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1 Introduction .........................................................................................................5
Units for Temperature-Dependent Parameters .....................................................6
Pure Component Temperature-Dependent Properties............................................6
Extrapolation Methods ......................................................................................9
Contents 1
Activity Coefficient Models ............................................................................... 89
Bromley-Pitzer Activity Coefficient Model................................................. 90
Chien-Null ........................................................................................... 93
Constant Activity Coefficient .................................................................. 94
COSMO-SAC ........................................................................................ 95
Electrolyte NRTL Activity Coefficient Model (GMENRTL) ............................. 98
ENRTL-SAC ....................................................................................... 111
Hansen ............................................................................................. 116
Ideal Liquid ....................................................................................... 117
NRTL (Non-Random Two-Liquid) .......................................................... 117
NRTL-SAC Model ................................................................................ 119
Pitzer Activity Coefficient Model............................................................ 139
Polynomial Activity Coefficient ............................................................. 150
Redlich-Kister .................................................................................... 152
Scatchard-Hildebrand ......................................................................... 153
Three-Suffix Margules......................................................................... 153
Symmetric and Unsymmetric Electrolyte NRTL Activity Coefficient Model... 154
UNIFAC Activity Coefficient Model......................................................... 175
UNIFAC (Dortmund Modified)............................................................... 177
UNIFAC (Lyngby Modified)................................................................... 178
UNIQUAC Activity Coefficient Model ...................................................... 180
Van Laar Activity Coefficient Model ....................................................... 181
Wagner Interaction Parameter ............................................................. 182
Wilson Activity Coefficient Model .......................................................... 183
Wilson Model with Liquid Molar Volume ................................................. 184
Vapor Pressure and Liquid Fugacity Models...................................................... 185
General Pure Component Liquid Vapor Pressure ..................................... 186
API Sour Model .................................................................................. 190
Braun K-10 Model .............................................................................. 191
Chao-Seader Pure Component Liquid Fugacity Model .............................. 191
Grayson-Streed Pure Component Liquid Fugacity Model .......................... 192
Kent-Eisenberg Liquid Fugacity Model ................................................... 192
Maxwell-Bonnell Vapor Pressure Model.................................................. 194
Solid Antoine Vapor Pressure Model ...................................................... 194
General Pure Component Heat of Vaporization ................................................. 194
DIPPR Heat of Vaporization Equation .................................................... 195
Watson Heat of Vaporization Equation .................................................. 195
PPDS Heat of Vaporization Equation ..................................................... 196
IK-CAPE Heat of Vaporization Equation ................................................. 196
NIST TDE Watson Heat of Vaporization Equation .................................... 197
Clausius-Clapeyron Equation ............................................................... 197
Molar Volume and Density Models .................................................................. 198
API Liquid Molar Volume ..................................................................... 198
Brelvi-O'Connell ................................................................................. 200
Chueh-Prausnitz Liquid Molar Volume Model .......................................... 201
Clarke Aqueous Electrolyte Volume....................................................... 202
COSTALD Liquid Volume ..................................................................... 205
Debye-Hckel Volume......................................................................... 206
Liquid Constant Molar Volume Model..................................................... 207
General Pure Component Liquid Molar Volume ....................................... 207
Rackett/Campbell-Thodos Mixture Liquid Volume ................................... 212
Modified Rackett Liquid Molar Volume ................................................... 213
Rackett Extrapolation Method .............................................................. 214
2 Contents
General Pure Component Solid Molar Volume......................................... 216
Liquid Volume Quadratic Mixing Rule .................................................... 218
Heat Capacity Models ................................................................................... 218
Aqueous Infinite Dilution Heat Capacity................................................. 218
Criss-Cobble Aqueous Infinite Dilution Ionic Heat Capacity ...................... 219
General Pure Component Liquid Heat Capacity....................................... 219
General Pure Component Ideal Gas Heat Capacity .................................. 224
General Pure Component Solid Heat Capacity ........................................ 228
Solubility Correlations ................................................................................... 230
Henry's Constant................................................................................ 230
Water Solubility ................................................................................. 231
Hydrocarbon Solubility ........................................................................ 232
Other Thermodynamic Property Models ........................................................... 233
Cavett .............................................................................................. 233
Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity... 233
Electrolyte NRTL Enthalpy Model (HMXENRTL) ....................................... 236
Electrolyte NRTL Gibbs Free Energy Model (GMXENRTL) .......................... 238
Liquid Enthalpy from Liquid Heat Capacity Correlation............................. 240
Enthalpies Based on Different Reference States ..................................... 241
Helgeson Equations of State ................................................................ 246
Quadratic Mixing Rule ......................................................................... 249
Contents 3
TRAPP Thermal Conductivity Model....................................................... 288
Wassiljewa-Mason-Saxena Mixing Rule ................................................. 289
Diffusivity Models ......................................................................................... 289
Chapman-Enskog-Wilke-Lee (Binary).................................................... 290
Chapman-Enskog-Wilke-Lee (Mixture) .................................................. 291
Dawson-Khoury-Kobayashi (Binary) ..................................................... 291
Dawson-Khoury-Kobayashi (Mixture) .................................................... 292
Nernst-Hartley ................................................................................... 293
Wilke-Chang (Binary) ......................................................................... 294
Wilke-Chang (Mixture) ........................................................................ 295
Surface Tension Models................................................................................. 295
Liquid Mixture Surface Tension ............................................................ 296
API Surface Tension ........................................................................... 296
IAPS Surface Tension for Water ........................................................... 297
General Pure Component Liquid Surface Tension .................................... 297
Onsager-Samaras .............................................................................. 300
Modified MacLeod-Sugden ................................................................... 301
Index ..................................................................................................................331
4 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 Methods | 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 Temperature-
Dependent 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:
Thermodynamic property models
Transport property models
Nonconventional solid property models
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.
Categories of Models
Category Sections
Thermodynamic Equation-of-State Models
Property 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
1 Introduction 5
Category Sections
Transport Property Viscosity Models
Models Thermal Conductivity Models
Diffusivity Models
Surface Tension Models
Nonconventional Solid General Enthalpy and Density Models
Property Models Enthalpy and Density Models for Coal and Char
6 1 Introduction
NIST TDE Watson
1 Introduction 7
As the previous table shows, a property is associated with an element of the
submodel-selection parameter. For example, THRSWT element 1 controls the
submodel for solid volume.
The following table shows the values for THRSWT or TRNSWT, and the
corresponding submodels.
Parameter Values
(Equation Number) Submodel
0 Aspen
1 to 127 DIPPR
200 to 211 BARIN
301 to 302 PPDS or property-specific methods
400 PML
401 to 404 IK-CAPE
501 to 515 NIST
8 1 Introduction
Available DIPPR Equations
Equation
Number Equation Form
100
101
102
103
104
105
106
107
114
115
116
127
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-versus-
temperature 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:
1 Introduction 9
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
ASME Steam Tables ESH2O0,ESH2O VL X
BWR-Lee-Starling ESBWR0, ESCSTBWR V L X X
Benedict-Webb-Rubin-Starling ESBWRS, ESBWRS0 VL X X
GERG2008 VL X X
Hayden-O'Connell ESHOC0,ESHOC V X X
HF equation-of-state ESHF0, ESHF V X X
IAPWS-95 Steam Tables VL X
Ideal Gas ESIG0, ESIG V X X
Lee-Kesler * ESLK VL X
Lee-Kesler-Plcker ESLKP0,ESLKP VL X X
Other Models
Property Model Model Property Phase(s) Pure Mixture
Name
Cavett Liquid Enthalpy Departure DHL0CVT, DHL, L X X
DHL2CVT DHLMX
BARIN Equations for Gibbs SLV X
Energy, Enthalpy, Entropy and
Heat Capacity
Bromley-Pitzer Enthalpy HAQPT2 HLMX L X
Bromley-Pitzer Gibbs Energy GAQPT2 GLMX L X
Equation-of-State Models
The Aspen Physical Property System has the following built-in equation-of-
state property models. This section describes the equation-of-state property
models available.
Model Type
ASME Steam Tables Fundamental
BWR-Lee-Starling Virial
Benedict-Webb-Rubin-Starling Virial
GERG2008 Fundamental/mixing rules
Hayden-O'Connell Virial and association
HF Equation-of-State Ideal and association
Huron-Vidal mixing rules Mixing rules
IAPWS-95 Steam Tables Fundamental
Ideal Gas Ideal
Lee-Kesler Virial
Lee-Kesler-Plcker Virial
MHV2 mixing rules Mixing rules
NBS/NRC Steam Tables Fundamental
Nothnagel Ideal
PC-SAFT Association
Peng-Robinson Cubic
Standard Peng-Robinson Cubic
Peng-Robinson Alpha functions Alpha functions
Peng-Robinson-MHV2 Cubic
Peng-Robinson-Wong-Sandler Cubic
Predictive SRK Cubic
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 hydrogen-
containing systems.
General Form:
Where:
Mixing Rules:
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 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:
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, n-
heptane, 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.
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).
(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
)
Where:
R = molar gas constant = 8.314472 J/mol-K.
