Professional Documents
Culture Documents
AspenPhysPropModelsV7 2 Ref
AspenPhysPropModelsV7 2 Ref
Property System
Contents
Contents..................................................................................................................1
1 Introduction .........................................................................................................5
Units for Temperature-Dependent Parameters .....................................................6
Pure Component Temperature-Dependent Properties............................................7
Extrapolation Methods .................................................................................... 10
2 Thermodynamic Property Models .......................................................................11
Equation-of-State Models ................................................................................ 15
ASME Steam Tables.............................................................................. 16
BWR-Lee-Starling................................................................................. 16
Benedict-Webb-Rubin-Starling ............................................................... 17
GERG2008 Equation of State ................................................................. 20
Hayden-O'Connell ................................................................................ 22
HF Equation-of-State ............................................................................ 25
IAPWS-95 Steam Tables ....................................................................... 29
Ideal Gas ............................................................................................ 29
Lee-Kesler ........................................................................................... 29
Lee-Kesler-Plcker ............................................................................... 31
NBS/NRC Steam Tables ........................................................................ 32
Nothnagel ........................................................................................... 33
Copolymer PC-SAFT EOS Model.............................................................. 35
Peng-Robinson..................................................................................... 47
Standard Peng-Robinson ....................................................................... 49
Peng-Robinson-MHV2 ........................................................................... 50
Predictive SRK (PSRK) .......................................................................... 51
Peng-Robinson-Wong-Sandler................................................................ 51
Redlich-Kwong ..................................................................................... 51
Redlich-Kwong-Aspen ........................................................................... 52
Redlich-Kwong-Soave ........................................................................... 53
Redlich-Kwong-Soave-Boston-Mathias .................................................... 55
Redlich-Kwong-Soave-Wong-Sandler ...................................................... 56
Redlich-Kwong-Soave-MHV2.................................................................. 57
Schwartzentruber-Renon....................................................................... 57
Soave-Redlich-Kwong ........................................................................... 59
SRK-Kabadi-Danner.............................................................................. 61
SRK-ML............................................................................................... 63
VPA/IK-CAPE Equation-of-State ............................................................. 64
Peng-Robinson Alpha Functions.............................................................. 69
Huron-Vidal Mixing Rules ...................................................................... 79
MHV2 Mixing Rules ............................................................................... 81
Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules ........................... 82
Contents
Contents
Contents
Contents
1 Introduction
This manual describes the property models available in the Aspen Physical
Property System and defines the parameters used in each model. The
description for each model lists the parameter names used to enter values on
the Properties Parameters forms.
This manual also lists the pure component temperature-dependent properties
that the Aspen Physical Property System can calculate from a model that
supports several equations or submodels. See Pure Component TemperatureDependent Properties (below).
Many parameters have default values indicated in the Default column. A dash
() indicates that the parameter has no default value and you must provide a
value. If a parameter is missing, calculations stop. The lower limit and upper
limit for each parameter, when available, indicate the reasonable bounds for
the parameter. The limits are used to detect grossly erroneous parameter
values.
The property models are divided into the following categories:
The property types for each category are discussed in separate sections. The
following table (below) provides an organizational overview of this manual.
The tables labeled Thermodynamic Property Models, Transport Property
Models, and Nonconventional Solid Property Models present detailed lists of
models. These tables also list the Aspen Physical Property System model
names, and their possible use in different phase types, for pure components
and mixtures.
Electrolyte and conventional solid property models are presented in
Thermodynamic Property Models.
1 Introduction
Categories of Models
Category
Sections
Thermodynamic
Property Models
Equation-of-State Models
Activity Coefficient Models (Including Electrolyte Models)
Vapor Pressure and Liquid Fugacity Models
Heat of Vaporization Models
Molar Volume and Density Models
Heat Capacity Models
Solubility Correlations
Other
Transport Property
Models
Viscosity Models
Thermal Conductivity Models
Diffusivity Models
Surface Tension Models
1 Introduction
Watson
DIPPR
PPDS
IK-CAPE
1 Introduction
Property
SubmodelSelection
Parameter
Element
Number
Available Submodels
DIPPR Equation
Numbers
( = default)
Solid Volume
THRSWT/1
100
Liquid Vapor
Pressure
THRSWT/3
Heat of
Vaporization
THRSWT/4
Solid Heat
Capacity
THRSWT/5
100, 102
Liquid Heat
Capacity
THRSWT/6
100, 114
107, 127
Second Virial
Coefficient
DIPPR
104
101, 115
102
Aspen (Hakim-Steinberg-Stiel),
DIPPR, PPDS, IK-CAPE, NIST
106
THRSWT/8
101
Submodel
Aspen
1 to 127
DIPPR
200 to 211
BARIN
301 to 302
400
PML
401 to 404
IK-CAPE
501 to 515
NIST
1 Introduction
Set the fourth element of the THRSWT parameter to 106, and the 1-3 and 5-8
elements to 0. If you want to set the other temperature-dependent properties
to use what is defined for that component in the databank, leave the element
blank.
The following table lists the available DIPPR equations and the corresponding
equation (submodel) number.
116
127
1 Introduction
Extrapolation Methods
Many temperature dependent property models have upper and lower
temperature limits. The Aspen Physical Property System usually extrapolates
linearly beyond such limits. It calculates the slope of the property-versustemperature curve, or the ln(property)-versus-temperature curve for models
expressed in logarithmic form, at the upper or lower temperature limit. For
temperatures beyond the limit, it uses a linear model with this slope which
meets the curve from the equation at the temperature limit. Thus the model
is:
For T beyond the upper or lower limit, where Tlim is that limit and Z is the
property or ln(property) as appropriate. Some liquid molar volume models are
actually molar density models which then return the reciprocal of the density
as the liquid molar volume. In these models, the extrapolation occurs for the
density calculation.
There are certain exceptions, detailed below.
For these models, the extrapolation maintains the slope of ln(property) versus
1/T. This applies to the Extended Antoine vapor pressure equation and the
Andrade and DIPPR liquid viscosity equations. Note that the equation for
Henry's Constant is extrapolated by ln(Henry) versus T.
Exception 3: No Extrapolation
The equations for certain models are used directly at all temperatures, so that
no extrapolation is performed. These models are the Wagner vapor pressure
equation, the Aly and Lee equation for the DIPPR Ideal Gas Heat Capacity
(using the CPIGDP parameter), and the Water Solubility and Hydrocarbon
Solubility models. The equations for temperature-dependent binary
interaction parameters are also used directly at all temperatures with no
extrapolation.
10
1 Introduction
2 Thermodynamic Property
Models
Equation-of-State Models
A pure component equation of state model calculates PHIL, PHIV, DHL, DHV,
DGL, DGV, DSL, DSV, VL, and VV. Most mixture equation of state models
calculate PHILMX, PHIVMX, DHLMX, DHVMX, DGLMX, DGVMX, DSLMX,
DSVMX, VLMX, and VVMX. Those marked with * only calculate DHLMX,
DHVMX, DGLMX, DGVMX, DSLMX, DSVMX, VLMX, and VVMX. The alpha
functions and mixing rules are options available in some of the models.
Property Model
Model Name(s)
Phase(s)Pure
Mixture
ESH2O0,ESH2O
VL
BWR-Lee-Starling
ESBWR0, ESCSTBWR V L
Benedict-Webb-Rubin-Starling
ESBWRS, ESBWRS0
VL
Hayden-O'Connell
ESHOC0,ESHOC
HF equation-of-state
ESHF0, ESHF
Ideal Gas
ESIG0, ESIG
Lee-Kesler *
ESLK
VL
Lee-Kesler-Plcker
ESLKP0,ESLKP
VL
ESSTEAM0,ESSTEAM
VL
11
Property Model
Model Name(s)
Phase(s)Pure
Mixture
Nothnagel
ESNTH0,ESNTH
PC-SAFT
ESPSAFT, ESPSAFT0
VL
Peng-Robinson
ESPR0, ESPR
VL
Standard Peng-Robinson
ESPRSTD0,ESPRSTD
VL
Peng-Robinson-Wong-Sandler * ESPRWS0,ESPRWS
VL
Peng-Robinson-MHV2 *
ESPRV20,ESPRV2
VL
Predictive SRK *
ESRKSV10, ESRKSV1 V L
Redlich-Kwong
ESRK0, ESRK
Redlich-Kwong-Aspen
ESRKA0,ESRKA
VL
Redlich-Kwong-Soave
ESRKSTD0,ESRKSTD
VL
Redlich-Kwong-Soave-BostonMathias
ESRKS0, ESRKS
VL
Redlich-Kwong-Soave-MHV2 *
ESRKSV20, ESRKSV2 V L
Redlich-Kwong-Soave-WongSandler *
ESRKSWS0, ESRKSWS V L
Schwartzentruber-Renon
ESRKU0,ESRKU
VL
Soave-Redlich-Kwong
ESSRK0, ESSRK
VL
SRK-Kabadi-Danner
ESSRK0, ESSRK
VL
SRK-ML
ESRKSML0, ESRKSML V L
VL
VL
VL
VL
VL
VL
12
Property Model
Model Name
Phase(s)Pure
Mixture
Bromley-Pitzer
GMPT2
Chien-Null
GMCHNULL
GMCONS
COSMO-SAC
COSMOSAC
Electrolyte NRTL
GMENRTL, GMELC,
GMENRHG
L L1 L2
ENRTLSAC
Hansen
HANSEN
Ideal Liquid
GMIDL
L L1 L2
NRTLSAC
Pitzer
GMPT1
GMPOLY
LS
Property Model
Model Name
Phase(s)Pure
Mixture
Redlich-Kister
GMREDKIS
LS
Scatchard-Hildebrand
GMXSH
GMENRTLS
Three-Suffix Margules
GMMARGUL
LS
UNIFAC
GMUFAC
L L1 L2
GMUFLBY
L L1 L2
GMUFDMD
L L1 L2
UNIQUAC
GMUQUAC
L L1 L2
GMENRTLQ
van Laar
GMVLAAR
GMWIP
Wilson
GMWILSON
GMWSNVOL
Model
Name
Property Phase(s)Pure
Mixture
PL0XANT
PL
L L1 L2
API Sour
SWEQ
PHILMX
Braun K-10
BK10
PHILMX
Chao-Seader
PHL0CS
PHIL
Grayson-Streed
PHL0GS
PHIL
Kent-Eisenberg
ESAMINE
PHILMX, L
GLMX,
HLMX,
SLMX
Maxwell-Bonnell
PL0MXBN PL
L L1 L2
Solid Antoine
PS0ANT
PS
Model Name
Phase(s)Pure
Mixture
DHVLWTSN
Clausius-Clapeyron Equation
DHVLCC
Model Name
Phase(s)Pure
Mixture
VL2API
Brelvi-O'Connell
VL1BROC
13
Property Model
Model Name
Phase(s)Pure
Mixture
VAQCLK
VL0CTD,VL2CTD
Debye-Hckel Volume
VAQDH
VL0CONS
Rackett/Campbell-Thodos
Mixture Liquid Volume
VL2RKT
Modified Rackett
VL2MRK
VS0POLY
Model
Name
Property Phase(s)Pure
Mixture
HL0DIP
HL, DHL
CPIG
HS0POLY HS
Model
Name
Property Phase(s)Pure
Mixture
Henry's constant
HENRY1
HNRY,
WHNRY
Water solubility
Hydrocarbon solubility
Other Models
Property Model
14
Model
Name
Property Phase(s)Pure
Mixture
DHL,
DHLMX
SLV
Bromley-Pitzer Enthalpy
HAQPT2
HLMX
GAQPT2
GLMX
Property Model
Model
Name
Property Phase(s)Pure
Mixture
HMXENRTL, HLMX
HAQELC,
HMXELC,
HMXENRHG
GMXENRTL, HLMX
GAQELC,
GMXELC,
GMXENRHG
DHL0HREF DHL
LV
Pitzer Enthalpy
HAQPT1
HLMX
GAQPT1
GLMX
LV
Equation-of-State Models
The Aspen Physical Property System has the following built-in equation-ofstate property models. This section describes the equation-of-state property
models available.
Model
Type
Fundamental
BWR-Lee-Starling
Virial
Benedict-Webb-Rubin-Starling
Virial
Hayden-O'Connell
HF Equation-of-State
Mixing rules
Ideal Gas
Ideal
Lee-Kesler
Virial
Lee-Kesler-Plcker
Virial
Mixing rules
Fundamental
Nothnagel
Ideal
PC-SAFT
Association
Peng-Robinson
Cubic
Standard Peng-Robinson
Cubic
Alpha functions
Peng-Robinson-MHV2
Cubic
Peng-Robinson-Wong-Sandler
Cubic
Predictive SRK
Cubic
Mixing rules
Redlich-Kwong
Cubic
15
Model
Type
Redlich-Kwong-Aspen
Cubic
Standard Redlich-Kwong-Soave
Cubic
Redlich-Kwong-Soave-Boston-Mathias
Cubic
Redlich-Kwong-Soave-MHV2
Cubic
Redlich-Kwong-Soave-Wong-Sandler
Cubic
Alpha functions
Schwartzentruber-Renon
Cubic
Soave-Redlich-Kwong
Cubic
SRK-Kabadi-Danner
Cubic
SRK-ML
Cubic
VPA/IK-CAPE equation-of-state
Mixing rules
References
ASME Steam Tables, Thermodynamic and Transport Properties of Steam,
(1967).
K. V. Moore, Aerojet Nuclear Company, prepared for the U.S. Atomic Energy
Commision, ASTEM - A Collection of FORTRAN Subroutines to Evaluate the
1967 ASME equations of state for water/steam and derivatives of these
equations.
BWR-Lee-Starling
The Benedict-Webb-Rubin-Lee-Starling equation-of-state is the basis of the
BWR-LS property method. It is a generalization by Lee and Starling of the
virial equation-of-state for pure fluids by Benedict, Webb and Rubin. The
equation is used for non-polar components, and can manage hydrogencontaining systems.
General Form:
Where:
Mixing Rules:
16
Where:
Parameter
Name/Element
Symbol
Default
MDS Lower
Limit
Upper
Limit
Units
TCBWR
Tci
TC
5.0
2000.0
TEMPERATURE
VC
0.001
3.5
MOLEVOLUME
OMEGA
-0.5
3.0
-5.0
1.0
-5.0
1.0
VCBWR
Vci
BWRGMA
i
ij
ij
BWRKV
BWRKT
Binary interaction parameters BWRKV and BWRKT are available in the Aspen
Physical Property System for a large number of components from Brul et al.
(1982) and from Watanasiri et al. (1982). (See Physical Property Data,
Chapter 1).
References
M.R. Brul, C.T. Lin, L.L. Lee, and K.E. Starling, AIChE J., Vol. 28, (1982) p.
616.
Brul et al., Chem. Eng., (Nov., 1979) p. 155.
Watanasiri et al., AIChE J., Vol. 28, (1982) p. 626.
Benedict-Webb-Rubin-Starling
The Benedict-Webb-Rubin-Starling equation-of-state is the basis of the BWRS
property method. It is a modification by Han and Starling of the virial
equation-of-state for pure fluids by Benedict, Webb and Rubin. This equationof-state can be used for hydrocarbon systems that include the common light
gases, such as H2S, CO2 and N2.
The form of the equation-of-state is:
17
Where:
kij = kji
In the mixing rules given above, A0i, B0i, C0i, D0i, E0i, ai, bi, ci, di, i, i are pure
component constants which can be input by the user. For methane, ethane,
propane, iso-butane, n-butane, iso-pentane, n-pentane, n-hexane, nheptane, n-octane, ethylene, propylene, nitrogen, carbon dioxide, and
hydrogen sulfide, values of the parameters in the table below are available in
the EOS-LIT databank in the Aspen Properties Enterprise Database.
If the values of these parameters are not given, and not available from the
databank, the Aspen Physical Property System will calculate them using the
18
critical temperature, the critical volume (or critical density), the acentric
factor and generalized correlations given by Han and Starling.
When water is present, by default Benedict-Webb-Rubin-Starling uses the
steam table to calculate the enthalpy, entropy, Gibbs energy, and molar
volume of water. The total properties are mole-fraction averages of these
values with the properties calculated by the equation of state for other
components. Fugacity coefficient is not affected. An option code can disable
this use of the steam table.
For best results, the binary parameter kij must be regressed using phaseequilibrium data such as VLE data.
Parameter
Name/
Element
Symbol Default
BWRSTC
Tci
TC
5.0
BWRSVC
Vci
VC
0.001 3.5
MOLE-VOLUME
BWRSOM
OMEGA
0.5
2.0
BWRSA/1
B0i
MOLE-VOLUME
BWRSA/2
A0i
PRESSURE * MOLEVOL^2
BWRSA/3
C0i
PRESSURE *
TEMPERATURE^2 *
MOLE-VOLUME^2
BWRSA/4
MOLE-VOLUME^2
BWRSA/5
bi
MOLE-VOLUME^2
BWRSA/6
ai
PRESSURE * MOLEVOL^3
BWRSA/7
MOLE-VOLUME^3
BWRSA/8
ci
PRESSURE *
TEMPERATURE^2 *
MOLE-VOLUME^3
BWRSA/9
D0i
PRESSURE *
TEMPERATURE^3 *
MOLE-VOLUME^2
BWRSA/10
di
PRESSURE *
TEMPERATURE * MOLEVOLUME^3
BWRSA/11
E0i
PRESSURE *
TEMPERATURE^4 *
MOLE-VOLUME^2
BWRAIJ
kij
2000.0 TEMPERATURE
Methane
Ethane
Propane
n-Butane
B0i
0.723251
0.826059
0.964762
1.56588
A0i
7520.29
13439.30
18634.70
32544.70
C0i
2.71092x108
2.95195x109
7.96178x109
1.37436x1010
D0i
1.07737x1010
2.57477x1011
4.53708x1011
3.33159x1011
E0i
3.01122x1010
1.46819x1013
2.56053x1013
2.30902x1012
19
Parameter
Methane
Ethane
Propane
n-Butane
bi
0.925404
3.112060
5.462480
9.140660
ai
2574.89
22404.50
40066.40
71181.80
7
3.64238x107
di
47489.1
702189.0
1.50520x10
0.468828
0.909681
2.014020
4.009850
ci
4.37222x108
6.81826x109
2.74461x1010
7.00044x1010
1.48640
2.99656
4.56182
7.54122
Parameter
n-Pentane
n-Hexane
n-Heptane
n-Octane
B0i
2.44417
2.66233
3.60493
4.86965
A0i
51108.20
45333.10
77826.90
2.23931x10
D0i
1.01769x10
12
E0i
3.90860x1013
6.26433x1014
6.36251x1012
3.46419x1013
bi
16.607000
29.498300
27.441500
10.590700
ai
162185.00
434517.00
359087.00
131646.00
8351150.0
1.85906x108
C0i
5.26067x10
10
5.52158x10
12
81690.60
10
3.27460x10
6.15662x10
10
9.96546x1010
7.77123x10
12
7.90575x1012
di
3.88521x10
7.067020
9.702300
21.878200
34.512400
ci
1.35286x1011
3.18412x1011
3.74876x1011
6.42053x1011
11.85930
14.87200
24.76040
21.98880
References
M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.
334.
M. S. Han, and K. E. Starling, "Thermo Data Refined for LPG. Part 14:
Mixtures", Hydrocarbon Processing, Vol. 51, No. 5, (1972), p. 129.
K. E. Starling, "Fluid Themodynamic Properties for Light Petroleum Systems",
Gulf Publishing Co., Houston, Texas (1973).
20
(1)
Where the ideal-gas contribution o and residual contribution
mixture density, temperature, and molar composition are:
r at a given
(2)
(3)
In eq. (2), the ideal-gas contribution of the reduced Helmholtz free energy for
component i is given by:
(5)
In eq. (3), the pure substance contribution to the residual part of the reduced
Helmholtz free energy for component i is given by:
(6)
In eq. (3), the mixture contribution to the residual part of the reduced
Helmholtz free energy is given by:
(7)
21
(9)
Where:
R = molar gas constant = 8.314472 J/mol-K.
noi,k, doi,k, toi,k, and coi,k = coefficients and exponents of eq. (6) for pure
components
Fij = Composition dependent factor
nij,k = Coefficients and dij,k, tij,k, ij,k, ij,k, ij,k, and ij,k = the exponents in eq.
(7) for all binary specific and generalized departure functions
v,ij and v,ij in eq. (8) and T,ij and T,ij in eq. (9) = Binary interaction
parameters
Reference
"The GERG-2004 Wide-Range Equation of State for Natural Gases and Other
Mixtures" O. Kunz, R. Klimeck, W. Wagner, M. Jaeschke; GERG TM15 2007;
ISBN 978-3-18-355706-6; Published for GERG and printed in Germany by
VDI Verlag GmbH (2007).
Kunz, O., Wagner, W., "The new GERG-2004 XT08 wide-range equation of
state for natural gases and other mixtures." To be submitted to Fluid Phase
Equilibria (beginning of 2010).
Hayden-O'Connell
The Hayden-O'Connell equation-of-state calculates thermodynamic properties
for the vapor phase. It is used in property methods NRTL-HOC, UNIF-HOC,
UNIQ-HOC, VANL-HOC, and WILS-HOC, and is recommended for nonpolar,
polar, and associating compounds. Hayden-O'Connell incorporates the
chemical theory of dimerization. This model accounts for strong association
and solvation effects, including those found in systems containing organic
acids, such as acetic acid. The equation-of-state is:
Where:
22
, where
, where
Cross-Interactions
The previous equations are valid for dimerization and cross-dimerization if
these mixing rules are applied:
Chemical Theory
When a compound with strong association
is present in a mixture,
the entire mixture is treated according to the chemical theory of dimerization.
23
with
In this case, molar volume is equal to V/nt.
This represents true total volume over the true number of species nt.
However, the reported molar volume is V/na.
This represents the true total volume over the apparent number of species na.
If dimerization does not occur, na is defined as the number of species. V/na
reflects the apparently lower molar volume of an associating gas mixture.
The chemical equilibrium constant for the dimerization reaction on pressure
basis Kp, is related to the true mole fractions and fugacity coefficients:
Where:
yi and yj
yij
Kij
ij
= 1 for i=j
= 0 for
Apparent mole fractions yia are reported, but in the calculation real mole
fractions yi, yj, and yij are used.
The heat of reaction due to each dimerization is calculated according to:
The sum of the contributions of all dimerization reactions, corrected for the
ratio of apparent and true number of moles is added to the molar enthalpy
departure
24
Upper
Limit
Units
TC
2000.0
TEMPERATURE
PC
Tci
pci
gyr
5.0
10
5
-11
10
PRESSURE
5x10
-9
RGYR
ri
10
MUP
pi
0.0
5x10-24
LENGTH
DIPOLEMOMENT
HOCETA
0.0
The binary parameters HOCETA for many component pairs are available in the
Aspen Physical Property System. These parameters are retrieved
automatically when you specify any of the following property methods: NRTLHOC, UNIF-HOC, UNIQ-HOC, VANL-HOC, and WILS-HOC.
References
J.G. Hayden and J.P. O'Connell, "A Generalized Method for Predicting Second
Virial Coefficients," Ind. Eng. Chem., Process Des. Dev., Vol. 14,No. 3,
(1975), pp. 209 216.
HF Equation-of-State
HF forms oligomers in the vapor phase. The non-ideality in the vapor phase is
found in important deviations from ideality in all thermodynamic properties.
The HF equation accounts for the vapor phase nonidealities. The model is
based on chemical theory and assumes the formation of hexamers.
Species like HF that associate linearly behave as single species. For example,
they have a vapor pressure curve, like pure components. The component on
which a hypothetical unreacted system is based is often called the apparent
(or parent) component. Apparent components react to the true species.
Electrolyte Calculation in Physical Property Methods discusses apparent and
true species. Abbott and van Ness (1992) provide details and basic
thermodynamics of reactive systems.
The temperature-dependent hexamerization equilibrium constant, can fit the
experimentally determined association factors. The built-in functionality is:
(1)
The constants C0 and C1 are from Long et al. (1943), and C2 and C3 are set to
0. The correlation is valid between 270 and 330 K, and can be extrapolated to
about 370 K (cf. sec. 4). Different sets of constants can be determined by
experimental data regression.
25
(2)
Where the true number of species is given by 1/f. The association factor is
easily determined from (p, V, T) experiments. For a critical evaluation of data
refer to Vanderzee and Rodenburg (1970).
If only one reaction is assumed for a mixture of HF and its associated species,
(refer to Long et al., 1943), then:
(3)
If p1 represents the true partial pressure of the HF monomer, and p6
represents the true partial pressure of the hexamer, then the equilibrium
constant is defined as:
(4)
(5)
If all hexamer were dissociated, the apparent total pressure would be the
hypothetical pressure where:
pa = p1 + 6p6 = p + 5p6
(6)
When physical ideality is assumed, partial pressures and mole fractions are
proportional. The total pressure in equation 5 represents the true number of
species. The apparent total pressure from equation 6 represents the apparent
number of species:
(7)
26
K is known from Long et al., or can be regressed from (p,V,T) data. The
apparent mole fraction of HF, ya, is known to the user and the simulator, but
p1, or y = p1/p must also be known in order to calculate the thermodynamic
properties of the mixture. Equation 9 must be solved for p1.
Equation 9 can be written as a polynomial in p1 of degree 6:
K(6 - 5ya)(p1)6 + p1 - pya = 0
(9a)
From the fugacity coefficient, the Gibbs energy departure of the mixture or
pure apparent components can be calculated:
(12)
(12a)
27
(13)
(14)
(17)
From the Gibbs energy departure and enthalpy departure, the entropy
departure can be calculated:
(18)
Temperature derivatives for the thermodynamic properties can be obtained
by straightforward differentiation.
Usage
The HF equation-of-state should only be used for vapor phase calculations. It
is not suited for liquid phase calculations.
The HF equation-of-state can be used with any activity coefficient model for
nonelectrolyte VLE. Using the Electrolyte NRTL model and the data package
MHF2 is strongly recommended for aqueous mixtures (de Leeuw and
Watanasiri, 1993).
Parameter
Name/Element
Symbol
Default
MDS Lower
Limit
Upper
Limit
Units
ESHFK/1
C0
43.65
ESHFK/2
C1
-8910
ESHFK/3
C2
ESHFK/4
C3
References
M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing
Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,
Vol. 77, (1992) pp. 53 119.
28
References
Wanger W. and A. Pru, The IAPWS Formation 1995 for the Thermodynamic
Properties of Ordinary Water Substance for General and Scientific Use, J.
Phys. Chem. Ref. Data, 31(2), 387- 535, 2002.
Ideal Gas
The ideal gas law (ideal gas equation-of-state) combines the laws of Boyle
and Gay-Lussac. It models a vapor as if it consisted of point masses without
any interactions. The ideal gas law is used as a reference state for equationof-state calculations, and can be used to model gas mixtures at low pressures
(without specific gas phase interactions).
The equation is:
p = RT / Vm
Lee-Kesler
This equation-of-state model is based on the work of Lee and Kesler (1975).
In this equation, the volumetric and thermodynamic properties of fluids based
on the Curl and Pitzer approach (1958) have been analytically represented by
a modified Benedict-Webb-Rubin equation-of-state (1940). The model
calculates the molar volume, enthalpy departure, Gibbs free energy
departure, and entropy departure of a mixture at a given temperature,
pressure, and composition for either a vapor or a liquid phase. Partial
derivatives of these quantities with respect to temperature can also be
calculated.
Unlike the other equation-of-state models, this model does not calculate
fugacity coefficients.
29
Z(1)
Z(0) and Z(1) are assumed universal functions of the reduced temperature and
pressure.
Curl and Pitzer (1958) were quite successful in correlating thermodynamic
and volumetric properties using the above approach. Their application
employed tables of properties in terms of reduced temperature and pressure.
A significant weakness of this method is that the various properties (for
example, entropy departure and enthalpy departure) will not be exactly
thermodynamically consistent with each other. Lee and Kesler (1975)
overcame this drawback by an analytic representation of the tables with an
equation-of-state. In addition, the range was extended by including new data.
In the Lee-Kesler implementation, the compressibility factor of any fluid has
been written in terms of a simple fluid and a reference as follows:
In the above equation both Z(0) and Z(1) are represented as generalized
equations of the BWR form in terms of reduced temperature and pressure.
Thus,
Equations for the enthalpy departure, Gibbs free energy departure, and
entropy departure are obtained from the compressibility factor using standard
thermodynamic relationships, thus ensuring thermodynamic consistency.
In the case of mixtures, mixing rules (without any binary parameters) are
used to obtain the mixture values of the critical temperature and pressure,
and the acentric factor.
This equation has been found to provide a good description of the volumetric
and thermodynamic properties of mixtures containing nonpolar and slightly
polar components.
30
Symbol
Definition
Tc
TCLK
TC
Critical temperature
Pc
PCLK
PC
Critical pressure
OMGLK
OMEGA
Acentric factor
References
M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.
334.
R. F. Curl and K.S. Pitzer, Ind. Eng. Chem., Vol. 50, (1958), p. 265.
B. I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975), p. 510.
Lee-Kesler-Plcker
The Lee-Kesler-Plcker equation-of-state is the basis for the LK-PLOCK
property method. This equation-of-state applies to hydrocarbon systems that
include the common light gases, such as H2S and CO2. It can be used in gasprocessing, refinery, and petrochemical applications.
The general form of the equation is:
Where:
The fo and fR parameters are functions of the BWR form. The fo parameter is
for a simple fluid, and fR is for reference fluid n-octane.
=
=
Zm
Where:
Vcij
Tcij
Zci
kij
kji
31
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
TCLKP
Tci
TC
2000.0
TEMPERATURE
PCLKP
pci
PC
VCLKP
Vci
VC
0.001
3.5
MOLEVOLUME
OMGLKP
OMEGA
-0.5
2.0
LKPZC
Zci
fcn() (Method 1)
fcn(pci,Vci,Tci)
(Method 2)
0.1
0.5
LKPKIJ
kij
fcn(TciVci / TcjVcj)
5.0
5.0
5.0
PRESSURE
Method 1 is the default for LKPZC; Method 2 can be invoked by setting the
value of LKPZC equal to zero.
Binary interaction parameters LKPKIJ are available for a large number of
components in the Aspen Physical Property System, from Knapp et al.
References
B.I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975) p. 510; errata: AIChE J.,
Vol. 21, (1975) p. 1040.
V. Plcker, H. Knapp, and J.M. Prausnitz, Ind. Eng. Chem., Process Des. Dev.,
Vol. 17, (1978), p. 324.
H. Knapp, R. Dring, L. Oellrich, U. Plcker, and J. M. Prausnitz. "Vapor-Liquid
Equilibria for Mixtures of Low Boiling Substances." Dechema Chemistry Data
Series, Vol. VI.
32
References
L. Haar, J.S. Gallagher, and J.H. Kell, "NBS/NRC Steam Tables," (Washington:
Hemisphere Publishing Corporation, 1984).
