SECTION 25

Equilibrium Ratio (K) Data

The equilibrium ratio (Ki) of a component i in a multicom- Data for N2-CH4 and N2-C2H6 show that the K-values in this
ponent mixture of liquid and vapor phases is defined as the system have strong compositional dependence. The compo-
ratio of the mole fraction of that component in the vapor phase nent volatility sequence is N2-CH4-C2H6 and the K-values are
to that in the liquid phase. functions of the amount of methane in the liquid phase. For
yi example, at –123°C and 2070 kPa (abs), the K-values depend-
Ki = Eq 25-1 ing on composition vary from:
xi
For an ideal system (ideal gas and ideal solution), this equi- N2 CH4 C2H6
librium ratio is reduced to the ratio of the vapor pressure of 10.2 0.824* 0.0118
component i to the total pressure of the system.
3.05 0.635 0.035*
P∗i
Ki = Eq 25-2 where * indicates the limiting infinite dilution K-value. See
P
reference 5 for the data on this ternary.
This section presents an outline procedure to calculate the
liquid and vapor compositions of a two-phase mixture in equi- The charts retained in this edition represent roughly 12% of
librium using the concept of a pseudobinary system and the the charts included in previous editions. These charts are a
convergence pressure equilibrium charts. Discussion of CO2 compromise set for gas processing as follows:
separation, alternate methods to obtain K values, and equa- a. hydrocarbons — 3000 psia Pk [20 700 kPa (abs)]
tions of state follow.
b. nitrogen — 2000 psia Pk [13 800 kPa (abs)]
c. hydrogen sulfide — 3000 psia Pk [20 700 kPa (abs)]
K-DATA CHARTS
The pressures in a. through c. above refer to convergence
These charts show the vapor-liquid equilibrium ratio, Ki, for pressure, Pk, of the charts from the Tenth Edition of this data
use in example and approximate flash calculations. The charts book. They should not be used for design work or related ac-
will not give accurate answers, particularly in the case of ni- tivities. Again, their retention in this edition is for illustration
trogen. They are included only to support example flash cal- and approximation purposes only; however, they can be very
culations and to support quick estimation of K-values in other useful in such a role. The critical locus chart used in the con-
hand calculations. vergence pressure method has also been retained (Fig. 25-8).
Previous editions of this data book presented extensive sets The GPA/GPSA sponsors investigations in hydrocarbon sys-
of K-data based on the GPA Convergence Pressure, Pk, tems of interest to gas processors. Detailed results are given
method. A component’s K-data is a strong function of tempera- in the annual proceedings and in various research reports and
ture and pressure and a weaker function of composition. The technical publications, which are listed in Section 1.
convergence pressure method recognizes composition effects Example 25-1 — Binary System Calculation
in predicting K-data. The convergence pressure technique can
To illustrate the use of binary system K-value charts, as-
be used in hand calculations, and it is still available as com-
sume a mixture of 60 kmols of methane and 40 kmols of eth-
puter correlations for K-data prediction.
ane at –87°C and 345 kPa (abs). From the chart on page 25-10,
There is now general availability of computers. This availabil- the K-values for methane and ethane are 10 and 0.35 respec-
ity coupled with the more refined K-value correlations in modern tively.
process simulators has rendered the previous GPA convergence Solution Steps
pressure charts outdated. Complete sets of these charts are avail-
able from GPA as a Technical Publication, TP-22. From the definition of K-value, Eq 25-1:

FIG. 25-1
Nomenclature

yi P* = vapor pressure, kPa (abs)

Ki = equilibrium ratio,
xi R = universal gas constant, (kPa (abs) • m3) / (kmol • K)
L = ratio of moles of liquid to moles of total mixture T = temperature, K or °C
V = ratio of moles of vapor to moles of total mixture
N = mole fraction in the total mixture or system
xi = mole fraction of component i in the liquid phase
ω = acentric factor yi = mole fraction of component i in the vapor phase
P = absolute pressure, kPa (abs) Subscripts
Pk = convergence pressure, kPa (abs), psia i = component

