the pT study
has been carried out over a temperature range from (283.15 to
338.15) K and a pressure range from (0.1 to 60.0) MPa for the
studied chemicals. Experimental density data were tted to the
TRIDEN and from the tted equation, related properties, such as
isobaric thermal expansion, , and isothermal compressibility, kT,
have been obtained. On the other hand, in order to achieve an
impression of the molecular hydrophobicity, the log P (logarithm
of 1 octanol/water partition coecient) has been calculated
making use of the AGLOPs method.1214 The results have been
analyzed in terms of molecular interactions. Finally, a
comparative study for the furfural family (furfural, 5-methylfurfural, furfuryl alcohol, and tetrahydrofurfuryl alcohol) was
performed to assess how the small dierences in their structure
can aect their thermophysical behavior.

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 %

have been conrmed by GC chromatography, and no further


purication was considered to be necessary.
To obtain pT behavior, a high pressure and high temperature
Anton Paar DMA HP cell connected to an Anton Paar DMA
5000 densimeter has been used. The density of the sample was
determined by measuring the oscillation period of the U-shaped
tube made from Hastelloy C-276 gold. The cell temperature is
controlled at 0.01 K by means of an integrated Peltier
thermostat. The required pressure was created by a hand pump
750.1100 from Sitec, Switzerland, and measured by a pressure
transducer US181 from Measuring Specialties, USA. The
uncertainty in the pressure measurement is 5 kPa. For
evacuating the whole apparatus a vacuum pump was employed.
Details of the calibration and procedure have been reported in a
previous paper,15,16 the estimated uncertainty of our density
measurements is 5105 gcm3.
Densities, , and speed of sounds, u, of the pure compounds
were determined simultaneously with an Anton Paar DSA 5000
vibrating tube densimeter and sound analyzer, automatically
thermostatted at 0.005 K. The calibration was carried out with
ultrapure water supplied by SH Calibration service GmbH and

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

dx.doi.org/10.1021/je400783h | J. Chem. Eng. Data XXXX, XXX, XXXXXX

Journal of Chemical & Engineering Data

Article

Table 2. Experimental Densities, , as a Function of Temperature and Pressurea


/kgm3 at p/MPa
T/K

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

liquid saturation densities, the Rackett equation used here is a


further modication of the modied form as suggested by
Spencer and Danner:21
0 =

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)

where n is the number of experimental data.


TRIDEN parameters along with the corresponding deviation
were collected in Table 5. The deviations between experimental
and correlated densities are close to the uncertainty of the
experimental densities and randomly distributed.
Isobaric expansibility, p, and isothermal compressibility, T,
have been calculated. The temperature and pressure derivatives
of density have been evaluated using the TRIDEN equation. The
calculated values of these properties over the wide temperature
and pressure ranges can be found in the Supporting Information,
Tables S1 and S2.
A linear dependence of several properties such as refractive
index, speed of sound, surface tension, and static permittivity
with temperature in the range of measurements under study has
been found. These experimental data have been correlated with
the following equation:

(1)

(2)

(3)

where o is the density at atmospheric pressure and is the


density.
For the Rackett equation parameters AR, BR, CR, and DR are
tting parameters and T is the absolute temperature.
All parameters can be simultaneously tted to temperaturedependent experimental density data at atmospheric pressure
(p0 = 0.1 MPa).
In the case of the Tait equation and eqs 2 and 3, p is the
pressure expressed in MPa and the tting parameters are b0, b1,
b2, b3, and ET in eq 3 and the parameter CT in eq 2 that
was treated as temperature independent. The relative root
mean-square deviations, RMSDr, between experimental and
correlated density values were used as statistical values for
TRIDENT ts:

Y = AT + B

(5)

where Y is the studied property and A and B are adjustable


parameters. The best linear tting parameters and relative rootmean square deviations between experimental and correlated
values are gathered in Table 6.
Values of density as a function of temperature and pressure
and its derivatives, isobaric expansibilities, and isothermal
compressibilities are plotted in Figures 1 and 2. The isobaric
C

dx.doi.org/10.1021/je400783h | J. Chem. Eng. Data XXXX, XXX, XXXXXX

Journal of Chemical & Engineering Data

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).

expansibilities, p, and isothermal compressibilities, T, at


T = 313.15 K and at atmospheric pressure are presented in
Table 7.

