6770 Ind. Eng. Chem. Res.

2006, 45, 6770-6777

Measurement and Modeling of the Solubility of Water in Supercritical Methane

and Ethane from 310 to 477 K and Pressures from 3.4 to 110 MPa
Matt Yarrison, Kenneth R. Cox, and Walter G. Chapman*
Department of Chemical and Biomolecular Engineering, Rice UniVersity, 6100 S. Main St. MS 362,
Houston, Texas 77005

We describe a new flow cell apparatus for measuring the water content of gases up to 120 MPa at 490 K that
uses a combination of gravimetric and electrical resistance techniques to determine the solubility of water in
the gaseous phase. The new experimental data for the solubility of water in supercritical methane and ethane
were obtained with our apparatus spanning pressures from 3.4 to 110 MPa covering a temperature range
from 310 to 477 K. We model the experimental results by combining two equations of state; vapor-phase
fugacities and fugacity coefficients are calculated with a modified Peng-Robinson equation of state, and
aqueous-phase fugacities are calculated using an equation by Wagner and Pruss (J. Phys. Chem. Ref. Data
2002, 31, 387-535) or by a modification of a correlation developed by Saul and Wagner (J. Phys. Chem.
Ref. Data 1987, 16, 893-901). We compare the model results with new and existing experimental data and
with commercially available simulators. Our model reproduces the experimental data within 2-6% using
one adjustable parameter, indicating that the predictions of the model are equal to or superior to the
commercially available simulators.

1. Introduction mental apparatus, which consists of a gas cylinder (S), a 1000

Accurate knowledge of the equilibrium water content of
hydrocarbon gas mixtures is of vital importance to the energy
industry. This information is necessary to prevent corrosion
problems caused by moisture condensation in pipelines or
process equipment and to determine the dosage of chemical
inhibitor to avoid hydrate crystal formation in subsea and
terrestrial pipelines. Hydrates can block fluid transmission lines,
can cause serious damage to plant equipment, and are a serious
safety concern.
Despite the studies of Olds et al.,1 Reamer et al.,2 Deaton
and Frost,3 Kobayashi and Katz,4 McKetta and Katz,5 Culberson
and McKetta,6-8 and Culberson et al.,9 data for methane and
ethane are available in the open literature only to pressures of
70.0 MPa. Only Dhima 10 has measured the solubility of gas in
the aqueous phase (the other side of the phase diagram from
what we are measuring) between 70 and 100 MPa. Mohammadi
et al.,11-13 Chapoy et al.,14 and Gillespie and Wilson15 have
performed lower-pressure (∼0.1-34 MPa) and lower-temper-
ature (273-340 K) measurements for similar systems. As oil
and gas exploration moves to greater depths both on- and
offshore, reservoir pressures are frequently on the order of 100
MPa, beyond the range of reasonable extrapolation from existing
data. To gain a better understanding of the phase behavior of
these industrially important, highly nonideal systems at all
industrially relevant conditions, we systematically study the
solubility of water in methane and ethane over a pressure and
temperature range that covers reservoir conditions to platform
conditions.
2. Experimental Equipment
The solubility of water in these supercritical hydrocarbon
gases is measured using a flow scheme similar to that of
Prausnitz and Benson16 or Rigby and Prausnitz17 or of Song et
al.18 Figure 1 shows the important components of the experi-
* Corresponding author. Phone: (713) 348-4900. Fax: (713) 348-
5478. E-mail: wgchap@rice.edu.
10.1021/ie0513752 CCC: $33.50 © 2006 American Chemical Society
Published on Web 09/02/2006
cm3 boost pump (P1), a 500 cm3 main pump (P2), a temperature
equilibration coil (EC), a saturation cell (SC), throttling valves
(TV1 and TV2), an analysis train, and a flow meter (F). Both
EC and SC are contained in a thermostatically controlled air
bath, which is controlled to within 0.3 K using a 1.8 kW heater.
Gas enters the system from the cylinder and is compressed to
the desired pressure using positive displacement pumps P1 and
P2. From pump P2, the gas enters the equilibration coil, where
it is heated to bath temperature. All pressure and temperature
data from the pumps, heat bath, and saturation cell are recorded
using a data logger.
A detailed drawing of the saturation cell is given in Figure
2. The cell has a nominal internal volume of 1300 cm3, with an
internal diameter of ∼7.5 cm. Gas enters the cell and flows
through a glass dispersion frit (PF) which disperses the gas into
the liquid water as bubbles of a nominal diameter of 0.01 mm.
A stainless steel retaining ring (RR) holds the frit in place at
the bottom of the cell. The bubbles travel through the liquid
water phase and into the headspace of the saturation cell. A
stainless steel baffle and an antientrainment section (shown in
gray) prevent any water spray from leaving the saturation cell.
Gas exits the saturation cell through a throttle valve (TV1),
where the pressure is reduced to ∼1 bar before passing to the
analytical train. Three different pressure transducers (PT)
monitor cell pressure; pressures below 70 bar use a Heise
transducer, pressures from 70 to 700 bar use a Data Instruments
transducer, and pressures from 700 to 1400 bar use a Senso-
metrics transducer. All transducers are calibrated yearly using
a Ruska dead-weight tester. A J-type thermocouple (TC) located
in a thermowell (TW, shown by crosshatching) monitors cell
temperature. The J-type thermocouple was calibrated by OMEGA
engineering against the ice and boiling points of water and the
melting points of tin and zinc. An Autoclave Engineers rupture
disk (RD) mounted in the antientrainment section provides
overpressure protection. The dashed line indicates the ap-
proximate water level in the cell.
Analytical train A consists of the General Electric (GE)-
Panametrics moisture analyzer (PMA), three desiccant-charged

