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Aspen Physical Property System

Physical Property Models


Version Number: V7.3.2
February 2012
Copyright (c) 1981-2012 by Aspen Technology, Inc. All rights reserved.

Aspen Physical Property System and the aspen leaf are trademarks or registered trademarks of Aspen Technology,
Inc., Burlington, MA.

All other brand and product names are trademarks or registered trademarks of their respective companies.

This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech
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USA
Phone: (1) (781) 221-6400
Toll Free: (888) 996-7100
URL: http://www.aspentech.com
Contents
Contents..................................................................................................................1

1 Introduction .........................................................................................................5
Units for Temperature-Dependent Parameters .....................................................6
Pure Component Temperature-Dependent Properties............................................6
Extrapolation Methods ......................................................................................9

2 Thermodynamic Property Models .......................................................................11


Equation-of-State Models ................................................................................ 15
ASME Steam Tables.............................................................................. 16
BWR-Lee-Starling................................................................................. 16
Benedict-Webb-Rubin-Starling ............................................................... 17
GERG2008 Equation of State ................................................................. 20
Hayden-O'Connell ................................................................................ 22
HF Equation-of-State ............................................................................ 25
IAPWS-95 Steam Tables ....................................................................... 29
Ideal Gas ............................................................................................ 29
Lee-Kesler ........................................................................................... 29
Lee-Kesler-Plcker ............................................................................... 31
NBS/NRC Steam Tables ........................................................................ 32
Nothnagel ........................................................................................... 33
Copolymer PC-SAFT EOS Model.............................................................. 35
Peng-Robinson..................................................................................... 48
Standard Peng-Robinson ....................................................................... 50
Peng-Robinson-MHV2 ........................................................................... 52
Predictive SRK (PSRK) .......................................................................... 52
Peng-Robinson-Wong-Sandler................................................................ 53
Redlich-Kwong ..................................................................................... 53
Redlich-Kwong-Aspen ........................................................................... 54
Redlich-Kwong-Soave ........................................................................... 55
Redlich-Kwong-Soave-Boston-Mathias .................................................... 57
Redlich-Kwong-Soave-Wong-Sandler ...................................................... 58
Redlich-Kwong-Soave-MHV2.................................................................. 59
Schwartzentruber-Renon....................................................................... 59
Soave-Redlich-Kwong ........................................................................... 61
SRK-Kabadi-Danner.............................................................................. 64
SRK-ML............................................................................................... 66
VPA/IK-CAPE Equation-of-State ............................................................. 67
Peng-Robinson Alpha Functions.............................................................. 72
Huron-Vidal Mixing Rules ...................................................................... 83
MHV2 Mixing Rules ............................................................................... 84
Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules ........................... 86
Wong-Sandler Mixing Rules ................................................................... 88

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

3 Transport Property Models ...............................................................................251


Viscosity Models........................................................................................... 253
Andrade Liquid Mixture Viscosity .......................................................... 254
General Pure Component Liquid Viscosity .............................................. 255
API Liquid Viscosity ............................................................................ 258
API 1997 Liquid Viscosity .................................................................... 258
Aspen Liquid Mixture Viscosity ............................................................. 259
ASTM Liquid Mixture Viscosity .............................................................. 260
General Pure Component Vapor Viscosity .............................................. 261
Chapman-Enskog-Brokaw-Wilke Mixing Rule ......................................... 264
Chung-Lee-Starling Low-Pressure Vapor Viscosity .................................. 266
Chung-Lee-Starling Viscosity ............................................................... 267
Dean-Stiel Pressure Correction ............................................................ 269
IAPS Viscosity for Water...................................................................... 270
Jones-Dole Electrolyte Correction ......................................................... 270
Letsou-Stiel ....................................................................................... 272
Lucas Vapor Viscosity ......................................................................... 273
TRAPP Viscosity Model ........................................................................ 274
Twu Liquid Viscosity ........................................................................... 275
Viscosity Quadratic Mixing Rule............................................................ 277
Thermal Conductivity Models ......................................................................... 277
Chung-Lee-Starling Thermal Conductivity.............................................. 278
IAPS Thermal Conductivity for Water .................................................... 279
Li Mixing Rule .................................................................................... 280
Riedel Electrolyte Correction ................................................................ 280
General Pure Component Liquid Thermal Conductivity ............................ 281
Solid Thermal Conductivity Polynomial .................................................. 284
General Pure Component Vapor Thermal Conductivity............................. 284
Stiel-Thodos Pressure Correction Model................................................. 287
Vredeveld Mixing Rule......................................................................... 287

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

4 Nonconventional Solid Property Models ...........................................................303


General Enthalpy and Density Models ............................................................. 303
General Density Polynomial ................................................................. 303
General Heat Capacity Polynomial ........................................................ 304
Enthalpy and Density Models for Coal and Char................................................ 305
General Coal Enthalpy Model ............................................................... 308
IGT Coal Density Model ....................................................................... 315
IGT Char Density Model ...................................................................... 316

5 Property Model Option Codes ...........................................................................317


Option Codes for Transport Property Models .................................................... 317
Option Codes for Activity Coefficient Models .................................................... 319
Option Codes for Equation of State Models ...................................................... 320
Soave-Redlich-Kwong Option Codes ............................................................... 324
Option Codes for K-Value Models.................................................................... 325
Option Codes for Enthalpy Models .................................................................. 326
Option Codes for Gibbs Free Energy Models ..................................................... 328
Option Codes for Liquid Volume Models........................................................... 330

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

Units for Temperature-


Dependent Parameters
Some temperature-dependent parameters may be based on expressions
which involve logarithmic or reciprocal temperature terms. When the
coefficient of any such term is non-zero, in many cases the entire expression
must be calculated assuming that all the coefficients are in absolute
temperature units. In other cases, terms are independent from one another,
and only certain terms may require calculation using absolute temperature
units. Notes in the models containing such terms explain exactly which
coefficients are affected by this treatment.
When absolute temperature units are forced in this way, this affects the units
for coefficients you have entered as input parameters. If your input
temperature units are Fahrenheit (F), then Rankine (R) is used instead. If
your input units are Celsius (C), then Kelvin (K) is used instead.
If only constant and positive powers of temperature are present in the
expression, then your specified input units are used.
If the parameters include temperature limits, the limits are always interpreted
in user input units even if the expression is forced to absolute units.
Some equations may include a dimensionless parameter, the reduced
temperature Tr = T / Tc. This reduced temperature is calculated using
absolute temperature units. In most cases, input parameters associated with
such equations do not have temperature units.

Pure Component Temperature-


Dependent Properties
The following table lists the pure component temperature-dependent
properties that the Aspen Physical Property System can calculate from a
general model that supports several equations or submodels.
For example, the Aspen Physical Property System can calculate heat of
vaporization using these equations:
Watson
DIPPR
PPDS
IK-CAPE

6 1 Introduction
NIST TDE Watson

Pure Component Temperature-Dependent Properties


Submodel-
Selection
Parameter DIPPR Equation
Element Numbers
Property Number Available Submodels ( = default)
Solid Volume THRSWT/1 Aspen, DIPPR, IK-CAPE, 100
NIST
Liquid Volume THRSWT/2 Aspen (Rackett), DIPPR, 105, 116 for water
PPDS, IK-CAPE, NIST only
Liquid Vapor THRSWT/3 Aspen (Extended Antoine), 101
Pressure Wagner, BARIN, PPDS,
PML, IK-CAPE, NIST
Heat of THRSWT/4 Aspen (Watson), DIPPR, 106
Vaporization PPDS, IK-CAPE, NIST
Solid Heat THRSWT/5 Aspen, DIPPR, BARIN, IK- 100, 102
Capacity CAPE, NIST
Liquid Heat THRSWT/6 DIPPR, PPDS, BARIN, IK- 100, 114
Capacity CAPE, NIST
Ideal Gas Heat THRSWT/7 Aspen, DIPPR, BARIN, 107, 127
Capacity PPDS, IK-CAPE, NIST
Second Virial THRSWT/8 DIPPR 104
Coefficient
Liquid Viscosity TRNSWT/1 Aspen (Andrade), DIPPR, 101, 115
PPDS, IK-CAPE, NIST
Vapor Viscosity TRNSWT/2 Aspen (Chapman-Enskog- 102
Brokaw), DIPPR, PPDS, IK-
CAPE, NIST
Liquid Thermal TRNSWT/3 Aspen (Sato-Riedel), 100
Conductivity DIPPR, PPDS, IK-CAPE,
NIST
Vapor Thermal TRNSWT/4 Aspen (Stiel-Thodos), 102
Conductivity DIPPR, PPDS, IK-CAPE,
NIST
Liquid Surface TRNSWT/5 Aspen (Hakim-Steinberg- 106
Tension Stiel), DIPPR, PPDS, IK-
CAPE, NIST

Which equation is actually used to calculate the property for a given


component depends on which parameters are available. If parameters are
available for more than one equation, the Aspen Physical Property System
uses the parameters that were entered or retrieved first from the databanks.
The selection of submodels is driven by the data hierarchy, and controlled by
the submodel-selection parameters.
The thermodynamic properties use the THRSWT (thermo switch) submodel-
selection parameter, and the transport properties use the TRNSWT (transport
switch) submodel-selection parameter.

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

All built-in databank components have model-selection parameters (THRSWT,


TRNSWT) that are set to use the correct equations that are consistent with
the available parameters. For example, suppose that parameters for the
DIPPR equation 106 are available for liquid surface tension. For that
component, TRNSWT element 5 is set to 106 in the databank. If you are
retrieving data from an in-house or user databank, you should store the
appropriate values for THRSWT and TRNSWT in the databank, using the
appropriate equation number. Otherwise, the Aspen Physical Property System
will search for the parameters needed for the Aspen form of the equations.
If a component is available in more than one databank, the Aspen Physical
Property System uses the data and equations based on the databank list
order on the Components Specifications Selection sheet. For example,
suppose the databank search order is ASPENPCD, then PURE25, and that the
Aspen Physical Property System cannot find the parameters for a particular
submodel (equation) in the ASPENPCD databank. If the PURE25 databank
contains parameters for another equation, the Aspen Physical Property
System will use that equation (most likely the DIPPR equation) to calculate
the property for that component.
If your calculation contains any temperature-dependent property parameters,
(such as CPIGDP for DIPPR ideal gas heat capacity, entered on the Methods
| Parameters | Pure Component form), the Aspen Physical Property
System sets the corresponding THRSWT and TRNSWT elements for that
component to the default values shown in the table above. This default
setting might not always be correct. If you know the equation number, you
should enter it directly on the Methods | Parameters | Pure Component
form. For example, suppose you want to use the:
DIPPR equation form of heat of vaporization (DHVLDP) for a component
Aspen equations for the remaining temperature dependent properties
Set the fourth element of the THRSWT parameter to 106, and the 1-3 and 5-8
elements to 0. If you want to set the other temperature-dependent properties
to use what is defined for that component in the databank, leave the element
blank.
The following table lists the available DIPPR equations and the corresponding
equation (submodel) number.

8 1 Introduction
Available DIPPR Equations
Equation
Number Equation Form
100

101

102

103

104

105

106

107

114

115

116

127

For equations 114 and 116, t = 1-Tr.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
The following sections describe the Aspen, DIPPR, BARIN, IK-CAPE, PPDS, and
NIST equations for each property. For descriptions of the the BARIN equations
for heat capacity and enthalpy, see BARIN Equations for Gibbs Energy,
Enthalpy, Entropy, and Heat Capacity.

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.

Exception 1: Logarithmic Properties Based on Reciprocal


Temperature
This applies to property models expressed in the form (where a(T) includes
any additional dependency on temperature):

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 2: Aspen Ideal Gas Heat Capacity


The Aspen Ideal Gas Heat Capacity model has an explicit equation for
extrapolation at temperatures below the lower limit, which is described in the
model. At high temperatures it follows the usual rule of extrapolating
property-versus-temperature linearly.

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

This section describes the available thermodynamic property models in the


Aspen Physical Property System. The following table provides a list of
available models, with corresponding Aspen Physical Property System model
names. The table provides phase types for which the model can be used and
information on use of the model for pure components and mixtures.
Aspen Physical Property System thermodynamic property models include
classical thermodynamic property models, such as activity coefficient models
and equations of state, as well as solids and electrolyte models. The models
are grouped according to the type of property they describe.

Thermodynamic Property Models


Phases: V = Vapor; L = Liquid; S = Solid. An X indicates applicable to Pure or
Mixture.

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

2 Thermodynamic Property Models 11


Property Model Model Name(s) Phase(s) Pure Mixture
NBS/NRC Steam Tables ESSTEAM0,ESSTEAM VL X
Nothnagel ESNTH0,ESNTH V X X
PC-SAFT ESPSAFT, ESPSAFT0 VL X X
Peng-Robinson ESPR0, ESPR VL X X
Standard Peng-Robinson ESPRSTD0,ESPRSTD VL X X
Peng-Robinson-Wong-Sandler * ESPRWS0,ESPRWS VL X X
Peng-Robinson-MHV2 * ESPRV20,ESPRV2 VL X X
Predictive SRK * ESRKSV10, ESRKSV1 V L X X
Redlich-Kwong ESRK0, ESRK V X X
Redlich-Kwong-Aspen ESRKA0,ESRKA VL X X
Redlich-Kwong-Soave ESRKSTD0,ESRKSTD VL X X
Redlich-Kwong-Soave-Boston- ESRKS0, ESRKS VL X X
Mathias
Redlich-Kwong-Soave-MHV2 * ESRKSV20, ESRKSV2 V L X X
Redlich-Kwong-Soave-Wong- ESRKSWS0, ESRKSWS V L X X
Sandler *
Schwartzentruber-Renon ESRKU0,ESRKU VL X X
Soave-Redlich-Kwong ESSRK0, ESSRK VL X X
SRK-Kabadi-Danner ESSRK0, ESSRK VL X X
SRK-ML ESRKSML0, ESRKSML V L X X
VPA/IK-CAPE equation-of-state ESVPA0, ESVPA V X X
Peng-Robinson Alpha functions VL X
RK-Soave Alpha functions VL X
Huron-Vidal mixing rules VL X
MHV2 mixing rules VL X
PSRK mixing rules VL X
Wong-Sandler mixing rules VL X

Activity Coefficient Models (Including Electrolyte Models)


These models calculate GAMMA.
Property Model Model Name Phase(s) Pure Mixture
Bromley-Pitzer GMPT2 L X
Chien-Null GMCHNULL L X
Constant Activity Coefficient GMCONS S X
COSMO-SAC COSMOSAC L X
Electrolyte NRTL GMENRTL, GMELC, L L1 L2 X
GMENRHG
ENRTL-SAC (patent pending) ENRTLSAC L X
Hansen HANSEN L X
Ideal Liquid GMIDL L X
NRTL (Non-Random-Two-Liquid) GMRENON L L1 L2 X
NRTL-SAC (patent pending) NRTLSAC L X
Pitzer GMPT1 L X

12 2 Thermodynamic Property Models


Property Model Model Name Phase(s) Pure Mixture
Polynomial Activity Coefficient GMPOLY LS X
Redlich-Kister GMREDKIS LS X
Scatchard-Hildebrand GMXSH L X
Symmetric Electrolyte NRTL GMENRTLS L X
Three-Suffix Margules GMMARGUL LS X
UNIFAC GMUFAC L L1 L2 X
UNIFAC (Lyngby modified) GMUFLBY L L1 L2 X
UNIFAC (Dortmund modified) GMUFDMD L L1 L2 X
UNIQUAC GMUQUAC L L1 L2 X
Unsymmetric Electrolyte NRTL GMENRTLQ L X
van Laar GMVLAAR L X
Wagner interaction parameter GMWIP S X
Wilson GMWILSON L X
Wilson model with liquid molar GMWSNVOL L X
volume

Vapor Pressure and Liquid Fugacity Models


Property Model Model Property Phase(s)Pure Mixture
Name
General Pure Component Liquid PL0XANT PL L L1 L2 X
Vapor Pressure
API Sour SWEQ PHILMX L X
Braun K-10 BK10 PHILMX L X
Chao-Seader PHL0CS PHIL L X
Grayson-Streed PHL0GS PHIL L X
Kent-Eisenberg ESAMINE PHILMX, L X
GLMX,
HLMX,
SLMX
Maxwell-Bonnell PL0MXBN PL L L1 L2 X
Solid Antoine PS0ANT PS S X

Heat of Vaporization Models


These models calculate DHVL.
Property Model Model Name Phase(s) Pure Mixture
General Pure Component Heat DHVLWTSN L X
of Vaporization
Clausius-Clapeyron Equation DHVLCC L X

Molar Volume and Density Models


These models calculate VL (pure liquid), VLMX (liquid mixture), or VS (pure
solid), except for Brelvi-O'Connell which calculates VLPM.
Property Model Model Name Phase(s) Pure Mixture
API Liquid Volume VL2API L X
Brelvi-O'Connell VL1BROC L X

2 Thermodynamic Property Models 13


Property Model Model Name Phase(s) Pure Mixture
Chueh-Prausnitz VL0CPRKT, VL2CPRKT L X X
Clarke Aqueous Electrolyte VAQCLK L X
Volume
COSTALD Liquid Volume VL0CTD,VL2CTD L X X
Debye-Hckel Volume VAQDH L X
Liquid Constant Molar Volume VL0CONS L X
General Pure Component Liquid VL0RKT,VL2RKT L X
Molar Volume
Rackett/Campbell-Thodos VL2RKT L X X
Mixture Liquid Volume
Modified Rackett VL2MRK L X X
General Pure Component Solid VS0POLY S X
Molar Volume
Liquid Volume Quadratic Mixing VL2QUAD L X
Rule

Heat Capacity Models


Property Model Model Property Phase(s) Pure Mixture
Name
Aqueous Infinite Dilution Heat L X
Capacity Polynomial
Criss-Cobble Aqueous Infinite L X
Dilution Ionic Heat Capacity
General Pure Component Liquid HL0DIP HL, DHL L X
Heat Capacity
General Pure Component Ideal CPIG V X X
Gas Heat Capacity
General Pure Component Solid HS0POLY HS S X
Heat Capacity

Solubility Correlation Models


Property Model Model Property Phase(s) Pure Mixture
Name
Henry's constant HENRY1 HNRY, L X
WHNRY
Water solubility L X
Hydrocarbon solubility L 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

14 2 Thermodynamic Property Models


Property Model Model Property Phase(s) Pure Mixture
Name
Electrolyte NRTL Enthalpy HMXENRTL, HLMX L X
HAQELC,
HMXELC,
HMXENRHG
Electrolyte NRTL Gibbs Energy GMXENRTL, HLMX L X
GAQELC,
GMXELC,
GMXENRHG
Liquid Enthalpy from Liquid Heat DHL0DIP L X X
Capacity Correlation
Enthalpies Based on Different DHL0HREF DHL LV X X
Reference States
Helgeson Equations of State L X
Pitzer Enthalpy HAQPT1 HLMX L X
Pitzer Gibbs Energy GAQPT1 GLMX L X
Quadratic Mixing Rule LV 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

2 Thermodynamic Property Models 15


Model Type
PSRK mixing rules Mixing rules
Redlich-Kwong Cubic
Redlich-Kwong-Aspen Cubic
Standard Redlich-Kwong-Soave Cubic
Redlich-Kwong-Soave-Boston-Mathias Cubic
Redlich-Kwong-Soave-MHV2 Cubic
Redlich-Kwong-Soave-Wong-Sandler Cubic
RK-Soave Alpha functions Alpha functions
Schwartzentruber-Renon Cubic
Soave-Redlich-Kwong Cubic
SRK-Kabadi-Danner Cubic
SRK-ML Cubic
VPA/IK-CAPE equation-of-state Ideal and association
Wong-Sandler mixing rules Mixing rules

ASME Steam Tables


The ASME steam tables are implemented like any other equation-of-state in
the Aspen Physical Property System. The steam tables can calculate any
thermodynamic property of water or steam and form the basis of the STEAM-
TA property method. There are no parameter requirements. The ASME steam
tables are less accurate than the NBS/NRC steam tables.

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:

16 2 Thermodynamic Property Models


Where:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCBWR Tci TC X 5.0 2000.0 TEMPERATURE
*
VCBWR Vci VC X 0.001 3.5 MOLE-
VOLUME
BWRGMA i OMEGA X -0.5 3.0

BWRKV ij 0 X -5.0 1.0

BWRKT ij 0 X -5.0 1.0

Binary interaction parameters BWRKV and BWRKT are available in 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:

2 Thermodynamic Property Models 17


Where:

kij = kji

In the mixing rules given above, A0i, B0i, C0i, D0i, E0i, ai, bi, ci, di, i, i are pure
component constants which can be input by the user. For methane, ethane,
propane, iso-butane, n-butane, iso-pentane, n-pentane, n-hexane, 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.

18 2 Thermodynamic Property Models


If the values of these parameters are not given, and not available from the
databank, the Aspen Physical Property System will calculate them using the
critical temperature, the critical volume (or critical density), the acentric
factor and generalized correlations given by Han and Starling.
When water is present, by default Benedict-Webb-Rubin-Starling uses the
steam table to calculate the enthalpy, entropy, Gibbs energy, and molar
volume of water. The total properties are mole-fraction averages of these
values with the properties calculated by the equation of state for other
components. Fugacity coefficient is not affected. An option code can disable
this use of the steam table.
For best results, the binary parameter kij must be regressed using phase-
equilibrium data such as VLE data.
Parameter SymbolDefault MDS Lower Upper Units
Name/ Limit Limit
Element
BWRSTC Tci TC x 5.0 2000.0 TEMPERATURE
BWRSVC Vci VC x 0.001 3.5 MOLE-VOLUME
BWRSOM i OMEGA x 0.5 2.0
BWRSA/1 B0i fcn(i ,Vci , Tci) x MOLE-VOLUME
BWRSA/2 A0i fcn(i ,Vci , Tci) x PRESSURE * MOLE-
VOL^2
BWRSA/3 C0i fcn(i ,Vci , Tci) x PRESSURE *
TEMPERATURE^2 *
MOLE-VOLUME^2
BWRSA/4 i fcn(i ,Vci , Tci) x MOLE-VOLUME^2

BWRSA/5 bi fcn(i ,Vci , Tci) x MOLE-VOLUME^2


BWRSA/6 ai fcn(i ,Vci , Tci) x PRESSURE * MOLE-
VOL^3
BWRSA/7 i fcn(i ,Vci , Tci) x MOLE-VOLUME^3
BWRSA/8 ci fcn(i ,Vci , Tci) x PRESSURE *
TEMPERATURE^2 *
MOLE-VOLUME^3
BWRSA/9 D0i fcn(i ,Vci , Tci) x PRESSURE *
TEMPERATURE^3 *
MOLE-VOLUME^2
BWRSA/10 di fcn(i ,Vci , Tci) x PRESSURE *
TEMPERATURE * MOLE-
VOLUME^3
BWRSA/11 E0i fcn(i ,Vci , Tci) x PRESSURE *
TEMPERATURE^4 *
MOLE-VOLUME^2
BWRAIJ kij x

Constants Used with the correlations of Han and Starling


Parameter Methane Ethane Propane n-Butane
B0i 0.723251 0.826059 0.964762 1.56588
A0i 7520.29 13439.30 18634.70 32544.70
C0i 2.71092x108 2.95195x109 7.96178x109 1.37436x1010

2 Thermodynamic Property Models 19


Parameter Methane Ethane Propane n-Butane
10 11 11
D0i 1.07737x10 2.57477x10 4.53708x10 3.33159x1011
10 13 13
E0i 3.01122x10 1.46819x10 2.56053x10 2.30902x1012
bi 0.925404 3.112060 5.462480 9.140660
ai 2574.89 22404.50 40066.40 71181.80
di 47489.1 702189.0 1.50520x107 3.64238x107
i 0.468828 0.909681 2.014020 4.009850
8 9 10
ci 4.37222x10 6.81826x10 2.74461x10 7.00044x1010
i 1.48640 2.99656 4.56182 7.54122

Parameter n-Pentane n-Hexane n-Heptane n-Octane


B0i 2.44417 2.66233 3.60493 4.86965
A0i 51108.20 45333.10 77826.90 81690.60
10 10 10
C0i 2.23931x10 5.26067x10 6.15662x10 9.96546x1010
D0i 1.01769x1012 5.52158x1012 7.77123x1012 7.90575x1012
13 14 12
E0i 3.90860x10 6.26433x10 6.36251x10 3.46419x1013
bi 16.607000 29.498300 27.441500 10.590700
ai 162185.00 434517.00 359087.00 131646.00
di 3.88521x107 3.27460x107 8351150.0 1.85906x108
i 7.067020 9.702300 21.878200 34.512400
11 11 11
ci 1.35286x10 3.18412x10 3.74876x10 6.42053x1011
i 11.85930 14.87200 24.76040 21.98880

References
M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.
334.
M. S. Han, and K. E. Starling , "Thermo Data Refined for LPG. Part 14:
Mixtures", Hydrocarbon Processing, Vol. 51, No. 5, (1972), p. 129.
K. E. Starling, "Fluid Themodynamic Properties for Light Petroleum Systems",
Gulf Publishing Co., Houston, Texas (1973).

References for Parameter Data


K.E. Starling and M.S. Han, "Thermo data refined for LPG, part 14 Mixtures,"
Hydrocarbon Processing, (May 1972), pp. 129-132.
K.E. Starling and M.S. Han, "Thermo data refined for LPG, part 15 Industrial
applications," Hydrocarbon Processing, (June 1972), pp. 107-115.
K.E. Starling, "Fluid Thermodynamic Properties for Light Petroleum Systems,"
Gulf Publishing Co., Houston, Texas (1973).

GERG2008 Equation of State


The GERG2008 equation-of-state model is the basis for the GERG2008
property method.

20 2 Thermodynamic Property Models


The equation of state is based on a multi-fluid approximation explicit in the
reduced Helmholtz free energy:
(1)

Where the ideal-gas contribution o and residual contribution r at a given


mixture density, temperature, and molar composition are:
(2)

(3)

Where the reduced mixture density and inverse reduced mixture


temperature are:
(4)

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
)

The reduced mixture density is given by:


(8)

And the reduced mixture temperature is given by:

2 Thermodynamic Property Models 21


(9)

Where:
R = molar gas constant = 8.314472 J/mol-K.

c,i and Tc,i = critical density and critical temperature


nooi,k and ooi,k = Coefficients and parameters of eq. (5) for pure components
noi,k, doi,k, toi,k, and coi,k = coefficients and exponents of eq. (6) for pure
components
Fij = Composition dependent factor

nij,k = Coefficients and dij,k, tij,k, ij,k, ij,k, ij,k, and ij,k = the exponents in eq.
(7) for all binary specific and generalized departure functions

v,ij and v,ij in eq. (8) and T,ij and T,ij in eq. (9) = Binary interaction
parameters

Reference
"The GERG-2004 Wide-Range Equation of State for Natural Gases and Other
Mixtures" O. Kunz, R. Klimeck, W. Wagner, M. Jaeschke; GERG TM15 2007;
ISBN 978-3-18-355706-6; Published for GERG and printed in Germany by
VDI Verlag GmbH (2007).
Kunz, O., Wagner, W., "The new GERG-2004 XT08 wide-range equation of
state for natural gases and other mixtures." To be submitted to Fluid Phase
Equilibria (beginning of 2010).

Hayden-O'Connell
The Hayden-O'Connell equation-of-state calculates thermodynamic properties
for the vapor phase. It is used in property methods NRTL-HOC, UNIF-HOC,
UNIQ-HOC, VANL-HOC, and WILS-HOC, and is recommended for nonpolar,
polar, and associating compounds. Hayden-O'Connell incorporates the
chemical theory of dimerization. This model accounts for strong association
and solvation effects, including those found in systems containing organic
acids, such as acetic acid. The equation-of-state is:

Where:

For nonpolar, non-associating species:

, with

22 2 Thermodynamic Property Models


, where

For polar, associating species:

, with

, where

For chemically bonding species:

, and

Cross-Interactions
The previous equations are valid for dimerization and cross-dimerization if
these mixing rules are applied:

= 0 unless a special solvation contribution can be justified (for example, i


and j are in the same class of compounds). Many values are present in the
Aspen Physical Property System.

Chemical Theory

When a compound with strong association is present in a mixture,


the entire mixture is treated according to the chemical theory of dimerization.

2 Thermodynamic Property Models 23


The chemical reaction for the general case of a mixture of dimerizing
components i and j is:

Where i and j refer to the same component.


The equation-of-state becomes:

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 .

24 2 Thermodynamic Property Models


Parameter Name/ Symbol Default MDS Lower Upper Units
Element Limit Limit
TC Tci 5.0 2000.0 TEMPERATURE
5 8
PC pci 10 10 PRESSURE
gyr -11 -9
RGYR ri 10 5x10 LENGTH
MUP pi 0.0 5x10-24 DIPOLEMOMENT
HOCETA 0.0 X

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.

Molar Volume Calculation


The non-ideality of HF is often expressed using the association factor, f,
indicating the ratio of apparent number of species to the real number or
species. Assuming the ideal gas law for all true species in terms of (p, V, T)
behavior implies:

2 Thermodynamic Property Models 25


(2)

Where the true number of species is given by 1/f. The association factor is
easily determined from (p, V, T) experiments. For a critical evaluation of data
refer to Vanderzee and Rodenburg (1970).
If only one reaction is assumed for a mixture of HF and its associated species,
(refer to Long et al., 1943), then:
(3)

If p1 represents the true partial pressure of the HF monomer, and p6


represents the true partial pressure of the hexamer, then the equilibrium
constant is defined as:
(4)

The true total pressure is:


p = p1 + p6 (5)
If all hexamer were dissociated, the apparent total pressure would be the
hypothetical pressure where:
pa = p1 + 6p6 = p + 5p6 (6)
When physical ideality is assumed, partial pressures and mole fractions are
proportional. The total pressure in equation 5 represents the true number of
species. The apparent total pressure from equation 6 represents the apparent
number of species:
(7)

Note that the outcome of equation 7 is independent of the assumption of


ideality. Equation 7 can be used to compute the number of true species 1/f
for a mixture containing HF, but the association factor is defined differently.
If p1 and p6 are known, the molar volume or density of a vapor containing HF
can be calculated using equations 2 and 7. The molar volume calculated is the
true molar volume for 1 apparent mole of HF. This is because the volume of 1
mole of ideal gas (the true molar volume per true number of moles) is always
equal to about 0.0224 m3/mol at 298.15 K.

True Mole Fraction (Partial Pressure) Calculation


If you assume the ideal gas law for a mixture containing HF, the apparent HF
mole fraction is:
(8)

26 2 Thermodynamic Property Models


The denominator of equation 8 is given by equation 6. The numerator (the
apparent partial pressure of HF) is the hypothetical partial pressure only if all
of the hexamer was dissociated. If you substitute equation 4, then equation 8
becomes:
(9)

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).

Gibbs Energy and Fugacity


The apparent fugacity coefficient is related to the true fugacity coefficient and
mole fractions:
(10)

Equation 10 represents a correction to the ideal mixing term of the fugacity.


The ratio of the true number of species to the apparent number of species is
similar to the correction applied in equation 2. Since the ideal gas law is
assumed, the apparent fugacity coefficient is given by the equation. All
variables on the right side are known.
(11)

For pure HF, ya = 1:

From the fugacity coefficient, the Gibbs energy departure of the mixture or
pure apparent components can be calculated:
(12)

(12a)

Enthalpy and Entropy


For the enthalpy departure, the heat of reaction is considered. For an
arbitrary gas phase reaction:

2 Thermodynamic Property Models 27


(13)

(14)

Where i* is the pure component thermodynamic potential or molar Gibbs


energy of a component. Equation 4 represents the first two terms of the
general equation 14. The second or third equality relates the equilibrium
constant to the Gibbs energy of reaction, which is thus related to the enthalpy
of reaction:
(15)

All components are assumed to be ideal. The enthalpy departure is equal to


the heat of reaction, per apparent number of moles:
(16)

(17)

From the Gibbs energy departure and enthalpy departure, the entropy
departure can be calculated:
(18)

Temperature derivatives for the thermodynamic properties can be obtained


by straightforward differentiation.

Usage
The HF equation-of-state should only be used for vapor phase calculations. It
is not suited for liquid phase calculations.
The HF equation-of-state can be used with any activity coefficient model for
nonelectrolyte VLE. Using the Electrolyte NRTL model and the data package
MHF2 is strongly recommended for aqueous mixtures (de Leeuw and
Watanasiri, 1993).
Parameter 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.

28 2 Thermodynamic Property Models


V. V. De Leeuw and S. Watanasiri, "Modelling Phase Equilibria and Enthalpies
of the System Water and Hydroflouric 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 9
12, Carry-le-Rouet, France, 1993.
R. W. Long, J. H. Hildebrand, and W. E. Morrell, "The Polymerization of
Gaseous Hydrogen and Deuterium Flourides," J. Am. Chem. Soc., Vol. 65,
(1943), pp. 182 187.
C. E. Vanderzee and W. WM. Rodenburg, "Gas Imperfections and
Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride," J. Chem.
Thermodynamics, Vol. 2, (1970), pp. 461 478.

IAPWS-95 Steam Tables


The IAPWS-95 Steam Tables are implemented like any other equation-of-
state in the Aspen Physical Property System. These steam tables can calculate
any thermodynamic property of water. The tables form the basis of the
IAPWS-95 property method. There are no parameter requirements. They are
the most accurate steam tables in the Aspen Physical Property System.

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.

2 Thermodynamic Property Models 29


The compressibility factor and other derived thermodynamic functions of
nonpolar and slightly polar fluids can be adequately represented, at constant
reduced temperature and pressure, by a linear function of the acentric factor.
In particular, the compressibility factor of a fluid whose acentric factor is , is
given by the following equation:
Z = Z(0) + Z(1)
Where:
Z(0) = Compressibility factor of a simple fluid ( = 0)
Z(1) = Deviation of the compressibility factor of the real fluid from Z(0)
Z(0) and Z(1) are assumed universal functions of the reduced temperature and
pressure.
Curl and Pitzer (1958) were quite successful in correlating thermodynamic
and volumetric properties using the above approach. Their application
employed tables of properties in terms of reduced temperature and pressure.
A significant weakness of this method is that the various properties (for
example, entropy departure and enthalpy departure) will not be exactly
thermodynamically consistent with each other. Lee and Kesler (1975)
overcame this drawback by an analytic representation of the tables with an
equation-of-state. In addition, the range was extended by including new data.
In the Lee-Kesler implementation, the compressibility factor of any fluid has
been written in terms of a simple fluid and a reference as follows:

In the above equation both Z(0) and Z(1) are represented as generalized
equations of the BWR form in terms of reduced temperature and pressure.
Thus,

Equations for the enthalpy departure, Gibbs free energy departure, and
entropy departure are obtained from the compressibility factor using standard
thermodynamic relationships, thus ensuring thermodynamic consistency.
In the case of mixtures, mixing rules (without any binary parameters) are
used to obtain the mixture values of the critical temperature and pressure,
and the acentric factor.
This equation has been found to provide a good description of the volumetric
and thermodynamic properties of mixtures containing nonpolar and slightly
polar components.
Symbol Parameter Name Default Definition
Tc TCLK TC Critical temperature
Pc PCLK PC Critical pressure
OMGLK OMEGA Acentric factor

30 2 Thermodynamic Property Models


References
M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.
334.
R. F. Curl and K.S. Pitzer, Ind. Eng. Chem., Vol. 50, (1958), p. 265.
B. I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975), p. 510.

