Proceedings World Geothermal Congress 2005

Antalya, Turkey, 24-29 April 2005

Accurate Calculation of Thermodynamic Properties of H2O-CO2-CH4 Single and Binary

Fluids in P-T Ranges of Geothermal Interest

David Nieva
Instituto de Investigaciones Eléctricas, Reforma 113, Col. Palmira, Cuernavaca, Mor., Mexico 62490
dnieva@[Link]

Keywords: Water, carbon dioxide, methane, binary experimental P-V-T-X and solvus data was done by Nieva
mixtures, thermodynamic properties. and Barragán (2003).

ABSTRACT In this contribution, the above equation of state is integrated

and its ability to reproduce published thermodynamic
Duan, et al. (1992a, 1992b) developed an equation of state properties of single-component and binary (H2O-CO2; H2O-
(EOS), similar to that of Lee and Kesler (1975), that CH4) fluids is examined for the particular range of interest
describes P-V-T-X relations in the system H2O-CO2-CH4 for moderate and high temperature hydrothermal systems.
over the range 50-1000 oC / 0–1000 bar (0-1000 oC / 0-
8000 bar for single component fluids). An extensive
comparison of values calculated with this EOS and 2. EQUATION OF STATE
experimental P-V-T-X and solvus data was published by The Duan et al. (1992a, 1992b) equation of state, which
Nieva and Barragán (2003). will be referred to as the DMW EOS, may be written as
follows:
The equation of state, which will be referred to as DMW
EOS, was integrated in order to calculate thermodynamic 2 4 5
PV BVc CVc DVc EV
properties of single and binary fluids in the system H2O- Z= = 1+ + 2 + 4
+ 5c
CO2-CH4. Calculated values are compared with tabulated RT V V V V
data for water, carbon dioxide and methane, as well as their
binary mixtures.
FV
2
γV γV 2 2

For single component fluids the ability of the DMW EOS to

+ 2c ( β + c2 ) exp(− c2 ) (1)
V V V
reproduce tabulated data decreases, as expected, from the
nonpolar component to the condensed phase of the more where Z is the compressibility factor, P is pressure in bars,
polar component (pressurized liquid water). In a range of T is absolute temperature and V is specific volume in
interest for the analysis of middle to high temperature liter/mol. R is the ideal gas constant. The parameters B, C,
hydrothermal systems (125 – 375 oC), tabulated specific D and E are defined by equations of the form:
enthalpy data for methane, carbon dioxide and superheated
steam may be reproduced within ± 6, ± 9 and ± 54 KJ/Kg,
a2 a3
respectively. Published enthalpy data for H2O - CO2 and B = a1 + 2
+ 3
(2)
H2O – CH4 fluids may be reproduced within ± 11 and ± 25 Tr Tr
KJ/Kg. In more limited ranges (170 – 370 oC for steam and
240 – 370 oC for liquid), published enthalpy data for
the parameter F is given by
saturated steam and liquid water may be reproduced within
± 76 and ± 45 KJ/Kg, respectively.
α
F= 3
(3)
1. INTRODUCTION Tr
Water, carbon dioxide and methane are among the most
important constituents of crustal fluids, and knowledge of Vc, which is not the critical volume, is a function of the
their thermophysical properties has proved useful for the critical temperature and pressure
analysis of the thermal evolution of geological formations
(see for example Roedder, 1984; Ramboz et al., 1985).
RTc
Their geological importance has fostered studies of the P- Vc = (4)
V-T-X and solvus properties of binary fluids in the H2O- Pc
CO2-CH4 system for decades (see for example Blencoe et
al, 1999; Seitz and Blencoe, 1999; Fenghour et al., 1996;
and Tr is the reduced temperature (T/Tc).
Joffrion and Eubank, 1989; Zakirov, 1984; Takenouchi and
Kennedy, 1964; Tödheide and Franck, 1963; Malinin, 1959;
Values for the component-specific parameters a1, …, α, β
Donelly and Katz, 1954).
and γ are given by Duan et al. (1992a).
Duan, et al. (1992a, 1992b) developed an equation of state
In the application of Eqn. 1 to mixtures, Duan et al. (1992b)
(EOS), similar to that of Lee and Kesler (1975), that
utilize the mixing rule proposed by Benedict et al. (1942),
describes P-V-T-X relations in the system H2O-CO2-CH4
modified (following Anderko and Pitzer, 1991) with the
over the range 50-1000 oC / 0–1000 bar (0-1000 oC / 0-
introduction of second and third order adjustable
8000 bar for single component fluids). An extensive
parameters. Thus, the expression:
comparison of values calculated with this EOS and

