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i
i
T V n
V
m
RT
p
n
RT
V
d V Z
iej
_
,
1
]
1
1
1
(4)
Wher e:
= v or l
V = Tot al volume
n
i
= Mole number of component i
Physical Pr oper t y Met hods and Models 1-3
Ver sion 10
Chapter 1
Equat ions 2 and 3 ar e ident ical wit h t he only differ ence being t he phase t o which
t he var iables apply. The fugacit y coefficient
i
is obt ained fr om t he equat ion of
st at e, r epr esent ed by p in equat ion 4. See equat ion 45 for an example of an
equat ion of st at e.
In t he a ct i vi t y coeffi ci ent met hod :
f
i
v
=
i
v
i
y p (5)
f
i
l
= x f
i i i
l
*,
(6)
Wher e
i
v
is calculat ed accor ding t o equat ion 4,
i
= Liquid act ivit y coefficient of component i
f
i
l *,
= Liquid fugacit y of pur e component i at mixt ur e t emper at ur e
Equat ion 5 is ident ical t o equat ion 2. Again, t he fugacit y coefficient is calculat ed
fr om an equat ion of st at e. Equat ion 6 is t ot ally differ ent .
Each pr oper t y met hod in ASPEN PLUS is based on eit her t he equat ion-of-st at e
met hod or t he act ivit y coefficient met hod for phase equilibr ium calculat ions. The
phase equilibr ium met hod det er mines how ot her t her modynamic pr oper t ies, such
as ent halpies and molar volumes, ar e calculat ed.
Wit h an equat ion-of-st at e met hod, all pr oper t ies can be der ived fr om t he
equat ion of st at e, for bot h phases. Using an act ivit y coefficient met hod, t he vapor
phase pr oper t ies ar e der ived fr om an equat ion of st at e, exact ly as in t he
equat ion-of- st at e met hod. However t he liquid pr oper t ies ar e det er mined fr om
summat ion of t he pur e component pr oper t ies t o which a mixing t er m or an excess
t er m is added.
Equati on-of-State Method
The par t ial pr essur e of a component i in a gas mixt ur e is:
p y p
i i
(7)
The fugacit y of a component in an ideal gas mixt ur e is equal t o it s par t ial
pr essur e. The fugacit y in a r eal mixt ur e is t he effect ive par t ial pr essur e:
f y p
i
v
i
v
i
(8)
1-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
The cor r ect ion fact or
i
v
is t he fugacit y coefficient . For a vapor at moder at e
pr essur es,
i
v
is close t o unit y. The same equat ion can be applied t o a liquid:
f x p
i
l
i
l
i
(9)
A liquid differ s fr om an ideal gas much mor e t han a r eal gas differ s fr om an ideal
gas. Thus fugacit y coefficient s for a liquid ar e ver y differ ent fr om unit y. For
example, t he fugacit y coefficient of liquid wat er at at mospher ic pr essur e and
r oom t emper at ur e is about 0.03 (Haar et al., 1984).
An equat ion of st at e descr ibes t he pr essur e, volume and t emper at ur e (p,V,T)
behavior of pur e component s and mixt ur es. Usually it is explicit in pr essur e.
Most equat ions of st at e have differ ent t er ms t o r epr esent at t r act ive and r epulsive
for ces bet ween molecules. Any t her modynamic pr oper t y, such as fugacit y
coefficient s and ent halpies, can be calculat ed fr om t he equat ion of st at e.
Equat ion-of-st at e pr oper t ies ar e calculat ed r elat ive t o t he ideal gas pr oper t ies of
t he same mixt ur e at t he same condit ions. See Calculat ion of Pr oper t ies Using an
Equat ion-of-St at e Pr oper t y Met hod on page 1-7.
Vapor-Li qui d Equi li bri a
The r elat ionship for vapor -liquid equilibr ium is obt ained by subst it ut ing equat ions
8 and 9 in equat ion 1 and dividing by p:
i
v
i i
l
i
y x (10)
Fugacit y coefficient s ar e obt ained fr om t he equat ion of st at e (see equat ion 4 and
Calculat ion of Pr oper t ies Using an Equat ion-of-St at e Pr oper t y Met hod on page 1-
7). The calculat ion is t he same for super cr it ical and subcr it ical component s (see
Act ivit y Coefficient Met hod on page 1-10).
Physical Pr oper t y Met hods and Models 1-5
Ver sion 10
Chapter 1
Pressure-Temperature Di agram
Fluid phase equilibr ia depend not only on t emper at ur e but also on pr essur e. At
const ant t emper at ur e (and below t he mixt ur e cr it ical t emper at ur e), a mult i-
component mixt ur e will be in t he vapor st at e at ver y low pr essur e and in t he liquid
st at e at ver y high pr essur e. Ther e is an int er mediat e pr essur e r ange for which
vapor and liquid phases co-exist . Coming fr om low pr essur es, fir st a dew point is
found. Then mor e and mor e liquid will for m unt il t he vapor disappear s at t he
bubble point pr essur e. This is illust r at ed in t he figur e labeled Phase Envelope of a
Met hane-Rich Hydr ocar bon Mixt ur e. Cur ves of const ant vapor fr act ion (0.0, 0.2,
0.4, 0.6, 0.8 and 1.0) ar e plot t ed as a funct ion of t emper at ur e. A vapor fr act ion of
unit y cor r esponds t o a dew-point ; a vapor fr act ion of zer o cor r esponds t o a bubble
point . The ar ea confined bet ween dew-point and bubble-point cur ves is t he t wo-
phase r egion. The dew-point and bubble-point cur ves meet at high t emper at ur es
and pr essur es at t he cr it ical point . The ot her lines of const ant vapor fr act ions meet
at t he same point . In Phase Envelope of a Met hane-Rich Hydr ocar bon Mixt ur e,
t he cr it ical point is found at t he pr essur e maximum of t he phase envelope
(cr icondenbar ). This is not a gener al r ule.
At t he cr it ical point t he differ ences bet ween vapor and liquid vanish; t he mole
fr act ions and pr oper t ies of t he t wo phases become ident ical. Equat ion 10 can
handle t his phenomenon because t he same equat ion of st at e is used t o evaluat e
i
v
and
i
l
. Engineer ing t ype equat ions of st at e can model t he pr essur e
dependence of vapor -liquid equilibr ia ver y well. However , t hey cannot yet model
cr it ical phenomena accur at ely (see Equat ion-of-St at e Models on page 1-22).
Phase Envelope of a Methane-Rich Hydrocarbon Mixture
1-6 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
Retrograde Condensati on
Compr essing t he met hane-r ich mixt ur e shown in t he figur e labeled Phase
Envelope of a Met hane-Rich Hydr ocar bon Mixt ur e at 270 K (above t he mixt ure
cr it ical t emper at ur e) will show a dew-point . Then liquid will be for med up t o a
vapor fr act ion of about 0.75 (110 bar ). Upon fur t her compr ession t he vapor fr act ion
will decr ease again unt il a second dew-point is r eached. If t he pr ocess is car r ied out
wit h decr easing pr essur e, liquid is for med when expanding. This is t he opposit e of
t he mor e usual condensat ion upon compr ession. It is called r et r ogr ade
condensat ion and it happens oft en in nat ur al gas mixt ur es.
Li qui d-Li qui d and Li qui d-Li qui d-Vapor Equi li bri a
Liquid-liquid equilibr ia ar e less pr essur e dependent t han vapor -liquid equilibr ia,
but cer t ainly not pr essur e independent . The act ivit y coefficient met hod can model
liquid-liquid and liquid-liquid-vapor equilibr ia at low pr essur e as a funct ion of
t emper at ur e. However , wit h var ying pr essur e t he equat ion of st at e met hod is
needed (compar e Act ivit y Coefficient Met hod on page 1-10, Liquid-Liquid and
Liquid-Liquid-Vapor Equilibr ia). The equat ion-of-st at e met hod (equat ion 10) can be
applied t o liquid-liquid equilibr ia:
i
l
i
l
i
l
i
l
x x
1 1 2 2
(11)
and also t o liquid-liquid-vapor equilibr ia:
i
v
i i
l
i
l
i
l
i
l
y x x
1 1 2 2
(12)
Fugacit y coefficient s in all t he phases ar e calculat ed using t he same equat ion of
st at e. Fugacit y coefficient s fr om equat ions of st at e ar e a funct ion of composit ion,
t emper at ur e, and pr essur e. Ther efor e, t he pr essur e dependency of liquid-liquid
equilibr ia can be descr ibed.
Li qui d Phase Noni deali ty
Liquid-liquid separ at ion occur s in syst ems wit h ver y dissimilar molecules. Eit her
t he size or t he int er molecular int er act ions bet ween component s may be dissimilar .
Syst ems t hat demix at low pr essur es, have usually st r ongly dissimilar
int er molecular int er act ions, as for example in mixt ur es of polar and non-polar
molecules. In t his case, t he miscibilit y gap is likely t o exist at high pr essur es as
well. An examples is t he syst em dimet hyl-et her and wat er (Pozo and St r eet , 1984).
This behavior also occur s in syst ems of a fully- or near fully-fluor inat ed aliphat ic or
alicyclic fluor ocar bon wit h t he cor r esponding hydr ocar bon (Rowlinson and Swint on,
1982), for example cyclohexane and perfluorocyclohexane (Dyke et al., 1959; Hicks
and Young, 1971).
Syst ems which have similar int er act ions, but which ar e ver y differ ent in size, do
demix at higher pr essur es. For binar y syst ems, t his happens oft en in t he vicinit y
of t he cr it ical point of t he light component (Rowlinson and Swint on , 1982).
Physical Pr oper t y Met hods and Models 1-7
Ver sion 10
Chapter 1
Examples ar e:
Met hane wit h hexane or hept ane (van der Kooi, 1981; Davenpor t and
Rowlinson, 1963; Kohn, 1961)
Et hane wit h n-alkanes wit h carbon numbers fr om 18 t o 26 (Pet ers et al., 1986)
Carbon dioxide wit h n-alkanes wit h carbon numbers fr om 7 t o 20 (Fall et al.,
1985)
The mor e t he demixing compounds differ in molecular size, t he mor e likely it is
t hat t he liquid-liquid and liquid-liquid-vapor equilibr ia will int er fer e wit h
solidificat ion of t he heavy component . For example, et hane and pent acosane or
hexacosane show t his. Incr easing t he differ ence in car bon number fur t her causes
t he liquid-liquid separ at ion t o disappear . For example in mixt ur es of et hane wit h
n-alkanes wit h car bon number s higher t han 26, t he liquid-liquid separ at ion
becomes met ast able wit h r espect t o t he solid-fluid (gas or liquid) equilibr ia (Pet er s
et al., 1986). The solid cannot be handled by an equat ion-of-st at e met hod.
Critical Solution Temperature
In liquid-liquid equilibr ia, mut ual solubilit ies depend on t emper at ur e and pr essur e.
Solubilit ies can incr ease or decr ease wit h incr easing or decr easing t emper at ur e or
pr essur e. The t r end depends on t her modynamic mixt ur e pr oper t ies but cannot be
pr edict ed a priori. Immiscible phases can become miscible wit h incr easing or
decr easing t emper at ur e or pr essur e. In t hat case a liquid-liquid cr it ical point
occurs. Equat ions 11 and 12 can handle t his behavior, but engineering t ype
equat ions of st at e cannot model t hese phenomena accurat ely.
Calculation of Properties Using an Equation-of-State
Property Method
The equat ion of st at e can be r elat ed t o ot her pr oper t ies t hr ough fundament al
t her modynamic equat ions :
Fugacit y coefficient :
f y p
i
v
i
v
i
(13)
Ent halpy depar t ur e:
( ) ( ) ( ) H H p
RT
V
dV RT
V
V
T S S RT Z
m m
ig
ig m m
ig
m
V
_
,
_
,
+ +
ln 1 (14)
Ent r opy depar t ur e:
( )
S S
p
T
R
V
dV R
V
V
m m
ig
v
ig
V
_
,
1
]
1
+
_
,
ln (15)
Gibbs ener gy depar t ur e:
( ) ( ) G G p
RT
V
dV RT
V
V
RT Z
m m
ig
ig
V
m
_
,
_
,
ln 1 (16)
1-8 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
Molar volume:
Solve ( ) p T V
m
, for V
m
.
Fr om a given equat ion of st at e, fugacit ies ar e calculat ed accor ding t o equat ion 13.
The ot her t her modynamic pr oper t ies of a mixt ur e can be comput ed fr om t he
depar t ur e funct ions:
Vapor ent halpy:
( )
H H H H
m
v
m
ig
m
v
m
ig
+ (17)
Liquid ent halpy:
( )
H H H H
m
l
m
ig
m
l
m
ig
+ (18)
The molar ideal gas ent halpy, H
m
ig
is comput ed by t he expr ession
( ) H y H C T dT
m
ig
i f i
ig
p i
ig
T
T
i
ref
+
1
]
1
,
(19)
Wher e:
C
p i
ig
,
= Ideal gas heat capacit y
f i
ig
H
= St andar d ent halpy of for mat ion for ideal gas at 298.15 K and 1
at m
T
ref
= Refer ence t emper at ur e = 298.15 K
Ent r opy and Gibbs ener gy can be comput ed in a similar manner :
( )
G G G G
m
v
m
ig
m
v
m
ig
+ (20)
( )
G G G G
m
l
m
ig
m
l
m
ig
+ (21)
( )
S S S S
m
v
m
ig
m
v
m
ig
+ (22)
( )
S S S S
m
l
m
ig
m
l
m
ig
+ (23)
Vapor and liquid volume is comput ed by solving p(T,V
m
) for V
m
or comput ed by
an empir ical cor r elat ion.
Advantages and Disadvantages of the Equation-of-State
Method
You can use equat ions of st at e over wide r anges of t emper at ur e and pr essur e,
including subcr it ical and super cr it ical r egions. For ideal or slight ly non-ideal
syst ems, t her modynamic pr oper t ies for bot h t he vapor and liquid phases can be
comput ed wit h a minimum amount of component dat a. Equat ions of st at e ar e
suit able for modeling hydr ocar bon syst ems wit h light gases such as CO
2
, N
2
, and
H S
2
.
Physical Pr oper t y Met hods and Models 1-9
Ver sion 10
Chapter 1
For t he best r epr esent at ion of non-ideal syst ems, you must obt ain binar y
int er act ion par amet er s fr om r egr ession of exper iment al vapor -liquid equilibr ium
(VLE) dat a. Equat ion of st at e binar y par amet er s for many component pair s ar e
available in ASPEN PLUS.
The assumpt ions in t he simpler equat ions of st at e (Redlich-Kwong-Soave, Peng-
Robinson, Lee-Kesler -Plcker ) ar e not capable of r epr esent ing highly non-ideal
chemical syst ems, such as alcohol-wat er syst ems. Use t he act ivit y-coefficient
opt ions set s for t hese syst ems at low pr essur es. At high pr essur es, use t he
flexible and pr edict ive equat ions of st at e.
References
A.J . Davenport and J .S. Rowlinson, Trans. Faraday S oc., Vol. 59 (1963), p. 78,
(cit ed aft er van der Kooi, 1981).
D.E.L. Dyke, J .S. Rowlinson and R. Thacker , Trans. Faraday S oc., Vol. 55,
(1959), p. 903, (cit ed aft er Rowlinson and Swint on, 1982).
D.J . Fall, J .L. Fall, and K.D. Luks, "Liquid-liquid-vapor immiscibilit y Limit s in
Car bon Dioxide + n-Par affin Mixt ur es," J . Chem. Eng. Data , Vol. 30, No. 1,
(1985), pp. 82-88.
L. Haar , J .S. Gallagher , and J .H. Kell, NBS INRC S team Tables (Washingt on:
Hemispher e Publishing Cor por at ion, 1984).
C.P. Hicks and C.L. Young, Trans. Faraday S oc., Vol. 67, (1971), p.1605, (cit ed
aft er Rowlinson and Swint on, 1982).
J .P. Kohn, AIChE J . , Vol 7, (1961), p. 514, (cit ed aft er van der Kooi, 1981).
H.J . van der Kooi, Metingen en berekeningen aan het systeem methaan-n-
eiscosaan, Ph.D. t hesis, Delft Univer sit y of Technology (Delft : Delft se
Univer sit air e Per s, 1981) (In Dut ch).
C.J . Pet er s, R.N. Licht ent haler , and J . de Swaan Ar ons, "Thr ee Phase Equilibr ia
In Binar y Mixt ur es Of Et hane And Higher N-Alkanes," Fluid Phase Eq., Vol. 29,
(1986), pp. 495-504.
M.E. Pozo and W.B. St r eet , "Fluid Phase Equilibr ia for t he Syst em Dimet hyl
Et her /Wat er fr om 50 t o 200 C and Pr essur es t o 50.9 MPa," J . Chem. Eng. Data,
Vol. 29, No. 3, (1984), pp. 324-329.
J .S. Rowlinson and F.L. Swint on, Liquids and Liquid Mixtures, 3r d ed. (London,
et c.:But t er wor t hs, 1982), ch. 6.
1-10 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
Acti vi ty Coeffi ci ent Method
In an ideal liquid solut ion, t he liquid fugacit y of each component in t he mixt ur e is
dir ect ly pr opor t ional t o t he mole fr act ion of t he component .
f x f
i
l
i i
l
*,
(24)
The ideal solut ion assumes t hat all molecules in t he liquid solut ion ar e ident ical
in size and ar e r andomly dist r ibut ed. This assumpt ion is valid for mixt ur es
cont aining molecules of similar size and char act er . An example is a mixt ur e of
pent ane (n-pent ane) and 2,2-dimet hylpr opane (neopent ane) (Gmehling et al. ,
1980, pp. 95-99). For t his mixt ur e, t he molecules ar e of similar size and t he
int er molecular int er act ions bet ween differ ent component molecules ar e small (as
for all nonpolar syst ems). Idealit y can also exist bet ween polar molecules, if t he
int er act ions cancel out . An example is t he syst em wat er and 1,2-et hanediol
(et hyleneglycol) at 363 K (Gmehling et al., 1988, p. 124).
In gener al, you can expect non-idealit y in mixt ur es of unlike molecules. Eit her
t he size and shape or t he int er molecular int er act ions bet ween component s may
be dissimilar . For shor t t hese ar e called size and ener gy asymmet r y. Ener gy
asymmet r y occur s bet ween polar and non-polar molecules and also bet ween
differ ent polar molecules. An example is a mixt ur e of alcohol and wat er .
The act ivit y coefficient
i
r epr esent s t he deviat ion of t he mixt ur e fr om idealit y
(as defined by t he ideal solut ion):
f x f
i
l
i i i
l
*,
(25)
The gr eat er
i
deviat es fr om unit y, t he mor e non-ideal t he mixt ur e. For a pur e
component x
i
1 and
i
1, so by t his definit ion a pur e component is ideal. A
mixt ur e t hat behaves as t he sum of it s pur e component s is also defined as ideal
(compar e equat ion 24). This definit ion of idealit y, r elat ive t o t he pur e liquid, is
t ot ally differ ent fr om t he definit ion of t he idealit y of an ideal gas, which has an
absolut e meaning (see Equat ion-of-St at e Met hod on page 1-3). These for ms of
idealit y can be used next t o each ot her .
In t he major it y of mixt ur es,
i
is gr eat er t han unit y. The r esult is a higher
fugacit y t han ideal (compar e equat ion 25 t o equat ion 24). The fugacit y can be
int er pr et ed as t he t endency t o vapor ize. If compounds vapor ize mor e t han in an
ideal solut ion, t hen t hey incr ease t heir aver age dist ance. So act ivit y coefficient s
gr eat er t han unit y indicat e r epulsion bet ween unlike molecules. If t he r epulsion
is st r ong, liquid-liquid separ at ion occur s. This is anot her mechanism t hat
decr eases close cont act bet ween unlike molecules.
It is less common t hat
i
is smaller t han unit y. Using t he same r easoning, t his
can be int er pr et ed as st r ong at t r act ion bet ween unlike molecules. In t his case,
liquid-liquid separ at ion does not occur . Inst ead for mat ion of complexes is
possible.
Physical Pr oper t y Met hods and Models 1-11
Ver sion 10
Chapter 1
Vapor-Liquid Equilibria
In t he act ivit y coefficient appr oach, t he basic vapor -liquid equilibr ium
r elat ionship is r epr esent ed by:
i
v
i i i i
l
y p x f
*,
(26)
The vapor phase fugacit y coefficient
i
v
is comput ed fr om an equat ion of st at e
(see Equat ion-of-St at e Met hod on page 1-3). The liquid act ivit y coefficient
i
is
comput ed fr om an act ivit y coefficient model.
For an ideal gas,
i
v
1. For an ideal liquid,
i
1. Combining t his wit h equat ion
26 gives Raoult s law:
y p x p
i i i
l
*,
(27)
At low t o moder at e pr essur es, t he main differ ence bet ween equat ions 26 and 27
is due t o t he act ivit y coefficient . If t he act ivit y coefficient is lar ger t han unit y, t he
syst em is said t o show posit ive deviat ions fr om Raoult s law. Negat ive deviat ions
fr om Raoult s law occur when t he act ivit y coefficient is smaller t han unit y.
Li qui d Phase Reference Fugaci ty
The liquid phase r efer ence fugacit y f
i
l *,
fr om equat ion 26 can be comput ed in t hr ee
ways:
For sol vent s: The r efer ence st at e for a solvent is defined as pur e component in
t he liquid st at e, at t he t emper at ur e and pr essur e of t he syst em. By t his definit ion
i
appr oaches unit y as x
i
appr oaches unit y.
The liquid phase r efer ence fugacit y f
i
l *,
is comput ed as
( )
f T p p
i
l
i
v
i
l
i
l
i
l *, *, *, *, *,
, (28)
Wher e:
i
v *,
= Fugacit y coefficient of pur e component i at t he syst em
t emper at ur e and vapor pr essur es, as calculat ed fr om t he vapor
phase equat ion of st at e
p
i
l *,
= Liquid vapor pr essur es of component i at t he syst em t emper at ur e
i
l *,
= Poynt ing cor r ect ion for pr essur e
=
exp
*,
*,
1
RT
V dp
i
l
p
p
i
l
_
,
(29)
Wher e:
*, * ,
(34)
Wher e:
H
i
v *,
= Pur e component vapor ent halpy at T and vapor pr essur e
vap i
H
*
= Component vapor izat ion ent halpy
H
m
E l ,
= Excess liquid ent halpy
Excess liquid ent halpy H
m
E l ,
is r elat ed t o t he act ivit y coefficient t hr ough t he
expr ession
H RT x
T
m
E l
i
i
i
,
ln
2
(35)
Liquid mixt ur e Gibbs fr ee ener gy and ent r opy ar e comput ed as:
( )
S
T
H G
m
l
m
l
m
l
1
(36)
G G RT G
m
l
m
v
i
l
m
E l
i
+ ln
*, ,
(37)
Wher e:
G RT x
m
E l
i i
i
,
ln (38)
Liquid densit y is comput ed using an empir ical cor r elat ion.
Sol i d pha se: Solid mixt ur e ent halpy is comput ed as:
H x H H
m
s s
i
s
m
E s
i
i
+
*, ,
(39)
Wher e:
H
i
s *,
= Pur e component solid ent halpy at T
Physical Pr oper t y Met hods and Models 1-21
Ver sion 10
Chapter 1
H
m
E s ,
= The excess solid ent halpy
Excess solid ent halpy H
m
E s ,
is r elat ed t o t he act ivit y coefficient t hr ough t he
expr ession H RT x
T
m
E s
i
i
i
,
ln
2
(40)
Solid mixt ur e Gibbs ener gy is comput ed as:
G x G RT x x
m
s
i i
s
m
E s
i
i
s
i
s
i
+ +
*, ,
ln (41)
Wher e:
G RT x
m
E s
i
s
i
s
i
,
ln
(42)
The solid mixt ur e ent r opy follows fr om t he Gibbs ener gy and ent halpy:
( )
S
T
H G
m
s
m
s
m
s
1
(43)
Advantages and Disadvantages of the Activity Coefficient
Method
The act ivit y coefficient met hod is t he best way t o r epr esent highly non-ideal liquid
mixt ur es at low pr essur es. You must est imat e or obt ain binar y par amet er s fr om
exper iment al dat a, such as phase equilibr ium dat a. Binar y par amet er s for t he
Wilson, NRTL, and UNIQUAC models ar e available in ASPEN PLUS for a lar ge
number of component pair s. These binar y par amet er s ar e used aut omat ically. See
AS PEN PLUS Physical Property Data, Chapt er 1, for det ails.
Binar y par amet er s ar e valid only over t he t emper at ur e and pr essur e r anges of
t he dat a. Binar y par amet er s out side t he valid r ange should be used wit h caut ion,
especially in liquid-liquid equilibr ium applicat ions. If no par amet er s ar e
available, t he pr edict ive UNIFAC models can be used.
The act ivit y coefficient appr oach should be used only at low pr essur es (below 10
at m). For syst ems cont aining dissolved gases at low pr essur es and at small
concent r at ions, use Henr ys law. For highly non-ideal chemical syst ems at high
pr essur es, use t he flexible and pr edict ive equat ions of st at e.
References
Collect ion, Aliphat ic Hydr ocar bons, C4 - C6, Chemistry Data S eries Vol 1, Part 6a,
D. Bier ens and R.Ecker man, eds., (Fr ankfur t /Main: Dechema, 1980).
1-22 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
J . Gmehling, U. Onken and W. Ar lt , "Vapor -Liquid Equilibr ium Dat a Collect ion,
Aqueous-Or ganic Syst ems, Supplement 2," Chemistry Data S eries Vol 1, Part 1b ,
D. Bier ens and R.Ecker man, eds., (Fr ankfur t /Main: Dechema, 1988).
H.A.J . Oonk, Phase Theory, The Thermodynamics of Heterogeneous Equilibria,
(Amst er dam, et c.: Elsevier Scient ific Publishing Company, 1981), Ch. 4.
Equati on-of-State Models
The simplest equat ion of st at e is t he ideal gas law:
p
RT
V
m
(44)
The ideal gas law assumes t hat molecules have no size and t hat t her e ar e no
int er molecular int er act ions. This can be called absolut e idealit y, in cont r ast t o
idealit y defined r elat ive t o pur e component behavior , as used in t he act ivit y
coefficient appr oach (see Act ivit y Coefficient Met hod on page 1-10).
Ther e ar e t wo main t ypes of engineer ing equat ions of st at e: cubic equat ions of
st at e and t he vir ial equat ions of st at e. St eam t ables ar e an example of anot her
t ype of equat ion of st at e.
Cubic Equations of State
In an ideal gas, molecules have no size and t her efor e no r epulsion. To cor r ect t he
ideal gas law for r epulsion, t he t ot al volume must be cor r ect ed for t he volume of t he
molecule(s), or covolume b. (Compar e t he fir st t er m of equat ion 45 t o equat ion 44.
The covolume can be int er pr et ed as t he molar volume at closest packing.
The at t r act ion must decr ease t he t ot al pr essur e compar ed t o an ideal gas, so a
negat ive t er m is added, pr opor t ional t o an at t r act ion par amet er a. This t er m is
divided by an expr ession wit h dimension m
3
, because at t r act ive for ces ar e
pr opor t ional t o
1
6
r
, wit h r being t he dist ance bet ween molecules. An example of
t his class of equat ions is t he Soave-Redlich-Kwong equat ion of st at e (Soave,
1972):
( )
( )
( )
p
RT
V b
a T
V V b
m m m
+
(45)
Physical Pr oper t y Met hods and Models 1-23
Ver sion 10
Chapter 1
Equat ion 45 can be wr it t en as a cubic polynomial in V
m
. Wit h t he t wo t er ms of
equat ion 45 and using simple mixing r ules (see Mixt ur es, t his chapt er ). t he
Soave-Redlich-Kwong equat ion of st at e can r epr esent non-idealit y due t o
compr essibilit y effect s. The Peng-Robinson equat ion of st at e (Peng and Robinson ,
1976) is similar t o t he Soave-Redlich-Kwong equat ion of st at e. Since t he
publicat ion of t hese equat ions, many impr ovement s and modificat ions have been
suggest ed. A select ion of impor t ant modificat ions is available in ASPEN PLUS.
The or iginal Redlich-Kwong-Soave and Peng-Robinson equat ions will be called
st andar d cubic equat ions of st at e. Cubic equat ions of st at e in ASPEN PLUS ar e
based on t he Redlich-Kwong-Soave and Peng-Robinson equat ions of st at e.
Equat ions ar e list ed in t he following t able.
Cubic Equations of State in ASPEN PLUS
Redlich-Kwong(-Soave) based Peng-Robinson based
Redlich-Kwong Standard Peng-Robinson
Standard Redlich-Kwong-Soave Peng-Robinson
Redlich-Kwong-Soave Peng-Robinson-MHV2
Redlich-Kwong-ASPEN Peng-Robinson-WS
Schwartzentruber-Renon
Redlich-Kwong-Soave-MHV2
Predictive SRK
Redlich-Kwong-Soave-WS
Pure Components
In a st andar d cubic equat ion of st at e, t he pur e component par amet er s ar e
calculat ed fr om cor r elat ions based on cr it ical t emper at ur e, cr it ical pr essur e, and
acent r ic fact or . These cor r elat ions ar e not accur at e for polar compounds or long
chain hydr ocar bons. Int r oducing a mor e flexible t emper at ur e dependency of t he
at t r act ion par amet er (t he alpha-funct ion), t he qualit y of vapor pr essur e
r epr esent at ion impr oves. Up t o t hr ee differ ent alpha funct ions ar e built -in t o t he
following cubic equat ion-of-st at e models in ASPEN PLUS: Redlich-Kwong-Aspen,
Schwar t zenr uber -Renon, Peng-Robinson-MHV2, Peng-Robinson-WS, Pr edict ive
RKS, Redlich-Kwong-Soave-MHV2, and Redlich-Kwong-Soave-WS.
Cubic equat ions of st at e do not r epr esent liquid molar volume accur at ely. To
cor r ect t his you can use volume t r anslat ion, which is independent of VLE
comput at ion. The Schwar t zenr uber -Renon equat ion of st at e model has volume
t r anslat ion.
1-24 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
Mi xtures
The cubic equat ion of st at e calculat es t he pr oper t ies of a fluid as if it consist ed of
one (imaginar y) component . If t he fluid is a mixt ur e, t he par amet er s a and b of t he
imaginar y component must be calculat ed fr om t he pur e component par amet er s of
t he r eal component s using mixing r ules. The classical mixing r ules, wit h one binar y
int er act ion par amet er for t he at t r act ion par amet er , ar e not sufficient ly flexible t o
descr ibe mixt ur es wit h st r ong shape and size asymmet r y:
( ) ( )
a x x a a k
i j i j a ij
j i
1
2
1
,
(46)
b x b x x
b b
i i
i
i j
i j
j i
_
,
2
(47)
A second int er act ion coefficient is added for t he b par amet er in t he Redlich-
Kwong-Aspen (Mat hias, 1983) and Schwar t zent r uber -Renon (Schwar t zent r uber
and Renon, 1989) equat ions of st at e:
( )
b x x
b b
k
i j
i j
j i
b ij
_
,
2
1
,
(48)
This is effect ive t o fit vapor -liquid equilibr ium dat a for syst ems wit h st r ong size
and shape asymmet r y but it has t he disadvant age t hat k
b ij ,
is st r ongly cor r elat ed
wit h k
a ij ,
and t hat k
b ij ,
affect s t he excess molar volume (Ler mit e and Vidal ,
1988).
For st r ong ener gy asymmet r y, in mixt ur es of polar and non-polar compounds, t he
int er act ion par amet er s should depend on composit ion t o achieve t he desir ed
accur acy of r epr esent ing VLE dat a. Hur on-Vidal mixing r ules use act ivit y
coefficient models as mole fr act ion funct ions (Hur on and Vidal , 1979). These
mixing r ules ar e ext r emely successful in fit t ing because t hey combine t he
advant ages of flexibilit y wit h a minimum of dr awbacks (Ler mit e and Vidal ,
1988). However , wit h t he or iginal Hur on-Vidal appr oach it is not possible t o use
act ivit y coefficient par amet er s, det er mined at low pr essur es, t o pr edict t he high
pr essur e equat ion-of-st at e int er act ions.
Sever al modificat ions of Hur on-Vidal mixing r ules exist which use act ivit y
coefficient par amet er s obt ained at low pr essur e dir ect ly in t he mixing r ules (see
t he t able labeled Cubic Equat ions of St at e in ASPEN PLUS). They accur at ely
pr edict binar y int er act ions at high pr essur e. In pr act ice t his means t hat t he lar ge
dat abase of act ivit y coefficient dat a at low pr essur es (DECHEMA Chemist r y
Dat a Ser ies, Dor t mund Dat aBank) is now ext ended t o high pr essur es.
The MHV2 mixing r ules (Dahl and Michelsen, 1990), use t he Lyngby modified
UNIFAC act ivit y coefficient model (See Act ivit y Coefficient Models on page 1-32).
The qualit y of t he VLE pr edict ions is good.
Physical Pr oper t y Met hods and Models 1-25
Ver sion 10
Chapter 1
The pr edict ive SRK met hod (Holder baum and Gmehling, 1991; Fischer , 1993)
uses t he or iginal UNIFAC model. The pr edict ion of VLE is good. The mixing
r ules can be used wit h any equat ion of st at e, but it has been int egr at ed wit h t he
Redlich-Kwong-Soave equat ion of st at e in t he following way: new UNIFAC
gr oups have been defined for gaseous component s, such as hydr ogen. Int er act ion
par amet er s for t he new gr oups have been r egr essed and added t o t he exist ing
par amet er mat r ix. This ext ends t he exist ing low pr essur e act ivit y coefficient dat a
t o high pr essur es, and adds pr edict ion of gas solubilit ies at high pr essur es.
The Wong-Sandler mixing r ules (Wong and Sandler , 1992; Or bey et al., 1993)
pr edict VLE at high pr essur e equally well as t he MHV2 mixing r ules. Special
at t ent ion has been paid t o t he t heor et ical cor r ect ness of t he mixing r ules at
pr essur es appr oaching zer o.
Vi ri al Equati ons of State
Virial equat ions of st at e in ASPEN PLUS are:
Hayden-OConnell
BWR-Lee-St ar ling
Lee-Kesler -Plcker
This t ype of equat ion of st at e is based on a select ion of power s of t he expansion:
p RT
V
B
V
C
V
m m m
+ + +
_
,
1
3 3
... (49)
Tr uncat ion of equat ion 49 aft er t he second t er m and t he use of t he second vir ial
coefficient B can descr ibe t he behavior of gases up t o sever al bar . The Hayden-
O'Connell equat ion of st at e uses a complex comput at ion of B t o account for t he
associat ion and chemical bonding in t he vapor phase (see Vapor Phase
Associat ion on page 1-26).
Like cubic equat ions of st at e, some of t hese t er ms must be r elat ed t o eit her
r epulsion or at t r act ion. To descr ibe liquid and vapor pr oper t ies, higher or der
t er ms ar e needed. The or der of t he equat ions in V is usually higher t han cubic.
The Benedict -Webb-Rubin equat ion of st at e is a good example of t his appr oach. It
had many par amet er s gener alized in t er ms of cr it ical pr oper t ies and acent r ic
fact or by Lee and St ar ling (Br ul et al., 1982). The Lee-Kesler -Plcker equat ion
of st at e is anot her example of t his appr oach.
Vir ial equat ions of st at e for liquid and vapor ar e mor e flexible in descr ibing a
(p,V) isot her m because of t he higher degr ee of t he equat ion in t he volume. They
ar e mor e accur at e t han cubic equat ions of st at e. Gener alizat ions have been
focused mainly on hydr ocar bons, t her efor e t hese compounds obt ain excellent
r esult s. They ar e not r ecommended for polar compounds.
The st andar d mixing r ules give good r esult s for mixt ur es of hydr ocar bons and
light gases.
1-26 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
Vapor Phase Associ ati on
Nonpolar subst ances in t he vapor phase at low pr essur es behave almost ideally.
Polar subst ances can exhibit nonideal behavior or even associat ion in t he vapor
phase. Associat ion can be expect ed in syst ems wit h hydrogen bonding such as
alcohols, aldehydes and car boxylic acids. Most hydr ogen bonding leads t o dimer s.
HF is an except ion; it for ms mainly hexamer s. This sect ion uses dimer izat ion as an
example t o discuss t he chemical t heor y used t o descr ibe st r ong associat ion.
Chemical t heor y can be used for any t ype of r eact ion.
If associat ion occur s, chemical r eact ions t ake place. Ther efor e, a model based on
physical for ces is not sufficient . Some r easons ar e:
Two monomer molecules for m one dimer molecule, so t he t ot al number of
species decr eases. As a r esult t he mole fr act ions change. This has influence on
VLE and molar volume (densit y).
The heat of r eact ion affect s t her mal pr oper t ies like ent halpy C
p
.
The equilibr ium const ant of a dimer izat ion r eact ion
2
2
A A (50)
in t he vapor phase is defined in t er ms of fugacit ies:
K
f
f
A
A
2
2
(51)
Wit h:
f y p
i
v
i
v
i
(52)
and r ealizing t hat
i
v
is appr oximat ely unit y at low pr essur es:
K
y
y p
A
A
2
2
(53)
Equat ions 51-53 ar e expr essed in t er ms of t r ue species pr oper t ies. This may seem
nat ur al, but unless measur ement s ar e done, t he t r ue composit ions ar e not
known. On t he cont r ar y, t he composit ion is usually given in t er ms of unreacted or
appar ent species (Abbot t and van Ness, 1992), which r epr esent s t he imaginar y
st at e of t he syst em if no r eact ion t akes place. Super scr ipt s t and a ar e used t o
dist inguish clear ly bet ween t r ue and appar ent species. (For mor e on t he use of
appar ent and t r ue species appr oach, see Chapt er 5).
Physical Pr oper t y Met hods and Models 1-27
Ver sion 10
Chapter 1
K in equat ion 53 is only a funct ion of t emper at ur e. If t he pr essur e appr oaches
zer o at const ant t emper at ur e,
y
y
A
A
2
2
,which is a measur e of t he degr ee of
associat ion, must decr ease. It must go t o zer o for zer o pr essur e wher e t he ideal
gas behavior is r ecover ed. The degr ee of associat ion can be consider able at
at mospher ic pr essur e: for example acet ic acid at 293 K and 1 bar is dimer ized at
about 95% (Pr ausnit z et al., 1986).
The equilibr ium const ant is r elat ed t o t he t her modynamic pr oper t ies of r eact ion:
ln K
G
RT
H
RT
S
R
r r r
+
(54)
The Gibbs ener gy, t he ent halpy, and t he ent r opy of r eact ion can be appr oximat ed
as independent of t emper at ur e. Then fr om equat ion 54 it follows t hat ln K
plot t ed against
1
T
is appr oximat ely a st r aight line wit h a posit ive slope (since t he
r eact ion is exot her mic) wit h incr easing
1
T
. This r epr esent s a decr ease of ln K
wit h incr easing t emper at ur e. Fr om t his it follows (using equat ion 53) t hat t he
degr ee of associat ion decr eases wit h incr easing t emper at ur e.
It is convenient t o calculat e equilibr ia and t o r epor t mole fr act ions in t er ms of
appar ent component s. The concent r at ions of t he t r ue species have t o be
calculat ed, but ar e not r epor t ed. Vapor -liquid equilibr ia in t er ms of appar ent
component s r equir e appar ent fugacit y coefficient s. The fugacit y coefficient s of t he
t r ue species ar e expect ed t o be close t o unit y (ideal) at at mospher ic pr essur e.
However t he appar ent fugacit y coefficient needs t o r eflect t he decr ease in
appar ent par t ial pr essur e caused by t he decr ease in number of species. The
appar ent par t ial pr essur e is r epr esent ed by t he t er m y p
i
a
in t he vapor fugacit y
equat ion applied t o appar ent component s:
f y p
i
a v
i
a v
i
a , ,
(55)
In fact t he appar ent and t r ue fugacit y coefficient s ar e dir ect ly r elat ed t o each
ot her by t he change in number of component s (Not hnagel et al., 1973; Abbot t and
van Ness, 1992):
i
a v
i
t v i
t
i
a
y
y
, ,
(56)
1-28 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
This is why appar ent fugacit y coefficient s of associat ing species ar e well below
unit y. This is illust r at ed in t he figur e labeled Appar ent Fugacit y of Vapor
Benzene and Pr opionic Acid for t he syst em benzene + pr opionic acid at 415 K and
101.325 kPa (1 at m) (Not hnagel et al., 1973). The effect of dimer izat ion clear ly
decr eases below appar ent pr opionic acid mole fr act ions of about 0.2 (par t ial
pr essur es of 20 kPa). The effect vanishes at par t ial pr essur es of zer o, as expect ed
fr om t he pr essur e dependence of equat ion 53. The appar ent fugacit y coefficient of
benzene incr eases wit h incr easing pr opionic acid mole fr act ion. This is because
t he t r ue mole fr act ion of pr opionic acid is higher t han it s appar ent mole fr act ion
(see equat ion 56).
Apparent Fugacity of Vapor Benzene and Propionic Acid
The vapor ent halpy depar t ur e needs t o be cor r ect ed for t he heat of associat ion.
The t r ue heat of associat ion can be obt ained fr om t he equilibr ium const ant :
( ) ( )
r m
t
r m
t
H T
d G
dT
RT
d K
dT
2 2
ln
(57)
The value obt ained fr om equat ion 57 must be cor r ect ed for t he r at io of t r ue t o
appar ent number of species t o be consist ent wit h t he appar ent vapor ent halpy
depar t ur e. Wit h t he ent halpy and Gibbs ener gy of associat ion (equat ions 57 and
54), t he ent r opy of associat ion can be calculat ed.
Physical Pr oper t y Met hods and Models 1-29
Ver sion 10
Chapter 1
The appar ent heat of vapor izat ion of associat ing component s as a funct ion of
t emper at ur e can show a maximum. The incr ease of t he heat of vapor izat ion wit h
t emper at ur e is pr obably r elat ed t o t he decr ease of t he degr ee of associat ion wit h
incr easing t emper at ur e. However , t he heat of vapor izat ion must decr ease t o zer o
when t he t emper at ur e appr oaches t he cr it ical t emper at ur e. The figur e labeled
Liquid and Vapor Ent halpy of Acet ic Acid illust r at es t he ent halpic behavior of
acet ic acid. Not e t hat t he ent halpy effect due t o associat ion is ver y lar ge.
Liquid and Vapor Enthalpy of Acetic Acid
The t r ue molar volume of an associat ing component is close t o t he t r ue molar
volume of a non-associat ing component . At low pr essur es, wher e t he ideal gas
law is valid, t he t r ue molar volume is const ant and equal t o p/RT, independent of
associat ion. This means t hat associat ed molecules have a higher molecular mass
t han t heir monomer s, but t hey behave as an ideal gas, just as t heir monomer s.
This also implies t hat t he mass densit y of an associat ed gas is higher t han t hat of
a gas consist ing of t he monomer s. The appar ent molar volume is defined as t he
t r ue t ot al volume per appar ent number of species. Since t he number of appar ent
species is higher t han t he t r ue number of species t he appar ent molar volume is
clear ly smaller t han t he t r ue molar volume.
The chemical t heor y can be used wit h any equat ion of st at e t o comput e t r ue
fugacit y coefficient s. At low pr essur es, t he ideal gas law can be used.
1-30 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
For dimer izat ion, t wo appr oaches ar e commonly used: t he Not hagel and t he
Hayden-OConnel equat ions of st at e. For HF hexamer izat ion a dedicat ed
equat ion of st at e is available in ASPEN PLUS.
Not hnagel et al. (1973) used a t r uncat ed van der Waals equat ion of st at e. They
cor r elat ed t he equilibr ium const ant s wit h t he covolume b, a polar it y par amet er p
and t he par amet er d. b can be det er mined fr om gr oup cont r ibut ion met hods
(Bondi, 1968) (or a cor r elat ion of t he cr it ical t emper at ur e and pr essur e (as in
ASPEN PLUS). D and p ar e adjust able par amet er s. Many values for d and p ar e
available in t he Not hnagel equat ion of st at e in ASPEN PLUS. Also cor r ect ion
t er ms for t he heat s of associat ion of unlike molecules ar e built -in. The
equilibr ium const ant , K, has been cor r elat ed t o T
b
, T
c
, b, d, and p.
Hayden and OConnell (1975) used t he vir ial equat ion of st at e (equat ion 49),
t r uncat ed aft er t he second t er m. They developed a cor r elat ion for t he second
vir ial coefficient of polar , nonpolar and associat ing species based on t he cr it ical
t emper at ur e and pr essur e, t he dipole moment and t he mean r adius of gyr at ion.
Associat ion of like and unlike molecules is descr ibed wit h t he adjust able
par amet er . Pur e component and binar y values for ar e available in
ASPEN PLUS.
The HF equat ion of st at e (de Leeuw and Wat anasir i, 1993) assumes t he
for mat ion of hexamer s only. The fugacit ies of t he t r ue species ar e assumed t o be
ideal, and is t her efor e suit ed for low pr essur es. Special at t ent ion has been paid t o
t he r obust ness of t he algor it hm, and t he consist ency of t he r esult s wit h t heor y.
The equat ion of st at e has been int egr at ed wit h t he elect r olyt e NRTL act ivit y
coefficient model t o allow t he r igor ous r epr esent at ion of absor pt ion and st r ipping
of HF wit h wat er . It can be used wit h ot her act ivit y coefficient models for
hydr ocar bon + HF mixt ur es.
References
M. Abbot t and M. C. Van Ness, "Ther modynamics of Solut ions Cont aining
React ive Species: A Guide t o Fundament als and Applicat ions," Fluid Phase
Equilibria, Vol 77, (1992), pp. 53-119.
Bondi, "Physical Pr oper t ies of Moelcular Liquids, Cr yst als, and Glasses," Wiley,
New Yor k, 1968.
M.R. Br ul, C.T. Lin, L.L. Lee, and K.E. St ar ling, "Mult ipar amet er Cor r esponding
St at es Cor r elat ion of Coal-Fluid Ther modynamic Pr oper t ies," AIChE J ., Vol. 28,
No. 4, (1982), pp. 616 637.
Dahl and M.L. Michelsen, "High-Pr essur e Vapor -Liquid Equilibr ium wit h a
UNIFAC-based Equat ion of St at e", AIChE J ., Vol. 36, No. 12 (1990), pp. 1829-
1836.
Physical Pr oper t y Met hods and Models 1-31
Ver sion 10
Chapter 1
Fischer , Die PSRK-Met hode: Eine Zustandsgleichung unter Verwendung des
UNIFAC-Gruppenbeitragsmodells, VDI For t schr it t ber icht e, Reihe 3:
Ver fahr enst echnik, Nr . 324 (Dsseldor f: VDI Ver lag GmbH, 1993).
J .G. Hayden and J .P. O'Connell, " A Gener alized Met hod for Pr edict ing Second
Vir ial Coefficient s, " Ind. Eng. Chem. Process Des. Dev., Vol. 14, No. 3, (1975),
pp. 209-216.
Holder baum and J . Gmehling, "PSRK: A Gr oup Cont r ibut ion Equat ion of St at e
based on UNIFAC", Fluid Phase Eq., Vol. 70, (1991), pp. 251-265.
M.-J . Hur on and J . Vidal, "New Mixing Rules in Simple Equat ions of st at e for
r epr esent ing Vapour -Liquid Equilibr ia of St r ongly Non-ideal Mixt ur es," Fluid
Phase Eq., Vol. 3, (1979), pp. 255-271.
V.V. de Leeuw and S. Wat anasir i, " Modelling Phase Equilibr ia And Ent halpies
Of The Syst em Wat er And Hydr ofluor ic Acid Using A 'HF Equat ion Of St at e' In
Conjunct ion Wit h The Elect r olyt e NRTL Act ivit y Coefficient Model," Pr esent ed
at t he 13
t h
Eur opean Seminar on Applied Ther modynamics, 9
t h
-12
t h
J une 1993,
Car r y-le-Rouet , Fr ance.
Ch. Ler mit e and J . Vidal, "Les r gles de mlange appliques aux quat ions
d't at ." Revue de l'Inst it ut Fr anais du Pt r ole, Vol. 43, No. 1, (1988), pp. 73-94.
P.M. Mat hias, "A Ver sat ile Phase Equilibr ium Equat ion of St at e," Ind. Eng.
Chem. Process Des. Dev. Vol. 22, (1983), pp. 385-391.
K.-H. Not hnagel, D.S. Abr ams, and J .M. Pr ausnit z, "Gener alized Cor r elat ion for
Fugacit y Coefficient s in Mixt ur es at Moder at e Pr essur es. Applicat ions of
Chemical Theor y of Vapor Imper fect ions," Ind. Eng. Chem. Process Des. Dev.,
Vol. 12, No. 1, (1973), pp. 25-35.
Or bey, S.I. Sandler , and D.S. Wong, "Accur at e equat ion of st at e pr edict ions at
high t emper at ur es and pr essur es using t he exist ing UNIFAC model," Fluid
Phase Eq., Vol. 85, (1993), pp. 41-54.
D.-Y. Peng and D.B. Robinson, "A New Two-Const ant Equat ion of st at e," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 59-64.
J .M. Pr ausnit z, R.N. Licht ent haler , and E. Gomes de Azevedo, Molecular
Thermodynamics of Fluid-Phase Equilibria, 2
nd
ed., (Englewood Cliffs: Pr ent ice-
Hall Inc., 1986), pp. 137-151.
Schwar t zent r uber and H. Renon, "Ext ension of UNIFAC t o High Pr essur es and
Temper at ur es by t he Use of a Cubic Equat ion of St at e," Ind. Eng. Chem. Res.,
Vol. 28, (1989), pp. 1049-1955.
Soave, "Equilibr ium Const ant s for a Modified Redlich-Kwong Equat ion of St at e,"
Chem. Eng. S ci., Vol. 27, (1972), pp. 1196-1203.
1-32 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
D.S. Wong and S.I. Sandler , "A Theor et ically Cor r ect New Mixing Rule for Cubic
Equat ions of St at e for Bot h Highly and Slight ly Non-ideal Mixt ur es," AIChE J .,
Vol. 38, (1992), pp. 671-680.
Acti vi ty Coeffi ci ent Models
This sect ion discusses t he char act er ist ics of act ivit y coefficient models. The
descr ipt ion is divided int o t he following cat egor ies:
Molecular models (cor r elat ive models for non-elect r olyt e solut ions )
Gr oup cont r ibut ion models (pr edict ive models for non-elect r olyt e solut ions)
Elect r olyt e act ivit y coefficient models
Molecular Models
The ear ly act ivit y coefficient models such as van Laar and Scat char d-Hildebr and,
ar e based on t he same assumpt ions and pr inciples of r egular solut ions. Excess
ent r opy and excess molar volume ar e assumed t o be zer o, and for unlike
int er act ions, Londons geomet r ic mean r ule is used. Binar y par amet er s wer e
est imat ed fr om pur e component pr oper t ies. The van Laar model is only useful as
cor r elat ive model. The Scat char d-Hildebr and can pr edict int er act ions fr om
solubilit y par amet er s for non-polar mixt ur es. Bot h models pr edict only posit ive
deviat ions fr om Raoult s law (see Act ivit y Coefficient Met hod on page 1-10).
The t hr ee-suffix Mar gules and t he Redlich-Kist er act ivit y coefficient models ar e
flexible ar it hmet ic expr essions.
Local composit ion models ar e ver y flexible, and t he par amet er s have much mor e
physical significance. These models assume or der ing of t he liquid solut ion,
accor ding t o t he int er act ion ener gies bet ween differ ent molecules. The Wilson
model is suit ed for many t ypes of non-idealit y but cannot model liquid-liquid
separ at ion. The NRTL and UNIQUAC models can be used t o descr ibe VLE, LLE
and ent halpic behavior of highly non-ideal syst ems. The WILSON, NRTL and
UNIQUAC models ar e well accept ed and ar e used on a r egular basis t o model
highly non-ideal syst ems at low pr essur es.
A det ailed discussion of molecular act ivit y coefficient models and under lying
t heor ies can be found in Pr ausnit z et al. (1986).
Physical Pr oper t y Met hods and Models 1-33
Ver sion 10
Chapter 1
Group Contribution Models
The UNIFAC act ivit y coefficient model is an ext ension of t he UNIQUAC model. It
applies t he same t heor y t o funct ional gr oups t hat UNIQUAC uses for molecules. A
limit ed number of funct ional gr oups is sufficient t o for m an infinit e number of
differ ent molecules. The number of possible int er act ions bet ween gr oups is ver y
small compar ed t o t he number of possible int er act ions bet ween component s fr om a
pur e component dat abase (500 t o 2000 component s). Gr oup-gr oup int er act ions
det er mined fr om a limit ed, well chosen set of exper iment al dat a ar e sufficient t o
pr edict act ivit y coefficient s bet ween almost any pair of component s.
UNIFAC (Fr edenslund et al., 1975; 1977) can be used t o pr edict act ivit y
coefficient s for VLE. For LLE a differ ent dat aset must be used. Mixt ur e
ent halpies, der ived fr om t he act ivit y coefficient s (see Act ivit y Coefficient Met hod
on page 1-10) ar e not accur at e.
UNIFAC has been modified at t he Technical Univer sit y of Lyngby (Denmar k).
The modificat ion includes an impr oved combinat or ial t er m for ent r opy and t he
gr oup-gr oup int er act ion has been made t emper at ur e dependent . The t hr ee
UNIFAC models ar e available in ASPEN PLUS. For det ailed infor mat ion on each
model, see Chapt er 3.
This model can be applied t o VLE, LLE and ent halpies (Lar sen et al. , 1987).
Anot her UNIFAC modificat ion comes fr om t he Univer sit y of Dor t mund
(Ger many). This modificat ion is similar t o Lyngby modified UNIFAC, but it can
also pr edict act ivit y coefficient s at infinit e dilut ion (Weidlich and Gmehling,
1987).
Electrolyte Models
In elect r olyt e solut ions a lar ger var iet y of int er act ions and phenomena exist t han
in non-elect r olyt e solut ions. Besides physical and chemical molecule-molecule
int er act ions, ionic r eact ions and int er act ions occur (molecule-ion and ion-ion).
Elect r olyt e act ivit y coefficient models (Elect r olyt e NRTL, Pit zer ) ar e t her efor e mor e
complicat ed t han non-elect r olyt e act ivit y coefficient models. Elect r olyt es dissociat e
so a few component s can for m many species in a solut ion. This causes a mult it ude
of int er act ions, some of which ar e st r ong. This sect ion gives a summar y of t he
capabilit ies of t he elect r olyt e act ivit y coefficient models in ASPEN PLUS. For
det ails, see Chapt er 3 and Appendices A, B, and C.
The Pit zer elect r olyt e act ivit y coefficient model can be used for t he
r epr esent at ion of aqueous elect r olyt e solut ions up t o 6 molal st r engt h (for
lit er at ur e r efer ences, see Appendix C). The model handles gas solubilit ies.
Excellent r esult s can be obt ained, but many par amet er s ar e needed.
1-34 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
The Elect r olyt e NRTL model is an ext ension of t he molecular NRTL model (for
lit er at ur e r efer ences, see Appendix B). It can handle elect r olyt e solut ions of any
st r engt h, and is suit ed for solut ions wit h mult iple solvent s, and dissolved gases.
The flexibilit y of t his model makes it ver y suit able for any low-t o-moder at e
pr essur e applicat ion.
Elect r olyt e par amet er dat abanks and dat a packages for indust r ially impor t ant
applicat ions have been developed for bot h models (see AS PEN PLUS Physical
Property Data, Chapt er 1). If par amet er s ar e not available, use dat a r egr ession,
or t he Br omley-Pit zer act ivit y coefficient model.
The Br omley-Pit zer act ivit y coefficient model is a simplificat ion of t he Pit zer
model (for lit er at ur e r efer ences, see Appendix A). A cor r elat ion is used t o
calculat e t he int er act ion par amet er s. The model is limit ed in accur acy, but
pr edict ive.
References
Fr edenslund, R.L. J ones, and J .M. Pr ausnit z, "Gr oup-Cont r ibut ion Est imat ion of
Act ivit y Coefficient s in Nonideal Liquid Mixt ur es," AIChE J ., Vol. 21, (1975), pp.
1086-1099.
Fr edenslund, J . Gmehling, and P. Rasmussen , Vapor-Liquid Equilibria Using
UNIFAC, (Amst er dam: Elsevier , 1977).
B.L. Lar sen, P. Rasmussen, and Aa. Fr edenslund, "A Modified UNIFAC Gr oup-
Cont r ibut ion Model for t he Pr edict ion of Phase Equilibr ia and Heat s of Mixing,"
Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 2274-2286.
J .M. Pr ausnit z, R.N. Licht ent haler , and E. Gomes de Azevedo, Molecular
Thermodynamics of Fluid-Phase Equilibria, 2
nd
ed., (Englewood Cliffs: Pr ent ice-
Hall Inc., 1986), pp. 137-151.
Weidlich and J . Gmehling, "A Modified UNIFAC Model. 1. Pr edict ion of VLE, h
E
,
," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 1372-1381.
Transport Property Methods
ASPEN PLUS pr oper t y met hods can comput e t he following t r anspor t pr oper t ies:
Viscosit y
Ther mal conduct ivit y
Diffusion coefficient
Sur face t ension
Physical Pr oper t y Met hods and Models 1-35
Ver sion 10
Chapter 1
Each pur e component pr oper t y is calculat ed eit her fr om an empir ical equat ion or
fr om a semi-empir ical (t heor et ical) cor r elat ion. The coefficient s for t he empir ical
equat ion ar e det er mined fr om exper iment al dat a and ar e st or ed in t he
ASPEN PLUS dat abank. The mixt ur e pr oper t ies ar e calculat ed using appr opr iat e
mixing r ules. This sect ion discusses t he met hods for t r anspor t pr oper t y calculat ion.
The pr oper t ies t hat have t he most in common in t heir behavior ar e viscosit y and
t her mal conduct ivit y. This is r eflect ed in similar met hods t hat exist for t hese
pr oper t ies and t her efor e t hey ar e discussed t oget her .
Viscosity and Thermal Conductivity Methods
When t he pr essur e appr oaches zer o, viscosit y and t her mal conduct ivit y ar e linear
funct ions of t emper at ur e wit h a posit ive slope. At a given t emper at ur e, viscosit y
and t her mal conduct ivit y incr ease wit h incr easing densit y (densit y incr eases for
any fluid wit h incr easing pr essur e).
Det ailed molecular t heor ies exist for gas phase viscosit y and t her mal
conduct ivit y at low pr essur es. Some of t hese can account for polar it y. These low
pr essur e pr oper t ies ar e not exact ly ideal gas pr oper t ies because non-idealit y is
t aken int o account . Examples ar e t he Chapman-Enskog-Br okaw and t he Chung-
Lee-St ar ling low pr essur e vapor viscosit y models and t he St iel-Thodos low
pr essur e vapor t her mal conduct ivit y model. Residual pr oper t y models ar e
available t o account for pr essur e or densit y effect s. These models calculat e t he
differ ence of a cer t ain pr oper t y wit h r espect t o t he low pr essur e value. The
met hod used is:
( ) ( ) ( ) ( ) ( )
x p x p x p x p + 0 0 (58)
Wher e:
x = Viscosit y or t her mal conduct ivit y
Most of t he low pr essur e models r equir e mixing r ules for calculat ing mixt ur e
pr oper t ies.
Anot her class of models calculat e t he high pr essur e pr oper t y dir ect ly fr om
molecular par amet er s and st at e var iables. For example t he TRAPP models for
hydr ocar bons use cr it ical par amet er s and acent r ic fact or as molecular
par amet er s. The models use t emper at ur e and pr essur e as st at e var iables.
The Chung-Lee-St ar ling models use cr it ical par amet er s, acent r ic fact or , and
dipole moment as molecular par amet er s. The models use t emper at ur e and
densit y as st at e var iables. These models gener ally use mixing r ules for molecular
par amet er s, r at her t han mixing r ules for pur e component pr oper t ies.
1-36 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
Vapor viscosit y, t her mal conduct ivit y, and vapor diffusivit y ar e int er r elat ed by
molecular t heor ies. Many t her mal conduct ivit y met hods t her efor e r equir e low
pr essur e vapor viscosit y eit her in calculat ing t her mal conduct ivit y or in t he
mixing r ules.
Liquid pr oper t ies ar e oft en descr ibed by empir ical, cor r elat ive models:
Andr ade/DIPPR for liquid viscosit y and Sat o-Riedel for t her mal conduct ivit y.
These ar e accur at e in t he t emper at ur e and pr essur e r anges of t he exper iment al
dat a used in t he fit . Mixing r ules for t hese pr oper t ies do not pr ovide a good
descr ipt ion for t he excess pr oper t ies.
Cor r esponding-st at es models such as Chung-Lee-St ar ling and TRAPP can
descr ibe bot h liquid and vapor pr oper t ies. These models ar e mor e pr edict ive and
less accur at e t han a cor r elat ive model, but ext r apolat e well wit h t emper at ur e
and pr essur e. Chung-Lee-St ar ling allows t he use of binar y int er act ion
par amet er s and an associat ion par amet er , which can be adjust ed t o exper iment al
dat a.
Di ffusi on Coeffi ci ent Methods
It is evident t hat diffusion is r elat ed t o viscosit y, so sever al diffusion coefficient
met hods, r equir e viscosit y, for bot h liquid and for vapor diffusion coefficient s.
(Chapman-Enskog-Wilke-Lee and Wilke-Chang models).
Vapor diffusion coefficient s can be calculat ed fr om molecular t heor ies similar t o
t hose discussed for low pr essur e vapor viscosit y and t her mal conduct ivit y.
Similar ly, pr essur e cor r ect ion met hods exist . The Dawson-Khour y-Kobayashi
model calculat es a pr essur e cor r ect ion fact or which r equir es t he densit y as input .
Liquid diffusion coefficient s depend on act ivit y and liquid viscosit y.
Binar y diffusion coefficient s ar e r equir ed in pr ocesses wher e mass t r ansfer is
limit ed. Binar y diffusion coefficient s descr ibe t he diffusion of one component at
infinit e dilut ion in anot her component . In mult icomponent syst ems t his
cor r esponds t o a mat r ix of values.
The aver age diffusion coefficient of a component in a mixt ur e does not have any
quant it at ive applicat ions; it is an infor mat ive pr oper t y. It is comput ed using a
mixing r ule for vapor diffusion coefficient s and using mixt ur e input par amet er s
for t he Wilke-Chang model.
Physical Pr oper t y Met hods and Models 1-37
Ver sion 10
Chapter 1
Surface Tensi on Methods
Sur face t ension is calculat ed by empir ical, cor r elat ive models such as Hakim-
St einber g-St iel/DIPPR. An empir ical linear mixing r ule is used t o comput e mixt ur e
sur face t ension.
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Properties Of Gases And Liquids,
4
t h
ed., (New Yor k, et c: McGr aw-Hill Book Company, 1987).
Nonconventi onal Component Enthalpy
Calculati on
Nonconvent ional component s gener ally do not par t icipat e in phase equilibr ium
calculat ions, but ar e included in ent halpy balances. For a pr ocess unit in which
no chemical change occur s, only sensible heat effect s of nonconvent ional
component s ar e significant . In t his case, t he ent halpy r efer ence st at e may be
t aken as t he component at any ar bit r ar y r efer ence t emper at ur es (for example,
298.15 K). If a nonconvent ional component is involved in a chemical r eact ion, an
ent halpy balance is meaningful only if t he ent halpy r efer ence st at e is consist ent
wit h t hat adopt ed for convent ional component s: t he const it uent s element s must
be in t heir st andar d st at es at 1 at m and 298.15 K. The ent halpy is calculat ed as:
H h C dT
s
f
s
p
s
T
T
ref
+
(59)
Fr equent ly t he heat of for mat ion
f
s
h is unknown and cannot be obt ained
dir ect ly because t he molecular st r uct ur e of t he component is unknown. In many
cases, it is possible t o calculat e t he heat of for mat ion fr om t he heat of combust ion
c
s
h , because t he combust ion pr oduct s and element al composit ion of t he
component s ar e known:
f
s
c
s
f cp
s
h h h + (60)
f cp
s
h is t he sum of t he heat s of for mat ion of t he combust ion pr oduct s mult iplied
by t he mass fr act ions of t he r espect ive element s in t he nonconvent ional
component . This is t he appr oach used in t he coal ent halpy model HCOALGEN
(see Chapt er 3). This appr oach is r ecommended for comput ing DHFGEN for t he
ENTHGEN model.
1-38 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
Symbol Definitions
Roman Letters Definitions
a Equation of state energy parameter
b Equation of state co-volume
B Second virial coefficient
C
p
Heat capacity at constant pressure
C Third virial coefficient
f Fugacity
G Gibbs energy
H Henrys constant
H Enthalpy
k Equation of state binary parameter
K Chemical equilibrium constant
n Mole number
p Pressure
R Universal gas constant
S Entropy
T Temperature
V Volume
x,y Molefraction
Z Compressibility factor
Greek Letters Definitions
Activity coefficient
Poynting correction
Fugacity coefficient
Thermodynamic potential
Superscripts Definitions
c Combustion property
I Component index
f Formation property
continued
Physical Pr oper t y Met hods and Models 1-39
Ver sion 10
Chapter 1
Symbol Definitions (Continued)
Roman Letters Definitions
m Molar property
vap Vaporization property
r Reaction property
ref Reference state property
* Pure component property, asymmetric convention
At infinite dilution
a Apparent property
E Excess property
ig Ideal gas property
l Liquid property
l2 Second liquid property
l1 First liquid property
s Solid property
t True property
v Vapor property
Footnotes
1
The Gibbs ener gy has been t r ansfor med by a cont r ibut ion linear in t he mole
fr act ion, such t hat t he Gibbs ener gy of pur e liquid wat er (t her modynamic
pot ent ial of wat er ) has been shift ed t o t he value of pur e liquid n-but anol. This is
done t o make t he Gibbs ener gy minimizat ion visible on t he scale of t he gr aph.
This t r ansfor mat ion has no influence on t he r esult of Gibbs ener gy minimizat ion
(Oonk, 1981).
2
The pur e component molar Gibbs ener gy is equal t o t he pur e component
t her modynamic pot ent ial. The ISO and IUPAC r ecommendat ion t o use t he
t her modynamic pot ent ial is followed.
y y y y
1-40 Physical Pr oper t y Met hods and Models
Ver sion 10
Overview of
ASPEN PLUS
Property
Methods
Physical Pr oper t y Met hods and Models 2-1
Ver sion 10
Chapter 2
2 Property Method
Descriptions
This chapt er descr ibes t he ASPEN PLUS pr oper t y met hods. Topics include:
Classificat ion of pr oper t y met hods
Recommended use
Pr oper t y met hod descr ipt ions, or ganized by applicat ion
Since ASPEN PLUS pr oper t y met hods ar e t ailor ed t o classes of compounds and
oper at ing condit ions, t hey fit most engineer ing needs. Cust omizat ion of pr oper t y
met hods is explained in Chapt er 4.
2-2 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Classi fi cati on of Property Methods and
Recommended Use
A pr oper t y met hod is a collect ion of pr oper t y calculat ion r out es. (For mor e on
r out es, see Chapt er 4). The pr oper t ies involved ar e needed by unit oper at ion
models.
Ther modynamic pr oper t ies:
Fugacit y coefficient (or equivalent : chemical pot ent ial, K-value)
Ent halpy
Ent r opy
Gibbs ener gy
Volume
Tr anspor t pr oper t ies:
Viscosit y
Ther mal conduct ivit y
Diffusion coefficient
Sur face t ension
Pr oper t y met hods allow you t o specify a collect ion of pr oper t y calculat ion
pr ocedur es as one ent it y, for example, you might use t hem in a unit oper at ion, or in
a flowsheet (see AS PEN PLUS User Guide, Chapt er 7).
It is impor t ant t o choose t he r ight pr oper t y met hod for an applicat ion t o ensur e
t he success of your simulat ion. To help you choose a pr oper t y met hod, fr equent ly
encount er ed applicat ions ar e list ed wit h r ecommended pr oper t y met hods.
(Mult iple pr oper t y met hods oft en apply. A class of pr oper t y met hods is
r ecommended, as opposed t o an individual pr oper t y met hod.)
The classes of pr oper t y met hods available ar e:
IDEAL
Liquid fugacit y and K-value cor r elat ions
Pet r oleum t uned equat ions of st at e
Equat ions of st at e for high pr essur e hydr ocar bon applicat ions
Flexible and pr edict ive equat ions of st at e
Liquid act ivit y coefficient s
Elect r olyt e act ivit y coefficient s and cor r elat ions
Solids pr ocessing
St eam t ables
Aft er you have decided which pr oper t y met hod class your applicat ion needs, r efer
t o t he cor r esponding sect ion in t his chapt er for mor e det ailed r ecommendat ions.
See Chapt er 3 for det ailed infor mat ion on models and t heir par amet er
r equir ement s. Gener al usage issues, such as using Henr ys law and t he fr ee-wat er
appr oximat ion, ar e discussed in AS PEN PLUS User Guide, Chapt er 7.