Lee-Kesler-Plcker
The Lee-Kesler-Plcker equation-of-state is the basis for the LK-PLOCK
property method. This equation-of-state applies to hydrocarbon systems that
include the common light gases, such as H2S and CO2. It can be used in 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.

The mixing rules are:


Vcm =

Zm =

Where:
Vcij =

Tcij =

Zci =

kij = kji

2 Thermodynamic Property Models 31


The binary parameter kij is determined from phase-equilibrium data
regression, such as VLE data. The Aspen Physical Property System stores the
binary parameters for a large number of component pairs. These binary
parameters are used automatically with the LK-PLOCK property method. If
binary parameters for certain component pairs are not available, they can be
estimated using built-in correlations. The correlations are designed for binary
interactions among the components CO, CO2, N2, H2, CH4 alcohols and
hydrocarbons. If a component is not CO, CO2, N2, H2, CH4 or an alcohol, it is
assumed to be a hydrocarbon.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
TCLKP Tci TC x 5.0 2000.0 TEMPERATURE
PCLKP pci PC x PRESSURE

VCLKP Vci VC x 0.001 3.5 MOLE-


VOLUME
OMGLKP I OMEGA x -0.5 2.0
LKPZC Zci Method 1: fcn() x 0.1 0.5
Method 2:
fcn(pci,Vci,Tci)
LKPKIJ kij fcn(TciVci / TcjVcj) x 5.0 5.0

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.

NBS/NRC Steam Tables


The NBS/NRC Steam Tables are implemented like any other equation-of-state
in the Aspen Physical Property System. These steam tables can calculate any
thermodynamic property of water. The tables form the basis of the
STEAMNBS and STMNBS2 property methods. There are no parameter
requirements. The STMNBS2 model uses the same equations as STEAMNBS
but with different root search method. The STEAMNBS method is
recommended for use with the SRK, BWRS, MXBONNEL and GRAYSON2
property methods.

32 2 Thermodynamic Property Models


References
L. Haar, J.S. Gallagher, and J.H. Kell, "NBS/NRC Steam Tables," (Washington:
Hemisphere Publishing Corporation, 1984).

Nothnagel
The Nothnagel equation-of-state calculates thermodynamic properties for the
vapor phase. It is used in property methods NRTL-NTH, UNIQ-NTH, 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 =

nc = Number of components in the mixture


The chemical reaction for the general case of a mixture of dimerizing
components i and j is:

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
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

2 Thermodynamic Property Models 33


association, the quantity V/na reflects the apparent contraction in an
associating mixture.
The heat of reaction due to each dimerization can be calculated:

The heat of reaction for the mixed dimerization of components i and j is by


default the arithmetic mean of the heats of reaction for the dimerizations of

the individual components. Parameter is a small empirical correction


factor to this value:

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 equilibrium constants can be computed using either built-in calculations


or parameters you entered.
Built-in correlations:

The pure component parameters b, d, and p are stored in the Aspen


Physical Property System for many components.
Parameters you entered:

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

34 2 Thermodynamic Property Models


Parameter Symbol Default Lower Upper Limit Units
Name/Element Limit
NTHK/4 Di 0 TEMPERATURE

NTHDDH 0 MOLE-
ENTHALPY

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.

Copolymer PC-SAFT EOS Model


This section describes the Copolymer Perturbed-Chain Statistical Associating
Fluid Theory (PC-SAFT). This equation-of-state model is used through the PC-
SAFT property method.
The copolymer PC-SAFT represents the completed PC-SAFT EOS model
developed by Sadowski and co-workers (Gross and Sadowski, 2001, 2002a,
2002b; Gross et al., 2003; Becker et al., 2004; Kleiner et al., 2006). Unlike
the PC-SAFT EOS model (POLYPCSF) in Aspen Plus, the copolymer PC-SAFT
includes the association and polar terms and does not apply mixing rules to
calculate the copolymer parameters from its segments. Its applicability covers
fluid systems from small to large molecules, including normal fluids, water,
alcohols, and ketones, polymers and copolymers and their mixtures.

2 Thermodynamic Property Models 35


References
Gross, J., & Sadowski, G. (2001). Perturbed-Chain SAFT: An equation of state
based on a perturbation theory for chain molecules. Ind. Eng. Chem. Res.,
40, 1244-1260.
Gross, J., & Sadowski, G. (2002a). Modeling polymer systems using the
perturbed-chain statistical associating fluid theory equation of state. Ind. Eng.
Chem. Res., 41, 1084-1093.
Gross, J., & Sadowski, G. (2002b). Application of the Perturbed-Chain SAFT
Equation of State to Associating Systems. Ind. Eng. Chem. Res., 41, 5510-
5515.
Gross, J., Spuhl, O., Tumakaka, F., & Sadowski, G. (2003). Modeling
Copolymer Systems Using the Perturbed-Chain SAFT Equation of State. Ind.
Eng. Chem. Res., 42, 1266-1274.
Becker, F., Buback, M., Latz, H., Sadowski, G., & Tumakaka, F. (2004).
Cloud-Point Curves of Ethylene-(Meth)acrylate Copolymers in Fluid Ethene up
to High Pressures and Temperatures Experimental Study and PC-SAFT
Modeling. Fluid Phase Equilibria, 215, 263-282.
Kleiner, M., Tumakaka, F., Sadowski, G., Latz, H., & Buback, M. (2006).Phase
Equilibria in Polydisperse and Associating Copolymer Solutions: Poly(ethane-
co-(meth)acrylic acid) Monomer Mixtures. Fluid Phase Equilibria, 241, 113-
123..

Copolymer PC-SAFT Fundamental Equations


The copolymer PC-SAFT model is based on the perturbation theory. The
underlying idea is to divide the total intermolecular forces into repulsive and
attractive contributions. The model uses a hard-chain reference system to
account for the repulsive interactions. The attractive forces are further divided
into different contributions, including dispersion, polar, and association.
Using a generated function, , the copolymer PC-SAFT model in general can
be written as follows:

where hc, disp, assoc, and polar are contributions due to hard-chain fluids,
dispersion, association, and polarity, respectively.

The generated function is defined as follows:

where ares is the molar residual Helmholtz energy of mixtures, R is the gas
constant, T is the temperature, is the molar density, and Zm is the
compressibility factor; ares is defined as:

36 2 Thermodynamic Property Models


where a is the Helmholtz energy of a mixture and aig is the Helmholtz energy
of a mixture of ideal gases at the same temperature, density and composition
xi. Once is known, any other thermodynamic function of interest can be
easily derived. For instance, the fugacity coefficient i is calculated as follows:

with

where is a partial derivative that is always done to the mole fraction


stated in the denominator, while all other mole fractions are considered
constant.

Applying to the departure equations, departure functions of enthalpy,


entropy, and Gibbs free energy can be obtained as follows:
Enthalpy departure:

Entropy departure:

Gibbs free energy departure:

The following thermodynamic conditions must be satisfied:

Hard-chain Fluids and Chain Connectivity


In PC-SAFT model, a molecule is modeled as a chain molecule by a series of
freely-jointed tangent spheres. The contribution from hard-chain fluids as a
reference system consists of two parts, a nonbonding contribution (i.e., hard-

2 Thermodynamic Property Models 37


sphere mixtures prior to bonding to form chains) and a bonding contribution
due to chain formation:

where is the mean segment in the mixture, hs is the contribution from


hard-sphere mixtures on a per-segment basis, and chain is the contribution
due to chain formation. Both and hs are well-defined for mixtures
containing polymers, including copolymers; they are given by the following
equations:

where mi, i, and i are the segment number, the segment diameter, and
the segment energy parameter of the segment type in the copolymer
component i, respectively. The segment number mi is calculated from the
segment ratio parameter ri:

where Mi is the total molecular weight of the segment type in the


copolymer component i and can be calculated from the segment weight
fraction within the copolymer:

where wi is the weight fraction of the segment type in the copolymer


component i, and Mi is the molecular weight of the copolymer component i.
Following Sadowski and co-workers work ( Gross et al., 2003; Becker et al.,
2004), the contribution from the chain connectivity can be written as follows:

38 2 Thermodynamic Property Models


with

where Bii is defined as the bonding fraction between the segment type
and the segment type within the copolymer component i, is the number of
the segment types within the copolymer component i, and ghsi,j(di,j) is the
radial distribution function of hard-sphere mixtures at contact.
However, the calculation for Bii depends on the type of copolymers. We
start with a pure copolymer system which consists of only two different types
of segments and ; this gives:

with

We now apply these equations to three common types of copolymers; a)


alternating, b) block, and c) random.

For an alternating copolymer, m = m; there are no or adjacent


sequences. Therefore:

For a block copolymer, there is only one pair and the number of and
pairs depend on the length of each block; therefore:

For a random copolymer, the sequence is only known in a statistical sense. If


the sequence is completely random, then the number of adjacent pairs is
proportional to the product of the probabilities of finding a segment of type
and a segment of type in the copolymer. The probability of finding a
segment of type is the fraction of segments z in the copolymer:

The bonding fraction of each pair of types can be written as follows:

2 Thermodynamic Property Models 39


where C is a constant and can be determined by the normalization condition
set by Equation 2.70; the value for C is unity. 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

The generalization of three common types of copolymers from two types of


different segments to multi types of different segments within a copolymer
is straightforward.

For a generalized alternative copolymer, m = m = ... = mr = m/ ; there


are no adjacent sequences for the same type of segments. Therefore,

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:

40 2 Thermodynamic Property Models


For a generalized random copolymer, the sequence is only known in a
statistical sense. If the sequence is completely random, then the number of
adjacent pairs is proportional to the product of the probabilities of finding
a segment of type and a segment of type in the copolymer. The
probability of finding a segment of type is the fraction of segments z in
the copolymer:

The bonding fraction of each pair of types can be written as follows:

where C is a constant and can be determined by the normalization condition.


Therefore,

That is,

Put C into the equation above, we obtain:

Copolymer PC-SAFT Dispersion Term


The equations for the dispersion term are given as follows:

2 Thermodynamic Property Models 41


where i,j and i,j are the cross segment diameter and energy parameters,
respectively; only one adjustable binary interaction parameter, i,j is
introduced to calculate them:

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).

Association Term for Copolymer Mixtures - 2B


Model
The association term in PC-SAFT model in general needs an iterative
procedure to calculate the fraction of a species (solvent or segment) that are
bounded to each association-site type. Only in pure or binary systems, the
fraction can be derived explicitly for some specific models. We start with
general expressions for the association contribution for copolymer systems as
follows:

42 2 Thermodynamic Property Models


where A is the association-site type index, is the association-site
number of the association-site type A on the segment type in the
copolymer component i, and is the mole fraction of the segment type
in the copolymer component i that are not bonded with the association-site
type A; it can be estimated as follows:

with

where is the cross effective association volume and is the


cross association energy; they are estimated via simple combination rules:

where and are the effective association volume and the


association energy between the association-site types A and B, of the
segment type in the copolymer component i, respectively.

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,

where Ni is the number of the segment type in the copolymer component i


and M is the molecular weight of the segment type . In other words, the
association-site number for each site type within a segment is the same;
therefore, we can rewrite the equations above as follows:

2 Thermodynamic Property Models 43


To calculate , this equation has to be solved iteratively for each
association-site type associated with a species in a component. In practice,
further assumption is needed for efficiency. The commonly used model is the
so-called 2B model ( Huang and Radosz, 1990; Gross and Sadowski, 2002b).
It assumes that an associating species (solvent or segment) has two
association sites, one is designed as the site type A and another as the site
type B. Similarly to the hydrogen bonding, type A treats as a donor site with
positive charge and type B as an acceptor site with negative charge; only the
donor-acceptor association bonding is permitted and this concept applies to
both pure systems (self-association such as water) and mixtures (both self-
association and cross-association such as water-methanol). Therefore, we can
rewrite these equations as follows:

It is easy to show that

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.

Polar Term for Copolymer PC-SAFT


The equations for the polar term are given by Jog et al. (2001) as follows:

44 2 Thermodynamic Property Models


In the above equations, I2() and I3() are the pure fluid integrals and i
and (xp)i are the dipole moment and dipolar fraction of the segment type

within the copolymer component i, respectively. Both and

are dimensionless. In terms of them, we can have:

Rushbrooke et al. (1973) have shown that

Then I2() and I3() are computed in terms of by the expressions:

2 Thermodynamic Property Models 45


Reference
Jog, P. K., Sauer, S. G., Blaesing, J., & Chapman, W. G. (2001), Application
of Dipolar Chain Theory to the Phase Behavior of Polar Fluids and Mixtures.
Ind. Eng. Chem. Res., 40, 4641.
Rushbrooke, G. S., & Stell, G., Hoye, J. S. (1973), Molec. Phys., 26, 1199.
Ominik, A., Chapman, W.G., Kleiner, M., & Sadowski, G. (2005), Modeling of
Polar Systems with the Perturbed-Chain SAFT Equation of State. Investigation
of the Performance of Two Polar Terms. Ind. Eng. Chem. Res., 44, 6928
Sauer, S.G., & Chapman (2003), A Parametric Study if Dipolar Chain Theory
with Applications to Ketone Mixtures. Ind. Eng. Chem. Res., 42, 5687

Copolymer PC-SAFT EOS Model Parameters

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

where Tref is a reference temperature and the default value is 298.15 K.


The following table lists the copolymer PC-SAFT EOS model parameters
implemented in Aspen Plus. Some values for these parameters can be found
in the PC-SAFT and POLYPCSF databanks.
Parameter Symbol Default Lower Upper MDS Units Comments
Name/ Limit Limit Keyword
Element
PCSFTM m X Unary
PCSFTV X Unary
PCSFTU /k X TEMP Unary

46 2 Thermodynamic Property Models


Parameter Symbol Default Lower Upper MDS Units Comments
Name/ Limit Limit Keyword
Element
PCSFTR r X Unary
PCSFAU AB
/k X TEMP Unary

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

Parameter Input and Regression for Copolymer


PC-SAFT
Since the copolymer PC-SAFT is built based on the segment concept, the
unary (pure) parameters must be specified for a solvent or a segment.
Specifying a unary parameter for a polymer component (homopolymer or
copolymer) will be ignored by the simulation. For a non-association and non-
polar solvent, three unary parameters PCSFTM, PCSFTU, and PCSFTV must be
specified. For a non-association and non-polar segment, these three unary
parameters PCSFTR, PCSFTU, and PCSFTV must be specified. For an
association species (solvent or segment), two additional unary parameters
PCSFAU and PCSFAV must be specified. For a polar species (solvent or
segment), two additional unary parameters PCSFMU and PCSFXP must be
specified.

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

2 Thermodynamic Property Models 47


the SEGMENT databank. If unary parameters are not available for a species
(solvent or segment) in a calculation, the user can perform an Aspen Plus
Data Regression Run (DRS) to obtain unary parameters. For non-polymer
components (mainly solvents), the unary parameters are usually obtained by
fitting experimental vapor pressure and liquid molar volume data. To obtain
unary parameters for a segment, experimental data on liquid density of the
homopolymer that is built by the segment should be regressed. Once the
unary parameters are available for a segment, the ideal-gas heat capacity
parameter CPIG may be regressed for the same segment using experimental
liquid heat capacity data for the same homopolymer. In addition to unary
parameters, the binary parameter PCSKIJ for each solvent-solvent pair, or
each solvent-segment pair, or each segment-segment pair, can be regressed
using vapor-liquid equilibrium (VLE) data in the form of TPXY data in Aspen
Plus.

Note: In Data Regression Run, a homopolymer must be defined as an


OLIGOMER type, and the number of the segment that builds the oligomer
must be specified.

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

48 2 Thermodynamic Property Models


a0 =

(the standard quadratic mixing term, where kij has


been made temperature-dependent)
kij =

kij = kji
a1

(an additional, asymmetric term used to model


highly non-linear systems)
lij =

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 =

(the Peneloux volume correction term)


ci =

(the Peneloux volume correction term for pure


components, calculated from the critical
temperature and pressure and the Rackett
parameter)
For best results, the binary parameters kij and lij must be determined from
regression of phase equilibrium data such as VLE data. The Aspen Physical
Property System also has built-in kij and lij for a large number of component
pairs in the EOS-LIT databank from Knapp et al. These parameters are used
automatically with the PENG-ROB property method. Values in the databank
can be different than those used with other models such as Soave-Redlich-
Kwong or Redlich-Kwong-Soave, and this can produce different results.
The model has option codes which can be used to customize the model, by
selecting a different alpha function and other model options. See Peng-
Robinson Alpha Functions for a description of the alpha functions. See Option

2 Thermodynamic Property Models 49


Codes for Equation of State Models (under ESPR and ESPR0) for a list of the
option codes.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PRTC Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PRPC pci PC x 10 10 PRESSURE
OMGPR i OMEGA x -0.5 2.0

PRZRA zRA RKTZRA x


PRKBV/1 kij(1) 0 x
PRKBV/2 kij(2) 0 x TEMPERATURE
PRKBV/3 kij(3) 0 x TEMPERATURE
PRKBV/4 Tlower 0 x TEMPERATURE
PRKBV/5 Tupper 1000 x TEMPERATURE
PRLIJ/1 lij(1) 0 x
PRLIJ/2 lij(2) 0 x TEMPERATURE
PRLIJ/3 lij(3) 0 x TEMPERATURE
PRLIJ/4 Tlower 0 x TEMPERATURE
PRLIJ/5 Tupper 1000 x TEMPERATURE

References
D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.
P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules
for multicomponent mixtures: the problem of invariance," Fluid Phase
Equilibria, Vol 67, (1991), pp. 31-44.
H. Knapp, R. Dring, L. Oellrich, U. Plcker, and J. M. Prausnitz. "Vapor-Liquid
Equilibria for Mixtures of Low Boiling Substances." Dechema Chemistry Data
Series, Vol. VI.

Standard Peng-Robinson
The Standard Peng-Robinson equation-of-state is the original formulation of
the Peng-Robinson equation of state with the standard alpha function (see
Peng-Robinson Alpha Functions). It is 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:

50 2 Thermodynamic Property Models


b =

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 =

(the Peneloux volume correction term)


ci =

(the Peneloux volume correction term for pure


components, calculated from the critical
temperature and pressure and the Rackett
parameter)
The model has option codes which can be used to customize the model, by
selecting a different alpha function and other model options. See Peng-
Robinson Alpha Functions for a description of the alpha functions. See Option
Codes for Equation of State Models (under ESPRSTD and ESPRSTD0) for a list
of the option codes.
For best results, the binary parameter kij must be determined from regression
of phase equilibrium data such as VLE data. The Aspen Physical Property
System also has built-in kij for a large number of component pairs in the EOS-
LIT databank. These parameters are used automatically with the PENG-ROB
property method. Values in the databank can be different than those used
with other models such as Soave-Redlich-Kwong or Redlich-Kwong-Soave,
and this can produce different results.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCPRS Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PCPRS pci PC x 10 10 PRESSURE
OMGPRS i OMEGA x -0.5 2.0

2 Thermodynamic Property Models 51


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PRSZRA zRA RKTZRA x
PRKBV/1 kij(1) 0 x - - -
PRKBV/2 kij(2) 0 x - - TEMPERATURE
PRKBV/3 kij(3) 0 x - - TEMPERATURE
PRKBV/4 Tlower 0 x - - TEMPERATURE
PRKBV/5 Tupper 1000 x - - TEMPERATURE
PRLIJ/1 lij(1) 0 x
PRLIJ/2 lij(2) 0 x TEMPERATURE
PRLIJ/3 lij(3) 0 x TEMPERATURE
PRLIJ/4 Tlower 0 x TEMPERATURE
PRLIJ/5 Tupper 1000 x TEMPERATURE

References
D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.

Peng-Robinson-MHV2
This model uses the Peng-Robinson equation-of-state for pure compounds.
The mixing rules are the predictive MHV2 rules. Several alpha functions can
be used in the Peng-Robinson-MHV2 equation-of-state model for a more
accurate description of the pure component behavior. The pure component
behavior and parameter requirements are described in Standard 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.

Predictive SRK (PSRK)


This model uses the Redlich-Kwong-Soave equation-of-state for pure
compounds. The mixing rules are the predictive Holderbaum rules, or PSRK
method. Several alpha functions can be used in the PSRK equation-of-state
model for a more accurate description of the pure component behavior. The
pure component behavior and parameter requirements are described in
Standard Redlich-Kwong-Soave and in Soave Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The 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.

52 2 Thermodynamic Property Models


Peng-Robinson-Wong-Sandler
This model uses the Peng-Robinson equation-of-state for pure compounds.
The mixing rules are the predictive Wong-Sandler rules. Several alpha
functions can be used in the Peng-Robinson-Wong-Sandler equation-of-state
model for a more accurate description of the pure component behavior. The
pure component behavior and parameter requirements are described in Peng-
Robinson, and in Peng-Robinson Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The Wong-Sandler mixing rules are an example of modified Huron-Vidal
mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For
more details see Wong-Sandler Mixing Rules., this chapter.

Redlich-Kwong
The Redlich-Kwong equation-of-state can calculate vapor phase
thermodynamic properties for the following property methods: NRTL-RK,
UNIFAC, UNIF-LL, UNIQ-RK, VANL-RK, and WILS-RK. It is applicable for
systems at low to moderate pressures (maximum pressure 10 atm) for which
the vapor-phase nonideality is small. The Hayden-O'Connell model is
recommended for a more nonideal vapor phase, such as in systems
containing organic acids. It is not recommended for calculating liquid phase
properties.
The equation for the model is:
p =

Where:
=

b =

ai =

bi =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TC Tci 5.0 2000.0 TEMPERATURE
5 8
PC pci 10 10 PRESSURE

2 Thermodynamic Property Models 53


References
O. Redlich and J.N.S. Kwong, "On the Thermodynamics of Solutions V. An
Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,
(1949), pp. 223 244.

Redlich-Kwong-Aspen
The Redlich-Kwong-Aspen equation-of-state is the basis for the RK-ASPEN
property method. It can be used for hydrocarbon processing applications. It is
also used for more polar components and mixtures of hydrocarbons, and for
light gases at medium to high pressures.
The equation is the same as Redlich-Kwong-Soave:
p =

A quadratic mixing rule is maintained for:


a =

An interaction parameter is introduced in the mixing rule for:


b =

For ai an extra polar parameter is used:


ai =

bi =

The interaction parameters are temperature-dependent:


ka,ij =

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

RKAPOL i 0 x -2.0 2.0

RKAKA0 ka,ij0 0 x -5.0 5.0


RKAKA1 ka,ij1 0 x -15.0 15.0 TEMPERATURE
RKAKB0 kb,ij0 0 x -5.0 5.0

54 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
RKAKB1 kb,ij1 0 x -15.0 15.0 TEMPERATURE

References
Mathias, P.M., "A Versatile Phase Equilibrium Equation-of-state", Ind. Eng.
Chem. Process Des. Dev., Vol. 22, (1983), pp. 385 391.

Redlich-Kwong-Soave
This is the standard Redlich-Kwong-Soave equation-of-state, and is the basis
for the RK-SOAVE property method. It is recommended for hydrocarbon
processing applications, such as gas-processing, refinery, and petrochemical
processes. Its results are comparable to those of the Peng-Robinson
equation-of-state.
The equation is:

Where:

a0 is the standard quadratic mixing term:

a1 is an additional, asymmetric (polar) term:

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).

2 Thermodynamic Property Models 55


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.
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

The model uses option codes which are described in Soave-Redlich-Kwong


Option Codes.
For best results, binary parameters kij must be determined from phase-
equilibrium data regression (for example, VLE data). The Aspen Physical
Property System also has built-in kij for a large number of component pairs in
the EOS-LIT databank from Knapp et al. These binary parameters are used
automatically with the RK-SOAVE property method. Values of kij in the
databank can be different than those used with other models such as Soave-
Redlich-Kwong or Standard Peng-Robinson, and this can produce different
results.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKSS Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PCRKSS pci PC x 10 10 PRESSURE
OMRKSS i OMEGA x -0.5 2.0

RKSKBV/1 kij(1) 0 x -5.0 5.0


RKSKBV/2 kij(2) 0 x TEMPERATURE
RKSKBV/3 kij(3) 0 x TEMPERATURE
RKSKBV/4 Tk,lower 0 x TEMPERATURE
RKSKBV/5 Tk,upper 1000 x TEMPERATURE
RKSLBV/1 lij(1) 0 x
RKSLBV/2 lij(2) 0 x TEMPERATURE
RKSLBV/3 lij(3) 0 x TEMPERATURE
RKSLBV/4 Tl,lower 0 x TEMPERATURE
RKSLBV/5 Tl,upper 1000 x TEMPERATURE

References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 1203.

56 2 Thermodynamic Property Models


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.
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.

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:

a0 is the standard quadratic mixing term:

a1 is an additional, asymmetric (polar) term:

b =

ai =

bi =

kij = kji

2 Thermodynamic Property Models 57


; ;
The parameter ai is calculated by the standard Soave formulation at
supercritical temperatures. If the component is supercritical, the Boston-
Mathias extrapolation is used (see Soave Alpha Functions).
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

The model uses option codes which are described in Soave-Redlich-Kwong


Option Codes.
For best results, binary parameters kij must be determined from phase-
equilibrium data regression (for example, VLE data).
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKS Tci TC x 5.0 2000.0 TEMPERATURE
PCRKS pci PC x 105 108 PRESSURE
OMGRKS i OMEGA x -0.5 2.0

RKSKBV/1 kij(1) 0 x -5.0 5.0


RKSKBV/2 kij(2) 0 x TEMPERATURE
RKSKBV/3 kij(3) 0 x TEMPERATURE
RKSKBV/4 Tk,lower 0 x TEMPERATURE
RKSKBV/5 Tk,upper 1000 x TEMPERATURE
RKSLBV/1 lij(1) 0 x
RKSLBV/2 lij(2) 0 x TEMPERATURE
RKSLBV/3 lij(3) 0 x TEMPERATURE
RKSLBV/4 Tl,lower 0 x TEMPERATURE
RKSLBV/5 Tl,upper 1000 x TEMPERATURE

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-

58 2 Thermodynamic Property Models


Sandler equation-of-state model for a more accurate description of the pure
component behavior. The pure component behavior and parameter
requirements are described in Standard Redlich-Kwong-Soave, and in Soave
Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The Wong-Sandler mixing rules are an example of modified Huron-Vidal
mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For
more details, see Wong-Sandler Mixing Rules.

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 =

2 Thermodynamic Property Models 59


c =

ai =

bi =

ci =

(for T < Tci)

(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

60 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
RKUPP0 q0i x
RKUPP1 q1i 0 x
RKUPP2 q2i 0 x
RKUC0 c0i 0 x
RKUC1 c1i 0 x
RKUC2 c2i 0 x
RKUKA0 ka,ij0 0 x
RKUKA1 ka,ij1 0 x TEMPERATURE
RKUKA2 ka,ij2 0 x TEMPERATURE
RKULA0 lij0 0 x
RKULA1 lij1 0 x TEMPERATURE
RKULA2 lij2 0 x TEMPERATURE
RKUKB0 kb,ij0 0 x
RKUKB1 kb,ij1 0 x TEMPERATURE
RKUKB2 kb,ij2 0 x TEMPERATURE

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.

2 Thermodynamic Property Models 61


Improvement in speed of computation for equation based calculation is
achieved by using composition independent fugacity.
Optional Kabadi-Danner mixing rules for improved phase equilibrium
calculations in water-hydrocarbon systems (see SRK-Kabadi-Danner)
Optional Mathias alpha function

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:

a0 is the standard quadratic mixing term:

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

62 2 Thermodynamic Property Models


The enthalpy, entropy, Gibbs energy, and molar volume of water are
calculated from the steam tables. The total properties are mole-fraction
averages of these values with the properties calculated by the equation of
state for other components. Fugacity coefficient is not affected.
For best results, the binary parameter kij must be determined from phase
equilibrium data regression (for example, VLE data). The Aspen Physical
Property System also has built-in kij for a large number of component pairs in
the SRK-ASPEN databank, regressed by AspenTech. These parameters are
used automatically with the SRK property method. Values of kij in the
databank can be different than those used with other models such as
Standard Redlich-Kwong-Soave or Standard Redlich-Kwong-Soave, and this
can produce different results.
The model uses option codes which are described in Soave-Redlich-Kwong
Option Codes.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
SRKTC Tci TC x 5.0 2000.0 TEMPERATURE

SRKPC pci PC x 105 108 PRESSURE


SRKOMG i OMEGA x 0.5 2.0

SRKZRA zRA RKTZRA x


SRKKIJ/1 kij(1) 0 x
SRKKIJ/2 kij(2) 0 x TEMPERATURE
SRKKIJ/3 kij(3) 0 x TEMPERATURE
SRKKIJ/4 Tlower 0 x TEMPERATURE
SRKKIJ/5 Tupper 1000 x TEMPERATURE
SRKLIJ/1 lij(1) 0 x
SRKLIJ/2 lij(2) 0 x TEMPERATURE
SRKLIJ/3 lij(3) 0 x TEMPERATURE
SRKLIJ/4 Tlower 0 x TEMPERATURE
SRKLIJ/5 Tupper 1000 x TEMPERATURE

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.

2 Thermodynamic Property Models 63


SRK-Kabadi-Danner
The SRK-Kabadi-Danner property model uses the SRK equation-of-state with
improved phase equilibrium calculations for mixtures containing water and
hydrocarbons. These improvements are achieved by using the Kabadi-Danner
mixing rules.
The form of the equation-of-state is:

Where:

a0 is the standard quadratic mixing term:

Where:

;
The best values of kwj (w = water) were obtained from experimental data.
Results are given for seven homologous series.

Best Fit Values of kwj for Different Homologous Series


with Water
Homologous series kwj
Alkanes 0.500
Alkenes 0.393
Dialkenes 0.311
Acetylenes 0.348
Naphthenes 0.445
Cycloalkenes 0.355
Aromatics 0.315

aKD is the Kabadi-Danner term for water:

Where:

Gi is the sum of the group contributions of different groups which make up a


molecule of hydrocarbon i.

64 2 Thermodynamic Property Models


gl is the group contribution parameter for groups constituting hydrocarbons.

Groups Constituting Hydrocarbons and Their Group


Contribution Parameters
Group l gl , atm m6 x 105
CH4 1.3580
CH3 0.9822
CH2 1.0780
> CH 0.9728
>C< 0.8687
CH2 (cyclic) 0.7488
> CH (cyclic) 0.7352
CH = CH (cyclic) 0.6180
CH2 = CH2 1.7940
CH2 = CH 1.3450
CH2 = C< 0.9066
CH CH 1.6870
CH C 1.1811
CH = 0.5117
> C = (aromatic) 0.3902

This value is obtained from very little data. Might not be reliable.
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

The model uses option codes which are described in Soave-Redlich-Kwong


Option Codes.
SRK-Kabadi-Danner uses the same parameters as SRK, with added
interaction parameters. Do not specify values for the SRKLIJ parameters
when using SRK-KD.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
SRKTC Tci TC x 5.0 2000.0 TEMPERATURE

SRKPC pci PC x 105 108 PRESSURE

2 Thermodynamic Property Models 65


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
SRKOMG i OMEGA x 0.5 2.0
SRKWF Gi 0 x
SRKZRA zRA RKTZRA x
SRKKIJ/1 kij(1) 0 x
SRKKIJ/2 kij(2) 0 x TEMPERATURE
SRKKIJ/3 kij(3) 0 x TEMPERATURE
SRKKIJ/4 Tlower 0 x TEMPERATURE
SRKKIJ/5 Tupper 0 x TEMPERATURE

References
V. Kabadi and R. P. Danner, "A Modified Soave-Redlich-Kwong Equation of
State for Water-Hydrocarbon Phase Equilibria", Ind. Eng. Chem. Process Des.
Dev., Vol. 24, No. 3, (1985), pp. 537-541.

SRK-ML
The SRK-ML property model is the same as the Soave-Redlich-Kwong model
with 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

SMLPC pci PC x 105 108 PRESSURE


SMLOMG i OMEGA x 0.5 2.0

SMLZRA zRA RKTZRA x


SMLCMP 0 x
SRKMLP x -2.0 2.0
SRKGLP x
SMLKIJ/1 kij(1) 0 x
SMLKIJ/2 kij(2) 0 x TEMPERATURE
SMLKIJ/3 kij(3) 0 x TEMPERATURE
SMLKIJ/4 Tlower 0 x TEMPERATURE
SMLKIJ/5 Tupper 1000 x TEMPERATURE

The model uses option codes which are described in Soave-Redlich-Kwong


Option Codes.

66 2 Thermodynamic Property Models


Additional Parameters
SMLZRA is used in Peneloux-Rauzy volume translation as described in Soave-
Redlich-Kwong. This volume translation feature can be enabled by setting
option code 4 to 1, but is disabled by default (in which case this parameter is
not used).
SMLCMP is the Composition Independent Fugacity Calculation Flag. You can
use this flag to indicate the component for which its fugacity coefficient in the
mixture will be calculated such that it is independent of composition. The
calculated fugacity coefficient of that component is simply the pure-
component fugacity coefficient. This is a simplification. Enter a value of 1 for
the element i to indicate that the fugacity coefficient of component i is
independent of composition. This parameter defaults to zero.
SRKMLP is a polar parameter for the Mathias alpha function.
SRKGLP is a vector of parameters for the Gibbons-Laughton alpha function.

VPA/IK-CAPE Equation-of-State
The VPA/IK-CAPE equation of state is similar to the HF equation of state but
allows dimerization, tetramerization and hexamerization to occur
simultaneously. The main assumption of the model is that only molecular
association causes the gas phase nonideality. Attractive forces between the
molecules and the complexes are neglected.
There are three kinds of associations, which can be modeled:
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

zMij = True concentration of cross-dimers of components i


and j, for i,j 1 to 5.
p0 = Reference pressure
k = Number of components

2 Thermodynamic Property Models 67


Association Equilibria
Every association equilibrium reaction
(1)

(2)

is described by the equilibrium constants


(3)

(4)

By setting
(5)

(6)

their temperature dependence can be reproduced.


To evaluate the true concentration of every complex zin, the following
nonlinear systems of equations are to be solved:
Total mass balance:
The sum of true concentrations is unity.

(7)

Mass balance for every component i>1:


The ratio of the monomers of each component i>1 and component i=1
occurring in the various complexes must be equal to the ratio of their
apparent concentrations.

(8)

Thus, a system of k nonlinear equations for k unknowns zi1 has been


developed. After having solved it, all the zin and zMij can be determined using

68 2 Thermodynamic Property Models


equations (3, 4). This is the main step to evaluate all the properties needed
for a calculation.

Specific Volume of the Gas Phase


The compressibility factor is defined by the ratio between the number of
complexes and the number of monomers in the complexes.

(9)

The compressibility factor itself is


(10)

Fugacity Coefficient
As is well-known from thermodynamics, the fugacity coefficient can be
calculated by
(11)

Isothermal Enthalpy Departure


According to the ASPEN enthalpy model, an equation of state must supply an
expression to compute the isothermal molar enthalpy departure between zero
pressure and actual pressure. In the following section this enthalpy
contribution per mole monomers is abbreviated by ha.
Taking this sort of gas phase non-ideality into account, the specific enthalpy
per mole can be written as
(12)

with
(13)

to evaluate ha, a mixture consisting of N monomers integrated in the


complexes is considered. The quota of monomers i being integrated in a
complex of degree n is given by

2 Thermodynamic Property Models 69


(14)

and
(16)

respectively. For the reactions mentioned above:


(1)

(2)

the enthalpies of reaction are


(17)

(18)

as the van't Hoff equation


(19)

holds for this case.


