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Attribution Non-Commercial (BY-NC)

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∗

Wei-Yin Chen

Jiangping Liu

University of Mississippi

134 Anderson Hall

University, MS 38677

Copyright©

∗

Corresponding author. Tel. (662) 915-5651; Fax. (662) 915-7023

E-mail address: cmchengs@olemiss.edu

1

Appendix A. Mixing Rules

Several mixing rules have been employed for depicting the parameters a and b

of a cubic EOS for mixtures. A complete discussion of these missing rules can be found

The traditional van der Waals one fluid mixing rules stipulate the parameters of a

a = ∑∑ xi x j ( aii a jj ) ( 1− k )

0.5

ij (A-1)

bii + b jj

b = ∑∑ xi x j (A-2)

2

In Eq. A-1, kij is the binary interaction parameter, which is usually recovered by using

the experimental data. Through the expression relating the parameters between a cubic

EOS and a virial EOS, i.e., B = a / RT , it can be shown that the van der Waals mixing

second virial coefficient on composition. These mixing rules can be used to describe

mixtures such as hydrocarbons, but not accurately for polar and associating compounds.

With these mixing and combining rules and the PRSV EOS, the fugacity

G

2 ∑ y j a2 j

b2

φ = exp ( Z − 1) − ln ( Z − B ) +

G

A b2

− j =1

( )

Z + 1+ 2 B

ln (A-3)

2

b

2 2B b

a

( )

Z + 1 − 2 B

2

Mixing Rules of Vidal and Huron (HV)

Vidal and Huron[2] demonstrated that the traditional van der Waals mixing rules

are consistent with the regular solution theory and has limited capability in fitting excess

Gibbs energy data for polar species over a wide pressure range. They devised a

procedure that successfully matched the excess Gibbs energy, G E , derived from an

equation of state with that from an activity coefficient model at infinite pressure. Their

procedure yielded a mixing rule with the parameters a and b in a cubic EOS:

a GE

a = b ∑ xi i + * (A-4)

bi C

parameter.[3] For the PRSV EOS, this parameter is -0.62323. In matching G E , Vidal and

Huron also assumed that V = b , and V E = 0 . The fugacity coefficient, φ2 , for the HV

G

b

φ2G = exp 2 ( Z − 1 ) − ln ( Z − B )−

1 a2

+

ln ( γ 2 ) ( )

Z + 1+ 2 B

ln (A-5)

b

2 2 b 2RT C*

( )

Z + 1− 2 B

The novelty of the Vidal and Huron’s combination of an EOS and an activity

(excess Gibbs model) has inspired a family of matching procedures over the last two

decades. Of special interest is the use of predictive GE models in this EOS/GE models,

such as the UNIFAC class, as it renders the EOS/GE algorithm totally predictive.

3

Mixing Rules of Modified Huron-Vidal (MHV)

Since the low-pressure group interaction parameters have been constantly updated

for UNIFAC, the traditional UNIFAC may not be adequate for a predictive EOS/GE

proposed a procedure that matches excess free energies at zero pressure. Nevertheless,

this procedure requires solving the molar volume of liquid species from an EOS, which is

not always feasible, as the isotherms of a cubic EOS do not necessary cross the molar

volume axis at high temperatures. To resolve this issue, Michelsen [5] developed a

The mixing rules resulted from the matching at zero pressure include the

parameter b in the same form as Eq. A-2, and the parameter a , a solution of the

following expression:

GE b

q ( α ) = ∑ xi q ( α i ) + + ∑ xi ln (A-6)

i RT i bi

where

V 0 a

q ( α ) = − ln − 1 + C* (A-7)

b bRT

q ( α ) = q0 + q1α (A-8)

4

Later, in the so-called MHV2 model, a quadratic correlation was proposed for q ( α ) for

improved flexibility:[7]

where the parameters q1 and q2 in the above expression are chosen to ensure continuity

of q ( α ) and its derivatives. The recommended values of q1 and q2 are -0.41754 and

-0.00461, respectively for the PRSV EOS.[4] Substituting Eq. A-9 into Eq. A-6 yields:

