J. Chem.

Thermodynamics 102 (2016) 155163

Contents lists available at ScienceDirect

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

Measurements and correlations of density, viscosity, and vapour-liquid

equilibrium for fluoro alcohols
Lianzheng Zhang, Dongmei Xu, Jun Gao , Liwen Zhao, Zhishan Zhang, Chunlu Li
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China

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

Article history: The measurements of density, viscosity for 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-

Received 20 April 2016 pentanol are reported at different temperatures and pressure of 101.3 kPa. The experimental values of
Received in revised form 3 July 2016 densities and viscosities of the above two fluoro alcohols were correlated successfully by a second-
Accepted 4 July 2016
order polynomial and by a VogelTammannFulcher equation, respectively. Meanwhile, isobaric
Available online 5 July 2016
vapour-liquid equilibrium results for two binary systems of (methanol + 2,2,3,3,4,4,5,5-octafluoro-1-
pentanol) and (2,2,3,3-tetrafluoro-1-propanol + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were determined
Keywords:
by a modified Rose type still. Both the Herington area method and the van Ness point to point test method
2,2,3,3-Tetrafluoro-1-propanol
2,2,3,3,4,4,5,5-Octafluoro-1-pentanol
were adopted to confirm the thermodynamic consistency of the experimental VLE findings, for which the
Density test results showed good thermodynamic consistency. The Wilson and non-random two-liquid (NRTL)
Viscosity activity coefficient models were used to correlate the measured VLE values at different temperatures.
Vapour-liquid equilibrium The correlation results indicate good agreement with the experimental values. Also the binary interaction
parameters of the two activity coefficients models were regressed. With the calculation of GE, the negative
deviation behaviour was observed for the two binary systems.
2016 Elsevier Ltd.

1. Introduction
Fluoro alcohol is a kind of compound in which the hydrogen of
the carbon-hydrogen bond is partially substituted by fluorine
atoms. Owing to its small radius and high electronegativity, the
energy of the carbon-fluorine bond formation is greater than that
of carbon-hydrogen bond [1]. Consequently, the fluorine atom
added into traditional alcohols can make the hydrogen atom of
hydroxylic more acidic than that in hydrocarbon alcohols [2] and
provide a good surface activity and biological activity for the tradi-
tional alcohols. Because of its special structure, fluoro alcohols
have extensive applications in the synthesis of medicine, pesticides
[3], dyestuffs [4], variety of solvents and surfactant [5,6].
In a number of fluoro alcohols, 2,2,2-trifluoroethanol (TFE) is
applied as a working fluid for energy transformation processes in
many fields because of its suitable thermodynamic properties
and thermal stability [7]. The 2,2,3,3-tetrafluoro-1-propanol (TFP)
and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (OFP) have been applied
widely as solvents due to their good solubility, volatility, non-
toxicity, non-corrosiveness, excellent lubricity and surface activity.
Particularly 2,2,3,3-tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5-octa
fluoro-1-pentanol are used as solvents in the production of CD-R
Corresponding author.
E-mail address: gao@sdust.edu.cn (J. Gao).
and DVD-R discs since they can dissolve a variety of organic com-
pounds [8].
Although the importance of fluoro alcohols for the industrial
applications has been emphasized, very few experimental values
for the physical chemistry properties are available. Up to now, a
few experimental values of density, viscosity and vapour-liquid
equilibrium or liquid-liquid equilibrium for fluoro alcohols are
available in the literature [1,2,9,10,1923]. And the measurement
of density [11], viscosity [12], vapour pressure [7,13], vapour-
liquid equilibrium [14], and excess thermodynamic properties
[1518] for pure 2,2,2-trifluoroethanol and its binary mixtures
are reported.
In this work, the density and viscosity of 2,2,3,3-tetrafluoro-1-
propanol and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol are reported
over a wide temperature range at atmospheric pressure. The iso-
baric vapour-liquid equilibrium of (methanol + 2,2,3,3,4,4,5,5-octa
fluoro-1-pentanol) and (2,2,3,3-tetrafluoro-1-propanol + 2,2,3,
3,4,4, 5,5-octafluoro-1-pentanol) have been determined. Based on
the experimental results obtained, the density was correlated by
using a second-order polynomial. The viscosity was correlated
by the VogelTammannFulcher (VTF) equation. The vapour-
liquid equilibrium (VLE) of two binary systems of
(methanol + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol) and (2,2,3,3-
tetrafluoro-1-propanol + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol) was
determined by a modified Rose type equilibrium still. Both binary