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:
, with
, with
, where
, and
Cross-Interactions
The previous equations are valid for dimerization and cross-dimerization if
these mixing rules are applied:
Chemical Theory
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 = True mole fractions of monomers
yij = True mole fraction of dimer
i = True fugacity coefficient of component i
Kij = Equilibrium constant for the dimerization of i and j, on a
pressure basis
=
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 .
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: NRTL-
HOC, 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.
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)
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)
A second order Newton-Raphson technique is used to determine p1. Then p6
can be calculated by equation 5, and f is known (equation 7).
From the fugacity coefficient, the Gibbs energy departure of the mixture or
pure apparent components can be calculated:
(12)
(12a)
(14)
(17)
From the Gibbs energy departure and enthalpy departure, the entropy
departure can be calculated:
(18)
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 Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
ESHFK/1 C0 43.65
ESHFK/2 C1 -8910
ESHFK/3 C2 0
ESHFK/4 C3 0
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.
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 equation-
of-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.
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.
Symbol Parameter Name Default Definition
Tc TCLK TC Critical temperature
Pc PCLK PC Critical pressure
OMGLK OMEGA Acentric factor
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 gas-
processing, 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
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.
Nothnagel
The Nothnagel equation-of-state calculates thermodynamic properties for the
vapor phase. It is used in property methods NRTL-NTH, UNIQ-NTH, VANL-
NTH, 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 =
Where:
yi and yj = True mole fractions of monomers
yij = True mole fraction of dimer
i = True fugacity coefficient of component i
Kij = Equilibrium constant for the dimerization of i and j, on a
pressure basis
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
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:
In this method, you enter Ai, Bi, Ci, and Di on the Methods | Parameters |
Pure Component | 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.
Parameter Symbol Default Lower Upper Limit Units
Name/Element Limit
TC Tci 5.0 2000.0 TEMPERATURE
TB Tbi 4.0 2000.0 TEMPERATURE
PC pci 105 108 PRESSURE
NTHA/1 bi 0.199 RTci / pci 0.01 1.0 MOLE-VOLUME
NTHA/2 di 0.33 0.01 3.0
NTHA/3 pi 0 0.0 1.0
NTHK/1 Ai PRESSURE
NTHK/2 Bi 0 TEMPERATURE
NTHK/3 Ci 0 TEMPERATURE
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.
where hc, disp, assoc, and polar are contributions due to hard-chain fluids,
dispersion, association, and polarity, respectively.
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:
with
Entropy departure:
where mi, i, and i are the segment number, the segment diameter, and
the segment energy parameter of the segment type in the copolymer
component i, respectively. The segment number mi is calculated from the
segment ratio parameter ri:
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
For a block copolymer, there is only one pair and the number of and
pairs depend on the length of each block; therefore:
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
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,
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
The association-site number of the site type A on the segment type in the
copolymer component i is equal to the number of the segment type in the
copolymer component i,
Therefore
References
Huang, S. H., & Radosz, M. (1990). Equation of State for Small, Large,
Polydisperse, and Associating Molecules. Ind. Eng. Chem. Res., 29, 2284.
Gross, J., & Sadowski, G. (2002b). Application of the Perturbed-Chain SAFT
Equation of State to Associating Systems. Ind. Eng. Chem. Res., 41, 5510-
5515.
Pure parameters
Each non-association species (solvent or segment) must have a set of three
pure-component parameter; two of them are the segment diameter and the
segment energy parameter . The third parameter for a solvent is the
segment number m and for a segment is the segment ratio parameter r. For
an association species, two additional parameters are the effective association
volume (AB) and the association energy (AB). For a polar species, two
additional parameters are the dipole moment and the segment dipolar
fraction xp.
Binary parameters
There are three types of binary interactions in copolymer systems: solvent-
solvent, solvent-segment, and segment-segment. The binary interaction
parameter i,j allows complex temperature dependence:
with
PCSFAV AB X Unary
PCSFMU X Unary
PCSFXP xp X Unary
PCSKIJ/1 ai,j 0.0 X Binary,
Symmetric
PCSKIJ/2 bi,j 0.0 X Binary,
Symmetric
PCSKIJ/3 ci,j 0.0 X Binary,
Symmetric
PCSKIJ/4 di,j 0.0 X Binary,
Symmetric
PCSKIJ/5 ei,j 0.0 X Binary,
Symmetric
PCSKIJ/6 Tref 298.15 X TEMP Binary,
Symmetric
Note that the SI units for the segment diameter (PCSFTV) and dipole
moment (PCSFMU) are much too large to be practical. The implementation
of PC-SAFT in Aspen Plus has the unit in Angstroms () for the segment
diameter and in Debye (D) for the dipole moment; these units are not allowed
to be changed in PC-SAFT.
The binary parameter PCSKIJ can be specified for each solvent-solvent pair,
or each solvent-segment pair, or each segment-segment pair. By default, the
binary parameter is set to be zero.
A databank called PC-SAFT contains both unary and binary PC-SAFT
parameters available from literature; it must be used with the PC-SAFT
property method. The unary parameters available for segments are stored in
Peng-Robinson
The Peng-Robinson equation-of-state is the basis for the PR-BM property
method. 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 (see Standard Peng-Robinson). 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 as used in the PR-BM property
method is:
Where:
b =
a = a0+a1
kij = kji
a1
In general, .
ai =
bi =
If the Peneloux volume correction is used (option code 4), then the molar
volume is calculated from:
V = Vm - c
Where:
Vm = Molar volume calculated by the equation of state
without the correction
c =
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 the basis for the PENG-ROB property
method and it is recommended for hydrocarbon processing applications such
as gas processing, refinery, and petrochemical processes. Its results are
comparable to those of the standard Redlich-Kwong-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:
a =
ai =
bi =
kij =
If the Peneloux volume correction is used (option code 4), then the molar
volume is calculated from:
V = Vm - c
Where:
Vm = Molar volume calculated by the equation of state
without the correction
c =
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 Peng-
Robinson, 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.
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 PSRK method is an example of modified Huron-Vidal mixing rules. A brief
introduction is provided in Huron-Vidal Mixing Rules. For more details, see
Predictive Soave-Redlich-Kwong-Gmehling 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.
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:
=
b =
ai =
bi =
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 =
kb,ij =
For best results, binary parameters kij must be determined from phase-
equilibrium data regression, such as VLE data.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKA Tci TC x 5.0 2000.0 TEMPERATURE
PCRKA pci PC x 105 108 PRESSURE
OMGRKA i OMEGA x -0.5 2.0
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:
b =
ai =
bi =
kij = kji
; ;
The parameter ai is calculated according to the standard Soave formulation
(see Soave Alpha Functions, equations 1, 2, 3, 5, and 6).
References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 1203.
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-of-
state with the Boston-Mathias alpha function (see Soave 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 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:
b =
ai =
bi =
kij = kji
References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-
state," 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-Wong-
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.
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 =
b =
ai =
bi =
ci =
(for T Tci)
The latter equation is used to ensure bi-ci remains
positive in supercritical conditions.
g0i = bi (covolume)
g2i =
g1i =
ka,ij =
lij =
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 Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKU Tci TC x 5.0 2000.0 TEMPERATURE
PCRKU pci PC x 105 108 PRESSURE
OMGRKU i OMEGA x -0.5 2.0
Absolute temperature units are assumed for ka,ij , lij , and kb,ij2.
2 2
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.
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-of-
state," 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 Redlich-
Kwong-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 Redlich-
Kwong-Soave model. However, this model has several important differences.
A volume translation concept introduced by Peneloux and Rauzy is used to
improve molar liquid volume calculated from the cubic equation of state.
Improvement in water properties is achieved by using the NBS Steam
Table.
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:
;
a1 is an additional, asymmetric (polar) term:
Where:
; ;
If the Peneloux volume correction is used (option code 4), then the molar
volume is calculated from:
V = Vm - c
Where:
Vm is the molar volume calculated from the equation of state without the
correction
References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich-
Kwong-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.
Where:
Where:
;
The best values of kwj (w = water) were obtained from experimental data.
Results are given for seven homologous series.
Where:
This value is obtained from very little data. Might not be reliable.
If the Peneloux volume correction is used (option code 4), then the molar
volume is calculated from:
V = Vm - c
Where:
Vm is the molar volume calculated from the equation of state without the
correction
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 these 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
The Peneloux volume correction is disabled by default. (It can be enabled
using option code 4.)
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
SMLTC Tci TC x 5.0 2000.0 TEMPERATURE
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:
Dimerization (examples: formic acid, acetic acid)
Tetramerization (example: acetic acid)
Hexamerization (example: hydrogen fluoride)
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:
yi = Apparent concentration
zin = True concentration, for component i and degree of
association n=1, 2, 4, 6
(2)
(4)
By setting
(5)
(6)
(7)
(8)
(9)
Fugacity Coefficient
As is well-known from thermodynamics, the fugacity coefficient can be
calculated by
(11)
with
(13)
and
(16)
(2)
(18)
(20)
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)
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.
(2)
Note: You can choose any of the alpha functions described here, but you
cannot define multiple property methods based on this model using different
alpha functions within the same run.
