Fluid Phase Equilibria 260 (2007) 4959

Measurement of VLE (TPx or TPxy data) for hydrogen

sulfide + (dimethylsulfide or ethylmethylsulfide or carbon disulfide)
and methane solubilities in (dimethylsulfide or ethylmethylsulfide
or methylmercaptan or ethylmercaptan)
P. Guilbot a , K. Fischer b , A. Valtz a , P. Theveneau a , A. Baba-Ahmed a , D. Richon a,
a

Mines Paris/ParisTech, CEP/TEP, CNRS FRE 2861, 35 Rue Saint Honore, 77305 Fontainebleau, France
b Laboratory for Thermophysical Properties (LTP GmbH), Institute at the University of Oldenburg,
Marie-Curie-Str. 10, 26129 Oldenburg, France
Received 10 May 2006; received in revised form 4 July 2007; accepted 4 July 2007
Available online 10 July 2007

Abstract
VLE data (gas solubilities (TPx data) or complete TPxy data) were measured for the following systems:

hydrogen sulfide (H2 S) + dimethylsulfide (DMS) at 278, 293, 313, and 333 K.
H2 S + ethylmethylsulfide (EMS) at 293 and 313 K.
H2 S + carbon disulfide (CS2 ) at 273, 298, 323, and 348 K.
methane (CH4 ) + DMS at 253, 273, 293, and 313 K.
CH4 + EMS at 248, 273, 293, and 313 K.
CH4 + methylmercaptan (MM) at 243, 258, 273, 293, and 298 K.
CH4 + ethylmercaptan (EM) at 273, 293, and 313 K.

These data were used to establish new binary interaction parameters for the predictive SoaveRedlichKwong (PSRK) group contribution of
state. The extension of the PSRK parameter matrix allows now to perform reliable phase equilibrium calculations for systems with any hydrocarbons
and sulfur compounds. The mean relative deviation of PSRK compared to the experimental data for the bubble point pressures is less than 2% and
the mean absolute deviation for the vapor phase composition is 0.03 in terms of mole fraction.
2007 Elsevier B.V. All rights reserved.
Keywords: VLE measurements; H2 S; Carbonylsulfide; Dimethylsulfide; Ethylmethylsulfide; Ethylmercaptan; Methylmercaptan; Methane; Binary interaction
parameters; PSRK equation

1. Introduction
The idea of the study presented here was born while being
faced with a large demand from gas processing industry for
partition coefficients of sulfur compounds in solvents containing volatile hydrocarbons and hydrogen sulfide. Experimental
studies mainly performed by ARMINES and funded by Gas
Processors Association (GPA) in the project 876 [1,2] and after

Corresponding author. Tel.: +33 1 64 69 49 65; fax: +33 1 64 69 49 68.

E-mail address: dominique.richon@ensmp.fr (D. Richon).

0378-3812/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2007.07.013

in the project 986 provided a large VLE database for multicomponent systems, whereas almost no data are available for the
binary subsystems with respect to the sulfur compounds. The
attempt of a correlation in order to enable at least interpolations
did not allow a reliable and consistent representation of the total
set of experimental data, because in most cases several equation
of state (EoS) binary interaction parameters had to be fitted to
VLE data of multicomponent systems, whereby the data were
available only at very limited composition.
A group contribution approach (predictive Soave
RedlichKwong: PSRK [37]) should then be applied to
compare the experimental data from GPA project 876 with

50

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

predicted values using PSRK. The advantage of this approach is

that any compound could be considered and not only the investigated sulfur compounds. Unfortunately the direct calculation
was not possible, because a major part of the required group
interaction parameters were not available, namely between
the methane and the sulfide groups, the methane and the thiol
groups, the H2 S and the sulfide groups and the H2 S and the CS2
groups. The initially missing interaction parameters between
the H2 S and the COS groups were established in a previous
work [8].
Prior to the acquisition of experimental data a number of
assumptions were introduced in order to allow calculations and
explore the potential of PSRK for the given problem. If the group
interaction parameters for the methane group were missing, the
corresponding values for the alkane group were used. If the
group interaction parameters for the sulfur groups were missing,
the interaction parameter values were set to zero. A comparison of the available experimental data for binary, ternary and
quaternary systems with PSRK predictions showed promising
agreement. The accuracy of the existing experimental data (Kvalues mainly for sulfur trace compounds, Ki = yi /xi ) from GPA
project 876 was assumed to be indicated by the dispersion of
deviations between experiment and calculation, e.g. about 30%
when CH4 and H2 S were involved, and about 20% when they

were not present. The reliability of the prediction was assumed

to be roughly indicated by the mean value of deviations, e.g.
25% when including CH4 and H2 S containing systems, and 9%
when CH4 and H2 S were excluded. These results provided the
idea to investigate systems with CH4 and H2 S in combination
with sulfur compounds in order to establish reliable interaction
parameters.
2. Experimental
The chemicals were purchased from the following commercial suppliers with the given purities in terms of % GC: CH4
from Airgaz (purity 99.95%), H2 S from Air Liquide (purity
99.5%), DMS from Acros (purity > 99%), EMS from Aldrich
(purity > 99%), MM from Aldrich (purity 99.5%), EM from
Merck (purity > 99%) and CS2 from Merck (purity > 99.9%).
The used apparatus allows to work with both the synthetic
(as described in [8]) and analytical [9] methods, see Fig. 1. The
principle of the synthetic method is to inject precisely known
amounts of the pure components into a thermo-regulated equilibrium chamber, and to measure the system pressure as a function
of global composition. These data can be treated with mass
and volume balances in order to obtain the bubble point line
for mixtures (TPx-data). The analytic method allows the direct

Fig. 1. Flow diagram of equipment. Co1: variable volume cell for component 1; Co2: variable volume cell for component 2; DAU: data acquisition unit; DDD:
digital displacement transducer; DL: degassed liquid; DT: displacement transducer; FVC: fixed volume cell; GC: gas chromatograph; LB: liquid bath; LS: liquid
sampler; LVi loading valve i; Me: methane cylinder; MS: magnetic stirrer; PP: platinum probe; N: pressurized nitrogen; PTh: high pressure pressure transducer;
PTl: low pressure pressure transducer; SD: stirring device; SM: sample monitoring; SV: home made shut off valve; TR: thermal regulator; Vi: shut off valve i; VP:
vacuum pump; VS: vapor sampler.

