Fluid Phase Equilibria 259 (2007) 23–32

High-pressure vapor–liquid equilibria for CO2 + alkanol systems

and densities of n-dodecane and n-tridecane
Octavio Elizalde-Solis, Luis A. Galicia-Luna ∗ , Luis E. Camacho-Camacho
Instituto Politécnico Nacional, ESIQIE, Laboratorio de Termodinámica, UPALM, Edif. Z, Secc. 6, 1ER piso,
Lindavista, C.P. 07738, México, D.F., Mexico
Received 31 December 2006; received in revised form 11 April 2007; accepted 12 April 2007
Available online 24 April 2007

Abstract
An apparatus based on the static-analytic method was used to measure the vapor–liquid equilibria (VLE) for CO2 + alkanol systems. Equilibrium
measurements for the CO2 + 1-propanol system were performed from 344 to 426 K. For the case of the CO2 + 2-propanol system, measurements
were made from 334 to 443 K, and for the CO2 + 1-butanol were obtained from 354 to 430 K. VLE data were correlated with the Peng–Robinson
equation of state using the classical and the Wong–Sandler mixing rules. Moreover, compressed liquid densities for the n-dodecane and n-tridecane
were obtained via a vibrating tube densitometer at temperatures from 313 to 363 K and pressures up to 25 MPa. The Starling and Han (BWRS),
and The five-parameter Modified Toscani-Swarcz (MTS) equations were used to correlate them. The experimental density data were compared
with those from literature, and with the calculated values obtained from available equations for these n-alkanes.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Vapor–liquid equilibria; Density; Alkanes; Alkanols; Carbon dioxide

1. Introduction
Accurate thermodynamic data as volumetric properties
and phase equilibria of pure compounds and mixtures (i.e.
CO2 + alkanes, CO2 + alkanols) are of great significance in the
chemical, oil and biotechnology areas, and for the development
and validation of thermodynamic models. In this context, it is
especially important to know the global phase behavior of sys-
tems within the range of working pressures and temperatures.
Carbon dioxide in combination with alkanols is an attractive
supercritical solvent [1,2], but there is a lack of VLE data for
some binary systems containing CO2 and alkanols at high tem-
peratures. In addition, accurate densities of alkanes are required
as basic information for process development. The volumetric
properties for alkanes reported here are part of a project focused
on sulfur compound extraction from commercial fuels using
supercritical fluids to fulfill sulfur content regulations in mexi-
can fossil fuels [3]. Measurements of phase equilibrium of the
binary systems and the volumetric properties of the fluids stud-
∗ Corresponding author. Tel.: +52 55 5729 6000x55133;
fax: +52 55 5586 2728.
E-mail address: lgalicial@ipn.mx (L.A. Galicia-Luna).
ied in this work constitute a set of experimental data, which are
part of a project currently undergoing at the Thermodynamics
Laboratory of the E.S.I.Q.I.E. (Instituto Politécnico Nacional of
Mexico).
In this work, measurements of vapor–liquid equilibria for
the CO2 + 1-propanol, CO2 + 2-propanol and CO2 + 1-butanol
systems were performed using a static-analytic apparatus. The
experimental data for each binary mixture were compared with
those reported in literature and good agreement with published
sets of data is observed. The degree of smoothness in the
equilibrium ratios in both binary mixtures indicates an excel-
lent internal consistency of the experimental measurements. In
addition, compressed liquid densities for n-dodecane and n-
tridecane are reported from 313 to 363 K in the pressure range
of 1–25 MPa. The obtained densities were found in agreement
with those reported in literature.
2. Experimental
2.1. Materials
Purities and critical properties of the chemical substances
used for the experimental measurements are presented in

0378-3812/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2007.04.023
24 O. Elizalde-Solis et al. / Fluid Phase Equilibria 259 (2007) 23–32

Table 1 desired value by adding or removing CO2 from the cell. When
Characteristics of materials temperature and pressure remained constant, about 1 ␮l of the
Chemicals CAS number Purity (%) Supplier CO2 + alkanol mixture (vapor or liquid phase) was taken using
Carbon dioxide [124-38-9] 99.995 Infra, Mexico
a ROLSITM sampler-injector [4] and sent to the GC through a
Helium [7440-59-7] 99.998 Infra, Mexico thermoregulated line to ensure the complete vaporization of the
Nitrogen [7727-37-9] 99.998 Infra, Mexico sample. Mole fractions of each phase were determined by taking
1-Propanol [71-23-8] 99.7 (anhydrous) Aldrich, USA as minimum five consecutive samples. Composition uncertain-
2-Propanol [67-63-0] 99.5 (anhydrous) Aldrich, USA ties were calculated to be within ±1%. The isothermal envelopes
1-Butanol [71-36-3] 99.8 (anhydrous) Aldrich, USA
n-Dodecane [112-40-3] >99 (anhydrous) Sigma, USA
were obtained by fixing a new pressure to measure the vapor and
n-Tridecane [629-50-5] >99 Aldrich, USA liquid mole fraction. Some critical points were obtained for the
Water [7732-18-5] 99.95 HPLC Aldrich, USA CO2 + 1-propanol, and + 2-propanol systems following the same
procedure described by Silva-Oliver et al. [2].