http://dx.doi.org/10.1016/j.jct.2016.07.011
0021-9614/ 2016 Elsevier Ltd.
156 L. Zhang et al. / J. Chem. Thermodynamics 102 (2016) 155163
systems were confirmed by the Herington [24] area method and the
point to point van Ness method [25] for thermodynamics consis-
tency test. Two activity coefficient models by Wilson [26] and the
non-random two-liquid (NRTL) [27] were used to correlated the
measured values. Meanwhile, the binary interaction parameters
were obtained that can be used in the optimization and design of
the separation process.
2. Experimental
2.1. Materials
The chemicals used in this work were 2,2,3,3-tetrafluoro-1-
propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and methanol, all
were analytical pure reagents. The 2,2,3,3-tetrafluoro-1-propanol
and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were supplied by Shan-
dong Zhongfu Chemical Technology Co., Ltd., and methanol was
from Tianjin Fuyu Fine Chemical Co., Ltd., for which the initial mass
fractions were 0.999, 0.995, and 0.997, respectively. The purities of
those reagents were checked and confirmed by gas chromatogra-
phy. All reagents were used without further purification. Table 1
shows some relevant detailed information on those chemicals.
2.2. Apparatus and measurements
2.2.1. Density measurements
The measurement of density (q) was carried out by an Anton
Paar DMA 5000 M densimeter at atmospheric pressure (P) of
101.3 kPa with temperature range from 293.15 K to 342.25 K. The
densimeter was calibrated with dried air and ultrapure water
before the test of samples. The automatic control equipment main-
tained the temperature fluctuation of the tested systems within
0.01 K. The uncertainty for density in this work was within
0.001 g
cm3.
2.2.2. Viscosity measurements
The viscosity (g) for all samples was measured by an Anton Paar
AMVn viscometer within the temperature ranging from 295.65 K
to 333.15 K at 101.3 kPa. The viscometer maintained the efflux
deflected time within 0.001 s and the temperature fluctuation
within 0.05 K. The uncertainty of viscosity in the present work
was 0.07 mPa
s.
2.2.3. Vapour-liquid equilibrium measurements
The VLE measurement of two binary systems of (methanol +
2,2,3,3,4,4,5,5-octafluoro-1-pentanol) and (2,2,3,3-tetrafluoro-1-
propanol + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol) was carried out
in a modified Rose type still, which was described in detail in pre-
vious work [28,29]. During the measurement, both the condensed
vapour phase and the liquid phase was recirculated consecutively
to provide intimate contact of the phases so that the equilibrium
state was achieved as soon as possible. The temperature was mea-
sured by using a precise mercury thermometer, Tianjin Glass
Instrument Factory, and the pressure was kept by a U-shaped dif-
ferential manometer, Nanjing Hengyuan Automatic Gauge Co., Ltd.
With the two-step automatic control system, the fluctuation was
Table 1
Suppliers and Mass Fractions of the Chemical Reagent.
Component CAS Suppliers
2,2,3,3-Tetrafluoro-1-propanol 76-37-9 Shandong Zhongfu Chemical Technology Co., Ltd.
2,2,3,3,4,4,5,5-Octafluoro-1-pentanol 355-80-6 Shandong Zhongfu Chemical Technology Co., Ltd.
Methanol 67-56-1 Tianjin Fuyu Fine Chemical Co., Ltd.
a
Gas chromatograph.