Figure 1. Schematic of experimental apparatus. Data from all thermocouples, pressure transducers, and the PMA, if in use, are logged real-time using
LabVIEW. U-tubes are weighed using a Sartorius scale accurate to 0.01 mg.
Figure 2. Schematic showing the saturation cell. The cell is made from
A-286 alloy stainless steel and has a maximum pressure rating of 2000 bar
at 204 °C. A standard NIST type high-pressure closure is used to seal the
cell with a poly(tetrafluoroethylene) (PTFE) or Aflas O-ring. The equilibrium
coil, closure nut, and baffles are omitted for clarity.
stainless steel u-tubes (U), and a gas flow meter (F). The PMA
measures the water content by measuring the resistance across
an aluminum oxide sensor; as the water present in the gas stream
changes, so does the resistance across the sensor, which is
converted by the PMA into a mole fraction and a mass of water
per volume reading. The unit is calibrated by GE using National
Institute of Standards and Technology (NIST) traceable stan-
dards and is recalibrated by GE yearly. Both PMA and the
desiccant-charged tubes are used at temperatures below 333 K,
but temperature limitations of the PMA prevent its use above
this temperature. All tubing between the throttle valve (TV1)
Ind. Eng. Chem. Res., Vol. 45, No. 20, 2006 6771
and the analytical train is maintained 10-20 K above air bath
temperature using electrical heating tape to prevent condensa-
tion. When using the desiccant-charged u-tubes, the density of
the sample gas inside the u-tubes will generally be slightly
different from the density of the air inside the tubes when
charging with desiccant. This buoyancy difference can lead to
minor measurement errors if not taken into account. After
several experimental tests, we found that purging the u-tubes
with dried sample gas (dried using a combination of Dehydrite,
magnesium perchlorate, and molecular sieve 4a) before and after
the experimental run is sufficient to eliminate buoyancy effects.
A Sartorius CP-5000 series scale, with an accuracy of 0.01 mg,
is used to weigh the u-tubes. The scale is checked periodically
against a set of standard-grade Ohaus weights.
3. Materials
The methane and ethane used are ultrahigh-purity grade
(99.995% pure) from the Matheson gas company. Standard
laboratory-grade, deionized, UV-sterilized water with a maxi-
mum conductance of 0.25 micro siemens (µS) is used without
further distillation. The anhydrous ACS-grade magnesium
perchlorate used is from VWR.
4. Experimental Procedure
Deionized water (2 L) is vacuum boiled in a 4 L sample
cylinder to remove dissolved oxygen and nitrogen. Methane or
ethane (hereafter referred to as simply “gas”) is bubbled slowly
into the cylinder until the pressure in the sample cylinder reaches
∼0.2 MPa. After a 1 h equilibration period, the gas is vented
and the process is repeated twice more to ensure that no
unwanted oxygen or nitrogen remain dissolved in the water.
After degassing, the water is used to completely fill the 1.3 L
saturation cell. Gas is used to displace 300-400 cm3 of water
in order to create a gas cap in the saturation cell, and sufficient
gas is added to pressurize the cell and equilibration coil to ∼2
MPa. The heat bath is set to the desired temperature T and
allowed to equilibrate for ∼12 h until the cell internal temper-
ature has stabilized.
Methane or ethane from gas source S fills pumps P1 and P2,
which fill the saturation cell with gas at the desired pressure.
Since compression tends to raise the cell temperature ∼0.5 K,
the cell is allowed to come to thermal equilibrium with the bath
before an experiment starts. Once the cell is at the same
temperature as the bath, the throttle valves are opened so that
gas flows out of the cell and into the analysis train at a rate of
6772 Ind. Eng. Chem. Res., Vol. 45, No. 20, 2006
Figure 3. Water content of supercritical methane. Circles are data from
this work, diamonds are those of Olds et al.,1 and squares are those of Rigby
and Prausnitz.17 Lines are the water contents predicted using the modeling
procedure outlined in this paper, using the mixing rules in eq 18. Please
note that y-axis is -log(yH2O) and not yH2O.
0.014-0.028 L‚s-1 of expanded gas at ambient temperature and
pressure. Cell pressure is maintained through a continuous flow
of gas from pump P2. Approximately 17 L of gas is used to
equilibrate the analysis train so it is at steady state. Upon equili-
bration, flow switches from the vent to the chemical absorption
traps or PMA. An experiment will use between 17 and 56 L of
expanded gas, and a typical experiment will deposit in excess
of 100 mg of water in the u-tube traps. Cell and pump pressures
are constantly monitored, and the pump P2 flow rate is manually
adjusted to maintain cell pressure throughout the experiment.
Once the desired volume of gas passes through the analysis
train, the throttle and u-tube valves are closed and the traps are
removed, sealed, and weighed. Gas volume is recorded using
the flow meter, and this volume is corrected from ambient
temperature and pressure to 0.1013 MPa and 288.65 K. Each
(pressure, temperature) point is repeated a minimum of three
times to ensure repeatability and accuracy. The u-tubes are made
from 3/8 in. o.d. stainless steel tubing and use Dow-Corning
glass wool to hold the solid desiccant in place. At the beginning
of each experiment, the tubes are packed with fresh desiccant
and flushed with dry sample gas, sealed using Suba-Seal
stoppers, and weighed. Experiments have shown that the sealed
tubes do not pick up more than 0.01 mg of mass over a 24 h
period and that traps do not pick up more than 0.01 mg of mass
when the traps are connected and disconnected to/from the
expansion train. These results indicate that the measurement
technique is adequate. Once enough gas has flowed through
the expansion train so that it is at steady state, the tubes are
connected to the expansion train and the wet-test flow meter
using Tygon tubing and clamps. After the experiment, the tubes
are disconnected, sealed, and weighed. The tubes are then
flushed with dry sample gas and reweighed.
5. Experimental Results
The data covering the temperature range spanning 310-477
K and the pressure range from 3.4 to 110 MPa are presented in
Figure 3 for methane and in Figure 4 for ethane. The data of
Olds et al.1, Rigby and Prausnitz,17 and Reamer et al.2 are plotted
for reference. The experimental data are shown in Table 1 for
methane and in Table 2 for ethane, while the raw data from the
Figure 4. Water content of supercritical ethane. Diamonds are data from
this investigation, squares are those of Reamer et al.,2 while lines are
calculated using the model outlined in this paper. Note that y-axis is
-log(yH2O).
electrical resistance and the gravimetric measurements are listed
in Tables 3 and 4. Uncertainties are listed along with the data
in Tables 1 and 2, but generally range from 2 to 6%. Uncer-
tainties reported are from a propagation-of-error analysis or from
the observed deviation in measurements, whichever is greater.
The reported results are the average of the experimental runs.
6. Modeling
To make the data more useful for engineering practice, we
have developed an accurate engineering model for the methane
+ water and ethane + water systems. The vapor phase is
modeled using the Peng-Robinson (PR) equation of state (EoS),
while the aqueous phase is modeled using an equation of state
based on the work of Saul and Wagner.19 Using the Saul and
Wagner formulation allows quick and accurate water fugacity
calculations with a minimum of parameters.
6.1. Conditions for Equilibrium. For binary water +
hydrocarbon systems, the phase-equilibrium relationship for
water is
yH2Oφ̂H2OP ) (1 - xHC)f H(T,P),pure
2O
(1)
where P is the pressure, f H(T,P),pure
2O
is the fugacity of pure liquid
water evaluated at temperature T and pressure P, yH2O is the
mole fraction of water in the vapor phase, φ̂H2O is the fugacity
coefficient for water in the vapor phase calculated using the
PR equation of state, and xHC is the mole fraction of the
hydrocarbon dissolved in the liquid water. Here, we have
assumed that the liquid water phase is so rich in water that the
activity coefficient of water is ∼1.
6.2. Calculating Water Fugacity. We have used two
approaches to calculate the fugacity of pure liquid water: the
equation by Wagner and Pruss20 and a modification of the Saul
and Wagner19 formulation. Each water model gives similar
results over the range of conditions studied here. Here, we only
present our modification of the Saul and Wagner formulation.
The fugacity of water is written as
ln(fH2O(P,T)pure) )
( )
VHL 2O(P,T)
ln(φHsat2O(T)PHsat2O(T)) + ∫P
P
sat
RT
dP (2)
where φHsat2O(T) is the fugacity coefficient of water at saturation,
 Ind. Eng. Chem. Res., Vol. 45, No. 20, 2006 6773