For each monomer being integrated in a complex of degree n, its contribution
to the enthalpy departure is hin / n or hMij / 2, respectively. Hence, ha can
easily be derived by

(20)

Isothermal entropy and Gibbs energy departure:


A similar expression for ga should hold as it does for the enthalpy departure
(eq. 20):
(21)

70 2 Thermodynamic Property Models


using
(22)

and
(23)

(24)

Using the association model, more different species occur than can be
distinguished. Thus, the equivalent expression for the entropy of mixing
should be written with the true concentrations. As eq. 24 refers to 1 mole
monomers, the expression should be weighted by the compressibility factor
representing the true number of moles. The new expression is
(25)

For ga we obtain
(26)

and, analogously,
(27)

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
DMER/1 Ai2 0 X
DMER/2 Bi2 0 X TEMPERATURE
TMER/1 Ai4 0 X
TMER/2 Bi4 0 X TEMPERATURE
HMER/1 Ai6 0 X
HMER/2 Bi6 0 X TEMPERATURE

References
M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing
Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,
Vol. 77, (1992) pp. 53119.
V. V. De Leeuw and S. Watanasiri, "Modeling Phase Equilibria and Enthalpies
of the System Water and Hydrofluoric Acid Using an HF Equation-of-state in
Conjunction with the Electrolyte NRTL Activity Coefficient Model," Paper
Presented at the 13th European Seminar on Applied Thermodynamics, June
912, Carry-le-Rouet, France, 1993.

2 Thermodynamic Property Models 71


R. W. Long, J. H. Hildebrand, and W. E. Morrell, "The Polymerization of
Gaseous Hydrogen and Deuterium Fluorides," J. Am. Chem. Soc., Vol. 65,
(1943), pp. 182187.
C. E. Vanderzee and W. Wm. Rodenburg, "Gas Imperfections and
Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride," J. Chem.
Thermodynamics, Vol. 2, (1970), pp. 461478.

Peng-Robinson Alpha Functions


The pure component parameters for the Peng-Robinson equation-of-state are
calculated as follows:
(1)

(2)

These expressions are derived by applying the critical constraints to the


equation-of-state under these conditions:
(3)

The parameter is a temperature function. It was originally introduced by


Soave in the Redlich-Kwong equation-of-state. This parameter improves the
correlation of the pure component vapor pressure.

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)

Equation 3 is still represented. The parameter mi can be correlated with the


acentric factor:
(5)

Equations 1 through 5 are the standard Peng-Robinson formulation. The


Peng-Robinson alpha function is adequate for hydrocarbons and other
nonpolar compounds, but is not sufficiently accurate for polar compounds.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
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
OMGPR i OMEGA X -0.5 2.0

72 2 Thermodynamic Property Models


Boston-Mathias Extrapolation
For light gases at high reduced temperatures (> 5), equation 4 gives
unrealistic results. The boundary conditions are that attraction between
molecules should vanish for extremely high temperatures, and reduces
asymptotically to zero. Boston and Mathias derived an alternative function for
temperatures higher than critical:
(6)

With
=

Where mi is computed by equation 5, and equation 4 is used for subcritical


temperatures. Additional parameters are not needed.

Extended Gibbons-Laughton Alpha Function


The extended Gibbons-Laughton alpha function is suitable for use with both
polar and nonpolar components. It has the flexibility to fit the vapor pressure
of most substances from the triple point to the critical point.

Where Tr is the reduced temperature; Xi, Yi and Zi are substance dependent


parameters.
This function is equivalent to the standard Peng-Robinson alpha function if

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
PRGLP/1 X X
PRGLP/2 Y 0 X
PRGLP/3 Z 0 X
PRGLP/4 n 2 X
PRGLP/5 Tlower 0 X TEMPERATURE
PRGLP/6 Tupper 1000 X TEMPERATURE

Twu Generalized Alpha Function


The Twu generalized alpha function is a theoretically-based function that is
currently recognized as the best available alpha function. It behaves better
than other functions at supercritical conditions (T > Tc) and when the acentric
factor is large. The improved behavior at high values of acentric factor is
important for high molecular weight pseudocomponents. There is no limit on
the minimum value of acentric factor that can be used with this function.

2 Thermodynamic Property Models 73


Where the L, M, and N are parameters that vary depending on the equation of
state and whether the temperature is above or below the critical temperature
of the component.
For Peng-Robinson equation of state:
Subcritical T Supercritical T
(0)
L 0.272838 0.373949
M(0) 0.924779 4.73020
(0)
N 1.19764 -0.200000
(1)
L 0.625701 0.0239035
M(1) 0.792014 1.24615
(1)
N 2.46022 -8.000000

Twu Alpha Function


The Twu alpha function is a theoretically-based function that is currently
recognized as the best available alpha function. It behaves better than other
functions at supercritical conditions (T > Tc).

Where the L, M, and N are substance-dependent parameters that must be


determined from regression of pure-component vapor pressure data or other
data such as liquid heat capacity.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PRTWUP/1 L X
PRTWUP/2 M 0 X
PRTWUP/3 N 0 X

Mathias-Copeman Alpha Function


This is an extension of the Peng-Robinson alpha function which provides a
more accurate fit of vapor pressure for polar compounds.
(7)

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

74 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PRMCP/1 c1,i X
PRMCP/2 c2,i 0 X
PRMCP/3 c3,i 0 X

Schwartzentruber-Renon-Watanasiri Alpha Function


The Schwartzentruber-Renon-Watanasiri alpha function is:
(8)

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)

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCPR Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCPR pci PC X 10 10 PRESSURE
OMGPR i OMEGA X -0.5 2.0

PRSRP/1 X

PRSRP/2 0 X

PRSRP/3 0 X

HYSYS Alpha Function


The HYSYS alpha function uses the same equation as the standard Peng-
Robinson alpha function when < 0.49, and otherwise it uses equation 4
with the following definition of m to correct the behavior for large values of
acentric factor:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCPR Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCPR pci PC X 10 10 PRESSURE
OMGPR i OMEGA X -0.5 2.0

2 Thermodynamic Property Models 75


Use of Alpha Functions
The alpha functions in Peng-Robinson-based equation-of-state models is
provided in the following table. You can verify and change the value of
possible option codes on the Methods | Selected Methods | Models sheet.
Alpha function Model name First Option code
Standard PR/ ESPR0, ESPR 0
Boston-Mathias ESPRWS0, ESPRWS 0
ESPRV20, ESPRV2 0
Standard Peng Robinson ESPRSTD0, ESPRSTD 1
Extended Gibbons- ESPR0, ESPR 2
Laughton
Twu Generalized alpha ESPR0, ESPR 3
function
Twu alpha function ESPR0, ESPR 4
HYSYS alpha function ESPRSTD0, ESPRSTD 5
Mathias-Copeman ESPRWS0, ESPRWS 2
ESPRV20, ESPRV2 2
Schwartzentruber- ESPRWS0, ESPRWS 3 (default)
Renon- ESPRV20, ESPRV2 3 (default)
Watanasiri

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.

Soave Alpha Functions


The pure component parameters for the Redlich-Kwong equation-of-state are
calculated as:

76 2 Thermodynamic Property Models


(1)

(2)

These expressions are derived by applying the critical constraint to the


equation-of-state under these conditions:
(3)

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)

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC Tci 5.0 2000.0 TEMPERATURE
PC pci 105 108 PRESSURE

Soave Modification
The parameter i is a temperature function introduced by Soave in the
Redlich-Kwong equation-of-state to improve the correlation of the pure
component vapor pressure:
(5)

Equation 3 still holds. The parameter mi can be correlated with the acentric
factor:
(6)

Equations 1, 2, 3, 5 and 6 are the standard Redlich-Kwong-Soave


formulation. The Soave alpha function is adequate for hydrocarbons and other
nonpolar compounds, but is not sufficiently accurate for polar compounds.
Parameter 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
OMGRKS i OMEGA X -0.5 2.0

2 Thermodynamic Property Models 77


Boston-Mathias Extrapolation
For light gases at high reduced temperatures (> 5), equation 5 gives
unrealistic results. The boundary conditions are that attraction between
molecules should vanish for extremely high temperatures, and reduces
asymptotically to zero. Boston and Mathias derived an alternative function for
temperatures higher than critical:
(7)

With
di =

ci =

Where:
mi = Computed by equation 6
Equation 5 = Used for subcritical temperatures
Additional parameters are not needed.

Mathias Alpha Function


This is an extension of the Soave alpha function which provides a more
accurate fit of vapor pressure for polar compounds.
(8)

For i=0, equation 8 reduces to the standard Redlich-Kwong-Soave


formulation, equations 5 and 6. For temperatures above critical, the Boston-
Mathias extrapolation is used, that is, equation 7 with:
(9)

(10)

The Mathias alpha function is used in the Redlich-Kwong-Aspen model, which


is the basis for the RK-ASPEN property method. This alpha function is also
available as an option for SRK, SRKKD, SRK-ML, RK-SOAVE, and RKS-BM.
See Soave-Redlich-Kwong Option Codes for more information.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKA Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCRKA pci PC X 10 10 PRESSURE
OMGRKA i OMEGA X -0.5 2.0
i X -2.0 2.0

78 2 Thermodynamic Property Models


RKAPOL for Redlich-Kwong-Aspen, SRKPOL for SRK and SRKKD, SRKMLP for
SRK-ML, RKSPOL for RKS-BM, or RKSSPO for RK-SOAVE.

Extended Mathias Alpha Function


An extension of the Mathias approach is:
(11)

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)

This alpha function is used in the Redlich-Kwong-UNIFAC model which is the


basis for the SR-POLAR property method.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKU Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCRKU pci PC X 10 10 PRESSURE
OMGRKU i OMEGA X -0.5 2.0
RKUPP0 p1,i X
RKUPP1 p2,i 0 X
RKUPP2 p3,i 0 X

Mathias-Copeman Alpha Function


The Mathias-Copeman alpha function is suitable for use with both polar and
nonpolar components. It has the flexibility to fit the vapor pressure of most
substances from the triple point to the critical point.
(14)

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

2 Thermodynamic Property Models 79


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
RKSMCP/3 c3,i 0 X

Schwartzentruber-Renon-Watanasiri Alpha Function


The Schwartzentruber-Renon-Watanasiri alpha function is:
(15)

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)

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
OMGRKS i OMEGA X -0.5 2.0
RKSSRP/1 p1,i X
RKSSRP/2 p2,i 0 X
RKSSRP/3 p3,i 0 X

Extended Gibbons-Laughton Alpha Function


The extended Gibbons-Laughton alpha function is suitable for use with both
polar and nonpolar components. It has the flexibility to fit the vapor pressure
of most substances from the triple point to the critical point.

Where Tr is the reduced temperature; Xi, Yi and Zi are substance dependent


parameters.
This function is equivalent to the standard Soave alpha function if

This function is not intended for use in supercritical conditions. To avoid


predicting negative alpha, when Tri>1 the Boston-Mathias alpha function is
used instead.

80 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SRKGLP/1 X X
SRKGLP/2 Y 0 X
SRKGLP/3 Z 0 X
SRKGLP/4 n 2 X
SRKGLP/5 Tlower 0 X TEMPERATURE
SRKGLP/6 Tupper 1000 X TEMPERATURE

Twu Generalized Alpha Function


The Twu generalized alpha function is a theoretically-based function that is
currently recognized as the best available alpha function. It behaves better
than other functions at supercritical conditions (T > Tc) and when the acentric
factor is large. The improved behavior at high values of acentric factor is
important for high molecular weight pseudocomponents. There is no limit on
the minimum value of acentric factor that can be used with this function.

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

Use of Alpha Functions


The use of alpha functions in Soave-Redlich-Kwong based equation-of-state
models is given in the following table. You can verify and change the value of
possible option codes on the Methods | Selected Methods | Models sheet.
Alpha Function Model Name First Option Code
original RK ESRK0, ESRK
standard RKS ESRKSTD0, ESRKSTD
* 1, 2 (default)
standard RKS/Boston-Mathias * 0
ESRKSWS0, ESRKSWS 1
ESRKSV10, ESRKV1 1
ESRKSV20, ESRKSV2 1

2 Thermodynamic Property Models 81


Alpha Function Model Name First Option Code
Mathias/Boston-Mathias ESRKA0, ESRKA
Extended Mathias/Boston- ESRKU0, ESRKU
Mathias
Mathias-Copeman ESRKSV10, ESRKSV1 2
ESRKSV20, ESRKSV2 2
Schwartzentruber-Renon- ESPRWS0, ESPRWS 3 (default)
Watanasiri ESRKSV10, ESRKSV1 3 (default)
ESRKSV20, ESRKSV2 3 (default)
Twu generalized * 5
Gibbons-Laughton with Patel * 3
extension
Mathias for T < Tc; Boston- * 4
Mathias for T > Tc

* ESRKSTD0, ESRKSTD, ESRKS0, ESRKS, ESSRK, ESSRK0, ESRKSML,


ESRKSML0. The default alpha function (option code 2) for these models is the
standard RKS alpha function, except that the Grabovsky-Daubert alpha
function is used for H2: = 1.202 exp(-0.30228xTri)

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.

82 2 Thermodynamic Property Models


Huron-Vidal Mixing Rules
Huron and Vidal (1979) used a simple thermodynamic relationship to equate
the excess Gibbs energy to expressions for the fugacity coefficient as
computed by equations of state:
(1)

Equation 1 is valid at any pressure, but cannot be evaluated unless some


assumptions are made. If Equation 1 is evaluated at infinite pressure, the
mixture must be liquid-like and extremely dense. It can be assumed that:
(2)

(3)

Using equations 2 and 3 in equation 1 results in an expression for a/b that


contains the excess Gibbs energy at an infinite pressure:
(4)

Where:
(5)

The parameters 1and 2depend on the equation-of-state used. In general a


cubic equation-of-state can be written as:
(6)

Values for 1and 2 for the Peng-Robinson and the Soave-Redlich-Kwong


equations of state are:
Equation-of-state 1 2
Peng-Robinson

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.

2 Thermodynamic Property Models 83


The Huron-Vidal mixing rules combine extreme flexibility with thermodynamic
consistency, unlike many other mole-fraction-dependent equation-of-state
mixing rules. The Huron-Vidal mixing rules do not allow flexibility in the
description of the excess molar volume, but always predict reasonable excess
volumes.
The Huron-Vidal mixing rules are theoretically incorrect for low pressure,
because quadratic mole fraction dependence of the second virial coefficient (if
derived from the equation-of-state) is not preserved. Since equations of state
are primarily used at high pressure, the practical consequences of this
drawback are minimal.
The Gibbs energy at infinite pressure and the Gibbs energy at an arbitrary
high pressure are similar. But the correspondence is not close enough to
make the mixing rule predictive.
There are several methods for modifying the Huron-Vidal mixing rule to make
it more predictive. The following three methods are used in Aspen Physical
Property System equation-of-state models:
The modified Huron-Vidal mixing rule, second order approximation
(MHV2)
The Predictive SRK Method (PSRK)
The Wong-Sandler modified Huron-Vidal mixing rule (WS)
These mixing rules are discussed separately in the following sections. They
have major advantages over other composition-dependent equation-of-state
mixing rules.

References
M.- J. Huron and J. Vidal, "New Mixing Rules in Simple Equations of State for
representing Vapour-liquid equilibria of strongly non-ideal mixtures," Fluid
Phase Eq., Vol. 3, (1979), pp. 255-271.

MHV2 Mixing Rules


Dahl and Michelsen (1990) use a thermodynamic relationship between excess
Gibbs energy and the fugacity computed by equations of state. This
relationship is equivalent to the one used by Huron and Vidal:
(1)

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:

84 2 Thermodynamic Property Models


(3)

and
(4)

With:
(5)

The constants 1 and 2, which depend only on the equation-of-state (see


Huron-Vidal Mixing Rules) occur in equations 2 and 4.
Instead of using infinite pressure for simplification of equation 1, the condition
of zero pressure is used. At p = 0 an exact relationship between the
compacity and can be derived. By substitution the simplified equation q()
is obtained, and equation 1 becomes:
(6)

However, q() can only be written explicitly for = 5.8. Only an


approximation is possible below that threshold. Dahl and Michelsen use a
second order polynomial fitted to the analytical solution for 10 < < 13 that
can be extrapolated to low alpha:
(7)

Since q()is a universal function (for each equation-of-state), the


combination of equations 6 and 7 form the MHV2 mixing rule. Excess Gibbs
energies, from any activity coefficient model with parameters optimized at
low pressures, can be used to determine , if i, bi, and b are known. To
compute b, a linear mixing rule is assumed as in the original Huron-Vidal
mixing rules:
(8)

This equation is equivalent to the assumption of zero excess molar volume.


The MHV2 mixing rule was the first successful predictive mixing rule for
equations of state. This mixing rule uses previously determined activity
coefficient parameters for predictions at high pressures. UNIFAC was chosen
as a default for its predictive character. The Lyngby modified UNIFAC
formulation was chosen for optimum performance (see UNIFAC (Lyngby
Modified)). However, any activity coefficient model can be used when its
binary interaction parameters are known.
Like the Huron-Vidal mixing rules, the MHV2 mixing rules are not flexible in
the description of the excess molar volume. The MHV2 mixing rules are
theoretically incorrect at the low pressure limit. But the practical

2 Thermodynamic Property Models 85


consequences of this drawback are minimal (see Huron-Vidal Mixing Rules,
this chapter).
Reference: S. Dahl and M.L. Michelsen, "High-Pressure Vapor-Liquid
Equilibrium with a UNIFAC-based Equation-of-state," AIChE J., Vol. 36,
(1990), pp. 1829-1836.

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)

The Helmholtz energy is calculated by integration. AE is obtained by:


(2)

Where both Ai* and Am are calculated by using equation 1. Ai* and Am are
written in terms of equation-of-state parameters.
The simplification of constant packing fraction (Vm / b) is used:
(3)

With:
(4)

Therefore:
(5)

The mixing rule is:


(6)

Where ' is slightly different from for the Huron-Vidal mixing rule:
(7)

86 2 Thermodynamic Property Models


Where 1 and 2, depend on the equation-of-state (see Huron-Vidal Mixing
Rules). If equation 6 is applied at infinite pressure, the packing fraction goes
to 1. The excess Helmholtz energy is equal to the excess Gibbs energy. The
Huron-Vidal mixing rules are recovered.
The goal of these mixing rules is to be able to use binary interaction
parameters for activity coefficient models at any pressure. These parameters
have been optimized at low pressures. UNIFAC is chosen for its predictive
character. Two issues exist: the packing fraction is not equal to one, and the
excess Gibbs and Helmholtz energy are not equal at the low pressure where
the UNIFAC parameters have been derived.
Fischer (1993) determined that boiling point, the average packing fraction for
about 80 different liquids with different chemical natures was 1.1. Adopting
this value, the difference between liquid excess Gibbs energy and liquid
excess Helmholtz energy can be computed as:
(8)

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:

At the University of Oldenburg in Germany, the UNIFAC groups were


extended with often-occurring gases. New group interactions were
determined from gas-solvent data, specific to the Redlich-Kwong-Soave
equation-of-state. The new built-in parameters to the Aspen Physical Property
System are activated when using the PSRK equation-of-state model.
The PSRK method has a lot in common with the Huron-Vidal mixing rules. The
mole fraction is dependent on the second virial coefficient and excess volume
is predicted. These are minor disadvantages.

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).

2 Thermodynamic Property Models 87


T. Holderbaum and J. Gmehling, "PSRK: A Group Contribution Equation-of-
state based on UNIFAC," Fluid Phase Eq., Vol. 70, (1991), pp. 251-265.
J. Li, K. Fischer, and J. Gmehling, "Prediction of vapor-liquid equilibria for
asymmetric systems at low and high pressures with the PSRK model," Fluid
Phase Equilib., 1998, 143, 71-82

Wong-Sandler Mixing Rules


These mixing rules 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)

The Helmholtz energy is obtained by integration, AE is obtained by:


(2)

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)

Where depends on the equation-of-state (see Huron-Vidal Mixing Rules).


Equation 3 is completely analogous to the Huron-Vidal mixing rule for the
excess Gibbs energy at infinite pressure. (See equation 4, Huron-Vidal Mixing
Rules.) The excess Helmholtz energy can be approximated by the excess
Gibbs energy at low pressure from any liquid activity coefficient model. Using
the Helmholtz energy permits another mixing rule for b than the linear mixing
rule. The mixing rule for b is derived as follows. The second virial coefficient
must depend quadratically on the mole fraction:
(4)

With:
(5)

The relationship between the equation-of-state at low pressure and the virial
coefficient is:
(6)

88 2 Thermodynamic Property Models


(7)

Wong and Sandler discovered the following mixing rule to satisfy equation 4
(using equations 6 and 7):

The excess Helmholtz energy is almost independent of pressure. It can be


approximated by the Gibbs energy at low pressure. The difference between
the two functions is corrected by fitting kij until the excess Gibbs energy from
the equation-of-state (using the mixing rules 3 and 8) is equal to the excess
Gibbs energy computed by an activity coeffecient model. This is done at a
specific mole fraction and temperature.
This mixing rule accurately predicts the VLE of polar mixtures at high
pressures. UNIFAC or other activity coeffecient models and parameters from
the literature are used. Gas solubilities are not predicted. They must be
regressed from experimental data.
Unlike other (modified) Huron-Vidal mixing rules, the Wong and Sandler
mixing rule meets the theoretical limit at low pressure. The use of kij does
influence excess molar volume behavior. For calculations where densities are
important, check whether they are realistic.

References
D. S. Wong and S. I. Sandler, "A Theoretically Correct New Mixing Rule for
Cubic Equations of State for Both Highly and Slightly Non-ideal Mixtures,"
AIChE J., Vol. 38, (1992), pp. 671 680.
D. S. Wong, H. Orbey, and S. I. Sandler, "Equation-of-state Mixing Rule for
Non-ideal Mixtures Using Available Activity Coefficient Model Parameters and
That Allows Extrapolation over Large Ranges of Temperature and Pressure",
Ind Eng Chem. Res., Vol. 31, (1992), pp. 2033 2039.
H. Orbey, S. I. Sandler and D. S. Wong, "Accurate Equation-of-state
Predictions at High Temperatures and Pressures Using the Existing UNIFAC
Model," Fluid Phase Eq., Vol. 85, (1993), pp. 41 54.

Activity Coefficient Models


The Aspen Physical Property System has the following built-in activity
coefficient models. This section describes the activity coefficient models
available.
Model Type
Bromley-Pitzer Electrolyte
Chien-Null Regular solution, local composition
Constant Activity Coefficient Arithmetic

2 Thermodynamic Property Models 89


Model Type
COSMO-SAC Regular solution
Electrolyte NRTL Electrolyte
ENRTL-SAC Segment contribution, electrolyte
Hansen Regular solution
Ideal Liquid Ideal
NRTL (Non-Random-Two-Liquid) Local composition
NRTL-SAC Segment contribution
Pitzer Electrolyte
Polynomial Activity Coefficient Arithmetic
Redlich-Kister Arithmetic
Scatchard-Hildebrand Regular solution
Symmetric Electrolyte NRTL Electrolyte, pure fused salt
reference state for ions
Three-Suffix Margules Arithmetic
UNIFAC Group contribution
UNIFAC (Lyngby modified) Group contribution
UNIFAC (Dortmund modified) Group contribution
UNIQUAC Local composition
Unsymmetric Electrolyte NRTL Electrolyte
Van Laar Regular solution
Wagner interaction parameter Arithmetic
Wilson Local composition
Wilson with Liquid Molar Volume Local composition

Bromley-Pitzer Activity Coefficient Model


The Bromley-Pitzer activity coefficient model is a simplified Pitzer activity
coefficient model with Bromley correlations for the interaction parameters.
See Working Equations for a detailed description. This model has predictive
capabilities. It can be used to compute activity coefficients for aqueous
electrolytes up to 6 molal ionic strength, but is less accurate than the Pitzer
model if the parameter correlations are used. The model should not be used
for mixed-solvent electrolyte systems.
The Bromley-Pitzer model in the Aspen Physical Property System involves
user-supplied parameters, used in the calculation of binary parameters for the
electrolyte system.

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

90 2 Thermodynamic Property Models


The user must:
Supply these elements using a Methods | Parameters | Binary | T-
Dependent form.
Specify Comp ID i and Comp ID j on this form, using the same order that
appears on the Components | Specifications | Selection sheet form.
Parameter Name Symbol No. of Elements Default Units
Ionic Unary Parameters
GMBPB ion 1 0

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

2 Thermodynamic Property Models 91


Where:
xi = Mole fraction of ion i
xw = Mole fraction of water
Mw = Molecular weight of water (g/mol)
ni = Moles of ion i

B, C, and are interaction parameters, and f(I) is an electrostatic term as


a function of ionic strength; these terms are discussed in Pitzer Activity
Coefficient Model, which has a detailed discussion of the Pitzer model.

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.

92 2 Thermodynamic Property Models


Chien-Null
The Chien-Null model calculates liquid activity coefficients and it can be used
for highly non-ideal systems. The generalized expression used in its derivation
can be adapted to represent other well known formalisms for the activity
coefficient by properly defining its binary terms. This characteristic allows the
model the use of already available binary parameters regressed for those
other liquid activity models with thermodynamic consistency.
The equation for the Chien-Null liquid activity coeficient is:

Where:
Rji = Aji / Aij
Aii = 0

Aij = aij + bij / T


Subscripts i and j are component indices.
The choice of model and parameters can be set for each binary pair
constituting the process mixture by assigning the appropriate value to the
ICHNUL parameter.
The Regular Solution and Scatchard-Hamer models are regained by
substituting in the general expression (ICHNUL = 1 or 2).
Vji = Sji = Vj*,l / Vi*,l
Where:
Vj*,l = Liquid molar volume of component i
The Chien-Null activity coefficient model collapses to the Margules liquid
activity coefficient expression by setting (ICHNUL = 3):
Vji = Sji = 1
The Van Laar Liquid activity coefficient model is obtained when the V and S
parameters in the Chien-Null models are set to the ratio of the cross terms of
A (ICHNUL = 4:)
Vji = Sji = Aji / Aij
Finally, the Renon or NRTL model is obtained when we make the following
susbstitutions in the Chien-Null expression for the liquid activity (ICHNUL =
5).
Sji = RjiAji / Aij

Aji = 2jiGji
Vji = Gji

2 Thermodynamic Property Models 93


The following are defined for the Non-Random Two-Liquid activity coefficient
model, where:

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

The parameter ICHNUL is used to identify the activity model parameters


available for each binary pair of interest. The following values are allowed for
ICHNUL:
ICHNUL = 1 or 2, sets the model to the Scatchard-Hamer or regular solution
model for the associated binary;
ICHNUL = 3, sets the model to the Three-Suffix Margules activity model for
the associated binary;
ICHNUL = 4, sets the model to the Van Laar formalism for the activity model
for the associated binary;
ICHNUL = 5, sets the model to the NRTL (Renon) formalism for the activity
model for the associated binary.
ICHNUL = 6, sets the model to the full Chien-Null formalism for the activity
model for the associated binary.
When you specify a value for the ICHNUL parameter that is different than the
default, you must enter the appropriate binary model parameters for the
chosen activity model directly. The routine will automatically convert the
expressions and parameters to conform to the Chien-Null formulation.

Constant Activity Coefficient


This approach is used exclusively in metallurgical applications where multiple
liquid and solid phases can coexist. You can assign any value to the activity
coefficient of component i. Use the Properties | Parameters | Pure

94 2 Thermodynamic Property Models


Component | Scalar form.
The equation is:

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

2 Thermodynamic Property Models 95


Where:

i = Activity coefficient of component i

iSG = Staverman-Guggenheim model for combinatorial


contribution to i

i(m) = Segment activity coefficient of segment m in


component i

S(m) = Segment activity coefficient of segment m in


solvent mixture

pi(m) = Sigma profile of component i

pi(m) = Sigma profile of solvent mixture

= Surface charge density

W(m,n) = Exchange energy between segments m and n


WHB(m,n) = Hydrogen-bonding contribution to exchange energy
between segments m and n
z = Coordination number, 10
Vi = Molecular volume of component i
Ai = Molecular surface area of component i
aeff = Standard segment surface area, 7.50 2
Veff = Standard component volume, 66.69 3
Aeff = Standard component surface area, 79.53 2

' = Misfit energy constant

96 2 Thermodynamic Property Models


The Cosmo-SAC model does not require binary parameters. For each
component, it has six input parameters. CSACVL is the component volume
parameter which is always defined in cubic angstroms, regardless of chosen
units sets. SGPRF1 to SGPRF5 are five molecular component sigma profile
parameters; each can store up to 12 points of sigma profile values. All six
input parameters are obtained from COSMO calculation. The Aspen Physical
Property System includes a database of sigma profiles for over 1400
compounds from Mullins et al. (2006). The parameters were obtained by
permission from the Virginia Tech Sigma Profile Database website
(http://www.design.che.vt.edu/VT-2004.htm). Aspen Technology, Inc. does
not claim proprietary rights to these parameters.

Note: Starting in version V7.2, additional parameters SGPRF6 and SGPRF7


are available in Aspen Plus and Aspen Properties, as part of a planned
expansion to allow larger sigma profiles to be used. In V7.3.2, three
additional sets of parameters are added as part of further expansion to model
electrolyte systems. They are the component ionic sigma profile from
SGPRE1 through SGPRE7, the molecular sigma profile for ionic pair
from SGPBF1 through SGPBF7, and the ionic sigma profile for ionic pair from
SGPBE1 through SGPBE7. However, the model is not yet updated to use
these parameters and you should not yet try to use sigma profiles larger than
51 elements.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CSACVL Vi x VOLUME (3)
SGPRF1 Ai pi(1-12) x
SGPRF2 Ai pi(13-24) x
SGPRF3 Ai pi(25-36) x
SGPRF4 Ai pi(37-48) x
SGPRF5 Ai pi(49-51) x

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

2 Thermodynamic Property Models 97


Systems from a New Expression for COSMO Solvation Models," presented at
the AIChE Annual Meeting, Indianapolis, IN, 3-8 November (2002).
S.-T. Lin and S. I. Sandler, "A Priori Phase Equilibrium Prediction from a
Segment Contribution Solvation Model," Ind. Eng. Chem. Res. 41, 899
(2002).
E. Mullins, et al. "Sigma-Profile Database for Using COSMO-Based
Thermodynamic Methods," Ind. Eng. Chem. Res. 45, 4389 (2006).

Electrolyte NRTL Activity Coefficient Model


(GMENRTL)
The Electrolyte NRTL activity coefficient model (GMENRTL) is a versatile
model for the calculation of activity coefficients. Using binary and pair
parameters, the model can represent aqueous electrolyte systems as well as
mixed solvent electrolyte systems over the entire range of electrolyte
concentrations. This model can calculate activity coefficients for ionic species
and molecular species in aqueous electrolyte systems as well as in mixed
solvent electrolyte systems. The model reduces to the well-known NRTL
model when electrolyte concentrations become zero (Renon and Prausnitz,
1969).
The electrolyte NRTL model uses the infinite dilution aqueous solution as the
reference state for ions. It adopts the Born equation to account for the
transformation of the reference state of ions from the infinite dilution mixed
solvent solution to the infinite dilution aqueous solution.
Water must be present in the electrolyte system in order to compute the
transformation of the reference state of ions. Thus, it is necessary to
introduce a trace amount of water to use the model for nonaqueous
electrolyte systems.
The Aspen Physical Property System uses the electrolyte NRTL model to
calculate activity coefficients, enthalpies, and Gibbs energies for electrolyte
systems. Model development and working equations are provided in
Theoretical Basis and Working Equations.
The adjustable parameters for the electrolyte NRTL model include the:
Pure component dielectric constant coefficient of nonaqueous solvents
Born radius of ionic species
NRTL parameters for molecule-molecule, molecule-electrolyte, and
electrolyte-electrolyte pairs
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 of the dielectric constant of
solvent B is:

98 2 Thermodynamic Property Models


Each type of electrolyte NRTL parameter consists of both the nonrandomness
factor, , and energy parameters, . The temperature dependency relations
of the electrolyte NRTL parameters are:
Molecule-Molecule Binary Parameters:

Electrolyte-Molecule Pair Parameters:

Electrolyte-Electrolyte Pair Parameters:


For the electrolyte-electrolyte pair parameters, the two electrolytes must
share either one common cation or one common anion:

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

2 Thermodynamic Property Models 99


Parameter Symbol No. of Default MDS Units
Name Elements
Dielectric Constant Unary Parameters
NRTL/6 GBB' 0 x TEMPERATURE
GB'B 0 x TEMPERATURE
Electrolyte-Molecule Pair Parameters
GMELCC Cca,B 1 0 x
CB,ca 1 0 x
GMELCD Dca,B 1 0 x TEMPERATURE
DB,ca 1 0 x TEMPERATURE
GMELCE Eca,B 1 0 x
EB,ca 1 0 x
GMELCN ca,B = B,ca 1 .2 x
Electrolyte-Electrolyte Pair Parameters
GMELCC Cca',ca'' 1 0 x
Cca'',ca' 1 0 x
Cc'a,c''a 1 0 x
Cc''a,c'a 1 0 x

GMELCD Dca',ca'' 1 0 x TEMPERATURE
Dca'',ca' 1 0 x TEMPERATURE
Dc'a,c''a 1 0 x TEMPERATURE
Dc''a,c'a 1 0 x TEMPERATURE
GMELCE Eca',ca'' 1 0 x
Eca'',ca' 1 0 x
Ec'a,c''a 1 0 x
Ec''a,c'a 1 0 x
GMELCN ca',ca'' = ca'',ca' 1 .2 x

c'a,c''a = c''a,c'a 1 .2 x

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.

Theoretical Basis and Working Equations


In this section, the theoretical basis of the model is explained and the working
equations are given. The different ways parameters can be obtained are
discussed with references to the databank directories and the Data

100 2 Thermodynamic Property Models


Regression System (DRS). The parameter requirements of the model are
given in Electrolyte NRTL Activity Coefficient Model.

Development of the Model


The Electrolyte NRTL model was originally proposed by Chen et al., for
aqueous electrolyte systems. It was later extended to mixed solvent
electrolyte systems (Mock et al., 1984, 1986). The model is based on two
fundamental assumptions:
The like-ion repulsion assumption: states that the local composition of
cations around cations is zero (and likewise for anions around anions).
This is based on the assumption that the repulsive forces between ions of
like charge are extremely large. This assumption may be justified on the
basis that repulsive forces between ions of the same sign are very strong
for neighboring species. For example, in salt crystal lattices the immediate
neighbors of any central ion are always ions of opposite charge.
The local electroneutrality assumption: states that the distribution of
cations and anions around a central molecular species is such that the net
local ionic charge is zero. Local electroneutrality has been observed for
interstitial molecules in salt crystals.
Chen proposed an excess Gibbs energy expression which contains two
contributions: one contribution for the long-range ion-ion interactions that
exist beyond the immediate neighborhood of a central ionic species, and the
other related to the local interactions that exist at the immediate
neighborhood of any central species.
The unsymmetric Pitzer-Debye-Hckel model and the Born equation are used
to represent the contribution of the long-range ion-ion interactions, and the
Non-Random Two Liquid (NRTL) theory is used to represent the local
interactions. The local interaction contribution model is developed as a
symmetric model, based on reference states of pure solvent and pure
completely dissociated liquid electrolyte. The model is then normalized by
infinite dilution activity coefficients in order to obtain an unsymmetric model.
This NRTL expression for the local interactions, the Pitzer-Debye-Hckel
expression, and the Born equation are added to give equation 1 for the
excess Gibbs energy (see the following note).
(1)

This leads to
(2)

Note: The notation using * to denote an unsymmetric reference state is well-


accepted in electrolyte thermodynamics and will be maintained here. The
reader should be warned not to confuse it with the meaning of * in classical
thermodynamics according to IUPAC/ISO, referring to a pure component
property. In fact in the context of G or , the asterisk as superscript is never
used to denote pure component property, so the risk of confusion is minimal.
For details on notation, see Chapter 1 of Physical Property Methods.