GE b

q1 α mix − ∑ xiαii + q2 ( αii2 − ∑ xi αii2 ) = + ∑ xi ln mix (A-10)

i RT i bii

φ = exp

G

b2

( Z − 1) − ln ( Z − B ) −

(

1 ∂ ( Nα ) Z + 1 + 2 B )

ln (A-11)

2

b

2 2 ∂N 2 Z + 1 − 2 B

(

)

where

b b

q1α 2 + q2 (α 2 + α22 ) + ln ( γ 2 ) + ln + 2 − 1

∂ ( Nα ) b2 b (A-12)

=

∂N 2 q1 + 2q2α

HV and MHV1 models, which results in the following mixing rule for a :

λ 1 − λ G E 1 − λ b a

a = bRT * + + ∑ xi ln + ∑ xi ln i (A-13)

C q1 RT q1 i bi i bi RT

combined rules. They have suggested the value λ = 0.36 for the original UNIFAC for

5

low pressure systems, and values in the range from 0.65 to 0.75 for the modified

UNIFAC for high pressure systems. The value of q1 is set equal to -0.52. Eq. A-2 is

b2

ln ( φ2G ) = ( Z −1 ) − ln ( Z − B )

b

1 a2 λ 1−λ 1 − λ b b2 ( )

Z + 1 + 2 B (A-14)

− + *+ ln ( γ ) + ln + − 1 ln

2 2 b2 RT C q1

2

q1 b2 b ( )

Z + 1 − 2 B

Although the traditional van der Waals mixing rules fail to model the excess

Gibbs energy over a wide range of pressures, their quadratic dependence on compositions

mixtures, which is stipulated by statistical mechanics. The mixing rules of Huron and

Vidal are linear and do not satisfy the quadratic requirement. Wong and Sandler[10, 11]

derived a general form of mixing rules first by combining the quadratic dependence of

the second virial coefficient on composition and the relation between the second virial

coefficient and the parameters in a cubic EOS. The second equation in their mixing rules

was derived by taking the limit of the excess Helmholtz free energy for a cubic EOS

mixture at infinite pressure. Helmholtz free energy is less pressure dependent, and can be

approximated by excess Gibbs energy at low pressure where most experimental data are

collected. The resultant mixing rules are pressure independent and satisfy the quadratic

requirement:

6

a

RT ∑∑ xi x j b −

i j RT ij

b= (A-15)

a GE

RT − ∑ xi i + *

i bi C

GE a

a = b * + ∑ xi i (A-16)

C bi

where

a 1 ai a j

b − = bi − + bj − ( 1 − kij ) (A-17)

RT ij 2 RT RT

or

a 1 ai a j

b − = ( bi + b j ) − ( 1 − kij ) (A-18)

RT ij 2 RT

In our calculation, we use Eq. A-18. kij is a second virial coefficient binary interaction

experimental dependence of kij renders the WS model not a fully predictive scheme.

The fugacity coefficient expression for the solid solute in supercritical extraction

∂Nb ∂N 2

ln ( φ2G ) = ( Z − 1) − ln ( Z − B )

b

1

N ( ∂N a ∂N 2 ) ∂Nb ∂N 2 Z + 1 − 2 B ( )

2

(A-19)

a

+ − ln

2 2bRT a b (

Z + 1 + 2 B )

∂Nb 1 1 ∂N 2 a Q ∂ND

= − 1 − (A-20)

∂N 2 1 − D N ∂N2 ( 1 − D ) 2 ∂N2

7

and

1 ∂N 2 a ∂Nb ∂ND

= RTD + RTb (A-21)

N ∂N 2 ∂N2 ∂N2

where

a

Q = ∑∑ x2 x j b − (A-22)

2 j RT 2 j

GE a

D= *

+ x2 2 (A-23)

C RT b2 RT

1 ∂N 2Q a

= 2∑ x j b − (A-24)

N ∂N 2 j RT 2 j

and

∂ND a ln ( λ2 )

= 2 + (A-25)

∂N 2 b2 RT C*

temperatures, Orbey and Sandler[12] assumed that there is an universal linear algebraic

the Helmholtz free energy at infinite pressure and assuming u = 1 , they generated a new

set of mixing rules, or the HVOS model in short, that involves parameter a in the

following form:

a 1 GE b

a = bRT ∑ xi i + * + ∑ xi ln (A-26)

i bi RT C RT i bi

The fugacity coefficient for the HVOS mixing rules for PRSV equation becomes

8

b2

ln ( φ2G ) = ( Z − 1) − ln ( Z − B )

b

−

1 a2

+

ln ( γ 2 ) 1 b 1 b2 ( )