Table 1. Experimentally Determined Values for Water Solubility in Supercritical Methanea

temperature, K
310.9 313.9 366.5 422.04 466.5 477.5
pressure, MPa 104 104 103 102 10 10
3.45 ( 0.0007 22.09 ( 1.1 23.54 ( 0.8 12.46 ( 0.42 4.15 ( 0.2 5.46 ( 0.17
6.89 ( 0.0007 12.48 ( 0.6 13.25 ( 0.4 7.46 ( 0.37 2.24 ( 0.11 2.95 ( 0.1
20.68 ( 0.086 6.997 ( 0.3 6.56 ( 0.2 3.16 ( 0.16 0.84 ( 0.04 1.13 ( 0.06
41.37 ( 0.086 5.636 ( 0.3 3.96 ( 0.2 2.04 ( 0.1 0.60 ( 0.03 0.70 ( 0.04
62.05 ( 0.68 4.90 ( 0.25 3.44 ( 0.15 1.65 ( 0.08 0.46 ( 0.02 0.57 ( 0.03
75.84 ( 0.69 4.72 ( 0.25 3.13 ( 0.15 1.43 ( 0.08 0.40 ( 0.02 0.51 ( 0.03
89.63 ( 0.69 4.67 ( 0.25 2.88 ( 0.15 1.37 ( 0.08
96.53 ( 0.69 0.35 ( 0.02 0.494 ( 0.03
110.32 ( 0.69 0.33 ( 0.02 0.455 ( 0.02
a Mole fractions and errors are reported multiplied by the power of 10 listed in that column. Uncertainties listed are calculated using a propagation of error

analysis or the observed variance, whichever was largest.