2 Thermodynamic Property Models 101


References
C.-C. Chen, H.I. Britt, J.F. Boston, and L.B. Evans, "Local Compositions Model
for Excess Gibbs Energy of Electrolyte Systems: Part I: Single Solvent, Single
Completely Dissociated Electrolyte Systems:, AIChE J., Vol. 28, No. 4, (1982),
p. 588-596.
C.-C. Chen, and L.B. Evans, "A Local Composition Model for the Excess Gibbs
Energy of Aqueous Electrolyte Systems," AIChE J., Vol. 32, No. 3, (1986), p.
444-459.
B. Mock, L.B. Evans, and C.-C. Chen, "Phase Equilibria in Multiple-Solvent
Electrolyte Systems: A New Thermodynamic Model," Proceedings of the 1984
Summer Computer Simulation Conference, p. 558.
B. Mock, L.B. Evans, and C.-C. Chen, "Thermodynamic Representation of
Phase Equilibria of Mixed-Solvent Electrolyte Systems," AIChE J., Vol. 32, No.
10, (1986), p. 1655-1664.

Long-Range Interaction Contribution


The Pitzer-Debye-Hckel formula, normalized to mole fractions of unity for
solvent and zero for electrolytes, is used to represent the long-range
interaction contribution.
(3)

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

s = Dielectric constant of the solvent

T = Temperature
k = Boltzmann constant
Ix = Ionic strength (mole fraction scale)
xi = Mole fraction of component i

102 2 Thermodynamic Property Models


zi = Charge number of ion i

= "Closest approach" parameter

Taking the appropriate derivative of equation 3, an expression for the activity


coefficient can then be derived.
(6)

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:

w = Dielectric constant of water

ri = Born radius of the ionic species i


The expression for the activity coefficient can be derived from (7):
(8)

The Debye-Hckel theory is based on the infinite dilution reference state for
ionic species in the actual solvent media. For systems with water as the only
solvent, the reference state is the infinite dilution aqueous solution. For
mixed-solvent systems, the reference state for which the Debye-Hckel
theory remains valid is the infinite dilution solution with the corresponding
mixed-solvent composition. However, the molecular weight Ms, the mass
density ds, and the dielectric constant s for the single solvent need to be
extended for mixed solvents; simple composition average mixing rules are
adequate to calculate them as follows:
(6a)

(7a)

(8a)

(8b)

2 Thermodynamic Property Models 103


(8c)

(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

m = Dielectric constant of the solvent m

Vw* = Molar volume of water using 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.
It should be understood that equations 6a-8a should be used only in
equations 3, 4, and 7. Ms, ds, and s were already assumed as constants when
deriving equations 6 and 8 for mixed-solvent systems.

Local Interaction Contribution


The local interaction contribution is accounted for by the Non-Random Two
Liquid theory. The basic assumption of the NRTL model is that the nonideal
entropy of mixing is negligible compared to the heat of mixing: this is indeed
the case for electrolyte systems. This model was adopted because of its
algebraic simplicity and its applicability to mixtures that exhibit liquid phase
splitting. The model does not require specific volume or area data.
The effective local mole fractions Xji and Xii of species j and i, respectively, in
the neighborhood of i are related by:
(9)

Where:
Xj = xjCj
(Cj = zj for ions and Cj = unity for molecules)
Gji =

ji =

ji = Nonrandomness factor

104 2 Thermodynamic Property Models


gji and gii are energies of interaction between species j and i, and i and i,
respectively. Both gij and ij are inherently symmetric (gij = gji and ij = ji).
Similarly,
(10)

Where:
Gji,ki =

ji,ki =

ji,ki = Nonrandomness factor

Apparent Binary Systems


The derivations that follow are based on a simple system of one completely
dissociated liquid electrolyte ca and one solvent B. They will be later extended
to multicomponent systems. In this simple system, three different
arrangements exist:

In the case of a central solvent molecule with other solvent molecules,


cations, and anions in its immediate neighborhood, the principle of local
electroneutrality is followed: the surrounding cations and anions are such that
the neighborhood of the solvent is electrically neutral. In the case of a central
cation (anion) with solvent molecules and anions (cations) in its immediate
neighborhood, the principle of like-ion repulsion is followed: no ions of like
charge exist anywhere near each other, whereas opposite charged ions are
very close to each other.
The effective local mole fractions are related by the following expressions:
(11)
(central solvent cells)
(12)
(central cation cells)
(13)
(central anion cells)
Using equation 11 through 13 and the notation introduced in equations 9 and
10 above, expressions for the effective local mole fractions in terms of the
overall mole fractions can be derived.

2 Thermodynamic Property Models 105


(14)

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)

The reference Gibbs energy is determined for the reference states of


completely dissociated liquid electrolyte and of pure solvent. The reference
Gibbs energies per mole are then:
(20)

(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)

106 2 Thermodynamic Property Models


The assumption of local electroneutrality applied to cells with central solvent
molecules may be stated as:
(25)

Combining this expression with the expression for the effective local mole
fractions given in equations 9 and 10, the following equality is obtained:
(26)

The following relationships are further assumed for nonrandomness factors:


(27)

(28)

and,
(29)

It can be inferred from equations 9, 10, and 26 to 29 that:


(30)

(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)

This leads to:


(33)

By taking the appropriate derivatives of equation 33, expressions for the


activity coefficients of all three species can be determined.
(34)

2 Thermodynamic Property Models 107


(35)

(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)

The activity coefficient equation for cations is given by:

108 2 Thermodynamic Property Models


(39)

The activity coefficient equation for anions is given by:


(40)

Where:
(41)

(42)

(43)

(44)

(45)

(46)

(47)

(48)

2 Thermodynamic Property Models 109


It should be understood that and remained constant in
equation 37 when deriving the activity coefficients given by equations 38-40.

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

110 2 Thermodynamic Property Models


systems; however, for concentrated systems, pair parameters are required
for accurate representation.
See Physical Property Data, Chapter 1, for the pair parameters available from
the electrolyte NRTL model databank. The table contains pair parameters for
some electrolytes in aqueous solution at 100C. These values were obtained
by using the Aspen Physical Property Data Regression System (DRS) to
regress vapor pressure and mole fraction data at T=100C with SYSOP15S
(Handbook of Chemistry and Physics, 56th Edition, CRC Press, 1975, p. E-1).
In running the DRS, standard deviations for the temperature (C), vapor
pressure (mmHg), and mole fractions were set at 0.2, 1.0, and 0.001,
respectively. In addition, complete dissociation of the electrolyte was
assumed for all cases.

Option Codes for Electrolyte NRTL Activity


Coefficient Model (GMENRTL)
The electrolyte NRTL activity coefficient model (GMENRTL) has three option
codes and the option codes can affect the performance of this model.
Option code 1. Use this option code to specify the default values of pair
parameters for water/solute and solvent/solute; the solute represents a
cation/anion pair. The value (1) sets the default values to zero and the value
(3) sets the default values for water/solute to (8,-4) and for solvent/solute to
(10,-2). The value (3) is the default choice of the option code.
Option code 2. Not used.
Option code 3. Always leave this option code set to the value (1) to use the
solvent/solvent binary parameters obtained from NRTL parameters.

ENRTL-SAC
eNRTL-SAC (ENRTLSAC, patent pending) is an extension of the nonrandom
two-liquid segment activity coefficient model (NRTL-SAC, patent pending) by
Chen and Song (Ind. Eng. Chem. Res., 2004, 43, 8354) to include
electrolytes in the solution. It can be used in usable in Aspen Properties and
Aspen Polymers. It is intended for the computation of ionic activity
coefficients and solubilities of electrolytes, organic and inorganic, in common
solvents and solvent mixtures. In addition to the three types of molecular
parameters defined for organic nonelectrolytes in NRTL-SAC (hydrophobicity
X, hydrophilicity Z, and polarity Y- and Y+), an electrolyte parameter, E, is
introduced to characterize both local and long-range ion-ion and ion-molecule
interactions attributed to ionized segments of electrolytes.
In applying the segment contribution concept to electrolytes, a new
conceptual electrolyte segment e corresponding to the electrolyte parameter
E, is introduced. This conceptual segment e would completely dissociate to a
cationic segment (c) and an anionic segment (a), both of unity charge. All
electrolytes, organic or inorganic, symmetric or unsymmetric, univalent or
multivalent, are to be represented with this conceptual uni-univalent
electrolyte segment e together with previously defined hydrophobic segment
x, polar segments y- and y+, and hydrophilic segment z in NRTL-SAC.

2 Thermodynamic Property Models 111


A major consideration in the extension of NRTL-SAC for electrolytes is the
treatment of the reference state for activity coefficient calculations. While the
conventional reference state for nonelectrolyte systems is the pure liquid
component, the conventional reference state for electrolytes in solution is the
infinite-dilution aqueous solution and the corresponding activity coefficient is
unsymmetric. The equation for the logarithm of the unsymmetric activity
coefficient of an ionic species is

With

112 2 Thermodynamic Property Models


2 Thermodynamic Property Models 113
Where:
I, J = Component index
i, j, m, c, a = Conceptual segment index
m = Conceptual molecular segment, x, y-, y+, z
c = Conceptual cationic segment
a = Conceptual anionic segment
i, j = m,c,a

I* = Unsymmetric activity coefficient of an ionic species I

I*lc = NRTL term

I*PDH = Pitzer-Debye-Hckel term

I*FH = Flory-Huggins term

= Aqueous-phase infinite-dilution reference state

i = Activity coefficient of conceptual segment i

rI = Total segment number of component I


xI = Mole fraction of component I
rI,i = Number of conceptual segment i containing in component I
xi = Segment mole fraction of conceptual segment i in mixtures

ij = NRTL binary non-randomness factor parameter for


conceptual segments

ij = NRTL binary interaction energy parameter for conceptual


segments

A = Debye-Hckel parameter

= Closest approach parameter, 14.9

Ix = Ionic strength (segment mole fraction scale)


= Average solvent molecular weight, g/mol

= Average solvent density, g/cm3

114 2 Thermodynamic Property Models


NA = Avogadros number
Qe = Absolute electronic charge
= Average solvent dielectric constant

w = Water dielectric constant

rc = Born radius of cationic segment


ra = Born radius of anionic segment

NRTL binary parameters for conceptual segments


The NRTL binary parameters between conceptual molecular segments in are
determined by available VLE and LLE data between reference molecules
defined in NRTLSAC.
Segment (1) x x y- y+ x
Segment (2) y- z z z y+
12 1.643 6.547 -2.000 2.000 1.643

21 1.834 10.949 1.787 1.787 1.834

12 = 21 0.2 0.2 0.3 0.3 0.2

NaCl is used as the reference electrolyte for the conceptual electrolyte


segment e. The NRTL binary parameters between conceptual molecular
segments and the electrolyte segment e are determined from literature data
or preset as follows:
Segment (1) x y- y+ z
Segment (2) e e e e
12 15 12 12 8.885

21 5 -3 -3 -4.549

12 = 21 0.2 0.2 0.2 0.2

Parameters used in ENRTLSAC


Each component can have up to five parameters, rI,i (i = x, y-, y+, z, e),
although only one or two of these parameters are needed for most solvents
and ionic species in practice. Since conceptual segments apply to all species,
these five parameters are implemented together as a binary parameter,
NRTLXY(I, i) where I represents a component index and i represents a
conceptual segment index.

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)

2 Thermodynamic Property Models 115


Others Flory-Huggins term removed

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:

i = Activity coefficient of component i

Vi = Molar volume of component i

id = Hansen solubility parameter of component i for nonpolar


effect

ip = Hansen solubility parameter of component i for polar effect

ih = Hansen solubility parameter of component i for hydrogen-


bonding effect

i = Volume fraction of component i

116 2 Thermodynamic Property Models


xi = Mole fraction of component i
R = Gas constant
T = Temperature
The Hansen model does not require binary parameters. For each component,
it has four input parameters.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DELTAD id x PRESSURE^0.5

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.

First Option Code in Hansen model


0 Hansen volume input by user (default)
Other values Hansen volume calculated by Aspen Plus

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

NRTL (Non-Random Two-Liquid)


The NRTL model calculates liquid activity coefficients for the following
property methods: NRTL, NRTL-2, NRTL-HOC, NRTL-NTH, and NRTL-RK. It is
recommended for highly non-ideal chemical systems, and can be used for VLE

2 Thermodynamic Property Models 117


and LLE applications. The model can also be used in the advanced equation-
of-state mixing rules, such as Wong-Sandler and MHV2.
The equation for the NRTL model is:

for Tlower T Tupper


Where:
Gij =

ij =

ij =

ii = 0

Gii = 1
aij, bij, eij, and fij are unsymmetrical. That is, aij may not be equal to aji, etc.

Recommended cij Values for Different Types of Mixtures


cij Mixtures
0.30 Nonpolar substances; nonpolar with polar non-associated liquids; small
deviations from ideality
0.20 Saturated hydrocarbons with polar non-associated liquids and systems that
exhibit liquid-liquid immiscibility
0.47 Strongly self-associated substances with nonpolar substances

The 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

118 2 Thermodynamic Property Models


Note: If any of bij, dij, or eij is non-zero, absolute temperature units are
assumed for bij, dij, eij, and fij. Otherwise, user input units for temperature are
used. The temperature limits are always interpreted in user input units.
The NRTL-2 property method uses data set 2 for NRTL. All other NRTL
methods use data set 1.

References
H. Renon and J.M. Prausnitz, "Local Compositions in Thermodynamic Excess
Functions for Liquid Mixtures," AIChE J., Vol. 14, No. 1, (1968), pp. 135
144.

NRTL-SAC Model
NRTL-SAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model and extended to handle
electrolytes, but usable in Aspen Plus or Aspen Properties without Aspen
Polymers. NRTL-SAC can be used for fast, qualitative estimation of the
solubility of complex organic compounds in common solvents. It can also be
used as a general activity coefficient model in Aspen Plus, Aspen Properties,
and HYSYS.
Conceptually, the model treats the liquid non-ideality of mixtures containing
complex organic molecules (solute) and small molecules (solvent) in terms of
interactions between three pairwise interacting conceptual segments:
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.

2 Thermodynamic Property Models 119


The conceptual segment contribution approach in NRTL-SAC represents a
practical alternative to the UNIFAC functional group contribution approach.
This approach is suitable for use in the industrial practice of carrying out
measurements for a few selected solvents and then using NRTL-SAC to
quickly predict other solvents or solvent mixtures and to generate a list of
suitable solvent systems.
The NRTL-SAC model calculates liquid activity coefficients.

Note: This is the updated version of NRTL-SAC, represented with property


model GMNRTLS and property method NRTL-SAC. This version does not
require the specification of components as oligomers. For the old version, see
NRTLSAC for Segments/Oligomers and ENRTL-SAC.
For the model equations, see NRTL-SAC Model Derivation.

Parameters used in NRTL-SAC


Each component can have up to five parameters, rx,I, ry-,I, ry+,I, rz,I, and re,I,
representing the equivalent number of segments of each type for the NRTL
activity coefficient model. Only one or two of these molecular parameters are
needed for most solvents in practice. These parameters are implemented
together as pure parameter XYZE with five elements representing these five
parameters. Values for this parameter are available for many common
solvents in the NRTL-SAC databank.
Parameter Symbol Default MDS Lower Upper Limit Units
Name/ Limit
Element
XYZE/1 rx,I
XYZE/2 ry-,I
XYZE/3 ry+,I
XYZE/4 rz,I
XYZE/5 re,I

Electrolytes must be modeled as ion pairs in this system, while the individual
ions are components in the Aspen Physical Property System, so for these ion
pairs, the five parameters are stored in binary parameter BXYZE which has
elements corresponding to those of XYZE.
Parameter 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

The conceptual segment numbers of a cationic component and

an anionic component come from the dissociation of their


corresponding electrolyte component CA, as defined by the chemical equation
describing the dissociation of the electrolyte:

120 2 Thermodynamic Property Models


with

Since an electrolyte component CA can be measured by up to five conceptual

segments , we can calculate ri,C and ri,A as follows for systems of


single electrolyte.

For an electrolyte system where multi-electrolytes may be generated, a


simple mixing rule is used:

where YC is a cationic charge composition fraction and YA is an anionic charge


composition fraction; they are defined as follows:

Notice that electrolyte here is meant to represent an ion-pair composed of a


cationic component and an anionic component in the solutions. The result is
that electrolytes are generated from all possible combinations of ions in the
solution; each generated electrolyte is not necessarily associated with an ion-
pair through the dissociation.

Option Codes in NRTL-SAC


Three option codes are available for NRTL-SAC to select the reference state
and to optionally exclude the Flory-Huggins and long-range interaction terms:

2 Thermodynamic Property Models 121


Option CodeValue Meaning
1 0 Reference state for ions is unsymmetric: infinite dilution in
aqueous solution (default)
2 Reference state for ions is symmetric: pure fused salts
2 0 Flory-Huggins term included (default)
1 Flory-Huggins term removed
3 0 Long-range interaction term included (default)
1 Long-range interaction term removed

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.

NRTL-SAC Reference States


The NRTL-SAC activity coefficient model for component I is composed of the
local composition term, ln Ilc, the Pitzer-Debye-Hckel long-range interaction
term, ln IPDH, and the Flory-Huggins term, IFH:
(1)

This equation needs to be normalized based on the reference states of


molecular and ionic components.

Reference state for molecular components


The reference state for a molecular component is defined as follows:
(2)

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.

Reference state for ionic components


The standard state of pure liquids is hypothetical for ionic components in
electrolyte systems. The symmetric reference state is defined as the pure
fused salt state of each electrolyte component in the system.
However, the conventional reference state for ionic components is the
infinite-dilution activity coefficient in pure water; it is also called the
unsymmetric reference state for ionic components. In NRTL-SAC model, we
will consider both of these reference states; the unsymmetric state is the
default.

122 2 Thermodynamic Property Models


Pure fused salt state of an electrolyte component
For an electrolyte component CA, the pure fused salt state can be defined as
follows:
(3)

(4)

where is the mean ionic activity coefficient of the electrolyte component


and is related to the corresponding cationic and anionic activity coefficients C
and A by this expression:
(5)

where C is the cationic stoichiometric coefficient and A is the anionic


stoichiometric coefficient, and =C+A (one mole of salt releases moles of
ions in solution). They are given by the chemical equation describing the
dissociation of the electrolyte. Therefore Eq. 5 can be written in terms of
charge numbers zC and zA:
(6)

At the pure fused salt state:


(7)

(8)

(9)

The symmetric reference state defined by Eq. 3 is restricted to systems


containing a single electrolyte component. For multi-electrolyte systems, the
symmetric reference state can be generalized from Eq. 3 as follows:
(10)

where I applies to all molecular components in the system. The symmetric


reference state is a molecular-component-free media.

Infinite-dilution aqueous solution


The condition of infinite-dilution solution for ionic components can be written
as follows:
(11)

This condition applies to all ionic components in the solution. In infinite-


dilution aqueous solutions, water must be present and is assumed to
represent the entire solution, so the unsymmetric reference state can be
written as follows:

2 Thermodynamic Property Models 123


(12)

This equation applies to all ionic components in the solution.

NRTL-SAC Local Composition Term


The segment-based excess Gibbs free energy of the local interactions for
systems with multiple molecular segments m and a single electrolyte segment
e (with a single cation segment c and anion segment a) can be written as
follows:
(13)

(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)

We can then rewrite the excess Gibbs free energy as follows:

124 2 Thermodynamic Property Models


(21)

with
(22)

The local composition contribution to the segment activity coefficient can be


calculated as follows:
(23)

The local composition contribution to the activity coefficients for molecular


segments, the cationic segment, and the anionic segment can be calculated
out as follows:
(24
)

(25)

2 Thermodynamic Property Models 125


(26)

The local composition term for the logarithm of the activity coefficient of
component I , before normalization to a chosen reference state, is computed
as the sum of the individual segment contributions.
(27)

Specifically, for non-electrolyte (molecular) components, the activity


coefficients are given as follows:
(28)

For a cationic component, we have


(29)

For an anionic component, we have


(30)

Molecular components
Applying Eq. 1, the normalization for molecular components can be done as
follows:
(31)

where mlc,I is the activity coefficient of the molecular segment m contained in


component I,
(32)

Ionic components with symmetric reference state


Applying Eq. 10, the local composition contribution to the symmetric activity
coefficients for ionic components in multi-electrolyte systems can be
normalized as follows:
(33)

126 2 Thermodynamic Property Models


(34)

(35)

where I applies to all molecular components in the solution and Ix0 is the ionic
strength at the symmetric reference state. In the case that electrolytes are
made up of only the conceptual 1-1 electrolyte segment and none of the
molecular segments, this reference state is equivalent to the molten state of
the conceptual 1-1 electrolyte.

Ionic components with infinite dilution aqueous solution


reference state
Applying Eq. 12, the unsymmetric activity coefficients for ionic components in
aqueous solutions can be normalized as follows:
(36)

(37)

where and are activity coefficients at the infinite dilution aqueous


solution:
(38)

(39)

NRTL-SAC Long-Range Interaction Term


To account for the long-range ion-ion interactions, the model uses the
symmetric Pitzer-Debye-Hckel (PDH) formula (Pitzer, 1986) on the segment
basis:
(40)

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

2 Thermodynamic Property Models 127


molar volume and dielectric constant of the solvent, Qe is the electron charge,
kB is the Boltzmann constant, zi is the charge number of segment i, and Ix0
represents Ix at the reference state. Since the "single 1-1 electrolyte segment
e=ca" is defined in the model, we can obtain:
(43)

For the symmetric reference state,


(44)

And for the unsymmetric reference state,


(45)

The long-range contribution to the activity coefficient of segment i can be


derived as follows:
(46)

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)

The original Debye-Hckel theory is based on a single electrolyte with water


as the solvent. The molar volume v and the dielectric constant for the
single solvent water need to be extended for mixed-solvents based on the
molecular solvent properties; a simple composition average mixing rule is
proposed to calculate them as follows:
(49)

(50)

where S is a solvent component, MS is the solvent molecular weight, and each


sum is over all solvent components in the solution.

128 2 Thermodynamic Property Models


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.
(51)

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)

where I applies to all molecular components in the system.

Ionic components with symmetric reference state


Applying Eq. 10, the symmetric activity coefficients for ionic components from
the long range contribution are given as follows:
(54)

(55)

(56)

where I applies to all molecular components in the solution.

Ionic components with infinite dilution aqueous solution


Applying Eq. 12, the unsymmetric activity coefficients for ionic components
from the long range contribution in aqueous solutions are given as follows:
(57)

(58)

Segment based Born correction term to activity coefficient


If the infinite dilution aqueous solution is chosen as the reference state, we
need to correct the change of the reference state from the mixed-solvent
composition to aqueous solution for the Debye-Hckel term. The Born term
(Robinson and Stokes, 1970; Rashin and Honig, 1985) is used for this
purpose:

2 Thermodynamic Property Models 129


(59)

where ri is the Born radius of segment species i and w is the dielectric


constant of water. GBorn is the Born term correction to the unsymmetric
Pitzer-Debye-Hckel formula Gex,PDH.
The Born correction activity coefficient of component i can be derived as
follows:
(60)

For a molecular segment, the correction to the activity coefficient is zero:


(61)

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)

Activity coefficients given by Eq. 65 are already normalized for molecular


components as well as for ionic components with the infinite-dilution aqueous
solution reference state.

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.

130 2 Thermodynamic Property Models


NRTL-SAC Flory-Huggins Term
We use the Flory-Huggins term to describe the combinatorial term:
(66)

(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)

The contribution to the activity coefficient of component I from the


combinatorial term is thus:
(70)

Molecular components
It is easy to show that activity coefficients for molecular components from the
Flory-Huggins term are normalized; that is
(71)

where I applies to all molecular components in the solution.

Ionic components with symmetric reference state


Applying Eq. 10, the symmetric activity coefficients for ionic components from
the Flory-Huggins term can be carried out as follows:
(72)

(73)

with
(74)

2 Thermodynamic Property Models 131


(75)

(76)

(77)

where I applies to all molecular components in the solution.

Ionic components with infinite dilution aqueous solution


Applying Eq. 12, the unsymmetric activity coefficients for ionic components in
aqueous solutions can be carried out as follows:
(78)

(79)

where and are activity coefficients at the infinite dilution


aqueous solution:
(80)

(81)

Henry Components in NRTL-SAC


Light gases (i.e. Henry components) are usually supercritical at the
temperature and pressure of the system. In that case pure component vapor
pressure is meaningless and therefore the pure liquid state at the
temperature and pressure of the system cannot serve as the reference state.
The reference state for a Henry component is redefined to be at infinite
dilution (that is, xI0) and at the temperature and pressure of the system.
The liquid phase reference fugacity, fI*,l, becomes the Henrys constant for
Henry components in the solution, HI, and the activity coefficient, I, is
converted to the infinite dilution reference state through the relationship:
(82)

where is the infinite dilution activity coefficient of Henry component I


(xI0) in the solution. By this definition I* approaches unity as
xI approaches zero. The phase equilibrium relationship for Henry components
becomes:

132 2 Thermodynamic Property Models


(83)

The Henrys Law is available in all activity coefficient property methods. The
model calculates the Henrys constant for a dissolved gas component in all
solvent components in the mixture:
(84)

(85)

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)

Notice that xH0 applies to all Henry components in the solution.

2 Thermodynamic Property Models 133


NRTLSAC for Segments/Oligomers
This is the original NRTLSAC model added in version 2006, which requires
that components be defined as oligomers. It is retained for compatibility, but
new models should use the NRTL-SAC model.
NRTL-SAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model, usable in Aspen Properties and
Aspen Polymers. NRTL-SAC can be used for fast, qualitative estimation of the
solubility of complex organic compounds in common solvents. 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.
The conceptual segment contribution approach in NRTL-SAC represents a
practical alternative to the UNIFAC functional group contribution approach.
This approach is suitable for use in the industrial practice of carrying out
measurements for a few selected solvents and then using NRTL-SAC to
quickly predict other solvents or solvent mixtures and to generate a list of
suitable solvent systems.
The NRTL-SAC model calculates liquid activity coefficients.
The equation for the NRTL-SAC model is:

with

134 2 Thermodynamic Property Models


G = exp(-)
Where:
I, J = Component index
i, j, m = Conceptual segment indexx, y-, y+, z

I = Activity coefficient of component I

IC = IFH = Flory-Huggins term for combinatorial contribution to I


IR = Ilc = NRTL term for local composition interaction contribution to
I
I = Segment mole fraction of component I

pI = Effective component size parameter

sI and I = Empirical parameters for pI

rI = Total segment number of component I


xI = Mole fraction of component I
rI,m = Number of conceptual segment m containing in component
I
xi = Segment mole fraction of conceptual segment i in mixtures

im = NRTL binary non-randomness factor parameter for


conceptual segments

im = NRTL binary interaction energy parameter for conceptual


segments

2 Thermodynamic Property Models 135


NRTL binary parameters for conceptual segments
The NRTL binary parameters between conceptual segments in NRTLSAC are
determined by available VLE and LLE data between reference molecules
defined above.
Segment 1 x x y- y+ x
Segment 2 y- z z z y+
12 1.643 6.547 -2.000 2.000 1.643

21 1.834 10.949 1.787 1.787 1.834

12 = 21 0.2 0.2 0.3 0.3 0.2

Parameters used in NRTLSAC


Each component can have up to four parameters, rI,x, rI,y-, rI,y+, and rI,z
although only one or two of these molecular parameters are needed for most
solvents in practice. Since conceptual segments apply to all molecules, these
four molecular parameters are implemented together as a binary parameter,
NRTLXY(I, m) where I represents a component (molecule) index and m
represents a conceptual segment index.
In addition, the Flory-Huggins size parameter, FHSIZE , is used in NRTLSAC
to calculate the effective component size parameter, pI. The Flory-Huggins
combinatorial term can be turned off by setting I = 0 for each component in
mixtures.
Parameter Symbol Default MDS Lower Upper Units Comment
Name/ Limit Limit
Element
NRTLXY rI,m Binary,
symmetric
FHSIZE/1 sI 1.0 1E-15 1E15 Unary
FHSIZE/2 I 1.0 -1E10 1E10 Unary

Option codes
The Flory-Huggins term is included by default in the NRTLSAC model. You can
remove this term using the first option code. The table below lists the values
for this option code.
0 Flory-Huggins term included (default)
Others Flory-Huggins term removed

NRTLSAC molecular parameters for common solvents


The molecular parameters are identified for 62 solvents and published.
Solvent name rI,x rI,y- rI,y+ rI,z
ACETIC-ACID 0.045 0.164 0.157 0.217
ACETONE 0.131 0.109 0.513
ACETONITRILE 0.018 0.131 0.883
ANISOLE 0.722
BENZENE 0.607 0.190

136 2 Thermodynamic Property Models


Solvent name rI,x rI,y- rI,y+ rI,z
1-BUTANOL 0.414 0.007 0.485
2-BUTANOL 0.335 0.082 0.355
N-BUTYL-ACETATE 0.317 0.030 0.330
METHYL-TERT-BUTYL-ETHER 1.040 0.219 0.172
CARBON-TETRACHLORIDE 0.718 0.141
CHLOROBENZENE 0.710 0.424
CHLOROFORM 0.278 0.039
CUMENE 1.208 0.541
CYCLOHEXANE 0.892
1,2-DICHLOROETHANE 0.394 0.691
1,1-DICHLOROETHYLENE 0.529 0.208
1,2-DICHLOROETHYLENE 0.188 0.832
DICHLOROMETHANE 0.321 1.262
1,2-DIMETHOXYETHANE 0.081 0.194 0.858
N,N-DIMETHYLACETAMIDE 0.067 0.030 0.157
N,N-DIMETHYLFORMAMIDE 0.073 0.564 0.372
DIMETHYL-SULFOXIDE 0.532 2.890
1,4-DIOXANE 0.154 0.086 0.401
ETHANOL 0.256 0.081 0.507
2-ETHOXYETHANOL 0.071 0.318 0.237
ETHYL-ACETATE 0.322 0.049 0.421
ETHYLENE-GLYCOL 0.141 0.338
DIETHYL-ETHER 0.448 0.041 0.165
ETHYL-FORMATE 0.257 0.280
FORMAMIDE 0.089 0.341 0.252
FORMIC-ACID 0.707 2.470
N-HEPTANE 1.340
N-HEXANE 1.000
ISOBUTYL-ACETATE 1.660 0.108
ISOPROPYL-ACETATE 0.552 0.154 0.498
METHANOL 0.088 0.149 0.027 0.562
2-METHOXYETHANOL 0.052 0.043 0.251 0.560
METHYL-ACETATE 0.236 0.337
3-METHYL-1-BUTANOL 0.419 0.538 0.314
METHYL-BUTYL-KETONE 0.673 0.224 0.469
METHYLCYCLOHEXANE 1.162 0.251
METHYL-ETHYL-KETONE 0.247 0.036 0.480
METHYL-ISOBUTYL-KETONE 0.673 0.224 0.469
ISOBUTANOL 0.566 0.067 0.485

2 Thermodynamic Property Models 137


Solvent name rI,x rI,y- rI,y+ rI,z
N-METHYL-2-PYRROLIDONE 0.197 0.322 0.305
NITROMETHANE 0.025 1.216
N-PENTANE 0.898
1-PENTANOL 0.474 0.223 0.426 0.248
1-PROPANOL 0.375 0.030 0.511
ISOPROPYL-ALCOHOL 0.351 0.070 0.003 0.353
N-PROPYL-ACETATE 0.514 0.134 0.587
PYRIDINE 0.205 0.135 0.174
SULFOLANE 0.210 0.457
TETRAHYDROFURAN 0.235 0.040 0.320
1,2,3,4-TETRAHYDRONAPHTHALENE 0.443 0.555
TOLUENE 0.604 0.304
1,1,1-TRICHLOROETHANE 0.548 0.287
TRICHLOROETHYLENE 0.426 0.285
M-XYLENE 0.758 0.021 0.316
WATER 1.000
TRIETHYLAMINE 0.557 0.105
1-OCTANOL 0.766 0.032 0.624 0.335

Reference
C.-C. Chen and Y. Song, "Solubility Modeling with a Nonrandom Two-Liquid
Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004).

Using NRTLSAC
NRTLSAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model, usable in Aspen Properties and
Aspen Polymers. NRTLSAC can be used for fast, qualitative estimation of the
solubility of complex organic compounds in common solvents. For more
information about the model, see NRTLSAC for Segments/Oligomers.

Note: A newer version of NRTL-SAC comes with its own property method
named NRTL-SAC and does not require the specification of a method and
oligomer components as described below.
The NRTLSAC model for Segments/Oligomers in the Aspen Physical Property
System is a liquid activity coefficient model called NRTLSAC. To specify it:
1 On the 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.

138 2 Thermodynamic Property Models


On the Methods | Parameters | Binary Interaction | NRTL-1 form, enter
the binary parameters between conceptual segments. In the following
example, the conceptual segments are named X, Y-, Y+, and Z.
Segment 1 X X Y- Y+ X
Segment 2 Y- Z Z Z Y+
AIJ 1.643 6.547 -2.000 2.000 1.643
AJI 1.834 10.949 1.787 1.787 1.834
CIJ 0.2 0.2 0.3 0.3 0.2

On the Methods | Parameters | Binary Interaction | NRTLXY-1 form,


enter a non-zero value for at least one of the four parameters for each
component.

Pitzer Activity Coefficient Model


The Pitzer model was developed as an improvement upon an earlier model
proposed by Guggenheim ( 1935, 1955). The earlier model worked well at low
electrolyte concentrations, but contained discrepancies at higher
concentrations (>0.1M). The Pitzer model resolved these discrepancies,
without resorting to excessive arrays of higher-order terms.

Important: The model can be used for aqueous electrolyte systems, up to 6


molal ionic strength. It cannot be used for systems with any other solvent or
mixed solvents. Any non-water molecular components are considered solutes
and treated as Henry components.
This section provides theoretical background for the model. All model
equations and parameter requirements are included.
The Pitzer model is commonly used in the calculation of activity coefficients
for aqueous electrolytes up to 6 molal ionic strength. Do not use this model if
a non-aqueous solvent exists. Henry's law parameters are required for all
other components in the aqueous solution. The model development and
working equations are provided in the following sections. Parameter
conversion between the Pitzer notation and our notation is also provided.
The Pitzer model in the Aspen Physical Property System involves user-
supplied parameters that are used in the calculation of binary and ternary
parameters for the electrolyte system.
Five elements (P1 through P5) account for the temperature dependencies of

parameters (0), (1), (2), (3), C , , and . These parameters follow the
temperature dependency relation:

Where:
Tref = 298.15 K
The user must:
Supply these elements for the binary parameters using a Methods |
Parameters | Binary | T-Dependent form.