This approach was also adopted by Peng and Robinson:
(4)
With
=
For c2,i = 0 and c3,i = 0, this expression reduces to the standard Peng-
Robinson formulation if c2,i = mi. You can use vapor pressure data if the
temperature is subcritical to regress the constants. If the temperature is
supercritical, c2,i and c3,i are set to 0.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCPR Tci TC X 5.0 2000.0 TEMPERATURE
PCPR pci PC X 105 108 PRESSURE
Where mi is computed by equation 5. The polar parameters p1,i, p2,i and p3,i
are comparable with the c parameters of the Mathias-Copeman expression.
Equation 8 reduces to the standard Peng-Robinson formulation if the polar
parameters are zero. Equation 8 is used only for below-critical temperatures.
For above-critical temperatures, the Boston-Mathias extrapolation is used.
Use equation 6 with:
(9)
(10)
PRSRP/1 X
PRSRP/2 0 X
PRSRP/3 0 X
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 Equation-
of-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-of-
state," 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)
Note: You can choose any of the alpha functions described here, but you
cannot define multiple property methods based on this model using different
alpha functions within the same run.
In the Redlich-Kwong equation-of-state, alpha is:
(4)
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)
With
di =
ci =
Where:
mi = Computed by equation 6
Equation 5 = Used for subcritical temperatures
Additional parameters are not needed.
(10)
Where mi is computed by equation 6. If the polar parameters p1,i, p2,i and p3,i
are zero, equation 11 reduces to the standard Redlich-Kwong-Soave
formulation. You can use vapor pressure data to regress the constants if the
temperature is subcritical. Equation 11 is used only for temperatures below
critical.
The Boston-Mathias extrapolation is used for temperatures above critical, that
is, with:
(12)
(13)
For c2,i=0 and c3,i=0 this expression reduces to the standard Redlich-Kwong-
Soave formulation if c1,i=mi. If the temperature is subcritical, use vapor
pressure data to regress the constants. If the temperature is supercritical, set
c2,i and c3,i to 0.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKS Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCRKS pci PC X 10 10 PRESSURE
RKSMCP/1 c1,i X
RKSMCP/2 c2,i 0 X
Where mi is computed by equation 6 and the polar parameters p1,i, p2,i and
p3,i are comparable with the c parameters of the Mathias-Copeman
expression. Equation 15 reduces to the standard Redlich-Kwong-Soave
formulation if the polar parameters are zero. Equation 15 is very similar to
the extended Mathias equation, but it is easier to use in data regression. It is
used only for temperatures below critical. The Boston-Mathias extrapolation is
used for temperatures above critical, that is, use equation 7 with:
(16)
(17)
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)
L 0.544000 0.379919
(0)
M 1.01309 5.67342
N(0) 0.935995 -0.200000
(1)
L 0.544306 0.0319134
(1)
M 0.802404 1.28756
N(1) 3.10835 -8.000000
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 Equation-
of-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-of-
state," 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.
(3)
Where:
(5)
Redlich-Kwong-Soave 1 0
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.
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:
and
(4)
With:
(5)
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)
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)
Where ' is slightly different from for the Huron-Vidal mixing rule:
(7)
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
n-C10H22. To address the issue, the Li correction (Li et al., 1998) is
applied.
With the Li correction, the R and Q parameters for groups CH3, CH2, CH, and
C in UNIFAC are modified. R* and Q*, the effective values of R and Q, are
calculated based on the original values and nc, the number of alkyl carbons
(single-bonded carbons in CH3, CH2, CH, and C groups), as follows, for
nc<45:
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).
Where both Ai* and Am are calculated by using equation 1. Ai* and Am are
written in terms of equation-of-state parameters.
Like Huron and Vidal, the limiting case of infinite pressure is used. This
simplifies the expressions for Ai* and Am. Equation 2 becomes:
(3)
With:
(5)
The relationship between the equation-of-state at low pressure and the virial
coefficient is:
(6)
Wong and Sandler discovered the following mixing rule to satisfy equation 4
(using equations 6 and 7):
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.
Parameters (0), (1), (2), (3), and have five elements to account for
temperature dependencies. Elements P1 through P5 follow the temperature
dependency relation:
Where:
Tref = 298.15K
GMBPD ion 1 0
Cation-Anion Parameters
GMBPB0 (0) 5 0
GMBPB1 (1) 5 0
GMBPB2 (2) 5 0
GMBPB3 (3) 5 0
Cation-Cation Parameters
GMBPTH cc' 5 0
Anion-Anion Parameters
GMBPTH aa' 5 0
Molecule-Ion and Molecule-Molecule Parameters
GMBPB0 (0) 5 0
GMBPB1 (1) 5 0
Working Equations
The complete Pitzer equation (Frst and Renon, 1982) for the excess Gibbs
energy is (see also equation 4):
(1)
Where:
GE = Excess Gibbs energy
R = Gas constant
T = Temperature
nw = Kilograms of water
zi = Charge number of ion i
= molality of ion i
The C term and the term are dropped from equation 1 to give the
simplified Pitzer equation.
(2)
Where:
Bij = 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.
Where:
Rji = Aji / Aij
Aii = 0
Aji = 2jiGji
Vji = Gji
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.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
ICHNUL 3 1 6
CHNULL/1 aij 0
CHNULL/2 bij 0
CHNULL/3 Vij 0
i = ai
Parameter Symbol Default MDS Upper Lower Units
Name/Element Limit Limit
GMCONS ai 1.0 x
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-
SAC complements the UNIFAC group-contribution method, because it is
applicable to virtually any mixture.
The Cosmo-SAC model calculates liquid activity coefficients. The equation for
the Cosmo-SAC model is:
With
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 Description
Code
1 COSMO-SAC model by Lin and Sandler (2002)
2 COSMO-RS model by Klamt (1995)
3 Lin and Sandler model with modified exchange energy (Lin
et al., 2002)
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
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 1
BB 1 0
CB 1 298.15 TEMPERATURE
Ionic Born Radius Unary Parameters
RADIUS ri 1 3x10-10 LENGTH
Molecule-Molecule Binary Parameters
NRTL/1 ABB' 0 x
AB'B 0 x
NRTL/2 BBB' 0 x TEMPERATURE
BB'B 0 x TEMPERATURE
NRTL/3 BB' = B'B .3 x
NRTL/4 0 x TEMPERATURE
NRTL/5 FBB' 0 x TEMPERATURE
FB'B 0 x TEMPERATURE
c'a,c''a = c''a,c'a 1 .2 x
Certain Electrolyte NRTL activity coefficient model parameters are used with
reciprocal temperature terms:
CPDIEC
NRTL/2
GMELCD for electrolyte-electrolyte or electrolyte-molecule pairs
When any of these parameters is specified, absolute temperature units are
used for the calculations in this model.
Reference: 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.
This leads to
(2)
with
(4)
(5)
Where:
xi = Mole fraction of component i
Ms = Molecular weight of the solvent
A = Debye-Hckel parameter
NA = Avogadro's number
ds = Mass density of solvent
Qe = Electron charge
T = Temperature
k = Boltzmann constant
Ix = Ionic strength (mole fraction scale)
xi = Mole fraction of component i
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:
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)
(8d)
Where:
xm = Mole fraction of the solvent m in the solution
Mm = Molecular weight of the solvent m
Vm l = Molar volume of the solvent mixture
Where:
Xj = xjCj
(Cj = zj for ions and Cj = unity for molecules)
Gji =
ji =
ji = Nonrandomness factor
Where:
Gji,ki =
ji,ki =
i = c, a, or B
(15)
(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 . These are then related to the
effective local mole fractions:
(17)
(18)
(19)
(21)
(22)
Where:
zc = Charge number on cations
za = Charge number on anions
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)
Combining this expression with the expression for the effective local mole
fractions given in equations 9 and 10, the following equality is obtained:
(26)
(28)
and,
(29)
(31)
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)
(36)
Multicomponent Systems
The Electrolyte NRTL model can be extended to handle multicomponent
systems.
The excess Gibbs energy expression is:
(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:
(41)
(42)
(43)
(44)
(45)
(46)
(47)
(48)
Parameters
The model adjustable parameters include:
Pure component dielectric constant coefficient of nonaqueous solvents
Born radius of ionic species
NRTL interaction parameters for molecule-molecule, molecule-electrolyte,
and electrolyte-electrolyte pairs
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, .
The pure component dielectric constant coefficients of nonaqueous solvents
and Born radius of ionic species are required only for mixed-solvent
electrolyte systems.
The temperature dependency relations of these parameters are given in
Electrolyte NRTL Activity Coefficient Model.
Heat of mixing is calculated from temperature derivatives of activity
coefficients. Heat capacity is calculated from secondary temperature
derivative of the activity coefficient. As a result, the temperature dependent
parameters are critical for modeling enthalpy correctly. It is recommended
that enthalpy data and heat capacity data be used to obtain these
temperature dependency parameters. See also Electrolyte NRTL Enthalpy and
Electrolyte NRTL Gibbs Energy.
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
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.
