ARTICLE

pubs.acs.org/jced

Vapor
Liquid Equilibria of Binary and Ternary Systems Containing

Carbon Dioxide, Alkane, and Benzothiophene
Luis E. Camacho-Camacho,† Luis A. Galicia-Luna,*,† and Octavio Elizalde-Solis‡
†
Laboratorio de Termodinamica, SEPI-ESIQIE, Instituto Politecnico Nacional, UPALM, Ed. Z, Secc. 6, 1 piso, Lindavista, C.P. 07738,
Mexico, D.F.
‡
Departamento de Ingeniería Química Petrolera, ESIQIE, Instituto Politecnico Nacional, UPALM, Edif. 8, 2 piso, Lindavista, C.P. 07738,
Mexico, D.F.

ABSTRACT: Experimental vapor
liquid equilibrium (VLE) data of binary and ternary systems are reported covering all of the
phase envelopes up to near the critical point. The carbon dioxide + dodecane, carbon dioxide + benzothiophene, and carbon dioxide +
nonane + benzothiophene systems were studied at (318.14, 344.75, 373.23, and 417.91) K, 373.93 K, and (313.09, 343.73, and
373.74) K, respectively. The apparatus is based on the static
analytic method with an on-line ROLSI (rapid on-line sampler

injector) sampler to allow fast determination of the VLE. Standard uncertainties for the measured properties in this work were
estimated to be p ( 0.01 MPa, T ( 0.03 K, liquid mole fraction xCO2 ( 0.0036, and vapor mole fraction yCO2 ( 0.0016. The
experimental VLE data for carbon dioxide + dodecane were found to be in agreement with those available in the literature at 318 K.
Furthermore, the corresponding results for the ternary system indicate a high selectivity of nonane in the vapor phase instead of
benzothiophene. Data obtained in this work were correlated with the Peng
Robinson equation of state using the Wong
Sandler
mixing rules.

’ INTRODUCTION from (313.2 to 343.2) K, Hottovy et al.16 the three liquid

Experimental vapor
liquid equilibria (VLE), volumetric liquid
vapor phase equilibrium line at low temperatures, and
properties, and solubility data of alkanes in supercritical fluids Henni et al.17 dew points far from the critical pressure at (313,
such as carbon dioxide are important information in the petro- 353, and 393) K. The only VLE data that cover the entire phase
leum process design area. Reliable experimental thermodynamic envelope are those reported by Gardeler et al.18 at 318.15 K. These
properties are also needed to test the approach of new or data were found to be in agreement with the experimental data
developed equations of state. obtained in this work. No VLE data have been published for the
The present study belongs to a systematic experimental VLE other binary and ternary systems.
and volumetric property determinations of alkanes (pentane,
hexane, octane, nonane, undecane, and tridecane) in carbon
’ EXPERIMENTAL SECTION
dioxide.1
5 These linear alkanes have been used in research as
representative compounds of fuels,6
8 while innovations regard- Materials. Anhydrous nonane (C9H20, certified purity 0.991
ing desulfurization pathways at the laboratory scale are commonly mole fraction), dodecane (C12H26, certified purity 0.9942 mole
based on benzothiophene as a model sulfur compound.9
14 fraction), and benzothiophene (C8H6S, certified purity 0.995 mole
Therefore, the aim of this work is to report accurate experimental fraction) were purchased from Sigma-Aldrich. Carbon dioxide
VLE data for the carbon dioxide + dodecane, carbon dioxide + (CO 2, mole fraction purity > 0.99995) and helium (He,
benzothiophene, and carbon dioxide + nonane + benzothio- mole fraction purity > 0.99998) were supplied by Air Products-
phene systems in a wide range of temperature and pressure. Infra. Chemicals were used as received without any further
Nonane was mixed with the sulfur compound to simulate a fuel purification. The water content for nonane was 1.9 3 10
4 and
model and understand the selectivity of the solvent over both 3.7 3 10
4 for dodecane in mole fraction. It was determined by
solutes. means of a Karl Fischer coulometer (831, Metrohm).
The VLE for the ternary system mixture modeling require Apparatus. Experimental VLE data for the studied systems
binary interaction parameters. Hence, the corresponding behavior were measured isothermally by means of a static
analytic
for the carbon dioxide + benzothiophene was determined at apparatus described elsewhere.4,5 It consists of a 100 cm3 tita-
373.93 K, while Camacho-Camacho et al.1 have already published nium view cell (EC) coupled to a HP 5890 gas chromatograph
the VLE for the binary carbon dioxide + nonane. Afterward, the (GC) and is capable to operate at temperatures up to 673 K and
ternary system behavior was predicted from the binary interaction pressures up to 60 MPa. Figure 1 shows a scheme of the
parameters obtained in this work and those reported earlier.1 experimental apparatus. The gas chromatograph used to perform
Some authors have published the phase equilibria for the carbon
dioxide + dodecane system in different regions.15
18 Nieuwoudt Received: June 14, 2011
and du Rand15 presented scarce isothermal phase equilibrium data Accepted: September 27, 2011
near the critical pressure for the carbon dioxide + dodecane system Published: October 20, 2011