Nothnagel
The Nothnagel equation-of-state calculates thermodynamic properties for the
vapor phase. It is used in property methods NRTL-NTH, UNIQ-NTH, VANLNTH, and WILS-NTH. It is recommended for systems that exhibit strong vapor
phase association. The model incorporates the chemical theory of
dimerization to account for strong association and solvation effects, such as
those found in organic acids, like acetic acid. The equation-of-state is:
Where:
b
bij
nc
Where:
yi and yj
yij
Kij
When accounting for chemical reactions, the number of true species nt in the
mixture changes. The true molar volume V/nt is calculated from the
equation-of-state. Since both V and nt change in about the same proportion,
this number does not change much. However, the reported molar volume is
the total volume over the apparent number of species: V/na. Since the
apparent number of species is constant and the total volume decreases with
33
The sum of the contributions of all dimerization reactions, corrected for the
ratio of apparent and true number of moles, is added to the molar enthalpy
departure:
Built-in correlations:
The pure component parameters b, d, and p are stored in the Aspen
Physical Property System for many components.
In this method, you enter Ai, Bi, Ci, and Di on the Properties Parameters
Unary.T-Dependent form. The units for Kii is pressure-1; use absolute units for
temperature. If you enter Kii and Kjj, then Kij is computed from
If you enter Ai, Bi, Ci, and Di, the equilibrium constants are computed using
the parameters you entered. Otherwise the equilibrium constants are
computed using built-in correlations.
34
Parameter
Name/Element
Symbol Default
Lower
Limit
TC
Tci
5.0
2000.0
TEMPERATURE
TB
Tbi
4.0
2000.0
TEMPERATURE
10
10
PC
pci
NTHA/1
bi
1.0
PRESSURE
MOLE-VOLUME
NTHA/2
di
0.33
0.01
3.0
NTHA/3
pi
0.0
1.0
NTHK/1
Ai
PRESSURE
NTHK/2
Bi
TEMPERATURE
NTHK/3
Ci
TEMPERATURE
NTHK/4
Di
TEMPERATURE
Parameter
Name/Element
Symbol Default
NTHDDH
Lower
Limit
MOLEENTHALPY
For the following systems, the values given in Nothnagel et al., 1973 are
used by default:
Methyl chloride/acetone
Acetonitrile/acetaldehyde
Acetone/chloroform
Chloroform/diethyl amine
Acetone/benzene
Benzene/chloroform
Chloroform/diethyl ether
Chloroform/propyl formate
Chloroform/ethyl acetate
Chloroform/methyl acetate
Chloroform/methyl formate
Acetone/dichloro methane
n-Butane/n-perfluorobutane
n-Pentane/n-perfluoropentane
n-Pentane/n-perfluorohexane
References
K.-H. Nothnagel, D. S. Abrams, and J.M. Prausnitz, "Generalized Correlation
for Fugacity Coefficients in Mixtures at Moderate Pressures," Ind. Eng. Chem.,
Process Des. Dev., Vol. 12, No. 1 (1973), pp. 25 35.
35
account for the repulsive interactions. The attractive forces are further divided
into different contributions, including dispersion, polar, and association.
Using a generated function, , the copolymer PC-SAFT model in general can
be written as follows:
where hc, disp, assoc, and polar are contributions due to hard-chain fluids,
dispersion, association, and polarity, respectively.
The generated function
is defined as follows:
where ares is the molar residual Helmholtz energy of mixtures, R is the gas
constant, T is the temperature, is the molar density, and Zm is the
compressibility factor; ares is defined as:
where a is the Helmholtz energy of a mixture and aig is the Helmholtz energy
of a mixture of ideal gases at the same temperature, density and composition
xi. Once is known, any other thermodynamic function of interest can be
easily derived. For instance, the fugacity coefficient i is calculated as follows:
with
where
is a partial derivative that is always done to the mole fraction
stated in the denominator, while all other mole fractions are considered
constant.
Applying to the departure equations, departure functions of enthalpy,
entropy, and Gibbs free energy can be obtained as follows:
Enthalpy departure:
Entropy departure:
36
where
is the mean segment in the mixture, hs is the contribution from
hard-sphere mixtures on a per-segment basis, and chain is the contribution
due to chain formation. Both
and hs are well-defined for mixtures
containing polymers, including copolymers; they are given by the following
equations:
where mi, i, and i are the segment number, the segment diameter, and
the segment energy parameter of the segment type in the copolymer
37
with
where Bii is defined as the bonding fraction between the segment type
and the segment type within the copolymer component i, is the number of
the segment types within the copolymer component i, and ghsi,j(di,j) is the
radial distribution function of hard-sphere mixtures at contact.
However, the calculation for Bii depends on the type of copolymers. We
start with a pure copolymer system which consists of only two different types
of segments and ; this gives:
with
38
or adjacent
For a block copolymer, there is only one pair and the number of
pairs depend on the length of each block; therefore:
and
A special case is the Sadowskis model for random copolymer with two types
of segments only ( Gross et al., 2003; Becker et al., 2004). In this model, the
bonding fractions are calculated as follows:
When z < z
When z < z
39
For a generalized block copolymer, there is only one pair for each adjacent
type of segment pairs ( ) and the number of pairs for a same type
depends on the length of the block; therefore:
That is,
40
where i,j and i,j are the cross segment diameter and energy parameters,
respectively; only one adjustable binary interaction parameter, i,j is
introduced to calculate them:
41
In above equations, the model constants a1i, a2i, a3i, b1i, b2i, and b3i are fitted
to pure-component vapor pressure and liquid density data of n-alkanes (
Gross and Sadowski, 2001).
with
where
is the cross effective association volume and
is the
cross association energy; they are estimated via simple combination rules:
where
and
are the effective association volume and the
association energy between the association-site types A and B, of the
segment type in the copolymer component i, respectively.
42
in the
in the
To calculate
, this equation has to be solved iteratively for each
association-site type associated with a species in a component. In practice,
further assumption is needed for efficiency. The commonly used model is the
so-called 2B model ( Huang and Radosz, 1990). It assumes that an
associating species (solvent or segment) has two association sites, one is
designed as the site type A and another as the site type B. Similarly to the
hydrogen bonding, type A treats as a donor site with positive charge and type
B as an acceptor site with negative charge; only the donor-acceptor
association bonding is permitted and this concept applies to both pure
systems (self-association such as water) and mixtures (both self-association
and cross-association such as water-methanol). Therefore, we can rewrite
these equations as follows:
Therefore
43
In the above equations, I2() and I3() are the pure fluid integrals and i
and (xp)i are the dipole moment and dipolar fraction of the segment type
within the copolymer component i, respectively. Both
and
44
by the expressions:
Reference
Jog, P. K., Sauer, S. G., Blaesing, J., & Chapman, W. G. (2001), Application
of Dipolar Chain Theory to the Phase Behavior of Polar Fluids and Mixtures.
Ind. Eng. Chem. Res., 40, 4641.
Rushbrooke, G. S., & Stell, G., Hoye, J. S. (1973), Molec. Phys., 26, 1199.
Binary parameters
There are three types of binary interactions in copolymer systems: solventsolvent, solvent-segment, and segment-segment. The binary interaction
parameter i,j allows complex temperature dependence:
with
45
Unary
PCSFTV
Unary
PCSFTU
/k
TEMP
Unary
PCSFTR
Unary
PCSFAU
AB/k
TEMP
Unary
PCSFAV
AB
Unary
PCSFMU
Unary
PCSFXP
xp
Unary
PCSKIJ/1
ai,j
0.0
Binary,
Symmetric
PCSKIJ/2
bi,j
0.0
Binary,
Symmetric
PCSKIJ/3
ci,j
0.0
Binary,
Symmetric
PCSKIJ/4
di,j
0.0
Binary,
Symmetric
PCSKIJ/5
ei,j
0.0
Binary,
Symmetric
PCSKIJ/6
Tref
298.15
TEMP
Binary,
Symmetric
46
Peng-Robinson
The Peng-Robinson equation-of-state is the basis for the PENG-ROB and PRBM property methods. The model has been implemented with choices of
different alpha functions (see Peng-Robinson Alpha Functions) and has been
extended to include advanced asymmetric mixing rules.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
By default, the PENG-ROB property method uses the literature version of the
alpha function and mixing rules. The PR-BM property method uses the
Boston-Mathias alpha function and standard mixing rules. These default
property methods are recommended for hydrocarbon processing applications
such as gas processing, refinery, and petrochemical processes. Their results
are comparable to those of the property methods that use the standard
Redlich-Kwong-Soave equation-of-state.
When advanced alpha function and asymmetric mixing rules are used with
appropriately obtained parameters, the Peng-Robinson model can be used to
accurately model polar, non-ideal chemical systems. Similar capability is also
available for the Soave-Redlich-Kwong model.
The equation for the Peng-Robinson model is:
Where:
47
= a0+a1
a0
=
(the standard quadratic mixing term, where kij has
been made temperature-dependent)
kij
=
kij = kji
a1
=
In general,
ai
bi
ci
For best results, the binary parameters kij and lij must be determined from
regression of phase equilibrium data such as VLE data. The Aspen Physical
Property System also has built-in kij and lij for a large number of component
pairs in the EOS-LIT databank from Knapp et al. These parameters are used
automatically with the PENG-ROB property method. Values in the databank
can be different than those used with other models such as Soave-RedlichKwong or Redlich-Kwong-Soave, and this can produce different results.
The model has option codes which can be used to customize the model, by
selecting a different alpha function and other model options. See PengRobinson Alpha Functions for a description of the alpha functions. See Option
Codes for Equation of State Models (under ESPR) for a list of the option
codes.
48
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
PRTC
Tci
TC
5.0
2000.0
TEMPERATURE
10
10
PRPC
pci
PC
OMGPR
OMEGA x
-0.5
2.0
PRESSURE
PRZRA
zRA
RKTZRA x
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
PRKBV/1
kij(1)
PRKBV/2
kij(2)
TEMPERATURE
PRKBV/3
kij(3)
TEMPERATURE
PRKBV/4
Tlower
TEMPERATURE
PRKBV/5
Tupper
1000
TEMPERATURE
PRLIJ/1
lij(1)
PRLIJ/2
lij(2)
TEMPERATURE
PRLIJ/3
lij(3)
TEMPERATURE
PRLIJ/4
Tlower
TEMPERATURE
PRLIJ/5
Tupper
1000
TEMPERATURE
References
D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.
P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules
for multicomponent mixtures: the problem of invariance," Fluid Phase
Equilibria, Vol 67, (1991), pp. 31-44.
H. Knapp, R. Dring, L. Oellrich, U. Plcker, and J. M. Prausnitz. "Vapor-Liquid
Equilibria for Mixtures of Low Boiling Substances." Dechema Chemistry Data
Series, Vol. VI.
Standard Peng-Robinson
The Standard Peng-Robinson equation-of-state is the original formulation of
the Peng-Robinson equation of state with the standard alpha function (see
Peng-Robinson Alpha Functions). It is recommended for hydrocarbon
processing applications such as gas processing, refinery, and petrochemical
processes. Its results are comparable to those of the standard RedlichKwong-Soave equation of state.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The equation for this model is:
Where:
b
49
ai
bi
kij
The model has option codes which can be used to customize the model, by
selecting a different alpha function and other model options. See PengRobinson Alpha Functions for a description of the alpha functions. See Option
Codes for Equation of State Models (under ESPRSTD) for a list of the option
codes.
For best results, the binary parameter kij must be determined from regression
of phase equilibrium data such as VLE data. The Aspen Physical Property
System also has built-in kij for a large number of component pairs in the EOSLIT databank. These parameters are used automatically with the PENG-ROB
property method. Values in the databank can be different than those used
with other models such as Soave-Redlich-Kwong or Redlich-Kwong-Soave,
and this can produce different results.
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCPRS
Tci
TC
5.0
2000.0
TEMPERATURE
10
10
PCPRS
pci
PC
OMGPRS
OMEGA x
-0.5
2.0
PRESSURE
PRKBV/1
kij(1)
PRKBV/2
kij(2)
TEMPERATURE
PRKBV/3
kij(3)
TEMPERATURE
PRKBV/4
Tlower
TEMPERATURE
PRKBV/5
Tupper
1000
TEMPERATURE
References
D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.
Peng-Robinson-MHV2
This model uses the Peng-Robinson equation-of-state for pure compounds.
The mixing rules are the predictive MHV2 rules. Several alpha functions can
be used in the Peng-Robinson-MHV2 equation-of-state model for a more
accurate description of the pure component behavior. The pure component
behavior and parameter requirements are described in Standard PengRobinson, or in Peng-Robinson Alpha Functions.
The MHV2 mixing rules are an example of modified Huron-Vidal mixing rules.
A brief introduction is provided in Huron-Vidal Mixing Rules. For more details,
see MHV2 Mixing Rules.
50
Peng-Robinson-Wong-Sandler
This model uses the Peng-Robinson equation-of-state for pure compounds.
The mixing rules are the predictive Wong-Sandler rules. Several alpha
functions can be used in the Peng-Robinson-Wong-Sandler equation-of-state
model for a more accurate description of the pure component behavior. The
pure component behavior and parameter requirements are described in PengRobinson, and in Peng-Robinson Alpha Functions.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The Wong-Sandler mixing rules are an example of modified Huron-Vidal
mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For
more details see Wong-Sandler Mixing Rules., this chapter.
Redlich-Kwong
The Redlich-Kwong equation-of-state can calculate vapor phase
thermodynamic properties for the following property methods: NRTL-RK,
UNIFAC, UNIF-LL, UNIQ-RK, VANL-RK, and WILS-RK. It is applicable for
systems at low to moderate pressures (maximum pressure 10 atm) for which
the vapor-phase nonideality is small. The Hayden-O'Connell model is
recommended for a more nonideal vapor phase, such as in systems
containing organic acids. It is not recommended for calculating liquid phase
properties.
The equation for the model is:
p
Where:
51
=
b
ai
bi
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TC
Tci
5.0
2000.0
TEMPERATURE
PC
pci
10
10
PRESSURE
References
O. Redlich and J.N.S. Kwong, "On the Thermodynamics of Solutions V. An
Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,
(1979), pp. 223 244.
Redlich-Kwong-Aspen
The Redlich-Kwong-Aspen equation-of-state is the basis for the RK-ASPEN
property method. It can be used for hydrocarbon processing applications. It is
also used for more polar components and mixtures of hydrocarbons, and for
light gases at medium to high pressures.
The equation is the same as Redlich-Kwong-Soave:
p
bi
52
ka,ij
kb,ij
For best results, binary parameters kij must be determined from phaseequilibrium data regression, such as VLE data.
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKA
Tci
TC
5.0
2000.0
TEMPERATURE
10
10
PCRKA
pci
PC
OMGRKA
-0.5
2.0
RKAPOL
i
i
OMEGA x
PRESSURE
-2.0
2.0
RKAKA0
ka,ij0
-5.0
5.0
RKAKA1
ka,ij1
-15.0
15.0
TEMPERATURE
RKAKB0
kb,ij0
-5.0
5.0
RKAKB1
kb,ij1
-15.0
15.0
TEMPERATURE
References
Mathias, P.M., "A Versatile Phase Equilibrium Equation-of-state", Ind. Eng.
Chem. Process Des. Dev., Vol. 22, (1983), pp. 385 391.
Redlich-Kwong-Soave
This is the standard Redlich-Kwong-Soave equation-of-state, and is the basis
for the RK-SOAVE property method. It is recommended for hydrocarbon
processing applications, such as gas-processing, refinery, and petrochemical
processes. Its results are comparable to those of the Peng-Robinson
equation-of-state.
The equation is:
Where:
53
ai
bi
kij = kji
;
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKSS
Tci
TC
5.0
2000.0
TEMPERATURE
10
10
PCRKSS
pci
PC
PRESSURE
OMRKSS
OMEGA x
-0.5
2.0
RKSKBV/1
kij(1)
-5.0
5.0
RKSKBV/2
kij(2)
TEMPERATURE
RKSKBV/3
kij(3)
TEMPERATURE
RKSKBV/4
Tk,lower
TEMPERATURE
RKSKBV/5
Tk,upper
1000
TEMPERATURE
RKSLBV/1
lij(1)
RKSLBV/2
lij(2)
TEMPERATURE
RKSLBV/3
lij(3)
TEMPERATURE
RKSLBV/4
Tl,lower
TEMPERATURE
RKSLBV/5
Tl,upper
1000
TEMPERATURE
References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-ofstate," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 1203.
54
Redlich-Kwong-Soave-Boston-Mathias
The Redlich-Kwong-Soave-Boston-Mathias equation-of-state is the basis for
the RKS-BM property method. It is the Redlich-Kwong-Soave equation-ofstate with the Boston-Mathias alpha function (see Soave Alpha Functions). It
is recommended for hydrocarbon processing applications, such as gasprocessing, refinery, and petrochemical processes. Its results are comparable
to those of the Peng-Robinson-Boston-Mathias equation-of-state.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The equation is:
p
Where:
ai
bi
kij = kji
55
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKS
Tci
TC
5.0
2000.0
TEMPERATURE
PCRKS
pci
PC
105
108
PRESSURE
OMGRKS
OMEGA x
-0.5
2.0
RKSKBV/1
kij(1)
-5.0
5.0
RKSKBV/2
kij(2)
TEMPERATURE
RKSKBV/3
kij(3)
TEMPERATURE
RKSKBV/4
Tk,lower
TEMPERATURE
RKSKBV/5
Tk,upper
1000
TEMPERATURE
RKSLBV/1
lij(1)
RKSLBV/2
lij(2)
TEMPERATURE
RKSLBV/3
lij(3)
TEMPERATURE
RKSLBV/4
Tl,lower
TEMPERATURE
RKSLBV/5
Tl,upper
1000
TEMPERATURE
References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-ofstate," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 1203.
Redlich-Kwong-Soave-Wong-Sandler
This equation-of-state model uses the Redlich-Kwong-Soave equation-of-state
for pure compounds. The predictive Wong-Sandler mixing rules are used.
Several alpha functions can be used in the Redlich-Kwong-Soave-WongSandler equation-of-state model for a more accurate description of the pure
component behavior. The pure component behavior and parameter
requirements are described in Standard Redlich-Kwong-Soave, and in Soave
Alpha Functions.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The Wong-Sandler mixing rules are an example of modified Huron-Vidal
mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For
more details, see Wong-Sandler Mixing Rules.
56
Redlich-Kwong-Soave-MHV2
This equation-of-state model uses the Redlich-Kwong-Soave equation-of-state
for pure compounds. The predictive MHV2 mixing rules are used. Several
alpha functions can be used in the RK-Soave-MHV2 equation-of-state model
for a more accurate description of the pure component behavior. The pure
component behavior and its parameter requirements are described in
Standard Redlich-Kwong-Soave, and in Soave Alpha Functions.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The MHV2 mixing rules are an example of modified Huron-Vidal mixing rules.
A brief introduction is provided in Huron-Vidal Mixing Rules. For more details,
see MHV2 Mixing Rules.
Schwartzentruber-Renon
The Schwartzentruber-Renon equation-of-state is the basis for the SR-POLAR
property method. It can be used to model chemically nonideal systems with
the same accuracy as activity coefficient property methods, such as the
WILSON property method. This equation-of-state is recommended for highly
non-ideal systems at high temperatures and pressures, such as in methanol
synthesis and supercritical extraction applications.
The equation for the model is:
p
Where:
a
ai
bi
ci
=
(for T < Tci)
ka,ij
lij
57
kb,ij
ka,ij
ka,ji
lij
-lji
kb,ij
kb,ji
The binary parameters ka,ij, kb,ij, and lij are temperature-dependent. In most
cases, ka,ij0 and lij0 are sufficient to represent the system of interest.
VLE calculations are independent of c. However, c does influence the fugacity
values and can be adjusted to (liquid) molar volumes. For a wide temperature
range, adjust ci0 to the molar volume at 298.15K or at boiling temperature.
The ai are calculated using the Extended Mathias Alpha Function, as described
in Soave Alpha Functions.
Warning: Using c1i and c2i can cause anomalous behavior in enthalpy and
heat capacity. Their use is strongly discouraged.
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKU
Tci
TC
5.0
2000.0
TEMPERATURE
PCRKU
pci
PC
105
108
PRESSURE
OMGRKU
OMEGA x
-0.5
2.0
RKUPP0
q0i
RKUPP1
q1i
RKUPP2
q2i
RKUC0
c0i
RKUC1
c1i
RKUC2
c2i
RKUKA0
ka,ij0
RKUKA1
ka,ij1
TEMPERATURE
RKUKA2
ka,ij2
TEMPERATURE
RKULA0
lij0
RKULA1
lij1
TEMPERATURE
RKULA2
lij2
TEMPERATURE
RKUKB0
kb,ij0
RKUKB1
kb,ij1
TEMPERATURE
RKUKB2
kb,ij2
TEMPERATURE
Absolute temperature units are assumed for ka,ij , lij , and kb,ij2.
For polar components (dipole moment >> 0), if you do not enter q0i, the
system estimates q0i, q1i, q2i from vapor pressures using the Antoine vapor
pressure model.
If you do not enter at least one of the binary parameters ka,ij0, ka,ij2, lij0,
lij2, kb,ij0, or kb,ij2 the system estimates ka,ij0, ka,ij2, lij0, and lij2 from the UNIFAC
or Hayden O'Connell models.
58
RKUC0, RKUC1, and RKUC2 are treated as having units m3/kmol. No unit
conversion to other molar volume units is done.
References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-ofstate," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203.
J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic Equation-of-State," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 1049 1955.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For RedlichKwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723.
Soave-Redlich-Kwong
The Soave-Redlich-Kwong equation-of-state is the basis of the SRK property
method. This model is based on the same equation of state as the RedlichKwong-Soave model. However, this model has several important differences.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
This equation-of-state can be used for hydrocarbon systems that include the
common light gases, such as H2S, CO2 and N2.
The form of the equation-of-state is:
Where:
Where:
;
59
Where:
;
The enthalpy, entropy, Gibbs energy, and molar volume of water are
calculated from the steam tables. The total properties are mole-fraction
averages of these values with the properties calculated by the equation of
state for other components. Fugacity coefficient is not affected.
For best results, the binary parameter kij must be determined from phase
equilibrium data regression (for example, VLE data). The Aspen Physical
Property System also has built-in kij for a large number of component pairs in
the SRK-ASPEN databank, regressed by AspenTech. These parameters are
used automatically with the SRK property method. Values of kij in the
databank can be different than those used with other models such as
Standard Redlich-Kwong-Soave or Standard Redlich-Kwong-Soave, and this
can produce different results.
The model uses option codes which are described in Soave-Redlich-Kwong
Option Codes.
60
Parameter
Name/
Element
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
SRKTC
Tci
TC
5.0
2000.0
TEMPERATURE
SRKPC
pci
PC
105
108
PRESSURE
SRKOMG
OMEGA
0.5
2.0
SRKZRA
zRA
RKTZRA
SRKKIJ/1
kij(1)
SRKKIJ/2
kij(2)
TEMPERATURE
SRKKIJ/3
kij(3)
TEMPERATURE
SRKKIJ/4
Tlower
TEMPERATURE
SRKKIJ/5
Tupper
1000
TEMPERATURE
SRKLIJ/1
lij(1)
SRKLIJ/2
lij(2)
TEMPERATURE
Parameter
Name/
Element
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
SRKLIJ/3
lij(3)
TEMPERATURE
SRKLIJ/4
Tlower
TEMPERATURE
SRKLIJ/5
Tupper
1000
TEMPERATURE
References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-ofstate," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For RedlichKwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723.
P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules
for multicomponent mixtures: the problem of invariance," Fluid Phase
Equilibria, Vol 67, (1991), pp. 31-44.
SRK-Kabadi-Danner
The SRK-Kabadi-Danner property model uses the SRK equation-of-state with
improved phase equilibrium calculations for mixtures containing water and
hydrocarbons. These improvements are achieved by using the Kabadi-Danner
mixing rules.
The form of the equation-of-state is:
Where:
Where:
;
The best values of kwj (w = water) were obtained from experimental data.
Results are given for seven homologous series.
kwj
Alkanes
0.500
Alkenes
0.393
Dialkenes
0.311
61
Homologous series
kwj
Acetylenes
0.348
Naphthenes
0.445
Cycloalkenes
0.355
Aromatics
0.315
Where:
gl , atm m6 x 105
CH4
1.3580
CH3
0.9822
CH2
1.0780
> CH
0.9728
>C<
0.8687
CH2 (cyclic)
0.7488
> CH (cyclic)
0.7352
CH = CH (cyclic)
0.6180
CH2 = CH2
1.7940
CH2 = CH
1.3450
CH2 = C<
0.9066
CH CH
1.6870
CH C
1.1811
CH =
0.5117
> C = (aromatic)
0.3902
This value is obtained from very little data. Might not be reliable.
The model uses option codes which are described in Soave-Redlich-Kwong
Option Codes.
SRK-Kabadi-Danner uses the same parameters as SRK, with added
interaction parameters. Do not specify values for the SRKLIJ parameters
when using SRK-KD.
62
Parameter
Name/
Element
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
SRKTC
Tci
TC
5.0
2000.0
TEMPERATURE
SRKPC
pci
PC
105
108
PRESSURE
SRKOMG
OMEGA
0.5
2.0
SRKWF
Gi
SRKZRA
zRA
RKTZRA
SRKKIJ/1
kij(1)
SRKKIJ/2
kij(2)
TEMPERATURE
SRKKIJ/3
kij(3)
TEMPERATURE
SRKKIJ/4
Tlower
TEMPERATURE
SRKKIJ/5
Tupper
TEMPERATURE
References
V. Kabadi and R. P. Danner, "A Modified Soave-Redlich-Kwong Equation of
State for Water-Hydrocarbon Phase Equilibria", Ind. Eng. Chem. Process Des.
Dev., Vol. 24, No. 3, (1985), pp. 537-541.
SRK-ML
The SRK-ML property model is the same as the Soave-Redlich-Kwong model
with two exceptions:
kij does not equal kji for non-ideal systems; they are unsymmetric, and a
different set of parameters is used, as shown below.
The lij are calculated from the equation lij = kji - kij
Parameter
Name/
Element
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
SMLTC
Tci
TC
5.0
2000.0
TEMPERATURE
SMLPC
pci
PC
105
108
PRESSURE
SMLOMG
OMEGA
0.5
2.0
SMLZRA
zRA
RKTZRA
SMLCMP
SRKMLP
-2.0
2.0
SRKGLP
SMLKIJ/1
kij(1)
SMLKIJ/2
kij(2)
TEMPERATURE
SMLKIJ/3
kij(3)
TEMPERATURE
SMLKIJ/4
Tlower
TEMPERATURE
SMLKIJ/5
Tupper
1000
TEMPERATURE
63
Additional Parameters
SMLZRA is used in Peneloux-Rauzy volume translation as described in SoaveRedlich-Kwong. This volume translation feature can be enabled by setting
option code 4 to 1, but is disabled by default (in which case this parameter is
not used).
SMLCMP is the Composition Independent Fugacity Calculation Flag. You can
use this flag to indicate the component for which its fugacity coefficient in the
mixture will be calculated such that it is independent of composition. The
calculated fugacity coefficient of that component is simply the purecomponent fugacity coefficient. This is a simplification. Enter a value of 1 for
the element i to indicate that the fugacity coefficient of component i is
independent of composition. This parameter defaults to zero.
SRKMLP is a polar parameter for the Mathias alpha function.
SRKGLP is a vector of parameters for the Gibbons-Laughton alpha function.
VPA/IK-CAPE Equation-of-State
The VPA/IK-CAPE equation of state is similar to the HF equation of state but
allows dimerization, tetramerization and hexamerization to occur
simultaneously. The main assumption of the model is that only molecular
association causes the gas phase nonideality. Attractive forces between the
molecules and the complexes are neglected.
There are three kinds of associations, which can be modeled:
To get the largest possible flexibility of the model all these kinds of
association can occur simultaneously, for example, in a mixture containing
acetic acid and HF. Up to five components can associate, and any number of
inert components are allowed. This is the only difference between this model
and the HF equation of state, which account only the hexamerization of HF.
Symbols
In the following description, these symbols are used:
64
yi
Apparent concentration
zin
zMij
p0
Reference pressure
Number of components
Association Equilibria
Every association equilibrium reaction
(1)
(2)
is described by the equilibrium constants
(3)
(4)
By setting
(5)
(6)
their temperature dependence can be reproduced.
To evaluate the true concentration of every complex zin, the following
nonlinear systems of equations are to be solved:
Total mass balance:
The sum of true concentrations is unity.
(7)
(8)
65
equations (3, 4). This is the main step to evaluate all the properties needed
for a calculation.
(9)
Fugacity Coefficient
As is well-known from thermodynamics, the fugacity coefficient can be
calculated by
(11)
66
(14)
and
(16)
(20)
67
using
(22)
and
(23)
(24)
Using the association model, more different species occur than can be
distinguished. Thus, the equivalent expression for the entropy of mixing
should be written with the true concentrations. As eq. 24 refers to 1 mole
monomers, the expression should be weighted by the compressibility factor
representing the true number of moles. The new expression is
(25)
For
ga we obtain
(26)
and, analogously,
(27)
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
DMER/1
Ai2
DMER/2
Bi2
TEMPERATURE
TMER/1
Ai4
TMER/2
Bi4
TEMPERATURE
HMER/1
Ai6
HMER/2
Bi6
TEMPERATURE
References
M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing
Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,
Vol. 77, (1992) pp. 53119.
V. V. De Leeuw and S. Watanasiri, "Modeling Phase Equilibria and Enthalpies
of the System Water and Hydrofluoric Acid Using an HF Equation-of-state in
Conjunction with the Electrolyte NRTL Activity Coefficient Model," Paper
Presented at the 13th European Seminar on Applied Thermodynamics, June
912, Carry-le-Rouet, France, 1993.
68
(2)
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCPR
Tci
TC
5.0
2000.0
TEMPERATURE
PCPR
pci
PC
105
108
PRESSURE
OMGPR
OMEGA X
-0.5
2.0
69
Boston-Mathias Extrapolation
For light gases at high reduced temperatures (> 5), equation 4 gives
unrealistic results. The boundary conditions are that attraction between
molecules should vanish for extremely high temperatures, and reduces
asymptotically to zero. Boston and Mathias derived an alternative function for
temperatures higher than critical:
(6)
With
=
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
PRGLP/1
PRGLP/2
PRGLP/3
PRGLP/4
PRGLP/5
Tlower
TEMPERATURE
PRGLP/6
Tupper
1000
TEMPERATURE
70
Where the L, M, and N are parameters that vary depending on the equation of
state and whether the temperature is above or below the critical temperature
of the component.
For Peng-Robinson equation of state:
Subcritical T
Supercritical T
0.272838
0.373949
(0)
0.924779
4.73020
(0)
1.19764
-0.200000
L(1)
0.625701
0.0239035
(1)
0.792014
1.24615
(1)
2.46022
-8.000000
L(0)
M
M
N
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
PRTWUP/1
PRTWUP/2
PRTWUP/3
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCPR
Tci
TC
5.0
2000.0
TEMPERATURE
PCPR
pci
PC
10
10
PRESSURE
71
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
PRMCP/1
c1,i
PRMCP/2
c2,i
PRMCP/3
c3,i
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCPR
Tci
TC
5.0
2000.0
TEMPERATURE
10
10
PCPR
pci
PC
OMGPR
OMEGA X
-0.5
2.0
PRESSURE
PRSRP/1
PRSRP/2
PRSRP/3
72
Model name
Standard PR/
Boston-Mathias
ESPR0, ESPR
ESPRWS0, ESPRWS
ESPRV20, ESPRV2
0
0
0
Extended GibbonsLaughton
ESPR0, ESPR
ESPR0, ESPR
ESPR0, ESPR
Alpha function
Model name
Mathias-Copeman
ESPRWS0, ESPRWS
ESPRV20, ESPRV2
2
2
SchwartzentruberRenonWatanasiri
ESPRWS0, ESPRWS
ESPRV20, ESPRV2
3 (default)
3 (default)
References
J. F. Boston and P.M. Mathias, "Phase Equilibria in a Third-Generation Process
Simulator" in Proceedings of the 2nd International Conference on Phase
Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin,
(17-21 March 1980) pp. 823-849.