2 Thermodynamic Property Models 139


Supply these elements for on the Methods | Parameters |
Electrolyte Ternary form.
Specify Comp ID i and Comp ID j (and Comp ID k for ) on these forms,
using the same order that appears on the Components Specifications
Selection sheet.
The parameters are summarized in the following table. There is a Pitzer
parameter databank in the Aspen Physical Property System (see Physical
Property Data).
Parameter Provides No. of Default MDS Units
Name P1 - P5 for Elements
Cation-Anion Parameters
GMPTB0 (0) 5 0 x

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 =

(pair potential of mean force)

140 2 Thermodynamic Property Models


With:
zi = Charge of ion i
Qe = Electron charge

j(r) = Average electric potential for ion j

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

2 Thermodynamic Property Models 141


evaluated using experimental data. He selected mathematical expressions for
these parameters that best fit experimental data.
Pitzer's model can be applied to aqueous systems of strong electrolytes and
to aqueous systems of weak electrolytes with molecular solutes. These
applications are discussed in the following section.
In the Aspen Physical Property System, this model is applied using the
reference state of infinite dilution solution in water for non-water molecular
solutes and ionic species. The properties such as DHAQFM are obtained at 25
C and 1 atm.

Application of the Pitzer Model to Aqueous Strong


Electrolyte Systems
Pitzer modified his basic equation to make it more useful for data correlation
of aqueous strong electrolytes. He defined a set of more directly observable
parameters to represent combinations of the second and third virial
coefficients. The modified Pitzer equation is:
(3)

zi = Charge of ion i

Subscripts c, c', and a, a' denote cations and anions of the solution. B, C, ,
and are interaction parameters. f(I) is an electrostatic term as a function of
ionic strength. The cation-anion parameters B and C are characteristic for an
aqueous single-electrolyte system. These parameters can be determined by
the properties of pure (apparent) electrolytes. B is expressed as a function of
(0) and (1), or of (0), (2), and (3) (see equations 11 through 15).
The parameters and are for the difference of interaction of unlike ions of
the same sign from the mean of like ions. These parameters can be measured
from common-ion mixtures. Examples are NaCl + KCl + H2O or NaCl + NaNO3
+ H2O (sic, Pitzer, 1989). These terms are discussed in detail later in this
section.
Frst and Renon (1982) propose the following expression as the Pitzer
equation for the excess Gibbs energy:
(4)

142 2 Thermodynamic Property Models


The difference between equations 3 and 4 is that Pitzer orders cation before
anions. Frst and Renon do not. All summations are taken over all ions i and j
(both cations and anions). This involves making the parameter matrices Bij,
Cij, ij, and ijk symmetric, as follows:
Second-order parameters are written Bij if i and j are ions of different sign. Bij
= 0 if the sign of zi = sign of zj, and Bii = 0. Since cations are not ordered
before anions, Bij = Bji. This eliminates the 2 in the second term in brackets in
Pitzer's original expression (equation 3). Second-order parameters are written
ij if i and j are ions of the same sign. Thus ij = 0 if the sign of zi is different
from the sign of zj, and ii = 0 with ij = ji.
Third-order parameters are written Cij if i and j are ions with different signs.
Cij = 0 if the sign of zi = sign of zj, and Cii = 0 with Cij = Cji. The factor of 2 in
the fifth bracketed term in Pitzer's original expression (equation 3) becomes

1/2 in equation 4. The matrix C is symmetric and is extended to all


ions to make the equation symmetric.

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)

Calculation of Activity Coefficients


The natural logarithm of the activity coefficient for ions is calculated from
equation 4a to give:

2 Thermodynamic Property Models 143


(5)

Where is neglected and ij and 'ij are the electrostatic unsymmetric mixing
effects:

The X parameters are calculated differently on the option code.


For option code = 1, there is no unsymmetric mixing correction term:

For option code = 0 (default), the unsymmetric mixing correction term is in


polynomial form:

For option code = 1, the unsymmetric mixing correction term is in integral


form:

144 2 Thermodynamic Property Models


For water the logarithm of the activity coefficient is calculated similarly, as
follows:
Applying:

to equation 3 and using:

Where Nw = moles water, gives:


(6)

f(I), the electrostatic term, is expressed as a function of ionic strength I :


(7)

I, the ionic strength, is defined as:


(8)

Taking the derivative of equation 7 with respect to I, gives:


(9)

So that:
(10)

This equation is used in equation 6. In equations 7 and 9, is the usual Debye-


Hckel constant for the osmotic coefficient, determined from:

2 Thermodynamic Property Models 145


(11)

Where:
NA = Avogadro's constant
dw = Water density

B = Dielectric constant of solvent B

b is an adjustable parameter, which has been optimized in this model to equal


1.2.
B and B' need expressions so that equations 5 and 6 can completely be solved
for the activity coefficients. The parameter B is determined differently for
different electrolyte pairings. For 1-n electrolytes (1-1, 1-2, 2-1, and so on)
the following expression gives the parameter B:
(12)

with 1=2.0.
For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), B is determined
by the following expression:
(13)

with 2 = 12.0 and 3 = 1.4.


By taking appropriate derivatives, expressions for B' can be derived for 1n
electrolytes:
(14)

and for n-m electrolytes:


(15)

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:

146 2 Thermodynamic Property Models


(16)

For water as a solvent:


(17)

Where:

m = Activity coefficient (molality scale)

x = Activity coefficient (mole fraction scale)

Application of the Pitzer Model to Aqueous


Electrolyte Systems with Molecular Solutes
In aqueous weak electrolyte systems with molecular solutes, the second and
third virial coefficients in the basic Pitzer equation for molecule-ion and
molecule-molecule interactions must be considered. The following extensions
of Pitzer's interaction parameters are made.
The second-order parameters Bij are extended to include molecule-molecule
and molecule-ion interaction parameters.

The third-order parameters ijk are extended to molecule-molecule-molecule


interactions. The following expressions relate ijk to Pitzer's original ijk:

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.

2 Thermodynamic Property Models 147


Parameter Conversion
For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), the parameter
(3) corresponds to Pitzer's (1). (2) is the same in both the Aspen Physical
Property System and original Pitzer models. Pitzer refers to the n-m
electrolyte parameters as (1), (2), (0). (0) and (2) retain their meanings in
both models, but Pitzer's (1) is (3) in the Aspen Physical Property System. Be
careful to make this distinction when entering n-m electrolyte parameters.

Pitzer often gives values of (0), (1), (2), (3), and C that are corrected by
some factors (see Pitzer and Mayorga (1973) for examples). These factors
originate from one of Pitzer's earlier expressions for the excess Gibbs energy:
(18)

Where:
=

na = Mole number of anions


nc = Mole number of cation

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

Perform the necessary conversions and enter the parameters as:


= 0.3524

= 1.6815

= 0.00520

Parameter Sources
Binary and ternary parameters for the Pitzer model for various electrolyte
systems are available from Pitzer's series on the thermodynamics of
electrolytes. These papers and the electrolyte parameters they give are:

148 2 Thermodynamic Property Models


Reference Parameters available

(Pitzer, 1973) Binary parameters ((0), (1), C ) for 13
dilute aqueous electrolytes
(Pitzer and Mayorga, 1973) Binary parameters for 1-1 inorganic
electrolytes, salts of carboxylic acids (1-1),
tetraalkylammonium halids, sulfonic acids
and salts, additional 1-1 organic salts, 2-1
inorganic compounds, 2-1 organic
electrolytes, 3-1 electrolytes, 4-1 and 5-1
electrolytes
(Pitzer and Mayorga, 1974) Binary parameters for 2-2 electrolytes in
water at 25C
(Pitzer and Kim, 1974) Binary and ternary parameters for mixed
electrolytes, binary mixtures without a
common ion, mixed electrolytes with three
or more solutes
(Pitzer, 1975) Ternary parameters for systems mixing
doubly and singly charged ions
(Pitzer and Silvester, 1976) Parameters for phosphoric acid and its buffer
solutions
(Pitzer, Roy and Silvester, 1977) Parameters and thermodynamic properties
for sulfuric acid
(Silvester and Pitzer, 1977) Data for NaCl and aqueous NaCl solutions
(Pitzer, Silvester, and Peterson, 1978) Rare earth chlorides, nitrates, and
perchlorates
(Peiper and Pitzer, 1982) Aqueous carbonate solutions, including
mixtures of sodium carbonate, bicarbonate,
and chloride
(Phutela and Pitzer, 1983) Aqueous calcium chloride
(Conceicao, de Lima, and Pitzer, 1983) Saturated aqueous solutions, including
mixtures of sodium chloride, potassium
chloride, and cesium chloride
(Pabalan and Pitzer, 1987) Parameters for polynomial unsymmetric
mixing term
(Kim and Frederick, 1988) Parameters for integral unsymmetric mixing
term

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.

2 Thermodynamic Property Models 149


Kim, H. and W.J. Frederick, "Evaluation of Pitzer Ion Interaction Parameters
of Aqueous Mixed Electrolyte Solution at 25C, Part 2: Ternary Mixing
Parameters," J. Chem. Eng. Data, 33, (1988), pp. 278-283.
Pabalan, R.T. and K.S. Pitzer, "Thermodynamics of Concentrated Electrolyte
Mixtures and the Prediction of Mineral Solubilities to High Temperatures for
Mixtures in the system Na-K-Mg-Cl-SO4-OH-H2O," Geochimica Acta, 51,
(1987), pp. 2429-2443.
Peiper, J.C. and K.S. Pitzer, "Thermodynamics of Aqueous Carbonate
Solutions Including Mixtures of Sodium Carbonate, Bicarbonate, and
Chloride," J. Chem. Thermodynamics, Vol. 14, (1982), pp. 613-638.
Phutela, R.C. and K.S. Pitzer, "Thermodynamics of Aqueous Calcium
Chloride," J. Solution Chem., Vol. 12, No. 3, (1983), pp. 201-207.
Pitzer, K.S., "Thermodynamics of Electrolytes. I. Theoretical Basis and
General Equations, " J. Phys. Chem., Vol. 77, No. 2, (1973), pp. 268-277.
Pitzer, K.S., J. Solution Chem., Vol. 4, (1975), p. 249.
Pitzer, K.S., "Fluids, Both Ionic and Non-Ionic, over Wide Ranges of
Temperature and Composition," J. Chen. Thermodynamics, Vol. 21, (1989),
pp. 1-17. (Seventh Rossini lecture of the commission on Thermodynamics of
the IUPAC, Aug. 29, 1988, Prague, ex-Czechoslovakia).
Pitzer, K.S. and J.J. Kim, "Thermodynamics of Electrolytes IV; Activity and
Osmotic Coefficients for Mixed Electrolytes," J.Am. Chem. Soc., Vol. 96
(1974), p. 5701.
Pitzer, K.S. and G. Mayorga, "Thermodynamics of Electrolytes II; Activity and
Osmotic Coefficients for Strong Electrolytes with One or Both Ions Univalent,"
J. Phys. Chem., Vol. 77, No. 19, (1973), pp. 2300-2308.
Pitzer, K.S. and G. Mayorga, J. Solution Chem., Vol. 3, (1974), p. 539.
Pitzer, K.S., J.R. Peterson, and L.F. Silvester, "Thermodynamics of
Electrolytes. IX. Rare Earth Chlorides, Nitrates, and Perchlorates, "J. Solution
Chem., Vol. 7, No. 1, (1978), pp. 45-56.
Pitzer, K.S., R.N. Roy, and L.F. Silvester, "Thermodynamics of Electrolytes 7
Sulfuric Acid," J. Am. Chem. Soc., Vol. 99, No. 15, (1977), pp. 4930-4936.
Pitzer, K.S. and L.F. Silvester, J. Solution Chem., Vol. 5, (1976), p. 269.
Silvester, L.F. and K.S. Pitzer, "Thermodynamics of Electrolytes 8 High-
Temperature Properties, Including Enthalpy and Heat Capacity, With
Application to Sodium Chloride," J. Phys. Chem., Vol. 81, No. 19, (1977), pp.
1822-1828.

Polynomial Activity Coefficient


This model represents activity coefficient as an empirical function of
composition and temperature. It is used frequently in metallurgical
applications where multiple liquid and solid solution phases can exist.
The equation is:

150 2 Thermodynamic Property Models


Where:
Ai =

Bi =

Ci =

Di =

Ei =

For any component i, the value of the activity coefficient can be fixed:

i = fi
This model is not part of any property method. To use it:
1 On the 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

Note: If you specify GMPLYP on the Methods | Parameters | Pure


Component | T-Dependent sheet, you can only enter the first 12 elements.
If you want to specify values for elements 13 to 15, you should go to the
Customize | Add-Input | Add After sheet and enter the values of all 15
elements as in the following example:

2 Thermodynamic Property Models 151


PROP-DATA GMPLYP-1
IN-UNITS SI
PROP-LIST GMPLYP
PVAL WATER 0.0 1.5 0.0 &
0.0 0.0 0.0 &
0.0 0.0 0.0 &
0.0 0.0 0.0 &
0.0 16. 0.0

Redlich-Kister
This model calculates activity coefficients. It is a polynomial in the difference
between mole fractions in the mixture. It can be used for liquid and solid
mixtures (mixed crystals).
The equation is:

Where:
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

152 2 Thermodynamic Property Models


Reference
J. P. Novak, J. Matous, and J. Pick, Studies in Modern Thermodynamics,
Volume 7: Liquid-Liquid Equilibria, Appendix 4, Elsevier, 1987.

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 =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TC Tci x 5.0 2000.0 TEMPERATURE
3 5
DELTA i x 10 10 SOLUPARAM
*,CVT
VLCVT1 Vi x 0.0005 1.0 MOLE-
VOLUME
GMSHVL Vi*,l x 0.01 1.0 MOLE-
VOLUME

GMSHXL kij 0.0 x -5 5

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:

Where kij is a binary parameter:

2 Thermodynamic Property Models 153


For any component i, the value of the activity coefficient can be fixed:

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).

Symmetric and Unsymmetric Electrolyte


NRTL Activity Coefficient Model
The Symmetric Electrolyte NRTL activity coefficient model (GMENRTLS) uses a
symmetric reference state for ions as pure fused salts, rather than infinite
dilution in aqueous solution. This basis is easier to use for nonaqueous and
mixed-solvent systems, and eliminates the need to introduce water into
otherwise water-free systems. It also allows the model to reduce to the
standard NRTL model when there are no electrolytes in the system. The
ENRTL-SR property method is based on this model.
Chemical constants, enthalpy, and Gibbs free energy are calculated with
respect to the symmetric ionic reference state.
The Unsymmetric Electrolyte NRTL activity coefficient model (GMENRTLQ)
uses the same equations as GMENRTLS, but the unsymmetric reference state
for ions (infinite dilution in aqueous solution). The ENRTL-RK property method
is based on this model. Unlike the original Electrolyte NRTL activity coefficient
model, GMENRTLQ is also used to calculate enthalpy and Gibbs free energy
from thermodynamics based on the unsymmetric ionic reference state.
These models also handle zwitterions.

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

154 2 Thermodynamic Property Models


ca,m where ca represents an ion pair), and electrolyte-electrolyte pairs (ca,ca'
= ca',ca and ca,c'a = c'a,ca while ca,ca' ca',ca and ca,c'a c'a,ca)
The parameters for ion pairs are temperature-dependent:

where .
The NRTL parameters are used for molecule-molecule parameters, with
temperature dependence:

The temperature dependency of the dielectric constant is given by:

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:

2 Thermodynamic Property Models 155


Parameter Symbol No. of Default MDS Units
Name Elements
Dielectric Constant Unary Parameters
CPDIEC a 1
b 1 0
ref
T 1 298.15 TEMPERATURE
Ionic Born Radius Unary Parameters
RADIUS ri 1 3x10-10 LENGTH
Molecule-Molecule Binary Parameters
NRTL/1 aij 0 x
aji 0 x
NRTL/2 bij 0 x TEMPERATURE
bji 0 x TEMPERATURE
NRTL/3 cij=cji .3 x
NRTL/4 dij=dji 0 x TEMPERATURE
NRTL/5 eij 0 x TEMPERATURE
eji 0 x TEMPERATURE
NRTL/6 fji 0 x TEMPERATURE
fji 0 x TEMPERATURE
Electrolyte-Molecule Pair Parameters
GMENCC Cca,m 1 0 x
Cm,ca 1 0 x
GMENCD Dca,m 1 0 x TEMPERATURE
Dm,ca 1 0 x TEMPERATURE
GMENCE Eca,m 1 0 x
Em,ca 1 0 x
GMENCN ca,m = m,ca 1 .2 x
Electrolyte-Electrolyte Pair Parameters
GMENCC Cca,c'a 1 0 x
Cc'a,ca 1 0 x
Cca,ca' 1 0 x
Cca',ca 1 0 x
GMENCD Dca,c'a 1 0 x TEMPERATURE
Dc'a,ca 1 0 x TEMPERATURE
Dca,ca' 1 0 x TEMPERATURE
Dca',ca 1 0 x TEMPERATURE
GMENCE Eca,c'a 1 0 x
Ec'a,ca 1 0 x
Eca,ca' 1 0 x
Eca',ca 1 0 x
GMENCN ca,c'a = c'a,ca 1 .2 x

ca,ca' = ca',ca 1 .2 x

156 2 Thermodynamic Property Models


Zwitterions in Symmetric and Unsymmetric
Electrolyte NRTL
The Symmetric and Unsymmetric Electrolyte NRTL models support
zwitterions, compounds with both positive and negative charges but net
charge of zero. Zwitterions are defined as:
Components of type Conventional, similar to solvents
Parameter ZWITTER set to 1; all other components in the Aspen Physical
Property System default to zero for ZWITTER
Parameter PLXANT/1 less than -1.0E10 so that they are non-volatile.
Zwitterions are handled as follows:
A zwitterion interacts with other molecular species through NRTL
parameters only, excluding any interactions through Henry constants and
pair parameters.
The activity coefficient is calculated as a solute.
The contribution from zwitterions to the solution enthalpy and Gibbs free
energy are calculated as solutes using the infinite dilution heat capacity
model CPAQ0, DGAQFM, and DHAQFM.

Working Equations for Symmetric and


Unsymmetric Electrolyte NRTL
The symmetric and unsymmetric electrolyte NRTL models have two
contributions, one from local interactions that exist at the immediate
neighbourhood of any species, and the other from the long-range ion-ion
interactions that exist beyond the immediate neighbourhood of an ionic
species. To account for the local interactions, the model uses the electrolyte
NRTL expression. To account for the long-range interactions, the model uses
the Pitzer-Debye-Hckel (PDH) formula (Pitzer, 1980, 1986). The following
equation is the basis of the electrolyte NRTL model for the excess Gibbs free
energy of electrolyte systems:
(1)

The excess Gibbs free energy Gmex is defined as:


(2)

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.

The activity coefficient i of component i can be derived from Eq. 1 as follows:


(3)

or

2 Thermodynamic Property Models 157


(4)

Each of these terms will be discussed in subsequent sections.

Reference States in Electrolyte Systems


The activity coefficient needs to be normalized by choosing a reference state
for any molecular and ionic component, respectively.

Reference state for molecular components


The reference state for a molecular component m is defined as follows:
(5)

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.

Reference state for ionic components


The standard state of pure liquids is hypothetical for ionic components in
electrolyte systems. Instead, the symmetric reference state is defined as the
pure fused salt state of each electrolyte component in the system.
However, the conventional reference state for ionic components is the
infinite-dilution activity coefficients; it is also called the unsymmetric
reference state for ionic components.
GMENRTLS uses the symmetric reference state, while GMENRTLQ uses the
unsymmetric reference state.

Pure fused salt state of an electrolyte component


For an electrolyte component ca, the pure fused salt state can be defined as
follows:
(6)

(7)

Where is the mean ionic activity coefficient of the electrolyte component


and is related to the corresponding cationic and anionic activity coefficients c
and a by this expression:
(8)

where c is the cationic stoichiometric coefficient and a is the anionic


stoichiometric coefficient, and =c+a (one mole of salt releases moles of
ions in solution). They are given by the chemical equation describing the
dissociation of the electrolyte:

158 2 Thermodynamic Property Models


(9)

with
(10)

Therefore Eq. 4 can be written in terms of charge numbers zc and za:


(11)

At the pure fused salt state, the total moles of ionic components (for one
mole of salt) are:

=c+a (12)

therefore
(13)

(14)

(15)

The symmetric reference state defined by Eq. 6 is restricted to systems


containing a single electrolyte component. For multi-electrolyte systems, the
symmetric reference state can be generalized from Eq. 6 as follows:
(16)

where m applies to all molecular components in the system. The symmetric


reference state is a molecular-component-free medium.

Infinite-dilution aqueous solution


The condition of infinite-dilution aqueous solution for ionic components can be
written as follows:
xc=xa=0 (17)
This condition applies to all ionic components in the solution, and water must
be present in the solution for this reference state. In terms of the activity
coefficients for ionic components, the condition for the aqueous solution as
the unsymmetric reference state can be written as follows (where w=water):
(18)

This equation applies to all ionic components in the solution.

2 Thermodynamic Property Models 159


Local Interaction Term
In an electrolyte system, all component species can be categorized as one of
three types: molecular species (solvents), m; cationic species (cations), c;
and anionic species (anions), a. The model assumes that there are three
types of local composition interactions. The first type consists of a central
molecular species with other molecular species, cationic species, and anionic
species in the immediate neighbourhood. Here, local electroneutrality is
maintained. The other two types are based on the like-ion repulsion
assumption and have either a cationic or anionic species as the central
species. They also have an immediate neighbourhood consisting of molecular
species and oppositely charged ionic species. Accordingly, the excess Gibbs
energy from local interactions for an electrolyte system can be written as
follows:
(19
)

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)

The contribution to the activity coefficient of component i can be derived as


follows:
(24)

The results are:

160 2 Thermodynamic Property Models


(25)

(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)

However, as seen in the preceding equations, we need these parameters for


molecule-molecule, molecule-cation, molecule-anion, and cation-anion pairs.
The molecule-molecule parameters are given directly by the model's
adjustable binary parameters. The remaining parameters cm, am, mc, ma,
ca, ac, cm, am, mc, ma, ca, and ac, are calculated from these parameters.

2 Thermodynamic Property Models 161


The parameters for pairs involving cations and anions are calculated from
the adjustable binary parameters by applying a simple composition-average
mixing rule.
(29)

(30)

(31)

(32)

where Yc is a cationic charge composition fraction and Ya is an anionic charge


composition fraction, defined as follows:
(33)

(34)

G for these pairs is calculated the same way:


(35)

(36)

(37)

(38)

(39)

(40)

And then the binary parameters are calculated from G using Eq. 23:
(41)

162 2 Thermodynamic Property Models


Normalized contributions to activity coefficients
From Eq. 5, it is easy to show that the local interaction contributions to
activity coefficients for all molecular components are normalized; that is
(42)

for all molecular components m in the system.


For ionic components with symmetric reference state, apply Eq. 16 to find:
(43)

(44)

(45)

(46)

(47)

(48)

where xm0 applies to all molecular components in the solution.


For ionic components with infinite-dilution aqueous solution as reference
state, apply Eq. 18 to get:
(49)

(50)

where and are local interaction contributions to activity


coefficients at infinite dilution aqueous solution:

2 Thermodynamic Property Models 163


(51)

(52)

Long-Range Interaction Term


To account for the long-range ion-ion interactions, the Symmetric and
Unsymmetric Electrolyte NRTL models use the symmetric Pitzer-Debye-Hckel
(PDH) formula (Pitzer, 1986):
(53)

with
(54)

(55)

where n is the total mole number of the solution, A is the Debye-Hckel


parameter, Ix is the ionic strength, is the closest approach parameter, NA is
Avogadro's number, vs is the molar volume of the solvent, Qe is the electron
charge, s is the dielectric constant of the solvent, kB is the Boltzmann
constant, zi is the charge number of component i, and Ix0 represents Ix at the
reference state.
For the unsymmetric reference state, Ix0 = 0.
For the symmetric reference state, the Debye-Hckel theory is originally
based on a single electrolyte with water as the solvent. Therefore, we can
obtain Ix0 from Eqs. 13 and 14:
(56)

For multi-electrolyte systems with mixed-solvents, Ix0 can take this form:
(57)

(58)

164 2 Thermodynamic Property Models


(59)

so that
(60)

where xm0 applies to all molecular components in the solution. This


definition ensures that the excess Gibbs free energy from the long range
interactions will be zero at the symmetric reference state regardless of how
many electrolytes are present in the solution.
The contribution to the activity coefficient from component i can be derived
as:
(61)

For a solvent component, this is:


(62)

For a cation or anion component:


(63)

For the unsymmetric reference state:


(64)

And for the symmetric reference state:


(65)

(66)

2 Thermodynamic Property Models 165


(67)

or
(68)

(69)

The Debye-Hckel theory is original based on a single electrolyte with water


as the solvent. The molar volume vs and the dielectric constant s for the
single solvent need to be extended for mixed-solvents; a simple composition
average mixing rule is adequate to calculate them as follows:
(70)

(71)

where s is a solvent component in the mixture and Msis the solvent molecular
weight. Each sum is over all solvent components in the solution.

Born term correction


If the infinite dilution aqueous solution is chosen as the reference state, we
need to correct the the Debye-Hckel term for the change of the reference
state from the mixed-solvent composition to aqueous solution. The Born term
(Robinson and Stokes, 1970; Rashin and Honig, 1985) is used for this
purpose:
(72)

where NA is the Avogadro constant and R is the gas constant. is the


Born term correction to the unsymmetric Pitzer-Debye-Hckel formula,

, and w is the dielectric constant of water, and ri is the Born radius


of species i.
The Born contribution to the activity coefficient of component i can be derived
as follows:

166 2 Thermodynamic Property Models


(73)

For a cation or anion component, this is:


(74)

The correction to the activity coefficient for a solvent component is zero:


(75)

Henry Components in the Symmetric and


Unsymmetric Electrolyte NRTL Models
Light gases (Henry components) are usually supercritical at the temperature
and pressure of the system. In that case, pure component vapor pressure is
meaningless and therefore the pure liquid state at the temperature and
pressure of the system cannot serve as the reference state. The reference
state for a Henry component is redefined to be at infinite dilution (that is, at
xi0) and at the temperature and pressure of the system.
The liquid phase reference fugacity, fi*,l, becomes the Henrys constant for
Henry components in the solution, Hi, and the activity coefficient, i, is
converted to the infinite dilution reference state through the relationship:
(76)


where i is the infinite dilution activity coefficient of Henry component i
(xi0) in the solution.

By this definition i* approaches unity as xi approaches zero. The phase


equilibrium relationship for Henry components becomes:
(77)

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)

2 Thermodynamic Property Models 167



where His and is are the Henrys constant and the infinite dilution activity
coefficient of the dissolved gas component i in the solvent component s (xi0
and xs1), respectively.
Since ionic species exist only in the liquid phase and therefore do not
participate directly in vapor-liquid equilibria, the activities of Henry
components are mainly through the local interactions with solvents. We can
calculate the activity coefficients for Henry components as follows:
(80)

(81)

(82)

where xh0 applies to all Henry components in the solution.

Activity Coefficient Basis for Henry Components


Regardless of the reference state for ionic components, there are two

possibilities for the basis of unsymmetric activity coefficients h of Henry
components: aqueous and mixed-solvent. This can be specified on the Setup
| Calculation Options | Reactions sheet. Mixed-solvent is the default.

For mixed-solvent basis, h is calculated as follows:


(83)

where xh0 applies to all Henry components and xi0 to all ionic
components in the solution.
For aqueous basis, the unsymmetric activity coefficients of Henry components
are calculated as follows:
(84)

Electrolyte Chemical Equilibria


In determining the composition of an electrolyte system, it is important to
know the equilibrium constants of the reactions taking place. An equilibrium
constant is expressed as the product of the activity of each species raised to
its stoichiometric coefficients. Two different scales are used in Aspen Plus: the
molality scale and the mole fraction scale but both are based on aqueous
electrolyte chemical equilibrium. For instance, the equilibrium constant for the
mole fraction scale in Aspen Plus is written in one of these:
(85)

(86)

168 2 Thermodynamic Property Models


Where:
K = Equilibrium constant
xw = Water mole fraction

w = Water activity coefficient

xs = Non-water solvent mole fraction

s = Non-water solvent activity coefficient

xi = Mole fraction of solute component (Henry or


ion)

i* = Unsymmetric activity coefficient of solute


component

i = Stoichiometric coefficient

The above equations are limited to aqueous electrolyte chemical equilibria


only. Therefore, the chemical constants in Aspen Plus databanks for
electrolyte systems with infinite dilution aqueous reference state cannot be
used for electrolyte systems with the symmetric reference state for ionic
components.
The chemical constants for electrolyte systems with the symmetric reference
state can be written in these forms:
(87)

(88)

where i indicates a molecular or ionic component and h represents a Henry


component. Eq. 83 or 84 is used for calculation of the unsymmetric activity
coefficients of Henry components. However, the calculation for the activity
coefficients of ionic components is carried out with the symmetric reference
state.

Other Thermophysical Properties


The activity coefficient model can be related to other properties through
fundamental thermodynamic equations. These properties (called excess liquid
functions) are relative to the ideal liquid mixture at the same condition:
Excess molar liquid Gibbs free energy
(89)

Excess molar liquid enthalpy


(90)

Excess molar liquid entropy

2 Thermodynamic Property Models 169


(91)

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)

Where is the liquid Gibbs free energy of mixing; it is defined as the


difference between the Gibbs free energy of the mixture and that of the pure

component and is the ideal Gibbs free energy of mixing. Once the
excess liquid functions are known, the thermodynamic properties of liquid
mixtures can be computed as follows:
(95)

(96)

(97)

where Hil and Hiig are the enthalpy and ideal gas enthalpy of component i at
the system conditions. Similarly, Gil and Giig are the Gibbs free energy and
ideal gas Gibbs free energy of component i at the system conditions. In Aspen
Plus, both Hiig and Giig are computed by the expressions:
(98
)

(99
)

170 2 Thermodynamic Property Models


where is the standard enthalpy of formation of ideal gas at

, is the ideal gas heat capacity, and is the

standard Gibbs free energy of formation of ideal gas at .


However, the above equations are directly not applicable to mixtures
containing ionic components because the ideal gas model becomes invalid for
ionic components.
The formulation to calculate the enthalpy and Gibbs free energy for
electrolyte systems can be carried out as follows:
(100)

(101)

(102)

where indexes s, h, and ca are meant to represent the contributions from


solvents, Henry components and ionic components, respectively.

Solvents
The contribution from solvents can be written as follows:
(103)

(104)

(105)

(106)

(107)

(108)

where is the liquid fugacity coefficient of pure solvent


component i, pisat is the vapor pressure of pure component at the system
temperature T, iv is the vapor fugacity coefficient of pure component at T
and pisat (normally calculated from an equation-of-state model), and

2 Thermodynamic Property Models 171


is the Poynting pressure correction from pisat to p,
l
and Vi is the liquid molar volume at T and p.

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)

172 2 Thermodynamic Property Models


(121)

where Hiref and Giref are the enthalpy and Gibbs free energy of ionic
component i at the system conditions with a specified reference state
(symmetric or unsymmetric).
The property calculations for solvents and Henry components are the same
when the reference state is changed. Only for ionic components do the
property methods need to be specified with a reference state. The methods
with the unsymmetric reference state are available already in Aspen Plus and
Aspen Properties. New methods are needed only for the symmetric reference
state. Overall, the calculated total enthalpy or Gibbs free energy for the same
electrolyte solution should be the same, regardless of the reference state
specified.
Enthalpy and Gibbs free energy of ionic components with the symmetric
reference state can be written as follows:
(122)

(123)

where and are enthalpy and Gibbs free energy of ionic component
i with the unsymmetric reference state, respectively, and available already in
Aspen Plus and Aspen Properties. Hi and Gi are the new contributions from
the symmetric reference state.

The unsymmetric enthalpy for an ionic component is calculated from

the infinite dilution aqueous phase heat capacity as follows:


(124)

where Tref = 298.15K. By default, is calculated from the aqueous


infinite dilution heat capacity polynomial. If the polynomial model parameters

are not available, is calculated from the Criss-Cobble correlation.

The unsymmetric Gibbs free energy for an ionic component is

calculated from the infinite dilution aqueous phase heat capacity as


follows:
(125)

2 Thermodynamic Property Models 173


(126)

where the term RT ln (1000/Mw) is added because and

are based on a molality scale, and is based on a mole fraction scale.

Hi and Gi for the symmetric reference state


The reference state for ionic components in the symmetric electrolyte NRTL
model is the pure fused salts containing these ions, so the enthalpy or Gibbs
free energy of the ionic components at the symmetric reference state is the
enthalpy contributions or the Gibbs free energy contributions of these ions to
the system of the pure fused salts. The condition of the pure fused salts can
be defined as follows:
(127)

which applies to all molecular components in the solution.


Given that the calculated total enthalpy or total Gibbs free energy of an
electrolyte solution by any reference state should be the same, the
formulation of enthalpy or Gibbs free energy of the ionic components at the
symmetric reference state can be derived from the unsymmetric electrolyte
NRTL enthalpy or Gibbs free energy calculations at the condition that all
molecular components (solvents and Henry components) approach zero, i.e.
the pure fused salts. Applying Eq. 127, the system enthalpy and Gibbs free
energy with the unsymmetric reference state can be expressed as:
(128
)

(129
)

where and are the total enthalpy and total Gibbs


free energy of the solution calculated by the unsymmetric electrolyte NRTL
model at the limit of all molecular components approach zero, that is, the

pure fused salts state, and and are the


excess enthalpy and excess Gibbs free energy of ion i at the same limit
condition.
Applying Eq. 127, the system enthalpy and Gibbs free energy with the
symmetric reference state can be expressed as:
(130)

174 2 Thermodynamic Property Models


(131)

Comparing Eqs. 130 and 131 to Eqs. 128 and 129, we can get:
(132)

(133)

Therefore, the enthalpy and Gibbs free energy of ionic components with the
symmetric reference state can be written as:
(134)

(135)

One of advantages with the symmetric reference state is its capability to


model non-aqueous electrolyte systems without introducing a trace amount of
water. However, for calculating system enthalpy, entropy, and Gibbs free
energy correctly, water must be defined in the component list so that the
corrections showed by Eqs. 132 and 133 can be calculated from the
unsymmetric reference state.

References for Symmetric and Unsymmetric


Electrolyte NRTL
C.-C. Chen and L.B. Evans, "A Local Composition Model for the Excess Gibbs
Energy of Aqueous Electrolyte Systems," AIChE Journal, 1986, 32, 444.
Y. Song and C.-C. Chen, "Symmetric Nonrandom Two-Liquid Activity
Coefficient Model for Electrolytes" (to be published).
K.S. Pitzer, "Electrolytes. From Dilute Solutions to Fused Salts," J. Am. Chem.
Soc., 1980, 102, 2902-2906.
K.S. Pitzer and J.M. Simonson, "Thermodynamics of Multicomponent, Miscible,
Ionic Systems: Theory and Equations," J. Phys. Chem., 1986, 90, 3005-3009.
R.A. Robinson and R.H. Stokes, Electrolyte Solutions, Second Revised Edition.
Butterworths: London, 1970.
A.A. Rashin and B. Honig, "Reevaluation of the Born Model of Ion Hydration,"
J. Phys. Chem., 1985, 89 (26), pp 55885593.

UNIFAC Activity Coefficient Model


The UNIFAC model calculates liquid activity coefficients for the following
property methods: UNIFAC, UNIF-HOC, and UNIF-LL. Because the UNIFAC
model is a group-contribution model, it is predictive. All published group

2 Thermodynamic Property Models 175


parameters and group binary parameters are stored in the Aspen Physical
Property System.
The equation for the original UNIFAC liquid activity coefficient model is made
up of a combinatorial and residual term:

ln = ln ic + ln ir
ln ic =

Where the molecular volume and surface fractions are:

and
Where nc is the number of components in the mixture. The coordination
number z is set to 10. The parameters ri and qi are calculated from the group
volume and area parameters:

and

Where ki is the number of groups of type k in molecule i, and ng is the


number of groups in the mixture.
The residual term is:

k is the activity coefficient of a group at mixture composition, and ki is the


activity coefficient of group k in a mixture of groups corresponding to pure i.
The parameters k and ki are defined by:

With:

And:

176 2 Thermodynamic Property Models


The parameter Xk is the group mole fraction of group k in the liquid:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
UFGRP (k,k, m, m, ...)