Physical Pr oper t y Met hods and Models 2-3
Ver sion 10
Chapter 2
Recommended Classes of Property Methods for Different Applications
Oil and Gas Production
Application Recommended Property Method
Reservoir systems Equations of state for high pressure hydrocarbon applications
Platform separation Equations of state for high pressure hydrocarbon applications
Transportation of oil and gas by pipeline Equations of state for high pressure hydrocarbon applications
Refinery
Application Recommended Property Method
Low pressure applications(up to several atm)
Vacuum tower Atmospheric crude tower
Petroleum fugacity and K-value correlations (and assay data analysis)
Medium pressure applications (up to several
tens of atm) Coker main fractionator, FCC
main fractionator
Petroleum fugacity and K-value correlations Petroleum-tuned equations of state
(and assay data analysis)
Hydrogen-rich applications Reformer
Hydrofiner
Selected petroleum fugacity correlations Petroleum-tuned equations of state (and
assay data analysis)
Lube oil unit De-asphalting unit Petroleum-tuned equations of state (and assay data analysis)
Gas Processing
Application Recommended Property Method
Hydrocarbon separations Demethanizer C3-
splitter
Equations of state for high pressure hydrocarbon applications (with k
ij
)
Cryogenic gas processing Air separation Equations of state for high pressure hydrocarbon applications Flexible and
predictive equations of state
Gas dehydration with glycols Flexible and predictive equations of state
Acid gas absorption with
Methanol (rectisol)
NMP (purisol)
Flexible and predictive equations of state
Continued
2-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Gas Processing (continued)
Application Recommended Property Method
Acid gas absorption with
Water
Ammonia
Amines
Amines + methanol (amisol)
Caustic
Lime
Hot carbonate
Electrolyte activity coefficients
Claus process Flexible and predictive equations of state
Petrochemicals
Application Recommended Property Method
Ethylene plant
Primary fractionator
Light hydrocarbons separation train
Quench tower
Petroleum fugacity correlations
(and assay data analysis)
Equations of state for high pressure hydrocarbon applications
Equations of state for high pressure hydrocarbon applications
Aromatics
BTX extraction
Liquid activity coefficients (very sensitive to parameters)
Substituted hydrocarbons
VCM plant
Acrylonitrile plant
Equations of state for high pressure hydrocarbon applications
Ether production
MTBE, ETBE, TAME
Liquid activity coefficients
Ethylbenzene and styrene plants Equations of state for high pressure hydrocarbon applications and Ideal (with
Watsol) or liquid activity coefficient
Terephthalic acid Liquid activity coefficients (with dimerization in acetic acid section)
Chemicals
Application Recommended Property Method
Azeotropic separations
Alcohol separation
Liquid activity coefficients
Carboxylic acids
Acetic acid plant
Liquid activity coefficients
Phenol plant Liquid activity coefficients
Liquid phase reactions
Estrification
Liquid activity coefficients
continued
Physical Pr oper t y Met hods and Models 2-5
Ver sion 10
Chapter 2
Chemicals (continued)
Application Recommended Property Method
Ammonia plant Equations of state for high pressure hydrocarbon applications (with k
ij
)
Fluorochemicals Liquid activity coefficients (and HF equation of state)
Inorganic Chemicals
Caustic
Acids
Phosphoric acid
Sulphuric acid
Nitric acid
Hydrochloric acid
Hydrofluoric acid
Electrolyte activity coefficients
Electrolyte activity coefficient (and HF equation of state)
Coal Processing
Application Recommended Property Method
Size reduction
crushing, grinding
Solids processing (with coal analysis and particle size distribution)
Separation and cleaning
sieving, cyclones,
preciptition, washing
Solids processing (with coal analysis and and particle size distribution)
Combustion Equations of state for high pressure hydrocarbon applications (with combustion
databank)
Acid gas absorption See Gas Processing earlier in this discussion.
Coal gasification and liquefaction See Synthetic Fuel later in this discussion.
Power Generation
Application Recommended Property Method
Combustion
Coal
Oil
Equations of state for high pressure hydrocarbon applications (with combustion
databank)
(and assay analyis with coal correlations)
(and assay analyis)
Steam cycles
Compressors
Turbines
Steam tables
Acid gas absorption See Gas Processing earlier in this discussion.
continued
2-6 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Synthetic Fuel
Application Recommended Property Method
Synthesis gas Equations of state for high pressure hydrocarbon applications
Coal gasification Equations of state for high pressure hydrocarbon applications
Coal liquefaction Equations of state for high pressure hydrocarbon applications with k
ij
and assay
analysis with coal correlations)
Environmental
Application Recommended Property Method
Solvent recovery Liquid activity coefficients
(Substituted) hydrocarbon stripping Liquid activity coefficients
Acid gas stripping from
Methanol (rectisol)
NMP (purisol)
Flexible and predictive equations of state
Acid gas stripping from
Water
Ammonia
Amines
Amines + methanol (amisol)
Caustic
Lime
Hot carbonate
Electrolyte activity coefficients
Claus process Flexible and predictive equations of state
Acids
Stripping
Neutralization
Electrolyte activity coefficients
Water and Steam
Application Recommended Property Method
Steam systems Steam tables
Coolant Steam tables
continued
Physical Pr oper t y Met hods and Models 2-7
Ver sion 10
Chapter 2
Mineral and Metallurgical Processes
Application Recommended Property Method
Mechanical processing
crushing, grinding,
sieving, washing
Solids Processing (with inorganic databank)
Hydrometallurgy
Mineral leaching
Electrolyte activity coefficients
Pyrometallurgy
Smelter
Converter
Solids Processing (with inorganic databank)
IDEAL Property Method
The IDEAL pr oper t y met hod accommodat es bot h Raoult s law and Henr ys law.
This met hod uses t he:
Ideal act ivit y coefficient model for t he liquid phase ( 1)
Ideal gas equat ion of st at e Pv RT for t he vapor phase
Racket t model for liquid molar volume
The IDEAL pr oper t y met hod is r ecommended for syst ems in which ideal behavior
can be assumed, such as:
Syst ems at vacuum pr essur es
Isomer ic syst ems at low pr essur es
In t he vapor phase, small deviat ions fr om t he ideal gas law ar e allowed. These
deviat ions occur at :
Low pr essur es (eit her below at mospher ic pr essur e, or at pr essur es not
exceeding 2 bar )
Ver y high t emper at ur es
Ideal behavior in t he liquid phase is exhibit ed by molecules wit h eit her :
Ver y small int er act ions (for example, par affin of similar car bon number )
Int er act ions t hat cancel each ot her out (for example, wat er and acet one)
The IDEAL pr oper t y met hod:
Can be used for syst ems wit h and wit hout noncondensable component s.
Per manent gases can be dissolved in t he liquid. You can use Henr ys law,
which is valid at low concent r at ions, t o model t his behavior .
Does not include t he Poynt ing cor r ect ion
Ret ur ns heat of mixing of zer o
Is used t o init ialize FLASH algor it hm
The t r anspor t pr oper t y models for t he vapor phase ar e all well suit ed for ideal
gases. The t r anspor t pr oper t y models for t he liquid phase ar e empir ical equat ions
for fit t ing exper iment al dat a.
2-8 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
The IDEAL pr oper t y met hod is somet imes used for solids pr ocessing wher e VLE
is unimpor t ant (for example, in coal pr ocessing). For t hese, however , t he SOLIDS
pr oper t y met hod is r ecommended. See Solids Handling Pr oper t y Met hod on page
2-67 for document at ion on solid phase pr oper t ies.
Mi xture Types
Ideal mixt ur es wit h and wit hout noncondensable component s. You should not
use IDEAL for nonideal mixt ur es.
Range
IDEAL is appr opr iat e only at low pr essur e and low liquid mole fr act ions of t he
noncondensable component s (if pr esent ).
Use of Henrys Law
To use Henr ys law for noncondensable component s, you must designat e t hese
component s as Henr ys component s on t he Component s Henr y-Comps for m.
Henr y's const ant model par amet er s (HENRY) must be available for t he solut e
wit h at least one solvent . Use t he Pr oper t ies Par amet er s Binar y Int er act ion for m
(HENRY-1) t o ent er Henr y's const ant s or t o r eview built -in par amet er s. ASPEN
PLUS cont ains an ext ensive collect ion of Henr ys const ant s for many solut es in
solvent s. Solvent s ar e wat er and ot her or ganic component s. ASPEN PLUS uses
t hese par amet er s aut omat ically when you specify t he IDEAL pr oper t y met hod.
The following t able list s t her modynamic and t r anspor t pr oper t y models used in
IDEAL, and t heir minimum par amet er r equir ement s.
Parameters Required for the IDEAL Property Method
General
Property/Purpose Parameter Requirements
Mass balance,
Conversion Mass-basisMole-basis
MW
Conversion Stdvol-basisMole-basis VLSTD
Using Free-water option: solubility of water in
organic phase
WATSOL
Enthalpy of reaction DHFORM
Gibbs energy of reaction DGFORM
continued
Physical Pr oper t y Met hods and Models 2-9
Ver sion 10
Chapter 2
Thermodynamic Properties
Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient
Enthalpy, entropy,
Gibbs energy
Density
Ideal gas law
Ideal gas heat capacity
Ideal gas law
CPIG or CPIGDP
Liquid mixture
Fugacity coefficient
Ideal liquid activity coefficient
Extended Antoine vapor pressure
Henrys constant
Brelvi-OConnell
PLXANT
Solvent: VC, Solute-solvent: HENRY
Solvent: TC, PC, (ZC or RKTZRA), Solute:
(VC or VLBROC)
Enthalpy, entropy Watson/DIPPR TC, (DHVLWT or DHVLDP)
Density Rackett TC, PC, (VC or VCRKT), (ZC or RKTZRA)
Transport Properties
Properties Models Parameter Requirements
Vapor mixture
Viscosity
Thermal conductivity
Diffusivity
Chapman-Enskog-Brokaw/
DIPPR
Stiel-Thodos low pres./
DIPPR
Chapman-Enskog-Wilke-Lee
MW; (MUP and (STKPAR or LJPAR)) or
MUVDIP
MW or
KVDIP
MW; MUP and (STKPAR or LJPAR)
Surface tension Hakim-Steinberg-Stiel/
DIPPR
(TC, PC, OMEGA) or
SIGDIP
Liquid mixture
Viscosity
Thermal Conductivity
Diffusivity
Andrade/DIPPR
Sato-Riedel/DIPPR
Wilke-Chan
MULAND or MULDIP
(MW, TC, TB) or KLDIP
MW, VB
2-10 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Property Methods for Petroleum Mi xtures
The pr oper t y met hods in t he following t able ar e designed for mixt ur es of
hydr ocar bons and light gases. K-value models and liquid fugacit y cor r elat ions ar e
used at low and medium pr essur es. Pet r oleum-t uned equat ions of st at e ar e used at
high pr essur es. The hydr ocar bons can be fr om nat ur al gas or cr ude oil: t hat is,
complex mixt ur es t hat ar e t r eat ed using pseudocomponent s. These pr oper t y
met hods ar e oft en used for r efiner y applicat ions. Densit y and t r anspor t pr oper t ies
ar e calculat ed by API pr ocedur es when possible.
The following t able list s t he common and t he dist inct ive models of t he pr oper t y
met hods. The par amet er r equir ement s of t he dist inct ive models ar e given in t he
t ables labeled Par amet er s Requir ed for t he CHAO-SEA Pr oper t y Met hod on page
2-13, Par amet er s Requir ed for t he GRAYSON Pr oper t y Met hod on page 2-15,
Par amet er s Requir ed for t he PENG-ROB Pr oper t y Met hod on page 2-16, and
Par amet er s Requir ed for t he RK-SOAVE Pr oper t y Met hod on page 2-18.
Par amet er r equir ement s for t he common models ar e in t he t able labeled
Par amet er s Requir ed for Common Models on page 2-18. For det ails on t hese
models, see Chapt er 3
Property Methods for Petroleum Mixtures
Liquid Fugacity and K-Value Models
Property Method Name Models
BK10 Braun K10 K-value model
CHAO-SEA Chao-Seader liquid fugacity, Scatchard-Hildebrand activity coefficient
GRAYSON Grayson-Streed liquid fugacity, Scatchard-Hildebrand activity coefficient
Petroleum-Tuned Equations of State
Property Method Name Models
PENG-ROB Peng-Robinson
RK-SOAVE Redlich-Kwong-Soave
Common Models for Property Methods for Petroleum Mixtures
Property Model
Liquid enthalpy Lee-Kesler
Liquid molar volume API
continued
Physical Pr oper t y Met hods and Models 2-11
Ver sion 10
Chapter 2
Common Models for Property Methods for Petroleum Mixtures (Continued)
Property Model
Vapor viscosity Chapman-Enskog-Brokaw
Vapor thermal conductivity Stiel-Thodos/DIPPR
Vapor diffusivity Dawson-Khoury-Kobayashi
Surface tension API surface tension
Liquid viscosity API
Liquid thermal conductivity Sato-Riedel/DIPPR
Liquid diffusivity Wilke-Chang
Liquid Fugacity and K-Value Model Property Methods
The BK10 pr oper t y met hod is gener ally used for vacuum and low pr essur e
applicat ions (up t o sever al at m). The CHAO-SEA pr oper t y met hod and t he
GRAYSON pr oper t y met hod can be used at higher pr essur es. GRAYSON has t he
widest r anges of applicabilit y (up t o sever al t ens of at m). For hydr ogen-r ich
syst ems, GRAYSON is r ecommended.
These pr oper t y met hods ar e less suit ed for high-pr essur e applicat ions in r efiner y
(above about 50 at m). Pet r oleum-t uned equat ion of st at e pr oper t y met hods ar e
pr efer r ed for high pr essur es.
These pr oper t y met hods ar e not suit ed for condit ions close t o cr it icalit y, as occur
in light oil r eser voir s, t r anspor t at ion of gas by pipelines, and in some gas
pr ocessing applicat ions. St andar d equat ions of st at e for non-polar component s
ar e pr efer r ed. If polar compounds ar e pr esent , such as in gas t r eat ment , use
flexible and pr edict ive equat ions of st at e for polar compounds.
BK10
The BK10 propert y met hod uses t he Braun K-10 K-value correlat ions. The
cor r elat ions wer e developed fr om t he K10 char t s for bot h r eal component s and oil
fr act ions. The r eal component s include 70 hydr ocar bons and light gases. The oil
fr act ions cover boiling r anges 450 700 K (350 800F). Pr opr iet ar y met hods wer e
developed t o cover heavier oil fr act ions.
2-12 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Mi xture Types
Best r esult s ar e obt ained wit h pur ely aliphat ic or pur ely ar omat ic mixt ur es wit h
nor mal boiling point s r anging fr om 450 t o 700 K. For mixt ur es of aliphat ic and
ar omat ic component s, or napht enic mixt ur es, t he accur acy decr eases. For mixt ur es
wit h light gases, and medium pr essur es, CHAO-SEA or GRAYSON ar e
r ecommended.
Range
The BK10 pr oper t y met hod is suit ed for vacuum and low pr essur e applicat ions (up
t o sever al at m). For high pr essur es, pet r oleum-t uned equat ions of st at e ar e best
suit ed.
The applicable t emper at ur e r ange of t he K10 char t is 133 800 K (-220 980F).
It can be used up t o 1100 K (1520F).
The par amet er s for t he Br aun K-10 ar e all built -in. You do not need t o supply
t hem. See t he t able Par amet er s Requir ed for Common Models on page 2-18 for
par amet er r equir ement s of models common t o pet r oleum pr oper t y met hods.
CHAO-SEA
The CHAO-SEA pr oper t y met hod uses t he:
Chao-Seader cor r elat ion for r efer ence st at e fugacit y coefficient
Scat char d-Hildebr and model for act ivit y coefficient
Redlich-Kwong equat ion of st at e for vapor phase pr oper t ies
Lee-Kesler equat ion of st at e for liquid and vapor ent halpy
API met hod for liquid molar volume, viscosit y and sur face t ension
Models list ed in t he t ables labeled Par amet er s Requir ed for t he CHAO-SEA
Pr oper t y Met hod on page 2-13 and Parameters Required for Common Models on
page 2-18
The t ables labeled Par amet er s Requir ed for t he CHAO-SEA Pr oper t y Met hod on
page 2-13 and Parameters Required for Common Models on page 2-18 pr ovide
t her modynamic and t r anspor t pr oper t y models, and t heir par amet er r equir ement s.
The CHAO-SEA pr oper t y met hod is pr edict ive. It can be used for cr ude t ower s,
vacuum t ower s, and some par t s of t he et hylene pr ocess. It is not r ecommended
for syst ems cont aining hydr ogen.
Physical Pr oper t y Met hods and Models 2-13
Ver sion 10
Chapter 2
Mi xture Types
The CHAO-SEA pr oper t y met hod was developed for syst ems cont aining
hydr ocar bons and light gases, such as car bon dioxide and hydr ogen sulfide, but
wit h t he except ion of hydr ogen. If t he syst em cont ains hydr ogen, use t he
GRAYSON pr oper t y met hod.
Range
Use t he CHAO-SEA pr oper t y met hod for syst ems wit h t emper at ur e and pr essur e
limit s of
200 < T < 533 K
0.5 < T
ri
< 1.3
T
rm
< 0.93
P < 140 at m
Wher e:
T
ri
= Reduced t emper at ur e of a component
T
rm
= Reduced t emper at ur e of t he mixt ur e
Do not use t his pr oper t y met hod at ver y high pr essur es, especially near t he
mixt ur e cr it ical point , because of anomalous behavior in t hese r egions.
Parameters Required for the CHAO-SEA Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density
Enthalpy, entropy,
Gibbs free energy
Redlich-Kwong
Ideal gas heat capacity,
Redlich-Kwong
TC, PC
CPIG or CPIGDP
TC, PC
Liquid mixture
Fugacity coefficient,
Gibbs free energy
Scatchard-Hildebrand activity coefficient
Chao-Seader pure component fugacity
coefficient
TC, DELTA, VLCVT1; GMSHVL
TC, PC, OMEGA
2-14 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
GRAYSON
The GRAYSON pr oper t y met hod uses t he:
Gr ayson-St r eed cor r elat ion for r efer ence st at e fugacit y coefficient s
Scr at char d-Hildlebr and model for act ivit y coefficient s
Redlich-Kwong equat ion of st at e for vapor phase pr oper t ies
Lee-Kesler equat ion of st at e for liquid and vapor ent halpy
API met hod for liquid molar volume, viscosit y and sur face t ension
Refer t o t he t ables labeled Parameters Required for the GRAYSON Property Method
on page 2-15 and Par amet er s Requir ed for Common Models on page 2-18 for
t her modynamic and t r anspor t pr oper t y models, and t heir par amet er r equir ement s.
The GRAYSON pr oper t y met hod is pr edict ive. It can be used for cr ude t ower s,
vacuum t ower s, and some par t s of t he et hylene pr ocess. It is r ecommended for
syst ems cont aining hydr ogen.
Mi xture Types
The GRAYSON pr oper t y met hod was developed for syst ems cont aining
hydr ocar bons and light gases, such as car bon dioxide and hydr ogen sulfide. It is
r ecommended over t he CHAO-SEA pr oper t y met hod when t he syst em cont ains
hydrogen.
Range
Use t he GRAYSON pr oper t y met hod for syst ems wit h t emper at ur e and pr essur e
limit s of:
200K < T < 700K
05 . < T
ri
P < 210 atm
Wher e:
T
ri
= Reduced t emper at ur e coefficient
Do not use t his pr oper t y met hod at ver y high pr essur es, especially near t he
mixt ur e cr it ical point , because of anomalous behavior in t hese r egions.
Physical Pr oper t y Met hods and Models 2-15
Ver sion 10
Chapter 2
Parameters Required for the GRAYSON Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density
Enthalpy, entropy,
Gibbs free energy
Redlich-Kwong
Ideal gas heat capacity, Redlich-Kwong
TC, PC
CPIG or CPIGDP
TC, PC
Liquid mixture
Fugacity coefficient,
Gibbs free energy
Scatchard-Hildebrand activity coefficient
Grayson-Streed pure component fugacity
coefficient
TC, DELTA, VLCVT1;GMSHVL
TC, PC, OMEGA
Petroleum-Tuned Equati on-of-State Property Methods
Pet r oleum-t uned equat ion-of-st at e pr oper t y met hods ar e based on equat ions of
st at e for nonpolar compounds wit h built -in binar y par amet er s. These pr oper t y
met hods use t he API/Racket t model for liquid densit y t o over come t he dr awback of
poor liquid densit y calculat ed by cubic equat ions of st at e. Liquid viscosit y and
sur face t ensions ar e calculat ed by API models.
Equat ions of st at e ar e compar able in per for mance when compar ing VLE. BWR-
LS is r ecommended for hydr ogen-r ich syst ems.
Pr oper t y met hods based on liquid fugacit y cor r elat ions or K-value models ar e
gener ally pr efer r ed for low pr essur e r efiner y applicat ions. Pet r oleum-t uned
equat ion-of-st at e models can handle cr it ical point s, but some ot her models of t he
pr oper t y met hods (such as liquid densit y and liquid viscosit y) ar e not suit ed for
condit ions close t o cr it icalit y, as occur in light oil r eser voir s, t r anspor t at ion of gas
by pipe lines, and in some gas pr ocessing applicat ions. For t hese cases, equat ion-
of-st at e pr oper t y met hods for high pr essur e hydr ocar bon applicat ions ar e
pr efer r ed. If polar compounds ar e pr esent , such as in gas t r eat ment , use flexible
and pr edict ive equat ions of st at e for polar compounds.
PENG-ROB
The PENG-ROB pr oper t y met hod uses t he:
Peng-Robinson cubic equat ion of st at e for all t her modynamic pr oper t ies except
liquid molar volume
API met hod for liquid molar volume of pseudocomponent s and t he Racket t
model for r eal component s
2-16 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Refer t o t he t ables labeled Parameters Required for the PENG-ROB Property Method
on page 16 and Par amet er s Requir ed for Common Models on page 2-18 for
t her modynamic and t r anspor t pr oper t y models, and t heir r equir ed par amet er s.
This pr oper t y met hod is compar able t o t he RK-SOAVE pr oper t y met hod. It is
r ecommended for gas-pr ocessing, r efiner y, and pet r ochemical applicat ions.
Sample applicat ions include gas plant s, cr ude t ower s, and et hylene plant s.
For accur at e r esult s in your VLE or LLE calculat ions, you must use binar y
par amet er s, such as t he ASPEN PLUS built -in binar y par amet er s. Use t he
Pr oper t ies Par amet er s Binar y Int er act ion PRKIJ -1 for m t o r eview available
built -in binar y par amet er s. You can also use t he Dat a Regr ession Syst em (DRS)
t o det er mine t he binar y par amet er s fr om exper iment al phase equilibr ium dat a
(usually binar y VLE dat a).
Mi xture Types
Use t he PENG-ROB pr oper t y met hod for nonpolar or mildly polar mixt ur es.
Examples ar e hydr ocar bons and light gases, such as car bon dioxide, hydr ogen
sulfide, and hydr ogen. For syst ems wit h polar component s, use t he SR-POLAR,
PRWS, RKSWS, PRMHV2, RKSMHV2, PSRK, WILSON, NRTL, VANLAAR, or
UNIQUAC pr oper t y met hods.
This pr oper t y met hod is par t icular ly suit able in t he high t emper at ur e and high
pr essur e r egions, such as in hydr ocar bon pr ocessing applicat ions or super cr it ical
ext r act ions.
Range
You can expect r easonable r esult s at all t emper at ur es and pr essur es. The PENG-
ROB pr oper t y met hod is consist ent in t he cr it ical r egion. Ther efor e, it does not
exhibit anomalous behavior , unlike t he act ivit y coefficient pr oper t y met hods.
Result s ar e least accur at e in t he r egion near t he mixt ur e cr it ical point .
Parameters Required for the PENG-ROB Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient
Density
Enthalpy, entropy,
Gibbs free energy
Peng-Robinson
Ideal gas heat capacity,
Peng-Robinson
TCPR or TC; PCPR or PC; OMGPR or
OMEGA CPIG or CPIGDP
Liquid mixture
Fugacity coefficient
Enthalpy, entropy,
Gibbs energy
Peng-Robinson
Ideal gas heat capacity,
Peng-Robinson
TCPR or TC; PCPR or PC; OMGPR or
OMEGA CPIG or CPIGDP
Physical Pr oper t y Met hods and Models 2-17
Ver sion 10
Chapter 2
RK-SOAVE
The RK-SOAVE pr oper t y met hod uses t he:
Redlich-Kwong-Soave (RKS) cubic equat ion of st at e for all t her modynamic
pr oper t ies except liquid molar volume
API met hod for liquid molar volume of pseudocomponent s and t he Racket t
model for r eal component s
Refer t o t he t ables labeled Par amet er s Requir ed for t he RK-SOAVE Pr oper t y
Met hod on page 2-18 and Par amet er s Requir ed for Common Models on page 2-18
for t her modynamic and t r anspor t pr oper t y models, and r equir ed par amet er s for
t his pr oper t y met hod.
This pr oper t y met hod is compar able t o t he PENG-ROB pr oper t y met hod. It is
r ecommended for gas-pr ocessing, r efiner y, and pet r ochemical applicat ions.
Example applicat ions include gas plant s, cr ude t ower s, and et hylene plant s. The
RK-SOAVE pr oper t y met hod has built -in binar y par amet er s, RKSKIJ , t hat ar e
used aut omat ically in ASPEN PLUS.
For accur at e r esult s in your VLE and LLE calculat ions, you must use binar y
par amet er s. You can use t he ASPEN PLUS built -in par amet er s. Use t he
Pr oper t ies Par amet er s Binar y Int er act ion RKSKIJ -1 for m t o r eview available
built -in binar y par amet er s. You can also use t he Dat a Regr ession Syst em (DRS)
t o det er mine t he binar y par amet er s fr om exper iment al phase equilibr ium dat a
(usually binar y VLE dat a).
Mi xture Types
Use t he RK-SOAVE pr oper t y met hod for nonpolar or mildly polar mixt ur es.
Examples ar e hydr ocar bons and light gases, such as car bon dioxide, hydr ogen
sulfide, and hydr ogen. For syst ems wit h polar component s, such as alcohols, use
t he SR-POLAR, WILSON, NRTL, VANLAAR, or UNIQUAC pr oper t y met hods.
This pr oper t y met hod is par t icular ly suit able in t he high t emper at ur e and high
pr essur e r egions, such as in hydr ocar bon pr ocessing applicat ions or super cr it ical
ext r act ions.
Range
You can expect r easonable r esult s at all t emper at ur es and pr essur es. The RK-
SOAVE pr oper t y met hod is consist ent in t he cr it ical r egion. Ther efor e, unlike t he
act ivit y coefficient pr oper t y met hods, it does not exhibit anomalous behavior .
Result s ar e least accur at e in t he r egion near t he mixt ur e cr it ical point .
2-18 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Parameters Required for the RK-SOAVE Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density
Enthalpy, entropy
Gibbs free energy
Redlich-Kwong-Soave
Ideal gas heat capacity,
Redlich-Kwong-Soave
TC, PC, OMEGA
CPIG or CPIGDP,
TC, PC, OMEGA
Liquid mixture
Fugacity coefficient
Enthalpy, entropy,
Gibbs free energy
Redlich-Kwong-Soave
Ideal gas heat capacity,
Redlich-Kwong-Soave
TC, PC, OMEGA
CPIG or CPIGDP
TC, PC, OMEGA
Common Models
The following t able list s t he models used in all pet r oleum pr oper t y met hods and
t heir par amet er r equir ement s.
Parameters Required for Common Models
General
Property/Purpose Parameter Requirements
Mass balance, Conversion Mass-basisMole-basis MW
Conversion Stdvol-basisMole-basis VLSTD
Initialization of Flash calculations PLXANT
Using Free-water option: solubility of water in organic phase WATSOL
Enthalpy of reaction DHFORM
Gibbs energy of reaction DGFORM
Physical Pr oper t y Met hods and Models 2-19
Ver sion 10
Chapter 2
Thermodynamic Properties
Property Models Parameter Requirements
Liquid mixture
Enthalpy,
Entropy
Density
Ideal heat capacity,
Lee-Kesler
Real components:
Rackett/DIPPR
Pseudo components:
(CPIG or CPIGDP)
TC, PC, OMEGA
TC, PC, VCRKT
TB, API
Transport Properties
Property Models Paremeter Requirements
Vapor mixture
Viscosity
Thermal Conductivity
Diffusivity
Chapman-Enskog-Brokaw/
DIPPR
Stiel-Thodos/
DIPPR
Dawson Khoury-Kobayashi -
MW, (MUP and (STKPAR or LJPAR)) or MUVDIP
MW or KVDIP (and vapor viscosity parameters)
MW, MUP, (STKPAR or LJPAR), VC
Liquid mixture
Viscosity
Thermal Conductivity
Diffusivity
API
Sato-Riedel/
DIPPR
Wilke-Chang
TB, API
(MW, TB, TC) or
KLDIP
MW, VB
Surface tension API TB, TC, SG
2-20 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Equati on-of-State Property Methods for
Hi gh-Pressure Hydrocarbon Appli cati ons
The following t able, Equat ion of St at e Pr oper t y Met hods for Hydr ocar bons at
High Pr essur e, list s pr oper t y met hods for mixt ur es of hydr ocar bons and light
gases. The pr oper t y met hods can deal wit h high pr essur es and t emper at ur es, and
mixt ur es close t o t heir cr it ical point (for example, pipeline t r anspor t at ion of gas
or super cr it ical ext r act ion). All t her modynamic pr oper t ies of vapor and liquid
phases ar e calculat ed fr om t he equat ions of st at e. (See Chapt er 1). The TRAPP
models for viscosit y and t her mal conduct ivit y can descr ibe t he cont inuit y of gas
and liquid beyond t he cr it ical point , compar able t o an equat ion of st at e.
The hydr ocar bons can be fr om complex cr ude or gas mixt ur es t r eat ed using
pseudocomponent s. But t he pr oper t y met hods for pet r oleum mixt ur es ar e bet t er
t uned for t hese applicat ions at low t o medium pr essur es. Unless you use fit t ed
binar y int er act ion par amet er s, no gr eat accur acy should be expect ed close t o t he
cr it ical point . Liquid densit ies ar e not accur at ely pr edict ed for t he cubic
equat ions of st at e.
In t he pr esence of polar component s (for example, in gas t r eat ment ), flexible and
pr edict ive equat ions of st at e should be used. For mixt ur es of polar and nonpolar
compounds at low pr essur es, use an act ivit y-coefficient -based pr oper t y met hod.
The following t able list s t he common and dist inct ive models of t he pr oper t y
met hods BWR-LS, LK-PLOCK, PR-BM, and RKS-BM. The par amet er
r equir ement s of t he common models ar e given in t he t able labeled Par amet er s
Requir ed for Common Models on page 2-25. The par amet er r equir ement s for t he
dist inct ive models ar e in t he t ables labeled Par amet er s Requir ed for t he BWR-LS
Pr oper t y Met hod on page 2-22, Par amet er s Requir ed for t he LK-PLOCK Pr oper t y
Met hod on page 2-23, Par amet er s Requir ed for t he PR-BM Pr oper t y Met hod on
page 2-24, and Par amet er s Requir ed for t he RKS-BM Pr oper t y Met hod on page
2-25.
Equation-of-State Property Methods for Hydrocarbons at High Pressure
Property Method Name Models
BWR-LS BWR-Lee-Starling
LK-PLOCK Lee-Kesler-Plcker
PR-BM Peng-Robinson-Boston-Mathias
RKS-BM Redlich-Kwong-Soave-Boston-Mathias
continued
Physical Pr oper t y Met hods and Models 2-21
Ver sion 10
Chapter 2
Equation-of-State Property Methods for Hydrocarbons at High Pressure
Property Common Models
Vapor viscosity TRAPP
Vapor thermal conductivity TRAPP
Vapor diffusivity Dawson-Khoury-Kobayashi
Surface tension API surface tension
Liquid viscosity TRAPP
Liquid thermal conductivity TRAPP
Liquid diffusivity Wilke-Chang
BWR-LS
The BWR-LS propert y met hod is based on t he BWR-Lee-St arling equat ion of st at e.
It is t he gener alizat ion (in t er ms of pur e component cr it ical pr oper t ies) of t he
Benedict -Webb-Rubin vir ial equat ion of st at e. The pr oper t y met hod uses t he
equat ion of st at e for all t her modynamic pr oper t ies. Refer t o t he t able labeled
Par amet er s Requir ed for t he BWR-LS Pr oper t y Met hod on page 2-22 and
Par amet er s Requir ed for Common Models on page 2-25 for t her modynamic and
t r anspor t pr oper t y models and t heir par amet er r equir ement s.
The BWR-LS pr oper t y met hod is compar able t o PENG-ROB, RK-SOAVE, and LK-
PLOCK for phase equilibr ium calculat ions, but is mor e accur at e t han PENG-
ROB and RK-SOAVE for liquid molar volume and ent halpy. You can use it for
gas pr ocessing and r efiner y applicat ions. It is suit ed for hydr ogen-cont aining
syst ems, and has shown good r esult s in coal liquefact ion applicat ions.
For accur at e r esult s, use t he binar y int er act ion par amet er s. Built -in binar y
par amet er s BWRKV and BWRKT ar e available for a lar ge number of component
pair s. ASPEN PLUS uses t hese binar y par amet er s aut omat ically. Use t he
Pr oper t ies Par amet er s Binar y Int er act ion BWRKV-1 and BWRKT-1 for ms t o
r eview available built -in binar y par amet er s. You can also use t he Dat a
Regr ession Syst em (DRS) t o det er mine t he binar y par amet er s fr om exper iment al
phase equilibr ium dat a (usually binar y VLE dat a).
Mi xture Types
Use t he BWR-LS pr oper t y met hod for nonpolar or slight ly polar mixt ur es, and light
gases. Asymmet r ic int er act ions bet ween long and shor t molecules ar e well
pr edict ed.
2-22 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Range
You can expect r easonable r esult s up t o medium pr essur es. At ver y high pr essur es,
unr ealist ic liquid-liquid demixing may be pr edict ed. High pr essur e liquid-liquid
demixing occur s bet ween shor t and long chain hydr ocar bons and also, for example,
bet ween car bon dioxide and longer hydr ocar bon chains at high pr essur es.
Parameters Required for the BWR-LS Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density
Enthalpy,
Entropy,
Gibbs energy
BWR-Lee-Starling
Ideal heat capacity,
BWR-Lee-Starling
TC, VC, OMEGA
(CPIG or CPIGDP) and
TC, VC, OMEGA
Liquid mixture
Fugacity coefficient,
Density
Enthalpy,
Entropy,
Gibbs energy
BWR-Lee-Starling
Ideal heat capacity,
BWR-Lee-Starling
TC, VC, OMEGA
(CPIG or CPIGDP) and
TC, VC, OMEGA
LK-PLOCK
The LK-PLOCK pr oper t y met hod is based on t he Lee-Kesler -Plcker equat ion of
st at e, which is a vir ial-t ype equat ion. LK-PLOCK uses t he:
EOS t o calculat e all t her modynamic pr oper t ies except liquid molar volume
API met hod for liquid molar volume of pseudocomponent s and t he Racket t
model for r eal component s
You can use LK-PLOCK for gas-pr ocessing and r efiner y applicat ions, but t he RK-
SOAVE or t he PENG-ROB pr oper t y met hods ar e pr efer r ed.
Refer t o t he t ables labeled Par amet er s Requir ed for t he LK-PLOCK Pr oper t y
Met hod on page 2-23 and Par amet er s Requir ed for Common Models on page 2-25
for t her modynamic and t r anspor t pr oper t y models, and t heir par amet er
r equir ement s.
For accur at e r esult s in VLE calculat ions, use binar y par amet er s. Built -in binar y
par amet er s LKPKIJ ar e available for a lar ge number of component pair s. ASPEN
PLUS uses t hese binar y par amet er s aut omat ically. Use t he Pr oper t ies
Par amet er s Binar y Int er act ion LKPKIJ -1 for m t o r eview available built -in binar y
par amet er s. You can also use t he Dat a Regr ession Syst em (DRS) t o det er mine
t he binar y par amet er s fr om exper iment al phase equilibr ium dat a (usually binar y
VLE dat a).
Physical Pr oper t y Met hods and Models 2-23
Ver sion 10
Chapter 2
This pr oper t y met hod also has built -in cor r elat ions for est imat ing binar y
par amet er s among t he component s CO, CO
2
, N
2
, H
2
, CH
4
, alcohols, and
hydr ocar bons. Component s not belonging t o t he classes list ed above ar e assumed
t o be hydr ocar bons.
Mi xture Types
Use t he LK-PLOCK pr oper t y met hod for nonpolar or mildly polar mixt ur es.
Examples ar e hydr ocar bons and light gases, such as car bon dioxide, hydr ogen
sulfide, and hydrogen.
Range
You can expect r easonable r esult s at all t emper at ur es and pr essur es. The
LK-PLOCK pr oper t y met hod is consist ent in t he cr it ical r egion. It does not exhibit
anomalous behavior , unlike t he act ivit y coefficient pr oper t y met hods. Result s ar e
least accur at e in t he r egion near t he mixt ur e cr it ical point .
Parameters Required for the LK-PLOCK Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density
Enthalpy, entropy
Gibbs free energy
Lee-Kesler-Plcker
Ideal gas heat capacity,
Lee-Kesler-Plcker
TC, PC, VC, OMEGA
(CPIG or CPIGDP)
and TC, PC, VC, OMEGA
Liquid mixture
Fugacity coefficient,
Density
Enthalpy, entropy
Gibbs free energy
Lee-Kesler-Plcker
Ideal gas heat capacity,
Lee-Kesler-Plcker
TC, PC, VC, OMEGA
(CPIG or CPIGDP)
and TC, PC, VC, OMEGA
PR-BM
The PR-BM propert y met hod uses t he Peng Robinson cubic equat ion of st at e wit h
t he Bost on-Mat hias alpha funct ion for all t her modynamic pr oper t ies.
Refer t o t he t ables labeled Par amet er s Requir ed for t he PR-BM Pr oper t y Met hod
on page 2-24 and Par amet er s Requir ed for Common Models on page 2-25 for
t her modynamic and t r anspor t pr oper t y models, and t heir r equir ed par amet er s.
This pr oper t y met hod is compar able t o t he RKS-BM pr oper t y met hod. It is
r ecommended for gas-pr ocessing, r efiner y, and pet r ochemical applicat ions.
Sample applicat ions include gas plant s, cr ude t ower s, and et hylene plant s.
2-24 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
For accur at e r esult s in your VLE calculat ions, you must use binar y par amet er s.
ASPEN PLUS does not have built -in binar y par amet er s for t his pr oper t y met hod.
Mi xture Types
Use t he PR-BM pr oper t y met hod for nonpolar or mildly polar mixt ur es. Examples
ar e hydr ocar bons and light gases, such as car bon dioxide, hydr ogen sulfide, and
hydrogen.
Range
You can expect r easonable r esult s at all t emper at ur es and pr essur es. The PR-BM
pr oper t y met hod is consist ent in t he cr it ical r egion. Result s ar e least accur at e in
t he r egion near t he mixt ur e cr it ical point .
Parameters Required for the PR-BM Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor or liquid mixture
Fugacity coefficient
Density
Enthalpy, entropy,
Gibbs free energy
Peng-Robinson
Ideal gas heat capacity,
Peng-Robinson
PC, TC, OMEGA
CPIG or CPIGDP,
TC,PC, OMEGA
RKS-BM
The RKS-BM pr oper t y met hod uses t he Redlich-Kwong-Soave (RKS) cubic
equat ion of st at e wit h Bost on-Mat hias alpha funct ion for all t her modynamic
pr oper t ies.
This pr oper t y met hod is compar able t o t he PR-BM pr oper t y met hod. It is
r ecommended for gas-pr ocessing, r efiner y, and pet r ochemical applicat ions.
Example applicat ions include gas plant s, cr ude t ower s, and et hylene plant s.
For accur at e r esult s in your VLE calculat ions, you must use binar y par amet er s.
ASPEN PLUS does not have built -in binar y par amet er s for t his pr oper t y met hod.
Mi xture Types
Use t he RKS-BM pr oper t y met hod for nonpolar or mildly polar mixt ur es. Examples
ar e hydr ocar bons and light gases, such as car bon dioxide, hydr ogen sulfide, and
hydrogen.
Physical Pr oper t y Met hods and Models 2-25
Ver sion 10
Chapter 2
Range
You can expect r easonable r esult s at all t emper at ur es and pr essur es. The RKS-BM
pr oper t y met hod is consist ent in t he cr it ical r egion. Result s ar e least accur at e in
t he r egion near t he mixt ur e cr it ical point .
Refer t o t he t ables labeled Par amet er s Requir ed for t he RKS-BM Pr oper t y
Met hod on page 2-25 and Par amet er s Requir ed for Common Models on page 2-25
for t her modynamic and t r anspor t pr oper t y models, and t heir r equir ed
par amet er s.
Parameters Required for the RKS-BM Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor or liquid mixture
Fugacity coefficient
Density
Enthalpy, entropy,
Gibbs free energy
Redlich-Kwong-Soave
Ideal gas heat capacity,
Redlich-Kwong-Soave
TC, PC, OMEGA
CPIG or CPIGDP,
TC,PC, OMEGA
Common Models
The following t able labeled Par amet er s Requir ed for Common Models list s t he
models common t o equat ion-of-st at e pr oper t y met hods for highpr essur e
hydr ocar bon applicat ions and t heir par amet er r equir ement s.
Parameters Required for Common Models
General
Property/Purpose Parameter Requirements
Mass balance, Conversion Mass-
basisMole-basis
MW
Conversion Stdvol-basisMole-basis VLSTD
Initialization of Flash calculations PLXANT
Using Free-water option: solubility of water in
organic phase
WATSOL
Enthalpy of reaction DHFORM
Gibbs energy of reaction DGFORM
continued
2-26 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Transport
Property Models Parameter Requirements
Vapor Mixture
Viscosity
Thermal Conductivity
Diffusivity
TRAPP
TRAPP
Dawson-Khoury-Kobayashi
TC, PC, OMEGA
TC, PC, OMEGA
MW, MUP, (STKPAR or LJPAR), VC
Surface tension API TB, TC, SG
Liquid mixture
Viscosity
Thermal Conductivity
Diffusivity
TRAPP
TRAPP
Wilke-Chang
TC, PC, OMEGA
TC, PC, OMEGA
MW, VB
Flexi ble and Predi cti ve Equati on-of-State
Property Methods
The t able labeled Flexible and Predictive Equation-of-State Property Methods on page
2-28 list s pr oper t y met hods for mixt ur es of polar and non-polar component s and
light gases. The pr oper t y met hods can deal wit h high pr essur es and t emper at ur es,
mixt ur es close t o t heir cr it ical point , and liquid-liquid separ at ion at high pr essur e.
Examples of applicat ions ar e gas dr ying wit h glycols, gas sweet ening wit h
met hanol, and super cr it ical ext r act ion.
Pur e component t her modynamic behavior is modeled using t he Peng-Robinson or
Redlich-Kwong-Soave equat ions of st at e. They ar e ext ended wit h flexible alpha-
funct ions wit h up t o t hr ee par amet er s, for ver y accur at e fit t ing of vapor
pr essur es. This is impor t ant in separ at ions of ver y closely boiling syst ems and for
polar compounds. In some cases t hey ar e ext ended wit h a volume t r anslat ion
t er m for accur at e fit t ing of liquid densit ies (see t he t able labeled Flexible and
Pr edict ive Equat ion-of-St at e Pr oper t y Met hods on page 2-28).
Par amet er s for t he Schwar t zent r uber -Renon and Mat hias-Copeman alpha
funct ions ar e available for many component s in t he PURECOMP dat abank.
Physical Pr oper t y Met hods and Models 2-27
Ver sion 10
Chapter 2
Mixing r ules for t hese models var y. Ext ended classical mixing r ules ar e used for
fit t ing hydr ogen-r ich syst ems or syst ems wit h st r ong size and shape asymmet r y
(Redlich-Kwong-Aspen). Composit ion and t emper at ur e-dependent mixing r ules
fit st r ongly non-ideal high pr essur e syst ems (SR-POLAR). Modified Hur on-Vidal
mixing r ules can pr edict non-idealit y at high pr essur e fr om low-pr essur e (gr oup-
cont r ibut ion) act ivit y coeffient models (Wong-Sandler , MHV2, PSRK). The
pr edict ive capabilit ies of modified Hur on-Vidal mixing r ules ar e super ior t o t he
pr edict ive capabilit ies of SR-POLAR. The differ ences among capabilit ies of t he
modified Hur on-Vidal mixing r ules ar e small (see Chapt er 3).
The Wong-Sandler , MHV2, and Holder baum-Gmehling mixing r ules use act ivit y
coefficient models t o calculat e excess Gibbs or Helmholt z ener gy for t he mixing
r ules. The pr oper t y met hods wit h t hese mixing r ules use t he UNIFAC or Lyngby
modified UNIFAC gr oup cont r ibut ion models. Ther efor e, t hey ar e pr edict ive. You
can use any ASPEN PLUS act ivit y coefficient models wit h t hese mixing r ules,
including user models. Use t he Pr oper t ies Met hods Models sheet t o modify t he
pr oper t y met hod. See Chapt er 4 for det ails on how t o modify a pr oper t y met hod.
The Chung-Lee-St ar ling models for viscosit y and t her mal conduct ivit y can
descr ibe t he cont inuit y of gas and liquid beyond t he cr it ical point . This is
compar able t o an equat ion of st at e. These models can fit t he behavior of polar
and associat ing component s. Det ails about t he pur e component models and
mixing r ules ar e found in Chapt er 3.
For mixt ur es of polar and non-polar compounds at low pr essur es, act ivit y
coefficient models ar e pr efer r ed. For non-polar mixt ur es of pet r oleum fluids and
light gases at low t o medium pr essur es, t he pr oper t y met hods for pet r oleum
mixt ur es ar e r ecommended. The flexible and pr edict ive equat ions of st at e ar e not
suit ed for elect r olyt e solut ions.
The following t able, Flexible and Pr edict ive Equat ion-of-St at e Pr oper t y Met hods,
list s flexible and pr edict ive equat ion-of-st at e pr oper t y met hods, t he dist inct ive
equat ion-of-st at e models on which t hey ar e based, and some of t heir
char act er ist ics. The t able also gives t he models t hat t he pr oper t y met hods have
in common. Par amet er r equir ement s of t he common models ar e given in t he t able
labeled Par amet er s Requir ed for Common Flexible and Pr edict ive Models on
page 2-36. Par amet er r equir ement s for t he dist inct ive models ar e in t he t ables
labeled Par amet er s Requir ed for t he PRMHV2 Pr oper t y Met hod on page 2-29,
Par amet er s Requir ed for t he PRWS Pr oper t y Met hod on page 2-30, Par amet er s
Requir ed for t he PSRK Pr oper t y Met hod on page 2-31, Par amet er s Requir ed for
t he RK-ASPEN Pr oper t y Met hod on page 2-32, Par amet er s Requir ed for t he
RKSMHV2 Pr oper t y Met hod on page 2-33, Par amet er s Requir ed for t he RKSWS
Pr oper t y Met hod on page 2-34, and Par amet er s Requir ed for t he SR-POLAR
Pr oper t y Met hod on page 2-35.
2-28 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Flexible and Predictive Equation-of-State Property Methods
Property Method Name Equation of State Volume Shift
Reg
LLE
Lit
Reg
Henry
Lit
Reg
Vapor Phase
EOS Name
Poynting
Correction
NRTL 1 X X X X X Ideal Gas law
NRTL-2 2 X X X X X Ideal Gas law
NRTL-RK 1 X X X Redlich-Kwong X
NRTL-HOC 1 X X X Hayden-O'Connell X
NRTL-NTH 1 X X Nothnagel X
An X indicates the parameters were regressed by AspenTech from experimental data in the Dortmund
Databank (DDB).
The NRTL model can descr ibe VLE and LLE of st r ongly nonideal solut ions. The
model r equir es binar y par amet er s. Many binar y par amet er s for VLE and LLE,
fr om lit er at ur e and fr om r egr ession of exper iment al dat a, ar e included in t he
ASPEN PLUS dat abanks. For det ails, see ASPEN PLUS Physical Property Data,
Chapt er 1.
2-44 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
You can model t he solubilit y of super cr it ical gases using Henr ys law. Henr y
coefficient s ar e available in t he ASPEN PLUS dat abanks for many solut es wit h
wat er and ot her solvent s (see ASPEN PLUS Physical Property Data, Chapt er 1).
The pr oper t y met hods wit h a vapor phase model t hat can be used up t o moder at e
pr essur es, have t he Poynt ing cor r ect ion included in t he liquid fugacit y coefficient
calculat ion (see t he t able labeled NRTL Pr oper t y Met hods on page 2-44.
Heat of mixing is calculat ed using t he NRTL model.
You can use separ at e dat a set s for t he NRTL binar y par amet er s t o model
pr oper t ies or equilibr ia at differ ent condit ions. It is also possible t o use one dat a
set for VLE and a second dat a set for LLE (use NRTL and NRTL-2) pr oper t y
met hods ar e ident ical except for t he dat a set number t hey use. For example, you
can use t hese pr oper t y met hods in differ ent flowsheet sect ions or column
sect ions.
Mi xture Types
The NRTL model can handle any combinat ion of polar and non-polar compounds,
up t o ver y st r ong nonidealit y.
Range
Par amet er s should be fit t ed in t he t emper at ur e, pr essur e, and composit ion r ange of
oper at ion. No component should be close t o it s cr it ical t emper at ur e.
Par amet er r equir ement s for t he NRTL act ivit y coefficient model ar e given in t he
t able labeled Par amet er s Requir ed for NRTL Pr oper t y Met hods on page 2-45. For
det ails about t he model, see Chapt er 3.
Physical Pr oper t y Met hods and Models 2-45
Ver sion 10
Chapter 2
Parameters Required for NRTL Property Methods
Thermodynamic Properties Models Parameter Requirements
Liquid mixture
Fugacity coefficient,
Gibbs energy
Enthalpy,
Entropy
Density
NRTL liquid activity coefficient
Extended Antoine vapor pressure
Henrys constant
Brelvi-OConnell
Ideal gas heat capacity
Watson/DIPPR heat of vaporization
NRTL liquid activity coefficient
Rackett
NRTL
PLXANT
Solvent: VC,
Solute-solvent: HENRY
Solvent: TC, PC, (ZC or RKTZRA), Solute:
(VC or VLBROC)
CPIG or CPIGDP
TC, (DHVLWT or DHVLDP)
NRTL
TC, PC, (VC or VCRKT),
(ZC or ZCRKT)
UNIFAC
UNIFAC is an act ivit y coefficient model, like NRTL or UNIQUAC. But it is based
on gr oup cont r ibut ions, r at her t han molecular cont r ibut ions. Wit h a limit ed
number of gr oup par amet er s and gr oup-gr oup int er act ion par amet er s, UNIFAC
can pr edict act ivit y coefficient s. The following table list s t he pr oper t y met hods based
on UNIFAC.
2-46 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
UNIFAC Property Methods
Property
Method Name
Model
Name
Parameters
Rev. Yr
Tmin
/K
Tmax
/K
Henry
Lit
Reg
Vapor Phase
EOS Name
Poynting
Correction
UNIFAC UNIFAC 5, 1991 290 420 X X Redlich-
Kwong
X
UNIF-LL UNIFAC , 1991 280 310 X X Redlich-
Kwong
X
UNIF-HOC UNIFAC 5, 1991 290 420 X X Hayden-
O'Connell
X
UNIF-DMD DMD-UNIF 1, 1993 290 420 X X Redlich-
Kwong-
Soave
X
UNIF-LBY LBY-UNIF , 1987 290 420 X X Ideal Gas
law
An X indicates the parameters were regressed by AspenTech from experimental data in the Dortmund
Databank (DDB).
The or iginal ver sion of UNIFAC can pr edict VLE and LLE, using t wo set s of
par amet er s. So t her e ar e t wo pr oper t y met hods based on t he or iginal UNIFAC
model, one using t he VLE dat as et (UNIFAC), t he ot her using t he LLE dat a set
(UNIF-LL).
Ther e ar e t wo modificat ions t o t he UNIFAC model. They ar e named aft er t he
locat ion of t he univer sit ies wher e t hey wer e developed: Lyngby in Denmar k, and
Dor t mund in Ger many. The cor r esponding pr oper t y met hods ar e UNIF-LBY and
UNIF-DMD. Bot h modificat ions:
Include mor e t emper at ur e-dependent t er ms of t he gr oup-gr oup int er act ion
par amet er s
Pr edict VLE and LLE wit h a single set of par amet er s
Pr edict heat s of mixing bet t er
In t he Dor t mund modificat ion, t he pr edict ion for act ivit y coefficient s at infinit e
dilut ion is impr oved. For det ails on t he models, see Chapt er 3.
You can model t he solubilit y of super cr it ical gases using Henr ys law. Henr y
coefficient s ar e available in t he ASPEN PLUS dat abanks for many solut es wit h
wat er and ot her solvent s (see ASPEN PLUS Physical Property Data, Chapt er 1).
The opt ions set s wit h a vapor phase model t hat can be used up t o moder at e
pr essur es, have t he Poynt ing cor r ect ion included in t he liquid fugacit y coefficient
calculat ion (see t he t able labeled UNIFAC Pr oper t y Met hods on page 2-47).
Heat s of mixing ar e calculat ed using t he UNIFAC or modified UNIFAC models.
Physical Pr oper t y Met hods and Models 2-47
Ver sion 10
Chapter 2
Mi xture Types
The UNIFAC and modified UNIFAC models can handle any combinat ion of polar
and nonpolar compounds. Dissolved gas in solut ions can be handled wit h Henrys
Law. However , gas-solvent int er act ions ar e not pr edict ed by UNIFAC.
Range
No component should be close t o it s cr it ical t emper at ur e. Appr oximat e t emper at ur e
r anges ar e indicat ed in t he t able labeled UNIFAC Pr oper t y Met hods on page 2-47.
The par amet er set s for all UNIFAC models ar e r egular ly r evised and ext ended.
The t able labeled UNIFAC Pr oper t y Met hods on page 2-47 gives t he r evision
number cur r ent ly used in ASPEN PLUS. For det ails on t he par amet er s used, see
Physical Property Data, Chapt er 3.
The minimum par amet er r equir ement s for t he UNIFAC and modified UNIFAC
models ar e given in t he following t able. For det ails about t he models, see Chapt er
3.
Parameters Required for the UNIFAC Property Methods
Thermodynamic Properties Models Parameter Requirements
Liquid mixture
Fugacity coefficient, UNIFAC UFGRPD
Gibbs energy or:
Dortmund modified UNIFAC UFGRPL
or:
Lyngby modified UNIFAC PLXANT
Extended Antoine vapor pressure Solvent: VC,
Henrys constant Solute-solvent: HENRY
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA), Solute:
(VC or VLBROC)
Enthalpy, Entropy Ideal gas heat capacity CPIG or CPIGDP
Watson/DIPPR heat of vaporization TC, (DHVLWT or DHVLDP)
UNIFAC UFGRP
or:
Dortmund modified UNIFAC UFGRPD
or:
Lyngby modified UNIFAC UFGRPL
Density Rackett TC, PC, (VC or VCRKT), (ZC or ZCRKT)
2-48 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
UNIQUAC
The pr oper t y met hods t hat use t he UNIQUAC act ivit y coefficient model ar e
list ed in t he following table.
UNIQUAC Property Methods
Binary Parameters
Property Method
Name
Dataset Number VLE
Lit
Reg
LLE
Lit
Reg
Henry
Lit
Reg
Vapor Phase
EOS Name
Poynting
Correction
UNIQUAC 1 X X X X X X Ideal Gas law
UNIQ-2 2 X X X X X X Ideal Gas law
UNIQ-RK 1 X X X Redlich-Kwong X
UNIQ-HOC 1 X X X Hayden-O'Connell X
UNIQ-NTH 1 X X Nothnagel X
An X indicates the parameters were regressed by AspenTech from experimental data in the Dortmund
Databank (DDB).
The UNIQUAC model can describe st rongly nonideal liquid solut ions and liquid-
liquid equilibria. The model requires binary paramet ers. Many binary paramet ers
for VLE and LLE, fr om lit er at ur e and fr om r egr ession of exper iment al dat a, ar e
included in t he ASPEN PLUS dat abanks (for det ails, see ASPEN PLUS Physical
Property Data, Chapt er 1).
You can model t he solubilit y of super cr it ical gases using Henr ys law. Henr y
coefficient s ar e available fr om t he dat abank (see ASPEN PLUS Physical Property
Data, Chapt er 1).
The pr oper t y met hods wit h a vapor phase model t hat can be used up t o moder at e
pr essur es, have t he Poynt ing cor r ect ion included in t he liquid fugacit y coefficient
calculat ion (see t he t able labeled UNIQUAC Pr oper t y Met hods on page 2-49).
Heat s of mixing ar e calculat ed using t he UNIQUAC model.
You can use separ at e dat a set s for t he UNIQUAC binar y par amet er s t o model
pr oper t ies or equilibr ia at differ ent condit ions. It is also possible t o use one dat a
set for VLE and a second dat a set for LLE (use UNIQUAC and UNIQ-2). The
pr oper t y met hods ar e ident ical except for t he dat a set number t hey use. For
example, you can use t hese opt ions set s in differ ent flowsheet sect ions or column
sect ions.
Physical Pr oper t y Met hods and Models 2-49
Ver sion 10
Chapter 2
Mi xture Types
The UNIQUAC model can handle any combinat ion of polar and non-polar
compounds, up t o ver y st r ong nonidealit y.
Range
Par amet er s should be fit t ed in t he t emper at ur e, pr essur e, and composit ion r ange of
oper at ion. No component should be close t o it s cr it ical t emper at ur e.
Par amet er r equir ement s for t he UNIQUAC act ivit y coefficient model ar e given in
t he following t able. For det ails about t he model, see Chapt er 3.
Parameters Required for UNIQUAC Property Methods
Thermodynamic Properties Models Parameter Requirements
Liquid mixture
Fugacity coefficient,
Gibbs energy UNIQUAC liquid activity coefficient GMUQR, GMUQQ, UNIQ
Extended Antoine vapor pressure PLXANT
Henrys constant Solvent: VC,
Solute-solvent: HENRY
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA),
Solute: (VC or VLBROC)
Enthalpy,
Entropy Ideal gas heat capacity CPIG or CPIGDP
Watson/DIPPR heat of vaporization TC, (DHVLWT or DHVLDP)
UNIQUAC liquid activity coefficient GMUQR, GMUQQ, UNIQ
Density Rackett TC, PC, (VC or VCRKT), (ZC or ZCRKT)
Van Laar
The pr oper t y met hods t hat use t he Van Laar act ivit y coefficient model ar e list ed
in t he following table.
2-50 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Van Laar Property Methods
Binary Parameters
Property Method
Name
Dataset number VLE
Lit
Reg
LLE
Lit
Reg
Henry
Lit
Reg
An X indicates the parameters were regressed by AspenTech from experimental data in the Dortmund
Databank (DDB).
The Van Laar model can descr ibe nonideal liquid solut ions wit h posit ive deviat ions
fr om Raoult s law (see Chapt er 1). The model r equir es binar y par amet er s.
You can model t he solubilit y of super cr it ical gases using Henr ys law. Henr y
coefficient s ar e available fr om t he ASPEN PLUS dat abank (see ASPEN PLUS
Physical Property Data, Chapt er 1).
The pr oper t y met hods wit h a vapor phase model t hat can be used up t o moder at e
pr essur es, have t he Poynt ing cor r ect ion included in t he liquid fugacit y coefficient
calculat ion (see t he t able labeled Van Laar Pr oper t y Met hods on page 2-51).
Heat s of mixing ar e calculat ed using t he Van Laar model.
You can use separ at e dat a set s t o model pr oper t ies or equilibr ia at differ ent
condit ions (use VANLAAR and VANL-2). The pr oper t y met hods ar e ident ical
except for t he dat a set number t hey use. For example, you can use t hese pr oper t y
met hods in differ ent flowsheet or column sect ions.
Mi xture Types
The Van Laar model can handle any combinat ion of polar and non-polar
compounds wit h posit ive deviat ions fr om Raoult s law.
Range
Par amet er s should be fit t ed in t he t emper at ur e r ange of oper at ion. No component
should be close t o it s cr it ical t emper at ur e.
Par amet er r equir ement s for t he Van Laar act ivit y coefficient model ar e given in
t he t able labeled Par amet er s Requir ed for Van Laar Pr oper t y Met hods on page 2-
51. For det ails about t he model, see Chapt er 3.
Physical Pr oper t y Met hods and Models 2-51
Ver sion 10
Chapter 2
Parameters Required for Van Laar Property Methods
Thermodynamic Properties Models Parameter Requirements
Liquid mixture
Fugacity coefficient,
Gibbs energy Van Laar liquid activity coefficient VANL
Extended Antoine vapor pressure PLXANT
Henrys constant Solvent: VC,
Solute-solvent: HENRY
Brelvi-OConnell Solvent: TC, PC, ( ZC or RKTZRA),
Solute: (VC or VLBROC)
Enthalpy,
Entropy Ideal gas heat capacity CPIG or CPIGDP
Watson/DIPPR heat of vaporization TC, (DHVLWT or DHVLDP)
Van Laar liquid activity coefficient VANL
Density Rackett TC, PC, (VC or VCRKT), (ZC or ZCRKT)
Wi lson
The pr oper t y met hods t hat use t he Wilson act ivit y coefficient model ar e list ed in
t he following table.
Wilson Property Methods
Binary Parameters
Property Method
Name
Dataset number VLE
Lit
Reg
LLE
Lit
Reg
Henry
Lit
Reg
Vapor Phase
EOS Name
Poynting
Correction
WILSON 1 X X X X Ideal Gas law
WILS-2 2 X X X X Ideal Gas law
WILS-GLR 1 X X Ideal Gas law ----
WILS-LR 1 X X Ideal Gas law ----
WILS-RK 1 X X X Redlich-Kwong X
WILS-HOC 1 X X X Hayden-O'Connell X
WILS-NTH 1 X X Nothnagel X
An X indicates the parameters were regressed by AspenTech from experimental data in the Dortmund
Databank (DDB).
2-52 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
The Wilson model can descr ibe st r ongly nonideal liquid solut ions. The model
cannot handle t wo liquid phases. In t hat case use NRTL or UNIQUAC. The model
r equir es binar y par amet er s. Many binar y par amet er s for VLE, fr om lit er at ur e and
fr om r egr ession of exper iment al dat a, ar e included in t he ASPEN PLUS dat abanks
(for det ails, see ASPEN PLUS Physical Property Data, Chapt er 1).
The solubilit y of super cr it ical gases can be modeled using Henr ys law. Henr y
coefficient s ar e available fr om t he dat abank for many solut es wit h wat er and
ot her solvent s (see ASPEN PLUS Physical Property Data, Chapt er 1).
The pr oper t y met hods wit h a vapor phase model t hat can be used up t o moder at e
pr essur es, have t he Poynt ing cor r ect ion included in t he liquid fugacit y coefficient
calculat ion (see t he t able labeled Wilson Pr oper t y Met hods on page 2-52).
Heat s of mixing ar e calculat ed using t he Wilson model.
You can use separ at e dat a set s for t he Wilson binar y par amet er s t o model
pr oper t ies or equilibr ia at differ ent condit ions (use WILSON and WILS-2). The
pr oper t y met hods ar e ident ical except for t he dat a set number t hey use. For
example, you can use t hese pr oper t y met hods in differ ent flowsheet or column
sect ions.
Mi xture Types
The Wilson model can handle any combinat ion of polar and non-polar compounds,
up t o ver y st r ong nonidealit y.
Range
Par amet er s should be fit t ed in t he t emper at ur e, pr essur e, and composit ion r ange of
oper at ion. No component should be close t o it s cr it ical t emper at ur e.
Par amet er r equir ement s for t he Wilson act ivit y coefficient model ar e given in t he
t able below. For det ails about t he model, see Chapt er 3.
Parameters Required for the Wilson Property Methods
Thermodynamic Properties Models Parameter Requirements
Liquid mixture
Fugacity coefficient,
Gibbs energy Wilson liquid activity coefficient WILSON
Extended Antoine vapor pressure PLXANT
Henrys constant Solvent: VC, Solute-solvent: HENRY
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA), Solute: (VC or
VLBROC)
Physical Pr oper t y Met hods and Models 2-53
Ver sion 10
Chapter 2
Parameters Required for the Wilson Property Methods (continued)
Thermodynamic Properties Models Parameter Requirements
Enthalpy,
Entropy
Ideal gas heat capacity CPIG or CPIGDP
Watson/DIPPR heat of
vaporization
TC, (DHVLWT or DHVLDP)
Wilson liquid activity coefficient WILSON
Density Rackett TC, PC, (VC or VCRKT), (ZC or ZCRKT)
Common Models
The following table descr ibes t he models common t o act ivit y coefficient pr oper t y
met hods and t heir par amet er r equir ement s.
Parameters Required For Common Models
General
Property/Purpose Parameter Requirements
Mass balance, Conversion Mass-basisMole-basis MW
Conversion Stdvol-basisMole-basis VLSTD
Using Free-water option: solubility of water in organic phase WATSOL
Enthalpy of reaction DHFORM
Gibbs energy of reaction DGFORM
Transport Properties
Property Models Parameter Requirements
Vapor mixture
Viscosity Chapman-Enskog-Brokaw/ DIPPR MW; (MUP and (STKPAR or LJPAR)) or
MUVDIP
Thermal conductivity Stiel-Thodos low pres./ DIPPR MW or KVDIP
Diffusivity Chapman-Enskog-Wilke-Lee MW; MUP and (STKPAR or LJPAR)
Surface tension Hakim-Steinberg-Stiel/ DIPPR (TC, PC, OMEGA) or SIGDIP
Liquid mixture
Viscosity Andrade/DIPPR MULAND or MULDIP
Thermal Conductivity Sato-Riedel/DIPPR (MW, TC, TB) or KLDIP
Diffusivity Wilke-Chang MW, VB
2-54 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Electrolyte Property Methods
The following t able lists property methods for elect r olyt e solut ions. Elect r olyt e
solut ions ar e ext r emely nonideal because of t he pr esence of char ged species.
Pr oper t y met hods based on cor r elat ions can handle specific component s under
well-descr ibed condit ions; r igor ous models ar e gener ally applicable. The
ELECNRTL propert y met hod can handle mixed solvent syst ems at any
concent r at ion. The PITZER pr oper t y met hod is accur at e for aqueous solut ions up
t o 6M. Binar y par amet er s for many component pair s ar e available in t he
dat abanks. B-PITZER is pr edict ive but less accur at e. You can use t hese pr oper t y
met hods at low pr essur es (maximum 10 at m). ENRTL-HF is similar t o
ELECNRTL, but wit h a vapor phase model for t he st r ong HF associat ion. This
pr oper t y met hod should be used at low pr essur es (maximum 3 at m). Per manent
gases in liquid solut ion can be modeled by using Henr ys law. Tr anspor t pr oper t ies
ar e calculat ed by st andar d cor r elat ions wit h cor r ect ions for t he pr esence of
elect r olyt es.
Electrolyte Property Methods
Correlation-Based Property Methods
Property Method Correlation System
AMINES Kent-Eisenberg MEA, DEA, DIPA, DGA
APISOUR API Sour water correlation H2O, NH3, CO2, H2S
Activity Coefficient Model-Based Property Methods
Property Method Gamma Model Name Vapor Phase EOS Name
ELECNRTL Electrolyte NRTL Redlich-Kwong
ENRTL-HF Electrolyte NRTL HF equation of state
ENRTL-HG Electrolyte NRTL Redlich-Kwong
PITZER Pitzer Redlich-Kwong-Soave
PITZ-HG Pitzer Redlich-Kwong-Soave
B-PITZER Bromley-Pitzer Redlich-Kwong-Soave
Common Models For Rigorous Property Methods
Property Model
Vapor pressure Extended Antoine
Liquid molar volume Rackett/Clarke
continued
Physical Pr oper t y Met hods and Models 2-55
Ver sion 10
Chapter 2
Common Models For Rigorous Property Methods (continued)
Property Model
Heat of vaporization Watson/DIPPR
Infinite dilution heat capacity Criss-Cobble
Vapor viscosity Chapman-Enskog-Brokaw
Vapor thermal conductivity Stiel-Thodos/DIPPR
Vapor diffusivity Dawson-Khoury-Kobayashi
Surface tension Hakim-Steinberg-Stiel/DIPPR - Onsager-Samara
Liquid viscosity Andrade/DIPPR - Jones-Dole
Liquid thermal conductivity Sato-Riedel/DIPPR - Riedel
Liquid diffusivity Wilke-Chang - Nernst-Hartley
Do not use t he elect r olyt e pr oper t y met hods for nonelect r olyt e syst ems. See
Classificat ion of Pr oper t y Met hods and Recommended Use on page 2-2 for mor e
help.
For gener al t her modynamic pr inciples, see Chapt er 1. Chapt er 5 cont ains
specifics on elect r olyt e simulat ion. For det ails on met hods, see Chapt er 4. The
pr oper t y met hod descr ipt ions give t he minimum par amet er r equir ement s for t he
t her modynamic pr oper t y models used, also of t he common t her modynamic
pr oper t y models. The gener al and t r anspor t pr oper t y par amet er r equir ement s for
coefficient -based pr oper t y met hods ar e in t he t able labeled Par amet er s Requir ed
for Gener al and Tr anspor t Pr oper t y Models on page 2-66. For det ails on models,
see Chapt er 3.
AMINES
The AMINES pr oper t y met hoduses t he Kent -Eisenber g met hod for K-values and
ent halpy. It is designed for syst ems cont aining wat er , one of four et hanolamines,
hydr ogen sulfide, car bon dioxide, and ot her component s t ypically pr esent in gas-
sweet ening pr ocesses. It can be used for t he following four amines:
Monoet hanolamine (MEA)
Diet hanolamine (DEA)
Diisopr opanolamine (DIPA)
Diglycolamine (DGA)
2-56 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Range
Use t he AMINES pr oper t y met hod for amine syst ems wit h r anges of:
MEA DEA DIPA DGA
Temperature (F) 90 280 90 275 90 260 90 280
Maximum H2s or CO2 Loading (moles
gas/mole amine)
0.5 0.8 0.75 0.5
Amine Concentration in Solution (mass
percent)
15 30 20 40 20 40 40 65
If t he amine concent r at ion is out side t he r ecommended r ange, t he Chao-Seader
met hod is used for K-values (only for t hat par t icular pr oper t y evaluat ion).
Refer t o t he following t able for par amet er r equir ement s for t his pr oper t y met hod.
Parameters Required for the AMINES Property Method
General
Property/Purpose Parameter Requirements
Mass balance, Conversion Mass-basisMole-basis MW
Conversion Stdvol-basisMole-basis VLSTD
Using free-water option: solubility of water in organic phase WATSOL
Enthalpy of reaction DHFORM
Gibbs energy of reaction DGFORM
Thermodynamic Properties
Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient
Density
Redlich-Kwong, TC; PC
Enthalpy, entropy Ideal gas heat capacity/DIPPR CPIG or CPIGDP
Liquid mixture
Fugacity coefficient
Gibbs energy
Scatchard-Hildebrand activity coefficient TC; DELTA; VLCVT1; GMSHVL
Chao-Seader pure component fugacity
coefficient
TC; PC; OMEGA
continued
Physical Pr oper t y Met hods and Models 2-57
Ver sion 10
Chapter 2
Thermodynamic Properties (continued)
Properties Models Parameter Requirements
Extended Antoine vapor pressure (amines and
water only)
PLXANT
Kent-Eisenberg (H2S and CO2 only)
Enthalpy, entropy Watson heat of vaporization and DIPPR model TC; PC;DHVLWT or DHVLDP
Density Rackett molar volume TC; PC: VC or VCRKT; ZC or ZCRKT
Transport Properties
Properties Models Parameter Requirements
Vapor mixture Dean-Stiel
Viscosity MW; (MUP and (STKPAR or LJPAR)) or
MUVDIP; TC, PC, VC
Thermal conductivity Stiel-Thodos MW, TC, PC, VC, ZC
Diffusivity Dawson-Khoury-Kobayaski MW; MUP and (STKPAR or LJPAR); VC
Surface tension Hakim-Steinberg-Stiel/ DIPPR (TC, PC, OMEGA) or SIGDIP
Liquid mixture
Viscosity Andrade/DIPPR MULAND or MULDIP
Thermal Conductivity Sato-Riedel/DIPPR (MW, TC, TB) or KLDIP
Diffusivity Wilke-Chang MW, VB
APISOUR
The APISOUR pr oper t y met hod:
Uses t he API pr ocedur e for K-values and ent halpy of sour wat er syst ems.