Tables 1 and 2, respectively. Gases were used as received. Alka-
nes and alkanols were used without any further purification,
except for a careful degassing before these were used.
2.2. Procedure
2.2.1. Static-analytic view cell
The static-analytic apparatus used to measure vapor–liquid
equilibrium has been previously tested [1,2]. The maximum tem-
perature and pressure of the view cell are 673 K and 60 MPa.
The high-pressure view cell is connected on-line to a gas chro-
matograph (GC5890 II, Hewlett-Packard) for the mole fraction
determination. An Isco syringe pump (100 DM, USA) is used
to feed CO2 . Two platinum probes Pt100 (Specitec, France)
connected to a digital indicator (F250, Automatic Systems Lab-
oratories, USA) were used for reading the cell temperature.
Pressure inside the cell was measured with a pressure transducer
(PDCR 910-1756, Druck, UK) connected to a digital indicator
(DPI 145, Druck, UK). The calibration procedures for the tem-
perature probes and the pressure transducer gives uncertainties
estimated to be within ±0.03 K, and ±0.04%, respectively, as
previously described [1].
The gas chromatograph is equipped with a thermal conduc-
tivity detector (TCD). A stainless steel 1/8 in. packed column
(Porapak Q 80/100, Alltech) was used for the sample separation.
A column length of 4-ft at 443 K, and 473 K in the TCD were
the conditions used for the CO2 + 1-propanol, or +2-propanol
systems. For the CO2 + 1-butanol system, samples were sepa-
rated in a column length of 3 ft and at 468 K, and the TCD was
thermoregulated at 483 K.
First, n-alkanol was loaded in the high-pressure view cell,
and it was degassed under vigorous stirring. The cell was fed
with CO2 by means of the syringe pump. Then, the air bath was
set to the desired temperature. Meanwhile, pressure was set to a
Table 2
Critical properties and acentric factor of pure components [16]
Tc (K) pc (MPa)
CO2 304.12 7.374
1-Propanol 536.78 5.175
2-Propanol 508.30 4.762
1-Butanol 563.05 4.423
n-Dodecane 658.00 1.820
n-Tridecane 675.00 1.680
2.2.2. Static-synthetic view cell
A complete description of this apparatus has been given by
Zúñiga-Moreno et al. [5]. The apparatus is mainly constituted of
a variable volume cell made of sapphire containing a piston for
the sample compression. The cell is coupled to a vibrating U-
tube densitometer, (DMA 60/512P, Anton Paar). A cathetometer
equipped with a camera allows an enlarged visualization of the
sapphire tube. An air bath and liquid bath are used to heat the
cell and densitometer, respectively. Platinum probes Pt100 (Spe-
citec, France) connected to a digital indicator (F250, Automatic
Systems Laboratories) were used to monitor temperature in the
cell and densitometer with an estimated uncertainty of ±0.03 K.
Pressure measurements (uncertainty within ±0.008 MPa) were
made with a pressure transducer (250, Sedeme) connected to
a digital multimeter (34401A, HP). The densitometer calibra-
tion was carried out following the classical method described
elsewhere [5,6]. Water and nitrogen were used as reference flu-
ids. Densities for water and nitrogen were calculated with the
equations of state proposed by Wagner and Pruß [7], and Span
et al. [8], respectively. Experimental densities were obtained
according with the following equation,
ρF (p, T ) = ρH2 O (p, T )
[μ2F (p, T )−μ2H2 O (p, T )][ρH2 O (p, T )−ρN2 (p, T )]
+
μ2H2 O (p, T )−μ2N2 (p, T )
(1)
where ρF (p,T) is the studied fluid density, ρH2 O (p, T ) and
ρN2 (p, T ) are the reference fluid densities, in kg m−3 , μi (p,T)
are the vibrating periods in s−1 for each fluid at the same condi-
tions of temperature and pressure. The estimated uncertainties
of experimental densities were ±0.20 kg m−3 . They were cal-
culated with the law of propagation of errors, as described
elsewhere [9].
The sapphire cell was first loaded with about 10 ml of the
alkane, and was placed in the air bath to be connected to the den-
sitometer. The pure component and the apparatus were degassed
ω by a vacuum pump. Then, these were set to the same temperature,
0.225 and the cell was carefully pressurized by moving the piston with
0.629 the help of a gas compressor, which uses nitrogen as pressuring
0.665 fluid. The feeding valve was open to fill full the densitometer
0.590 with the n-alkane.
0.576
0.618
At constant temperature from 1 to 25 MPa, the vibrating
period of the substance displayed in the universal counter (5313
 O. Elizalde-Solis et al. / Fluid Phase Equilibria 259 (2007) 23–32 25

