Fluid Phase Equilibria 236 (2005) 193–204

Compressed liquid densities and excess volumes of CO2 + thiophene

binary mixtures from 313 to 363 K and pressures up to 25 MPa
Abel Zúñiga-Moreno, Luis A. Galicia-Luna ∗ , Felix F. Betancourt-Cárdenas
Instituto Politécnico Nacional, ESIQIE, Laboratorio de Termodinámica, Edif. Z, Secc. 6, 1er piso,
UPALM Zacatenco, 07738 Lindavista, México, D.F., México

Received 29 January 2005; received in revised form 17 June 2005; accepted 5 July 2005
Available online 19 August 2005

Abstract

Experimental densities for the CO2 (1) + thiophene (2) binary mixtures are reported from 313 to 363 K and up to 25 MPa. Densities were
measured for thiophene and for binary mixtures at five different compositions, x1 = 0.1990, 0.3818, 0.5661, 0.6996, and 0.9217. Densities of
thiophene were correlated by four different models, the Benedict–Webb–Rubin–Starling equation of state (BWRS EoS), the Tait equation (TE),
the Toscani and Szwarc (TS) model, and a proposed modification for this last model (MTS). These models represent densities of thiophene
with a percent standard deviation of 3.90 × 10−3 , 1.97 × 10−2 , 2.76 × 10−2 , and 5.54 × 10−3 , respectively. The excess molar volumes were
determined using densities for thiophene calculated from the BWRS EoS and densities for CO2 calculated from the Span–Wagner EoS. The
volumetric behavior and excess molar volumes of CO2 + thiophene mixtures were modeled using the PC-SAFT EoS.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Density; Thiophene; Carbon dioxide; PC-SAFT; Correlation; Excess molar volume; Vibrating tube densitometer

1. Introduction measured vapor–liquid equilibria of binary mixtures formed

Removal of sulfur compounds from oil cuts is performed
by hydrodesulfurization in the refining industry. However,
the high energy and hydrogen consumption would make this
method very expensive in few years [1]. Thiophene is an
undesirable sulfur compound found in commercial fuels [2].
The use of supercritical CO2 is a possible method to extract
this kind of compound. Information such as phase equilib-
ria and volumetric properties of mixtures containing CO2 ,
thiophene, and cosolvents at high pressures are needed to
develop new supercritical fluid processes. Accurate densities
of pure compounds and mixtures are required for many engi-
neering calculations where fluid flow or mixing is an impor-
tant factor in the design of separation processes. Recently,
Elizalde-Solis and Galicia-Luna [2] reported the solubility
of thiophene in CO2 , and in CO2 + 1-propanol. Triday [3]
∗ Corresponding author. Tel.: +52 55 5729 6000x55133;
fax: +52 55 5586 2728.
E-mail address: lgalicial@ipn.mx (L.A. Galicia-Luna).
by thiophene and light alcohols. Toghiani et al. [4] measured
vapor–liquid equilibria of the methanol + thiophene binary
mixtures. Data reported in the last two papers were below the
atmospheric pressure. No volumetric experimental data were
found for these systems in the literature. This paper contains
experimental compressed liquid densities for thiophene and
CO2 + thiophene mixtures from 313 to 363 K at pressures up
to 25 MPa made with a vibrating tube densitometer.
The knowledge of volumetric properties over a wide range
of temperatures and pressures are important for practical
applications in the industry. Therefore, it is essential to dis-
pose of models able to predict or correlate phase equilibria
and PvTx properties. The volumetric properties of polar and
non-polar pure fluids have been successfully correlated by
empirical models in the literature [5–7] but not for mixtures.
In this work, the compressed liquid densities of pure thio-
phene have been correlated using four models; the BWRS
EoS [8], and three simple empirical models. For mixtures,
the 11 parameters of the BWRS EoS make it not suitable for
practical applications in the industry, while the other models

0378-3812/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2005.07.017
194 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204

cannot be extended to mixtures. It is well known that the cubic
EoSs do not represent the liquid phase appropriately; there-
fore different mixing rules have been used to improve the
representation of PvT properties for mixtures [9]. Theoreti-
cal EoSs have improved the representation of the volumetric
properties [10,11] especially in the liquid phase.
The SAFT EoS has been one of the most successful
equations to represent real fluids [10]. In this work, the PC-
SAFT EoS presented by Gross and Sadowski [11] is used
to study the representation of the volumetric properties for
the CO2 + thiophene mixtures. This EoS is a modification of
the original SAFT, which has been developed by employing
the perturbation theory of Barker and Henderson with a hard
chain fluid as reference. This improves the representation of
the fluid properties in comparison with SAFT EoS [11] using
three molecular parameters for each fluid. PvT data of pure
non-polar fluids were used by the authors to improve the
volumetric behavior of this equation [11] consequently the
improvement of the representation of densities for mixtures.
2. Experimental
2.1. Materials
except for a careful degassing of thiophene and water under
stirring and vacuum.
2.2. Apparatus and procedure
The apparatus and experimental procedure used in this
work has been described and tested previously [12–14]. A
diagram of the experimental apparatus is shown in Fig. 1.
The uncertainty of temperature measurements is estimated
to be ±0.03 K. The pressure measurements were recorded
directly in the equilibrium cell by means of a 25 MPa pres-
sure transducer (Sedeme, France). The estimated uncertainty
of pressure measurements is ±0.008 MPa. Calibration of
the vibrating tube densitometer was performed with water
and nitrogen as the reference fluids for the classical method
[15]. Densities of water and nitrogen were obtained from
the reference equations of state proposed by Wagner and
Pruß [16] and Span et al. [17], respectively. Calibrating pro-
cedures for the platinum temperature probes, the pressure
transducer, and the vibrating tube densitometer can be found
in previous papers [12,18]. The estimated uncertainty of the
experimental compressed liquid densities presented in this
work is ±0.20 kg m−3 in the range of the reported data, as
previously described [19].