D.-Y. Peng and D.B. Robinson, "A New Two-Constant Equation-of-state," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 59-64.
P.M. Mathias and T.W. Copeman, "Extension of the Peng-Robinson Equationof-state To Complex Mixtures: Evaluation of the Various Forms of the Local
Composition Concept",Fluid Phase Eq., Vol. 13, (1983), p. 91.
J. Schwartzentruber, H. Renon, and S. Watanasiri, "K-values for Non-Ideal
Systems:An Easier Way," Chem. Eng., March 1990, pp. 118-124.
G. Soave, "Equilibrium Constants for a Modified Redlich-Kwong Equation-ofstate," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203.
C.H. Twu, J. E. Coon, and J.R. Cunningham, "A New Cubic Equation of State,"
Fluid Phase Equilib., Vol. 75, (1992), pp. 65-79.
C.H. Twu, D. Bluck, J.R. Cunningham, and J.E. Coon, "A Cubic Equation of
State with a New Alpha Function and a New Mixing Rule," Fluid Phase Equilib.,
Vol. 69, (1991), pp. 33-50.
(2)
73
(4)
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TC
Tci
5.0
2000.0
TEMPERATURE
PC
pci
105
108
PRESSURE
Soave Modification
The parameter i is a temperature function introduced by Soave in the
Redlich-Kwong equation-of-state to improve the correlation of the pure
component vapor pressure:
(5)
Equation 3 still holds. The parameter mi can be correlated with the acentric
factor:
(6)
Equations 1, 2, 3, 5 and 6 are the standard Redlich-Kwong-Soave
formulation. The Soave alpha function is adequate for hydrocarbons and other
nonpolar compounds, but is not sufficiently accurate for polar compounds.
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKS
Tci
TC
5.0
2000.0
TEMPERATURE
PCRKS
pci
PC
OMGRKS
OMEGA X
10
10
-0.5
2.0
PRESSURE
Boston-Mathias Extrapolation
For light gases at high reduced temperatures (> 5), equation 5 gives
unrealistic results. The boundary conditions are that attraction between
molecules should vanish for extremely high temperatures, and
reduces
asymptotically to zero. Boston and Mathias derived an alternative function for
temperatures higher than critical:
(7)
With
di
ci
Where:
74
mi
Computed by equation 6
Equation 5
(10)
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKA
TC
5.0
2000.0
TEMPERATURE
Tci
PCRKA
pci
PC
OMGRKA
OMEGA X
-0.5
2.0
-2.0
2.0
10
10
PRESSURE
RKAPOL for Redlich-Kwong-Aspen, SRKPOL for SRK and SRKKD, SRKMLP for
SRK-ML, RKSPOL for RKS-BM, or RKSSPO for RK-SOAVE.
75
(13)
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKU
Tci
TC
5.0
2000.0
TEMPERATURE
10
10
PCRKU
pci
PC
PRESSURE
OMGRKU
OMEGA X
-0.5
2.0
RKUPP0
p1,i
RKUPP1
p2,i
RKUPP2
p3,i
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKS
Tci
TC
5.0
2000.0
TEMPERATURE
10
PCRKS
pci
PC
10
RKSMCP/1
c1,i
PRESSURE
RKSMCP/2
c2,i
RKSMCP/3
c3,i
76
(17)
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
TCRKS
Tci
TC
5.0
2000.0
TEMPERATURE
10
10
PCRKS
pci
PC
PRESSURE
OMGRKS
OMEGA X
-0.5
2.0
RKSSRP/1
p1,i
RKSSRP/2
p2,i
RKSSRP/3
p3,i
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
SRKGLP/1
SRKGLP/2
SRKGLP/3
SRKGLP/4
SRKGLP/5
Tlower
TEMPERATURE
SRKGLP/6
Tupper
1000
TEMPERATURE
77
Where the L, M, and N are parameters that vary depending on the equation of
state and whether the temperature is above or below the critical temperature
of the component.
For Soave-Redlich-Kwong:
Subcritical T
Supercritical T
0.544000
0.379919
(0)
1.01309
5.67342
(0)
0.935995
-0.200000
L(1)
0.544306
0.0319134
(1)
0.802404
1.28756
(1)
3.10835
-8.000000
L(0)
M
M
N
Model Name
original RK
ESRK0, ESRK
standard RKS
ESRKSTD0, ESRKSTD
*
1, 2 (default)
standard RKS/Boston-Mathias *
ESRKSWS0, ESRKSWS
ESRKSV10, ESRKV1
ESRKSV20, ESRKSV2
0
1
1
1
Mathias/Boston-Mathias
ESRKA0, ESRKA
Extended Mathias/BostonMathias
ESRKU0, ESRKU
Mathias-Copeman
ESRKSV10, ESRKSV1
ESRKSV20, ESRKSV2
2
2
Schwartzentruber-RenonWatanasiri
ESPRWS0, ESPRWS
ESRKSV10, ESRKSV1
ESRKSV20, ESRKSV2
3 (default)
3 (default)
3 (default)
Twu generalized
78
References
J. F. Boston and P.M. Mathias, "Phase Equilibria in a Third-Generation Process
Simulator" in Proceedings of the 2nd International Conference on Phase
Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin,
(17-21 March 1980), pp. 823-849.
P. M. Mathias, "A Versatile Phase Equilibrium Equation-of-state", Ind. Eng.
Chem. Process Des. Dev., Vol. 22, (1983), pp. 385391.
P.M. Mathias and T.W. Copeman, "Extension of the Peng-Robinson Equationof-state To Complex Mixtures: Evaluation of the Various Forms of the Local
Composition Concept", Fluid Phase Eq., Vol. 13, (1983), p. 91.
O. Redlich and J. N. S. Kwong, "On the Thermodynamics of Solutions V. An
Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,
(1949), pp. 223244.
J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic Equation-of-state," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 10491055.
J. Schwartzentruber, H. Renon, and S. Watanasiri, "K-values for Non-Ideal
Systems:An Easier Way," Chem. Eng., March 1990, pp. 118-124.
G. Soave, "Equilibrium Constants for a Modified Redlich-Kwong Equation-ofstate," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203.
C.H. Twu, W.D. Sim, and V. Tassone, "Getting a Handle on Advanced Cubic
Equations of State", Chemical Engineering Progress, Vol. 98 #11 (November
2002) pp. 58-65.
79
Where:
(5)
Peng-Robinson
Redlich-Kwong-Soave
This expression can be used at any pressure as a mixing rule for the
parameter. The mixing rule for b is fixed by equation 3. Even when used at
other pressures, this expression contains the excess Gibbs energy at infinite
pressure. You can use any activity coeffecient model to evaluate the excess
Gibbs energy at infinite pressure. Binary interaction coefficients must be
regressed. The mixing rule used contains as many binary parameters as the
activity coefficient model chosen.
This mixing rule has been used successfully for polar mixtures at high
pressures, such as systems containing light gases. In theory, any activity
coefficient model can be used. But the NRTL equation (as modified by Huron
and Vidal) has demonstrated better performance.
The Huron-Vidal mixing rules combine extreme flexibility with thermodynamic
consistency, unlike many other mole-fraction-dependent equation-of-state
mixing rules. The Huron-Vidal mixing rules do not allow flexibility in the
description of the excess molar volume, but always predict reasonable excess
volumes.
The Huron-Vidal mixing rules are theoretically incorrect for low pressure,
because quadratic mole fraction dependence of the second virial coefficient (if
derived from the equation-of-state) is not preserved. Since equations of state
are primarily used at high pressure, the practical consequences of this
drawback are minimal.
The Gibbs energy at infinite pressure and the Gibbs energy at an arbitrary
high pressure are similar. But the correspondence is not close enough to
make the mixing rule predictive.
There are several methods for modifying the Huron-Vidal mixing rule to make
it more predictive. The following three methods are used in Aspen Physical
Property System equation-of-state models:
80
These mixing rules are discussed separately in the following sections. They
have major advantages over other composition-dependent equation-of-state
mixing rules.
References
M.- J. Huron and J. Vidal, "New Mixing Rules in Simple Equations of State for
representing Vapour-liquid equilibria of strongly non-ideal mixtures," Fluid
Phase Eq., Vol. 3, (1979), pp. 255-271.
The advantage is that the expressions for mixture and pure component
fugacities do not contain the pressure. They are functions of compacity V/b
and :
(2)
Where:
(3)
and
(4)
With:
(5)
The constants 1 and 2, which depend only on the equation-of-state (see
Huron-Vidal Mixing Rules) occur in equations 2 and 4.
Instead of using infinite pressure for simplification of equation 1, the condition
of zero pressure is used. At p = 0 an exact relationship between the
compacity and can be derived. By substitution the simplified equation q()
is obtained, and equation 1 becomes:
(6)
81
Predictive Soave-Redlich-Kwong-Gmehling
Mixing Rules
These mixing rules by Holderbaum and Gmehling (1991) use a relationship
between the excess Helmholtz energy and equation-of-state. They do not use
a relationship between equation-of-state properties and excess Gibbs energy,
as in the Huron-Vidal mixing rules. The pressure-explicit expression for the
equation-of-state is substituted in the thermodynamic equation:
(1)
82
Where both Ai* and Am are calculated by using equation 1. Ai* and Am are
written in terms of equation-of-state parameters.
The simplification of constant packing fraction (Vm / b) is used:
(3)
With:
(4)
Therefore:
(5)
The mixing rule is:
(6)
Where
The result is a predictive mixing rule for cubic equations of state. But the
original UNIFAC formulation gives the best performance for any binary pair
with interactions available from UNIFAC. Gas-solvent interactions are
unavailable. However, it has poor accuracy for highly asymmetric such as CH4
83
References
K. Fischer, "Die PSRK-Methode: Eine Zustandsgleichung unter Verwendung
des UNIFAC-Gruppenbeitragsmodells," (Dsseldorf: VDI Fortschrittberichte,
Reihe 3: Verfahrenstechnik, Nr. 324, VDI Verlag GmbH, 1993).
T. Holderbaum and J. Gmehling, "PSRK: A Group Contribution Equation-ofstate based on UNIFAC," Fluid Phase Eq., Vol. 70, (1991), pp. 251-265.
J. Li, K. Fischer, and J. Gmehling, "Prediction of vapor-liquid equilibria for
asymmetric systems at low and high pressures with the PSRK model," Fluid
Phase Equilib., 1998, 143, 71-82
84
Like Huron and Vidal, the limiting case of infinite pressure is used. This
simplifies the expressions for Ai* and Am. Equation 2 becomes:
(3)
Where
The relationship between the equation-of-state at low pressure and the virial
coefficient is:
(6)
(7)
Wong and Sandler discovered the following mixing rule to satisfy equation 4
(using equations 6 and 7):
85
influence excess molar volume behavior. For calculations where densities are
important, check whether they are realistic.
References
D. S. Wong and S. I. Sandler, "A Theoretically Correct New Mixing Rule for
Cubic Equations of State for Both Highly and Slightly Non-ideal Mixtures,"
AIChE J., Vol. 38, (1992), pp. 671 680.
D. S. Wong, H. Orbey, and S. I. Sandler, "Equation-of-state Mixing Rule for
Non-ideal Mixtures Using Available Activity Coefficient Model Parameters and
That Allows Extrapolation over Large Ranges of Temperature and Pressure",
Ind Eng Chem. Res., Vol. 31, (1992), pp. 2033 2039.
H. Orbey, S. I. Sandler and D. S. Wong, "Accurate Equation-of-state
Predictions at High Temperatures and Pressures Using the Existing UNIFAC
Model," Fluid Phase Eq., Vol. 85, (1993), pp. 41 54.
86
Model
Type
Bromley-Pitzer
Electrolyte
Chien-Null
Arithmetic
COSMO-SAC
Regular solution
Electrolyte NRTL
Electrolyte
ENRTL-SAC
Hansen
Regular solution
Ideal Liquid
Ideal
NRTL (Non-Random-Two-Liquid)
Local composition
NRTL-SAC
Segment contribution
Pitzer
Electrolyte
Arithmetic
Redlich-Kister
Arithmetic
Scatchard-Hildebrand
Regular solution
Three-Suffix Margules
Arithmetic
UNIFAC
Group contribution
Group contribution
Group contribution
UNIQUAC
Local composition
Electrolyte
Van Laar
Regular solution
Arithmetic
Model
Type
Wilson
Local composition
Local composition
Where:
Tref
298.15K
Specify Comp ID i and Comp ID j on this form, using the same order that
appears on the Components Specifications Selection sheet form.
ion
ion
Cation-Anion Parameters
GMBPB0
GMBPB1
GMBPB2
GMBPB3
(0)
(1)
(2)
(3)
Cation-Cation Parameters
GMBPTH
cc'
Anion-Anion Parameters
GMBPTH
aa'
(0)
87
(1)
Working Equations
The complete Pitzer equation (Frst and Renon, 1982) for the excess Gibbs
energy is (see also equation 4):
(1)
Where:
GE
Gas constant
Temperature
nw
Kilograms of water
zi
molality of ion i
Where:
xi
xw
Mw
ni
Moles of ion i
Where:
Bij
88
f(ij(0),ij(1),ij(2),ij(3))
Therefore, the simplified Pitzer equation has two types of binary interaction
parameters, 's and ''s. There are no ternary interaction parameters with
the simplified Pitzer equation.
Note that the Pitzer model parameter databank described in Physical Property
Data, Chapter 1, is not applicable to the simplified Pitzer equation.
A built-in empirical correlation estimates the (0) and (1) parameters for
cation-anion pairs from the Bromley ionic parameters, ion and ion (Bromley,
1973). The estimated values of (0)'s and (1)'s are overridden by the user's
input. For parameter naming and requirements, see Bromley-Pitzer Activity
Coefficient Model.
References
L.A. Bromley, "Thermodynamic Properties of Strong Electrolytes in Aqueous
Solution, " AIChE J., Vol. 19, No. 2, (1973), pp. 313 320.
W. Frst and H. Renon, "Effects of the Various Parameters in the Application
of Pitzer's Model to Solid-Liquid Equilibrium. Preliminary Study for Strong 1-1
Electrolytes," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),
pp. 396-400.
Parameter Conversion
For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), the parameter
(3) corresponds to Pitzer's (1); (2) is the same in both Aspen Physical
Property System and original Pitzer models. Pitzer refers to the n-m
electrolyte parameters as (1), (2), (0). (0) and (2) retain their meanings in
both models, but Pitzer's (1) is Aspen Physical Property System (3). Be
careful to make this distinction when entering n-m electrolyte parameters.
Chien-Null
The Chien-Null model calculates liquid activity coefficients and it can be used
for highly non-ideal systems. The generalized expression used in its derivation
can be adapted to represent other well known formalisms for the activity
coefficient by properly defining its binary terms. This characteristic allows the
model the use of already available binary parameters regressed for those
other liquid activity models with thermodynamic consistency.
The equation for the Chien-Null liquid activity coeficient is:
Where:
Rji = Aji / Aij
Aii = 0
89
ij = aij + bij / T
Cij = cij + dij (T - 273.15 K)
cji = cij
dji = dij
The binary parameters CHNULL/1, CHNULL/2, and CHNULL/3 can be
determined from regression of VLE and/or LLE data. Also, if you have
parameters for many of the mixture pairs for the Margules, Van Laar,
Scatchard-Hildebrand, and NRTL (Non-Random-Two-Liquid) activity models,
you can use them directly with the Chien-Null activity model after selecting
the proper code (ICHNUL) to identify the source model and entering the
appropriate activity model parameters.
90
Parameter
Name/Element
Upper
Limit
Units
ICHNUL
CHNULL/1
aij
CHNULL/2
bij
CHNULL/3
Vij
i = ai
Parameter
Name/Element
Lower
Limit
Units
GMCONS
ai
1.0
COSMO-SAC
Cosmo-SAC is a solvation model that describes the electric fields on the
molecular surface of species that are polarizable. It requires a fairly
complicated quantum mechanical calculation, but this calculation must be
done only once for a particular molecule; then the results can be stored. In its
final form, it uses individual atoms as the building blocks for predicting phase
equilibria instead of functional groups. This model formulation provides a
considerably larger range of applicability than group-contribution methods.
The calculation for liquid nonideality is only slightly more computationally
intensive than activity-coefficient models such as NRTL or UNIQUAC. Cosmo-
91
With
92
Where:
iSG
i(m)
m in
S(m)
m in
pi(m)
pi(m)
W(m,n)
WHB(m,n)
= Coordination number, 10
Vi
Ai
aeff
Veff
Aeff
'
m and n
The Cosmo-SAC model does not require binary parameters. For each
component, it has six input parameters. CSACVL is the component volume
parameter which is always defined in cubic angstroms, regardless of chosen
units sets. SGPRF1 to SGPRF5 are five component sigma profile parameters;
each can store up to 12 points of sigma profile values. All six input
parameters are obtained from COSMO calculation. The Aspen Physical
Property System includes a database of sigma profiles for over 1400
compounds from Mullins et al. (2006). The parameters were obtained by
permission from the Virginia Tech Sigma Profile Database website
(http://www.design.che.vt.edu/VT-2004.htm). Aspen Technology, Inc. does
not claim proprietary rights to these parameters.
Note: Starting in version V7.2, additional parameters SGPRF6 through
SGPRF9 and SGPR10 through SGPR14 are available in Aspen Plus and
Aspen Properties, as part of a planned expansion to allow larger sigma
profiles to be used. However, the model is not yet updated to use these
parameters and you should not yet try to use sigma profiles larger than 51
elements.
93
Parameter
Symbol
Name/Element
Default
MDS Lower
Limit
Upper
Limit
Units
CSACVL
Vi
VOLUME (3)
SGPRF1
Ai pi(1-12)
SGPRF2
Ai pi(13-24)
SGPRF3
Ai pi(25-36)
SGPRF4
Ai pi(37-48)
SGPRF5
Ai pi(49-51)
Option Codes
The primary version of COSMO-SAC is the model by Lin and Sandler (2002).
Two other versions are available using an option code, as detailed in the table
below:
Option
Code
Description
References
A. Klamt, "Conductor-like Screening Model for Real Solvents: A New Approach
to the Quantitative Calculation of Solvation Phenomena," J. Phys. Chem. 99,
2224 (1995).
S.-T. Lin, P. M. Mathias, Y. Song, C.-C. Chen, and S. I. Sandler,
"Improvements of Phase-Equilibrium Predictions for Hydrogen-Bonding
Systems from a New Expression for COSMO Solvation Models," presented at
the AIChE Annual Meeting, Indianapolis, IN, 3-8 November (2002).
S.-T. Lin and S. I. Sandler, "A Priori Phase Equilibrium Prediction from a
Segment Contribution Solvation Model," Ind. Eng. Chem. Res. 41, 899
(2002).
E. Mullins, et al. "Sigma-Profile Database for Using COSMO-Based
Thermodynamic Methods," Ind. Eng. Chem. Res. 45, 4389 (2006).
94
The electrolyte NRTL model uses the infinite dilution aqueous solution as the
reference state for ions. It adopts the Born equation to account for the
transformation of the reference state of ions from the infinite dilution mixed
solvent solution to the infinite dilution aqueous solution.
Water must be present in the electrolyte system in order to compute the
transformation of the reference state of ions. Thus, it is necessary to
introduce a trace amount of water to use the model for nonaqueous
electrolyte systems.
The Aspen Physical Property System uses the electrolyte NRTL model to
calculate activity coefficients, enthalpies, and Gibbs energies for electrolyte
systems. Model development and working equations are provided in
Theoretical Basis and Working Equations.
The adjustable parameters for the electrolyte NRTL model include the:
95
Where:
Tref = 298.15K
Many parameter pairs are included in the electrolyte NRTL model parameter
databank (see Physical Property Data, Chapter 1).
Parameter
Symbol
No. of
Default MDS Units
Name
Elements
Dielectric Constant Unary Parameters
CPDIEC
AB
BB
CB
1
Ionic Born Radius Unary Parameters
298.15
TEMPERATURE
RADIUS
ri
1
Molecule-Molecule Binary Parameters
3x10-10
LENGTH
NRTL/1
ABB'
AB'B
BBB'
TEMPERATURE
BB'B
TEMPERATURE
NRTL/3
BB' = B'B
.3
NRTL/4
TEMPERATURE
NRTL/5
FBB'
TEMPERATURE
FB'B
TEMPERATURE
GBB'
TEMPERATURE
GB'B
TEMPERATURE
GMELCC
NRTL/2
NRTL/6
GMELCD
GMELCE
GMELCN
Cca,B
CB,ca
Dca,B
TEMPERATURE
DB,ca
TEMPERATURE
Eca,B
EB,ca
ca,B = B,ca
.2
GMELCD
GMELCE
96
Cca',ca''
Cca'',ca'
Cc'a,c''a
Cc''a,c'a
Dca',ca''
TEMPERATURE
Dca'',ca'
TEMPERATURE
Dc'a,c''a
TEMPERATURE
Dc''a,c'a
TEMPERATURE
Eca',ca''
Parameter
Symbol
No. of
Default MDS Units
Name
Elements
Dielectric Constant Unary Parameters
GMELCN
Eca'',ca'
Ec'a,c''a
Ec''a,c'a
ca',ca'' = ca'',ca'
c'a,c''a = c''a,c'a
.2
.2
Certain Electrolyte NRTL activity coefficient model parameters are used with
reciprocal temperature terms:
CPDIEC
NRTL/2
97
This leads to
(2)
Note: The notation using * to denote an unsymmetric reference state is wellaccepted in electrolyte thermodynamics and will be maintained here. The
reader should be warned not to confuse it with the meaning of * in classical
thermodynamics according to IUPAC/ISO, referring to a pure component
property. In fact in the context of G or , the asterisk as superscript is never
used to denote pure component property, so the risk of confusion is minimal.
For details on notation, see Chapter 1 of Physical Property Methods.
References
C.-C. Chen, H.I. Britt, J.F. Boston, and L.B. Evans, "Local Compositions Model
for Excess Gibbs Energy of Electrolyte Systems: Part I: Single Solvent, Single
Completely Dissociated Electrolyte Systems:, AIChE J., Vol. 28, No. 4, (1982),
p. 588-596.
C.-C. Chen, and L.B. Evans, "A Local Composition Model for the Excess Gibbs
Energy of Aqueous Electrolyte Systems," AIChE J., Vol. 32, No. 3, (1986), p.
444-459.
B. Mock, L.B. Evans, and C.-C. Chen, "Phase Equilibria in Multiple-Solvent
Electrolyte Systems: A New Thermodynamic Model," Proceedings of the 1984
Summer Computer Simulation Conference, p. 558.
B. Mock, L.B. Evans, and C.-C. Chen, "Thermodynamic Representation of
Phase Equilibria of Mixed-Solvent Electrolyte Systems," AIChE J., Vol. 32, No.
10, (1986), p. 1655-1664.
98
(3)
with
(4)
(5)
Where:
xi
Ms
Debye-Hckel parameter
NA
Avogadro's number
ds
Qe
Electron charge
Temperature
Boltzmann constant
Ix
xi
zi
The Born equation is used to account for the Gibbs energy of transfer of ionic
species from the infinite dilution state in a mixed-solvent to the infinite
dilution state in aqueous phase.
(7)
Where:
ri
99
The expression for the activity coefficient can be derived from (7):
(8)
The Debye-Hckel theory is based on the infinite dilution reference state for
ionic species in the actual solvent media. For systems with water as the only
solvent, the reference state is the infinite dilution aqueous solution. For
mixed-solvent systems, the reference state for which the Debye-Hckel
theory remains valid is the infinite dilution solution with the corresponding
mixed-solvent composition. However, the molecular weight Ms, the mass
density ds, and the dielectric constant s for the single solvent need to be
extended for mixed solvents; simple composition average mixing rules are
adequate to calculate them as follows:
(6a)
(7a)
(8a)
(8b)
(8c)
(8d)
Where:
xm
Mm
Vw*
xnws
Vnwsl
Liquid molar volume for the mixture of all nonwater solvents. It is calculated using the
Rackett equation.
Vm
100
Where:
Xj
xjCj
(Cj = zj for ions and Cj = unity for molecules)
Gji
ji
ji
Nonrandomness factor
gji and gii are energies of interaction between species j and i, and i and i,
respectively. Both gij and ij are inherently symmetric (gij = gji and ij = ji).
Similarly,
(10)
Where:
Gji,ki
ji,ki
ji,ki
Nonrandomness factor
101
(12)
(13)
(16)
To obtain an expression for the excess Gibbs energy, let the residual Gibbs
energies, per mole of cells of central cation, anion, or solvent, respectively, be
,
, and
effective local mole fractions:
102
za
The molar excess Gibbs energy can be found by summing all changes in
residual Gibbs energy per mole that result when the electrolyte and solvent in
their reference state are mixed to form the existing electrolyte system. The
expression is:
(23)
Using the previous relation for the excess Gibbs energy and the expressions
for the residual and reference Gibbs energy (equations 17 to 19 and 20 to
22), the following expression for the excess Gibbs energy is obtained:
(24)
103
The binary parameters ca,B , ca,B and B,ca are now the adjustable parameters
for an apparent binary system of a single electrolyte and a single solvent.
The excess Gibbs energy expression (equation 24) must now be normalized
to the infinite dilution reference state for ions:
(32)
(35)
(36)
Multicomponent Systems
The Electrolyte NRTL model can be extended to handle multicomponent
systems.
The excess Gibbs energy expression is:
104
(37)
Where:
j and k can be any species (a, C, or B)
The activity coefficient equation for molecular components is given by:
(38)
Where:
105
(41)
(42)
(43)
(44)
(45)
(46)
(47)
(48)
Parameters
The model adjustable parameters include:
Note that for the electrolyte-electrolyte pair parameters, the two electrolytes
must share either one common cation or one common anion.
Each type of the electrolyte NRTL parameter consists of both the
nonrandomness factor, , and energy parameters, .
106
Obtaining Parameters
In the absence of electrolytes, the electrolyte NRTL model reduces to the
NRTL equation which is widely used for non-electrolyte systems. Therefore,
molecule-molecule binary parameters can be obtained from binary
nonelectrolyte systems.
Electrolyte-molecule pair parameters can be obtained from data regression of
apparent single electrolyte systems.
Electrolyte-electrolyte pair parameters are required only for mixed
electrolytes with a common ion. Electrolyte-electrolyte pair parameters can
affect trace ionic activity precipitation. Electrolyte-electrolyte pair parameters
can be obtained by regressing solubility data of multiple component
electrolyte systems.
When the electrolyte-molecule and electrolyte-electrolyte pair parameters are
zero, the electrolyte NRTL model reduces to the Debye-Hckel limiting law.
Calculation results with electrolyte-molecule and electrolyte-electrolyte pair
parameters fixed to zero should be adequate for very dilute weak electrolyte
systems; however, for concentrated systems, pair parameters are required
for accurate representation.
See Physical Property Data, Chapter 1, for the pair parameters available from
the electrolyte NRTL model databank. The table contains pair parameters for
some electrolytes in aqueous solution at 100C. These values were obtained
by using the Aspen Physical Property Data Regression System (DRS) to
regress vapor pressure and mole fraction data at T=100C with SYSOP15S
(Handbook of Chemistry and Physics, 56th Edition, CRC Press, 1975, p. E-1).
In running the DRS, standard deviations for the temperature (C), vapor
pressure (mmHg), and mole fractions were set at 0.2, 1.0, and 0.001,
respectively. In addition, complete dissociation of the electrolyte was
assumed for all cases.
107
Option code 1. Use this option code to specify the default values of pair
parameters for water/solute and solvent/solute; the solute represents a
cation/anion pair. The value (1) sets the default values to zero and the value
(3) sets the default values for water/solute to (8,-4) and for solvent/solute to
(10,-2). The value (3) is the default choice of the option code.
Option code 2. Not used.
Option code 3. Always leave this option code set to the value (1) to use the
solvent/solvent binary parameters obtained from NRTL parameters.
ENRTL-SAC
eNRTL-SAC (ENRTLSAC, patent pending) is an extension of the nonrandom
two-liquid segment activity coefficient model (NRTL-SAC, patent pending) by
Chen and Song (Ind. Eng. Chem. Res., 2004, 43, 8354) to include
electrolytes in the solution. It can be used in usable in Aspen Properties and
Aspen Polymers. It is intended for the computation of ionic activity
coefficients and solubilities of electrolytes, organic and inorganic, in common
solvents and solvent mixtures. In addition to the three types of molecular
parameters defined for organic nonelectrolytes in NRTL-SAC (hydrophobicity
X, hydrophilicity Z, and polarity Y- and Y+), an electrolyte parameter, E, is
introduced to characterize both local and long-range ion-ion and ion-molecule
interactions attributed to ionized segments of electrolytes.
In applying the segment contribution concept to electrolytes, a new
conceptual electrolyte segment e corresponding to the electrolyte parameter
E, is introduced. This conceptual segment e would completely dissociate to a
cationic segment (c) and an anionic segment (a), both of unity charge. All
electrolytes, organic or inorganic, symmetric or unsymmetric, univalent or
multivalent, are to be represented with this conceptual uni-univalent
electrolyte segment e together with previously defined hydrophobic segment
x, polar segments y- and y+, and hydrophilic segment z in NRTL-SAC.
A major consideration in the extension of NRTL-SAC for electrolytes is the
treatment of the reference state for activity coefficient calculations. While the
conventional reference state for nonelectrolyte systems is the pure liquid
component, the conventional reference state for electrolytes in solution is the
infinite-dilution aqueous solution and the corresponding activity coefficient is
unsymmetric. The equation for the logarithm of the unsymmetric activity
coefficient of an ionic species is
With
108
109
Where:
110
I, J
Component index
i, j, m, c, a
i, j
m,c,a
I*
I*lc
NRTL term
I*PDH
Pitzer-Debye-Hckel term
I*FH
Flory-Huggins term
rI
xI
rI,i
xi
ij
ij
Debye-Hckel parameter
Ix
NA
Avogadros number
Qe
rc
ra
x
z
yz
y+
z
x
y+
12
21
12 = 21
1.643
6.547
-2.000
2.000
1.643
1.834
10.949 1.787
1.787
1.834
0.2
0.2
0.3
0.2
0.3
111
segments and the electrolyte segment e are determined from literature data
or preset as follows:
Segment (1) x
Segment (2) e
ye
y+
e
z
e
12
21
12 = 21
15
12
12
8.885
-3
-3
-4.549
0.2
0.2
0.2
0.2
Option codes
There are three option codes in ENRTLSAC. The first is used to enable or
disable the Flory-Huggins term. The other two are only used internally and
you should not change their values. The Flory-Huggins term is included by
default in eNRTL-SAC model. You can remove this term using the first option
code. The table below lists the values for the first option code.
0
Others
References
C.-C. Chen and Y. Song, "Solubility Modeling with a Nonrandom Two-Liquid
Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004).
