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
13 !n"erson #all
University$ M% 3&'((
Copyright
)
*ovem+er 13$ ,--(

Correspon"ing author.

/el. 0'',1 213-3'314 5a6. 0'',1 213-(-,3
E-mail a""ress7 cmchengs8olemiss.e"u
1
Appendix A. Mixing Rules
%everal mi6ing rules have +een employe" for "epicting the parameters
a
an" b
of a cu+ic E9% for mi6tures. ! complete "iscussion of these missing rules can +e foun"
in the +oo: +y 9r+ey an" %an"ler.
;1<

van der Waals Mixing Rules
/he tra"itional van "er Waals one flui" mi6ing rules stipulate the parameters of a
mi6ture through the follo=ing e6pressions7
( ) ( )
-.3
1
i j ii jj ij
a x x a a k

0!-11
,
ii jj
i j
b b
b x x
+

0!-,1
>n E?. !-1$
ij
k
is the +inary interaction parameter$ =hich is usually recovere" +y using
the e6perimental "ata. /hrough the e6pression relating the parameters +et=een a cu+ic
E9% an" a virial E9%$ i.e.$
@ B a RT
$ it can +e sho=n that the van "er Waals mi6ing
rules conform to the statistical mechanics re?uirement of ?ua"ratic "epen"ence of the
secon" virial coefficient on composition. /hese mi6ing rules can +e use" to "escri+e
mi6tures such as hy"rocar+ons$ +ut not accurately for polar an" associating compoun"s.
With these mi6ing an" com+ining rules an" the AB%C E9%$ the fugacity
coefficient$
,
G
$ in a homogeneous phase can +e e6presse" as7
( ) ( )
( )
( )
,
1
, ,
,
,
1 ,
e6p 1 ln ln
, , 1 ,
j j
j G
y a
Z B
b b A
Z Z B
b b a B Z B

1 _
_
+ +
1

+
1

+

1
,
, ]

0!-31
,
Mixing Rules of Vidal and Huron (HV)
Ci"al an" #uron
;,<
"emonstrate" that the tra"itional van "er Waals mi6ing rules
are consistent =ith the regular solution theory an" has limite" capa+ility in fitting e6cess
Di++s energy "ata for polar species over a =i"e pressure range. /hey "evise" a
proce"ure that successfully matche" the e6cess Di++s energy$
E
G $ "erive" from an
e?uation of state =ith that from an activity coefficient mo"el at infinite pressure. /heir
proce"ure yiel"e" a mi6ing rule =ith the parameters
a
an" b in a cu+ic E9%7
E
E
i
i
i
a G
a b x
b C
1 _
+
1
, ]

0!-1
b is =ritten in a simple van "er Waals form as E?. !-,.
E
C is an E9%-"epen"ent
parameter.
;3<
5or the AB%C E9%$ this parameter is --.',3,3. >n matching
E
G $ Ci"al an"
#uron also assume" that V b $ an" -
E
V . /he fugacity coefficient$
,
G
$ for the #C
mo"el can +e e6presse" +y7
( ) ( )
( )
( )
( )
, , ,
, E
,
1 ,
ln 1
e6p 1 ln ln
, , 1 ,
G
Z B
b a
Z Z B
b b RT C
Z B

1 _
+ +
_
1
+

1
+
,
, ]
0!-31
/he novelty of the Ci"al an" #uronFs com+ination of an E9% an" an activity
0e6cess Di++s mo"el1 has inspire" a family of matching proce"ures over the last t=o
"eca"es. 9f special interest is the use of pre"ictive D
E
mo"els in this E9%@D
E
mo"els$
such as the U*>5!C class$ as it ren"ers the E9%@D
E
algorithm totally pre"ictive.
3
Mixing Rules of Modified Huron-Vidal (MHV)
%ince the lo=-pressure group interaction parameters have +een constantly up"ate"
for U*>5!C$ the tra"itional U*>5!C may not +e a"e?uate for a pre"ictive E9%@D
E
algorithm that =as "erive" +y matching D
E
at infinite pressure. !s a reme"y$ Mollerup
;<
propose" a proce"ure that matches e6cess free energies at Gero pressure. *evertheless$
this proce"ure re?uires solving the molar volume of li?ui" species from an E9%$ =hich is
not al=ays feasi+le$ as the isotherms of a cu+ic E9% "o not necessary cross the molar
volume a6is at high temperatures. /o resolve this issue$ Michelsen
;3<
"evelope" a
e6trapolation proce"ure to appro6imate the molar volume at Gero pressure.
/he mi6ing rules resulte" from the matching at Gero pressure inclu"e the
parameter b in the same form as E?. !-,$ an" the parameter
a
$ a solution of the
follo=ing e6pression7
( ) ( ) ln
E
i i i
i i
i
G b
q x q x
RT b