CO2 and nitrogen were supplied by Infra Air Products
Mexico with a certified purity of 99.995 mol%. Aldrich Co.
Inc. supplied thiophene and water with specified purities of
99.7 and 99.995 mol.%, respectively. All compounds were
used as received and no further purification was performed
2.3. Loading of the measurement cell
The thiophene and CO2 + thiophene mixtures were load-
ing using the procedure presented in precedent papers
[12,15]. The mass of each compound was determined with

Fig. 1. Schematic flow diagram of the experimental apparatus: AB, air bath; CA, cathetometer; DMA 60 period meter; DPI 145 digital indicator of pressure;
EC, equilibrium cell; GC, gas compressor; PI, Isco pump; LB, liquid bath; VTD, vibrating tube densitometer; MC, measurement cell; MR, magnetic rod; PT,
pressure transducer; M, multimeter; PTPi, platinum probe i; TD, digital indicator of temperature F250; Vi, shut-off valve i; VSE, variable speed engine; VP,
vacuum pump; FV, feeding valve; P, piston; ST, sapphire tube; B, cylindrical support; C, cap; PC, pressurization circuit; O, window.
 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204 195

a Sartorius comparator balance (MCA1200) at an accuracy where v is the specific volume of the fluid. Eq. (5) was mod-
of ±10−7 kg. The resulting uncertainty for the mole fraction ified and the proposed expression is (MTS):
composition of the mixtures is less than ±10−4 .
d 1 + d2 P
v= (6)
d3 − d4 T + d5 T 1/2 + d6 P
3. Modeling
where the corresponding constants for Eqs. (5) and (6) are
obtained by minimizing the deviations between the model
3.1. Pure liquid densities
and the experimental compressed liquid densities of the pure
fluid as reported by Toscani and Szwarc [5]. The MTS model
The experimental compressed liquid densities of thio-
improves the representation of the volumetric properties of
phene were correlated using four different equations, the
thiophene compare to the TS model, as will be discussed in
BWRS EoS [8], the Tait equation (TE) [7], a polynomial
the results section.
model proposed by Toscani and Szwarc (TS) [5], and a pro-
The statistical values used to evaluate the different corre-
posed modification of the Toscani and Szwarc model (MTS).
lations are the absolute average deviation (AAD), the mean
The BWRS EoS [8] has 11 parameters and it is expressed as
deviation (bias), the standard deviation (SDV) and the root
follows:
mean square (RMS), defined as follows:
RT B0 RT − A0 − C0 /T 2 + D0 /T 3 − E0 /T 4  exptl 
P= +
V V2 Vi − Vicalcd
%Vi = 100 (7)
bRT − a − d/T α(a + d/T ) Vi
exptl
+ 3
+
V V6
1
n
c(1 + u/V 2 ) exp(−u/V 2 ) AAD = |%Vi | (8)
+ (1) n
V 3T 2 i=1

where V is the molar volume.

1
n
The Tait equation [7] is given by: bias = (%Vi ) (9)
n
ρ0 i=1
ρ=
 (2)
BT +P 
1 − CT ln 
BT +P0  1 
n
SDV =  (%Vi − bias)2 (10)
where P0 is a reference pressure equal to 0.1 MPa, and ρ0 is n−1
i=1
calculated with a modified Rackett equation [7]:

 n
AR 1
ρ0 = [1+(1−T/CR )DR ]
(3) RMS =  (%Vi )2 (11)
BR n
i=1
Densities for thiophene at atmospheric pressure reported in
Table 1 were correlated to obtain the constants AR , BR , CR , 3.2. Binary mixture densities and excess molar volumes
and DR of the Rackett equation. BT is given by [7]:
T The experimental volumetric properties of the binary
BT = b0 + b1 (4) mixtures have been predicted using the PC-SAFT EoS. A
ET
detailed explanation for the EoS can be found in the origi-
The TS model [5] is expressed by the equation: nal paper [11]. Only the required expressions are presented
here.
A + BP + CP 1/2
v= (5) PC-SAFT EoS can be written in terms of the compress-
D − ET + P + FP 1/2 ibility factor for non-associating fluids, as [11]:

Table 1 Z = 1 + Zhc + Zdisp (12)

Experimental densities of thiophene at atmospheric pressure
T (K) ρ (kg m−3 ) where Zhc represents the contribution given by the hard chain
293.15 1063.59 fluid, and Zdisp represent the contribution by dispersion forces
303.15 1051.55 between molecules [11]. These contribution are reported by
313.15 1039.32 Gross and Sadowski as [11]:
323.15 1026.98
333.15 1014.58  ∂ ln giihs
343.15 1002.15 Zhc = m̄Zhs − xi (mi − 1)ρ (13)
353.15 989.76 ∂ρ
i
196 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204