r 2011 American Chemical Society 4109 dx.doi.org/10.1021/je200586g | J. Chem. Eng. Data 2011, 56, 4109–4115
Journal of Chemical & Engineering Data ARTICLE

Figure 1. Experimental scheme of the static
analytic apparatus for phase equilibrium measurements:3 AB, air bath; Ci, cylinder gases; EC, equilibrium
cell; GC, gas chromatograph; PC, computer; PI, pressure indicator; PT, pressure transducer; S, stirring device; SC, sampler controller; SP, syringe pump;
TI, temperature indicator; TP, temperature probe; Vi, needle valves; VP, vacuum pump.

the sample analysis was set at the following conditions: injector (c) Samples of the liquid phase in the EC were sent to the
temperature (483 K); thermal conductivity detector (TCD) GC for the component quantification. It was carried out
temperature (513 K); gradient in the oven temperature (350 K with an automatic online ROLSI (rapid on-line sampler

for 1 min, 70 K 3 min
1 up to 513 K for 3.67 min); Alltech packed injector, Armines)20 sampler injector which is moved in
column (Chromosorb Q 80/100, stainless steel 1/8 in. diameter  vertical position. At each temperature and pressure, several
2 ft length); carrier gas (helium at 30 cm3 3 min
1); and reference samples were taken and analyzed to reach the equilibrium
TCD gas (helium at 45 cm3 3 min
1). Prior to VLE determina- composition. This criterium was determined when the last
tions, GC calibration was completed according to the procedure five consecutive had to be within 0.5 % of deviation between
described by Elizalde-Solis and Galicia-Luna.5 Combined un- the maximum and minimum values of CO2 composition for
certainties for the mole fraction were estimated to be less than liquid phases and 0.05 % for the vapor phase; hence the
0.0035 for u(xCO2) and 0.0016 for u(yCO2) in the whole range of combined uncertainty values could be a minimum.
measurements. (d) The sampler
injector was moved to the vapor phase, and the
Measurements of pressure were performed by means of a above-mentioned step was repeated. For this work, only the
pressure transducer (PDCR 4010-A093, DRUCK), and the vapor phase and a single liquid phase were present in the EC.
standard uncertainty u(p) was less than 0.01 MPa. Equilibrium (e) The pressure was increased by adding CO2 to EC, and steps
temperatures were measured by two 100 Ω platinum probes c and d were repeated. Finally, the temperature set-point of
(PT100, Specitec). The temperature uncertainty u(T) was with- AB was changed to a new value, and procedures b to d were
in 0.03 K. Uncertainties were evaluated according to the NIST repeated again to accomplish VLE measurements.
Technical Note 1297.19
VLE Measurements. Experimental data were obtained iso-
thermally according to the following procedure: ’ MODELING
(a) About 50 cm3 of the solute (alkane, benzothiophene, or its As the basis for the study, experimental VLE data were
corresponding mixture with a volume relation of 1:1) was correlated with the Peng
Robinson equation of state21 (PR
loaded to the equilibrium cell. Chemicals and the pipelines EoS, eq 1) coupled to the classical (CMR) and the Wong