Z + 1 + 2 B

+ * ln + * − 1 ln

(A-27)

2 2 b2 RT C* C b2 C b ( )

Z + 1 − 2 B

could predict thermodynamic properties over a large temperature and pressure range,

were mainly fitted to vapor-liquid equilibrium data around atmospheric pressure and it

continues to introduce new group and new group interaction parameters based on

experimental data.

a 1 GE b

a = bRT ∑ xi i + + ∑ xi ln (A-28)

i bi RT A0 RT i bi

References

State and Their Mixing Rules, Cambridge University Press, Cambridge, U.K. (1998)

2. Huron. M., and J. Vidal, “New Mixing Rules in Simple Equations of State for

Representing Vapor-Liquid Equilibria of Strongly Non-ideal Mixtures,” Fluid Phase

Equilibira, 3, 255-271 (1979)

3. Orbey. H., and S. I. Sandler, “Analysis of Excess Free Energy Based Equations of

State Models,” AIChE Journal, 42(8), 2327-2334 (1996)

9

4. Mollerup, J. M., “A note on the derivation of Mixing Rules from Excess Gibbs Energy

Models,” Fluid Phase Equilibria, 25, 323-326 (1986)

State,” Fluid Phase Equilibria, 60, 213-219 (1990)

6. Span, R., and W. Wagner, “A New Equation of State for Carbon Dioxide Covering the

Fluid Region from the Triple-Point Temperature to 1100K at Pressures up to 800 MPa,”

Journal of Physical and Chemical Reference Data, 25(6), 1509-1596 (1996)

7. Dahl, S., A. Fredenslund, and P. Rasmussen, “The MHV2 Model: A UNIFAC-Based

Equation of State Model for Prediction of Gas Solubility and Vapor-Liquid Equilibria at

Low and High Pressures,” Ind. Eng. Chem. Res., 30, 1936-1945 (1991)

Liquid Equilibrium with the LCVM Model: A Linear Combination of the Vidal and

Michelsen Mixing Rules Coupled with the Original UNIFAC and the t-mPR Equation of

State,” Fluid Phase Equilibria, 92, 75-106 (1994)

Containing Organic Compounds and Supercritical Carbon Dioxide,” J. Supercrit. Fluids.,

9, 88-98 (1996)

10. Wong, D. S. H., and S. I. Sandler, “A Theoretically Correct Mixing Rule for Cubic

Equations of State,” AIChE J., 38(5), 671-680 (1992)

11. Wong, D. S. H., H. Orbey, and S. I. Sandler, “Equation of State Mixing Rule for

Nonideal Mixtures Using Available Activity Coefficient Model Parameters and That

Allows Extrapolation Over Large Ranges of Temperature and Pressure,” Ind. Eng. Chem.

Res., 31(8), 2033-2039 (1992)

12. Orbey, H., and S. I. Sandler, “On the Combination of Equation of State and Excess

Free Energy Models,” Fluid Phase Equilibria, 111, 53-70 (1995c)

13. Holderbaum, T., and J. Gmehling, “PSRK: A Group Contribution Equation of State

Based on UNFAC,” Fluid Phase Equilibria, 70, 251-265 (1991)

Contribution Equation of State. 5. Prediction of the Solubility of High-Boiling

Compounds in Supercritical Gases with the Group Contribution Equation of State

Volume-Translated Peng-Robinson,” Ind. Eng. Chem. Res., 43(20), 6569-6576 (2004)

15. Gmehling. J., J. D. Li, and S. Martin, “A Modified UNIFAC Model. 2. Present

Parameter Matrix and Results for Different Thermodynamic Properties,” Industrial and

engineering chemistry research, 32,178-193 (1993)

10

16. Gmehling, J., “Company Consortium for the Revision, Extension and Further

Development of the Group Contribution Methods UNIFAC, Mod. UNIFAC (Do) and the

Predictive Equation of State PSRK,” <http://134.106.215.86/UNIFAC/> (2006)

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