Table 3
Experimental vapor–liquid equilibria for the CO2 + 1-propanol system
T = 344.82 K T = 373.16 K

p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2

11.457 0.607 0.944 12.063 0.493 0.938

12.024 0.695 0.907 13.740 0.597 0.917
12.233 0.753 0.894 14.561 0.690 0.869
12.321 0.802 0.889 14.774 0.729 0.852
14.855 0.744 0.842
14.875 0.756 0.831
14.978 0.769 0.821

T = 397.48 K T = 426.68 K

p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2

12.348 0.417 0.877 10.602 0.177 0.794

14.052 0.486 0.858 12.505 0.251 0.735
15.436 0.620 0.822 14.432 0.356 0.643
15.759 0.689 0.785 14.934 0.409 0.603
15.769 0.705 0.781 15.270 0.511 0.565
15.335 0.540 0.540

A, HP) was registered to calculate the n-alkane densities. A new
temperature was fixed to start again with the vibrating period
readings.
3. Results and modelling
3.1. Vapor liquid equilibria
High-temperature vapor–liquid equilibrium (VLE) data for
the CO2 + 1-propanol system were measured at 344.82, 373.16,
397.48, 426.68 K near the critical pressure, and are presented in
Table 3. The critical point was only measured at 426.68 K for the
studied system. Equilibrium ratios (Ki = yi /xi ) for this mixture
show good internal consistency of the experimental data, and
converge to the unity at the critical point. These are presented in
Fig. 1.
For the CO2 + 2-propanol system, the vapor–liquid equilib-
rium measurements were performed from 334.04 to 443.46 K,
and three critical points were also obtained. These data are
listed in Table 4. VLE measurements were compared with those
reported in literature at ∼334 K in Fig. 2. A good trend was found
with the data reported by Suzuki et al. [10] and Radosz [11].
However, in Fig. 3 is observed some discrepancy with the data
reported by Radosz [11] at ∼354 K, it could be due to the slight
difference in measurement temperatures. In Fig. 4 is observed
that the experimental data are internally consistent due to their
smoothness degree, and collapse onto a single value, the criti-
cal point. K-values higher than 1 correspond to CO2 ; whereas,
K-values lower than 1 correspond to 2-propanol.
VLE data for the CO2 + 1-butanol system were obtained at
354.06, 398.98, and 430.25 K. These are presented in Table 5.

Fig. 1. Vapor–liquid equilibrium ratios for the CO2 + 1-propanol system. (䊉) Fig. 2. Vapor–liquid equilibrium data comparison for the CO2 + 2-propanol sys-
344.82 K; () 373.16 K; () 397.48 K; (♦) 426.68 K. Solid lines represent the tem at ∼334 K. (䊉) 334.04 K, this work; () 333.70 K, Suzuki et al. [10]; ()
calculated data using the PR EoS with the Wong–Sandler mixing rules. 334.88 K, Radosz [11].
26 O. Elizalde-Solis et al. / Fluid Phase Equilibria 259 (2007) 23–32

Table 4
Experimental vapor–liquid equilibria for the CO2 + 2-propanol system
T = 334.04 K T = 344.23 K T = 353.72 K T = 373.18 K

p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2

9.187 0.644 0.966 2.030 0.060 0.940 10.074 0.566 0.950 10.490 0.474 0.912
9.912 0.767 0.954 3.575 0.125 0.967 11.153 0.671 0.934 12.039 0.585 0.898
10.166 0.819 0.939 4.944 0.196 0.972 11.854 0.741 0.910 12.981 0.676 0.864
10.350 0.871 0.925 6.570 0.312 0.975 12.043 0.771 0.887 13.351 0.747 0.816
10.354 0.888 0.888 8.025 0.424 0.972 12.166 0.794 0.874 13.383 0.758 0.809
8.659 0.467 0.969 12.192 0.802 0.866
9.487 0.551 0.961 12.210 0.828 0.828
10.356 0.666 0.951
10.612 0.702 0.945
10.826 0.734 0.926
11.027 0.781 0.916
11.115 0.808 0.905
11.145 0.842 0.910