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

determination of both the bubble and dew points. The mixture is

in liquid vapour state in the cell, both phases are microsampled.
The cell is composed of a sapphire tube pressed between two
hastelloy pieces. The bottom one holds one non-rotating stem
valve, one platinum probe and the stirring assembly. The top
one holds three feeding valves, one platinum probe, one capillary connected to two thermally controlled pressure transducers
(for low and high pressure measurements), and two capillaries for withdrawal of microsamples. The cell is placed inside a
temperature regulated liquid bath.
In the case of measurements for H2 S-DMS, H2 S-EMS and
H2 S-CS2 systems, the two components of the binary mixture
are introduced into the cell using two volumetric pumps (Co1
and Co2), each one connected to a pressure transducer, and consisting of a variable volume cylinder connected to an optical
displacement transducer and a pressurizing circuit.
When one component is in its liquid state at laboratory conditions it can be degassed inside the degassing flask fitted with
Co2. These volumetric pumps allow to precisely inject into the
cell known amounts of the two components at compressed liquid state as they are fitted with an optoelectronic device from
Heidenhain (accuracy of displacement: 1 m).
In the case of CH4 solubility measurements, a thermoregulated fixed volume cylinder was used. When CH4 was
injected into the cell, there was a drop of pressure in the cylinder, which was recorded by the pressure transducer placed on
the loading line.
For some systems, the two different independent experimental techniques (analytic and synthetic methods) and different
initial solvent loadings for the synthetic method were applied for
the same temperature in order to verify the raw data treatment
procedure for the synthetic measurements.
The phase equilibrium is achieved in a cylindrical cell made
of sapphire, the cell is immersed in a constant-temperature
liquid bath that controls and maintains the desired temperature within 0.01 K. In order to perform accurate temperature
measurements in the equilibrium cell and to check for thermal gradients, the temperature is measured at two locations
corresponding to the vapor and liquid phases through two calibrated 100  platinum resistance thermometers connected to
an HP data acquisition unit (HP34970A). The two 100  platinum probes, which are put inside wells drilled in the top
and in the bottom flanges of the cell are calibrated against
a 25  reference platinum probe (LyonAlemandLouyot).
Resulting uncertainty on temperatures is 0.01 K. Pressure is
measured by means of Druck pressure transducers connected
to the same data acquisition unit; the pressure transducers
are calibrated against a dead weight pressure balance (Desgranges & Huot 5202S, CP (0.3400) bar, Aubervilliers, France)
and against a mercury U-tube for lowest pressures. Pressure measurement uncertainties are estimated to be within
0.06 bar.
The synthetic method was applied with the following procedure.
The 30 cm3 the cell must has been calibrated accurately
within 0.005 cm3 . The two variable volume cells, which are
used for the loading of liquids, are different in diameter. The

51

variable volume cell Co2 (diameter of the piston: 2.019 cm)

is filled with the solvent which is kept at a compressed liquid state using a nitrogen pressurizing circuit. The variable
volume cell Co1 (diameter of the piston: 1.502 cm) is filled
with the solute, which is also kept at a compressed liquid
state. The cylinder used for methane storage, has a fixed volume (83.46 cm3 ). A known amount of solvent is introduced
into the equilibrium cell. The moving of the piston of corresponding variable volume cell when transferring the solvent
into the equilibrium cell is recorded through its displacement
transducer, DT. The pure vapor pressure of each subcritical
component is measured. It is important to measure both pure
fluid and mixture properties with the same transducers to prevent from systematic deviations (due for instance to impurities).
Then the solute is injected into the cell through successive loadings. For each injection of solute we need to record the pressure
and the temperature of the solute variable volume cell and also
the displacement of its internal piston. All the experiments are
carried out isothermally. In the case of methane as the solute,
it is introduced from the fixed volume cylinder (FVC) into
the equilibrium cell. Pressure (P) and temperature (T) inside
FVC are recorded before and after each loading. Knowing the
methane density at each (P,T) conditions from the Setzmann
and Wagner equation [10], the methane loading can precisely be
calculated.
As PTz data are obtained experimentally with the synthetic method, these raw data have to be converted into PTx
data. Due to the precautions taken to do the experiment (for
instance minimized volume of vapor phase) and to the characteristics of the mixture itself (difference of volatility between
the two components), the vapor phase correction applied is
more or less important. In fact, if the volatility of the two components is similar, solubility data (x data) are very close to
the feed (z data). The vapor composition calculated using a
cubic equation of state combined with a GE mixing rule is not
considered as an experimental result, but has a certain (small)
influence on the mass balance conditions required for the flash
calculations.
In the particular case of methane solubility measurements,
the solvent (the sulfur component) and the solute (methane) are
very different in relative volatility, so that the correction made at
high pressure becomes important (even for a small vapor phase).
For this reason the procedure was tested by applying it to different independent measurements with different initial solvent
loadings, which is very sensitive for judging the data quality.
Since the results coincided within the expected accuracy, the
data treatment was confirmed to be reliable.
The use of the analytic method, the experimental study of
the various binary systems includes the calibration of pressure
transducers and platinum probes also, but in addition, the calibration of the detectors of the gas chromatograph (flame ionization
detector: FID and thermal conductivity detector: TCD). The
FID and TCD were repeatedly calibrated by introducing known
amounts of the various compounds through a gas syringe into
the injector of the GC.
The equilibrium cell and its loading lines are evacuated down
to 0.1 Pa prior to introduction of about 5 cm3 of solvent at room

52

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

Table 1
Experimental and calculated VLE data for the H2 S-DMS binary mixture

Fig. 2. Pxy diagrams of the H2 S (1)DMS (2) binary system at different

temperatures. Solid line: correlation using PSRK (Unifac).