Is designed for sour wat er syst ems cont aining only wat er , ammonia, hydr ogen
sulfide and car bon dioxide.
Is applicable in t he t emper at ur e r ange of 20 140C.
Has an over all aver age er r or bet ween measur ed and pr edict ed par t ial
pr essur es of about 30% for ammonia, car bon dioxide, and hydr ogen sulfide.
Does not r equir e any user -supplied par amet er s.
Is r ecommended for fast simulat ion of sour wat er syst ems at limit ed
concent r at ion. For mor e accur at e r esult s, use t he ELECNRTL pr oper t y met hod.
Par amet er r equir ement s for t he APISOUR pr oper t y met hod ar e list ed in t he
following table.
2-58 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Parameters Required for the APISOUR Property Method
General
Property/Purpose Parameter Requirements
Mass balance, Conversion Mass-basisMole-basis MW
Conversion Stdvol-basisMole-basis VLSTD
Using Free-water option: solubility of water in organic phase WATSOL
Enthalpy of reaction DHFORM
Gibbs energy of reaction DGFORM
Transport Properties
Properties Models Parameter Requirements
Vapor mixture
Viscosity Chapman-Enskog-Brokaw/ DIPPR MW; (MUP and (STKPAR or LJPAR)) or
MUVDIP
Thermal conductivity Stiel-Thodos low pres./ DIPPR MW or KVDIP
Diffusivity Chapman-Enskog-Wilke-Lee MW; MUP and (STKPAR or LJPAR)
Surface tension Hakim-Steinberg-Stiel/ DIPPR (TC, PC, OMEGA) or SIGDIP
Liquid mixture
Viscosity Andrade/DIPPR MULAND or MULDIP
Thermal Conductivity Sato-Riedel/DIPPR (MW, TC, TB) or KLDIP
Diffusivity Wilke-Chang MW, VB
ELECNRTL
The ELECNRTL pr oper t y met hodis t he most ver sat ile elect r olyt e pr oper t y met hod.
It can handle ver y low and ver y high concent r at ions. It can handle aqueous and
mixed solvent syst ems.
The ELECNRTL is fully consist ent wit h t he NRTL-RK pr oper t y met hod: t he
molecular int er act ions ar e calculat ed exact ly t he same way, t her efor e
ELECNRTL can use t he dat abank for binar y molecular int er act ion par amet er s
for t he NRTL-RK pr oper t y met hod.
Many binar y and pair par amet er s and chemical equilibr ium const ant s fr om
r egr ession of exper iment al dat a ar e included in ASPEN PLUS dat abanks. See
ASPEN PLUS Physical Property Data, Chapt er 2, for det ails on t he syst ems
included, t he sour ces of t he dat a, and t he r anges of applicat ion.
Physical Pr oper t y Met hods and Models 2-59
Ver sion 10
Chapter 2
The solubilit y of super cr it ical gases can be modeled using Henr ys law. Henr y
coefficient s ar e available fr om t he dat abank (see Chapt er 1).
Heat s of mixing ar e calculat ed using t he elect r olyt e NRTL model.
The Redlich-Kwong equat ion of st at e is used for all vapor phase pr oper t ies,
which cannot model associat ion behavior in t he vapor phase as occur s wit h
car boxylic acids or HF. For car boxylic acids, choose Hayden-OConnell or
Not hnagel; for HF choose ENRTL-HF.
Mi xture Types
Any liquid elect r olyt e solut ion unless t her e is associat ion in t he vapor phase.
Range
Vapor phase pr oper t ies ar e descr ibed accur at ely up t o medium pr essur es.
Int er act ion par amet er s should be fit t ed in t he r ange of oper at ion.
The par amet er r equir ement s for t he ELECNRTL pr oper t y met hod ar e given in
t he following t able, Par amet er s Requir ed for t he ELECNRTL Pr oper t y Met hod,
and Par amet er s Requir ed for Gener al and Tr anspor t Pr oper t y Models on page 2-
66. For det ails about t he model see Chapt er 3.
Parameters Required for the ELECNRTL Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density Redlich-Kwong TC, PC
Enthalpy,
Entropy,
Gibbs energy
[Ideal gas heat capacity/
DIPPR/
Barin correlation
and
Redlich-Kwong
CPIG or
CPIGDP or
CPIXP1, CPIXP2, CPIXP3]
TC, PC
Liquid mixture
Fugacity coefficient,
Gibbs energy
Electrolyte NRTL Mol.: CPDIEC
Ion: RADIUS
Mol.-Mol.: NRTL
Mol.-Ion, Ion-Ion: GMELCC, GMELCD
GMELCE, GMELCN
Extended Antoine vapor pressure PLXANT
Henrys constant Solvent: VC, Mol. solute-solvent: HENRY
continued
2-60 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Parameters Required for the ELECNRTL Property Method (continued)
Thermodynamic Properties Models Parameter Requirements
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA), Mol.
solute: (VC or VLBROC)
Enthalpy,
Entropy
[Ideal gas heat capacity/
DIPPR
and
Watson/DIPPR heat of vaporization
or
[Infinite dilution heat capacity / Criss-Cobble
Electrolyte NRTL
CPIG or
CPIGDP
Solvent: TC, (DHVLWT or DHVLDP)]
Ions: CPAQ0 or
Ions: IONTYP, S025C ]
Mol.: CPDIEC
Ion: RADIUS
Mol.-Mol.: NRTL
Mol.-Ion, Ion-Ion: GMELCC, GMELCD
GMELCE, GMELCN
Density Rackett/Clarke Mol.: TC, PC, (VC or VCRKT), (ZC or ZCRKT)
Ion-ion: VLCLK
Solid pure (and mixture)
Enthalpy,
Entropy
Solids heat capacity polynomial/ Barin
correlation
CPSP01 or CPSXP1 to CPSXP7
Density Solids molar volume polynomial VSPOLY
ENRTL-HF
The ENRTL-HF pr oper t y met hod is similar t o t he ELECNRTL pr oper t y met hod
except t hat it uses t he HF equat ion of st at e as vapor phase model.
The HF equat ion of st at e pr edict s t he st r ong associat ion of HF in t he vapor phase
at low pr essur es. Associat ion (mainly hexamer izat ion) affect s bot h vapor phase
pr oper t ies (for example, ent halpy and densit y) and liquid phase pr oper t ies (for
example, ent halpy).
A dat a package is available t o accur at ely model vapor and liquid phases of HF
and wat er mixt ur es in any pr opor t ion.
Mi xture Types
The HF equat ion of st at e r eliably pr edict s t he st r ong associat ion effect s of HF in
t he vapor phase. The liquid can be any liquid elect r olyt e solut ion.
Range
Usage should not exceed pr essur es of 3 at m.
Physical Pr oper t y Met hods and Models 2-61
Ver sion 10
Chapter 2
Par amet er s for t he HF equat ion of st at e ar e built -in for t emper at ur es up t o 373
K. Par amet er s can be ent er ed and r egr essed using t he ASPEN PLUS Dat a
Regr ession Syst em (DRS) if needed. For det ails about t he model, see Chapt er 3.
For t he par amet er r equir ement s for t he elect r olyt e NRTL model, r efer t o t he
ELECNRTL pr oper t y met hod, in t he t able labeled Par amet er s Requir ed for t he
ELECNRTL Pr oper t y Met hod on page 2-59. For gener al and t r anspor t pr oper t y
par amet er r equir ement s, see t he t able labeled Par amet er s Requir ed for Gener al
and Tr anspor t Pr oper t y Models on page 2-66.
ENRTL-HG
The ENRTL-HG pr oper t y met hod is similar t o t he ELECNRTL pr oper t y met hod,
except it uses t he Helgeson model for st andar d pr oper t ies calculat ions. The
Helgeson model is a ver y accur at e and flexible equat ion of st at e t hat calculat es
st andar d ent halpy, ent r opy, Gibbs fr ee ener gy and volume for component s in
aqueous solut ions. The Helgeson model should pr ovide mor e accur at e ent halpy and
Gibbs fr ee ener gy of pr ocess st r eams up t o high t emper at ur es and pr essur es. The
model is also used t o calculat e Gibbs fr ee ener gy for use in est imat ing chemical
equilibr ium const ant s (for bot h equilibr ium and salt pr ecipit at ion r eact ions) when
t hey ar e missing. Equilibr ium const ant s calculat ed using t he Helgeson model have
been found t o be r easonably accur at e and ext r apolat e well wit h r espect t o
t emper at ur e.
Mi xture Types
Any liquid elect r olyt e solut ion is accept able, unless t her e is associat ion in t he vapor
phase.
Range
Vapor phase pr oper t ies ar e descr ibed accur at ely up t o medium pr essur es.
Int er act ion par amet er s should be fit t ed in t he r ange of oper at ion.
For par amet er r equir ement s for t he elect r olyt e NRTL model, see t he ELECNRTL
pr oper t y met hod, in t he t able labeled Par amet er s Requir ed for t he ELECNRTL
Pr oper t y Met hod on page 2-59. For gener al and t r anspor t pr oper t y par amet er
r equir ement s, see t he t able labeled Par amet er s Requir ed for Gener al and
Tr anspor t Pr oper t y Models on page 2-66.
2-62 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
PITZER
The PITZER pr oper t y met hod is based on an aqueous elect r olyt e act ivit y coefficient
model. It has no over lap wit h ot her act ivit y coefficient models. It can accur at ely
calculat e t he behavior of aqueous elect r olyt e solut ions wit h or wit hout molecular
solut es up t o 6 molal ionic st r engt h.
Many int er act ion par amet er s fr om r egr ession of exper iment al dat a ar e included
in dat abanks and dat a packages (for det ails, see Chapt er 1).
You can model t he solubilit y of super cr it ical gases using Henr ys law. Henr y
coefficient s ar e available fr om t he ASPEN PLUS dat abanks (see Chapt er 1).
Heat s of mixing ar e calculat ed using t he Pit zer model.
The Redlich-Kwong-Soave equat ion of st at e is used for t he vapor phase fugacit y
coefficient , all ot her vapor phase pr oper t ies ar e assumed ideal. Redlich-Kwong-
Soave cannot model associat ion behavior in t he vapor phase (for example,
car boxylic acids or HF). For car boxylic acids, choose a non-elect r olyt e act ivit y
coefficient model wit h Hayden-OConnell or Not hnagel; for HF choose ENRTL-
HF or WILS-HF.
Mi xture Types
You can use t he Pit zer model for any aqueous elect r olyt e solut ion up t o 6M ionic
st r engt h, not showing associat ion in t he vapor phase.
Range
Vapor phase fugacit ies ar e descr ibed accur at ely up t o medium pr essur es.
Int er act ion par amet er s should be fit t ed in t he r ange of oper at ion.
The par amet er r equir ement s for t he PITZER pr oper t y met hod ar e given in t he
t able labeled Par amet er s Requir ed for t he PITZER Pr oper t y Met hod on page 2-63
and t he t able labeled Par amet er s Requir ed for Gener al and Tr anspor t Pr oper t y
Models on page 2-66. For det ails about t he model, see Chapt er 3.
Physical Pr oper t y Met hods and Models 2-63
Ver sion 10
Chapter 2
Parameters Required for the PITZER Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density
Redlich-Kwong-Soave TC, PC, OMEGA
Enthalpy,
Entropy,
Gibbs energy
[Ideal gas heat capacity/
DIPPR/
Barin correlation
and
Redlich-Kwong
CPIG or
CPIGDP or
CPIXP1, CPIXP2, CPIXP3]
TC, PC, OMEGA
Liquid mixture
Fugacity coefficient,
Gibbs energy
Pitzer Cation-anion: GMPTB0, GMPTB1, GMPTB2,
GMPTB3, GMPTC
Cation-cation: GMPTTH
Anion-anion: GMPTTH
Cation1-cation2-common anion: GMPTPS
Anion1-anion2-common cation: GMPTPS
Molecule-ion, Mol. Mol.: GMPTB0,
GMPTB1, GMPTC
Extended Antoine vapor pressure PLXANT
Henry's constant Solvent: VC, Mol. Solute-solvent: HENRY
Brelvi-O'Connell Solvent: TC, PC, (ZC or RKTZRA), Mol.
Solute: (VC or VLBROC)
Enthalpy,
Entropy [Ideal gas heat capacity/ DIPPR
and
Watson/DIPPR heat of vaporization
or
[Infinite dilution heat capacity /
CPIG or
CPIGDP
Solvent: TC, (DHVLWT or DHVLDP)]
Ions: CPAQ0 or
Criss-Cobble Ions: IONTYP, S025C ]
Pitzer Cation-anion:
GMPTB0,GMPTB1,GMPTB2,GMPTB3,GMPT
C
Cation-cation: GMPTTH
Anion-anion: GMPTTH
Cation1-cation2-common anion: GMPTPS
Anion1-anion2-common cation: GMPTPS
Molecule-ion, Mol. Mol.:
GMPTB0,GMPTB1,GMPTC
Density Rackett/Clarke Mol.: TC, PC, (VC or VCRKT), (ZC or ZCRKT)
Ion-ion: VLCLK
continued
2-64 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
Parameters Required for the PITZER Property Method (continued)
Thermodynamic Properties Models Parameter Requirements
Solid pure (and mixture)
Enthalpy,
Entropy
Solids heat capacity polynomial/
Barin correlation
CPSP01 or
CPSXP1 to CPSXP7
Density Solids molar volume polynomial VSPOLY
B-PITZER
The B-PITZER pr oper t y met hod is based on t he simplified Pit zer aqueous
elect r olyt e act ivit y coefficient model, which neglect s t hir d or der int er act ions. It can
pr edict t he behavior of aqueous elect r olyt e solut ions up t o 6 molal ionic st r engt h. It
is not as accur at e as ELECNRTL or PITZER wit h fit t ed par amet er s. But , it is
bet t er t han using t hese pr oper t y met hods wit hout int er act ion par amet er s.
You can model t he solubilit y of super cr it ical gases using Henr ys law. Henr y
coefficient s ar e available fr om t he ASPEN PLUS dat abanks (see Chapt er 1).
Heat s of mixing ar e calculat ed using t he Br omley-Pit zer model.
The Redlich-Kwong-Soave equat ion of st at e is used for t he vapor phase fugacit y
coefficient . All ot her vapor phase pr oper t ies ar e assumed ideal. Redlich-Kwong-
Soave cannot model associat ion behavior in t he vapor phase (for example wit h
car boxylic acids or HF). For car boxylic acids, choose a non-elect r olyt e act ivit y
coefficient model wit h Hayden-OConnell or Not hnagel; for HF, choose ENRTL-
HF or WILS-HF.
Mi xture Types
You can use t he B-PITZER model for any aqueous elect r olyt e solut ion up t o 6M
ionic st r engt h, not showing associat ion in t he vapor phase.
Range
Vapor phase fugacit ies ar e descr ibed accur at ely up t o medium pr essur es.
Int er act ion par amet er s should be fit t ed in t he r ange of oper at ion.
The par amet er r equir ement s for t he B-PITZER pr oper t y met hod ar e given in t he
t able labeled Par amet er s Requir ed for t he B-PITZER Pr oper t y Met hod on page 2-
65 and t he t able labeled Par amet er s Requir ed for Gener al and Tr anspor t
Pr oper t y Models on page 2-66. For det ails about t he model, see Chapt er 3.
Physical Pr oper t y Met hods and Models 2-65
Ver sion 10
Chapter 2
Parameters Required for the B-PITZER Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density Redlich-Kwong-Soave TC, PC, OMEGA
Enthalpy,
Entropy,
Gibbs energy
[Ideal gas heat capacity/ DIPPR/ Barin
correlation and Redlich-Kwong
CPIG or CPIGDP or CPIXP1, CPIXP2,
CPIXP3] TC, PC, OMEGA
Liquid mixture
Fugacity coefficient,
Gibbs energy
Bromley-Pitzer Ionic: GMBPB, GMBPD Optional:
Cation-anion: GMPTB0, GMPTB1, GMPTB2,
GMPTB3
Cation-cation: GMPTTH
Anion-anion: GMPTTH
Molecule-ion, Mol.-Mol.: GMPTB0, GMPTB1
Extended Antoine vapor pressure PLXANT
Henrys constant Solvent: VC, Mol. Solute-solvent: HENRY
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA), Mol.
Solute: (VC or VLBROC)
Enthalpy,
Entropy
[Ideal gas heat capacity/ DIPPR and
Watson/DIPPR heat of vaporization or[Infinite
dilution heat capacity / Criss-Cobble
CPIG or
CPIGDP
Solvent: TC, (DHVLWT or DHVLDP)]
Ions: CPAQ0 or
Ions: IONTYP, S025C ]
Bromley-Pitzer Ionic: GMBPB, GMBPD
Optional:
Cation-anion: GMPTB0, GMPTB1, GMPTB2,
GMPTB3
Cation-cation:GMPTTH
Anion-anion: GMPTTH
Molecule-ion, Mol.-Mol.: GMPTB0, GMPTB1
Density Rackett/Clarke Mol.: TC, PC, (VC or VCRKT), (ZC or ZCRKT)
Ion-ion: VLCLK
Solid pure (and mixture)
Enthalpy,
Entropy
Solids heat capacity polynomial/ Barin
correlation
CPSP01 or CPSXP1 to CPSXP7
Density Solids molar volume polynomial VSPOLY
2-66 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Method
Descriptions
PITZ-HG
The PITZ-HG pr oper t y met hod is similar t o t he PITZER pr oper t y met hod, except it
uses t he Helgeson model for st andar d pr oper t ies calculat ions. The Helgeson model
is a ver y accur at e and flexible equat ion of st at e t hat calculat es st andar d ent halpy,
ent r opy, Gibbs fr ee ener gy and volume for component s in aqueous solut ions. The
Helgeson model should pr ovide mor e accur at e ent halpy and Gibbs fr ee ener gy of
pr ocess st r eams up t o high t emper at ur es and pr essur es. The Helgeson model is
also used t o calculat e Gibbs fr ee ener gy for use in est imat ing chemical equilibr ium
const ant s (for bot h equilibr ium and salt pr ecipit at ion r eact ions) when t hey ar e
missing. Equilibr ium const ant s calculat ed using t he Helgeson model have been
found t o be r easonably accur at e and ext r apolat e well wit h r espect t o t emper at ur e.
Mi xture Types
You can use t his pr oper t y met hod for any aqueous elect r olyt e solut ion up t o 6M
ionic st r engt h, not showing associat ion in t he vapor phase.
Range
Vapor phase fugacit ies ar e descr ibed accur at ely up t o medium pr essur es.
Int er act ion par amet er s should be fit t ed in t he r ange of oper at ion.
The par amet er r equir ement s for t he PITZ-HG pr oper t y met hod ar e given in t he
t able labeled Par amet er s Requir ed for t he PITZER Pr oper t y Met hod on page 2-63
and t he following t able, Par amet er s Requir ed for Gener al and Tr anspor t
Pr oper t y Models. For det ails about t he model, see Chapt er 3.
General and Transport Property Model Parameter
Requi rements
The following table descr ibes t he gener al and t r anspor t pr oper t y models used and
t heir par amet er r equir ement s for act ivit y coefficient -based elect r olyt e pr oper t y
met hods.
Parameters Required for General and Transport Property Models
General
Property/Purpose Parameter Requirements
Mass balance,
Continued
Physical Pr oper t y Met hods and Models 2-67
Ver sion 10
Chapter 2
General (continued)
Property/Purpose Parameter Requirements
Conversion Mass-
basisMole-basis
MW
Enthalpy of reaction Solvents, Mol. Solutes: DHFORM
Solids, Salts: (DHSFRM or CPSXP1 to CPSXP7)
Ions: DHAQFM
Gibbs energy of reaction Solvents, Mol. Solutes: DGFORM
Solids,Salts: (DGSFRM or CPSXP1 to CPSXP7)
Ions: DGAQFM
Transport Properties
Property Models Parameter Requirements
Vapor mixture
Viscosity Chapman-Enskog-Brokaw/ DIPPR MW; (MUP and (STKPAR or LJPAR)) or
MUVDIP
Thermal conductivity Stiel-Thodos low pres./ DIPPR MW or KVDIP
Diffusivity Chapman-Enskog-Wilke-Lee MW; MUP and (STKPAR or LJPAR)
Surface tension Hakim-Steinberg-Stiel/ DIPPR Onsager-
Samaras
Pure
Mixture
Pure
Mixture
Pure
Mixture
Pure
Mixture
Pure
Mixture
Pure
Mixture
Pure
Mixture
Pure
Mixture
Pure
Mixture
Wher e:
Z Z fcn T T V V
m m c m cm
( ) (1)
, ( , , , )
0
Mixing Rules:
V x x V
cm
a
i j cij
a
j i
*,
V T x x T V
cm
b
c i j cij cij
b
j i
V T x x V
cm
b
c i j ij cij
c
j i
Wher e:
a b c 4 5 3 35 5 . / ; . /
V V V
cij ij ci cj
( ) ( )
* * /
1
3 1 2
( )
/
i j
1 2
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TCBWR
T
ci
TC X 5.0 2000.0 TEMPERATURE
VCBWR
V
ci
*
VC X 0.001 3.5 MOLE-VOLUME
BWRGMA
i
OMEGA X -0.5 3.0
BWRKV
ij
0 X -5.0 1.0
BWRKT
ij
0 X -5.0 1.0
Binary interaction parameters BWRKV and BWRKT are available in AS PEN PLUS for a large number
of components. (S ee ASPEN PLUS Physical Pr oper t y Dat a , Chapter 1).
References
M.R. Br ul, C.T. Lin, L.L. Lee, and K.E. St ar ling, AIChE J ., Vol. 28, (1982) p.
616.
Br ul et al., Chem. Eng., (Nov., 1979) p. 155.
Wat anasir i et al., AIChE J ., Vol. 28, (1982) p. 626.
Hayden-OConnell
The Hayden-O'Connell equat ion-of-st at e calculat es t her modynamic pr oper t ies for
t he vapor phase. It is used in pr oper t y met hods NRTL-HOC, UNIF-HOC,
UNIQ-HOC, VANL-HOC, and WILS-HOC, and is r ecommended for nonpolar ,
polar , and associat ing compounds. Hayden-O'Connell incor por at es t he chemical
t heor y of dimer izat ion. This model account s for st r ong associat ion and solvat ion
effect s, including t hose found in syst ems cont aining or ganic acids, such as acet ic
acid. The equat ion-of-st at e is:
Z
B
RT
m
p
+ 1
Wher e:
B x x B T
i
i j
j
ij
( )
B B B B B B
ij free nonpolar ij free polar ij metastable ij bound ij chem ij
+ + + +
( ) ( ) ( ) ( ) ( )
3-10 Physical Pr oper t y Met hods and Models
Ver sion10
Property
Model
Descriptions
For nonpolar , non-associat ing species:
B f T
free nonpolar I np np np
( , , , ) , wit h
np np c c
g T p
1
( , , )
np np c
g T
2
( , )
, wher e
np
gyr
f r
2
( )
For polar , associat ing species:
B f T
free nonpolar fp fp np
3
( , , , ) , wit h
fp np np
g
3
( , , )
fp np np
g
4
( , , ) , wher e
5
( , , , )
np np np
T p,
For chemically bonding species:
B B f T
metastable bound c c
+
4
( , , , ) p , and
B f T
chem c c
5
( , , , )
c np np
g
3
( , , )
c np np
g
6
( , , , )
Cross-Interactions
The pr evious equat ions ar e valid for dimer izat ion and cr oss-dimer izat ion if t hese
mixing r ules ar e applied:
+ +
_
,
0 7 0 6
1 1
1 2
. ( ) .
/
i j
i j
( )
/
i j
1 2
+ +
_
,
0 7 0 6
1 1
1 2
. ( ) .
/
i j
i j
( )
/
i j
1 2
np
n pi n pj
+ ( )
, ,
2
Physical Pr oper t y Met hods and Models 3-11
Ver sion 10
Chapter 3
p p p ( )
/
i j
1 2
0 unless a special solvat ion cont r ibut ion can be just ified (for example, i and j
ar e in t he same class of compounds). Many values ar e pr esent in ASPEN
PLUS.
Chemi cal Theory
When a compound wit h st r ong associat ion ( . ) 45 is pr esent in a mixt ur e, t he
ent ir e mixt ur e is t r eat ed accor ding t o t he chemical t heor y of dimer izat ion.
The chemical r eact ion for t he gener al case of a mixt ur e of dimer izing component s
i and j is:
K
ij
i j ij +
Wher e i and j r efer t o t he same component .
The equat ion-of-st at e becomes:
pV
RT
n
Bp
RT
t
+
_
,
1 wit h B y B
i
nc
ij free ij
j
nc
1 1
( )
In t his case, molar volume is equal t o:
V
n
t
This r epr esent s t r ue t ot al volume over t he t r ue number of species n
t
. However ,
t he r epor t ed molar volume is:
V
n
a
This r epr esent s t he t r ue t ot al volume over t he appar ent number of species n
a
. If
dimer izat ion does not occur , n
a
is defined as t he number of species.
V
n
a
r eflect s
t he appar ent ly lower molar volume of an associat ing gas mixt ur e.
The chemical equilibr ium const ant for t he dimer izat ion r eact ion on pr essur e
basis K
p
, is r elat ed t o t he t r ue mole fr act ions and fugacit y coefficient s:
y
y y
K p
ij
i j
ij
i j
ij
3-12 Physical Pr oper t y Met hods and Models
Ver sion10
Property
Model
Descriptions
Wher e:
y
i
and y
j
= Tr ue mole fr act ions of monomer s
y
ij
= Tr ue mole fr act ion of dimer
i
= Tr ue fugacit y coefficient of component i
K
ij
= Equilibr ium const ant for t he dimer izat ion of i and j, on a
pr essur e basis
=
+ + ( ) ( ) / B B B RT
bound metastable chem ij ij
2
ij
= 1 for i=j
= 0 for i j
Appar ent mole fr act ions y
i
a
ar e r epor t ed, but in t he calculat ion r eal mole
fr act ions y
i
, y
j
, and y
ij
ar e used.
The heat of r eact ion due t o each dimer izat ion is calculat ed accor ding t o:
r m
r m
ij
H T
G
T
RT
K
T
2 2
d
d
d
( )
(ln )
d
The sum of t he cont r ibut ions of all dimer izat ion r eact ions, cor r ect ed for t he r at io
of appar ent and t r ue number of moles is added t o t he molar ent halpy depar t ur e
H H
m m
ig
.
Parameter Name/ Element Symbol Default MDS Lower Limit Upper Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
PC
p
ci
10
5
10
8
PRESSURE
RGYR
r
i
gyr
10
11
5 10
5 9
x
LENGTH
MUP
p
i
0.0
5 10
5 24
x
DIPOLEMOMENT
HOCETA
0.0 x
The binary parameters HOCETA for many component pairs are available in AS PEN PLUS . These
parameters are retrieved automatically when you specify any of the following property methods: NRTL-
HOC, UNIF-HOC, UNIQ-HOC, VANL-HOC, and WILS -HOC.
Physical Pr oper t y Met hods and Models 3-13
Ver sion 10
Chapter 3
References
J .G. Hayden and J .P. OConnell, "A Gener alized Met hod for Pr edict ing Second
Vir ial Coefficient s," Ind. Eng. Chem., Process Des. Dev. , Vol. 14,No. 3, (1974), pp.
209 216.
HF Equati on-of-State
HF for ms oligomer s in t he vapor phase. The non-idealit y in t he vapor phase is
found in impor t ant deviat ions fr om idealit y in all t her modynamic pr oper t ies. The
HF equat ion account s for t he vapor phase nonidealit ies. The model is based on
chemical t heor y and assumes t he for mat ion of hexamer s.
Species like HF t hat associat e linear ly behave as single species. For example,
t hey have a vapor pr essur e cur ve, like pur e component s. The component on
which a hypot het ical unr eact ed syst em is based is oft en called t he appar ent (or
par ent ) component . Appar ent component s r eact t o t he t r ue species. Elect r olyt e
Simulat ion, Chapt er 5, discusses appar ent and t r ue species. Abbot t and van Ness
(1992) pr ovide det ails and basic t her modynamics of r eact ive syst ems.
The t emper at ur e-dependent hexamer izat ion equilibr ium const ant , can fit t he
exper iment ally det er mined associat ion fact or s. The built -in funct ionalit y is:
10
0
1
2 3
log ln K C
C
T
C T C T + + + (1)
The const ant s C
0
and C
1
ar e fr om Long et al. (1943), and C
2
and C
3
ar e set t o 0.
The cor r elat ion is valid bet ween 270 and 330 K, and can be ext r apolat ed t o about
370 K (cf. sec. 4). Differ ent set s of const ant s can be det er mined by exper iment al
dat a r egr ession.
Molar Volume Calculation
The non-idealit y of HF is oft en expr essed using t he associat ion fact or , f,
indicat ing t he r at io of appar ent number of species t o t he r eal number or species.
Assuming t he ideal gas law for all t r ue species in t er ms of (p, V, T) behavior
implies:
pV
f
RT
m
_
,
1
(2)
Wher e t he t r ue number of species is given by
1
f
. The associat ion fact or is easily
det er mined fr om (p, V, T) exper iment s. For a cr it ical evaluat ion of dat a r efer t o
Vander zee and Rodenbur g (1970).
If only one r eact ion is assumed for a mixt ur e of HF and it s associat ed species,
(r efer t o Long et al., 1943), t hen:
3-14 Physical Pr oper t y Met hods and Models
Ver sion10
Property
Model
Descriptions
6
6
HF HF ( ) (3)
If p
1
r epr esent s t he t r ue par t ial pr essur e of t he HF monomer , and p
6
r epr esent s
t he t r ue par t ial pr essur e of t he hexamer , t hen t he equilibr ium const ant is
defined as:
K
p
p
6
1
6
( )
(4)
The t r ue t ot al pr essur e is:
p p p +
1 6
(5)
If all hexamer wer e dissociat ed, t he appar ent t ot al pr essur e would be t he
hypot het ical pr essur e wher e:
p p p p p
a
+ +
1 6 6
6 5 (6)
When physical idealit y is assumed, par t ial pr essur es and mole fr act ions ar e
pr opor t ional. The t ot al pr essur e in equat ion 5 r epr esent s t he t r ue number of
species. The appar ent t ot al pr essur e fr om equat ion 6 r epr esent s t he appar ent
number of species:
f
p
p
p p
p p
p p
p
y
a
+
+
+
+
1 6
1 6
6
6
6 5
1 5 (7)
Not e t hat t he out come of equat ion 7 is independent of t he assumpt ion of idealit y.
Equat ion 7 can be used t o comput e t he number of t r ue species
1
f
for a mixt ur e
cont aining HF, but t he associat ion fact or is defined differ ent ly.
If p
1
and p
6
ar e known, t he molar volume or densit y of a vapor cont aining HF
can be calculat ed using equat ions 2 and 7. The molar volume calculat ed is t he
t r ue molar volume for 1 appar ent mole of HF. This is because t he volume of 1
mole of ideal gas (t he t r ue molar volume per t r ue number of moles) is always
equal t o about 0.0224 m3/mol at 298.15 K.
True Mole Fraction (Partial Pressure) Calculation
If you assume t he ideal gas law for a mixt ur e cont aining HF, t he appar ent HF
mole fr act ion is:
y
p
p
p p
p p
a
a
a
+
+
1 1 6
6
6
5
(8)
Physical Pr oper t y Met hods and Models 3-15
Ver sion 10
Chapter 3
The denominat or of equat ion 8 is given by equat ion 6. The numer at or (t he
appar ent par t ial pr essur e of HF) is t he hypot het ical par t ial pr essur e only if all of
t he hexamer was dissociat ed. If you subst it ut e equat ion 4, t hen equat ion 8
becomes:
y
p K p
p K p
a
+
+
1 1
6
1
6
6
5
( )
( )
(9)
K is known fr om Long et al., or can be r egr essed fr om (p,V,T) dat a. The appar ent
mole fr act ion of HF, y
a
, is known t o t he user and t he simulat or , but
p
1
, or y
p
p
1
must also be known in or der t o calculat e t he t her modynamic
pr oper t ies of t he mixt ur e. Equat ion 9 must be solved for p
1
Equat ion 9 can be wr it t en as a polynomial in p
1
of degr ee 6:
K y p p py
a a
( )( ) 6 5 0
1
6
1
+ (9a)
A second or der Newt on-Raphson t echnique is used t o det er mine p
1
. Then p
6
can
be calculat ed by equat ion 5, and f is known (equat ion 7).
Gibbs Energy and Fugacity
The appar ent fugacit y coefficient is r elat ed t o t he t r ue fugacit y coefficient and
mole fr act ions:
ln ln ln
i
a
i a
y
y
_
,
1
(10)
Equat ion 10 r epr esent s a cor r ect ion t o t he ideal mixing t er m of t he fugacit y. The
r at io of t he t r ue number of species t o t he appar ent number of species is similar t o
t he cor r ect ion applied in equat ion 2. Since t he ideal gas law is assumed, t he
appar ent fugacit y coefficient is given by t he equat ion. All var iables on t he r ight
side ar e known.
i
a
a a
y
y
p
py
1 1
(11)
For pur e HF, y
a
1:
ln ln
*,
i
a
y
1
3-16 Physical Pr oper t y Met hods and Models
Ver sion10
Property
Model
Descriptions
Fr om t he fugacit y coefficient , t he Gibbs ener gy depar t ur e of t he mixt ur e or pur e
appar ent component s can be calculat ed:
G G RT RT
p
p
ig
i
a
ref
i
+
ln ln (12)
+
*, *,
ln ln
ig
i
a
ref
RT RT
p
p
(12a)
Enthalpy and Entropy
For t he ent halpy depar t ur e, t he heat of r eact ion is consider ed. For an ar bit r ar y
gas phase r eact ion:
v A v B v C v D
A B C D
+ + (13)
RT K RT
p p
p p
C
v
D
v
A
v
B
v
c D
A B
ln ln (14)
Wher e
i
*
is t he pur e component t her modynamic pot ent ial or molar Gibbs ener gy
of a component . Equat ion 4 r epr esent s t he fir st t wo t er ms of t he gener al equat ion
14. The second or t hir d equalit y r elat es t he equilibr ium const ant t o t he Gibbs
ener gy of r eact ion, which is t hus r elat ed t o t he ent halpy of r eact ion:
r m
r m
H T
G
T
RT
K
T
2 2
d
d
(ln )
(15)
All component s ar e assumed t o be ideal. The ent halpy depar t ur e is equal t o t he
heat of r eact ion, per appar ent number of moles:
H H
f
H
m m
ig
r m
1
(16)
H H
f
H
HF HF
ig
r m
* *,
1
(17)
Fr om t he Gibbs ener gy depar t ur e and ent halpy depar t ur e, t he ent r opy depar t ur e
can be calculat ed:
G H TS
m m m
(18)
Temper at ur e der ivat ives for t he t her modynamic pr oper t ies can be obt ained by
st r aight for war d differ ent iat ion.
Usage
The HF equat ion-of-st at e should only be used for vapor phase calculat ions. It is
not suit ed for liquid phase calculat ions.
Physical Pr oper t y Met hods and Models 3-17
Ver sion 10
Chapter 3
The HF equat ion-of-st at e can be used wit h any act ivit y coefficient model for
nonelect r olyt e VLE. Using t he Elect r olyt e NRTL model and t he dat a package
MHF2 is st r ongly r ecommended for aqueous mixt ur es (de Leeuw and Wat anasir i ,
1993).
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
ESHFK/1
C
0
43.65
ESHFK/2
C
1
-8910
ESHFK/3
C
2
0
ESHFK/4
C
3
0
References
M. M. Abbot t and H. C. van Ness, "Ther modynamics of Solut ions Cont aining
React ive Species, a Guide t o Fundament als and Applicat ions," Fluid Phase Eq.,
Vol. 77, (1992) pp. 53 119.
V. V. De Leeuw and S. Wat anasir i, "Modelling Phase Equilibr ia and Ent halpies
of t he Syst em Wat er and Hydr oflour ic Acid Using an HF Equat ion-of-st at e in
Conjunct ion wit h t he Elect r olyt e NRTL Act ivit y Coefficient Model," Paper
pr esent ed at t he 13t h Eur opean Seminar on Applied Ther modynamics, J une 9
12, Car r y-le-Rouet , Fr ance, 1993.
R. W. Long, J . H. Hildebr and, and W. E. Mor r ell, "The Polymer izat ion of Gaseous
Hydr ogen and Deut er ium Flour ides," J . Am. Chem. Soc., Vol. 65, (1943), pp.
182 187.
C. E. Vander zee and W. WM. Rodenbur g, "Gas Imper fect ions and
Ther modynamic Excess Pr oper t ies of Gaseous Hydr ogen Flour ide," J . Chem.
Ther modynamics, Vol. 2, (1970), pp. 461 478.
Ideal Gas
The ideal gas law (ideal gas equat ion-of-st at e) combines t he laws of Boyle and
Gay-Lussac. It models a vapor as if it consist ed of point masses wit hout any
int er act ions. The ideal gas law is used as a r efer ence st at e for equat ion-of-st at e
calculat ions, and can be used t o model gas mixt ur es at low pr essur es (wit hout
specific gas phase int er act ions).
The equat ion is:
p
RT
V
m
Wher e:
Z
( ) 0
= Compr essibilit y fact or of a simple fluid ( ) 0
Z
( ) 1
=
Deviat ion of t he compr essibilit y fact or of t he r eal fluid fr om Z
( ) 0
Z
( ) 0
and Z
( ) 1
ar e assumed univer sal funct ions of t he r educed t emper at ur e and
pr essur e.
Cur l and Pit zer (1958) wer e quit e successful in cor r elat ing t her modynamic and
volumet r ic pr oper t ies using t he above appr oach. Their applicat ion employed
t ables of pr oper t ies in t er ms of r educed t emper at ur e and pr essur e. A significant
weakness of t his met hod is t hat t he var ious pr oper t ies (for example, ent r opy
depar t ur e and ent halpy depar t ur e) will not be exact ly t her modynamically
consist ent wit h each ot her . Lee and Kesler (1975) over came t his dr awback by an
analyt ic r epr esent at ion of t he t ables wit h an equat ion-of-st at e. In addit ion, t he
r ange was ext ended by including new dat a.
In t he Lee-Kesler implement at ion, t he compr essibilit y fact or of any fluid has
been wr it t en in t er ms of a simple fluid and a r efer ence as follows:
Z Z Z Z
r
r +
( ) ( ) ( )
( ) ( )
0 0
Equat ions for t he ent halpy depar t ur e, Gibbs fr ee ener gy depar t ur e, and ent r opy
depar t ur e ar e obt ained fr om t he compr essibilit y fact or using st andar d
t her modynamic r elat ionships, t hus ensur ing t her modynamic consist ency.
In t he case of mixt ur es, mixing r ules (wit hout any binar y par amet er s) ar e used t o
obt ain t he mixt ur e values of t he cr it ical t emper at ur e and pr essur e, and t he
acent r ic fact or .
This equat ion has been found t o pr ovide a good descr ipt ion of t he volumet r ic and
t her modynamic pr oper t ies of mixt ur es cont aining nonpolar and slight ly polar
component s.
Symbol Parameter Name Default Definition
T
c
TCLK TC Critical temperature
P
c
PCLK PC Critical pressure
OMGLK OMEGA Acentric factor
References
B. I. Lee and M.G. Kesler , AIChEJ , Vol. 21, (1975), p. 510.
R. F. Cur l and K.S. Pit zer , Ind. Eng. Chem., Vol. 50, (1958), p. 265.
M. Benedict , G. B. Webb, and L. C. Rubin, J . Chem. Phys., Vol. 8, (1940), p. 334.
Lee-Kesler-Plcker
The Lee-Kesler -Plcker equat ion-of-st at e is t he basis for t he LK-PLOCK pr oper t y
met hod. This equat ion-of-st at e applies t o hydr ocar bon syst ems t hat include t he
common light gases, such as H S
2
and CO
2
. It can be used in gas-pr ocessing,
r efiner y, and pet r ochemical applicat ions.
The gener al for m of t he equat ion is:
Z Z Z Z
m m
o
R m
o
m
R
+
( )
Wher e:
Z f T T V V
m
o
o c m cm
( , , , )
Z f T T V V
m
R
R c m cm
( , , , )
3-20 Physical Pr oper t y Met hods and Models
Ver sion10
Property
Model
Descriptions
The f
o
and f
R
par amet er s ar e funct ions of t he BWR for m. The f
o
par amet er is
for a simple fluid, and f
R
is for r efer ence fluid n-oct ane.
p Z RT V
c cm c cm
/
The mixing r ules ar e:
V
cm
=
i
i
j
j cij
x x V
V T
cm c
1
4
=
i
i
j
j cij cij
x x V T
1
4
=
x
i i
i
Z
m
=
x Z
i ci
i
Wher e:
V
cij
=
[ ]
V V
ci cj
1
3
1
3
3
8
+
T
cij
=
( )( ) 1
1
2
+ k T T
ij ci cj
Z
ci
= 0 2905 0 085
1
2
. .
( )
( )
'
i
ci ci
ci
p V
RT
Method
Method
k
ij
= k
ji
The binar y par amet er k
ij
is det er mined fr om phase-equilibr ium dat a r egr ession,
such as VLE dat a. ASPEN PLUS st or es t he binar y par amet er s for a lar ge
number of component pair s. These binar y par amet er s ar e used aut omat ically
wit h t he LK-PLOCK pr oper t y met hod. If binar y par amet er s for cer t ain
component pair s ar e not available, t hey can be est imat ed using built -in
cor r elat ions. The cor r elat ions ar e designed for binar y int er act ions among t he
component s CO CO N H CH , , , ,
2 2 2 4
alcohols and hydr ocar bons. If a component is
not CO CO N H CH , , , ,
2 2 2 4
or an alcohol, it is assumed t o be a hydr ocar bon.
Physical Pr oper t y Met hods and Models 3-21
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCLKP
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCLKP
p
ci
PC x
10
5
10
8
PRESSURE
VCLKP
V
ci
VC x 0.001 3.5 MOLE-VOLUME
OMGLKP
I
OMEGA x -0.5 2.0
LKPZC
Z
ci
fcn( )
(Method 1)
fcn p V T
ci ci ci
( , , )
(Method 2)
x 0.1 0.5
LKPKIJ
k
ij
fcn
T
T V
ci
V
ci
cj cj
( )
x 5.0 5.0
Method 1 is the default; Method 2 can be invoked by setting the value of LKPZC equal to zero.
Binary interaction parameters LKPKIJ are availablefor a large number of components in AS PEN PLUS .
References
B.I. Lee and M.G. Kesler , AIChE J ., Vol. 21, (1975) p. 510; er r at a: AIChE J .,
Vol. 21, (1975) p. 1040.
V. Plcker , H. Knapp, and J .M. Pr ausnit z, Ind. Eng. Chem., Pr ocess Des. Dev.,
Vol. 17, (1978), p. 324.
NBS/NRC Steam Tables
The NBS/NRC St eam Tables ar e implement ed like any ot her equat ion-of-st at e in
ASPEN PLUS. These st eam t ables can calculat e any t her modynamic pr oper t y of
wat er . The t ables for m t he basis of t he STEAMNBS pr oper t y met hod. Ther e ar e
no par amet er r equir ement s. They ar e t he most accur at e st eam t ables in
ASPEN PLUS.
References
L. Haar , J .S. Gallagher , and J .H. Kell, "NBS/NRC St eam Tables," (Washingt on:
Hemispher e Publishing Cor por at ion, 1984).
3-22 Physical Pr oper t y Met hods and Models
Ver sion10
Property
Model
Descriptions
Nothnagel
The Not hnagel equat ion-of-st at e calculat es t her modynamic pr oper t ies for t he
vapor phase. It is used in pr oper t y met hods NRTL-NTH, UNIQ-NTH, VANL-
NTH, and WILS-NTH. It is r ecommended for syst ems t hat exhibit st r ong vapor
phase associat ion. The model incor por at es t he chemical t heor y of dimer izat ion t o
account for st r ong associat ion and solvat ion effect s, such as t hose found in
or ganic acids, like acet ic acid. The equat ion-of-st at e is:
p
RT
V b
m
Wher e:
b =
y b y b
i i ij ij
j
i
i
nc
i
nc
+
1 1 1
b
ij
=
( ) b b
i j
1 1
3 3
3
8
+
nc = Number of component s in t he mixt ur e
The chemical r eact ion for t he gener al case of a mixt ur e of dimer izing component s
i and j is:
K
i j ij +
The chemical equilibr ium const ant for t he dimer izat ion r eact ion on pr essur e
basis K
p
is r elat ed t o t he t r ue mole fr act ions and fugacit y coefficient s:
y
y y
K p
ij
i j
ij
i j
ij
Wher e:
y
i
and y
j
= Tr ue mole fr act ions of monomer s
y
ij
= Tr ue mole fr act ion of dimer
i
= Tr ue fugacit y coefficient of component i
K
ij
= Equilibr ium const ant for t he dimer izat ion of i and j, on a
pr essur e basis
Physical Pr oper t y Met hods and Models 3-23
Ver sion 10
Chapter 3
When account ing for chemical r eact ions, t he number of t r ue species n
t
in t he
mixt ur e changes. The t r ue molar volume
V
n
t
_
,
r m
r m
ij
H T
d G
dT
RT
d K
dT
2 2
( )
(ln )
The sum of t he cont r ibut ions of all dimer izat ion r eact ions, cor r ect ed for t he r at io
of appar ent and t r ue number of moles, is added t o t he molar ent halpy depar t ur e:
( ) H H
m
v
m
ig
The equilibr ium const ant s can be comput ed using eit her built -in calculat ions or
par amet er s you ent er ed.
Built -in cor r elat ions:
ln( ) ( , , , , , , ) RTK fcn T b b d d p p
IJ i j i j i j
10
5
10
8
PRESSURE
NTHA/1
b
i
0199 . RT
p
ci
ci
0.01 1.0 MOLE-VOLUME
NTHA/2
d
i
0.33 0.01 3.0
NTHA/3
p
i
0 0.0 1.0
NTHK/1
A
i
PRESSURE
NTHK/2
B
i
0 TEMPERATURE
NTHK/3
C
i
0 TEMPERATURE
NTHK/4
D
i
0 TEMPERATURE
References
K.-H. Not hnagel, D. S. Abr ams, and J .M. Pr ausnit z, "Gener alized Cor r elat ion for
Fugacit y Coefficient s in Mixt ur es at Moder at e Pr essur es," Ind. Eng. Chem.,
Pr ocess Des. Dev., Vol. 12, No. 1 (1973), pp. 25 35.
Physical Pr oper t y Met hods and Models 3-25
Ver sion 10
Chapter 3
Peng-Robinson-Boston-Mathias
The Peng-Robinson-Bost on-Mat hias equat ion-of-st at e is t he basis for t he PR-BM
pr oper t y met hod. It is t he Peng-Robinson equat ion-of-st at e wit h t he Bost on-
Mat hias alpha funct ion (see Peng-Robinson Alpha Funct ions). It is r ecommended
for hydr ocar bon pr ocessing applicat ions such as gas pr ocessing, r efiner y, and
pet r ochemical pr ocesses. It s r esult s ar e compar able t o t hose of t he Redlich-
Kwong-Soave equat ion-of-st at e.
The equat ion for t he BM model is:
p =
RT
V b
a
V V b b V b
m m m m
+ + ( ) ( )
Wher e:
b =
x b
i i
i
a =
x x a a k
i j i j ij
j i
( ) ( )
. 0 5
1
b
i
= fcn T p
ci ci
( , )
a
i
= fcn T T p
ci ci i
( , , , )
k
ij
= k
ji
The par amet er
i
is calculat ed by t he st andar d Peng-Robinson for mulat ion at
super cr it ical t emper at ur es. If t he component is super cr it ical, t he Bost on-Mat hias
ext r apolat ion is used (see Peng-Robinson Alpha Funct ions on page 3-36).
For best r esult s, t he binar y par amet er k
ij
must be det er mined fr om phase
equilibr ium dat a r egr ession, (for example, VLE dat a).
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCPR
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCPR
p
ci
PC x
10
5
10
8
PRESSURE
OMGPR
i
OMEGA x -0.5 2.0
PRKIJ
k
ij
0 x -5.0 5.0
Binary interaction parameters PRKIJ are available for a large number of components in AS PEN PLUS .
3-26 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
References
D.-Y. Peng and D. B. Robinson, "A New Two-Const ant Equat ion-of-st at e,"
Ind Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.
Peng-Robi nson-MHV2
This model uses t he Peng-Robinson equat ion-of-st at e for pur e compounds. The
mixing r ules ar e t he pr edict ive MHV2 r ules. Sever al alpha funct ions can be used
in t he Peng-Robinson-MHV2 equat ion-of-st at e model. For a mor e accur at e
descr ipt ion of t he pur e component behavior . The pur e component behavior and
par amet er r equir ement s ar e descr ibed in St andar d Peng-Robinson on page 3-34,
or in Peng-Robinson Alpha Funct ions on page 3-36.
The MHV2 mixing r ules ar e an example of modified Hur on-Vidal mixing r ules. A
br ief int r oduct ion is pr ovided in Hur on-Vidal Mixing Rules on page 3-46. For
mor e det ails, see MHV2 Mixing Rules, t his chapt er .
Predi cti ve SRK (PSRK)
This model uses t he Redlich-Kwong-Soave equat ion-of-st at e for pur e compounds.
The mixing r ules ar e t he pr edict ive Holder baum r ules, or PSRK met hod. Sever al
alpha funct ions can be used in t he PSRK equat ion-of-st at e model. For a mor e
accur at e descr ipt ion of t he pur e component behavior . The pur e component
behavior and par amet er r equir ement s ar e descr ibed in St andar d Redlich-Kwong-
Soave on page 3-35 and in Soave Alpha Funct ions on page 3-40.
The PSRK met hod is an example of modified Hur on-Vidal mixing r ules. A br ief
int r oduct ion is pr ovided in Hur on-Vidal Mixing Rules on page 3-46. For mor e
det ails, see Pr edict ive Soave-Redlich-Kwong-Gmehling Mixing Rules, t his
chapt er .
Peng-Robinson-Wong-Sandler
This model uses t he Peng-Robinson equat ion-of-st at e for pur e compounds. The
mixing r ules ar e t he pr edict ive Wong-Sandler r ules. Sever al alpha funct ions can
be used in t he Peng-Robinson-Wong-Sandler equat ion-of-st at e model. For a mor e
accur at e descr ipt ion of t he pur e component behavior . The pur e component
behavior and par amet er r equir ement s ar e descr ibed in Peng-Robinson, and in
Peng-Robinson Alpha Funct ions on page 3-36.
The Wong-Sandler mixing r ules ar e an example of modified Hur on-Vidal mixing
r ules. A br ief int r oduct ion is pr ovided in Hur on-Vidal Mixing Rules on page 3-46.
For mor e det ails see Wong-Sandler Mixing Rules, t his chapt er .
Physical Pr oper t y Met hods and Models 3-27
Ver sion 10
Chapter 3
Redlich-Kwong
The Redlich-Kwong equat ion-of-st at e can calculat e vapor phase t her modynamic
pr oper t ies for t he following pr oper t y met hods: NRTL-RK, UNIFAC, UNIF-LL,
UNIQ-RK, VANL-RK, and WILS-RK. It is applicable for syst ems at low t o
moder at e pr essur es (maximum pr essur e 10 at m) for which t he vapor -phase
nonidealit y is small. The Hayden-OConnell model is r ecommended for a mor e
nonideal vapor phase, such as in syst ems cont aining or ganic acids. It is not
r ecommended for calculat ing liquid phase pr oper t ies.
The equat ion for t he model is:
p =
RT
V b
a
T
V V b
m m m
+
0 5 .
( )
Wher e:
a
=
x a
i i
i
b =
x b
i i
i
a
i
=
0 42748023
2 1 5
.
.
R T
p
ci
ci
b
i
=
0 08664035 . RT
p
ci
ci
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TC T
ci
5.0 2000.0 TEMPERATURE
PC p
ci
10
5
10
8
PRESSURE
References
O. Redlich and J .N.S. Kwong, "On t he Ther modynamics of Solut ions V. An
Equat ion-of-st at e. Fugacit ies of Gaseous Solut ions," Chem. Rev., Vol. 44, (1979),
pp. 223 244.
3-28 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Redlich-Kwong-Aspen
The Redlich-Kwong-Aspen equat ion-of-st at e is t he basis for t he RK-ASPEN
pr oper t y met hod. It can be used for hydr ocar bon pr ocessing applicat ions. It is
also used for mor e polar component s and mixt ur es of hydr ocar bons, and for light
gases at medium t o high pr essur es.
The equat ion is t he same as Redlich-Kwong-Soave:
p =
RT
V b
a
V V b
m m m
+ ( )
A quadr at ic mixing r ule is maint ained for :
a =
x x a a k
i j i j a ij
j i
( ) ( )
.
,
0 5
1
An int er act ion par amet er is int r oduced in t he mixing r ule for :
b =
x x
b b
k
i j
i j
b ij
j i
( )
( )
,
2
1
For a
i
an ext r a polar par amet er is used:
a
i
= fcn T T p
ci ci i i
( , , , , )
b
i
= fcn T p
ci ci
( , )
The int er act ion par amet er s ar e t emper at ur e-dependent :
k
a ij ,
=
k k
T
a ij a ij , ,
0 1
1000
+
k
b ij ,
=
k k
T
b ij b ij , ,
0 1
1000
+
For best r esult s, binar y par amet er s k
ij
must be det er mined fr om phase-
equilibr ium dat a r egr ession, such as VLE dat a.
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCRKS
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCRKA
p
ci
PC x 10
5
10
8
PRESSURE
continued
Physical Pr oper t y Met hods and Models 3-29
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
OMGRKA
i
OMEGA x -0.5 2.0
RKAPOL
i
0 x -2.0 2.0
RKAKA0
k
a ij ,
0
0 x -5.0 5.0
RKAKA1
k
a ij ,
1
0 x -15.0 15.0 TEMPERATURE
RKAKB0
k
b ij ,
0
0 x -5.0 5.0
RKAKB1
k
b ij ,
1
0 x -15.0 15.0 TEMPERATURE
Absolute temperature units are assumed. S ee the ASPEN PLUS User Guide.
References
Mat hias, P.M., "A Ver sat ile Phase Equilibr ium Equat ion-of-st at e", Ind. Eng.
Chem. Process Des. Dev., Vol. 22, (1983), pp. 385 391.
Redlich-Kwong-Soave-Boston-Mathias
The Redlich-Kwong-Soave-Bost on-Mat hias equat ion-of-st at e is t he basis for t he
RKS-BM pr oper t y met hod. It is t he Redlich-Kwong-Soave equat ion-of-st at e wit h
t he Bost on-Mat hias alpha funct ion (see Soave Alpha Funct ions on page 3-40). It is
r ecommended for hydr ocar bon pr ocessing applicat ions, such as gas-pr ocessing,
r efiner y, and pet r ochemical pr ocesses. It s r esult s ar e compar able t o t hose of t he
Peng-Robinson-Bost on-Mat hias equat ion-of-st at e.
The equat ion is:
p =
RT
V b
a
V V b
m m m
+ ( )
Wher e:
a =
x x a a k
i j i j ij
j i
( ) ( )
. 0 5
1
b =
x b
i i
i
a
i
= fcn T T p
ci ci i
( , , , )
b
i
= fcn T p
ci ci
( , )
3-30 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
k
ij
= k
ji
The par amet er a
i
is calculat ed by t he st andar d Soave for mulat ion at
super cr it ical t emper at ur es. If t he component is super cr it ical, t he Bost on-Mat hias
ext r apolat ion is used (see Soave Alpha Funct ions on page 3-40).
For best r esult s, binar y par amet er s k
ij
must be det er mined fr om phase-
equilibr ium dat a r egr ession (for example, VLE dat a).
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCRKS
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCRKS
p
ci
PC x 10
5
10
8
PRESSURE
OMGRKS
i
OMEGA x -0.5 2.0
RKSKIJ
k
ij
0 x -5.0 5.0
Binary interaction parameters RKS KIJ are available for a large number of components in AS PEN PLUS .
References
G. Soave, "Equilibr ium Const ant s for Modified Redlich-Kwong Equat ion-of-
st at e," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 1203.
Redlich-Kwong-Soave-Wong-Sandler
This equat ion-of-st at e model uses t he Redlich-Kwong-Soave equat ion-of-st at e for
pur e compounds. The pr edict ive Wong-Sandler mixing r ules ar e used. Sever al
alpha funct ions can be used in t he Redlich-Kwong-Soave-Wong-Sandler equat ion-
of-st at e model for a mor e accur at e descr ipt ion of t he pur e component behavior .
The pur e component behavior and par amet er r equir ement s ar e descr ibed in
St andar d Redlich-Kwong-Soave on page 3-35, and in Soave Alpha Funct ions on
page 3-40.
The Wong-Sandler mixing r ules ar e an example of modified Hur on-Vidal mixing
r ules. A br ief int r oduct ion is pr ovided in Hur on-Vidal Mixing Rules on page 3-46.
For mor e det ails, see Wong-Sandler Mixing Rules, t his chapt er .
Physical Pr oper t y Met hods and Models 3-31
Ver sion 10
Chapter 3
Redlich-Kwong-Soave-MHV2
This equat ion-of-st at e model uses t he Redlich-Kwong-Soave equat ion-of-st at e for
pur e compounds. The pr edict ive MHV2 mixing r ules ar e used. Sever al alpha
funct ions can be used in t he RK-Soave-MHV2 equat ion-of-st at e model. For a
mor e accur at e descr ipt ion of t he pur e component behavior . The pur e component
behavior and it s par amet er r equir ement s ar e descr ibed in St andar d Redlich-
Kwong-Soave on page 3-35, and in Soave Alpha Funct ions on page 3-40.
The MHV2 mixing r ules ar e an example of modified Hur on-Vidal mixing r ules. A
br ief int r oduct ion is pr ovided in Hur on-Vidal Mixing Rules on page 3-46. For
mor e det ails, see MHV2 Mixing Rules, t his chapt er .
Schwartzentruber-Renon
The Schwar t zent r uber -Renon equat ion-of-st at e is t he basis for t he SR-POLAR
pr oper t y met hod. It can be used t o model chemically nonideal syst ems wit h t he
same accur acy as act ivit y coefficient pr oper t y met hods, such as t he WILSON
pr oper t y met hod. This equat ion-of-st at e is r ecommended for highly non-ideal
syst ems at high t emper at ur es and pr essur es, such as in met hanol synt hesis and
super cr it ical ext r act ion applicat ions.
The equat ion for t he model is:
p =
RT
V c b
a
V c V c b
M m m
+
+ + + ( )( )
Wher e:
a =
x x a a k l x x
i j
j i
i j a ij ij i j
( ) [ ( )]
,
0.5
1
b =
x x
b b
k
i j
j i
i j
b ij
+
2
1 ( )
,
c =
x c
i i
i
a
i
= fcn T T p q q q
ci ci i i i i
( , , , , , , )
0 1 2
b
i
= fcn T p
ci ci
( , )
c
i
=
fcn
T
T
c c c
ci
i i i
, , ,
0 1 2
_
,
q
i 0
x
RKUPP1
q
i 1
0 x
RKUPP2
q
i 2
0 x
RKUC0
c
i 0
0 x
RKUC1
c
i 1
0 x
RKUC2
c
i 2
0 x
For polar components (dipole moment >> 0), if you do not enter q
i 0
, the system estimates q
i 0
, q
i 1
, q
i 2
from vapor pressures using the Antoine vapor pressure model.
continued
Physical Pr oper t y Met hods and Models 3-33
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
RKUKA0
k
a ij ,
0
0 x
RKUKA1
k
a ij ,
1
0 x TEMPERATURE
RKUKA2
k
a ij ,
2
0 x TEMPERATURE
RKULA0
l
ij
0
0 x
RKULA1
l
ij
1
0 x TEMPERATURE
RKULA2
l
ij
2
0 x TEMPERATURE
RKUKB0
k
b ij ,
0
0 x
RKUKB1
k
b ij ,
1
0 x TEMPERATURE
RKUKB2
k
b ij ,
2
0 x TEMPERATURE
For polar components (dipole moment >> 0), if you do not enter q
i 0
, the system estimates q
i 0
, q
i 1
, q
i 2
from vapor pressures using the Antoine vapor pressure model.
+ + ( ) ( )
Wher e:
b =
x b
i i
i
a =
x x a a k
i j i j ij
j i
( ) ( )
. 0 5
1
b
i
= fcn T p
ci ci
( , )
a
i
= fcn T T p
ci ci i
( , , , )
k
ij
= k
ji
The par amet er a
i
is calculat ed accor ding t o t he st andar d Peng-Robinson
for mulat ion (see Peng-Robinson Alpha Funct ions on page 36, equat ions 1 t hr ough
5).
For best r esult s, t he binar y par amet er k
ij
must be det er mined fr om phase
equilibr ium dat a r egr ession, (for example, VLE dat a). ASPEN PLUS also has
built -in k
ij
for alar ge number of component pair s. These par amet er s ar e used
aut omat ically wit h t he PENG-ROB pr oper t y met hod.
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCPR
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCPR
p
ci
PC x
10
5
10
8
PRESSURE
OMGPR
i
OMEGA x -0.5 2.0
PRKIJ
k
ij
0 x -5.0 5.0
Physical Pr oper t y Met hods and Models 3-35
Ver sion 10
Chapter 3
References
D.-Y. Peng and D. B. Robinson, "A New Two-Const ant Equat ion-of-st at e," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.
Standard Redlich-Kwong-Soave
The St andar d Redlich-Kwong-Soave-Bost on-Mat hias equat ion-of-st at e is t he
basis for t he RK-SOAVE pr oper t y met hod. It is It is r ecommended for
hydr ocar bon pr ocessing applicat ions, such as gas-pr ocessing, r efiner y, and
pet r ochemical pr ocesses. It s r esult s ar e compar able t o t hose of t he Peng-
Robinson equat ion-of-st at e.
The equat ion is:
p
RT
V b
a
V V b
m m m
+ ( )
Wher e:
p
RT
V b
a
V V b b V b
m m m m
+ + ( ) ( )
Wher e:
a =
x x a a k
i j i j ij
j i
( ) ( )
. 0 5
1
b =
x b
i i
i
a
i
= fcn T T p
ci ci i
( , , , )
b
i
= fcn T p
ci ci
( , )
k
ij
= k
ji
The par amet er a
i
is calculat ed accor ding t o t he st andar d Soave for mulat ion (see
Soave Alpha Funct ions on page 3-40, equat ions 1, 2, 3, 5, and 6).
For best r esult s, binar y par amet er s k
ij
must be det er mined fr om phase-
equilibr ium dat a r egr ession (for example, VLE dat a). ASPEN PLUS also has
built -in k
ij
for a lar ge number of component pair s. These binar y par amet er s ar e
used aut omat ically wit h t he RK-SOAVE pr oper t y met hod.
3-36 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCRKS
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCRKS
p
ci
PC x
10
5
10
8
PRESSURE
OMGRKS
i
OMEGA x -0.5 2.0
RKSKIJ
k
ij
0 x -5.0 5.0
Binary interaction parameters RKS KIJ are available for a large number of components in AS PEN PLUS .
References
G. Soave, "Equilibr ium Const ant s for Modified Redlich-Kwong Equat ion-of-
st at e," Chem. Eng. S ci., Vol. 27, (1972), pp. 1196 1203.
J . Schwar t zent r uber and H. Renon, "Ext ension of UNIFAC t o High Pr essur es
and Temper at ur es by t he Use of a Cubic Equat ion-of-st at e," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 1049 1955.
A. Peneloux, E. Rauzy, and R. Fr eze, "A Consist ent Cor r ect ion For Redlich-
Kwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723.
Peng-Robinson Alpha Functions
The pur e component par amet er s for t he Peng-Robinson equat ion-of-st at e ar e
calculat ed as follows:
a
R T
p
i i
ci
ci
0 45724
2 2
. (1)
b
RT
p
i
ci
ci
0 07780 . (2)
These expr essions ar e der ived by applying t he cr it ical const r aint s t o t he
equat ion-of-st at e under t hese condit ions:
i ci
T ( ) . 10 (3)
The par amet er is a t emper at ur e funct ion. It was or iginally int r oduced by
Soave in t he Redlich-Kwong equat ion-of-st at e. This par amet er impr oves t he
cor r elat ion of t he pur e component vapor pr essur e. This appr oach was also
adopt ed by Peng and Robinson:
i i ri
T m T ( ) [ ( )] + 1 1
1
2
2
(4)
Physical Pr oper t y Met hods and Models 3-37
Ver sion 10
Chapter 3
Equat ion 3 is st ill r epr esent ed. The par amet er m
i
can be cor r elat ed wit h t he
acent r ic fact or :
m
i i i
+ 037464 154226 0 26992
2
. . . (5)
Equat ions 1 t hr ough 5 ar e t he st andar d Peng-Robinson for mulat ion.
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCPR
T
ci
TC X 5.0 2000.0 TEMPERATURE
PCPR
p
ci
PC X
10
5
10
8
PRESSURE
OMGPR
i
OMEGA X -0.5 2.0
Boston-Mathias Extrapolation
For light gases at high r educed t emper at ur es (> 5), equat ion 4 gives unr ealist ic
r esult s. The boundar y condit ions ar e t hat at t r act ion bet ween molecules should
vanish for ext r emely high t emper at ur es, and r educes asympt ot ically t o zer o.
Bost on and Mat hias der ived an alt er nat ive funct ion for t emper at ur es higher
t han cr it ical:
i i ri
d
T c T
i
( ) [exp[ ( )]] 1
2
(6)
Wit h
d
i
=
1
2
+
m
i
c
i
=
1
1
d
i
Wher e m
i
is comput ed by equat ion 5. and equat ion 4 is used for subcr it ical
t emper at ur es. Addit ional par amet er s ar e not needed.
Mathias-Copeman Alpha Function
m
i
is a const ant for each component in equat ion 4. For ver y high accur acy or
st r ongly cur ved vapor pr essur e behavior as a funct ion of t emper at ur e, t he
Mat hias-Copeman funct ion is highly flexible
i T i ri i ri i ri
c T c T c T
( ) , , ,
[ ( ) ( ) ( ) ] + + + 1 1 1 1
1 2
2
3
3 2
1
2
1
2
1
2
(7)
3-38 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
For c
i 2,
= 0 and t his expr ession r educes t o t he st andar d Peng-Robinson
for mulat ion if c m
i i 1,
= . You can use vapor pr essur e dat a if t he t emper at ur e is
subcr it ical t o r egr ess t he const ant s. If t he t emper at ur e is super cr it ical, c
i 2,
and
c
i 3,
ar e set t o 0.
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCPR
T
ci
TC X 5.0 2000.0 TEMPERATURE
PCPR
p
ci
PC X
10
5
10
8
PRESSURE
PRMCP/1
c
i 1,
X
PRMCP/2
c
i 2,
0 X
PRMCP/3
c
i 3,
0 X
Schwartzentruber-Renon-Watanasiri Alpha Function
This met hod combines t he flexibilit y of t he Mat hias-Copeman appr oach and t he
cor r ect ion for highly r educed t emper at ur es by Bost on and Mat hias:
i i ri ri i i ri ri
T m T T p p T p T ( ) [ ( ) ( )( )]
, , ,
+ + + 1 1 1
1
2
1
2
1 2 3 1
2 2
(8)
Wher e m
i
is comput ed by equat ion 5. The polar par amet er s p
i 1,
, p
i 2,
and p
i 3,
ar e
compar able wit h t he c par amet er s of t he Mat hias-Copeman expr ession. Equat ion
8 r educes t o t he st andar d Peng-Robinson for mulat ion if t he polar par amet er s ar e
zer o. You can use vapor pr essur e dat a t o r egr ess t he const ant s if t he t emper at ur e
is subcr it ical. Equat ion 8 is used only for below-cr it ical t emper at ur es. For above-
cr it ical t emper at ur es, t he Bost on-Mat hias ext r apolat ion is used. Use equat ion 6
wit h:
d m p p p
i i i i i
+ + + 1
1
2 1 2 3
( )
, , ,
(9)
c
d
i
i
1
1
(10)
Physical Pr oper t y Met hods and Models 3-39
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCPR
T
ci
TC X 5.0 2000.0 TEMPERATURE
PCPR
p
ci
C X
10
5
10
8
PRESSURE
OMGPR
i
OMEGA X -0.5 2.0
PRSRP/1
p
i 1,
X
PRSRP/2
p
i 2,
0 X
PRSRP/3
p
i 3,
0 X
Use of Alpha Functions
The alpha funct ions in Peng-Robinson-based equat ion-of-st at e models is pr ovided
in t he following t able. You can ver ify and change t he value of possible opt ion
codes on t he Pr oper t ies Pr oper t y Met hod Model for m.
Alpha function Model name First Option code
Standard Peng Robinson ESPRSTD0, ESPRSTD
Standard PR/Boston-Mathias ESPR0, ESPR
ESPRWS0, ESPRWS
ESPRV20, ESPRV2
1
1
Mathias-Copeman ESPRWS0, ESPRWS
ESPRV20, ESPRV2
2
2
Schwartzentruber-Renon-Watanasiri ESPRWS0, ESPRWS
ESPRV20, ESPRV2
3 (default)
3 (default)
References
J . F. Bost on and P.M. Mat hias, "Phase Equilibr ia in a Thir d-Gener at ion Pr ocess
Simulat or " in Pr oceedings of t he 2nd Int er nat ional Confer ence on Phase
Equilibr ia and Fluid Pr oper t ies in t he Chemical Pr ocess Indust r ies, West Ber lin,
(17-21 Mar ch 1980) pp. 823-849.