25-1
 yC1 Ni
KC1 = = 10 Σxi = Σ = 1.0 Eq 25-5
xC1 L + VKi
Other useful versions may be written as
yC2
KC2 = = 0.35 Ni
xC2 L = Σ Eq 25-6
1 + (V/L) Ki
Rewriting for this binary mixture: KiNi
Σyi = Eq 25-7
1 − yC1 L + VKi
= 0.35
1 − xC1 At the phase boundary conditions of bubble point (L = 1.00)
and dew point (V = 1.00), these equations reduce to
Solving the above equations simultaneously:
Σ Ki Ni = 1.0 (bubble point) Eq 25-8
xC1 = 0.0674
and
yC1 = 0.674 Σ Ni/Ki = 1.0 (dew point) Eq 25-9
Also by solving in the same way: These are often helpful for preliminary calculations where
the phase condition of a system at a given pressure and tem-
xC2 = 0.9326 perature is in doubt. If ΣKiNi and ΣNi/Ki are both greater than
1.0, the system is in the two phase region. If ΣKiNi is less than
yC2 = 0.326 1.0, the system is all liquid. If ΣNi/Ki is less than 1.0, the system
To find the amount of vapor in the mixture, let v denote is all vapor.
kmols of vapor. Summing the moles of methane in each phase Example 25-2 — A typical high pressure separator gas is used
gives: for feed to a natural gas liquefaction plant, and a preliminary
Σ kmols C1 + C2 = 100 kmols step in the process involves cooling to –30°C at 4140 kPa (abs)
to liquefy heavier hydrocarbons prior to cooling to lower tem-
kmols C1 + kmols C1 = 60 kmols peratures where these components would freeze out as solids.
in vapor in liquid
Solution Steps
(yC1 × v) + (xc1 [100 − v]) = 60 kmo ls The feed gas composition is shown in Fig. 25-3. The flash
equation 25-5 is solved for three estimated values of L as
(0.674 × v) + (0.0674 [100 − v]) = 60 kmols shown in columns 3, 4, and 5. By plotting estimated L versus
calculated Σxi, the correct value of L where Σxi = 1.00 is L =
v = 87.8
0.030, whose solution is shown in columns 6 and 7. The gas
The mixture consists of 87.8 kmols of vapor and 12.2 kmols composition is then calculated using yi = Kixi in column 8. This
of liquid. "correct" value is used for purposes of illustration. It is not a
completely converged solution, for xi = 1.00049 and yi =
0.99998, columns 7 and 8 of Fig. 25-3. This error may be too
FLASH CALCULATION PROBLEM large for some applications.
To illustrate the calculation of multicomponent vapor-liquid Example 25-3 — Dew Point Calculation
equilibrium using the flash equations and the K-charts, a A gas stream at 40°C and 5500 kPa (abs) is being cooled in
problem is worked out in detail below. a heat exchanger. Find the temperature at which the gas starts
to condense.
The variables are defined in Fig. 25-1. Note that the K-value
is implied to be at thermodynamic equilibrium. Solution Steps
The approach to find the dew point of the gas stream is simi-
A situation of reproducible steady state conditions in a piece lar to the previous example. The equation for dew point con-
of equipment does not necessarily imply that classical thermo-
dition (ΣNi/Ki = 1.0) is solved for two estimated dew point
dynamic equilibrium exists. If the steady composition differs
temperatures as shown in Fig. 25-4. By interpolation, the tem-
from that for equilibrium, the reason can be the result of time-
perature at which ΣNi/Ki = 1.0 is estimated at –41.4°C.
limited mass transfer and diffusion rates. This warning is
made because it is not at all unusual for flow rates through Note that the heaviest component is quite important in dew
equipment to be so high that equilibrium is not attained or point calculations. For more complex mixtures, the charac-
even closely approached. In such cases, equilibrium flash cal- terization of the heavy fraction as a pseudocomponent such as
culations as described here fail to predict conditions in the hexane or octane will have a significant effect on dew point
system accurately, and the K-values are suspected for this fail- calculations.
ure—when in fact they are not at fault.
Carbon Dioxide
Using the relationships
Early conflicting data on CO2 systems was used to prepare
yi K-data (Pk = 4000) charts for the 1966 Edition. Later, experi-
Ki = Eq 25-3
xi ence showed that at low concentrations of CO2, the rule of
thumb
L + V = 1.0 Eq 25-4

KCO2 = √ KC1 • KC2 Eq 25-10
By writing a material balance for each component in the
liquid, vapor, and total mixture, one may derive the flash equa- could be used with a plus or minus 10% accuracy. Develop-
tion in various forms. A common one is, ments in the use of CO2 for reservoir drive have led to exten-