temperature. Then, the solute is introduced into the cell directly

from Co1 (through preliminary evacuated transfer lines) to pressure level corresponding to the pressure of the first measurement.
More solute is introduced after each sampling and analysis steps
up to the new desired pressure. After each introduction of gas
into the cell, efficient stirring is started, and pressure is stabilized within a few minutes, measurements are performed only
when pressure is constant within experimental uncertainty for
at least 10 min (pressure remains constant during sampling as
withdrawn amounts are negligible compared to total phases volumes).
The sampling is carried out using RolsiTM capillary
sampler-injector [11]. (www.rolsi.com). The sampler-injector is
connected to the cell through 0.1 mm internal diameter capillary
tubing. The withdrawn samples less than 1 mg are then swept
to the GC for analysis. For each equilibrium condition, at least
three samples are withdrawn from the vapor phase and from the
liquid phase, using the samplers and analyzed in order to check
for measurement repeatability.
3. Results and discussion
In Tables 17 all the experimental data are summarized,
and they are also compared with the obtained PSRK calculations. Data regression required for the establishment of the
PSRK interaction parameters is described elsewhere [12]. For
each investigated system, the data are also shown graphically in
comparison with the final PSRK-results. (Figs. 28)
TPx data corresponding to methane solubilities have been
used to obtain the Henry coefficients from an individual EoS
correlation of each data series, from which the slope of methane
fugacity versus methane mole fraction concentration can be calculated; the experimental Henry constants are listed in Table 8.
The temperature dependence of the Henry constants is shown in
Figs. 912 along with the final PSRK calculations.
It can be seen that the PSRK model describes the typical shape
of the temperature dependence of the Henry coefficients, which
runs through a maximum indicating a minimum gas solubility.
The estimated accuracy of both the experimental and calculated
Henry coefficients is better than 5%.

Pexp (bar)

Pcal (bar)

diff P (bar)

P%

xH2 Sexp

T = 278.46 K
0.29
0.63
0.98
1.42
1.88
2.38
2.90
4.22
5.35
6.17
6.90
7.48
7.96
8.34
8.76
9.33
9.65
9.88
10.08
10.25
10.39
10.54
10.68
10.77

0.29
0.62
0.97
1.40
1.86
2.36
2.88
4.19
5.32
6.12
6.83
7.38
7.84
8.21
8.60
9.15
9.46
9.68
9.87
10.04
10.19
10.34
10.49
10.58

0.00
0.01
0.02
0.02
0.02
0.02
0.02
0.02
0.03
0.05
0.07
0.10
0.12
0.14
0.16
0.18
0.19
0.20
0.20
0.20
0.20
0.20
0.19
0.19

0.0
1.5
1.7
1.5
1.3
1
0.8
0.5
0.6
0.8
1
1.3
1.5
1.6
1.8
1.9
2
2
2
2
1.9
1.9
1.8
1.7

0.0000
0.0486
0.0963
0.1517
0.2062
0.2619
0.3155
0.4382
0.5309
0.5926
0.6445
0.6834
0.7151
0.7401
0.7667
0.803
0.8239
0.8385
0.8515
0.8628
0.8729
0.8825
0.8924
0.8989

T = 293.43 K
0.54
3.68
3.85
4.02
4.24
5.04
5.42
5.88
6.44
7.21
8.13
8.80
9.61
10.55
11.83
12.85
14.13
15.47

0.54
3.44
3.60
3.77
3.98
4.76
5.13
5.59
6.14
6.92
7.85
8.54
9.38
10.35
11.69
12.74
14.07
15.45

0.00
0.24
0.25
0.26
0.27
0.29
0.29
0.30
0.30
0.29
0.27
0.26
0.23
0.20
0.14
0.10
0.06
0.02

0.0
6.6
6.5
6.4
6.2
5.7
5.4
5
4.6
4
3.4
2.9
2.4
1.9
1.2
0.8
0.4
0.1

0.0000
0.2527
0.2645
0.2769
0.2921
0.3452
0.3697
0.3986
0.4324
0.4776
0.5293
0.5658
0.6084
0.656
0.7189
0.767
0.8263
0.8874

yH2 Sexp

yH2 Scal

P%

y

T = 293.41 K (y = yexp ycalc )

3.49
3.63
0.2668
5.10
5.39
0.3862
7.25
7.58
0.5149
9.00
9.21
0.6003
11.20
11.30
0.7011
12.97
13.00
0.7787
14.60
14.57
0.8487
16.27
16.12
0.9178
17.00
16.66
0.9421

0.879
0.9253
0.9559
0.968
0.9808
0.987
0.9926
0.996

0.8841
0.9336
0.9623
0.9745
0.9846
0.9902
0.9942
0.9972
0.9981

4
5.6
4.6
2.4
0.9
0.2
0.3
0.9
2

0.0052
0.0083
0.0065
0.0065
0.0038
0.0033
0.0016
0.0012

T = 313.22 K
3.03

3.52
3.51
5.88
5.99
9.05
9.33
11.87
12.21

0.6678
0.7257
0.855
0.918
0.9447

0.7146
0.8515
0.92
0.9485

0.3
1.9
3.2
2.9

0.0111
0.0035
0.002
0.0037

Pexp (bar)

Pcal (bar)

xH2 Sexp

0.1461
0.2726
0.4159
0.5222

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

Table 1 (Continued )
Pcal (bar)

xH2 Sexp

yH2 Sexp

yH2 Scal

P%

y

15.09
16.07
18.46
21.04
25.49
26.55

0.6174
0.6478
0.7192
0.7926
0.9143
0.9429

0.9631

0.9763
0.9838
0.9936

0.9658
0.9702
0.979
0.9862
0.9952
0.9969

2.8
2.9
3.1
2.1
0.9
0.5

0.0027

0.0027
0.0024
0.0016

T = 333.20 K
3.83
3.77
5.01

3.40

8.04
8.12
11.94
12.20
16.14
16.62
19.11
19.58
19.92
20.49
23.89
24.76
27.89
28.52
31.91
32.80
36.00
36.25
37.98
38.62
40.45
40.36