Table 2. Experimentally Determined Values for Solubility of Water using the following correlations:19

[ ]
in Supercritical Ethanea
temperature, K PHsat2O Tc
pressure, 314.8 366.5 422.0 466.5 ln ) (-7.858 23τ + 1.839 91τ1.5 - 11.781 1τ3 +
Pc T
MPa 104 103 102 10
3.45 ( 0.0007 22.46 ( 0.67 12.114( 0.36 4.154 ( 0.16 22.670 75τ3.5 - 15.939 3τ4 + 1.775 16τ7.5) (4)
3.59 ( 0.0007 21.88 ( 1.09
6.89 ( 0.086 12.77 ( 1.09 12.38 ( 0.37 6.957 ( 0.21 2.163 ( 0.11 Fsat(T)
20.68 ( 0.086 8.37 ( 0.41 6.43 ( 0.2 2.794 ( 0.08 0.920 ( 0.06 ) 1 + 1.992 06τ1/3 + 1.101 23τ2/3 -
41.37 ( 0.68 7.33 ( 0.36 4.06 ( 0.1 1.819 ( 0.05 0.658 ( 0.04
Fc
62.05 ( 0.68 5.82 ( 0.25 3.29 ( 0.1 1.583 ( 0.05 0.510 ( 0.03 0.512 506τ5/3 - 1.752 63τ16/3 - 45.448 5τ43/3 -
75.84 ( 0.69 4.93 ( 0.25 3.02 ( 0.1 1.498 ( 0.04 0.455 ( 0.03
89.63 ( 0.69 4.49 ( 0.25 2.87 ( 0.1 1.382 ( 0.04 675 615τ110/3 (5)
96.53 ( 0.69 0.401 ( 0.03
110.32 ( 0.69 0.372 ( 0.02 T
τ)1- (6)
a Mole fractions and errors are reported multiplied by the power of 10 Tc
listed in that column.
F(P,T) ) Fsat(T) + (P - PHsat2O)(8.48 × 10-6T2 - 5.91 ×
Table 3. Experimentally Determined Mole Fractions of Water in
Methane from Gravimetric and Electric Resistance Measurements
10-3T + 1.39) + b(T) (7)
for Methanea
274 < T < 510 K

( ( ))
pressure, mol fraction, mol fraction,
MPa gravimetric resistance reported Tc - T
Methane, 310.8 K b(T) ) 143 exp -14
Tc
3.45 2.228E-03 2.150E-03 2.209E-03
6.89 1.197E-03 1.400E-03 1.248E-03
20.68 7.076E-04 6.760E-04 6.997E-04 510 < T < 640 K (8)

( ( ))
41.37 5.821E-04 5.080E-04 5.636E-04
Methane, 313.9 K
Tc - T
62.05 4.914E-04 4.870E-04 4.903E-04
b(T) ) 143 exp -14 erf((P - PHsat2O)a(T))
Tc
75.84 4.733E-04 4.660E-04 4.715E-04
89.63 4.727E-04 4.510E-04 4.673E-04
a
a(T) ) 7.129 × 10-4T + 0.3692
The reported average was calculated using a weight average with a
weight of 0.75 assigned to the gravimetric measurement and 0.25 assigned
1
for the resistance measurement. VL ) (9)
F(P,T)

VHL 2O(P,T) is the liquid water volume, P and PHsat2O(T) are the
system pressure and the water saturation pressure, respec-
tively, R is the universal gas constant, and T is the system
temperature. The fugacity from eq 2 is plotted against steam
table data in Figure 5. φHsat2O is calculated using the following
correlation
274 < T < 647 K
274
φHsat2O ) 1 - 0.001 340 927 477 538 65 exp 9.7 1 - ( ( T
+ ))
1.956 70 × 10-3 (3)
which we fitted to the data of the 1995 steam tables;21
it is shown in Figure 6. The vapor pressure is calculated
Tc is the critical temperature of water, Fc is the critical density
of water, and Pc (MPa) is the critical pressure of water.
Equations 3-9 are intended for use with water in the liquid
state in the range from 273.15 to 640 K and have been validated
against experimental data within that temperature range for
pressures up to 200 MPa. Equation 7 is a modification of Saul
and Wagner’s19 saturation pressure correlation that makes the
density and, consequently, the liquid volume more accurate.
Equation 7 is simply a best fit function using least-squares
regression. Including the effect of pressure on the liquid density
is significant. For comparison, the approximation of using the
saturated liquid density at all pressures is shown as a dashed
line in Figure 7. A few comparisons are shown with the 1995
NIST/ASME steam tables in Figure 7. Both the NIST imple-
mentation21 of Wagner and Pruss’20 equation of state for water
6774 Ind. Eng. Chem. Res., Vol. 45, No. 20, 2006