With
A = Debye-Hckel parameter
21 5 -3 -3 -4.549
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 Flory-Huggins term included (default)
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
Where:
DELTAP ip x PRESSURE^0.5
DELTAH ih x PRESSURE^0.5
HANVOL Vi x VOLUME
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.
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
ij =
ij =
ii = 0
Gii = 1
aij, bij, eij, and fij are unsymmetrical. That is, aij may not be equal to aji, etc.
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 Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
NRTL/1 aij 0 x -100.0 100.0
NRTL/2 bij 0 x -30000 30000.0 TEMPERATURE
NRTL/3 cij 0.30 x 0.0 1.0
NRTL/4 dij 0 x -0.02 0.02 TEMPERATURE
NRTL/5 eij 0 x TEMPERATURE
NRTL/6 fij 0 x TEMPERATURE
NRTL/7 Tlower 0 x TEMPERATURE
NRTL/8 Tupper 1000 x TEMPERATURE
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:
hydrophobic segment (x), hydrophilic segment (z), and polar segments (y-
and 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.
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 Symbol Default MDS Lower Upper Limit Units
Name/ Limit
Element
BXYZE/1 rx,CA
BXYZE/2 ry-,CA
BXYZE/3 ry+,CA
BXYZE/4 rz,CA
BXYZE/5 re,CA
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.
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.
(4)
(8)
(9)
(14)
(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)
(25)
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)
Molecular components
Applying Eq. 1, the normalization for molecular components can be done as
follows:
(31)
(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.
(37)
(39)
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
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)
(55)
(56)
(58)
For the univalent cation or anion segment, the activity coefficient can be
carried out as follows:
(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)
Molecular components
It is easy to show that activity coefficients for molecular components from the
Flory-Huggins term are normalized; that is
(71)
(73)
with
(74)
(76)
(77)
(79)
(81)
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)
where HIS and 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 all three activity coefficients for Henry components as follows:
(86)
(87)
(88)
with
(89)
(90)
(91)
(92)
(93)
(94)
with
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 Flory-Huggins term included (default)
Others Flory-Huggins term removed
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 Methods | Specifications sheet, specify method filter 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.
Where:
Tref = 298.15 K
The user must:
Supply these elements for the binary parameters using a Methods |
Parameters | Binary | T-Dependent form.
GMPTB1 (1) 5 0 x
GMPTB2 (2) 5 0 x
GMPTB3 (3) 5 0 x
GMPTC 5 0 x
C
Cation-Cation Parameters
GMPTTH cc' 5 0 x
Anion-Anion Parameters
GMPTTH aa' 5 0 x
Ternary Parameters
GMPTPS, ijk 1 (in each 0 x
GMPTP1, parameter)
GMPTP2,
GMPTP3,
GMPTP4
Molecule-Ion and Molecule-Molecule Parameters
GMPTB0 (0) 5 0 x
GMPTB1 (1) 5 0 x
GMPTC 5 0 x
C
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
r = Radius
qij =
k = Boltzmann's constant
T = 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 = Excess Gibbs energy
R = Gas constant
T = Temperature
nw = Kilograms of water
mi =
(molality of ion i)
With:
xi = Mole fraction of ion i
xw = Mole fraction of water
Mw = Molecular weight of water (g/mol)
ni = Moles of ion i
The function f(I) is an electrostatic term that expresses the effect of long-
range 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 molecule-
molecule 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
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)
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)
Where is neglected and ij and 'ij are the electrostatic unsymmetric mixing
effects:
So that:
(10)
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)
The parameters (0), (1), (2), (3) and also C, , and can be found in
Pitzer's articles .
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:
Where:
iii = 6iii
However, molecule-molecule interactions were not taken into account by
Pitzer and coworkers. So iii is an artificially introduced quantity.
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 user-
supplied parameters. These parameters are used in the calculation of binary
and ternary parameters for the electrolyte system. These parameters include
the cation-anion parameters (0), (1), (2), (3) and C , cation-cation
parameter cc', anion-anion parameter aa', cation1-cation2-common anion
parameter cc'a, anion1-anion2-common cation parameter caa', and the
molecule-ion and molecule-molecule parameters (0), (1), and, C . The
parameter names in the Aspen Physical Property System and their
requirements are discussed in Pitzer Activity Coefficient Model.
Where:
=
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:
4/3(0) = 0.4698
4/3(1) = 2.242
= 0.00979
= 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:
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.
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 Methods | Specifications sheet, specify an activity coefficient
model, such as NRTL.
2 Click the Methods | Selected 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 Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
GMPLYP/1 ai1 0 x
GMPLYP/2 ai2 0 x
GMPLYP/3 ai3 0 x
GMPLYP/4 bi1 0 x
GMPLYP/5 bi2 0 x
GMPLYP/6 bi3 0 x
GMPLYP/7 ci1 0 x
GMPLYP/8 ci2 0 x
GMPLYP/9 ci3 0 x
GMPLYP/10 di1 0 x
GMPLYP/11 di2 0 x
GMPLYP/12 di3 0 x
GMPLYP/13 ei1 0 x
GMPLYP/14 ei2 0 x
GMPLYP/15 ei3 0 x
GMPLYO fi x
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:
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/ Symbol Default MDS Lower Upper Units
Element Limit Limit
GMRKTB/1 aij 0 x
GMRKTB/2 bij 0 x
GMRKTB/3 cij 0 x
GMRKTB/4 dij 0 x
GMRKTB/5 eij 0 x
GMRKTB/6 fij 0 x
GMRKTB/7 gij 0 x
GMRKTB/8 hij 0 x
GMRKTB/9 mij 0 x
GMRKTB/10 nij 0 x
GMRKTO vi x
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 =
i =
Vm*,l =
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:
i = di
Parameter Name/ Symbol Default MDS Lower Upper Units
Element Limit Limit
GMMRGB/1 aij 0 x TEMPERATURE
GMMRGB/2 bij 0 x
GMMRGB/3 cij 0 x
GMMRGO di x
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).
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
where .
The NRTL parameters are used for molecule-molecule parameters, with
temperature dependence:
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:
ca,ca' = ca',ca 1 .2 x
where Gm is the Gibbs free energy of electrolyte systems and Gmid is the Gibbs
free energy of an ideal solution at the same conditions of temperature,
pressure, and composition.
or
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.
(7)
with
(10)
At the pure fused salt state, the total moles of ionic components (for one
mole of salt) are:
=c+a (12)
therefore
(13)
(14)
(15)
or
(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)
(26)
(27)
Binary Parameters
The adjustable binary parameters for these models include molecule-
molecule, 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)
(30)
(31)
(32)
(34)
(36)
(37)
(38)
(39)
(40)
And then the binary parameters are calculated from G using Eq. 23:
(41)
(44)
(45)
(46)
(47)
(48)
(50)
(52)
with
(54)
(55)
For multi-electrolyte systems with mixed-solvents, Ix0 can take this form:
(57)
(58)
so that
(60)
(66)
or
(68)
(69)
(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.
where i is the infinite dilution activity coefficient of Henry component i
(xi0) in the solution.
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)
(81)
(82)
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)
i = Stoichiometric coefficient
(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)
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
)
(101)
(102)
Solvents
The contribution from solvents can be written as follows:
(103)
(104)
(105)
(106)
(107)
(108)
Henry components
The contribution from Henry components can be written as follows:
(109)
(110)
(111)
(112)
(113)
(114)
(115)
Ionic components
The contribution from ionic components can be written as follows:
(116)
(117)
(118)
(119)
(120)
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
Aspen Plus and Aspen Properties. Hi and Gi are the new contributions from
the symmetric reference state.
(129
)
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)
ln = ln ic + ln ir
ln ic =
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
With:
And:
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 Components | 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,
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.
GMUFDQ Qk
GMUFDR Rk
UNIFDM/1 amn,1 0 TEMPERATURE
UNIFDM/2 amn,2 0 TEMPERATURE
UNIFDM/3 amn,3 0 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 Components | Molecular Structure | Functional Group
sheet. See Physical Property Data, Chapter 3, for a list of the Dortmund
modified UNIFAC functional groups.
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.
J. Gmehling, J. Li, and M. Schiller, "A Modified UNIFAC Model. 2. Present
Parameter Matrix and Results for Different Thermodynamic Properties," Ind.
Eng. Chem. Res., Vol. 32, (1993), pp. 178193.
Where k and ki have the same meaning as in the original UNIFAC, but
defined as:
With:
GMUFLQ Qk
GMUFLR Rk
UNIFLB/1 amn,1 0 TEMPERATURE
UNIFLB/2 amn,2 0 TEMPERATURE
UNIFLB/3 amn,3 0 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 Components | Molecular Structure |
Functional Group sheet. See Physical Property Data, Chapter 3, for a list of
the Larsen modified UNIFAC functional groups.
Where:
i =
i' =
i =
li =
t i' =
ij =
z = 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 Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
GMUQR ri x
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.
Where:
zi =
Ai =
Bi =
Ci =
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 Lower Limit Upper Units
Name/Element Limit
VANL/1 aij 0 x -50.0 50.0
VANL/2 bij 0 x -15000.0 15000.0 TEMPERATURE
VANL/3 cij 0 x -50.0 50.0
VANL/4 dij 0 x -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).