0.074

0.2378
0.3646
0.4822
0.5526
0.573
0.6639
0.7376
0.8167
0.8777
0.9184
0.9477

0.4714
0.6115
0.4097
0.7806
0.864
0.9106

0.9318
0.9555
0.9645
0.9781
0.984
0.9902
0.993

0.4671

0.78
0.8702
0.9176
0.9373
0.9422
0.9603
0.9717
0.9818
0.9883
0.9923
0.9951

1.6

1.1
2.1
2.9
2.5
2.8
3.7
2.3
2.8
0.7
1.7
0.2

0.0042

0.0005
0.0062
0.007

0.0104
0.0047
0.0073
0.0037
0.0043
0.0021
0.002

Pexp (bar)
14.68
15.61
17.90
20.61
25.27
26.67

exp: experimental, calc: calculated using the PSRK correlation, diff

P = Pexp Pcalc , P% = [(Pexp Pcalc )/Pexp ]%).

Fig. 3. Pxy diagrams of the H2 S (1)EMS (2) binary system at different

temperatures. Solid line: correlation using PSRK (Unifac).

53

Table 2
Experimental and calculated VLE data for the H2 S-EMS binary mixture
Pexp (bar)

Pcal (bar)

diff P (bar)

P%

xH2 Sexp

T = 293.23 K
0.17
0.67
1.23
1.82
2.57
3.51
4.65
5.71
6.98
8.42
9.57
10.50
11.30
11.94
12.47
12.93
13.35
13.70
14.06
14.42
14.67
14.97
15.24
15.48
15.74

0.17
0.69
1.26
1.86
2.63
3.58
4.72
5.78
7.02
8.42
9.53
10.42
11.19
11.80
12.31
12.76
13.16
13.51
13.86
14.21
14.47
14.77
15.05
15.30
15.57

0.00
0.02
0.03
0.05
0.06
0.07
0.07
0.06
0.04
0.00
0.04
0.08
0.11
0.14
0.16
0.18
0.19
0.20
0.20
0.20
0.20
0.20
0.19
0.19
0.17

0.00
2.6
2.8
2.7
2.4
2.1
1.6
1.1
0.6
0
0.4
0.8
1
1.2
1.3
1.4
1.4
1.4
1.4
1.4
1.4
1.3
1.3
1.2
1.1

0.0000
0.0483
0.0987
0.149
0.2094
0.2781
0.3546
0.4201
0.4917
0.5663
0.6223
0.6654
0.7012
0.7295
0.7525
0.7727
0.7907
0.8061
0.8215
0.8373
0.8487
0.8617
0.8743
0.8853
0.8974

T = 313.33 K
0.40
1.49
2.57
3.71
4.77
5.84
6.93
8.21
9.36
10.50
11.58
12.65
13.53
14.54
16.24
17.52
18.65
19.57
20.57
21.39
22.21
23.00
23.79
24.56
25.17

0.40
1.48
2.55
3.68
4.73
5.80
6.87
8.14
9.27
10.41
11.47
12.53
13.40
14.39
16.07
17.34
18.46
19.38
20.38
21.20
22.03
22.83
23.64
24.43
25.05

0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.09
0.10
0.11
0.12
0.13
0.15
0.16
0.18
0.18
0.19
0.19
0.19
0.18
0.17
0.16
0.14
0.12

0.00
0.5
0.6
0.7
0.8
0.8
0.8
0.9
0.9
0.9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.9
0.9
0.8
0.7
0.7
0.6
0.5

0.0000
0.0653
0.1253
0.1845
0.2358
0.2852
0.3322
0.3842
0.4285
0.4705
0.5083
0.5442
0.5728
0.6044
0.6558
0.6931
0.7251
0.7508
0.7784
0.8007
0.823
0.8444
0.8658
0.8867
0.9031

exp: experimental, calc: calculated using the PSRK correlation, diff

P = Pexp Pcalc , P% = [(Pexp Pcalc )/Pexp ]%).

Fig. 4. Pxy diagrams of the H2 S (1)CS2 (2) binary system at different temperatures. Solid line: correlation using PSRK (Unifac).

54

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

Table 3
Experimental and calculated VLE data for the H2 S-CS2 binary mixture
xH2 Sexp

yH2 Sexp

yH2 Scal

P%

T = 273.08 K
0.17
0.17
3.45

4.01

4.87

7.47
7.26
10.33
10.33

0.0000

0.6207
1.0000

0.0000
0.9460
0.9596
0.9658
0.9821
1.0000

0.0000

0.9855
1.0000

0.0

2.8
0.0

0.0000

0.0033
0.0000

T = 298.40 K
0.49
0.49
4.23

4.68

5.11

6.07

7.10
6.13
8.69
8.20
12.27
11.52
13.09
12.92
13.79
13.64
16.05
15.97
19.34
19.28
20.24
20.24

0.1919
0.2821
0.463
0.5541
0.6038
0.7655
0.9563
1.0000

0
0.8758
0.8817
0.9043
0.9211
0.9368
0.9488

0.9722
0.9818
0.9979
1.0000

0.0000

0.926
0.9472
0.9666
0.9725
0.9753
0.9839
0.9962
1.0000

0.0

13.7
5.7
6.1
1.3
1.1
0.5
0.3
0.0

0.0000

0.0108
0.0016

0.0031
0.0021
0.0017
0.0000

T = 323.50 K
1.16
1.16
5.27

6.69

8.05

9.59

11.24
11.27
13.93
14.29
21.73
22.01
22.96
23.06
27.23
27.40
33.66
33.65
35.64
35.64