Table 4. Experimentally Determined Mole Fractions of Water in

Ethane from Gravimetric and Electric Resistance Measurements for
Ethanea
pressure, mol fraction, mol fraction,
MPa gravimetric resistance reported
Ethane, 314.8 K
3.59 2.181E-03 2.209E-03 2.188E-03
6.89 1.239E-03 1.390E-03 1.277E-03
20.68 8.417E-04 8.220E-04 8.368E-04
41.37 7.310E-04 7.370E-04 7.325E-04
62.05 5.798E-04 5.900E-04 5.824E-04
75.84 4.952E-04 4.850E-04 4.926E-04 Figure 7. Comparisons of improved correlation from eq 7 vs NIST21 steam
89.63 4.508E-04 4.430E-04 4.488E-04 table data. The dashed lines are values of the saturated liquid density
a The reported average was calculated using a weight average with a calculated from eq 5 to show the effect of pressure on liquid density.
weight of 0.75 assigned to the gravimetric measurement and 0.25 assigned
for the resistance measurement.

Figure 8. Comparison of XHC as calculated by eq 10 with experimental

data of O’Sullivan and Smith.25 Error bars are 6%.

hydrocarbon in the aqueous phase, y and x are the mole fractions

of the hydrocarbon in the vapor and liquid phases, respectively,
and Hi,H2O(T,P) is the Henry’s constant for species i in water at
temperature T and pressure P. The amount of hydrocarbon gas
Figure 5. Fugacity of water as calculated by eq 2 vs fugacities from the in the liquid phase can be calculated by explicitly solving for
1995 steam tables.
xHC.
As the hydrocarbons used in this investigation have low
solubilities in the water-rich phase even at pressures up to 110
MPa, they are adequately represented10 using the Krichevsky-
Kasarnovsky22 equation,
∞
f LHC VHC,H2O
ln(HHC,H2O(T,P)) ) ln ) lnHi,0 + (P - PHsat2O)
xHC RT
(11)

where f LHC is the fugacity of the hydrocarbon component i in

Figure 6. Fugacity coefficient at saturation φsat is shown here from 274 to
640 K.
and the Saul and Wagner treatment as modified above give
similar results.
A relationship similar to eq 1 can be written for the
hydrocarbons in the aqueous phase,
yHCφ̂HCP ) f VHC ) f LHC ) xHCHHC,H2O(T,P)
where H is the Henry’s constant of hydrocarbon in the liquid
water phase at temperature T and system pressure P, f VHC is the
fugacity in the vapor phase, f LHC is the fugacity of the
water, xHC is the mole fraction of component i dissolved in the
water at temperature T and system pressure P, HHC,0 is the
Henry’s law constant for the hydrocarbon species in water at T
∞
and water saturation pressure, and VHC,H 2O
is the partial molar
volume of the hydrocarbon in water at infinite dilution. HHC,O
is calculated using a method developed by Harvey,23 while
∞
VHC,H 2O
is calculated using the corresponding states method of
Lyckman et al.24 For reference, the solubility of methane in
water is shown in Figure 8 in comparison with the data of
O’Sullivan and Smith.25 Model results based on eq 11 have been
found to reproduce the experimental data within 0.3-12% of
the experimental value. However, this is not to say that using
eq 11 will always produce such results. Any error in the value
∞
of VHC,H 2O
will produce large deviations in the value of xHC at
high pressures, as P - PHsat2O becomes large at high pressures.
(10)
For example, an error of 10% in the partial molar volume of
methane at infinite dilution will create a 0.1% error in the
Henry’s constant at 1 MPa, a 6% error at 50 MPa, and a 20%
error at 150 MPa at 324 K. We can, therefore, expect the
maximum possible uncertainty in xHC to be on the order of 20-
 Ind. Eng. Chem. Res., Vol. 45, No. 20, 2006 6775
∞ Table 5. Parameters Used in Peng-Robinson EoSa
30%, as the uncertainties in VHC,H2O
are on the order of 5 cm3/
mol or ∼16%. component Pc (MPa) Tc (K) ω Fc (kg/m3)
6.3. Equation of State. The gas-phase fugacities of water water 22.12 647.3 0.344 322
and hydrocarbon components are calculated using the Peng- methane 4.604 190.6 0.011 163
Robinson (PR) equation of state.26 The PR26 equation of state ethane 4.88 305.4 0.099 207
can be written in dimensionless form as a Values taken from Poling et al.31