D.-Y. Peng and D.B. Robinson, "A New Two-Const ant Equat ion-of-st at e," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 59-64.
P.M. Mat hias and T.W. Copeman, "Ext ension of t he Peng-Robinson Equat ion-of-
st at e To Complex Mixt ur es: Evaluat ion of t he Var ious For ms of t he Local
Composit ion Concept ",Fluid Phase Eq., Vol. 13, (1983), p. 91.
3-40 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
J . Schwar t zent r uber , H. Renon, and S. Wat anasir i, "K-values for Non-Ideal
Syst ems:An Easier Way," Chem. Eng., Mar ch 1990, pp. 118-124.
G. Soave, "Equilibr ium Const ant s for a Modified Redlich-Kwong Equat ion-of-
st at e," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203.
Soave Alpha Functions
The pur e component par amet er s for t he Redlich-Kwong equat ion-of-st at e ar e
calculat ed as:
a
R T
p
i i
ci
ci
0 42747
2 2
. (1)
b
RT
p
i
ci
ci
0 08664 . (2)
These expr essions ar e der ived by applying t he cr it ical const r aint t o t he equat ion-
of-st at e under t hese condit ions:
i ci
T ( ) . 10 (3)
In t he Redlich-Kwong equat ion-of-st at e, alpha is:
i
ri
T
1
1
2
(4)
It was not r efer r ed t o as alpha but equat ion 4 was incor por at ed int o equat ion 1.
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
PC
p
ci
10
5
10
8
PRESSURE
Soave Modification
The par amet er is a t emper at ur e funct ion int r oduced by Soave in t he Redlich-
Kwong equat ion-of-st at e t o impr ove t he cor r elat ion of t he pur e component vapor
pr essur e:
i i ri
T m T ( ) [ ( )] + 1 1
1
2
2
(5)
Equat ion 3 st ill holds. The par amet er m
i
can be cor r elat ed wit h t he acent r ic
fact or :
Physical Pr oper t y Met hods and Models 3-41
Ver sion 10
Chapter 3
m
i i i
+ 0 48 157 0176
2
. . . (6)
Equat ions 1, 2, 3, 5 and 6 ar e t he st andar d Redlich-Kwong-Soave for mulat ion.
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCRKS
T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKS
p
ci
PC X
10
5
10
8
PRESSURE
OMGRKS
i
OMEGA X -0.5 2.0
Boston-Mathias Extrapolation
For light gases at high r educed t emper at ur es (> 5), equat ion 4 gives unr ealist ic
r esult s. The boundar y condit ions ar e t hat at t r act ion bet ween molecules should
vanish for ext r emely high t emper at ur es, and r educes asympt ot ically t o zer o.
Bost on and Mat hias der ived an alt er nat ive funct ion for t emper at ur es higher
t han cr it ical:
i i ri
d
T c T
i
( ) [exp[ ( )]] 1
2
(7)
Wit h
d
i
=
1
2
+
m
i
c
i
=
1
1
d
i
Wher e:
m
i
= Comput ed by equat ion 6
Equat ion 5 = Used for subcr it ical t emper at ur es
Addit ional par amet er s ar e not needed.
Mathias Alpha Function
In equat ion 4, m
i
is a const ant for each component . For high accur acy or for
highly cur ved vapor pr essur e behavior as a funct ion of t emper at ur e, such as wit h
polar compounds, t he Mat hias funct ion is mor e flexible:
3-42 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
i i ro i ri ri
T m T T T ( ) [ ( ) ( )( . )] + 1 1 1 0 7
1
2
1
2
2
(8)
For
i
0 , equat ion 8 r educes t o t he st andar d Redlich-Kwong-Soave
for mulat ion, including equat ion 6 for m
i
. For t emper at ur es above cr it ical, t he
Bost on-Mat hias ext r apolat ion is used, t hat is, equat ion 6 wit h:
d
m
i
i
i
+ + 1
2
03 . (9)
c
d
i
i
1
1
(10)
Parameter Name/
Element
Symbol Default MDS Upper Limit Lower Limit Units
TCRKA
T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKA
p
ci
PC X
10
5
10
8
PRESSURE
OMGRKA
i
OMEGA X -0.5 2.0
RKAPOL
i
X -2.0 2.0
Extended Mathias Alpha Function
An ext ension of t he Mat hias appr oach is:
( )
i i ri
i
ri i i ri
T m T p T p T p T + + + [ ( ) ( )( )]
,
, ,
1 1 1 1
1
2
1
2
1
2 3
2 2
(11)
Wher e m
i
is comput ed by equat ion 6. If t he polar par amet er s p
i 1,
, p
i 2,
and p
i 3,
ar e zer o, equat ion 11 r educes t o t he st andar d Redlich-Kwong-Soave for mulat ion.
You can use vapor pr essur e dat a t o r egr ess t he const ant s if t he t emper at ur e is
subcr it ical. Equat ion 11 is used only for t emper at ur es below cr it ical. The Bost on-
Mat hias ext r apolat ion is used for t emper at ur es above cr it ical, t hat is, wit h:
( )
d m p p p
i i i i i
+ +
1
2 1 2 3
1
, , ,
(12)
c
d
i
i
1
1
(13)
Physical Pr oper t y Met hods and Models 3-43
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCRKU
T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKU
p
ci
PC X
10
5
10
8
PRESSURE
OMGRKU
i
OMEGA X -0.5 2.0
RKUPP0
p
i 1,
X
RKUPP1
p
i 2,
0 X
RKUPP2
p
i 3,
0 X
Mathias-Copeman Alpha Function
The Mat hias-Copeman Alpha Funct ion appr oach is anot her ext ension of t he
Mat hias appr oach. For high accur acy or st r ongly cur ved vapor pr essur e behavior
as a funct ion of t emper at ur e, t he Mat hias-Copeman funct ion is highly flexible:
i i ri i ri i ri
T m T c T c T ( ) [ ( ) ( ) ( ) ]
, ,
+ + + 1 1 1 1
1
2
1
2
1
2
2
2
3
3 2
(14)
For c
i 2
0
,
and c
i 3
0
,
t his expr ession r educes t o t he st andar d Redlich-Kwong-
Soave for mulat ion if c m
i i 1,
. If t he t emper at ur e is subcr it ical, use vapor
pr essur e dat a t o r egr ess t he const ant s. If t he t emper at ur e is super cr it ical, set c
i 2,
and c
i 3,
t o 0.
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCRKS
T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKS
p
ci
PC X
10
5
10
8
PRESSURE
RKSMCP/1
c
i 1,
X
RKSMCP/2
c
i 2,
0 X
RKSMCP/3
c
i 3,
0 X
Schwartzentruber-Renon-Watanasiri Alpha Function
This met hod combines t he flexibilit y of t he Mat hias-Copeman appr oach and t he
cor r ect ion for high r educed t emper at ur es by Bost on and Mat hias:
i i ri ri i i ri i ri
T m T T p p T p T ( ) [ ( ) ( )( )]
, , ,
+ + + 1 1 1
1
2
1 2 3
2 2
(15)
3-44 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Wher e m
i
is comput ed by equat ion 6 and t he polar par amet er s p
i 1,
, p
i 2,
and
p
i 3,
ar e compar able wit h t he c par amet er s of t he Mat hias-Copeman expr ession.
Equat ion 15 r educes t o t he st andar d Redlich-Kwong-Soave for mulat ion if t he
polar par amet er s ar e zer o. Use vapor pr essur e dat a t o r egr ess t he const ant s if
t he t emper at ur e is subcr it ical. Equat ion 15 is ver y similar t o t he ext ended
Mat hias equat ion, but it is easier t o use in dat a r egr ession. It is used only for
t emper at ur es below cr it ical. The Bost on-Mat hias ext r apolat ion is used for
t emper at ur es above cr it ical, t hat is, use equat ion 6 wit h:
d
m
p p p
i
i
i i i
+ + + 1
2
1 2 3
( )
, , ,
(16)
c
d
i
i
1
1
(17)
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCPR
T
ci
TC X 5.0 2000.0 TEMPERATURE
PCPR
p
ci
PC X
10
5
10
8
PRESSURE
OMGPR
i
OMEGA X -0.5 2.0
RKSSRP/1
p
i 1,
X
RKSSRP/2
p
i 2,
0 X
RKSSRP/3
p
i 3,
0 X
Use of Alpha Functions
The use of alpha funct ions in Soave-Redlich-Kwong based equat ion-of-st at e
models is given in t he following t able. You can ver ify and change t he value of
possible opt ion codes on t he Pr oper t ies Pr oper t y Met hod Model for m.
Alpha Function Model Name First Option Code
original RK ESRK0, ESRK
standard RKS ESRKSTD0, ESRKSTD
standard RKS/Boston-Mathias ESRKS0, ESRKS0
ESRKSWS0, ESRKSWS
ESRKSV10, ESRKV1
ESRKSV20, ESRKSV2
1
1
1
continued
Physical Pr oper t y Met hods and Models 3-45
Ver sion 10
Chapter 3
Alpha Function Model Name First Option Code
Mathias/Boston-Mathias ESRKA0, ESRKA
Extended Mathias/Boston-Mathias ESRKU0, ESRKU
Mathias-Copeman ESRKSW0, ESRKSW
ESRKSV10, ESRKSV1
ESRKSV20, ESRKSV2
2
2
2
Schwartzentruber-Renon-Watanasiri ESPRWS0, ESPRWS
ESRKSV10, ESRKSV1
ESRKSV20, ESRKSV2
3 (default)
3 (default)
3 (default)
References
J . F. Bost on and P.M. Mat hias, "Phase Equilibr ia in a Thir d-Gener at ion Pr ocess
Simulat or " in Pr oceedings of t he 2nd Int er nat ional Confer ence on Phase
Equilibr ia and Fluid Pr oper t ies in t he Chemical Pr ocess Indust r ies, West Ber lin,
(17-21 Mar ch 1980), pp. 823-849.
P. M. Mat hias, "A Ver sat ile Phase Equilibr ium Equat ion-of-st at e", Ind. Eng.
Chem. Pr ocess Des. Dev., Vol. 22, (1983), pp. 385391.
P.M. Mat hias and T.W. Copeman, "Ext ension of t he Peng-Robinson Equat ion-of-
st at e To Complex Mixt ur es: Evaluat ion of t he Var ious For ms of t he Local
Composit ion Concept ", Fluid Phase Eq., Vol. 13, (1983), p. 91.
O. Redlich and J . N. S. Kwong, "On t he Ther modynamics of Solut ions V. An
Equat ion-of-st at e. Fugacit ies of Gaseous Solut ions," Chem. Rev., Vol. 44, (1949),
pp. 223244.
J . Schwar t zent r uber and H. Renon, "Ext ension of UNIFAC t o High Pr essur es
and Temper at ur es by t he Use of a Cubic Equat ion-of-st at e," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 10491055.
J . Schwar t zent r uber , H. Renon, and S. Wat anasir i, "K-values for Non-Ideal
Syst ems:An Easier Way," Chem. Eng., Mar ch 1990, pp. 118-124.
G. Soave, "Equilibr ium Const ant s for a Modified Redlich-Kwong Equat ion-of-
st at e," Chem Eng. S ci., Vol. 27, (1972), pp. 1196-1203.
3-46 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Huron-Vi dal Mi xi ng Rules
Hur on and Vidal (1979) used a simple t her modynamic r elat ionship t o equat e t he
excess Gibbs ener gy t o expr essions for t he fugacit y coefficient as comput ed by
equat ions of st at e:
G RT x RT
m
E
i i
i
ln ln
*
(1)
Equat ion 1 is valid at any pr essur e, but cannot be evaluat ed unless some
assumpt ions ar e made. If Equat ion 1 is evaluat ed at infinit e pr essur e, t he
mixt ur e must be liquid-like and ext r emely dense. It can be assumed t hat :
V p b ( ) (2)
V p
E
( ) 0 (3)
Using equat ions 2 and 3 in equat ion 1 r esult s in an expr ession for a/b t hat
cont ains t he excess Gibbs ener gy at an infinit e pr essur e:
a
b
x
a
b
G p
i
i
i
m
E
i
( ) (4)
Wher e:
+
+
_
,
1 1
1
1 2
1
2
ln (5)
The par amet er s
1
and
2
depend on t he equat ion-of-st at e used. In gener al a
cubic equat ion-of-st at e can be wr it t en as:
p
RT
V b
a
V b V b
m m
+ + ( ) ( )( )
1 2
(6)
Values for
1
and
2
for t he Peng-Robinson and t he Soave-Redlich-Kwong
equat ions of st at e ar e:
Equation-of-state
1
2
Peng-Robinson
1 2 1 2 +
Redlich-Kwong-Soave 1 0
Physical Pr oper t y Met hods and Models 3-47
Ver sion 10
Chapter 3
This expr ession can be used at any pr essur e as a mixing r ule for t he par amet er .
The mixing r ule for b is fixed by equat ion 3. Even when used at ot her pr essur es,
t his expr ession cont ains t he excess Gibbs ener gy at infinit e pr essur e. You can use
any act ivit y coeffecient model t o evaluat e t he excess Gibbs ener gy at infinit e
pr essur e. Binar y int er act ion coefficient s must be r egr essed. The mixing r ule used
cont ains as many binar y par amet er s as t he act ivit y coefficient model chosen.
This mixing r ule has been used successfully for polar mixt ur es at high pr essur es,
such as syst ems cont aining light gases. In t heor y, any act ivit y coefficient model
can be used. But t he NRTL equat ion (as modified by Hur on and Vidal) has
demonst r at ed bet t er per for mance.
The Hur on-Vidal mixing r ules combine ext r eme flexibilit y wit h t her modynamic
consist ency, unlike many ot her mole-fr act ion-dependent equat ion-of-st at e mixing
r ules. The Hur on-Vidal mixing r ules do not allow flexibilit y in t he descr ipt ion of
t he excess molar volume, but always pr edict r easonable excess volumes.
The Hur on-Vidal mixing r ules ar e t heor et ically incor r ect for low pr essur e,
because quadr at ic mole fr act ion dependence of t he second vir ial coefficient (if
der ived fr om t he equat ion-of-st at e) is not pr eser ved. Since equat ions of st at e ar e
pr imar ily used at high pr essur e, t he pr act ical consequences of t his dr awback ar e
minimal.
The Gibbs ener gy at infinit e pr essur e and t he Gibbs ener gy at an ar bit r ar y high
pr essur e ar e similar . But t he cor r espondence is not close enough t o make t he
mixing r ule pr edict ive. Ther e ar e sever al met hods for modifying t he Hur on-Vidal
mixing r ule t o make it mor e pr edict ive. The following t hr ee met hods ar e used in
ASPEN PLUS equat ion-of-st at e models:
The modified Hur on-Vidal mixing r ule, second or der appr oximat ion (MHV2)
The Pr edict ive SRK Met hod (PSRK)
The Wong-Sandler modified Hur on-Vidal mixing r ule (WS)
These mixing r ules ar e discussed separ at ely in t he following sect ions. They have
major advant ages over ot her composit ion-dependent equat ion-of-st at e mixing
r ules.
References
M.- J . Hur on and J . Vidal,"New Mixing Rules in Simple Equat ions of St at e for
r epr esent ing Vapour -liquid equilibr ia of st r ongly non-ideal mixt ur es," Fluid
Phase Eq., Vol. 3, (1979), pp. 255-271.
3-48 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
MHV2 Mixing Rules
Dahl and Michelsen (1990) use a t her modynamic r elat ionship bet ween excess
Gibbs ener gy and t he fugacit y comput ed by equat ions of st at e. This r elat ionship
is equivalent t o t he one used by Hur on and Vidal:
G
RT
f
RT
x
f
RT
m
E
i
i
i
_
,
_
,
ln ln (1)
The advant age is t hat t he expr essions for mixt ur e and pur e component fugacit ies
do not cont ain t he pr essur e. They ar e funct ions of compacit y V/b and :
ln ln ,
* *
f
RT
b Q
V
b
i
i
i
i
i
_
,
_
,
(2)
Wher e:
i
i
i
a
b RT
(3)
and
ln ln ,
f
RT
b Q
V
b
i
m
_
,
+
_
,
(4)
wit h
a
bRT
(5)
The const ant s
1
and
2
,which depend only on t he equat ion-of-st at e (see Hur on-
Vidal Mixing Rules, t his chapt er ) occur in equat ions 2 and 4.
Inst ead of using infinit e pr essur e for simplificat ion of equat ion 1, t he condit ion of
zer o pr essur e is used. At p= 0 an exact r elat ionship bet ween t he compacit y and
can be der ived. By subst it ut ion t he simplified equat ion q( ) is obt ained, and
equat ion 1 becomes:
G p
RT
x
b
b
q x q
m
E
i
i
i i
i i
( )
ln ( ) ( )
_
,
0
(6)
However , q( ) can only be wr it t en explicit ly for 58 . . Only an appr oximat ion
is possible below t hat t hr eshold. Dahl and Michelsen use a second or der
polynomial fit t ed t o t he analyt ical solut ion for 10 13 < < t hat can be
ext r apolat ed t o low alpha:
q q q
i
( ) +
2
2
(7)
Physical Pr oper t y Met hods and Models 3-49
Ver sion 10
Chapter 3
Since q( ) is a univer sal funct ion (for each equat ion-of-st at e), t he combinat ion of
equat ions 6 and 7 for m t he MHV2 mixing r ule. Excess Gibbs ener gies, fr om any
act ivit y coefficient model wit h par amet er s opt imized at low pr essur es, can be
used t o det er mine , if
i
, b
i
, and b ar e known. To comput e b, a linear mixing
r ule is assumed as in t he or iginal Hur on-Vidal mixing r ules:
b x b
i i
i
(8)
This equat ion is equivalent t o t he assumpt ion of zer o excess molar volume.
The MHV2 mixing r ule was t he fir st successful pr edict ive mixing r ule for
equat ions of st at e. This mixing r ule uses pr eviously det er mined act ivit y
coefficient par amet er s for pr edict ions at high pr essur es. UNIFAC was chosen as
a default for it s pr edict ive char act er . The Lyngby modified UNIFAC for mulat ion
was chosen for opt imum per for mance (see UNIFAC (Lyngby Modified) on page 3-
72). However , any act ivit y coefficient model can be used when it s binar y
int er act ion par amet er s ar e known.
Like t he Hur on-Vidal mixing r ules, t he MHV2 mixing r ules ar e not flexible in t he
descr ipt ion of t he excess molar volume. The MHV2 mixing r ules ar e t heor et ically
incor r ect at t he low pr essur e limit . But t he pr act ical consequences of t his
dr awback ar e minimal (see Hur on-Vidal Mixing Rules, t his chapt er ).
References
S. Dahl and M.L. Michelsen, "High-Pr essur e Vapor -Liquid Equilibr ium wit h a
UNIFAC-based Equat ion-of-st at e," AIChE J ., Vol. 36, (1990), pp. 1829-1836.
Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules
These mixing r ules by Holder baum and Gmehling (1991) use a r elat ionship
bet ween t he excess Helmholt z ener gy and equat ion-of-st at e. They do not use a
r elat ionship bet ween equat ion-of-st at e pr oper t ies and excess Gibbs ener gy, as in
t he Hur on-Vidal mixing r ules. The pr essur e-explicit expr ession for t he equat ion-
of-st at e is subst it ut ed in t he t her modynamic equat ion:
p
A
V
T
_
,
(1)
The Helmholt z ener gy is calculat ed by int egr at ion. A
E
is obt ained by:
A A x A RT x x
m
E
m i i i i
I i
*
ln (2)
Wher e bot h A
i
*
and A
m
ar e calculat ed by using equat ion 1. A
i
*
and A
m
ar e
wr it t en in t er ms of equat ion-of-st at e par amet er s.
3-50 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
The simplificat ion of const ant packing fr act ion ( / ) V b
m
is used:
V
b
V
b
i
l
i
m
l *,
(3)
Wit h:
b x b
i i
i
(4)
Ther efor e:
V p
m
E
( ) 0 (5)
The mixing r ule is:
a
b
x
a
b
A p
i
i
i
m
E
i
( ) (6)
Wher e is slight ly differ ent fr om for t he Hur on-Vidal mixing r ule:
ln
+
+
_
,
1
1 2
1
2
V
b
L
V
b
m
m
(7)
Wher e
1
and
2
, depend on t he equat ion-of-st at e (see Hur on-Vidal Mixing
Rules, t his chapt er ). If equat ion 6 is applied at infinit e pr essur e, t he packing
fr act ion goes t o 1. The excess Helmholt z ener gy is equal t o t he excess Gibbs
ener gy. The Hur on-Vidal mixing r ules ar e r ecover ed.
The goal of t hese mixing r ules is t o be able t o use binar y int er act ion par amet er s
for act ivit y coefficient models at any pr essur e. These par amet er s have been
opt imized at low pr essur es. UNIFAC is chosen for it s pr edict ive char act er . Two
issues exist : t he packing fr act ion is not equal t o one, and t he excess Gibbs and
Helmholt z ener gy ar e not equal at t he low pr essur e wher e t he UNIFAC
par amet er s have been der ived.
Fischer (1993) det er mined t hat boiling point , t he aver age packing fr act ion for
about 80 differ ent liquids wit h differ ent chemical nat ur es was 1.1. Adopt ing t his
value, t he differ ence bet ween liquid excess Gibbs ener gy and liquid excess
Helmholt z ener gy can be comput ed as:
A p G p atm pdV x pdV
m
E l
m
E l
m
l
i i
l
V b
V b
i
V b
V b
i
l
i
l
m
l
m
l
, , *,
. .
( ) ( )
*,
*,
+
1
11 11
(8)
Physical Pr oper t y Met hods and Models 3-51
Ver sion 10
Chapter 3
The r esult is a pr edict ive mixing r ule for cubic equat ions of st at e. But t he
or iginal UNIFAC for mulat ion gives t he best per for mance for any binar y pair
wit h int er act ions available fr om UNIFAC. Gas-solvent int er act ions ar e
unavailable.
At t he Univer sit y of Oldenbur g in Ger many, t he UNIFAC gr oups wer e ext ended
wit h oft en-occur r ing gases. New gr oup int er act ions wer e det er mined fr om gas-
solvent dat a, specific t o t he Redlich-Kwong-Soave equat ion-of-st at e. The new
built -in par amet er s t o ASPEN PLUS ar e act ivat ed when using t he PSRK
equat ion-of-st at e model.
The PSRK met hod has a lot in common wit h t he Hur on-Vidal mixing r ules. The
mole fr act ion is dependent on t he second vir ial coefficient and excess volume is
pr edict ed. These ar e minor disadvant ages.
References
T. Holder baum and J . Gmehling, "PSRK: A Gr oup Cont r ibut ion Equat ion-of-st at e
based on UNIFAC," Fluid Phase Eq., Vol. 70, (1991), pp. 251-265.
K. Fischer , "Die PSRK-Met hode: Eine Zust andsgleichung unt er Ver wendung des
UNIFAC-Gr uppenbeit r agsmodells," (Dsseldor f: VDI For t schr it t ber icht e, Reihe
3: Ver fahr enst echnik, Nr . 324, VDI Ver lag GmbH, 1993).
Wong-Sandler Mixing Rules
These mixing r ules use a r elat ionship bet ween t he excess Helmholt z ener gy and
equat ion-of-st at e. They do not use a r elat ionship bet ween equat ion-of-st at e
pr oper t ies and excess Gibbs ener gy, as in t he Hur on-Vidal mixing r ules. The
pr essur e-explicit expr ession for t he equat ion-of-st at e is subst it ut ed in t he
t her modynamic equat ion:
p
A
V
T
_
,
(1)
The Helmholt z ener gy is obt ained by int egr at ion, A
E
is obt ained by:
A A x A RT x x
m
E
m i i i i
i i
*
ln (2)
Wher e bot h A
i
*
and A
m
ar e calculat ed by using equat ion 1. A
i
*
and A
m
ar e
wr it t en in t er ms of equat ion-of-st at e par amet er s.
Like Hur on and Vidal, t he limit ing case of infinit e pr essur e is used. This
simplifies t he expr essions for A
i
*
and A
m
. Equat ion 2 becomes:
a
b
x
a
b
A p
i
i
i
m
E
i
( ) (3)
3-52 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Wher e depends on t he equat ion-of-st at e (see Hur on-Vidal Mixing Rules , t his
chapt er ).
Equat ion 3 is complet ely analogous t o t he Hur on-Vidal mixing r ule for t he excess
Gibbs ener gy at infinit e pr essur e. (See equat ion 4, Hur on-Vidal Mixing Rules ,
t his chapt er .) The excess Helmholt z ener gy can be appr oximat ed by t he excess
Gibbs ener gy at low pr essur e fr om any liquid act ivit y coefficient model. Using t he
Helmholt z ener gy per mit s anot her mixing r ule for b t han t he linear mixing r ule.
The mixing r ule for b is der ived as follows. The second vir ial coefficient must
depend quadr at ically on t he mole fr act ion:
B T x x B
i j ij
j i
( )
(4)
Wit h:
B
B B
k
ij
ii jj
ij
( )
( )
2
1 (5)
The r elat ionship bet ween t he equat ion-of-st at e at low pr essur e and t he vir ial
coefficient is:
B b
a
RT
(6)
B b
a
RT
ii i
i
(7)
Wong and Sandler discover ed t he following mixing r ule t o sat isfy equat ion 4
(using equat ions 6 and 7):
b
x x B
A p
RT
x B
i j ij
j i
m
E
i ij
i
1
( )
_
,
+
_
,
+
1 2 3 4 5
2 2
1 1
Wher e:
T
ref
= 298.15K.
The user must :
Supply t hese element s using a Pr oper t ies Par amet er s Binar y.T-Dependent
for m.
Specify Comp ID i and Comp ID j on t his for m, using t he same or der t hat
appear s on t he Component s.Main for m.
Physical Pr oper t y Met hods and Models 3-55
Ver sion 10
Chapter 3
Parameter Name Symbol No. of Elements Default Units
Ionic Unary Parameters
GMBPB
ion
1 0
GMBPD
ion
1
1 0
Cation-Anion Parameters
GMBPB0
( ) 0
5 0
GMBPB1
( ) 1
5 0
GMBPB2
( ) 2
5 0
GMBPB3
( ) 3
5 0
Cation-Cation Parameters
GMBPTH
cc
5 0
Anion-Anion Parameters
GMBPTH
aa
5 0
Molecule-IonParameters
Molecule-Molecule
Parameters
GMBPB0
( ) 0
5 0
GMBPB1
( ) 1
5 0
Chien-Null
The Chien-Null model calculat es liquid act ivit y coefficient s and it can be used for
highly non-ideal syst ems. The gener alized expr ession used in it s der ivat ion can
be adapt ed t o r epr esent ot her well known for malisms for t he act ivit y coefficient
by pr oper ly defining it s binar y t er ms. This char act er ist ic allows t he model t he
use of alr eady available binar y par amet er s r egr essed for t hose ot her liquid
act ivit y models wit h t her modynamic consist ency.
The equat ion for t he Chien-Null liquid act ivit y coeficient is:
ln
i
ji i ji j
j j
ji j ji j
j j
k
jk i jk j
j j
jk j jk j
j j
ik
jk j
j
ik
jk j
j
ik
jk j
j
ik
jk j
j
k
A x R x
S x V x
x
A x R x
S x V x
A
A x
R
R x
S
S x
V
V x
+ +
_
,
1
]
1
1
1
1
1
2
3-56 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Wher e:
R
A
A
ji
ji
ij
A
ii
0
A
A
ji
ij
1
A a
b
T
ij ij
ij
+
Subscr ipt s i and j ar e component indices.
The choice of model and par amet er s can be set for each binar y pair const it ut ing
t he pr ocess mixt ur e by assigning t he appr opr iat e value t o t he ICHNUL
par amet er .
The Regular Solut ion and Scat char d-Hamer models ar e r egained by subst it ut ing
in t he gener al expr ession (ICHNUL = 1 or 2).
V S
V
V
ji ji
j
l
i
l
*,
*,
Wher e:
V
j
l *,
= Liquid molar volume of component i
The Chien-Null act ivit y coefficient model collapses t o t he Mar gules liquid act ivit y
coefficient expr ession by set t ing (ICHNUL = 3):
V S
ji ji
1
The Van Laar Liquid act ivit y coefficient model is t he obt ained when t he V and S
par amet er s in t he Chien-Null models ar e set t o t he r at io of t he cr oss t er ms of A
(ICHNUL = 4:)
V S
A
A
ji ji
ji
ij
Finally, t he Renon or NRTL model is obt ained when we make t he following
susbst it ut ions in t he Chien-Null expr ession for t he liquid act ivit y (ICHNUL = 5).
S R
A
A
ji ji
ji
ij
( )
ij ij
ij
a
b
T
+
C c d T K
ij ij ij
+ ( . ) 27315
c c
ji ij
d d
ji ij
3 1 6
CHNULL/1
a
ij
0
CHNULL/2
b
ij
0
CHNULL/3 Vij 0
The parameter ICHNUL is used to identify the activity model parameters available for each binary pair
of interest. The following values are allowed for ICHNUL:
ICHNUL = 1 or 2, sets the model to the S catchard-Hamer or regular s olution model for the associated
binary;
ICHNUL = 3, sets the model to the Three-S uffix Margules activity model for the associated binary;
ICHNUL = 4, sets the model to the Van Laar formalism for the activity model for the associated binary;
ICHNUL = 5, sets the model to the NRTL (Renon) formalism for the activity model for the associated
binary.
3-58 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
ICHNUL = 6, sets the model to the full Chien-Null formalism for the activity model for the associated
binary.
When you specify a value for the ICHNUL parameter that is different than the default, you must enter
the appropriate binary model parameters for the chosen activity model directly. The routine will
automatically convert the expressions and parameters to conform to the Chien-Null formulation.
Constant Acti vi ty Coeffi ci ent
This appr oach is used exclusively in met allur gical applicat ions wher e mult iple
liquid and solid phases can coexist . You can assign any value t o t he act ivit y
coefficient of component i. Use t he Pr oper t ies Par amet er s Unar y.Scalar for m.
The equat ion is:
i i
a
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
GMCONS
a
i
1.0 x
Electrolyte NRTL Acti vi ty Coeffi ci ent Model
ASPEN PLUS uses t he elect r olyt e NRTL model t o calculat e act ivit y coefficient s,
ent halpies, and Gibbs ener gies for elect r olyt e syst ems. Model development and
wor king equat ions ar e pr ovided in Appendix B.
The adjust able par amet er s for t he elect r olyt e NRTL model include t he:
Pur e component dielect r ic const ant coefficient of nonaqueous solvent s
Bor n r adius of ionic species
NRTL par amet er s for molecule-molecule, molecule-elect r olyt e, and
elect r olyt e-elect r olyt e pair s
The pur e component dielect r ic const ant coefficient s of nonaqueous solvent s and
Bor n r adius of ionic species ar e r equir ed only for mixed-solvent elect r olyt e
syst ems. The t emper at ur e dependency of t he dielect r ic const ant of solvent B is:
B B B
B
T A B
T C
( ) +
_
,
1 1
Each t ype of elect r olyt e NRTL par amet er consist s of bot h t he nonr andomness
fact or , , and ener gy par amet er s, . The t emper at ur e dependency r elat ions of
t he elect r olyt e NRTL par amet er s ar e:
Molecule-Molecule Binar y Par amet er s:
BB BB
BB
BB BB
A
B
T
F T G T
ln( ) + + +
Physical Pr oper t y Met hods and Models 3-59
Ver sion 10
Chapter 3
Elect r olyt e-Molecule Pair Par amet er s:
ca B ca B
ca B
ca B
ref
ref
C
D
T
E
T T
T
T
T
, ,
,
,
( )
ln + +
+
_
,
1
]
1
B ca B ca
B ca
B ca
ref
ref
C
D
T
E
T T
T
T
T
, ,
,
,
( )
ln + +
+
_
,
1
]
1
Elect r olyt e-Elect r olyt e Pair Par amet er s:
For t he elect r olyt e-elect r olyt e pair par amet er s, t he t wo elect r olyt es must shar e
eit her one common cat ion or one common anion:
c a c a c a c a
c a c a
c a c a
ref
ref
C
D
T
E
T T
T
T
T
, ,
,
,
( )
ln + +
+
_
,
1
]
1
ca ca ca ca
ca ca
ca ca
ref
ref
C
D
T
E
T T
T
T
T
, ,
,
,
( )
ln + +
+
_
,
1
]
1
Wher e:
T
ref
= 298.15K
Many par amet er pair s ar e included in t he elect r olyt e NRTL model par amet er
dat abank (see AS PEN PLUS Physical Property Data, Chapt er 1).
Parameter Name Symbol No. of
Elements
Default MDS Units
Dielectric Constant Unary Parameters
CPDIEC
A
B
1
B
B
1 0
C
B
1 298.15 TEMPERATURE
If dielectric constant parameters are missing for a solvent, the dielectric constant of water is
automatically assigned.
B
B B
0 x TEMPERATURE
NRTL/3
BB B B
.3 x
NRTL/4 0 x TEMPERATURE
NRTL/5
F
BB
0 x TEMPERATURE
F
B B
0 x TEMPERATURE
NRTL/6
G
BB
0 x TEMPERATURE
G
B B
0 x TEMPERATURE
Electrolyte-Molecule Pair Parameters
GMELCC
C
ca B ,
1 0 x
C
B ca ,
1 0 x
GMELCD
D
ca B ,
1 0 x TEMPERATURE
D
B ca ,
1 0 x TEMPERATURE
GMELCE
E
ca B ,
1 0 x
E
B ca ,
1 0 x
GMELCN
ca B B ca , ,
1 .2 x
D
ca ca ,
1 0 x TEMPERATURE
D
c a c a ,
1 0 x TEMPERATURE
D
c a c a ,
1 0 x TEMPERATURE
GMELCE
E
ca ca ,
1 0 x
E
ca ca ,
1 0 x
E
c a c a ,
1 0 x
E
c a c a ,
1 0 x
GMELCN
ca ca ca ca , ,
1 .2 x
c a c a c a c a , ,
1 .2 x
If dielectric constant parameters are missing for a solvent, the dielectric constant of water is
automatically assigned.
i
j ji ji
j
k ki
k
j ij
k kj
k
ij
m mj mj
m
k kj
k
j
x G
x G
x G
x G
x G
x G
+
_
,
Wher e:
G
ij
= exp( )
ij ij
ij
= a
b
T
e T f T
ij
ij
ij ij
+ + + ln
ij
= c d T K
ij ij
+ ( . ) 27315
ii
= 0
G
ii
= 1
a
ij
a
ji
b
ij
b
ji
c
ij
c
ji
d
ij
d
ji
Physical Pr oper t y Met hods and Models 3-63
Ver sion 10
Chapter 3
Recommended
c
ij
Values for Different Types of Mixtures
c
ij
Mixtures
0.30 Nonpolar substances; nonpolar with polar non-associated liquids; small deviations from
ideality
0.20 Saturated hydrocarbons with polar non-associated liquids and systems that exhibit
liquid-liquid immiscibility
0.47 Strongly self-associated substances with nonpolar substances
The binar y par amet er s a
ij
, b
ij
, c
ij
, d
ij
, e
ij
, and f
ij
can be det er mined fr om VLE
and/or LLE dat a r egr ession. ASPEN PLUS has a lar ge number of built -in binar y
par amet er s for t he NRTL model. The binar y par amet er s have been r egr essed
using VLE and LLE dat a fr om t he Dor t mund Dat abank. The binar y par amet er s
for t he VLE applicat ions wer e r egr essed using t he ideal gas, Redlich-Kwong, and
Hayden OConnell equat ions of st at e. See AS PEN PLUS Physical Property Data,
Chapt er 1 for det ails.
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
NRTL/1
a
ij
0 x -100.0 100.0
NRTL/2
b
ij
0 x -30000 30000.0 TEMPERATURE
NRTL/3
c
ij
0.30 x 0.0 1.0
NRTL/4
d
ij
0 x -0.02 0.02 TEMPERATURE
NRTL/5
e
ij
0 x TEMPERATURE
NRTL/6
f
ij
0 x TEMPERATURE
0
,
( )
1
,
( )
2
,
( )
3
, c
_
,
+
_
,
+
1 2 3 4 5
2
2 1 1
Wher e:
Tr ef = 298.15 K
The user must :
Supply t hese element s using a Pr oper t ies Par amet er s Binar y.T-Dependent
for m.
Specify Comp ID i and Comp ID j on t his for m, using t he same or der t hat
appear s on t he Component s.Main for m.
The par amet er s ar e summar ized in t he following t able. Ther e is a Pit zer
par amet er dat abank in ASPEN PLUS (see AS PEN PLUS Physical Property
Data, Chapt er 1).
Parameter Name Symbol No. of Elements Default MDS Units
Cation-Anion Parameters
GMPTB0
( ) 0
5 0 x
GMPTB1
( ) 1
5 0 x
GMPTB2
( ) 2
5 0 x
GMPTB3
( ) 3
5 0 x
GMPTC
C
5 0 x
Cation-Cation Parameters
GMPTTH
cc
5 0 x
Anion-Anion Parameters
GMPTTH
aa
5 0 x
Cation1-Cation 2-Common Anion Parameters
GMPTPS
cc a
1 0 x
continued
Physical Pr oper t y Met hods and Models 3-65
Ver sion 10
Chapter 3
Parameter Name Symbol No. of Elements Default MDS Units
Anion1-Anion2-Common Cation Parameters
GMPTPS
ca a
1 0 x
Molecule-Ion and Molecule-Molecule Parameters
GMPTB0
( ) 0
5 0 x
GMPTB1
( ) 1
5 0 x
GMPTC
C
5 0 x
Polynomial Activity Coefficient
This model r epr esent s act ivit y coeficient as an empir ical funct ion of composit ion
and t emper at ur e. It is used fr equent ly in met allur gical applicat ions wher e
mult iple liquid and solid solut ion phases can exist .
The equat ion is:
ln
i i i i i i i i i i
A B x C x D x E x + + + +
2 3 4
Wher e:
A
i
= a T a a T
i i i 1 2 3
+ + ln( )
B
i
= b T b b T
i i i 1 2 3
+ + ln( )
C
i
= c T c c T
i i i 1 2 3
+ + ln( )
D
i
= d T d d T
i i i 1 2 3
+ + ln( )
E
i
= e T e e T
i i i 1 2 3
+ + ln( )
For any component i, t he value of t he act ivit y coefficient can be fixed:
i i
f
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
GMPLYP/1
a
i1
0 x
GMPLYP/2
a
i2
0 x
GMPLYP/3
a
i3
0 x
GMPLYP/4
b
i1
0 x
continued
3-66 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
GMPLYP/5
b
i 2
0 x
GMPLYP/6
b
i3
0 x
GMPLYP/7
c
i1
0 x
GMPLYP/8
c
i 2
0 x
GMPLYP/9
c
i3
0 x
GMPLYP/10
d
i1
0 x
GMPLYP/11
d
i2
0 x
GMPLYP/12
d
i3
0 x
GMPLYP/13
e
i1
0 x
GMPLYP/14
e
i2
0 x
GMPLYP/15
e
i3
0 x
GMPLYO
f
i
x
Redlich-Kister
This model calculat es act ivit y coefficient s. It is a polynomial in t he differ ence
bet ween mole fr act ions in t he mixt ur e. It can be used for liquid and solid
mixt ur es (mixed cr yst als).
The equat ion is:
( )
( )
( ) ( )
( )
( )
[ ]
ln
, ,
i j n ij i j
n
i j j k n jk j k
n
j k
n k
nc
n j
nc
x A x x nx x x x A x x n x x
1
]
1
2
1
2
2
1
5
1 1
5
1
2 1
Wher e:
nc = Number of component s
A
ij 1,
= a T b
ij ij
+
A
ij 2,
= c T d
ij ij
+
A
ij 3,
= e T f
ij ij
+
A
ij 4,
= g T h
ij ij
+
Physical Pr oper t y Met hods and Models 3-67
Ver sion 10
Chapter 3
A
ij 5,
= m T n
ij ij
+
For any component i, t he value of t he act ivit y coefficient can be fixed:
i i
v
Parameter Name/ Element Symbol Default MDS Upper Limit Lower Limit Units
GMRKTB/1
a
ij
0 x
GMRKTB/2
b
ij
0 x
GMRKTB/3
c
ij
0 x
GMRKTB/4
d
ij
0 x
GMRKTB/5
e
ij
0 x
GMRKTB/6
f
ij
0 x
GMRKTB/7
g
ij
0 x
GMRKTB/8
h
ij
0 x
GMRKTB/9
m
ij
0 x
GMRKTB/10
n
ij
0 x
GMRKTO
v
i
x
Scatchard-Hildebrand
The Scat char d-Hildebr and model calculat es liquid act ivit y coefficient s. It is used
in t he CHAO-SEA pr oper t y met hod and t he GRAYSON pr oper t y met hod.
The equat ion for t he Scat char d-Hildebr and model is:
ln ( )
*,
i
i
l
j k ji jk
k j
V
RT
A A
1 2
Wher e:
A
ij
=
( )
2
2
i j
i
=
x V
V
i i
l
m
l
*,
3-68 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
V
m
L *,
= x V
i i
l
i
*,
The Scat char d-Hildebr and model does not r equir e binar y par amet er s.
Parameter
Name/Element
Symbol Default MDS Upper Limit Lower Limit Units
TC
T
ci
x 5.0 2000.0 TEMPERATURE
DELTA
i
x
10
3
10
5
SOLUPARAM
VLCVT1
V
i
CVT *,
x 0.0005 1.0 MOLE-VOLUME
GMSHVL
V
i
I *,
V V
T
i
I
i
CVT
ci
*, *,
. .
.
_
,
57 30
29815
x 0.01 1.0 MOLE-VOLUME
Three-Suffi x Margules
This model can be used t o descr ibe t he excess pr oper t ies of liquid and solid
solut ions. It does not find much use in chemical engineer ing applicat ions, but is
st ill widely used in met allur gical applicat ions. Not e t hat t he binar y par amet er s
for t his model do not have physical significance.
The equat ion is:
( ) ( ) ( ) ( )
ln
i ij ji j jl j l ij jl j j i jl ljj l j
l
nc
j
nc
j
nc
l
nc
j
nc
j
nc
k k x k x x k k x x x k k x x + +
1
2
2
2
Wher e k
ij
is a binar y par amet er :
( ) k a T b c T
ij ij ij ij
+ + ln
For any component i, t he value of t he act ivit y coefficient can be fixed:
i i
d
Parameter Name/ Element Symbol Default MDS Upper Limit Lower Limit Units
GMMRGB/1
a
ij
0 x TEMPERATURE
GMMRGB/2
b
ij
0 x
GMMRGB/3
c
ij
0 x
GMMRGO
d
i
x
Physical Pr oper t y Met hods and Models 3-69
Ver sion 10
Chapter 3
References
M. Mar gules, "ber die Zusammenset zung der gest t igt en Dmpfe von
Mischungen," Sit zungsber . Akad. Wiss. Vienna, Vol. 104, (1895), p. 1293.
D.A. Gaskell, Int r oduct ion t o Met allur gical Ther modyanics, 2nd ed., (New Yor k:
Hemispher e Publishing Cor p., 1981), p. 360.
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Pr oper t ies of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987).
UNIFAC
The UNIFAC model calculat es liquid act ivit y coefficient s for t he following
pr oper t y met hods: UNIFAC, UNIF-HOC, and UNIF-LL. Because t he UNIFAC
model is a gr oup-cont r ibut ion model, it is pr edict ive. All published gr oup
par amet er s and gr oup binar y par amet er s ar e st or ed in ASPEN PLUS.
The equat ion for t he or iginal UNIFAC liquid act ivit y coefficient model is made up
of a combinat or ial and r esidual t er m:
ln = ln ln
i
c
i
r
+
ln
i
c
= ln ln
i
i
i
i
i
i
i
i
x x
Z
_
,
+ +
1
]
1
1
2
1
Wher e t he molecular volume and sur face fr act ions ar e:
i
i i
j j
j
nc
x r
x r
and
i
i i
j j
j
nc
x
z
q
x
z
q
2
2
Wher e nc is t he number of component s in t he mixt ur e. The coor dinat ion number
z is set t o 10. The par amet er s r i and qi ar e calculat ed fr om t he gr oup volume and
ar ea par amet er s:
r v R
i ki k
k
ng
and q v Q
i ki k
k
ng
Wher e
ki
is t he number of gr oups of t ype k in molecule i, and ng is t he number
of gr oups in t he mixt ur e. The r esidual t er m is:
[ ]
ln ln ln
i
r
ki k k
i
k
ng
3-70 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
k
is t he act ivit y coefficient of a gr oup at mixt ur e composit ion, and
k
i
is t he
act ivit y coefficient of gr oup k in a mixt ur e of gr oups cor r esponding t o pur e i. The
par amet er s
k
and
k
i
ar e defined by:
ln ln
k k m mk
m km
n nm
n
ng
m
ng
m
ng
Q
_
,
_
,
1
Wit h:
k
k k
m m
m
ng
X
z
Q
X
z
Q
2
2
And:
mn
b T
mn
e
/
The par amet er X
k
is t he gr oup mole fr act ion of gr oup k in t he liquid:
X
x
x
k
kj j
j
nc
mj j
m
ng
j
nc
Parameter Name/Element SymbolT Default MDS Lower Limit Upper Limit Units
UFGRP
( )
ki mi
...
GMUFQ
Q
k
GMUFR
R
k
GMUFB
b
kn
TEMPERATURE
The par amet er UFGRP st or es t he UNIFAC funct ional gr oup number and number
of occur r ences of each gr oup. UFGRP is st or ed in t he ASPEN PLUS pur e
component dat abank for most component s. For nondat abank component s, ent er
UFGRP on t he Pr oper t ies Molecular St r uct ur e Funct ional Gr oup sheet . See
AS PEN PLUS Physical Property Data, Chapt er 3, for a list of t he UNIFAC
funct ional gr oups.
Physical Pr oper t y Met hods and Models 3-71
Ver sion 10
Chapter 3
References
Aa. Fr edenslund, R.L. J ones and J .M. Pr ausnit z, AIChE J ., Vol. 21, (1975),
p. 1086.
Aa. Fr edenslund, J . Gmehling and P. Rasmussen, "Vapor -Liquid Equilibr ia using
UNIFAC," (Amst er dam: Elsevier , 1977).
H.K. Hansen, P. Rasmussen, Aa. Fr edenslund, M. Schiller , and J . Gmehling,
"Vapor -Liquid Equilibr ia by UNIFAC Gr oup Cont r ibut ion. 5 Revision and
Ext ension", Ind. Eng. Chem. Res., Vol. 30, (1991), pp. 2352-2355.
UNIFAC (Dortmund Modified)
The UNIFAC modificat ion by Gmehling and cowor ker s (Weidlich and Gmehling,
1987; Gmehling et al., 1993), is slight ly differ ent in t he combinat or ial par t . It is
ot her wise unchanged compar ed t o t he or iginal UNIFAC:
ln ln ln
i
c i
i
i
i
i
i
i
i
i
x x
z
q
_
,
+ +
_
,
1
2
1
Wit h:
i
i
i
j j
j
x
r
x r
3
4
3
4
The t emper at ur e dependency of t he int er act ion par amet er s is:
a a a T a T
mn mn mn mn
+ +
, , , 1 2 3
2
Parameter Name/Element SymbolT Default MDS Lower Limit Upper Limit Units
UFGRPD
( ) k m
ki mi
...
GMUFDQ
Q
k
GMUFDR
R
k
UNIFDM/1
a
mn,1
0 TEMPERATURE
UINFDM/2
a
mn, 2
0 TEMPERATURE
UNIFDM/3
a
mn,3
0 TEMPERATURE
3-72 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
The par amet er UFGRPD st or es t he gr oup number and t he number of occur r ences
of each gr oup. UFGRPD is st or ed in t he ASPEN PLUS pur e component
dat abank. For nondat abank component s, ent er UFGRPD on t he Pr oper t ies
Molecular St r uct ur e Funct ional Gr oup sheet . See AS PEN PLUS Physical
Property Data, Chapt er 3, for a list of t he Dor t mund modified UNIFAC funct ional
gr oups.
References
U. Weidlich and J . Gmehling, "A Modified UNIFAC Model 1. Pr edict ion of VLE,
h
E
and
," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 13721381.
J . Gmehling, J . Li, and M. Schiller , "A Modified UNIFAC Model. 2. Pr esent
Par amet er Mat r ix and Result s for Differ ent Ther modynamic Pr oper t ies," Ind.
Eng. Chem. Res., Vol. 32, (1993), pp. 178193.
UNIFAC (Lyngby Modified)
The equat ions for t he "t emper at ur e-dependent UNIFAC" (Lar sen et al., 1987) ar e
similar t o t he or iginal UNIFAC:
ln ln ln
i i
c
i
r
+ ,
ln ln
i
c i
i
i
i
x x
_
,
+ 1
Volume fr act ions ar e modified:
i
i i
j j
j
nc
x r
x r
2
3
2
3
Wit h:
r R
i ki k
k
ng
( )
ln ln ln
i
r
ki k k
i
k
ng
Physical Pr oper t y Met hods and Models 3-73
Ver sion 10
Chapter 3
Wher e
k
and
k
i
have t he same meaning as in t he or iginal UNIFAC, but
defined as:
ln ln
k k m mk
m
ng
m km
n nm
n
ng
m
ng
z
Q
_
,
_
,
1
]
1
1
1
1
2
1
Wit h:
k
k k
m m
m
ng
X
z
Q
X
z
Q
2
2
mn
a T
e
mn
The t emper at ur e dependency of a is descr ibed by a funct ion inst ead of a const ant :
( ) a a a T a T
T
T
mn mn mn mn
+ + +
_
,
, , ,
. ln
.
.
1 2 3
29815
29815
29815
Parameter Name/Element Symbol T Default MDS Lower Limit Upper Limit Units
UFGRPL
( )
ki mi
...
GMUFLQ
Q
k
GMUFLR
R
k
UNIFLB/1
a
mn,1
0 TEMPERATURE
UNIFLB/2
a
mn, 2
0 TEMPERATURE
UNIFLB/3
a
mn,3
0 TEMPERATURE
The par amet er UFGRPL st or es t he modified UNIFAC funct ional gr oup number
and t he number of occur r ences of each gr oup. UFGRPL is st or ed in t he
ASPEN PLUS pur e component dat abank. For nondat abank component s, ent er
UFGRP on t he Pr oper t ies Molec-St r uct .Func Gr oup for m. See AS PEN PLUS
Physical Property Data, Chapt er 3, for a list of t he Lar sen modified UNIFAC
funct ional gr oups.
3-74 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
References
B. Lar sen, P. Rasmussen, and Aa. Fr edenslund, "A Modified UNIFAC Gr oup-
Cont r ibut ion Model for Pr edict ion of Phase Equilibr ia and Heat s of Mixing," Ind.
Eng. Chem. Res., Vol. 26, (1987), pp. 2274 2286.
UNIQUAC
The UNIQUAC model calculat es liquid act ivit y coefficient s for t hese pr oper t y
met hods: UNIQUAC, UNIQ-2, UNIQ-HOC, UNIQ-NTH, and UNIQ-RK. It is
r ecommended for highly non-ideal chemical syst ems, and can be used for VLE
and LLE applicat ions. This model can also be used in t he advanced equat ions of
st at e mixing r ules, such as Wong-Sandler and MHV2.
The equat ion for t he UNIQUAC model is:
ln ln ln ln
i
i
i
i
i
i
i i i j ij j i i
i
i
j j
j j
x
z
q q t q t l q
x
x l + + +
2
Wher e:
i
= q x q q q x
i i T T k k
k
;
i
=
q x q q q x
i i T T k k
k
;
i
=
i i i T T k k
k
r x r r r x
;
l
i
= ( )
z
r q r
i i i
2
1 +
t
i
=
k ki
k
ij
= exp( ln a b T C T d T
ij ij ij ij
+ + +
z = 10
a
ij
a
ji
b
ij
b
ji
c
ij
c
ji
Physical Pr oper t y Met hods and Models 3-75
Ver sion 10
Chapter 3
d
ij
d
ji
The binar y par amet er s a
ij
, b
ij
, c
ij
, and d
ij
can be det er mined fr om VLE and/or
LLE dat a r egr ession. ASPEN PLUS has a lar ge number of built -in par amet er s
for t he UNIQUAC model. The binar y par amet er s have been r egr essed using VLE
and LLE dat a fr om t he Dor t mund Dat abank. The binar y par amet er s for VLE
applicat ions wer e r egr essed using t he ideal gas, Redlich-Kwong, and Hayden-
OConnell equat ions of st at e. See Chapt er 1, AS PEN PLUS Physical Property
Data, for det ails.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
GMUQR
r
i
x
GMUQQ
q
i
x
GMUQQ1
q
i
q x
UNIQ/1
a
ij
0 x -50.0 50.0
UNIQ/2
b
ij
0 x -15000.0 15000.0 TEMPERATURE
UNIQ/3
c
ij
0 x TEMPERATURE
UNIQ/4
d
ij
0 x TEMPERATURE
B
i
= ( ) x A x
j ji i
j
1
C
i
= x C x
j ij i
j
( ) 1
A
ij
= a b T
ij ij
+
C
ij
= c d T
ij ij
+
C
ij
= C
ji
A
ii
= B C
ii ii
0
a
ij
a
ji
b
ij
b
ji
Parameters
Name/Element
Symbol Default MDS Lower Limit Upper Limit Units
VANL/1
a
ij
0 x -50.0 50.0
VANL/2
b
ij
0 x -15000.0 15000.0 TEMPERATURE
VANL/3
c
ij
0 x -50.0 50.0
VANL/4
d
ij
0 x -15000.0 15000.0 TEMPERATURE
1
Wher e:
ln
A jl j l
l
nc
j
nc
k x x j l A
1
2
and
The par amet er
i
ref
is t he r efer ence act ivit y coefficient of solut e i:
( ) ln ln
i
ref
i i i
a T b c T + +
k
ij
is a binar y par amet er :
( ) k d T e f T
ij ij ij ij
+ + ln
For any component i, t he value of t he act ivit y coefficient can be fixed:
i i
g
This model is r ecommended for dilut e solut ions.
Parameter Name/ Element Symbol Default MDS Lower Limit Upper Limit Units
GMWIPR/1
a
i
0 x TEMPERATURE
GMWIPR/2
b
i
0 x
GMWIPR/3
c
i
0 x
GMWIPB/1
d
ij
0 x TEMPERATURE
GMWIPB/2
e
ij
0 x
GMWIPB/3
f
ij
0 x
GMWIPO
g
i
x
GMWIPS
0 x
GMWIPS is used to identify the solvent component. You must set GMWIPS to 1.0 for the solvent
component. This model allows only one solvent.
3-78 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
References
A.D. Pelt on and C. W. Ball, "A Modified Int er act ion Par amet er For malism for
Non-Dilut e Solut ions," Metallurgical Transactions A, Vol. 17A, (J uly 1986),
p. 1211.
Wilson
The Wilson model calculat es liquid act ivit y coefficient s for t he pr oper t y met hods:
WILSON, WILS2, WILS-HOC, WILS-NTH, WILS-RK, and WILS-HF. It is
r ecommended for highly nonideal syst ems, especially alcohol-wat er syst ems. It
can also be used in t he advanced equat ion-of-st at e mixing r ules, such as Wong-
Sandler and MHV2. This model cannot be used for liquid-liquid equilibr ium
calculat ions.
The equat ion for t he Wilson model is:
ln ln
i ij j
j
ji j
jk k
k
j
A x
A x
A x
_
,
1
Wher e:
ln A
ij
= a b T c T d T
ij ij ij ij
+ + + ln
a
ij
a
ji
b
ij
b
ji
c
ij
c
ji
d
ij
d
ji
The binar y par amet er s a
ij
, b
ij
, c
ij
, and d
ij
must be det er mined fr om VLE dat a
r egr ession. ASPEN PLUS has a lar ge number of built -in binar y par amet er s for
t he Wilson model. The binar y par amet er s have been r egr essed using VLE dat a
fr om t he Dor t mund Dat abank. The binar y par amet er s wer e r egr essed using t he
ideal gas, Redlich-Kwong, and Hayden-OConnell equat ions of st at e. See Chapt er
1, AS PEN PLUS Physical Property Data, for det ails.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
WILSON/1 a
ij
0 x -50.0 50.0
WILSON/2 b
ij
0 x -15000.0 15000.0 TEMPERATURE
WILSON/3 c
ij
0 x - TEMPERATURE
WILSON/4 d
ij
0 x TEMPERATURE
_
,
1
Wher e:
ln A
ij
=
ln
V
V
b
T
j
i
ij
+
b
ij
b
ji
V
i
and V
j
ar e liquid molar volume at t he syst em t emper at ur e calculat ed using
t he Racket t model.
The binar y par amet er s b
ij
and b
ji
must be det er mined fr om VLE dat a r egr ession.
Ther e ar e no built -in binar y par amet er s for t his model.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
WSNVOL/1
b
ij
0 x -15000.0 15000.0 TEMPERATURE
PLXANT/2
C
i 2
x TEMPERATURE
PLXANT/3, . . . , 7
C C
i i 3 7
, ...,
0 x TEMPERATURE
PLXANT/8
C
i 8
0 x TEMPERATURE
PLXANT/9
C
i 9
1000 x TEMPERATURE
If elements 5, 6, or 7 are non-zero, absolute temperature units are assumed for elements 1 through 7.
Physical Pr oper t y Met hods and Models 3-81
Ver sion 10
Chapter 3
Wagner Vapor Pressure Equation
The Wagner vapor pr essur e equat ion is t he best equat ion for cor r elat ion.
However , it s r esult s ar e sensit ive t o t he values of Tc and pc. The equat ion is used
if t he par amet er WAGNER is available:
( ) ( ) ( ) ( )
[ ]
ln
*,
.
p C T C T C T C T T
ri
l
i ri i ri i ri i ri ri
+ + +
1 2
1 5
3
3
4
4
1 1 1 1
Wher e:
T T T
ri ci
p p p
ri
l
i
l
ci
*, *,
+
+ +
2
1
RR NCOO H O
K
RR NH HCO +
+
2
2
3
H O CO
K
H HCO
2 2
3
3
+
+
+
H O
K
H OH
2
4
+
+
HCO
K
H CO
3
5
3
2 +
+
H S
K
H HS
2
6 2
+
+
HS
K
H S
+
+
7 2
Wher e:
R and R = Alcohol subst it ut ed alkyl gr oups
The equilibr ium const ant s ar e given by:
ln K A A T A T A T A T
i i i i i i
+ + + +
1 2 3
2
4
3
5
4
The chemical equilibr ium equat ions ar e solved simult aneously wit h t he balance
equat ions. This obt ains t he mole fr act ions of fr ee H S
2
and CO
2
in solut ion. The
equilibr ium par t ial pr essur es of H S
2
and CO
2
ar e r elat ed t o t he r espect ive fr ee
concent r at ions by Henr ys const ant s:
ln H B B T
i i i
+
1 2
The appar ent fugacit ies and par t ial molar ent halpies, Gibbs ener gies and
ent r opies of H S
2
and CO
2
ar e calculat ed by st andar d t her modynamic
r elat ionships. The chemical r eact ions ar e always consider ed.
3-84 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
The values of t he coefficient s for t he seven equilibr ium const ant s ( ) A A
i i 1 5
, ..., and
for t he t wo Henr ys const ant s B
i 1
and B
i 2
ar e built int o ASPEN PLUS. The
coefficient s for t he equilibr ium const ant s wer e det er mined by r egr ession. All
available dat a for t he four amines wer e used: monoet hanolamine,
diet hanolamine, disopr opanolamine and diglycolamine.
You ar e not r equir ed t o ent er any par amet er s for t his model.
References
R.L. Kent and B. Eisenber g, Hydrocarbon Processing, (Febr uar y 1976), pp. 87-92.
Physical Pr oper t y Met hods and Models 3-85
Ver sion 10
Chapter 3
Heat of Vaporization Model
ASPEN PLUS uses t wo models t o calculat e pur e component heat of vapor izat ion:
t he Wat son/DIPPR model and t he Clausius-Clapeyr on model. For t he
Wat son/DIPPR model, t he DIPPR equat ion is t he primary equat ion used for all
component s. The Wat son equat ion is used in PCES.
DIPPR Equation
The equat ion for t he DIPPR heat of vapor izat ion model is:
( )
( )
vap i i ri
C C T C T C T
i i
H C T C T C
i i ri i ri i ri *
+ + +
1 6 7
1
2 3 4
2
5
3
for
Wher e:
T T T
ri ci
_
,
>
+
1
1
1 1
1
1
Wher e:
( )
vap i
H T
*
1
= Heat of vapor izat ion at t emper at ur e T
1
3-86 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default Lower Limit Upper Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
DHVLWT/1
( )
vap i
H T
*
1
5 10
4
X 5 10
8
X
MOLE-ENTHALPY
DHVLWT/2
T
1
4.0 3500.0 TEMPERATURE
DHVLWT/3
a
i
0.38 -2.0 2.0
DHVLWT/4
b
i
0 -2.0 2.0
DHVLWT/5
T
min
0 0.0 1500.0 TEMPERATURE
Clausi us-Clapeyron Equati on
ASPEN PLUS can calculat e heat of vapor izat ion using t he Clausius-Clapeyr on
equat ion:
( )
vap i
i
l
i
v
i
l
H
d p
dT
T V V
*
*,
*, *,
Wher e:
d p
dT
i
l *,
= Slope of t he vapor pr essur e cur ve calculat ed fr om t he Ext ended
Ant oine equat ion
V
i
v *,
= Vapor molar volume calculat ed fr om t he Redlich-Kwong
equat ion-of-st at e
V
i
l *,
= Liquid molar volume calculat ed fr om t he Racket t equat ion
For par amet er r equir ement s, see Ext ended Ant oine/Wagner , t he Racket t model,
and Redlich-Kwong, all in t his chapt er .
Molar Volume and Densi ty Models
ASPEN PLUS has 10 built -in molar volume and densit y models available. This
sect ion descr ibes t he molar volume and densit y models.
Model Type
API Liquid Volume Liquid volume
Brelvi-O'Connell Partial molar liquid volume of gases
continued
Physical Pr oper t y Met hods and Models 3-87
Ver sion 10
Chapter 3
Model Type
Clarke Aqueous Electrolyte Volume Liquid volume
Costald Liquid Volume Liquid volume
Debije-Hckel Volume Electrolyte liquid volume
Rackett/DIPPR Pure Component Liquid Volume Liquid volume/liquid density
Rackett Mixture Liquid Volume Liquid volume
Modified Rackett Liquid volume
Solids Volume Polynomial Solid volume
API Liquid Volume
This model calculat es liquid molar volume for a mixt ur e, using t he API pr ocedur e
and t he Racket t model. Ideal mixing is assumed:
V x V x V
m
l
p p
l
r r
l
+
Wher e:
x
p
= Mole fr act ion of pseudocomponent s
x
r
= Mole fr act ion of r eal component s
For pseudocomponent s, t he API pr ocedur e is used:
( ) V fcn T T API
p
l
b
, ,
Wher e:
fcn = A cor r elat ion based on API Figur e 6A3.5 (API Technical Data Book,
Pet r oleum Refining, 4t h edit ion)
For r eal component s, t he mixt ur e Racket t model is used:
( )
[ ]
V
RT Z
p
r
l
c
RA T
c
r
+ 1 1
2 7
See t he Racket t model for descr ipt ions.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TB
T
b
4.0 2000.0 TEMPERATURE
API API -60.0 500.0
3-88 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TB
T
b
4.0 2000.0 TEMPERATURE
API API -60.0 500.0
TC
T
c
5.0 2000.0 TEMPERATURE
PC
p
c
10
5
10
8
PRESSURE
RKTZRA
Z
RA
r
ZC 0.1 0.5
Brelvi-OConnell
The Br elvi-OConnell model calculat es par t ial molar volume of a super cr it ical
component i at infinit e dilut ion in pur e solvent A. Par t ial molar volume at
infinit e dilut ion is r equir ed t o comput e t he effect of pr essur e on Henr ys const ant .
(See Henr ys Const ant on page 3-103.) The gener al for m of t he Br elvi-OConnell
model is:
( )
V fcn V V V
iA i
BO
A
BO
A
l
, ,
*
Wher e:
i = Solut e or dissolved-gas component
A = Solvent component
The liquid molar volume of solvent is obt ained fr om t he Racket t model:
( )
[ ]
V
RT Z
p
i
l cA A
RA T
cA
rA
*,
+ 1 1
2 7
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TC
T
cA
5.0 2000.0 TEMPERATURE
PC
p
cA
105 108 PRESSURE
continued
Physical Pr oper t y Met hods and Models 3-89
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
RKTZRA
Z
A
RA
ZC x 0.1 1.0
VLBROC/1
V
i
BO
VC x -1.0 1.0 MOLE-VOLUME
VLBROC/2 0 x -0.1 0.1 TEMPERATURE
References
S.W. Br elvi and J .P. OConnell, AIChE J ., Vol. 18, (1972), p. 1239.
S.W. Br elvi and J .P. OConnell, AIChE J ., Vol. 21, (1975), p. 157.
Clarke Aqueous Electrolyte Volume
The Clar ke model calculat es liquid molar volume for elect r olyt es solut ions. The
model is applicable t o mixed solvent s and is based on:
Amagat s law (equat ion 1)
The r elat ionship bet ween t he par t ial molar volume of an elect r olyt e and it s
mole fr act ion in t he solvent (equat ion 2)
All quant it ies ar e expr essed in t er ms of appar ent component s.
Apparent Component Approach
Amagat s law is:
V x V
m
l
i i
i
(1)
For wat er and molecular solut es, V V
i i
*
and is comput ed fr om t he Racket t
equat ion. If wat er is t he only molecular component , t he ASME st eam t able is
used t o comput e V
i
*
for wat er .
For elect r olyt es:
V V A
x
x
ca ca ca
ca
ca
+
+
1
(2)
Wher e:
x
ca
= Appar ent elect r olyt e mole fr act ion
The mole fr act ions x
ca
ar e r econst it ut ed ar bit r ar ily fr om t he t r ue ionic
concent r at ions, even if you use t he appar ent component appr oach. This t echnique
is explained in Elect r olyt e Simulat ion, Chapt er 5.
3-90 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
The r esult is t hat elect r olyt es ar e gener at ed fr om all possible combinat ions of
ions in solut ion. For example: given an aqueous solut ion of CA
2+
, Na
+
, SO
4
2
,
Cl
Wher e:
V
m
l t ,
= Liquid volume per number of t r ue species
V
m
l a ,
=
Liquid volume per number of appar ent species, V
m
l
of equat ion 1
n
a
= Number of appar ent species
n
t
= Number of t r ue species
The appar ent molar volume is calculat ed as explained in t he pr eceding
subsect ion.
Temperature Dependence
The t emper at ur e dependence of t he molar volume of t he solut ion is
appr oximat ely equal t o t he t emper at ur e dependence of t he molar volume of t he
solvent mixt ur e:
( ) ( )
( )
( )
V T V K
x V T
x V K
m
l
m
l
B B
l
B
B B
l
B
298
298
*,
*,
Physical Pr oper t y Met hods and Models 3-91
Ver sion 10
Chapter 3
Wher e:
B = Any solvent
Parameter Name/Element Applicable Components Symbol Default Units
VLCLK/1 Cation-Anion
V
ca
MOLE-VOLUME
VLCLK/2 Cation-Anion
A
ca
0.020 MOLE-VOLUME
If VLCLK/ 1 is missing, it is calculated based on VLBROC and CHARGE. If VLBROC is missing, the
default value of
012 10
2
. x is used.
COSTALD Liquid Volume
The equat ion for t he COSTALD liquid volume model is:
( )
V V V V
m
sat
m
CTD
m
R
m
R
, , 0
1
Wher e:
V
m
R, 0
and V
m
R, 5
ar e funct ions or T
r
for 0 25 095 . . < T
r
For 095 10 . . < T
r
, t her e is a linear int er polat ion bet ween t he liquid densit y at
T
r
= 0.95 and t he vapor densit y at T
r
= 1.05. This model can be used t o calculat e
sat ur at ed and compr essed liquid molar volume. The compr esed liquid molar
volume is calculat ed using t he Tait equat ion.
Mixing Rules:
V xV xV xV
m
CTD
i i
CTD
i
i i
CTD
i i
CTD
I
+
_
,
_
,
1
]
1
1
1
4
2 3 1 3
3
*. *. *,
V T x x V T
m
CTD
c i j ij
CTD
cij
j i
x
i i
i
Wher e:
( )
V T V T V T
ij
CTD
cij i
CTD
ci j
CTD
cj
*, *,
1
2
3-92 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
VSTCTD
V
i
CTD *,
VC X 0.001 3.5 MOLE-VOLUME
OMGCTD
i
OMEGA X -0.5 2.0
References
R.W. Hankinson and G.H. Thomson, AIChE J ., Vol. 25, (1979), p. 653.
G.H. Thomson, K.R. Br obst , and R.W. Hankinson, AIChE J ., Vol. 28, (1982), p. 4,
p. 671.
Debije-Hckel Volume
The Debije-Hckel model calculat es liquid molar volume for aqueous elect r olyt e
solut ions.
The equat ion for t he Debije-Hckel volume model is:
V x V x V
m w w k k
k
+
*
Wher e:
V
k
_
,
+
10
3
1
3
1
2
ln
Wher e:
V
k
_
,
2 10 3
1
6
x
ln
p
w
Wher e:
A
_
,
w A
e
w B
N
Q
k T
w
= Densit y of wat er (kg / m
-3
)
w
= Dielect r ic const ant of wat er ( Fm
1
), a funct ion of pr essur e and
t emper at ur e (Br adley and Pit zer , 1979)
Parameter Name Applicable Components Symbol Default Units
VLBROC Ions, molecular Solutes
V
k
0 MOLE-VOLUME
References
H.C. Helgeson and D.H. Kir kham, "Theor et ical pr edict ion of t he t her modynamic
behavior of aqueous elect r olyt es at high pr essur e and t emper at ur e. I.
Ther modynamic/elect r ost at ic pr oper t ies of t he solvent ", Am. J . S ci., 274, 1089
(1974).
Rackett/DIPPR Pure Component Liquid Volume
Two equat ions ar e available for pur e component liquid molar volume: t he Racket t
equat ion and t he DIPPR equat ion. The DIPPR equat ion is used if t he par amet er
DNLDIP is available for a given component . The Racket t equat ion is used if t he
par amet er RKTZRA is available.