Where:
For any component i, the value of the activity coefficient can be fixed:
i = gi
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.
Where:
ln Aij =
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.
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
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
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.
Where:
Tri = T / Tci
pri*,l = pi*,l / pci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
Where:
Tri = T / Tci
pri*,l = pi*,l / pci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
WAGNER/1 C1i x
WAGNER/2 C2i 0 x
WAGNER/3 C3i 0 x
WAGNER/4 C4i 0 x
TC Tci TEMPERATURE
PC pci PRESSURE
Where:
Tri = T / Tci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
WAGNER25/1 C1i x
WAGNER25/2 C2i 0 x
WAGNER25/3 C3i 0 x
WAGNER25/4 C4i 0 x
WAGNER25/5 ln pci 0 x
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.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
LNVP1/1, ...,8 C1i, ..., C8i x PRESSURE
TEMPERATURE
LOGVP1/1, ..., 8 C1i, ..., C8i x PRESSURE
TEMPERATURE
LNPR1/1, ..., 8 C1i, ..., C8i x PRESSURE
TEMPERATURE
LOGPR1/1, ..., 8 C1i, ..., C8i x PRESSURE
TEMPERATURE
LNPR2/1,2 C1i, C2i x
LNVPEQ/1 (equation
number)
LNVPEQ/2 Tlower 0 X TEMPERATURE
TC Tci TEMPERATURE
PC pci PRESSURE
PLTDEPOL/3 C3i 0 X
References
Reid, Prausnitz, and Poling, The Properties of Gases and Liquids, 4th ed.,
(New York: McGraw-Hill, 1987).
Harlacher and Braun, "A Four-Parameter Extension of the Theorem of
Corresponding States," Ind. Eng. Chem. Process Des. Dev., Vol. 9, (1970), p.
479.
W. Wagner, Cryogenics, Vol. 13, (1973), pp. 470-482.
D. Ambrose, M. B. Ewing, N. B. Ghiassee, and J. C. Sanchez Ochoa "The
ebulliometric method of vapor-pressure measurement: vapor pressures of
benzene, hexafluorobenzene, and naphthalene," J. Chem. Thermodyn. 22
(1990), p. 589.
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).
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:
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:
References
H.G. Grayson and C.W. Streed, Paper 20-PO7, Sixth World Petroleum
Conference, Frankfurt, June 1963.
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.
Where:
Tri = T / Tci
.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DHVLDP/1 C1i x MOLE-ENTHALPY
DHVLDP/2, ..., 5 C2i, ..., C5i 0 x
DHVLDP/6 C6i 0 x TEMPERATURE
DHVLDP/7 C7i 1000 x TEMPERATURE
TC Tci 5.0 2000.0 TEMPERATURE
Where:
Clausius-Clapeyron Equation
The Aspen Physical Property System can calculate heat of vaporization using
the Clausius Clapeyron equation:
Where:
= Slope of the vapor pressure curve calculated from the Extended
Antoine equation
Where:
xp = Mole fraction of pseudocomponents
xr = Mole fraction of real components
For pseudocomponents, the API procedure is used:
Where:
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.
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 = Solute or dissolved-gas component
A = Solvent component
VBO = V1 + TV2
The above correlation applies to both solute and solvent.
The liquid molar volume of solvent is obtained from the Rackett model:
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.
Where
Vm =Liquid molar volume of the mixture
Vms =Liquid molar volume at saturation, calculated using the Rackett
model for mixtures or the General liquid volume model for pure
components
Zcm = Critical compressibility factor of the mixture = xiZci
Zci =Critical compressibility factor of component i
N =
P =System pressure
Pvp =
Saturation pressure = for
mixtures, or calculated using the General vapor pressure model
for pure components
Pcm =Critical pressure of the mixture
T =Temperature
Trm =Reduced temperature = T/Tcm
Tcm =Critical temperature of the mixture
Reference
Chueh, P.L. and J.M. Prausnitz, AIChE J. 15, 471 (1969).
Where:
Vm l = Liquid molar volume for electrolyte solutions.
Vsl = Liquid molar volume for solvent mixtures.
Vel = Liquid molar volume for electrolytes.
Where:
xw = Mole fraction of water
Vw* = Molar volume of water from the steam table.
xnws = Sum of the mole fractions of all non-water
solvents.
Vnwsl = Liquid molar volume for the mixture of all non-
water solvents. It is calculated using the
Rackett equation.
For electrolytes:
(3)
(4)
(5)
(6)
Where:
xca = Apparent mole fraction of electrolyte ca
Vca = Liquid molar volume for electrolyte ca
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 = Number of moles of apparent electrolyte ca
zc = Charge of c
zfactor = zc if c and a have the same number of
charges; otherwise 1.
nc = Number of moles of cation c
na = Number of moles of anion a
Where:
Vml,t = Liquid volume per number of true species
Vml,a = Liquid volume per number of apparent species, Vml
of equation 1
na = Number of apparent species
t
n = Number of true species
The apparent molar volume is calculated as explained in the preceding
subsection.
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)
If VLBROC/1 is missing, the default value of -0.0012 is used. See the Brelvi-
O'Connell model for VLBROC and also Rackett/Campbell-Thodos Mixture
Liquid Volume for additional parameters used in the Rackett equation.
Where:
VmR,0 and VmR, are functions or Tr for
Where B and C are functions of T, , Tc, Pc and Psat is the saturated pressure
at T.
Where:
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:
Vw* 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:
Where:
= Partial molar ionic volume at infinite dilution
Vk
zk = Charge number of ion k
Av = Debye-Hckel constant for volume
b = 1.2
I =
the ionic strength, with
mk = Molarity of ion k
Av is computed as follows:
Where:
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).
* When no value is provided for VLCONS, the General Pure Component Liquid
Molar Volume model is used to calculate the liquid molar volume.
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
Methods | Selected 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:
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.
PPDS
The PPDS equation is:
IK-CAPE
The IK-CAPE equation is:
Rackett
The Rackett equation is:
Where:
Tr = T / Tci
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.
Rackett
The equation for the Rackett model is:
Where:
Tc =
ZmRA =
Vcm =
Tr = T / Tc
Campbell-Thodos
The Campbell-Thodos model uses the same equation as the Rackett model,
above, except that ZmRA is allowed to vary with temperature:
ZmRA =
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.
kij =
ZmRA =
Zi*,RA =
Vcm =
Tr = T / Tc
MRKKIJ/2 Bij 0 x
MRKKIJ/3 Cij 0 x
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.
Details
First the volume V0 at 0.99Tc and the critical volume Vc are calculated:
Aspen Polynomial
The equation for the Aspen solids volume polynomial is:
IK-CAPE Equation
The IK-CAPE equation is:
DIPPR
The DIPPR equation is:
Option Codes
Option Code Value Descriptions
1 0 Use normal pure component liquid volume model for all
components (default)
1 Use steam tables for water
2 0 Use mole basis composition (default)
1 Use mass basis composition
Parameter
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VLQKIJ Kij 0 x - -
This model is not part of any property method. To use it, you will need to
define a property method on the Methods | Selected 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.
versus T is linearly extrapolated using the slope at C8i for T < C8i
Parameter Applicable Symbol Default Units
Name/Element Components
CPAQ0/1 Ions, molecular solutes C1i TEMPERATURE and
HEAT CAPACITY
CPAQ0/2,,6 Ions, molecular solutes C2i, ..., C6i 0 TEMPERATURE and
HEAT CAPACITY
CPAQ0/7 Ions, molecular solutes C7i 0 TEMPERATURE
CPAQ0/8 Ions, molecular solutes C8i 1000 TEMPERATURE
Cations MOLE-ENTROPY
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:
One of the parameters for calculating heat capacity (see table) is
available.
The component is not supercritical (HENRY-COMP).
The model uses a specific method (see Methods in Property Calculation
Methods and Routes):
Where
= Reference enthalpy calculated at Tref
= Enthalpy of vaporization
Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.
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.)
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:
When THRSWT/6 is 506, the TDE equation is used to calculate liquid heat
capacity:
These equations are also used to calculate ideal gas enthalpies, entropies,
and Gibbs energies.
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.
Absolute temperature units are assumed for C3i and C5i. The temperature
limits are always interpreted in user input units.
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 Default MDS Lower Upper Units
Name/Element Limit Limit
CPIALEE/1 C1i x MOLE-HEAT-
CAPACITY
CPIALEE/2 C2i 0 x MOLE-HEAT-
CAPACITY
CPIALEE/3 C3i 0 x TEMPERATURE
CPIALEE/4 C4i 0 x MOLE-HEAT-
CAPACITY
CPIALEE/5 C5i 0 x TEMPERATURE
CPIALEE/8 C6i 0 x TEMPERATURE
CPIALEE/9 C7i 1000 x 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:
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.
The enthalpy, entropy, and Gibbs energy of solids are also calculated from
these equations:
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:
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.)
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 Gas solubility in liquid
Water solubility Water solubility in organic liquid
Hydrocarbon solubility Hydrocarbon solubility in water-rich
liquid
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) =
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.
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.
