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Fluid Phase Equilibria 200 (2002) 287293

Isobaric vapourliquid equilibria data for the binary system


1-propanol + 1-pentanol and isobaric vapourliquidliquid
equilibria data for the ternary system
water + 1-propanol + 1-pentanol at 101.3 kPa
Juan Carlos Asensi, Julia Molt, Mara del Mar Olaya,
Francisco Ruiz, Vicente Gomis
Departamento de Ingeniera Qumica, Universidad de Alicante, Apartado 99, 03080-Alicante, Spain
Received 7 December 2001; accepted 29 January 2002

Abstract
Consistent vapourliquid equilibrium (VLE) data for the binary system 1-propanol+1-pentanol and for the ternary
system water + 1-propanol + 1-pentanol are reported at 101.3 kPa. An instrument using ultrasound to promote the
emulsification of the partly miscible liquid phases have been used in the determination of the vapourliquidliquid
equilibrium (VLLE). The VLE and VLLE data were correlated using UNIQUAC. 2002 Elsevier Science B.V.
All rights reserved.
Keywords: Vapourliquidliquid equilibrium; Data; Water; 1-Propanol; 1-Pentanol

1. Introduction
Heterogeneous azeotropic distillation is a widely used technique for separating binary azeotropic mixtures into their components. The technique works by adding a third component, which causes liquidliquid
phase separation over a broad range of compositions in the ternary phase diagram. This is an efficient
method for moving across distillation boundaries caused by the presence of azeotropes in the mixture.
Many examples show the importance of heterogeneous azeotropic distillation [1,2]. However, the number
of ternary systems for which experimental vapourliquidliquid equilibrium (VLLE) data are published
is very limited.
For example, if we consider the ternary system water + 1-propanol + 1-pentanol at 101.3 kPa, we can
find published sets of data for the following sub-systems: vapourliquid equilibrium (VLE) for the binary
system water + 1-propanol (for example in [3]), VLE for the binary system water + 1-pentanol (for

Corresponding author. Tel.: +34-96-590-3400; fax: +34-96-590-3826.


E-mail address: vgomis@ua.es (V. Gomis).
0378-3812/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 ( 0 2 ) 0 0 0 4 0 - 7

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J.C. Asensi et al. / Fluid Phase Equilibria 200 (2002) 287293

example in [4]), VLE for the ternary system [5] and LLE for the ternary system at different temperatures
[6]. For the binary system 1-propanol+1-pentanol Villa Rivera [7] obtained VLE data at 53 and 100.9 kPa,
(but only partially since the vapor compositions were not obtained experimentally), and Mara et al. [8]
reported isothermal data at 313.15 K. Isobaric VLE data for the binary system 1-propanol + 1-pentanol
and VLLE for the ternary system have not been reported at 101.3 kPa.
The objective of the present paper is to complete the system determining experimentally the isobaric VLE of the binary system 1-propanol + 1-pentanol and the VLLE of the ternary system water +
1-propanol + 1-pentanol at 101.3 kPa.
2. Experimental section
2.1. Chemicals
The organic liquids used were obtained from Merck: 1-propanol, 1-pentanol, and 2-propanol had
nominal purities >99.5, >98.5, and >99.7 mass%, respectively. The 2-propanol was used as the internal
standard for chromatography. All chemicals were used as supplied after chromatography failed to show
any significant organic impurities. The KarlFischer method determined that the water content in the
chemicals was negligible. The water used was ultrapure (nanopure Barnstead ultrapure system).
2.2. Apparatus and procedure
The vessel used in this work was an all-glass, dynamic recirculating still equipped with a Cottrell
pump (Labodest model manufactured by Fischer Labor und Verfahrenstechnik, Germany). However, a
modification to this commercial apparatus was made to determine VLLE data where a perfect mixture
of the circulating heterogeneous liquid is necessary. The modification consists of an ultrasound system
(Braun Labsonic L) that is coupled to the boiling flask. The incoming liquid is dispersed immediately and
forced upwards producing a global agitation of the liquid in the boiling flask. The resultant instrument is
described in detail in a previous paper [9]. In this paper, it was shown that the instrument works perfectly
in the determination of VLLE data for binary and ternary systems.
The equilibrium temperatures were measured by means of a Pt-100 thermometer connected to an
ERTCO-Hart (model 5614) with an uncertainty of 0.006 K according to the certificate of calibration
(scale ITS 90 [10]). A Fischer M101 phase equilibrium control system was used to measure and control
the pressure and the heating power. The measured pressure in the still was 101.3 0.1 kPa. The pressure
measurement device was checked by measuring the normal boiling point of water.
In each experiment, after the pressure was fixed, heating and shaking of the initial liquid mixture was
started. The still was operated until equilibrium was reached. Equilibrium conditions were assumed when
temperature and pressure remained constant for at least 30 min. After this, sampling of the different phases
was carried out as explained elsewhere [9].
The analysis of the equilibrium phases was carried out using a gas chromatograph Shimadzu GC-14B
coupled with a personal computer using the Shimadzu CLASS-VP Chromatography Data System. Separation of the components was achieved on a 2 m 3 mm column packed with Porapack Q 80/100. To
determine the amount of 1-propanol and 1-pentanol, a flame ionization detector (FID) was used. The
water was analyzed using a thermal conductivity detector (TCD). A column temperature program was