C.-C. Chen and Y. Song, "Extension of Nonrandom Two-Liquid Segment
Activity Coefficient Model for Electrolytes," Ind. Eng. Chem. Res. 44, 8909
(2005).
Hansen
Hansen is a solubility parameter model and is commonly used in the solvent
selection process. It is based on the regular solution theory and Hansen
solubility parameters. This model has no binary parameters and its application
merely follows the empirical guide like dissolves like.
The Hansen model calculates liquid activity coefficients. The equation for the
Hansen model is:
with
112
Where:
Vi
id
ip
ih
xi
= Gas constant
= Temperature
The Hansen model does not require binary parameters. For each component,
it has four input parameters.
Parameter
Symbol
Name/Element
Default
MDS
Lower Upper
Limit
Limit
Units
PRESSURE^0.5
PRESSURE^0.5
DELTAH
id
ip
ih
PRESSURE^0.5
HANVOL
Vi
VOLUME
DELTAD
DELTAP
Option codes
The Hansen volume is implemented as an input parameter. If the Hansen
volume is not input by the user it will be calculated by an Aspen Plus internal
method. You can also request the Aspen Plus method using Option Codes in
Aspen Plus Interface. The table below lists the option codes.
113
Other values
Reference
Frank, T. C.; Downey, J. R.; Gupta, S. K. "Quickly Screen Solvents for
Organic Solids," Chemical Engineering Progress 1999, December, 41.
Hansen, C. M. Hansen Solubility Parameters: A Users Handbook; CRC Press,
2000.
Ideal Liquid
This model is used in Raoult's law. It represents ideality of the liquid phase.
This model can be used for mixtures of hydrocarbons of similar carbon
number. It can be used as a reference to compare the results of other activity
coefficient models.
The equation is:
ln
i = 0
for Tlower
T Tupper
Where:
Gij
ij
ij
ii
Gii
aij, bij, eij, and fij are unsymmetrical. That is, aij may not be equal to aji, etc.
114
Mixtures
0.30
0.20
0.47
The binary parameters aij, bij, cij, dij, eij, and fij can be determined from VLE
and/or LLE data regression. The Aspen Physical Property System has a large
number of built-in binary parameters for the NRTL model. The binary
parameters have been regressed using VLE and LLE data from the Dortmund
Databank. The binary parameters for the VLE applications were regressed
using the ideal gas, Redlich-Kwong, and Hayden O'Connell equations of state.
See Physical Property Data, Chapter 1, for details.
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
NRTL/1
aij
-100.0
100.0
NRTL/2
bij
-30000
30000.0
TEMPERATURE
NRTL/3
cij
0.30
0.0
1.0
NRTL/4
dij
-0.02
0.02
TEMPERATURE
NRTL/5
eij
TEMPERATURE
NRTL/6
fij
TEMPERATURE
NRTL/7
Tlower
TEMPERATURE
NRTL/8
Tupper
1000
TEMPERATURE
Note: If any of bij, dij, or eij is non-zero, absolute temperature units are
assumed for bij, dij, eij, and fij. Otherwise, user input units for temperature are
used. The temperature limits are always interpreted in user input units.
The NRTL-2 property method uses data set 2 for NRTL. All other NRTL
methods use data set 1.
References
H. Renon and J.M. Prausnitz, "Local Compositions in Thermodynamic Excess
Functions for Liquid Mixtures," AIChE J., Vol. 14, No. 1, (1968), pp. 135
144.
NRTL-SAC Model
NRTL-SAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model and extended to handle
electrolytes, but usable in Aspen Plus or Aspen Properties without Aspen
Polymers. NRTL-SAC can be used for fast, qualitative estimation of the
solubility of complex organic compounds in common solvents. It can also be
used as a general activity coefficient model in Aspen Plus, Aspen Properties,
and HYSYS.
Conceptually, the model treats the liquid non-ideality of mixtures containing
complex organic molecules (solute) and small molecules (solvent) in terms of
interactions between three pairwise interacting conceptual segments:
115
hydrophobic segment (x), hydrophilic segment (z), and polar segments (yand y+). In practice, these conceptual segments become the molecular
descriptors used to represent the molecular surface characteristics of each
solute or solvent molecule. Hexane, water, and acetonitrile are selected as
the reference molecules for the hydrophobic, hydrophilic, and polar segments,
respectively. The molecular parameters for all other solvents can be
determined by regression of available VLE or LLE data for binary systems of
solvent and the reference molecules or their substitutes.
The treatment results in four component-specific molecular parameters:
hydrophobicity X, hydrophilicity Z, and polarity Y- and Y+. The two types of
polar segments, Y- and Y+, are used to reflect the wide variations of
interactions between polar molecules and water.
NRTL-SAC can also be used to model electrolyte systems. In this case, an
electrolyte segment e, corresponding to the electrolyte parameter E, is
introduced. This conceptual segment e completely dissociates to a cationic
segment (c) and an anionic segment (a), both of unit charge. All electrolytes,
organic or inorganic, symmetric or unsymmetric, univalent or multivalent, are
to be represented with this conceptual 1-1 electrolyte segment e together
with the previously defined hydrophobic segment x, polar segments y- and
y+, and hydrophilic segment z in NRTL-SAC. The reference state for ions is by
default an unsymmetric state based on infinite dilution in aqueous solution,
but an option code is available to select the symmetric state of pure fused
salts. When there are no electrolytes present, the segment e is unused and
the current model reduces to the non-electrolyte version of NRTL-SAC present
in earlier releases.
The conceptual segment contribution approach in NRTL-SAC represents a
practical alternative to the UNIFAC functional group contribution approach.
This approach is suitable for use in the industrial practice of carrying out
measurements for a few selected solvents and then using NRTL-SAC to
quickly predict other solvents or solvent mixtures and to generate a list of
suitable solvent systems.
The NRTL-SAC model calculates liquid activity coefficients.
Note: This is the updated version of NRTL-SAC, represented with property
model GMNRTLS and property method NRTL-SAC. This version does not
require the specification of components as oligomers. For the old version, see
NRTLSAC for Segments/Oligomers and ENRTL-SAC.
For the model equations, see NRTL-SAC Model Derivation.
116
Parameter
Name/
Element
Symbol
Default
MDS
Lower
Limit
XYZE/1
rx,I
XYZE/2
ry-,I
XYZE/3
ry+,I
XYZE/4
rz,I
XYZE/5
re,I
Electrolytes must be modeled as ion pairs in this system, while the individual
ions are components in the Aspen Physical Property System, so for these ion
pairs, the five parameters are stored in binary parameter BXYZE which has
elements corresponding to those of XYZE.
Parameter
Name/
Element
Symbol
Default
MDS
Lower
Limit
BXYZE/1
rx,CA
BXYZE/2
ry-,CA
BXYZE/3
ry+,CA
BXYZE/4
rz,CA
BXYZE/5
re,CA
and
an anionic component
come from the dissociation of their
corresponding electrolyte component CA, as defined by the chemical equation
describing the dissociation of the electrolyte:
with
117
Meaning
2
3
References
C.-C. Chen and Y. Song, "Extension of Nonrandom Two-Liquid Segment
Activity Coefficient Model for Electrolytes," Ind. Eng. Chem. Res., 2005, 44,
8909.
Y. Song and C.-C. Chen, "Symmetric Nonrandom Two-Liquid Segment Activity
Coefficient Model for Electrolytes," Ind. Eng. Chem. Res., 2009, 48, 5522.
118
This definition is the so-called standard state of pure liquids for molecular
components and it is also called the symmetric reference state for molecular
components.
(5)
119
(6)
(8)
(9)
This condition applies to all ionic components in the solution. In infinitedilution aqueous solutions, water must be present and is assumed to
represent the entire solution, so the unsymmetric reference state can be
written as follows:
(12)
(14)
120
(15)
(16)
where I is the component index, i is the segment index, ri,I is the number of
segment i in component I, xI is the mole fraction of component I, xi is the
segment fraction of segment i, and ns is the total number of all segments in
the system.
Since there is only a single 1-1 electrolyte segment, the pair parameters
between a molecular segment and the electrolyte segment can be simplified
as follows:
(17)
(18)
(19)
(20)
with
(22)
121
(24)
(25)
(26)
The local composition term for the logarithm of the activity coefficient of
component I , before normalization to a chosen reference state, is computed
as the sum of the individual segment contributions.
(27)
122
(29)
Molecular components
Applying Eq. 1, the normalization for molecular components can be done as
follows:
(31)
(34)
(35)
where I applies to all molecular components in the solution and Ix0 is the ionic
strength at the symmetric reference state. In the case that electrolytes are
made up of only the conceptual 1-1 electrolyte segment and none of the
molecular segments, this reference state is equivalent to the molten state of
the conceptual 1-1 electrolyte.
123
where
solution:
and
with
(41)
(42)
where ns is the total segment number of the solution, R is the gas constant,
A is the Debye-Hckel parameter, Ix is the segment-based ionic strength,
is the closest approach parameter, NA is Avogadro's number, v and are the
molar volume and dielectric constant of the solvent, Qe is the electron charge,
kB is the Boltzmann constant, zi is the charge number of segment i, and Ix0
represents Ix at the reference state. Since the "single 1-1 electrolyte segment
e=ca" is defined in the model, we can obtain:
(43)
124
For a molecular segment, the activity coefficient can be carried out as follows:
(47)
For the univalent cation or anion segment, the activity coefficient can be
carried out as follows:
(48)
(50)
Molecular components
For molecular components, the activity coefficients are given as follows:
(52)
From Eq. 47, it is easy to show that the PDH term activity coefficients for all
molecular components are normalized; that is
(53)
125
(55)
(56)
(58)
For the univalent cation or anion segment, the activity coefficient can be
carried out as follows:
126
(62)
Specifically,
(63)
(64)
The long range interaction term for the logarithm of the activity coefficient of
component I is computed as the sum of the individual segment contributions.
(65)
References
Pitzer, K.S., J.M. Simonson, "Thermodynamics of Multicomponent, Miscible,
Ionic Systems: Theory and Equations," J. Phys. Chem., 1986, 90, 3005-3009.
Robinson, R.A., Stokes, R.H., Electrolyte Solutions, 2nd revised edition,
Dover, 1970.
Rashig, A.A., Honig, B., "Reevaluation of the Born Model of Ion Hydration," J.
Phys. Chem., 1985, 89, 5588.
(67)
where Gex,FH is the Flory-Huggins term for the excess Gibbs energy, I is the
segment fraction of component I, and rI is the number of all conceptual
segments in component I:
(68)
(69)
127
Molecular components
It is easy to show that activity coefficients for molecular components from the
Flory-Huggins term are normalized; that is
(71)
with
(74)
(75)
(76)
(77)
128
where
and
aqueous solution:
where
is the infinite dilution activity coefficient of Henry component I
(xI0) in the solution. By this definition I* approaches unity as
xI approaches zero. The phase equilibrium relationship for Henry components
becomes:
(83)
The Henrys Law is available in all activity coefficient property methods. The
model calculates the Henrys constant for a dissolved gas component in all
solvent components in the mixture:
(84)
(85)
129
components are mainly through the local interactions with solvents. We can
calculate all three activity coefficients for Henry components as follows:
(86)
(87)
(88)
with
(89)
(90)
(91)
(92)
(93)
(94)
130
and Y+, are used to reflect the wide variations of interactions between polar
molecules and water.
The conceptual segment contribution approach in NRTL-SAC represents a
practical alternative to the UNIFAC functional group contribution approach.
This approach is suitable for use in the industrial practice of carrying out
measurements for a few selected solvents and then using NRTL-SAC to
quickly predict other solvents or solvent mixtures and to generate a list of
suitable solvent systems.
The NRTL-SAC model calculates liquid activity coefficients.
The equation for the NRTL-SAC model is:
with
G = exp(-)
Where:
131
I, J
Component index
i, j, m
IC = IFH
IR = Ilc
pI
rI
xI
rI,m
xi
im
im
sI and
x
z
yz
y+
z
x
y+
12
21
12 = 21
1.643
6.547
-2.000
2.000
1.643
1.834
10.949 1.787
1.787
1.834
0.2
0.2
0.3
0.2
0.3
132
Parameter
Name/
Element
Lower
Limit
Upper
Limit
Units Comment
NRTLXY
rI,m
Binary,
symmetric
FHSIZE/1
sI
1.0
1E-15
1E15
Unary
FHSIZE/2
1.0
-1E10
1E10
Unary
Option codes
The Flory-Huggins term is included by default in the NRTLSAC model. You can
remove this term using the first option code. The table below lists the values
for this option code.
0
Others
rI,x
rI,y-
rI,y+
rI,z
ACETIC-ACID
0.045
0.164
0.157
0.217
ACETONE
0.131
0.109
0.513
ACETONITRILE
0.018
0.131
0.883
ANISOLE
0.722
BENZENE
0.607
1-BUTANOL
0.414
0.007
0.485
2-BUTANOL
0.335
0.082
0.355
N-BUTYL-ACETATE
0.317
0.030
0.330
METHYL-TERT-BUTYL-ETHER
1.040
0.219
0.172
CARBON-TETRACHLORIDE
0.718
0.141
CHLOROBENZENE
0.710
0.424
CHLOROFORM
0.278
0.039
CUMENE
1.208
0.541
CYCLOHEXANE
0.892
1,2-DICHLOROETHANE
0.394
0.691
1,1-DICHLOROETHYLENE
0.529
0.208
1,2-DICHLOROETHYLENE
0.188
0.832
DICHLOROMETHANE
0.321
1.262
1,2-DIMETHOXYETHANE
0.081
0.194
0.858
N,N-DIMETHYLACETAMIDE
0.067
0.030
0.157
N,N-DIMETHYLFORMAMIDE
0.073
0.564
0.372
DIMETHYL-SULFOXIDE
0.532
2.890
1,4-DIOXANE
0.154
0.086
ETHANOL
0.256
0.081
0.190
0.401
0.507
133
Solvent name
rI,x
rI,y-
rI,y+
2-ETHOXYETHANOL
0.071
0.318
ETHYL-ACETATE
0.322
0.049
0.237
0.421
0.141
ETHYLENE-GLYCOL
DIETHYL-ETHER
0.448
ETHYL-FORMATE
0.257
0.041
0.338
0.165
0.280
0.089
FORMAMIDE
0.341
0.252
FORMIC-ACID
0.707
N-HEPTANE
2.470
1.340
N-HEXANE
1.000
ISOBUTYL-ACETATE
1.660
ISOPROPYL-ACETATE
0.552
0.154
0.498
METHANOL
0.088
0.149
0.027
0.562
2-METHOXYETHANOL
0.052
0.043
0.251
0.560
METHYL-ACETATE
0.236
0.337
3-METHYL-1-BUTANOL
0.419
0.538
METHYL-BUTYL-KETONE
0.673
METHYLCYCLOHEXANE
1.162
METHYL-ETHYL-KETONE
0.247
0.036
0.480
METHYL-ISOBUTYL-KETONE
0.673
0.224
0.469
ISOBUTANOL
0.566
N-METHYL-2-PYRROLIDONE
0.197
NITROMETHANE
0.025
N-PENTANE
0.898
1-PENTANOL
0.474
0.223
1-PROPANOL
0.375
0.030
ISOPROPYL-ALCOHOL
0.351
0.070
0.003
N-PROPYL-ACETATE
0.514
0.134
0.587
PYRIDINE
0.205
0.135
0.174
SULFOLANE
0.210
TETRAHYDROFURAN
0.235
0.040
1,2,3,4-TETRAHYDRONAPHTHALENE 0.443
0.555
0.108
0.224
0.314
0.469
0.251
0.067
0.322
0.485
0.305
1.216
0.426
0.248
0.511
0.353
0.457
0.320
TOLUENE
0.604
0.304
1,1,1-TRICHLOROETHANE
0.548
0.287
TRICHLOROETHYLENE
0.426
0.285
M-XYLENE
0.758
0.021
0.316
1.000
WATER
134
rI,z
TRIETHYLAMINE
0.557
0.105
1-OCTANOL
0.766
0.032
0.624
0.335
Reference
C.-C. Chen and Y. Song, "Solubility Modeling with a Nonrandom Two-Liquid
Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004).
Using NRTLSAC
NRTLSAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model, usable in Aspen Properties and
Aspen Polymers. NRTLSAC can be used for fast, qualitative estimation of the
solubility of complex organic compounds in common solvents. For more
information about the model, see NRTLSAC for Segments/Oligomers.
Note: A newer version of NRTL-SAC comes with its own property method
named NRTL-SAC and does not require the specification of a method and
oligomer components as described below.
The NRTLSAC model for Segments/Oligomers in the Aspen Physical Property
System is a liquid activity coefficient model called NRTLSAC. To specify it:
1. On the Properties | Specifications sheet, specify process type ALL.
2. Specify base method NRTLSAC.
In order to use this version of NRTLSAC, all components must be defined as
oligomers. Four conceptual segments also must be defined. On the
Components | Polymers | Oligomers sheet, enter a number for at least
one conceptual segment for each oligomer component, as required by the
definition of an oligomer. These numbers are not used by NRTL-SAC.
On the Properties | Parameters | Binary Interaction | NRTL-1 form,
enter the binary parameters between conceptual segments. In the following
example, the conceptual segments are named X, Y-, Y+, and Z.
Segment 1 X
Segment 2 Y-
X
Z
YZ
Y+
Z
X
Y+
AIJ
1.643
6.547
-2.000
2.000
1.643
AJI
1.834
10.949 1.787
1.787
1.834
CIJ
0.2
0.2
0.3
0.2
0.3
135
This section provides theoretical background for the model. All model
equations and parameter requirements are included.
The Pitzer model is commonly used in the calculation of activity coefficients
for aqueous electrolytes up to 6 molal ionic strength. Do not use this model if
a non-aqueous solvent exists. Henry's law parameters are required for all
other components in the aqueous solution. The model development and
working equations are provided in the following sections. Parameter
conversion between the Pitzer notation and our notation is also provided.
The Pitzer model in the Aspen Physical Property System involves usersupplied parameters that are used in the calculation of binary and ternary
parameters for the electrolyte system.
Five elements (P1 through P5) account for the temperature dependencies of
parameters (0), (1), (2), (3), C , , and . These parameters follow the
temperature dependency relation:
Where:
Tref
298.15 K
Provides
P1 - P5 for
No. of
Default MDS Units
Elements
Cation-Anion Parameters
5
GMPTB3
(0)
(1)
(2)
(3)
GMPTC
GMPTB0
GMPTB1
GMPTB2
Cation-Cation Parameters
GMPTTH
cc'
Anion-Anion Parameters
GMPTTH
aa'
Ternary Parameters
136
Parameter
Name
Provides
P1 - P5 for
No. of
Default MDS Units
Elements
GMPTPS,
GMPTP1,
GMPTP2,
GMPTP3,
GMPTP4
ijk
1 (in each 0
parameter)
GMPTB1
(0)
(1)
GMPTC
GMPTB0
Model Development
The Pitzer model analyzes "hard-core" effects in the Debye-Hckel theory. It
uses the following expansion as a radial distribution function:
(1)
Where:
gij
Distribution function
Radius
qij
=
(pair potential of mean force)
With:
zi
Charge of ion i
Qe
Electron charge
j(r)
Boltzmann's constant
Temperature
This radial distribution function is used in the so-called pressure equation that
relates this function and the intermolecular potential to thermodynamic
properties. From this relation you can obtain an expression for the osmotic
coefficient.
Pitzer proposes a general equation for the excess Gibbs energy. The basic
equation is:
(2)
Where:
GE
137
Gas constant
Temperature
nw
Kilograms of water
mi
=
(molality of ion i)
With:
xi
xw
Mw
ni
Moles of ion i
The function f(I) is an electrostatic term that expresses the effect of longrange electrostatic forces between ions. This takes into account the hard-core
effects of the Debye-Hckel theory. This term is discussed in detail in the
following section. The parameters ij are second virial coefficients that
account for the short-range forces between solutes i and j. The parameters
ijk account for the interactions between solutes, i, j, k. For ion-ion
interactions, ij is a function of ionic strength. For molecule-ion or moleculemolecule interactions this ionic strength dependency is neglected. The
dependence of ijk on ionic strength is always neglected. The matrices ij and
ijk are also taken to be symmetric (that is, ij = ji).
Pitzer modified this expression for the Gibbs energy by identifying
combinations of functions. He developed interaction parameters that can be
evaluated using experimental data. He selected mathematical expressions for
these parameters that best fit experimental data.
Pitzer's model can be applied to aqueous systems of strong electrolytes and
to aqueous systems of weak electrolytes with molecular solutes. These
applications are discussed in the following section.
In the Aspen Physical Property System, this model is applied using the
reference state of infinite dilution solution in water for non-water molecular
solutes and ionic species. The properties such as DHAQFM are obtained at 25
C and 1 atm.
138
(3)
zi
Charge of ion i
Subscripts c, c', and a, a' denote cations and anions of the solution. B, C, ,
and are interaction parameters. f(I) is an electrostatic term as a function of
ionic strength. The cation-anion parameters B and C are characteristic for an
aqueous single-electrolyte system. These parameters can be determined by
the properties of pure (apparent) electrolytes. B is expressed as a function of
(0) and (1), or of (0), (2), and (3) (see equations 11 through 15).
The parameters and are for the difference of interaction of unlike ions of
the same sign from the mean of like ions. These parameters can be measured
from common-ion mixtures. Examples are NaCl + KCl + H2O or NaCl + NaNO3
+ H2O (sic, Pitzer, 1989). These terms are discussed in detail later in this
section.
Frst and Renon (1982) propose the following expression as the Pitzer
equation for the excess Gibbs energy:
(4)
The difference between equations 3 and 4 is that Pitzer orders cation before
anions. Frst and Renon do not. All summations are taken over all ions i and j
(both cations and anions). This involves making the parameter matrices Bij,
Cij, ij, and ijk symmetric, as follows:
Second-order parameters are written Bij if i and j are ions of different sign. Bij
= 0 if the sign of zi = sign of zj, and Bii = 0. Since cations are not ordered
before anions, Bij = Bji. This eliminates the 2 in the second term in brackets in
Pitzer's original expression (equation 3). Second-order parameters are written
ij if i and j are ions of the same sign. Thus ij = 0 if the sign of zi is different
from the sign of zj, and ii = 0 with ij = ji.
Third-order parameters are written Cij if i and j are ions with different signs.
Cij = 0 if the sign of zi = sign of zj, and Cii = 0 with Cij = Cji. The factor of 2 in
the fifth bracketed term in Pitzer's original expression (equation 3) becomes
1/2 in equation 4. The matrix C is symmetric and
ions to make the equation symmetric.
is extended to all
139
ijk is written for three different ions ijk = kij = jki , and ikk = 0. ijk = 0
if the sign of zi =sign of zj =sign of zk. The factor of 1/6 is different from 1/2
in the last term in brackets in Pitzer's original expression. Pitzer distinguishes
between cations and anions. In Pitzer's original model this parameter appears
twice, as cc'a and c'ca. In this modified model, it appears six times, as cc'a;
c'ca; acc'; ac'c; cac'; and c'ac. Frst and Renon's expression, equation 4,
calculates the expressions for activity coefficients and osmotic coefficients.
Pitzer (1975) modified his model by adding the electrostatic unsymmetrical
mixing effects, producing this modified Pitzer equation for the excess Gibbs
energy:
(4a)
140
141
(8)
Taking the derivative of equation 7 with respect to I, gives:
(9)
So that:
(10)
This equation is used in equation 6. In equations 7 and 9, is the usual DebyeHckel constant for the osmotic coefficient, determined from:
(11)
Where:
NA
Avogadro's constant
dw
Water density
with
1=2.0.
For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), B is determined
by the following expression:
(13)
with
142
After the activity coefficients are calculated, they can be converted to the
mole fraction scale from the molality scale by the following relations:
For solutes:
(16)
Where:
iii = 6iii
However, molecule-molecule interactions were not taken into account by
Pitzer and coworkers. So iii is an artificially introduced quantity.
143
The equations for activity coefficients and the Gibbs free energy are the same
as equations 3 through 6.
Parameters
The Pitzer model in the Aspen Physical Property System involves usersupplied parameters. These parameters are used in the calculation of binary
and ternary parameters for the electrolyte system. These parameters include
Parameter Conversion
For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), the parameter
(3) corresponds to Pitzer's (1). (2) is the same in both the Aspen Physical
Property System and original Pitzer models. Pitzer refers to the n-m
electrolyte parameters as (1), (2), (0). (0) and (2) retain their meanings in
both models, but Pitzer's (1) is (3) in the Aspen Physical Property System. Be
careful to make this distinction when entering n-m electrolyte parameters.
Pitzer often gives values of (0), (1), (2), (3), and C that are corrected by
some factors (see Pitzer and Mayorga (1973) for examples). These factors
originate from one of Pitzer's earlier expressions for the excess Gibbs energy:
(18)
Where:
=
na
nc
Here (0), (1), (2), and (3) are multiplied by a factor of 2ncna. C is multiplied
by a factor of 2(ncna)3/2.
Aspen Physical Property System accounts for these correcting factors. Enter
the parameters without their correcting factors.
For example, Pitzer gives the values of parameters for MgCl2 as:
144
4/3(0)
0.4698
4/3(1)
2.242
0.00979
0.3524
1.6815
0.00520
Parameter Sources
Binary and ternary parameters for the Pitzer model for various electrolyte
systems are available from Pitzer's series on the thermodynamics of
electrolytes. These papers and the electrolyte parameters they give are:
Reference
Parameters available
(Pitzer, 1973)
(Pitzer, 1975)
145
Reference
Parameters available
Pitzer References
Conceicao, M., P. de Lima, and K.S. Pitzer, "Thermodynamics of Saturated
Aqueous Solutions Including Mixtures of NaCl, KCl, and CsCl, "J. Solution
Chem, Vol. 12, No. 3, (1983), pp. 171-185.
Frst, W. and H. Renon, "Effects of the Various Parameters in the Application
of Pitzer's Model to Solid-Liquid Equilibrium. Preliminary Study for Strong 1-1
Electrolytes," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),
pp. 396-400.
Guggenheim, E.A., Phil. Mag., Vol. 7, No. 19, (1935), p. 588.
Guggenheim, E.A. and J.C. Turgeon, Trans. Faraday Soc., Vol. 51, (1955), p.
747.
Kim, H. and W.J. Frederick, "Evaluation of Pitzer Ion Interaction Parameters
of Aqueous Mixed Electrolyte Solution at 25C, Part 2: Ternary Mixing
Parameters," J. Chem. Eng. Data, 33, (1988), pp. 278-283.
Pabalan, R.T. and K.S. Pitzer, "Thermodynamics of Concentrated Electrolyte
Mixtures and the Prediction of Mineral Solubilities to High Temperatures for
Mixtures in the system Na-K-Mg-Cl-SO4-OH-H2O," Geochimica Acta, 51,
(1987), pp. 2429-2443.
Peiper, J.C. and K.S. Pitzer, "Thermodynamics of Aqueous Carbonate
Solutions Including Mixtures of Sodium Carbonate, Bicarbonate, and
Chloride," J. Chem. Thermodynamics, Vol. 14, (1982), pp. 613-638.
Phutela, R.C. and K.S. Pitzer, "Thermodynamics of Aqueous Calcium
Chloride," J. Solution Chem., Vol. 12, No. 3, (1983), pp. 201-207.
Pitzer, K.S., "Thermodynamics of Electrolytes. I. Theoretical Basis and
General Equations, " J. Phys. Chem., Vol. 77, No. 2, (1973), pp. 268-277.
Pitzer, K.S., J. Solution Chem., Vol. 4, (1975), p. 249.
Pitzer, K.S., "Fluids, Both Ionic and Non-Ionic, over Wide Ranges of
Temperature and Composition," J. Chen. Thermodynamics, Vol. 21, (1989),
pp. 1-17. (Seventh Rossini lecture of the commission on Thermodynamics of
the IUPAC, Aug. 29, 1988, Prague, ex-Czechoslovakia).
Pitzer, K.S. and J.J. Kim, "Thermodynamics of Electrolytes IV; Activity and
Osmotic Coefficients for Mixed Electrolytes," J.Am. Chem. Soc., Vol. 96
(1974), p. 5701.
Pitzer, K.S. and G. Mayorga, "Thermodynamics of Electrolytes II; Activity and
Osmotic Coefficients for Strong Electrolytes with One or Both Ions Univalent,"
J. Phys. Chem., Vol. 77, No. 19, (1973), pp. 2300-2308.
Pitzer, K.S. and G. Mayorga, J. Solution Chem., Vol. 3, (1974), p. 539.
146
Where:
Ai
Bi
Ci
Di
Ei
For any component i, the value of the activity coefficient can be fixed:
i = fi
This model is not part of any property method. To use it:
1. On the Properties | Specifications sheet, specify an activity coefficient
model, such as NRTL.
2. Click the Properties | Property Methods folder.
3. In the Object Manager, click New.
4. In the Create New ID dialog box, enter a name for the new method.
5. In the Base Property Method field, select NRTL.
6. Click the Models tab.
7. Change the Model Name for GAMMA from GMRENON to GMPOLY.
Parameter
Name/Element
Symbol
Default
MDS
Lower
Limit
Upper
Limit
Units
GMPLYP/1
ai1
GMPLYP/2
ai2
GMPLYP/3
ai3
147
Parameter
Name/Element
Symbol
Default
MDS
Lower
Limit
Upper
Limit
Units
GMPLYP/4
bi1
GMPLYP/5
bi2
GMPLYP/6
bi3
GMPLYP/7
ci1
GMPLYP/8
ci2
GMPLYP/9
ci3
GMPLYP/10
di1
GMPLYP/11
di2
GMPLYP/12
di3
GMPLYP/13
ei1
GMPLYP/14
ei2
GMPLYP/15
ei3
GMPLYO
fi
0.0
0.0
0.0
0.0
0.0
&
&
&
&
Redlich-Kister
This model calculates activity coefficients. It is a polynomial in the difference
between mole fractions in the mixture. It can be used for liquid and solid
mixtures (mixed crystals).
The equation is:
Where:
148
nc
Number of components
A1,ij
aij / T + bij
A2,ij
cij / T + dij
A3,ij
eij / T + fij
A4,ij
gij / T + hij
A5,ij
mij / T + nij
An,ii
An,jj = 0.0
An,ji
An,ij(-1)(n-1)
An,kj
An,jk(-1)(n-1)
For any component i, the value of the activity coefficient can be fixed:
i = vi
Parameter Name/
Element
Symbol
Default
MDS
Lower
Limit
Upper
Limit
Units
GMRKTB/1
aij
GMRKTB/2
bij
GMRKTB/3
cij
GMRKTB/4
dij
GMRKTB/5
eij
GMRKTB/6
fij
GMRKTB/7
gij
GMRKTB/8
hij
GMRKTB/9
mij
GMRKTB/10
nij
GMRKTO
vi
Scatchard-Hildebrand
The Scatchard-Hildebrand model calculates liquid activity coefficients. It is
used in the CHAO-SEA property method and the GRAYSON property method.