∂(ηI1 ) 2 3 Densities of pure fluids and mixtures are calculated by

Zdisp = −2πρ m εσ
∂η an iterative procedure using Eq. (12). The three molecular
parameters required by the EoS (segment number m, segment
∂(ηI2 )
− πρm̄ C1 + C2 ηI2 m2 ε2 σ 3 (14) diameter σ, and segment energy parameter ε/k) are obtained
∂η by fitting the model to vapor pressure and saturated liquid
density data of the fluid [11].
The expressions for the hard sphere mixture are presented The excess molar volumes for the binary mixtures reported
as [11]: were calculated over the entire temperature and pressure
ζ3 3ζ1 ζ2 3ζ 3 − ζ3 ζ23 intervals according to the relation:
Zhs = + + 2 (15)
1 − ζ3 ζ0 (1 − ζ3 )2
ζ0 (1 − ζ3 )3 x1 MW1 + x2 MW2
VE = − (x1 V1 + x2 V2 ) (27)
ρmix
1 d i dj 3ζ2
gijhs = + where VE is the excess molar volume, ρmix the density of the
1 − ζ3 di + d j (1 − ζ3 )2
mixture, V1 and V2 the pure component molar volumes, x1
2
di dj 2ζ22 and x2 the mole fractions of CO2 and thiophene, respectively,
+ (16) and MW1 and MW2 are the molecular weights of CO2 and
di + d j (1 − ζ3 )3
thiophene, respectively.
π 
ζn = ρ xi mi din n ∈ {0, 1, 2, 3} (17)
6
i 4. Results and discussion
while the expressions for the Zdisp contribution are [11]:
Compressed liquid densities of thiophene at temperatures

6 from 313 to 363 K and pressures up to 25 MPa are reported
I1 (η, m) = ai (m)ηi (18) in Table 2. Experimental densities of thiophene reported in
i=0 Tables 1 and 2 were correlated with Eqs. (1), (2), (5), and
(6). We have used the Marquardt–Levenberg least squares

6
I2 (η, m) = bi (m)ηi (19) optimization using the following objective function, S:
i=0
−1
8η − 2η2 20η − 27η2 + 12η3 − 2η4
C1 = 1 + m̄ + (1 − m̄) (20)
(1 − η)4 [(1 − η)(2 − η)]2
8 + 20η − 4η2 40 − 48η + 12η2 + 2η3
C2 = −C12 m̄ + (1 − m̄) (21)
(1 − η)5 [(1 − η)(2 − η)]3
The constants required for the power series in Eqs. (18)
and (19) are reported elsewhere [11]. The mixing rules based
on the van der Waals one fluid theory reported by Gross and  2
Sadowski were used in this work. These are expressed as  ρexptl − ρcalcd
[11]: S= i i
exptl
(28)
ρi
εij  3
i

m2 εσ 3 = xi xj mi m j σij (22) to correlate the parameters of the four models, as reported
kT
i j previously [12]. The obtained parameters for the four mod-
 εij 2 3 els and the statistical values to evaluate the correlations are
m 2 ε2 σ 3 = xi xj mi mj σij (23) reported in Table 3.
kT
i j The relative deviations between experimental data and
 those calculated by the various models for thiophene are pre-
m̄ = xi m i (24) sented in Figs. 2 and 3. As observed in the different scales,
i
the BWRS EoS and MTS show a better representation of the
together with the conventional combining rules [11], which compressed liquid densities of thiophene. The MTS model
are employed to determinate the parameters of unlike seg- improves the representation of the densities of thiophene
ments. compare to the TS model obtaining similar results than those
1 obtained by the 11-parameter BWRS EoS for the entire range
σij = (σi + σj ) (25) of temperature and pressure reported in this work. We tested
2
√ a higher order polynomial expression for the temperature
εij = εi εj (1 − kij ) (26) dependency of BT in the TE. No improvement in the behavior
 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204 197

Table 2
Compressed liquid densities of thiophene at six different temperatures
T (K) = 313.09 T (K) = 323.01 T (K) = 332.85 T (K) = 342.77 T (K) = 352.67 T (K) = 362.51
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 )
1.029 1040.96 1.047 1028.97 1.015 1016.93 1.039 1004.75 1.064 992.39 1.007 979.80
1.969 1041.84 2.059 1029.98 2.035 1018.00 2.072 1005.93 2.003 993.54 2.022 981.13
2.970 1042.78 3.070 1031.02 3.004 1019.06 3.033 1007.02 3.024 994.79 3.029 982.49
3.987 1043.71 4.047 1031.99 3.964 1020.05 4.023 1008.17 4.003 995.98 4.004 983.74
5.055 1044.72 5.002 1032.90 4.991 1021.14 5.027 1009.26 5.048 997.22 5.006 985.01
5.952 1045.51 6.005 1033.90 6.001 1022.17 6.033 1010.36 6.013 998.36 6.003 986.27
6.937 1046.43 7.068 1034.92 7.014 1023.21 7.008 1011.44 7.013 999.51 6.999 987.50
8.032 1047.39 8.021 1035.81 7.998 1024.20 7.998 1012.50 8.050 1000.73 7.993 988.73
9.218 1048.44 9.013 1036.76 9.009 1025.23 9.005 1013.59 9.018 1001.82 9.007 989.99
10.045 1049.18 10.005 1037.67 9.995 1026.19 10.000 1014.65 10.003 1002.93 9.993 991.16
11.012 1050.03 10.991 1038.62 10.989 1027.18 10.963 1015.65 11.003 1004.07 10.997 992.36
12.014 1050.90 12.034 1039.58 12.006 1028.17 12.009 1016.72 12.004 1005.16 11.993 993.56
12.995 1051.74 12.977 1040.44 13.009 1029.18 13.023 1017.82 12.998 1006.25 12.838 994.53
13.961 1052.59 13.999 1041.38 13.971 1030.09 13.928 1018.74 14.005 1007.34 14.038 995.94
14.970 1053.43 14.991 1042.26 15.006 1031.04 15.009 1019.83 15.038 1008.46 15.044 997.10
15.953 1054.26 15.995 1043.17 15.990 1032.01 15.998 1020.79 16.006 1009.49 16.029 998.18
17.004 1055.16 16.998 1044.03 17.050 1033.03 17.025 1021.80 17.027 1010.58 17.006 999.27
18.003 1055.95 17.983 1044.93 17.976 1033.88 17.995 1022.80 18.001 1011.60 18.016 1000.40
18.904 1056.76 18.951 1045.78 19.018 1034.92 19.013 1023.79 19.031 1012.65 18.987 1001.47
20.001 1024.73 20.017 1013.74

