APPENDIX A Component Properties

Equation of state models require the critical point and accentric factor as pure component
input parameters. The data used in this study are as follows:

Carbon Dioxide (Span and Wagner, 1996)

Critical Temperature (K) 304.128
Critical Pressure (MPa) 7.3773
Accentric Factor (-) 0.22491 (see below)
Molecular Weight (g/mol) 44.0098

Hydrogen Sulfide (Goodwin, 1983)

Critical Temperature (K) 373.40
Critical Pressure (MPa) 8.9629
Accentric Factor (-) 0.09578 (see below)
Molecular Weight (g/mol) 34.0758

The acentric factor of the pure components were derived from the vapor pressure data
and the basic definition of the acentric factor:

ω = − log(Prsat @ Tr = 0.7) + 1

For carbon dioxide this involved extrapolating the vapor pressure expression. The triple point of
carbon dioxide is 216.59 K, which is a reduced temperature of 0.7122.
According to the method of Peneloux et al. (1982), the volume shift parameter should be
obtained by fitting the saturated liquid density at Tr = 0.7. In this work, the shift parameters were
obtained by minimizing the AAE for the saturated liquid density over the following temperature
ranges:

CO2: 0.898 < Tr < 0.950

H2S: 0.732 < Tr < 0.950
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The lower reduced temperature corresponds to 0°C, the lowest temperature of interest in this
study. For the SRK the following Peneloux-type volume shift parameters were used:

c CO 2 = −8.6650 cm 3 /mol

c H 2 S = −3.3826 cm 3 /mol

And for the PR equation the following parameters were used here:

c CO 2 = −1.7493 cm 3 /mol

c H 2 S = +2.2176 cm 3 /mol

For the Mathias-type correction to the PR equation the s parameter was obtained by
fitting the saturated liquid density at Tr = 0.7 (or nearly so). The vc values were obtained by
minimizing the AAE for the range of saturated liquid given above.

s CO 2 = 1.585 cm 3 /mol (from matching the saturated liquid density

at Tr = 0.712, CO2 triple point)

s H 2 S = 2.998 cm 3 /mol (from matching the saturated liquid density at Tr = 0.7097)

v c,CO 2 = 96.001 cm 3 /mol (2% larger than the experimental critical volume)

v c,H 2 S = 100.490 cm 3 /mol (2.5% larger than the experimental critical volume)

For the PT equation the following parameters were used in this study:

CO2: F = 0.707727 ζ c = 0.309

H2S: F = 0.583165 ζ c = 0.320

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which were taken from the paper of Patel and Teja (1982). The above values result in smaller
errors in the density than the values from the generalized correlations.

Mixtures
Equation of state models require binary interaction parameters for multi-component input
parameters. The binary interaction coefficients for H2S – CO2 used in this study are as follows:

0.0989 for SRK

0.0974 for PR
0.0975 for PT

The values for the SRK and PR equations are from Knapp et al. (1982). These values are those
given in the popular book by Reid et al. (1987). The interaction parameter for the PT equation is
an estimate based on the values for the other two equations.

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APPENDIX B Equation of State Summary

The material that follows provides the details of the three equations of state used in this
study. Only the equations are provided, no discussion or derivation.

Soave-Redlich-Kwong Equation of State

R ⋅T a
P= −
v − b v ⋅ ( v + b)

Z 3 − Z 2 + (A − B − B 2 ) ⋅ Z − (A ⋅ B) = 0

where:

(R ⋅ Tci ) 2
a ci = 0.42748 ⋅
Pci

a i = a ci ⋅ α i

α i 0.5 = 1 + m i ⋅ (1 − Tri 0.5 )

m i = 0.48 + 1.574 ⋅ ωi − 0.176 ⋅ ωi 2

N N
a = ∑∑ x i x j ⋅ (a i a j ) 0.5 ⋅ (1 − k ij )
i j

a ⋅P
A=
(R ⋅ T) 2

R ⋅ Tci
b i = 0.08664 ⋅
Pci

N
b = ∑ x i ⋅ bi
i

b⋅P
B=
R ⋅T

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Peng-Robinson Equation of State

R ⋅T a
P= −
v − b v ⋅ ( v + b) + b ⋅ ( v − b)

Z 3 − (1 − B) ⋅ Z 2 + (A − 2 ⋅ B − 3 ⋅ B 2 ) ⋅ Z − (A ⋅ B − B 2 − B 3 ) = 0

where

(R ⋅ Tci ) 2
a ci = 0.457235 ⋅
Pci

a i = a ci ⋅ α i

α i 0.5 = 1 + m i ⋅ (1 − Tri 0.5 )

m i = 0.37464 + 1.54226 ⋅ ù i − 0.26992 ⋅ ù i

2

N N
a = ∑∑ x i x j ⋅ (a i a j ) 0.5 ⋅ (1 − k ij )
i j

a ⋅P
A=
(R ⋅ T) 2

R ⋅ Tci
b i = 0.077796 ⋅
Pci

N
b = ∑ x i ⋅ bi
i

b⋅P
B=
R ⋅T

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The Patel-Teja Equation of State

R ⋅T a
P= −
v − b v ⋅ ( v + b) + c ⋅ ( v − b )

Z 3 + (C − 1) ⋅ Z 2 + (−2 ⋅ B ⋅ C − B 2 − B − C + A) ⋅ Z + (B 2 ⋅ C + B ⋅ C − A ⋅ B) = 0

where

(R ⋅ Tci ) 2
a ci = Ω a ⋅
Pci

a i = a ci ⋅ α i

α i 0.5 = 1 + F ⋅ (1 − Tri 0.5 )

N N
a = ∑∑ x i x j ⋅ (a i a j ) 0.5 ⋅ (1 − k ij )
i j

a ⋅P
A=
(R ⋅ T) 2

(R ⋅ Tci )
bi = Ω b ⋅
Pci

N
b = ∑ x i ⋅ bi
i

b⋅P
B=
R ⋅T

(R ⋅ Tci )
ci = Ωc ⋅
Pci

N
c = ∑ x i ⋅ ci
i

c⋅P
C=
R ⋅T

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 Ω a = 3 ⋅ ζ c 2 + 3 ⋅ (1 − 2 ⋅ ζ c ) ⋅ Ω b + Ω b 2 − 3 ⋅ ζ c 3

and Ωb is the smallest real root of the following equation:

Ω b 3 + (2 − 3 ⋅ ζ c ) ⋅ Ω b 2 + 3 ⋅ ζ c 2 ⋅ Ω b − ζ c 3 = 0

Ωc = 1 − 3 ⋅ ζ c

The parameters F and ζ c can be optimized from a set of data or they can be obtained from the
following generalized equations:

F = 0.452413 + 1.30982 ⋅ ω − 0.295937 ⋅ ω 2

ζ c = 0.329032 − 0.076799 ⋅ ω − 0.0211947 ⋅ ω 2

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