25-2
 FIG. 25-2
Sources of K-Value Charts

Charts available from sources as indicated

Component Binary Convergence pressures, kPa (abs) [psia]
Data 5500 6900 10 300 13 800 20 700 34 500 69 000
[800] [1000] [1500] [2000] [3000] [5000] [10,000]
Nitrogen *
Methane * ∇ ∇ ∇ ∇ ∇ ∇
Ethylene
Ethane * ∇ ∇ ∇ ∇ ∇ × ×
Propylene
Propane * ∇ ∇ ∇ ∇ ∇ × ×
iso-Butane × × × × ×
n-Butane *† × × × × ×
iso-Pentane × × × × ×
n-Pentane *† × × × × ×
Hexane *† × × × × ×
Heptane *† × × × × ×
Octane × × × × ×
Nonane × × × × ×
Decane × × × × ×
Hydrogen sulfide × ×
Carbon dioxide ∗∗ Use KCO2 = √

KC1 • KC2
* Binary data from Price & Kobayashi; Wichterle & Kobayashi; Stryjek, Chappelear, & Kobayashi; and Chen & Kobayashi
∇ Drawn for 1972 Edition based on available data
Reused from 1966 Edition Note: The charts shown in bold outline are published in this
× Reused from 1957 Edition edition of the data book. The charts shown in the shaded area are
† Prepared for Second Revisions 1972 Edition or revised published in a separate GPA Technical Publication (TP-22), as
** Limited to CO2 concentration of 10 mole percent of feed or less well as the 10th Edition.

sive investigations in CO2 processing. See the GPA research Because the solid region extends to a pressure above the
reports (listed in Section 1) and the Proceedings of GPA con- methane critical pressure, it is not possible to fractionate pure
ventions. The reverse volatility at high concentration of pro- methane from a CO2-methane system without entering the
pane and/or butane has been used effectively in extractive solid formation region. It is possible to perform a limited sepa-
distillation to effect CO2 separation from methane and eth- ration of CO2 and methane if the desired methane can contain
ane.23 In general, CO2 lies between methane and ethane in significant quantities of CO2.
relative volatility.
At an operating pressure above 4860 kPa (abs), the methane
Separation of CO2 and Methane purity is limited by the CO2-methane critical locus (Fig. 25-6).
For example, operating at 4930 kPa (abs), it is theoretically
The relative volatility of CO2 and methane at typical oper- possible to avoid solid CO2 formation (Fig. 25-7 and 16-33).
ating pressures is quite high, usually about 5 to 1. From this The limit on methane purity is fixed by the approach to the
standpoint, this separation should be quite easy. However, at mixture critical. In this case, the critical binary contains 6%
processing conditions, the CO2 will form a solid phase if the CO2. A practical operating limit might be 10-15% CO2.
distillation is carried to the point of producing high purity
methane. One approach to solving the methane-CO2 distillation prob-
lem is by using extractive distillation (See Section 16, Hydro-
Fig. 25-5 depicts the phase diagram for the methane-CO2 carbon Recovery). The concept is to add a heavier hydrocarbon
binary system.21 The pure component lines for methane and stream to the condenser in a fractionation column. Around
CO2 vapor-liquid equilibrium form the left and right bounda- 10 GPA research reports present data on various CO2 systems
ries of the phase envelope. Each curve terminates at its critical which are pertinent to the design of such a process.
point; methane at –83°C, 4604 kPa (abs) and CO2 at 31°C,
7382 kPa (abs). The unshaded area is the vapor-liquid region. CO2-Ethane Separation
The shaded area represents the vapor-CO2 solid region which The separation of CO2 and ethane by distillation is limited
extends to a pressure of 4860 kPa (abs). by the azeotrope formation between these components. An

25-3
 FIG. 25-3
Flash Calculation at 4140 kPa and –30°C

Column
1 2 3 4 5 6 7 8
Trial values of L Final L = 0.030
Feed Gas 30°C
Component Composition 4140 kPa L = 0.020 L = 0.060 L = 0.040 Liquid Vapor
L + VKi
Ni Ni Ni Ni
Ni Ki xi = yi
L + V Ki L + V Ki L + V Ki L + V Ki