of the equation was observed therefore we kept only a linear
expression.
Compressed liquid densities and excess molar volumes
for the CO2 + thiophene mixtures from 313 to 363 K and
pressures up to 25 MPa at five different compositions are pre-
sented in Tables 4–8. The excess molar volumes have been
evaluated according to the Eq. (27), where V1 is calculated
from the equation of state proposed by Span and Wagner
[20] and V2 is calculated from the BWRS EoS [8] with the
parameters given in Table 3. Excess molar volumes for the

Table 3
Adjusted parameters for the correlation models for densities of thiophene
Parameters Values Parameters Values
BWRS Tait equation
B0 (cm3 mol−1 ) 526.44 AR (kg m−3 ) 6.530 × 10−2
A0 (bar cm6 mol−2 ) 2.4043 × 107 BR 6.832 × 10−3
C0 (bar K2 cm6 mol−2 ) −8.42940 × 1011 CR (K) 821.775
D0 (bar K3 cm6 mol−2 ) −1.70579 × 1013 DR 0.1279
E0 (bar K4 cm6 mol−2 ) −3.51784 × 1016 CT 6.624 × 10−2
b (cm6 mol−2 ) −11 822.536 b0 (MPa) 209.961
a (bar cm9 mol−3 ) 8.11430 × 107 b1 (MPa) −45.473
d (bar K cm9 mol−3 ) 1.23034 × 109 ET (K) 100.0
c (bar K2 cm9 mol−3 ) −1.91531 × 1014 AAD (%) 1.70 × 10−2
α (cm9 mol−3 ) 1.21085 × 107 bias (%) −4.82 × 10−3
u (cm6 mol−2 ) 2625.3664 SDV (%) 1.97 × 10−2
AAD (%) 2.50 × 10−3 RMS (%) 1.92 × 10−2
bias (%) −1.06 × 10−5
SDV (%) 3.90 × 10−3
RMS (%) 3.89 × 10−3
Toscani and Szwarc MTS
A (MPa1/2 m3 kg−1 ) −267457.04 d1 (MPa m3 kg−1 ) −23.9154
B (m3 kg−1 ) 284.246 d2 (m3 kg−1 ) −0.1386
C (MPa1/2 m3 kg−1 ) −8212.898 d3 (MPa) −27824.7
D (MPa) −3.84293 × 108 d4 (MPa K−1 ) −48.487
E (MPa K−1 ) −3.38840 × 105 d5 (MPa K−1/2 ) −690.921
F (MPa1/2 ) −8.43021 × 106 d6 −167.541
AAD (%) 2.01 × 10−2 AAD (%) 4.16 × 10−3
bias (%) −1.54 × 10−5 bias (%) −6.07 × 10−7
SDV (%) 2.76 × 10−2 SDV (%) 5.54 × 10−3
RMS (%) 2.75 × 10−2 RMS (%) 5.52 × 10−3
198 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204

Table 4
Experimental densities and excess molar volumes for the CO2 (1) + thiophene (2) mixture at x1 = 0.1990
T (K) = 313.07 T (K) = 322.95 T (K) = 332.85

P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 )
4.997 1030.05 −68.04 5.076 1016.50 −72.05 5.081 1002.75 −77.15
6.011 1031.17 −49.04 6.015 1017.63 −54.75 6.051 1004.04 −59.22
7.011 1032.32 −34.64 7.042 1018.88 −40.66 7.075 1005.38 −45.37
8.006 1033.43 −21.98 8.054 1020.10 −29.69 8.033 1006.63 −35.38
9.032 1034.56 −8.27 9.012 1021.25 −20.90 9.006 1007.88 −27.17
10.022 1035.65 −4.56 9.975 1022.38 −13.23 10.006 1009.13 −20.20
11.026 1036.74 −3.50 11.019 1023.61 −7.71 11.013 1010.42 −14.47
12.001 1037.83 −2.94 12.001 1024.72 −5.42 12.053 1011.71 −10.09
13.018 1038.90 −2.55 12.978 1025.86 −4.28 13.009 1012.87 −7.50
13.993 1039.92 −2.27 14.026 1027.05 −3.55 14.005 1014.10 −5.85
14.989 1040.95 −2.05 15.010 1028.15 −3.09 15.042 1015.31 −4.77
16.012 1042.03 −1.86 16.019 1029.28 −2.73 16.037 1016.53 −4.07
17.005 1043.03 −1.71 17.005 1030.36 −2.46 17.034 1017.71 −3.56
18.003 1044.05 −1.58 18.005 1031.46 −2.23 18.013 1018.85 −3.17
19.065 1045.15 −1.46 19.000 1032.53 −2.05 19.004 1019.98 −2.86
20.016 1021.13 −2.60