In Figure 3, experimental refractive index, and calculated molar


refraction values are shown. The molar refraction, Rm, of the
studied compounds has been calculated from experimental data
D

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Table 4. Experimental Vapor Pressures as a Function of


Temperaturea

Table 6. Fitting Parameters and Relative Root-Mean Square


Deviations for the Measured Properties

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)

where 0, B, and T0 are adjustable parameters, which are provided


along with the corresponding relative root mean square deviations in
Table 6.
The static permittivities are graphically shown in Figure 4.
From experimental data, the dipolar moment at T = 313.15 K has
been calculated through the Onsager equation.25

of density and refractive index making use of the Lorentz


Lorenz relation.
nD2 1

The calculated values of isentropic compressibility for the


chemicals studied are plotted in Figure 3.
The temperature dependence of surface tension of studied
chemicals can be found in Figure 4. From experimental surface
tension measurements, the entropy and enthalpy of surface
formation per unit surface area have been calculated using the
following equations:

Table 5. Parameters of the TRIDEN Equation and Relative


Root Mean Square Deviations, RMSDr, between
Experimental and Correlated Densities

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

compressibility has been obtained from density and speed of


sound experimental values, thorough NewtonLaplace equation:
1
s =
u 2
(7)

Standard uncertainties u are u(T) = 0.01 K; u(p) = 50 Pa.

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)

where is the Boltzmann constant, NA is the Avogadro constant


and M is the molar mass. The values of the dipolar moment are
shown in Table 7.

where Vm is the molar volume.


The experimental speeds of sound are shown in Figure 3.
Assuming that ultrasonic absorption is negligible, isentropic
E

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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.

where t is temperature in Celsius degrees and A, B, and C


are adjustable parameters that are gathered in Table 5. The
experimental data are represented in Figure 5. From the slope
of vapor pressure curves, the enthalpy of vaporization can be
determined using the ClausiusClapeyron equation, values for
this property at T = 373.15 K are shown in Table 7.
Finally, log P has been calculated (logarithm of 1-octanol/
water partition coecient) making use of the AGLOPs method
to know the molecular hydrophobicity which is an important
characteristic in catalytic reactions.1214 AGLOPs values found
for studied compounds are given in Table 7.

Table 7. Calculated Properties at Atmospheric Pressure;


Isobaric Expansibility, p, Isothermal Compressibility, T,
Entropy of Surface Formation, S, and Dipolar Moment, ,
at T = 313.15 K, Enthalpy of Vaporization, Hvap, at T =
373.15 K, and log P
property/unit

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

The vapor pressure of the studied solvents has also been


determined. The results have been correlated using the Antoine
equation:
B
log p = A
(12)
C+t
F

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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.

because of the presence of a hydroxyl and a keton group, but only


tetrahydrofurfuryl alcohol is a protic solvent. Furthermore,
dispersive interactions between alkyl chains also must be taken
into account.16,26
The density plots as a function of pressure and temperature are
very similar for the studied chemicals; the density values decrease
with temperature at constant pressure due to the thermal
expansion and the weakening of molecular interactions;
moreover, at a xed temperature, density increases with pressure,
as expected. Density values (Figures 1 and 2), in almost all the
ranges of temperatures and pressures analyzed, follow the order
furfural > furfuryl alcohol > 5-methylfurfural > tetrahydrofurfuryl
alcohol.