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Q = (∑ xi Qi1 / 3 ) 3 (5)
fluids also the temperature derivatives of the binary
interaction parameters. The resulting expression is:
i

C' ρr D' ρ r E' ρ r

2 4 5
where Qi represents the ith single-component value is used UR
to obtain the mixture value in the case of parameters D, E = B' ρ r + + + −
and F. Temperature dependent second and third order RT 2 4 5
adjustable parameters are utilized to evaluate B, C and γ for
binary fluids. F'β ρ 1
2

[ + ( F ' γ + Fγ '− Fβγ ' )( r + 2 ) −

The mixing rule expressions and those for the binary 2γ 2γ 2γ
interaction parameters for H2O-CO2, H2O-CH4 and CO2-
CH4 mixtures are described by Duan et al. (1992b).
ρr 4
ρr 2 1
Fγ ' ( + + 2 ) ] exp(−γρ r ) -
2

3. CALCULATION OF THERMODYNAMIC 2 γ γ
PROPERTIES
P-V-T data allows the calculation of residual functions: Fγ ' F ' Fβγ '
+ ( β + 1) − (10)
M R (T , P) = M (T , P) − M * (T ) (6) 2γ 2
2γ 2γ 2

where M could be the internal energy, the entropy, or any where B’, C’, etc. are derivatives with respect to the
other of the thermodynamic functions of state of the system. reciprocal of the absolute temperature.
MR and M* stand for the reduced and ideal property,
respectively. The ideal gas properties of each component may be
obtained from the ideal heat capacities, as follows:
Expressions for the compressibility factor, such as Eqn. 1,
T
also allow the calculation of residual functions, provided
E * = ∫ C v dT
*
their partial derivatives describe correctly the dependence (11)
of Z with respect to temperature. 0

It can be shown (see for example, Hall et al., 1983) that: and
ρ
dρ T
Cp
*
A = RT ∫ ( Z − 1)
R
− ln Z (7) S *
=∫ dT
0
ρ T
(12)
0

and where the ideal specific heat capacities at constant volume

and pressure are related by the expression:
ρ
∂Z dρ
U R = R∫ ( )p (8)
= Cv + R
* *
0
∂ (1 / T ) ρ Cp (13)

The integral in Eqn. 7 is trivial, since the compressibility The ideal specific heat capacity at constant volume in the
factor is explicit in the density. The resulting expression is: case of nonlinear molecules is given by:

Cρ r Dρ r Eρ r Tvib 2 T
2 4 5
AR = 3R + ∑ R ( ) sinh − 2 ( vib )
*
= Bρ r + + + − Cv (14)
RT 2 4 5 Tvi b 2T 2T

F β 1 and for linear molecules by :

( )( + ρ r + ) exp(−γρ r ) +
2 2

2 γ γ 5 Tvib 2 T
=( ) R + ∑ R( ) sinh − 2 ( vib )
*
Cv (15)
F ln Z 2 Tvi b 2T 2T
( )( β + 1) − (9)
2γ RT where the summations are over the values of the
characteristic vibrational temperatures (Tvib) of the
where we have used the notation: molecule. Values of the characteristic vibrational
temperatures for H2O, CO2 and CH4, are given by Callen
2
Vc BVc CVc (1960).
ρr = Bρ r = Cρ r =
2
; ;
V V V2 Eqns. 14 and 15 include the contributions to the heat
capacity of the translational, rotational and vibrational
an so on. modes, and are accurate up to a temperature above which
contributions from electronic transitions between molecular
The integral in Eqn. 8 is more complicated because it orbitals become significant (ca 10,000 K).
involves the derivative with respect to temperature of the
parameters B, C, D, E, F, γ, and, for the case of binary

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 Nieva

The resulting expressions for the ideal internal energy and above 275 oC, and is increasingly overestimated below this
entropy applicable to H2O and CH4 (i.e. nonlinear temperature; overestimation is within 4.1% down to 250 oC,
molecules) are: within 10% down to 220 oC, and grossly increases below
this temperature. The enthalpy of compressed liquid in the
Tvib pressure range of 25-1000 bar is reproduced within ±6% for
U * = 3RT + R∑ (16) temperatures above 240 oC; for temperatures below 180 oC
Tvi b exp(Tvib / T ) it is grossly overestimated.