J.C. Asensi et al. / Fluid Phase Equilibria 200 (2002) 287293

289

used: initial temperature = 160 C, initial time = 8 min, rate of column oven temperature rise = 40 C
min1 , final temperature = 200 C and final time = 7 min. The helium flow rate was 50 ml min1 . To
obtain quantitative results the external standard method was applied for the analysis of the vapour phases.
For the analysis of the liquid phases the internal standard method was used. The standard compound
used for this purpose was 2-propanol which is completely miscible with water and the organic phase.
The addition of 2-propanol prevents phase separation effects when changing the temperature after the
separation of the phases. The relative accuracy of the mole fraction measurements was 2%.

3. Results and discussion


Binary VLE data for the binary system 1-propanol + 1-pentanol at 101.3 kPa are presented in Table 1
and Fig. 1. These binary data were found to be thermodynamically consistent as tested by Fredenslunds
consistency test [11].
VLLE measurements for the ternary system water + 1-propanol + 1-pentanol at 101.3 kPa are listed
in Table 2. Fig. 2 shows these data: tie-lines which connect conjugated liquid phases, the vapour line and
also the non-isothermal binodal curve. The ternary VLLE experimental data were found to be thermodynamically consistent as tested by the point-to-point LW method of Wisniak [12]. All the values of
D = 100(L W)/(L + W) were less than 2. Vapour pressures were calculated with the Antoine equation,
whose parameters Ai , Bi and Ci for water, 1-propanol and 1-pentanol were taken from [13]. The tests
used do not reveal any substantial inconsistency in the data.
Table 1
Experimental VLE data (mole fraction) for the binary system 1-propanol (1) + 1-pentanol (2) at 101.3 kPa
T (K)

370.85
371.97
372.77
374.67
375.02
375.57
377.38
380.30
382.11
384.44
388.68
395.29
397.57
400.90
403.15
405.25
406.51
407.65
408.68

Liquid phase

Vapour phase

x1

x2

y1

y2

0.965
0.928
0.900
0.811
0.795
0.778
0.721
0.627
0.575
0.502
0.394
0.250
0.204
0.145
0.110
0.077
0.057
0.042
0.028

0.035
0.072
0.100
0.189
0.205
0.222
0.279
0.373
0.425
0.498
0.606
0.750
0.796
0.855
0.890
0.923
0.943
0.958
0.972

0.993
0.979
0.971
0.957
0.952
0.947
0.928
0.881
0.848
0.804
0.722
0.580
0.512
0.402
0.320
0.232
0.189
0.139
0.092

0.007
0.021
0.029
0.043
0.048
0.053
0.072
0.119
0.152
0.196
0.278
0.420
0.488
0.598
0.680
0.768
0.811
0.861
0.908

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Fig. 1. VLE diagram for the binary system 1-propanol + 1-pentanol at 101.3 kPa.