_
+ +

,

0!-'1
=here
( )
-
E
ln 1
V a
q C
b bRT

_
+

,
0!-(1
/he superscript - for molar volume "elineates its value at - P . Michelsen
;'<
appro6imate"
q
+y a polynomial function of a bRT $ a "imensionless energy
parameter. %pecifically$ in the so-calle" M#C1 mo"el$ Michelsen chose an a linear
appro6imation for ( ) q
$ i.e.$
( )
- 1
q q q +
0!-&1

Later$ in the so-calle" M#C, mo"el$ a ?ua"ratic correlation =as propose" for ( ) q
for
improve" fle6i+ility7
;(<
( )
,
- 1 ,
q q q q + +
0!-21
=here the parameters
1
q
an"
,
q
in the a+ove e6pression are chosen to ensure continuity
of ( ) q
an" its "erivatives. /he recommen"e" values of
1
q
an"
,
q
are --.1(3 an"
--.--'1$ respectively for the AB%C E9%.
;<
%u+stituting E?. !-2 into E?. !-' yiel"s7
( )
, ,
1 ,
ln
E
mix
mix i ii ii i ii i
i i
ii
b G
q x q x x
RT b

_
+ +

,

0!-1-1
/his process results in the follo=ing e6pression for fugacity coefficient7
( ) ( )
( )
( )
( )
,
,
,
1 ,
1
e6p 1 ln ln
, ,
1 ,
G
Z B
N b
Z Z B
b N
Z B

1 _
+ +
_
1


1
+
,
, ]
0!-111
=here
( )
( )
, ,
,
1 , , , ,
,
, 1 ,
0 1 ln ln 1
,
b b
q q
N b b
N q q

_
+ + + + +

+
0!-1,1
Mixing Rules of Linear Combination of Huron-Vidal and Michelsen Models (LCVM)
Hou:ouvalas et al.
;&$ 2<
propose" a mi6ing rule +y linearly com+ining the

Fs of
#C an" M#C1 mo"els$ =hich results in the follo=ing mi6ing rule for
a
7
E
1 1
1 1
ln ln
E
i
i i
i i
i i
a G b
a bRT x x
C q RT q b b RT

1 _ _ _
+ + +
1
, , , ]

0!-131
=here is an a"Iusta+le parameter that "etermines the relative importance of the
com+ine" rules. /hey have suggeste" the value J -.3' for the original U*>5!C for
3
lo= pressure systems$ an" values in the range from -.'3 to -.(3 for the mo"ifie"
U*>5!C for high pressure systems. /he value of
1
q
is set e?ual to --.3,. E?. !-, is
again for b . /he fugacity coefficient resulte" from this com+ination is
( ) ( ) ( )
( )
( )
( )
,
,
, ,
, E
, ,
ln 1 ln
1 ,
1 1 1
ln ln 1 ln
1 1 , , 1 ,
G
b
Z Z B
b
Z B
a b b
b RT C q q b b
Z B

_
+ +
1 _ _

+ + + +
' ; 1

+ , , ]
,
0!-11
Mixing Rules of Wong and Sandler (WS)
!lthough the tra"itional van "er Waals mi6ing rules fail to mo"el the e6cess
Di++s energy over a =i"e range of pressures$ their ?ua"ratic "epen"ence on compositions
lea" to a ?ua"ratic "epen"ence of the secon" virial coefficient on composition for
mi6tures$ =hich is stipulate" +y statistical mechanics. /he mi6ing rules of #uron an"
Ci"al are linear an" "o not satisfy the ?ua"ratic re?uirement. Wong an" %an"ler
;1-$ 11<
"erive" a general form of mi6ing rules first +y com+ining the ?ua"ratic "epen"ence of
the secon" virial coefficient on composition an" the relation +et=een the secon" virial
coefficient an" the parameters in a cu+ic E9%. /he secon" e?uation in their mi6ing rules
=as "erive" +y ta:ing the limit of the e6cess #elmholtG free energy for a cu+ic E9%
mi6ture at infinite pressure. #elmholtG free energy is less pressure "epen"ent$ an" can +e
appro6imate" +y e6cess Di++s energy at lo= pressure =here most e6perimental "ata are
collecte". /he resultant mi6ing rules are pressure in"epen"ent an" satisfy the ?ua"ratic
re?uirement7
'
E
i j
i j ij
E
i
i
i i
a
RT x x b
RT
b
a G
RT x
b C
_

1 _
+
1
, ]

0!-131
E
E
i
i
i
a G
a b x
C b
1
+
1
]