T (K) = 342.66 T (K) = 352.59 T (K) = 362.38

5.097 988.63 −81.57 4.979 974.07 −88.86 5.067 959.54 −91.04
6.031 989.99 −64.00 5.990 975.64 −68.86 6.020 961.18 −72.20
7.084 991.48 −49.61 7.029 977.28 −54.23 7.006 962.87 −58.08
8.010 992.78 −39.97 8.024 978.80 −43.71 8.052 964.61 −46.85
9.020 994.19 −31.61 9.035 980.29 −35.34 9.004 966.16 −38.89
10.077 995.61 −24.58 9.983 981.70 −29.03 9.993 967.76 −32.23
11.049 996.93 −19.31 11.018 983.20 −23.40 11.055 969.42 −26.44
11.932 998.15 −15.37 12.014 984.65 −18.96 12.043 970.93 −22.03
13.009 999.54 −11.60 13.125 986.24 −14.97 13.005 972.44 −18.46
13.997 1000.84 −9.08 14.000 987.44 −12.45 14.008 973.98 −15.38
14.996 1002.14 −7.28 15.014 988.92 −10.15 14.980 975.41 −12.93
16.043 1003.48 −5.97 15.934 990.14 −8.53 16.011 976.94 −10.84
17.018 1004.66 −5.10 17.055 991.66 −7.04 17.005 978.39 −9.22
18.018 1005.93 −4.43 17.954 992.83 −6.14 18.009 979.82 −7.92
19.016 1007.17 −3.92 19.034 994.28 −5.29 19.011 981.22 −6.89
20.032 1008.42 −3.50 20.005 995.52 −4.70 20.040 982.70 −6.04

Fig. 2. Relative deviations between experimental data and those calculated
with the BWRS EoS and the MTS model fitted on data reported in this work
for thiophene at the following temperatures: (䊉), 313.09 K; (
), 323.01 K;
(), 332.85 K; (), 342.77; (), 352.67 K; ( ), 362.51 K. Closed and open
symbols are for the BWRS EoS and the MTS, respectively.
Fig. 3. Relative deviations between experimental data and those calculated
with the TS and the TE models fitted on data reported in this work for thio-
phene at the following temperatures: (䊉), 313.09 K; (
), 323.01 K; (),
332.85 K; (), 342.77; (), 352.67 K; ( ), 362.51 K. Closed and open sym-
bols are for the TS and the TE models, respectively.
 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204 199

Table 5
Experimental densities and excess molar volumes for the CO2 (1) + thiophene (2) mixture at x1 = 0.3818
T (K) = 313.14 T (K) = 323.08 T (K) = 332.96

P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 )
5.783 1008.02 −100.96
6.953 1010.44 −67.60 6.997 994.07 −78.70 6.987 977.03 −88.53
8.014 1012.13 −41.74 8.053 995.85 −56.67 8.041 979.02 −67.26
9.021 1013.70 −15.92 9.009 997.45 −39.88 9.012 980.85 −51.58
9.948 1015.07 −8.67 10.081 999.25 −23.77 10.018 982.65 −38.17
10.945 1016.60 −6.51 11.041 1000.81 −14.38 11.007 984.44 −27.41
12.015 1018.22 −5.31 12.024 1002.40 −10.00 12.018 986.20 −19.18
13.025 1019.65 −4.56 12.998 1003.93 −7.84 13.030 987.96 −13.87
13.973 1021.04 −4.05 14.011 1005.51 −6.48 13.998 989.61 −10.80
15.006 1022.52 −3.61 15.018 1007.08 −5.56 14.969 991.25 −8.83
15.992 1023.89 −3.27 15.936 1008.44 −4.94 16.045 993.04 −7.36
17.012 1025.32 −2.98 17.059 1010.13 −4.35 17.024 994.61 −6.40
18.039 1026.72 −2.73 17.995 1011.52 −3.95 18.020 996.22 −5.65
18.908 1027.86 −2.55 19.010 1013.01 −3.59 19.050 997.85 −5.03

T (K) = 342.91 T (K) = 352.85 T (K) = 362.73

7.074 959.84 −94.90 7.014 941.65 −103.73
7.993 961.78 −76.51 8.124 944.24 −81.46 8.081 925.80 −88.62
8.982 963.81 −60.75 9.071 946.38 −66.70 9.009 928.21 −73.82
10.027 965.93 −47.32 10.020 948.55 −54.69 10.010 930.72 −60.95
11.019 967.88 −36.93 11.000 950.66 −44.49 11.009 933.15 −50.51
11.995 969.76 −28.62 12.010 952.84 −35.87 11.996 935.49 −42.00
12.980 971.64 −22.05 13.005 954.93 −28.94 13.008 937.87 −34.79
14.033 973.60 −16.88 14.021 956.99 −23.27 14.001 940.11 −28.95
15.024 975.41 −13.48 15.021 958.98 −18.92 15.006 942.32 −24.12
15.980 977.13 −11.16 16.002 960.92 −15.65 16.002 944.47 −20.25
17.026 978.96 −9.34 17.007 962.89 −13.10 17.016 946.62 −17.09
18.022 980.70 −8.06 18.002 964.77 −11.18 18.023 948.72 −14.60
19.019 982.41 −7.07 19.018 966.66 −9.66 19.014 950.73 −12.65

CO2 + thiophene mixtures are plotted in Figs. 4 and 5. Fig. 4
shows that the excess molar volumes become less negative
as pressure increases at constant temperature. On the other
hand, when temperature is increased, excess molar volumes
become more negative at constant pressure as it is shown
in Fig. 5. Similar behavior is observed for all reported data.
Densities for the binary mixtures for each composition were
correlated using the MTS model. The obtained parameters,
temperature, pressure, and density intervals, and the statisti-
cal values to evaluate the correlations are reported in Table 9.