The equation for the Scatchard-Hildebrand model is:
Where:
Aij
Vm*,l
Parameter
Symbol
Name/Element
Default
MDS Lower
Limit
Upper
Limit
Units
TC
2000.0
TEMPERATURE
Tci
5.0
149
Parameter
Symbol
Name/Element
Default
MDS Lower
Limit
Upper
Limit
Units
DELTA
103
105
SOLUPARAM
VLCVT1
Vi*,CVT
0.0005
1.0
MOLEVOLUME
GMSHVL
Vi*,l
0.01
1.0
MOLEVOLUME
GMSHXL
kij
-5
0.0
Three-Suffix Margules
This model can be used to describe the excess properties of liquid and solid
solutions. It does not find much use in chemical engineering applications, but
is still widely used in metallurgical applications. Note that the binary
parameters for this model do not have physical significance.
The equation is:
For any component i, the value of the activity coefficient can be fixed:
i = di
Parameter Name/ Symbol
Element
Default MDS
Lower
Limit
Upper
Limit
Units
GMMRGB/1
aij
TEMPERATURE
GMMRGB/2
bij
GMMRGB/3
cij
GMMRGO
di
References
M. Margules, "ber die Zusammensetzung der gesttigten Dmpfe von
Mischungen," Sitzungsber. Akad. Wiss. Vienna, Vol. 104, (1895), p. 1293.
D.A. Gaskell, Introduction to Metallurgical Thermodyanics, 2nd ed., (New
York: Hemisphere Publishing Corp., 1981), p. 360.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987).
150
Parameters
Both symmetric and unsymmetric models share the same binary and pair
parameters. The adjustable model parameters are the symmetric non-random
factor parameters, , and the asymmetric binary interaction energy
parameters, . These parameters exist for molecule-molecule pairs (mm' =
m'm while mm' m'm), molecule-electrolyte pairs (m,ca = ca,m while m,ca
ca,m where ca represents an ion pair), and electrolyte-electrolyte pairs (ca,ca'
= ca',ca and ca,c'a = c'a,ca while ca,ca' ca',ca and ca,c'a c'a,ca)
The parameters for ion pairs are temperature-dependent:
151
where
Option codes can affect the performance of this model. See Option Codes for
Activity Coefficient Models for details.
The following table lists the parameters used by GMENRTLS and GMENRTLQ:
Parameter
Symbol
No. of
Default MDS Units
Name
Elements
Dielectric Constant Unary Parameters
CPDIEC
T
1
Ionic Born Radius Unary Parameters
298.15
TEMPERATURE
RADIUS
ri
1
Molecule-Molecule Binary Parameters
3x10-10
LENGTH
NRTL/1
ref
aij
aji
bij
TEMPERATURE
bji
TEMPERATURE
NRTL/3
cij=cji
.3
NRTL/4
dij=dji
TEMPERATURE
NRTL/5
eij
TEMPERATURE
eji
TEMPERATURE
fji
NRTL/2
NRTL/6
152
TEMPERATURE
fji
TEMPERATURE
GMENCC
Cca,m
Cm,ca
Parameter
Symbol
No. of
Default MDS Units
Name
Elements
Dielectric Constant Unary Parameters
GMENCD
GMENCE
GMENCN
Dca,m
TEMPERATURE
Dm,ca
TEMPERATURE
Eca,m
Em,ca
ca,m = m,ca
.2
GMENCD
GMENCE
GMENCN
Cca,c'a
Cc'a,ca
Cca,ca'
Cca',ca
Dca,c'a
TEMPERATURE
Dc'a,ca
TEMPERATURE
Dca,ca'
TEMPERATURE
Dca',ca
TEMPERATURE
Eca,c'a
Ec'a,ca
Eca,ca'
Eca',ca
ca,c'a = c'a,ca
ca,ca' = ca',ca
.2
.2
The contribution from zwitterions to the solution enthalpy and Gibbs free
energy are calculated as solutes using the infinite dilution heat capacity
model CPAQ0, DGAQFM, and DHAQFM.
153
or
(4)
Each of these terms will be discussed in subsequent sections.
154
(8)
where c is the cationic stoichiometric coefficient and a is the anionic
stoichiometric coefficient, and =c+a (one mole of salt releases moles of
ions in solution). They are given by the chemical equation describing the
dissociation of the electrolyte:
(9)
with
(10)
Therefore Eq. 4 can be written in terms of charge numbers zc and za:
(11)
At the pure fused salt state, the total moles of ionic components (for one
mole of salt) are:
=c+a
(12)
therefore
(13)
155
(14)
(15)
The symmetric reference state defined by Eq. 6 is restricted to systems
containing a single electrolyte component. For multi-electrolyte systems, the
symmetric reference state can be generalized from Eq. 6 as follows:
(16)
where m applies to all molecular components in the system. The symmetric
reference state is a molecular-component-free medium.
(17)
This condition applies to all ionic components in the solution, and water must
be present in the solution for this reference state. In terms of the activity
coefficients for ionic components, the condition for the aqueous solution as
the unsymmetric reference state can be written as follows (where w=water):
(18)
This equation applies to all ionic components in the solution.
or
156
(20)
with
(21)
(22)
where the first term is the contribution when a molecular species is at the
center, the second is the contribution when a cationic species is at the center,
and the third term is the contribution when an anionic species is at the
center. In Eq. 21, Ci=zi (charge number) for ionic species and Ci=1 for
molecular species. Finally, in Eqs. 19 and 20, G and are local binary
quantities related to each other by the NRTL non-random factor parameter :
(23)
The contribution to the activity coefficient of component i can be derived as
follows:
(24)
(26)
157
(27)
Binary Parameters
The adjustable binary parameters for these models include moleculemolecule, molecule-electrolyte, and electrolyte-electrolyte binary parameters,
where electrolyte here means an ion-pair composed of a cationic species and
an anionic species. For each of these types, there are asymmetric binary
interaction energy parameters, , and symmetric non-random factor
parameters, (for calculating G). That is to say that the following are the
adjustable parameters:
(28)
158
(34)
159
(45)
(46)
(47)
(48)
where xm0 applies to all molecular components in the solution.
For ionic components with infinite-dilution aqueous solution as reference
state, apply Eq. 18 to get:
(49)
(50)
where
and
are local interaction contributions to activity
coefficients at infinite dilution aqueous solution:
(51)
(52)
160
with
(54)
(55)
(58)
(59)
so that
(60)
where xm0 applies to all molecular components in the solution. This
definition ensures that the excess Gibbs free energy from the long range
interactions will be zero at the symmetric reference state regardless of how
many electrolytes are present in the solution.
The contribution to the activity coefficient from component i can be derived
as:
(61)
161
(66)
(67)
or
(68)
(69)
162
(70)
(71)
where s is a solvent component in the mixture and Msis the solvent molecular
weight. Each sum is over all solvent components in the solution.
163
meaningless and therefore the pure liquid state at the temperature and
pressure of the system cannot serve as the reference state. The reference
state for a Henry component is redefined to be at infinite dilution (that is, at
xi0) and at the temperature and pressure of the system.
The liquid phase reference fugacity, fi*,l, becomes the Henrys constant for
Henry components in the solution, Hi, and the activity coefficient, i, is
converted to the infinite dilution reference state through the relationship:
(76)
The Henrys Law is available in all activity coefficient property methods. The
model calculates the Henrys constant for a dissolved gas component in all
solvent components in the mixture:
(78)
(79)
where His and is are the Henrys constant and the infinite dilution activity
coefficient of the dissolved gas component i in the solvent component s (xi0
and xs1), respectively.
Since ionic species exist only in the liquid phase and therefore do not
participate directly in vapor-liquid equilibria, the activities of Henry
components are mainly through the local interactions with solvents. We can
calculate the activity coefficients for Henry components as follows:
(80)
(81)
(82)
where xh0 applies to all Henry components in the solution.
164
h is calculated as follows:
(83)
where xh0 applies to all Henry components and xi0 to all ionic
components in the solution.
For aqueous basis, the unsymmetric activity coefficients of Henry components
are calculated as follows:
(84)
(86)
Where:
K
Equilibrium constant
xw
xs
xi
i*
Stoichiometric coefficient
165
(88)
The excess liquid functions given by Equations 89-91 are calculated from the
same activity coefficient model. In practice, however, the activity coefficient i
is often derived first from the excess liquid Gibbs free energy of a mixture
from an activity coefficient model:
(92)
with
(93)
(94)
166
Where
is the liquid Gibbs free energy of mixing; it is defined as the
difference between the Gibbs free energy of the mixture and that of the pure
component and
is the ideal Gibbs free energy of mixing. Once the
excess liquid functions are known, the thermodynamic properties of liquid
mixtures can be computed as follows:
(95)
(96)
(97)
where Hil and Hiig are the enthalpy and ideal gas enthalpy of component i at
the system conditions. Similarly, Gil and Giig are the Gibbs free energy and
ideal gas Gibbs free energy of component i at the system conditions. In Aspen
Plus, both Hiig and Giig are computed by the expressions:
(98)
(99)
where
is the
167
Solvents
The contribution from solvents can be written as follows:
(103)
(104)
(105)
(106)
(107)
(108)
where
is the liquid fugacity coefficient of pure solvent
component i, pisat is the vapor pressure of pure component at the system
temperature T, iv is the vapor fugacity coefficient of pure component at T
and pisat (normally calculated from an equation-of-state model), and
is the Poynting pressure correction from pisat to p,
and Vi is the liquid molar volume at T and p.
l
Henry components
The contribution from Henry components can be written as follows:
(109)
(110)
(111)
(112)
(113)
168
(114)
(115)
Ionic components
The contribution from ionic components can be written as follows:
(116)
(117)
(118)
(119)
(120)
(121)
where Hiref and Giref are the enthalpy and Gibbs free energy of ionic
component i at the system conditions with a specified reference state
(symmetric or unsymmetric).
The property calculations for solvents and Henry components are the same
when the reference state is changed. Only for ionic components do the
property methods need to be specified with a reference state. The methods
with the unsymmetric reference state are available already in Aspen Plus and
Aspen Properties. New methods are needed only for the symmetric reference
state. Overall, the calculated total enthalpy or Gibbs free energy for the same
electrolyte solution should be the same, regardless of the reference state
specified.
Enthalpy and Gibbs free energy of ionic components with the symmetric
reference state can be written as follows:
(122)
(123)
where
and
are enthalpy and Gibbs free energy of ionic component
i with the unsymmetric reference state, respectively, and available already in
169
is calculated from
as follows:
(124)
is
as
(125)
(126)
and
170
the pure fused salts. Applying Eq. 127, the system enthalpy and Gibbs free
energy with the unsymmetric reference state can be expressed as:
(128)
(129)
where
and
are the total enthalpy and total Gibbs
free energy of the solution calculated by the unsymmetric electrolyte NRTL
model at the limit of all molecular components approach zero, that is, the
pure fused salts state, and
and
are the
excess enthalpy and excess Gibbs free energy of ion i at the same limit
condition.
Applying Eq. 127, the system enthalpy and Gibbs free energy with the
symmetric reference state can be expressed as:
(130)
(131)
Comparing Eqs. 130 and 131 to Eqs. 128 and 129, we can get:
(132)
(133)
Therefore, the enthalpy and Gibbs free energy of ionic components with the
symmetric reference state can be written as:
(134)
(135)
171
ln
ic
ln
ic + ln ir
and
Where nc is the number of components in the mixture. The coordination
number z is set to 10. The parameters ri and qi are calculated from the group
volume and area parameters:
and
Where ki is the number of groups of type k in molecule i, and ng is the
number of groups in the mixture.
The residual term is:
172
With:
And:
Parameter
Symbol
Name/Element
m, ...)
Upper Units
Limit
UFGRP
(k,k, m,
GMUFQ
Qk
GMUFR
Rk
GMUFB
bkn
TEMPERATURE
The parameter UFGRP stores the UNIFAC functional group number and
number of occurrences of each group. UFGRP is stored in the Aspen Physical
Property System pure component databank for most components. For
nondatabank components, enter UFGRP on the Properties Molecular Structure
Functional Group sheet. See Physical Property Data, Chapter 3, for a list of
the UNIFAC functional groups.
UNIFAC-PSRK
The PSRK property method uses GMUFPSRK, the UNIFAC-PSRK model, which
is a variation on the standard UNIFAC model. UNIFAC-PSRK has special
groups defined for the light gases CO2, H2, NH3, N2, O2, CO, H2S, and argon,
and the group binary interaction parameters are temperature-dependent,
173
using the values in parameter UNIFPS, instead of the constant value from
GMUFB used above, so that:
References
Aa. Fredenslund, J. Gmehling and P. Rasmussen, "Vapor-Liquid Equilibria
using UNIFAC," (Amsterdam: Elsevier, 1977).
Aa. Fredenslund, R.L. Jones and J.M. Prausnitz, AIChE J., Vol. 21, (1975), p.
1086.
H.K. Hansen, P. Rasmussen, Aa. Fredenslund, M. Schiller, and J. Gmehling,
"Vapor-Liquid Equilibria by UNIFAC Group Contribution. 5 Revision and
Extension", Ind. Eng. Chem. Res., Vol. 30, (1991), pp. 2352-2355.
With:
Parameter
Symbol
Name/Element
m, ...)
Units
UFGRPD
(k,k, m,
GMUFDQ
Qk
GMUFDR
Rk
UNIFDM/1
amn,1
TEMPERATURE
UNIFDM/2
amn,2
TEMPERATURE
UNIFDM/3
amn,3
TEMPERATURE
The parameter UFGRPD stores the group number and the number of
occurrences of each group. UFGRPD is stored in the Aspen Physical Property
System pure component databank. For nondatabank components, enter
UFGRPD on the Properties Molecular Structure Functional Group sheet. See
Physical Property Data, Chapter 3, for a list of the Dortmund modified UNIFAC
functional groups.
174
References
U. Weidlich and J. Gmehling, "A Modified UNIFAC Model 1. Prediction of VLE,
hE and
," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 13721381.
With:
Where k and
defined as:
With:
175
Parameter
Symbol
Name/Element
m, ...)
Default MDS
UFGRPL
(k,k, m,
GMUFLQ
Qk
GMUFLR
Rk
UNIFLB/1
amn,1
TEMPERATURE
UNIFLB/2
amn,2
TEMPERATURE
UNIFLB/3
amn,3
TEMPERATURE
The parameter UFGRPL stores the modified UNIFAC functional group number
and the number of occurrences of each group. UFGRPL is stored in the Aspen
Physical Property System pure component databank. For nondatabank
components, enter UFGRP on the Properties | Molecular Structure |
Functional Group sheet. See Physical Property Data, Chapter 3, for a list of
the Larsen modified UNIFAC functional groups.
Reference: B. Larsen, P. Rasmussen, and Aa. Fredenslund, "A Modified
UNIFAC Group-Contribution Model for Prediction of Phase Equilibria and Heats
of Mixing," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 2274 2286.
Where:
176
i'
li
t i'
ij
10
aij, bij, cij, and dij are unsymmetrical. That is, aij may not be equal to aji, etc.
Absolute temperature units are assumed for the binary parameters aij, bij, cij,
dij, and eij.
can be determined from VLE and/or LLE data regression. The Aspen Physical
Property System has a large number of built-in parameters for the UNIQUAC
model. The binary parameters have been regressed using VLE and LLE data
from the Dortmund Databank. The binary parameters for VLE applications
were regressed using the ideal gas, Redlich-Kwong, and Hayden-O'Connell
equations of state. See Physical Property Data, Chapter 1, for details.
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
GMUQR
ri
GMUQQ
qi
GMUQQ1
qi'
UNIQ/1
aij
-50.0
50.0
UNIQ/2
bij
-15000.0
15000.0
TEMPERATURE
UNIQ/3
cij
TEMPERATURE
UNIQ/4
dij
TEMPERATURE
UNIQ/5
Tlower
0K
TEMPERATURE
UNIQ/6
Tupper
1000 K x
TEMPERATURE
UNIQ/7
eij
TEMPERATURE
References
D.S. Abrams and J.M. Prausnitz, "Statistical Thermodynamics of liquid
mixtures: A new expression for the Excess Gibbs Energy of Partly or
Completely Miscible Systems," AIChE J., Vol. 21, (1975), p. 116.
A. Bondi, "Physical Properties of Molecular Crystals, Liquids and Gases," (New
York: Wiley, 1960).
Simonetty, Yee and Tassios, "Prediction and Correlation of LLE," Ind. Eng.
Chem. Process Des. Dev., Vol. 21, (1982), p. 174.
177
Where:
zi
Ai
Bi
Ci
Aij
Cij
Cij
Cji
Aii
Bii = Cii = 0
aij and bij are unsymmetrical. That is, aij may not be equal to aji, and bij may
not be equal to bji.
Parameters
Symbol DefaultMDS
Name/Element
Units
VANL/1
aij
-50.0
50.0
VANL/2
bij
-15000.0
15000.0
TEMPERATURE
VANL/3
cij
-50.0
50.0
VANL/4
dij
-15000.0
15000.0
TEMPERATURE
The VANL-2 property method uses data set 2 for VANL. All other Van Laar
methods use data set 1.
References
J.J. Van Laar, "The Vapor Pressure of Binary Mixtures," Z. Phys. Chem., Vol.
72, (1910), p. 723.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed. (New York: McGraw-Hill, 1987).
178
Where:
The parameter
For any component i, the value of the activity coefficient can be fixed:
i = gi
This model is recommended for dilute solutions.
Parameter Name/ Symbol Default MDS
Element
Lower
Limit
Upper
Limit
Units
GMWIPR/1
ai
TEMPERATURE
GMWIPR/2
bi
GMWIPR/3
ci
GMWIPB/1
dij
TEMPERATURE
GMWIPB/2
eij
GMWIPB/3
fij
GMWIPO
gi
GMWIPS
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.
References
A.D. Pelton and C. W. Bale, "A Modified Interaction Parameter Formalism for
Non-Dilute Solutions," Metallurgical Transactions A, Vol. 17A, (July 1986),
p. 1211.
179
Where:
ln Aij
Units
WILSON/1
aij
-50.0
50.0
WILSON/2
bij
-15000.0
15000.0
TEMPERATURE
WILSON/3
cij
TEMPERATURE
WILSON/4
dij
TEMPERATURE
WILSON/5
Tlower
0K
TEMPERATURE
WILSON/6
Tupper
1000 K x
TEMPERATURE
WILSON/7
eij
TEMPERATURE
The WILS-2 property method uses data set 2 for WILSON. All other Wilson
methods use data set 1.
In the original formulation of the Wilson model, aij = ln Vj/Vi, cij = dij = eij =
0, and
bij = -(ij - ii)/R, where Vj and Vi are pure component liquid molar volume at
25C.
If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.
180
References
G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.
Where:
ln Aij
Vj and Vi are pure component liquid molar volume at the system temperature
calculated using the General Pure Component Liquid Molar Volume model. The
extended form of ln Aij provides more flexibility in fitting phase equilibrium
and enthalpy data. aij, bij, cij, dij, and eij are unsymmetrical. That is, aij may
not be equal to aji, etc.
The binary parameters aij, bij, cij, dij, and eij must be determined from data
regression of VLE and/or heat-of-mixing data. There are no built in binary
parameters for this model.
Parameter
Symbol Default MDS
Name/Element
Lower
Limit
Upper
Limit
Units
WSNVOL/1
aij
-50.0
50.0
WSNVOL/2
bij
-15000.0
15000.0
TEMPERATURE
WSNVOL/3
cij
TEMPERATURE
WSNVOL/4
dij
TEMPERATURE
WSNVOL/5
eij
TEMPERATURE
WSNVOL/6
Tlower
0K
TEMPERATURE
WSNVOL/7
Tupper
1000 K x
TEMPERATURE
Pure component parameters for the General Pure Component Liquid Molar
Volume model are also required.
In the original formulation of the Wilson model, aij = cij = dij = eij = 0 and
. Vj and Vi are calculated at 25C.
181
If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.
Reference: G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.
Type
Vapor pressure
API Sour
Vapor pressure
Braun K-10
Vapor pressure
Chao-Seader
Fugacity
Grayson-Streed
Fugacity
Kent-Eisenberg
Fugacity
Maxwell-Bonnell
Vapor pressure
Solid Antoine
Vapor pressure
182
If THRSWT/3
is
Extended Antoine
PLXANT
200-211
Barin
301
Wagner
WAGNER
302
WAGNER
400
PML
401
IK-CAPE
PLPO
501
PLTDEPOL
502
NIST Wagner 25
WAGNER25
Default MDS
Lower Upper
Limit
Limit
Units
PLXANT/1
C1i
PRESSURE,
TEMPERATURE
PLXANT/2
C2i
TEMPERATURE
TEMPERATURE
PLXANT/8
C8i
TEMPERATURE
PLXANT/9
C9i
1000
TEMPERATURE
If C5i, C6i, or C7i is non-zero, absolute temperature units are assumed for all
coefficients C1i through C7i. The temperature limits are always in user input
units.
Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.
Where:
Tri = T / Tci
pri*,l = pi*,l / pci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
Note: Reduced temperature Tr is always calculated using absolute
temperature units.
183
Where:
Tri = T / Tci
pri*,l = pi*,l / pci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
WAGNER/1
C1i
WAGNER/2
C2i
WAGNER/3
C3i
WAGNER/4
C4i
WAGNER/5
C5i
TEMPERATURE
WAGNER/6
C6i
1000
TEMPERATURE
TC
Tci
TEMPERATURE
PC
pci
PRESSURE
Where:
Tri = T / Tci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
184
Parameter
Name/Element
Symbol
Default MDS
WAGNER25/1
C1i
WAGNER25/2
C2i
WAGNER25/3
C3i
WAGNER25/4
C4i
WAGNER25/5
ln pci
WAGNER25/6
Tci
WAGNER25/7
Tlower
WAGNER25/8
Tupper
Lower
Limit
Upper
Limit
Units
TEMPERATURE
TEMPERATURE
1000
TEMPERATURE
Symbol
PLPO/1
C1i
PLPO/2, ..., 10
PLPO/11
PLPO/12
Default MDS
Lower Upper
Limit Limit
Units
PRESSURE
TEMPERATURE
TEMPERATURE
C11i
TEMPERATURE
C12i
1000
TEMPERATURE
Where:
Tri = T / Tci
pri*,l = pi*,l / pci
LNVPEQ/2 and LNVPEQ/3 are the lower and upper temperature limits,
respectively.
In equations 1-4, if elements 4, 7, or 8 are non-zero, absolute temperature
units are assumed for all elements.
185
Parameter
Name/Element
Symbol
Default
MDS Lower
Limit
Upper
Limit
Units
LNVP1/1, ...,8
PRESSURE
TEMPERATURE
LOGVP1/1, ..., 8
PRESSURE
TEMPERATURE
LNPR1/1, ..., 8
PRESSURE
TEMPERATURE
LOGPR1/1, ..., 8
PRESSURE
TEMPERATURE
LNPR2/1,2
C1i, C2i
LOGPR2/1,2
C1i, C2i
LNVPEQ/1
(equation
number)
LNVPEQ/2
Tlower
TEMPERATURE
LNVPEQ/3
Tupper
1000
TEMPERATURE
TC
Tci
TEMPERATURE
PC
pci
PRESSURE
Symbol
DefaultMDS
Lower Upper
Limit Limit
Units
PLTDEPOL/1
C1i
PLTDEPOL/2
C2i
PLTDEPOL/3
C3i
TEMPERATURE
PLTDEPOL/9
Tlower
TEMPERATURE
PLTDEPOL/10
Tupper
1000
TEMPERATURE
X
TEMPERATURE
References
Reid, Prausnitz, and Poling, The Properties of Gases and Liquids, 4th ed.,
(New York: McGraw-Hill, 1987).
186
Average Error, %
Up to 60 C
Above 60 C
Ammonia
10
36
Carbon dioxide
11
24
Hydrogen sulfide
12
29
Detail of the model is described in the reference below and is too involved to
be reproduced here.
Reference
New Correlation of NH3, CO2, and H2S Volatility Data from Aqueous Sour
Water Systems, API Publication 955, March 1978 (American Petroleum
Institute).
187
References
B.C. Cajander, H.G. Hipkin, and J.M. Lenoir, "Prediction of Equilibrium Ratios
from Nomograms of Improved Accuracy," Journal of Chemical Engineering
Data, vol. 5, No. 3, July 1960, p. 251-259.
J.M. Lenoir, "Predict K Values at Low Temperatures, part 1," Hydrocarbon
Processing, p. 167, September 1969.
J.M. Lenoir, "Predict K Values at Low Temperatures, part 2," Hydrocarbon
Processing, p. 121, October 1969.
Where:
=
Parameter
Name/Element
Units
TC
Tci
5.0
2000.0
TEMPERATURE
PC
pci
105
108
PRESSURE
OMEGA
-0.5
2.0
References
K.C. Chao and J.D. Seader, "A General Correlation of Vapor-Liquid Equilibria
in Hydrocarbon Mixtures," AIChE J., Vol. 7, (1961), p. 598.
Where:
188
Parameter
Name/Element
Units
TC
Tci
5.0
TEMPERATURE
2000.0
Parameter
Name/Element
Units
PC
pci
105
108
PRESSURE
OMEGA
-0.5
2.0
References
H.G. Grayson and C.W. Streed, Paper 20-PO7, Sixth World Petroleum
Conference, Frankfurt, June 1963.
Where:
R'
189
The apparent fugacities and partial molar enthalpies, Gibbs energies and
entropies of H2S and CO2 are calculated by standard thermodynamic
relationships. The chemical reactions are always considered.
The values of the coefficients for the seven equilibrium constants (A1i, ... A5i)
and for the two Henry's constants B1i and B2i are built into the Aspen Physical
Property System. The coefficients for the equilibrium constants were
determined by regression. All available data for the four amines were used:
monoethanolamine, diethanolamine, disopropanolamine and diglycolamine.
You are not required to enter any parameters for this model.
References
R.L. Kent and B. Eisenberg, Hydrocarbon Processing, (February 1976),
pp. 87-92.
References
API procedure 5A1.15 and 5A1.13.
190
Parameter
Name/
Element
Symbol
Default MDS
Units
PSANT/1
C1i
PRESSURE,
TEMPERATURE
PSANT/2
C2i
TEMPERATURE
PSANT/3
C3i
TEMPERATURE
PSANT/4
C4i
TEMPERATURE
PSANT/5
C5i
1000
TEMPERATURE
Watson
DHVLWT
106
DIPPR
DHVLDP
301
PPDS
DHVLDS
401
IK-CAPE
DHVLPO
505
DHVLTDEW
Where:
Tri = T / Tci
Note: Reduced temperature Tr is always calculated using absolute
temperature units.
Linear extrapolation of vapHi* versus T occurs outside of temperature bounds,
using the slope at the temperature bound, except that vapHi* is zero for
.
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
DHVLDP/1
MOLE-ENTHALPY
C1i
DHVLDP/6
C6i
TEMPERATURE
DHVLDP/7
C7i
1000
TEMPERATURE
TC
Tci
5.0
2000.0
TEMPERATURE
191
Where:
vapHi*(T1)
Symbol
Default Lower
Limit
Upper
Limit
Units
TC
Tci
2000.0
TEMPERATURE
5.0
4
DHVLWT/1
vapHi*(T1)
5x10
DHVLWT/2
T1
4.0
3500.0
TEMPERATURE
DHVLWT/3
ai
0.38
-2.0
2.0
DHVLWT/4
bi
-2.0
2.0
DHVLWT/5
Tmin
0.0
1500.0
TEMPERATURE
5x10
MOLE-ENTHALPY
192
Parameter
Name/Element
Symbol
Upper
Limit
Units
TC
Tci
5.0
2000.0
TEMPERATURE
DHVLDS/1
C1i
DHVLDS/2
C2i
DHVLDS/3
C3i
DHVLDS/4
C4i
DHVLDS/5
C5i
DHVLDS/6
C6i
TEMPERATURE
DHVLDS/7
C7i
1000
TEMPERATURE
Default MDS
Lower
Limit
Upper
Limit
Units
DHVLPO/1
MOLEENTHALPY
MOLEENTHALPY
TEMPERATURE
DHVLPO/11
C11i
TEMPERATURE
DHVLPO/12
C12i
1000
TEMPERATURE
C1i
Default MDS
Lower
Limit
Upper
Limit
Units
DHVLTDEW/1
C1i
DHVLTDEW/5
Tci
TEMPERATURE
DHVLTDEW/6
nTerms
DHVLTDEW/7
Tlower
TEMPERATURE
DHVLTDEW/8
Tupper
1000
TEMPERATURE
193
Clausius-Clapeyron Equation
The Aspen Physical Property System can calculate heat of vaporization using
the Clausius Clapeyron equation:
Where:
=
Vi*,v
Vi*,l
Type
Liquid volume
Brelvi-O'Connell
Liquid volume
Liquid volume
Debye-Hckel Volume
Liquid volume
Liquid volume/liquid
density
Liquid volume
Modified Rackett
Liquid volume
Liquid volume
194
Where:
xp
xr
Where:
fcn
At high density, the Ritter equation is used (adapted from Ritter, Lenoir, and
Schweppe, Petrol. Refiner 37 [11] 225 (1958)):
API: 0 - 95
Temperature: 0 - 1000 F
Lower
Limit
Upper
Limit
Units
TB
Tb
4.0
2000.0
TEMPERATURE
API
API
-60.0
500.0
TC
Tc
5.0
2000.0
TEMPERATURE
195
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
PC
pc
RKTZRA
RA
105
108
PRESSURE
ZC
0.1
0.5
There are two versions of this model: VL2API and VL2API5. Model VL2API is
used in route VLMX20, while model VL2API5 is used in route VLMX24.
The main difference between the VL2API and VL2API5 models is as follows:
The VL2API model calculates the liquid density for each pseudocomponent
using the API procedure 6A3.5 (or Ritter equation), then computes the
density of the pseudocomponent mixture as a mole-fraction-weighted
average.
The VL2API5 model calculates the liquid density of the mixture of the
pseudocomponents as a whole. It first computes the specific gravity and
mean average boiling point of the pseudocomponent mixture, then uses the
API procedure 6A3.5 (or Ritter equation) to compute the mixture liquid
density.
Both models use the same procedure 6A3.10 for pressure correction.
Experience shows that VL2API5 is less sensitive to how the
pseudocomponents are generated from the same assay (number of cut
points, etc.).
Brelvi-O'Connell
The Brelvi-O'Connell model calculates partial molar volume of a supercritical
component i at infinite dilution in pure solvent A. Partial molar volume at
infinite dilution is required to compute the effect of pressure on Henry's
constant. (See Henry's Constant.)
The general form of the Brelvi-O'Connell model is:
Where:
i
= Solvent component
The liquid molar volume of solvent is obtained from the Rackett model:
196
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
TC
TcA
5.0
2000.0
TEMPERATURE
PC
pcA
10
RKTZRA
ZARA
ZC
0.1
10
1.0
PRESSURE
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
VLBROC/1
ViBO
VC
-1.0
1.0
MOLE-VOLUME
VLBROC/2
-0.1
0.1
TEMPERATURE
References
S.W. Brelvi and J.P. O'Connell, AIChE J., Vol. 18, (1972), p. 1239.
S.W. Brelvi and J.P. O'Connell, AIChE J., Vol. 21, (1975), p. 157.
The relationship between the partial molar volume of an electrolyte and its
mole fraction in the solvent (equation 4)
Vsl
Vel
Vw*
xnws
Vnwsl
Liquid molar volume for the mixture of all nonwater solvents. It is calculated using the
Rackett equation.