were carefully degassed under vigorous stirring for 1 h. Sandler22 (WSMR) mixing rules. The PR EoS is
Carbon dioxide flowed through the tubing to the EC for
RT aðTÞ
ensuring a complete evacuation of air at a desired pressure. p¼
ð1Þ
(b) The air bath (AB) temperature was initially set to the v
b vðv þ bÞ þ bðv
bÞ
lowest value for each system. Thermal equilibrium was The CMR are calculated with the next equations
reached after almost 5 h when temperature values on the
indicator were within its reported uncertainty. Then, the am ¼ ∑i ∑j xi xjðai ajÞ1=2ð1
kijÞ ð2Þ
pressure in the EC was increased by adding CO2. Pressure
became stable after 1 h. Slow stirring was applied through-
out the experimental measurements to ensure complete
mixing of the compounds in both phases.
bm ¼ ∑i xi bi ð3Þ

4110 dx.doi.org/10.1021/je200586g |J. Chem. Eng. Data 2011, 56, 4109–4115

Journal of Chemical & Engineering Data ARTICLE

Table 1. Critical Properties and Acentric Factor of the Pure Table 2. Vapor
Liquid Equilibria for the CO2 + Dodecane
Substances23,24 Systema
CAS No. Tc/K pc/MPa ω p/MPa xCO2 u(xCO2) yCO2 u(yCO2) KCO2 KC12

CO2 [124-38-9] 304.12 7.374 0.225 T = 318.14 K

nonane [111-84-2] 594.60 2.290 0.445 1.78 0.196 0.0010 0.997 0.0013 5.083 0.003
dodecane [112-40-3] 658.00 1.820 0.576
2.53 0.268 0.0006 0.998 0.0016 3.723 0.003
benzothiophene [95-15-8] 754.00 4.140 0.296
3.45 0.354 0.0022 0.999 0.0013 2.826 0.001
5.03 0.489 0.0011 0.999 0.0012 2.044 0.001
where kij is the interaction parameter for the binary mixture. 6.49 0.612 0.0020 0.998 0.0002 1.631 0.003
Critical values of each compound were obtained elsewhere23,24 8.14 0.750 0.0015 0.995 0.0004 1.327 0.020
and are listed in Table 1.
9.10 0.906 0.0023 0.989 0.0002 1.092 0.115
The WSMR are computed as:
T = 344.75 K
∑i ∑j xi xj ðb
ða=RTÞÞij 3.16 0.265 0.0005 0.995 0.0006 3.759 0.006
bm ¼ ð4Þ 4.77 0.375 0.0018 0.997 0.0015 2.656 0.004
1
∑ xi ðai =bi RTÞ
ðAE∞ =CRTÞ 6.35 0.472 0.0012 0.998 0.0014 2.114 0.002
i
7.42 0.538 0.0024 0.998 0.0010 1.856 0.002
8.21 0.589 0.0035 0.998 0.0011 1.695 0.003
where

 9.08 0.632 0.0011 0.998 0.0006 1.578 0.004
a ðbi
ðai =RTÞÞ þ ðbj
ðaj =RTÞÞ 9.92 0.675 0.0010 0.997 0.0006 1.478 0.007
b
¼ ð1
kij Þ
RT ij 2 10.66 0.708 0.0011 0.995 0.0015 1.406 0.015

ð5Þ T = 373.23 K
3.30 0.235 0.0018 0.990 0.0011 4.216 0.013
! 4.80 0.320 0.0016 0.995 0.0013 3.108 0.006
AE 6.54 0.411 0.0025 0.996 0.0006 2.421 0.006
∑i
ai
am ¼ bm xi þ ∞ ð6Þ 8.04 0.482 0.0013 0.996 0.0014 2.067 0.007
bi C
9.73 0.553 0.0027 0.996 0.0014 1.800 0.009
11.11 0.616 0.0020 0.995 0.0013 1.616 0.013
C = ln(21/2
1)/21/2 for the PR EoS. The excess Helmholtz free 12.76 0.674 0.0031 0.993 0.0011 1.474 0.020
energy at infinite pressure, AE∞, can be expressed with the excess 14.10 0.720 0.0014 0.990 0.0012 1.375 0.034
Gibbs free energy at low pressure, GγE, by using the NRTL
15.42 0.762 0.0026 0.974 0.0011 1.278 0.107
model:25
16.19 0.787 0.0013 0.967 0.0014 1.228 0.155