controlled within 0.03 kPa. The uncertainties of temperature and
pressure were 0.3 K and 0.05 kPa, respectively. In each measure-
ment, the mixture was gradually heated until a condensation
reflux rate of 23 drops per second was achieved. Then the temper-
ature of the system was recorded every 5 min until there was no
change of the temperature, the constant temperature was kept
for at least 50 min to reach the equilibrium state. Meanwhile, the
samples of the condensed vapour and liquid phases were with-
drawn into a gas chromatograph vials immediately for analysis.
The gas chromatograph vial was filled as much as possible to avoid
any loss of the volatile component.
The gas chromatograph (SP 6890) was equipped with a capillary
column (DB-WAX, 30 m  0.53 mm  1.00 lm, Agilent Technolo-
gies) and a thermal conductivity detector (TCD), Shandong Lunan
Ruihong Chemical Instruments Co., Ltd. The carrier gas was high-
purity hydrogen which the purity was 0.99999, and its flow rate
was 12 mL
min1. For analysis, the initial oven temperature was
kept 413.15 K. Both the injector and the detector were set at
443.15 K. All the samples of the two phases were analysed at least
three times, then the average value was adopted. For each binary
sample, the peak area of gas chromatography was calibrated
through five standard mixtures of known composition which were
prepared gravimetrically to cover the whole composition range.
The gravimetric uncertainty was 0.0001 g. In each experiment,
the condensed vapour and liquid phases were tested more than
three times to reduce the errors and ensure that a high accuracy
of the VLE results could be attained. With the workstation software
N2000 developed by Zhejiang University, the compositions of all
the samples were determined. The mole compositions were
checked by those obtained by mass. The uncertainty of mole frac-
tion was 0.001.
3. Results and discussion
3.1. Density
The experimental density for 2,2,3,3-tetrafluoro-1-propanol, 2,
2,3,3,4,4,5,5-octafluoro-1-pentanol were determined at pressure
of 101.3 kPa which is shown in Table 2 and plotted in Fig. 1. Exper-
imental values of density increase from 1.4010 to 1.4932 g
cm3 for
2,2,3,3-tetrafluoro-1-propanol and from 1.5960 to 1.6742 g
cm3
for 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, respectively, within the
temperature range from 293.15 K to 342.25 K.
Meanwhile, the literature density values for 2,2,3,3-tetrafluoro-
1-propanol and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol are compared
in detail in Fig. 1. For 2,2,3,3-tetrafluoro-1-propanol, there are
three points of density reported in the previous literature, which
are 1.476 g
cm3 [2], 1.45322 g
cm3 [19] at 298 K, and
1.482 g
cm3 [9] at 298.15 K, respectively. For 2,2,3,3,4,4,5,5-octa
fluoro-1-pentanol, only one point of density was reported as
1.6583 g
cm3 [30] at 298.15 K. Compared to the measured values
in this work, the density, 1.482 g
cm3 , in Takagis work shows a
deviation of 0.0046 g
cm3 for 2,2,3,3-tetrafluoro-1-propanol, and
1.6583 g
cm3 in Terrys work with a deviation of 0.0113 g
cm3
for 2,2,3,3,4,4,5,5-octafluoro-1-pentanol as shown in Fig. 1.
Mass fraction Purification method Analysis method
0.999 None GCa
0.995 None GCa
0.997 None GCa
 L. Zhang et al. / J. Chem. Thermodynamics 102 (2016) 155163 157