0.0000

0.2172
0.2982
0.5556
0.5957
0.7603
0.9528
1.0000

0.0000
0.7603
0.8241
0.8473
0.8808
0.9011
0.9167

0.9566
0.9714
0.9945
1.0000

0.0000

0.9012
0.9242
0.9576
0.961
0.974
0.9933
1.0000

0.0

0.3
2.6
1.3
0.4
0.6
0
0.0

0.0000

0.0001
0.0076
0.9576
0.0044
0.0026
0.0011
0.0000

T = 348.45 K
2.40
2.40
8.01

9.98

11.94

14.18
14.83
16.55
17.25
20.66
21.58
35.27
36.15
42.91
42.73
54.42
54.22
58.12
58.12

0.0000

0.1754
0.2145
0.2893
0.5953
0.7451
0.9502
1.0000

0.0000
0.5965
0.7311
0.7914
0.8285
0.857
0.8837

0.9419
0.9752
1.0000

0.0000

0.8366
0.86
0.8891
0.9411
0.9576
0.988
1.0000

0.0

4.6
4.3
4.5
2.5
0.4
0.4
0.0

0.0000
0.5965
0.7311
0.7914
0.0082
0.003
0.0055
0.9411
0.0157
0.0128
0.0000

Pexp (bar)

Pcal (bar)

exp: experimental, calc: calculated using the PSRK correlation, diff

P = Pexp Pcalc , P% = [(Pexp Pcalc )/Pexp ]%).

Table 4
Experimental and calculated VLE data for the CH4 -DMS binary mixture
Pexp (bar)

Pcal (bar)

diff P (bar)

P%

xCH4exp

T = 252.89 K
0.08
0.87
2.30
4.57
7.21
10.40
15.16
20.08
24.95
48.16
63.01
69.63
78.65
86.30
92.93
97.30
100.88

0.08
0.88
2.32
4.61
7.27
10.48
15.29
20.25
25.17
48.64
63.69
70.41
79.57
87.36
94.10
98.56
102.21

0.00
0.01
0.02
0.04
0.06
0.09
0.13
0.18
0.23
0.48
0.68
0.78
0.92
1.05
1.18
1.26
1.33

0.0
0.7
0.8
0.8
0.8
0.8
0.9
0.9
0.9
1.0
1.1
1.1
1.2
1.2
1.3
1.3
1.3

0.0000
0.0020
0.0055
0.0112
0.0177
0.0256
0.0373
0.0494
0.0612
0.1165
0.1503
0.1650
0.1843
0.2002
0.2136
0.2222
0.2290

T = 253.06 K
0.08
1.42
2.99
4.62
7.70
13.00
18.79
34.60
39.54
49.25
55.03
60.82
65.62
70.29
75.16
80.51
85.73
91.31
95.82
103.36

0.08
1.46
3.08
4.76
7.92
13.37
19.33
35.52
40.58
50.49
56.39
62.29
67.17
71.93
76.87
82.32
87.61
93.27
97.85
105.48

0.00
0.04
0.09
0.14
0.23
0.38
0.53
0.92
1.04
1.24
1.36
1.47
1.56
1.64
1.71
1.81
1.88
1.96
2.03
2.12

0.0
2.9
2.9
3.0
2.9
2.9
2.8
2.7
2.6
2.5
2.5
2.4
2.4
2.3
2.3
2.2
2.2
2.1
2.1
2.1

0.0000
0.0034
0.0074
0.0115
0.0193
0.0326
0.0471
0.0858
0.0977
0.1206
0.1340
0.1471
0.1578
0.1681
0.1786
0.1899
0.2006
0.2118
0.2207
0.235

T = 272.76 K
0.22
1.56
2.46
4.61
4.69
7.37
9.27
10.08
14.45
14.62
19.17
21.02
25.44
30.57
35.57
40.68
45.46
50.16
50.72
55.21
60.23
65.02
69.82

0.22
1.57
2.48
4.64
4.71
7.42
9.33
10.15
14.54
14.71
19.29
21.16
25.60
30.76
35.79
40.94
45.74
50.47
51.04
55.56
60.60
65.42
70.25

0.00
0.01
0.01
0.03
0.03
0.05
0.06
0.06
0.09
0.09
0.12
0.13
0.16
0.19
0.22
0.26
0.29
0.32
0.32
0.34
0.37
0.40
0.43

0.0
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6

0.0000
0.0031
0.0051
0.0100
0.0102
0.0163
0.0206
0.0224
0.0323
0.0327
0.0429
0.0471
0.0569
0.0683
0.0794
0.0906
0.1010
0.1112
0.1124
0.1220
0.1327
0.1428
0.1529

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

Table 4 (Continued )

Table 4 (Continued )

Pcal (bar)

diff P (bar)

P%

xCH4exp

Pexp (bar)

74.69
75.20
79.47
85.15
89.32
89.60
94.29
99.01
101.95

75.16
75.66
79.96
85.67
89.87
90.15
94.87
99.61
102.56

0.46
0.46
0.49
0.52
0.55
0.55
0.58
0.60
0.61

0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6

0.1630
0.1640
0.1728
0.1843
0.1926
0.1932
0.2025
0.2118
0.2175

74.48
79.70
84.73
89.85
95.43
100.72

T = 293.16 K
0.53
5.28
10.39
16.07
23.30
30.86
35.72
40.01
46.01
50.27
55.57
58.56
65.65
70.47
75.34
83.16
88.54
93.68
99.86

0.53
5.28
10.38
16.06
23.30
30.87
35.73
40.02
46.03
50.31
55.62
58.62
65.73
70.57
75.47
83.32
88.73
93.89
100.11

0.00
0.00
0.01
0.01
0.01
0.00
0.01
0.01
0.03
0.04
0.05
0.06
0.08
0.10
0.12
0.16
0.19
0.21
0.25

0.0
0.1
0.1
0.0
0.0
0.0
0.0
0.0
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2
0.3

0.0000
0.0102
0.0210
0.0331
0.0484
0.0643
0.0744
0.0833
0.0958
0.1046
0.1155
0.1216
0.1361
0.1458
0.1557
0.1713
0.1820
0.1922
0.2044