T = 398.62 K T = 413.45 K T = 432.58 K T = 443.46 K

p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2

9.588 0.306 0.872 5.028 0.161 0.809 10.049 0.274 0.733 3.334 0.069 0.443
10.689 0.373 0.859 6.145 0.202 0.822 11.392 0.377 0.704 4.264 0.102 0.515
11.998 0.462 0.843 6.964 0.237 0.831 12.155 0.428 0.676 5.138 0.136 0.560
13.406 0.582 0.802 8.082 0.284 0.835 12.782 0.509 0.641 6.321 0.176 0.607
13.788 0.614 0.760 9.011 0.326 0.831 12.864 0.527 0.631 7.240 0.214 0.620
9.940 0.368 0.825 12.933 0.569 0.569 8.508 0.268 0.634
10.882 0.415 0.818 9.785 0.329 0.644
11.804 0.465 0.797 11.029 0.400 0.633
13.109 0.589 0.676 11.610 0.459 0.585

Experimental results in terms of equilibrium ratios were com- The VLE data for these systems were correlated with the
pared with those reported in literature at ∼354 K in Fig. 5. Taking Peng–Robinson equation of state (PR EoS) [14] using classical
into account the differences in temperature, good trend was and Wong–Sandler [15] mixing rules. The PR EoS is expressed
observed between our VLE measurements and those reported as
by Silva-Oliver and Galicia-Luna [12] as can be observed. Nev-
ertheless, the data reported in this work disagree with those RT a(T )
p= − (2)
reported by Chen et al. [13]. Moreover, according to the VLE v − b v(v + b) + b(v − b)
behavior for the K-values, those data present some inconsistency
for the heavy component.

Fig. 4. Vapor–liquid equilibrium ratios for the CO2 + 2-propanol system. (䊉)
334.04 K; () 344.23 K; () 353.72 K; (♦) 373.18 K; () 398.62 K; ( )
Fig. 3. Vapor–liquid equilibrium data comparison for the CO2 + 2-propanol 413.45 K; (×) 432.58 K; (夽) 443.46 K. Solid lines represent the calculated data
system at ∼354 K. (䊉) 353.72 K, this work; () 354.49 K, Radosz [11]. using the PR EoS with the Wong–Sandler mixing rules.
 O. Elizalde-Solis et al. / Fluid Phase Equilibria 259 (2007) 23–32 27

Table 5
Experimental vapor–liquid equilibria for the CO2 + 1-butanol system
T = 354.06 K T = 398.98 K T = 430.25 K

p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2 p (MPa) xCO2 yCO2

2.067 0.096 0.989 2.125 0.080 0.942 2.369 0.074 0.838

3.569 0.169 0.989 3.537 0.134 0.949 4.114 0.134 0.877
5.078 0.239 0.989 5.005 0.188 0.955 5.554 0.175 0.901
6.453 0.301 0.988 6.569 0.241 0.956 7.047 0.224 0.912
8.179 0.384 0.986 8.231 0.307 0.955 8.591 0.275 0.913
9.581 0.457 0.983 9.566 0.358 0.953 10.108 0.324 0.910
10.487 0.506 0.981 11.024 0.416 0.950 11.492 0.375 0.903
11.976 0.602 0.975 12.528 0.478 0.944 13.048 0.450 0.895
12.984 0.683 0.951 14.009 0.545 0.934 14.511 0.523 0.883
15.527 0.622 0.909 16.127 0.609 0.843

where p and T are the pressure and temperature, v the molar with
volume. a(T) and b are the parameters obtained from the critical  a  (bi − (ai /RT )) + (bj − (aj /RT ))
temperature Tc and critical pressure pc , and the acentric factor ω b− = (1 − kij )
RT ij 2
of each pure component. The critical properties and the acentric
(6)
factor taken from literature [16] are presented in Table 2.
For mixtures, the classical mixing rule is used to determinate and
the EoS constants as follows  
  ai Gexc
γ
am = xi xj (ai aj )1/2 (1 − kij ) (3) am = bm xi + (7)
bi C
i j i
√ √
 For the PR EoS C = ln( 2 − 1)/ 2 and Gexc γ is the excess
bm = xi bi (4)
Gibbs energy. The activity coefficient model used in Eqs. (5)
i
and (7) is the NRTL model [17]:
where kij is the interaction parameter for the binary mixture. 
The Wong–Sandler mixing rule is represented as: τji gji xj
Gexc  j
   γ
= xi  (8)
xi xj b − RTa
ij RT gki xk
i
i j
bm =  Gexc
(5) k
1− xi biaRT
i
− γ
CRT δij
i τij = (9)
RT
gij = exp(−αij τij ) (10)