Table 2
Values of experimental and calculated density, q, viscosity, g, for 2,2,3,3-tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol in different temperatures at 101.3 kPa.a

T/K TFP/g
cm3 OFP/g
cm3 T/K TFP/mPa
s OFP/mPa
s

qexp qcal qexp qcal gexp gcal gexp gcal
293.15 1.4932 1.4944 1.6742 1.6761 295.65 5.0291 5.0761 13.1131 13.5600
301.55 1.4828 1.4810 1.6670 1.6650 297.55 12.1638 11.6483
306.15 1.4742 1.4732 1.6590 1.6584 298.65 4.4895 4.4540
309.05 1.4686 1.4681 1.6552 1.6541 300.15 4.2738 4.1816 10.6354 10.8144
312.65 1.4602 1.4616 1.6492 1.6486 302.15 3.7942 3.8528 9.8974 9.8114
316.15 1.4542 1.4550 1.6430 1.6430 304.15 3.5945 3.5586 8.7389 8.9183
319.35 1.4476 1.4489 1.6364 1.6377 306.15 3.2597 3.2945 8.0401 8.1215
323.25 1.4418 1.4412 1.6304 1.6310 307.65 3.0668 3.1140 7.4159 7.5799
327.05 1.4340 1.4335 1.6232 1.6243 309.15 2.9539 2.9470 7.0723 7.0814
330.65 1.4274 1.4260 1.6178 1.6177 311.65 2.7028 2.6954 6.2897 6.3358
334.35 1.4168 1.4181 1.6096 1.6107 313.15 2.5676 2.5587 5.9399 5.9341
338.25 1.4090 1.4095 1.6038 1.6031 318.15 2.1530 2.1676 4.8217 4.8011
342.25 1.4010 1.4004 1.5960 1.5951 323.15 1.8482 1.8564 3.8553 3.9214
328.15 1.6235 1.6056 3.2983 3.2313
333.15 1.4082 1.4011 2.7817 2.6847
a
Standard uncertainties u of temperature T, pressure P, density q, and viscosity g are u(T) = 0.01 K for density and u(T) = 0.05 K for viscosity, u(P) = 1 kPa, u(q) =
0.001 g
cm3, and u(g) = 0.07 mPa
s.

Fig. 1. Experimental densities, q, 2,2,3,3-tetrafluoro-1-propanol, values in this work (j), data in the literature (s [19], 4 [2], h [9]) and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol,
values in this work (d), data in the literature ( [29]) versus temperature, T;


calculated values.

For both components, the experimental values for density were
correlated by a function of temperature with a second-order poly-
nomial, which is expressed as follows:
qT A0 A1
T A2
T 2
where Ai is the coefficient of the equation which is listed in Table 3.
And the correlation coefficient R2 for densities of 2,2,3,3-
tetrafluoro-1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol are
0.9982 and 0.9975, respectively. The deviations of density between
the experimental values and those calculated by Eq. (1) were
obtained at temperatures from 293.15 K to 342.25 K. The maximum
deviation was 0.0018 g
cm3 for 2,2,3,3-tetrafluoro-1-propanol and
1
0.0020 g
cm3 for 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, respec-
tively, which indicate that the experimental density values for
2,2,3,3-tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5-octafluoro-1-pen
tanol can be well correlated by the second-order polynomial.

Table 3
Ai are coefficients of the second-order polynomial for density, Eq. (1); A, B, and T0 are coefficients for the VogelTammannFulcher (VTF) correlation, Eq. (2), as well as the
corresponding R2 for 2,2,3,3-tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol.

Coefficients for density Coefficients for VTF correlation

A0 A1 A2 R2 A B T0 R2
TFP 1.2745 0.0030 7.79E06 0.9982 3.9519 170.7006 4.0818 0.9984
OFP 1.3508 0.0035 8.07E06 0.9975 7.4997 99.1294 20.0365 0.9990
158 L. Zhang et al. / J. Chem. Thermodynamics 102 (2016) 155163