0!-1'1
=here
( )
1
1
,
j
i
i j ij
ij
a
a a
b b b k
RT RT RT
1 _
_ _
+
1
, ,
, ]
0!-1(1
or
( ) ( )
1
1
,
i j
i j ij
ij
a a
a
b b b k
RT RT
_
+

,
0!-1&1
>n our calculation$ =e use E?. !-1&.
ij
k
is a secon" virial coefficient +inary interaction
parameter$ it has to +e o+taine" e6perimentally near the con"itions of interests. /he
e6perimental "epen"ence of
ij
k
ren"ers the W% mo"el not a fully pre"ictive scheme.
/he fugacity coefficient e6pression for the soli" solute in supercritical e6traction
for the W% mi6ing rule is7
( ) ( ) ( )
( )
( )
( )
,
,
,
,
,
ln 1 ln
1
1 ,
ln
, ,
1 ,
G
Nb N
Z Z B
b
N a N
Z B
Nb N a
N
a b bRT
Z B

1
1
+
1

1
+
1
1
+ +
1
]
]
0!-121
/he partial "erivatives in the a+ove e6pression are
( )
,
,
, , ,
1 1
1
1
1
Nb N a Q ND
N D N N N
D
_ _

, ,
0!-,-1
(
an"
,
, , ,
1 N a Nb ND
RTD RTb
N N N N
_ _ _
+


, , ,
0!-,11
=here
,
,
,
j
j
j
a
Q x x b
RT
_


,
0!-,,1
,
, E
,
E
a G
D x
C RT b RT
+
0!-,31
,
, ,
1
,
j
j j
N Q a
x b
N N RT
_ _

,
,

0!-,1
an"
( )
, ,
E
, ,
ln a ND
N b RT C

+

0!-,31
Mixing Rules of Modified Huron-Vidal Model (HVS)
/o appro6imate the molar volume of li?ui" at high pressures an" high
temperatures$ 9r+ey an" %an"ler
;1,<
assume" that there is an universal linear alge+raic
core volume as
V ub
$ =here
u
is a positive constant greater than unity. Hy matching
the #elmholtG free energy at infinite pressure an" assuming
1 u
$ they generate" a ne=
set of mi6ing rules$ or the #C9% mo"el in short$ that involves parameter
a
in the
follo=ing form7
E
1
ln
E
i
i i
i i
i i
a G b
a bRT x x
b RT C RT b
1 _ _
+ +
1

1 , , ]

0!-,'1
an" b is the same as E?. !-,.
/he fugacity coefficient for the #C9% mi6ing rules for AB%C e?uation +ecomes
&
( ) ( ) ( )
( )
( )
( )
,
,
, , ,
E E E
, ,
ln 1 ln
1 ,
ln 1 1 1
ln 1 ln
, ,
1 ,
G
b
Z Z B
b
Z B
a b b
b RT C C b C b
Z B

_
+ +
1 _
_

+ + +
1

, +
, ]
,
0!-,(1
!redictive Soave-Redlich-"#on Model (!SR")
Dmehling et al
;13-1'<
"evelope" A%BK 0Are"ictive %oave-Be"lich-K=ong1 mo"el
+ase" on the %oave-Be"lich-K=ong E9% an" group contri+ution 0mo"ifie" U*>5!C1. >t
coul" pre"ict thermo"ynamic properties over a large temperature an" pressure range$
especially vapor-li?ui" e?uili+ria at high pressures using U*>5!C parameters =hich
=ere mainly fitte" to vapor-li?ui" e?uili+rium "ata aroun" atmospheric pressure an" it
continues to intro"uce ne= group an" ne= group interaction parameters +ase" on
e6perimental "ata.
/he mi6ing rule is similar as M#C1 mo"el7
-
1
ln
E
i
i i
i i
i i
a G b
a bRT x x
b RT A RT b
1 _ _
+ +
1

1 , , ]

0!-,&1
=here
-
-.'''3 A
an" b is the same as E?. !-,.
References
1. 9r+ey$ #.$ an" %. >. %an"ler$ Modeling Vao!"#iquid Equilib!ia$ Cubi% Equa&ion' o(
)&a&e and T*ei! Mixing Rule'$ Cam+ri"ge University Aress$ Cam+ri"ge$ U.K. 0122&1
,. #uron. M.$ an" J. Ci"al$ L*e= Mi6ing Bules in %imple E?uations of %tate for
Bepresenting Capor-Li?ui" E?uili+ria of %trongly *on-i"eal Mi6tures$M +luid P*a'e
Equilibi!a$ 3$ ,33-,(1 012(21
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2
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%tate$M +luid P*a'e Equilib!ia$ !$ ,13-,12 0122-1
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%tate$M +luid P*a'e Equilib!ia$ "2$ (3-1-' 01221
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1-
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11