For these CO2 + alkanol systems the nonrandomness parameter

αji was fixed to 0.3. The interaction parameters k12 , and τ 12 , τ 21
(NRTL model parameters) were obtained by a VLE calculation
algorithm by minimizing the following objective function, F:
⎡  2  cal 2 ⎤
NP  Nc
yijcal − yijex pj − pex
F= ⎣ +
j ⎦ (11)
yijex pex
j
j=1 i=1

using the Levenberg–Marquardt method [18]. Here NP is the

number of data points, Nc the number of components, y the
vapor mole fraction, and the superscripts cal and ex denotes the
calculated and experimental values, respectively.
The correlated results show good agreement with the exper-
imental values for the CO2 + alkanol systems. The percentage
deviation for the bubble pressure was calculated by
Fig. 5. Comparison of the vapor–liquid equilibrium ratios for the CO2 + 1-
butanol system. (䊉) 354.06 K; () 398.98 K; () 430.25 K; () 355.38 K, 
NP
Silva-Oliver and Galicia-Luna [12]; (×) 353.15 K, Chen et al. [13]. Solid lines 100 |pex
i − pi |
cal
p = (12)
represent the predicted data using the PR EoS with the Wong–Sandler mixing NP pex
i
rules. i=1
28 O. Elizalde-Solis et al. / Fluid Phase Equilibria 259 (2007) 23–32

Table 6
Interaction parameters, deviations in pressure and vapor mole fraction from correlations
System CO2 + alkanol T (K) PR EoS with classical mixing rule PR EoS with Wong–Sandler mixing rule

k12 p (%) y k12 NRTL parameters p (%) y

τ 12 (kJ mol−1 ) τ 21 (kJ mol−1 )

1-Propanol 344.82 0.076 31.1 0.149 0.367 30.9912 7.1317 1.6 0.013
373.16 0.082 6.2 0.077 0.396 40.5361 4.1112 0.7 0.006
397.48 – – – 0.434 48.3672 4.8423 1.6 0.005
426.68 – – – 0.337 38.7726 6.9897 0.7 0.012
2-Propanol 334.04 – – – 0.369 31.5232 4.8273 1.2 0.013
344.23 0.114 14.3 0.014 0.368 32.9091 4.0078 1.7 0.012
353.72 0.083 2.3 0.051 0.396 37.4252 3.9616 0.3 0.008
373.18 0.083 3.4 0.036 0.474 52.8548 5.3609 0.6 0.024
398.62 0.122 7.1 0.050 0.455 46.9754 4.8565 0.3 0.015
413.45 0.111 3.0 0.018 0.460 3.9218 −0.4157 0.8 0.015
432.58 0.140 4.7 0.073 0.536 601.8358 6.8739 0.6 0.007
443.46 0.113 3.6 0.062 0.323 20.2170 −1.0686 1.5 0.020
1-Butanol 354.06 0.094 5.7 0.003 0.500 5.9266 −1.1719 0.5 0.003
398.98 0.082 3.7 0.005 0.496 5.8454 −1.7607 0.9 0.008
430.25 0.084 4.8 0.006 0.505 5.3641 −1.6214 2.8 0.011

And the absolute mean deviation in the vapor phase mole fraction The deviations for p and y for these calculations are shown in
was: Table 6.

3.2. Density data


NP
1
y = |yiex − yical | (13) Experimental densities of n-dodecane and n-tridecane were
NP
i=1 measured and they are listed in Tables 7 and 8. Measurements

Table 7
Experimental densities of n-dodecane
T = 313.09 K T = 322.97 K T = 332.80 K T = 342.69 K T = 352.51 K T = 362.29 K
p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 )