and Joffrion and Eubank (1989) calculated thermodynamic

properties of H2O-CH4 mixtures over the range 125-225
oC / 0.7-120 bar / 0.1-0.5 XH2O from experimental
S * = 4 R ln T + densities. The DMW EOS reproduces the published values
within 1%, except at the low temperature / high pressure
⎡ T 1 ⎤
R ∑ ⎢( vib ) exp( −Tvib / T ) − ( ) ln(1 − exp( −Tvib / T )) ⎥
limit for each composition, where deviations are larger but
never exceeding 3.4%. The deviation distribution is about
Tvi b ⎣ 4T 4 ⎦ the same for all compositions.
(17)
Patel and Eubank (1988) reported the thermodynamic
properties of H2O-CO2 mixtures over the range 50-225 oC /
0.9-100 bar / 0.02-0.5 XH2O, which were calculated from
whereas for CO2 they are given by expressions similar to experimental densities. For fluids with less than 10% molar
Eqns. 16 and 17, but with the subtraction of (1/2)RT and content of water, the DMW EOS invariably underestimates
(1/2)RlnT, respectively. the published value for enthalpy, with an error spread of 3
percentage units, centered at -3%, except for cases at the
The ideal Helmholtz free energy may then be obtained by extreme temperature and pressure limit for each
the relation: composition where deviations are larger but never
exceeding 6 percentage units. For fluids with higher water
A* = U * − TS * (18) content (25 and 50 molar percent), deviations show a spread
of about 3.5 percentage units, centered about -2%, except
From the reduced and ideal internal energy (and Helmholtz for cases at the extreme temperature and pressure limit for
free energy) one may obtain the internal energy (and XH2O = 0.25 where deviations are larger but never
Helmholtz free energy) for the real gas from Eqn. 6. All exceeding 6.8 percentage units.
other thermodynamic functions may be obtained from A
and U. Joyce and Blencoe (1994) measured the fugacity of H2O in
water-carbon dioxide mixtures at 500 bar in the range 400-
4. COMPARISON WITH PUBLISHED DATA 700 oC, and calculated the activity of water from the
expression:
Setzmann and Wagner (1991) presented an extensive
tabulation of thermodynamic properties for methane, as
calculated with their equation of state. The DMW EOS, f H 2O
through the formulae described above, reproduces their
a H 2O = (19)
values of enthalpy in the range 7-350 oC / 0.25-2000 bar
f o H 2O
within ±11.1 KJ/Kg, which in most cases (excepting those
close to zero enthalpy in the arbitrary scale) represents a where foi and fi represent the fugacity of the ith component
deviation within 1%. At higher temperatures (up to 350 oC) by itself and in the mixture, respectively, at the same
deviations are higher, but never exceeding 1.25% of the conditions of pressure and temperature.
tabulated value. At 5000 bar and the same temperature
The DMW EOS reproduces these activity values within the
range the deviations reach up to 15.6 KJ/Kg, particularly at
experimental error in the high water fraction range
the lower temperature range.
(XH2O>0.4), and underestimates the measured values at
Sweigert et al. (1946) utilized published experimental data lower water contents; the underestimation is larger at the
to generate a tabulation of thermodynamic properties of lower end of the temperature range (see Fig. 1).
CO2. The tabulated enthalpy is reproduced with deviations
Excess values of thermodynamic parameters in a gas
smaller that 2% in the range 10–450 oC / 0.014-210 bar. In
mixture are defined as their value in the mixed system
the temperature range of 500-800 oC the deviations are
minus their value in a system comprised by the
smaller than 5.4%, and at temperatures up to 980 oC
corresponding amounts of the unmixed gases. Wormald and
deviations reach up to 7.6%. The deviations, which above
Colling (1984) measured excess molar enthalpies in H2O-
340 oC are invariably underestimations, increase with
CH4 fluids at 180 – 425oC / 3 – 12.6 MPa / XH2O = 0.3 –
temperature.
0.7. For temperatures in the range 180-325oC the DMW
The values provided by the DMW EOS for the enthalpy of EOS reproduces the excess enthalpy values with deviations
superheated steam were compared with those tabulated by smaller than 290 J/mol, which represent deviations of the
Keenan et al. (1978) for the range 120-1000 oC / 1-1000 system’s enthalpy smaller than 2.4% for all pressures and
bar. Invariably the calculated values are smaller, and in compositions. At 425 oC, all pressures and XH2O = 0.5 it
general deviations increase with pressure. Deviations are invariably underestimates the experimental values, with
within 2.1% in the range 1-50 bar, and within 3.7% for very small deviations at low pressures, and deviations up to
higher pressures. The enthalpy of saturated steam is –3.5% of the system’s enthalpy at 126 bar. Performance at
reproduced within 2% in the range 170-340 oC, with 375 oC is particularly complex, with the DMW EOS
deviations increasing gradually above and below this range, invariably underestimating the experimental values, and
reaching up to +4.3% at 370 oC and -5.3% at 60 oC. The with deviations of system’s enthalpy increasing with
enthalpy of saturated water is reproduced within 1.7% pressure, reaching up to –12% at 126 bar. This contrasting