C1 0.9010 3.7 0.24712 0.25466 0.25084 3.61900 0.24896 0.92117

CO2** 0.0106 1.23 0.00865 0.00872 0.00868 1.22310 0.00867 0.01066
C2 0.0499 0.41 0.11830 0.11203 0.11508 0.42770 0.11667 0.04783
C3 0.0187 0.082 0.18633 0.13642 0.15751 0.10954 0.17071 0.01400
iC4 0.0065 0.034 0.12191 0.07068 0.08948 0.06298 0.10321 0.00351
nC4 0.0045 0.023 0.10578 0.05513 0.07249 0.05231 0.08603 0.00198
iC5 0.0017 0.0085 0.06001 0.02500 0.03530 0.03825 0.04445 0.00038
nC5 0.0019 0.0058 0.07398 0.02903 0.04170 0.03563 0.05333 0.00031
C6 0.0029 0.0014 0.13569 0.04730 0.07014 0.03136 0.09248 0.00013
C7+* 0.0023 0.00028 0.11334 0.03817 0.05712 0.03027 0.07598 0.00002
TOTALS 1.0000 1.17121 0.77714 0.89834 1.00049 0.99998
C7 0.00042
C8 0.00014
* Average of nC7 + nC8 properties
** √
KC1 • KC2

FIG. 25-4
Dew Point Calculation at 5500 kPa (abs)

Column
1 2 3 4 5
Feed Estimated T = -45°C Estimated T = -40°C
Ni Ni
Component Ni Ki Ki
Ki Ki
CH4 0.854 2.73 0.313 2.75 0.311
CO2 0.051 0.866 0.059 0.910 0.056
C2H6 0.063 0.275 0.229 0.300 0.210
C3H8 0.032 0.070 0.457 0.080 0.400
Σ= 1.000 1.058 0.977

KCO2 calculated as √

KC1 • KC2
 1.000 − 0.977 
Linear interpolation: Tdew = −40 − [−40 − (− 45)]   = −41.4°C
 1.058 − 0.977 
Alternatively iterate until Σ Ni/Ki = 1.0

azeotropic composition of approximately 67% CO2, 33% ethane Separation of CO2 and H2S
is formed at virtually any pressure.24
The distillative separation of CO2 and H2S can be performed
Fig. 25-7 shows the CO2-ethane system at two different with traditional methods. The relative volatility of CO2 to H2S
pressures. The binary is a minimum boiling azeotrope at both is quite small. While an azeotrope between H2S and CO2 does
pressures with a composition of about two-thirds CO2 and one- not exist, vapor-liquid equilibrium behavior for this binary ap-
third ethane. Thus, an attempt to separate CO2 and ethane to proaches azeotropic character at high CO2 concentra-
nearly pure components by distillation cannot be achieved by tions25(See Section 16, Hydrocarbon Recovery).
traditional methods, and extractive distillation is required.26
(See Section 16, Hydrocarbon Recovery)

25-4
 FIG. 25-5 K-VALUE CORRELATIONS
Phase Diagram CH4-CO2 Binary21
Numerous procedures have been devised to predict K-val-
ues. These include equations of state (EOS), combinations of
equations of state with liquid theory or with tabular data, and
corresponding states correlations. This section describes sev-
eral of the more popular procedures currently available. It
does not purport to be all-inclusive or comparative.
Equations of state have appeal for predicting thermody-
namic properties because they provide internally consistent
values for all properties in convenient analytical form. Two
popular state equations for K-value predictions are the
Benedict-Webb-Rubin (BWR) equation and the Redlich-
Kwong equation.
The original BWR equation17 uses eight parameters for each
component in a mixture plus a tabular temperature depend-
ence for one of the parameters to improve the fit of vapor-pres-
sure data. This original equation is reasonably accurate for
light paraffin mixtures at reduced temperatures of 0.6 and
above.8 The equation has difficulty with low temperatures,
non-hydrocarbons, non-paraffins, and heavy paraffins.