3.2. Viscosity the VLE values for the two binary systems were determined in a
modified Rose type still at 101.3 kPa. The measured VLE values
The experimental dynamic viscosity for 2,2,3,3-tetrafluoro-1- are all expressed in mole fraction and shown in Tables 4 and 5,
propanol and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol determined at and the corresponding equilibrium phase diagrams of those two
101.3 kPa is reported in Table 2 and plotted in Fig. 2. As shown systems are presented in Figs. 3 and 4, respectively. Azeotropic
in Fig. 2, the experimental dynamic viscosity of 2,2,3,3- behaviour for the two systems was not observed.
tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol
decreases with increasing temperature from 295.65 K to
3.3.2. Thermodynamic consistency test for the experimental VLE data
333.15 K. Meanwhile, three values of viscosity for 2,2,3,3-
The thermodynamic consistency of the measured VLE values for
tetrafluoro-1-propanol, 4.872 mPa
s [9] at 298.15 K, 4.861 mPa
s
the two binary systems of (methanol + 2,2,3,3,4,4,5,5-octafluoro-1-
and 2.156 mPa
s [10] at 298.15 K and 323.15 K, respectively, are
pentanol) and (2,2,3,3-tetrafluoro-1-propanol + 2,2,3,3,4,4,5,5-octa
compared to the measured values as shown in Fig. 2, and devia-
fluoro-1-pentanol) were verified by the semi-empirical Herington
tions were found. Compared to the literature, the deviations
area method [24]. With this method, the experimental results
between the measured values in this work and those in the litera-
could be considered to be thermodynamic consistent if the values
ture are 0.3218 mPa
s, 0.3108 mPa
s, 0.3078 mPa
s, respectively.
In many literature references, there are different equations to Table 4
describe the temperature dependence of viscosity [3133], in Isobaric experimental VLE values for temperature T, liquid phase x1, vapour phase y1,
which the most cited expressions to correlate viscosity at atmo- activity coefficient c, and calculated excess Gibbs energy GE for the {methanol (1)
+ 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (2)} binary system at 101.3 kPa.a
spheric pressure is VogelTammannFulcher (VTF):
No. T/K x1 y1 c1 c2 G/J
mol1
g=mPa
s expA B=T=K  T 0  2
1 413.25 0.0000 0.0000 1.0118 0.0000
where A, B, and T 0 are the adjustable parameters. As seen in Table 3, 2 390.20 0.1788 0.6147 0.5936 1.0333 334.6392
the correlation coefficient R2 for the viscosity of 2,2,3,3-tetrafluoro- 3 385.45 0.2211 0.7102 0.6360 0.9763 378.3411
4 380.00 0.2655 0.7821 0.6858 0.9584 408.0624
1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol are 0.9984 and
5 375.05 0.3174 0.8332 0.7111 0.9601 433.8480
0.9990, respectively. The three adjustable parameters are listed in 6 370.90 0.3641 0.8737 0.7406 0.9244 445.4968
Table 3. The deviations between the experimental results and those 7 366.50 0.4165 0.9041 0.7722 0.9203 446.4478
fitted by Eq. (2) were calculated, which show that the results calcu- 8 363.21 0.4586 0.9236 0.7986 0.9108 439.2744
9 361.48 0.4816 0.9341 0.8151 0.8853 432.4903
lated by the VTF equation are in a good agreement with the mea-
10 359.22 0.5101 0.9419 0.8379 0.9135 420.0403
sured viscosity, for which the maximum deviations are 0.0179 for 11 357.58 0.5336 0.9532 0.8576 0.8324 409.1073
2,2,3,3-tetrafluoro-1-propanol and 0.4469 for 2,2,3,3,4,4,5,5-octa 12 355.25 0.5645 0.9613 0.8866 0.8204 390.1823
fluoro-1-pentanol, respectively. 13 351.30 0.6387 0.9744 0.9139 0.7874 345.2047
14 348.35 0.6957 0.9815 0.9407 0.7787 300.5838
15 344.25 0.8030 0.9908 0.9581 0.7326 207.2210
3.3. Vapour-liquid equilibrium 16 342.65 0.8439 0.9927 0.9704 0.7953 165.9211
17 340.40 0.8930 0.9956 1.0026 0.7848 112.6424
3.3.1. Experimental results 18 339.20 0.9298 0.9975 1.0108 0.7233 74.0450
In this work, the vapour-liquid equilibrium for two binary 19 338.13 0.9641 0.9988 1.0178 0.7180 37.7878
20 337.45 1.0000 1.0000 1.0090 0.0000
systems of (methanol + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol)
a
and (2,2,3,3-tetrafluoro-1-propanol + 2,2,3,3, 4,4,5,5-octafluoro-1- Standard uncertainties u of temperature T, composition x1, y1 and pressure P are
pentanol) are reported. With the method mentioned in Section 2.2, u(T) = 0.3 K, u(x1) = u(y1) = 0.001 and u(P) = 0.05 kPa.