The expression for the liquid mole fraction of water in the ith hydrocarbon
species is:
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:
Cavett
The general form for the Cavett model is:
Enthalpy:
(2)
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:
Solid Phase
The parameters in range n are valid for temperature: Tn,ls < T < Tn,hs
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 Upper Units
/Element Limit Limit
CPLXPn/1 Tn,ll x TEMPERATURE
CPLXPn/2 Tn,hl x TEMPERATURE
l
CPLXPn/3 an,i x
l
CPLXPn/4 bn,i 0 x
CPLXPn/5 cn,il 0 x
l
CPLXPn/6 dn,i 0 x
l
CPLXPn/7 en,i 0 x
CPLXPn/8 fn,il 0 x
l
CPLXPn/9 gn,i 0 x
l
CPLXPn/10 hn,i 0 x
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.)
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.)
where the subscript k refers to any ion or molecular solute and the term RT
ln(1000/Mw) is added because f Hk ,aq and f Gk ,aq are based on a molality
scale, while k is based on mole fraction scale.
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.
Where:
Hi*,ig = Ideal gas enthalpy
Hi*,v - Hi*,ig = Vapor enthalpy departure from equation of state
Where:
Hmig = Enthalpy of ideal gas mixture
=
HmE,l =
Where:
Hiref,l = Reference enthalpy for liquid state at Tiref,l
Cp,i*,l = Liquid heat capacity of component i
The saturated liquid Gibbs free energy is calculated as follows:
Where:
Giref,l = Reference Gibbs free energy for liquid state at Tiref,l
p = System pressure
Where:
Hiref,ig = Ideal gas enthalpy of formation for liquid state at
298.15K
Giref,ig = Ideal gas Gibbs free energy of formation for liquid
state at 298.15K
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 liquid-
reference 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 = Temperature of conversion from liquid to vapor
enthalpy for component i
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.
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 ideal gas heat capacity at temperature T can be obtained by
differentiating the ideal gas enthalpy equation above with respect to
temperature. If the conversion temperature Ticon,l is specified and not equal to
T, then only the last term depends on T and the calculated ideal gas heat
And then the ideal gas heat capacity, calculated by differentiating this
equation, is:
Where:
Where:
Hiref,ig = Reference state enthalpy for ideal gas at Tiref,ig
= Heat of formation of ideal gas at 298.15 K by default
ref,ig
Ti = Reference temperature corresponding to Hiref,ig.
Defaults to 298.15 K
Ticon,ig = The temperature at which one crosses from vapor
state to liquid state. This is a user defined
temperature that defaults to the system temperature
T. Ticon,igmay be selected such that heat of
vaporization of component i at the temperature is
most accurate.
The ideal gas enthalpy is calculated as follows:
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 Default MDS Lower Upper Units
Name/Element Limit Limit
RSTATE 1
ref,ig
TREFHI Ti TEMPERATURE
DHFORM Hiref,ig MOLE ENTHALPY
con,ig
TCONHI Ti T TEMPERATURE
= Born coefficient
Units for AHGPAR are complex, and involve temperature, pressure, and
mole-enthalpy. If pressure is under 200 bar, AHGPAR may not be required.
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:
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.
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).
Model Model name Phase(s) Pure Mixture
Andrade Liquid Mixture MUL2ANDR L X
Viscosity
General Pure Component MUL0ANDR L X
Liquid Viscosity
API Liquid Viscosity MUL2API L X
API 1997 Liquid Viscosity MULAPI97 L X
Aspen Liquid Mixture Viscosity MUASPEN L X
ASTM Liquid Mixture Viscosity MUL2ASTM L X
General Pure Component MUV0CEB V X
Vapor Viscosity *
Chapman-Enskog-Brokaw- MUV2BROK, V X
Wilke Mixing Rule * MUV2WILK
Chung-Lee-Starling Low MUV0CLSL, V X X
Pressure * MUV2CLSL
Chung-Lee-Starling MUV0CLS2, VL X X
MUV2CLS2,
MUL0CLS2,
MUL2CLS2
Dean-Stiel Pressure Correction MUV0DSPC, V X X
** MUV2DSPC
IAPS Viscosity MUV0H2O, VL X
MUL0H2O
Jones-Dole Electrolyte MUL2JONS L X
Correction
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 Phase(s) BinaryMixture
Chapman-Enskog-Wilke-Lee DV0CEWL V X
Binary
Chapman-Enskog-Wilke-Lee DV1CEWL V X
Mixture
Viscosity Models
The Aspen Physical Property System has the following built-in viscosity
models:
Model Type
Andrade Liquid Mixture Viscosity Liquid
General Pure Component Liquid Viscosity Pure component liquid
API liquid viscosity Liquid
API 1997 liquid viscosity Liquid
General Pure Component Vapor Viscosity Low pressure vapor,
pure components
Chapman-Enskog-Brokaw-Wilke Mixing Rule Low pressure vapor,
mixture
Chung-Lee-Starling Low Pressure Low pressure vapor
Chung-Lee-Starling Liquid or vapor
Dean-Stiel Pressure correction Vapor
IAPS viscosity Water or steam
Jones-Dole Electrolyte Correction Electrolyte
Letsou-Stiel High temperature liquid
Lucas Vapor
TRAPP viscosity Vapor or liquid
Aspen Liquid Mixture Viscosity Liquid
ASTM Liquid Mixture Viscosity Liquid
Where:
kij =
mij =
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 Jones-Dole Electrolyte Viscosity model
DL0WCA Wilke-Chang Diffusivity model (binary)
DL1WCA Wilke-Chang Diffusivity model (mixture)
DL0NST Nernst-Hartley Electrolyte Diffusivity model (binary)
DL1NST Nernst-Hartley Electrolyte Diffusivity model (mixture)
The binary parameters kij and mij allow accurate representation of complex
liquid mixture viscosity. Both binary parameters default to zero.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
ANDKIJ/1 aij 0
ANDKIJ/2 bij 0
ANDMIJ/1 cij 0
ANDMIJ/2 dij 0
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:
Exponential
Absolute temperature units are assumed for C2i. The temperature limits
are always interpreted in user input units.
Polynomial
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 = A correlation based on API Procedures and Figures 11A4.1, 11A4.2, and
11A4.3 (API Technical Data Book, Petroleum Refining, 4th edition)
Vml is obtained from the API liquid volume model.
For real components, the General model is used.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TB Tbi 4.0 2000.0 TEMPERATURE
API APIi -60.0 500.0
Where:
fcn = A correlation based on API Procedures and Figures 11A4.2, 11A4.3, and
11A4.4 (API Technical Data Book, Petroleum Refining, 1997 edition)
Where:
Xi = Mole fraction or weight fraction of component i
kij = Symmetric binary parameter (kij = kji)
lij = Antisymmetric binary parameter (lij = -lji)
The pure component liquid viscosity i*,l is calculated by the General Pure
Component Liquid Viscosity model.
The binary parameters kij and lij allow accurate representation of complex
liquid mixture viscosity temperature dependence. Both binary parameters
default to zero. Both binary parameters, kij and lij, have to be specified for
each component-component pair.
with
Where:
Tref = Reference temperature and the default value = 298.15 K
One option code is used with this model. It determines whether Xi is mole
fraction (default, option value 0) or weight fraction (option value 1).
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MUKIJ/1 aij 0 X --- --- ---
MUKIJ/2 bij 0 X --- --- ---
MUKIJ/3 cij 0 X --- --- ---
MUKIJ/4 dij 0 X --- --- ---
Where:
wi = Weight fraction of component i
Chapman-Enskog-Brokaw
The equation for the Chapman-Enskog model is:
Where:
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.
Absolute temperature units are assumed for C2i . The temperature limits are
always interpreted in user input units.
Sutherland Equation
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.
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:
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).
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:
Where:
Tcij =
ij =
Mij =
ij =
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.
Chung-Lee-Starling Viscosity
The Chung-Lee-Starling viscosity equation for vapor and liquid, high and low
pressure is:
With:
f2 =
FC =
The polar parameter is tabulated for certain alcohols and carboxylic acids.
For low pressures, f1 is reduced to 1.0 and f2 becomes negligible. The
equation reduces to the low pressure vapor viscosity model by Chung-Lee and
Starling.
The previous equations can be used for mixtures when applying these mixing
rules:
Where:
Vcij =
ij =
Mij =
ij =
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.
M =
pc =
Vcm =
Zcm =
rm = Vcm / Vmv
w=fcn(T, p)
Where:
fcn = Correlation developed by IAPS
The models are only applicable to water. There are no parameters required
for the models.
Where:
Jones-Dole
The Jones-Dole equation is:
(1)
Where:
= Concentration of apparent electrolyte ca (2)
La = (5)
Lc = (6)
Bca = (7)
Breslau-Miller
The Breslau-Miller equation is:
(8)
Carbonell
The Carbonell equation is:
(10)
Where:
Mk = Molecular weight of an apparent electrolyte
component k
You must provide parameters for the model used for the calculation of the
liquid mixture viscosity of the solvent mixture.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
CHARGE z 0.0
MW M 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).