FIG. 25-6
Isothermal Dew Point and Frost Point Data for Methane-Carbon Dioxide32

25-5
 FIG. 25-7 computer. It had shortcomings in the inherent accuracy of its
solutions and has been replaced.
Vapor-Liquid Equilibria CO2-C2H621
Prausnitz and Chueh have developed16 a procedure for high-
pressure systems employing a modified Redlich-Kwong equa-
tion for the vapor phase and for liquid-phase compressibility
together with a modified Wohl-equation model for liquid phase
activity coefficients. Complete computer program listings are
given in their book. Parameters are given for most natural gas
components. Adler et al. also use the Redlich-Kwong equa-
tion for the vapor and the Wohl equation form for the liquid
phase.6
The corresponding states principle10 is used in all the pro-
cedures discussed above. The principle assumes that the be-
havior of all substances follows the same equation forms and
equation parameters are correlated versus reduced critical
properties and acentric factor. An alternate corresponding
states approach is to refer the behavior of all substances to the
properties of a reference substance, these properties being
given by tabular data or a highly accurate state equation de-
veloped specifically for the reference substance.
The deviations of other substances from the simple critical-
parameter-ratio correspondence to the reference substance
are then correlated. Mixture rules and combination rules, as
usual, extend the procedure to mixture calculations. Leland
and co-workers have developed9 this approach extensively for
hydrocarbon mixtures.
"Shape factors" are used to account for departure from sim-
Improvements to the BWR include additional terms for tem- ple corresponding states relationships, with the usual refer-
perature dependence, parameters for additional compounds, ence substance being methane. The shape factors are
and generalized forms of the parameters. developed from PVT and fugacity data for pure components.
Starling20 has included explicit parameter temperature de- The procedure has been tested over a reduced temperature
pendence in a modified BWR equation which is capable of pre- range of 0.4 to 3.3 and for pressures to 27.6 MPa (abs). Sixty-
dicting light paraffin K-values at cryogenic temperatures. two components have been correlated including olefinic,
naphthenic, and aromatic hydrocarbons.
The Redlich-Kwong equation has the advantage of a simple
analytical form which permits direct solution for density at The Soave Redlich-Kwong (SRK)13 is a modified version of
specified pressure and temperature. The equation uses two the Redlich-Kwong equation. One of the parameters in the
parameters for each mixture component, which in principle original Redlich-Kwong equation, a, is modified to a more tem-
permits parameter values to be determined from critical prop- perature dependent term. It is expressed as a function of the
erties. acentric factor. The SRK correlation has improved accuracy in
predicting the saturation conditions of both pure substances
However, as with the BWR equation, the Redlich-Kwong and mixtures. It can also predict phase behavior in the critical
equation has been made useful for K-value predictions by em- region, although at times the calculations become unstable
pirical variation of the parameters with temperature and with around the critical point. Less accuracy has been obtained
acentric factor11, 18, 19 and by modification of the parameter- when applying the correlation to hydrogen-containing mix-
combination rules.15, 19 Considering the simplicity of the tures.
Redlich-Kwong equation form, the various modified versions
predict K-values remarkably well. Peng and Robinson14 similarly developed a two-constant
Redlich-Kwong equation of state in 1976. In this correlation,
Interaction parameters for non-hydrocarbons with hydro- the attractive pressure term of the semi-empirical van der
carbon components are necessary in the Redlich-Kwong equa- Waals equation has been modified. It accurately predicts the
tion to predict the K-values accurately when high concentra- vapor pressures of pure substances and equilibrium ratios of
tions of non-hydrocarbon components are present. They are mixtures. In addition to offering the same simplicity as the
especially important in CO2 fractionation processes, and in SRK equation, the Peng-Robinson equation is more accurate
conventional fractionation plants to predict sulfur compound in predicting the liquid density.
distribution.
In applying any of the above correlations, the original criti-
The Chao-Seader correlation7 uses the Redlich-Kwong cal/physical properties used in the derivation must be inserted
equation for the vapor phase, the regular solution model for into the appropriate equations. One may obtain slightly dif-
liquid-mixture non-ideality, and a pure-liquid property corre- ferent solutions from different computer programs, even for
lation for effects of component identity, pressure, and tempera- the same correlation. This can be attributed to different itera-
ture in the liquid phase. The correlation has been applied to a tion techniques, convergence criteria, initial estimation val-
broad spectrum of compositions at temperatures from –45°C to ues, etc. Determination and selection of interaction
150°C and pressures to 13 800 kPa. The original (P,T) limita- parameters and selection of a particular equation of state
tions have been reviewed.12 The Chao-Seader correlation was must be done carefully, considering the system components,
the first correlation specifically developed for use on a digital the operating conditions, etc.