Fig. 2. Experimental viscosities, g, 2,2,3,3-tetrafluoro-1-propanol in this work (j), data in the literature (h [9], 4 [10]) and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, values in
this work (d) versus temperature, T;


calculated values.
 L. Zhang et al. / J. Chem. Thermodynamics 102 (2016) 155163 159

Table 5 of the component in the vapour phase Dy to be less than 1. This cri-
Isobaric experimental VLE data of temperature T, liquid phase x1, vapour phase y1, terion is presented as follows:
activity coefficient c, and calculated excess Gibbs energy GE for the {2,2,3,3-
tetrafluoro-1-propanol (1) + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (2)} binary system
1X N  
at 101.3 kPa.a Dy 100yexp
i  ycal
i
 5
N i1
E 1
No. T/K x1 y1 c1 c2 G /J
mol
1 413.57 0.0000 0.0000 1.0018 0.0000 where N is the number of experimental points; exp represents the
2 407.14 0.1661 0.3501 0.7959 0.9587 157.9545 experimental data points, and cal represents the values that were
3 403.52 0.2555 0.4999 0.8169 0.9309 244.8396 calculated by the NRTL model.
4 401.69 0.3011 0.5607 0.8190 0.9261 287.9292
The mean absolute deviations of the vapour phase for the above
5 399.40 0.3569 0.6299 0.8291 0.9166 338.9309
6 398.25 0.3922 0.6616 0.8196 0.9226 366.6570
two binary systems are 0.1681, and 0.9640, respectively, which
7 397.54 0.4028 0.6791 0.8364 0.9124 377.9556 indicates that the VLE measurements passed the test and are
8 395.23 0.4605 0.7348 0.8481 0.9048 421.8526 reliable.
9 394.15 0.4863 0.7629 0.8615 0.8825 439.6882
10 393.49 0.5041 0.7758 0.8623 0.8849 450.1324
3.3.3. Correlation for vapour-liquid equilibrium data
11 390.45 0.6068 0.8419 0.8540 0.8777 482.0750
12 387.75 0.6998 0.8985 0.8609 0.8147 472.0365 The vapour-liquid equilibrium relation can be expressed as
13 385.45 0.7561 0.9276 0.8861 0.7791 449.2377 follows:
14 384.15 0.8104 0.9551 0.8948 0.6891 410.3668 h i
15 383.15 0.8526 0.9752 0.8913 0.4817 340.0057 yi uVi P0 xi ci uSi PSi exp V li P0  PSi =RT 6
16 382.28 1.0000 1.0000 0.8022 0.0000
a
Standard uncertainties u of temperature T, composition x1, y1 and pressure P are Since the pressure P0 was 101.3 kPa, the Poynting factor, uSi and
V
u(T) = 0.3 K, u(x1) = u(y1) = 0.001 and u(P) = 0.05 kPa. u associated with the non-ideality of the vapour phase are all
i
close to 1, Eq. (6) were simplified to calculate activity coefficient
of |D  J| were smaller than 10 [34]. The D and J are defined by the ci considering the non-ideality of the liquid phase, which is
following equations: expressed as Eq. (7) and all calculated values are listed in Tables
D 100jA  B=A Bj 3 4 and 5:

ci Pyi =PSi xi 7
J 150jDT max =T min j 4
where xi and yi represent the equilibrium mole fraction of compo-
where A is the area above the zero line on the plot of ln(c1 =c2 ) vs. x, nent i for the liquid phase and the vapour phase, respectively; P is
and B is the area below the zero line on this plot;
the total pressure of the equilibrium system, 101.3 kPa, and PSi is
DT max T max  T min (K), T min and T max are the minimum and the
the vapour pressure of pure component i at the system tempera-
maximum boiling points, respectively. The values of |D  J| for the
ture. Here, the vapour pressure equation by Wagner [3537] for flu-
two binary systems were 8.925, and 5.573, respectively, which
oro alcohols was selected and is as follows:
indicates that the VLE values for the two systems are consistent  
with respect to the thermodynamics. ln P Si =kPa lnP ci =kPa
Besides the Herington consistency method, the measured VLE 1:5 2:5 5
C 1i 1  T ri C 2i 1  T ri C 3i 1  T ri C 4i 1  T ri
values were also verified by the point-to-point test of the van Ness
T ri
[25] method. This test requires the mean absolute deviation
8
between the experimental values and the calculated mole fractions

Fig. 3. Equilibrium diagram for the binary system {methanol (1) + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (2)} at 101.3 kPa: d, T  x for experimental values, s, T  y for
experimental values; - - - Wilson;


