Mathcad Modules for Supercritical Fluid Extraction Based on Mixing Rules

Appendix A – Mixing Rules

∗
Wei-Yin Chen
Jiangping Liu

Department of Chemical Engineering

University of Mississippi
134 Anderson Hall
University, MS 38677

Copyright©

November 13, 2007

∗
Corresponding author. Tel. (662) 915-5651; Fax. (662) 915-7023
E-mail address: cmchengs@olemiss.edu

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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

in the book by Orbey and Sandler.[1]

van der Waals Mixing Rules

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

mixture through the following expressions:

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

rules conform to the statistical mechanics requirement of quadratic dependence of the

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

coefficient, φ2 , in a homogeneous phase can be expressed as:

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  


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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 

b is written in a simple van der Waals form as Eq. A-2. C * is an EOS-dependent

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

model can be expressed by:


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.

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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

algorithm that was derived by matching GE at infinite pressure. As a remedy, Mollerup[4]

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

extrapolation procedure to approximate the molar volume at zero pressure.

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

The superscript 0 for molar volume delineates its value at P = 0 . Michelsen[6]

approximated q by a polynomial function of α = a bRT , a dimensionless energy

parameter. Specifically, in the so-called MHV1 model, Michelsen chose an a linear

approximation for q ( α ) , i.e.,

q ( α ) = q0 + q1α (A-8)

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

improved flexibility:[7]

q ( α ) = q0 + q1α + q2α 2 (A-9)

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

This process results in the following expression for fugacity coefficient:

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

Mixing Rules of Linear Combination of Huron-Vidal and Michelsen Models (LCVM)

Boukouvalas et al.[8, 9] proposed a mixing rule by linearly combining the α ’s of

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  

where λ is an adjustable parameter that determines the relative importance of the

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

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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

again for b . The fugacity coefficient resulted from this combination 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 


Mixing Rules of Wong and Sandler (WS)

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

lead to a quadratic dependence of the second virial coefficient on composition for

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:

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  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

parameter, it has to be obtained experimentally near the conditions of interests. The

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

The fugacity coefficient expression for the solid solute in supercritical extraction

for the WS mixing rule is:

∂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  )
 

The partial derivatives in the above expression are

∂Nb 1  1 ∂N 2 a  Q  ∂ND 
=  − 1 −  (A-20)
∂N 2 1 − D  N ∂N2  ( 1 − D ) 2  ∂N2 

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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*

Mixing Rules of Modified Huron-Vidal Model (HVOS)

To approximate the molar volume of liquid at high pressures and high

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

core volume as V = ub , where u is a positive constant greater than unity. By matching

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   

and b is the same as Eq. A-2.

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

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 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 


Predictive Soave-Redlich-Kwon Model (PSRK)

Gmehling et al [13-16] developed PSRK (Predictive Soave-Redlich-Kwong) model

based on the Soave-Redlich-Kwong EOS and group contribution (modified UNIFAC). It

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

especially vapor-liquid equilibria at high pressures using UNIFAC parameters which

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.

The mixing rule is similar as MHV1 model:

 a 1  GE  b  
a = bRT  ∑ xi i +  + ∑ xi ln     (A-28)
 i bi RT A0  RT i  bi   

where A0 = −0.64663 and b is the same as Eq. A-2.

References

1. Orbey, H., and S. I. Sandler, Modeling Vapor-Liquid Equilibria: Cubic Equations of

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)

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4. Mollerup, J. M., “A note on the derivation of Mixing Rules from Excess Gibbs Energy
Models,” Fluid Phase Equilibria, 25, 323-326 (1986)

5. Michelsen, M. L., “A Modified Huron-Vidal Mixing Rule for Cubic Equations of

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)

8. Boukouvala, C., N. Spiliotis, P. Coutsikos, and N. Tzouvaras, “Prediction of Vapor-

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)

9. Yakoumis, I. V., and V. Konstantinos, “Application of the LCVM Model to Systems

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)

14. Ahlers, J., T. Yamaguchi, and J. Gmehling, “Development of a Universal Group

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)

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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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