25-6
 EQUATIONS OF STATE  R2 Tc2 
ac = 0.42747  
Refer to original papers for mixing rules for multicomponent  Pc 
mixtures. α1/2 = 1 + m (1 − T1/2
r )
30
van der Waals m = 0.48 + 1.574 ω − 0.176 ω2
Z − (1 + B) Z + AZ − AB = 0
3 2
 R Tc 
b = 0.08664  
aP  Pc 
A = 2 2
R T
Peng Robinson 31
bP
B = Z3 − (1 − B) Z2 + (A − 3B2 − 2B) Z − (AB − B2 − B3) = 0
RT
27 R2 T2c aP
a = A =
64 Pc R2 T2

R Tc bP
b = B =
8 Pc RT
 R2 T2c 
Redlich-Kwong 28 a = 0.45724  α
Z3 − Z2 + (A − B − B2) Z − AB = 0  Pc 
α1/2 = 1 + m (1 − T1/2
r )
aP
A = 2 2.5
R T m = 0.37464 + 1.54226 ω − 0.26992 ω2

B =
bP  R Tc 
RT b = 0.0778  
 Pc 
 R2 Tc2.5 
a = 0.42747  
 Pc  Benedict-Webb-Rubin-Starling (BWRS) 20, 29
 R Tc  RT  Co Do Eo  1
b = 0.0867   P = + Bo R T − Ao − 2 + 3 − 4  2
V  T T T V
 Pc 
Soave Redlich-Kwong (SRK) 13  d 1  d 1
+ bRT − a −  3 + α a +  6
 T V  T V
Z − Z + (A − B − B ) Z − AB = 0
3 2 2

−γ 2
⁄V
aP
A = 2 2 c  1  γ 
+ 3  2  1 + 2 
R T V T   V 
bP
B =
RT
a = ac α Note: ω, the acentric factor is defined in Section 23, p. 23-30.