AE∞ GEγ
∑j xj τji Gji 17.54 0.845 0.0015 0.958 0.0011 1.135 0.265

RT
¼
RT
¼ ∑i ∑ xk Gki
xi ð7Þ T = 417.91 K

k
1.64 0.104 0.0018 0.969 0.0012 9.325 0.035
3.12 0.186 0.0033 0.986 0.0014 5.281 0.017
where 4.55 0.256 0.0028 0.990 0.0004 3.856 0.013
6.04 0.326 0.0022 0.990 0.0007 3.037 0.014
Gji ¼ expð
αji τji Þ ð8Þ
7.46 0.385 0.0027 0.990 0.0013 2.571 0.016
9.08 0.447 0.0013 0.989 0.0012 2.212 0.019
αji was fixed at 0.3. Gji are factors of local composition, and τji are
10.51 0.499 0.0026 0.989 0.0004 1.978 0.022
the binary interaction parameters. Parameters kij, τij, and τji were
optimized by using the Levenberg
Marquardt method, and they 11.99 0.550 0.0015 0.988 0.0005 1.794 0.027
are minimized with the following objective function, 13.51 0.599 0.0028 0.986 0.0009 1.647 0.034
2 14.98 0.640 0.0026 0.983 0.0014 1.534 0.047
0 12 0 12 3
exptl exptl 16.53 0.690 0.0025 0.979 0.0012 1.419 0.067
6 Nc @yij
yij A pcalcd
pj
NP calcd
7
OF ¼ ∑ ∑ 4
j¼1 i¼1
exptl
yij
þ @ j
pj
exptl
A5 ð9Þ 18.09 0.732 0.0033 0.972 0.0011 1.327 0.104
19.45 0.767 0.0027 0.960 0.0008 1.251 0.172
20.37 0.802 0.0020 0.943 0.0014 1.176 0.286
where NP stands for the number of data points, Nc represents
a
Standard uncertainties are: u(T) = 0.03 K, u(p) = 0.01 MPa, u(KCO2) e
the number of compounds, p is the pressure at equilibrium, y is 0.02 x(KCO2).
the vapor mole fraction, and superscripts calcd and exptl indicate
calculated and experimental data, respectively. The absolute The absolute average deviation for mole composition follows the
average deviation of bubble pressure was calculated as next equation:

 NP exptl

jpi
pi calcd j NP
∑ jyi exptl
yi calcd j
1
∑
100
Δp ¼ ð10Þ Δy ¼ ð11Þ
NP i ¼ 1 pi exptl NP i¼1

4111 dx.doi.org/10.1021/je200586g |J. Chem. Eng. Data 2011, 56, 4109–4115

Journal of Chemical & Engineering Data ARTICLE

Table 3. Vapor
Liquid Equilibria for the CO2 + Table 4. Vapor
Liquid Equilibria for the CO2 + Nonane +
Benzothiophene Systema Benzothiophene Systema
p/MPa xCO2 u(xCO2) yCO2 u(yCO2) KCO2 KBT p/MPa xCO2 xC9 yCO2 yC9