GMUFQ Qk
GMUFR Rk
GMUFB bkn TEMPERATURE

The parameter UFGRP stores the UNIFAC functional group number and
number of occurrences of each group. UFGRP is stored in the Aspen Physical
Property System pure component databank for most components. For
nondatabank components, enter UFGRP on the 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:

Where a, b, and c are the three elements of UNIFPS.

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.

UNIFAC (Dortmund Modified)


The UNIFAC modification by Gmehling and coworkers (Weidlich and
Gmehling, 1987; Gmehling et al., 1993), is slightly different in the
combinatorial part. It is otherwise unchanged compared to the original
UNIFAC:

2 Thermodynamic Property Models 177


With:

The temperature dependency of the interaction parameters is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
UFGRPD (k,k, m, m, ...)

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.

UNIFAC (Lyngby Modified)


The equations for the "temperature-dependent UNIFAC" (Larsen et al., 1987)
are similar to the original UNIFAC:

Volume fractions are modified:

178 2 Thermodynamic Property Models


With:

Where k and ki have the same meaning as in the original UNIFAC, but
defined as:

With:

The temperature dependency of a is described by a function instead of a


constant:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
UFGRPL (k,k, m, m, ...)

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.

2 Thermodynamic Property Models 179


Reference: B. Larsen, P. Rasmussen, and Aa. Fredenslund, "A Modified
UNIFAC Group-Contribution Model for Prediction of Phase Equilibria and Heats
of Mixing," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 2274 2286.

UNIQUAC Activity Coefficient Model


The UNIQUAC model calculates liquid activity coefficients for these property
methods: UNIQUAC, UNIQ-2, UNIQ-HOC, UNIQ-NTH, and UNIQ-RK. It is
recommended for highly non-ideal chemical systems, and can be used for VLE
and LLE applications. This model can also be used in the advanced equations
of state mixing rules, such as Wong-Sandler and MHV2.
The equation for the UNIQUAC model is:

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

180 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
GMUQQ qi x
GMUQQ1 qi' q x
UNIQ/1 aij 0 x -50.0 50.0
UNIQ/2 bij 0 x -15000.0 15000.0 TEMPERATURE
UNIQ/3 cij 0 x TEMPERATURE
UNIQ/4 dij 0 x TEMPERATURE
UNIQ/5 Tlower 0K x TEMPERATURE
UNIQ/6 Tupper 1000 K x TEMPERATURE
UNIQ/7 eij 0 x TEMPERATURE

Absolute temperature units are assumed for elements 2 through 4 and 7 of


UNIQ.
The UNIQ-2 property method uses data set 2 for UNIQ. All other UNIQUAC
methods use data set 1.

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.

Van Laar Activity Coefficient Model


The Van Laar model (Van Laar 1910) calculates liquid activity coefficients for
the property methods: VANLAAR, VANL-2, VANL-HOC, VANL-NTH, and VANL-
RK. It can be used for highly nonideal systems.

Where:
zi =

Ai =

Bi =

Ci =

2 Thermodynamic Property Models 181


Aij =

Cij =

Cij = Cji
Aii = Bii = Cii = 0
aij and bij are unsymmetrical. That is, aij may not be equal to aji, and bij may
not be equal to bji.
Parameters Symbol DefaultMDS 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).

Wagner Interaction Parameter


The Wagner Interaction Parameter model calculates activity coefficients. This
model is used for dilute solutions in metallurgical applications.
The relative activity coefficient with respect to the reference activity
coefficient of a solute i (in a mixture of solutes i, j, and l and solvent A) is:

Where:

The parameter iref is the reference activity coefficient of solute i:

kij is a binary parameter:

For any component i, the value of the activity coefficient can be fixed:

i = gi

182 2 Thermodynamic Property Models


This model is recommended for dilute solutions.
Parameter Name/ Symbol Default MDS Lower Upper Units
Element Limit Limit
GMWIPR/1 ai 0 x TEMPERATURE
GMWIPR/2 bi 0 x
GMWIPR/3 ci 0 x
GMWIPB/1 dij 0 x TEMPERATURE
GMWIPB/2 eij 0 x
GMWIPB/3 fij 0 x
GMWIPO gi x
GMWIPS 0 x

GMWIPS is used to identify the solvent component. You must set GMWIPS to
1.0 for the solvent component. This model allows only one solvent.

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.

Wilson Activity Coefficient Model


The Wilson model calculates liquid activity coefficients for the following
property methods: WILSON, WILS2, WILS-HOC, WILS-NTH, WILS-RK, WILS-
HF, WILS-LR, and WILS-GLR. It is recommended for highly nonideal systems,
especially alcohol-water systems. It can also be used in the advanced
equation-of-state mixing rules, such as Wong-Sandler and MHV2. This model
cannot be used for liquid-liquid equilibrium calculations.
The equation for the Wilson model is:

Where:

ln Aij =

The extended form of ln Aij provides more flexibility in fitting phase


equilibrium and enthalpy data. aij, bij, cij, dij, and eij are unsymmetrical. That
is, aij may not be equal to aji, etc.
The binary parameters aij, bij, cij, dij, and eij must be determined from data
regression or VLE and/or heat-of-mixing data. The Aspen Physical Property
System has a large number of built-in binary parameters for the Wilson
model. The binary parameters have been regressed using VLE data from the
Dortmund Databank. The binary parameters were regressed using the ideal
gas, Redlich-Kwong, and Hayden-O'Connell equations of state. See Physical
Property Data, Chapter 1, for details.

2 Thermodynamic Property Models 183


Parameter Symbol Default MDS Lower Limit Upper Units
Name/Element Limit
WILSON/1 aij 0 x -50.0 50.0
WILSON/2 bij 0 x -15000.0 15000.0 TEMPERATURE

WILSON/3 cij 0 x - TEMPERATURE

WILSON/4 dij 0 x TEMPERATURE

WILSON/5 Tlower 0K x TEMPERATURE
WILSON/6 Tupper 1000 K x TEMPERATURE
WILSON/7 eij 0 x TEMPERATURE

The WILS-2 property method uses data set 2 for WILSON. All other Wilson
methods use data set 1.
In the original formulation of the Wilson model, aij = ln Vj/Vi, cij = dij = eij =
0, and
bij = -(ij - ii)/R, where Vj and Vi are pure component liquid molar volume at
25C.
If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.

References
G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.

Wilson Model with Liquid Molar Volume


This Wilson model (used in the method WILS-VOL) calculates liquid activity
coefficients using the original formulation of Wilson (Wilson 1964) except that
liquid molar volume is calculated at system temperature, instead of at 25C.
It is recommended for highly nonideal systems, especially alcohol water
systems. It can be used in any activity coefficient property method or in the
advanced equation of state mixing rules, such as Wong Sandler and MHV2.
This model cannot be used for liquid liquid equilibrium calculations.
The equation for the Wilson model is:

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

184 2 Thermodynamic Property Models


and enthalpy data. aij, bij, cij, dij, and eij are unsymmetrical. That is, aij may
not be equal to aji, etc.
The binary parameters aij, bij, cij, dij, and eij must be determined from data
regression of VLE and/or heat-of-mixing data. There are no built in binary
parameters for this model.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
WSNVOL/1 aij 0 x -50.0 50.0
WSNVOL/2 bij 0 x -15000.0 15000.0 TEMPERATURE

WSNVOL/3 cij 0 x TEMPERATURE

WSNVOL/4 dij 0 x TEMPERATURE

WSNVOL/5 eij 0 x TEMPERATURE

WSNVOL/6 Tlower 0K x TEMPERATURE
WSNVOL/7 Tupper 1000 K x TEMPERATURE

Pure component parameters for the General Pure Component Liquid Molar
Volume model are also required.
In the original formulation of the Wilson model, aij = cij = dij = eij = 0 and

. Vj and Vi are calculated at 25C.


If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.
Reference: G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.

Vapor Pressure and Liquid


Fugacity Models
The Aspen Physical Property System has the following built-in vapor pressure
and liquid fugacity models. This section describes the vapor pressure and
liquid fugacity models available.
Model Type
General Pure Component Liquid Vapor Vapor pressure
Pressure
API Sour Vapor pressure
Braun K-10 Vapor pressure
Chao-Seader Fugacity
Grayson-Streed Fugacity
Kent-Eisenberg Fugacity
Maxwell-Bonnell Vapor pressure

2 Thermodynamic Property Models 185


Model Type
Solid Antoine Vapor pressure

General Pure Component Liquid Vapor


Pressure
The Aspen Physical Property System has several submodels for calculating
vapor pressure of a liquid. It uses parameter THRSWT/3 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/3 Then this equation is And this parameter is used
is used
0 Extended Antoine PLXANT
200-211 Barin CPLXP1, CPLXP2, CPIXP1, CPIXP2,
and CPIXP3
301 Wagner WAGNER
302 PPDS Modified Wagner WAGNER
400 PML LNVPEQ and one of LNVP1, LOGVP1,
LNPR1, LOGPR1, LNPR2, LOGPR2
401 IK-CAPE PLPO
501 NIST TDE Polynomial PLTDEPOL
502 NIST Wagner 25 WAGNER25

Extended Antoine Equation


Parameters for many components are available for the extended Antoine
equation from the Aspen Physical Property System pure component databank.
This equation can be used whenever the parameter PLXANT is available.
The equation for the extended Antoine vapor pressure model is:

Extrapolation of ln pi*,l versus 1/T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/ Element Limit Limit
PLXANT/1 C1i x PRESSURE,
TEMPERATURE
PLXANT/2 C2i x TEMPERATURE

PLXANT/3, . . . , 7 C3i, ..., C7i 0 x TEMPERATURE

PLXANT/8 C8i 0 x TEMPERATURE

PLXANT/9 C9i 1000 x TEMPERATURE

If C5i, C6i, or C7i is non-zero, absolute temperature units are assumed for all
coefficients C1i through C7i. The temperature limits are always in user input
units.

186 2 Thermodynamic Property Models


Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.

Wagner Vapor Pressure Equation


The Wagner vapor pressure equation is the best equation for correlation. The
equation can be used if the parameter WAGNER is available:

Where:
Tri = T / Tci
pri*,l = pi*,l / pci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.

PPDS Modified Wagner Vapor Pressure Equation


The PPDS equation also uses the same parameter WAGNER as the standard
Wagner equation:

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

WAGNER/5 C5i 0 x TEMPERATURE

WAGNER/6 C6i 1000 x TEMPERATURE

TC Tci TEMPERATURE

PC pci PRESSURE

2 Thermodynamic Property Models 187


NIST Wagner 25 Liquid Vapor Pressure Equation
This equation is the same as the PPDS Modified Wagner equation above, but
it uses parameter WAGNER25 instead of WAGNER, and it uses critical
properties from this parameter set also.

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

WAGNER25/6 Tci x TEMPERATURE

WAGNER25/7 Tlower 0 x TEMPERATURE

WAGNER25/8 Tupper 1000 x TEMPERATURE

IK-CAPE Vapor Pressure Equation


The IK-CAPE model is a polynomial equation. If the parameter PLPO is
available, the Aspen Physical Property System can use the IK-CAPE vapor
pressure equation:

Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PLPO/1 C1i X PRESSURE
TEMPERATURE
PLPO/2, ..., 10 C2i , ..., C10i 0 X TEMPERATURE

PLPO/11 C11i 0 X TEMPERATURE

PLPO/12 C12i 1000 X TEMPERATURE

188 2 Thermodynamic Property Models


PML Vapor Pressure Equations
The PML vapor pressure equations are modified versions of the Antoine and
Wagner equations. Each equation comes in two alternate forms, identical
except for the use of natural or base-10 logarithms. Parameter LNVPEQ/1
specifies the number of the equation used. Each equation uses a separate
parameter: LNVP1 for equation 1, LOGVP1 for 2, LNPR1 for 3, LOGPR1 for 4,
LNPR2 for 5, and LOGPR2 for 6.
Equation 1 (natural logarithm) and 2 (base 10 logarithm):

Equation 3 (natural logarithm) and 4 (base 10 logarithm):

Equation 5 (natural logarithm) and 6 (base 10 logarithm):

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

LOGPR2/1,2 C1i, C2i x

LNVPEQ/1 (equation
number)
LNVPEQ/2 Tlower 0 X TEMPERATURE

LNVPEQ/3 Tupper 1000 X TEMPERATURE

TC Tci TEMPERATURE

PC pci PRESSURE

2 Thermodynamic Property Models 189


NIST TDE Polynomial for Liquid Vapor Pressure
This equation can be used for calculating vapor pressure when parameter
PLTDEPOL is available.

Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.


If elements 2, 3, 6, or 8 are non-zero, absolute temperature units are
assumed for all elements.
Parameter Symbol DefaultMDS Lower Upper Units
Name/Element Limit Limit
PLTDEPOL/1 C1i X

PLTDEPOL/2 C2i 0 X TEMPERATURE

PLTDEPOL/3 C3i 0 X

PLTDEPOL/4, ..., 8 C4i , ..., C8i 0 X TEMPERATURE

PLTDEPOL/9 Tlower 0 X TEMPERATURE

PLTDEPOL/10 Tupper 1000 X TEMPERATURE

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.

API Sour Model


The API Sour model is based on the API sour water model for correlating the
ammonia, carbon dioxide, and hydrogen sulfide volatilities from aqueous sour
water system. The model assumes aqueous phase chemical equilibrium
reactions involving CO2, H2S, and NH3. The model is not usable with chemistry
in the true component approach. Use the apparent component approach with
this model.
The model is applicable from 20 C to 140 C. The authors developed the model
using available phase equilibrium data and reported average errors between
the model and measured partial pressure data as follows
Compound Average Error, %
Up to 60 C Above 60 C

190 2 Thermodynamic Property Models


Compound Average Error, %
Up to 60 C Above 60 C

Ammonia 10 36
Carbon dioxide 11 24
Hydrogen sulfide 12 29

Detail of the model is described in the reference below and is too involved to
be reproduced here.

Reference
New Correlation of NH3, CO2, and H2S Volatility Data from Aqueous Sour
Water Systems, API Publication 955, March 1978 (American Petroleum
Institute).

Braun K-10 Model


The BK10 model uses the Braun K-10 K-value correlations, which were
developed from the K10 charts (K-values at 10 psia) for both real and pseudo
components. The form of the equation used is an extended Antoine vapor
pressure equation with coefficients specific to real components and pseudo
component boiling ranges.
This method is strictly applicable to heavy hydrocarbons at low pressures.
However, our model includes coefficients for a large number of hydrocarbons
and light gases. For pseudocomponents the model covers boiling ranges 450
700 K (350 800F). Heavier fractions can also be handled using the
methods developed by AspenTech.

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.

Chao-Seader Pure Component Liquid


Fugacity Model
The Chao-Seader model calculates pure component fugacity coefficient, for
liquids. It is used in the CHAO-SEA property method. This is an empirical
model with the Curl-Pitzer form. The general form of the model is:

Where:

2 Thermodynamic Property Models 191


=

Parameter Symbol Default MDS Lower Limit Upper Units


Name/Element Limit
TC Tci 5.0 2000.0 TEMPERATURE
PC pci 105 108 PRESSURE
OMEGA i -0.5 2.0

References
K.C. Chao and J.D. Seader, "A General Correlation of Vapor-Liquid Equilibria
in Hydrocarbon Mixtures," AIChE J., Vol. 7, (1961), p. 598.

Grayson-Streed Pure Component Liquid


Fugacity Model
The Grayson-Streed model calculates pure component fugacity coefficients for
liquids, and is used in the GRAYSON/GRAYSON2 property methods. It is an
empirical model with the Curl-Pitzer form. The general form of the model is:

Where:

Parameter Symbol Default MDS Lower Limit Upper Units


Name/Element Limit
TC Tci 5.0 2000.0 TEMPERATURE
5 8
PC pci 10 10 PRESSURE
OMEGA i -0.5 2.0

References
H.G. Grayson and C.W. Streed, Paper 20-PO7, Sixth World Petroleum
Conference, Frankfurt, June 1963.

Kent-Eisenberg Liquid Fugacity Model


The Kent-Eisenberg model calculates liquid mixture component fugacity
coefficients and liquid enthalpy for the AMINES property method.
The chemical equilibria in H2S + CO2 + amine systems are described using
these chemical reactions:

192 2 Thermodynamic Property Models


Where:
R' = Alcohol substituted alkyl groups
The equilibrium constants are given by:

The chemical equilibrium equations are solved simultaneously with the


balance equations. This obtains the mole fractions of free H2S and CO2 in
solution. The equilibrium partial pressures of H2S and CO2 are related to the
respective free concentrations by Henry's constants:

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.

2 Thermodynamic Property Models 193


Maxwell-Bonnell Vapor Pressure Model
The Maxwell-Bonnell model calculates vapor pressure using the Maxwell-
Bonnell vapor pressure correlation for all hydrocarbon pseudo-components as
a function of temperature. This is an empirical correlation based on API
procedure 5A1.15, 5A1.13. This model is used in property method MXBONNEL
for calculating vapor pressure and liquid fugacity coefficients (K-values).

References
API procedure 5A1.15 and 5A1.13.

Solid Antoine Vapor Pressure Model


The vapor pressure of a solid can be calculated using the Antoine equation.
Parameters for some components are available for the extended Antoine
equation from the Aspen Physical Property System pure component databank.
This equation can be used whenever the parameter PSANT is available.
The equation for the solid Antoine vapor pressure model is:

Extrapolation of ln pi*,s versus 1/T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Limit Upper Units
Name/ Limit
Element
PSANT/1 C1i x PRESSURE,
TEMPERATURE
PSANT/2 C2i x TEMPERATURE
PSANT/3 C3i 0 x TEMPERATURE
PSANT/4 C4i 0 x TEMPERATURE
PSANT/5 C5i 1000 x TEMPERATURE

General Pure Component Heat


of Vaporization
The Aspen Physical Property System has several submodels for calculating
pure component heat of vaporization. It uses parameter THRSWT/4 to
determine which submodel is used. See Pure Component Temperature-
Dependent Properties for details.
If THRSWT/4 Then this equation is used And this parameter is
is used
0 Watson DHVLWT
106 DIPPR DHVLDP
301 PPDS DHVLDS
401 IK-CAPE DHVLPO

194 2 Thermodynamic Property Models


If THRSWT/4 Then this equation is used And this parameter is
is used
505 NIST TDE Watson equation DHVLTDEW

DIPPR Heat of Vaporization Equation


The DIPPR equation is used to calculate heat of vaporization when THRSWT/4
is set to 106. (Other DIPPR equations may sometimes be used. See Pure
Component Temperature-Dependent Properties for details.)
The equation for the DIPPR heat of vaporization model is:

Where:
Tri = T / Tci

Note: Reduced temperature Tr is always calculated using absolute


temperature units.

Linear extrapolation of vapHi* versus T occurs outside of temperature bounds,


using the slope at the temperature bound, except that vapHi* is zero for

.
Parameter Symbol 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

Watson Heat of Vaporization Equation


The Watson equation is used to calculate heat of vaporization when
THRSWT/4 is set to 0. See Pure Component Temperature-Dependent
Properties for details.
The equation for the Watson model is:

Where:

vapHi*(T1) = Heat of vaporization at temperature T1

Linear extrapolation of vapHi* versus T occurs below the minimum


temperature bound, using the slope at the temperature bound.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
TC Tci 5.0 2000.0 TEMPERATURE

2 Thermodynamic Property Models 195


Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
DHVLWT/1 vapHi*(T1) 5x104 5x108 MOLE-ENTHALPY

DHVLWT/2 T1 4.0 3500.0 TEMPERATURE


DHVLWT/3 ai 0.38 -2.0 2.0
DHVLWT/4 bi 0 -2.0 2.0
DHVLWT/5 Tmin 0 0.0 1500.0 TEMPERATURE

PPDS Heat of Vaporization Equation


The PPDS equation is used to calculate heat of vaporization when THRSWT/4
is set to 301. See Pure Component Temperature-Dependent Properties for
details.
The equation for the PPDS model is:

where R is the gas constant.

Linear extrapolation of vapHi* versus T occurs outside of temperature bounds,


using the slope at the temperature bound.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC Tci 5.0 2000.0 TEMPERATURE
DHVLDS/1 C1i
DHVLDS/2 C2i 0
DHVLDS/3 C3i 0
DHVLDS/4 C4i 0
DHVLDS/5 C5i 0
DHVLDS/6 C6i 0 TEMPERATURE
DHVLDS/7 C7i 1000 TEMPERATURE

IK-CAPE Heat of Vaporization Equation


The IK-CAPE equation is used to calculate heat of vaporization when
THRSWT/4 is set to 401. See Pure Component Temperature-Dependent
Properties for details.
The equation for the IK-CAPE model is:

Linear extrapolation of vapHi* versus T occurs outside of temperature bounds,


using the slope at the temperature bound

196 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DHVLPO/1 C1i X MOLE-
ENTHALPY
DHVLPO/2, ..., C2i, ..., C10i 0 X MOLE-
10 ENTHALPY
TEMPERATURE
DHVLPO/11 C11i 0 X TEMPERATURE
DHVLPO/12 C12i 1000 X TEMPERATURE

NIST TDE Watson Heat of Vaporization


Equation
The NIST TDE Watson equation is used to calculate heat of vaporization when
THRSWT/4 is set to 505. See Pure Component Temperature-Dependent
Properties for details.
The equation is:

Linear extrapolation of vapHi* versus T occurs outside of temperature bounds,


using the slope at the temperature bound
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DHVLTDEW/1 C1i X
DHVLTDEW/2, 3, C2i, C3i, C4i 0 X
4
DHVLTDEW/5 Tci X TEMPERATURE
DHVLTDEW/6 nTerms 4 X
DHVLTDEW/7 Tlower 0 X TEMPERATURE
DHVLTDEW/8 Tupper 1000 X TEMPERATURE

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

Vi*,v = Vapor molar volume calculated from the Redlich Kwong


equation of state

2 Thermodynamic Property Models 197


Vi*,l = Liquid molar volume calculated from the Rackett equation
For parameter requirements, see General Pure Component Liquid Vapor
Pressure, the General Pure Component Liquid Molar Volume model, and
Redlich Kwong.

Molar Volume and Density


Models
The Aspen Physical Property System has the following built-in molar volume
and density models available. This section describes the molar volume and
density models.
Model Type
API Liquid Volume Liquid volume
Brelvi-O'Connell Partial molar liquid
volume of gases
Chueh-Prausnitz Liquid volume
Clarke Aqueous Electrolyte Volume Liquid volume
COSTALD Liquid Volume Liquid volume
Debye-Hckel Volume Electrolyte liquid volume
Liquid Constant Molar Volume Model Liquid volume
General Pure Component Liquid Molar Liquid volume/liquid
Volume density
Rackett/Campbell-Thodos Mixture Liquid Liquid volume
Volume
Modified Rackett Liquid volume
General Pure Component Solid Molar Volume Solid volume
Liquid Volume Quadratic Mixing Rule Liquid volume

API Liquid Molar Volume


This model calculates liquid molar volume for a mixture, using the API
procedure and the Rackett model. Ideal mixing is assumed:

Where:
xp = Mole fraction of pseudocomponents
xr = Mole fraction of real components
For pseudocomponents, the API procedure is used:

Where:

198 2 Thermodynamic Property Models


fcn = A correlation based on API procedure 6A3.5 (API Technical Data
Book, Petroleum Refining, 4th edition)
At high density, the Ritter equation is used (adapted from Ritter, Lenoir, and
Schweppe, Petrol. Refiner 37 [11] 225 (1958)):

Where SG is the specific gravity, Tb is the mean average boiling point in


Rankine, T is the temperature of the system in Rankine, and the mass volume
is produced in units of cubic feet per pound-mass.
This procedure is valid over the following conditions:
UOPK: 10.5 - 12.5
API: 0 - 95
Mean Average Boiling Point: 0 - 1100 F
Temperature: 0 - 1000 F
Calculated density: 0.4 - 1.05 g/cc
The effect of pressure is automatically accounted for using procedure 6A3.10.
This procedure has the following validity range:
Density at low pressure: 0.7 - 1.0 g/cc
Pressure: 0 - 100,000 psig
For real components, the mixture Rackett model is used:

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
See the Rackett model for descriptions.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TB Tb 4.0 2000.0 TEMPERATURE
API API -60.0 500.0
TC Tc 5.0 2000.0 TEMPERATURE
5 8
PC pc 10 10 PRESSURE
RKTZRA ZRA ZC 0.1 0.5

There are two versions of this model: VL2API and VL2API5. Model VL2API is
used in route VLMX20, while model VL2API5 is used in route VLMX24.
The main difference between the VL2API and VL2API5 models is as follows:
The VL2API model calculates the liquid density for each pseudocomponent
using the API procedure 6A3.5 (or Ritter equation), then computes the
density of the pseudocomponent mixture as a mole-fraction-weighted
average.

2 Thermodynamic Property Models 199


The VL2API5 model calculates the liquid density of the mixture of the
pseudocomponents as a whole. It first computes the specific gravity and
mean average boiling point of the pseudocomponent mixture, then uses the
API procedure 6A3.5 (or Ritter equation) to compute the mixture liquid
density.
Both models use the same procedure 6A3.10 for pressure correction.
Experience shows that VL2API5 is less sensitive to how the
pseudocomponents are generated from the same assay (number of cut
points, etc.).

Brelvi-O'Connell
The Brelvi-O'Connell model calculates partial molar volume of a supercritical
component i at infinite dilution in pure solvent A. Partial molar volume at
infinite dilution is required to compute the effect of pressure on Henry's
constant. (See Henry's Constant.)
The general form of the Brelvi-O'Connell model is:

Where:
i = 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:

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC TcA 5.0 2000.0 TEMPERATURE
PC pcA 105 108 PRESSURE
RKTZRA ZARA ZC x 0.1 1.0
VLBROC/1 V1 VC x -1.0 1.0 MOLE-VOLUME
VLBROC/2 V2 0 x -0.1 0.1 TEMPERATURE

References
S.W. Brelvi and J.P. O'Connell, AIChE J., Vol. 18, (1972), p. 1239.
S.W. Brelvi and J.P. O'Connell, AIChE J., Vol. 21, (1975), p. 157.

200 2 Thermodynamic Property Models


Chueh-Prausnitz Liquid Molar Volume
Model
The Chueh-Prausnitz model is used to calculate liquid molar volume for pure
components and mixtures. It uses the Rackett model to calculate the
saturated molar volume then applies a pressure correction term. The mixture
form of the model is described below. The equations reduce to the pure
component version.

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

m = Acentric factor of the mixture = xii


i =Acentric factor of component i
Tcm and Pcm are calculated by:
Vcm = xiZciTci/Pci
Tcm = [xiZciTci3/2/Pci]2/Vcm2
Pcm = ZcmTcm/Vcm
Tci = Critical temperature of component i
Pci = Critical pressure of component i

2 Thermodynamic Property Models 201


Note: Reduced temperature Tr is always calculated using absolute
temperature units.
Note: Above Tr=0.99 an extrapolation method is used to smooth the
transition to constant molar volume equal to the critical volume.
The parameters required for the model are the same as those for the Rackett
model with the addition of the acentric factor, i
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
TC Tci 5.0 2000.0 TEMPERATURE
5 8
PC pci 10 10 PRESSURE
VCRKT Vci VC x 0.001 3.5 MOLE-
VOLUME
RKTZRA Zi*,RA ZC x 0.1 1.0
RKTKIJ kij x -5.0 5.0

OMEGA i -0.5 2.0

Reference
Chueh, P.L. and J.M. Prausnitz, AIChE J. 15, 471 (1969).

Clarke Aqueous Electrolyte Volume


The Clarke model calculates liquid molar volume for electrolytes solutions.
The model is applicable to mixed solvents and is based on:
Molar volume of molecular solvents (equation 2)
The relationship between the partial molar volume of an electrolyte and its
mole fraction in the solvent (equation 4)
All quantities are expressed in terms of apparent components.
If option code 1 is set to 1, the liquid volume quadratic mixing rule is used
instead. The default option uses this equation to calculate the liquid molar
volume for electrolyte solutions:
(1)

Where:
Vm l = Liquid molar volume for electrolyte solutions.
Vsl = Liquid molar volume for solvent mixtures.
Vel = Liquid molar volume for electrolytes.

Apparent Component Approach


For molecular solvents, the liquid molar volume is calculated by:

202 2 Thermodynamic Property Models


(2)

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

2 Thermodynamic Property Models 203


For example: given an aqueous solution of Ca2+, Na+, SO42-, Cl- four
electrolytes are found: CaCl2, Na2SO4, CaSO4, and NaCl. The Clarke
parameters of all four electrolytes are used. You can rely on the default,
which calculates the Clarke parameters from ionic parameters. Otherwise, you
must enter parameters for any electrolytes that may not exist in the
components list. If you do not want to use the default, the first step in using
the Clarke model is to add any needed components for electrolytes not in the
components list.

True Component Approach


The true molar volume is obtained from the apparent molar volume:
(8)

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)

Where Vml(298.15K) is calculated from equation 1.


Parameter Applicable Symbol Default Units
Name/Element Components
VLCLK/1 Cation-Anion MOLE-VOLUME

VLCLK/2 Cation-Anion Aca 0.020 MOLE-VOLUME

If VLCLK/1 is missing, it is calculated based on VLBROC and CHARGE as


follows:
(10)

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.

204 2 Thermodynamic Property Models


Reference
C.C. Chen, private communication.

COSTALD Liquid Volume


The equation for the COSTALD liquid volume model is:

Where:

VmR,0 and VmR, are functions or Tr for

For , there is a linear interpolation between the liquid density at


Tr = 0.95 and the vapor density at Tr = 1.05. This model can be used to
calculate saturated and compressed liquid molar volume. The compressed
liquid molar volume is calculated using the Tait equation:

Where B and C are functions of T, , Tc, Pc and Psat is the saturated pressure
at T.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Mixing Rules:

Where:

To improve results, the Aspen Physical Property System uses a special


correlation for water when this model is used. Changing the VSTCTD and
OMGCTD parameters for water will not affect the results of the special
correlation.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC Tci 5.0 2000.0 TEMPERATURE
VSTCTD Vr*,CTD VC X 0.001 3.5 MOLE-VOLUME
OMGCTD r OMEGA X -0.5 2.0

2 Thermodynamic Property Models 205


References
R.W. Hankinson and G.H. Thomson, AIChE J., Vol. 25, (1979), p. 653.
G.H. Thomson, K.R. Brobst, and R.W. Hankinson, AIChE J., Vol. 28, (1982),
p. 4, p. 671.

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:

A = Debye-Hckel constant for the osmotic


coefficients (Pitzer, 1979)

w = Density of water (kg / m3)

206 2 Thermodynamic Property Models


w = Dielectric constant of water (Fm-1), a function
of pressure and temperature (Bradley and
Pitzer, 1979)
The above equation for Vk can also apply to non-water molecular species
since the second term on the right is zero; it is assumed to be the infinite
dilution partial volume for molecular species.

Vk in general is calculated from the Brelvi-O'Connell correlation:

Vk = V1 + TV2
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VLBROC/1 V1 0 x -1.0 1.0 MOLE-VOLUME
VLBROC/2 V2 0 x -0.1 0.1 TEMPERATURE

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).

Liquid Constant Molar Volume Model


This model, VL0CONS, uses a constant value entered by the user as the pure
component liquid molar volume. It is not a function of temperature or
pressure. This is used with the solids handling property method for modeling
nonconventional solids.
Parameter Name Default MDS Units
VLCONS * x MOLE-VOLUME

* When no value is provided for VLCONS, the General Pure Component Liquid
Molar Volume model is used to calculate the liquid molar volume.

General Pure Component Liquid Molar


Volume
The Aspen Physical Property System has several submodels for calculating
liquid molar volume. It uses parameter THRSWT/2 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/2 is This equation is used And this parameter is used
0 Rackett RKTZRA
100-116 DIPPR DNLDIP

2 Thermodynamic Property Models 207


If THRSWT/2 is This equation is used And this parameter is used
301 PPDS DNLPDS
401 IK-CAPE VLPO
503 NIST ThermoML DNLTMLPO
Polynomial
504 NIST TDE expansion DNLEXSAT
514 NIST TDE Rackett DNLRACK
515 NIST COSTALD DNLCOSTD

For liquid molar volume of mixtures, the Rackett mixture equation is always
used by default. This is not necessarily consistent with the pure component
molar volume or density. If you need consistency, select route VLMX26 on the
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:

This equation is similar to the Rackett equation.


DIPPR equation 116 is the default equation for water.

= 1 - T / Tc
Other DIPPR equations, such as equation 100, may be used for some
substances. Check the value of THRSWT/2 to determine the equation used.
See Pure Component Temperature-Dependent Properties for details about
DIPPR equations.

In either case, linear extrapolation of i*,l versus T occurs outside of


temperature bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DNLDIP/1 C1i x MOLE-DENSITY
DNLDIP/2 C2i 0 x
DNLDIP/3 C3i Tci x TEMPERATURE
DNLDIP/4 C4i 0 x
DNLDIP/5 C5i 0 x
DNLDIP/6 C6i 0 x TEMPERATURE
DNLDIP/7 C7i 1000 x TEMPERATURE

208 2 Thermodynamic Property Models


For equation 116, the units are MOLE-DENSITY for parameters DNLDIP/1
through DNLDIP/5 and the default for DNLDIP/3 is 0. For equation 105,
DNLDIP/5 is not used, and absolute temperature units are assumed for
DNLDIP/3.

PPDS
The PPDS equation is:

Linear extrapolation of i*,l versus T occurs outside of temperature bounds.


Parameter Symbol DefaultMDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0
VC Vci 0.001 3.5 MOLE-VOLUME
TC Tci 5.0 2000.0 TEMPERATURE
DNLPDS/1 C1i MASS-DENSITY
DNLPDS/2 C2i 0 MASS-DENSITY
DNLPDS/3 C3i 0 MASS-DENSITY
DNLPDS/4 C4i 0 MASS-DENSITY
DNLPDS/5 C5i 0 x TEMPERATURE
DNLPDS/6 C6i 1000 x TEMPERATURE

IK-CAPE
The IK-CAPE equation is:

Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VLPO/1 C1i X MOLE-
VOLUME
VLPO/2, ..., 10 C2i, ..., C10i 0 X MOLE-
VOLUME
TEMPERATURE
VLPO/11 C11i 0 X TEMPERATURE
VLPO/12 C12i 1000 X TEMPERATURE

NIST ThermoML Polynomial


This equation can be used when parameter DNLTMLPO is available.

2 Thermodynamic Property Models 209


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DNLTMLPO/1 C1i X MOLE-
DENSITY
DNLTMLPO/2, 3, C2i, C3i, C4i 0 X MOLE-
4 DENSITY
TEMPERATURE
DNLTMLPO/5 nTerms 4 X
DNLTMLPO/6 0 X TEMPERATURE

DNLTMLPO/7 1000 X TEMPERATURE

Rackett
The Rackett equation is:

Where:
Tr = T / Tci

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Note: Above Tr=0.99 an extrapolation method is used to smooth the
transition to constant molar volume equal to the critical volume.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
TC Tci 5.0 2000.0 TEMPERATURE
PC pci 105 108 PRESSURE
*,RA
RKTZRA Zi ZC x 0.1 1.0

NIST TDE Rackett Parameters


This equation can be used when the parameter DNLRACK is available.

Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
DNLRACK/1 Zc x
DNLRACK/2 n 2/7 x
DNLRACK/3 Tci x TEMPERATURE

210 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
DNLRACK/4 pci 0 x PRESSURE
DNLRACK/5 Tlower 0 x TEMPERATURE
DNLRACK/6 Tupper 1000 x TEMPERATURE

NIST COSTALD Parameters


This equation can be used when the parameter DNLCOSTD is available.

Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
DNLCOSTD/1 Voi x VOLUME
DNLCOSTD/2 0 x

DNLCOSTD/3 Tci x TEMPERATURE


DNLCOSTD/4 Tlower 0 x TEMPERATURE
DNLCOSTD/5 Tupper 1000 x TEMPERATURE

NIST TDE Expansion


This equation can be used when the parameter DNLEXSAT is available.

Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
DNLEXSAT/1 ci x MOLE-
DENSITY
DNLEXSAT/2 C1i x MOLE-
DENSITY
DNLEXSAT/3, C2i, ..., C6i 0 x MOLE-
..., DNLEXSAT/7 DENSITY
DNLEXSAT/8 Tci x TEMPERATURE

2 Thermodynamic Property Models 211


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
DNLEXSAT/9 nTerms 6 x
DNLEXSAT/10 Tlower 0 x TEMPERATURE
DNLEXSAT/11 Tupper 1000 x TEMPERATURE

References
H.G. Rackett, J.Chem. Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.

Rackett/Campbell-Thodos Mixture Liquid


Volume
The Rackett equation calculates liquid molar volume for all activity coefficient
based and petroleum tuned equation of state based property methods. In the
last category of property methods, the equation is used in conjunction with
the API model. The API model is used for pseudocomponents, while the
Rackett model is used for real components. (See API Liquid Volume .)
Campbell-Thodos is a variation on the Rackett model which allows the
compressibility term Zi*,RA to vary with temperature.

Rackett
The equation for the Rackett model is:

Where:
Tc =

ZmRA =

Vcm =

Tr = T / Tc

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Note: Above Tr=0.99 an extrapolation method is used to smooth the
transition to constant molar volume equal to the critical volume.

212 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
TC Tci 5.0 2000.0 TEMPERATURE
5 8
PC pci 10 10 PRESSURE
VCRKT Vci VC x 0.001 3.5 MOLE-
VOLUME
RKTZRA Zi*,RA ZC x 0.1 1.0
RKTKIJ kij x -5.0 5.0

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 =

Campbell-Thodos uses a separate set of parameters, RACKET. Tmin and Tmax


define the temperature range where the equation is applicable.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
RACKET/1 R*Tci/Pci R*Tci/Pci MOLE-
VOLUME
RACKET/2 Zi*,RA RKTZRA x 0.1 1.0
RACKET/3 di 0 x 0 0.11
RACKET/4 Tmin 0 x TEMPERATURE
RACKET/5 Tmax 1000 x TEMPERATURE

The Campbell-Thodos model is used when RACKET/3 is set to a value less


than 0.11. Do not change this parameter unless you intend to use this model.

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.

Modified Rackett Liquid Molar Volume


The Modified Rackett equation improves the accuracy of liquid mixture molar
volume calculation by introducing additional parameters to compute the pure
component parameter RKTZRA and the binary parameter kij.
The equation for the Modified Rackett model is:

2 Thermodynamic Property Models 213


Where:
Tc =

kij =

ZmRA =

Zi*,RA =

Vcm =

Tr = T / Tc

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Note: Above Tr=0.99 an extrapolation method is used to smooth the
transition to constant molar volume equal to the critical volume.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MRKZRA/1 ai RKTZRA x 0.1 0.5
MRKZRA/2 bi 0 x
MRKZRA/3 ci 0 x
MRKKIJ/1 Aij x

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.

Rackett Extrapolation Method


The Rackett equation has a formula involving an exponent of 1+(1-Tr )2/7
which is invalid above the critical temperature. As a result, a special
extrapolation method is required for this equation. This method involves the

214 2 Thermodynamic Property Models


calculation of an intermediate temperature T00 near the critical temperature.
When the temperature exceeds T00, the volume is constant at the critical
volume. When the temperature is between 0.99Tc and T00, a circle equation is
used to smoothly interpolate the volume between the value and slope at
0.99Tc and the constant value at T00.

Details
First the volume V0 at 0.99Tc and the critical volume Vc are calculated:

Then the volume difference is calculated, as well as the temperature


difference required for the circle equation:

From this, the required intermediate temperature T00 can be calculated:

Then the volume V00 at the circle's center can be calculated:

2 Thermodynamic Property Models 215


Finally, the equation of the circle is used to determine any point (T,V) for
0.99Tc < T < T00:

General Pure Component Solid Molar


Volume
The Aspen Physical Property System has several submodels for calculating
solid molar volume. It uses parameter THRSWT/1 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/1 is This equation is used And this parameter is
used
0 Aspen VSPOLY
100 DIPPR DNSDIP
401 IK-CAPE VSPO
503 NIST ThermoML DNSTMLPO
polynomial

Aspen Polynomial
The equation for the Aspen solids volume polynomial is:

Linear extrapolation of Vi*,s versus T occurs outside of temperature bounds.


Parameter Applicable Symbol MDS Default Units
Name Components
VSPOLY/1 Salts, CI solids C1i x MOLE-VOLUME
TEMPERATURE
VSPOLY/2, ..., 5 Salts, CI solids C2i, ..., C5i x 0 MOLE-VOLUME
TEMPERATURE
VSPOLY/6 Salts, CI solids C6i x 0 MOLE-VOLUME
TEMPERATURE
VSPOLY/7 Salts, CI solids C7i x 1000 MOLE-VOLUME
TEMPERATURE

IK-CAPE Equation
The IK-CAPE equation is:

216 2 Thermodynamic Property Models


Linear extrapolation of Vi*,s versus T occurs outside of temperature bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VSPO/1 C1i X MOLE-
VOLUME
VSPO/2, ..., 10 C2i, ..., C10i 0 X MOLE-
VOLUME
TEMPERATURE
VSPO/11 C11i 0 X TEMPERATURE
VSPO/12 C12i 1000 X TEMPERATURE

DIPPR
The DIPPR equation is:

Linear extrapolation of i*,s versus T occurs outside of temperature bounds.


Vi*,s = 1 / i*,s
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
The model returns solid molar volume for pure components.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DNSDIP/1 C1i x MOLE-
DENSITY
DNSDIP/2, ..., 5 C2i, ..., C5i 0 x MOLE-
DENSITY,
TEMPERATURE
DNSDIP/6 C6i 0 x TEMPERATURE
DNSDIP/7 C7i 1000 x TEMPERATURE

NIST ThermoML Polynomial

Linear extrapolation of i*,s versus T occurs outside of temperature bounds.


Vi*,s = 1 / i*,s
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DNSTMLPO/1 C1i x MOLE-
DENSITY
DNSTMLPO/2,...,8 C2i, ..., C8i 0 x MOLE-
DENSITY,
TEMPERATURE
DNSTMLPO/9 nTerms 8 x
DNSTMLPO/10 Tlower 0 x TEMPERATURE
DNSTMLPO/11 Tupper 1000 x TEMPERATURE

2 Thermodynamic Property Models 217


Liquid Volume Quadratic Mixing Rule
With i and j being components, the liquid volume quadratic mixing rule 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.

Heat Capacity Models


The Aspen Physical Property System has five built-in heat capacity models.
This section describes the heat capacity models available.
Model Type
Aqueous Infinite Dilution Heat Capacity Electrolyte liquid
Polynomial
Criss-Cobble Aqueous Infinite Dilution Electrolyte liquid
Ionic Heat Capacity
General Pure Component Liquid Heat Liquid
Capacity
General Pure Component Ideal Gas Heat Ideal gas
Capacity
General Pure Component Solid Heat Solid
Capacity

Aqueous Infinite Dilution Heat Capacity


The aqueous phase infinite dilution enthalpies, entropies, and Gibbs energies
are calculated from the heat capacity polynomial. The values are used in the
calculation of aqueous and mixed solvent properties of electrolyte solutions:

218 2 Thermodynamic Property Models


versus T is linearly extrapolated using the slope at C7i for T < C7i

versus T is linearly extrapolated using the slope at C8i for T < C8i
Parameter 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

If any of C4i through C6i is non-zero, absolute temperature units are


assumed for C1i through C6i . Otherwise, user input units for temperature are
used. The temperature limits are always interpreted in user input units.

Criss-Cobble Aqueous Infinite Dilution Ionic


Heat Capacity
The Criss-Cobble correlation for aqueous infinite dilution ionic heat capacity is
used if no parameters are available for the aqueous infinite dilution heat
capacity polynomial. From the calculated heat capacity, the thermodynamic
properties entropy, enthalpy and Gibbs energy at infinte dilution in water are
derived:

Parameter Applicable Symbol Default Units


Name Components
IONTYP Ions Ion Type 0
SO25C Anions MOLE-ENTROPY

Cations MOLE-ENTROPY

General Pure Component Liquid Heat


Capacity
The Aspen Physical Property System has several submodels for calculating
liquid heat capacity. It uses parameter THRSWT/6 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/6 is This equation is used And this parameter is used
100 DIPPR CPLDIP

2 Thermodynamic Property Models 219


If THRSWT/6 is This equation is used And this parameter is used
200-211 Barin CPLXP1, CPLXP2
301 PPDS CPLPDS
401 IK-CAPE heat capacity CPLPO
polynomial
403 IK-CAPE liquid heat CPLIKC
capacity
503 NIST ThermoML CPLTMLPO
polynomial
506 NIST TDE equation CPLTDECS

This liquid heat capacity model is used to calculate pure component liquid
heat capacity and pure component liquid enthalpy. To use this model, two
conditions must exist:
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

= Ideal gas enthalpy

= Vapor enthalpy departure

= Enthalpy of vaporization

Tref is the reference temperature; it defaults to 298.15 K. You can enter a


different value for the reference temperature. This is useful when you want to
use this model for very light components or for components that are solids at
298.15K.
Activate this model by specifying the route DHL09 for the property DHL on
the Methods | Selected Methods | Routes sheet. For equation of state
property method, you must also modify the route for the property DHLMX to
use a route with method 2 or 3, instead of method 1. For example, you can
use the route DHLMX00 or DHLMX30. You must ascertain that the route for
DHLMX that you select contains the appropriate vapor phase model and heat
of mixing calculations. Click the View button on the form to see details of the
route.
Optionally, you can specify that this model is used for only certain
components. The properties for the remaining components are then
calculated by the standard model. Use the parameter COMPHL to specify the

220 2 Thermodynamic Property Models


components for which this model is used. By default, all components with the
CPLDIP or CPLIKC parameters use this model.

Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.

DIPPR Liquid Heat Capacity


The DIPPR equation is used to calculate liquid heat capacity when parameter
THRSWT/6 is 100.
The DIPPR equation is:

Linear extrapolation occurs for Cp*,l versus T outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPLDIP/1 C1i x MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPLDIP/2, ..., 5 C2i, ..., C5i 0 x MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPLDIP/6 C6i 0 x TEMPERATURE
CPLDIP/7 C7i 1000 x TEMPERATURE
ref
TREFHL T 298.15 TEMPERATURE
COMPHL

To specify that the model is used for a component, enter a value of 1.0 for
COMPHL.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)

PPDS Liquid Heat Capacity


The PPDS equation is used to calculate liquid heat capacity when parameter
THRSWT/6 is 301.
The PPDS equation is:

Where R is the gas constant.


Linear extrapolation occurs for Cp*,l versus T outside of bounds.

2 Thermodynamic Property Models 221


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPLPDS/1 C1i
CPLPDS/2 C2i 0
CPLPDS/3 C3i 0
CPLPDS/4 C4i 0
CPLPDS/5 C5i 0
CPLPDS/6 C6i 0
CPLPDS/7 C7i 0 x TEMPERATURE
CPLPDS/8 C8i 0.99 TC x TEMPERATURE

IK-CAPE Liquid Heat Capacity


Two IK-CAPE equations can be used to calculate liquid heat capacity. Linear
extrapolation occurs for Cp*,l versus T outside of bounds for either equation.
When THRSWT/6 is 403, the IK-CAPE liquid heat capacity equation is used.
The equation is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
CPLIKC/1 C1i x MOLE-HEAT-
T CAPACITY
CPLIKC/2,...,4 C2i, ..., C4i 0 x MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPLIKC/5 C5i 0 x MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPLIKC/6 C6i 0 x TEMPERATURE
CPLIKC/7 C7i 1000 x TEMPERATURE

If C5i is non-zero, absolute temperature units are assumed for C2i through
C5i. Otherwise, user input units for temperature are used. The temperature
limits are always interpreted in user input units.
When THRSWT/6 is 401, the IK-CAPE heat capacity polynomial is used.The
equation is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
CPLPO/1 C1i X MOLE-CAPACITY
CPLPO/2,,10 C2i, ..., C10i 0 X MOLE-CAPACITY
TEMPERATURE
CPLPO/11 C11i 0 X TEMPERATURE

222 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPLPO/12 C12i 1000 X TEMPERATURE

See Pure Component Temperature-Dependent Properties for details on the


THRSWT parameters.

NIST Liquid Heat Capacity


Two NIST equations can be used to calculate liquid heat capacity. Linear
extrapolation occurs for Cp*,l versus T outside of bounds for either equation.
When THRSWT/6 is 503, the ThermoML polynomial is used to calculate liquid
heat capacity:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
CPLTMLPO/1 C1i X J/K^2/mol
CPLTMLPO/2,,5 C2i, ..., C5i 0 X J/K^2/mol
CPLTMLPO/6 nTerms 5 X
CPLTMLPO/7 Tlower 0 X TEMPERATURE
CPLTMLPO/8 Tupper 1000 X TEMPERATURE

When THRSWT/6 is 506, the TDE equation is used to calculate liquid heat
capacity:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
CPLTDECS/1 C1i X MOLE-HEAT-
CAPACITY
CPLTDECS/2,,4 C2i, ..., C4i 0 X MOLE-HEAT-
CAPACITY
CPLTDECS/5 B 0 X MOLE-HEAT-
CAPACITY
CPLTDECS/6 Tci X TEMPERATURE
CPLTDECS/7 nTerms 4 X
CPLTDECS/8 Tlower 0 X TEMPERATURE
CPLTDECS/9 Tupper 1000 X TEMPERATURE

See Pure Component Temperature-Dependent Properties for details on the


THRSWT parameters.

2 Thermodynamic Property Models 223


General Pure Component Ideal Gas Heat
Capacity
The Aspen Physical Property System has several submodels for calculating
ideal gas heat capacity. It uses parameter THRSWT/7 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/7 is This equation is used And this parameter is
used
0 Ideal gas heat capacity CPIG
polynomial
107, 127 DIPPR 107 or 127 CPIGDP
200-211 Barin CPIXP1, CPIXP2, CPIXP3
301 PPDS CPIGDS
401 IK-CAPE heat capacity CPIGPO
polynomial
503 NIST ThermoML CPITMLPO
polynomial
513 NIST Aly-Lee CPIALEE

These equations are also used to calculate ideal gas enthalpies, entropies,
and Gibbs energies.

Aspen Ideal Gas Heat Capacity Polynomial


The ideal gas heat capacity polynomial is available for components stored in
ASPENPCD, AQUEOUS, and SOLIDS databanks. This model is also used in
PCES.

Cp*,ig is linearly extrapolated using slope at


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
CPIG/1 C1i MOLE-HEAT-CAPACITY,
TEMPERATURE
CPIG/2, ..., 6 C2i, ..., C6i 0 MOLE-HEAT-CAPACITY,
TEMPERATURE
CPIG/7 C7i 0 TEMPERATURE
CPIG/8 C8i 1000 TEMPERATURE
CPIG/9, 10, C9i, C10i, C11i MOLE-HEAT-CAPACITY,
11 TEMPERATURE

If C10i or C11i is non-zero, then absolute temperature units are assumed for
C9i through C11i. Otherwise, user input temperature units are used for all
parameters. User input temperature units are always used for C1i through C8i.

224 2 Thermodynamic Property Models


NIST ThermoML Polynomial
This equation can be used when parameter CPITMLPO is available.

Parameter Symbol Default MDS Lower Upper Units


Name/ Limit Limit
Element
CPITMLPO /1 C1i x J/K^2/mol
CPITMLPO /2, C2i, ..., C6i 0 x J/K^2/mol
..., 6
CPITMLPO/7 nTerms 6 x
CPITMLPO /8 Tlower 0 x TEMPERATURE
CPITMLPO /9 Tupper 1000 x TEMPERATURE

DIPPR Equation 107


The DIPPR ideal gas heat capacity equation 107 by Aly and Lee 1981 is:

No extrapolation is used with this equation.


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIGDP/1 C1i x MOLE-HEAT-
CAPACITY
CPIGDP/2 C2i 0 x MOLE-HEAT-
CAPACITY
CPIGDP/3 C3i 0 x TEMPERATURE
CPIGDP/4 C4i 0 x MOLE-HEAT-
CAPACITY
CPIGDP/5 C5i 0 x TEMPERATURE
CPIGDP/6 C6i 0 x TEMPERATURE
CPIGDP/7 C7i 1000 x TEMPERATURE

Absolute temperature units are assumed for C3i and C5i. The temperature
limits are always interpreted in user input units.

DIPPR Equation 127


The DIPPR ideal gas heat capacity equation 127 is:

2 Thermodynamic Property Models 225


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIGDP/1 C1i x MOLE-HEAT-
CAPACITY
CPIGDP/2 C2i 0 x MOLE-HEAT-
CAPACITY
CPIGDP/3 C3i 0 x TEMPERATURE
CPIGDP/4 C4i 0 x MOLE-HEAT-
CAPACITY
CPIGDP/5 C5i 0 x TEMPERATURE
CPIGDP/6 C6i 0 x MOLE-HEAT-
CAPACITY
CPIGDP/7 C7i 0 x TEMPERATURE

Absolute temperature units are assumed for C3i, C5i and C7i.

Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.

NIST Aly-Lee
This equation is the same as the DIPPR Aly and Lee equation 107 above, but
it uses a different parameter set. Note that elements 6 and 7 of the CPIALEE
parameter are not used in the equation.
Parameter Symbol 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:

226 2 Thermodynamic Property Models


where R is the gas constant.
Linear extrapolation of Cp*,ig versus T is performed outside temperature
bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIGDS/1 C1i TEMPERATURE
CPIGDS/2, , 8 C2i, ..., C8i 0
CPIGDS/9 C9i 0 TEMPERATURE
CPIGDS/10 C10i 1000 TEMPERATURE

IK-CAPE Heat Capacity Polynomial


The equation is:

Linear extrapolation of Cp*,ig versus T is performed outside temperature


bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIGPO/1 C1i X MOLE-CAPACITY
CPIGPO/2,,10 C2i, ..., C10i 0 X MOLE-CAPACITY
TEMPERATURE
CPIGPO/11 C11i 0 X TEMPERATURE
CPIGPO/12 C12i 1000 X TEMPERATURE

References
Data for the Ideal Gas Heat Capacity Polynomial: Reid, Prausnitz and Poling,
The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987).
The Aspen Physical Property System combustion data bank, JANAF
Thermochemical Data, Compiled and calculated by the Thermal Research
Laboratory of Dow Chemical Company.
F. A. Aly and L. L. Lee, "Self-Consistent Equations for Calculating the Ideal
Gas Heat Capacity, Enthalpy, and Entropy, Fluid Phase Eq., Vol. 6, (1981), p.
169.

2 Thermodynamic Property Models 227


General Pure Component Solid Heat
Capacity
The Aspen Physical Property System has several submodels for calculating
solid heat capacity. It uses parameter THRSWT/5 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/5 is This equation is used And this parameter is
used
0 Aspen solid heat capacity CPSPO1
polynomial
100 or 102 DIPPR CPSDIP
200-211 Barin CPSXP1, CPSXP2, ,
CPSXP7
401 IK-CAPE heat capacity CPSPO
polynomial
503 NIST ThermoML CPSTMLPO
polynomial

The enthalpy, entropy, and Gibbs energy of solids are also calculated from
these equations:

Aspen Solid Heat Capacity Polynomial


The Aspen equation is:

Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.


Parameter Applicable Symbol MDS Default Units
Name Components
CPSPO1/1 Solids, Salts C1i x
CPSPO1/2, ..., 6 Solids, Salts C2i, ..., C6i x 0
CPSPO1/7 Solids, Salts C7i x 0
CPSPO1/8 Solids, Salts C8i x 1000

The units are TEMPERATURE and HEAT-CAPACITY for all elements. If any of
C4i through C6i are non-zero, absolute temperature units are assumed for
elements C1i through C6i. Otherwise, user input temperature units are
assumed for all elements. The temperature limits are always interpreted in
user input units.

Barin
See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity
for details about this submodel.

DIPPR
There are two DIPPR equations that may generally be used.
The more common one, DIPPR equation 100, is:

228 2 Thermodynamic Property Models


Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPSDIP/1 C1i x MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPSDIP/2,...,5 C2i, ..., C5i 0 x MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPSDIP/6 C6i 0 x TEMPERATURE
CPSDIP/7 C7i 1000 x TEMPERATURE

DIPPR equation 102 is:

Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPSDIP/1 C1i x MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPSDIP/2 C2i x
CPSDIP/3,4 C3i, C4i 0 x TEMPERATURE
CPSDIP/6 C6i 0 x TEMPERATURE
CPSDIP/7 C7i 1000 x TEMPERATURE

If C3i or C4i are non-zero or C2i is negative, absolute temperature units are
assumed for elements C1i through C4i. Otherwise, user input temperature
units are assumed for all elements. The temperature limits are always
interpreted in user input units.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)

NIST ThermoML Polynomial


The equation is:

Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPSTMLPO/1 C1i x J/K^2/mol
CPSTMLPO/2,...,5 C2i, ..., C5i 0 x J/K^2/mol
CPSTMLPO/6 nTerms 5 x
CPSTMLPO/7 Tlower 0 x TEMPERATURE
CPSTMLPO/8 Tupper 1000 x TEMPERATURE

2 Thermodynamic Property Models 229


IK-CAPE Heat Capacity Polynomial
The equation is:

Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPSPO/1 C1i X MOLE-CAPACITY
CPSPO/2,,10 C10i 0 X MOLE-CAPACITY
TEMPERATURE
CPSPO/11 C11i 0 X TEMPERATURE
CPSPO/12 C12i 1000 X TEMPERATURE

Solubility Correlations
The Aspen Physical Property System has three built-in solubility correlation
models. This section describes the solubility correlation models available.
Model Type
Henry's constant 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) =

Linear extrapolation occurs for ln HiA versus T outside of bounds.

230 2 Thermodynamic Property Models


HiA(T, P) =

The parameter is obtained from the Brelvi-O'Connell model. pA*,l is


obtained from the Antoine model. is obtained from the appropriate activity
coefficient model.
The Henry's constants aiA, biA, ciA, diA, and eiA are specific to a solute-solvent
pair. They can be obtained from regression of gas solubility data. The Aspen
Physical Property System has a large number of built-in Henry's constants for
many solutes in solvents. These parameters were obtained using data from
the Dortmund Databank. In addition, a small number of Henry's constants
from the literature are available in the BINARY databank. See Physical
Property Data, Chapter 1, for details.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VC VcA 0.001 3.5 MOLE-VOLUME
HENRY/1 aiA x PRESSURE,
TEMPERATURE
HENRY/2 biA 0 x TEMPERATURE
HENRY/3 ciA 0 x TEMPERATURE
HENRY/4 diA 0 x TEMPERATURE
HENRY/5 TL 0 x TEMPERATURE
HENRY/6 TH 2000 x TEMPERATURE
HENRY/7 eiA 0 x TEMPERATURE

If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.

If aiA is missing, is set to zero and the weighting factor wA is


renormalized.

Reference for BINARY Databank


E. Wilhelm, R. Battino, and R.J. Wilcock, "Low-Pressure Solubility of Gases in
Liquid Water," Chemical Reviews, 1977, Vol. 77, No. 2, pp 219 - 262.

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:

2 Thermodynamic Property Models 231


No extrapolation is used with this equation.
The parameters for about 60 components are stored in the Aspen Physical
Property System pure component databank.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
WATSOL/1 C1i fcn(Tbi, SGi, Mi) -10.0 33.0
WATSOL/2 C2i fcn(Tbi, SGi, Mi) -10000.0 3000.0 TEMPERATURE
WATSOL/3 C3i 0 -0.05 0.05 TEMPERATURE
WATSOL/4 C4i 0 0.0 500 TEMPERATURE
WATSOL/5 C5i 1000 4.0 1000 TEMPERATURE

Absolute temperature units are assumed for elements 2 through 5.

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:

No extrapolation is used with this equation.


The parameters for about 40 components are stored in the Aspen Physical
Property System pure component databank.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
HCSOL/1 C1i fcn(carbon -1000.0 1000.0
number)
HCSOL/2 C2i 0 -100000.0 100000.0 TEMPERATURE
HCSOL/3 C3i 0 -100.0 100.0 TEMPERATURE
HCSOL/4 C4i 0 0.0 500 TEMPERATURE
HCSOL/5 C5i 1000 4.0 1000 TEMPERATURE

For Hydrocarbons and pseudocomponents, the default values are estimated


by the method given by API Procedure 9A2.17 at 25 C.
Absolute temperature units are assumed for elements 2 and 3. The
temperature limits are always interpreted in user input units.

232 2 Thermodynamic Property Models


Reference
C. Tsonopoulos, Fluid Phase Equilibria, 186 (2001), 185-206.

Other Thermodynamic Property


Models
The Aspen Physical Property System has some built-in additional
thermodynamic property models that do not fit in any other category. This
section describes these models:
Cavett Liquid Enthalpy Departure
Barin Equations for Gibbs Energy, Enthalpy, Entropy and Heat Capacity
Electrolyte NRTL Enthalpy
Electrolyte NRTL Gibbs Energy
Liquid Enthalpy from Liquid Heat Capacity Correlation
Enthalpies Based on Different Reference States
Helgeson Equations of State
Quadratic Mixing Rule

Cavett
The general form for the Cavett model is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TC Tci 5.0 2000.0 TEMPERATURE
5 8
PC pci 10 10 PRESSURE
DHLCVT ZC X 0.1 0.5

Barin Equations for Gibbs Energy, Enthalpy,


Entropy, and Heat Capacity
The following equations are used when parameters from the Aspen Physical
Property System inorganic databank are retrieved.
Gibbs energy:
(1)

Enthalpy:
(2)

2 Thermodynamic Property Models 233


Entropy:
(3)

Heat capacity:
(4)

refers to an arbitrary phase which can be solid, liquid, or ideal gas. For each
phase, multiple sets of parameters from 1 to n are present to cover multiple
temperature ranges. The value of the parameter n depends on the phase.
(See tables that follow.) When the temperature is outside all these
temperature ranges, linear extrapolation of properties versus T is performed
using the slope at the end of the nearest temperature bound.
The four properties Cp, H, S, and G are interrelated as a result of the
thermodynamic relationships:

There are analytical relationships between the expressions describing the


properties Cp, H, S, and G (equations 1 to 4). The parameters an,i to hn,i can
occur in more than one equation.
The Aspen Physical Property System has other models which can be used to
calculate temperature-dependent properties which the BARIN equations can
calculate. The Aspen Physical Property System uses the parameters in
THRSWT to determine which model is used. See Pure Component
Temperature-Dependent Properties for details.
If this parameter is 200 to 211 Then the BARIN equations are
used to calculate
THRSWT/3 Liquid vapor pressure
THRSWT/5 Solid heat capacity
THRSWT/6 Liquid heat capacity
THRSWT/7 Ideal gas heat capacity

The liquid vapor pressure is computed from Gibbs energy as follows:


ln p = (GL - GV)/RT + ln pref
where p is the vapor pressure, and pref is the reference pressure 101325 Pa.
Thus, parameters for both liquid and vapor are necessary to calculate vapor
pressure.

Solid Phase
The parameters in range n are valid for temperature: Tn,ls < T < Tn,hs

234 2 Thermodynamic Property Models


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
CPSXPn/1 Tn,ls x TEMPERATURE
s
CPSXPn/2 Tn,h x TEMPERATURE
s
CPSXPn/3 an,i x
CPSXPn/4 bn,is 0 x
s
CPSXPn/5 cn,i 0 x
s
CPSXPn/6 dn,i 0 x
CPSXPn/7 en,is 0 x
s
CPSXPn/8 fn,i 0 x
s
CPSXPn/9 gn,i 0 x
s
CPSXPn/10 hn,i 0 x

n is 1 through 7. CPSXP1 vector stores solid parameters for the first


temperature range. CPSXP2 vector stores solid parameters for the second
temperature range, and so on.
TEMPERATURE, ENTHALPY, ENTROPY

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 2. CPLXP1 stores liquid parameters for the first temperature


range. CPLXP2 stores liquid parameters for the second temperature range.
TEMPERATURE, ENTHALPY, ENTROPY

Ideal Gas Phase


The parameters in range n are valid for temperature: Tn,lig < T < Tn,hig
When you specify this parameter, be sure to specify at least elements 1
through 3.

2 Thermodynamic Property Models 235


Parameter Name Symbol Default MDS Lower Upper Units
/Element Limit Limit
CPIXPn/1 Tn,lig x TEMPERATURE
ig
CPIXPn/2 Tn,h x TEMPERATURE
ig
CPIXPn/3 an,i x
CPIXPn/4 bn,iig 0 x
ig
CPIXPn/5 cn,i 0 x
ig
CPIXPn/6 dn,i 0 x
CPIXPn/7 en,iig 0 x
ig
CPIXPn/8 fn,i 0 x
ig
CPIXPn/9 gn,i 0 x
CPIXPn/10 hn,iig 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

Electrolyte NRTL Enthalpy Model


(HMXENRTL)
The equation for the electrolyte NRTL enthalpy model (HMXENRTL) is:

The molar enthalpy Hm* and the molar excess enthalpy Hm*E are defined with
the asymmetrical reference state: the pure solvent water and infinite dilution
of molecular solutes and ions. (here * refers to the asymmetrical reference
state.)
Hw* is the pure water molar enthalpy, calculated from the Ideal Gas model
and the ASME Steam Table equation-of-state. (here * refers to pure
component.)

Hs*,l is the enthalpy contribution from a non-water solvent. It is calculated as


usual for components in activity coefficient models:

Hs*,l(T) = Hs*,ig + DHVs(T,p) - Hs,vap(T).


The term DHVs(T,p) = Hs*,v - Hs*,ig is the vapor enthalpy departure
contribution to liquid enthalpy; option code 5 determines how this is
calculated.

The aqueous infinite dilution thermodynamic enthalpy Hk is calculated from

the infinite dilution aqueous phase heat capacity as follows:

236 2 Thermodynamic Property Models


where the subscript k refers to any ion or molecular solute. By default,
is calculated from the aqueous infinite dilution heat capacity polynomial. If

the polynomial model parameters are not available, is calculated from


the Criss-Cobble correlation for ionic solutes.
For molecular solutes (e.g. Henry components), if the aqueous infinite dilution

heat capacity polynomial model parameters are not available, Hk is
calculated from Henry's law:

Hm*E is calculated from the electrolyte NRTL activity coefficient model.


See Criss-Cobble correlation model and Henry's law model for more
information.
Parameter Applicable Symbol Default Units
Name Components
IONTYP Ions Ion 0
SO25C Cations ,aq MOLE-ENTROPY
Sc (T=298)
Anions ,aq MOLE-ENTROPY
Sa (T=298)
DHAQFM Ions, Molecular Solutes f Hk,aq MOLE-ENTHALPY

CPAQ0 Ions, Molecular Solutes ,aq HEAT-CAPACITY
Cp,k

DHFORM Molecular Solutes f Hi*,ig MOLE-ENTHALPY

Water, Solvents f Hw*,ig MOLE-ENTHALPY


*,ig
CPIG Molecular Solutes Cp,i
*,ig
Water, Solvents Cp,w

IONTYP is not needed if CPAQ0 is given for ions.


DHFORM is not used if DHAQFM and CPAQ0 are given for molecular solutes
(components declared as Henry's components). If CPAQ0 is missing, DHFORM
and Henry's constants are used to calculate infinite dilution enthalpy for
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.

2 Thermodynamic Property Models 237


Option Codes for Electrolyte NRTL Enthalpy Model
(HMXENRTL)
The electrolyte NRTL enthalpy model (HMXENRTL) has seven option codes
and the option codes can affect the performance of this model.
Option code 1. Use this option code to specify the default values of pair
parameters for water/solute and solvent/solute; the solute represents a
cation/anion pair. The value (1) sets the default values to zero and the value
(3) sets the default values for water/solute to (8,-4) and for solvent/solute to
(10,-2). The value (3) is the default choice of the option code.
Option code 2. Use this option code to specify the vapor phase equation-of-
state (EOS) model used for the liquid enthalpy calculation. The value (0) sets
the ideal gas EOS model and the value (1) sets the HF EOS model. The value
(0) is the default.
Option code 3. Always leave this option code set to the value (1) to use the
solvent/solvent binary parameters obtained from NRTL parameters.
Option code 4. Not used.
Option code 5. Use this option code to specify how the vapor phase enthalpy
departure (DHV) is calculated. The value (0) sets DHV = 0, the value (1)
specifies using Redlich-Kwong equation of state, and the value (3) specifies
using Hayden-OConnell equation of state. The value (0) is the default.
Option code 6. Not used.
Option code 7. Use this option code to specify the method for handling
Henry components and multiple solvents. The value (0) sets the pure liquid
enthalpy to that calculated by aqueous infinite dilution heat capacity (only
water as solvent) and the value (1) sets the pure liquid enthalpy for Henry
components using Henrys law. Use value (1) when there are multiple
solvents. The value (0) is the default.

Electrolyte NRTL Gibbs Free Energy Model


(GMXENRTL)
The equation for the NRTL Gibbs free energy model (GMXENRTL) is:

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.)

The departure function is obtained from the ASME steam tables.

238 2 Thermodynamic Property Models


s*,l is the Gibbs free energy contribution from a non-water solvent. It is
calculated as usual for components in activity coefficient models.

The aqueous infinite dilution thermodynamic potential k is calculated from
the infinite dilution aqueous phase heat capacity polynomial model, by
default. Subscript k refers to any ion or molecular solute. If polynomial model
parameters are not available, it is calculated from the Criss-Cobble model for
ionic solutes:

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.

By default, is calculated from the aqueous infinite dilution heat


capacity polynomial. If the polynomial model parameters are not available,

is calculated from the Criss-Cobble correlation for ionic solutes.


For molecular solutes (e.g. Henry components), if the aqueous infinite dilution

heat capacity polynomial model parameters are not available, k is
calculated from Henry's law:

Gm*E is calculated from the electrolyte NRTL activity coefficient model.


See the Criss-Cobble correlation model and Henry's law model for more
information.
Parameter Applicable Symbol Default Units
Name Components
IONTYP Ions Ion 0
SO25C Cations ,aq MOLE-ENTROPY
Sc (T=298)
Anions ,aq MOLE-ENTROPY
Sa (T=298)
DGAQFM Ions, Molecular Solutes f Gk,aq MOLE-ENTHALPY

CPAQ0 Ions, Molecular Solutes ,aq HEAT-CAPACITY
Cp,k

DGFORM Molecular Solutes f Gi MOLE-ENTHALPY

Water, Solvents f Gw MOLE-ENTHALPY

2 Thermodynamic Property Models 239


Parameter Applicable Symbol Default Units
Name Components
CPIG Molecular Solutes Cp,i*,ig
*,ig
Water, Solvents Cp,w

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.