1.022 735.79 1.025 728.33 1.023 721.08 1.019 713.80 1.021 706.54 1.015 699.21
2.023 736.60 2.028 729.17 2.019 721.96 2.025 714.75 2.027 707.55 2.020 700.31
3.017 737.36 3.026 729.97 3.022 722.81 3.025 715.67 3.013 708.48 3.015 701.33
4.026 738.14 4.034 730.78 4.030 723.69 4.014 716.58 4.019 709.46 4.012 702.34
5.023 738.89 5.021 731.59 5.026 724.53 5.015 717.47 5.027 710.45 5.029 703.40
6.032 739.66 6.017 732.37 6.035 725.36 6.017 718.36 6.014 711.35 6.009 704.36
7.011 740.38 7.017 733.17 7.014 726.16 7.021 719.25 7.020 712.33 7.029 705.38
8.009 741.15 8.041 733.99 8.025 727.03 8.007 720.13 8.000 713.23 8.013 706.30
9.026 741.91 9.015 734.73 9.017 727.84 9.019 721.03 9.024 714.18 9.012 707.31
10.008 742.66 10.016 735.50 10.020 728.67 10.018 721.86 10.009 715.07 10.038 708.31
11.022 743.39 11.019 736.28 11.023 729.46 11.016 722.71 11.022 715.96 11.027 709.22
12.012 744.09 12.011 737.01 12.022 730.26 12.013 723.56 12.012 716.84 12.009 710.09
13.019 744.82 13.028 737.78 13.004 731.04 13.021 724.39 13.026 717.71 13.007 711.04
14.017 745.55 14.041 738.53 14.008 731.81 14.020 725.21 14.017 718.60 14.015 711.96
15.025 746.22 14.994 739.22 15.018 732.57 15.030 726.04 15.021 719.45 15.008 712.81
16.025 746.91 16.027 739.96 16.023 733.35 16.024 726.83 16.022 720.30 16.034 713.71
17.015 747.58 17.001 740.64 17.014 734.08 17.011 727.58 17.012 721.08 17.030 714.59
18.022 748.26 18.015 741.35 18.006 734.82 18.025 728.36 18.027 721.95 18.011 715.43
19.025 748.93 19.032 742.07 19.024 735.59 19.023 729.15 19.013 722.74 19.021 716.29
20.013 749.59 20.004 742.74 20.023 736.32 20.013 729.88 20.028 723.53 20.007 717.15
21.015 750.23 21.009 743.43 21.009 737.01 21.006 730.67 21.021 724.33 21.017 717.94
22.011 750.90 22.023 744.14 22.009 737.73 22.021 731.41 22.023 725.14 22.032 718.77
23.021 751.53 23.009 744.80 23.018 738.45 23.014 732.15 23.008 725.88 23.002 719.60
24.015 752.21 24.013 745.50 24.018 739.17 24.013 732.89 24.020 726.65 24.005 720.38
24.354 752.42 24.507 745.83 24.665 739.63 24.725 733.44 24.813 727.31 24.809 721.05
 O. Elizalde-Solis et al. / Fluid Phase Equilibria 259 (2007) 23–32 29

Table 8
Experimental densities of n-tridecane
T = 313.01 K T = 322.92 K T = 332.78 K T = 342.64 K T = 352.47 K T = 362.25 K

p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 ) p (MPa) ρ (kg m−3 )

1.023 743.49 1.017 736.15 1.015 729.19 1.022 722.03 1.013 714.88 1.020 707.72
2.030 744.27 2.006 736.94 2.020 730.06 2.014 722.93 2.022 715.88 2.026 708.74
3.025 745.05 3.025 737.83 3.022 730.83 3.025 723.84 3.010 716.80 3.018 709.77
4.027 745.74 4.021 738.62 4.016 731.63 4.021 724.70 4.020 717.71 4.006 710.71
5.014 746.51 5.021 739.42 5.020 732.47 5.020 725.59 5.019 718.65 5.021 711.73
6.024 747.18 6.043 740.18 6.016 733.27 6.020 726.44 6.011 719.55 6.019 712.70
7.021 747.95 7.018 740.90 7.006 734.09 7.008 727.27 7.017 720.47 7.029 713.67
8.036 748.69 8.022 741.72 8.018 734.90 8.026 728.15 8.014 721.35 8.017 714.54
9.019 749.41 9.008 742.44 9.013 735.71 9.007 728.98 9.022 722.24 9.011 715.51
10.018 750.14 10.012 743.18 10.008 736.52 10.010 729.81 10.031 723.11 10.011 716.42
11.030 750.86 11.015 743.93 11.016 737.30 11.012 730.63 11.010 723.98 11.021 717.35
12.006 751.51 12.006 744.71 12.007 738.05 12.014 731.46 12.003 724.82 12.018 718.24
13.017 752.24 13.030 745.38 13.012 738.79 13.011 732.27 13.024 725.71 13.014 719.11
14.035 752.95 14.010 746.12 14.021 739.55 14.008 733.03 14.013 726.54 14.000 719.97
15.021 753.59 15.026 746.81 15.011 740.26 15.029 733.84 15.007 727.34 15.017 720.85
16.019 754.27 16.024 747.53 16.020 741.03 16.006 734.58 16.016 728.16 16.026 721.70
17.019 754.94 17.016 748.22 17.015 741.74 17.016 735.35 17.007 728.94 17.019 722.52
18.024 755.61 18.010 748.89 18.005 742.47 18.019 736.09 18.020 729.77 18.034 723.36
19.025 756.27 19.007 749.56 19.017 743.19 19.006 736.85 19.011 730.53 19.016 724.17
20.043 756.91 20.023 750.22 20.014 743.89 20.001 737.59 20.013 731.29 20.004 725.00
21.011 757.52 21.020 750.92 21.016 744.66 21.023 738.34 21.032 732.07 21.015 725.80
22.020 758.16 22.010 751.57 22.046 745.35 22.008 739.06 22.020 732.84 22.022 726.63
23.018 758.79 23.040 752.26 22.994 745.97 23.005 739.79 23.020 733.60 23.008 727.42
24.004 759.44 24.006 752.95 24.032 746.67 24.032 740.52 24.021 734.36 24.034 728.22
25.036 760.12 25.006 753.60 25.030 747.38 25.024 741.14 25.024 735.14 25.010 729.02