For liquid molar volume of mixt ur es, t he Racket t mixt ur e equat ion is always
used. This is not necessar ily consist ent wit h t he pur e component molar volume or
densit y.
3-94 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
DIPPR
The DIPPR equat ion is:
( )
*, ( / )
/
l
i i
T C
i i
C C C T C
i
C
i
+
1 2
1 1
6 7
3
4
for
This equat ion is similar t o t he Racket t equat ion. It r et ur ns liquid molar volume
for pur e component s.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
/1
C
i 1
x MOLE-DENSITY
DNLDIP/2
C
i 2
0 x
DNLDIP/3
C
i 3
T
ci
x TEMPERATURE
DNLDIP/4
C
i 4
0 x
DNLDIP/5
C
i 5
0 x
DNLDIP/6
C
i 6
0 x TEMPERATURE
DNLDIP/7
C
i 7
1000 x TEMPERATURE
If element 3 is non-zero, absolute temperature units are assumed for element 3. (S ee Chapter 5.)
Rackett
The equat ion for t he Racket t model is:
( )
[ ]
V
RT Z
p
i
l
ci i
RA
T
ci
r
_
,
+
*,
1 1
2 7
Wher e:
T
r
=
T
T
ci
Parameter Name/
Element
Symbol Default MDS Lower Limit Upper Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
PC
p
ci
10
5
10
8
PRESSURE
RKTZRA
Z
i
RA *,
ZC x 0.1 1.0
Physical Pr oper t y Met hods and Models 3-95
Ver sion 10
Chapter 3
References
H.G. Racket t , J .Chem, Eng. Dat a., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner , J . Chem. Eng. Dat a, Vol. 17, (1972), p. 236.
Rackett Mi xture Li qui d Volume
The Racket t equat ion calculat es liquid molar volume for all act ivit y
coefficient -based and pet r oleum-t uned equat ion-of-st at e based pr oper t y met hods.
In t he last cat egor y of pr oper t y met hods, t he equat ion is used in conjunct ion wit h
t he API model. The API model is used for pseudocomponent s, while t he Racket t
model is used for r eal component s. (See API Liquid Volume on page 3-87.)
The equat ion for t he Racket t model is:
( )
( )
V
RT Z
P
m
l
c m
RA
c
T
r
1
]
1
1 1
2
7
Wher e:
T
c
=
( ) ( )
x x V V T T k V
i j ci cj ci cj ij
j i
cm
1
2
1
2
T
P
c
c
=
x
T
P
i
ci
ci
i
Z
m
RA
=
x Z
i i
RA
i
*,
V
cm
=
xV
i ci
i
T
r
= T
T
c
3-96 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter
Name/Element
Symbol Default MDS Lower Limit Upper Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
PC
p
ci
10
5
10
8
PRESSURE
VCRKT
V
ci
VC x 0.001 3.5 MOLE-VOLUME
RKTZRA
Z
i
RA *,
ZC x 0.1 1.0
RKTKIJ
k
ij
( )
( )
1
8
1
2
1
3
1
3
3
+
V V
V V
ci cj
ci cj
x -5.0 5.0
References
H.G. Racket t , J .Chem, Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner , J . Chem. Eng. Data, Vol. 17, (1972), p. 236.
Modi fi ed Rackett
The Modified Racket t equat ion impr oves t he accur acy of liquid mixt ur e molar
volume calculat ion by int r oducing addit ional par amet er s t o comput e t he pur e
component par amet er RKTZRA and t he binar y par amet er k
ij
.
The equat ion for t he Modified Racket t model is:
( )
( )
V
RT Z
P
m
l c m
RA
c
T
r
1
]
1
1 1
2
7
Wher e:
T
c
=
( ) ( )
x x V V T T k V
i j ci cj ci cj ij
j i
cm
1
2
1
2
k
ij
=
A B T C T
ij ij ij
+ +
2
T
P
c
c
=
x
T
P
i
ci
ci
i
Z
m
RA
=
x Z
i i
RA
i
*,
T
r
= T
T
c
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MRKZRA/1
a
i
RKTZRA x 0.1 0.5
MRKZRA/2
b
i
0 x
MRKZRA/3
c
i
0 x
MRKKIJ/1
A
ij
0 x
MRKKIJ/2
B
ij
0 x
MRKKIJ/3
C
ij
0 x
References
H.G. Racket t , J .Chem, Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner , J . Chem. Eng. Data, Vol. 17, (1972), p. 236.
Solids Volume Polynomial
The equat ion for t he solids volume polynomial is:
( ) V T C C T C T C T C T C T C
i
s
i i i i i i
*,
+ + + +
1 2 3
2
4
3
5
4
6 7
for
Parameter Name Applicable Components Symbol MDS Default Units
VSPOLY/1 Salts, CI solids
C
i 1
x
VSPOLY/2, . . . , 5 Salts, CI solids
C C
i i 2 5
, ...,
x 0
VSPOLY/6 Salts, CI solids
C
i 6
x 0
VSPOLY/7 Salts, CI solids
C
i 7
x 1000
CPAQ0 Ions, molecular solutes
C C
i i 2 5
, ...,
0
CPAQ0 Ions, molecular solutes
C
i 6
0
CPAQ0 Ions, molecular solutes
C
i 7
1000
( )
H T
i
l ref *,
is calculat ed as:
( ) ( )
H T H H H H
i
l ref
i
ig
i
v
i
ig
vap i
l *, *, *, *, *,
+
T
ref
is t he r efer ence t emper at ur e; it default s t o 298.15 K. You can ent er a
differ ent value for t he r efer ence t emper at ur e. This is useful when you want t o
use t his model for ver y light component s or for component s t hat ar e solids at
298.15K.
Act ivat e t his met hod by specifying t he r out e DHL09 for t he pr oper t y DHL on t he
Pr oper t ies Pr oper t y Met hods Rout es sheet . For equat ion-of-st at e pr oper t y met hod,
you must also modify t he r out e for t he pr oper t y DHLMX t o use a r out e wit h
met hod 2 or 3, inst ead of met hod 1. For example, you can use t he r out e DHLMX00
or DHLMX30. You must ascer t ain t hat t he r out e for DHLMX t hat you select
cont ains t he appr opr iat e vapor phase model and heat of mixing calculat ions. Click
t he View but t on on t he for m t o see det ails of t he r out e.
3-100 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Opt ionally, you can specify t hat t his model is used for only cer t ain component s.
The pr oper t ies for t he r emaining component s ar e t hen calculat ed by t he st andar d
model. Use t he par amet er COMPHL t o specify t he component s for which t his
model is used. By default , all component s wit h t he CPLDIP par amet er s use t his
model.
The equat ion is:
C C C T C T C T C T for C T C
p i
l
i i i i i i i ,
*,
+ + + +
1 2 3
2
4
3
5
4
6 7
Linear ext r apolat ion occur s for C
p
l *,
ver sus T out side of bounds.
Parameter
Name/Element Symbol Default MDS Lower Limit Upper Limit Units
CPLDIP/1
C
i 1
T
x MOLE-HEAT-CAPACITY,
TEMPERATURE
CPLDIP/2,...,5
C C
i i 2 5
, ...,
0 x MOLE-HEAT-CAPACITY,
TEMPERATURE
CPLDIP/6
C
i 6
0 x TEMPERATURE
CPLDIP/7
C
i 7
1000 x TEMPERATURE
TREFHL
T
ref
298.15 TEMPERATURE
COMPHL
TEMPERATURE
To specify that the model is used for a component, enter a value of 1.0 for this component parameter.
Ideal Gas Heat Capacity/DIPPR
The DIPPR ideal gas heat capacit y equat ion is used for most component s in t he
ASPEN PLUS pur e component s dat abank. It is used when t he par amet er
CPIGDP is available for a given component .
DIPPR
The equat ion for t he DIPPR ideal gas heat capacit y model by Ali and Lee 1981 is:
( ) ( )
C C C
C T
C T
C
C T
C T
C T C
p
ig
i i
i
i
i
i
i
i i
*,
sinh cosh
+
_
,
+
_
,
1 2
3
3
2
4
5
5
2
6 7
for
This model is also used t o calculat e ideal gas ent halpies, ent r opies, and Gibbs
ener gies.
Physical Pr oper t y Met hods and Models 3-101
Ver sion 10
Chapter 3
Parameter
Name/Element Symbol Default MDS Lower Limit Upper Limit Units
CPIGDP/1
C
i 1
x MOLE-HEAT-CAPACITY
CPIGDP/2
C
i 2
0 x MOLE-HEAT-CAPACITY
CPIGDP/3
C
i 3
0 x TEMPERATURE
CPIGDP/4
C
i 4
0 x MOLE-HEAT-CAPACITY
CPIGDP/5
C
i 5
0 x TEMPERATURE
CPIGDP/6
C
i 6
0 x TEMPERATURE
CPIGDP/7
C
i 7
1000 x TEMPERATURE
If elements 10 or 11 are non-zero, absolute temperature units are assumed for elements 9 through 11.
3-102 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
References
Dat a for t he Ideal Gas Heat Capacit y Polynomial: Reid, Pr ausnit z and Poling,
The Properties of Gases and Liquids, 4t h ed., (New Yor k: McGr aw-Hill, 1987).
ASPEN PLUS combust ion dat a bank, J ANAF Ther mochemical Dat a, Compiled
and calculat ed by t he Ther mal Resear ch Labor at or y of Dow Chemical Company.
F. A. Aly and L. L. Lee, "Self-Consist ent Equat ions for Calculat ing t he Ideal Gas
Heat Capacit y, Ent halpy, and Ent r opy, Fluid Phase Eq., Vol. 6, (1981), p. 169.
Solids Heat Capacity Polynomial
The ent halpy, ent r opy, and Gibbs ener gy of solids ar e calculat ed fr om t he heat
capacit y polynomial:
C C C T C T
C
T
C
T
C
T
C T C
p i
s
i i i
i i i
i i ,
*,
+ + + + +
1 2 3
2 4 5
2
6
7 8
for
C
p i ,
*,8
linear ly ext r apolat ed using t he slope at C
i 7
for T C
i
<
7
and
C
p i ,
*,8
linear ly ext r apolat ed using t he slope at C
i 8
for T C
i
>
8
Parameter Name
Applicable
Components
Symbol MDS Default Units
CPSPO1/1 Solids, Salts
C
i 1
x
CPSPO1/2, . . . , 6 Solids, Salts
C C
i i 2 6
, ...,
x 0
CPSPO1/7 Solids, Salts
C
i 7
x 0
CPSPO1/8 Solids, Salts
C
i 8
x 1000
If elements 4, 5, or 6 are non-zero, absolute temperature units are assumed for elements 1 through 6.
Wher e:
w
A
=
( )
( )
x V
x V
A cA
B cB
B
2
3
2
3
( )
ln ,
*,
H T p
iA A
l
= a b T c T d T T T T
iA iA iA iA L H
+ + + ln for
( ) H T P
iA
, =
( )
H T p
RT
V dp
iA A
l
iA
p
p
a
l
, exp
*,
*,
1
_
,
a
iA
x PRESSURE,
TEMPERATURE
HENRY/2
b
iA
0 x TEMPERATURE
HENRY/3
c
iA
0 x TEMPERATURE
HENRY/4
d
iA
0 x TEMPERATURE
HENRY/5
T
L
0 x TEMPERATURE
HENRY/6
T
H
2000 x TEMPERATURE
If a
iA
is missing, ln
H
iA
iA
If elements 2 or 3 are non-zero, absolute temperature units are assumed for elements 1 through 4.
Water Solubi li ty
This model calculat es solubilit y of wat er in a hydr ocar bon-r ich liquid phase. The
model is used aut omat ically when you model a hydr ocar bon-wat er syst em wit h
t he fr ee-wat er opt ion. See Chapt er 6 for det ails.
The expr ession for t he liquid mole fr act ion of wat er in t he it h hydr ocar bon
species is:
ln x C
C
T
C T C T C
wi i
i
i i i
+ +
1
2
3 4 5
for
The par amet er s for 60 hydr ocar bon component s ar e st or ed in t he ASPEN PLUS
pur e component dat abank.
Parameter
Name/Element Symbol Default MDS Lower Limit Upper Limit Units
WATSOL/1
C
i 1
( ) fcn T ASG M
bi i i
, ,
-10.0 33.0 TEMPERATURE
WATSOL/2
C
i 2
( ) fcn T ASG M
bi i i
, ,
-10000.0 3000.0 TEMPERATURE
WATSOL/3
C
i 3
0 -0.05 0.05 TEMPERATURE
WATSOL/5
C
i 5
1000 4.0 1000 TEMPERATURE
*, *,
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
PC
p
ci
10
5
10
8
PRESSURE
DHLCVT
Z
i ,
ZC X 0.1 0.5
3-106 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
BARIN Equati ons for Gi bbs Energy, Enthalpy, Entropy,
and Heat Capacity
The following equat ions ar e used when par met er s fr om t he ASPEN PLUS
inor ganic dat abank ar e r et r ieved.
Gi bbs ener gy:
( ) G a b T c T T d T e T f T g T h T
i n i n i n i n i n i n i n i n i
*,
, , , , , , , ,
ln
+ + + + + + +
2 3 4 1 2
(1)
Ent ha l py:
H a c T d T e T ef T g T eh T
i n i n i n i n i n i n i n i
*,
, , , , , , ,
+ + + +
2 3 4 1 2
2 2 (2)
Ent r opy:
( ) S b c T d T e T f T g T h T
i n i n i n i n i n i n i n i
*,
, , , , , , ,
ln
+ + +
1 2 3 4 2
2 3 2 3
(3)
Hea t ca pa ci t y:
C c d T e T f T g T h T
p i n i n i n i n i n i n i ,
*,
, , , , , ,
2 6 12 2 6
2 3 2 3
(4)
r efer s t o an ar bit r ar y phase which can be solid, liquid, or ideal gas. For each
phase, mult iple set s of par amet er s fr om 1 t o n ar e pr esent t o cover mult iple
t emper at ur e r anges. The value of t he par amet er n depends on t he phase. (See
t ables t hat follow.)
The four pr oper t ies C
p
, H, S , and G ar e int er r elat ed as a r esult of t he
t her modynamic r elat ionships:
( ) ( )
H T H T C dT
i i
ref
p i
T
T
ref
*, *,
,
*,
( ) ( )
S T S T
C
T
dT
i i
ref p i
T
T
ref
*, *, ,
*,
G H TS
i i i
*, *, *,
Ther e ar e analyt ical r elat ionships bet ween t he expr essions descr ibing t he
pr oper t ies C
p
, H, S , and G (equat ions 1 t o 4). The par amet er s a
n i ,
t o h
n i ,
can occur
in mor e t han one equat ion.
Solid Phase
The par amet er s in r ange n
n is 1 through 7.CPS XP1 vector stores solid parameters for the first temperature range. CPS XP2 vector
stores solid parameters for the second temperature range, and so on.
n is 1 through 2. CPLXP1 stores liquid parameters for the first temperature range. CPLXP2 stores
liquid parameters for the second temperature range.
n is 1 through 2. CPLXP1 stores liquid parameters for the first temperature range. CPLXP2 stores
liquid parameters for the second temperature range.
n is 1 through 3. CPIXP1 vector stores ideal gas parameters for the first temperature range. CPIXP2
vector stores ideal gas parameters for the second temperature range, and so on.
29815
298 15
The pr oper t y H
k
,
,
,
. 298 15
H
m
E *
is excess ent halpy and is calculat ed fr om t he elect r olyt e NRTL act ivit y
coefficient model.
See Cr iss-Cobble model and Henr ys law model, t his chapt er , for mor e
infor mat ion
Parameter Name Applicable Components Symbol Default Units
IONTYP Ions
Ion 0
SO25C Cations
( ) S T
c
aq
,
298
MOLE-ENTROPY
Anions
( ) S T
a
aq
,
298
MOLE-ENTROPY
DHAQFM Ions, Molecular Solutes
f k
aq
H
,
MOLE-ENTHALPY
CPAQ0 Ions, Molecular Solutes
C
p k
aq
,
,
HEAT-CAPACITY
f i
ig
H
*,
MOLE-EHTHALPY
Water
f w
ig
H
*,
MOLE-ENTHALPY
CPIG Molecular Solutes
C
p i
ig
,
*,
Water
C
p w
ig
,
*,
Not needed if DHAQFM and CPAQ0 are given for molecular solutes
The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If elements 10 or 11 of CPIG
are non-zero, absolute temperature units are assumed for all elements. (S ee ASPEN PLUS User Guide.)
Electrolyte NRTL Gibbs Energy
The equat ion for t he NRTL Gibbs ener gy model is:
G x x x x G
m w w k k j j m
E
j k
* * *
ln + + +
The molar Gibbs ener gy and t he molar excess Gibbs ener gy G
m
*
and G
m
E *
ar e
defined wit h t he asymmet r ical r efer ence st at e: as pur e wat er and infinit e
dilut ion of molecular solut es and ions. (* r efer s t o t he asymmet r ical r efer ence
st at e.) The ideal mixing t er m is calculat ed nor mally, wher e j r efer s t o any
component . The molar Gibbs ener gy of pur e wat er (or t her modynamic pot ent ial)
w
*
is calculat ed fr om t he ideal gas cont r ibut ion. This is a funct ion of t he ideal
gas heat capacit y and t he depar t ur e funct ion. (her e * r efer s t o t he pur e
component .)
( )
w w
ig
w w
ig * *, * *,
+
The depar t ur e funct ion is obt ained fr om t he ASME st eam t ables.
The aqueous infinit e dilut ion t her modynamic pot ent ial
k
is calculat ed fr om t he
infinit e dilut ion aqueous phase heat capacit y polynomial model, by default .
k r efer s t o any ion or molecular solut e. If polynomial model par amet er s ar e not
available, it is calculat ed fr om t he Cr iss-Cobble model for ions and fr om Henr ys
law for molecular solut es:
( )
k f k
aq
pk
aq
fcn G C
, ,
,
G
E *
is calculat ed fr om t he elect r olyt e NRTL act ivit y coefficient model.
Physical Pr oper t y Met hods and Models 3-111
Ver sion 10
Chapter 3
See t he Cr iss-Cobble model and Henr ys law model, t his chapt er , for mor e
infor mat ion.
Parameter Name
Applicable
Components Symbol Default Units
IONTYP Ions
Ion 0
SO25C Cations
( ) S T
c
aq
,
298
MOLE-ENTROPY
Anions
( ) S T
a
aq
,
298
MOLE-ENTROPY
DGAQFM Ions, molecular solutes
f k
aq
G
,
MOLE-ENTHALPY
CPAQ0 Ions, molecular solutes
C
p k
aq
,
,
HEAT-CAPACITY
DGFORM Molecular solutes
f i
G
MOLE-ENTHALPY
Water
f w
G
MOLE-ENTHALPY
CPIG Molecular solutes
C
p i
ig
,
*,
Water
C
p w
ig
,
*,
Not needed if DHAQFM and CPAQ0 are given for molecular solutes
The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If elements 10 or 11 of CPIG
are non-zero, absolute temperature units are assumed for all elements. (S ee ASPEN PLUS User Guide.)
Li qui d Enthalpy from Li qui d Heat Capaci ty Correlati on
Liquid ent halpy is dir ect ly calculat ed by int egr at ion of liquid heat capacit y:
( ) ( ) H T H T C dT
i
l
i
l ref
p i
l
T
T
ref
*, *,
,
*,
+
vap i
l
H
*,
= Heat of vapor izat ion fr om Wat son/DIPPR model
T
ref
= Refer ence t emper at ur e, specified by user . Default s t o 298.15
K
See DIPPR Liquid Heat Capacit y on page 3-99 for par amet er r equir ement and
addit ional det ails.
Enthalpi es Based on Di fferent Reference States
Two pr oper t y met hods, WILS-LR and WILS-GLR, ar e available t o calculat e
ent halpies based on differ ent r efer ence st at es. The WILS-LR pr oper t y met hod is
based on sat ur at ed liquid r efer ence st at e for all component s. The WILS-GLR
pr oper t y met hod allows bot h ideal gas and sat ur at ed liquid r efer ence st at es.
These pr oper t y met hods use an ent halpy met hod t hat opt imizes t he accur acy
t r adeoff bet ween liquid heat capacit y, heat of vapor izat ion, and vapor heat
capacit y at act ual pr ocess condit ions. This highly r ecommended met hod
eliminat es many of t he pr oblems associat ed wit h accur at e t her mal pr oper t ies for
bot h phases, especially t he liquid phase.
The liquid ent halpy of mixt ur e is calculat ed by t he following equat ion (see t he
t able labeled Liquid Ent halpy Met hods in Chapt er 4):
( ) H H H H
m
l
m
ig
m
l
m
ig
+
Wher e:
H
m
ig
= Ent halpy of ideal gas mixt ur e
=
x H
i i
ig
i
*,
H
i
ig *,
= Ideal gas ent halpy of pur e component i
( ) H H
m
l
m
ig
_
,
ln
For subcr it ical component s:
H H
m
l
m
ig
=
( )
x H H H
A A
l
A
ig
A
m
E l *, *, ,
+
H
m
E l ,
=
_
,
RT x
T
B
B
B
2
ln
H H
A
l
A
ig *, *,
Wher e:
H
i
ref l ,
=
Refer ence ent halpy for liquid st at e at T
i
ref l ,
=
0 at T
i
ref l ,
of 273.15 K by default
C
p i
l
,
*,
= Liquid heat capacit y of component i
The ideal gas ent halpy at t emper at ur e T is calculat ed fr om liquid ent halpy as
follows:
( ) ( ) H H C dT H T H T p C dT
i
ig
i
ref l
p i
l
vap i i
con l
T
T
v i i
con l
i
l
p i
ig
T
T
i
ref l
i
con l
i
con l
*, ,
,
*, * ,
,
* , *,
,
*,
,
,
,
, + + +
Wher e:
T
i
con l ,
= Temper at ur e of conver sion fr om liquid t o vapor ent halpy
for component i
( )
vap i i
con l
H T
* ,
= Heat of vapor izat ion of component i at t emper at ur e of
T
con l ,
3-114 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
( ) H T p
v i
con l
i
l
,
* , *,
,
= Vapor ent halpy depar t ur e of component i at t he
conver sion t emper at ur e and vapor pr essur e p
i
l *,
p
i
l *,
= Liquid vapor pr essur e of component i
C
p i
ig
,
*,
= Ideal gas heat capacit y of component i
T
i
con l ,
is t he t emper at ur e at which one cr osses fr om liquid st at e t o t he vapor
st at e. This is a user -defined t emper at ur e t hat default s t o t he syst em t emper at ur e
T. T
i
con l ,
may be select ed such t hat heat of vapor izat ion for component i at t he
t emper at ur e is most accur at e.
The vapor ent halpy is calculat ed fr om ideal gas ent halpy as follows:
( ) H H H T P
i
v
i
ig
v i
*, *,
,
*
, +
Wher e:
( ) H T P
v i ,
*
,
= Vapor ent halpy depar t ur e of pur e component i at t he syst em
t emper at ur e and pr essur e
The liquid heat capacit y and t he ideal gas heat capacit y can be calculat ed fr om
t he ASPEN, DIPPR, or BARIN models. The heat of vapor izat ion can be
calculat ed fr om t he Wat son/DIPPR model. The ent halpy depar t ur e is obt ained
fr om an equat ion-of-st at e.
Parameter
Name/Element Symbol Default MDS
Lower
Limit Upper Limit Units
RSTATE
2
TREFHL
T
i
ref l ,
TEMPERATURE
DHLFRM
H
i
ref l ,
O MOLE-ENTHALPY
TCONHL
T
i
con l ,
T TEMPERATURE
For WILS -LR property method TREFHL defaults to 273.15K. For WILS -GLR property method ,
TREFHL defaults to 298.15 K.
Liquid heat capacit y is r equir ed for all component s.
Physical Pr oper t y Met hods and Models 3-115
Ver sion 10
Chapter 3
Ideal Gas as Reference State
The sat ur at ed liquid ent halpy is calculat ed as follows:
( ) ( ) H H C dT H T p H T p C dT
i
l
i
ref ig
p i
ig
v i i
con ig
i
l
T
T
vap i i
con ig
i
l
p i
l
T
T
i
ref ig
con ig
i
con ig
*, ,
,
*,
,
* , *, * , *,
,
*,
, ,
,
,
,
+ + +
Wher e:
H
i
ref ig ,
=
Refer ence st at e ent halpy for ideal gas at T
i
ref ig ,
= Heat of for mat ion of ideal gas at 298.15 K by default
T
i
ref ig ,
=
Refer ence t emper at ur e cor r esponding t o H
i
ref ig ,
. Default s t o
298.15 K
T
i
con ig ,
= The t emper at ur e at which one cr osses fr om vapor st at e t o liquid
st at e. This is a user -defined t emper at ur e t hat default s t o t he
syst em t emper at ur e T. T
i
con ig ,
may be select ed such t hat heat of
vapor izat ion of component i at t he t emper at ur e is most accur at e.
The ideal gas ent halpy is calculat ed as follows:
H H C dT
i
ig
i
ref ig
p i
ig
T
T
i
ref ig
*, ,
,
*,
,
+
TREFHI
T
i
ref ig ,
TEMPERATURE
DHFORM
H
i
ref ig ,
MOLE-ENTHALPY
TCONHI
T
i
con l ,
T TEMPERATURE
Enthalpy reference state. RS TATE can be 1 (for ideal gas) or 2 (for liquid)
For components with TB << 298.15 K, RS TATE defaults to 1 (ideal gas). TREFHI defaults to 298.15 K.
For components with TB >> 298.15 K, RS TATE defaults to 2 (liquid). TREFHL defaults to 298.15 K.
Physical Pr oper t y Met hods and Models 3-117
Ver sion 10
Chapter 3
Helgeson Equati ons of State
The Helgeson equat ions of st at e for st andar d volume V
o
, heat capacit y C
p
o
,
ent r opy S
o
, ent halpy of for mat ion H
o
, and Gibbs ener gy of for mat ion G
o
at
infinit e dilut ion in aqueous phase ar e:
( ) ( )
( )
V
p p T
Q
p
C
T
T
T
p p
p
p
TX TY
T
T
o
T
p
o
r
r
p
a a a a
c
c
a a
+
+
_
,
+ +
+
_
,
1
]
1
_
,
+
_
,
_
,
+
+
+
_
,
1
]
1
+ +
_
,
_
1 2 3 4
1
2
2 3 3 4
1 1 1 1
1
2
2
1
1
ln
( )
( )
( )
,
_
,
_
,
_
,
1
]
1
1
+
_
,
+
+
+
_
,
1
]
1
+
_
,
_
,
2
2
1
2
2
3 4
1 1 1
1 1
1
T
S S
T
T T T
T T
T T
T
p p
p
p
Y
T
Y
p
o
Tr
o
r r
r
r
r
r
p
Tr Tr
c
c
a a
Pr
Pr Pr
ln ln
ln
( ) ( )
( )
( )
H H T T
T T
p p
p
p
T
T
p p
p
p
TY
T
T
o
f
o
r
r
r
r
r
r
p
Tr
Tr
c c a a
a a
+
_
,
+ +
+
+
_
,
_
,
+
+
+
_
,
1
]
1
+
_
,
+
_
,
_
,
1 2 1 2
2 3 4
1 1
2 1
1
1
1
1
ln
ln
Pr
Pr
( ) ( )
( )
( )
1
1 1
1
1 1 2
2 2
3
_
,
_
,
+
1
]
1
+ +
+
+
_
,
_
,
_
,
_
,
1
]
1
1
+
Tr r Tr
o
f
o
Tr
o
r
r
r r
r
r
r
r
T Y
G G S T T T
T
T
T T p p
p
p
T T
T T T T
T T
T
p p
c a a
c
a
Pr Pr
Pr
ln ln
ln
( )
( )
r
r
Tr
Tr
Tr Tr r
a
p
p
Y T T
+
+
+
_
,
1
]
1
+
_
,
_
,
+
4
1
1
1
1
ln
Pr
Pr
Pr Pr
3-118 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Wher e:
Q
P
X
T T
Y
T
T
P P
P
_
,
_
,
_
,
1
]
1
1
_
,
1
1
1
2
2
2
ln
ln ln
ln
Wher e:
1 4 a a
, ...,
0
CHGPAR/1, . , 2
1 2 c c
,
x
DHAQHG
H
f
o 0 -0.5*10
10
0.5*10
10
MOLE-ENTHALPY
DGAQHG
G
f
o 0 -0.5*10
10
0.5*10
10
MOLE-ENTHALPY
S25HG
S
Tr
o
Pr
0 -0.5*10
10
0.5*10
10
MOLE-ENTROPY
OMEGHG
Tr Pr
0 -0.5*10
10
0.5*10
10
MOLE-ENTHALPY
2 2
Wher e:
k
ij
=
a
b
T
ij
ij
+
m
ij
=
c
d
T
ij
ij
+
The pur e component liquid viscosit y
i
l *,
can be calculat ed by t wo equat ions:
Andr ade
DIPPR liquid viscosit y
The binar y par amet er s k
ij
and m
ij
allow accur at e r epr esent at ion of complex liquid
mixt ur e viscosit y. Bot h binar y par amet er s default t o zer o.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
ANDKIJ/1
a
ij
0
ANDKIJ/2
b
ij
0
ANDMIJ/1
c
ij
0
ANDMIJ/2
d
ij
0
Physical Pr oper t y Met hods and Models 3-123
Ver sion 10
Chapter 3
Andrade
The Andr ade equat ion is:
ln ln
*,
i
l
i
i
i l h
A
B
T
C T T T T + + for
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MULAND/1
A
i
X VISCOSITY,
TEMPERATURE
MULAND/2
B
i
X TEMPERATURE
MULAND/3
C
i
X TEMPERATURE
MULAND/4
T
l
0.0 X TEMPERATURE
MULAND/5
T
h
500.0 X TEMPERATURE
If elements 2 or 3 are non-zero, absolute temp erature units are assumed for elements 1 to 3.
DIPPR Li qui d Vi scosi ty
The equat ion for t he DIPPR liquid viscosit y model is:
ln ln
*,
i
l
i i i i
C
i i
C C T C T C T C T C
i
+ + +
1 2 3 4 6 7
5
for
If t he MULDIP par amet er s for a given component ar e available, t he DIPPR
equat ion is used inst ead of t he Andr ade model. The Andr ade model is also used
by PCES.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MULDIP/1
C
i 1
X VISCOSITY,
TEMPERATURE
MULDIP/2,..., 5
C C
i i 2 5
, ...,
0 X TEMPERATURE
MULDIP/6
C
i 6
0 X TEMPERATURE
MULDIP/7
C
i 7
1000 X TEMPERATURE
l
bi i m
l
fcn T x T API V , , , ,
Wher e:
fcn = A cor r elat ion based on API Pr ocedur es and Figur es 11A4.1, 11A4.2,
and 11A4.3 (API Technical Data Book, Pet r oleum Refining, 4t h edit ion)
V
m
l
is obt ained fr om t he API liquid volume model.
For r eal component s, t he Andr ade/DIPPR model is used.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TB
T
bi
4.0 2000.0 TEMPERATURE
API
API
i
-60.0 500.0
Chapman-Enskog-Brokaw/DIPPR
The pur e component low pr essur e vapor viscosit y
i
*,
(p = 0) can be calculat ed
using t wo equat ions:
Chapman-Enskog
DIPPR vapor viscosit y
Chapman-Enskog-Brokaw
The equat ion for t he Chapman-Enskog model is:
( )
i
i
i
p
M T
*,
. x
0 2 669 10
26
2
Wher e:
=
( ) fcn T k
i
,
Physical Pr oper t y Met hods and Models 3-125
Ver sion 10
Chapter 3
Polar par amet er is used t o det er mine whet her t o use t he St ockmayer or
Lennar d-J ones pot ent ial par amet er s: k (ener gy par amet er ) and (collision
diamet er ). To calculat e , t he dipole moment p and eit her t he St ockmayer
par amet er s or t he dipole moment T
b
and V
bm
ar e needed. The polar it y cor r ect ion
is fr om Br okaw.
Parameter
Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
MUP
p
i
0.0 5x10-24 DIPOLEMOMENT
STKPAR/1
( )
i
ST
k
( ) fcn T V
bi bi i
, , p
X TEMPERATURE
STKPAR/2
i
ST
( ) fcn T V
bi bi i
, , p
X LENGTH
LJPAR/1
( )
i
LJ
k
( ) fcn T
ci i
,
X TEMPERATURE
LJPAR/2
i
LJ
( ) fcn T p
ci ci i
, ,
X LENGTH
DIPPR Vapor Viscosity
The equat ion for t he DIPPR vapor viscosit y model is:
( ) ( )
i i
C
i i i i
p C T C T C T C T C
i
*,
/ + + 0 1
1 3 4
2
6 7
2
for
If t he MUVDIP par amet er s for a given component ar e available, t he DIPPR
equat ion is used inst ead of t he Chapman-Enskog-Br okaw model. PCES uses t he
DIPPR vapor viscosit y model.
Parameter Name/Element Symbol Default MDS LoweLimit Upper Limit Units
MUVDIP/1
C
i 1
X VISCOSITY
MUVDIP/2
C
i 2
0 X
MUVDIP/3, 4
C C
i i 3 4
,
0 X TEMPERATURE
MUVDIP/5
C
i 5
0 X
MUVDIP/6
C
i 6
0 X TEMPERATURE
MUVDIP/7
C
i 7
1000 X TEMPERATURE
If elements 2, 3, or 4 are non-zero, absolute temperature units are assumed for elements 1 through 4.
3-126 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling. The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 392.
Chapman-Enskog-Brokaw-Wilke Mixing Rule
The low pr essur e vapor mixt ur e viscosit y is calculat ed by t he Wilke appr oximat ion
of t he Chapman-Enskog equat ion:
( )
( )
p
y p
y
i
i i
j ij
j
0
0
*,
For
ij
,t he for mulat ion by Br okaw is used:
( )
ij
i
j
p
1
]
1
1
*,
*,
0
Wher e:
A
ij
=
( )
fcn M M
i j
, , and t he cor r ect ion fact or for polar gases
Sij =
( )
( )
fcn k T
ST
, ,
Polar par amet er is used t o det er mine whet her t o use t he St ockmayer or
Lennar d-J ones pot ent ial par amet er s: k (ener gy par amet er ) and (collision
diamet er ). To calculat e , t he dipole moment p, and eit her t he St ockmayer
par amet er s or T
b
and V
bm
ar e needed.
The pur e component vapor viscosit y
i
*,
(p = 0) can be calculat ed using t he
Chapman- Enskog-Br okaw/DIPPR (or anot her ) low pr essur e vapor viscosit y
model.
Ensur e t hat you supply par amet er s for
i
*,
(p = 0).
Physical Pr oper t y Met hods and Models 3-127
Ver sion 10
Chapter 3
Parameter
Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
MUP
p
i
0.0 5x10-24 DIPOLEMOMENT
STKPAR/1
( )
i
ST
k
( ) fcn T V
bi bi i
, , p
X TEMPERATURE
STKPAR/2
i
ST
( ) fcn T V
bi bi i
, , p
X LENGTH
References
R.C. Reid, J .M. Pr ausnit z, and T.K. Sher wood, The Properties of Gases and
Liquids, 3r d ed., (New Yor k: McGr aw-Hill, 1977), pp. 410416.
Chung-Lee-Starling Low-Pressure Vapor Viscosity
The low-pressure vapor viscosit y by Chung, Lee, and St arling is:
( )
( )
p
MT F
V
C
cm
0
0 40785
1
2
2
3
.
fcn T
r
The shape and polar it y cor r ect ion is:
( ) F fcn
c r
, , p
The par amet er p
r
is t he r educed dipolemoment :
( )
p
p
r
cm c
V T
4152
1
2
.
The polar par amet er is t abulat ed for cer t ain alcohols and car boxylic acids.
The pr evious equat ions can be used for mixt ur es when applying t hese mixing
r ules:
V y y V
cm i j cij
j i
T
y y T V
V
c
i j cij cij
j i
cm
3-128 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
M
x x T V M
T V
i j cij cij ij
j i
c cm
1
]
1
1
2
3
2
3
2
x x V
V
i j ij cij
j i
cm
p
p
r
cm c
V T
1313
1
2
.
p
p p
4
i
2
j
2
x x V
V
i j c
j i
cij
x x
i j ij
j i
Wher e:
V
cij
=
( )( )
1
1
2
ij ci cj
V V
ij
= 0 (in almost all cases)
T
cij
=
( )( )
1
1
2
ij ci cj
T T
ij
= 0 (in almost all cases)
ij
=
( )
i j
+
2
M
ij
=
( )
2
1
2
M M
M M
i j
i j
+
1
]
1
1
ij
=
( )
i j
1
2
Physical Pr oper t y Met hods and Models 3-129
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TCCLS
T
ci
TC x 5.0 2000.0 TEMPERATURE
VCCLS
V
ci
VC x 0.001 3.5 MOLE-VOLUME
MW
M
i
1.0 5000.0
MUP
p
i
0.0
5 10
24
x
DIPOLEMOMENT
OMGCLS
i
OMEGA x -0.5 2.0
CLSK
i
0.0 x 0.0 0.5
CLSKV
ij
0.0 x -0.5 -0.5
CLSKT
ij
0.0 x -0.5 0.5
The model specific parameters also affect the Chung-Lee-S tarling Viscosity and the Chung-Lee-S tarling
Thermal Conductivity models.
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 396, p. 413.
Chung-Lee-Starling Viscosity
The Chung-Lee-St arling viscosit y equat ion for vapor and liquid, high and low
pr essur e is:
( ) ( )
+
40 785 36344
1
2
2
3
1
2
2
3
1 2
. . MT F
V
f
MT
V
f
C
cm
c
cm
Wit h:
f
1
=
( ) fcn V
m cm r
, , , , p
f
2
=
( ) fcn
r
, , p
F
2
=
( ) fcn
r
, , p
The molar densit y can be calculat ed using an equat ion-of-st at e model (for example,
t he Benedict -Webb-Rubin). The par amet er p
r
is t he r educed dipolemoment :
( )
p
p
r
cm c
V T
4152
1
2
.
3-130 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
The polar par amet er is t abulat ed for cer t ain alcohols and car boxylic acids.
For low pr essur es, f
1
is r educed t o 1.0 and f
2
becomes negligible. The equat ion
r educes t o t he low pr essur e vapor viscosit y model by Chung-Lee and St ar ling.
The pr evious equat ions can be used for mixt ur es when applying t hese mixing
r ules:
V y y V
cm i j cij
j i
T
y y T V
V
c
i j cij cij
j i
cm
M
x x T V M
T V
i j cij cij ij
j i
c cm
1
]
1
1
2
3
2
3
2
x x V
V
i j ij cij
j i
cm
p
p
r
cm c
V T
1313
1
2
.
p
p p
4
i
2
j
2
x x V
V
i j c
j i
cij
x x
i j ij
j i
Wher e:
V
cij
=
( )( )
1
1
2
ij ci cj
V V
ij
= 0 (in almost all cases)
T
cij
=
( )( )
1
1
2
ij ci cj
T T
ij
= 0 (in almost all cases)
ij
=
( )
i j
+
2
Physical Pr oper t y Met hods and Models 3-131
Ver sion 10
Chapter 3
M
ij
=
( )
2
1
2
M M
M M
i j
i j
+
1
]
1
1
ij
=
( )
i j
1
2
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TCCLS
T
ci
TC x 5.0 2000.0 TEMPERATURE
VCCLS
V
ci
VC x 0.001 3.5 MOLE-VOLUME
MW
M
i
1.0 5000.0
MUP
p
i
0.0
5 10
24
x
DIPOLEMOMENT
OMGCLS
i
OMEGA x -0.5 2.0
CLSK
i
0.0 x 0.0 0.5
CLSKV
ij
0.0 x -0.5 -0.5
CLSKT
ij
0.0 x -0.5 0.5
The model specific parameters affect the results of the Chung-Lee-S tarling Thermal Conductivity and Low
Pressure Viscosity models as well.
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 427.
Dean-Sti el Pressure Correcti on
The pr essur e cor r ect ion t o low pr essur e vapor viscosit y or t he r esidual vapor
viscosit y by Dean and St iel is:
( ) ( )
( )
p p
m
rm
1
]
1
0
108
10 10
1 439
1111
1 858
.
.
.
.
Wher e
M =
y M
i i
i
p
c
=
Z RT
V
cm c
cm
V
cm
= y V
i ci
i
Z
cm
= y Z
i ci
i
rm
=
V
V
cm
m
The par amet er <$EV sub m sup {^v}> is obt ained fr om Redlich-Kwong equat ion-
of-st at e.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
VC
V
ci
0.001 3.5 MOLE-VOLUME
IAPS Viscosity for Water
The IAPS viscosit y models, developed by t he Int ernat ional Associat ion for
Pr oper t ies of St eam, calculat e vapor and liquid viscosit y for wat er and st eam.
These models ar e used in opt ion set s STEAMNBS and STEAM-TA.
The gener al for m of t he equat ion for t he IAPS viscosit y models is:
( )
w
fcn T p ,
Wher e:
fcn = Cor r elat ion developed by IAPS
The models ar e only applicable t o wat er . Ther e ar e no par amet er s r equir ed for t he
models.
Physical Pr oper t y Met hods and Models 3-133
Ver sion 10
Chapter 3
Jones-Dole Electrolyte Correction
The J ones-Dole model calculat es t he cor r ect ion t o t he liquid mixt ur e viscosit y of a
solvent mixt ur e, due t o t he pr esence of elect r olyt es:
l
solv ca
l
ca
+
_
,
1 (1)
Wher e:
solv
= Viscosit y of t he liquid solvent mixt ur e, calculat ed by t he
Andr ade/DIPPR model
ca
l
= Cont r ibut ion t o t he viscosit y cor r ect ion due t o appar ent elect r olyt e
ca
The par amet er
ca
l
can be calculat ed by t hr ee differ ent equat ions.
If these parameters are available Use this equation
IONMOB and IONMUB Dole-Jones
IONMUB Breslau-Miller
Carbonell
Jones-Dole
The J ones-Dole equat ion is:
ca
l
ca ca
a
ca ca
a
A c B c + 2)
Wher e:
c
x
V
ca
a ca
a
m
l
+ +
1
]
1
1
(4)
L
a
= l l T
a a , , 1 2
+ (5)
L
c
= l l T
c c , , 1 2
+ (6)
3-134 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
B
ca
=
( ) ( )
b b T b b T
c c a a , , , , 1 2 1 2
+ + + (7)
Breslau-Miller
The Br eslau-Miller equat ion is:
( )
ca
l
e ca
a
ca
a
V c c + 25 10 05
2
. . V
e
(8)
Wher e t he effect ive volume V
c
is given by:
( )
V
B
e
ca
0 002
2 60
.
.
for salt s involving univalent ions (9)
( )
V
B
e
ca
0 011
506
.
.
for ot her salt s (9a)
Carbonell
The Carbonell equat ion is:
ca
l
k k
a
k
ca
a
M x
c
T
_
,
1
]
1
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
TC
T
ci
5.0 2000.0 TEMPERATURE
PC
p
ci
10
5
10
5
PRESSURE
OMEGA
i
-0.5 2.0
References
R.C. Reid, J .M. Pr ansnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 471.
Lucas Vapor Viscosi ty
The equat ion for t he Lucas vapor viscosit y model is:
( ) ( )
p
YF F
p Q
0
Wher e t he dimensionless low pr essur e viscosit y is given by:
( ) ( ) ( ) ( ) ( )
p fcn T F p F p
r P Q
0 0 0
3-136 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
The dimensionless-making gr oup is:
N
T
M p
A
c
c
2
1
6
1
2
2
3
The pr essur e cor r ect ion fact or Y is:
( ) Y fcn p T
r r
,
The polar and quant um cor r ect ion fact or s at high and low pr essur e ar e:
F
P
=
( ) ( )
fcn Y F p
P
, 0
F
Q
=
( ) ( )
fcn Y F p
Q
, 0
( ) F p
Pi
0 =
( ) fcn T p Z
ri ci ci i
, , , p
( ) F p
Qi
0 =
( ) fcn T
ri
, but is only nonunit y for t he quant um gat es i H E
2 2
,
and He.
The Lucas mixing r ules ar e:
T
c
= y T
i ci
i
p
c
=
RT
y Z
y V
V
RZ T
p
c
i ci
i
i ci
i
ci
ci ci
ci
,
M =
y M
i i
i
( ) F p
P
0 = ( ) y F p
i Pi
0
( ) F p
Q
0 = ( ) A y F p
i Qi
0 ,
Wher e A differ s fr om unit y only for cer t ain mixt ur es.
Physical Pr oper t y Met hods and Models 3-137
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TCLUC
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCLUC
p
ci
PC x
10
5
10
8
PRESSURE
ZCLUC
Z
ci
ZC x 0.1 0.5
MW
M
i
1.0 5000.0
MUP
p
i
0.0
5 10
24
x
DIPOLEMOMENT
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 421, 431.
TRAPP Viscosity Model
The gener al for m for t he TRAPP viscosit y model is:
( ) fcn t p x M T p V Z
i ci ci ci ci i
, , , , , , , ,
Wher e:
The par amet er x is t he mole fr act ion vect or ; fcn is a cor r esponding st at es
cor r elat ion based on t he model for vapor and liquid viscosit y TRAPP, by t he
Nat ional Bur eau of St andar ds (NBS, cur r ent ly NIST). The model can be used for
bot h pur e component s and mixt ur es. The model should be used for nonpolar
component s only.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
TCTRAP
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCTRAP
p
ci
PC x
10
5
10
8
PRESSURE
VCTRAP
V
ci
VC x 0.001 3.5 MOLE-VOLUME
ZCTRAP
Z
ci
ZC x 0.1 1.0
OMGRAP
i
OMEGA x -0.5 3.0
References
J .F. Ely and H.J .M. Hanley, "Pr edict ion of Tr anspor t Pr oper t ies. 1. Viscosit ies of
Fluids and Mixt ur es," Ind. Eng. Chem. Fundam., Vol. 20, (1981), pp. 323332.
3-138 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Thermal Conducti vi ty Models
ASPEN PLUS has eight built -in t her mal conduct ivit y models. This sect ion
descr ibes t he t her mal conduct ivit y models available.
Model Type
Chung-Lee-Starling Vapor or liquid
IAPS Water or stream
Li Mixing Rule Liquid mixture
Riedel Electrolyte Correction Electrolyte
Sato-Riedel/DIPPR Liquid
Stiel-Thodos/DIPPR Low pressure vapor
Stiel-Thodos Pressure Correction Vapor
TRAPP Thermal Conductivity Vapor or liquid
Vredeveld Mixing Rule Liquid mixture
Wassiljewa-Mason-Saxena Mixing Rule Low pressure vapor
Chung-Lee-Starli ng Thermal Conducti vi ty
The main equat ion for t he Chung-Lee-St ar ling t her mal conduct ivit y model is:
( )
+
312 0
1 2
. p
M
f f
Wher e:
f
1
= ( ) fcn
m r
, , , p
f
2
= ( ) fcn T M V
c cm rm r
, , , , , , p
= ( ) fcn C T
r
, ,
( ) p 0 can be calcuat ed by t he low pr essur e Chung-Lee-St ar ling model. The
molar densit y can be calculat ed using an equat ion-of-st at e model (for example,
t he Benedict -Webb-Rubin equat ion-of-st at e). The par amet er p
r
is t he r educed
dipolemoment :
( )
p
p
r
cm c
V T
4152
1
2
.
The polar par amet er is t abulat ed for cer t ain alcohols and car boxylic acids.
Physical Pr oper t y Met hods and Models 3-139
Ver sion 10
Chapter 3
For low pr essur es, f
1
is r educed t o 1.0 and f
2
is r educed t o zer o. This gives t he
Chung-Lee-St ar ling expr ession for t her mal conduct ivit y of low pr essur e gases.
The same expr essions ar e used for mixt ur es. The mixt ur e expr ession for ( ) p 0
must be used. (See Chung-Lee-St arling Low-Pressure Vapor Viscosit y on page 3-
127.)
C x C
i i
i
,
M
x x T V M
T V
i j cij cij ij
j i
c cm
1
]
1
1
2
3
2
3
2
x x V
V
i j ij cij
j i
cm
p
p
r
cm c
V T
1313
1
2
.
p
p p
4
i
2
j
2
x x V
V
i j c
j i
cij
x x
i j ij
j i
Where:
V
cij
=
( )( )
1
1
2
ij ci cj
V V
ij
= 0 (in almost all cases)
T
cij
=
( )( )
1
1
2
ij ci cj
T T
ij
= 0 (in almost all cases)
ij
=
( )
i j
+
2
M
ij
=
( )
2
1
2
M M
M M
i j
i j
+
1
]
1
1
ij
=
( )
i j
1
2
3-140 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TCCLS
T
ci
TC x 5.0 2000.0 TEMPERATURE
VCCLS
V
ci
VC x 0.001 3.5 MOLE-VOLUME
MW
M
i
1.0 5000.0
MUP
p
i
0.0 5 10
24
x
DIPOLEMOMENT
OMGCLS
i
OMEGA x -0.5 2.0
CLSK
i
0.0 x 0.0 0.5
CLSKV
ij
0.0 x -0.5 -0.5
CLSKT
ij
0.0 x -0.5 0.5
The model-specific parameters also affect the results of the Chung-Lee-S tarling viscosity models.
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Pr oper t ies of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 505, 523.
IAPS Thermal Conducti vity for Water
The IAPS t her mal conduct ivit y models wer e developed by t he Int er nat ional
Associat ion for Pr oper t ies of St eam. These models can calculat e vapor and liquid
t her mal conduct ivit y for wat er and st eam. They ar e used in opt ion set s
STEAMNBS and STEAM-TA.
The gener al for m of t he equat ion for t he IAPS t her mal conduct ivit y models is:
( )
w
fcn T p ,
Wher e:
fcn = Cor r elat ion developed by IAPS
The models ar e only applicable t o wat er . No par amet er s ar e r equir ed.
Li Mi xi ng Rule
Liquid mixt ur e t her mal conduct ivit y is calculat ed using Li equat ion (Reid et .al.,
1987):
l
i j i j ij
Physical Pr oper t y Met hods and Models 3-141
Ver sion 10
Chapter 3
Wher e:
( ) ( )
ij i
l
j
l
+
1
]
1
2
1
1
1
*, *,
i
i i
l
j i j
l
xV
xV
*,
*,
The pur e component liquid molar volume V
i
l *,
is calculat ed fr om t he Racket t
model.
The pur e component t her mal conduct ivit y
i
l *,
can be calculat ed by t wo equat ions:
Sat o-Riedel
DIPPR
See t he Sat o-Riedel/DIPPR model for descr ipt ions.
Riedel Electrolyte Correction
The Riedel model can calculat e t he cor r ect ion t o t he liquid mixt ur e t her mal
conduct ivit y of a solvent mixt ur e, due t o t he pr esence of elect r olyt es:
( ) ( ) ( )
( )
( )
l
solv
l
c a
a
m
l
ca
solv
l
solv
l
T T a a
x
V
T
T
ca
+ +
1
]
1
1
293
293
Wher e:
solv
l
= Ther mal conduct ivit y of t he liquid solvent mixt ur e, calculat ed by
t he Sat o-Riedel model
x
ca
a
= Mole fr act ion of t he appar ent elect r olyt e ca
a a
c a
, = Reidel ionic coefficient
V
m
l
= Appar ent molar volume comput ed by t he Clar ke densit y model
Appar ent elect r olyt e mole fr act ions ar e comput ed fr om t he t r ue ion mole-fr act ions
and ionic char ge number . They can also be comput ed if you use t he appar ent
component appr oach. A mor e det ailed discussion of t his met hod is found in
Chapt er 5.
You must pr ovide par amet er s for t he Sat o-Riedel model. This model is used for
t he calculat ion of t he t her mal conduct ivit y of solvent mixt ur es.
3-142 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default Lower Limit Upper Limit Units
CHARGE z 0.0
IONRDL a 0.0
i
l
i
ri
bri
M
T
T
*,
.
+
+
_
,
11053152 3 20 1
3 20 1
1
2
2
3
2
3
Wher e:
T
bri
= T T
bi ci
T
ri
= T T
ci
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
TC
T
ci
5.0 2000.0 TEMPERATURE
TB
T
bi
4.0 2000.0 TEMPERATURE
DIPPR
The DIPPR equat ion is:
i
l
i i i i i i i
C C T C T C T C T C T C
*,
+ + + +
1 2 3
2
4
3
5
4
6 7
for
Linear ext r apolat ion of
*,l
ver sus T occur s out side of bounds.
If t he KLDIP par amet er s for a given component ar e available, t he DIPPR model
is used inst ead of t he Sat o-Riedel model. The DIPPR model is also used by PCES.
Physical Pr oper t y Met hods and Models 3-143
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
KLDIP/1
C
i 1
x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLDIP/2, , 5
C C
i i 2 5
, ...,
0 x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLDIP/6
C
i 6
0 x TEMPERATURE
KLDIP/7
C
i 7
100
0
x TEMPERATURE
Vredeveld Mi xi ng Rule
Liquid mixt ur e t her mal conduct ivit y is calculat ed using t he Vr edeveld equat ion
(Reid et al., 1977):
( )
l
i
l
i i
j j
j i
x M
x M
_
,
1
]
1
1
*,
2
1
2
Pur e component t her mal conduct ivit y
i
l *,
can be calcualt ed by t wo equat ions:
Sat o-Riedel
DIPPR
See t he Sat o-Riedel/DIPPR model for descr ipt ions.
References
R.C. Reid, J .M. Pr ausnit z, and T.K. Sher wood, The Properties of Gases and
Liquids, 4t h ed., (New Yor k: McGr aw-Hill, 1977), p. 533.
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 550.
Stiel-Thodos/DIPPR
The pur e component t her mal conduct ivit y for low pr essur e gasses can be calculat ed
by t wo equat ions:
St iel-Thodos
DIPPR vapor t her mal conduct ivit y
3-144 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Stiel-Thodos
The St iel-Thodos equat ion is:
( ) ( )
i i pi
ig
i
C R M
*, *, *,
. . x + 115 169 10
4
Wher e:
( )
i
p
*,
0 can be obt ained fr om t he Chapman-Enskog-Br okaw model.
C
pi
ig *,
is obt ained fr om t he Ideal Gas Heat Capacit y model.
R is t he univer sal gas const ant .
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
DIPPR Vapor Thermal Conductivity
The DIPPR equat ion for vapor t hermal conduct ivit y is:
( )
i
l
i
C
i i i i
C T C T C T C T C
i
*,
+ +
1 3 4
2
6 7
2
1 for
Linear ext r apolat ion of
i
*
ver sus T occur s out side of bounds.
If t he KVDIP par amet er s for a given component ar e available, t he DIPPR
equat ion is used inst ead of t he St iel-Thodos equat ion. The DIPPR equat ion is
also used in PCES.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
KVDIP/1
C
i 1
x THERMAL
CONDUCTIVITY
KVDIP/2
C
i 2
0 x
KVDIP/3, 4
C C
i i 3 4
,
0 x TEMPERATURE
KVDIP/5 0 x
KVDIP/6
C
i 6
0 x TEMPERATURE
KVDIP/7
C
i 7
1000 x TEMPERATURE
If elements 2, 3, or 4 are non-zero, absolute temperature units are assumed for elements 1 through 4.
Physical Pr oper t y Met hods and Models 3-145
Ver sion 10
Chapter 3
References
R.C. Reid, J .M. Praunit z, and B.E. Poling, The Properties of Gases and Liquid,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 494.
Stiel-Thodos Pressure Correction Model
The pr essur e cor r ect ion t o a pur e component or mixt ur e t her mal conduct ivit y at
low pr essur e is given by:
( ) ( )
fcn p y M T V Z
n
rm i i ci ci ci
0 , , , , , ,
Wher e:
rm
= y
V
V
i
ci
m
i
p
y p
y A
i i
j ij
j
i
0
0
*,
( )
( )
( ) ( )
[ ]
A
n p
n p
M M M M
ij
i
j
j i i j
+
1
]
1
1
1
]
1
1
+ 1
0
0
8 1
1
2
1
4
1
2
1
2
*,
*,
i
*,
= Calculat ed by t he St iel-Thodos model or t he DIPPR t her mal
conduct ivit y model (St iel-Thodos/DIPPR)
( )
i
p
*,
0
= Obt ained fr om t he Chapman-Enskog-Br okaw model
C
pi
ig *,
= Obt ained fr om t he Ideal Gas Heat Capacit y model
R = Univer sal gas const ant
You must supply par amet er s for ( )
i
p
*,
0 and
i
*.,
.
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), pp. 530 531.
3-148 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Di ffusi vi ty Models
ASPEN PLUS has seven built -in diffusivit y models. This sect ion descr ibes t he
diffusivit y models available.
Model Type
Chapman-Enskog-Wilke-Lee (Binary) Low pressure vapor
Chapman-Enskog-Wilke-Lee (Mixture) Low pressure vapor
Dawson-Khoury-Kobayashi (Binary) Vapor
Dawson-Khoury-Kobayashi (Mixture) Vapor
Nernst-Hartley Electrolyte
Wilke-Chang (Binary) Liquid
Wilke-Chang (Mixture) Liquid
Chapman-Enskog-Wi lke-Lee (Bi nary)
The binar y diffusion coefficient at low pr essur es ( ) D p
ij
0 is calculat ed using
t he Chapman-Enskog-Wilke-Lee model:
( ) ( )
[ ]
( )
[ ]
D p f M
T f M
p
ij
ok D
0 21989 10 50665 10
22 3
2
2
3
. x . x
Wher e:
( ) ( ) ( )
[ ]
f M M M M M
i j i j
+
1
2
The collision int egr al for diffusion is:
D
=
( )
fcn T k
ij
,
The binar y size and ener gy par amet er s ar e defined as:
ij
=
( )
i j
+
2
ij
=
( )
i j
1
2
Polar par amet er is used t o det er mine whet her t o use t he St ockmayer or
Lennar d-J ones pot ent ial par amet er s: k (ener gy par amet er ) and (collision
diamet er ). To calculat e , t he dipole moment p , and eit her t he St ockmayer
par amet er s or T
b
and V
bm
ar e needed.
Physical Pr oper t y Met hods and Models 3-149
Ver sion 10
Chapter 3
Parameter
Name/Element
Symbol Default MDS Lower Limit Upper Limit Units
MW
M
i
1.0 5000.0
MUP
p
i
0.0
5 10
24
X
DIPOLEMOMENT
STKPAR/1
( ) k
ST
( ) fcn T V
i bi bi
p , ,
x TEMPERATURE
STKPAR/2
ST ( ) fcn T V
i bi bi
p , ,
x LENGTH
LJPAR/1
( ) k
LJ
( ) fcn T
ci i
,
x TEMPERATURE
LJPAR/2
LJ ( ) fcn T
ci i i
, p ,
x LENGTH
References
R.C. Reid, J .M. Praunit z, and B.E. Poling, The Properties of Gases and Liquids, 4t h
ed., (New Yor k: McGr aw-Hill, 1987), p. 587.
Chapman-Enskog-Wilke-Lee (Mixture)
The diffusion coefficient of a gas int o a gas mixt ur e at low pr essur es is calculat ed
using Blancs law:
( )
( )
D p y
D p
y
i j
ij
j j i j i
1
]
1
1
0
0
The binar y diffusion coefficient ( ) D p
ij
1 x
rm cm m
V V
m m
V 1
V
y V y V
y y
cm
i ci j cj
i j
+
+
* *
( ) D p
ij
m
and V
m
1
]
1
1
The binar y diffusion coefficient D
ij
_
,
+
2 1, ,
(1)
Wher e:
F =
9 65 10
7
. x C/kmole (Far adays number )
x
k
= Mole fr act ion of any molecular species k
z
i
= Char ge number of species i
The binar y diffusion coefficient of t he ion wit h r espect t o a molecular species is set
equal t o t he effect ive diffusivit y of t he ion in t he liquid mixt ur e:
D D
ik i
(2)
3-152 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
The binar y diffusion coefficient of an ion i wit h r espect t o an ion j is set t o t he
mean of t he effect ive diffusivit ies of t he t wo ions:
( )
D
D D
ij
j
2
Parameter Name/Element Symbol Default
Lower
Limit Upper Limit Units
CHARGE z 0.0
IONMOB/1
I
1
AREA, MOLES
IONMOB/2
I
2
0.0 AREA, MOLES, TEMPERATURE
References
A. L. Hor vat h, Handbook of Aqueous Electrolyte S olutions, (Chichest er : Ellis
Hor wood, Lt d, 1985).
Wilke-Chang (Binary)
The Wilke-Chang model calculat es t he liquid diffusion coefficient of component i in
a mixt ur e at finit e concent r at ions:
( ) ( )
D D D
ij
l
ij
l
x
ji
l
x
j i
, ,
The equat ion for t he Wilke-Chang model at infinit e dilut ion is:
( )
( )
D
M T
n V
ij
l
j j
j
l
bi
l
,
*,
.
. x 117282 10
16
0 6
1
2
j
= Associat ion fact or of solvent
n
j
l
= Liquid viscosit y of t he solvent simulat ion. This can be obt ained fr om
t he Andr ade/DIPPR model. You must pr ovide par amet er s for one of
t hese models.
Physical Pr oper t y Met hods and Models 3-153
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default Lower Limit Upper Limit Units
MW
M
j
1.0 5000.0
VB
V
bi
l *,
0.001 3.5 MOLE-VOLUME
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 598600.
Wilke-Chang (Mixture)
The Wilke-Chang model calculat es t he liquid diffusion coefficient of component i in
a mixt ur e.
The equat ion for t he Wilke-Chang model is:
( )
( )
D
M T
n V
i
l
l
bi
l
117282 10
16
0 6
1
2
. x
*,
.
Wit h:
M
x M
x
j j j
j i
j
j i
Wher e:
j
= Associat ion fact or of solvent
n
l
= Mixt ur e liquid viscosit y of all nondiffusing component s. This can be
obt ained fr om t he Andr ade/DIPPR or anot her liquid mixt ur e viscosit y
model. You must pr ovide par amet er s for one of t hese models.
Parameter Name/Element Symbol Default Lower Limit Upper Limit Units
MW
M
j
1.0 5000.0
VB
V
bi
l *,
0.001 3.5 MOLE-VOLUME
DLWC 1
3-154 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
References
R.C. Reid, J .M. Praunsnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h ed., (New Yor k: McGr aw-Hill, 1987), p. 618.
Surface Tensi on Models
ASPEN PLUS has four built -in sur face t ension models.This sect ion descr ibes t he
sur face t ension models available.
Model Type
API Liquid-vapor
IAPS Water-stream
Hakim-Steinberg-Stiel/DIPPR Liquid-vapor
Onsager-Samaras Electrolyte Correction Electrolyte liquid-vapor
API Surface Tension
The liquid mixt ur e sur face t ension for hydr ocar bons is calculat ed using t he API
model. This model is r ecommended for pet r oleum and pet r ochemical applicat ions.
It is used in t he CHAO-SEA, GRAYSON, LK-PLOCK, PENG-ROB, and RK-
SOAVE opt ion set s. The gener al for m of t he model is:
( )
l
bi ci
fcn T x T SG T , , , ,
Wher e:
fcn = A cor r elat ion based on API Pr ocedur e 10A32 (API Technical Data Book,
Petroleum Refining, 4th edition)
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TB
T
bi
4.0 2000.0 TEMPERATURE
SG SG 0.1 2.0
TC
T
ci
5.0 2000 TEMPERATURE
Physical Pr oper t y Met hods and Models 3-155
Ver sion 10
Chapter 3
IAPS Surface Tension for Water
The IAPS sur face t ension model was developed by t he Int er nat ional Associat ion for
Pr oper t ies of St eam. It calculat es liquid sur face t ension for wat er and st eam. This
model is used in opt ion set s STEAMNBS and STEAM-TA.
The gener al for m of t he equat ion for t he IAPS sur face t ension model is:
( )
w
fcn T p ,
Wher e:
fcn = Cor r elat ion developed by IAPS
The model is only applicable t o wat er . No par amet er s ar e r equir ed.
Haki m-Stei nberg-Sti el/DIPPR
The liquid mixt ur e sur face t ension is calculat ed using t he equat ion:
l
i i
l
i
x
*,
The pur e component liquid sur face t ension can be calculat ed by t wo equat ions:
Hakim-St einber g-St iel
DIPPR liquid sur face t ension
Hakim-Steinberg-Stiel
The Hakim-St einberg-St iel equat ion is:
i
l
ci ci pi
ri
m
p T Q
T
i
*,
. x
.
_
,
4 60104 10
1
0 4
7
2
3
1
3
Wher e:
Q
pi
= 01574 0359 1769 1369 0510 1298
2 2
. . . . . . + +
i i i i i i
m
i
= 1210 05385 14 61 32 07 1656 22 03
2 2
. . . . . . + +
i i i i i i
The par amet er
i
is t he St iel polar fact or .
3-156 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default Lower Limit Upper Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
PC
p
ci
10
5
10
8
PRESSURE
OMEGA
i
-0.5 2.0
CHI
i
0
DIPPR Liquid Surface Tension
The DIPPR equat ion for liquid surface t ension is:
( )
( )
i
l
i ri
C C T C T C T
i i
C T C T C
i i ri i ri i ri *,
+ + +
1 6 7
1
2 3 4
2
5
3
for
Wher e:
T
ri
= T T
ci
If t he SIGDIP par amet er s for a given component ar e available, use t he DIPPR
equat ion. The DIPPR model is used by PCES.
Parameter Name/Element Symbol Default Lower Limit Upper Limit Units
SIGDIP/1
C
i 1
SURFACE-TENSION
SIGDIP/2, . . . , 5
C C
i i 2 5
,...,
0
SIGDIP/6
C
i 6
0 TEMPERATURE
SIGDIP/7
C
i 7
1000 TEMPERATURE
References
R.C. Reid, J .M. Pr ausnit z, and B.E. Poling, The Properties of Gases and Liquids,
4t h. ed., (New Yor k: McGr aw-Hill, 1987), p. 638.
Onsager-Samaras
The Onsager -Samar as model calculat es t he cor r ect ion t o t he liquid mixt ur e sur face
t ension ofa solvent mixt ur e, due t o t he pr esence of elect r olyt es:
+
solv ca
a
ca
ca
x (1)
Physical Pr oper t y Met hods and Models 3-157
Ver sion 10
Chapter 3
Wher e:
solv
= Sur face t ension of t he solvent mixt ur e calculat ed by t he Hakim-
St einber g-St iel model
x
ca
a
= Mole fr act ion of t he appar ent elect r olyt e ca
ca
= Cont r ibut ion t o t he sur face t ension cor r ect ion due t o appar ent
elect r olyt e ca
For each appar ent elect r olyt e ca, t he cont r ibut ion t o t he sur face t ension cor r ect ion
is calculat ed as:
( )
ca
solv
ca
a solv
ca
a
c
T
c
'
80 0
113 10
13
3
.
log
.
x
(2)
Wher e:
solv
= Dielect r ic const ant of t he solvent mixt ur e
c
ca
a
=
x
V
ca
a
m
l
V
m
l
= Liquid molar volume calculat ed by t he Clar ke model
Appar ent elect r olyt e mole fr act ions ar e comput ed fr om t he t r ue ion mole-fr act ions
and ionic char ge number . They ar e also comput ed if you use t he appar ent
component appr oach. See Chapt er 5 for a mor e det ailed discussion of t his met hod.
You must pr ovide par amet er s for t he Hakim-St einber g-St iel model, used for t he
calculat ion of t he sur face t ension of t he solvent mixt ur e.
Parameter Name/Element Symbol Default Lower Limit Upper Limit Units
CHARGE z 0.0
References
A. L. Hor vat h, Handbook of Aqueous Electrolyte S olutions, (Chichest er : Ellis, Lt d.
1985).
3-158 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Nonconventi onal Soli d Property Models
This sect ion descr ibes t he nonconvent ional solid densit y and ent halpy models
available in ASPEN PLUS. The following t able list s t he available models and t heir
model names. Nonconvent ional component s ar e solid component s t hat cannot be
char act er ized by a molecular for mula. These component s ar e t r eat ed as pur e
component s for pr ocess simulat ion, t hough t hey ar e complex mixt ur es.
Nonconventional Solid Property Models
General Enthalpy and Density Models Model name Phase(s)
General density polynomial DNSTYGEN S
General heat capacity polynomial ENTHGEN S
Enthalpy and Density Models for Coal and Char
General coal enthalpy model HCOALGEN S
IGT coal density model DCOALIGT S
IGT char density model DCHARIGT S
General Enthalpy and Densi ty Models
ASPEN PLUS has t wo built -in gener al ent halpy and densit y models. This sect ion
descr ibes t he gener al ent halpy and densit y models available.
Model
General Density Polynomial
Heat Capacity Polynomial
General Density Polynomial
DNSTYGEN is a gener al model t hat gives t he densit y of any nonconvent ional solid
component . It uses a simple mass fr act ion weight ed aver age for t he r ecipr ocal
t emper at ur e-dependent specific densit ies of it s individual const it uent s. Ther e may
be up t o t went y const it uent s wit h mass per cent ages. You must define t hese
const it uent s, using t he gener al component at t r ibut e GENANAL. The equat ions
ar e:
i
s
ij
ij
i
w
1
Physical Pr oper t y Met hods and Models 3-159
Ver sion 10
Chapter 3
i j
s
i j i j i j i j
a a T a T a T
, , , , ,
+ + +
1 2 3
2
4
3
Where:
w
ij
= Mass fr act ion of t he jt h const it uent in component i
i j
s
,
= Densit y of t he jt h consit uent in component i
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
DENGEN/1+4 (J-1)
a
i j , 1
x
DENGEN/2+4 (J-1)
a
i j , 2
x 0
DENGEN/3+4 (J-1)
a
i j , 3
x 0
DENGEN/4+4 (J-1)
a
i j , 4
x 0
, ,
h h C dT
i j
s
f j
s
p j
s
T
, ,
.
+
298 15
C a a T a T a T
p j
s
i j i j i j i j , , , , ,
+ + +
1 2 3
2
4
3
Wher e:
w
ij
= Mass fr act ion of t he jt h const it uent in component i
3-160 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
h
i
s
= Specific ent halpy of solid component i
f j
s
h
= Specific ent halpy of for mat ion of const it uent j
C
P
s
i j ,
= Heat capacit y of t he jt h const it uent in component i
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
DHFGEN/J
f j
s
h
x 0 MASS-ENTHALPY
HCGEN/1+4 (J-1)
a
i j , 1
x
HCGEN/2+4
a
i j , 2
x 0
HCGEN/3+4 (J-1)
a
i j , 3
x 0
HCGEN/4+4 (J-1)
a
i j , 4
x 0
_
,
1
2
Wher e:
w = The value det er mined for weight fr act ion
w
d
= The value on a dr y basis
w
H O
2
= The moist ur e weight fr act ion
For hydr ogen, t he for mula includes a cor r ect ion for fr ee-moist ur e hydr ogen:
w
w w
w
H
d
H H O
H O
0119
1
2
2
.