T = 313.30 K
1.12
3.04
7.70
14.54
20.42
29.31
34.97
44.48
50.54
55.50
61.68
68.84
73.91
85.04
90.61
96.08
100.37

1.12
2.99
7.53
14.23
20.01
28.78
34.38
43.85
49.91
54.87
61.09
68.33
73.46
84.81
90.52
96.14
100.57

0.00
0.05
0.16
0.31
0.41
0.53
0.59
0.63
0.64
0.62
0.59
0.51
0.44
0.23
0.09
0.06
0.20

0.0
1.6
2.1
2.1
2.0
1.8
1.7
1.4
1.3
1.1
1.0
0.7
0.6
0.3
0.1
0.1
0.2

0.0000
0.0039
0.0133
0.0271
0.0389
0.0569
0.0683
0.0875
0.0997
0.1097
0.1221
0.1366
0.1468
0.1692
0.1805
0.1915
0.2002

T = 313.43 K
1.12
5.29
8.76
11.86
14.52
19.00
23.84
27.97
32.81
37.57
45.11
50.65
56.30
62.06
68.26

1.12
5.27
8.72
11.81
14.47
18.94
23.76
27.90
32.74
37.51
45.07
50.64
56.32
62.13
68.38

0.00
0.02
0.04
0.05
0.06
0.07
0.07
0.07
0.07
0.07
0.04
0.01
0.02
0.06
0.12

0.0
0.4
0.4
0.4
0.4
0.4
0.3
0.3
0.2
0.2
0.1
0.0
0.0
0.1
0.2

0.0000
0.0086
0.0157
0.0221
0.0275
0.0367
0.0466
0.0550
0.0649
0.0746
0.0899
0.1011
0.1125
0.1242
0.1366

Pexp (bar)

55

Pcal (bar)

diff P (bar)

P%

xCH4exp

74.66
79.94
85.05
90.24
95.90
101.28

0.18
0.24
0.31
0.39
0.48
0.56

0.2
0.3
0.4
0.4
0.5
0.6

0.1491
0.1596
0.1697
0.1799
0.1911
0.2016

Pexp (bar)

Pcal (bar)

xCH4exp

yCH4exp

yCH4cal

P%

y

T = 313.16 K
3.40
5.00
10.04
15.00
20.03
29.96
40.06
50.03
60.11
70.04
80.10
90.04
100.02
110.10
120.00

3.74
5.42
10.30
15.63
21.01
31.43
42.12
52.40
62.89
71.76
83.97
92.50
103.23
113.94
124.68

0.0055
0.0089
0.0190
0.0300
0.0410
0.0623
0.0840
0.1047
0.1258
0.1434
0.1676
0.1844
0.2054
0.2264
0.2472

0.6552
0.7502
0.8729
0.9080
0.9284
0.9463
0.9539
0.9582
0.9603
0.9615
0.9612
0.9606
0.9591
0.9572
0.9550

0.6904
0.7815
0.8776
0.9136
0.9311
0.9473
0.9548
0.9584
0.9601
0.9606
0.9602
0.9594
0.9578
0.9557
0.9531

9.9
8.4
2.6
4.2
4.9
4.9
5.1
4.7
4.6
2.5
4.8
2.7
3.2
3.5
3.9

0.0351
0.0313
0.0046
0.0056
0.0027
0.0010
0.0009
0.0001
0.0003
0.0009
0.0010
0.0012
0.0013
0.0015
0.0019

exp: experimental. calc: calculated using the PSRK correlation. diff

P = Pexp Pcalc. P% = [(Pexp Pcalc )/Pexp ]%.

Table 5
Experimental and calculated VLE data for the CH4 -EMS binary mixture
Pexp (bar)

Pcal (bar)

diff P (bar)

P%

xCH4exp

T = 247.76 K
0.01
1.15
3.66
7.10
10.21
14.72
19.13
24.42
29.18
33.96
41.84
56.18
66.68
77.21
85.84
97.35

0.01
1.15
3.64
7.06
10.16
14.65
19.03
24.30
29.04
33.80
41.64
55.91
66.34
76.79
85.35
96.74

0.000
0.006
0.019
0.036
0.051
0.073
0.094
0.118
0.140
0.162
0.201
0.277
0.342
0.421
0.494
0.611

0.0
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.6
0.6

0.0000
0.0035
0.0111
0.0215
0.0308
0.0442
0.0571
0.0725
0.0861
0.0995
0.1212
0.1590
0.1851
0.2098
0.2289
0.2527

T = 272.96 K
0.06
0.82
2.18
4.45
9.00
13.81
18.76
24.04
37.96
54.10
58.82

0.06
0.78
2.07
4.23
8.56
13.17
17.95
23.09
36.78
52.99
57.81

0.00
0.04
0.11
0.23
0.44
0.64
0.81
0.96
1.18
1.11
1.02

0.0
5.0
5.2
5.1
4.9
4.6
4.3
4.0
3.1
2.1
1.7

0.0000
0.0019
0.0054
0.0111
0.0226
0.0347
0.0471
0.0603
0.0947
0.1339
0.1452

56

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

Table 5 (Continued )
Pcal (bar)

diff P (bar)

P%

xCH4exp

73.79
80.01
84.90
99.08
108.44
116.32

73.29
79.83
85.03
100.32
110.65
119.47

0.50
0.18
0.12
1.24
2.21
3.15

0.7
0.2
0.1
1.3
2.0
2.7

0.1805
0.1949
0.2061
0.2380
0.2586
0.2756

T = 293.41 K
0.17
1.79
3.15
5.08
11.71
16.46
21.03
27.84
32.93
38.57
44.12
48.65
53.80
59.17
63.98
68.73
74.00
79.96
86.56
92.14
97.79
103.42

0.17
1.74
3.06
4.94
11.41
16.06
20.55
27.27
32.31
37.92
43.46
48.01
53.18
58.61
63.47
68.32
73.69
79.81
86.62
92.40
98.29
104.18