were performed at pressures from 1 to 25 MPa and temperatures Statistical values were calculated to evaluate the correlations
from 313 a 363 K. The obtained data were correlated with the according to the equations given by Zúñiga-Moreno et al. [20].
equation of state proposed by Starling and Han (BWRS EoS) Deviations between the experimental density data and those
[19] calculated with Eq. (14) for n-dodecane were obtained; the min-
imum deviation is −0.026% and the maximum is +0.021%,
RT (B0 RT − A0 − C0 /T 2 + D0 /T 3 − E0 /T 4 ) for n-tridecane, these values are −0.020% and +0.028% for
p= +
v v2 minimum and maximum deviations respectively. Deviations for
(bRT − a − d/T ) α(a + d/T ) n-dodecane are plotted in Fig. 6.
+ + In the case of deviations for n-dodecane with Eq. (15), the
v3 v6
minimum value is –0.028% and the maximum value is +0.020%,
c(1 + u/v2 )exp(u/v2 )
+ (14)
v3 T 2

v is the molar volume in cm3 mol−1 and R is the universal gas

constant.
The five-parameter Modified Toscani-Swarcz equation
(MTS) [6] was used to correlate the experimental data,

c 1 + c2 p
V̄ = (15)
c3 − (c4 /T + c5 /T 1/3 ) + p

where V is the specific volume of the n-alkane, (V̄ = 1/ρ)

in m3 kg−1 and ci are the equation parameters. The adjusted
parameters can be seen in Table 9, they were obtained by using
the Marquardt–Levenberg least-squares optimization algorithm
[18] with the following objective function:
 2
 ρex − ρcal Fig. 6. Deviations of compressed liquid densities for n-dodecane at (䊉)
S= i i
(16) 313.09 K, () 322.97 K, () 332.80 K, () 342.69 K, () 352.51 K, ()
ρiex
i 362.29 K. ρex this work, ρcal computed with Eq. (14).
30 O. Elizalde-Solis et al. / Fluid Phase Equilibria 259 (2007) 23–32

Table 9
Adjusted parameters of Eq. (14) and Eq. (15) for n-dodecane and n-tridecane,
this work
Parameter Dodecane Tridecane

BWRS EoS
B0 (cm3 mol−1 ) 3599.65 3296.78
A0 (bar cm6 mol−2 ) 1.5446 × 1008 1.5825 × 1008
C0 (bar K2 cm6 mol−2 ) 7.8720 × 1012 9.8715 × 1012
D0 (bar K3 cm6 mol−2 ) 7.1028 × 1014 −1.0934 × 1014
E0 (bar K3 cm6 mol−2 ) 5.3369 × 1016 −1.5585 × 1017
b (cm6 mol−2 ) −3.1752 × 1005 −2.4415 × 1005
a (bar cm9 mol−3 ) −4.2976 × 1009 −5.3888 × 1009
d (bar K cm9 mol−3 ) −1.2132 × 1011 −2.8226 × 1011
c (bar K2 cm9 mol−3 ) 1.2300 × 1015 1.2300 × 1010
α (cm9 mol−3 ) −8.1786 × 1007 −9.3114 × 1007
u (cm6 mol−2 ) 1.4000 × 1009 1.4000 × 1009
AAD (%) 9.07 × 10−3 8.54 × 10−3
Bias (%) 2.62 × 10−4 3.39 × 10−4
SDV (%) 1.12 × 10−2 1.04 × 10−2 Fig. 8. Deviations of compressed liquid densities for n-dodecane between exper-
RMS (%) 1.12 × 10−2 1.04 × 10−2 imental data from literature, ρlit and those calculated with Eq. (15), ρcal at
(䊉) 298.15 K, () 323.15 K, () 348.15 K, and () 373.15 K. Ref. [21] black
Five-parameter MTS symbols, Ref. [22] white symbols, Ref. [23] crossed symbols.
c1 (MPa kg−1 m3 ) 0.1779 0.1844
c2 (kg−1 m3 ) 0.00116 0.00115
c3 (MPa) −146.142 −160.481 In order to test the consistency of density data, comparisons of
c4 (K MPa) 23551.86 26710.10 experimental data for n-dodecane from literature [21–23] with
c5 (K1/3 MPa) −2390.713 −2598.717
those calculated with Eq. (15) were performed. Although the
AAD (%) 9.70 × 10−3 7.63 × 10−3
Bias (%) 0.60 × 10−5 0.30 × 10−5 deviations with all the sources are similar, the best agreement is
SDV (%) 1.12 × 10−2 9.42 × 10−3 with the densities reported by Caudwell et al. [21], the maximum
RMS (%) 1.12 × 10−2 9.39 × 10−3 deviations for twelve data points in the range of temperature from
For both equations 298.15 to 373.15 K and pressures up to 42.2 MPa are within
Tmin (K) 313.09 313.01 −0.113 to +0.088%, as can be seen in Fig. 8.
Tmax (K) 362.29 362.25 For n-dodecane density data obtained here were compared
pmin (MPa) 1.00 1.00 with the equation of state proposed by Lemmon and Huber [24],
pmax (MPa) 25.00 25.00
NP 150 150
one of the most recent equations to represent the thermodynamic
properties of this n-alkane. Deviations calculated are within the
experimental uncertainty reported here (see Fig. 9), except for
for n-tridecane, the values are −0.021% and +0.029% for min- the 313 K isotherm (+0.4 kg m−3 ). The absolute average devi-
imum and maximum values, respectively (see Fig. 7). Eqs. ation (AAD) for this set of data is 0.016%, this value is lower
(14) and (15) represent n-dodecane and n-tridecane density data than those reported by Lemmon and Huber [24] for the source of
within the experimental uncertainty.