The miner al mat t er cont ent is calculat ed using t he modified Par r for mula:
w w w w
MM A Sp Cl
+ + 113 0 47 . .
The ash t er m cor r ect s for wat er lost by decomposit ion of clays in t he ash
det er minat ion. The aver age wat er const it ut ion of clays is assumed t o be 11.2
per cent . The sulfur t er m allows for loss in weight of pyr it ic sulfur when pyr it e is
bur ned t o fer r ic oxide. The or iginal Par r for mula assumed t hat all sulfur is
pyr it ic sulfur . This for mula included sulfat ic and or ganic sulfur in t he miner al-
mat t er calculat ion. When infor mat ion r egar ding t he for ms of sulfur is available,
use t he modified Par r for mula t o give a bet t er appr oximat ion of t he per cent of
inor ganic mat er ial pr esent . Because chlor ine is usually small for Unit ed St at es
coals, you can omit chlor ine fr om t he calculat ion.
Cor r ect analyses fr om a dr y basis t o a dr y, miner al-mat t er -fr ee basis, using t he
for mula:
w
w w
w
dm
d d
MM
1
3-162 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Wher e:
w
d
= Cor r ect ion fact or for ot her losses, such as t he loss of car bon in
car bonat es and t he loss of hydr ogen pr esent in t he wat er
const it ut ion of clays
w W W
C
d
A
d
sp
d
+ 0 014 0 005 . .
w w w
H
d
A
d
Sp
d
0 013 0 02 . .
The oxygen and or ganic sulfur cont ent s ar e usually calculat ed by differ ence as:
W W W W W
O
dm
C
dm
H
dm
So
dm
N
dm
1
w w w w
S
dm
St
dm
Sp
dm
Ss
dm
Where:
C
p
= Heat capacit y / (J /kgK)
c
p
= Heat capacit y / (cal/gC)
h = Specific ent halpy
c
h = Specific heat of combust ion
f
h = Specific heat of for mat ion
R
O
= Mean-maximum r elect ance in oil
T = Temper at ur e/K
t = Temper at ur e/C
w = Weight fr act ion
= Specific densit y
Subscr ipt s:
A = Ash
C = Car bon
Cl = Chlor ine
FC = Fixed car bon
H = Hydr ogen
Physical Pr oper t y Met hods and Models 3-163
Ver sion 10
Chapter 3
H O
2
= Moist ur e
MM = Miner al mat t er
N = Nit r ogen
O = Oxygen
S o = Or ganic sulfur
S p = Pyr it ic sulfur
S t = Tot al sulfur
S = Ot her sulfur
VM = Volat ile mat t er
Super scr ipt s:
d = Dr y basis
m = Miner al-mat t er -fr ee basis
General Coal Enthalpy Model
The gener al coal model for comput ing ent halpy in ASPEN PLUS is HCOALGEN.
This model includes a number of differ ent cor r elat ions for t he following:
Heat of combust ion
Heat of for mat ion
Heat capacit y
You can select one of t hese cor r elat ions using an opt ion code in t he Pr oper t ies
Advanced NC-Pr ops for m. (See t he AS PEN PLUS User Guide, Chapt er 6). Use
opt ion codes t o specify a calculat ion met hod for pr oper t ies. Each element in t he
opt ion code vect or is used in t he calculat ion of a differ ent pr oper t y.
The t able labeled HCOALGEN Opt ion Codes list s model opt ion codes for
HCLOALGEN. The t able is followed by a det ailed descr ipt ion of t he calculat ions
used for each cor r elat ion.
The cor r elat ions ar e descr ibed int he following sect ion. The component at t r ibut es
ar e defined in AS PEN PLUS User Guide, Chapt er 6.
Heat of Combustion Correlations
The heat of combust ion of coal in t he HCOALGEN model is a gr oss calor ific value.
It is expr essed in Bt u/lb of coal on a dr y miner al-mat t er -fr ee basis. ASTM St andar d
D-2015 defines st andar d condit ions for measur ing gr oss calor ific value. Init ial
oxygen pr essur e is 20 t o 40 at mospher es. Pr oduct s ar e in t he for m of ash; liquid
wat er ; and gaseous CO
2
, SO
2
, and NO
2
.
3-164 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
You can calculat e net calor ific value fr om gr oss calor ific value by making a
deduct ion for t he lat ent heat of vapor izat ion of wat er .
Heat of combust ion values ar e conver t ed back t o a dr y, miner al-mat t er -
cont aining basis wit h a cor r ect ion for t he heat of combust ion of pyr it e. The
for mula is:
( )
c i
d
MMi c i
dm
sp i
h w h w + 1 5400
,
The heat of combust ion cor r elat ions wer e evaluat ed by t he Inst it ut e of Gas
Technology (IGT). They used dat a for 121 samples of coal fr om t he Penn St at e
Dat a Base (IGT, 1976) and 457 samples fr om a USGS r epor t (Swanson, et al.,
1976). These samples included a wide r ange of Unit ed St at es coal fields. The
const ant t er ms in t he HCOALGEN cor r elat ions ar e bias cor r ect ions obt ained
fr om t he IGT st udy.
Boi e Cor r el a t i on:
[ ]
c i
dm
i C i
dm
i H i
dm
i St i
dm
i O i
dm
i N i
dm
i
h a w a w a w a w a w a + + + + +
1 2 3 4 5
2
6
10
, , , , ,
Parameter Name/Element Symbol Default
BOIEC/1
a
1i
151.2
BOIEC/2
a
2i
499.77
BOIEC/3
a
3i
45.0
continued
Physical Pr oper t y Met hods and Models 3-165
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default
BOIEC/4
a
4i
-47.7
BOIEC/5
a
5i
27.0
BOIEC/6
a
6i
-189.0
Dul ong Cor r el a t i on:
[ ]
c i
dm
i C i
dm
i H i
dm
i S i
dm
i O i
dm
i N i
dm
i
h a w a w a w a w a w a + + + + +
1 2 3 4 5
2
5
10
, , , , ,
Parameter Name/Element Symbol Default
DLNGC/1
a
1i
145.44
DLNGC/2
a
2i
620.28
DLNGC/3
a
3i
40.5
DLNGC/4
a
4i
-77.54
DLNGC/5
a
5i
-16.0
Gr ummel a nd Da vi s Cor r el a t i on:
( )
( )
( )
c i
dm
i i H i
dm
A i
d
i C i
dm
i H i
dm
i S i
dm
i O i
dm
i
h
a a w
w
a w a w a w a w a
+
+ + + +
5 2
1 2 3 4
2
6
1
10
,
,
, , , ,
Parameter Name/Element Symbol Default
GMLDC/1
a
1i
0.3333
GMLDC/2
a
2i
654.3
GMLDC/3
a
3i
0.125
GMLDC/4
a
4i
0.125
GMLDC/5
a
5i
424.62
GMLDC/6
a
6i
-2.0
3-166 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Mot t a nd Spooner Cor r el a t i on:
[ ]
c i
dm
i C i
dm
i H i
dm
i S i
dm
i O i
dm
i O i
dm
h a w a w a w a w a w + + +
1 2 3 4
2
7
10 015
, , , , ,
. for
c i
dm
i C i
dm
i H i
dm
i S i
dm
i
i O i
dm
A i
d O i
dm
i O i
dm
h a w a w a w a
a w
w
w a w + +
_
,
1
]
1
1
+
1 2 3 6
5 2
7
1
10 015
, , ,
,
,
, ,
. for
Parameter Name/Element Symbol Default
MTSPC/1
a
1i
144.54
MTSPC/2
a
2i
610.2
MTSPC/3
a
3i
40.3
MTSPC/4
a
4i
62.45
MTSPC/5
a
5i
30.96
MTSPC/6
a
6i
65.88
MTSPC/7
a
7i
-47.0
IGT Cor r el a t i on:
[ ]
c i
dm
i C i
d
i H i
d
i S i
d
i A i
d
i
h a w a w a w a w a + + + +
1 2 3 4
2
5
10
, , , ,
Parameter Name/Element Symbol Default
CIGTC/1
a
1i
178.11
CIGTC/2
a
2i
620.31
CIGTC/3
a
3i
80.93
CIGTC/4
a
4i
44.95
CIGTC/5
a
5i
-5153.0
User Input Value of Heat Combustion
Parameter Name/Element Symbol Default
HCOMB
c i
d
h
0
Physical Pr oper t y Met hods and Models 3-167
Ver sion 10
Chapter 3
Standard Heat of Formation Correlations
Ther e ar e t wo st andar d heat of for mat ion cor r elat ions for t he HCOALGEN model:
Heat of combust ion-based
Dir ect
Hea t of Combust i on-Ba sed Cor r el a t i on This is based on t he assumpt ion t hat
combust ion r esult s in complet e oxidat ion of all element s except sulfat ic sulfur and
ash, which ar e consider ed iner t . The numer ical coefficient s ar e combinat ions of
st oichiomet r ic coefficient s and heat of for mat ion for CO
2
, H O
2
, HCl , and NO
2
.at
298.15K:
f i
d
c i
d
H i
d
C i
d
S i
d
N i
d
Cl i
d
h h w w w
w w
+ +
( . x . x . x
. x . x )
, , ,
, ,
1418 10 3278 10 9 264 10
2 418 10 1426 10 10
6 5 4
6 4 2
Di r ect Cor r el a t i on Nor mally small, r elat ive t o it s heat of combust ion. An
er r or of 1% in t he heat of a combust ion-based cor r elat ion pr oduces about a 50%
er r or when it is used t o calculat e t he heat of for mat ion. For t his r eason, t he
following dir ect cor r elat ion was developed, using dat a fr om t he Penn St at e Dat a
Base. It has a st andar d deviat ion of 112.5 Bt u/lb, which is close t o t he limit , due
t o measur ement in t he heat of combust ion:
[ ]
( )
[ ]
( ) ( ) ( ) ( )
[ ]
( ) ( )( )
f i
d
i c i
dm
i H i
dm
i H i
d
i Sp
d
i Ss
d
i o i i C i
d
FC i
d
i VM
d
i C i
dm
i St i
dm
i c i
d
FC i
d
i VM i
d
i o i i VM i
d
C i
d
FC i
d
i
h a w a w a w a w a w
a R a w w a w
a w a w a w w a w
a R a w w w a
+ + + +
+ + + +
+ + + +
+ + +
1 2 3 4 5
2
6 7 8
2
9
2
10
2
11
2
12
2
4
13
2
14
4
15
10
10
10
10
, , ,
, , ,
, , , , ,
, , , ,
Wher e:
Parameter Name/Element Symbol Default
HFC/1
a
1i
1810.123
HFC/2
a
2i
-502.222
HFC/3
a
3i
329.1087
HFC/4
a
4i
121.766
HFC/5
a
5i
-542.393
HFC/6
a
6i
1601.573
HFC/7
a
7i
424.25
continued
3-168 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default
HFC/8
a
8i
-525.199
HFC/9
a
9i
-11.4805
HFC/10
a
10i
31.585
HFC/11
a
11i
13.5256
HFC/12
a
12i
11.5
HFC/13
a
13i
-685.846
HFC/14
a
14i
-22.494
HFC/15
a
15i
-64836.19
Heat Capacity Kirov Correlations
The Kir ov cor r elat ion (1965) consider ed coal t o be a mixur e of moist ur e, ash, fixed
car bon, and pr imar y and secondar y volat ile mat t er . Pr imar y volat ile mat t er is any
volat ile mat t er equal t o t he t ot al volat ile mat t er cont ent , up t o 10%. The
cor r elat ion developed by Kir ov t r eat s t he heat capacit y as a weight ed sum of t he
heat capacit ies of t he const it uent s:
C w C
p i
d
j p ij
j
ncn
, ,
1
C a a T a T a T
p ij i j i j i j i j , , , , ,
+ + +
1 2 3
2
4
3
Where:
i = Component index
j = Const it uent index j = 1, 2 , ... , ncn
1 = Moist ur e
2 = Fixed car bon
3 = Pr imar y volat ile mat t er
4 = Secondar y volat ile mat t er
5 = Ash
w
j
= Mass fr act ion of jt h const it uent on dr y basis
Physical Pr oper t y Met hods and Models 3-169
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default
CP1C/1
a
i,11
1.0
CP1C/2
a
i,12
0
CP1C/3
a
i,13
0
CP1C/4
a
i,14
0
CP1C/5
a
i,21
0.165
CP1C/6
a
i,22
68 10
4
. x
CP1C/7
a
i,23
4 2 10
7
. x
CP1C/8
a
i,24
0
CP1C/9
a
i,31
0.395
CP1C/10
a
i,32
81 10
4
. x
CP1C/11
a
i,33
0
CP1C/12
a
i,34
0
CP1C/13
a
i, 41
0.71
CP1C/14
a
i,42
61 10
4
. x
CP1C/15
a
i,43
0
CP1C/16
a
i,44
0
CP1C/17
a
i,51
0.18
CP1C/18
a
i,52
14 10
4
. x
CP1C/19
a
i,53
0
CP1C/20
a
i,54
0
3-170 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
Cubic Temperature Equation
The cubic t emper at ur e equat ion is:
c a a t a t a t
p
d
i i i i
+ + +
1 2 3
2
4
3
Parameter Name/Element Symbol Default
CP2C/1
a
1i
0.438
CP2C/2
a
2i
7576 10
3
. x
CP2C/3
a
3i 8 793 10
5
. x
CP2C/4
a
4i
2587 10
7
. x
The default values of t he par amet er s wer e developed by Gomez, Gayle, and Taylor
(1965). They used select ed dat a fr om t hr ee lignit es and a subbit uminous B coal,
over a t emper at ur e r ange fr om 32.7 t o 176.8C.
HCOALGEN Option Codes
Option Code Number
Option Code
Value Calculation Method Parameter Names Component Attributes
1 Heat of Combustion
1 Boie correlation BOIEC ULTANAL
SULFANAL
PROXANAL
2 Dulong correlation DLNGC ULTANAL
SULFANAL
PROXANAL
3 Grummel and Davis
correlation
GMLDC ULTANAL
SULFANAL
PROXANAL
4 Mott and Spooner
correlation
MTSPC ULTANAL
ULFANAL
ROXANAL
5 IGT correlation CIGTC ULTANAL
ROXANAL
6 User input value HCOMB ULTANAL
ROXANAL
continue
Physical Pr oper t y Met hods and Models 3-171
Ver sion 10
Chapter 3
HCOALGEN Option Codes (continued)
Option Code Number
Option Code
Value Calculation Method Parameter Names Component Attributes
2 Standard Heat of Formation
1 Heat-of-combusion-
based correlation
ULTANAL
ULFANAL
2 Direct correlation HFC ULTANAL
SULFANAL
PROXANAL
3 Heat Capacity
1 Kirov correlation CP1C PROXANAL
2 Cubic temperature
equation
CP2C
4 Enthalpy Basis
1 Elements in their
standard states at
298.15K and 1 atm
2 Component at 298.15
K
IGT Coal Densi ty Model
The DCOALIGT model gives t he t r ue (skelet al or solid-phase) densit y of coal on a
dry basis. It uses ult imat e and sulfur analyses. The model is based on equat ions
fr om IGT (1976):
( )
[ ]
i
i
dm
i
dm
A i
d
Sp i
d
A i
d
Sp i
d
w w w w
i
dm
i i H i
dm
i H i
d m
i H i
dm
a a w a wW a w
+ + +
1
1 2 3 4
3
, ,
,
,
( )
( )
W
W w w
w w
H i
dm
H i
d
A i
d
Sp i
d
A i
d
Sp i
d
,
, , ,
, ,
. .
. .
+
10 0 013 0 02
1 113 0 475
2
The equat ion for
i
dm
is good for a wide r ange of hydr ogen cont ent s, including
ant hr acit ies and high t emper at ur e cokes. The st andar d deviat ion of t his cor r elat ion
for a set of 190 point s collect ed by IGT fr om t he lit er at ur e was
3-172 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
12 10
6
x
m kg
3
. The point s ar e essent ially unifor m over t he whole r ange. This is
equivalent t o a st andar d deviat ion of about 1.6% for a coal having a hydr ogen
cont ent of 5%. It incr eases t o about 2.2% for a coke or ant hr acit e having a
hydr ogen cont ent of 1%.
Physical Pr oper t y Met hods and Models 3-173
Ver sion 10
Chapter 3
Parameter Name/Element Symbol Default
DENIGT/1
a
1i
0.4397
DENIGT/2
a
2i
0.1223
DENIGT/3
a
3i
-0.01715
DENIGT/4
a
4i
0.001077
IGT Char Density Model
The DGHARIGT model gives t he t r ue (skelet al or solid-phase) densit y of char or
coke on a dry basis. It uses ult imat e and sulfur analyses. This model is based on
equat ions fr om IGT (1976):
( )
i
d i
dm
A i
d
i
dm
A i
d
w w
+
3
3 1
, ,
( ) ( )
i
d
i i H i
dm
i H i
d m
i H i
dm
a a w a w a w
+ + +
1
1 2 2
2
3
3
, ,
,
,
( )
w
w
w
H i
dm H i
d
A i
d
,
,
,
1
Parameter Name/Element Symbol Default
DENIGT/1
a
1i
0.4397
DENIGT/2
a
2i
0.1223
DENIGT/3
a
3i
-0.01715
DENIGT/4
a
4i
0.001077
The densit ies of gr aphit ic high-t emper at ur e car bons (including cokes) r ange fr om
2 2 10
3
. x t o 2 26 10
3
. x kg m
3
. Densit ies of nongr aphit ic high-t emper at ur e car bons
(der ived fr om char s) r ange fr om 2 0 10
3
. x t o 2 2 10
3
. x kg m
3
. Most of t he dat a used
in developing t his cor r elat ion wer e for car bonized coking coals. Alt hough dat a on a
few chars (carbonized non-coking coals) were included, none has a hydrogen
cont ent less t han 2%. The correlat ion is probably not accurat e for high t emperat ure
chars.
3-174 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Model
Descriptions
References
I.M. Chang, B.S. Thesis, Massachuset t s Inst it ut e of Technology, 1979.
M. Gomez, J .B. Gayle, and A.R. Taylor , J r ., Heat Content and S pecific Heat of
Coals and Related Products, U.S. Bur eau of Mines, R.I. 6607, 1965.
IGT (Inst it ut e of Gas Technology), Coal Conversion S ystems Technical Data
Book, Sect ion PMa. 44.1, 1976.
N.Y. Kir ov, "Specific Heat s and Tot al Heat Cont ent s of Coals and Relat ed
Mat er ials ar e Elevat ed Temper at ur es," BCURA Monthly Bulletin, (1965), pp. 29,
33.
V.E. Swanson et al., Collection, Chemical Analysis and Evaluation of Coal
S amples in 1975, U.S. Geological Sur vey, Open-File Repor t (1976), pp. 76468.
y y y y
Physical Pr oper t y Met hods and Models 4-1
Ver sion 10
Chapter 4
4 Property Calculation
Methods and Routes
In ASPEN PLUS t he met hods and models used t o calculat e t her modynamic and
t r anspor t pr oper t ies ar e packaged in pr oper t y met hods. Each pr oper t y met hod
cont ains all t he met hods and models needed for a simulat ion. A unique
combinat ion of met hods and models for calculat ing a pr oper t y is called a route.
The AS PEN PLUS User Guide, Chapt er 7, descr ibes t he pr oper t y met hods
available in ASPEN PLUS, pr ovides guidelines for choosing an appr opr iat e
pr oper t y met hod for your simulat ion, and descr ibes how t o modify pr oper t y
met hods t o suit your simulat ion needs by r eplacing pr oper t y models.
This chapt er discusses:
Major , subor dinat e, and int er mediat e pr oper t ies in ASPEN PLUS
Calculat ion met hods available
Rout ing concept s
Pr oper t y models available
Tr acing r out es
Modifying and cr eat ing pr oper t y met hods
Modifying and cr eat ing r out es
4-2 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Introducti on
Most pr oper t ies ar e calculat ed in sever al st eps. An example is t he calculat ion of t he
fugacit y coefficient of a component in a liquid mixt ur e:
i
l
i i
l
*,
(1)
Where:
i
l *,
=
i
i
l
p
p
*,
*,
(2)
Equat ions 1 and 2 ar e bot h der ived fr om t her modynamics. The equat ions r elat e t he
pr oper t ies of int er est
( )
i
l
i
l
,
*,
t o ot her pr oper t ies
( )
i i
l
i
l
p , ,
*, *,
and st at e variables
( ) x p
i
, . In gener al, t his t ype of equat ion is der ived fr om univer sal scient ific
pr inciples. These equat ions ar e called methods.
In t he comput at ion of t he liquid mixt ur e fugacit y, you need t o calculat e:
Act ivit y coefficient ( )
i
Vapor pr essur e
( )
p
i
l *,
Pur e component vapor fugacit y coefficient
This t ype of pr oper t y is usually calculat ed using equat ions t hat depend on
univer sal par amet er s like T
c
and p
c
; st at e var iables, such as T and p; and
cor r elat ion par amet er s. The use of cor r elat ion par amet er s makes t hese equat ions
much less univer sal and mor e subject ive t han met hods. For dist inct ion, we call
t hem models. Oft en sever al models exist t o calculat e one pr oper t y. For example, t o
calculat e
i
you can use t he NRTL, UNIQUAC, or UNIFAC model.
The r eason for t r eat ing models and met hods separ at ely is t o allow for maximum
flexibilit y in pr oper t y calculat ions. Ther efor e t he descr ipt ions pr ovided should
help show t he flexibilit y of t he ASPEN PLUS pr oper t y syst em, r at her t han
const it ut e definit ions. For det ailed descr ipt ions and list s of available met hods
and models, see Met hods and Rout es and Models, t his chapt er .
A complet e calculat ion r out e consist s of a combinat ion of met hods and models. A
number of fr equent ly used r out es have been defined in ASPEN PLUS. Rout es
t hat belong logically t oget her have been gr ouped t o for m pr oper t y met hods. For
mor e about pr oper t y met hods, see Chapt er 2. Rout es ar e discussed in det ail in
Rout es and Models, t his chapt er .
To choose a differ ent calculat ion r out e for a given pr oper t y r out e t han what is
defined in a pr oper t y met hod, you can exchange r out es or models in pr oper t y
met hods (see Modifying and Cr eat ing Pr oper t y Met hods, t his chapt er ).
Physical Pr oper t y Met hods and Models 4-3
Ver sion 10
Chapter 4
For a specific pr oper t y, t her e ar e many choices of models and met hods used t o
build a r out e. Ther efor e ASPEN PLUS does not cont ain all possible r out es as
pr edefined r out es. However you can fr eely const r uct calculat ion r out es accor ding
t o your needs. This is a unique feat ur e of ASPEN PLUS. Modifying and cr eat ing
new r out es fr om exist ing met hods, r out es and models, and using t hem in
modified or new pr oper t y met hods is explained in Modifying and Cr eat ing
Rout es, t his chapt er .
Physi cal Properti es i n ASPEN PLUS
The following pr oper t ies may be r equir ed by unit oper at ions in ASPEN PLUS
simulat ions:
Ther modynamic Pr oper t ies
Fugacit y coefficient s (for K-values)
Ent halpy
Ent r opy
Gibbs ener gy
Molar volume
Tr anspor t Pr oper t ies
Viscosit y
Ther mal conduct ivit y
Diffusion coefficient
Sur face t ension
The pr oper t ies r equir ed by unit oper at ion models in ASPEN PLUS ar e called major
properties and ar e list ed in t he t able labeled Major Pr oper t ies in ASPEN PLUS on
page 4-4. A major pr oper t y may depend on ot her major pr oper t ies. In addit ion, a
major pr oper t y may depend on ot her pr oper t ies t hat ar e not major pr oper t ies.
These ot her pr oper t ies can be divided int o t wo cat egor ies: subor dinat e pr oper t ies
and int er mediat e pr oper t ies.
S ubordinate properties may depend on ot her major , subor dinat e or int er mediat e
pr oper t ies, but ar e not dir ect ly r equir ed for unit oper at ion model calculat ions.
Examples of subor dinat e pr oper t ies ar e ent halpy depar t ur e and excess ent halpy.
The t able labeled Subor dinat e Pr oper t ies in ASPEN PLUS on page 4-6 list s t he
subor dinat e pr oper t ies.
Intermediate properties ar e calculat ed dir ect ly by pr oper t y models, r at her t han as
fundament al combinat ions of ot her pr oper t ies. Common examples of
int er mediat e pr oper t ies ar e vapor pr essur e and act ivit y coefficient s. The t able
labeled Int er mediat e Pr oper t ies in ASPEN PLUS on page 4-8 list s t he
int er mediat e pr oper t ies.
Major and subor dinat e pr oper t ies ar e obt ained by a met hod evaluat ion.
Int er mediat e pr oper t ies ar e obt ained by a model evaluat ion.
4-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Major Properties in ASPEN PLUS
Property Name Symbol Description
PHlV
i
v *,
Vapor pure component fugacity coefficient
PHIL
i
l *,
Liquid pure component fugacity coefficient
PHlS
i
s *,
Solid pure component fugacity coefficient
PHlV
i
v
Vapor fugacity coefficient of a component in a mixture
PHlLMX
i
l
Liquid fugacity coefficient of a component in a mixture
PHlSMX
i
s
Solid fugacity coefficient of a component in a mixture
HV
H
i
v *,
Vapor pure component molar enthalpy
HL
H
i
l *,
Liquid pure component molar enthalpy
HS
H
i
s *,
Solid pure component molar enthalpy
HVMX
H
i
v
Vapor mixture molar enthalpy
HLMX
H
i
l
Liquid mixture molar enthalpy
HSMX
H
i
s
Solid mixture molar enthalpy
GV
i
v *,
Vapor pure component molar Gibbs free energy
GL
i
l *,
Liquid pure component molar Gibbs free energy
GS
i
s *,
Solid pure component molar Gibbs free energy
GVMX
G
i
v
Vapor mixture molar Gibbs free energy
GLMX
G
i
l
Liquid mixture molar Gibbs free energy
GSMX
G
i
s
Solid mixture molar Gibbs free energy
SV
S
i
v *,
Vapor pure component molar entropy
SL
S
i
l *,
Liquid pure component molar entropy
SS
S
i
s *,
Solid pure component molar entropy
SVMX
S
i
v
Vapor mixture molar entropy
continued
Physical Pr oper t y Met hods and Models 4-5
Ver sion 10
Chapter 4
Major Properties in ASPEN PLUS
SLMX
S
i
l
Liquid mixture molar entropy
SSMX
S
i
s
Solid mixture molar entropy
VV
V
i
v *,
Vapor pure component molar volume
VL
V
i
l *,
Liquid pure component molar volume
VS
V
i
s *,
Solid pure component molar volume
VVMX
V
i
v
Vapor mixture molar volume
VLMX
V
i
l
Liquid mixture molar volume
VSMX
V
i
s
Solid mixture molar volume<F20MI>
MUV
i
v *,
Vapor pure component viscosity
MUL
i
l *,
Liquid pure component viscosity
MUVMX
i
v
Vapor mixture viscosity
MULMX
i
l
Liquid mixture viscosity
KV
i
v *,
Vapor pure component thermal conductivity
KL
i
l *,
Liquid pure component thermal conductivity
KS
i
s *,
Solid pure component thermal conductivity
KVMX
i
v
Vapor mixture thermal conductivity
KLMX
i
l
Liquid mixture thermal conductivity
KSMX
i
s
Solid mixture thermal conductivity
DV
D
ij
v
Vapor binary diffusion coefficient
DL
D
ij
l
Liquid binary diffusion coefficient
DVMX
D
i
v
Vapor diffusion coefficient of a component in a mixture
DLMX
D
i
l
Liquid diffusion coefficient of a component in a mixture
SIGL
i
l *,
Pure component surface tension
SIGLMX
l
Mixture surface tension
4-6 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Subordinate Properties in ASPEN PLUS
Property Name Symbol Description
DHV
H H
i
v
i
ig *, *,
*,l
Pure component liquid fugacity coefficient pressure
correction
PHISPC
*,s
Pure component solid fugacity coefficient pressure
correction
GAMPC
E
Liquid activity coefficient pressure correction, symmetric
convention
GAMPC1
*E
Liquid activity coefficient pressure correction, asymmetric
convention
HNRYPC
iA
i
v
p
*,
( ) 0
Pure component low pressure vapor viscosity
MUVPC
i
v
i
v
p p
*, *,
( ) ( ) 0
Pure component vapor viscosity pressure correction
MUVMXLP
v
p ( ) 0
Low pressure vapor mixture viscosity
MUVMXPC
v v
p p ( ) ( ) 0
Vapor mixture viscosity pressure correction
KVLP
i
v
p
*,
( ) 0
Pure component low pressure vapor thermal conductivity
continued
4-8 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Subordinate Properties in ASPEN PLUS
Property Name Symbol Description
KVLP
i
v
i
v
p p
*, *,
( ) ( ) 0 0
Pure component vapor thermal conductivity pressure
correction
KVMXLP
v
p ( ) 0
Low pressure, vapor mixture thermal conductivity
KVMXPC
v v
p p ( ) ( ) 0
Vapor mixture thermal conductivity pressure correction
Intermediate Properties in ASPEN PLUS
Property Name Symbol Description
GAMMA
Liquid phase activity coefficient
GAMUS
*
Liquid phase activity coefficient, unsymmetric convention
GAMMAS
s
Solid phase activity coefficient
WHNRY w Henrys constant mixing rule weighting factor
PL
p
i
l *,
Liquid pure component vapor pressure
PS
p
i
s *,
Solid pure component vapor pressure
DHVL
vap i
H
*
Pure component enthalpy of vaporization
DHLS
fus i
H
*
Pure component enthalpy of fusion
DHVS
sub i
H
*
Pure component enthalpy of sublimation
VLPM
V
i
l
Partial molar liquid volume
Physical Pr oper t y Met hods and Models 4-9
Ver sion 10
Chapter 4
Methods
This sect ion descr ibes t he met hods available for calculat ing t he major and
subor dinat e pr oper t ies in ASPEN PLUS.
A met hod is an equat ion used t o calculat e physical pr oper t ies based on univer sal
scient ific pr inciples only, such as t her modynamics. This equat ion may cont ain
assumpt ions, such as t he vapor can be t r eat ed as ideal gas or t he pr essur e is low
enough t o neglect t he pr essur e cor r ect ion. The equat ion may need pr oper t ies and
st at e var iables but not cor r elat ion par amet er s t o calculat e a specific pr oper t y.
Applied t her modynamics indicat e t hat t her e usually is mor e t han one met hod for
calculat ing a par t icular pr oper t y. For example, t he ent halpy depar t ur e of a
component in t he liquid phase, H H
i
l
i
ig *, *,
can be calculat ed fr om it s fugacit y
coefficient in t he liquid phase:
H H RT
T
i
l
i
ig i
l
*, *,
*,
ln
2
This met hod is oft en used for super cr it ical solut es in liquid solut ion.
Alt er nat ively, t he liquid depar t ur e funct ion can be calculat ed fr om t he vapor
ent halpy depar t ur e and t he heat of vapor izat ion:
H H H H H
i
l
i
ig
i i
ig
vap i
*, *, *, *,
Bot h met hods ar e equally valid. Ther e is anot her possibilit y, which is t o calculat e
t he depar t ur e funct ion dir ect ly by an equat ion of st at e. Equat ions of st at e use
cor r elat ion par amet er s and ar e t her efor e classified as models, so:
( ) H H f p T
i
l
i
ig *, *,
, , correlation parameters
This is not a met hod but r at her a valid alt er nat ive t o calculat e t he ent halpy
depar t ur e. To make t he model available t o t he list of met hods, a simple met hod is
used t hat r efer s t o a model:
( ) H H f p T
i
l
i
ig *, *,
, , specified model
In gener al, a list of met hods available for a pr oper t y will be similar t o t he list
pr esent ed her e for t he ent halpy depar t ur e. Compar e t he t ables on pages 4-11
t hr ough 4-36.
4-10 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
In a met hod you can have any number of major pr oper t ies, subor dinat e
pr oper t ies, or models. Usually t her e is a met hod t hat can be used wit h an
equat ion-of-st at e appr oach and an alt er nat ive t hat is used wit h t he act ivit y
coefficient appr oach (see Chapt er 1). Ther e is always a met hod t hat r efer s t o a
model. Alt hough t her e ar e a limit ed number of t her modynamic met hods, in
gener al, all t he exist ing t her modynamic met hods for each pr oper t y ar e pr esent .
Tr anspor t pr oper t y met hods ar e not as univer sal as t her modynamic met hods.
Ther efor e t he t r anspor t pr oper t y met hods offer ed in ASPEN PLUS might not be
exhaust ive, but mult iple met hods for one pr oper t y also exist .
All physical pr oper t y met hods available for calculat ing major and subor dinat e
pr oper t ies in ASPEN PLUS ar e pr ovided in t he t ables on pages 4-11 t hr ough 4-
36. For each major or subor dinat e pr oper t y, t hese t ables list :
Pr oper t y symbol and name
Pr oper t y t ype: major or subor dinat e
Met hods available for calculat ing t he pr oper t y
For each met hod t he fundament al equat ion is given. The t able also list s which
infor mat ion is needed t o specify each st ep in t he met hod (see Rout es and Models,
this chapter).
Example 1 Methods for calculating liquid mixture enthalpy
Fr om t he t able labeled Liquid Ent halpy Met hods on page 4-18, t her e ar e four
met hods for calculat ing HLMX:
Met hod 1 HLMX is calculat ed dir ect ly by an empir ical model. The model may
depend on t emper at ur e T, pr essur e p, liquid composit ion, and cer t ain
model-specific par amet er s.
( ) H f T p x parameters
l l
i
, , ,
Met hod 2 HLMX is calculat ed fr om t he ideal liquid mixt ur e ent halpy and
excess ent halpy.
H x H H
m
l
i i
l
m
E l
+
*, ,
( ) HLMX x HL HLXS
i i
+
The major pr oper t y HLMX depends on t he liquid pur e component ent halpy, HL,
and t he liquid mixt ur e excess ent halpy, HLXS. HL is also a major pr oper t y, while
HLXS is a subor dinat e pr oper t y.
Physical Pr oper t y Met hods and Models 4-11
Ver sion 10
Chapter 4
Met hod 3 HLMX is calculat ed fr om t he ideal gas mixt ur e ent halpy, HIGMX, and
t he liquid mixt ur e ent halpy depar t ur e, DHLMX.
( )
H H H H
m
l
m
ig
m
l
m
ig
+
( ) HLMX HIGMX DHLMX +
The subor dinat e pr oper t y DHLMX can be calculat ed by one of t wo met hods as
list ed in t he t able labeled Liquid Ent halpy Met hods on page 4-18. In all t he
equat ion-of-st at e pr oper t y met hods, DHLMX is calculat ed dir ect ly by an equat ion
of st at e (t hat is, met hod 1 is used for DHLMX).
Met hod 4 HLMX is calculat ed dir ect ly by t he Elect r olyt e model.
( )
H f x
m
l t
Where:
x
t
= The component t r ue mole fr act ions
( x
t
is also t he symbol for t he subor dinat e pr oper t y XTRUE:
HLMX = f (XTRUE)).
Vapor Fugacity Coefficient Methods
Property Symbol
and Name
Property Type Method
Code
Method Route Structure Information Required
i
v *,
PHIV
Major 1 Specified model
i
v *,
Model name
i
v
PHIVMX
Major 1 Specified model
i
v
Model name (Default:
i
v
1)
2
( )
i
v
i i
v
f y ,
*,
i
v *,
Route ID
i
v
Model name
3
( )
i
v
i
f
i
Model name
i
v
Model name
4-12 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Liquid Fugacity Coefficient Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
i
l *,
PHIL
Major 1 Specified model
i
l *,
Model name
2
( )
i
v
i
l
i
l
i
l
T p p
p
*, *, *, *,
, p
l *,
Model name
i
v *,
Model name
(Default:
*,v
1)
*,l
Route ID
(Default:
i
l *,
1)
3 Specified model for supercritical components For
subcritical components:
( )
i
v
i
l i
l
l
p
p
T p
p
p RT
V dp
i
l
*, *,
*,
*,
, exp
*,
1
_
,
i
l *,
Model name
p
l *,
Model name
i
l *,
Model name
V
i
l *,
Model Name
i
l *,
PHILPC
Subord. 1
exp
*,
*,
1
RT
V dp
l
p
p
i
l
_
,
p
l *,
Model name
V
i
l *,
Model Name
Integration option code
(Default:1 point)
2 Specified model
i
l *,
Model name
i
l
PHILMX
Major 1 Specified model
i
l
Model name
2
i i
l
i
E *,
i
Model name
(Default:
i
1)
i
l *,
Route ID
i
E
Route ID
(Default:
i
E
1)
3 Unsymmetric Convention
For subcritical components (A or B):
A
l *,
Route ID
continued
Physical Pr oper t y Met hods and Models 4-13
Ver sion 10
Chapter 4
Liquid Fugacity Coefficient Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
A
l
A A A
l
*,
A
Model name
(Default:
A
1)
For supercritical components (I or j)
i
l
i
i
i
H
p
_
,
Where:
ln ln ln
A
A
A
j
jA
j
j j
w
x
x
H H
iA
_
,
_
,
1
]
1
1
H
jA
Route ID
ln ln
H
w
H
i
i
B
B iB
iB
_
,
_
,
w
B
Model name
( ) ln lim ln
i
x
i
j j
0
w
B
Model option code (see
Chapter 3)
w
B
B
1
Method Option code
0: Do not calculate H
i
1: Calculate H
i
(Default = 0 )
4
i i
l
i
E *,
i
Model name
(Default:
i
1)
i
l *,
Route ID
i
E
Route ID
(Default:
i
E
1)
Where:
( )
i
t
f x (Default:
i
E
1)
x
t
Route ID
5 Unsymmetric Convention
For subcritical components (A or B):
i
l *,
Route ID
continued
4-14 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Liquid Fugacity Coefficient Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
A
l
A A A
l
*,
A
Model name
(Default:
A
1)
Where:
( )
A
t
f x x
t
Route ID
For supercritical components (i or j)
i
l
i
i
i
H
p
_
,
Where:
ln ln ln
A
A
A
j
jA
j
j j
W
X
x
H H
iA
_
,
_
,
1
]
1
1
H
jA
Route ID
ln ln
H
w
H
i
i
B
B
iB
iB
_
,
_
,
w
B
Model name
( ) ln lim ln
i
x
i
j j
0
w
B
Model option code (see
Chapter 3)
w
B
B
1
Method Option code
0: Do not calculate H
i
1: Calculate H
i
(Default = 0 )
6
i
l
i
f ( )
i
Model name
i
l
Model name
x
t
XTRUE
Subord. 1
( ) x f T x
t
i i
, , , Chemistry
i
Model name
i
E
GAMPC
Subord. 1
( )
exp
*,
1
RT
V V dp
i
l
i
l
p
p
ref
_
,
V
i
l
Model name
V
i
l *,
Model name
Integration option code
continued
Physical Pr oper t y Met hods and Models 4-15
Ver sion 10
Chapter 4
Liquid Fugacity Coefficient Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
(Default: 1 point)
2 Specified model
i
E
Model name
i
E *,
GAMPC1
Subord. 1
exp
1
RT
V dp
i
l
p
p
ref
_
,
V
i
l
Model name
Integration option code
(Default: 1 point)
2 Specified model
i
E *,
Model name
H
iA
HNRY
Subord. 1 Specified model
H
iA
Model name
2
( )
H p T
iA
ref
iA
,
H
iA
Model name
iA
Route ID
(Default:
iA
= 1)
p
ref
defined by the p
ref
option code of HNRYPC
iA
HNRYPC
Subord. 1
exp
1
RT
V dp
i
l
p
p
ref
_
,
p
A
l *,
Model name (if
needed for p
ref
)
p
ref
Option code
1: p
ref
= 0
2: p
ref
= 1 atm
3: p
ref
= p
A
l *,
(T)
(Default = 2)
V
i
Model name
Integration code
(Default: 1 point)
2 Specified model
iA
Model name
4-16 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Solid Fugacity Coefficient Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
i
s *,
PHIS
Major 1 Specified Model
i
s *,
Model name
2
( )
i
v
i
s
i
s i
s
T p p
p
*, *, *,
*,
,
p
i
s *,
Model name
i
v *,
Model name
(Default:
i
v *,
= 1)
i
s *,
Route ID
(Default:
i
s *,
= 1)
3
i
s
i
l *, *,
i
s *,
Model name
i
l *,
Route ID
i
s *,
PHISPC
Subord. 1
exp
*,
*,
1
RT
V dp
i
s
p
p
s
_
,
p
i
s *,
Model name
V
i
s *,
Model name
Integration option code
(Default: 1 point)
2 Specified model
i
s *,
Model name
i
s
PHISMX
Major 1 Specified model
i
s
Model name
2
( )
i
s
i
s
i
s
f x ,
*,
i
s *,
Route ID
i
s
Model name
3
i
s
i
s *,
i
s
Model name
i
s *,
Route ID
Physical Pr oper t y Met hods and Models 4-17
Ver sion 10
Chapter 4
Vapor Enthalpy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
H
i
*,
HV
Major 1 Specified model
H
i
*,
Model name
2
( )
H H H
i
ig
i i
ig *, *, *,
+
( )
H H
i i
ig *, *,
Route ID
(Default: H H
i i
ig *, *,
= 0)
3
H H
i
l
vap i
*, *
+ H
i
l *,
Route ID
vap i
H
*
Model name
H H
i i
ig *, *,
DHV
Subord. 1 Specified model
( )
H H
i i
ig *, *,
Model name
2
_
,
RT
T
i
v
2
ln
*,
i
v *,
Model name
H
m
HVMX
Major 1 Specified model
H
m
Model name
2
y H
i i
i
*,
H
i
*,
Route ID
3
( )
H H H
m
ig
m m
ig
+
( )
H H
m m
ig
Route ID
(Default: H H
m m
ig
=0 )
H H
m m
ig
DHVMX
Subord. 1 Specified model
( )
H H
m m
ig
Model name
2
_
,
RT y
T
i
i
i
v
2
ln
i
v
Model name
4-18 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Liquid Enthalpy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
H
i
l *,
HL
Major 1 Specified model
H
i
l *,
Model name
2
( )
H H H
i
ig
i
l
i
ig *, *, *,
+
( )
H H
i
l
i
ig *, *,
Route
ID
H H
i
l
i
ig *, *,
DHL
Subor
d.
1 Specified model
( )
H H
i
l
i
ig *, *,
Model
name
2
_
,
RT
T
i
l
2
ln
*,
i
l *,
Model name
3
( )
( )
( )
( )
( ) ( ) ( )
H T p H T H T
H T p H T p
i
v
i
l
i
ig
vap i
i
l
i
l
i
l
*, *, *, *
*, *, *,
,
, ,
+
p
i
l
Model name
( )
H H
i
v
i
ig *, *,
Route ID
(Default: H H
i
v
i
ig *, *,
= 0 )
vap i
l
H Model name
( ) ( ) ( )
H T p H T p
i
l
i
l
i
l *, *, *,
, ,
Route ID
(Default:
( ) ( )
H T p H T p
i
l
i
l
i
l *, *, *,
, ,
= 0)
( )
( )
H T p
H T p
i
l
i
l
i
l
*,
*, *,
,
,
DHLPC
Subor
d.
1
( ) ( ) ( )
( ) ( )
( )
H T p H T
H T p H T
i
l
i
ig
i
l
pi
l
i
ig
*, *,
*, *, *,
,
,
p
i
l *,
Model name
( )
H H
i
l
i
ig *, *,
Route
ID
2
V T
V
T
dp
i
l i
l
p p
p
i
*,
*,
_
,
1
]
1
1
p
i
l *,
Model name
V
i
l *,
Model name
Integration option code
(Default: 1 point )
3 Specified model
( ) ( ) ( )
H T p H T p
i
l
i
l
i
l *, *, *,
, ,
Model name
continued
Physical Pr oper t y Met hods and Models 4-19
Ver sion 10
Chapter 4
Liquid Enthalpy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
H
m
l
HLMX
Major 1 Specified model
H
m
l
Model name
2
x H H
i
i i
l
m
E l *, ,
+
H
i
l *,
Route ID
H
i
E l ,
Route ID
(Default: H
i
E l ,
=0)
3
( )
H H H
m
ig
m
l
m
ig
+
( )
H H
m
l
m
ig
Route ID
4
Electrolyte model
( )
x
t
H
m
l
Model name
x
t
Route ID
H H
m
l
m
ig
DHLMX
Subor
d.
1 Specified model
( )
H H
m
l
m
ig
Model
name
2
( )
x H H H
i i
l
i
ig
i
m
E I *, *, ,
+
( )
H H
i
l
i
ig *, *,
Route ID
H
m
E l ,
Route ID
(Default: H
m
E l ,
= 0 )
continued
4-20 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Liquid Enthalpy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
3 Unsymmetric convention For subcritical components A or
B:
( )
x H H H
A A
I
A
ig
i
m
E I *, *, ,
+
H RT x
T
m
E I
B
B
B
,
ln
_
,
_
,
RT x
T
j
j
j
I
2
ln
where:
_
,
i
i
i
H
p
ln ln
H H
i
B
iB
_
,
_
,
( ) ln lim ln
x
i
i
0
w
B
B
1
( )
H H
A
I
A
ig *, *,
Route
ID
where:
B
Model name
H
iB
Route ID
w
B
Model name
w
B
Model option code
(see Chapter 3)
H
m
E l ,
HLXS
Subor
d.
1 Specified model
H
m
E l ,
Model name
2
H RT x
T
m
E l
i
i
i
,
ln
_
,
2
i
Model name
Physical Pr oper t y Met hods and Models 4-21
Ver sion 10
Chapter 4
Solid Enthalpy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
H
i
s *,
HL
Major 1 Specified model
H
i
s *,
Model name
2
( )
H H H
i
ig
i
s
i
ig *, *, *,
+
( )
H H
i
s
i
ig *, *,
Route ID
H H
i
s
i
ig *, *,
DHS
Subord. 1 Specified model
( )
H H
i
s
i
ig *, *,
Model name
2
( ) ( )
( )
( )
( ) ( ) ( )
H T p H T H T
H T p H T p
i
v
i
s
i
g
sub i
i
s
i
s
i
s
*, *, *, *
*, *, *,
,
, ,
+
p
i
s *,
Model name
( )
H H
i
v
i
ig *, *,
Route ID
(Default: H H
i
v
i
ig *, *,
= 0 )
( )
sub i
H T
*
Model name
( ) ( ) ( )
H T p H T p
i
s
i
s
i
s *, *, *,
, ,
Route ID
(Default:
( ) ( )
H T p H T p
i
s
i
s
i
s *, *, *,
, ,
= 0 )
( ) ( )
H T p H T p
i
s
i
s
i
s *, *, *,
, ,
DHSPC
Subord. 1
V T
V
T
dp
i
s i
s
p
p
*,
*,
_
,
1
]
1
p
i
s *,
Model name
V
i
s *,
Model name
Integration option code
(Default: 1 point)
H
m
s
HSMX
Major 1 Specified model Model name
2
x H H
i
s
i
s
m
E s
i
*, ,
+
H
m
s
Route ID
H
i
s *,
Route ID
H
m
E s ,
(Default: H
m
E s ,
= 0 )
3
( )
H H H
m
ig
m
s
m
ig
+
( )
H H
m
s
m
ig
Route ID
continued
4-22 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Solid Enthalpy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
H H
m
s
m
ig
DHSMX
Subord. 1 Specified model
( )
H H
m
s
m
ig
Model name
2
( )
x H H H
i
s
i
s
i
ig
m
E s
i
*, *, ,
+
( )
H H
i
s
i
ig *, *,
Route ID
H
m
E s ,
Route ID
(Default: H
m
E s ,
= 0 )
H
m
E s ,
HSXS
Subord. 1 Specified model
H
m
E s ,
Model name
2
H RT x
T
m
E s
i
s i
s
i
,
ln
_
,
i
Model name
Vapor Gibbs Energy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
i
v *,
GV
Major 1 Specified model
i
v *,
Model name
2
( )
i
ig
i
v
i
ig *, *, *,
+
( )
i
v
i
ig *, *,
Route ID
(Default:
i
v
i
ig *, *,
= 0 )
i
v
i
ig *, *,
DGV
Subord. 1 Specified model
( )
i
v
i
ig *, *,
Model name
2
RT RT
p
p
i
v
ref
ln ln
*,
+
_
,
i
v *,
Route ID
G
m
v
GVMX
Major 1 Specified model
G
m
v
Model name
continued
Physical Pr oper t y Met hods and Models 4-23
Ver sion 10
Chapter 4
Vapor Gibbs Energy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
2
y RT y y
i i
v
i i
i i
*,
ln +
i
v *,
Route ID
3
( )
G G G
m
ig
m
v
m
ig
+
( )
G G
m
v
m
ig
Route ID
(Default: G G
m
v
m
ig
= 0 )
G G
m
v
m
ig
DGVMX
Subord. 1 Specified model
( )
G G
m
v
m
ig
Model name
2
RT y RT
p
p
i i
v
ref
i
ln ln +
_
,
i
v *,
Route ID
(Default:
i
v *,
= 1 )
Liquid Gibbs Energy Methods
Property Symbol
and Name
Property
Type
Method
Code
Method Route Structure Information Required
i
l *,
GL
Major 1 Specified model
i
l *,
Model name
2
( )
i
ig
i
l
i
ig *, *, *,
+
( )
i
l
i
ig *, *,
Route ID
i
l
i
ig *, *,
DGL
Subord. 1 Specified model
( )
i
l
i
ig *, *,
Model name
2
RT RT
p
p
l
ref
ln ln
*,
+
_
,
i
l *,
Route ID
3
( ) ( )
( )
( ) ( ) ( )
i
l
i
l
i
ig
i
l
i
l
i
l
T p T
T p T p
*, *, *,
*, *, *,
,
, ,
+
p
i
l *,
Model name
( )
i
l
i
ig *, *,
Route ID
(Default:
i
l
i
ig *, *,
= 0)
( ) ( ) ( )
i
l
i
l
i
l
T p T p
*, *, *,
, , R
oute ID
(Default:
( ) ( )
i
l
i
l
i
l
T p T p
*, *, *,
, , =
0 )
continued
4-24 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Liquid Gibbs Energy Methods (continued)
Property Symbol
and Name
Property
Type
Method
Code
Method Route Structure Information Required
( )
( )
i
l
i
l
i
l
T p
T p
*,
*, *,
,
,
DGLPC
Subord. 1
( ) ( ) ( )
( ) ( )
( )
*, *,
*, *, *,
,
,
l
i
ig
i
l
i
l
i
ig
T p T
T p T
p
i
l *,
Model name
( )
i
l
i
ig *, *,
Route ID
2
V dp
i
l
p
p
i
l
*,
*,
p
i
l *,
Model name
V
i
l *,
Model Name
Integration option code
(Default: 1 point)
G
m
l
GLMX
Major 1 Specified model
G
m
l
Model name
2
x RT x x G
i i
l
i i m
E l
i i
*, ,
ln + +
i
l *,
Route ID
G
m
E l ,
Route ID
(Default: G
m
E l ,
= 0 )
3
( )
G G G
m
ig
m
l
m
ig
+
4
Electrolyte model
( )
x
t Model name
x
t
Route ID
G G
m
l
m
ig
DGLMX
Subord. 1 Specified model
( )
G G
m
l
m
ig
Model name
2
( )
x G
i i
l
i
ig
m
E l
i
*, *, ,
+
( )
i
l
i
ig *, *,
Route ID
G
m
E l ,
Route ID
(Default: G
m
E l ,
= 0 )
G
m
E l ,
GLXS
Subord. 1 Specified model
G
m
E l ,
Model name
2
RT x
i
i
i
ln
i
Model name
Physical Pr oper t y Met hods and Models 4-25
Ver sion 10
Chapter 4
Solid Gibbs Energy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
i
s *,
GL
Major 1 Specified model
i
s *,
Model name
2
( )
i
ig
i
s
i
ig *, *, *,
+
( )
i
s
i
ig *, *,
Route ID
i
s
i
ig *, *,
DGL
Subord. 1 Specified model
( )
i
s
i
ig *, *,
Model name
2
RT RT
p
p
s
ref
ln ln
*,
+
_
,
i
s *,
Route ID
3
( ) ( )
( )
( ) ( ) ( )
i
s
i
s
i
ig
i
s
i
s
i
s
T p T
T p T p
*, *, *,
*, *, *,
,
, ,
+
p
i
s *,
Model name
( ) ( )
( )
i
s
i
s
i
ig
T p T
*, *, *,
,
Route ID
(Default:
( ) ( )
i
l
i
s
i
ig
T p T
*, *, *,
, =
0)
( ) ( ) ( )
i
s
i
s
i
s
T p T p
*, *, *,
, , R
oute ID
(Default:
( ) ( )
i
s
i
s
i
s
T p T p
*, *, *,
, , =
0 )
( )
( )
i
s
i
s
i
s
T p
T p
*,
*, *,
,
,
DGLPC
Subord. 1
V dp
i
l
p
p
i
l
*,
*,
p
i
l *,
Model name
V
i
l *,
Model Name
Integration option code
(Default: 1 point)
G
m
s
GLMX
Major 1 Specified model
G
m
s
Model name
2
x G RT x x
i
s
i
s
m
E s
i
s
i
s
i i
*, ,
ln + +
i
s *,
Route ID
G
m
E s ,
Route ID
(Default: G
m
E s ,
= 0 )
3
( )
G G G
m
ig
m
s
m
ig
+
continued
4-26 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Solid Gibbs Energy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
G G
m
s
m
ig
DGLMX
Subord. 1 Specified model
( )
G G
m
s
m
ig
Model name
2
( )
x G
i
s
i
s
i
ig
m
E s
i
*, *, ,
+
( )
i
s
i
ig *, *,
Route ID
G
m
E s ,
Route ID
(Default: G
m
E s ,
= 0 )
G
m
E s ,
GLXS
Subord. 1 Specified model
G
m
E s ,
Model name
2
RT x
i
s
i
i
s
ln
i
Model name
Vapor Entropy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
S
i
v *,
SV
Major 1
( )
1
T
H
i
v
i
v *, *,
H
i
v *,
Route ID
2
( )
S S S
i
ig
i
v
i
ig *, *, *,
+
( )
S S
i
v
i
ig *, *,
Route ID
(Default: S S
i
v
i
ig *, *,
= 0 )
3 Specified model
S
i
v *,
Model name
S S
i
v
i
ig *, *,
DSV
Subord. 1
H H
T T
i
v
i
ig
i
v
i
ig *, *, *, *,
_
,
_
,
( )
H H
i
v
i
ig *, *,
Route ID
(Default: H H
i
v
i
ig *, *,
= 0 )
( )
i
v
i
ig *, *,
Route ID
(Default:
i
v
i
ig *, *,
= 0)
2
( )
T
i
v
i
ig *, *,
( )
i
v
i
ig *, *,
Model name
S
m
v
Major 1
( )
1
T
H G
m
v
m
v
H
m
v
Route ID
G
m
v
Route ID
continued
Physical Pr oper t y Met hods and Models 4-27
Ver sion 10
Chapter 4
Vapor Entropy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
2
( )
S S S
m
ig
m
v
m
ig
+
( )
S S
m
v
m
ig
Route ID
(Default: S S
m
v
m
ig
= 0 )
3 Specified model
S
m
v
Model name
S S
m
v
m
ig
DSVMX
Subord. 1 Specified model
( )
S S
m
v
m
ig
Model name
2
H H
T
G G
T
m
v
m
ig
m
v
m
ig
_
,
_
,
( )
H H
m
v
m
ig
Route ID
(Default: H H
m
v
m
ig
= 0 )
( )
G G
m
v
m
ig
Route ID
(Default G G
m
v
m
ig
= 0)
3
( )
T
G G
m
v
m
ig
( )
G G
m
v
m
ig
Model name
Liquid Entropy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
S
i
l *,
SL
Major 1
( )
1
T
H
i
l
i
l *, *,
H
i
l *,
Route ID
i
l *,
Route ID
2
( )
S S S
i
ig
i
v
i
ig *, *, *,
+
( )
S S
i
l
i
ig *, *,
Route ID
3 Specified model
S
i
l *,
Model name
S S
i
l
i
ig *, *,
DSL
Subord. 1
H H
T T
i
l
i
ig
i
l
i
ig *, *, *, *,
_
,
_
,
( )
H H
i
l
i
ig *, *,
Route ID
2
( )
T
i
l
i
ig *, *,
( )
i
l
i
ig *, *,
Route ID
( )
i
l
i
ig *, *,
Model name
continued
4-28 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Liquid Entropy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
3 Specified Model
( )
S S
i
l
i
ig *, *,
Model name
S
m
l
SLMX
Major 1
( )
1
T
H G
m
l
m
l
H
m
l
Route ID
G
m
l
Route ID
2
( )
S S S
m
ig
m
l
m
ig
+
( )
S S
m
l
m
ig
Route ID
3 Specified model
S
m
l
Model name
4
( )
S f H G x
m
l
m
l
m
l t
, , H
m
l
model
G
m
l
model
x
t
Route ID
S S
m
l
m
ig
DSLMX
Subord. 1 Specified model
( )
S S
m
l
m
ig
Model name
2
H H
T
G G
T
m
l
m
ig
m
l
m
ig
_
,
_
,
( )
H H
m
l
m
ig
Route ID
( )
G G
m
l
m
ig
Route ID
3
( )
T
G G
m
l
m
ig
( )
G G
m
l
m
ig
Model name
Solid Entropy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
S
i
s *,
SS
Major 1 Specified model
S
i
s *,
Model name
2
( )
1
T
H
i
s
i
s *, *,
H
i
s *,
Route ID
i
s *,
Route ID
continued
Physical Pr oper t y Met hods and Models 4-29
Ver sion 10
Chapter 4
Solid Entropy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
S S
i
s
i
ig *, *,
DSS
Subord. 1
H H
T T
i
s
i
ig
i
s
i
ig *, *, *, *,
_
,
_
,
( )
H H
i
s
i
ig *, *,
Route ID
( )
i
s
i
ig *, *,
Route ID
2 Specified model
( )
S S
i
s
i
ig *, *,
Model name
S
m
s
SSMX
Major 1
( )
1
T
H G
m
s
m
s
H
m
s
Route ID
G
m
s
Route ID
2
( )
S S S
m
ig
m
s
m
ig
+
( )
S S
m
s
m
ig
Route ID
S S
m
s
m
ig
DSSMX
Subord. 1 Specified model
( )
S S
m
s
m
ig
Model name
2
H H
T
G G
T
m
s
m
ig
m
s
m
ig
_
,
_
,
( )
H H
m
s
m
ig
Route ID
( )
G G
m
s
m
ig
Route ID
3
( )
T
G G
m
s
m
ig
( )
G G
m
s
m
ig
Model name
Molar Volume Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
V
i
v *,
VV
Major 1 Specified model
V
i
v *,
Model name
V
m
v
VVMX
Major 1 Specified model
V
m
v
Model name
2
( )
V f y V
m
v
i i
v
,
*,
V
i
v *,
Route ID
V
m
v
Model name
continued
4-30 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Molar Volume Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
3
( ) V f
m
v
i
i
Model name
V
m
v
Model name (eos only)
V
i
l *,
VL
Major 1 Specified model
V
i
l *,
Model name
V
m
l
VLMX
Major 1 Specified model
V
m
l
Model name
2
( )
V f x V
m
l
i i
l
,
*,
V
i
l *,
Route ID
V
m
l
Model name
3
Electrolyte model
( )
x
t
V
i
l *,
Model name
x
t
Route ID
4
( ) V f
m
l
i
i
Model name
V
m
l
Model name (eos only)
V
i
s *,
VS
Major 1 Specified model
V
i
s *,
Model name
V
m
s
VSMX
Major 1 Specified model
V
m
s
Model name
2
( )
V f x V
m
s
i
s
i
s
,
*,
V
i
s *,
Route ID
V
m
s
Model name
Physical Pr oper t y Met hods and Models 4-31
Ver sion 10
Chapter 4
Viscosity Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
n
i
v *,
MUV
Major 1 Specified model
i
v *,
Model name
2
( )
i
v
i
v
p
*, *,
0
( ) ( )
i
v
p
*,
0 Route ID
3
( )
i
v
i
v
f V
*, *,
V
i
v *,
Route ID
i
v *,
Model name
4
( )
( ) ( ) ( )
i
v
i
v
i
v
i
v
p
p p
*, *,
*, *,
+
0
0
( ) ( )
i
v
p
*,
0 Route ID
( ) ( ) ( )
i
v
i
v
p p
*, *,
0
Route
ID
( )
i
v
p
*,
0
MUVLP
Subord. 1 Specified model
( ) ( )
i
v
p
*,
0 Model name
( )
( )
i
v
i
v
p
p
*,
*,
_
,
0
MUVPC
Subord. 1 Specified model
( ) ( ) ( )
i
v
o
v
p p
*, *,
0 M
odel name
2
( ) ( ) ( ) ( )
i
v
o
v
i
v
p p f V
*, *, *,
0 V
i
v *,
Route ID
Model name
n
v
MUVMX
Major 1 Specified model
v
Model name
2
( )
v
i i
v
f y ,
*,
i
v *,
Route ID
v
Model name
3
( )
v v
p 0
( ) ( )
v
p 0 Route ID
4
( )
v
m
v
f V V
m
v
Route ID
5
( )
( ) ( ) ( )
i
v
i
v
i
v
i
v
p
p p
+
0
0
v
Model name
( ) ( )
v
p 0 Route ID
( ) ( ) ( )
i
v
i
v
p p 0
Route ID
continued
4-32 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Viscosity Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
( ) ( )
v
p 0
MUVMXLP
Subord. 1 Specified model
( ) ( )
v
p 0 Model name
2
( ) ( ) ( ) ( )
v
i i
v
p f y p 0 0 ,
*,
( ) ( )
i
v
p
*,
0
Route ID
( ) ( )
v
p 0
Model name
( )
( )
v
v
p
p
_
,
0
MUVMXP
C
Subord. 1 Specified model
( ) ( ) ( )
v v
p p 0
Model
name
2
( ) ( ) ( ) ( )
v v
m
v
p p f V 0
V
m
v
Route ID
( ) ( ) ( )
v v
p p 0
Model
name
i
l *,
MUL
Major 1 Specified model
i
l *,
Model name
2
( )
i
l
i
l
f V
*, *,
V
i
l *,
Route ID
i
l *,
Model Name
l
MULMX
Major 1 Specified model
l
Model name
2
( )
l
i i
l
f x ,
*,
i
l *,
Route ID
l
Model name
3
( )
l
m
l
f V V
m
l
Route ID
l
Model name
Physical Pr oper t y Met hods and Models 4-33
Ver sion 10
Chapter 4
Thermal Conductivity Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
i
v *,
MUV
Major 1 Specified model
i
v *,
Model name
2
( ) ( )
i
v
i
v
p
*, *,
0 ( ) ( )
i
v
p
*,
0 Route ID
3
( )
( ) ( ) ( )
i
v
i
v
i
v
i
v
p
p p
*, *,
*, *,
+
0
0
( ) ( )
i
v
p
*,
0 Route ID
( ) ( ) ( )
i
v
i
v
p p
*, *,
0
Route ID
4
( ) ( )
i
v
i
v
i
v
f V p
*, *, *,
, 0 V
i
v *,
Route ID
( )
i
v
p
*,
0 Model name
i
v *,
Model Name
( )
i
v
p
*,
0
KVLP
Subord. 1 Specified model
( )
i
v
p
*,
0 Model name
2
( ) ( ) ( )
i
v
i
v
p f p
*, *,
0 0 ( )
i
v
p
*,
0 Route ID
i
v *,
Model name
( )
( )
i
v
i
v
p
p
*,
*,
0
KVPC
Subord. 1 Specified model
( ) ( ) ( )
i
v
i
v
p p
*, *,
0
Model name
2
( ) ( ) ( ) ( )
i
v
i
v
i
v
p p f V
*, *, *,
0 V
i
v *,
Route ID
( ) ( ) ( )
i
v
i
v
p p
*, *,
0
Model name
v
KVMX
Major 1 Specified model
v
Model name
2
( )
v
i i
v
f y ,
*,
i
v *,
Route ID
v
Model name
3
( )
v v
p 0
( ) ( )
v
p 0 Route ID
continued
4-34 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Thermal Conductivity Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
4
( )
( ) ( ) ( )
v v
v v
p
p p
+
0
0
( ) ( )
v
p 0 Route ID
( ) ( ) ( )
v v
p p 0 Route
ID
5
( ) ( )
v
m
v v
f V p , 0 V
m
v
Route ID
( ) ( )
v
p 0 Route ID
v
Model name
( )
v
p 0
KVMXLP
Subord. 1 Specified model
( ) ( )
v
p 0 Model name
2
( )
( ) ( ) ( )
v
i i
v
i
v
p
f y p p
0
0 0 , ,
*, *,
i
v *,
Route ID
( )
i
v
p
*,
0 Route ID
( ) ( )
v
p 0 Model name
( ) ( )
v v
p p 0
KVMXPC
Subord. 1 Specified model
( ) ( ) ( )
v v
p p 0
Model name
2
( ) ( ) ( ) ( )
v v
m
v
p p f V 0
Route ID
( ) ( ) ( ) ( ) ( ) ( )
v v v v
p p p p 0 0
Model name
i
l *,
KL
Major 1 Specified model
i
l *,
Model name
2
( ) ( )
i
l
i
l
i
v
f V p
*, *, *,
, 0 V
i
l *,
Route ID
( ) ( )
i
v
p
*,
0 Route ID
i
l *,
Model name
l
KLMX
Major 1 Specified model
l
Model name
2
( )
l
i i
l
f x ,
*,
i
l *,
Route ID
l
Model name
continued
Physical Pr oper t y Met hods and Models 4-35
Ver sion 10
Chapter 4
Thermal Conductivity Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
3
( ) ( )
l
m
l v
f V p , 0 V
m
l
Route ID
( ) ( )
v
p 0 Route ID
l
Model name
i
s *,
KS
Major 1 Specified model
i
s *,
Model name
s
KSMX
Major 1 Specified model
s
Model name
2
( )
s
i
s
i
s
f x ,
*,
i
s *,
Route ID
s
Model name
Diffusion Coefficient Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
D
ij
v
DV
Major 1 Specified model
D
ij
v
Model name
D
i
v
DVMX
Major 1 Specified model
D
i
v
Model name
2
( )
D f y D
i
v
i ij
v
, D
ij
v
Route ID
y
i
Model name
D
ij
l
DL
Major 1 Specified model Model name
D
i
l
DLMX
Major 1 Specified model Model name
2
( )
D f x D
i
l
i ij
l
, D
ij
l
Route ID
D
i
l
Model name
4-36 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Surface Tension Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information Required
i
l *,
SIGL
Major 1 Specified model Model name
l
SIGLMX
Major 1 Specified model Model name
2
( )
l
i i
l
f x ,
*,
i
l *,
Route ID
l
Model name
Routes And Models
This sect ion explains t he st r uct ur e of physical pr oper t y calculat ions by showing t he
r elat ionship bet ween models and r out es, and bet ween r out es on differ ent levels. It
also explains how t o t r ace a calculat ion r out e.
Concept of Routes
Each pr oper t y value needed for a met hod evaluat ion is obt ained fr om eit her
anot her met hod evaluat ion or a model evaluat ion. Pr oper t ies obt ained by met hod
evaluat ion ar e major or subor dinat e pr oper t ies. Pr oper t ies obt ained by a model
evaluat ion ar e int er mediat e pr oper t ies. The calculat ion of t he t op-level pr oper t y is
dict at ed by:
Pr oper t y name
Met hod
Sub-level r out e for each major or subor dinat e pr oper t y
Model name for each int er mediat e pr oper t y (somet imes wit h a model opt ion
code)
This infor mat ion is called a r out e. Ther e is not necessar ily a major or subor dinat e
pr oper t y in each met hod, but if one occur s in t he met hod of t he pr oper t y of int er est ,
t hen t he r out e depends on sub-level r out es. Ther e can be any number of levels in a
r out e. Each level needs t he infor mat ion list ed pr eviously t o be complet ely specified.
This way a t r ee of infor mat ion is for med. Since a model does not depend on
lower -level infor mat ion, you can t hink of it as an end-point of a t r ee br anch. Model
opt ion codes ar e discussed in Models, this chapter. (Example 1 discusses a r out e
t hat does not depend on ot her r out es.)
Physical Pr oper t y Met hods and Models 4-37
Ver sion 10
Chapter 4
Each built -in r out e in ASPEN PLUS has a unique r out e ID, which is composed of
t he pr oper t y name (see t he t ables labeled Major Pr oper t ies in ASPEN PLUS,
Subor dinat e Pr oper t ies in ASPEN PLUS, and Int er mediat e Pr oper t ies in ASPEN
PLUS, all ear lier in t his chapt er ) and a number , for example HLMX10. Ther efor e
t he r out e ID can be used t o r epr esent t he r out e infor mat ion. (See example 2 for a
r out e which depends on a secondar y r out e.)
Rout e IDs associat ed wit h t he r out e infor mat ion r epr esent a unique combinat ion
of sub-level r out es and models. Ther efor e, a t op-level r out e ID specifies t he full
calculat ion t r ee. Because of t he uniqueness of r out e IDs, you can use t hem for
document ing your simulat ion.
A pr oper t y met hod can calculat e a fixed list of pr oper t ies (see Physical Pr oper t ies
in ASPEN PLUS, t his chapt er ). The calculat ion pr ocedur e of each pr oper t y
const it ut es a r out e and has a r out e ID. Ther efor e, a pr oper t y met hod consist s of a
collect ion of t he r out e IDs of t he pr oper t ies it can calculat e. The Pr oper t y
Met hods Rout es sheet shows t he r out es used in a pr oper t y met hod. If you want t o
see all of t he built -in r out es used for calculat ing t he pr oper t y specified in t he
Pr oper t y field, use t he list box in a Rout e ID field (see t he figur e labeled
Pr oper t ies Pr oper t y Met hods Rout es Sheet .