Fig. 4. Excess molar volumes for the CO2 (1) + thiophene (2) binary mix- Fig. 5. Excess molar volumes for the CO2 (1) + thiophene (2) binary mix-
tures at ∼313.11 K reported in this work: (䊉), 10 MPa; (), 11 MPa; (), tures at ∼11 MPa reported in this work: (䊉), 313.11 K; (), 323.03 K; (),
12 MPa; (), 13 MPa; (), 14 MPa; (), 15 MPa; —, trend. 332.91 K; (), 342.75 K. (), 352.72 K; (), 362.56 K; —, trend.
200 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204

Table 6
Experimental densities and excess molar volumes for the CO2 (1) + thiophene (2) mixture at x1 = 0.5661
T (K) = 313.06 T (K) = 322.96
P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 )
7.053 983.33 −96.07
8.092 985.63 −58.47 8.142 964.89 −80.92
8.911 987.46 −26.18 9.024 967.04 −58.10
10.009 989.71 −12.21 10.004 969.41 −36.04
11.009 991.78 −9.20 11.043 971.85 −20.71
11.980 993.76 −7.63 12.049 974.11 −14.25
13.003 995.81 −6.52 13.009 976.27 −11.18
13.999 997.77 −5.74 14.014 978.41 −9.22
15.006 999.68 −5.12 15.031 980.61 −7.88
15.996 1001.53 −4.63 16.040 982.75 −6.90
17.015 1003.44 −4.21 17.014 984.76 −6.16
17.998 1005.25 −3.86 18.012 986.77 −5.55
19.007 1007.09 −3.56 19.036 988.76 −5.03

T (K) = 332.79 T (K) = 342.69

7.987 943.05 −100.34
9.035 945.99 −75.19 9.071 923.94 −87.20
10.035 948.77 −55.53 10.000 926.85 −69.65
11.015 951.37 −39.76 11.013 929.94 −53.91
12.021 953.97 −27.69 11.994 932.85 −41.56
13.022 956.49 −19.99 13.024 935.81 −31.47
14.010 958.85 −15.41 13.996 938.48 −24.49
15.020 961.27 −12.47 15.008 941.20 −19.35
16.037 963.66 −10.47 16.016 943.82 −15.80
17.014 965.85 −9.07 17.021 946.37 −13.27
18.001 968.08 −7.99 18.030 948.87 −11.39
19.018 970.30 −7.11 19.004 951.23 −10.00

The molecular parameters for the two pure components
required for the PC-SAFT EoS were taken from the litera-
ture for CO2 [10], whereas for thiophene were obtained by
fitting the EoS to its saturation properties. Experimental data
for thiophene [21] together with the DIPPR correlations [22]
were used to obtain values for the vapor pressure and satu-
rated liquid density data from the triple point up to the critical
point. The resulting molecular parameters are reported in
Table 10; the AAD obtained for the vapor pressure and satu-
rated liquid density data were 0.76 and 0.58%, respectively.
The liquid densities for thiophene were calculated at the same
conditions reported in Table 2 using these parameters. The
relative deviations between experimental and calculated val-
ues are less than 1%, and they are plotted in Fig. 6.
In order to model the volumetric properties of the mixture
it was necessary to obtain the binary interaction parame-
ter (kij ). The kij parameter was adjusted using vapor–liquid
equilibria data reported by Elizalde-Solis and Galicia-Luna

Table 7
Experimental densities and excess molar volumes for the CO2 (1) + thiophene (2) mixture at x1 = 0.6996
T (K) = 313.14 T (K) = 323.09 T (K) = 333.04

P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 )
7.991 974.06 −77.76 8.069 950.76 −103.36
9.112 977.19 −26.70 9.063 953.71 −71.54 9.091 929.67 −92.50
9.872 979.01 −16.61 10.074 956.72 −43.86 10.017 932.84 −70.11
10.946 981.56 −12.15 11.045 959.45 −26.45 11.036 936.19 −49.91
11.951 983.92 −10.05 11.999 962.01 −18.62 11.989 939.22 −35.69
13.033 986.45 −8.59 13.038 964.85 −14.42 13.024 942.40 −25.66
13.991 988.63 −7.65 14.005 967.35 −12.08 14.004 945.28 −19.95
14.931 990.71 −6.92 14.998 969.82 −10.42 14.904 947.84 −16.56
15.988 993.02 −6.26 16.004 972.38 −9.19 16.043 951.03 −13.68
16.994 995.20 −5.74 17.044 974.92 −8.20 17.013 953.62 −11.94
18.022 997.41 −5.29 17.927 976.97 −7.52 18.048 956.36 −10.52
19.011 958.88 −9.48
 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204 201