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behavior at 375 oC is attributed to the vicinity of a 5. DISCUSSION

discontinuity in the temperature dependence of the second On the basis of an extensive comparison with published
order H2O-CH4 interaction parameter. volumetric and solvus data, Nieva and Barragán (2003)
determined the regions of best applicability of the DMW
1.200
EOS. In general, the equation of state behaves best at
1.000 conditions well removed from the boundaries of its nominal
range of applicability (pressures close to 1000 or 50 bar;
ACTIVITY OF H2O

0.800 temperatures close to 50 oC), and for H2O-CO2 fluids also

removed from the vicinity of the critical curve (as defined
0.600
by data from Takenouchi and Kennedy, 1964). For binary
0.400 fluids, an important source of error derives from the
discontinuities in the temperature dependence of the binary
0.200 interaction parameters; in fact, the derivative with respect
to temperature does not exist at those discontinuities. As
0.000
0.000 0.200 0.400 0.600 0.800 suggested by Nieva and Barragán (2003), a possible means
XH O
2
for solving the problems associated with those
discontinuities is to perform a series of calculations on both
sides and interpolating.
Figure 1: Activity of water vs molar fraction of water in
H2O-CO2 fluids at 50 MPa and 678.2 K. The solid line is As expected, the DMW EOS behaves best when applied to
calculated with the DMW EOS. The closed circles the simplest single-component fluid (methane) and worst
represent data from Joyce and Blencoe (1994). The for the condensed phase of the more complex component
vertical bars represent the experimental uncertainty (saturated and pressurized liquid water).
Blencoe et al. (1999) calculated excess Gibbs free energies In the range 7 – 350 oC / 0.25-2000 bar, the DMW EOS is
of H2O-CO2 mixtures from experimental density data able to calculate the enthalpy of methane tabulated by
measured at 400 oC ; 0–400 MPa (Seitz and Blencoe, 1999) Setzmann and Wagner (1991) within ± 11 KJ/Kg, which
and P-V-T-X data from synthetic fluid inclusions (Sterner represents ± 1.85% of a “median” enthalpy value (600
and Bodnar, 1991). Excess Gibbs free energies calculated KJ/Kg).
with the DMW EOS show the same qualitative trends than
the values calculated by Blencoe et al. (1999), namely The DMW EOS tends to underestimate the enthalpy of CO2
continuous positive values asymmetric toward H2O, and (as reported by Sweigert et al., 1946). The tabulated values
maxima increasing with pressure. Fig. 2, which is to be for the range 10 – 790 oC / 0.014 – 210 bar are reproduced
compared with Fig. 6a of Blencoe et al. (1999), shows the with an error distribution centered at -34 KJ/Kg. The width
excess Gibbs free energy as a function of the molar fraction of the error distribution is ± 46 KJ/Kg, which represents ±
of carbon dioxide. The DMW EOS gives maxima of 1171 5.2% with respect to a median enthalpy value (890 KJ/Kg).
and 1429 J/mol at 50 and 100 MPa, respectively, as
compared with values of 1300 and 1800 J/mol reported by The DMW EOS invariably underestimates the enthalpy of
those authors. These differences in value of excess Gibbs superheated steam in the range 120 – 1000 oC / 1 – 1000
free energy represent underestimations of the order of bar (as tabulated by Keenan at al., 1978), with an error
about 4.4% with respect to the Gibbs free energy of the gas distribution centered at -77 KJ/Kg. The width of the error
mixture. distribution is ± 54 KJ/Kg, which represents ± 1.7% with
respect to a median enthalpy value (3200 KJ/Kg).
Smith and Wormald (1984) measured excess molar
enthalpies of H2O-CO2 fluids at one atmosphere in the In the range 170 – 370 oC, the DMW EOS reproduces the
range 90-120 oC / 0.416-0.645 XH2O. The DMW EOS tabulated enthalpy of saturated steam with an error
invariably overestimates these values by differences smaller distribution centered at 25 KJ/Kg, and an error width of ±
than 75 J/mol, constituting differences of less than 1.1 % of 76 KJ/Kg, which represents ± 2.9% with respect to a
the enthalpy of the system. median enthalpy value (2600 KJ/Kg). In a more limited
range (240 – 370 oC) the tabulated values for the enthalpy
Wormald et al. (1986) measured excess molar enthalpies in of saturated liquid are reproduced with an error distribution
the same system at XH2O = 0.5 in the range 175-425 oC / centered at 22 KJ/Kg. The error width is ± 45 KJ/Kg, which
0.44-13.4 MPa. At each experimental temperature the represents ± 3% with respect to a median enthalpy value
deviations increase with the experimental pressure. At (1500 KJ/Kg).
temperatures in the range 175-225 oC the deviation of
system’s enthalpy is smaller than 1.5%. For temperatures in The DMW EOS reproduces the tabulated enthalpy of
the range 250-275 oC deviations are smaller than 3.1%. For pressurized liquid water in the range 240 – 380 oC with an
temperatures of 300 oC and 325oC, deviations are smaller error distribution centered at 0.5 KJ/Kg, and an error width
than 3.1% at pressures lower than 67 bar and 88 bar, of ± 60 KJ/Kg, which represents ± 4.3% with respect to a
respectively; deviations are larger at higher pressures, but median enthalpy value (1400 KJ/Kg).
never exceeding 4.8%. At 375 oC deviations are within
1.5% at all pressures. At the temperature of 425 oC the Tested against tabulated enthalpy data from Joffrion and
system’s enthalpy is grossly underestimated at all pressures Eubank (1989) and excess enthalpy data from Wormald and
above 1.6 MPa. This is in sharp contrast with the relatively Colling (1984) for the system H2O-CH4 in the range 125 –
good reproduction of the system’s Gibbs free energy 325 oC / 0.7 – 126 bar / XH2O = 0.1 – 0.5, the DMW EOS
derived from Blencoe et al. (1999) values of excess Gibbs can reproduce the published values within ± 25 KJ/Kg,
free energy, at similar temperatures and even higher which represents ± 3.7% with respect to a median enthalpy
pressures. See next section for further discussion on this value (680 KJ/Kg). The equation cannot reproduce the data
point. from Wormald and Colling (1984) at ca 375 oC, given the