Z)
1
-
AMix
(
BMix/Z
(1 - BMix/Z) BMix 1 + 2BMix/Z - (BMix/Z)2 ) (12)
Table 6. Binary Interaction Parameters (kij) Used for Mixing Rule
in Equations 18 and 19
temperature, K
where 310.9 313.7 314.8 366.4 422 466.4 477.6

aiiP Lorentz-Berthelot Mixing Rule

P
biF ≡ Bi/ZZ ≡ Aii ≡ 2 2 (13) methane 0.48 0.48 0.47 0.45 0.41 0.37
FRT RT ethane 0.49 0.51 0.46 0.43 0.42
Linear Mixing Rule
R2Tc,i2 Tc,i methane 0.045 0.045 0.039 0.052 0.075
ai ≡ ζiRi; ζi ≡ 0.457 235 53 bi ≡ 0.077 960 7R
Pc,i Pc,i Table 7. Coefficients Used to Interpolate the Binary Interaction
Parameter (kij) for the Mixing Rules Used in This Work, Valid from
(14) 310 to 477 K
A × 106 B × 103 C
Rii ≡ [1 + κi(1 - xTr,i)]2
Lorentz-Berthelot Mixing Rule
κi ≡ 0.374 64 + 1.542 26ωi - 0.269 93ωi2 methane -3.5867 2.3165 0.1007
T ethane -5.5729 3.9974 -0.2206
Tr ) (15) Linear Mixing Rule
Tc,i
methane 3.0087 -2.1472 0.4221
and finally, taking the appropriate derivatives, the fugacity
of temperature. Equation 19 gives good agreement with the data
coefficient for the binary system is
using kij ) 0; however, better agreement is obtained on fitting
Bi kij. Since the best fitted value of A12 is the same regardless of
AMix
ln(φ̂Vi ) ) (ZV - 1) - ln(ZV - BMix) - ln whether eq 18 or eq 19 is used, a small kij in eq 19 for the
B x8
Mix Mix
B methane/water system corresponds to a large kij in eq 18. The

( ZV + (1 - x2)BMix )(
ZV + (1 + x2)BMix 2(y1Ai1 + y2Ai2)
AMix
-
Bi
BMix ) (16)
purpose of introducing eq 19 is to demonstrate that the large
kij's produced from the geometric mixing rule are reasonable in
this case. Both mixing rules reproduce the solubility data for
2 2 2
the methane + water and ethane + water systems to within
AMix ) ∑i ∑j yiyjAijBMix ) ∑i yiBi (17)
2-7% average absolute deviation (AAD) over the experimental
pressure and temperature range where

The form of the mixing rules used in eq 17 is sometimes

called van der Waals mixing rules; however, the form used here
is empirical. Numerous investigators26,27 have suggested the
AAD )
1
n
∑n( |yexp - ycalc|
y exp
) × 100 (20)

cross-interaction parameter, A12, should be of the form

A12 ) (1 - kij)xA11A22
where kij is a fitted parameter, component 1 is water, and
component 2 is the hydrocarbon. This approximation is fairly
accurate if the attractions between molecules are only due to
van der Waals interactions. For the water/hydrocarbon system,
eq 18 results in large values of kij. This occurs since, in the
Peng-Robinson equation of state, the fitted A11 (pure water)
includes not only van der Waals attractions but also contributions
from hydrogen bonding and strong dipole-dipole interactions.
A large kij is needed since the attraction between water and
hydrocarbon molecules is only due to van der Waals interactions.
We expect that the van der Waals interaction between water
and methane should be closer to the methane-methane van der
Waals attraction than to A12 from eq 18. Therefore, for the
methane/water system, we consider a simple, empirical mixing
rule of the form
A12 ) [A11kij + A22(1 - kij)]
where component 1 is water, component 2 is the hydrocarbon,
and kij is a fitted binary interaction parameter, which is a function
In this case, n is the number of experimental data points and
(18) yexp is the observed mole fraction of water in the gas phase.
Table 5 lists the parameters used in the model, and Table 6
lists the binary interaction parameters (kij). It should be noted
that, while the mixing rule used in eq 19 gives values for the
binary interaction parameter for the methane/water system that
are closer to zero, we would not expect the model to work well
for the ethane/water system. In this case, we might expect that
replacing A22 in eq 19 with A22/2, where the 2 represents the
carbon number of ethane, would give better results. Equation
19 was presented for illustrative purposes only. We propose to
use the geometric mixing rule for multicomponent mixtures.
6.4. Model Results. Calculations made using the mixing rule
in eq 18 are shown in Figures 3 and 4. AAD% results of 2-7%
are obtained by making kij a weak function of temperature.
Binary interaction parameters (kij) are shown in Table 6. For
both sets of mixing rules, the binary interaction parameters can
be interpolated using kij ) AT2 + BT + C, where T is in Kelvin
and A, B, and C are given in Table 7.
(19) Comparisons with Multiflash cubic plus association (CpA),28
Colorado School of Mines Gibbs Energy Minimization29 (CSM
GeM), and CALSEP’s PVT SIM30 are presented in Figure 9.
These calculations are presented using the default, recommended
6776 Ind. Eng. Chem. Res., Vol. 45, No. 20, 2006