Table 8
Experimental densities and excess molar volumes for the CO2 (1) + thiophene (2) mixture at x1 = 0.9217
T (K) = 313.13 T (K) = 323.06 T (K) = 332.93

P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 ) P (MPa) ρ (kg m−3 ) VE (cm3 mol−1 )
9.091 798.81 −26.88
10.071 813.05 −12.24 10.088 726.50 −43.76 10.438 603.48 −55.23
11.026 824.67 −8.32 11.019 748.28 −23.41 11.001 635.42 −44.94
12.059 836.13 −6.24 12.026 766.89 −13.87 12.001 673.08 −29.15
13.037 845.52 −5.01 13.007 781.83 −9.65 13.005 700.08 −18.84
14.012 854.21 −4.18 14.004 794.96 −7.27 13.949 720.24 −13.19
15.001 862.38 −3.56 15.030 806.90 −5.73 15.012 738.73 −9.42
16.014 870.06 −3.06 16.054 817.45 −4.67 16.019 754.17 −7.25
17.035 877.41 −2.68 17.033 826.57 −3.93 17.014 767.10 −5.76
18.056 884.26 −2.37 18.006 835.18 −3.38 18.009 778.74 −4.70
19.024 890.25 −2.16 19.038 843.46 −2.91 18.964 789.26 −3.96
19.849 895.22 −1.94 20.051 850.95 −2.53 20.027 798.89 −3.26
20.858 901.01 −1.75 21.005 857.68 −2.24 21.018 807.65 −2.77
21.968 907.04 −1.57 22.019 864.36 −1.98 22.031 815.99 −2.37
23.020 912.42 −1.42 23.033 870.67 −1.76 23.019 823.51 −2.04
24.013 917.38 −1.30 24.027 876.59 −1.58 23.954 830.07 −1.77
25.004 921.98 −1.18 24.980 882.14 −1.43 25.005 836.64 −1.48

T (K) = 342.87 T (K) = 352.83 T (K) = 362.71

12.636 603.65 −34.19
13.012 619.36 −30.59
14.059 652.70 −21.98
15.034 677.37 −16.39 14.911 602.27 −23.58
16.023 697.82 −12.50 16.013 634.02 −18.25
17.022 715.57 −9.81 17.026 657.59 −14.50 17.222 598.80 −17.42
17.998 730.64 −7.94 17.993 676.40 −11.77 18.006 617.56 −15.03
19.015 744.20 −6.50 19.043 694.93 −9.63 19.032 639.20 −12.47
20.047 756.55 −5.40 20.010 709.32 −8.07 20.005 657.59 −10.58
20.988 767.05 −4.64 20.978 722.10 −6.83 21.034 674.17 −8.91
21.946 776.60 −4.00 21.993 734.66 −5.84 22.031 688.89 −7.64
22.890 785.25 −3.48 22.956 745.25 −5.06 23.010 701.90 −6.63
24.002 794.56 −2.96 23.974 756.09 −4.43 23.964 714.08 −5.86
25.012 802.40 −2.57 25.068 765.60 −3.77 25.021 725.01 −5.03

Table 9
Parameters for the MTS density correlation model for the CO2 (1) + thiophene (2) binary mixtures
x1 = 0.1990 x1 = 0.3818 x1 = 0.5661 x1 = 0.6996 x1 = 0.9217
Tmin (K) 313.07 313.14 313.06 313.14 313.13
Tmax (K) 362.38 362.73 342.69 333.04 362.71
Pmin (MPa) 4.979 5.783 7.053 7.991 9.091
Pmax (MPa) 20.040 19.050 19.036 19.011 25.068
ρmin (kg m−3 ) 959.54 952.80 923.94 929.67 598.80
ρmax (kg m−3 ) 1045.15 1027.86 1007.09 997.41 921.98
Data points 94 78 48 33 83
d1 (MPa m3 kg−1 ) −3.5266 −190.26 −115.61 −7.6487 1.3645
d2 (m3 kg−1 ) −0.027 −2.202 −1.913 −0.154 −0.576
d3 (MPa) −3346.3 −113051 −28450.4 2218.18 5895.93
d4 (MPa K−1 ) −10.8829 −924.679 −811.891 −71.5513 −106.302
d5 (MPa K−1/2 ) −207.519 −20707.5 −19061.9 −1801.60 −2102.77
d6 −32.60681 −2558.08 −2181.36 −173.691 −554.173
AAD (%) 5.96 × 10−3 9.79 × 10−3 8.00 × 10−2 7.12 × 10−3 4.26 × 10−1
bias (%) −1.08 × 10−6 −3.55 × 10−6 −1.43 × 10−5 −1.60 × 10−6 −7.80 × 10−3
SDV (%) 7.37 × 10−3 1.34 × 10−2 9.90 × 10−2 9.09 × 10−3 6.27 × 10−1
RMS (%) 7.33 × 10−3 1.33 × 10−2 9.80 × 10−2 8.95 × 10−3 6.23 × 10−1
202 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204

Table 10
Molecular parameters employed in the PC-SAFT EoS
Compound MW m σ (Å) ε/k (K)
Carbon dioxide [11] 44.009 2.0729 2.7852 169.21
Thiophene 84.142 2.3644 3.5655 301.73

Fig. 8. Relative deviations in mixture densities at different compositions:

(), 0.1990; (), 0.3818; (), 0.5661; (♦), 0.6996; (), 0.9217.