4
 Nieva

vicinity of one of the discontinuities in the binary quantitative calculation of excess thermodynamic
interaction parameter k2,H2O-CH4. quantities.

Tested against tabulated enthalpy data from Patel and In the range of interest for the analysis or simulation of
Eubank (1988) and excess enthalpy data from Wormald et phenomena in middle to high temperature hydrothermal
al. (1986) and Smith and Wormald (1984) for the system systems (125 – 375 oC), accuracies are better (CH4: ± 6
H2O-CO2 in the range 50 – 375 oC / 0.9 – 104 bar / XH2O = KJ/Kg; CO2: ± 9 KJ/Kg; H2O–CO2: ± 11 KJ/Kg; H2O–CH4:
0.02 – 0.68, the DMW EOS can reproduce the published ± 25 KJ/Kg), again with pure water as the system
values within ± 12 KJ/Kg, which represents ± 4.6 % with reproduced with the least accuracy, in fact unacceptable
respect to a median enthalpy value (240 KJ/Kg). below 170 oC. For the simulation of a process where the
fluid changes from pure water to a binary mixture, it is
An important observation on the behavior of the DMW recommended that a suitable equation of state (or set of
EOS is its inability to reproduce the H2O-CO2 excess empirical expressions) is used for pure water, making sure
enthalpy values of Wormald et al. 81986) at 425 oC. This that values are referred to the same standard state.
results from the existence of a root on the expression for the
second virial coefficient for CO2 (Eqn. 2) at ca 425.2 oC., It is important to emphasize that the DMW EOS is unable
which in turn leads to a singularity in its temperature to reproduce physical quantities that depend on the
derivative. However, at 400 oC the DMW EOS gives a good derivative of Z with respect to temperature, around
semi-quantitative reproduction of the excess Gibbs free temperature values where the binary interaction parameters
energies of Blencoe et al. (1999) (see last section and Fig. are discontinuous, and where a virial coefficient becomes
2). zero.
2500
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