Properties Property Methods Routes Sheet
4-38 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Example 1 Route information for PHILMX, method 1
The fir st met hod fr om t he t able labeled Liquid Fugacit y Coefficient Met hods on
page 4-12 for t he calculat ion of t he fugacit y coefficient of component in a liquid
mixt ur e is specified model. The model can be an equat ion-of-st at e model, t hat
calculat es t he fugacit y coefficient as a funct ion of st at e var iables and cor r elat ion
par amet er s:
( )
l
i i
f p T x , , , correlation parameters
Ther e ar e many models t hat can be used t o calculat e
l
i
, such as t he
Redlich-Kwong-Soave model, t he Peng-Robinson model, or t he Hayden-OConnell
model. It is sufficient t o select a model name in or der t o complet ely specify a
r out e accor ding t o t his met hod.
Example 2 Route information for HLMX, method 3
The t hir d met hod for calculat ing t he liquid mixt ur e ent halpy H
l
m
(see t he t able
labeled Liquid Ent halpy Met hods on page 4-18):
( )
H H H H
l
m
ig
m
l
m
ig
m
+
In t his met hod, H
l
m
depends on t he ideal gas ent halpy and t he ent halpy
depar t ur e H H
l
m
ig
m
, a subor dinat e pr oper t y. The t able labeled Liquid Ent halpy
Met hods on page 4-18 indicat es in t he r ight most column t hat t he r equir ed
infor mat ion is t he r out e ID for t he subor dinat e pr oper t y. The t op-level r out e now
r efer s t o a sub-level r out e ID. For all met hods t hat use bot h an ideal gas
cont r ibut ion and a depar t ur e funct ion, ASPEN PLUS aut omat ically fills in t he
ideal gas calculat ion. You need t o specify only t he depar t ur e funct ion. To specify
t he sub-level r out e for t he ent halpy depar t ur e, you must choose a met hod. For
example, met hod 1: specified model (see t he t able labeled Liquid Ent halpy
Met hods on page 4-18). For t his met hod, t he r equir ed infor mat ion is t he model
name, such as t he Redlich-Kwong-Soave equat ion-of-st at e model.
Physical Pr oper t y Met hods and Models 4-39
Ver sion 10
Chapter 4
Models
A model consist s of one or mor e equat ions t o evaluat e a pr oper t y, and has st at e
var iables, univer sal par amet er s, and cor r elat ion par amet er s as input var iables.
Pr oper t ies obt ained by model evaluat ion ar e called int er mediat e pr oper t ies. They
never depend on major or subor dinat e pr oper t ies, which need a met hod evaluat ion.
In cont r ast t o met hods which ar e based on univer sal scient ific pr inciples only,
models ar e much mor e ar bit r ar y in nat ur e, and have const ant s which need t o be
det er mined by dat a fit t ing. An example of a model is t he Ext ended Ant oine vapor
pr essur e equat ion (see Chapt er 3). Equat ions of st at e have built -in cor r elat ion
par amet er s and ar e also models.
Models ar e somet imes used in mult iple r out es of a pr oper t y met hod. For
example, an equat ion-of-st at e model can be used t o calculat e all vapor and liquid
depar t ur e funct ions of an equat ion-of-st at e-based pr oper t y met hod. The Racket t
model can be used t o calculat e t he pur e component and mixt ur e liquid molar
volumes, (V
l
i
*,
and V
l
m
), and it can also be used in t he calculat ion of t he Poynt ing
cor r ect ion fact or , as par t of t he calculat ion of t he pur e component liquid fugacit y
coefficient .
The Pr oper t ies Pr oper t y Met hods Models sheet displays t he models t hat ar e
globally used in t he r out es of t he cur r ent pr oper t y met hod (see t he figur e labeled
Pr oper t ies Pr oper t y Met hods Models Sheet ). In specific r out es, except ions t o t he
global usage may occur . Modifying and Cr eat ing Rout es, t his chapt er , discusses
how t o ident ify t hese except ions. For a given model, click on t he Affect ed
Pr oper t ies but t on t o display a list of pr oper t ies which ar e affect ed by t he model
calculat ions. Use t he list box on t he Model Name field t o display a list of all
available models for a specific pr oper t y. You can also use t he t ables labeled
Ther modynamic Physical Pr oper t y Models on page 4-41, Tr anspor t Pr oper t y
Models on page 4-43, and Nonconvent ional Solid Pr oper t y Models on page 4-44. If
you need t o use a pr opr iet ar y model or a new model fr om t he lit er at ur e, you can
int er face t hese t o ASPEN PLUS (See AS PEN PLUS User Models.)
4-40 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Calculation
Methods and
Routes
Properties Property Methods Models Sheet
Some models have model opt ion codes t o specify differ ent possible calculat ion
opt ions. For example, t he model WHNRY has t hr ee opt ions t o calculat e t he
weight ing fact or fr om t he cr it ical molar volume. The calculat ion opt ion is
ident ified by t he model opt ion code. On t he Pr oper t y Met hods Models sheet , fir st
select t he model, t hen click t he Opt ion Codes but t on t o display a list of opt ion
code values for t he model. Use Help for descr ipt ions of t he opt ion codes.
Physical Pr oper t y Met hods and Models 4-41
Ver sion 10
Chapter 4
Thermodynamic Physical Property Models
Thermodynamic Properties Model Model Name Phase Properties
Antoine/Wagner PL0XANT L L1 L2 PL
API liquid volume VL2API L VLMX
Aqueous Electrolyte NRTL Enthalpy HAQELC L HLMX
Aqueous Electrolyte NRTL Gibbs Energy GAQELC L GLMX
ASME Steam Tables ESH2O0,ESH2O V L
Redlich-Kwong-Soave-Boston-
Mathias
ESRKS0, ESRKS V L
(1)
Wher e:
K
j
= Chemical equilibr ium const ant
v
i j ,
= React ion st oichiomet r ic coefficient of component i
a
i
= Act ivit y of component i
Comput at ion of t he solut ion chemist r y is oft en combined wit h phase equilibr ium
calculat ions. Typical elect r olyt e simulat ions involving solut ion chemist r y ar e:
Liquid (aqueous) phase equilibr ium (for example, calculat ing t he pH for t he
t it r at ion of or ganic acid wit h caust ic solut ion)
Vapor -liquid (aqueous) phase equilibr ium (for example, ext r act ive dist illat ion
wit h salt s as ext r act ive agent s, and sour wat er st r ipping)
Liquid (aqueous)-liquid (or ganic) phase equilibr ium (for example, hydr ocar bon-
sour wat er syst em and liquid-liquid ext r act ion of met als)
Liquid (aqueous)-solid equilibr ium of salt pr ecipit at ion (for example,
cr yst allizat ion of or ganic or inor ganic salt s)
Physical Pr oper t y Met hods and Models 5-3
Ver sion 10
Chapter 5
To simulat e an elect r olyt e syst em, you must pr oper ly ident ify all r elevant chemical
r eact ions. Physical int er act ions in solut ions ar e somet imes descr ibed by
post ulat ing chemical r eact ions at equilibr ium. The chemical t heor y of solut ions is
used only for r eal chemical r eact ions. Incor r ect assumpt ions about t he solut ion
chemist r y is t he major cause of inaccur acies in simulat ions of r eact ive chemical
syst ems.
Use t he Elect r olyt e Exper t Syst em t o ident ify all r elevant chemical r eact ions.
St ar t ing fr om t his set of r eact ions, you can r emove and/or add r eact ions as
r equir ed t o pr oper ly r epr esent your pr ocess.
You can use t he React ions Chemist r y for m t o descr ibe t he solut ion chemist r y and
t o ent er t he chemical equilibr ium const ant s. However , we st r ongly r ecommend
t hat you use t he Elec but t on on t he Component s.Main for m and allow t he
Elect r olyt es Exper t Syst em t o set up t he pr oper t y specificat ions for you.
For a syst em wit h a solvent dielect r ic const ant less t han 10, ionic r eact ions do
not t ake place. Ther efor e, ASPEN PLUS bypasses all solut ion chemist r y
calculat ions for such syst ems.
If you define t he r eact ions on t he React ions Chemist r y for m, ASPEN PLUS
checks for infeasible or r edundant r eact ions. If such r eact ions exist ,
ASPEN PLUS ignor es t hem dur ing t he calculat ions.
Apparent Component and True Component Approaches
As a r esult of t he solut ion chemist r y, a set of t r ue species is pr esent in t he liquid
phase t hat differ s fr om appar ent molecular component s. Appar ent or par ent
component s ar e pr esent in t he syst em if no r eact ions occur r ed. For example, t he
sour wat er st r ipper syst em has t hr ee appar ent molecular component s: wat er ,
ammonia, and hydr ogen sulfide. The t hr ee molecular component s dissociat e in t he
liquid phase. Ther e ar e four ionic r eact ions:
2
2 3
H O H O OH +
+
(2)
NH H O NH OH
3 2 4
+ +
+
(3)
H S H O H O HS
2 2 3
+ +
+
(4)
HS H O H O S
+
+ +
2 3
2
(5)
Five ionic species ar e t her eby pr oduced fr om t hese aqueous phase ionic r eact ions.
All component s in t hese r eact ions exist at chemical equilibr ium condit ions and ar e
t he t r ue component s of t he elect r olyt e syst em. The appar ent component s ar e H O
2
NH
3
,and H S
2
.
5-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
Simulation
These t wo set s of component s have major effect s on t he t r eat ment of elect r olyt e
pr ocess simulat ion. Appar ent component s ar e of major concer n t o some
elect r olyt e pr ocesses since pr ocess measur ement s ar e usually expr essed in t er ms
of appar ent component s. To ot her elect r olyt e pr ocesses, expr ession in t er ms of
t r ue species is t he only way t o char act er ize an elect r olyt e syst em. The select ion of
appar ent component s or t r ue component s t her efor e depends on t he t ype of
elect r olyt e syst em you simulat e.
Thr ee t ypes of molecular component s may be pr esent in an elect r olyt e syst em:
solvent s, molecular solut es, and elect r olyt es. As a r esult of elect r olyt e solut ion
chemist r y, ions, salt s, and nonvolat ile molecular solut es may be pr esent as
addit ional t r ue species. These component s ar e defined as:
Solvent : wat er is t he solvent for aqueous elect olyt e syst ems. For mixed-solvent
elect r olyt e syst ems, t her e ar e ot her solvent component s in addit ion t o wat er .
Molecular solut es ar e molecular species, ot her t han solvent compounds, t hat
exist in t he liquid phase in molecular for m. All molecular solut es ar e t r eat ed
wit h Henr ys law. They ar e oft en super cr it ical component s.
Elect r olyt es ar e also molecular species. However , st r ong elect r olyt es dissociat e
complet ely t o ionic species in t he liquid phase. Undissociat ed weak elect r olyt es
can be solvent component s or molecular solut es.
Ions ar e nonvolat ile ionic species t hat exist only in t he liquid phase.
Salt s ar e nonvolat ile molecular species t hat exist as solids.
Choosing the True or Apparent Approach
The appar ent component appr oach and t he t r ue component appr oach ar e
int er changeable because solut ion chemist r y based on appar ent component
composit ion defines t he t r ue component composit ion of a syst em. ASPEN PLUS
calculat es t her modynamic pr oper t ies of component s and mixt ur es expr essed in
t er ms of appar ent component composit ion fr om pr oper t ies expr essed in t er ms of
t r ue component composit ion. For example, t he liquid fugacit y coefficient of
ammonia wit h t he appar ent component appr oach is calculat ed fr om t he liquid
fugacit y coefficient of ammonia wit h t he t r ue component appr oach:
i
a l
i
t l i
t
i
a
x
x
, ,
(6)
Wher e:
i
a l ,
= Fugacit y coefficient of appar ent component i
i
t l ,
= Fugacit y coefficient of t r ue component i
x
i
= Liquid component mole fr act ion of component i (super scr ipt a
indicat es appar ent composit ion, t indicat es t r ue composit ion)
Physical Pr oper t y Met hods and Models 5-5
Ver sion 10
Chapter 5
Similar r elat ionships ar e est ablished for ot her pr oper t ies (Chen et al., 1983).
However , t he appar ent component mole fr act ions ar e not always calculat ed fr om
t he t r ue component mole fr act ions because ambiguit y can exist in t he
st oichiomet r ic r elat ions.
Using t he appar ent component appr oach in vapor -liquid equilibr ium implies:
The vapor -liquid equilibr ium is solved in t er ms of appar ent component s only.
The liquid solut ion chemist r y in t he liquid is solved in t er ms of t r ue and
appar ent component s.
This appr oach r est r ict s t he specificat ion of t he chemist r y, because t he r eact ion
pr oduct s (which ar e t r ue component s only by definit ion) cannot cont ain volat ile
component s. Only appar ent component s can t ake par t in vapor -liquid equilibr ium.
The t r ue component appr oach does not have t his r est r ict ion.
In pr ocess simulat ion, t he t r ue component appr oach r equir es t hat you specify t he
pr ocess in t er ms of t r ue component s. ASPEN PLUS car r ies t r ue component s and
t heir composit ions in each pr ocess st r eam and each unit oper at ion. Unit
oper at ion comput at ional algor it hms have been developed t o solve t he chemical
equilibr ium r elat ionship in addit ion t o t he unit -oper at ion descr ibing equat ions.
The appar ent component appr oach r equir es t hat you specify t he pr ocess only in
t er ms of appar ent component s. The solut ion chemist r y and t he t r ue component s
ar e handled by t he physical pr oper t y syst em and ar e t r anspar ent t o pr ocess
flowsheet s and unit oper at ions. The appar ent component appr oach makes it
possible t o use exist ing unit oper at ion comput at ional algor it hms, such as:
Flash algor it hms for vapor -liquid equilibr ium
Liquid phase split t ing algor it hms for liquid-liquid equilibr ium
Dist illat ion algor it hms
Rigor ous r epr esent at ion of t he (effect ive) par t ial molar pr oper t ies of appar ent
component s r equir es t he solut ion of t he chemical equilibr ium and t he knowledge of
t he par t ial molar pr oper t ies of t he t r ue component s.
Deciding whet her t o use t he appar ent component or t r ue component appr oach
can depend on:
Your per sonal pr efer ence
The way you specify t he pr ocess (in t er ms of appar ent component s or t r ue
component s)
Conver gence consider at ions
Gener ally, t he appar ent component appr oach is pr efer r ed for simple elect r olyt e
syst ems. It offer s t he advant age t hat only appar ent component s need t o be
comsider ed. When t he syst em gr ows mor e complex and it becomes difficult t o select
t he appar ent component s, t he t r ue component appr oach is pr efer r ed. For complex
dist illat ion columns or flowsheet specificat ions, t he t r ue component appr oach can
impr ove conver gence. When t he appar ent component s yield volat ile r eact ion
pr oduct s, always use t he t r ue component appr oach.
If you use t he appar ent component appr oach, solut ion chemist r y is r equir ed.
5-6 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
Simulation
Reconstitution of Apparent Component Mole Fractions
Sever al elect r olyt e pr oper t y models in ASPEN PLUS use t he t echnique of
const r uct ing a set of ar bit r ar y mole fr act ions of all possible appar ent component s
fr om a mixt ur e descr ibed in t er ms of composit ions of t r ue component s. These
models ar e list ed in t he following t able, and ar e discussed in det ail in Chapt er 3 .
Model Name Property
Clarke aqueous electrolyte volume Molar volume
Jones-Dole Viscosity
Riedel Thermal conductivity
Nernst-Hartley Diffusivity
Onsager-Samaras Surface tension
The mole fr act ions of t he appar ent component s ar e r econst it ut ed fr om mole
fr act ions of t r ue component s, even if you use t he appar ent component appr oach. All
possible appar ent component s ca fr om cat ions c and anions a ar e consider ed. For
example, if you dissolve calcium sulphat e and sodium chlor ide in wat er , t hen t he
solut ion cont ains: Na
+
, Ca
2+
, SO
4
2
, and C1
(7)
This solut ion gener at es all possible combinat ions of anions and cat ions. However ,
for t he case of 2-2 elect r olyt es, t he amount is mult iplied by 2, t o avoid t he
cr eat ion of, for example, ( ) Ca SO
2 4
2
inst ead of CaSO
4
. In gener al, t he cor r ect ion
fact or should be t he highest common fact or of t he char ges ( ) z
c
and ( ) z
a
, but t he
3-3 or 2-4 elect r olyt es ar e not known.
Fr om t his t he t ot al amount of appar ent moles and appar ent mole fr act ions can be
calculat ed:
x
n
n
k
a k
a
tot
a
(8)
Wher e k can r efer t o any solvent B, molecular solut e i, or appar ent elect r olyt e ca.
Physical Pr oper t y Met hods and Models 5-7
Ver sion 10
Chapter 5
Electrolyte Thermodynami c Models
In elect r olyt e pr ocess simulat ion, t he following t her mophysical pr oper t ies must be
comput ed at a given t emper at ur e, pr essur e and composit ion:
Act ivit y coefficient
Ent halpy
Refer ence st at e Gibbs ener gy
These pr oper t ies ar e necessar y t o per for m phase equilibr ium, chemical
equilibr ium, and mass and ener gy balance calculat ions. Act ivit y coefficient s ar e t he
most cr it ical pr oper t ies for pr ocess simulat ion. They det er mine t he flow r at es,
composit ions, and st abilit y of phases.
Advances in elect r olyt e t her modynamics have pr oduced sever al semi-empir ical
excess Gibbs ener gy models t hat cor r elat e and pr edict : act ivit y coefficient s of
individual ions, mean ionic act ivit y coefficient s, and act ivit y coefficient s of
molecular solvent s and solut es. The Pit zer equat ion, t he elect r olyt e NRTL Model,
and t he Zemait is equat ions ar e t he most widely adopt ed equat ions among t hese
models.
Pi tzer Equati on
The Pit zer equat ion is a virial expansion equat ion. The model requires second-
or der par amet er s at low concent r at ions, and bot h second- and t hir d-or der
par amet er s at high concent r at ions. The equat ion has been applied successfully t o
r epr esent dat a wit hin exper iment al er r or fr om dilut e solut ions up t o an ionic
st r engt h of six molal for bot h aqueous single st r ong elect r olyt e syst ems and
mult icomponent st r ong elect r olyt e syst ems (Pit zer , 1973). The Pit zer equat ion is
also ext ended t o model aqueous weak elect r olyt e syst ems (Chen et al., 1982). It
pr ovides a t her modynamically consist ent model t hat accur at ely r epr esent s
elect r olyt e nonidealit y for many indust r ial aqueous elect r olyt e syst ems.
This model is t he basis for t he PITZER pr oper t y met hod. For det ails on t he
model, see Pit zer Act ivit y Coefficient Model, Chapt er 3.
5-8 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
Simulation
Electrolyte NRTL Equati on
The elect r olyt e NRTL equat ion pr ovides anot her t her modynamically consist ent
model for aqueous elect r olyt e syst ems. This equat ion was developed wit h t he local
composit ion concept . This concept is similar t o t he NRTL (Non-Random Two
Liquid) model for nonelect r olyt e syst ems (Renon and Pr ausnit z, 1968). Wit h only
binar y par amet er s, t he equat ion sat isfact or ily r epr esent s physical int er act ions of
t r ue species in aqueous single elect r olyt e syst ems and mult icomponent elect r olyt e
syst ems over wide r anges of concent r at ions and t emper at ur es. This model can
r epr esent infinit ely dilut e elect r olyt e syst ems (wher e it r educes t o t he Debije-
Hckel model), nonelect r olyt e syst ems (wher e it r educes t o t he NRTL model), and
pure fused salt s. It connect s t hese limit ing syst ems. The equat ion has been
ext ended t o model mixed solvent elect rolyt e-syst ems (Mock et al., 1984).
This model is t he basis for t he ELECNRTL pr oper t y met hod. For det ails on t he
model, see Elect r olyt e NRTL Act ivit y Coefficient Model, Chapt er 3.
Zemai ti s Equati on (Bromley-Pi tzer Model)
The Zemait is equat ion is based on t he Bronst ed-Guggenheim mean ionic act ivit y
coefficient equat ion wit h t he Guggenheim t er m expr essed in Br omley's for m as
an expansion of ionic st r engt h. The act ivit y of solvent wat er in single elect r olyt e
syst ems is t hen comput ed by applicat ion of t he Gibbs-Duhem int egr at ion on t he
mean ionic act ivit y coefficient equat ion. In mult icomponent elect r olyt e syst ems, t he
act ivit y coefficient of solvent wat er is comput ed wit h t he Meissner appr oximat ion
t o avoid excessive Gibbs-Duhem int egr at ion (Br omley, 1973). Act ivit y coefficient s of
molecular solut es ar e est imat ed wit h t he Set schenow equat ion. The Zemait is
equat ion is not a t her modynamically consist ent model, and binar y par amet er s ar e
empir ical funct ions of ionic st r engt h. The model offer s t he advant age of pr edict ing
mean ionic act ivit y coefficient s for unmeasur ed elect r olyt e syst ems fr om Br omley's
cor r elat ion of binar y par amet er s (Meissner and Kusik, 1973). For det ails on t he
model, see Br omley-Pit zer Act ivit y Coefficient Model, Chapt er 3.
Future Models
Act ive r esear ch is being conduct ed in t he field of elect r olyt e t her modynamics
(Maur er , 1983). For example, models based on Mean Spher ical Appr oximat ion
(Planche and Renon, 1981, Wat anasir i et al., 1982) and equat ion of st at e elect r olyt e
models (Fr st and Renon, 1993) ar e being developed. Gener ally, t he t r end is
t owar d developing t her modynamically consist ent models wit h fewer adjust able
par amet er s, br oader applicabilit y, and gr eat er pr edict ive capabilit y. A br oad r ange
of elect r olyt e act ivit y coefficient models will soon be available.
Physical Pr oper t y Met hods and Models 5-9
Ver sion 10
Chapter 5
Electrolyte Data Regressi on
Dat a r egr ession is a cr it ical par t of elect r olyt e pr ocess simulat ion. For example,
elect r olyt e act ivit y coefficient models r equir e r egr ession of exper iment al dat a t o
det er mine model par amet er s. It may also be necessar y t o det er mine chemical
equilibr ium const ant s by dat a r egr ession.
The ASPEN PLUS Dat a Regr ession Syst em (DRS) can be used for elect r olyt es.
Ther e ar e t wo unique consider at ions for elect r olyt e syst ems:
Ions ar e nonvolat ile, so vapor -liquid phase equilibr ium const r aint s for ions ar e
not applicable.
The chemical equilibr ium const r aint of t he solut ion chemist r y must be
sat isfied.
Exper iment al dat a for elect r olyt e syst ems can be divided int o four main cat egor ies
for bot h single elect r olyt e syst ems and mult icomponent elect r olyt e syst ems:
Elect r olyt e pr oper t ies, such as mean ionic coefficient s
Molecular pr oper t ies, such as osmot ic coefficient , solvent vapor pr essur e, vapor -
liquid phase equilibr ium dat a, and liquid-liquid phase equilibr ium dat a
Solut ion pr oper t ies, such as liquid mixt ur e ent halpy and densit y
Salt solubilit y
Elect r olyt e dat a r egr ession is most oft en per for med on elect r olyt e pr oper t ies and
molecular pr oper t ies t o det er mine act ivit y coefficient model par amet er s. Solut ion
ent halpy dat a pr ovide valuable infor mat ion on t emper at ur e der ivat ives of act ivit y
coefficient s and can be used wit h ot her dat a t o det er mine t he t emper at ur e
dependency of act ivit y coefficient model par amet er s. These dat a can also be used t o
r egr ess chemical equilibr ium const ant s and act ivit y coefficient model par amet er s.
Salt sat ur at ion limit s can be used t o obt ain equilibr ium const ant s for salt
pr ecipit at ion (salt solubilit y pr oduct ).
See AS PEN PLUS User Guide, Chapt er 31, for det ails on dat a r egr ession.
References
L.A. Br omley, "Ther modynamic Pr oper t ies of St r ong Elect r olyt es in Aqueous
Solut ions," AIChE J ., Vol. 18, (1973), p. 313.
C.C. Chen, H.I. Br it t , J .F Bost on, and L.B. Evans, "Local Composit ion Model for
Excess Gibbs Ener gy of Elect r olyt e Syst ems," AIChE J ., Vol. 28, (1982), p. 588.
C.C. Chen, H.I. Br it t , J .F. Bost on, and W.M. Clar ke, "Ther modynamic Pr oper t y
Evaluat ion in Comput er -Based Flowsheet Simulat ion for Aqueous Elect r olyt e
Syst ems," Paper pr esent ed at t he Denver AIChE Meet ing, August , 1983.
5-10 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
Simulation
W. Fr st and H. Renon. "Repr esent at ion of Excess Pr oper t ies of Elect r olyt e
Solut ions Using a New Equat ion of St at e." AIChE J ., Vol. 39, No. 2, (1993), pp.
335-343.
G., Mauer , "Elect r olyt e Solut ions," Fluid Phase Equilibria, Vol. 13, (1983), p. 269.
H.P. Meissner and C.L. Kusik, "Aqueous Solut ions of Two or Mor e St r ong
Elect r olyt es-Vapor Pr essur es and Solubilit ies," Ind. Eng. Chem. Process Res.
Develop., Vol. 12, (1973), p. 205.
B. Mock, L.B. Evans, and C.-C. Chen, "Phase Equilibr ia in Mult iple-Solvent
Elect r olyt e Syst ems: A New Ther modynamic Model," Paper pr esent ed at t he
Bost on Summer Comput er Simulat ion Confer ence, J uly 1984.
Pit zer , K.S., "Ther modynamics of Elect r olyt es.I. Theor et ical Basis and Gener al
Equat ions," J . Phys. Chem., Vol. 77, (1973), p. 268.
H. Planche and H. Renon, "Mean Spher ical Appr oximat ion Applied t o a Simple
but Nonpr imit ive Model of Int er act ion for Elect r olyt e Solut ions and Polar
Subst ance," J . Phys. Chem, Vol. 85, (1981), p. 3924.
H. Renon and J .M. Pr ausnit z, "Local Composit ions in Ther modynamic Excess
Funct ion for Liquid Mixt ur es," AIChE J ., Vol. 14, (1968), p. 135.
S. Wat anasir i, M.R. Br ule, and L.L. Lee, "Pr edict ion of Ther modynamic
Pr oper t ies of Elect r olyt ic Solut ions Using t he Me an Spher ical
Appr oximat ion," J . Phys. Chem., Vol. 86, (1982), p. 282.
y y y y
Physical Pr oper t y Met hods and Models 6-1
Ver sion 10
Chapter 6
6 Free-Water and Rigorous
Three-Phase Calculations
This chapt er descr ibes fr ee-wat er and r igor ous t hr ee-phase calculat ions in
ASPEN PLUS. Guidelines t o help you choose t he most appr opr iat e met hod ar e
included.
The following t able list s t he unit oper at ion models t hat allow t hr ee-phase
calculat ions. The t able shows, for each model, whet her or not fr ee-wat er and/or
r igor ous t hr ee-phase calculat ions can be per for med.
Unit Operation Models That Allow Three-Phase Calculations
Name Description
Free-Water
Calculations
Water Decant
Stream
Rigorous Three-Phase
Calculations
Mixer
FSplit
Sep
Sep2
Stream mixer
Stream splitter
Component separator
Two outlet separator
YES
YES
YES
YES
YES
NO
NO
NO
YES
YES
YES
YES
DSTWU
Distl
SCFrac
RadFrac
MultiFrac
PetroFrac
BATCHFRAC
RATEFRAC
Extract
Shortcut distillation design
Shortcut distillation rating
Shortcut petroleum distillation
Rigorous distillation
Rigorous multicolumn distillation
Rigorous petroleum distillation
Rigorous batch distillation
Rate-based distillation
Rigorous liquid-liquid extractor
YES
YES
YES
YES
YES
YES
YES
YES
NO
YES
YES
YES
YES
YES
YES
NO
YES
NO
NO
NO
NO
YES
NO
NO
YES
NO
Condenser only
YES
YES
RStoic
RYield
RGibbs
Stoichiometric reactor
Yield reactor
Equilibrium reactor
Gibbs energy minimization
YES
YES
NO
YES
YES
NO
YES
YES
YES
Pump
Compr
MCompr
Pump/hydraulic turbine
Compressor/turbine
Multistage compressor/turbine
YES
YES
YES
YES
YES
YES
YES
YES
YES
Crystallizer Crystallizer NO NO NO
Pipeline
Dupl
Mult
Pipeline
Stream duplicator
Stream multiplier
YES
NO
YES
Condenser only
w
l *,
= The fugacit y coefficient of pur e liquid wat er , calculat ed using a fr ee-
wat er pr oper t y met hod (for example, t he STEAM-TA pr oper t y
met hod)
w
v
= The fugacit y coefficient of wat er in t he vapor phase mixt ur e,
calculat ed using t he pr imar y pr oper t y met hod
6-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Free-Water
and
Rigorous
Three-
Phase
Calculations
When a fr ee-wat er phase is pr esent , it s ot her t her modynamic pr oper t ies (such as
ent halpy) and t r anspor t pr oper t ies (such as viscosit y) ar e calculat ed using t he fr ee-
wat er pr oper t y met hod.
Organic Phase Properties
The K-value of wat er in t he or ganic phase is:
K
w w w
l
w
v * *,
Wher e:
w
= The act ivit y coefficient of wat er in t he or ganic phase
w
l *,
= The fugacit y coefficient of pur e liquid wat er , calculat ed using t he
fr ee-wat er pr oper t y met hod
w
v
= The fugacit y coefficient of wat er in t he vapor phase mixt ur e,
calculat ed using t he pr imar y pr oper t y met hod
You can select t he calculat ion met hods for
w
and
w
v
using t he Solu-wat er field
on t he Pr oper t ies.Main for m or t he Blockops for m.
Solu-water option
Calculate
w
from
Calculate
w
v
from
0
w
w
sol
x
1
Free-water property method
1
w
w
sol
x
1
Primary property method
2
( )
w w
f T x , where
w
w
sol
x
1
when x x
w w
sol
+ 1
a x
x
x
i
wi
sol
wi
sol
i
1
Wher e:
x
i
= Wat er -fr ee mole fr act ion of t he it h or ganic species
x
wi
sol
= Mole fr act ion solubilit y of wat er in t he it h species
The value of x
wi
sol
is calculat ed as a funct ion of t emper at ur e, using t he Wat er
Solubilit y model (WATSOL) descr ibed in Chapt er 3.
Rigorous Three-Phase Calculations
The unit oper at ion models t hat can per for m r igor ous t hr ee-phase or t wo-liquid-
phase calculat ions ar e indicat ed in t he t able labeled Unit Oper at ion Models That
Allow Thr ee-Phase Calculat ions on page 6-1.These calculat ions make no
assumpt ions about t he nat ur e of t he t wo liquid phases. ASPEN PLUS uses t he
pr imar y pr oper t y met hod t o calculat e t he K-values of all component s in bot h liquid
phases. The second liquid phase does not have t o be aqueous. If t he second liquid
phase is aqueous, t he solubilit y of or ganics in wat er is t r eat ed r igor ously. To obt ain
cor r ect t hr ee-phase r esult s, you must use t he appr opr iat e binar y par amet er s for
t he pr oper t y model used in t he pr oper t y met hod.
Specify r igor ous t hr ee-phase calculat ions at t he individual block level, using t he
flash opt ion NPHASE=3, except for Flash3. Flash3 has no flash opt ions, since it
per for ms only r igor ous t hr ee-phase flashes.
Ext r act always per for ms r igor ous t wo-liquid-phase calculat ions.
y y y y
6-6 Physical Pr oper t y Met hods and Models
Ver sion 10
Free-Water
and
Rigorous
Three-
Phase
Calculations
Physical Pr oper t y Met hods and Models 7-1
Ver sion 10
Chapter 7
7 Petroleum Components
Characterization Methods
ASPEN PLUS pr ovides a wide r ange of met hods for char act er izat ion of pet r oleum
component s, or pseudocomponent s. These met hods ar e used t o est imat e pr oper t y
par amet er s, such as cr it ical pr oper t ies, ideal gas heat capacit y, vapor pr essur e, and
liquid viscosit y. The following t able list s:
Par amet er s t hat ASPEN PLUS est imat es for pet r oleum component s
Met hods available (the literature references for each method are listed at the end of
this chapter)
Petroleum Components Characterization Methods
Parameter Description Model Available
MW Molecular weight Brule et al. (1982)
Hariu-Sage (1969)
Hariu-Sage-Aspen (1994)
Kesler-Lee (1976)
Riazi API (1987)
Riazi-Daubert (1980)
Tsang-Aspen (1978)
TC Critical temperature Brule et al. (1982)
Cavett (1962)
Kesler-Lee (1976)
Riazi API (1987)
Riazi-Daubert (1980)
Tsang-Aspen (1978)
Twu (1984)
PC Critical pressure Cavett (1962)
Kesler-Lee (1976)
Riazi API (1987)
Riazi-Daubert (1980)
Tsang-Aspen (1978)
Twu (1984)
continued
7-2 Physical Pr oper t y Met hods and Models
Ver sion 10
Petroleum
Components
Characterization
Methods
Petroleum Components Characterization Methods (continued)
Parameter Description Model Available
VC Critical volume Brule et al. (1982)
Reidel (1954)
Twu (1984)
PL Vapor pressure BK-10
Kesler-Lee (1980)
Maxwell-Bonnell (1955)
Tsang-SWAP (1978)
CPIG Ideal gas heat capacity Brule et al. (1982)
Cavett (1962)
Kesler-Lee (1976)
Mathias-Monks (1982)
Tsang-Aspen (1978)
VL Liquid molar volume Cavett
Rackett (Spencer, 1972)
DHVL Enthalpy of vaporization Vetere (1973)
OMEGA Acentric factor Defining relation
Kesler-Lee (1976)
Kesler-Lee-Aspen (1994)
MUL Liquid viscosity Watson (1935)
BWRGMA BWR orientation parameter Brule et al. (1982)
TCBWR BWR critical temperature Brule et al. (1982)
VCBWR BWR critical volume Brule et al. (1982)
DHFORM Standard enthalpy of formation Default to zero
Montgomery (1988)
DGFORM Standard Gibbs energy of formation Default to zero
Montgomery (1988)
WATSOL Water solubility in hydrocarbon ASPEN PLUS
API Kerosene
Hibbard-Schalla
RKSKIJ RKS binary parameters API 1978
API 1987
Physical Pr oper t y Met hods and Models 7-3
Ver sion 10
Chapter 7
Property Methods for Characteri zati on of Petroleum
Components
Since t her e ar e sever al met hods available for est imat ion of a given par amet er ,
ASPEN PLUS select s t he most appr opr iat e met hod for a given applicat ion. These
select ed met hods ar e used t o cr eat e an pr oper t y met hod. Ther e ar e five pr oper t y
met hods available:
The API-METH pr oper t y met hod consist s of met hods based mainly on t he API
pr ocedur e. This pr oper t y met hod is appr opr iat e for r efiner y applicat ions.
COAL-LIQ pr oper t y met hod consist s of met hods developed for coal liquid
applicat ions. The dat abase used t o develop t he cor r elat ions cont ains a lar ge
per cent age of ar omat ic compounds.
ASPEN pr oper t y met hod consist s of met hods developed by AspenTech for
pet r oleum component s and met hods based on t he API pr ocedur e. This met hod
is r ecommended.
LK pr oper t y met hod is based mainly on t he met hods of Kesler and Lee.
API-TWU pr oper t y met hod is based on t he ASPEN pr oper t y met hod, but uses
t he Twu cor r elat ions for cr it ical pr oper t ies.
The pr oper t y met hods available for char act er izat ion of pseudocomponent s ar e
list ed in t he following t able.
Property Methods for Pseudocomponents Characterization
Property Method ASPEN: Aspen Tech and API procedures
Property Method
Molecular weight Hariu-Sage-ASPEN
T
c
Riazi-Daubert
P
c
Riazi-Daubert
V
c
Reidel
Vapor pressure BK-10
Ideal gas capacity Kesler-Lee
Liquid molar volume Rackett
Enthalpy of vaporization Vetere
Acentric factor Kesler-Lee-ASPEN
Viscosity Watson
Water solubility ASPEN PLUS
Standard enthalpy of formation Montgomery
Standard Gibbs energy of formation Montgomery
RKS binary parameters API 1978
continued
7-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Petroleum
Components
Characterization
Methods
Property Method API-METH: API Procedures
Property Method
Molecular weight Hariu-Sage
T
c
Riazi-Daubert
P
c
Riazi-Daubert
V
c
Reidel
Vapor pressure Maxwell-Bonnell
Ideal gas heat capacity Kesler-Lee
Liquid molar volume Rackett
Enthalpy of vaporization Vetere
Acentric factor Kesler-Lee
Viscosity Watson
Water Solubility ASPEN PLUS
Standard enthalpy of formation Default to zero
Standard Gibbs energy of formation Default to zero
Water solubility in hydrocarbon ASPEN PLUS
RKS binary parameters API 1978
Property Method API-METH: For COAL-LIQ; For coal Liquids
Property Method
Molecular weight Hariu-Sage
Tc Tsang-ASPEN
Pc Tsang-ASPEN
Vc Reidel
Vapor pressure Tsang-SWAP
Ideal gas heat capacity Mathias-Monks
Liquid molar volume Rackett
Enthalpy of vaporization Vetere
Acentric factor Kesler-Lee
Viscosity Watson
BWR orientation parameter Brule et al.
BWR Tc Brule et al.
BWR Vc Brule et al.
Continued
Physical Pr oper t y Met hods and Models 7-5
Ver sion 10
Chapter 7
Property Method API-METH: For COAL-LIQ; For coal Liquids (Continued)
Property Method
Standard enthalpy of formation Default to zero
Standard Gibbs energy of formation Default to zero
RKS binary parameters API 1978
Property Method LK: Lee-Kesler
Property Method
Molecular weight Kesler-Lee
T
c
Kesler-Lee
P
c
Kesler-Lee
V
c
Reidel
Vapor pressure Kesler-Lee
Ideal gas heat capacity Kesler-Lee
Liquid molar volume Rackett
Enthalpy of vaporization Vetere
Acentric factor Kesler-Lee
Viscosity Watson
Standard enthalpy of formation ASPEN PLUS
Standard Gibbs energy of formation Montgomery
Water solubility in hydrocarbon Montgomery
RKS binary parameters API 1978
Property Method API-TWU: AspenTech, API, and Twu
Property Method
Molecular weight Hariu-Sage-ASPEN
T
c
Twu
P
c
Twu
V
c
Twu
Vapor pressure BK-10
Ideal gas heat capacity Kesler-Lee
Liquid molar volume Rackett
Enthalpy of vaporization Vetere
Continued
7-6 Physical Pr oper t y Met hods and Models
Ver sion 10
Petroleum
Components
Characterization
Methods
Property Method API-TWU: AspenTech, API, and Twu (Continued)
Property Method
Acentric factor Kesler-ASPEN
Viscosity Watson
Water solubility API kerosene-line
Standard enthalpy of formation Montgomery
Standard Gibbs energy of formation Montgomery
RKS binary parameters API 1978
References
M.R. Br ul, C.T. Lim, L.L. Lee, and K.E. St ar ling, AICHE J ., 28, p. 616 (1982).
R.H. Cavet t , "Physical Dat a for Dist illat ion Calculat ions Vapor -Liquid
Equilibr ia," Pr esent ed at 27t h Midyear Meet ing of API Division of Refining, May
15, 1982.
R.H. Cavet t , FLOWTRAN Physical Pr oper t ies Refer ence Manual, Monsant o
Company.
C.W. Edmist er , e. Applied Hydr ocar bon Ther modynamics, 2nd edit ion, Gulf
Publishing Co., (1988).
O.H. Har iu and R.C. Sage, Hydro. Proc., (1969).
M.G. Kesler and B.I. Lee, Hydro. Proc., 55 (3), p. 153, (1976).
M.G. Kesler and B.I. Lee, Hydro. Proc., 59 (7), p. 163, (1980).
P.M. Mat hias, and K.G. Monks, SRC-I Quar t er ly Pr ogr ess Repor t , Air Pr oduct s
and Chemicals, Inc., Apr il J une 1982.
Maxwell and Bonnell, API Pr ocedur e 5A1.15.
L. Reidel, API Pr odedur e 4A3.1.
M.R. Riazi and T.E. Dauber t , Hydro. Proc., 59 (3), p. 115, (1980).
D. B. Robinson and D. Y. Peng "The Char act er izat ion of t he Hept anes and
Heavier Fr act ions for t he GPA Peng-Robinson Pr ogr ams," GPA Resear ch Repor t
RR-28, Mar ch (1978).
C.F. Spencer and R.P. Danner , J . Chem Eng. Data., 17, (1972).
Physical Pr oper t y Met hods and Models 7-7
Ver sion 10
Chapter 7
M. Tsang, Comput er -Aided Indust r ial Pr ocess Design, The ASPEN Pr oject ,
Second Annual Repor t , J une 1, 1977 t o May 30, 1978; Submit t ed t o U.S. D.O.E.
by M.I.T. Depar t ment of Chemical Engineer ing and Ener gy Labor at or y under
Cont r act No. E(4918) 2295, Task No. 9, J une 15, 1978.
A. Vet er e, "Modificat ion of t he Kist iakowsky Equat ion for t he Calculat ion of t he
Ent halpies of Vapor izat ion of Pur e Compounds," Labor at or y Richer che Chimica
Indust r iale SNAM PROGETTI, San Donat o, Milanese, 1973.
K. Wat son et al., API Figur e 11A4.1.
C. H. Twu, Fluid Phase Equilibr ia, 16, p. 137 (1984).
y y y y
7-8 Physical Pr oper t y Met hods and Models
Ver sion 10
Petroleum
Components
Characterization
Methods
Physical Pr oper t y Met hods and Models 8-1
Ver sion 10
Chapter 8
8 Property Parameter
Estimation
This chapt er descr ibes:
Est imat ion met hods used by t he Pr oper t y Const ant Est imat ion Syst em (PCES)
How t o gener at e a r epor t for t he est imat ed par amet er s
If you r equest est imat ion, ASPEN PLUS, by default , est imat es all missing pr oper t y
par amet er s r equir ed by physical pr oper t y models. These par amet er s include any
not available in t he dat abank and not specified on Pr oper t ies Par amet er s for ms.
The following t able list s all t he par amet er s t hat ASPEN PLUS can est imat e.
Parameters Estimated by ASPEN PLUS
Pure Component Constants
Parameter Description Model
MW Molecular weight
TB Normal boiling point
TC Critical temperature
PC Critical pressure
VC Critical volume
ZC Critical compressibility factor
DHFORM Standard heat of formation at 25C
DGFORM Standard Gibbs free energy of formation at 25C
OMEGA Pitzer acentric factor
S ee Chapter 3.
continued
8-2 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Pure Component Constants (continued)
Parameter Description Model
S ee Chapter 3.
S ee Chapter 3.
Wher e:
R = Univer sal gas const ant
P
c
= Cr it ical pr essur e
V
c
= Cr it ical volume
T
c
= Cr it ical t emper at ur e
Acentri c Factor (OMEGA)
PCES pr ovides t wo met hods for est imat ing acent r ic fact or :
Definit ion met hod
Lee-Kesler met hod
8-10 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Defi ni ti on Method
When you use t he definit ion met hod, t he acent r ic fact or is calculat ed fr om it s
definit ion:
i
i
ci
P
P
_
,
log .
*
10
10
Wher e P
i
*
is vapor pr essur e calculat ed at r educed t emper at ur e, (
T
T
ci
) of 0.7.
When you use t he definit ion met hod, t he vapor pr essur e cor r elat ion par amet er s
PLXANT, TC, and PC must be available fr om t he dat abank or est imat ed.
Lee-Kesler Method
The Lee-Kesler met hod depends on TB, TC, and PC. This met hod is r ecommended
for hydr ocar bons. Lee and Kesler r epor t ed t hat t his met hod yields values of
acent r ic fact or s close t o t hose select ed by Passut and Danner (Ind. Eng. Chem.
Process Des. Dev. 12, 365, 1973).
Standard Enthalpy of Formati on (DHFORM)
PCES pr ovides t he following met hods for est imat ing st andar d ent halpy of
for mat ion:
Method Information Required
Benson Structure
Joback Structure
Bensonr8 Structure
Gani Structure
All met hods ar e gr oup cont r ibut ion met hods t hat apply t o a wide r ange of
compounds. The Benson Met hod is r ecommended.
Benson Method
The Benson met hod is a second-or der gr oup cont r ibut ion met hod. This met hod:
Account s for t he effect of neighbor ing at oms
Is mor e complex t o use t han t he J oback met hod
Repor t s mor e accur at e r esult s t han J oback (aver age er r or is 3.7 kJ /mol)
Table 3.2 in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t he Benson met hod.
Physical Pr oper t y Met hods and Models 8-11
Ver sion 10
Chapter 8
Joback Method
The J oback met hod is a fir st -or der gr oup cont r ibut ion met hod. It is simpler t o
use t han t he ot her available met hods, but is less accur at e. Repor t ed aver age er r or
is 8.9 kJ /mol.
Table 3.5 in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t he J oback met hod.
BensonR8 Method
This is t he Benson met hod pr ovided wit h Release 8 of ASPEN PLUS. It is
r et ained for upwar d compat ibilit y. The Benson met hod is pr efer r ed.
Gani Method
The Gani met hod uses cont r ibut ions fr om bot h fir st -or der and second-or der
gr oups. The second or der gr oups account for t he effect of neighbor ing at oms. Use
of second or der gr oups r esult s in higher accur acy t han t he J oback met hod
(aver age er r or is 3.71 kJ /mol) (AIChE J . 40,1697,1994).
Table 3.4A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups
for t his met hod.
Standard Gi bbs Free Energy of Formati on (DGFORM)
PCES pr ovides t he following met hods for est imat ing st andar d Gibbs fr ee ener gy
of for mat ion:
Method Information Required
Joback Structure
Benson Structure
Gani Structure
Benson Method
The Benson met hod is a second-or der gr oup cont r ibut ion met hod. For t his
pr oper t y, t he Benson met hod r equir es you t o ent er t he symmet r y number and t he
number of possible opt ical isomer s, if applicable. ASPEN PLUS does not gener at e
t his infor mat ion aut omat ically fr om t he gener al molecular st r uct ur e.
Table 3.2 in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t he Benson met hod.
8-12 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Joback Method
The J oback met hod is a fir st -or der gr oup cont r ibut ion met hod. It is simpler t o
use t han t he ot her available met hods, but is less accur at e. Repor t ed er r or s ar e in
t he r ange of 5 t o 10 kJ /mol. The er r or s ar e lar ger for complex mat er ials.
Table 3.5 in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t he J oback met hod.
Gani Method
The Gani met hod uses cont r ibut ions fr om bot h fir st -or der and second-or der
gr oups. The second or der gr oups account for t he effect of neighbor ing at oms. Use
of second or der gr oups r esult s in higher accur acy (AIChE J. 40, 1697, 1994).
The Gani met hod:
Is mor e complex t o use t han t he J oback met hod
Repor t s mor e accur at e r esult s t han J oback (aver age er r or is 3.24 kJ /mol)
Table 3.4A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups
for t his met hod
Heat of Vapori zati on at TB (DHVLB)
PCES est imat es heat of vapor izat ion at t he nor mal boiling point by applying t he
heat of vapor izat ion cor r elat ion (DHVLWT) at TB.
Li qui d Molar Volume at TB (VB)
PCES est imat es liquid molar volume at t he nor mal boiling point by applying t he
Racket t equat ion (RKTZRA) at TB.
Standard Li qui d Volume (VLSTD)
PCES est imat es st andar d liquid volume by applying t he Racket t liquid molar
volume cor r elat ion (RKTZRA) at 60F.
Radi us of Gyrati on (RGYR)
PCES est imat es r adius of gyr at ion fr om par achor (PARC).
Solubi li ty Parameter (DELTA)
The solubilit y par amet er is calculat ed fr om t he definit ion.
Physical Pr oper t y Met hods and Models 8-13
Ver sion 10
Chapter 8
UNIQUAC R and Q Parameters (GMUQR, GMUQQ)
PCES pr ovides t he Bondi met hod for est imat ing t he UNIQUAC R and Q
par amet er s. This met hod r equir es only molecular st r uct ur e as input . Table 3.3 in
AS PEN PLUS Physical Property Data list s t he funct ional gr oups.
Parachor (PARC)
PCES pr ovides one met hod for est imat ing Par achor . The Par achor met hod is a
gr oup-cont r ibut ion met hod. The funct ional gr oups for t his met hod ar e list ed in
Table 3.10 in AS PEN PLUS Physical Property Data.
Ideal Gas Heat Capaci ty (CPIG)
PCES pr ovides t hr ee met hods for est imat ing ideal gas heat capacit y:
Method Information Required
Data Ideal gas heat capacity data
Benson Structure
Joback Structure
PCES uses t he Ideal-Gas-Heat -Capacit y-Polynomial model for t his pr oper t y.
Bot h t he Benson and J oback met hods ar e gr oup-cont r ibut ion met hods t hat apply
t o a wide r ange of compounds.
Do not use t he Benson or J oback met hods out side t he t emper at ur e r ange of 280
t o 1100 K. Er r or s ar e gener ally less t han 1 t o 2%.
Benson Method
Benson is t he r ecommended met hod. It account s for t he effect of neighbor ing
at oms. In compar ison wit h t he J oback met hod, Benson:
Is mor e complex t o use
Repor t s mor e accur at e r esult s (aver age er r or 1.1% for 27 diver se compounds)
Table 3.2 in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t he Benson met hod.
Joback Method
The J oback met hod is a fir st -or der gr oup cont r ibut ion met hod. It is simpler t o
use t han t he Benson met hod, but is less accur at e. Repor t ed aver age er r or is 1.4%
for 28 diver se component s.
8-14 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Table 3.5 in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t he J oback met hod.
Data Method
The Dat a met hod det er mines par amet er s for t he ideal gas heat capacit y
polynomial. Exper iment al ideal gas heat capacit y dat a ar e fit t ed. You ent er t his
dat a on t he Pr oper t ies Dat a Pur e Component for m.
Vapor Pressure (PLXANT)
PCES pr ovides t he following met hods for est imat ing vapor pr essur e:
Method Information Required
Data Vapor pressure data
Riedel TB, TC, PC, (vapor pressure data)
Li-Ma Structure, TB, (vapor pressure data)
Mani TC, PC, (vapor pressure data)
The Ext ended Ant oine model is used for t his pr oper t y.
Data Method
The Dat a met hod det er mines par amet er s for t he Ext ended Ant oine equat ion by
fit t ing exper iment al vapor pr essur e dat a t hat you ent er on t he Pr oper t ies Dat a
Pur e Component for m.
Ri edel Method
The Riedel met hod est imat es par amet er s for t he Ext ended Ant oine vapor pr essur e
equat ion by applying t he Riedel par amet er and t he Plank-Riedel const r aint at t he
cr it ical point . It also makes use of t he condit ion t hat at t he nor mal boiling point ,
t he vapor pr essur e is 1 at m. The par amet er s ar e valid fr om TB t o TC. This met hod
is accur at e for nonpolar compounds, but not for polar compounds.
Li -Ma Method
The Li-Ma met hod is a gr oup cont r ibut ion met hod for est imat ing par amet er s for
t he Ext ended Ant oine vapor pr essur e equat ion. The par amet er s ar e valid fr om
TB t o TC. This met hod is accur at e for polar and nonpolar compounds. For 28
diver se compounds, t he r epor t ed aver age er r or was 0.61% (Fluid Phase Equilibria,
101, 101, 1994).
Table 3.6A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups
for t his met hod.
Physical Pr oper t y Met hods and Models 8-15
Ver sion 10
Chapter 8
Mani Method
The Mani met hod was developed by J uan-Carlos Mani of Aspen Technology. This
met hod est imat es paramet ers for t he Ext ended Ant oine vapor pressure equat ion
using t he Riedel equat ion when one or t wo experiment al vapor pressure dat a
values are available. This met hod can also be used t o est imat e TB and TC.
This met hod pr ovides ver y accur at e and r eliable est imat es of TB, TC and vapor
pr essur e cur ve when some exper iment al vapor pr essur e dat a values ar e available.
It is ver y useful for complex compounds t hat decompose at t emper at ur es below t he
nor mal boiling point s. The vapor pr essur e equat ion is applicable fr om t he lowest
t emper at ur e dat a point t o t he cr it ical t emper at ur e.
Heat of Vapori zati on (DHVLWT)
PCES pr ovides t he following met hods for est imat ing heat of vapor izat ion:
Method Information Required
Data Heat of vaporization data
Definition TC, PC, PL, (Heat of vaporization data)
Vetere MW, TB, (Heat of vaporization data)
Gani Structure, (Heat of vaporization data)
Ducros Structure, (Heat of vaporization data)
Li-Ma Structure, TB, (Heat of vaporization data)
The Wat son model is used for t his pr oper t y.
Data Method
The Dat a met hod det er mines t he Wat son par amet er s by fit t ing exper iment al heat
of vapor izat ion dat a t hat you ent er on t he Pr oper t ies Dat a Pur e Component for m.
Defi ni ti on Method
The Definit ion met hod calculat es heat of vapor izat ion fr om t he Clausius-Clapeyr on
equat ion. It requires vapor pressure, TC, and PC as input . The calculat ed heat of
vaporizat ion values are used t o det ermine t he paramet ers for t he Wat son equat ion.
When t he Riedel met hod was used t o est imat e vapor pr essur e, r epor t ed aver age
er r or for t he heat of vapor izat ion was 1.8% for 94 compounds.
Vetere Method
The Vet er e met hod est imat es heat of vapor izat ion at TB, t hen uses t he Wat son
equat ion t o ext r apolat e heat of vapor izat ion t o TC. Repor t ed aver age er r or is 1.6%.
8-16 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Gani Method
The Gani met hod is a gr oup cont r ibut ion met hod for est imat ing heat of
vaporizat ion at 298 K. It uses t he Wat son equat ion t o ext rapolat e heat of
vapor izat ion t o TC. This met hod r equir es only molecular st r uct ur e as input .
Table 3.4A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t his met hod.
Ducros Method
The Ducr os met hod is a gr oup cont r ibut ion met hod for est imat ing heat of
vapor izat ion at 298K. It uses t he Wat son equat ion t o ext r apolat e heat of
vapor izat ion t o TC (Thermochimica Acta, 36, 39, 1980; 44, 131, 1981; 54, 153, 1982; 75,
329, 1984). This met hod:
Uses mor e complex st r uct ur e cor r ect ion
Can be applied t o or gano-met allic compounds
Table 3.3A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t his met hod.
Li -Ma Method
The Li-Ma met hod is a gr oup cont r ibut ion met hod for est imat ing heat of
vapor izat ion at differ ent t emper at ur es. This met hod r equir es molecular st r uct ur e
and TB as input . Repor t ed aver age er r or for 400 diver se compounds was 1.05%
(Fluid Phase Equilibria, 1997).
Table 3.6A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups
for t his met hod.
Li qui d Molar Volume (RKTZRA)
PCES pr ovides t hr ee met hods for est imat ing liquid molar volume:
Method Information Required
Data Liquid molar volume data
Gunn-Yamada TC, PC.OMEGA
Le Bas Structure
The Racket t model is used for t his pr oper t y.
Physical Pr oper t y Met hods and Models 8-17
Ver sion 10
Chapter 8
Gunn-Yamada Method
The Gunn-Yamada met hod est imat es sat ur at ed liquid molar volume, when t he
r educed t emper at ur e is less t han 0.99. The calculat ed values ar e used t o det er mine
t he Racket t par amet er . This met hod:
Applies t o nonpolar and slight ly polar compounds
Is more accurat e t han t he Le Bas met hod
Le Bas Method
The Le Bas met hod est imat es liquid molar volume at TB. The r esult is used t o
det er mine t he Racket t par amet er . For 29 diver se compounds, an aver age er r or of
3.9% is r epor t ed. This met hod r equir es only molecular st r uct ur e as input . Table 3.6
in AS PEN PLUS Physical Property Data list s t he funct ional gr oups.
Data Method
The Dat a met hod det er mines t he Racket t par amet er by fit t ing t he exper iment al
liquid molar volume dat a t hat you ent er on t he Pr oper t ies Dat a Pur e Component
for m.
Li qui d Vi scosi ty (MULAND)
PCES pr ovides t he following met hods for est imat ing liquid viscosit y:
Method Information Required
Data Liquid viscosity data
Orrick-Erbar Structure, MW, VL, ZC, TC, PC
Letsou-Stiel MW, TC, PC, OMEGA
The Andr ade model is used for t his pr oper t y.
Orri ck-Erbar Method
Or r ick-Er bar is a gr oup-cont r ibut ion met hod t hat depends on liquid molar volume.
It is limit ed t o low t emper at ur es, r anging fr om above t he fr eezing point t o t he
r educed t emper at ur e of 0.75. This met hod:
Is not r eliable for highly br anched st r uct ur es
Does not apply t o inor ganic liquids or sulfur compounds
Repor t s an aver age er r or of 15% for 188 or ganic liquids
Table 3.9 in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t his met hod.
8-18 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Letsou-Sti el Method
The Let sou-St iel met hod is appr opr iat e for high t emper at ur es and for r educed
t emper at ur es of 0.76 t o 0.92. The aver age er r or is 3% for 14 liquids.
Data Method
The Dat a met hod det er mines t he Andr ade par amet er s by fit t ing exper iment al
liquid viscosit y dat a t hat you ent er on t he Pr oper t ies Dat a Pur e Component for m.
Vapor Vi scosi ty (MUVDIP)
PCES pr ovides t he following met hods for est imat ing vapor viscosit y:
Method Information Required
Data Vapor viscosity data
Reichenberg Structure, MW,TC, PC
The DIPPR vapor viscosit y cor r elat ion is used for t his pr oper t y.
Rei chenberg Method
Reichenber g is a gr oup-cont r ibut ion met hod. For nonpolar compounds, t he
expect ed er r or is bet ween 1 and 3%. For polar compounds, t he er r or s ar e higher ,
but usually less t han 4%. Table 3.11 in AS PEN PLUS Physical Property Data list s
t he funct ional gr oups for t his met hod.
Data Method
The Dat a met hod det er mines t he DIPPR vapor viscosit y cor r elat ion par amet er s by
fit t ing exper iment al vapor viscosit y dat a you ent er on t he Pr oper t ies Dat a Pur e
Component for m.
Li qui d Thermal Conducti vi ty (KLDIP)
PCES pr ovides t he following met hods for est imat ing liquid t her mal conduct ivit y:
Method Information Required
Data Liquid thermal conductivity data
Sato-Riedel MW, TB, TC
The DIPPR liquid t her mal conduct ivit y cor r elat ion is used for t his pr oper t y.
Physical Pr oper t y Met hods and Models 8-19
Ver sion 10
Chapter 8
Sato-Ri edel Method
When you use t he Sat o-Riedel met hod, accur acy var ies widely fr om 1 t o 20% for t he
compounds t est ed. The accur acy is poor for light and br anched hydr ocar bons.
Data Method
The Dat a met hod det er mines t he DIPPR liquid t her mal conduct ivit y cor r elat ion
par amet er s. This met hod fit s exper iment al liquid t her mal conduct ivit y dat a. Ent er
t his dat a on t he Pr oper t ies Dat a Pur e Component for m.
Vapor Thermal Conducti vi ty (KVDIP)
No est imat ion met hod is available for est imat ing vapor t her mal conduct ivit y. You
can use t he Dat a met hod t o fit exper iment al dat a dir ect ly t o t he DIPPR vapor
t her mal conduct ivit y cor r elat ion. Use t he Pr oper t ies Dat a Pur e Component for m t o
ent er exper iment al vapor t her mal conduct ivit y dat a.
Surface Tensi on (SIGDIP)
PCES pr ovides t he following met hods for est imat ing sur face t ension:
Method Information Required
Data Surface tension data
Brock-Bird TB, TC, PC
Macleod-Sugden TB, TC, PC, VL, PARC
Li-Ma Structure, TB
The DIPPR sur face t ension cor r elat ion is used for t his pr oper t y.
Data Method
The Dat a met hod det er mines t he DIPPR sur face t ension cor r elat ion par amet er s by
fit t ing exper iment al sur face t ension dat a. Ent er t his dat a on t he Pr oper t ies Dat a
Pur e Component for m.
Brock-Bi rd Method
The Br ock-Bir d met hod applies t o non-hydr ogen-bonded liquids. The expect ed er r or
is less t han 5%.
Macleod-Sugden Method
The Macleod-Sugden met hod applies t o nonpolar , polar , and hydr ogen-bonded
liquids. For hydr ogen-bonded liquids, er r or s ar e nor mally less t han 5 t o 10%.
8-20 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Li -Ma Method
The Li-Ma met hod is a gr oup cont r ibut ion met hod for est imat ing sur face t ension at
differ ent t emper at ur e. This met hod r equir es only molecular st r uct ur e and TB as
input . Repor t ed aver age er r or for 427 diver se compounds was 1.09% (Fluid Phase
Equilibria, 118, 13, 1996).
Table 3.6A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t his met hod.
Li qui d Heat Capaci ty (CPLDIP)
PCES pr ovides t he following met hods for est imat ing liquid heat capacit y:
Method Information Required
Data Liquid heat capacity data
Ruzicka Structure
The DIPPR liquid heat capacit y cor r elat ion is used for t his pr oper t y.
Data Method
The Dat a met hod det er mines t he DIPPR liquid heat capacit y cor r elat ion
par amet er s by fit t ing exper iment al liquid heat capacit y dat a. Ent er t his dat a on
t he Pr oper t ies Dat a Pur e Component for m.
Ruzi cka Method
The Ruzicka met hod is a gr oup cont r ibut ion met hod for est imat ing par amet er s for
t he DIPPR liquid heat capacit y cor r elat ion. The par amet er s ar e valid fr om t he
melt ing point t o t he normal boiling point . This met hod requires only molecular
st ruct ure as input . For 9772 diverse compounds, report ed average errors were 1.9%
and 2.9% for nonpolar and polar compounds, respect ively (J. Phys. Chem. Ref. Data,
22, 597, 1993; 22, 619, 1993).
Table 3.11A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t his met hod.
Physical Pr oper t y Met hods and Models 8-21
Ver sion 10
Chapter 8
Soli d Heat Capaci ty (CPSPO1)
PCES pr ovides t he following met hods for est imat ing solid heat capacit y:
Method Information Required
Data Solid heat capacity data
Mostafa Structure
The solid heat capacit y cor r elat ion is used for t his pr oper t y.
Data Method
The Dat a met hod det er mines t he solid heat capacit y cor r elat ion par amet er s by
fit t ing exper iment al liquid heat capacit y dat a. You ent er t his dat a on t he
Pr oper t ies Dat a Pur e Component for m.
Mostafa Method
The Most afa met hod is a gr oup cont r ibut ion met hod for est imat ing par amet er s for
t he solid heat capacit y cor r elat ion. This met hod is applied t o solid inor ganic salt s
which ar e divided t o cat ions, anions and ligands. Repor t ed aver age er r or s for 664
diver se solid inor ganic salt s, was 3.18% (Ind. Eng. Chem. RES., 35, 343, 1996).
Table 3.7A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t his met hod.
Soli d Standard Enthalpy of Formati on (DHSFRM)
Only t he Most afa met hod is available for est imat ing solid st andar d ent halpy of
for mat ion.
Mostafa Method
The Most afa met hod is a gr oup cont r ibut ion met hod. This met hod applies t o solid
inor ganic salt s which can be divided t o cat ions, anions and ligands. Repor t ed
aver age er r or s for 938 diver se solid inor ganic salt s was 2.57% (Ind. Eng. Chem.
RES., 34, 4577, 1995).
Tables 3.7A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t his met hod.
8-22 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Soli d Standard Gi bbs Free Energy of Formati on
(DGSFRM)
Only t he Most afa met hod is available for est imat ing solid st andar d Gibbs fr ee
ener gy of for mat ion.
Mostafa Method
The Most afa met hod is a gr oup cont r ibut ion met hod. This met hod applies t o solid
inor ganic salt s which can be divided t o cat ions, anions and ligands. Repor t ed
aver age er r or s for 687 diver se solid inor ganic salt s was 2.06% (Ind. Eng. Chem.
RES., 34, 4577, 1995).
Tables 3.7A in AS PEN PLUS Physical Property Data list s t he funct ional gr oups for
t his met hod.
Standard Enthalpy of Formati on of Aqueous Speci es
(DHAQHG)
PCES pr ovides t he following met hods for est imat ing st andar d ent halpy of
for mat ion of aqueous species for t he Helgeson elect r olyt e model:
Method Information Required
AQU-DATA DHAQFM
THERMO DGAQFM, S025C
AQU-EST1 DGAQFM
AQU-EST2 S025C
AQU-DATA Method
The AQU-DATA met hod uses dir ect ly exper iment al st andar d ent halpy of for mat ion
at infinit e dilut ion (DHAQFM) if it exist s in t he dat abank.
THERMO Method
The THERMO met hod est imat es st andar d ent halpy of for mat ion accor ding t o
t her modynamic r elat ionship if DGAQFM and S025C exist in t he dat abank, as
follows:
( ) DHAQHG DGAQFM + 298.15* S025C S025E
wher e S E 025 is t he sum of absolut e ent r opy of t he const it uent element s of a
compound at 25
o
C.
Physical Pr oper t y Met hods and Models 8-23
Ver sion 10
Chapter 8
AQU-EST1 Method
If DGAQFM is in t he dat abank, t he AQU-EST1 met hod est imat es st andard
ent halpy of format ion using an empirical relat ion developed by Aspen Technology,
as follows:
DHAQHG DGAQFM 1105 128228 . * .
AQU-EST2 Method
If S025C is in t he dat abank, t he AQU-EST2 met hod est imat es st andard ent halpy
of for mat ion using an empir ical r elat ion developed by Aspen Technology, as follows:
( ) DHAQHG S C S E + 1221113214 3137 4034 025 025 . . *
wher e S E 025 is t he sum of absolut e ent r opy of t he const it uent element s of a
compound at 25
o
C.
Standard Gi bbs Free Energy of Formati on of Aqueous
Speci es (DGAQHG)
PCES pr ovides t he following met hods for est imat ing st andar d Gibbs fr ee ener gy
of for mat ion of aqueous species for t he Helgeson elect r olyt e model:
Method Information Required
AQU-DATA DGAQFM
THERMO DHAQFM, S025C
AQU-EST1 DHAQFM
AQU-EST2 S025C
AQU-DATA Method
The AQU-DATA met hod uses dir ect ly exper iment al st andar d Gibbs fr ee ener gy of
for mat ion at infinit e dilut ion (DGAQFM) if it exist s in t he dat abank.
THERMO Method
If DHAQFM and S025C are in t he dat abank, t he THERMO met hod est imat es
st andar d Gibbs fr ee ener gy of for mat ion accor ding t o t her modynamic r elat ionship,
as follows:
( ) DGAQHG DHAQFM S C S E 29815 025 025 . *
wher e S E 025 is t he sum of absolut e ent r opy of t he const it uent element s of a
compound at 25
o
C.
8-24 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
AQU-EST1 Method
If DHAQFM is in t he dat abank, t he AQU-EST1 met hod est imat es st andard Gibbs
free energy of format ion using an empirical relat ion developed by Aspen
Technology, as follows:
( )
DGAQHG
DHAQFM
+128228
1105
.
.
AQU-EST2 Method
If S C 025 is in t he dat abank, t he AQU-EST2 met hod est imat es st andar d Gibbs
fr ee ener gy of for mat ion using an empir ical r elat ion developed by Aspen
Technology, as follows:
( ) DGAQHG S C S E + 122110 2752 2839 2534 025 025 . . *
wher e S E 025 is t he sum of absolut e ent r opy of t he const it uent element s of a
compound at 25
o
C.
Absolute Entropy of Aqueous Speci es (S25HG)
PCES pr ovides t he following met hods for est imat ing absolut e ent r opy of aqueous
species for t he Helgeson elect r olyt e model:
Method Information Required
AQU-DATA S025C
THERMO DGAQFM, DHAQFM
AQU-EST1 DGAQFM
AQU-EST2 DHAQFM
AQU-DATA Method
The AQU-DATA met hod uses direct ly t he experiment al absolut e ent ropy (S025C) if
it exist s in t he dat abank.
THERMO Method
If DGAQFM and DHAQFM are in t he dat abank, t he THERMO met hod est imat es
absolut e ent r opy accor ding t o t her modynamic r elat ionship, as follows:
( )
S HG
DHAQFM DGAQFM
S E
25
29815 025
+ .
wher e S E 025 is t he sum of absolut e ent r opy of t he const it uent element s of a
compound at 25
o
C.
Physical Pr oper t y Met hods and Models 8-25
Ver sion 10
Chapter 8
AQU-EST1 Method
If DGAQFM is in t he dat abank, t he AQU-EST1 met hod est imat es absolut e ent r opy
using an empir ical r elat ion developed by Aspen Technology, as follows:
S HG x DGAQFM S E 25 352205 10 4300788 025
4
+
. * .
wher e S E 025 is t he sum of absolut e ent r opy of t he const it uent element s of a
compound at 25
o
C.
AQU-EST2 Method
If DHAQFM is in t he dat abank, t he AQU-EST2 met hod est imat es absolut e ent ropy
using an empirical relat ion developed by Aspen Technology, as follows:
S HG x DHAQFM S E 25 3187349 10 389208 025
4
+
. .
*
Born Coeffi ci ent (OMEGHG)
Only t he Helgeson met hod is available for est imat ing t he Bor n coefficient of
aqueous species for t he Helgeson elect r olyt e model. This met hod r equir es S25HG
and CHARGE as input .
Helgeson Capaci ty Parameters (CHGPAR)
PCES pr ovides t he following met hods for est imat ing t he Helgeson capacit y
par amet er s of aqueous species for t he Helgeson elect r olyt e model:
Method Information Required
HG-AUQ OMEGHG, CPAQ0
HG-CRIS OMEGHG, S25HG, CHARGE, IONTYP
HG-EST OMEGHG, S25HG
HG-AQU Method
The HG-AQU met hod est imat es t he Helgeson capacit y par amet er s fr om t he
infinit e dilut ion heat capacit y CPAQ0.
HG-CRIS Method
The HG-CRIS met hod est imat es t he Helgeson capacit y par amet er s accor ding t o
t he Cr iss-Cobble met hod.
HG-EST Method
The HG-EST met hod est imat es t he Helgeson capacit y par amet er s using an
empir ical r elat ion developed by Aspen Technology.