Table 8. Experimental Mole Fraction Data and Model Predictions with AAD% for Methane + Water Binary System at 477.5 K
data CALSEP dev. % Multiflash dev. % CSM GeM dev. % this model dev. %
0.547 0.536 1.93 0.542 0.80 0.523 4.40 0.515 5.81
0.295 0.297 0.41 0.289 2.25 0.277 6.08 0.277 6.14
0.114 0.134 17.83 0.107 5.39 0.107 5.53 0.115 1.07
0.070 0.094 33.43 0.060 14.44 0.063 10.69 0.072 3.04
0.057 0.079 38.42 0.044 24.01 0.046 18.99 0.056 1.69
0.051 0.074 42.76 0.037 27.50 0.040 22.29 0.050 3.31
0.049 0.033 32.31 0.043 13.54
0.046 0.064 40.43 0.028 38.04 0.030 33.57 0.039 14.03
CALSEP AAD% 25.03 Multiflash AAD% 16.06 CSM GeM AAD% 16.73 this model AAD% 6.08

parameters for these systems. At low temperatures and low
pressures, all methods do an adequate job of predicting water
solubility in the hydrocarbon-rich phase, but as temperatures
and pressures increase, they tend to diverge from the experi-
mental measurements. Multiflash CpA and CSM GeM under-
estimate the amount of water in the vapor phase at high
pressures, while CALSEP tends to overestimate the amount of
water present in the vapor phase. CSM GeM gives the best
predictions next to the model presented here. It should be noted,
however, that the CSM GeM formalism was developed for use
at or near hydrate-formation conditions, so the results presented
here are an extreme test. It is strongly suspected that the CpA
model would provide much better results if fitted to the higher
pressure data, as it incorporates the statistical associating fluid
theory (SAFT) association term, which would greatly improve
calculations for the aqueous liquid phase. We would expect that,
for all models, if the model parameters were fitted to high-
pressure data, the calculated values would show improvement.
Table 8 lists the AAD% for methane + water at 477 K for the
various models shown in Figure 9.
Figure 9. Solubility of water in methane, including comparisons with
CALSEP, CSM GeM, Multiflash CpA, and our model at 366 and 477 K.
7. Conclusions
The water content in the hydrocarbon-rich phase of the binary
systems methane + water and ethane + water were measured
from 310 to 477 K over a pressure range of 3.4-110 MPa. At
∼310 K, both a gravimetric and an electrical resistance method
were used to measure the water content of the expanded gas
stream. Above 333 K, only gravimetric methods were employed.
A calculation method using the Peng-Robinson equation of
state and an accurate liquid water model was used to model the
experimental data acquired in this investigation and that of other
investigators, showing good agreement with binary data. Similar
calculations with commercially available process (see Figure
9) simulators show that commercial models can substantially
over- or underpredict the amount of water present in the vapor
phase at higher pressures.
Acknowledgment
We gratefully acknowledge the financial support of the Gas
Processors Association. We also thank Mr. Richard Chronister
for his invaluable mechanical assistance in fabricating the
equipment and Professor Derek Dyson for wise counsel. The
authors also thank Becky Yarrison for reading several drafts of
this paper for coherency and Ryan Dunnavant and John Cliver
for their help in screening experimental techniques and in
apparatus fabrication. We would also like to thank Professor
Wolfgang Arlt for his ideas in tuning the controller and Professor
Mark Thies for help in troubleshooting O-rings.
Literature Cited
(1) Olds, R. H.; Sage, B. H.; Lacey, W. N. Phase equilibria in
hydrocarbon systems. Composition of the dew-point gas of the methane-
water system. Ind. Eng. Chem. 1942, 34, 1223-7.
(2) Reamer, H. H.; Olds, R. H.; Sage, B. H.; Lacey, W. N. Phase
equilibria in hydrocarbon series. Composition of dew-point gas in ethane-
water system. Ind. Eng. Chem. 1943, 35, 790-3.
(3) Deaton, W. M.; Frost, E. M., Jr. Gas hydrates and their relation to
the operation of natural-gas pipe lines. U.S. Bur. Mines, Monograph 1946,
8.
(4) Kobayashi, R.; Katz, D. L. Vapor-liquid equilibria for binary
hydrocarbon-water systems. Ind. Eng. Chem. 1953, 45, 440--51.
(5) McKetta, J. J., Jr.; Katz, D. L. Phase relations of hydrocarbon-
water systems. Am. Inst. Min. Metall. Eng., Petr. Technol. 1947, 10 (1);
Tech. Pub. No. 2123.
(6) Culberson, O. L.; McKetta, J. J., Jr. Phase equilibria in hydrocarbon-
water systems. II. The solubility of ethane in water at pressures to 10,000
lb. per sq. in. Trans. Am. Inst. Min. Metall. Eng., Tech. Pub. 1950, (2932).
(7) Culberson, O. L.; McKetta, J. J., Jr. Phase equilibria in hydrocarbon-
water systems. IV. Vapor-liquid equilibrium constants in the methane-
water and ethane-water systems. Trans. Am. Inst. Min., Metall. Pet. Eng.
1951, 192; Tech. Pub. No. 3201.
(8) Culberson, O. L.; McKetta, J. J., Jr. Phase equilibria in hydrocarbon-
water systems. III. The solubility of methane in water at pressures to 10,000
pounds per square inch absolute. Trans. Am. Inst. Min. Metall. Eng., Tech.
Pub. 1951, (3082).
(9) Culberson, O. L.; Horn, A. B.; McKetta, J. J., Jr. Phase equilibria in
hydrocarbon-water systems. The solubility of ethane in water at pressures
to 1200 pounds per square inch. Am. Inst. Min. Metall. Eng., Tech. Pub.
1950, (2778), 1-6 (J. Pet. Technol. 2 (1)).
(10) Dhima, A. Solubilite des gaz naturels dans l’eau a pression elevee.
Ph.D. Thesis, Claude Bernard, Lyon, France, 1998.
(11) Mohammadi, A. H.; Chapoy, A.; Tohidi, B.; Richon, D. Water
Content Measurement and Modeling in the Nitrogen + Water System. J.
Chem. Eng. Data 2005, 50 (2), 541-5.
(12) Mohammadi, A. H.; Chapoy, A.; Richon, D.; Tohidi, B. Experi-
mental Measurement and Thermodynamic Modeling of Water Content in
Methane and Ethane Systems. Ind. Eng. Chem. Res. 2004, 43 (22), 7148-
62.
(13) Mohammadi, A. H.; Chapoy, A.; Tohidi, B.; Richon, D., Measure-
ments and Thermodynamic Modeling of Vapor-Liquid Equilibria in
Ethane-Water Systems from 274.26 to 343.08 K. Ind. Eng. Chem. Res.
2004, 43 (17), 5418-24.
(14) Chapoy, A.; Mohammadi, A. H.; Richon, D.; Tohidi, B., Gas
solubility measurement and modeling for methane-water and methane-