0.00
0.05
0.09
0.14
0.30
0.40
0.48
0.57
0.62
0.65
0.66
0.65
0.62
0.57
0.50
0.42
0.31
0.15
0.06
0.26
0.50
0.76

0.0
2.6
2.7
2.7
2.6
2.4
2.3
2.0
1.9
1.7
1.5
1.3
1.2
1.0
0.8
0.6
0.4
0.2
0.1
0.3
0.5
0.7

0.0000
0.0039
0.0072
0.0119
0.0278
0.0391
0.0500
0.0660
0.0780
0.0911
0.1039
0.1143
0.1260
0.1382
0.1490
0.1596
0.1712
0.1843
0.1987
0.2107
0.2228
0.2347

T = 313.35 K
0.40
3.79
8.82
16.94
20.73
26.19
30.07
34.84
39.75
46.67
51.18
54.99
61.41
67.00
71.37
75.45
82.44
87.67
91.30
96.43
99.57
104.08

0.40
3.62
8.44
16.24
19.90
25.21
28.99
33.67
38.50
45.35
49.84
53.65
60.11
65.76
70.20
74.37
81.55
86.96
90.73
96.09
99.39
104.15

0.00
0.16
0.39
0.70
0.83
0.98
1.08
1.18
1.25
1.32
1.34
1.34
1.31
1.25
1.17
1.08
0.89
0.71
0.57
0.34
0.18
0.07

0.0
4.3
4.4
4.1
4.0
3.8
3.6
3.4
3.2
2.8
2.6
2.4
2.1
1.9
1.6
1.4
1.1
0.8
0.6
0.3
0.2
0.1

0.0000
0.0077
0.0191
0.0374
0.0459
0.0581
0.0668
0.0774
0.0883
0.1037
0.1136
0.1220
0.1361
0.1483
0.1578
0.1666
0.1818
0.1930
0.2008
0.2118
0.2186
0.2282

Pexp (bar)

exp: experimental. calc: calculated using the PSRK correlation. diff

P = Pexp Pcalc . P% = [(Pexp Pcalc )/Pexp ]%).

Table 6
Experimental and calculated VLE data for the CH4 -MM binary mixture
Pexp (bar)

Pcal (bar)

diff P (bar)

P%

xCH4exp

T = 243.19 K
0.20
0.98
3.00
6.23
10.74
16.29
20.46
26.06
32.07
37.33
43.61
47.77
58.90
65.36
70.15
75.62
81.95

0.20
0.95
2.88
5.99
10.35
15.78
19.89
25.46
31.50
36.84
43.30
47.63
59.40
66.37
71.64
77.74
84.94

0.00
0.04
0.12
0.24
0.38
0.51
0.57
0.60
0.57
0.49
0.31
0.15
0.49
1.02
1.49
2.12
2.99

0.0
3.5
4.0
3.9
3.6
3.1
2.8
2.3
1.8
1.3
0.7
0.3
0.8
1.6
2.1
2.8
3.6

0.0000
0.0014
0.0050
0.0107
0.0187
0.0285
0.0358
0.0456
0.0561
0.0651
0.0757
0.0826
0.1007
0.1107
0.1180
0.1260
0.1349

T = 258.00 K
0.42
1.59
3.68
7.32
11.71
16.25
20.45
40.91
45.31
61.89
69.02
75.10
80.37

0.42
1.50
3.42
6.81
10.94
15.27
19.34
39.94
44.56
62.71
70.92
78.14
84.58

0.00
0.10
0.26
0.51
0.77
0.98
1.11
0.97
0.75
0.82
1.90
3.04
4.21

0.0
6.0
7.0
7.0
6.6
6.0
5.4
2.4
1.7
1.3
2.7
4.0
5.2

0.0000
0.0019
0.0053
0.0112
0.0183
0.0258
0.0326
0.0661
0.0733
0.1002
0.1115
0.1211
0.1292

T = 272.98 K
0.80
1.89
4.77
7.86
11.52
14.66
19.40
24.56
30.16
35.58
40.60
45.71
50.41
54.89
60.32
65.18
69.92
75.16

0.80
1.85
4.62
7.61
11.18
14.26
18.96
24.13
29.81
35.39
40.61
46.01
51.03
55.88
61.85
67.27
72.63
78.66

0.00
0.05
0.15
0.25
0.34
0.40
0.44
0.43
0.35
0.19
0.02
0.30
0.62
0.99
1.53
2.09
2.71
3.50

0.0
2.4
3.2
3.2
3.0
2.7
2.3
1.8
1.2
0.5
0.0
0.7
1.2
1.8
2.5
3.2
3.9
4.7

0.0000
0.0018
0.0064
0.0114
0.0173
0.0224
0.0301
0.0384
0.0475
0.0563
0.0645
0.0728
0.0804
0.0877
0.0965
0.1043
0.1119
0.1203

T = 293.35 K
1.70
5.96
9.65
13.66
19.27
24.49
31.74
36.07
40.81
45.96

1.70
5.81
9.40
13.33
18.88
24.10
31.47
35.93
40.87
46.30

0.00
0.15
0.26
0.34
0.39
0.38
0.27
0.14
0.06
0.34

0.0
2.5
2.6
2.5
2.0
1.6
0.8
0.4
0.1
0.7

0.0000
0.0066
0.0124
0.0186
0.0275
0.0357
0.0472
0.0541
0.0616
0.0699

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

Table 6 (Continued )
Pexp (bar)
50.70
63.30
68.33
75.37
79.88
T = 298.23 K
2.00
2.92
3.64
4.43
5.01
7.68
11.10
20.93
34.25
49.32
66.60

Pcal (bar)

diff P (bar)

P%

xCH4exp

51.36
65.12
70.76
78.78
84.00

0.66
1.82
2.43
3.41
4.13

1.3
2.9
3.6
4.5
5.2

0.0775
0.0978
0.1060
0.1175
0.1248

2.00
2.89
3.59
4.36
4.92
7.53
10.90
20.80
34.71
51.23
71.36

0.00
0.03
0.05
0.07
0.09
0.15
0.20
0.13
0.46
1.91
4.76

0.0
1.0
1.4
1.6
1.8
1.9
1.8
0.6
1.3
3.9
7.1

0.0000
0.0014
0.0025
0.0038
0.0047
0.0088
0.0142
0.0298
0.0515
0.0766
0.1062

exp: experimental. calc: calculated using the PSRK correlation. diff

P = Pexp Pcalc . P% = [(Pexp Pcalc )/Pexp ]%).