Fig. 9. Deviations of compressed liquid densities between experimental ρex and

Fig. 7. Deviations of compressed liquid densities for n-tridecane at (䊉) calculated data ρcal from Ref. [24] for n-dodecane (black symbols) and from Ref.
313.01 K, () 322.92 K, () 332.78 K, () 342.64 K, () 352.47 K, () [27] for n-tridecane (white symbols) at (䊉) ∼313 K, () ∼323 K, () ∼333 K,
362.25 K. ρex this work, ρcal computed with Eq. (15). () ∼343 K, () ∼353 K, ( ) ∼363 K.
 O. Elizalde-Solis et al. / Fluid Phase Equilibria 259 (2007) 23–32 31

p–ρ–T data used to fit their equation parameters. These results A0 , B0 , C0 , D0 , E0 BWRS equation parameters
show the good quality of our experimental densities. b equation of state excluded volume parameter
Comparisons between the experimental data for n-tridecane c1 –c5 parameters from Eq. (15)
measured by Daugé et al. [25] and those calculated with Eq. F objective function for VLE calculations
(15) were also done. Deviations in the temperature range from G Gibbs energy
313.15 to 353.15 K and pressure range from 0.1 to 40 MPa were g NRTL model parameter
calculated within the ±0.15%. The densities reported by Daugé k binary interaction coefficient
et al. [25] were compared with the experimental data of this K vapor–liquid equilibrium ratio
work at 20 MPa at the five different isotherms in the temperature Nc number of components
range mentioned above, deviations were 0.12, 0.03, 0.12, 0.08, NP number of experimental data points
and 0.18%, respectively. Also comparisons were done between p pressure in MPa
densities calculated with Eq. (15) and those reported by Doolittle R universal gas constant
[26], deviations in the pressure range from 0 to 30 MPa and the S objective function for density calculations
three temperatures reported (303.14–373.13 K) were less than T temperature in K
±0.084%, which are in good agreement. v molar volume in cm3 mol−1
The n-tridecane experimental densities measured here were x liquid mole fraction
compared with those values calculated with a Tait-type equation y vapor mole fraction
using the parameters reported by Khasanshin et al. [27]. Good
agreement was observed between our data and those calculated Greek letters
with the Tait-type equation as can be seen in Fig. 9. The range of α nonrandomness parameter
deviations is from −0.009 to + 0.052% with an AAD = 0.014%. δ interaction energy in Eq. (9)
These deviations were very similar to those obtained by Khasan- γ NRTL model parameter in Eqs. (8) and (9)
shin et al. [27] of AAD = 0.02% and a maximum deviation of μ vibrating period in Eq. (1)
0.05%. ρ density in kg m−3
ω acentric factor
4. Conclusions
Superscripts
Via a static-analytical set up, high-pressure vapor–liquid c critical property
equilibria measurements for the CO2 + 1-propanol system were cal calculated value
reported from 344 to 426 K. For the CO2 + 2-propanol system, ex experimental value
these were performed from 334 to 443 K, and three critical exc excess property
points were obtained. For the CO2 + 1-butanol binary system i, j, k molecular species
were obtained from 354 to 430 K. The experimental data for m mixture property
the three systems studied agree with literature data. VLE data γ activity coefficient
were correlated with the Peng–Robinson equation of state using
the classical and the Wong–Sandler mixing rules. A better Acknowledgements
agreement with the experimental data was found when the
Wong–Sandler mixing rules were used. The authors thank to IPN for the financial support. Special
Densities of n-dodecane and n-tridecane were measured in thanks are given to F.F. Betancourt-Cárdenas for his help.
the 1–25 MPa, and 313–363 K pressure and temperature ranges,
respectively. These data were compared with density values cal- References
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