ethane-n-butane-water systems at low-temperature conditions. Fluid Phase
Equilib. 2004, 220 (1), 111.
(15) Gillespie, P. C.; Wilson, G. M. GPA Research Report RR-48
Vapor-Liquid and Liquid-Liquid Equilibria: Water-Methane, Water-
Carbon Dioxide, Water-Hydrogen Sulfide, Water-n-Pentane, Water-
Methane-n-Pentane; Gas Processors Association: Tulsa, OK, 1982; pp
1-79.
(16) Prausnitz, J. M.; Benson, P. R. Solubility of liquids in compressed
hydrogen, nitrogen, and carbon dioxide. AIChE J. 1959, 5, 161-4.
(17) Rigby, M.; Prausnitz, J. M. Solubility of water in compressed
nitrogen, argon, and methane. J. Phys. Chem. 1968, 72 (1), 330-4.
(18) Song, K. Y.; Yarrison, M.; Chapman, W. Experimental low-
temperature water content in gaseous methane, liquid ethane, and liquid
propane in equilibrium with hydrate at cryogenic conditions. Fluid Phase
Equilib. 2004, 224 (2), 271-7.
(19) Saul, A.; Wagner, W. International equations for the saturation
properties of ordinary water substance. J. Phys. Chem. Ref. Data 1987, 16
(4), 893-901.
(20) Wagner, W.; Pruss, A. The IAPWS Formulation 1995 for the
Thermodynamic Properties of Ordinary Water Substance for General and
Scientific Use. J. Phys. Chem. Ref. Data 2002, 31, (2), 387-535.
(21) Harvey, A. H.; Peskin, A. P.; Klein, S. A. NIST/ASME Steam
Properties, 2.2; U.S. Department of Commerce: Gaithersburg, MD, 2004.
(22) Krichevsky, I. R.; Kasarnovsky, J. S. Thermodynamical calculations
of solubilities of nitrogen and hydrogen in water at high pressures. J. Am.
Chem. Soc. 1935, 57, 2168-72.
(23) Harvey, A. H. Semiempirical correlations for Henry’s constants
over large temperature ranges. AIChE J. 1996, 5, 1491-4.
Ind. Eng. Chem. Res., Vol. 45, No. 20, 2006 6777
(24) Lyckman, E. W.; Eckert, C. A.; Prausnitz, J. M. Generalized
reference fugacities for phase equilibrium thermodynamics. Chem. Eng. Sci.
1965, 20, 685-91.
(25) O’Sullivan, T. D.; Smith, N. O. The Solubility and Partial Molar
Volume of Nitrogen and Methane in Water and in Aqueous Sodium Chloride
from 50 to 125 °C and 100 to 600 Atm. J. Phys. Chem. 1970, 74 (7), 1460.
(26) Peng, D. Y.; Robinsion, D. B. A new two constant equation of
state. Ind. Eng. Chem. Fundam. 1976, 15, 59-64.
(27) Soave, G. Equilibrium constants from a modified Redlich-Kwong
equation of state. Chem. Eng. Sci. 1972, 27 (6), 1197-203.
(28) Yakoumis, I. V.; Kontogeorgis, G. M.; Voutsas, E. C.; Hendriks,
E. M.; Tassios, D. P. Prediction of Phase Equilibria in Binary Aqueous
Systems Containing Alkanes, Cycloalkanes, and Alkenes with the Cubic-
plus-Association Equation of State. Ind. Eng. Chem. Res. 1998, 37, 4175-
82.
(29) Ballard, A. L.; Sloan, E. D. The next generation of hydrate
prediction. Part III. Gibbs energy minimization formalism. Fluid Phase
Equilib. 2004, 218 (1), 15-31.
(30) CALSEP, CALSEP PVT SIM. In.
(31) Poling, B. E.; Prausnitz, J. M.; O’Connell, J. P. The properties of
gases and liquids, 5th ed.; McGraw-Hill: New York, 2001.
ReceiVed for reView December 9, 2005
ReVised manuscript receiVed June 15, 2006
Accepted July 5, 2006
IE0513752