For electrolytes:
197
(3)
(4)
(5)
(6)
Where:
xca
Vca
The mole fractions xca are reconstituted arbitrarily from the true ionic
concentrations, even if you use the apparent component approach. This
technique is explained in Electrolyte Calculation in Physical Property Methods.
The result is that electrolytes are generated from all possible combinations of
ions in solution. The following equation is consistently applied to determine
the amounts of each possible apparent electrolyte nca:
(7)
Where:
nca
zc
Charge of c
zfactor
nc
na
For example: given an aqueous solution of Ca2+, Na+, SO42-, Cl- four
electrolytes are found: CaCl2, Na2SO4, CaSO4, and NaCl. The Clarke
parameters of all four electrolytes are used. You can rely on the default,
which calculates the Clarke parameters from ionic parameters. Otherwise, you
must enter parameters for any electrolytes that may not exist in the
components list. If you do not want to use the default, the first step in using
the Clarke model is to add any needed components for electrolytes not in the
components list.
198
(8)
Where:
Vml,t
Vml,a
na
Temperature Dependence
The temperature dependence of the molar volume of the solution is
approximately equal to the temperature dependence of the molar volume of
the solvent mixture:
(9)
Applicable
Components
VLCLK/1
Cation-Anion
VLCLK/2
Cation-Anion
Symbol
Aca
Default
Units
MOLE-VOLUME
0.020
MOLE-VOLUME
If VLBROC/1 is missing, the default value of -0.0012 is used. See the BrelviO'Connell model for VLBROC and also Rackett/Campbell-Thodos Mixture
Liquid Volume for additional parameters used in the Rackett equation.
Reference
C.C. Chen, private communication.
199
Where:
Where:
Lower
Limit
Upper
Limit
Units
TC
Tci
5.0
2000.0
TEMPERATURE
VSTCTD
Vr*,CTD
VC
0.001
3.5
MOLE-VOLUME
OMGCTD
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. Brobst, and R.W. Hankinson, AIChE J., Vol. 28, (1982),
p. 4, p. 671.
200
Debye-Hckel Volume
The Debye-Hckel model calculates liquid molar volume for aqueous
electrolyte solutions.
The equation for the Debye-Hckel volume model is:
Where:
Vk is the molar volume for water and is calculated from the ASME steam
table.
Vk is calculated from the Debye-Hckel limiting law for ionic species. It is
assumed to be the infinite dilution partial volume for molecular solutes.
Where:
zk
Av
1.2
Vk
Molarity of ion k
Av is computed as follows:
Where:
A
Parameter Name
Applicable
Components
VLBROC
Symbol
Default
Units
MOLE-VOLUME
201
References
D. J. Bradley, K. S. Pitzer, "Thermodynamics of Electrolytes," J. Phys. Chem.,
83 (12), 1599 (1979).
H.C. Helgeson and D.H. Kirkham, "Theoretical prediction of the
thermodynamic behavior of aqueous electrolytes at high pressure and
temperature. I. Thermodynamic/electrostatic properties of the solvent", Am.
J. Sci., 274, 1089 (1974).
K.S. Pitzer, "Theory: Ion Interaction Approach," Activity Coefficients in
Electrolyte Solutions, Pytkowicz, R. ed., Vol. I, (CRC Press Inc., Boca Raton,
Florida, 1979).
Default
MDS
Units
VLCONS
MOLE-VOLUME
Rackett
RKTZRA
100-116
DIPPR
DNLDIP
301
PPDS
DNLPDS
401
IK-CAPE
VLPO
503
NIST ThermoML
Polynomial
DNLTMLPO
504
DNLEXSAT
514
DNLRACK
515
NIST COSTALD
DNLCOSTD
For liquid molar volume of mixtures, the Rackett mixture equation is always
used by default. This is not necessarily consistent with the pure component
molar volume or density. If you need consistency, select route VLMX26 on the
Properties | Property Methods form. This route calculates mixture molar
volume from the mole-fraction average of pure component molar volumes.
Many of these equations calculate density first, and return calculate liquid
molar volume based on that density:
202
DIPPR
DIPPR equation 105 is the default DIPPR equation for most substances:
= 1 - T / Tc
Other DIPPR equations, such as equation 100, may be used for some
substances. Check the value of THRSWT/2 to determine the equation used.
See Pure Component Temperature-Dependent Properties for details about
DIPPR equations.
In either case, linear extrapolation of
temperature bounds.
Parameter
Name/Element
Lower Upper
Limit Limit
Units
DNLDIP/1
C1i
MOLE-DENSITY
DNLDIP/2
C2i
DNLDIP/3
C3i
Tci
TEMPERATURE
DNLDIP/4
C4i
DNLDIP/5
C5i
DNLDIP/6
C6i
TEMPERATURE
DNLDIP/7
C7i
1000
TEMPERATURE
For equation 116, the units are MOLE-DENSITY for parameters DNLDIP/1
through DNLDIP/5 and the default for DNLDIP/3 is 0. For equation 105,
DNLDIP/5 is not used, and absolute temperature units are assumed for
DNLDIP/3.
PPDS
The PPDS equation is:
Linear extrapolation of
Parameter
Name/Element
Symbol
DefaultMDS Lower
Limit
Upper
Limit
Units
MW
Mi
5000.0
1.0
203
Parameter
Name/Element
Symbol
DefaultMDS Lower
Limit
Upper
Limit
Units
VC
Vci
0.001
3.5
MOLE-VOLUME
TC
Tci
5.0
2000.0
TEMPERATURE
DNLPDS/1
C1i
MASS-DENSITY
DNLPDS/2
C2i
MASS-DENSITY
DNLPDS/3
C3i
MASS-DENSITY
DNLPDS/4
C4i
MASS-DENSITY
DNLPDS/5
C5i
TEMPERATURE
DNLPDS/6
C6i
1000
TEMPERATURE
IK-CAPE
The IK-CAPE equation is:
Default MDS
Lower
Limit
Upper
Limit
Units
VLPO/1
C1i
MOLEVOLUME
VLPO/2, ..., 10
MOLEVOLUME
TEMPERATURE
VLPO/11
C11i
TEMPERATURE
VLPO/12
C12i
1000
TEMPERATURE
204
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
DNLTMLPO/1
MOLEDENSITY
MOLEDENSITY
TEMPERATURE
DNLTMLPO/5
DNLTMLPO/6
TEMPERATURE
DNLTMLPO/7
1000
TEMPERATURE
C1i
nTerms
Rackett
The Rackett equation is:
Where:
Tr = T / Tci
Note: Reduced temperature Tr is always calculated using absolute
temperature units.
Note: Above Tr=0.99 an extrapolation method is used to smooth the
transition to constant molar volume equal to the critical volume.
Parameter
Name/
Element
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
TC
Tci
5.0
2000.0
TEMPERATURE
10
ZC
0.1
PC
RKTZRA
pci
Zi
*,RA
10
1.0
PRESSURE
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
DNLRACK/1
Zc
DNLRACK/2
2/7
DNLRACK/3
Tci
TEMPERATURE
DNLRACK/4
pci
PRESSURE
DNLRACK/5
Tlower
TEMPERATURE
DNLRACK/6
Tupper
1000
TEMPERATURE
205
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
DNLCOSTD/1
Voi
VOLUME
DNLCOSTD/2
DNLCOSTD/3
Tci
TEMPERATURE
DNLCOSTD/4
Tlower
TEMPERATURE
DNLCOSTD/5
Tupper
1000
TEMPERATURE
Symbol
Default
MDS Lower
Limit
Upper
Limit
Units
DNLEXSAT/1
ci
MOLEDENSITY
DNLEXSAT/2
C1i
MOLEDENSITY
DNLEXSAT/3,
C2i, ..., C6i
..., DNLEXSAT/7
MOLEDENSITY
DNLEXSAT/8
Tci
TEMPERATURE
DNLEXSAT/9
nTerms
DNLEXSAT/10
Tlower
TEMPERATURE
DNLEXSAT/11
Tupper
1000
TEMPERATURE
References
H.G. Rackett, 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.
206
Rackett
The equation for the Rackett model is:
Where:
Tc
ZmRA
Vcm
Tr
T / Tc
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
TC
Tci
5.0
2000.0
TEMPERATURE
10
PC
pci
10
VCRKT
Vci
VC
0.001
3.5
MOLEVOLUME
RKTZRA
Zi*,RA
ZC
0.1
1.0
RKTKIJ
kij
-5.0
5.0
PRESSURE
207
Campbell-Thodos
The Campbell-Thodos model uses the same equation and parameters as the
Rackett model, above, except that ZmRAis allowed to vary with temperature:
ZmRA
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
RACKET/1
R*Tci/Pci
R*Tci/Pci
MOLEVOLUME
RACKET/2
Zi*,RA
RKTZRA
0.1
1.0
RACKET/3
di
0.11
RACKET/4
Tmin
TEMPERATURE
RACKET/5
Tmax
1000
TEMPERATURE
References
H.G. Rackett, 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.
Where:
Tc
kij
=
=
208
ZmRA
Zi*,RA
Vcm
Tr
T / Tc
Symbol Default
MDS
Lower
Limit
Upper
Limit
Units
MRKZRA/1
ai
RKTZRA
0.1
0.5
MRKZRA/2
bi
MRKZRA/3
ci
MRKKIJ/1
Aij
MRKKIJ/2
Bij
MRKKIJ/3
Cij
References
H.G. Rackett, 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.
209
Details
First the volume V0 at 0.99Tc and the critical volume Vc are calculated:
Finally, the equation of the circle is used to determine any point (T,V) for
0.99Tc < T < T00:
210
Aspen
VSPOLY
100
DIPPR
DNSDIP
401
IK-CAPE
VSPO
503
NIST ThermoML
polynomial
DNSTMLPO
Aspen Polynomial
The equation for the Aspen solids volume polynomial is:
Applicable
Components
Symbol
MDS
Default
Units
VSPOLY/1
Salts, CI solids
C1i
MOLE-VOLUME
TEMPERATURE
MOLE-VOLUME
TEMPERATURE
VSPOLY/6
Salts, CI solids
C6i
MOLE-VOLUME
TEMPERATURE
VSPOLY/7
Salts, CI solids
C7i
1000
MOLE-VOLUME
TEMPERATURE
IK-CAPE Equation
The IK-CAPE equation is:
Default MDS
Lower
Limit
Upper
Limit
Units
VSPO/1
MOLEVOLUME
C1i
211
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
VSPO/2, ..., 10
MOLEVOLUME
TEMPERATURE
VSPO/11
C11i
TEMPERATURE
VSPO/12
C12i
1000
TEMPERATURE
DIPPR
The DIPPR equation is:
Linear extrapolation of
Vi*,s = 1 /
i*,s
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
DNSDIP/1
C1i
MOLEDENSITY
DNSDIP/2, ..., 5
MOLEDENSITY,
TEMPERATURE
DNSDIP/6
C6i
TEMPERATURE
DNSDIP/7
C7i
1000
TEMPERATURE
Linear extrapolation of
Vi*,s = 1 /
212
i*,s
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
DNSTMLPO/1
C1i
MOLEDENSITY
MOLEDENSITY,
TEMPERATURE
DNSTMLPO/9
nTerms
DNSTMLPO/10
Tlower
TEMPERATURE
DNSTMLPO/11
Tupper
1000
TEMPERATURE
Option Codes
Option Code Value
Descriptions
Parameter
Parameter
Name/Element
Symbol
Default
MDS
Lower
Limit
Upper
Limit
Units
VLQKIJ
Kij
This model is not part of any property method. To use it, you will need to
define a property method on the Properties | Property Methods form.
Specify the route VLMXQUAD for VLMX on the Routes sheet of this form, or
the model VL2QUAD for VLMX on the Models sheet.
Type
Electrolyte liquid
Electrolyte liquid
Liquid
Ideal gas
Solid
213
versus T is linearly extrapolated using the slope at C7i for T < C7i
versus T is linearly extrapolated using the slope at C8i for T < C8i
Parameter
Name/Element
Applicable
Components
Symbol
Default Units
CPAQ0/1
TEMPERATURE and
HEAT CAPACITY
CPAQ0/2,,6
TEMPERATURE and
HEAT CAPACITY
CPAQ0/7
TEMPERATURE
CPAQ0/8
1000
TEMPERATURE
Default
Ion Type 0
Units
IONTYP
Ions
SO25C
Anions
MOLE-ENTROPY
Cations
MOLE-ENTROPY
214
100
CPLDIP
DIPPR
200-211
Barin
CPLXP1, CPLXP2
301
PPDS
CPLPDS
401
CPLPO
403
CPLIKC
503
NIST ThermoML
polynomial
CPLTMLPO
506
CPLTDECS
This liquid heat capacity model is used to calculate pure component liquid
heat capacity and pure component liquid enthalpy. To use this model, two
conditions must exist:
Where
= Reference enthalpy calculated at Tref
= Ideal gas enthalpy
= Vapor enthalpy departure
= Enthalpy of vaporization
Tref is the reference temperature; it defaults to 298.15 K. You can enter a
different value for the reference temperature. This is useful when you want to
use this model for very light components or for components that are solids at
298.15K.
Activate this model by specifying the route DHL09 for the property DHL on
the Properties Property Methods Routes sheet. For equation of state property
method, you must also modify the route for the property DHLMX to use a
route with method 2 or 3, instead of method 1. For example, you can use the
route DHLMX00 or DHLMX30. You must ascertain that the route for DHLMX
that you select contains the appropriate vapor phase model and heat of
mixing calculations. Click the View button on the form to see details of the
route.
Optionally, you can specify that this model is used for only certain
components. The properties for the remaining components are then
calculated by the standard model. Use the parameter COMPHL to specify the
215
components for which this model is used. By default, all components with the
CPLDIP or CPLIKC parameters use this model.
Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.
Default
MDS
Lower
Limit
Upper Units
Limit
CPLDIP/1
C1i
MOLE-HEATCAPACITY,
TEMPERATURE
CPLDIP/2, ..., 5
MOLE-HEATCAPACITY,
TEMPERATURE
CPLDIP/6
C6i
TEMPERATURE
CPLDIP/7
C7i
1000
TEMPERATURE
ref
TREFHL
298.15
TEMPERATURE
COMPHL
To specify that the model is used for a component, enter a value of 1.0 for
COMPHL.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
216
Parameter
Symbol
Name/Element
Default
MDS
Lower
Limit
Upper Units
Limit
CPLPDS/1
C1i
CPLPDS/2
C2i
CPLPDS/3
C3i
CPLPDS/4
C4i
CPLPDS/5
C5i
CPLPDS/6
C6i
CPLPDS/7
C7i
TEMPERATURE
CPLPDS/8
C8i
0.99 TC
TEMPERATURE
Parameter
Symbol
Name/Element
Upper
Limit
Units
CPLIKC/1
C1i
MOLE-HEATCAPACITY
CPLIKC/2,...,4
MOLE-HEATCAPACITY,
TEMPERATURE
CPLIKC/5
C5i
MOLE-HEATCAPACITY,
TEMPERATURE
CPLIKC/6
C6i
TEMPERATURE
CPLIKC/7
C7i
1000
TEMPERATURE
If C5i is non-zero, absolute temperature units are assumed for C2i through
C5i. Otherwise, user input units for temperature are used. The temperature
limits are always interpreted in user input units.
When THRSWT/6 is 401, the IK-CAPE heat capacity polynomial is used.The
equation is:
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
CPLPO/1
C1i
MOLE-CAPACITY
CPLPO/2,,10
MOLE-CAPACITY
TEMPERATURE
CPLPO/11
C11i
TEMPERATURE
217
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
CPLPO/12
1000
TEMPERATURE
C12i
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
CPLTMLPO/1
J/K^2/mol
J/K^2/mol
CPLTMLPO/6
nTerms
CPLTMLPO/7
Tlower
TEMPERATURE
CPLTMLPO/8
Tupper
1000
TEMPERATURE
C1i
When THRSWT/6 is 506, the TDE equation is used to calculate liquid heat
capacity:
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
CPLTDECS/1
MOLE-HEATCAPACITY
MOLE-HEATCAPACITY
CPLTDECS/5
MOLE-HEATCAPACITY
CPLTDECS/6
Tci
TEMPERATURE
CPLTDECS/7
nTerms
CPLTDECS/8
Tlower
TEMPERATURE
CPLTDECS/9
Tupper
1000
TEMPERATURE
C1i
218
CPIG
107, 127
CPIGDP
200-211
Barin
301
PPDS
CPIGDS
401
CPIGPO
503
NIST ThermoML
polynomial
CPITMLPO
513
NIST Aly-Lee
CPIALEE
These equations are also used to calculate ideal gas enthalpies, entropies,
and Gibbs energies.
Symbol
Default MDS
CPIG/1
C1i
MOLE-HEAT-CAPACITY,
TEMPERATURE
MOLE-HEAT-CAPACITY,
TEMPERATURE
CPIG/7
C7i
TEMPERATURE
CPIG/8
C8i
1000
TEMPERATURE
CPIG/9, 10,
11
MOLE-HEAT-CAPACITY,
TEMPERATURE
If C10i or C11i is non-zero, then absolute temperature units are assumed for
C9i through C11i. Otherwise, user input temperature units are used for all
parameters. User input temperature units are always used for C1i through C8i.
219
Parameter
Name/
Element
Symbol
Default MDS
CPITMLPO /1
C1i
J/K^2/mol
J/K^2/mol
CPITMLPO/7
nTerms
CPITMLPO /8
Tlower
TEMPERATURE
CPITMLPO /9
Tupper
1000
TEMPERATURE
Upper
Limit
Units
CPIGDP/1
C1i
MOLE-HEATCAPACITY
CPIGDP/2
C2i
MOLE-HEATCAPACITY
CPIGDP/3
C3i
TEMPERATURE
CPIGDP/4
C4i
MOLE-HEATCAPACITY
CPIGDP/5
C5i
TEMPERATURE
CPIGDP/6
C6i
TEMPERATURE
CPIGDP/7
C7i
1000
TEMPERATURE
Absolute temperature units are assumed for C3i and C5i. The temperature
limits are always interpreted in user input units.
220
Upper
Limit
Units
CPIGDP/1
C1i
MOLE-HEATCAPACITY
CPIGDP/2
C2i
MOLE-HEATCAPACITY
CPIGDP/3
C3i
TEMPERATURE
CPIGDP/4
C4i
MOLE-HEATCAPACITY
CPIGDP/5
C5i
TEMPERATURE
CPIGDP/6
C6i
MOLE-HEATCAPACITY
CPIGDP/7
C7i
TEMPERATURE
Absolute temperature units are assumed for C3i, C5i and C7i.
Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.
NIST Aly-Lee
This equation is the same as the DIPPR Aly and Lee equation 107 above, but
it uses a different parameter set. Note that elements 6 and 7 of the CPIALEE
parameter are not used in the equation.
Parameter
Symbol
Name/Element
Upper
Limit
Units
CPIALEE/1
C1i
MOLE-HEATCAPACITY
CPIALEE/2
C2i
MOLE-HEATCAPACITY
CPIALEE/3
C3i
TEMPERATURE
CPIALEE/4
C4i
MOLE-HEATCAPACITY
CPIALEE/5
C5i
TEMPERATURE
CPIALEE/8
C6i
TEMPERATURE
CPIALEE/9
C7i
1000
TEMPERATURE
Absolute temperature units are assumed for C3i and C5i. The temperature
limits are always interpreted in user input units.
PPDS
The PPDS equation is:
221
Default MDS
Lower
Limit
Upper
Limit
Units
CPIGDS/1
C1i
TEMPERATURE
CPIGDS/2, , 8
CPIGDS/9
C9i
TEMPERATURE
CPIGDS/10
C10i
1000
TEMPERATURE
Default MDS
Lower
Limit
Upper
Limit
Units
CPIGPO/1
C1i
MOLE-CAPACITY
CPIGPO/2,,10
MOLE-CAPACITY
TEMPERATURE
CPIGPO/11
C11i
TEMPERATURE
CPIGPO/12
C12i
1000
TEMPERATURE
References
Data for the Ideal Gas Heat Capacity Polynomial: Reid, Prausnitz and Poling,
The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987).
The Aspen Physical Property System combustion data bank, JANAF
Thermochemical Data, Compiled and calculated by the Thermal Research
Laboratory of Dow Chemical Company.
F. A. Aly and L. L. Lee, "Self-Consistent Equations for Calculating the Ideal
Gas Heat Capacity, Enthalpy, and Entropy, Fluid Phase Eq., Vol. 6, (1981), p.
169.
222
100 or 102
DIPPR
CPSDIP
200-211
Barin
CPSXP1, CPSXP2, ,
CPSXP7
401
CPSPO
503
NIST ThermoML
polynomial
CPSTMLPO
The enthalpy, entropy, and Gibbs energy of solids are also calculated from
these equations:
Applicable Symbol
Components
MDS
Default
Units
CPSPO1/1
CPSPO1/7
CPSPO1/8
1000
The units are TEMPERATURE and HEAT-CAPACITY for all elements. If any of
C4i through C6i are non-zero, absolute temperature units are assumed for
elements C1i through C6i. Otherwise, user input temperature units are
assumed for all elements. The temperature limits are always interpreted in
user input units.
Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.
DIPPR
There are two DIPPR equations that may generally be used.
The more common one, DIPPR equation 100, is:
223
Default
MDS
Lower
Limit
Upper Units
Limit
CPSDIP/1
C1i
MOLE-HEATCAPACITY,
TEMPERATURE
CPSDIP/2,...,5
MOLE-HEATCAPACITY,
TEMPERATURE
CPSDIP/6
C6i
TEMPERATURE
CPSDIP/7
C7i
1000
TEMPERATURE
Default
MDS
Lower
Limit
Upper Units
Limit
CPSDIP/1
C1i
MOLE-HEATCAPACITY,
TEMPERATURE
CPSDIP/2
C2i
CPSDIP/3,4
C3i, C4i
TEMPERATURE
CPSDIP/6
C6i
TEMPERATURE
CPSDIP/7
C7i
1000
TEMPERATURE
If C3i or C4i are non-zero or C2i is negative, absolute temperature units are
assumed for elements C1i through C4i. Otherwise, user input temperature
units are assumed for all elements. The temperature limits are always
interpreted in user input units.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
224
Parameter
Symbol
Name/Element
Default
MDS
Lower
Limit
Upper Units
Limit
CPSTMLPO/1
J/K^2/mol
J/K^2/mol
CPSTMLPO/6
nTerms
CPSTMLPO/7
Tlower
TEMPERATURE
C1i
Parameter
Symbol
Name/Element
Default
MDS
Lower
Limit
Upper Units
Limit
CPSTMLPO/8
1000
Tupper
TEMPERATURE
Default MDS
Lower
Limit
Upper
Limit
Units
CPSPO/1
C1i
MOLE-CAPACITY
CPSPO/2,,10
C10i
MOLE-CAPACITY
TEMPERATURE
CPSPO/11
C11i
TEMPERATURE
CPSPO/12
C12i
1000
TEMPERATURE
Solubility Correlations
The Aspen Physical Property System has three built-in solubility correlation
models. This section describes the solubility correlation models available.
Model
Type
Henry's constant
Water solubility
Hydrocarbon solubility
Henry's Constant
The Henry's constant model is used when Henry's Law is applied to calculate
K-values for dissolved gas components in a mixture. Henry's Law is available
in all activity coefficient property methods, such as the WILSON property
method. The model calculates Henry's constant for a dissolved gas component
(i) in one or more solvents (A or B):
Where:
wA
ln HiA(T, pA*,l)
225
The parameter
The Henry's constants aiA, biA, ciA, diA, and eiA are specific to a solute-solvent
pair. They can be obtained from regression of gas solubility data. The Aspen
Physical Property System has a large number of built-in Henry's constants for
many solutes in solvents. These parameters were obtained using data from
the Dortmund Databank. In addition, a small number of Henry's constants
from the literature are available in the BINARY databank. See Physical
Property Data, Chapter 1, for details.
Parameter
Name/Element
VC
VcA
0.001
3.5
MOLE-VOLUME
HENRY/1
aiA
PRESSURE,
TEMPERATURE
HENRY/2
biA
TEMPERATURE
HENRY/3
ciA
TEMPERATURE
HENRY/4
diA
TEMPERATURE
HENRY/5
TL
TEMPERATURE
HENRY/6
TH
2000
TEMPERATURE
HENRY/7
eiA
TEMPERATURE
If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.
If aiA is missing,
renormalized.
Water Solubility
This model calculates solubility of water in a hydrocarbon-rich liquid phase.
The model is used automatically when you model a hydrocarbon-water
system with the free-water option. See Free-Water Immiscibility Simplification
in Free-Water and Three-Phase Calculations for details.
226
The expression for the liquid mole fraction of water in the ith hydrocarbon
species is:
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
WATSOL/1
C1i
-10.0
33.0
WATSOL/2
C2i
-10000.0 3000.0
TEMPERATURE
WATSOL/3
C3i
-0.05
0.05
TEMPERATURE
WATSOL/4
C4i
0.0
500
TEMPERATURE
WATSOL/5
C5i
1000
4.0
1000
TEMPERATURE
Hydrocarbon Solubility
This model calculates solubility of hydrocarbon in a water-rich liquid phase.
The model is used automatically when you model a hydrocarbon-water
system with the dirty-water option. See Free-Water Immiscibility
Simplification in Free-Water and Rigorous Three-Phase Calculations for
details.
The expression for the liquid mole fraction of the ith hydrocarbon species in
water is:
Symbol Default
MDS Lower
Limit
Upper
Limit
Units
HCSOL/1
C1i
fcn(carbon
number)
-1000.0
1000.0
HCSOL/2
C2i
HCSOL/3
C3i
-100.0
100.0
TEMPERATURE
HCSOL/4
C4i
0.0
500
TEMPERATURE
HCSOL/5
C5i
1000
4.0
1000
TEMPERATURE
227
Reference
C. Tsonopoulos, Fluid Phase Equilibria, 186 (2001), 185-206.
Barin Equations for Gibbs Energy, Enthalpy, Entropy and Heat Capacity
Cavett
The general form for the Cavett model is:
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
TC
Tci
5.0
2000.0
TEMPERATURE
10
ZC
0.1
PC
pci
DHLCVT
10
0.5
PRESSURE
Gibbs energy:
(1)
Enthalpy:
(2)
228
Entropy:
(3)
Heat capacity:
(4)
refers to an arbitrary phase which can be solid, liquid, or ideal gas. For each
phase, multiple sets of parameters from 1 to n are present to cover multiple
temperature ranges. The value of the parameter n depends on the phase.
(See tables that follow.) When the temperature is outside all these
temperature ranges, linear extrapolation of properties versus T is performed
using the slope at the end of the nearest temperature bound.
The four properties Cp, H, S, and G are interrelated as a result of the
thermodynamic relationships:
THRSWT/5
THRSWT/6
THRSWT/7
Solid Phase
The parameters in range n are valid for temperature: Tn,ls < T < Tn,hs
229
Tn,ls
s
Upper
Limit
Units
TEMPERATURE
TEMPERATURE
CPSXPn/2
Tn,h
CPSXPn/3
an,i
CPSXPn/4
bn,is
CPSXPn/5
CPSXPn/6
dn,i
CPSXPn/7
en,is
CPSXPn/8
CPSXPn/9
CPSXPn/10
cn,i
fn,i
gn,i
hn,i
Liquid Phase
The parameters in range n are valid for temperature: Tn,ll < T < Tn,hl
When you specify this parameter, be sure to specify at least elements 1
through 3.
Parameter Name Symbol Default MDS Lower
/Element
Limit
Upper
Limit
Units
CPLXPn/1
Tn,ll
TEMPERATURE
CPLXPn/2
Tn,hl
TEMPERATURE
CPLXPn/4
bn,i
CPLXPn/5
cn,il
CPLXPn/6
dn,i
CPLXPn/7
en,i
CPLXPn/8
fn,il
gn,i
hn,i
CPLXPn/3
CPLXPn/9
CPLXPn/10
an,i
230
Tn,lig
Tn,h
ig
ig
Upper
Limit
Units
TEMPERATURE
TEMPERATURE
CPIXPn/3
an,i
CPIXPn/4
bn,iig
CPIXPn/5
ig
CPIXPn/6
dn,i
ig
CPIXPn/7
en,iig
CPIXPn/8
cn,i
fn,i
ig
CPIXPn/9
gn,i
ig
CPIXPn/10
hn,iig
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.
TEMPERATURE, ENTHALPY, ENTROPY
The molar enthalpy Hm* and the molar excess enthalpy Hm*E are defined with
the asymmetrical reference state: the pure solvent water and infinite dilution
of molecular solutes and ions. (here * refers to the asymmetrical reference
state.)
Hw* is the pure water molar enthalpy, calculated from the Ideal Gas model
and the ASME Steam Table equation-of-state. (here * refers to pure
component.)
Hs,vap(T).
as follows:
231
is calculated from
For molecular solutes (e.g. Henry components), if the aqueous infinite dilution
Applicable
Components
Symbol
Default Units
IONTYP
Ions
Ion
SO25C
Cations
Sc
(T=298)
MOLE-ENTROPY
Anions
Sa
(T=298)
MOLE-ENTROPY
DHAQFM
f Hk,aq
MOLE-ENTHALPY
CPAQ0
Cp,k
,aq
HEAT-CAPACITY
DHFORM
Molecular Solutes
f Hi*,ig
MOLE-ENTHALPY
Water, Solvents
f Hw*,ig
MOLE-ENTHALPY
*,ig
CPIG
Molecular Solutes
Water, Solvents
,aq
,aq
Cp,i
Cp,w
*,ig
232
The molar Gibbs free energy and the molar excess Gibbs free energy Gm* and
Gm*E are defined with the asymmetrical reference state: as pure water and
infinite dilution of molecular solutes and ions. (* refers to the asymmetrical
reference state.) The ideal mixing term is calculated normally, where j refers
to any component. The molar Gibbs free energy of pure water (or
thermodynamic potential) w* is calculated from the ideal gas contribution.
This is a function of the ideal gas heat capacity and the departure function.
(here * refers to the pure component.)
233
where the subscript k refers to any ion or molecular solute and the term RT
Applicable
Components
Symbol
Default Units
IONTYP
Ions
Ion
(T=298)
MOLE-ENTROPY
(T=298)
MOLE-ENTROPY
MOLE-ENTHALPY
SO25C
234
,aq
Cations
Sc
Anions
Sa
DGAQFM
f Gk,aq
CPAQ0
Cp,k
HEAT-CAPACITY
DGFORM
Molecular Solutes
f Gi
MOLE-ENTHALPY
Water, Solvents
f Gw
MOLE-ENTHALPY
,aq
,aq
Parameter
Name
Applicable
Components
Symbol
Default Units
CPIG
Molecular Solutes
Cp,i*,ig
Water, Solvents
Cp,w
*,ig
IONTYP and SO25C are not needed if CPAQ0 is given for ions.
DGFORM is not needed if DHAQFM and CPAQ0 are given for molecular
solutes.
The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If
CPIG/10 or CPIG/11 is non-zero, then absolute temperature units are
assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature
units are used for all elements of CPIG. User input temperature units are
always used for other elements of CPIG.
235
Where:
Hi*,ig
Hi*,v - Hi*,ig
vapHi*,l
Tref
Where:
Hmig
=
Hi*,ig
(Hml-Hmig)
236
HmE,l
HA*,l-HA*,ig
H*,ig and H*,l can be calculated based on either saturated liquid or ideal gas as
reference state as described in the sections that follow.