Letsou-Stiel
The Letsou-Stiel model calculates liquid viscosity at high temperatures for
0.76 Tr 0.98. This model is used in PCES.
(l)0 =
(l)1 =
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.
The polar and quantum correction factors at high and low pressure are:
FP =
FQ =
FPi (p = 0) =
pc =
M =
FP (p = 0) =
FQ (p = 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), p. 421, 431.
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.
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.
Option Codes
Option Code Value Descriptions
1 0 Use mole basis composition (default)
1 Use mass basis composition
Parameter
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MLQKIJ Kij - x - -
Where:
f1 =
f2 =
The polar parameter is tabulated for certain alcohols and carboxylic acids.
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:
Tcij =
ij =
Mij =
ij =
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:
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.
Where:
Sato-Riedel
The Sato-Riedel equation is (Reid et al., 1987):
Where:
Tbri = Tbi / Tci
Tri = T / Tci
PPDS
The equation is:
IK-CAPE
The IK-CAPE equation is:
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:
Stiel-Thodos
The Stiel-Thodos equation is:
Where:
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
PPDS
The equation is:
IK-CAPE Polynomial
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 Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
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.
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.
Where:
= Mole fraction vector
*,ig
Cpi = Ideal gas heat capacity calculated using the
General pure component ideal gas heat capacity
model
fcn = Corresponding states correlation based on the
model for vapor and liquid thermal conductivity
made 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.
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:
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.
Chapman-Enskog-Wilke-Lee (Binary)
The binary diffusion coefficient at low pressures is calculated using
the Chapman-Enskog-Wilke-Lee model:
Dijv=Djiv
Where:
D =
ij =
ij =
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):
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:
The parameters mv and Vmv are obtained from the Redlich-Kwong equation-
of-state model.
You must supply parameters for these two models.
Subscript i denotes a diffusing component. j denotes a solvent.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VC Vci x 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.
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 = 9.65x107C/kmole (Faraday's number)
xk = Mole fraction of any molecular species k
zi = Charge number of species i
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:
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:
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:
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.
Where:
x = Mole fraction
r = Exponent (specified by the option code)
Hadden (S. T. Hadden, Hydrocarbon Process Petrol Refiner, 45(10), 1966, p.
161) suggested that the exponent value r =1 should be used for most
hydrocarbon mixtures. However, Reid recommended the value of r in the
range of -1 to -3. The exponent value r can be specified using the models
Option Code (option code = 1, -1, -2, ..., -9 corresponding to the value of r).
The default value of r for this model is 1.
The pure component liquid surface tension i*,l is calculated by the General
Pure Component Liquid Surface Tension model.
Where:
fcn = A correlation based on API Procedure 10A32 (API Technical Data Book,
Petroleum Refining, 4th edition)
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.
w=fcn(T, p)
Where:
fcn = Correlation developed by IAPS
The model is only applicable to water. No parameters are required.
Hakim-Steinberg-Stiel
The Hakim-Steinberg-Stiel equation is:
Where:
mi =
CHI i 0
Where:
Tri = T / Tci
PPDS
The equation is:
IK-CAPE Polynomial
The IK-CAPE equation is:
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:
Where:
ccaa =
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:
References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 3rd. ed., (New York: McGraw-Hill, 1977).
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.
Where:
wij = Mass fraction of the jth constituent in component i
Where:
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.
Notation
Most correlations for the calculation of coal properties require proximate,
ultimate, and other analyses. These are converted to a dry, mineral-matter-
free 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 = The value determined for weight fraction
d
w = The value on a dry basis
= The moisture weight fraction
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 mineral-
matter 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:
Where:
Cp = Heat capacity / (J/kgK)
cp = Heat capacity / (cal/gC)
h = Specific enthalpy
= Specific density
Subscripts:
A = Ash
C = Carbon
Cl = Chlorine
FC = Fixed carbon
H = Hydrogen
H2O = Moisture
MM = Mineral matter
N = Nitrogen
O = Oxygen
So = Organic sulfur
Sp = Pyritic sulfur
St = Total sulfur
S = Other sulfur
VM = Volatile matter
Superscripts:
d = Dry basis
Dulong Correlation:
IGT Correlation:
The complete oxidation of sulfur (pyritic and organic sulfur) is based on the
calculated by:
The complete oxidation of nitrogen is based on the reaction
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
Where:
i = Component index
j = Constituent index j = 1, 2 , ... , ncn
Where the values of j represent:
1 Moisture
2 Fixed carbon
3 Primary volatile matter
4 Secondary volatile matter
5 Ash
wj = Mass fraction of jth constituent on dry basis
This correlation calculates heat capacity in cal/gram-C using temperature in
C. The parameters must be specified in appropriate units for this conversion.
Parameter Name/Element Symbol Default
CP1C/1 ai,11 1.0
CP1C/2 ai,12 0
CP1C/3 ai,13 0
CP1C/4 ai,14 0
CP1C/5 ai,21 0.165
CP1C/6 ai,22
CP1C/8 ai,24 0
CP1C/9 ai,31 0.395
CP1C/10 ai,32
CP1C/11 ai,33 0
CP1C/12 ai,34 0
CP1C/13 ai,41 0.71
CP1C/14 ai,42
CP1C/15 ai,43 0
CP1C/16 ai,44 0
CP1C/17 ai,51 0.18
CP1C/18 ai,52
CP1C/19 ai,53 0
CP1C/20 ai,54 0
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. This
correlation calculates heat capacity in cal/gram-C using temperature in C. The
parameters must be specified in appropriate units for this conversion.
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.
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.
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.
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.
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:
Standard Redlich-Kwong-Soave (ESRKSTD0, ESRKSTD)
Redlich-Kwong-Soave-Boston-Mathias (ESRKS0, ESRKS)
Soave-Redlich-Kwong (ESSRK, ESSRK0)
SRK-Kabadi-Danner (ESSRK, ESSRK0)
SRK-ML (ESRKSML, ESRKSML0)
The options for these models can be selected using the option codes
described in the following table:
Option Value Description
Code
1 0 Standard SRK alpha function for Tr < 1, Boston-Mathias alpha
function for Tr > 1
1 Standard SRK alpha function for all
2 Grabovsky Daubert alpha function for H2 and standard SRK
alpha function for others (default)
3 Extended Gibbons-Laughton alpha function for all components
(see notes 1, 2, 3)
4 Mathias alpha function
5 Twu generalized alpha function
2 0 Standard SRK mixing rules (default except for SRK-Kabadi-
Danner)
1 Kabadi Danner mixing rules (default for SRK-Kabadi-Danner)
(see notes 3, 4, 5)
Notes
1 The standard alpha function is always used for Helium.
2 If extended Gibbons-Laughton alpha function parameters are missing, the
Boston-Mathias extrapolation will be used if T > Tc, and the standard
alpha function will be used if T < Tc.
3 The extended Gibbons-Laughton alpha function should not be used with
the Kabadi-Danner mixing rules.
4 The Kabadi-Danner mixing rules should not be used if Lij parameters are
provided for water with any other components.
5 It is recommended that you use the SRK-KD property method rather than
change this option code.
6 The enthalpy, entropy, Gibbs energy, and molar volume of water are
calculated from the steam tables when this 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.