this discussion, we have included information regarding (furfural


and furfuryl alcohol) in Figures 3 to 5.
The analysis of a complete set of thermophysical properties
such as volumetric spectroscopic, supercial, or transport
properties is a common way to study the molecular behavior
of chemical compounds regardless of their molecular characteristics.2629 To get as much information as possible, it is
important to revise basic information about molecular behavior
of the studied compounds as a starting point for the analysis.
In the case of 5-methylfurfural and tetrahydrofurfuryl alcohol,
we can justify the experimental behavior taking into account
energetic and structural phenomena at the molecular level. As for
the rest of the furfural compounds, they are polar molecules
G

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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.

knowledge about molecular structure of the studied chemicals,


isentropic compressibility has been obtained. The results indicate
that tetrahydrofurfuryl alcohol shows the highest isentropic
compressibility value followed by 5-methylfurfural, furfuryl
alcohol, and furfural.
The refractive index also decreases with temperature and it
reveals that the highest value is obtained for 5-methylfurfural
(Figure 3). The trend is as follows: 5-methylfurfural > furfural >
furfuryl alcohol > tetrahydrofurfuryl alcohol.
Again, to get further information about the structural behavior,
the molar refraction, Rm, of the studied compounds has been
obtained from the experimental data of density and refractive index (Figure 3). In all cases this property increases
with temperature. Molar refraction is considered the hard core
volume of a mole of molecules; therefore, free molar volume
(unoccupied part of the molar volume)17 can be derived easily.
The free volume is strongly related to properties such as solute
solvation or gas solubility.30 The results obtained for molar
refraction indicate that the chemical that presents highest value
are 5-methylfurfural followed by tetrahydrofurfuryl alcohol,
furfural, and furfuryl alcohol. The calculated free volume for
the chemicals studied is 57.88 cm3mol1, 69.03 cm3mol1,
61.98 cm 3 mol 1 , and 71.09 cm 3 mol 1 for furfural,
5-methylfurfural, furfuryl alcohol, and tetrahydrofurfuryl alcohol,
respectively. Moreover, calculated free volume associated to
molar refraction shows the ratio free volume/molar volume at
T = 298.15 K is around 0.70 for all furfural chemicals.26
Taking into account the volumetric properties, we can get
some interesting information regarding to the molecular
structure of the chemicals; considering that the isoentropic
compressibility values for the compounds derived from furfural
are quite similar, we have to pay specic attention to the free
volume/molar volume relation, which was found to be lower for
furfural and 5-methylfurfural.
On the other hand, the tendency can also be explained by
taking into account isothermal compressibility results. Low
values for this property indicate good packing of the molecules;
the values for this property for furfural are smaller than for
5-methylfurfural. The same trend is followed by the alcohols; values
for furfuryl alcohol are smaller than tetrahydrofurfuryl alcohol.

Figure 5. Logarithm of pressures, p, as a function of the inverse of the


temperature for the studied solvents: , furfural; , furfuryl alcohol; ,
5-methylfurfural; , tetrahydrofurfuryl alcohol.

The calculated isobaric expansibilities and isothermal


compressibilities (Figures 1 and 2) for all the studied compounds
decrease with pressure when temperature is constant following
the general behavior of liquids. On the other hand, the p and
T values increase with temperature when pressure is constant.
For isobaric expansibilities, 5-methylfurfural shows higher values
followed by furfural, furfuryl alcohol, and tetrahydrofurfuryl
alcohol. However, for isothermal compressibility the trend
changes, the values being higher for tetrahydrofurfuryl alcohol,
followed by furfural, 5-methylfurfural, and furfuryl alcohol.
In the case of the speed of sound behavior related to
temperature (Figure 3), values for the studied chemicals decrease
with temperature, as expected. The tetrahydrofurfuryl alcohol
presents the highest value for this property, followed by
5-methylfurfural, furfuryl alcohol, and furfural.26 To get further
H

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The logarithm of 1-octanol/water partition coecient, log P,


has been calculated making use of the AGLOPs method to know
the molecular hydrophobicity, which is an important characteristic in catalytic reactions and environmental processes.1214
Knowledge of this property gives an idea of how the chemical will
behave in the environment. Furthermore, this parameter and the
solubility of the substance are directly related. Water solubility
will also aect the potential routes of exposure to the substance,
its bioavailability and its potential for biodegradation.34 AGLOPS
values found for 5-methylfurfural and tetrahydrofurfuryl
alcohol is log P = 0.69 and 0.28, respectively; these values are
slightly dierent from furfural with P = 0.43 and furfuryl alcohol
at P = 0.25.26