For the WILS-LR property method, H*,ig and H*,l are calculated based on the
saturated liquid reference state for all components.
For the WILS-GLR property method, H*,ig and H*,l can be calculated based on
the saturated liquid reference state for some components and the ideal gas
reference state for other components. You can set the value of a pure
component parameter called RSTATE to specify the reference state for each
component. RSTATE = 1 denotes ideal gas reference state. RSTATE = 2
denotes saturated liquid reference state. If it is not set, the following default
rules apply based on the normal boiling point of the component, i, TB(i):
Where:
Hiref,l
Cp,i*,l
Where:
Giref,l
i*,l
System pressure
pref
For the WILS-LR property method, Hiref,l and Giref,l default to zero (0). The
reference temperature Tiref,l defaults to 273.15K.
For the WILS-GLR property method, the reference temperature Tiref,l defaults
to 298.15K and Hiref,l defaults to:
237
Where:
Hiref,ig
Giref,ig
Hi*,v
Gi*,v
vapHi*
Note that we cannot default the liquid reference enthalpy and Gibbs free
energy to zero, as is the case for WILS-LR, because it will cause inconsistency
with the enthalpy of components that use ideal-gas reference state. The
default values used result in the enthalpies of all components being on the
same basis. In fact, if you enter values for Hiref,l and Giref,l for a liquidreference state component you must make sure that they are consistent with
each other and are consistent with the enthalpy basis of the remaining
components in the mixture. If you enter a value for Hiref,l, you should also
enter a value for Giref,l to ensure consistency.
When the liquid-reference state is used, the ideal gas enthalpy at
temperature T is not calculated from the integration of the ideal gas heat
capacity equation (see Ideal Gas as Reference State section below). For
consistency, it is calculated from liquid enthalpy as follows:
Where:
Ticon,l
vapHi*(Ticon,l)
Hi*,v(Ticon,l, pi*,l)
pi*,l
Ticon,l is the temperature at which one crosses from liquid state to the vapor
state. This is a user defined temperature that defaults to the system
temperature T. Ticon,l may be selected such that heat of vaporization for
component i at the temperature is most accurate.
238
Where:
Hi*,v(T, P)
The liquid heat capacity and the ideal gas heat capacity can be calculated
from the General Pure Component Liquid Heat Capacity and General Pure
Component Ideal Gas Heat Capacity, or other available models. The heat of
vaporization can be calculated from the General Pure Component Heat of
Vaporization, or other available models. The enthalpy departure is obtained
from an equation-of-state that is being used in the property method. For
WILS-LR and WILS-GLR, the ideal gas equation of state is used.
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
RSTATE
TREFHL
Tiref,l
TEMPERATURE
ref,l
MOLE ENTHALPY
ref,l
MOLE ENTHALPY
TEMPERATURE
DHLFRM
Hi
DGLFRM
Gi
TCONHL
Ticon,l
Where:
Hiref,ig
Tiref,ig
239
Ticon,ig
The liquid heat capacity and the ideal gas heat capacity can be calculated
from the General Pure Component Liquid Heat Capacity and General Pure
Component Ideal Gas Heat Capacity, or other available models. The heat of
vaporization can be calculated from the General Pure Component Heat of
Vaporization, or other available models. The enthalpy departure is obtained
from an equation of state that is being used in the property method. For
WILS-LR and WILS-GLR, the ideal gas equation of state is used.
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
RSTATE
TREFHI
Ti
ref,ig
TEMPERATURE
ref,ig
MOLE ENTHALPY
TEMPERATURE
DHFORM
Hi
TCONHI
Ticon,ig
, heat capacity
entropy
, enthalpy of formation
, and Gibbs energy of formation
at infinite dilution in aqueous phase are:
240
Where:
241
Where:
Born coefficient
Tr
Pr
Default MDS
Lower
Limit
Upper
Limit
Units
DHAQHG
-0.5x1010 0.5x1010
MOLE-ENTHALPY
DGAQHG
-0.5x1010 0.5x1010
MOLE-ENTHALPY
S25HG
-0.5x1010 0.5x1010
MOLE-ENTROPY
OMEGHG
-0.5x1010 0.5x1010
MOLE-ENTHALPY
References
Tanger, J.C. IV and H.C. Helgeson, "Calculation of the thermodynamic and
transport properties of aqueous species at high pressures and temperatures:
Revised equation of state for the standard partial properties of ions and
electrolytes," American Journal of Science, Vol. 288, (1988), p. 19-98.
Shock, E.L. and H.C. Helgeson, "Calculation of the thermodynamic and
transport properties of aqueous species at high pressures and temperatures:
242
The pure component properties Qi and Qj are calculated by the default model
for that property, unless modified by option codes. Composition xi and xj is in
mole fraction unless modified by option codes. Kij is a binary parameter
specific to the mixing rule for each property. A variation on the equation using
the logarithm of the property is used for viscosity.
243
This section describes the transport property models available in the Aspen
Physical Property System. The following table provides an overview of the
available models. This table lists the Aspen Physical Property System model
names, and their possible use in different phase types, for pure components
and mixtures.
Viscosity models
These models calculate MUL (pure) and/or MULMX (mixture) for the liquid
phase, and MUV (pure) and/or MUVMX (mixture) for the vapor phase, except
models marked with * calculate MUVLP (pure) and/or MUVMXLP (mixture) for
the vapor phase, and models marked with ** calculate MUVPC (pure) and
MUVMXPC (mixture).
244
Model
Model name
Phase(s) Pure
Mixture
MUL2ANDR
MUL0ANDR
MUL2API
MULAPI97
MUV0CEB
MUV2BROK,
MUV2WILK
Chung-Lee-Starling Low
Pressure *
MUV0CLSL,
MUV2CLSL
Chung-Lee-Starling
MUV0CLS2,
MUV2CLS2,
MUL0CLS2,
MUL2CLS2
VL
IAPS Viscosity
VL
MUV0H2O,
MUL0H2O
Model
Model name
Phase(s) Pure
Mixture
Jones-Dole Electrolyte
Correction
MUL2JONS
Letsou-Stiel
MUL0LEST,
MUL2LEST
Lucas
MUV0LUC,
MUV2LUC
TRAPP viscosity
MUL0TRAP,
MUL2TRAP,
MUV0TRAP,
MUV2TRAP
VL
MUL2TWU
Model name
Phase(s) Pure
Mixture
Chung-Lee-Starling Thermal
Conductivtity
KV0CLS2,
KV2CLS2,
KL0CLS2,
KL2CLS2
VL
V
L
X
X
Li Mixing Rule
KL2LI
KL2RDL
KL0SR,
KL2SRVR
Stiel-Thodos Pressure
Correction **
KV0STPC,
KV2STPC
KV0TRAP,
KV2TRAP,
KL0TRAP,
KL2TRAP
VL
KL2SRVR
Wassiljewa-Mason-Saxena
mixing rule *
KV2WMSM
Diffusivity models
These models calculate DL (binary) and/or DLMX (mixture) for the liquid
phase, and DV (binary) and/or DVMX (mixture) for the vapor phase.
Model
Model name
Chapman-Enskog-Wilke-Lee
Binary
DV0CEWL
245
Model
Model name
Chapman-Enskog-Wilke-Lee
Mixture
DV1CEWL
Dawson-Khoury-Kobayashi
Binary
DV1DKK
Dawson-Khoury-Kobayashi
Mixture
DV1DKK
Nernst-Hartley Electrolytes
DL0NST,
DL1NST
Wilke-Chang Binary
DL0WC2
Wilke-Chang Mixture
DL1WC
Model name
Phase(s) Pure
Mixture
SIG2API
SIG0HSS,
SIG2HSS
SIG0H2O
Onsager-Samaras Electrolyte
Correction
SIG2ONSG
Modified MacLeod-Sugden
SIG2MS
Viscosity Models
The Aspen Physical Property System has the following built-in viscosity
models:
Model
Type
Liquid
Liquid
Liquid
246
Chung-Lee-Starling
Liquid or vapor
Vapor
IAPS viscosity
Water or steam
Electrolyte
Letsou-Stiel
Lucas
Vapor
TRAPP viscosity
Vapor or liquid
Model
Type
Liquid
Liquid
Liquid
Liquid
Where:
kij
mij
Then fi is
0 (Default)
Note that the Andrade liquid mixture viscosity model is called from other
models. The first option codes of these models cause fi to be mole or mass
fraction when Andrade is used in the respective models. To maintain
consistency across models, if you set the first option code for MUL2ANDR to
1, you should also the set the first option code of the other models to 1, if
they are used in your simulation.
Model
Model Name
MUL2JONS
DL0WCA
DL1WCA
DL0NST
DL1NST
The binary parameters kij and mij allow accurate representation of complex
liquid mixture viscosity. Both binary parameters default to zero.
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
ANDKIJ/1
aij
ANDKIJ/2
bij
ANDMIJ/1
cij
ANDMIJ/2
dij
247
Andrade
MULAND
101, 115
MULDIP
301
PPDS
MULPDS
401
404
508
MULNVE
509
NIST PPDS9
MULPPDS9
Lower
Limit
Upper
Limit
Units
MULAND/1
Ai
VISCOSITY,
TEMPERATURE
MULAND/2
Bi
TEMPERATURE
MULAND/3
Ci
TEMPERATURE
MULAND/4
Tl
0.0
TEMPERATURE
MULAND/5
Th
500.0
TEMPERATURE
248
Upper
Limit
Units
MULDIP/1
C1i
MULDIP/2, ..., 5
VISCOSITY,
TEMPERATURE
TEMPERATURE
MULDIP/6
C6i
TEMPERATURE
MULDIP/7
C7i
1000
TEMPERATURE
If any of C3i through C5i are non-zero, absolute temperature units are
assumed for C3i through C5i. Otherwise, all coefficients are interpreted in user
input temperature units. The temperature limits are always interpreted in
user input units.
PPDS
The PPDS equation is:
Upper
Limit
Units
MULPDS/1
C1i
MULPDS/2
C2i
MULPDS/3
C3i
TEMPERATURE
MULPDS/4
C4i
TEMPERATURE
MULPDS/5
C5i
VISCOSITY
MULPDS/6
C6i
TEMPERATURE
MULPDS/7
C7i
TEMPERATURE
Upper
Limit
Units
MULPPDS9/1
C5i
MULPPDS9/2
Pa*S
C1i
MULPPDS9/3
C2i
TEMPERATURE
MULPPDS9/4
C3i
TEMPERATURE
MULPPDS9/5
C4i
TEMPERATURE
MULPPDS9/6
C6i
TEMPERATURE
MULPPDS9/7
C7i
TEMPERATURE
249
Exponential
Lower
Limit
Upper
Limit
Units
MULIKC/1
C1i
VISCOSITY
MULIKC/2
C2i
TEMPERATURE
MULIKC/3
C3i
VISCOSITY
MULIKC/4
C4i
TEMPERATURE
MULIKC/5
C5i
1000
TEMPERATURE
Absolute temperature units are assumed for C2i. The temperature limits
are always interpreted in user input units.
Polynomial
Upper
Limit
Units
MULPO/1
VISCOSITY
C1i
VISCOSITY,
TEMPERATURE
MULPO/11
C11i
TEMPERATURE
MULPO/12
C12i
1000
TEMPERATURE
250
Parameter
Symbol
Name/Element
Upper
Limit
Units
MULNVE/1
C1i
Parameter
Symbol
Name/Element
Upper
Limit
Units
TEMPERATURE
MULNVE/5
C5i
TEMPERATURE
MULNVE/6
C6i
1000
TEMPERATURE
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 439.
Where:
fcn
Lower
Limit
Upper
Limit
Units
TB
Tbi
4.0
2000.0
TEMPERATURE
API
APIi
-60.0
500.0
Where:
251
fcn
Lower
Limit
Upper
Limit
Units
TB
Tbi
4.0
2000.0
TEMPERATURE
API
APIi
-60.0
500.0
Where:
Xi
kij
lij
The binary parameters kij and lij allow accurate representation of complex
liquid mixture viscosity. Both binary parameters default to zero.
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
MUKIJ
kij
-100.0
100.0
MULIJ
lij
100.0
100.0
Where:
252
wi
log
Lower
Limit
Upper
Limit
Units
MULOGF
0.0
2.0
1.0
Chapman-EnskogBrokaw
STKPAR, LJPAR
102
DIPPR
MUVDIP
301
PPDS
MUVPDS
302
MUVCEB
401
IK-CAPE polynomial
equation
MUVPO
402
IK-CAPE Sutherland
equation
MUVSUT
503
NIST ThermoML
polynomial
MUVTMLPO
Chapman-Enskog-Brokaw
The equation for the Chapman-Enskog model is:
Where:
253
MDS Lower
Limit
Upper
Limit
Units
MW
1.0
5000.0
-24
Mi
MUP
pi
0.0
5x10
STKPAR/1
(i/k)ST
TEMPERATURE
STKPAR/2
iST
(i/k)LJ
iLJ
LENGTH
TEMPERATURE
LENGTH
LJPAR/1
LJPAR/2
fcn(Tci,
i)
fcn(Tci, pci,
i)
DIPOLEMOMENT
Symbol
Upper
Limit
Units
MUVDIP/1
C1i
VISCOSITY
MUVDIP/2
C2i
MUVDIP/3, 4
C3i, C4i
TEMPERATURE
MUVDIP/5
MUVDIP/6
C6i
TEMPERATURE
MUVDIP/7
C7i
1000
TEMPERATURE
If any of C2i through C4i are non-zero, absolute temperature units are
assumed for C1i through C4i. Otherwise, all coefficients are interpreted in user
input temperature units. The temperature limits are always interpreted in
user input units.
MUVDIP/5 is not used in this equation. It is normally set to zero. The
parameter is provided for consistency with other DIPPR equations.
PPDS
The PPDS submodel includes both the basic PPDS vapor viscosity equation
and the PPDS kinetic theory vapor viscosity equation. For either equation,
linear extrapolation of viscosity versus T occurs for temperatures outside
bounds.
254
Parameter
Name/Element
Symbol
Upper
Limit
Units
MUVPDS/1
C1i
VISCOSITY
MUVPDS/2
C2i
MUVPDS/3
C3i
MUVPDS/4
C4i
TEMPERATURE
MUVPDS/5
C5i
1000
TEMPERATURE
Parameter
Name/Element
Symbol
Upper
Limit
Units
MW
Mi
1.0
5000.0
MUVCEB/1
C1i
LENGTH
MUVCEB/2
C2i
TEMPERATURE
MUVCEB/3
C3i
MUVCEB/4
C4i
TEMPERATURE
MUVCEB/5
C5i
1000
TEMPERATURE
Absolute temperature units are assumed for C2i . The temperature limits are
always interpreted in user input units.
Sutherland Equation
Parameter
Name/Element
Symbol
Upper
Limit
Units
MUVSUT/1
C1i
VISCOSITY
MUVSUT/2
C2i
TEMPERATURE
MUVSUT/3
C3i
TEMPERATURE
255
Parameter
Name/Element
Symbol
Upper
Limit
Units
MUVSUT/4
C4i
1000
TEMPERATURE
If C2i is non-zero, absolute temperature units are assumed for C1i and C2i.
Otherwise, all coefficients are interpreted in user input temperature units. The
temperature limits are always interpreted in user input units.
Polynomial
Parameter
Name/Element
Symbol
Upper
Limit
Units
MUVPO/1
C1i
VISCOSITY
MUVPO/2, ..., 10
VISCOSITY,
TEMPERATURE
MUVPO/11
C11i
TEMPERATURE
MUVPO/12
C12i
1000
TEMPERATURE
Parameter
Name/Element
Symbol
Upper
Limit
Units
MUVTMLPO/1
C1i
Pa*s/T
Pa*s/T
MUVTMLPO/5
nTerms
MUVTMLPO/6
Tlower
TEMPERATURE
MUVTMLPO/7
Tupper
1000
TEMPERATURE
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling. The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 392.
Chapman-Enskog-Brokaw-Wilke Mixing
Rule
The low pressure vapor mixture viscosity is calculated by the Wilke
approximation of the Chapman-Enskog equation:
For
256
Where:
Where p is in debye.
The pure component vapor viscosity i*,v (p = 0) can be calculated using the
General Pure Component Vapor Viscosity (or another low pressure vapor
viscosity model).
Ensure that you supply parameters for
i*,v (p = 0).
Parameter
Name/
Element
Symbol
Default
MDS Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
0.0
5x10
-24
MUP
pi
STKPAR/1
(i/k)
ST
DIPOLEMOMENT
TEMPERATURE
257
Parameter
Name/
Element
Symbol
Default
MDS Lower
Limit
STKPAR/2
iST
Upper
Limit
Units
LENGTH
References
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of Gases and
Liquids, 3rd ed., (New York: McGraw-Hill, 1977), pp. 410416.
C1 is a constant of correlation.
The polar parameter is tabulated for certain alcohols and carboxylic acids.
The previous equations can be used for mixtures when applying these mixing
rules:
258
Where:
Vcij
ij
Tcij
ij
ij
Mij
ij
Lower
Limit
Upper
Limit
Units
TCCLS
Tci
TC
5.0
2000.0
TEMPERATURE
VCCLS
Vci
VC
0.001
3.5
MOLE-VOLUME
MW
Mi
1.0
5000.0
-24
MUP
pi
0.0
5x10
OMGCLS
i
i
ij
ij
OMEGA x
-0.5
2.0
0.0
0.0
0.5
0.0
-0.5
-0.5
0.0
-0.5
0.5
CLSK
CLSKV
CLSKT
DIPOLEMOMENT
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 396, p. 413.
259
Chung-Lee-Starling Viscosity
The Chung-Lee-Starling viscosity equation for vapor and liquid, high and low
pressure is:
With:
f1
f2
FC
260
Where:
Vcij
ij
Tcij
ij
ij
Mij
ij
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
TCCLS
Tci
TC
5.0
2000.0
TEMPERATURE
VCCLS
Vci
VC
0.001
3.5
MOLE-VOLUME
MW
Mi
1.0
5000.0
-24
MUP
pi
0.0
5x10
OMGCLS
i
i
ij
ij
OMEGA
-0.5
2.0
0.0
0.0
0.5
0.0
-0.5
-0.5
0.0
-0.5
0.5
CLSK
CLSKV
CLSKT
DIPOLEMOMENT
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 427.
261
Tc
pc
Vcm
Zcm
rm
Vcm / Vmv
Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
VC
Vci
0.001
3.5
MOLE-VOLUME
w=fcn(T, p)
Where:
fcn
The models are only applicable to water. There are no parameters required
for the models.
262
Where:
solv
cal
The parameter
Jones-Dole
IONMUB
Breslau-Miller
Carbonell
When the concentration of apparent electrolyte exceeds 0.1 M, the BreslauMiller equation is used instead.
Jones-Dole
The Jones-Dole equation is:
(1)
Where:
=
(2)
xcaa
(3)
Aca
(4)
La
(5)
263
Lc
(6)
Bca
(7)
Breslau-Miller
The Breslau-Miller equation is:
(8)
Where the effective volume Vc is given by:
(9)
for salts involving univalent ions
(9a)
for other salts
Carbonell
The Carbonell equation is:
(10)
Where:
Mk
You must provide parameters for the model used for the calculation of the
liquid mixture viscosity of the solvent mixture.
Parameter
Name/Element
Units
CHARGE
0.0
MW
1.0
5000.0
IONMOB/1
l1
AREA, MOLES
IONMOB/2
l2
0.0
AREA, MOLES,
TEMPERATURE
IONMUB/1
b1
MOLE-VOLUME
IONMUB/2
b2
0,0
MOLE-VOLUME,
TEMPERATURE
References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis
Horwood, 1985).
264
Letsou-Stiel
The Letsou-Stiel model calculates liquid viscosity at high temperatures for
0.76 Tr 0.98. This model is used in PCES.
Note: Reduced temperature Tr is always calculated using absolute
temperature units.
The general form for the model is:
l = (l)0 + (l)1
Where:
(l)0
(l)1
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
TC
Tci
5.0
2000.0
TEMPERATURE
PC
pci
10
OMEGA
-0.5
10
2.0
PRESSURE
References
R.C. Reid, J.M. Pransnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 471.
265
The polar and quantum correction factors at high and low pressure are:
FP
FQ
FPi (p = 0)
FQi (p = 0)
pc
FP (p = 0)
FQ (p = 0)
Lower
Limit
Upper
Limit
Units
TCLUC
Tci
TC
5.0
2000.0
TEMPERATURE
PCLUC
pci
PC
105
108
PRESSURE
ZCLUC
Zci
ZC
0.1
0.5
MW
Mi
1.0
5000.0
MUP
pi
0.0
5x10-24
DIPOLEMOMENT
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 421, 431.
266
Where:
The parameter
is the mole fraction vector; fcn is a corresponding states
correlation based on the model for vapor and liquid viscosity TRAPP, by the
National Bureau of Standards (NBS, currently NIST) . The model can be used
for both pure components and mixtures. The model should be used for
nonpolar components only.
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
TCTRAP
Tci
TC
5.0
2000.0
TEMPERATURE
10
PCTRAP
pci
PC
10
PRESSURE
VCTRAP
Vci
VC
0.001
3.5
MOLE-VOLUME
ZCTRAP
Zci
ZC
0.1
1.0
OMGRAP
OMEGA x
-0.5
3.0
References
J.F. Ely and H.J.M. Hanley, "Prediction of Transport Properties. 1. Viscosities
of Fluids and Mixtures," Ind. Eng. Chem. Fundam., Vol. 20, (1981), pp. 323
332.
267
Where:
268
SG
Tb
SG
1, 2
Tc
Reference
C.H. Twu, "Internally Consistent Correlation for Predicting Liquid Viscosities of
Petroleum Fractions," Ind. Eng. Chem. Process Des. Dev., Vol. 24 (1985), pp.
1287-1293
Option Codes
Option Code Value
Descriptions
Parameter
Parameter
Name/Element
Symbol
Default
MDS
Lower
Limit
Upper
Limit
Units
MLQKIJ
Kij
Type
Chung-Lee-Starling
Vapor or liquid
IAPS
Water or steam
Li Mixing Rule
Liquid mixture
Electrolyte
Liquid
Solid
Vapor
Vapor or liquid
Liquid mixture
269
Where:
f1
f2
For low pressures, f1 is reduced to 1.0 and f2 is reduced to zero. This gives
the Chung-Lee-Starling expression for thermal conductivity of low pressure
gases.
The same expressions are used for mixtures. The mixture expression for (p
= 0) must be used. (See Chung-Lee-Starling Low-Pressure Vapor Viscosity.)
Where:
270
Vcij
ij
Tcij
ij
ij
Mij
ij
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
TCCLS
Tci
TC
5.0
2000.0
TEMPERATURE
VCCLS
Vci
VC
0.001
3.5
MOLE-VOLUME
MW
Mi
1.0
5000.0
MUP
pi
0.0
5x10-24
DIPOLEMOMENT
OMGCLS
i
i
ij
ij
OMEGA x
-0.5
2.0
0.0
0.0
0.5
0.0
-0.5
-0.5
0.0
-0.5
0.5
CLSK
CLSKV
CLSKT
The model-specific parameters also affect the results of the Chung-LeeStarling Viscosity models.
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 505, 523.
w=fcn(T, p)
Where:
271
fcn
Li Mixing Rule
Liquid mixture thermal conductivity is calculated using Li equation (Reid
et.al., 1987):
Where:
The pure component liquid molar volume Vi*,l is calculated from the Rackett
model.
The pure component liquid thermal conductivity i*,l is calculated by the
General Pure Component Liquid Thermal Conductivity model.
Reference: R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases
and Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 550.
Where:
lsolv
xcaa
ac, aa
Vm l
Apparent electrolyte mole fractions are computed from the true ion molefractions and ionic charge number. They can also be computed if you use the
apparent component approach. A more detailed discussion of this method is
found in Electrolyte Calculation.
272
You must provide parameters for the Sato-Riedel model. This model is used
for the calculation of the thermal conductivity of solvent mixtures.
Parameter
Name/Element
Symbol
Default
Lower
Limit
Upper
Limit
Units
CHARGE
0.0
IONRDL
0.0
Exponent is -2
Exponent is 0.4
Sato-Riedel
100
DIPPR
KLDIP
301
PPDS
KLPDS
401
IK-CAPE
KLPO
503
NIST ThermoML
polynomial
KLTMLPO
510
KLPPDS8
Sato-Riedel
The Sato-Riedel equation is (Reid et al., 1987):
Where:
Tbri
Tbi / Tci
Tri
T / Tci
273
Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
TC
Tci
5.0
2000.0
TEMPERATURE
TB
Tbi
4.0
2000.0
TEMPERATURE
PPDS
The equation is:
Linear extrapolation of
Parameter
Name/Element
Symbol
Default MDS
Lower
Limit
Upper
Limit
Units
KLPDS/1
C1i
THERMALCONDUCTIVITY
KLPDS/2
C2i
KLPDS/3
C3i
KLPDS/4
C4i
KLPDS/5
C5i
TEMPERATURE
KLPDS/6
C6i
1000
TEMPERATURE
Parameter
Symbol
Name/Element
Default MDS
Lower Upper
Limit Limit
Units
KLPPDS8/1
THERMALCONDUCTIVITY
KLPPDS8/8
TCi
TEMPERATURE
KLPPDS8/9
nTerms
KLPPDS8/10
Tlower
TEMPERATURE
KLPPDS8/11
Tupper
1000
TEMPERATURE
C1i
274
Linear extrapolation of
Default MDS
Lower
Limit
Upper
Limit
Units
KLDIP/1
C1i
THERMALCONDUCTIVITY,
TEMPERATURE
KLDIP/2, ... , 5
THERMALCONDUCTIVITY,
TEMPERATURE
KLDIP/6
C6i
TEMPERATURE
KLDIP/7
C7i
1000
TEMPERATURE
Linear extrapolation of
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
KLTMLPO/1
THERMALCONDUCTIVITY,
TEMPERATURE
THERMALCONDUCTIVITY,
TEMPERATURE
KLTMLPO/5
nTerms
KLTMLPO/6
Tlower
TEMPERATURE
KLTMLPO/7
Tupper
1000
TEMPERATURE
C1i
IK-CAPE
The IK-CAPE equation is:
Linear extrapolation of
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
KLPO/1
THERMALCONDUCTIVITY
C1i
275
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
THERMALCONDUCTIVITY,
TEMPERATURE
KLPO/11
C11i
TEMPERATURE
KLPO/12
C12i
1000
TEMPERATURE
References
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1977), p. 533.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 550.
For mixtures:
Linear extrapolation of
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
KSPOLY/1
THERMAL
CONDUCTIVITY
KSPOLY/2, 3, 4, 5
b, c, d, e 0
THERMAL
CONDUCTIVITY,
TEMPERATURE
KSPOLY/6
TEMPERATURE
KSPOLY/7
1000
TEMPERATURE
276
Stiel-Thodos
102
DIPPR
KVDIP
301
PPDS
KVPDS
401
IK-CAPE
KVPO
503
NIST ThermoML
polynomial
KVTMLPO
Stiel-Thodos
The Stiel-Thodos equation is:
Where:
Cpi*,ig is obtained from the General Pure Component Ideal Gas Heat Capacity
model.
R is the universal gas constant.
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
Linear extrapolation of
Default MDS
Lower
Limit
Upper
Limit
Units
KVDIP/1
C1i
THERMAL
CONDUCTIVITY
KVDIP/2
C2i
KVDIP/3, 4
C3i, C4i
TEMPERATURE
KVDIP/5
KVDIP/6
C6i
TEMPERATURE
KVDIP/7
C7i
1000
TEMPERATURE
If any of C2i through C4i are non-zero, absolute temperature units are
assumed for C1i through C4i. Otherwise, all coefficients are interpreted in user
277
PPDS
The equation is:
Linear extrapolation of
Parameter
Symbol
Name/Element
Default
MDS
Lower Upper
Limit
Limit
Units
KVPDS/1
C1i
THERMALCONDUCTIVITY
KVPDS/2
C2i
THERMALCONDUCTIVITY
KVPDS/3
C3i
THERMALCONDUCTIVITY
KVPDS/4
C4i
THERMALCONDUCTIVITY
KVPDS/5
C5i
TEMPERATURE
KVPDS/6
C6i
1000
TEMPERATURE
IK-CAPE Polynomial
Linear extrapolation of
Parameter
Name/Element
Symbol
Upper Units
Limit
KVPO/1
C1i
THERMALCONDUCTIVITY
KVPO/2, ... , 10
THERMALCONDUCTIVITY,
TEMPERATURE
KVPO/11
C11i
TEMPERATURE
KVPO/12
C12i
1000
TEMPERATURE
Linear extrapolation of
278
Parameter
Symbol
Name/Element
Default MDS
Lower
Limit
Upper
Limit
Units
KVTMLPO/1
C1i
THERMALCONDUCTIVITY,
TEMPERATURE
KVTMLPO/2, ... ,
4
THERMALCONDUCTIVITY,
TEMPERATURE
KVTMLPO/5
nTerms
KVTMLPO/6
Tlower
TEMPERATURE
KVTMLPO/7
Tupper
1000
TEMPERATURE
References
R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquid,
4th ed., (New York: McGraw-Hill, 1987), p. 494.
Where:
rm
v(p = 0) can be obtained from the low pressure General Pure Component
Vapor Thermal Conductivity.
This model should not be used for polar substances, hydrogen, or helium.
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
TC
Tci
5.0
2000.0
TEMPERATURE
PC
105
108
PRESSURE
VC
Vci
0.001
3.5
MOLE-VOLUME
ZC
Zci
0.1
0.5
References
R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquids,
4th ed., (New York: McGraw-Hill, 1987), p. 521.
279
Where:
wi
i*,l
. In this case n is
-2
0.4
For most systems, the ratio of maximum to minimum pure component liquid
thermal conductivity is between 1 and 2, where the exponent -2 is
recommended, and is the default value used.
Pure component liquid thermal conductivity i*,l is calculated by the General
Pure Component Liquid Thermal Conductivity model.
Reference: R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of
Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1977), p. 533.
Where:
Cpi
*,ig
fcn
The model can be used for both pure components and mixtures. The model
should be used for nonpolar components only.
280
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
TCTRAP
Tci
TC
5.0
2000.0
TEMPERATURE
10
PCTRAP
pci
PC
10
VCTRAP
Vci
VC
0.001
3.5
PRESSURE
MOLE-VOLUME
ZCTRAP
Zci
ZC
0.1
1.0
OMGRAP
OMEGA
-0.5
3.0
References
J.F. Ely and H.J. M. Hanley, "Prediction of Transport Properties. 2. Thermal
Conductivity of Pure Fluids and Mixtures," Ind. Eng. Chem. Fundam., Vol. 22,
(1983), pp. 9097.
Where:
i*,v
i*,v(p = 0)
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
MW
Mi
1.0
5000.0
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), pp. 530531.
Diffusivity Models
The Aspen Physical Property System has seven built-in diffusivity models. This
section describes the diffusivity models available.