Fig. 5. Pxy diagrams of the CH4 (1)DMS (2) binary system at different
temperatures. Solid line: correlation using PSRK (Unifac).

Fig. 6. Pxy diagrams of the CH4 (1)EMS (2) binary system at different
temperatures. Solid line: correlation using PSRK (Unifac).

57

Table 7
Experimental and calculated VLE data for the CH4 -EM binary mixture
Pexp (bar)

Pcal (bar)

diff P (bar)

P%

xCH4exp

T = 272.94 K
0.25
0.92
2.20
5.53
7.80
10.25
15.37
20.04
25.20
29.73
35.36
40.17
64.65
69.66
74.39
89.62
93.59
97.44
103.70
107.05

0.25
0.94
2.24
5.63
7.94
10.43
15.62
20.33
25.54
30.09
35.72
40.51
64.70
69.59
74.20
88.91
92.73
96.40
102.36
105.53

0.00
0.01
0.04
0.10
0.14
0.18
0.25
0.30
0.33
0.35
0.36
0.35
0.05
0.06
0.19
0.70
0.87
1.04
1.34
1.52

0.0
1.5
1.8
1.8
1.8
1.7
1.6
1.5
1.3
1.2
1.0
0.9
0.1
0.1
0.3
0.8
0.9
1.1
1.3
1.4

0.0000
0.0017
0.0049
0.0132
0.0188
0.0248
0.0373
0.0484
0.0607
0.0712
0.0841
0.0950
0.1476
0.1578
0.1673
0.1965
0.2039
0.2109
0.2220
0.2278

T = 293.36 K
0.59
1.13
2.34
13.97
18.23
25.63
29.74
35.17
42.44
47.72
54.44
61.04
65.05
70.27
74.67
79.51
85.02
90.92
95.40
100.06
107.45

0.59
1.07
2.15
12.61
16.50
23.35
27.20
32.33
39.30
44.44
51.06
57.66
61.72
67.07
71.63
76.70
82.55
88.91
93.82
98.97
107.30

0.00
0.06
0.20
1.36
1.73
2.28
2.54
2.84
3.14
3.28
3.38
3.38
3.33
3.20
3.04
2.81
2.47
2.00
1.58
1.09
0.15

0.0
5.5
8.4
9.8
9.5
8.9
8.6
8.1
7.4
6.9
6.2
5.5
5.1
4.6
4.1
3.5
2.9
2.2
1.7
1.1
0.1

0.0000
0.0011
0.0036
0.0274
0.0362
0.0514
0.0599
0.0712
0.0862
0.0972
0.1112
0.1249
0.1333
0.1442
0.1534
0.1635
0.1750
0.1874
0.1968
0.2065
0.2221

T = 313.41 K
1.21
2.51
6.85
10.32
15.19
20.49
26.34
31.46
36.78
41.46
45.85
50.65
56.17
62.00
66.53
70.58
75.03
82.72
89.41
96.94
103.37

1.21
2.43
6.50
9.77
14.37
19.41
24.99
29.91
35.05
39.59
43.87
48.57
54.01
59.79
64.30
68.37
72.85
80.64
87.49
95.24
101.95

0.00
0.08
0.35
0.56
0.82
1.09
1.35
1.55
1.74
1.87
1.98
2.08
2.16
2.21
2.23
2.22
2.19
2.08
1.93
1.69
1.42

0.0
3.3
5.1
5.4
5.4
5.3
5.1
4.9
4.7
4.5
4.3
4.1
3.8
3.6
3.3
3.1
2.9
2.5
2.2
1.7
1.4

0.0000
0.0027
0.0117
0.0188
0.0289
0.0398
0.0518
0.0622
0.0731
0.0826
0.0915
0.1013
0.1124
0.1242
0.1333
0.1414
0.1503
0.1657
0.1791
0.1940
0.2068

exp: experimental. calc: calculated using the PSRK correlation. diff

P = Pexp Pcalc . P% = [(Pexp Pcalc )/Pexp ]%).

58

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

Fig. 7. Pxy diagrams of the CH4 (1)MM (2) binary system at different temperatures. Solid line: correlation using PSRK (Unifac).

Fig. 10. Experimental Henrys constants of CH4 in ethylmethylsulfide vs. temperature and prediction using PSRK (solid line).

Fig. 8. Pxy diagrams of the CH4 (1)EM (2) binary system at different temperatures. Solid line: correlation using PSRK (Unifac).

Fig. 11. Experimental Henrys constants of CH4 in methylmercaptan vs. temperature and prediction using PSRK (solid line).

Fig. 9. Experimental Henrys constants of CH4 in dimethylsulfide vs. temperature and prediction using PSRK (solid line).

Fig. 12. Experimental Henrys constants of CH4 in ethylmercaptan vs. temperature and prediction using PSRK (solid line).

P. Guilbot et al. / Fluid Phase Equilibria 260 (2007) 4959

Table 8
Henrys constant of CH4 in various sulfur compounds as a function of
temperature
T (K)

H (bar)

CH4 MM
243.19
272.98
293.35
298.23
348.11
257.99

538.5
597.1
619.0
614.0
665.6
591.7

CH4 EM
252.93
272.94
293.27
313.41

411.6
391.6
476.6
471.9

CH4 DMS
252.89
253.06
272.81
293.16
313.29
313.43
CH4 MS
247.76
272.96
293.41
313.35

390.6
3820
429.4
458.7
484.3
475.2
321.3
384.9
407.3
434.3

59

Acknowledgement
The financial support of Gas Processors Association is gratefully acknowledged.
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