This experimental data corroborate the relation found between


values of the isothermal compressibility and the extent of hydrogen
bonds that can be established between molecules of uids.31
As expected, surface tension of 5-methylfurfural and
tetrahydrofurfuryl alcohol decreases linearly as the temperature
increases (Figure 4). Surface tension is a property caused by the
cohesive forces between liquid molecules. The bulk of liquid
molecules of a pure compound are completely surrounded by
other molecules so that the forces of attraction between adjacent
molecules are equal in all the directions. On the contrary, the
molecules of the surface of the liquid at the liquid/gas interface
present unbalanced forces, resulting in an inward attraction. As it
is well-known the surface tension is the force per unit length
along the surface lm of a liquid in the liquid/gas boundary which
causes the lm to behave like an elastic sheet. Because of surface
tension, the molecules in a liquid/gas interface are in tension and
tend to contract in a minimum surface area.32 This property
shows the extent of the intermolecular interactions in the bulk
and therefore, it is a consequence of the structure of the
molecules on the surface. In this case the higher surface tension
values are presented by furfural followed by 5-methylfurfural,
furfuryl alcohol, and tetrahydrofurfuryl alcohol.
The static permittivity of 5-methylfurfural and tetrahydrofurfuryl alcohol decreases with temperature, as furfural and
furfuryl alcohol do (Figure 4). The highest static permittivity
value is shown by furfural, followed by 5-methylfurfural, furfuryl
alcohol, and tetrahydrofurfuryl alcohol.26 Furthermore, from
experimental data, dipolar moment has been calculated. The
dipolar moment of 5-methylfurfural and tetrahydrofurfuryl
alcohol at T = 313.15 K is 4.21 D and 2.69 D, respectively.
These two properties, static permittivity and dipolar moment,
can explain the values obtained for other properties that reect
mainly intermolecular interactions (surface tension for instance).
This means that despite the fact that alcohols are protic
solvents that can form hydrogen bonds between their molecules,
furfural and 5-methylfurfural show higher values for static permittivity that must make polar interactions of these compounds
quite important.
Regarding the transport properties, the dynamic viscosity values
for studied chemicals decrease with temperature (Figure 4).
Furthermore, dynamic viscosity increases when the alkyl chain
does. It is noticeable that the dynamic viscosity for tetrahydrofurfuryl alcohol and furfuryl alcohol is much higher than for
furfural and 5-methylfurfural.26 The stronger the intermolecular
forcers are, the higher the viscosity is. However, it is important to
highlight that viscosity does not only depend on the interactions,
but it also mimics the internal organization of the molecules and
their ability to ow.33 Values for viscosity increase if the molecules
entangle with one another. In this case, the eect of intermolecular
interactions seems to be predominant, as the values obtained for
dynamic viscosity follow the same trend as surface tension or polar
character.
Another important property that has to be studied in order for
solvents to fall within the green denomination is vapor pressure
because it determines the volatile organic compounds (VOCs)
character. The studied chemicals present low vapor pressures26
at T = 383.15 K. They followed the sequence: 5-methylfurfural <
tetrahydrofurfuryl alcohol < furfuryl alcohol < furfural (Figure 5).
These results indicate that the vapor pressures for the furfural
family are lower than some traditional solvents such as chloroform with values of 392.403 kPa, dichloromethane with 733.011 kPa,
benzene with 237.806 kPa, or toluene with 91.289 kPa in toluene;
therefore, they are expected to have a lower VOC character.

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

Additional tables as described in the text. This material is


available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*E-mail: bginer@usj.es. Tel: 34 976 060100.


Notes

The authors declare no competing nancial interest.


Funding

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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