NRTL.
160 L. Zhang et al. / J. Chem. Thermodynamics 102 (2016) 155163

Fig. 4. Equilibrium diagram for the binary system {2,2,3,3-tetrafluoro-1-propanol (1) + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (2)} at 101.3 kPa: , T  x for experimental
values, 4, T  y for experimental values; - - - Wilson;


NRTL.

where T ri TT , T ci represents the critical temperature and Pci repre- nents from the literature and those calculated by the Wagner equa-
ci

sents the critical pressure. For 2,2,3,3-tetrafluoro-1-propanol,
T ci 540 K, P ci 4131:59 kPa, C1 = 15.1128, C2 = 20.7171,
C3 = 29.5580, C4 = 17.6863. And for 2,2,3,3,4,4,5,5-octafluoro-1-p
entanol T ci 568 K, Pci 2889:37 kPa, C1 = 9.7230, C2 = 3.1921,
C3 = 6.3051, C4 = 4.6540. And the equation is valid for tempera-
ture from 381 K to 540 K for 2,2,3,3-tetrafluoro-1-propanol and
180 K to 568 K for 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, respec-
tively. The constant values for fluoro alcohols were obtained
directly from the Aspen property databank [38].
Considering the literature data for vapour pressure for the pure
compounds studied, methanol and 2,2,3,3-tetrafluoro-1-propanol
[2,39,40], the comparisons of the vapour pressures for the compo-
tion in this work are presented. As shown in Fig. 5, the calculated
vapour pressure of methanol is compared with those of the work
of Safarov [39] and Osada [40], which shows good agreement with
the literature values. Meanwhile, since the temperature range of
the vapour pressure for 2,2,3,3-tetrafluoro-1-propanol is different
between the study by Rochester [2] and this work, the Wagner
equation was extrapolated to the temperature range covered
Rochesters work. As shown in Fig. 6, a better agreement can be
found, which indicates that the Wagner equation has a reliability
in calculating the vapour pressure for 2,2,3,3-tetrafluoro-1-
propanol. Also the vapour pressure for 2,2,3,3,4,4,5,5-octafluoro-1
-pentanol was calculated by the Wagner equation, and no

Fig. 5. Comparisons between vapour pressure of methanol in Safarovs work, Osadas work and this work.
 L. Zhang et al. / J. Chem. Thermodynamics 102 (2016) 155163 161

Fig. 6. Comparisons of the vapour pressure of 2,2,3,3-tetrafluoro-1-propanol in Rochesters work and this work.

comparison was made due to the lack of literature data for 2,2,3, where N is the number of experimental data; r is standard devia-
3,4,4,5,5-octafluoro-1-pentanol. tion; T, P, x, and y are equilibrium temperature, pressure, liquid
The VLE experimental data of the two binary systems at phase mole fraction, and vapour phase mole fraction, respectively;
101.3 kPa were correlated by the Wilson [26] and NRTL [27] activ- and the superscripts of exp and cal represent the experimental
ity coefficient models, which were defined as follows: and calculated values, respectively.
X  X .X The optimized binary interaction parameters, the root mean
Wilson: ln ci 1  ln j
Aij x j  j
A ji x j A x
k jk k
9 square deviation (RMSD), the average absolute deviation (AAD)
for the equilibrium temperature (T) and the vapour phase compo-
where ln Aij aij bij =T. sition (y1) of the three models are listed in Table 6. Meanwhile, the
X xj sji Gji X xj Gij  P 
m xm smj Gmj
comparison between the calculated results and the determined
NRTL: ln ci P P s ij  P
data was represented graphically in Figs. 3 and 4, which indicate
k xk Gki k xk Gkj k xk Gkj
j j
that the regressed values are in good agreement with the measure-
10
ments. Therefore, both the Wilson and NRTL models are suitable
where sij aij bij =T; Gij expaij sij . for the correlation for the two binary systems.
The binary interaction parameters of those two models were The excess Gibbs energy GE was calculated in this work and the
obtained on the basis of the maximum likelihood method, and values used to evaluate the non-ideality of the two binary systems.
the objective function is defined as follows: The GE was calculated by the following equation:
2 !2 !2
X
N
T exp  T cal Pexp  Pcal GE RTx1 ln c1 x2 ln c2 12
OF 4 i i
i i

i1
T rP r where the activity coefficient ci was calculated by the NRTL model
 2  exp 2 # with the binary parameters listed in Tables 4 and 5. The excess
xexp  xcal yi  ycal
i i
i
11 Gibbs energy of the two binary systems plotted against the mole
rx ry fraction of 2,2,3,3-tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5-octa

Table 6
The binary interaction parameters, the root mean square deviation (RMSD) and the average absolute deviations (AAD) for the equilibrium temperature (T) and the vapour phase
composition (y1) of the Wilson and NRTL activity coefficient models.