25-7
 REFERENCES AND BIBLIOGRAPHY 23. Price, B. C., “Looking at CO2 recovery,” Oil & Gas J., p. 48-53
(Dec. 24, 1984).
1. Wilson, G. M., Barton, S. T., NGPA Report RR-2: “K-Values in 24. Nagahana, K., Kobishi, H., Hoshino, D., and Hirata, M., “Binary
Highly Aromatic and Highly Naphthenic Real Oil Absorber Sys- Vapor-Liquid Equilibria of Carbon Dioxide-Light Hydrocarbons
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2. Poettman, F. H., and Mayland, B. J., “Equilibrium Constants for 25. Sobocinski, D. P., Kurata, F., “Heterogeneous Phase Equilibria of
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terization Factors,” Petroleum Refiner 28, 101-102, July, 1949. p. 545 (1959).
3. White, R. R., and Brown, G. G., “Phase Equilibria of Complex 26. Ryan, J. M. and Holmes, A. S., “Distillation Separation of Carbon
Hydrocarbon Systems at Elevated Temperatures and Pressures,” Dioxide from Hydrogen Sulfide,” U.S. Patent No. 4,383,841
Ind. Eng. Chem. 37, 1162 (1942). (1983).
4. Grayson, H. G., and Streed, C. W., “Vapor-Liquid Equilibria for 27. Denton, R. D., Rule, D. D., “Combined Cryogenic Processing of
High Temperature, High Pressure Hydrogen-Hydrocarbon Sys- Natural Gas,” Energy Prog. 5, 40-44 (1985).
tems,” Proc. 6th World Petroleum Cong., Frankfort Main, III, Pa-
28. Redlich, O., Kwong, J. N. S., Chem. Rev. 44, 233 (1949).
per 20-DP7, p. 223 (1963).
29. Benedict, M., Webb, G. B., Rubin, L. C., “An Empirical Equation
5. Chappelear, Patsy, GPA Technical Publication TP-4, “Low Tem-
for Thermodynamic Properties of Light Hydrocarbons and Their
perature Data from Rice University for Vapor-Liquid and P-V-T
Mixtures,” Chem. Eng. Prog. 47, 419-422 (1951); J. Chem. Phys.
Behavior,” April (1974).
8, 334 (1940).
6. Adler, S. B., Ozkardesh, H., Schreiner, W. C., Hydrocarbon Proc.,
30. van der Waals, J., “Die Continuitat des Gasformigen und Flus-
47 (4) 145 (1968).
sigen Zustandes,” Barth, Leipzig (1899).
7. Chao, K. C., Seader, J. D., AIChEJ, 7, 598 (1961).
31. Peng, D. Y., Robinson, D. B., “A New Two-Constant Equation of
8. Barner, H. E., Schreiner, W. C., Hydrocarbon Proc., 45 (6) 161 State,” Ind. Eng. Chem. Fundamentals 15, 59-64 (1976).
(1966). 32. RR-76 Hong, J. H., Kobayashi, Riki, “Phase Equilibria Studies
9. Leach, J. W., Chappelear, P. S., and Leland, T. W., “Use of Molecu- for Processing of Gas from CO2 EOR Projects (Phase II).
lar Shape Factors in Vapor-Liquid Equilibrium Calculations with 33. Case, J. L., Ryan, B. F., Johnson, J. E., “Phase Behavior in High-
the Corresponding States Principle,” AIChEJ. 14, 568-576 (1968). CO2 Gas Processing,” Proc. 64th GPA Conv., p. 258 (1985).
10. Leland, T. W., Jr., and Chappelear, P. S., “The Corresponding
States Principle—A Review of Current Theory and Practice,” Ind.
Eng. Chem. 60, 15-43 (July 1968); K. C. Chao (Chairman), “Ap-
plied Thermodynamics,” ACS Publications, Washington, D.C.,
1968, p. 83. Additional References
11. Barner, H. E., Pigford, R. L., Schreiner, W. C., Proc. Am. Pet. Inst. See listing in Section 1 for GPA Technical Publications (TP) and Re-
(Div. Ref.) 46 244 (1966). search Reports (RR). Note that RR-64, RR-77, and RR-84 provide ex-
tensive evaluated references for binary, ternary, and multicomponent
12. Lenoir, J. M., Koppany, C. R., Hydrocarbon Proc. 46, 249 (1967). systems. Also as a part of GPA/GPSA Project 806, a computer data
13. Soave, Giorgio, “Equilibrium constants from a modified Redlich- bank is available through the GPA Tulsa office.
Kwong equation of state,” Chem. Eng. Sci. 27, 1197-1203 (1972). Another extensive tabulation of references only is available from El-
14. Peng, D. Y., Robinson, D. B., Ind. Eng. Chem. Fundamentals 15 sevier Publishers of Amsterdam for the work of E. Hala and
(1976). I. Wichterle of the Institute of Chemical Process Fundamentals,
Czechoslovak Academy of Sciences, Prague-Suchdol, Czechoslovakia.
15. Spear, R. R., Robinson, R. L., Chao, K. C., IEC Fund., 8 (1) 2 (1969).
Also, Hiza, M. J., Kidnay, A. J., and Miller, R. C., Equilibrium Prop-
16. Prausnitz, J. M., Cheuh, P. L., Computer Calculations for High- erties of Fluid Mixtures Volumes I and II, IFI/Plenum, New York,
Pressure Vapor-Liquid Equilibrium, Prentice-Hall (1968). 1975. See Fluid Phase Equilibria for various symposia.
17. Benedict, Webb, and Rubin, Chem. Eng. Prog. 47, 419 (1951).
18. Wilson, G. M., Adv. Cryro. Eng., Vol. II, 392 (1966).
K-DATA CHARTS FOLLOW
19. Zudkevitch, D., Joffe, J., AIChE J., 16 (1) 112 (1970). AS LISTED BELOW
20. Starling, K. E., Powers, J. E., IEC Fund., 9 (4) 531 (1970).
21. Holmes, A. S., Ryan, J. M., Price, B. C., and Stying, R. E., Proceed- Methane-Ethane Binary
ings of G.P.A., page 75 (1982). Nitrogen Pk 2000 psia (13 800 kPa)
22. Hwang, S. C., Lin, H. M., Chappelear, P. S., and Kobayashi, R.,
Methane through Decane Pk 3000 psia (20 700 kPa)
“Dew Point Values for the Methane Carbon Dioxide System,”
G.P.A. Research Report RR-21 (1976). Hydrogen Sulfide Pk 3000 psia (20 700 kPa)

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