T = 373.93 K T = 313.09 K
1.32 0.009 0.0031 0.957 0.0006 110.046 0.043 1.92 0.243 0.727 0.998 0.001
2.32 0.023 0.0026 0.966 0.0015 41.282 0.034 3.34 0.350 0.594 0.998 0.001
3.36 0.033 0.0032 0.987 0.0013 29.299 0.013 4.98 0.507 0.450 0.998 0.001
4.49 0.050 0.0025 0.993 0.0016 19.901 0.007 6.36 0.675 0.296 0.997 0.002
5.67 0.065 0.0014 0.994 0.0012 15.400 0.005 7.08 0.783 0.197 0.997 0.002
7.12 0.082 0.0035 0.994 0.0004 12.162 0.005 7.48 0.878 0.111 0.996 0.003
8.46 0.096 0.0029 0.993 0.0008 10.304 0.007 7.63 0.907 0.084 0.996 0.004
10.22 0.123 0.0027 0.988 0.0008 8.002 0.013 T = 343.73 K
11.78 0.136 0.0018 0.983 0.0014 7.193 0.019
1.61 0.144 0.804 0.994 0.005
13.45 0.164 0.0020 0.971 0.0010 5.919 0.033
3.00 0.246 0.698 0.995 0.004
14.79 0.181 0.0022 0.915 0.0007 5.031 0.103
4.44 0.354 0.590 0.996 0.003
a
Standard uncertainties are: u(T) = 0.03 K, u(p) = 0.01 MPa, u(KCO2) e 5.96 0.458 0.492 0.995 0.004
0.02 x(KCO2).
7.37 0.547 0.411 0.994 0.005
8.83 0.633 0.333 0.993 0.006
’ RESULTS AND DISCUSSION
10.53 0.745 0.230 0.987 0.012
Experimental VLE data were obtained isothermally with 11.46 0.816 0.166 0.975 0.022
pressure increments. The carbon dioxide + dodecane system
11.99 0.887 0.103 0.960 0.036
was measured at (318.14, 344.75, 373.23, and 417.91) K.
Compositions of carbon dioxide, equilibrium ratios of each T = 373.74 K
compound, and their corresponding standard uncertainties in 6.593 0.4027 0.553 0.989 0.010
both phases are presented in Table 2. VLE data for the second 9.133 0.5157 0.441 0.984 0.014
binary carbon dioxide + benzothiophene system at 373.93 K are 10.543 0.5929 0.370 0.983 0.016
listed in Table 3; this system has not been published in the 11.946 0.6497 0.320 0.978 0.020
literature. Table 4 summarizes the experimental data for the 13.484 0.7282 0.248 0.966 0.032
carbon dioxide + nonane + benzothiophene system at (313.09,
14.565 0.7918 0.190 0.950 0.047
343.73, and 373.74) K. The mole fraction for benzothiophene in
15.081 0.8261 0.159 0.932 0.062
carbon dioxide mixtures decreases when nonane is added to the a
system. Standard uncertainties are: u(T) = 0.03 K, u(p) = 0.01 MPa, u(xCO2) =
The PR EoS coupled to the CMR and WSMR was used to 0.0036, u(yCO2) = 0.0011, and the expanded uncertainties Uc are Uc (xCO2) =
0.0072, Uc (yCO2) = 0.0022 with a 0.95 level of confidence (k ≈ 2).
represent experimental VLE data for the binary systems. Opti-
mized parameters (kij, τij, τji) were obtained as temperature- Table 5. Bubble-Point Calculations for the Binary Systems
dependent and independent parameters. Table 5 lists the abso- Using the PR EoS
lute average deviation for the resulting correlations of the binary
systems; the lowest pressure deviation was obtained at 318.14 K Wong
Sandler
using the WSMR and the dependent parameters. The maximum
average deviation belonged to the independent parameter, and classical NRTL
no differences were found between the uses of any of the mixing
rules for this instance. τ12/ τ21/
The VLE behavior for the ternary system was predicted using T /K k12 %Δp Δy k12 kJ 3 mol
1 kJ 3 mol
1 %Δp Δy
bubble pressure calculations. These results are listed in Table 6. It
was accomplished with the base model (PR EoS/CMR). The Carbon Dioxide + Dodecane
temperature-independent interaction parameter for the carbon 318.14 0.0971 1.3 0.002 0.7723 10.2166
1.3756 0.2 0.002
dioxide + nonane mixture was obtained from the literature.1 344.75 0.0903 1.0 0.001 0.7897 9.3484
1.9794 0.4 0.002
Lower deviations in pressure and composition were found at 373.23 0.0885 1.1 0.003 0.7961 9.7009
2.6871 0.3 0.006
313.09 K. 417.91 0.0833 3.0 0.004 0.8105 9.4023
3.4698 0.3 0.007
Isothermal (p, T, xCO2, yCO2) trends for the carbon dioxide + T. I. P.a 0.1615 7.5 0.019 0.8447 9.1020
1.0046 7.5 0.005
dodecane are plotted in Figure 2 where symbols and lines stand
for experimental and calculated data, in that order. Calculations Carbon Dioxide + Benzothiophene
were carried out using the PR EoS + WSMR model with 373.93 0.3031 24.9 0.021 1.8410
5.0084 11.7121 6.1 0.021
a
temperature parameter dependence. Our VLE isotherm at Temperature-independent parameters.
318.14 K and that reported by Gardeler et al.18 at 318.15 K are
plotted in Figure 3. According to the trends and error bars, both were found in the literature to compare our results in the studied
sets of data are in agreement, and dew points follow the same temperature range. Equilibrium ratios (Ki = yi/xi) for the binary
trend; the enlarged image for the bubble region shows the error systems are depicted in Figure 4. Symbols represent experimental
bars for the vapor mole fraction overlap. No other sources of data data, and lines stand for predicted values by the PR EoS + WSMR
4112 dx.doi.org/10.1021/je200586g |J. Chem. Eng. Data 2011, 56, 4109–4115
Journal of Chemical & Engineering Data ARTICLE