be observed, the relative deviations are negative and less than

Fig. 6. Relative error for calculated densities of thiophene using PC-SAFT
EoS at different temperatures: (䊉), 313.09 K; (), 323.01 K; (
), 332.85 K;
(), 342.77 K; (), 352.67 K; (), 362.51 K.
for this system [2]. Bubble-point calculations for all four
isotherms were used. The AAD obtained is 4.39% for pres-
sure and 0.47% for vapor composition. The resulting kij for
the mixture is 0.0887; no temperature dependency was tested.
The representation of the phase equilibria with the PC-SAFT
EoS is shown in Fig. 7. As reported by other authors [11,23],
the PC-SAFT EoS does not predict correctly the critical point
of the mixture.
Densities of the mixture were calculated with the obtained
kij at the conditions reported in Tables 4–8. The obtained rel-
ative deviations for composition are plotted in Fig. 8. As can
1% for three compositions (x1 = 0.1990, 0.3818, and 0.5661).
For the case of x1 = 0.6996, the relative deviations are approx-
imately 2% and positive. For x1 = 0.9217 at low pressures
(P < 15 MPa) large deviations can be observed. This is due
to the proximity of the mixture critical point, according to
the data reported by Elizalde-Solis and Galicia-Luna [2]. At
the same composition (i.e., x1 = 0.9217) and higher pressures
(P > 15 MPa) errors are less than 1%. Also the excess molar
volumes for the mixtures have been calculated according to
Eq. (27). Volumes for pure fluids and mixtures have been
calculated with the PC-SAFT EoS. For 353.15 K calculated
excess molar volumes and those reported in Tables 4–8 are
plotted in Fig. 9. The curves obtained by the EoS are presented
in the single-phase region for the mixture. Similar behavior
is observed for the other temperatures.
The relative deviations of the excess molar volumes for the
different mixtures are plotted in Fig. 10. As can be observed,
the deviations increase with pressure. It is important to men-
tion that even with deviations of less than 1% for pure fluids,

Fig. 7. Vapor liquid equilibria for CO2 (1) + thiophene (2) at: (䊉), 383.03 K; Fig. 9. Excess molar volumes at 353.15 K. (), Experimental data; ,
(), 334.28 K; , PC-SAFT correlation with kij = 0.0887. PC-SAFT prediction.
 A. Zúñiga-Moreno et al. / Fluid Phase Equilibria 236 (2005) 193–204 203

established, where the presence of sulfur compounds is on

the order of parts per million and the main component of the
mixture is CO2 .

List of symbols
AAD average absolute deviation
bias mean deviation
kij binary interaction parameter between component i
and j
m number of segments per chain
MW molecular weight (g mol−1 )
n number of data points
P pressure (MPa)
P0 reference pressure (0.1 MPa)
R gas constant (bar cm3 mol−1 K−1 )
Fig. 10. Relative deviations in excess molar volumes at different composi- RMS root mean square
tions: (), 0.1990; (), 0.3818; (), 0.5661; (♦), 0.6996; (), 0.9217. SDV standard deviation
T temperature (K)
the representation of the excess molar volumes is poor, and v specific volume (m3 kg−1 )
deviations are less than 40%, except for x1 = 0.9218 where V molar volume (cm3 mol−1 )
for pressures from 20 to 25 MPa the deviations increase to up V E excess molar volume (cm3 mol−1 )
to 130%. x mol fraction

Greek letters
5. Conclusions ε depth of pair potential (J)
η packing fraction
In this work, new compressed liquid densities of thiophene ρ density (kg m−3 )
and CO2 + thiophene binary mixtures at five different com- ρ0 reference density (kg m−3 )
positions at temperatures from 313 to 363 K and pressures up σ segment diameter (Å)
to 25 MPa were reported. There are no density experimental
data concerning CO2 + thiophene mixtures in the literature. Superscripts
For pure thiophene, the BWRS EoS and the MTS model, pre- calcd calculated value
sented here, represent the densities with similar accuracy. The disp contribution due dispersive attraction
MTS model only employs six parameters to represent the liq- exptl experimental value
uid phase. This model was also used to correlate the density hc hard chain
data for CO2 + thiophene mixtures at constant composition. hs hard sphere
Deviations from the experimental data increase for rich-CO2 mix mixture property
mixtures because of mixtures become more compressible.
Subscripts
PC-SAFT EoS was used to correlate vapor–liquid equi-
1 carbon dioxide
libria of the CO2 + thiophene mixture. Densities of the
2 thiophene
CO2 + thiophene mixtures and excess molar volumes were
calculated with a kij = 0.0887 obtained for the PC-SAFT EoS.
This equation can reproduce the experimental densities with
Acknowledgments
AAD of 0.71% and 2.49% for thiophene and CO2 , respec-
tively in the range of temperatures and pressures reported
The authors thank CONACYT and IPN for their finan-
here. For binary mixtures, at pressures greater than 10 MPa
cial support. AZM and FFBC thank to Professors Néstor L.
the AAD is less or equal 2%, while at lower pressures the
Dı́az-Ramı́rez and José M. Hallen-López for the fellowship
deviations increase as temperature and pressure get closer
received. Special thanks are given to Dr. Andre Blasig for his
to the critical point of the mixture. The deviations for rich-
useful comments.
thiophene mixtures (x1 < 0.6) are less than 1% whereas the
deviations increase with increasing concentration of CO2 .
Although the AAD is small for the two pure components, the
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