Model Binary interaction parameters RMSD AAD

aij aji bij/K bji/K a y1a T/Kb d(y1)c d(T)d
Methanol (1) + 2,2,3,3-tetrafluoro-1-propanol (2)
Wilson 3.83 1.19 1089.08 260.38 0.003 0.30 0.002 0.27
NRTL 0.60 2.86 704.01 534.31 0.3 0.003 0.33 0.002 0.30
2,2,3,3-Tetrafluoro-1-propanol (1) + 2,2,3,3-tetrafluoro-1-propanol (2)
Wilson 1.85 3.82 1183.53 955.40 0.012 0.53 0.010 0.43
NRTL 3.65 1.69 904.17 1201.03 0.3 0.011 0.61 0.010 0.48
q

a PN  cal exp 2
RMSD (y) = i1 yi  yi =N .
r
2
b PN  cal exp
RMSD (T) = i1 T i  T i =N .
c Pn  cal exp 

d (y1) = n 1 y1  y1 .
1

P  exp 

d
d (T) = 1n n1 T cal
1  T 1 .
162 L. Zhang et al. / J. Chem. Thermodynamics 102 (2016) 155163
Fig. 7. Excess Gibbs energy calculated from the NRTL model versus mole fraction of liquid composition: methanol (1) + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol
(2); - - - 2,2,3,3-tetrafluoro-1-propanol (1) + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (2).
fluoro-1-pentanol is shown in Fig. 7. Both binary systems show neg-
ative deviations from Raoultss law over the whole composition
range.
4. Conclusions
The measurement for density, viscosity of pure 2,2,3,3-
tetrafluoro-1-propanol and 2,2,3,3,4,4,5,5-octafluoro-1-pentanol
with different temperatures at 101.3 kPa is reported. The density
was correlated as a function of temperature by a second-order
polynomial, and the viscosity was correlated by VogelTam
mannFulcher equation. The results show good agreement with
the experimental results. The correlation coefficients R2 for density
and viscosity are 0.9982, 0.9984 for 2,2,3,3-tetrafluoro-1-propanol
and 0.9975, 0.9990 for 2,2,3,3,4,4,5,5-octafluoro-1-pentanol,
respectively.
Meanwhile, the isobaric VLE for the two binary systems of
(methanol + 2,2,3,3,4,4,5,5-octafluoro-1-pentanol) and (2,2,3,3-
tetrafluoro-1-propanol + 2,2,3,3, 4,4,5,5-octafluoro-1-pentanol)
were determined at atmospheric pressure of 101.3 kPa by using a
modified Rose type equilibrium still. The Herington area method
and that of the van Ness point to point test method confirmed the
thermodynamic consistency of the experimental VLE values. For
the Herington semi-empirical method, the values of |D  J| are
8.925 and 5.573, respectively, and for van Ness test, Dy for the
two binary systems are 0.1681 and 0.9640, respectively. No azeo-
tropic point was observed for the two binary systems. The correla-
tions of the VLE values for (2,2,3,3-tetrafluoro-1-propanol
+ 2,2,3,3,4,4,5,5-octafluoro-1-pentanol) and (methanol + 2,2,3,3,4,
4,5,5-octafluoro-1-pentanol) were correlated by the Wilson and
NRTL activity coefficient models and the corresponding binary
interaction parameters were regressed. Negative deviation beha-
viour was observed for both binary systems. The binary interaction
parameters obtained can be used in the separation process for opti-
mization and design.
Acknowledgement
This work was supported by the National Scientific Research
Found of China (NSC 21306106).
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JCT 16-307