The UNIQUAC equation was used to correlate the seven ternary experimental VLLE data presented
in this paper. The data were treated as seven LLE data and fourteen VLE data. Equilibrium data of the
other regions of the system were included in the correlation. The number of equilibrium data of each one
of them was choosen to give similar weight to all the equilibrium regions: 34 VLE data of the ternary
system [5], 9 VLE data of the system water + 1-propanol [3], 9 VLE data of water + 1-pentanol [4] and
5 VLE data of 1-propanol + 1-pentanol (this work). The pure component molecular structure constants
for the UNIQUAC equation were those included in the databank of CHEMCAD V [14]. An ideal vapour
phase was assumed. For the purpose of fitting the parameters, a non-linear optimization method was used
to minimize the following objective function:



NV 
NV
NL
1000  Pexp Pcal 2  1   exp cal 2 1000  
OF =
+
(xexp xcal )2
NV
Pexp
exp
NV
NL

Table 2
Experimental VLLE data (mole fraction) for the ternary system water (1) + 1-propanol (2) + 1-pentanol (3) at 101.3 kPa
T (K)

368.95
368.15
367.05
365.60
364.68
364.01
363.69

Aqueous phase

Organic phase

Vapour phase

x1

x2

x3

x1

x2

x3

y1

y2

y3

0.996
0.993
0.988
0.977
0.972
0.963
0.952

0.0028
0.0069
0.018
0.022
0.030
0.040

0.0040
0.0046
0.0046
0.0047
0.0051
0.0064
0.0080

0.421
0.430
0.440
0.491
0.564
0.671
0.735

0.039
0.094
0.172
0.202
0.187
0.167

0.579
0.540
0.466
0.337
0.234
0.142
0.098

0.863
0.834
0.794
0.749
0.720
0.702
0.688

0.045
0.105
0.175
0.220
0.248
0.266

0.137
0.121
0.101
0.077
0.060
0.050
0.046

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291

Fig. 2. Representation of the tie-lines which connect conjugated liquid phases, the non-isothermal binodal curve, and the vapour
line for the ternary system water +1-propanol+1-pentanol at 101.3 kPa: bin, T = 368.95 K; 1, T = 368.15 K; 2, T = 367.05 K;
3, T = 365.60 K; 4, T = 364.68 K; 5, T = 364.01 K; 6, T = 363.69 K.

where P is the pressure, the liquid-phase activity coefficients, x the mole fraction, NV the number of
VLE data and NL is the number of LLE tie-lines. Factors 1000/NV, 1/NV and 1000/NL were chosen to
give similar weight to each one of the terms of the objective function.
The interaction parameters obtained and the mean absolute deviation are reported in Table 3. Mean
absolute deviations (MAD) between experimental and calculated vapour phase mole fractions and pressures were MAD(y water ) = 0.05, MAD(y1-propanol ) = 0.03, MAD(P ) = 5.6 kPa. For the liquid phases in
the LLE MAD(x) = 0.04. Therefore, a not too satisfactory correlation of the experimental temperaturecomposition results was obtained with the model.

Table 3
Optimized UNIQUAC binary parameters. Aij (K) for binary and ternary VLE and VLLE data of the system water (1)+1-propanol
(2) + 1-pentanol (3) at 101.3 kPa.
A12
A21
A13
A31
A23
A32

200.64
9.58
212.81
104.0
7.82
58.61

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Fig. 3. LLV and LV isotherms for the ternary system water + 1-propanol + 1-pentanol at 101.3 kPa, calculated with UNIQUAC
equation as a function of the liquid mole fraction.

Fig. 4. Vapour phase composition for the ternary system water + 1-propanol + 1-pentanol at 101.3 kPa calculated with the
UNIQUAC equation as a function of the liquid mole fraction; the basic grid represents the liquid composition (xi ); the parametric
curves indicate equilibrium vapour mole fractions of 1-propanol () and 1-pentanol (- - -).

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293

Fig. 3 shows the isotherms of the ternary system as a function of liquid mole fraction. In Fig. 4, the mole
fraction of component i in the liquid, xi , is represented by the basic grid, and the vapour mole fraction,
yi , in equilibrium with the liquid is shown as parametric curves.
List of symbols
MAD
mean absolute deviation
NL
number of LLE tie-lines
NV
number of VLE data
OF
objective function
P
pressure
x
mole fraction
Greek letter

activity coefficient
Subscripts
cal
calculated
exp
experimental
Acknowledgements
The authors wish to thank the Ministerio de Ciencia y Tecnologa for financial support of Project
BQU2000-0212.
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