about 90
A parameter conversion 92
working equations 91
activity coefficient models 89 BWR-Lee-Starling property model
list of property models 89 16
alpha functions 72, 76
Peng-Robinson 72
C
Soave 76
Andrade liquid mixture viscosity Cavett thermodynamic property
model 254 model 233
Andrade/DIPPR viscosity model Chao-Seader fugacity model 191
255 Chapman-Enskog 261, 264, 290,
Antoine/Wagner vapor pressure 291
model 186 Brokaw/DIPPR viscosity model
API model 198, 258, 296 261
liquid molar volume 198 Brokaw-Wilke mixing rule
liquid viscosity 258 viscosity model 264
surface tension 296 Wilke-Lee (binary) diffusion
API Sour model 190 model 290
applications 94 Wilke-Lee (mixture) diffusion
metallurgical 94 model 291
aqueous infinite dilution heat Chien-Null activity coefficient
capacity model 218 model 93
ASME steam tables 16 Chueh-Prausnitz model 201
Aspen liquid mixture viscosity Chung-Lee-Starling model 266,
model 259 267, 278
Aspen polynomial equation 216 low pressure vapor viscosity 266
ASTM 260 thermal conductivity 278
liquid viscosity 260 viscosity 267
Clarke electrolyte liquid volume
B model 202
Clausius-Clapeyron equation 197
Barin equations thermodynamic heat of vaporization 197
property model 233 coal 305
Benedict-Webb-Rubin-Starling property models 305
property model 17 constant activity coefficient model
Braun K-10 model 191 94
Brelvi-O'Connell model 200
Bromley-Pitzer activity coefficient
model 90, 91, 92
Index 331
copolymer PC-SAFT EOS property Riedel thermal conductivity 280
model 35, 36, 37, 41, 42, 44, electrolyte NRTL 98, 100, 236, 238
46, 47 activity coefficient model 98, 100
about 35 enthalpy thermodynamic
association term 42 property model 236
chain connectivity 37 Gibbs energy thermodynamic
dispersion term 41 property model 238
fundamental equations 36 eNRTL-SAC activity coefficient
parameters 46, 47 model 111
polar term 44 ENTHGEN nonconventional
COSMO-SAC solvation model 95 component heat capacity
COSTALD liquid volume model 205 model 304
Criss-Cobble aqueous infinite equation-of-state method 15
dilution ionic heat capacity property models 15
model 219 extrapolation 9
temperature limits 9
D
G
Dawson-Khoury-Kobayashi
diffusion model 291, 292 Grayson-Streed fugacity model 192
binary 291 group contribution activity
mixture 292 coefficient models 175, 177,
DCOALIGT coal density model 315 178
Dean-Stiel pressure correction Dortmund-modified UNIFAC 177
viscosity model 269 Lyngby-modified UNIFAC 178
Debye-Hckel volume model 206 UNIFAC 175
DGHARIGT char density model 316
diffusivity models 289 H
list 289
DIPPR equation 6, 221 Hakim-Steinberg-Stiel/DIPPR
DIPPR model 195, 207, 219, 224, surface tension 297
255, 261, 281, 284, 297 Hansen solubility parameter model
heat of vaporization 195 116
ideal gas heat capacity 224 Hayden-O'Connell 22
liquid heat capacity 219 property model 22
liquid volume 207 HCOALGEN 308
surface tension 297 general coal model for enthalpy
thermal conductivity 281, 284 308
viscosity 255, 261 heat of vaporization 194
DNSTYGEN nonconventional models 194
component density model 303 Helgeson thermodynamic property
model 246
HF equation of state 25
E
property model 25
electrolyte models 202, 236, 238, Huron-Vidal mixing rules 83
270, 280, 293, 300
Clarke liquid volume 202 I
electrolyte NRTL enthalpy 236
Gibbs energy 238 IAPS models for water 270, 279,
Jones-Dole viscosity 270 297
Nernst-Hartley diffusion 293 surface tension 297
Onsager-Samaras surface thermal conductivity 279
tension 300 viscosity 270
ideal gas heat capacity 224
332 Index
ideal gas law 29 Lucas vapor viscosity model 273
property model 29
ideal gas/DIPPR heat capacity M
model 224
ideal liquid activity coefficient Mathias alpha function 76
model 117 Mathias-Copeman alpha function
IGT density model for 315, 316 72, 76
char 316 Maxwell-Bonnell vapor pressure
coal 315 model 194
IK-CAPE equation 196, 222 MHV2 mixing rules 84
heat of vaporization 196 mixing rules 83, 84, 86, 88, 218,
liquid heat capacity 222 249, 264, 277, 280, 287, 289
Brokaw-Wilke viscosity model
264
J
Huron-Vidal 83
Jones-Dole electrolyte correction Li 280
viscosity model 270 liquid volume quadratic 218
MHV2 84
K predictive Soave-Redlich-Kwong-
Gmehling 86
Kent-Eisenberg fugacity model 192 quadratic 249
viscosity quadratic 277
L Vredeveld 287
Wassiljewa-Mason-Saxena 289
Lee-Kesler Plcker property model
Wong-Sandler 88
31
modified MacLeod-Sugden surface
Lee-Kesler property model 29
tension model 301
Letsou-Stiel viscosity model 272
Li mixing rule thermal conductivity
model 280 N
liquid constant molar volume Nernst-Hartley electrolyte diffusion
model 207 model 293
liquid enthalpy 240 NIST 223
thermodynamic property model liquid heat capacity 223
240 NIST TDE Watson equation 197
liquid heat capacity 221 heat of vaporization 197
DIPPR equation 221 nonconventional components 303,
liquid mixture 254, 280, 296 304, 308
surface tension 296 coal model for enthalpy 308
thermal conductivity 280 density polynomial model 303
viscosity 254 enthalpy and density models list
liquid thermal conductivity 281 303
general pure components 281 heat capacity polynomial model
liquid viscosity 254, 255, 258, 259, 304
260, 275 nonconventional solid property
Andrade equation 254 models 303
API 258 density 303
API 1997 258 enthalpy 303
Aspen 259 list of 303
ASTM 260 Nothnagel 33
pure components 255 property model 33
Twu 275 NRTL 98, 117
liquid volume quadratic mixing rule
218
Index 333
electrolyte NRTL property model predictive SRK property model
98 (PSRK) 52
property model 117 property models 5, 11, 15, 185,
NRTL-SAC 119, 122, 134 198, 218, 317
for Segments/Oligomers 134 equation-of-state list 15
model derivation 122 fugacity models list 185
property model 119 heat capacity models list 218
Using 138 list of 5
molar volume and density
O models list 198
option codes 317
Onsager-Samaras electrolyte thermodynamic list 11
surface tension model 300 vapor pressure model list 185
option codes 317, 319, 320, 324, property parameters 6
325, 326, 328, 330 temperature-dependent
activity coefficient models 319 properties 6
enthalpy models 326 PSRK 52
equation of state models 320 property model 52
Gibbs energy models 328 pure component properties 6
K-value models 325 temperature-dependent 6
liquid volume models 330
list 317
Q
Soave-Redlich-Kwong models
324 quadratic mixing rules 249
transport property models 317
R
P
Rackett 212, 213, 214
PC-SAFT property method 35 extrapolation method 214
property model 35 mixture liquid volume model 212
Peng-Robinson 48, 50, 52, 53, 72 modified model for molar volume
alpha functions 72 213
MHV2 property model 52 Rackett pure component liquid
property model 48 volume model 207
standard 50 Raoult's law 117
Wong-Sandler property model 53 Redlich-Kister activity coefficient
physical properties 11, 15 model 152
models 11, 15 Redlich-Kwong 53, 76
Pitzer activity coefficient model alpha function 76
139, 140, 142, 143, 147 property model 53
about 139 Redlich-Kwong-Aspen property
activity coefficients 143 model 54
aqueous strong electrolytes 142 Redlich-Kwong-Soave 55, 57, 58,
model development 140 59, 61, 76
parameters 147 alpha function list 76
polynomial activity coefficient Boston-Mathias property model
model 150 57
PPDS equation 196, 221 MHV2 property model 59
heat of vaporization 196 property model 55
liquid heat capacity 221 Soave-Redlich-Kwong property
predictive Soave-Redlich-Kwong- model 61
Gmehling mixing rules 86 Wong-Sandler property model 58
334 Index
Riedel electrolyte correction working equations 157
thermal conductivity model
280 T
temperature 9
S
extrapolating limits 9
Sato-Riedel/DIPPR thermal temperature-dependent properties
conductivity model 281 6
Scatchard-Hildebrand activity pure component 6
coefficient model 153 units 6
Schwartzentruber-Renon property thermal conductivity 277, 284
model 59 models list 277
Soave-Redlich-Kwong 61 solids 284
property model 61 thermo switch 6
Soave-Redlich-Kwong models 324 thermodynamic property 11, 233
options codes 324 list of additional models 233
solid Antoine vapor pressure models list 11
models 194 three-suffix Margules activity
solid thermal conductivity coefficient model 153
polynomial 284 THRSWT 6
solids polynomial heat capacity transport property 251
model 228 models list 251
solubility correlation models 230, transport switch 6
231, 232 TRAPP 274, 288
Henry's constant 230 thermal conductivity model 288
hydrocarbon 232 viscosity model 274
list 230 TRNSWT 6
water solubility model 231 Twu liquid viscosity model 275
SRK-Kabadi-Danner property
model 64 U
SRK-ML property model 66
standard Peng-Robinson property UNIFAC 175, 177, 178
model 50 activity coefficient model 175
standard Redlich-Kwong-Soave Dortmund modified activity
property model 55 coefficient model 177
steam tables 16, 32 Lyngby modified activity
NBS/NRC 32 coefficient model 178
property models 16 UNIQUAC 180
STEAMNBS property method 32 activity coefficient model 180
Stiel-Thodos pressure correction
thermal conductivity model V
287
Van Laar activity coefficient model
Stiel-Thodos thermal conductivity
181
model 284
vapor thermal conductivity 284
surface tension 295, 296, 301
general pure components 284
general pure components 297
vapor viscosity 261, 264, 266, 273
liquid mixtures 296
Brokaw-Wilke mixing rule
models list 295
viscosity model 264
modified MacLeod-Sugden 301
Chung-Lee-Starling 266
Symmetric and Unsymmetric
Lucas 273
Electrolyte NRTL activity
pure components 261
coefficient model 154, 157
viscosity 253
about 154
models 253
Index 335
viscosity quadratic mixing rule 277
VPA/IK-CAPE equation of state 67
Vredeveld mixing rule 287
W
Wagner Interaction Parameter
activity coefficient model 182
Wagner vapor pressure model 186
Wassiljewa-Mason-Saxena mixing
rule 289
Watson equation 195
heat of vaporization 195
Wilke-Chang diffusion model 294,
295
binary 294
mixture 295
WILS-GLR property method 241
WILS-LR property method 241
Wilson (liquid molar volume)
activity coefficient model 184
Wilson activity coefficient model
183
Wong-Sandler mixing rules 88
336 Index