8-26 Physical Pr oper t y Met hods and Models
Ver sion 10
Property
Parameter
Estimation
Bi nary Parameters (WILSON, NRTL, UNIQ)
PCES est imat es binar y par amet er s for t he WILSON, NRTL, and UNIQUAC
models, using infinit e-dilut ion act ivit y coefficient s. Infinit e-dilut ion act ivit y
coefficient s can be supplied by:
Labor at or y dat a ent er ed on t he Pr oper t ies Dat a Mixt ur e for m, wit h dat a
t ype=GAMINF
Est imat ion, using t he UNIFAC, UNIF-LL, UNIF-DMD or UNIF-LBY met hod
For best r esult s, use exper iment al infinit e-dilut ion act ivit y coefficient dat a. Of
t he four UNIFAC met hods, t he Dor t mund met hod (UNIF-DMD) gives t he most
accur at e est imat e of infinit e-dilut ion act ivit y coefficient s. This met hod is
r ecommended. See Chapt er 3 for det ailed descr ipt ions of t hese met hods.
If t he dat a is at a single t emper at ur e, PCES est imat es only t he second element of
t he par amet er , such as WILSON/2. If t he dat a cover a t emper at ur e r ange, PCES
est imat es bot h element s of t he par amet er , such as WILSON/1 and WILSON/2.
UNIFAC R and Q Parameters (GMUFR, GMUFQ,
GMUFDR, GMUFDQ, GMUFLR, GMUFLQ)
PCES pr ovides t he Bondi met hod for est imat ing t he R and Q par amet er s for
UNIFAC funct ional gr oups. ASPEN PLUS uses t hese par amet er s in t he UNIFAC,
Dor t mund UNIFAC, and Lyngby UNIFAC models. The Bondi met hod r equir es only
molecular st r uct ur e as input . Table 3.3 in AS PEN PLUS Physical Property Data
list s t he funct ional gr oups for t he Bondi met hod.
y y y y
Physical Pr oper t y Met hods and Models A-1
Ver sion 10
Appendix A
A Bromley-Pitzer Activity
Coefficient Model
The Br omley-Pit zer act ivit y coefficient model is a simplified Pit zer model wit h t he
int er act ion par amet er s est imat ed wit h t he Br omleys met hod. It can be used t o
comput e act ivit y coefficient s for aqueous elect r olyt es up t o 6 molal ionic st r engt h.
This model is less accur at e t han t he Pit zer model. The model should not be used for
mixed-solvent elect r olyt e syst ems
Worki ng Equati ons
The complet e Pit zer equat ion (Frst and Renon, 1982) for t he excess Gibbs energy
is (see also Appendix C, equat ion 4):
( )
G
RT
n f I B m m m m m z C m m m m m
E
W ij i j
j i
ij i j k k
k
ij i j
j i
ijk i j k
k j i j i
+ + +
_
,
1
]
1
1
2
1
6
(1)
Wher e:
G
E
= Excess Gibbs ener gy
R = Gas const ant
T = Temper at ur e
n
w
= Kilogr ams of wat er
z
i
= Char ge number of ion i
m
x
x
M n
n
i
i
w
w i
w
_
,
1000
= molalit y of ion i
A-2 Physical Pr oper t y Met hods and Models
Ver sion 10
Bromley-Pitzer
Activity
Coefficient
Model
Wher e:
x
i
= Mole fr act ion of ion i
x
w
= Mole fr act ion of wat er
M
w
= Molecular weight of wat er (g/mol)
n
i
= Moles of ion i
B, C, and ar e int er act ion par amet er s, and f(I) is an elect r ost at ic t er m as a
funct ion of ionic st r engt h; t hese t er ms ar e discussed in Appendix C. See Appendix
C for a det ailed discussion of t he Pit zer model.
The C t er m and t he t er m ar e dr opped fr om equat ion 1 t o give t he simplified
Pit zer equat ion.
( )
G
RT
n f I B m m m m
E
W ij i j
j i
ij i j
j i
+ +
1
]
1
(2)
Wher e:
B
ij
=
( ) ( ) ( ) ( )
( )
f
ij ij ij ij
0 1 2 3
, , ,
Ther efor e, t he simplified Pit zer equat ion has t wo t ypes of binar y int er act ion
par amet er s, s and s. Ther e ar e no t er nar y int er act ion par amet er s wit h t he
simplified Pit zer equat ion.
Not e t hat t he Pit zer model par amet er dat abank descr ibed in Physical Property
Data, Chapt er 1, is not applicable t o t he simplified Pit zer equat ion.
A built -in empir ical cor r elat ion est imat es t he
( )
0
and
( )
1
par amet er s for cat ion-
anion pair s fr om t he Br omley ionic par amet er s,
ion
and
ion
(Br omley, 1973). The
est imat ed values of
( )
0
s and
( )
1
s ar e over r idden by t he user 's input . For
par amet er naming and r equir ement s, see Br omley-Pit zer Act ivit y Coefficient
Model, Chapt er 3.
Parameter Conversi on
For 2-2 elect r olyt es, t he par amet er
( )
3
cor r esponds t o Pit zer 's
( )
1
;
( )
2
is t he same
in bot h ASPEN PLUS and or iginal Pit zer models. Pit zer r efer s t o t he 2-2
elect r olyt e par amet er s as
( )
1
,
( )
2
,
( )
0
,
( )
0
and
( )
2
r et ain t heir meanings in bot h
models, but Pit zer 's
( )
1
is ASPEN PLUS
( )
3
Be car eful t o make t his dist inct ion
when ent er ing 2-2 elect r olyt e par amet er s.
Physical Pr oper t y Met hods and Models A-3
Ver sion 10
Appendix A
References
L.A. Br omley, "Ther modynamic Pr oper t ies of St r ong Elect r olyt es in Aqueous
Solut ion, " AIChE J ., Vol. 19, No. 2, (1973), pp. 313 320.
Fr st and H. Renon, "Effect of t he Var ious Par amet er s in t he Applicat ion of
Pit zer 's Model t o Solid-Liquid Equilibr ium Pr eliminar y St udy for St r ong 1-1
Elect r olyt es, Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),
pp. 396 400.
y y y y
A-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Bromley-Pitzer
Activity
Coefficient
Model
Physical Pr oper t y Met hods and Models B-1
Ver sion 10
Appendix B
B Electrolyte NRTL Activity
Coefficient Model
The Elect r olyt e Non-Random Two Liquid (NRTL) model is a ver sat ile model for t he
calculat ion of act ivit y coefficient s. Using binar y and pair par amet er s, t he model
can r epr esent aqueous elect r olyt e syst ems as well as mixed solvent elect r olyt e
syst ems over t he ent ir e r ange of elect r olyt e concent r at ions. This model can
calculat e act ivit y coefficent s for ionic species and molecular species in aqueous
elect r olyt e syst ems as well as in mixed solvent elect r olyt e syst ems. The model
r educes t o t he well-known NRTL model when elect r olyt e concent r at ions become
zer o (Renon and Pr ausnit z, 1969).
The elect r olyt e NTRL model uses t he infinit e dilut ion aqueous solut ion as t he
r efer ence st at e for ions. It adopt s t he Bor n equat ion t o account for t he
t r ansfor mat ion of t he r efer ence st at e of ions fr om t he infinit e dilut ion mixed
solvent solut ion t o t he infinit e dilut ion aqueous solut ion.
Wat er must be pr esent in t he elect r olyt e syst em in or der t o comput e t he
t r ansfor mat ion of t he r efer ence st at e of ions. Thus, it is necessar y t o int r oduce a
t r ace amount of wat er t o use t he model for nonaqueous elect r olyt e syst ems.
Theoreti cal Basi s and Worki ng Equati ons
In t his appendix, t he t heor et ical basis of t he model is explained and t he wor king
equat ions ar e given. The differ ent ways par amet er s can be obt ained ar e discussed
wit h r efer ences t o t he dat abank dir ect or ies and t he Dat a Regr ession Syst em
(DRS). The par amet er r equir ement s of t he model ar e given in Elect r olyt e NRTL
Act ivit y Coefficient Model, Chapt er 3.
B-2 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
NRTL Activity
Coefficient
Model
Development of the Model
The Elect rolyt e NRTL model was originally proposed by Chen et al., for aqueous
elect r olyt e syst ems. It was lat er ext ended t o mixed solvent elect r olyt e syst ems
(Mock et al., 1984, 1986). The model is based on t wo fundament al assumpt ions:
The l i ke-i on r epul si on a ssumpt i on: st at es t hat t he local composit ion of
cat ions ar ound cat ions is zer o (and likewise for anions ar ound anions). This is
based on t he assumpt ion t hat t he r epulsive for ces bet ween ions of like char ge
ar e ext r emely lar ge. This assumpt ion may be just ified on t he basis t hat
r epulsive for ces bet ween ions of t he same sign ar e ver y st r ong for neighbor ing
species. For example, in salt cr yst al lat t ices t he immediat e neighbor s of any
cent r al ion ar e always ions of opposit e char ge.
The l oca l el ect r oneut r a l i t y a ssumpt i on: st at es t hat t he dist r ibut ion of
cat ions and anions ar ound a cent r al molecular species is such t hat t he net local
ionic char ge is zer o. Local elect r oneut r alit y has been obser ved for int er st it ial
molecules in salt cr yst als.
Chen pr oposed an excess Gibbs ener gy expr ession which cont ains t wo
cont r ibut ions: one cont r ibut ion for t he long-r ange ion-ion int er act ions t hat exist
beyond t he immediat e neighbor hood of a cent r al ionic species, and t he ot her r elat ed
t o t he local int er act ions t hat exist at t he immediat e neighbor hood of any cent r al
species.
The unsymmet r ic Pit zer -Debije-Hckel model and t he Bor n equat ion ar e used t o
r epr esent t he cont r ibut ion of t he long-r ange ion-ion int er act ions, and t he Non-
Random Two Liquid (NRTL) t heor y is used t o r epr esent t he local int er act ions.
The local int er act ion cont r ibut ion model is developed as a symmet r ic model,
based on r efer ence st at es of pur e solvent and pur e complet ely dissociat ed liquid
elect r olyt e. The model is t hen nor malized by infinit e dilut ion act ivit y coefficient s
in or der t o obt ain an unsymmet r ic model. This NRTL expr ession for t he local
int er act ions, t he Pit zer -Debije-Hckel expr ession, and t he Bor n equat ion ar e
added t o give equat ion 1 for t he excess Gibbs ener gy (see t he following not e).
G
RT
G
RT
G
RT
G
RT
m
E
m
E PDH
m
E Born
m
E lc * * , * , * ,
+ + (1)
This leads t o
ln ln ln ln
* * * *
i i
PDH
i
Born
i
lc
+ + (2)
NOTE: The not at ion using * t o denot e an unsymmet r ic r efer ence st at e is well-
accept ed in elect r olyt e t her modynamics and will be maint ained her e. The r eader
should be war ned not t o confuse it wit h t he meaning of * in classical
t her modynamics accor ding t o IUPAC/ISO, r efer r ing t o a pur e component
pr oper t y. In fact in t he cont ext of G or , t he ast er isk as super scr ipt is never
used t o denot e pur e component pr oper t y, so t he r isk of confusion is minimal. For
det ails on not at ion, see Chapt er 1.
Physical Pr oper t y Met hods and Models B-3
Ver sion 10
Appendix B
Long-Range Interacti on Contri buti on
The Pit zer -Debije-Hckel for mula, nor malized t o mole fr act ions of unit y for solvent
and zer o for elect r olyt es, is used t o r epr esent t he long-r ange int er act ion
cont r ibut ion.
( )
G
RT
x
M
A I
I
m
E PDH
k
k B
x
x
* ,
ln
_
,
_
,
_
,
1000
4
1
1
2
1
2
(3)
Wher e:
x
k
= Mole fr act ion of component k
M
B
= Molecular weight of t he solvent B
A
=
1
3
2
2
1000
1
2
3
2
N d Q
kT
A e
w
_
,
_
,
(4)
N
A
= Avogadr o's number
d = Densit y of solvent
Q
e
= Elect r on char ge
w
= Dielect r ic const ant of wat er
T = Temper at ur e
k = Bolt zmann const ant
I
x
= Ionic st r engt h (mole fr act ion scale):
I
x
=
1
2
2
x z
i i
i
(5)
x
i
= Mole fr act ion of component i
z
i
= Char ge number of ion i
= "Closest appr oach" par amet er
Taking t he appr opr iat e der ivat ive of equat ion 3, an expr ession for t he act ivit y
coefficient can t hen be der ived.
B-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
NRTL Activity
Coefficient
Model
( )
ln ln
*
i
PDH
B
i
x
i x x
x
M
A
z
I
z I I
I
_
,
_
,
+ +
+
1
]
1
1000 2
1
2
1
1
2
1
2
1
2
3
2
1
2
2 2
(6)
The Bor n equat ion is used t o account for t he Gibbs ener gy of t r ansfer of ionic
species fr om t he infinit e dilut ion st at e in a mixed-solvent t o t he infinit e dilut ion
st at e in aqueous phase.
G
RT
Q
kT
x z
r
m
E Born
e
w
i i
i
i
* ,
_
,
_
,
2
2
2
2
1 1
10
(7)
Wher e:
r
i
= Bor n r adius
The expr ession for t he act ivit y coefficient can be der ived fr om (7):
ln
*
i
Born e
w
i
i
Q
kT
z
r
_
,
2 2
2
2
1 1
10 (8)
Local Interacti on Contri buti on
The local int er act ion cont r ibut ion is account ed for by t he Non-Random Two Liquid
t heor y. The basic assumpt ion of t he NRTL model is t hat t he nonideal ent r opy of
mixing is negligible compar ed t o t he heat of mixing: t his is indeed t he case for
elect r olyt e syst ems. This model was adopt ed because of it s algebr aic simplicit y and
it s applicabilit y t o mixt ur es t hat exhibit liquid phase split t ing. The model does not
r equir e specific volume or ar ea dat a.
The effect ive local mole fr act ions X
ji
and X
ii
of species j and i, r espect ively, in
t he neighbor hood of i ar e r elat ed by:
X
X
X
X
G
ji
ii
j
i
ji
_
,
(9)
Wher e:
X
j
= x C
j j
( C z
j j
for ions and C
j
= unit y for molecules)
G
ji
=
( )
e
ji ji
Physical Pr oper t y Met hods and Models B-5
Ver sion 10
Appendix B
ji
=
g g
RT
ji ii
ji
= Nonr andomness fact or
g
ji
and g
ii
ar e ener gies of int er act ion bet ween species j and i, and i and i,
r espect ively. Bot h g
ij
and
ij
ar e inher ent ly symmet r ic ( g g
ji ij
and
ji ij
).
Similar ly,
X
X
X
X
G
ji
ki
j
k
ji ki
_
,
,
(10)
Wher e:
G
ji ki ,
=
( )
e
ji ki ji ki
, ,
ji ki ,
=
g g
RT
ji ki
ji ki ,
= Nonr andomness fact or
Apparent Bi nary Systems
The der ivat ions t hat follow ar e based on a simple syst em of one complet ely
dissociat ed liquid elect r olyt e ca and one solvent B. They will be lat er ext ended t o
mult icomponent syst ems. In t his simple syst em, t hr ee differ ent ar r angement s
exist :
solvent at
center
cation at
center
anion at
center
c
c
a
B
B B
a c
c
a
B
B
a
B
c
a
B
B
B-6 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
NRTL Activity
Coefficient
Model
In t he case of a cent r al solvent molecule wit h ot her solvent molecules, cat ions,
and anions in it s immediat e neighbor hood, t he pr inciple of local elect r oneut r alit y
is followed: t he sur r ounding cat ions and anions ar e such t hat t he neighbor hood of
t he solvent is elect r ically neut r al. In t he case of a cent r al cat ion (anion) wit h
solvent molecules and anions (cat ions) in it s immediat e neighbor hood, t he
pr inciple of like-ion r epulsion is followed: no ions of like char ge exist anywher e
near each ot her , wher eas opposit e char ged ions ar e ver y close t o each ot her .
The effect ive local mole fr act ions ar e r elat ed by t he following expr essions:
X X X
cB aB BB
+ + 1 (cent r al solvent cells) (11)
X X
Bc ac
+ 1 (cent r al cat ion cells) (12)
X X
Ba ca
+ 1 (cent r al anion cells) (13)
Using equat ion 11 t hr ough 13 and t he not at ion int r oduced in equat ions 9 and
10 above, expr essions for t he effect ive local mole fr act ions in t er ms of t he over all
mole fr act ions can be der ived.
X
X G
X G X G X G
iB
i iB
a cB c cB B BB
+ +
i = c, a, or B (14)
X
X
X X G
ac
a
a B Bc ac
+
,
(15)
X
X
X X G
ca
c
c B Ba ca
+
,
(16)
To obt ain an expr ession for t he excess Gibbs ener gy, let t he r esidual Gibbs
ener gies, per mole of cells of cent r al cat ion, anion, or solvent , r espect ively, be
( ) G c cell
m
, ( ) G a cell
m
, and ( ) G B cell
m
. These ar e t hen r elat ed t o t he
effect ive local mole fr act ions:
( ) ( ) G c cell z X g X g
m c Bc Bc ac ac
+ (17)
( ) ( ) G a cell z X g X g
m a Ba Ba ca ca
+ (18)
( ) G B cell X g X g X g
m aB aB cB cB BB BB
+ + (19)
The r efer ence Gibbs ener gy is det er mined for t he r efer ence st at es of complet ely
dissociat ed liquid elect r olyt e and of pur e solvent . The r efer ence Gibbs ener gies
per mole ar e t hen:
( ) G c cell z g
m c ac
(20)
( ) G a cell z g
m a ca
(21)
Physical Pr oper t y Met hods and Models B-7
Ver sion 10
Appendix B
( ) G B cell g
m BB
(22)
Wher e:
z
c
= Char ge number on cat ions
z
a
= Char ge number on anions
The molar excess Gibbs ener gy can be found by summing all changes in r esidual
Gibbs ener gy per mole t hat r esult when t he elect r olyt e and solvent in t heir
r efer ence st at e ar e mixed t o for m t he exist ing elect r olyt e syst em. The expr ession
is:
( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( )
G x G B cell G B cell x G c cell G c cell
x G a cell G a cell
m
E lc
m m m
ref
c m m
ref
a m m
ref
,
+
+
(23)
Using t he pr evious r elat ion for t he excess Gibbs ener gy and t he expr essions for
t he r esidual and r efer ence Gibbs ener gy (equat ions 17 t o 19 and 20 t o 22), t he
following expr ession for t he excess Gibbs ener gy is obt ained:
G
RT
X X X X X X z X X z
m
E lc
B cB cB B aB aB c Bc c Bc ac a Ba a Ba ca
,
, ,
+ + + (24)
The assumpt ion of local elect r oneut r alit y applied t o cells wit h cent r al solvent
molecules may be st at ed as:
X X
aB cB
(25)
Combining t his expr ession wit h t he expr ession for t he effect ive local mole
fr act ions given in equat ions 9 and 10, t he following equalit y is obt ained:
G G
aB cB
(26)
The following r elat ionships ar e fur t her assumed for nonr andomness fact or s:
aB cB ca B
,
(27)
Bc ac Ba ca B ca , , ,
(28)
and,
ca B B ca , ,
(29)
It can be infer r ed fr om equat ions 9, 10, and 26 t o 29 t hat :
aB cB ca B
,
(30)
Bc ac Ba ca B ca , , ,
(31)
B-8 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
NRTL Activity
Coefficient
Model
The binar y par amet er s,
ca B ,
,
ca B ,
and
B ca ,
ar e now t he adjust able par amet er s
for an appar ent binar y syst em of a single elect r olyt e and a single solvent .
The excess Gibbs ener gy expr ession (equat ion 24) must now be nor malized t o t he
infinit e dilut ion r efer ence st at e for ions:
G
RT
G
RT
x x
m
E lc
m
E lc
c c a a
* , ,
ln ln
(32)
This leads t o:
( )
( ) ( )
G
RT
X X X X X X X
X G X G
m
E lc
B cB aB ca B c Bc B ca a Ba B ca
c B ca c ca B a B ca aB ca B
* ,
, , ,
, , , ,
+ + +
+ +
(33)
By t aking t he appr opr iat e der ivat ives of equat ion 33, expr essions for t he act ivit y
coefficient s of all t hr ee species can be det er mined.
( ) ( )
( )
1
2
2 2
z
X G
X G X G X
X X G
X X G
X G
X X G
G
c
c
lc B cB cB
c cB a aB B
a Ba B Ba
c B Ba
B Bc Bc
a B Bc
Bc cB cB
ln
*
+ +
+
+
+
+
(34)
( ) ( )
( )
1
2
2 2
z
X G
X G X G X
X X G
X X G
X G
X X G
G
a
a
lc B aB aB
c cB a aB B
c Bc B Bc
a B Bc
B Ba Ba
c B Ba
Ba aB aB
ln
*
+ +
+
+
+
+
(35)
( ) ( )
( ) ( )
ln
B
lc
cB cB aB aB
c Bc B a
a Bc B
a Ba Ba c
c Ba B
c B cB cB
c cB a aB B
a B aB aB
c cB a aB B
X X
X G X
X G X
X G X
X G X
X X G
X G X G X
X X G
X G X G X
+ +
+
+
+
+ +
+ +
2 2
2 2
(36)
Physical Pr oper t y Met hods and Models B-9
Ver sion 10
Appendix B
Multi component Systems
The Elect r olyt e NRTL model can be ext ended t o handle mult icomponent syst ems.
The excess Gibbs ener gy expr ession is:
G
RT
X
X G
X G
X
X
X
X G
X G
X
X
X
X G
X G
m
E lc
B
B
j jB jB
j
k kB
k
c
c
a
a
a
a
j jc a c jc a c
j
k kc a c
k
a
a
c
c
c
c
j ja c a ja c a
j
k ka c a
k
,
, ,
,
, ,
,
+
_
,
_
,
(37)
Wher e:
j and k can be any species (a, C, or B)
The act ivit y coefficient equat ion for molecular component s is given by:
ln
,
,
,
, ,
,
,
,
B
lc
j jB jB
j
k kB
k
B BB
k kB
k
B
BB
k k kB
k
k k
k
a
a
a
a c
c Bc a c
k kc a c
k
Bc a c
k kc a c kc a c
k
k kc a c
k
c
c
c
a Ba c a
k ka c a
k
X G
X G
X G
X G
X G
X G
X
X
X G
X G
X G
X G
X
X
X G
X G
+
_
,
_
,
B
B
_
,
c a
Bc c a
k ka c a ka c a
k
k ka c a
k
X G
X G
,
, ,
,
(38)
The act ivit y coefficient equat ion for cat ions is given by:
1
z
X
X
X G
X G
X G
X G
X G
X G
X
X
X G
X G
X G
X G
c
c
lc a
a
a
a
k kc a c kc a c
k
k kc a c
k
B cB
k kB
k
B
cB
k k kB
k
k k
k
c
c
c
a ca c a
k ka c a
k
c a
ca c a
k ka c a ka c a
k
k ka c a
k
ln
, ,
,
,
,
,
, ,
,
_
,
_
,
_
,
B
B
_
,
(39)
B-10 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
NRTL Activity
Coefficient
Model
The act ivit y coefficient equat ion for anions is given by:
1
z
X
X
X G
X G
X G
X G
X G
X G
X
X
X G
X G
X G
X G
a
a
lc c
c
c
c
k ka c a ka c a
k
k ka c a
k
Bm aB
k kB
k
B
aB
k k kB
k
k k
k
a
a
a
c ac a c
k kc a c
k
a c
ac a c
k kc a c kc a c
k
k kc a c
k
ln
, ,
,
,
,
,
, ,
,
_
,
_
,
_
,
B
B
_
,
(40)
Wher e:
G
X G
X
cB
a ca B
a
a
a
,
(41)
G
X G
X
aB
c ca B
c
c
c
,
(42)
Bc cB
a B ca
a
a
a
X
X
,
(43)
Ba aB
c B ca
c
c
c
X
X
,
(44)
cB
cB
cB
G
ln
(45)
aB
aB
cB
G
ln
(46)
Ba ca aB ca B B ca , , ,
+ (47)
Bc ac cB ca B B ca , , ,
+ (48)
Physical Pr oper t y Met hods and Models B-11
Ver sion 10
Appendix B
Parameters
The model adjust able par amet er s include:
Pur e component dielect r ic const ant coefficient of nonaqueous solvent s
Bor n r adius of ionic species
NRTL int er act ion par amet er s for molecule-molecule, molecule-elect r olyt e, and
elect r olyt e-elect r olyt e pair s
Not e t hat for t he elect r olyt e-elect r olyt e pair par amet er s, t he t wo elect r olyt es must
shar e eit her one common cat ion or one common anion.
Each t ype of t he elect r olyt e NRTL par amet er consist s of bot h t he nonr andomness
fact or , , and ener gy par amet er s, .
The pur e component dielect r ic const ant coefficient s of nonaqueous solvent s and
Bor n r adius of ionic species ar e r equir ed only for mixed-solvent elect r olyt e
syst ems.
The t emper at ur e dependency r elat ions of t hese par amet er s ar e given in
Elect r olyt e NRTL Act ivit y Coefficient Model, Chapt er 3.
Heat of mixing is calculat ed fr om t emper at ur e der ivat ives of act ivit y coefficient s.
Heat capacit y is calculat ed fr om secondar y t emper at ur e der ivat ive of t he act ivit y
coefficient . As a r esult , t he t emper at ur e dependent par amet er s ar e cr it ical for
modeling ent halpy cor r ect ly. It is r ecommended t hat ent halpy dat a and heat
capacit y dat a be used t o obt ain t hese t emper at ur e dependency par amet er s. See
also Elect r olyt e NRTL Ent halpy and Elect r olyt e NRTL Gibbs Ener gy, Chapt er 3.
Obtai ni ng Parameters
In t he absence of elect r olyt es, t he elect r olyt e NRTL model r educes t o t he NRTL
equat ion which is widely used for non-elect r olyt e syst ems. Ther efor e, molecule-
molecule binar y par amet er s can be obt ained fr om binar y nonelect r olyt e syst ems.
Elect r olyt e-molecule pair par amet er s can be obt ained fr om dat a r egr ession of
appar ent single elect r olyt e syst ems.
Elect r olyt e-elect r olyt e pair par amet er s ar e r equir ed only for mixed elect r olyt es
wit h a common ion. Elect r olyt e-elect r olyt e pair par amet er s can affect t r ace ionic
act ivit y pr ecipit at ion. Elect r olyt e-elect r olyt e pair par amet er s can be obt ained by
r egr essing solubilit y dat a of mult iple component elect r olyt e syst ems.
B-12 Physical Pr oper t y Met hods and Models
Ver sion 10
Electrolyte
NRTL Activity
Coefficient
Model
When t he elect r olyt e-molecule and elect r olyt e-elect r olyt e pair par amet er s ar e
zer o, t he elect r olyt e NRTL model r educes t o t he Debije-Hckel limit ing law.
Simulat ion r esult s wit h elect r olyt e-molecule and elect r olyt e-elect r olyt e pair
par amet er s fixed t o zer o should be adequat e for ver y dilut e weak elect r olyt e
syst ems; however , for concent r at ed syst ems, pair par amet er s ar e r equir ed for
accur at e r epr esent at ion.
See Physical Property Data, Chapt er 1, for t he pair par amet er s available fr om
t he elect r olyt e NRTL model dat abank. The t able cont ains pair par amet er s for
some elect r olyt es in aqueous solut ion at 100C. These values wer e obt ained by
using t he ASPEN PLUS Dat a Regr ession Syst em (DRS) t o r egr ess vapor
pr essur e and mole fr act ion dat a at T=100C wit h SYSOP15S (Handbook of
Chemistry and Physics, 1975). In r unning t he DRS, st andar d deviat ions for t he
t emper at ur e (C), vapor pr essur e (mmHg), and mole fr act ions wer e set at 0.2,
1.0, and 0.001, r espect ively. In addit ion, complet e dissociat ion of t he elect r olyt e
was assumed for all cases.
References
C.-C. Chen, H.I. Br it t , J .F. Bost on, and L.B. Evans, "Local Composit ions Model for
Excess Gibbs Ener gy of Elect r olyt e Syst ems: Par t I: Single Solvent , Single
Complet ely Dissociat ed Elect r olyt e Syst ems:, AIChE J ., Vol. 28, No. 4, (1982),
p. 588-596.
C.-C. Chen, and L.B. Evans, "A Local Composit ion Model for t he Excess Gibbs
Ener gy of Aqueous Elect r olyt e Syst ems," AIChE J ., Vol. 32, No. 3, (1986),
p. 444-459.
Handbook of Chemistry and Physics, 56t h Edit ion, CRC Pr ess, 1975, p. E-1.
B. Mock, L.B. Evans, and C.-C. Chen, "Phase Equilibr ia in Mult iple-Solvent
Elect r olyt e Syst ems: A New Ther modynamic Model," Pr oceedings of t he 1984
Summer Comput er Simulat ion Confer ence, p. 558.
B. Mock, L.B. Evans, and C.-C. Chen, "Ther modynamic Repr esent at ion of Phase
Equilibr ia of Mixed-Solvent Elect r olyt e Syst ems," AIChE J ., Vol. 32, No. 10,
(1986), p. 1655-1664.
Renon, and J .M. Pr ausnit z, "Local Composit ions in Ther modynamic Excess
Funct ions for Liquid Mixt ur es", AIChE J ., Vol. 14, No. 1, (1968), pp. 135-144.
y y y y
Physical Pr oper t y Met hods and Models C-1
Ver sion 10
Appendix C
C Pitzer Activity
Coefficient Model
The Pit zer model was developed as an impr ovement upon an ear lier model
pr oposed by Guggenheim (1935, 1955). The ear lier model wor ked well at low
elect r olyt e concent r at ions, but cont ained discr epancies at higher concent r at ions
(>0.1M). The Pit zer model r esolved t hese discr epancies, wit hout r esor t ing t o
excessive ar r ays of higher -or der t er ms.
The model can be used for aqueous elect r olyt e syst ems, up t o 6 molal ionic
st r engt h. It cannot be used for mixed solvent elect r olyt e syst ems.
This appendix pr ovides t heor et ical backgr ound for t he model. All model
equat ions ar e included. Par amet er r equir ement s ar e discussed in Pit zer Act ivit y
Coefficient Model, Chapt er 3.
Model Development
The Pit zer model analyzes "har d-cor e" effect s in t he Debije-Hckel t heor y. It uses
t he following expansion as a r adial dist r ibut ion funct ion:
( ) ( ) ( ) g r q r q r
ij ij ij
+ 1
1
2
2
(1)
Wher e:
g
ij
= Dist r ibut ion funct ion
r = Radius
q
ij
=
( )
z Q
r
kT
i e
j
_
,
(molalit y of ion i)
Wit h:
x
i
= Mole fr act ion of ion i
x
w
= Mole fr act ion of wat er
M
w
= Molecular weight of wat er (g/mol)
n
i
= Moles of ion i
Physical Pr oper t y Met hods and Models C-3
Ver sion 10
Appendix C
The funct ion f(I) is an elect r ost at ic t er m t hat expr esses t he effect of long-r ange
elect r ost at ic for ces bet ween ions. This t akes int o account t he har d-cor e effect s of
t he Debije-Hckel t heor y. This t er m is discussed in det ail in t he following sect ion.
The par amet er s
ij
ar e second vir ial coefficient s t hat account for t he shor t -r ange
for ces bet ween solut es i and j. The par amet er s
ijk
account for t he int er act ions
bet ween solut es, i, j, k. For ion-ion int er act ions,
ij
is a funct ion of ionic st r engt h.
For molecule-ion or molecule-molecule int er act ions t his ionic st r engt h dependency
is neglect ed. The dependence of
ijk
on ionic st r engt h is always neglect ed. The
mat r ices
ij
and
ijk
ar e also t aken t o be symmet r ic (t hat is,
ij ji
).
Pit zer modified t his expr ession for t he Gibbs ener gy by ident ifying combinat ions
of funct ions. He developed int er act ion par amet er s t hat can be evaluat ed using
exper iment al dat a. He select ed mat hemat ical expr essions for t hese par amet er s
t hat best fit exper iment al dat a.
Pit zer 's model can be applied t o aqueous syst ems of st r ong elect r olyt es and t o
aqueous syst ems of weak elect r olyt es wit h molecular solut es. These applicat ions
ar e discussed in t he following sect ion.
Appli cati on of the Pi tzer Model to
Aqueous Strong Electrolyte Systems
Pit zer modified his basic equat ion t o make it mor e useful for dat a cor r elat ion of
aqueous st r ong elect r olyt es. He defined a set of mor e dir ect ly obser vable
par amet er s t o r epr esent combinat ions of t he second and t hir d vir ial coefficient s.
The modified Pit zer equat ion is:
( )
G
RT
n
f I m m B m z C
m m
m
m m
m
e
w
c a ca c c
c
ca
a c
c c cc
a cc a
a
a a aa
c caa
c
a a c c
+ +
_
,
_
,
+ +
_
,
+ +
_
,
1
]
1
1
1
1
1
1
2
2 2
(3)
z
i
= Char ge of ion i
C-4 Physical Pr oper t ies Met hods and Models
Ver sion 10
Pitzer
Activity
Coefficient
Model
Subscr ipt s c, c , and a, a denot e cat ions and anions of t he solut ion. B, C, , and
ar e int er act ion par amet er s. f(I) is an elect r ost at ic t er m as a funct ion of ionic
st r engt h. The cat ion-anion par amet er s B and C are charact erist ic for an aqueous
single-elect r olyt e syst em. These par amet er s can be det er mined by t he pr oper t ies of
pur e (appar ent ) elect r olyt es. B is expr essed as a funct ion of
( )
0
and
( )
1
or
( )
0
,
( )
2
and
( )
3
(see equat ions 11 t hrough 15).
The par amet er s and ar e for t he differ ence of int er act ion of unlike ions of
t he same sign fr om t he mean of like ions. These par amet er s can be measur ed
fr om common-ion mixt ur es. Examples ar e NaCl KCl H + +
2
0 or
NaCl NaNO H + +
3 2
0 (sic, Pit zer , 1989). These t er ms ar e discussed in det ail lat er
in subsequent sect ions of t his chapt er .
Fr st and Renon (1982) pr opose t he following expr ession as t he Pit zer equat ion
for t he excess Gibbs ener gy:
( )
G
RT
n
f I B m m m m m z C m m
m m m
E
w
ij i j
j i
ij i j k k
k j i j i
ij i j
ijk i j k
k j i
+ + +
_
,
1
]
1
1
1
1
1
2
1
6
(4)
The differ ence bet ween equat ions 3 and 4 is t hat Pit zer or der s cat ion befor e
anions. Fr st and Renon do not . All summat ions ar e t aken over all ions i and j
(bot h cat ions and anions). This involves making t he par amet er mat r ices B
ij
, C
ij
,
ij
, and
ijk
symmet r ic, as follows:
Second-or der par amet er s ar e wr it t en B
ij
if i and j ar e ions of differ ent sign.
B
ij
0 if t he sign of z
i
= sign of z
j
, and B
ii
0 . Since cat ions ar e not or der ed
befor e anions, B B
ij ji
. This eliminat es t he 2 in t he second t er m in br acket s in
Pit zer 's or iginal expr ession (equat ion 3). Second-or der par amet er s ar e wr it t en
ij
if i and j ar e ions of t he same sign. Thus
ij
0 if t he sign of z
i
is differ ent fr om
t he sign of z
j
, and
ii
0 wit h
ij ji
.
Thir d-or der par amet er s ar e wr it t en C
ij
if i and j ar e ions wit h differ ent signs.
C
ij
0 if t he sign of z
i
= sign of z
i
, and C
ii
0 wit h C C
ij ji
. The fact or of 2 in
t he fift h br acket ed t er m in Pit zer 's or iginal expr ession (equat ion 3) becomes 1/2
in equat ion 4. The mat r ix C is symmet r ic and m z
k k
is ext ended t o all ions t o
make t he equat ion symmet r ic.
Physical Pr oper t y Met hods and Models C-5
Ver sion 10
Appendix C
ijk
is wr it t en for t hr ee differ ent ions
ijk kij jki
, and
ikk
0 .
ijk
0 if
t he sign of z
i
=sign of z
i
=sign of z
k
. The fact or of 1/6 is differ ent fr om 1/2 in t he
last t er m in br acket s in Pit zer s or iginal expr ession. Pit zer dist inguishes bet ween
cat ions and anions. In Pit zer s or iginal model t his par amet er appear s t wice, as
cc a
and
c ca
. In t his modified model, it appear s six t imes, as
cc a
,
c ca
,
acc
,
ac c
,
cac
and
c ac
. Fr st and Renon's expr ession, equat ion 4, calculat es t he
expr essions for act ivit y coefficient s and osmot ic coefficient s.
Calculati on of Acti vi ty Coeffi ci ents
The nat ur al logar it hm of t he act ivit y coefficient for ions is calculat ed fr om equat ion
4 t o give:
ln
,
*
m i
E
i
i j ij i ij j k
k i j
ij j i jk j k
k j j
k k
k
ij j ijk j k
k j j
G
RT
n
z f m B z m m
m z C m m
m z C m m m
_
,
+ +
+ +
+
_
,
+
1
2
2
1
2
2
1
2
1
2
2
2
(5)
Wher e is neglect ed.
For wat er t he logar it hm of t he act ivit y coefficient is calculat ed similar ly, as
follows:
Applying:
ln
,
m w
E
w
G
RT
n
_
,
1000
Wher e N
w
moles wat er , gives:
C-6 Physical Pr oper t ies Met hods and Models
Ver sion 10
Pitzer
Activity
Coefficient
Model
1000
1
3
M
f If m m B B I m m
m z m m C m m m
w
m w i j ij
j i
ij
j i
i j ij
j i
k k k i j ij
j i
i j k ijk
k j i
ln
,
(6)
f(I), t he elect r ost at ic t er m, is expr essed as a funct ion of ionic st r engt h I :
( )
( )
[ ]
f I A
I
b
bI
_
,
4
1
1
2
ln (7)
I, t he ionic st r engt h, is defined as:
I m z
i i
i
1
2
2
(8)
Taking t he der ivat ive of equat ion 7 wit h r espect t o I, gives:
( )
( )
+
+ +
1
]
1
f I
df
dI
A
I
bI b
bI 2
1
2
1
1
2
1
2
1
2
ln (9)
So t hat :
f If
A I
bI
+
2
1
3
2
1
2
(10)
This equat ion is used in equat ion 6. In equat ions 7 and 9, is t he usual Debije-
Hckel const ant for t he osmot ic coefficient , det er mined fr om:
A
N d Q
kT
A w e
B
_
,
_
,
1
3
2
2
1000
1
2
3
2
(11)
Wher e:
N
A
= Avogadr o's const ant
d
w
= Wat er densit y
B
= Dielect r ic const ant of solvent B
b is an adjust able par amet er , which has been opt imized in t his model t o equal 1.2.
B and B need expr essions so t hat equat ions 5 and 6 can complet ely be solved for
t he act ivit y coefficient s. The par amet er B is det er mined differ ent ly for differ ent
elect r olyt e pair ings. For 1-n elect r olyt es (1-1, 1-2, 2-1, and so on) t he following
expr ession gives t he par amet er B:
Physical Pr oper t y Met hods and Models C-7
Ver sion 10
Appendix C
( )
( )
( )
B
I
I e
ij
ij
I
+ +
1
]
1
1
_
,
0
1
1
2 1
2
1 1
1
2
1
1
2
(12)
wit h
1
=2.0.
For 2-2 elect r olyt es, B is det er mined by t he following expr ession:
( )
( )
( )
( )
( )
B
I
I e
I
I e
ij
ij
I
ij
I
+ +
1
]
1
1
+ +
1
]
1
1
_
,
_
,
0
2
2
2 2
3
3
2 3
2
1 1
2
1 1
1
2
2
1
2
1
2
3
1
2
(13)
wit h
2
12 0 . and
3
14 . .
By t aking appr opr iat e der ivat ives, expr essions for B can be der ived for 1 n
elect r olyt es:
( )
( )
+ + +
1
]
1
1
_
,
B
I
I I e
I
2
4
1 1 2 2
1
2
2
1
2
1
2
(14)
and for 2-2 elect r olyt es:
( )
( )
( )
( )
( )
+ + +
1
]
1
1
+ + + +
_
,
1
]
1
1
_
,
_
,
B
I
I I e
I
I
I
e
I
I
2
144
1 1 12 72
2
14
1 1 14
14
2
2
2
2
12
3
2
2
2
1 4
1
2
1
2
1
2
.
.
.
.
(15)
The par amet er s
( )
0
,
( )
1
,
( )
2
,
( )
3
and also C, , and can be found in Pit zer 's
ar t icles (see Refer ences on page C-11).
Aft er t he act ivit y coefficient s ar e calculat ed, t hey can be conver t ed t o t he mole
fr act ion scale fr om t he molalit y scale by t he following r elat ions:
For ions:
x i m i
i
i
w
m
x
M
, ,
_
,
_
,
1000
(16)
For wat er :
x w
m i
i w
i
w
m M
x
,
,
exp
_
,
1000
(17)
C-8 Physical Pr oper t ies Met hods and Models
Ver sion 10
Pitzer
Activity
Coefficient
Model
Wher e:
m
= Act ivit y coefficient (molalit y scale)
x
= Act ivit y coefficient (mole fr act ion scale)
Appli cati on of the Pi tzer Model to
Aqueous Electrolyte Systems wi th
Molecular Solutes
In aqueous weak elect r olyt e syst ems wit h molecular solut es, t he second and t hir d
vir ial coefficient s in t he basic Pit zer equat ion for molecule-ion and molecule-
molecule int er act ions must be consider ed. The following ext ensions of Pit zer s
int er act ion par amet er s ar e made.
The second-or der par amet er s B
ij
ar e ext ended t o include molecule-molecule and
molecule-ion int er act ion par amet er s.
The t hir d-or der par amet er s
ijk
ar e ext ended t o molecule-molecule-molecule
int er act ions. The following expr essions r elat e
ijk
t o Pit zer s or iginal
ijk
:
iii iii
6
However , molecule-molecule int er act ions wer e not t aken int o account by Pit zer
and cowor ker s. So
iii
is an ar t ificially int r oduced quant it y.
The equat ions for act ivit y coefficient s and t he Gibbs fr ee ener gy ar e t he same as
equat ions 3 t hr ough 6.
Physical Pr oper t y Met hods and Models C-9
Ver sion 10
Appendix C
Parameters
The Pit zer model in ASPEN PLUS involves user -supplied par amet er s. These
par amet er s ar e used in t he calculat ion of binar y and t er nar y par amet er s for t he
elect r olyt e syst em. These par amet er s include t he cat ion-anion par amet er s
( )
0
,
( )
1
,
( )
2
,
( )
3
and C
aa
, cat ion1-cat ion2-common anion par amet er
cc a
, anion1-anion2-common
cat ion par amet er
caa
, and t he molecule-ion and molecule-molecule par amet er s
( )
0
,
( )
1
and, C
3
cor r esponds t o Pit zer s
( )
1
.
( )
2
is t he
same in bot h t he ASPEN PLUS and or iginal Pit zer models. Pit zer r efer s t o t he 2-2
elect r olyt e par amet er s as
( )
1
,
( )
2
,
( )
0
.
( )
0
and
( )
2
r et ain t heir meanings in
bot h models, but Pit zer s
( )
1
is
( )
3
in ASPEN PLUS. Be car eful t o make t his
dist inct ion when ent er ing 2-2 elect r olyt e par amet er s.
Pit zer oft en gives values of
( )
0
,
( )
1
,
( )
2
,
( )
3
, and C
1
]
1
2 3
3
2
2 2
(18)
Wher e:
C
ca
G
E
= 1 2C
ca
n
a
= Mole number of anions
n
c
= Mole number of cat ion
Her e
( )
0
,
( )
1
,
( )
2
, and
( )
3
ar e mult iplied by a fact or of 2n n
c a
. C is mult iplied
by a fact or of ( ) 2
3
2
n n
c a
.
ASPEN PLUS account s for t hese cor r ect ing fact or s. Ent er t he par amet er s
wit hout t heir cor r ect ing fact or s.
For example, Pit zer gives t he values of par amet er s for M Cl
g 2
as:
C-10 Physical Pr oper t ies Met hods and Models
Ver sion 10
Pitzer
Activity
Coefficient
Model
( )
4 3
0
= 0.4698
( )
4 3
1
= 2.242
2
3
5 2
C
= 0.00979
Per for m t he necessar y conver sions and ent er t he par amet er s as:
( )
Mg Cl
2
0
+
,
= 0.3524
( )
Mg Cl
2
0
+
,
= 1.6815
C
Mg Cl
2+
,
= 0.00520
Parameter Sources
Binar y and t er nar y par amet er s for t he Pit zer model for var ious elect r olyt e
syst ems ar e available fr om Pit zer s ser ies on t he t her modynamics of elect r olyt es.
These paper s and t he elect r olyt e par amet er s t hey give ar e:
Reference Parameters available
(Pitzer, 1973)
Binary parameters
( ) ( )
( )
0 1
, , C for 13 dilute aqueous electrolytes
(Pitzer and Mayorga, 1973) Binary parameters for 1-1 inorganic electrolytes, salts of carboxylic acids (1-1),
tetraalkylammonium halids, sulfonic acids and salts, additional 1-1 organic
salts, 2-1 inorganic compounds, 2-1 organic electrolytes, 3-1 electrolytes, 4-1
and 5-1 electrolytes
(Pitzer and Mayorga, 1974) Binary parameters for 2-2 electrolytes in water at 25C
(Pitzer and Kim, 1974) Binary and ternary parameters for mixed electrolytes, binary mixtures without a
common ion, mixed electrolytes with three or more solutes
(Pitzer, 1975) Ternary parameters for systems mixing doubly and singly charged ions
(Pitzer and Silvester, 1976) Parameters for phosphoric acid and its buffer solutions
(Pitzer, Roy and Silvester, 1977) Parameters and thermodynamic properties for sulfuric acid
(Pitzer and Silvester, 1977) Data for NaCl and aqueous NaCl solutions
(Pitzer, Silvester, and Peterson, 1978) Rare earth chlorides, nitrates, and perchlorates
(Peiper and Pitzer, 1982) Aqueous carbonate solutions, including mixtures of sodium carbonate,
bicarbonate, and chloride
(Phutela and Pitzer, 1983) Aqueous calcium chloride
(Pitzer, Conceicao, and deLima, 1983) Saturated aqueous solutions, including mixtures of sodium chloride, potassium
chloride, and cesium chloride
Physical Pr oper t y Met hods and Models C-11
Ver sion 10
Appendix C
References
C.-C. Chen, H.I. Br it t , J .I. Bost on and L.B. Evans, "Ext ension and Applicat ion of
t he Pit zer Equat ion for Vapor -Liquid Equilibr ium of Aqueous Elect r olyt e Syst ems
wit h Molecular Solut es," AIChE.J ., Vol. 25, (1979), pp. 820-831.
M. Conceicao, P. de Lima, and K.S. Pit zer , "Ther modynamics of Sat ur at ed
Aqueous Solut ions Including Mixt ur es of NaCl, KCl, and CsCl, "J . S olution
Chem, Vol. 12, No. 3, (1983), pp. 171-185.
W. Fr st and H. Renon, "Effect s of t he Var ious Par amet er s in t he Applicat ion of
Pit zer 's Model t o Solid-Liquid Equilibr ium. Pr eliminar y St udy for St r ong 1-1
Elect r olyt es," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982), pp. 396-
400.
E.A. Guggenheim, Phil. Mag., Vol. 7, No. 19, (1935), p. 588.
E.A. Guggenheim and J .C. Tur geon, Trans. Faraday S oc., Vol. 51, (1955), p. 747.
J .C. Peiper and K.S. Pit zer , "Ther modynamics of Aqueous Car bonat e Solut ions
Including Mixt ur es of Sodium Car bonat e, Bicar bonat e, and Chlor ide," J . Chem.
Thermodynamics, Vol. 14, (1982), pp. 613-638.
R.C. Phut ela and K.S. Pit zer , "Ther modynamics of Aqueous Calcium Chlor ide,"
J . S olution Chem., Vol. 12, No. 3, (1983), pp. 201-207.
K.S. Pit zer , "Ther modynamics of Elect r olyt es. I. Theor et ical Basis and Gener al
Equat ions, " J . Phys. Chem., Vol. 77, No. 2, (1973), pp. 268-277.
K.S. Pit zer , J . S olution Chem., Vol. 4, (1975), p. 249.
K.S. Pit zer , "Theor y: Ion Int er act ion Appr oach," Activity Coefficients in
Electrolyte S olutions, Pyt kowicz, R. ed., Vol. I, (CRC Pr ess Inc., Boca Rat on,
Flor ida, 1979).
K.S. Pit zer , "Fluids, Bot h Ionic and Non-Ionic, over Wide Ranges of Temper at ur e
and Composit ion," J . Chen. Thermodynamics, Vol. 21, (1989), pp. 1-17. (Sevent h
Rossini lect ur e of t he commission on Ther modynamics of t he IUPAC, Aug. 29,
1988, Pr ague, ex-Czechoslovakia).
K.S. Pit zer and J .J . Kim, "Ther modynamics of Elect r olyt es IV; Act ivit y and
Osmot ic Coefficient s for Mixed Elect r olyt es," J .Am. Chem. S oc., Vol. 96 (1974),
p. 5701.
K.S. Pit zer and G. Mayor ga, "Ther modynamics of Elect r olyt es II; Act ivit y and
Osmot ic Coefficient s for St r ong Elect r olyt es wit h One or Bot h Ions Univalent ,"
J . Phys. Chem., Vol. 77, No. 19, (1973), pp. 2300-2308.
K.S. Pit zer and L.F. Silvest er , "Ther modynamics of Elect r olyt es VI. Weak
Elect r olyt es Including H PO
3 4
," J . S olution Chem., Vol. 5, (1976), p. 269.
C-12 Physical Pr oper t ies Met hods and Models
Ver sion 10
Pitzer
Activity
Coefficient
Model
K.S. Pit zer and G. Mayor ga, J . Phys Chem., Vol. 77, (1973), p. 2300.
K.S. Pit zer and G. Mayor ga, J . S olution Chem., Vol. 3, (1974), p. 539.
K.S. Pit zer and L.F. Silvest er , J . S olution Chem., Vol. 5, (1976), p. 269.
K.S. Pit zer and R.N. Roy, and L.F. Silvest er , "Ther modynamics of Elect r olyt es 7
Sulfur ic Acid," J . Am. Chem. S oc., Vol. 99, No. 15, (1977), pp. 4930-4936.
K.S. Pit zer , J .R. Pet er son, and L.F. Silvest er , "Ther modynamics of Elect r olyt es.
IX. Rar e Ear t h Chlor ides, Nit r at es, and Per chlor at es, "J . S olution Chem., Vol. 7,
No. 1, (1978), pp. 45-56.
H. Renon, "Deviat ion fr om Idealit y in Elect r olyt e Solut ions," Foundation of
Computer-Aided Chemical Process Design, Vol. II, Engineering Foundations,
(1981), New Yor k.
L.F. Silvest er and K.S. Pit zer , "Ther modynamics of Elect r olyt es 8 High-
Temper at ur e Pr oper t ies, Including Ent halpy and Heat Capacit y, Wit h
Applicat ion t o Sodium Chlor ide, "J . Phys. Chem., Vol. 81, No. 19, (1977),
pp. 1822-1828.
y y y y
Physical Pr oper t y Met hods and Models Index-1
Release 10
Index
A
Acent r ic fact or est imat ion met hods 8-9
Act ivit y coefficient met hod
for calculat ing phase equilibr ium 1-3
list 1-10
Act ivit y coefficient models
char act er ist ics of 1-32
common models for 2-53
list of pr oper t y met hods 2-43
list of pr oper t y models 3-53
AMINES pr oper t y met hod 2-55
Andr ade/DIPPR viscosit y model 3-122
Ant oine/Wagner vapor pr essur e model 3-80
API model
liquid viscosit y 3-124
liquid volume 3-87
sur face t ension 3-154
API-METH pr oper t y met hod 7-3
APISOUR pr oper t y met hod 2-57
API-TWU pseudocomponent pr oper t y met hod 7-3
Appar ent component
appr oach 5-3
mole fr act ions 5-6
Applicat ions
chemical 1-17
liquid-liquid equilibr ium 1-21
met allur gical 1-17, 3-58
pet r ochemical 1-17
Aqueous infinit e dilut ion heat capacit y model 3-98
ASPEN pseudocomponent pr oper t y met hod 7-3
B
BARIN equat ions t her modynamic pr oper t y model 3-
106
Binar y par amet er s est imat ion met hods 8-26
BK10 pr oper t y met hod 2-11
B-PITZER pr oper t y met hod 2-64
Br elvi-OConnell model 3-88
Br omley-Pit zer act ivit y coefficient model 3-54, 0-1
BWR-Lee-St ar ling pr oper t y model 3-8
BWR-LS pr oper t y met hod 2-21
C
Cavet t t her modynamic pr oper t y model 3-105
CHAO-SEA pr oper t y met hod 2-11, 2-12
Chao-Seader fugacit y model 3-81
Chapman-Enskog
Br okaw/DIPPR viscosit y model 3-124
Br okaw-Wilke mixing r ule viscosit y model 3-126
Wilke-Lee (binar y) diffusion model 3-148
Wilke-Lee (mixt ur e) diffusion model 3-149
Chemical r eact ions for elect r olyt es 5-2
Chemist r y 5-2
Chien-Null act ivit y coefficient model 3-55
Chung-Lee-St ar ling model
low pr essur e vapor viscosit y 3-127
t her mal conduct ivit y 3-138
viscosit y 3-129
Clar ke elect r olyt e liquid volume model 3-89
Classes of pr oper t y met hods 2-2
Clausius-Clapeyr on equat ion for heat of vapor izat ion
3-86
Coal pr oper t y models 3-160
COAL-LIQ pr oper t y met hod 7-3
Const ant act ivit y coefficient model 3-58
COSTALD liquid volume model 3-91
Cr iss-Cobble aqueous infinit e dilut ion ionic heat
capacit y model 3-98
Cr it ical compr essibilit y fact or est imat ion met hods 8-
9
Cr it ical pr essur e est imat ion met hods 8-7
Cr it ical t emper at ur e est imat ion met hods 8-5
Cr it ical volume est imat ion met hods 8-8
Cubic equat ions of st at e 1-22
D
Dat a r egr ession
and elect r olyt es 5-9
Dawson-Khour y-Kobayashi diffusion model
binar y 3-150
mixt ur e 3-151
DCOALIGT coal densit y model 3-171
Dean-St iel pr essur e cor r ect ion viscosit y model 3-131
Debije-Huckel volume model 3-92
DGHARIGT char densit y model 3-173
Diffusion coefficient pr oper t y met hods 1-36, 4-35
Diffusivit y models list 3-148
Index-2 Physical Pr oper t y Met hods and Models
Ver sion 10
DIPPR model
heat of vapor izat ion 3-85
ideal gas heat capacit y 3-100
liquid heat capacit y 3-99
liquid sur face t ension 3-156
liquid t her mal conduct ivit y 3-142
liquid volume 3-93
sur face t ension 3-155
vapor t her mal conduct ivit y 3-144
vapor viscosit y 3-125
viscosit y 3-123
DNSTYGEN nonconvent ional component densit y
model 3-158
E
ELECNRTL pr oper t y met hod 2-58
Elect r olyt e act ivit y coefficient models 1-33
Elect r olyt e dat a r egr ession over view 5-9
Elect r olyt e models
Clar ke liquid volume 3-89
elect r olyt e NRTL 3-109
Gibbs ener gy 3-110
J ones-Dole viscosit y 3-133
Ner nst -Har t ley diffusion 3-151
Onsager -Samar as sur face t ension 3-156
Riedel t her mal conduct ivit y 3-141
Elect r olyt e NRTL
act ivit y coefficient model 3-58, 0-1
ent halpy t her modynamic pr oper t y model 3-109
equat ion 5-8
Gibbs ener gy t her modynamic pr oper t y model 3-
110
Elect r olyt e pr oper t y met hods 2-54, 2-66
ELECNRTL 2-58
ENRTL-HF 2-60
Elect r olyt e simulat ion
over view 5-1
Elect r olyt e t her modynamic models over view 5-7
ENRTL-HF pr oper t y met hod 2-60, 2-61, 2-66
Ent halpies model based on differ ent r efer ence st at es
3-112
Ent halpy and densit y models for coal and char 3-160
Ent halpy balances
nonconvent ional component s 1-37
Ent halpy of for mat ion est imat ion met hods
solid 8-21
st andar d ideal gas 8-10
ENTHGEN nonconvent ional component heat
capacit y model 3-159
Equat ion-of-st at e
common models for pr oper t y met hods 2-25
met hod for phase equilibr ium 1-2, 1-3
pr oper t y met hods
for high-pressure hydrocarbon applications 2-20
pr oper t y models 1-22, 3-7
F
Flexible and pr edict ive pr oper t y met hods
equat ion-of-st at e 2-26
Fr ee-wat er calculat ions 6-1
Fugacit y models list 3-80
G
Gener al models for nonconvent ional component s
coal model for ent halpy 3-163
densit y polynomial model 3-158
ent halpy and densit y models list 3-158
heat capacit y polynomial model 3-159
Gibbs ener gy of for mat ion est imat ion met hods
aqueous species 8-22
solid 8-22
st andar d ideal gas 8-11
GRAYSON pr oper t y met hod 2-11, 2-14
Gr ayson-St r eed fugacit y model 3-82
Gr oup cont r ibut ion act ivit y coefficient models 1-33
Dor t mund-modified UNIFAC 2-45, 3-71
Lyngby-modified UNIFAC 2-45, 3-72
UNIFAC 2-45, 3-69
H
Hakim-St einber g-St iel/DIPPR sur face t ension 3-155
Hayden-OConnell
pr oper t y met hods 2-41
pr oper t y model 3-9
HCOALGEN gener al coal model for ent halpy 3-163
Heat capacit y models list 3-98
Heat of vapor izat ion
est imat ion met hod at TB 8-12
est imat ion met hods 8-15
model 3-85
Helgeson t her modynamic pr oper t y model 3-117
Henr ys const ant solubilit y cor r elat ion model 3-103
Henr ys Law
noncondensable component s 2-8
HF equat ion of st at e
ENRTL-HF pr oper t y met hod 2-60, 2-61, 2-66
pr oper t y met hods using 2-42
pr oper t y model 3-13
Hur on-Vidal mixing r ules 3-46
I
IAPS models for wat er
Physical Pr oper t y Met hods and Models Index-3
Release 10
sur face t ension 3-155
t her mal conduct ivit y 3-140
viscosit y 3-132
Ideal gas heat capacit y est imat ion met hods 8-13
Ideal gas law 1-22
pr oper t y met hods using 2-39
pr oper t y model 3-17
Ideal gas/DIPPR heat capacit y model 3-100
Ideal liquid act ivit y coefficient model 3-62
IDEAL pr oper t y met hod 2-7
IGT densit y model for
char 3-173
coal 3-171
Int er mediat e pr oper t ies 4-3
J
J ones-Dole elect r olyt e cor r ect ion viscosit y model 3-
133
K
Kent -Eisenber g fugacit y model 3-82
L
Lee-Kesler Plcker pr oper t y model 3-19
Lee-Kesler pr oper t y model 3-18
Let sou-St iel viscosit y model 3-135
Li mixing r ule t her mal conduct ivit y model 3-140
Liquid act ivit y coefficient pr oper t y met hods
list 2-37
Liquid ent halpy
met hods 4-18, 4-19, 4-20
t her modynamic pr oper t y model 3-111
Liquid ent r ophy met hods 4-27, 4-28
Liquid fugacit y coefficient met hods 4-12, 4-13, 4-14,
4-15
Liquid Gibbs ener gy met hods 4-23, 4-24
Liquid heat capacit y est imat ion met hods 8-20
Liquid molar volume
est imat ion met hods 8-16
est imat ion met hods (at TB) 8-12
Liquid t her mal conduct ivit y est imat ion met hods 8-
18
Liquid viscosit y est imat ion met hods 8-17
Liquid-liquid equilibr ia
act ivit y coefficient met hod 1-13
equat ion-of-st at e met hod 1-6
Liquid-liquid-vapor equilibr ia
act ivit y coefficient met hod 1-13
LK pr oper t y met hod 7-3
LK-PLOCK pr oper t y met hod 2-22
Lucas vapor viscosit y model 3-135
M
Major pr oper t ies 4-3
Mat hias alpha funct ion 3-41
Mat hias-Copeman alpha funct ion 3-37, 3-38, 3-43
Met allur gical applicat ions
phase equilibr ia 1-17, 2-67
MHV2 mixing r ules 3-48
Models
(physical pr oper t ies)
definition 4-39
Models (physical pr oper t ies)
r eplacing 4-53
Modified Racket t model for molar volume 3-96
Molar volume and densit y models list 3-86
Molar volume met hods 4-29, 4-30
Molecular weight est imat ion met hod 8-3
N
Ner nst -Har t ley elect r olyt e diffusion model 3-151
Nonconvent ional component s
ent halpy calculat ions 1-37
Nonconvent ional solid pr oper t y models 4-44
densit y 3-158
ent halpy 3-158
list of 3-158
Nor mal boiling point est imat ion met hods 8-4
Not hnagel
pr oper t y met hods 2-40
pr oper t y model 3-22
NRTL
pr oper t y model 3-58
NRTL act ivit y coefficient model 2-43
O
Onsager -Samar as elect r olyt e sur face t ension model
3-156
P
Par achor est imat ion met hod 8-13
PCES
est imat ion met hods 8-1
PENG-ROB pr oper t y met hod 2-15
Peng-Robinson
alpha funct ions 3-36
Bost on-Mat hias pr oper t y model 3-25
MHV2 pr oper t y model 3-26
pr oper t y met hod 2-15
pr oper t y model 3-34
Wong-Sandler pr oper t y model 3-26
Pet r oleum component s char act er izat ion met hods 7-1
Index-4 Physical Pr oper t y Met hods and Models
Ver sion 10
Pet r oleum mixt ur es
common models for 2-18
pr oper t y met hods for 2-10, 2-18
Pet r oleum-t uned equat ion-of-st at e pr oper t y met hods
2-15
Phase equilibr ia and solids
act ivit y coefficient met hod 1-16
Phase equilibr ium calculat ion 1-2
Physical pr oper t ies
calculat ion met hods 4-9
major and subor dinat e pr oper t ies 4-3
models 3-3, 3-7, 4-39
over view 4-3
r out es 4-36
Pit zer act ivit y coefficient model 3-63, 5-7, 0-1
PITZER pr oper t y met hod 2-62
Polynomial act ivit y coefficient model 3-65
PR-BM pr oper t y met hod 2-23
Pr edict ive pr oper t y met hods
common models for 2-36
equat ion-of-st at e 2-26
Pr edict ive Soave-Redlich-Kwong-Gmehling mixing
r ules 3-49
Pr edict ive SRK pr oper t y model (PSRK) 3-26
PRMHV2 pr oper t y met hod 2-28
Pr oper t y Const ant Est imat ion Syst em
est imat ion met hods 8-1
Pr oper t y met hods
act ivit y coefficient common models 2-53
classes of 2-2
common models for equat ion-of-st at e 2-25
common models for pet r oleum mixt ur es 2-18
cr eat ing 4-51, 4-55
definit ion 2-2, 4-1
disffusion coefficient 1-36
equat ion-of-st at e 2-15, 2-20
flexible and pr edict ive equat ion-of-st at e 2-26
flexible and pr edict ive models 2-36
for char act er izing pet r oleum component s 7-3
for elect r olyt e solut ions 2-54, 2-66
for K-value models 2-11
for liquid fugacit y 2-11
for pet r oleum mixt ur es 2-10
liquid act ivit y coefficient 2-37
list 1-1
modifying 4-51
pet r oleum-t uned equat ion-of-st at e 2-15
sur face t ension 1-37
t her mal conduct ivit y 1-35
t her modynamic 1-2
t r anspor t 1-34
viscosit y 1-35
Pr oper t y models
equat ion-of-st at e list 3-7
list of 3-1
t her modynamic list 3-3
Pr oper t y par amet er s
est imat ing 8-1
PRWS pr oper t y met hod 2-29
PSRK
pr oper t y met hod 2-30
pr oper t y model 3-26
R
Racket t mixt ur e liquid volume model 3-95
Racket t /DIPPR pur e component liquid volume model
3-93
Radius of gyr at ion est imat ion met hod 8-12
Redlich-Kist er act ivit y coefficient model 3-66
Redlich-Kwong
alpha funct ion 3-40
equat ion-of-st at e 2-17, 2-24, 2-26, 2-40, 2-59, 2-
62
pr oper t y model 3-27
Redlich-Kwong-Aspen pr oper t y model 3-28
Redlich-Kwong-Soave
alpha funct ion equat ions 3-40
alpha funct ion list 3-44
Bost on-Mat hias pr oper t y model 3-29
MHV2 pr oper t y model 3-31
Wong-Sandler pr oper t y model 3-30
Redlich-Kwong-Soave pr oper t y model 3-35
Riedel elect r olyt e cor r ect ion t her mal conduct ivit y
model 3-141
Rigor ous t hr ee-phase calculat ions
list of unit oper at ion models 6-1
RK-ASPEN pr oper t y met hod 2-31
RKS-BM pr oper t y met hod 2-24
RKSMHV2 pr oper t y met hod 2-32
RK-SOAVE pr oper t y met hod 2-17
RKSWS pr oper t y met hod 2-33
Rout es
conflict ing 4-54
cr eat ing 4-57
definit ion 4-1, 4-36
modifying 4-57
r eplacing 4-51
t r acing 4-50
S
Sat o-Riedel/DIPPR t her mal conduct ivit y model 3-
142
Scat char d-Hildebr and act ivit y coefficient model 3-67
Physical Pr oper t y Met hods and Models Index-5
Release 10
Schwar t zent r uber -Renon pr oper t y model 3-31
Solid ent halpy met hods 4-21, 4-22
Solid ent halpy of for mat ion of aqueous species
est imat ion met hods 8-22
Solid ent r ophy met hods 4-28, 4-29
Solid fugacit y coefficient met hods 4-16
Solid Gibbs ener gy met hods 4-25, 4-26
Solid heat capacit y est imat ion met hods 8-21
Solid st andar d ent halpy of for mat ion est imat ion
met hods 8-21
Solid st andar d Gibbs fr ee ener gy of for mat ion
est imat ion met hods 8-22
Solids act ivit y coefficient met hod 1-16
Solids polynomial heat capacit y model 3-102
SOLIDS pr oper t y met hod 2-67
Solids volume polynomial model 3-97
Solubilit y cor r elat ion models
list 3-102
Solubilit y par amet er est imat ion met hod 8-12
Solut ion chemist r y 5-2
SR-POLAR pr oper t y met hod 2-34
St andar d ent halpy of for mat ion
aqueous species 8-22
est imat ion met hods 8-10
St andar d Gibbs fr ee ener gy of for mat ion
aqueous species 8-23
est imat ion met hods 8-11
St andar d liquid volume est imat ion met hod 8-12
St andar d Peng-Robinson pr oper t y model 3-34
St andar d Redlich-Kwong-Soave pr oper t y model 3-35
St eam t ables
ASME 2-71
list 2-71
NBS/NRC 3-21
pr oper t y met hods 2-71
pr oper t y models 3-8
STEAMNBS pr oper t y met hod 2-72, 3-21
STEAM-TA pr oper t y met hod 2-71
St iel-Thodos pr essur e cor r ect ion t her mal
conduct ivit y model 3-145
St iel-Thodos/DIPPR t her mal conduct ivit y model 3-
143
Subor dinat e pr oper t ies 4-3
Sur face t ension
est imat ion met hods 8-19
models list 3-154
pr oper t y met hods 1-37
Sur face t ension met hods 4-36
T
Ther mal conduct ivit y
models list 3-138
pr oper t y met hod 1-35
Ther mal conduct ivit y met hods 4-33, 4-34, 4-35
Ther modynamic pr oper t y
list of models 4-41, 4-42, 4-43
Ther modynamic pr oper t y
list of addit ional models 3-105
met hods 1-2
models list 3-3
Thr ee-suffix Mar gules act ivit y coefficient model 3-68
Tr acing r out es 4-50
Tr anspor t pr oper t y
met hods 1-34
models list 3-120
Tr anspor t pr oper t y models 4-43, 4-44
TRAPP
t her mal conduct ivit y model 3-145
viscosit y model 3-137
Tr ue component appr oach 5-3
U
UNIFAC
act ivit y coefficient model 2-45, 3-69
Dor t mund modified act ivit y coefficient model 3-
71
Lyngby modified act ivit y coefficient model 3-72
R and Q par amet er s est imat ion met hod 8-26
UNIQUAC
act ivit y coefficient model 2-48, 3-74
R and Q par amet er s est imat ion met hod 8-13
Unit oper at ion models
r igor ous t hr ee-phase calculat ions 6-1
V
Van Laar act ivit y coefficient model 2-49, 3-75
Vapor ent halpy met hods 4-17
Vapor ent r ophy met hods 4-26, 4-27
Vapor fugacit y coefficient met hods 4-11
Vapor Gibbs ener gy met hods 4-22, 4-23
Vapor phase associat ion 1-26
Vapor pr essur e est imat ion met hods 8-14
Vapor pr essur e model list 3-80
Vapor t her mal conduct ivit y est imat ion met hods 8-19
Vapor viscosit y est imat ion met hods 8-18
Vapor -liquid equilibr ia act ivit y coefficient met hod 1-
11
Vapor -liquid equlibr ia equat ion-of-st at e met hod 1-4
Vir ial equat ions of st at e 1-25
Viscosit y
met hods 4-31, 4-32
models 3-121
pr oper t y met hod 1-35
Index-6 Physical Pr oper t y Met hods and Models
Ver sion 10
W
Wagner Int er act ion Par amet er act ivit y coefficient
model 3-77
Wagner vapor pr essur e model 3-80
Wassiljewa-Mason-Saxena mixing r ule for t her mal
conduct ivit y 3-146
Wat er solubilit y model 3-104
Wat son equat ion for heat of vapor izat ion 3-85
Wilke-Chang diffusion model
binar y 3-152
mixt ur e 3-153
WILS-GLR pr oper t y met hod 3-112
WILS-LR pr oper t y met hod 3-112
Wilson (liquid molar volume) act ivit y coefficient
model 3-79
Wilson act ivit y coefficient model 2-51, 3-78
Wong-Sandler mixing r ules 3-51
Z
Zemait is equat ion 5-8