281
Model
Type
Chapman-Enskog-Wilke-Lee (Binary)
Chapman-Enskog-Wilke-Lee (Mixture)
Dawson-Khoury-Kobayashi (Binary)
Vapor
Dawson-Khoury-Kobayashi (Mixture)
Vapor
Nernst-Hartley
Electrolyte
Wilke-Chang (Binary)
Liquid
Wilke-Chang (Mixture)
Liquid
Chapman-Enskog-Wilke-Lee (Binary)
The binary diffusion coefficient at low pressures
the Chapman-Enskog-Wilke-Lee model:
is calculated using
Dijv=Djiv
Where:
ij
ij
Units
MW
1.0
5000.0
-24
MUP
pi
0.0
5x10
TB
Tbi
4.0
2000.0
TEMPERATURE
VB
Vb
0.001
3.5
MOLE-VOLUME
OMEGA
i
(i/k)ST
-0.5
2.0
TEMPERATURE
STKPAR/1
282
Mi
DIPOLEMOMENT
Parameter
Symbol Default
Name/Element
STKPAR/2
LJPAR/1
LJPAR/2
iST
(i/k)LJ
iLJ
i)
fcn(Tci, pci,
i)
Units
LENGTH
TEMPERATURE
LENGTH
References
R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquids,
4th ed., (New York: McGraw-Hill, 1987), p. 587.
Chapman-Enskog-Wilke-Lee (Mixture)
The diffusion coefficient of a gas into a gas mixture at low pressures is
calculated using an equation of Bird, Stewart, and Lightfoot by default (option
code 0):
Lower
Limit
Upper
Limit
Units
DVBLNC
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 597.
Dawson-Khoury-Kobayashi (Binary)
The binary diffusion coefficient Dijv at high pressures is calculated from the
Dawson-Khoury-Kobayashi model:
283
Dijv=Djiv
Lower
Limit
Upper
Limit
Units
VC
Vci
0.001
3.5
MOLE-VOLUME
References
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood. The Properties of Gases and
Liquids, 3rd ed., (New York: McGraw-Hill, 1977), pp. 560-565.
Dawson-Khoury-Kobayashi (Mixture)
The diffusion coefficient of a gas into a gas mixture at high pressure is
calculated using an equation of Bird, Stewart, and Lightfoot by default (option
code 0):
The binary diffusion coefficient Dijv at high pressures is calculated from the
Dawson-Khoury-Kobayashi model. (See Dawson-Khoury-Kobayashi (Binary).)
At low pressures (up to 1 atm) the binary diffusion coefficient is instead
calculated by the Chapman-Enskog-Wilke-Lee (Binary) model.
You must provide parameters for this model.
284
Parameter
Name/Element
Lower
Limit
Upper
Limit
Units
DVBLNC
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 597.
Nernst-Hartley
The effective diffusivity of an ion i in a liquid mixture with electrolytes can be
calculated using the Nernst-Hartley model:
(1)
Where:
F
xk
zi
The binary diffusion coefficient of the ion with respect to a molecular species
is set equal to the effective diffusivity of the ion in the liquid mixture:
(2)
The binary diffusion coefficient of an ion i with respect to an ion j is set to the
mean of the effective diffusivities of the two ions:
Symbol
Default
Lower Upper
Limit Limit
Units
CHARGE
0.0
IONMOB/1
l1
AREA, MOLES
IONMOB/2
l2
0.0
AREA, MOLES,
TEMPERATURE
285
References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis
Horwood, Ltd, 1985).
Wilke-Chang (Binary)
The Wilke-Chang model calculates the liquid diffusion coefficient of
component i in a mixture at finite concentrations:
Dijl = Djil
The equation for the Wilke-Chang model at infinite dilution is:
Vbi
jl
xi, xj
Parameter
Name/Element
Symbol
Default
Lower
Limit
Upper
Limit
Units
MW
Mj
1.0
5000.0
0.001
3.5
MOLE-VOLUME
VB
286
then
Vbi
*,l
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 598600.
Wilke-Chang (Mixture)
The Wilke-Chang model calculates the infinite-dilution liquid diffusion
coefficient of component i in a mixture.
The equation for the Wilke-Chang model is:
With:
Where:
nl
Symbol
Default Lower
Limit
Upper
Limit
Units
MW
Mj
1.0
5000.0
0.001
3.5
MOLE-VOLUME
VB
Vbi
DLWC
*,l
References
R.C. Reid, J.M. Praunsnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 618.
Type
Liquid-vapor
287
Model
Type
API
Liquid-vapor
IAPS
Water-stream
Liquid-vapor
Electrolyte liquid-vapor
Modified MacLeod-Sugden
Liquid-vapor
Where:
x
Mole fraction
Where:
fcn
The original form of this model is only designed for petroleum, and treats all
components as pseudocomponents (estimating surface tension from boiling
point, critical temperature, and specific gravity). If option code 1 is set to 0
(the default), it behaves this way. Set option code 1 to 1 for the model to use
the General Pure Component Liquid Surface Tension model to calculate the
surface tension of real components and the API model for pseudocomponents.
288
Lower
Limit
Upper
Limit
Units
TB
Tbi
4.0
2000.0
TEMPERATURE
SG
SG
0.1
2.0
TC
Tci
5.0
2000
TEMPERATURE
w=fcn(T, p)
Where:
fcn
Hakim-Steinberg-Stiel
106
DIPPR
SIGDIP
301
PPDS
SIGPDS
401
IK-CAPE polynomial
equation
SIGPO
505
SIGTDEW
511
SIGISTE
512
SIGPDS14
Hakim-Steinberg-Stiel
The Hakim-Steinberg-Stiel equation is:
Where:
289
Qpi
mi
The parameter
Parameter
Name/Element
Symbol
Default
Lower
Limit
Upper
Limit
Units
TC
Tci
5.0
2000.0
TEMPERATURE
PC
pci
OMEGA
i
i
-0.5
2.0
CHI
PRESSURE
Where:
Tri
T / Tci
Linear extrapolation of
Symbol
Default Lower
Limit
Upper
Limit
Units
SIGDIP/1
C1i
SURFACETENSION
SIGDIP/2, ..., 5
SIGDIP/6
C6i
TEMPERATURE
SIGDIP/7
C7i
1000
TEMPERATURE
PPDS
The equation is:
Linear extrapolation of
290
Parameter
Name/Element
Symbol
Upper
Limit
Units
SIGPDS/1
C1i
SURFACETENSION
Parameter
Name/Element
Symbol
Upper
Limit
Units
SIGPDS/2
C2i
SIGPDS/3
C3i
SIGPDS/4
C4i
TEMPERATURE
SIGPDS/5
C5i
1000
TEMPERATURE
Symbol
Upper
Limit
Units
SIGPDS14/1
C1i
N/m
SIGPDS14/2
C2i
SIGPDS14/3
C3i
SIGPDS14/4
Tci
TEMPERATURE
SIGPDS14/5
C4i
TEMPERATURE
SIGPDS14/6
C5i
1000
TEMPERATURE
IK-CAPE Polynomial
The IK-CAPE equation is:
Linear extrapolation of
Parameter
Name/Element
Symbol
Units
SIGPO/1
C1i
SURFACETENSION
SIGPO/2, ..., 10
SURFACETENSION
TEMPERATURE
SIGPO/11
C11i
TEMPERATURE
SIGPO/12
C12i
1000
TEMPERATURE
Parameter
Name/Element
Symbol
Upper
Limit
Units
SIGTDEW/1
C1i
291
Parameter
Name/Element
Symbol
Upper
Limit
Units
SIGTDEW/2, 3, 4
SIGTDEW/5
Tc
TEMPERATURE
SIGTDEW/6
nTerms
SIGTDEW/7
Tlower
TEMPERATURE
SIGTDEW/8
Tupper
1000
TEMPERATURE
Parameter
Name/Element
Symbol
Upper
Limit
Units
SIGISTE/1
C1i
N/m
SIGISTE/2, 3, 4
N/m
SIGISTE/5
Tci
TEMPERATURE
SIGISTE/6
nTerms
SIGISTE/7
Tlower
TEMPERATURE
SIGISTE/8
Tupper
1000
TEMPERATURE
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th. ed., (New York: McGraw-Hill, 1987), p. 638.
Onsager-Samaras
The Onsager-Samaras model calculates the correction to the liquid mixture
surface tension of a solvent mixture, due to the presence of electrolytes:
for salt concentration < 0.03 (1)
M
Where:
solv
xcaa
ca
For each apparent electrolyte ca, the contribution to the surface tension
correction is calculated as:
292
(2)
Where:
solv
ccaa
Vm l
Apparent electrolyte mole fractions are computed from the true ion molefractions and ionic charge number. They are also computed if you use the
apparent component approach. See Apparent Component and True
Component Approaches in the Electrolyte Calculation chapter for a more
detailed discussion of this method.
Above salt concentration 0.03 M, the slope of surface tension vs. mole
fraction is taken to be constant at the value from 0.03 M.
You must provide parameters for the General Pure Component Liquid Surface
Tension model, used for the calculation of the surface tension of the solvent
mixture.
Parameter
Name/Element
Symbol
Default
Lower
Limit
Upper
Limit
Units
CHARGE
0.0
References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis,
Ltd. 1985).
Modified MacLeod-Sugden
The modified MacLeod-Sugden equation for mixture liquid surface tension can
be derived from the standard MacLeod-Sugden equation by assuming that the
density of the vapor phase is zero. The modified MacLeod-Sugden equation is:
Where:
Vi*,l
293
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 3rd. ed., (New York: McGraw-Hill, 1977).
294
4 Nonconventional Solid
Property Models
This section describes the nonconventional solid density and enthalpy models
available in the Aspen Physical Property System. The following table lists the
available models and their model names. Nonconventional components are
solid components that cannot be characterized by a molecular formula. These
components are treated as pure components, though they are complex
mixtures.
Model name
Phase(s)
DNSTYGEN
ENTHGEN
Model name
Phase(s)
HCOALGEN
DCOALIGT
DCHARIGT
295
Where:
wij
ijs
Parameter
Name/Element
Symbol MDS
Units
DENGEN/1, 5, 9, , 77 ai,j1
MASS-ENTHALPY
and TEMPERATURE
DENGEN/2, 6, 10, ,
78
ai,j2
MASS-ENTHALPY
and TEMPERATURE
DENGEN/3, 7, 11, ,
79
ai,j3
MASS-ENTHALPY
and TEMPERATURE
DENGEN/4, 8, 12, ,
80
ai,j4
MASS-ENTHALPY
and TEMPERATURE
Where:
296
wij
h is
fhjs
Cp s
Parameter
Name/Element
Symbol MDS
Default
Lower
Limit
Upper
Limit
Units
DHFGEN/J
fhjs
MASS-ENTHALPY
HCGEN/1, 5, 9, , 77 ai,j1
MASS-ENTHALPY
and
TEMPERATURE
MASS-ENTHALPY
and
TEMPERATURE
MASS-ENTHALPY
and
TEMPERATURE
MASS-ENTHALPY
and
TEMPERATURE
The elements of GENANAL are used to input the mass percentages of the
constituents. The structure for HCGEN is: Elements 1 to 4 are the four
coefficients for the first constituent, elements 5 to 8 are the coefficients for
the second constitutent, and so on, for up to 20 constituents.
297
User models for density and enthalpy. See User Models for
Nonconventional Properties in Chapter 6 of Aspen Plus User Models, for
details on writing the subroutines for these user models.
Notation
Most correlations for the calculation of coal properties require proximate,
ultimate, and other analyses. These are converted to a dry, mineral-matterfree basis. Only the organic portion of the coal is considered.
Moisture corrections are made for all analyses except hydrogen, according to
the formula:
Where:
w
w
The mineral matter content is calculated using the modified Parr formula:
The ash term corrects for water lost by decomposition of clays in the ash
determination. The average water constitution of clays is assumed to be 11.2
percent. The sulfur term allows for loss in weight of pyritic sulfur when pyrite
is burned to ferric oxide. The original Parr formula assumed that all sulfur is
pyritic sulfur. This formula included sulfatic and organic sulfur in the mineralmatter calculation. When information regarding the forms of sulfur is
available, use the modified Parr formula to give a better approximation of the
percent of inorganic material present. Because chlorine is usually small for
United States coals, you can omit chlorine from the calculation.
Correct analyses from a dry basis to a dry, mineral-matter-free basis, using
the formula:
Where:
wd
298
The oxygen and organic sulfur contents are usually calculated by difference
as:
Where:
Cp
cp
Specific enthalpy
ch
fh
Ro
Temperature/K
Temperature/C
Weight fraction
Specific density
Subscripts:
A
Ash
Carbon
Cl
Chlorine
FC
Fixed carbon
Hydrogen
H2O
Moisture
MM
Mineral matter
Nitrogen
Oxygen
So
Organic sulfur
Sp
Pyritic sulfur
St
Total sulfur
Other sulfur
VM
Volatile matter
Superscripts:
d
Dry basis
299
Mineral-matter-free basis
Heat of combustion
Heat of formation
Heat capacity
You can select one of these correlations using an option code in the Properties
Advanced NC-Props form. (See the Aspen Plus User Guide, Chapter 6). Use
option codes to specify a calculation method for properties. Each element in
the option code vector is used in the calculation of a different property.
The table labeled HCOALGEN Option Codes (below) lists model option codes
for HCOALGEN. The table is followed by a detailed description of the
calculations used for each correlation.
The correlations are described in the following section. The component
attributes are defined in Aspen Plus User Guide, Chapter 6.
300
Parameter Name/Element
Symbol
Default
BOIEC/1
a1i
151.2
BOIEC/2
a2i
499.77
Parameter Name/Element
Symbol
Default
BOIEC/3
a3i
45.0
BOIEC/4
a4i
-47.7
BOIEC/5
a5i
27.0
BOIEC/6
a6i
-189.0
Parameter Name/Element
Symbol
Default
DLNGC/1
a1i
145.44
DLNGC/2
a2i
620.28
DLNGC/3
a3i
40.5
DLNGC/4
a4i
-77.54
DLNGC/5
a5i
-16.0
Dulong Correlation:
Parameter Name/Element
Symbol
Default
GMLDC/1
a1i
0.3333
GMLDC/2
a2i
654.3
GMLDC/3
a3i
0.125
GMLDC/4
a4i
0.125
GMLDC/5
a5i
424.62
GMLDC/6
a6i
-2.0
Parameter Name/Element
Symbol
Default
MTSPC/1
a1i
144.54
MTSPC/2
a2i
610.2
MTSPC/3
a3i
40.3
MTSPC/4
a4i
62.45
MTSPC/5
a5i
30.96
MTSPC/6
a6i
65.88
MTSPC/7
a7i
-47.0
IGT Correlation:
301
Parameter Name/Element
Symbol
Default
CIGTC/1
a1i
178.11
CIGTC/2
a2i
620.31
CIGTC/3
a3i
80.93
CIGTC/4
a4i
44.95
CIGTC/5
a5i
-5153.0
Parameter Name/Element
Symbol
Default
CIGT2/1
a1i
146.58
CIGT2/2
a2i
568.78
CIGT2/3
a3i
29.4
CIGT2/4
a4i
-6.58
CIGT2/5
a5i
-51.53
Symbol
Default
HCOMB
chid
Heat of combustion-based
Direct
302
is calculated by:
is calculated by:
The complete oxidation of sulfur (pyritic and organic sulfur) is based on the
reaction
is
calculated by:
The complete oxidation of nitrogen is based on the reaction
, and the numerical coefficient of
is calculated by:
is calculated by:
Direct Correlation: Normally small, relative to its heat of combustion. An error
of 1% in the heat of a combustion-based correlation produces about a 50%
error when it is used to calculate the heat of formation. For this reason, the
following direct correlation was developed, using data from the Penn State
Data Base. It has a standard deviation of 112.5 Btu/lb, which is close to the
limit, due to measurement in the heat of combustion:
Where:
Parameter Name/Element
Symbol
Default
HFC/1
a1i
1810.123
HFC/2
a2i
-502.222
HFC/3
a3i
329.1087
HFC/4
a4i
121.766
HFC/5
a5i
-542.393
HFC/6
a6i
1601.573
303
Parameter Name/Element
Symbol
Default
HFC/7
a7i
424.25
HFC/8
a8i
-525.199
HFC/9
a9i
-11.4805
HFC/10
a10i
31.585
HFC/11
a11i
13.5256
HFC/12
a12i
11.5
HFC/13
a13i
-685.846
HFC/14
a14i
-22.494
HFC/15
a15i
-64836.19
Where:
i
Component index
wj
304
Parameter Name/Element
Symbol
Default
CP1C/1
ai,11
1.0
CP1C/2
ai,12
CP1C/3
ai,13
CP1C/4
ai,14
CP1C/5
ai,21
0.165
CP1C/6
ai,22
Parameter Name/Element
Symbol
Default
CP1C/7
ai,23
CP1C/8
ai,24
CP1C/9
ai,31
0.395
CP1C/10
ai,32
CP1C/11
ai,33
CP1C/12
ai,34
CP1C/13
ai,41
0.71
CP1C/14
ai,42
CP1C/15
ai,43
CP1C/16
ai,44
CP1C/17
ai,51
0.18
CP1C/18
ai,52
CP1C/19
ai,53
CP1C/20
ai,54
Parameter Name/Element
Symbol
Default
CP2C/1
a1i
0.438
CP2C/2
a2i
CP2C/3
a3i
CP2C/4
a4i
The default values of the parameters were developed by Gomez, Gayle, and
Taylor (1965). They used selected data from three lignites and a
subbituminous B coal, over a temperature range from 32.7 to 176.8C.
Parameter
Names
Component
Attributes
Boie correlation
BOIEC
ULTANAL
SULFANAL
PROXANAL
Dulong
correlation
DLNGC
ULTANAL
SULFANAL
PROXANAL
Grummel and
GMLDC
Davis correlation
ULTANAL
SULFANAL
PROXANAL
ULTANAL
SULFANAL
PROXANAL
305
Parameter
Names
Component
Attributes
CIGTC
ULTANAL
PROXANAL
IGT correlation
Revised IGT
correlation
2 Standard Heat of Formation
CIGT2
ULTANAL
PROXANAL
ULTANAL
PROXANAL
Heat-of
combustionbased correlation
ULTANAL
SULFANAL
ULTANAL
SULFANAL
PROXANAL
PROXANAL
Cubic
temperature
equation
3 Heat Capacity
CP2C
4 Enthalpy Basis
Elements in their
standard states
at 298.15K and 1
atm
Component at
298.15 K
References
Gomez, M., J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of
Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965.
IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data
Book, Section PMa. 44.1, 1976.
Kirov, N.Y., "Specific Heats and Total Heat Contents of Coals and Related
Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965),
pp. 29, 33.
Swanson, V.E. et al., Collection, Chemical Analysis and Evaluation of Coal
Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76
468.
R. H. Perry and D. W. Green, eds., Perry's Chemical Engineers' Handbook, 7th
ed., McGraw-Hill (1997), p. 27-5.
306
The equation for idm is good for a wide range of hydrogen contents, including
anthracities and high temperature cokes. The standard deviation of this
correlation for a set of 190 points collected by IGT from the literature was
12x10-6 m3/kg. The points are essentially uniform over the whole range. This
is equivalent to a standard deviation of about 1.6% for a coal having a
hydrogen content of 5%. It increases to about 2.2% for a coke or anthracite
having a hydrogen content of 1%.
Parameter Name/Element
Symbol
Default
DENIGT/1
a1i
0.4397
DENIGT/2
a2i
0.1223
DENIGT/3
a3i
-0.01715
DENIGT/4
a4i
0.001077
Reference
IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data
Book, Section PMa. 44.1, 1976.
Default
DENIGT/1
a1i
0.4397
DENIGT/2
a2i
0.1223
DENIGT/3
a3i
-0.01715
DENIGT/4
a4i
0.001077
307
References
I.M. Chang, B.S. Thesis, Massachusetts Institute of Technology, 1979.
M. Gomez, J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of
Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965.
IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data
Book, Section PMa. 44.1, 1976.
N.Y. Kirov, "Specific Heats and Total Heat Contents of Coals and Related
Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965),
pp. 29, 33.
V.E. Swanson et al., Collection, Chemical Analysis and Evaluation of Coal
Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76
468.
308
Option Value
Code
Descriptions
SIG2HSS
-1,-2,
..., -9
-1,-2,
..., -9
SIG2ONSG
SIG2API
MUL2API,
MULAPI92
309
Model Name
Option Value
Code
MUL2ANDR,
1
DL0WCA, DL1WCA,
DL0NST, DL1NST
MUL2JONS
MUL2CLS,
MUL2CLS2
MUL2QUAD
KL2VR, KL2RDL
Descriptions
Original correlation
Exponent is -2
Exponent is 0.4
Option
Code
Value Descriptions
GMXSH
Equal weighting
WHENRY
310
Model Name
Option
Code
Value Descriptions
2
Size - VC1/3
Volume - VC
Not used
No unsymmetric mixing
Symmetric and Unsymmetric Electrolyte NRTL Activity Coefficient Model (GMENRTLS and
GMENRTLQ)
1
COSMOSAC
1
Model choice
1
Hansen
1
NRTL-SAC (GMNRTLS)
1
311
Model Name
Option
Code
2
3
Value Descriptions
2
Option
Code
ESBWRS, ESBWRS0 1
ESHOC, ESHOC0,
PHV0HOC
ESPR, ESPR0,
ESPRSTD,
ESPRSTD0
312
Value
Descriptions
Model Name
Option
Code
Value
Descriptions
ESPRWS,
1
ESPRWS0, ESPRV1,
ESPRV10, ESPRV2,
ESPRV20,
ESPSAFT,
ESPSAFT0
Alternative copolymer
Block copolymer
3
ESRKS, ESRKS0,
ESRKSTD,
ESRKSTD0, ESSRK,
ESSRK0, ESRKSML,
ESRKSML0
ESRKSW, ESRKSW0 1
ESRKU, ESRKU0
At TREF=25 C (default)
(TB(i) + TB(j))/2
100999
VLE (default)
LLE
Property diagnostic level flag (-1 to 8)
313
Model Name
Option
Code
Value
Hayden-O'Connell (default)
Redlich-Kwong
ESHF, ESHF0
Descriptions
Estimate (default)
Set to zero
ESRKSWS,
ESRKSWS0,
ESRKSV1,
ESRKSV10,
ESRKSV2,
ESRKSV20,
ESSTEAM,
ESSTEAM0
ESH2O, ESH2O0
Note: The enthalpy, entropy, Gibbs energy, and molar volume of water are
calculated from the steam tables when the relevant option is enabled. The
total properties are mole-fraction averages of these values with the properties
calculated by the equation of state for other components. Fugacity coefficient
is not affected.
314
Soave-Redlich-Kwong Option
Codes
There are five related models all based on the Soave-Redlich-Kwong equation
of state which are very flexible and have many options. These models are:
The options for these models can be selected using the option codes
described in the following table:
Option
Code
Value
Description
Notes
1. The standard alpha function is always used for Helium.
315
Option
Code
Value Descriptions
BK10
Value Descriptions
DHL0HREF
316
Value Descriptions
0
Corresponding state method. Calculates a pseudocritical temperature of the solvents and uses it
together with the actual critical temperatures of the
pure solvents to adjust the liquid enthalpy departure.
This results in a smoother transition of the liquid
enthalpy contribution when the component transforms
from subcritical to supercritical.
Vector NRTL(8)
317
Value Descriptions
HIG2ELC, HIG2HG
1
DHLELC
1
No unsymmetric mixing
PHILELC
1
Option
Code
Value Descriptions
318
Model Name
Option
Code
Value Descriptions
1
GLRELNRT, GLRELELC
1
Vector NRTL(8)
319
Model Name
Option
Code
Value Descriptions
GIG2ELC, GIG2HG
1
No unsymmetric mixing
Option
Code
Value Descriptions
VL2QUAD
2
VAQCLK
320
Index
A
activity coefficient models 86
list of property models 86
alpha functions 69, 73
Peng-Robinson 69
Soave 73
Andrade liquid mixture viscosity
model 247
Andrade/DIPPR viscosity model
248
Antoine/Wagner vapor pressure
model 182
API model 194, 251, 288
liquid molar volume 194
liquid viscosity 251
surface tension 288
API Sour model 187
applications 91
metallurgical 91
aqueous infinite dilution heat
capacity model 213
ASME steam tables 16
Aspen liquid mixture viscosity
model 252
Aspen polynomial equation 211
ASTM 252
liquid viscosity 252
B
Barin equations thermodynamic
property model 228
Benedict-Webb-Rubin-Starling
property model 17
Braun K-10 model 187
Brelvi-O'Connell model 196
Bromley-Pitzer activity coefficient
model 87, 88, 89
Index
about 87
parameter conversion 89
working equations 88
BWR-Lee-Starling property model
16
C
Cavett thermodynamic property
model 228
Chao-Seader fugacity model 188
Chapman-Enskog 253, 256, 282,
283
Brokaw/DIPPR viscosity model
253
Brokaw-Wilke mixing rule
viscosity model 256
Wilke-Lee (binary) diffusion
model 282
Wilke-Lee (mixture) diffusion
model 283
Chien-Null activity coefficient
model 89
Chung-Lee-Starling model 258,
260, 270
low pressure vapor viscosity 258
thermal conductivity 270
viscosity 260
Clarke electrolyte liquid volume
model 197
Clausius-Clapeyron equation 194
heat of vaporization 194
coal 297
property models 297
constant activity coefficient model
91
copolymer PC-SAFT EOS property
model 35, 37, 41, 42, 44, 45,
46
321
about 35
association term 42
chain connectivity 37
dispersion term 41
fundamental equations 35
parameters 45, 46
polar term 44
COSMO-SAC solvation model 91
COSTALD liquid volume model 199
Criss-Cobble aqueous infinite
dilution ionic heat capacity
model 214
enthalpy thermodynamic
property model 231
Gibbs energy thermodynamic
property model 233
eNRTL-SAC activity coefficient
model 108
ENTHGEN nonconventional
component heat capacity
model 296
equation-of-state method 15
property models 15
extrapolation 10
temperature limits 10
D
Dawson-Khoury-Kobayashi
diffusion model 283, 284
binary 283
mixture 284
DCOALIGT coal density model 306
Dean-Stiel pressure correction
viscosity model 262
Debye-Hckel volume model 201
DGHARIGT char density model 307
diffusivity models 281
list 281
DIPPR equation 7, 216
DIPPR model 191, 202, 214, 219,
248, 253, 273, 276, 289
heat of vaporization 191
ideal gas heat capacity 219
liquid heat capacity 214
liquid volume 202
surface tension 289
thermal conductivity 273, 276
viscosity 248, 253
DNSTYGEN nonconventional
component density model 295
E
electrolyte models 197, 231, 233,
263, 272, 285, 292
Clarke liquid volume 197
electrolyte NRTL enthalpy 231
Gibbs energy 233
Jones-Dole viscosity 263
Nernst-Hartley diffusion 285
Onsager-Samaras surface
tension 292
Riedel thermal conductivity 272
electrolyte NRTL 94, 97, 231, 233
activity coefficient model 94, 97
322
G
Grayson-Streed fugacity model 188
group contribution activity
coefficient models 172, 174,
175
Dortmund-modified UNIFAC 174
Lyngby-modified UNIFAC 175
UNIFAC 172
H
Hakim-Steinberg-Stiel/DIPPR
surface tension 289
Hansen solubility parameter model
112
Hayden-O'Connell 22
property model 22
HCOALGEN 300
general coal model for enthalpy
300
heat of vaporization 191
models 191
Helgeson thermodynamic property
model 240
HF equation of state 25
property model 25
Huron-Vidal mixing rules 79
I
IAPS models for water 262, 271,
289
surface tension 289
thermal conductivity 271
viscosity 262
ideal gas heat capacity 219
ideal gas law 29
property model 29
Index
Index
M
Mathias alpha function 73
Mathias-Copeman alpha function
69, 73
Maxwell-Bonnell vapor pressure
model 190
MHV2 mixing rules 81
mixing rules 79, 81, 82, 84, 213,
243, 256, 269, 272, 279, 281
Brokaw-Wilke viscosity model
256
Huron-Vidal 79
Li 272
liquid volume quadratic 213
MHV2 81
predictive Soave-Redlich-KwongGmehling 82
quadratic 243
viscosity quadratic 269
Vredeveld 279
Wassiljewa-Mason-Saxena 281
Wong-Sandler 84
modified MacLeod-Sugden surface
tension model 293
N
Nernst-Hartley electrolyte diffusion
model 285
NIST 218
liquid heat capacity 218
NIST TDE Watson equation 193
heat of vaporization 193
nonconventional components 295,
296, 300
coal model for enthalpy 300
density polynomial model 295
enthalpy and density models list
295
heat capacity polynomial model
296
nonconventional solid property
models 295
density 295
enthalpy 295
list of 295
Nothnagel 33
property model 33
NRTL 94, 114
electrolyte NRTL property model
94
property model 114
NRTL-SAC 115, 119, 130
323
324
Index
S
Sato-Riedel/DIPPR thermal
conductivity model 273
Scatchard-Hildebrand activity
coefficient model 149
Schwartzentruber-Renon property
model 57
Soave-Redlich-Kwong 59
property model 59
Soave-Redlich-Kwong models 315
options codes 315
solid Antoine vapor pressure
models 190
solid thermal conductivity
polynomial 276
solids polynomial heat capacity
model 223
solubility correlation models 225,
226, 227
Henry's constant 225
hydrocarbon 227
list 225
water solubility model 226
SRK-Kabadi-Danner property
model 61
SRK-ML property model 63
standard Peng-Robinson property
model 49
standard Redlich-Kwong-Soave
property model 53
steam tables 16, 32
NBS/NRC 32
property models 16
STEAMNBS property method 32
Stiel-Thodos pressure correction
thermal conductivity model
279
Stiel-Thodos thermal conductivity
model 276
surface tension 287, 288, 293
general pure components 289
liquid mixtures 288
models list 287
modified MacLeod-Sugden 293
Symmetric and Unsymmetric
Electrolyte NRTL activity
coefficient model 151, 154
about 151
working equations 154
T
extrapolating limits 10
temperature-dependent properties
6, 7
pure component 7
units 6
thermal conductivity 269, 276
models list 269
solids 276
thermo switch 7
thermodynamic property 11, 228
list of additional models 228
models list 11
three-suffix Margules activity
coefficient model 150
THRSWT 7
transport property 244
models list 244
transport switch 7
TRAPP 266, 280
thermal conductivity model 280
viscosity model 266
TRNSWT 7
Twu liquid viscosity model 267
U
UNIFAC 172, 174, 175
activity coefficient model 172
Dortmund modified activity
coefficient model 174
Lyngby modified activity
coefficient model 175
UNIQUAC 176
activity coefficient model 176
V
Van Laar activity coefficient model
178
vapor thermal conductivity 276
general pure components 276
vapor viscosity 253, 256, 258, 265
Brokaw-Wilke mixing rule
viscosity model 256
Chung-Lee-Starling 258
Lucas 265
pure components 253
viscosity 246
models 246
viscosity quadratic mixing rule 269
VPA/IK-CAPE equation of state 64
Vredeveld mixing rule 279
temperature 10
Index
325
W
Wagner Interaction Parameter
activity coefficient model 179
Wagner vapor pressure model 182
Wassiljewa-Mason-Saxena mixing
rule 281
Watson equation 191
heat of vaporization 191
Wilke-Chang diffusion model 286,
287
binary 286
mixture 287
WILS-GLR property method 236
WILS-LR property method 236
Wilson (liquid molar volume)
activity coefficient model 181
Wilson activity coefficient model
179
Wong-Sandler mixing rules 84
326
Index