Table 6. Bubble-Point Predictions for the Carbon Dioxide +

Nonane + Benzothiophene System Using the PR EOS +
Classical Mixing Rule
binary system kij

CO2 + nonane 0.09681

CO2 + benzothiophene 0.3031
nonane + benzothiophene 0.0000a

prediction for ternary system

T/K %Δp ΔyCO2

313.09 3.8 0.001

343.73 9.9 0.017
373.74 6.9 0.013
a
Considered as zero due to the absence of VLE data.
Figure 4. Experimental equilibrium ratios for the CO2 + dodecane
system: b, 318.14 K; 3, 344.75 K; 9, 373.23 K; ], 417.91 K. CO2 +
benzothiophene system at f, 373.93 K. Solid lines represent the
calculated data.

Figure 2. VLE for the CO2 + dodecane system. Experimental data at: b,
318.14 K; 3, 344.75 K; 9, 373.23 K; ], 417.91 K. Solid lines represent
the calculated data.

Figure 5. Experimental equilibrium ratios for the CO2 + nonane +

benzothiophene: b, O, 313.09 K; 1, 4, 343.73 K; 9, 0, 373.74 K.
Black symbols correspond to nonane, and open symbols denote
benzothiophene.

obtained in this work. The calculated values illustrate how much

these deviated from the experimental data. Deviations observed
in this figure are more evident than in Figure 2. The combined
uncertainties for equilibrium ratios were estimated to be less than
2 % of the value reported in Table 2.
Equilibrium ratios are plotted in Figure 5 for nonane and
benzothiophene in the ternary system. The experimental data
could be considered suitable according to the smoothness of the
isothermal trends. The separation factors (Sij = Ki/Kj) for the
CO2 + nonane + benzothiophene system are plotted in Figure 6
for nonane over benzothiophene. The separation factor is
observed to enhance as pressure decreases for each temperature,
Figure 3. VLE for the CO2 + dodecane system: b, 318 K, Gardeler obtaining the highest value at 313 K in the low pressure region. In
et al.;18 O, 318.14 K, this work. Horizontal lines represent error bars. contrast, due to the compositions of benzothiophene in the vapor
phase within the experimental uncertainty, the SC9/BT values
model using the temperature-independent parameters. The increase from low pressure, achieve a maximum of (SC9/BT =
smoothness of symbols confirms the internal consistency of data 3.16) for 6 MPa, and decrease again as pressure increases at
4113 dx.doi.org/10.1021/je200586g |J. Chem. Eng. Data 2011, 56, 4109–4115
Journal of Chemical & Engineering Data ARTICLE

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Corresponding Author
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Fax: (52) 55 5586-2728. nation of Vapor-Liquid Equilibrium Data for Asymmetric Systems. Ind.
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Funding Sources
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support. L.E.C.-C. thanks ex-Director of ESIQIE J. Salvador Note 1297; NIST: Gaithersburg, MD, 1994.
Meza-Espinoza for a Ph.D. fellowship from 2006
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