Option Codes for Electrolyte NRTL Gibbs Free Energy


Model (GMXENRTL)
The electrolyte NRTL Gibbs free energy model (GMXENRTL) has six option
codes and the option codes can affect the performance of this model.
Option code 1. Use this option code to specify the default values of pair
parameters for water/solute and solvent/solute; the solute represents a
cation/anion pair. The value (1) sets the default values to zero and the value
(3) sets the default values for water/solute to (8,-4) and for solvent/solute to
(10,-2). The value (3) is the default choice of the option code.
Option code 2. Use this option code to specify the vapor phase equation-of-
state (EOS) model used for the liquid Gibbs free energy calculation. The value
(0) sets the ideal gas EOS model and the value (1) sets the HF EOS model.
The value (0) is the default.
Option code 3. Always leave this option code set to the value (1) to use the
solvent/solvent binary parameters obtained from NRTL parameters.
Option code 4. Not used.
Option code 5. Use this option code to specify how the pure vapor phase
fugacity coefficient (PHIV) is calculated. The value (0) sets PHIV = 1 (ideal
gas law), the value (1) specifies using Redlich-Kwong equation of state, and
the value (3) specifies using Hayden-OConnell equation of state. The value
(0) is the default.
Option code 6. Use this option code to specify the method for handling
Henry components and multiple solvents. The value (0) sets the pure liquid
Gibbs free energy to that calculated by aqueous infinite dilution heat capacity
(only water as solvent) and the value (1) sets the pure liquid Gibbs free
energy for Henry components using Henrys law. Use value (1) when there
are multiple solvents. The value (0) is the default.

Liquid Enthalpy from Liquid Heat Capacity


Correlation
Liquid enthalpy is directly calculated by integration of liquid heat capacity:

240 2 Thermodynamic Property Models


The reference enthalpy is calculated at Tref as:

Where:
Hi*,ig = Ideal gas enthalpy
Hi*,v - Hi*,ig = Vapor enthalpy departure from equation of state

vapHi*,l = Heat of vaporization from General model

Tref = Reference temperature, specified by user. Defaults to


298.15 K
See General Pure Component Heat of Vaporization for parameter requirement
and additional details.

Enthalpies Based on Different Reference


States
Two property methods, WILS-LR and WILS-GLR, are available to calculate
enthalpies based on different reference states. The WILS-LR property method
is based on saturated liquid reference state for all components. The WILS-GLR
property method allows both ideal gas and saturated liquid reference states
for different components.
These property methods use an enthalpy method that optimizes the accuracy
tradeoff between liquid heat capacity, heat of vaporization, and vapor heat
capacity at actual process conditions. This highly recommended method
eliminates many of the problems associated with accurate thermal properties
for both phases, especially the liquid phase.
The liquid enthalpy of mixture is calculated by the following equation (see the
table labeled Liquid Enthalpy Methods):

Where:
Hmig = Enthalpy of ideal gas mixture
=

Hi*,ig = Ideal gas enthalpy of pure component i


(Hml-Hmig) = Enthalpy departure of mixture
For supercritical components, declared as Henry's components, the enthalpy
departure is calculated as follows:

2 Thermodynamic Property Models 241


For subcritical components:
Hml-Hmig =

HmE,l =

HA*,l-HA*,ig = Enthalpy departure of pure component A


H*,ig and H*,l can be calculated based on either saturated liquid or ideal gas as
reference state as described in the sections that follow.
For the WILS-LR property method, H*,ig and H*,l are calculated based on the
saturated liquid reference state for all components.
For the WILS-GLR property method, H*,ig and H*,l can be calculated based on
the saturated liquid reference state for some components and the ideal gas
reference state for other components. You can set the value of a pure
component parameter called RSTATE to specify the reference state for each
component. RSTATE = 1 denotes ideal gas reference state. RSTATE = 2
denotes saturated liquid reference state. If it is not set, the following default
rules apply based on the normal boiling point of the component, i, TB(i):
If TB(i) <= 298.15 K, ideal gas reference state is used
If TB(i) > 298.15 K, saturated liquid reference state is used.

Note: When H*,ig (HIG) is calculated based on saturated liquid reference


state, ideal gas Gibbs free energy and entropy (GIG and SIG) are also
calculated based on saturated liquid reference state to maintain
thermodynamic consistency, and liquid Gibbs free energy and entropy are
also calculated based on saturated liquid reference state since they are
calculated based on departure from the ideal gas values.

Saturated Liquid as Reference State


The saturated liquid enthalpy at temperature T is calculated as follows:

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

i*,l = Liquid fugacity coefficient of component i

p = System pressure

242 2 Thermodynamic Property Models


pref = Reference pressure (=101325 N/m2)
For the WILS-LR property method, Hiref,l and Giref,l default to zero (0). The
reference temperature Tiref,l defaults to 273.15K.
For the WILS-GLR property method, the reference temperature Tiref,l defaults
to 298.15K and Hiref,l defaults to:

And Giref,l defaults to:

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

Hi*,v = Vapor enthalpy departure of component i

Gi*,v = Vapor Gibbs free energy departure of component i

vapHi* = Enthalpy of vaporization of component i

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

vapHi*(Ticon,l) = Heat of vaporization of component i at


temperature of Tcon,l

Hi*,v(Ticon,l, pi*,l) = Vapor enthalpy departure of component i at the


conversion temperature and vapor pressure pi*,l
pi*,l = Liquid vapor pressure of component i

2 Thermodynamic Property Models 243


= Ideal gas heat capacity of 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

capacity is obtained from the general pure component ideal


gas heat capacity or other models.
However, if the conversion temperature is not specified, it defaults to T, and
the ideal gas enthalpy equation becomes:

And then the ideal gas heat capacity, calculated by differentiating this
equation, is:

The vapor enthalpy is calculated from ideal gas enthalpy as follows:

Where:

Hi*,v(T, P) = Vapor enthalpy departure of pure component i at the system


temperature and pressure
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 2
ref,l
TREFHL Ti TEMPERATURE
ref,l
DHLFRM Hi MOLE ENTHALPY
DGLFRM Giref,l MOLE ENTHALPY
con,l
TCONHL Ti T TEMPERATURE

Enthalpy reference state given by RSTATE. 2 denotes saturated liquid as


reference state.

244 2 Thermodynamic Property Models


For WILS-LR property method TREFHL defaults to 273.15K. For WILS-GLR
property method, TREFHL defaults to 298.15 K.
For WILS-LR property method, DHLFRM defaults to zero (0). For WILS-
GLR property method, DHLFRM defaults to the equation above.
For WILS-LR property method, DGLFRM defaults to zero (0). For WILS-
GLR property method, DGLFRM defaults to the equation above.
Liquid heat capacity equation is required for all components.

Ideal Gas as Reference State


The saturated liquid enthalpy is calculated as follows:

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 vapor 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

2 Thermodynamic Property Models 245


Enthalpy reference state RSTATE for a component. Value of 1 denotes ideal
gas.

For components with TB 298.15 K, RSTATE defaults to 1 (ideal gas).


TREFHI defaults to 298.15 K. For components with TB > 298.15 K, RSTATE
defaults to 2 (liquid) and TREFHI does not apply to these components. See
the Saturated Liquid as Reference State section for more details.

Helgeson Equations of State


The Helgeson equations of state for standard volume , heat capacity ,
entropy , enthalpy of formation , and Gibbs energy of formation
at infinite dilution in aqueous phase are:

246 2 Thermodynamic Property Models


Where:

2 Thermodynamic Property Models 247


Where:

= Pressure constant for a solvent (2600 bar for water)

= Temperature constant for a solvent (228 K for


water)

= Born coefficient

= Dielectric constant of a solvent

Tr = Reference temperature (298.15 K)


Pr = Reference pressure (1 bar)

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
AHGPAR/1, ... , a1, ..., a4 0
4
CHGPAR/1, ... , c1, c2 x
2
DHAQHG 0 -0.5x1010 0.5x1010 MOLE-ENTHALPY

DGAQHG 0 -0.5x1010 0.5x1010 MOLE-ENTHALPY

S25HG 0 -0.5x1010 0.5x1010 MOLE-ENTROPY

OMEGHG 0 -0.5x1010 0.5x1010 MOLE-ENTHALPY

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:

248 2 Thermodynamic Property Models


Correlation algorithms for ionic species and equation of state predictions to 5
kb and 1000 C," Geochimica et Cosmochimica Acta, Vol. 52, p. 2009-2036.
Shock, E.L., H.C. Helgeson, and D.A. Sverjensky, "Calculation of the
thermodynamic and transport properties of aqueous species at high pressures
and temperatures: Standard partial molal properties of inorganic neutral
species," Geochimica et Cosmochimica Acta, Vol. 53, p. 2157-2183.

Quadratic Mixing Rule


The quadratic mixing rule is a general-purpose mixing rule which can be
applied to various properties. For a given property Q, with i and j being
components, the rule is:

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.

2 Thermodynamic Property Models 249


250 2 Thermodynamic Property Models
3 Transport Property Models

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

3 Transport Property Models 251


Model Model name Phase(s) Pure Mixture
Letsou-Stiel MUL0LEST, L X X
MUL2LEST
Lucas MUV0LUC, V X X
MUV2LUC
TRAPP viscosity MUL0TRAP, VL X X
MUL2TRAP,
MUV0TRAP,
MUV2TRAP
Twu liquid viscosity MUL2TWU L X
Viscosity quadratic mixing rule MUL2QUAD L X

Thermal conductivity models


These models calculate KL (pure) and/or KLMX (mixture) for the liquid phase,
and KV (pure) and/or KVMX (mixture) for the vapor phase, except models
marked with * calculate KVLP (pure) and/or KVMXLP (mixture) for the vapor
phase, and models marked with ** calculate KVPC (pure) and KVMXPC
(mixture) for the vapor phase.
Model Model name Phase(s) Pure Mixture
Chung-Lee-Starling Thermal KV0CLS2, VL X X
Conductivtity KV2CLS2,
KL0CLS2,
KL2CLS2
IAPS Thermal Conductivity for KV0H2O V X
Water KL0H2O L X
Li Mixing Rule KL2LI L X X
Riedel Electrolyte Correction KL2RDL L X
General Pure Component KL0SR, L X X
Liquid Thermal Conductivity KL2SRVR
General Pure Component KV0STLP V X
Vapor Thermal Conductivity *
Stiel-Thodos Pressure KV0STPC, V X X
Correction ** KV2STPC
TRAPP Thermal Conductivity KV0TRAP, VL X X
KV2TRAP,
KL0TRAP,
KL2TRAP
Vredeveld Mixing Rule KL2SRVR L X X
Wassiljewa-Mason-Saxena KV2WMSM V X X
mixing rule *

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

252 3 Transport Property Models


Model Model name Phase(s) BinaryMixture
Dawson-Khoury-Kobayashi DV1DKK V X
Binary
Dawson-Khoury-Kobayashi DV1DKK V X
Mixture
Nernst-Hartley Electrolytes DL0NST, L X X
DL1NST
Wilke-Chang Binary DL0WC2 L X
Wilke-Chang Mixture DL1WC L X

Surface tension models


These models calculate SIGL (pure) and/or SIGLMX (mixture).
Model Model name Phase(s) Pure Mixture
Liquid Mixture Surface Tension SIG2IDL L X
API Surface Tension SIG2API L X
General Pure Component SIG0HSS, L X
Liquid Surface Tension SIG2HSS
IAPS surface tension SIG0H2O L X
Onsager-Samaras Electrolyte SIG2ONSG L X
Correction
Modified MacLeod-Sugden SIG2MS L X

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

3 Transport Property Models 253


Model Type
Twu liquid viscosity Liquid
Viscosity quadratic mixing rule Liquid

Andrade Liquid Mixture Viscosity


The liquid mixture viscosity is calculated by the modified Andrade equation:

Where:
kij =

mij =

fi depends on the option code for the model MUL2ANDR.


If first option code of Then fi is
MUL2ANDR is
0 (Default) Mole fraction of component i
1 Mass fraction of component i

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

The pure component liquid viscosity i is calculated by the General Pure


*,l

Component Liquid Viscosity model.

254 3 Transport Property Models


General Pure Component Liquid Viscosity
The Aspen Physical Property System has several submodels for calculating
pure component liquid viscosity. It uses parameter TRNSWT/1 to determine
which submodel is used. See Pure Component Temperature-Dependent
Properties for details.
If TRNSWT/1 is This equation is used And this parameter is used
0 Andrade MULAND
101, 115 DIPPR 101 or 115 MULDIP
301 PPDS MULPDS
401 IK-CAPE polynomial equation MULPO
404 IK-CAPE exponential equation MULIKC
508 NIST TDE equation MULNVE
509 NIST PPDS9 MULPPDS9

Andrade Liquid Viscosity


The Andrade equation is:

Linear extrapolation of ln(viscosity) versus 1/T occurs for temperatures


outside bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULAND/1 Ai X VISCOSITY,
TEMPERATURE
MULAND/2 Bi X TEMPERATURE
MULAND/3 Ci X TEMPERATURE
MULAND/4 Tl 0.0 X TEMPERATURE
MULAND/5 Th 500.0 X TEMPERATURE

If Bi or Ci is non-zero, absolute temperature units are assumed for Ai, Bi,


and Ci. Otherwise, all coefficients are interpreted in user input temperature
units. The temperature limits are always interpreted in user input units.

DIPPR Liquid Viscosity


There are two DIPPR equations for liquid viscosity. The value of TRNSWT/1
determines which one is used.
Equation 101 for the DIPPR liquid viscosity model is:

Equation 115 for the DIPPR liquid viscosity model is:

Linear extrapolation of ln(viscosity) versus 1/T occurs for temperatures


outside bounds.

3 Transport Property Models 255


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULDIP/1 C1i X VISCOSITY,
TEMPERATURE
MULDIP/2, ..., 5 C2i, ..., C5i 0 X TEMPERATURE
MULDIP/6 C6i 0 X TEMPERATURE
MULDIP/7 C7i 1000 X TEMPERATURE

If any of C3i through C5i are non-zero, absolute temperature units are
assumed for C3i through C5i. Otherwise, all coefficients are interpreted in user
input temperature units. The temperature limits are always interpreted in
user input units.

PPDS
The PPDS equation is:

Linear extrapolation of viscosity versus T occurs for temperatures outside


bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULPDS/1 C1i
MULPDS/2 C2i
MULPDS/3 C3i TEMPERATURE
MULPDS/4 C4i TEMPERATURE
MULPDS/5 C5i VISCOSITY
MULPDS/6 C6i TEMPERATURE
MULPDS/7 C7i TEMPERATURE

NIST PPDS9 Equation


This is the same as the PPDS equation above, but it uses parameter
MULPPDS9. Note that the parameters are in a different order.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULPPDS9/1 C5i VISCOSITY
MULPPDS9/2 C1i
MULPPDS9/3 C2i
MULPPDS9/4 C3i TEMPERATURE
MULPPDS9/5 C4i TEMPERATURE
MULPPDS9/6 C6i TEMPERATURE
MULPPDS9/7 C7i TEMPERATURE

256 3 Transport Property Models


IK-CAPE Liquid Viscosity Model
The IK-CAPE liquid viscosity model includes both exponential and polynomial
equations.

Exponential

Linear extrapolation of viscosity versus T occurs for temperatures outside


bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULIKC/1 C1i X VISCOSITY
MULIKC/2 C2i 0 X TEMPERATURE
MULIKC/3 C3i 0 X VISCOSITY
MULIKC/4 C4i 0 X TEMPERATURE
MULIKC/5 C5i 1000 X TEMPERATURE

Absolute temperature units are assumed for C2i. The temperature limits
are always interpreted in user input units.

Polynomial

Linear extrapolation of viscosity versus T occurs for temperatures outside


bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULPO/1 C1i X VISCOSITY
MULPO/2, ..., 10 C2i, ..., C10i 0 X VISCOSITY,
TEMPERATURE
MULPO/11 C11i 0 X TEMPERATURE
MULPO/12 C12i 1000 X TEMPERATURE

NIST TDE Equation

Linear extrapolation of viscosity versus T occurs for temperatures outside


bounds.
Absolute temperature units are assumed for C2i, C3i, and C4i. The temperature
limits are always interpreted in user input units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULNVE/1 C1i X

3 Transport Property Models 257


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULNVE/2, 3, 4 C2i, C3i, C4i 0 X TEMPERATURE
MULNVE/5 C5i 0 X TEMPERATURE
MULNVE/6 C6i 1000 X TEMPERATURE

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 439.

API Liquid Viscosity


The liquid mixture viscosity is calculated using a combination of the API and
General equations. This model is recommended for petroleum and
petrochemical applications. It is used in the CHAO-SEA, GRAYSON, LK-PLOCK,
PENG-ROB, and RK-SOAVE option sets.
For pseudocomponents, the API model is used:

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

API 1997 Liquid Viscosity


The liquid mixture viscosity is calculated using a combination of the API and
General equations. This model is recommended over the earlier API viscosity
model.
This model is applicable to petroleum fractions with normal boiling points from
150 F to 1200 F and API gravities between 0 and 75. Testing by AspenTech
indicates that this model is slightly more accurate than the Twu model for
light and medium boiling petroleum components, while the Twu model is
superior for heavy fractions.
For pseudocomponents, the API model is used:

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)

258 3 Transport Property Models


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

Aspen Liquid Mixture Viscosity


The liquid mixture viscosity is calculated by the equation:

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 --- --- ---

3 Transport Property Models 259


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MUKIJ/5 eij 0 X --- --- ---
MUKIJ/6 Tref 298.15 X --- --- ---
MULIJ/1 a'ij 0 X --- --- ---
MULIJ/2 b'ij 0 X --- --- ---
MULIJ/3 c'ij 0 X --- --- ---
MULIJ/4 d'ij 0 X --- --- ---
MULIJ/5 e'ij 0 X --- --- ---
MULIJ/6 Tref 298.15 X --- --- ---

Aspen Liquid Mixture Viscosity Model (MUASPEN) is a correlative model and it


is essentially a new mixing rule for calculating the mixture viscosity from the
pure component viscosities. It requires the pure component liquid viscosities
being calculated by another model before the mixture liquid viscosity can be
calculated. To ensure this prerequisite, the route MULMX14 was created
particularly for this model. To use this model in a property method you
create, you should specify or change the route for MULMX to MULMX14 rather
than changing the mixture liquid viscosity model to MUASPEN directly.

ASTM Liquid Mixture Viscosity


It is generally difficult to predict the viscosity of a mixture of viscous
components. For hydrocarbons, the following weighting method (ASTM ) is
known to give satisfactory results:

Where:
wi = Weight fraction of component i

m = Absolute viscosity of the mixture (N-sec/m2)

i = Absolute viscosity of component i (N-sec/m2)

log = Common logarithm (base 10)


f = An adjustable parameter, typically in the
range of 0.5 to 1.0
There are two significant differences in this implementation as compared with
the version from the book . The book uses kinematic viscosity in mm2/s
while the Aspen Physical Property System uses absolute viscosity in cP (=
0.001 N-sec/m2) with an equation in the same form. And f is treated as an
adjustable parameter in this model, while the book makes it a function of the
pure component kinematic viscosity.
The individual component viscosities are calculated by the General Pure
Component Liquid Viscosity model. The parameter f can be specified by
setting the value for MULOGF for the first component in the component list
(as defined on the Components | Specifications | Selection sheet).

260 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULOGF f 1.0 0.0 2.0

"Petroleum Refining, 1 Crude Oil, Petroleum Products, Process Flowsheets",


Institut Francais du Petrole Publications, 1995, p. 130.

General Pure Component Vapor Viscosity


The Aspen Physical Property System has several submodels for calculating
pure component low pressure vapor viscosity. It uses parameter TRNSWT/2
to determine which submodel is used. See Pure Component Temperature-
Dependent Properties for details.
If TRNSWT/2 is This equation is used And this parameter is
used
0 Chapman-Enskog- STKPAR, LJPAR
Brokaw
102 DIPPR MUVDIP
301 PPDS MUVPDS
302 PPDS kinetic theory MUVCEB
401 IK-CAPE polynomial MUVPO
equation
402 IK-CAPE Sutherland MUVSUT
equation
503 NIST ThermoML MUVTMLPO
polynomial

Chapman-Enskog-Brokaw
The equation for the Chapman-Enskog model is:

Where:

A parameter is used to determine whether to use the Stockmayer or


Lennard-Jones potential parameters for /k (energy parameter) and
(collision diameter). To calculate , the dipole moment p and either the
Stockmayer parameters or Tb and Vb are needed. The polarity correction is
from Brokaw.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0
-24
MUP pi 0.0 5x10 DIPOLEMOMENT
STKPAR/1 (i/k) ST fcn(Tbi, Vbi, pi) X TEMPERATURE

STKPAR/2 iST fcn(Tbi, Vbi, pi) X LENGTH

3 Transport Property Models 261


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
LJPAR/1 (i/k)LJ fcn(Tci, i) X TEMPERATURE

LJPAR/2 iLJ fcn(Tci, pci, i) X LENGTH

DIPPR Vapor Viscosity


The equation for the DIPPR vapor viscosity model is:

When necessary, the vapor viscosity is extrapolated beyond this temperature


range linearly with respect to T, using the slope at the temperature limits.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
PCES uses the DIPPR equation in estimating vapor viscosity.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MUVDIP/1 C1i X VISCOSITY
MUVDIP/2 C2i 0 X
MUVDIP/3, 4 C3i, C4i 0 X TEMPERATURE
MUVDIP/5 0 X
MUVDIP/6 C6i 0 X TEMPERATURE
MUVDIP/7 C7i 1000 X TEMPERATURE

If any of C2i through C4i are non-zero, absolute temperature units are
assumed for C1i through C4i. Otherwise, all coefficients are interpreted in user
input temperature units. The temperature limits are always interpreted in
user input units.
MUVDIP/5 is not used in this equation. It is normally set to zero. The
parameter is provided for consistency with other DIPPR equations.

PPDS
The PPDS submodel includes both the basic PPDS vapor viscosity equation
and the PPDS kinetic theory vapor viscosity equation. For either equation,
linear extrapolation of viscosity versus T occurs for temperatures outside
bounds.

PPDS Vapor Viscosity


The equation is:

262 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MUVPDS/1 C1i VISCOSITY
MUVPDS/2 C2i 0
MUVPDS/3 C3i 0
MUVPDS/4 C4i 0 TEMPERATURE
MUVPDS/5 C5i 1000 TEMPERATURE

PPDS Kinetic Theory Vapor Viscosity


The equation is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MW Mi 1.0 5000.0
MUVCEB/1 C1i LENGTH
MUVCEB/2 C2i TEMPERATURE
MUVCEB/3 C3i 0
MUVCEB/4 C4i 0 TEMPERATURE
MUVCEB/5 C5i 1000 TEMPERATURE

Absolute temperature units are assumed for C2i . The temperature limits are
always interpreted in user input units.

IK-CAPE Vapor Viscosity


The IK-CAPE vapor viscosity model includes both the Sutherland equation and
the polynomial equation. For either equation, linear extrapolation of viscosity
versus T occurs for temperatures outside bounds.

Sutherland Equation

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MUVSUT/1 C1i X VISCOSITY
MUVSUT/2 C2i 0 X TEMPERATURE
MUVSUT/3 C3i 0 X TEMPERATURE
MUVSUT/4 C4i 1000 X TEMPERATURE

If C2i is non-zero, absolute temperature units are assumed for C1i and C2i.
Otherwise, all coefficients are interpreted in user input temperature units. The
temperature limits are always interpreted in user input units.

3 Transport Property Models 263


Polynomial

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MUVPO/1 C1i X VISCOSITY
MUVPO/2, ..., 10 C2i, ..., C10i 0 X VISCOSITY,
TEMPERATURE
MUVPO/11 C11i 0 X TEMPERATURE
MUVPO/12 C12i 1000 X TEMPERATURE

NIST ThermoML Polynomial

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MUVTMLPO/1 C1i X Pa*s/T
MUVTMLPO/2, ..., 4 C2i , ..., C4i 0 X Pa*s/T
MUVTMLPO/5 nTerms 4 X
MUVTMLPO/6 Tlower 0 X TEMPERATURE
MUVTMLPO/7 Tupper 1000 X TEMPERATURE

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling. The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 392.

Chapman-Enskog-Brokaw-Wilke Mixing
Rule
The low pressure vapor mixture viscosity is calculated by the Wilke
approximation of the Chapman-Enskog equation:

For ij,the formulation by Brokaw is used:

Where:

264 3 Transport Property Models


The Stockmayer or Lennard-Jones potential parameters /k (energy
parameter) and (collision diameter) and the dipole moment p are used to
calculate The k represents Boltzmann's constant 1.38065 x 10-23 J/K. If the
Stockmayer parameters are not available, is estimated from Tb and Vb:

Where p is in debye.

The pure component vapor viscosity i*,v (p = 0) can be calculated using the
General Pure Component Vapor Viscosity (or another low pressure vapor
viscosity model).

Ensure that you supply parameters for i*,v (p = 0).


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
MW Mi 1.0 5000.0
-24
MUP pi 0.0 5x10 DIPOLEMOMENT
STKPAR/1 (i/k) ST fcn(Tbi, Vbi, pi) X TEMPERATURE

STKPAR/2 iST fcn(Tbi, Vbi, pi) X LENGTH

References
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of Gases and
Liquids, 3rd ed., (New York: McGraw-Hill, 1977), pp. 410416.

3 Transport Property Models 265


Chung-Lee-Starling Low-Pressure Vapor
Viscosity
The low-pressure vapor viscosity by Chung, Lee, and Starling is:

Where the viscosity collision integral is:

The shape and polarity correction is:

The parameter pr is the reduced dipolemoment:

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:

266 3 Transport Property Models


Vcij =

ij = 0 (in almost all cases)

Tcij =

ij = 0 (in almost all cases)

ij =

Mij =

ij =

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCCLS Tci TC x 5.0 2000.0 TEMPERATURE
VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME
MW Mi 1.0 5000.0
-24
MUP pi 0.0 5x10 DIPOLEMOMENT
OMGCLS i OMEGA x -0.5 2.0

CLSK i 0.0 x 0.0 0.5

CLSKV ij 0.0 x -0.5 -0.5

CLSKT ij 0.0 x -0.5 0.5

The model specific parameters also affect the Chung-Lee-Starling Viscosity


and the Chung-Lee-Starling Thermal Conductivity models.

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 396, p. 413.

Chung-Lee-Starling Viscosity
The Chung-Lee-Starling viscosity equation for vapor and liquid, high and low
pressure is:

With:

3 Transport Property Models 267


f1 =

f2 =

FC =

The molar density can be calculated using an equation-of-state model (for


example, the Benedict-Webb-Rubin). The parameter pr is the reduced
dipolemoment:

C1 and C2 are constants of correlation.

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 = 0 (in almost all cases)

268 3 Transport Property Models


Tcij =

ij = 0 (in almost all cases)

ij =

Mij =

ij =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCCLS Tci TC x 5.0 2000.0 TEMPERATURE
VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME
MW Mi 1.0 5000.0
-24
MUP pi 0.0 5x10 DIPOLEMOMENT
OMGCLS i OMEGA x -0.5 2.0

CLSK i 0.0 x 0.0 0.5

CLSKV ij 0.0 x -0.5 -0.5

CLSKT ij 0.0 x -0.5 0.5

The model specific parameters affect the results of the Chung-Lee-Starling


Thermal Conductivity and Low Pressure Viscosity models as well.

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.

Dean-Stiel Pressure Correction


The residual vapor viscosity or the pressure correction to low pressure vapor
viscosity by Dean and Stiel is:

Where v (p = 0) is obtained from a low pressure viscosity model (for


example, General Pure Component Vapor Viscosity). The dimensionless-
making factor is:

3 Transport Property Models 269


Tc =

M =

pc =

Vcm =

Zcm =

rm = Vcm / Vmv

The parameter Vmv is obtained from Redlich-Kwong equation-of-state.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0
VC Vci 0.001 3.5 MOLE-VOLUME

IAPS Viscosity for Water


The IAPS viscosity models, developed by the International Association for
Properties of Steam, calculate vapor and liquid viscosity for water and steam.
These models are used in option sets STEAMNBS and STEAM-TA.
The general form of the equation for the IAPS viscosity models is:

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.

Jones-Dole Electrolyte Correction


The Jones-Dole model calculates the correction to the liquid mixture viscosity
of a solvent mixture, due to the presence of electrolytes:

Where:

solv = Viscosity of the liquid solvent mixture, by default


calculated by the Andrade model

cal = Contribution to the viscosity correction due to


apparent electrolyte ca

270 3 Transport Property Models


The parameter solv can be calculated by different models depending on
option code 3 for MUL2JONS:
Option Code Solvent liquid mixture viscosity
Value model
Andrade liquid mixture viscosity
0
model (default)
1 Viscosity quadratic mixing rule
2 Aspen liquid mixture viscosity
model

The parameter cal can be calculated by three different equations.


If these parameters are available Use this equation

IONMOB and IONMUB Jones-Dole
IONMUB Breslau-Miller
Carbonell

When the concentration of apparent electrolyte exceeds 0.1 M, the Breslau-


Miller equation is used instead.

Jones-Dole
The Jones-Dole equation is:
(1)

Where:
= Concentration of apparent electrolyte ca (2)

xcaa = Mole fraction of apparent electrolyte ca (3)


Aca = (4)

La = (5)

Lc = (6)

Bca = (7)

When the electrolyte concentration exceeds 0.1 M, the Breslau-Miller equation


is used instead. This behavior can be disabled by setting the second option
code for MUL2JONS to 1.

Breslau-Miller
The Breslau-Miller equation is:
(8)

3 Transport Property Models 271


Where the effective volume Vc is given by:
(9)

for salts involving univalent ions


(9a)

for other salts

Carbonell
The Carbonell equation is:
(10)

Where:
Mk = 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

When IONMOB/1 is missing, the Jones-Dole model uses a nominal value of


5.0 and issues a warning. This parameter should be specified for ions, and not
allowed to default to this value.

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.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
The general form for the model is:

272 3 Transport Property Models


l = (l)0 + (l)1
Where:

(l)0 =

(l)1 =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MW Mi 1.0 5000.0
TC Tci 5.0 2000.0 TEMPERATURE
5 8
PC pci 10 10 PRESSURE
OMEGA i -0.5 2.0

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.

Lucas Vapor Viscosity


The equation for the Lucas vapor viscosity model is:

Where the dimensionless low pressure viscosity is given by:

The dimensionless-making group is:

The pressure correction factor Y is:

The polar and quantum correction factors at high and low pressure are:
FP =

FQ =

FPi (p = 0) =

3 Transport Property Models 273


FQi (p = 0) = fcn(Tri), but is only nonunity for the quantum
gates i = H2, D2, and He.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
The Lucas mixing rules are:
Tc =

pc =

M =

FP (p = 0) =

FQ (p = 0) =

Where A differs from unity only for certain mixtures.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCLUC Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PCLUC pci PC x 10 10 PRESSURE
ZCLUC Zci ZC x 0.1 0.5
MW Mi 1.0 5000.0
-24
MUP pi 0.0 5x10 DIPOLEMOMENT

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 421, 431.

TRAPP Viscosity Model


The general form for the TRAPP viscosity model is:

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.

274 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0
TCTRAP Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PCTRAP pci PC x 10 10 PRESSURE
VCTRAP Vci VC x 0.001 3.5 MOLE-VOLUME
ZCTRAP Zci ZC x 0.1 1.0
OMGRAP i OMEGA x -0.5 3.0

References
J.F. Ely and H.J.M. Hanley, "Prediction of Transport Properties. 1. Viscosities
of Fluids and Mixtures," Ind. Eng. Chem. Fundam., Vol. 20, (1981), pp. 323
332.

Twu Liquid Viscosity


The Twu liquid viscosity model is based upon the work of C.H. Twu (1985).
The correlation uses n-alkanes as a reference fluid and is capable of
predicting liquid viscosity for petroleum fractions with normal boiling points up
to 1340 F and API gravity up to -30.
Given the normal boiling point Tb and the specific gravity SG of the system to
be modeled, the Twu model estimates the viscosity of the n-alkane reference
fluid of the same normal boiling point at 100 F and 210 F, and its specific
gravity. These are used to estimates the viscosity of the system to be
modeled at 100 F and at 210 F, and these viscosities are used to estimate the
viscosity at the temperature of interest.

3 Transport Property Models 275


Where:
SG = Specific gravity of petroleum fraction
Tb = Normal boiling point of petroleum fraction, Rankine
SG = Specific gravity of reference fluid with normal
boiling point Tb
T = Temperature of petroleum fraction, Rankine

= Kinematic viscosity of petroleum fraction at T, cSt

i = Kinematic viscosity of petroleum fraction at 100 F


(i=1) and 210 F (i=2), cSt

1, 2 = Kinematic viscosity of reference fluid at 100 F and


210 F, cSt
Tc = Critical temperature of reference fluid, Rankine

276 3 Transport Property Models


Reference
C.H. Twu, "Internally Consistent Correlation for Predicting Liquid Viscosities of
Petroleum Fractions," Ind. Eng. Chem. Process Des. Dev., Vol. 24 (1985), pp.
1287-1293

Viscosity Quadratic Mixing Rule


With i and j being components, the viscosity quadratic mixing rule is:

The pure component viscosity is calculated by the General Pure Component


Liquid Viscosity model.

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 - -

Thermal Conductivity Models


The Aspen Physical Property System has eight built-in thermal conductivity
models. This section describes the thermal conductivity models available.
Model Type
Chung-Lee-Starling Vapor or liquid
IAPS Water or steam
Li Mixing Rule Liquid mixture
Riedel Electrolyte Correction Electrolyte
General Pure Component Liquid Thermal Liquid
Conductivity
Solid Thermal Conductivity Polynomial Solid
General Pure Component Vapor Thermal Low pressure vapor
Conductivity
Stiel-Thodos Pressure Correction Vapor
TRAPP Thermal Conductivity Vapor or liquid
Vredeveld Mixing Rule Liquid mixture
Wassiljewa-Mason-Saxena Mixing Rule Low pressure vapor

3 Transport Property Models 277


Chung-Lee-Starling Thermal Conductivity
The main equation for the Chung-Lee-Starling thermal conductivity model is:

Where:
f1 =

f2 =

(p = 0) can be calculated by the low pressure Chung-Lee-Starling model.


The molar density can be calculated using an equation-of-state model (for
example, the Benedict-Webb-Rubin equation-of-state). The parameter pr is
the reduced dipolemoment:

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:

278 3 Transport Property Models


Vcij =

ij = 0 (in almost all cases)

Tcij =

ij = 0 (in almost all cases)

ij =

Mij =

ij =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCCLS Tci TC x 5.0 2000.0 TEMPERATURE
VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME
MW Mi 1.0 5000.0
-24
MUP pi 0.0 5x10 DIPOLEMOMENT
OMGCLS i OMEGA x -0.5 2.0

CLSK i 0.0 x 0.0 0.5

CLSKV ij 0.0 x -0.5 -0.5

CLSKT ij 0.0 x -0.5 0.5

The model-specific parameters also affect the results of the Chung-Lee-


Starling Viscosity models.

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 505, 523.

IAPS Thermal Conductivity for Water


The IAPS thermal conductivity models were developed by the International
Association for Properties of Steam. These models can calculate vapor and
liquid thermal conductivity for water and steam. They are used in option sets
STEAMNBS and STEAM-TA.
The general form of the equation for the IAPS thermal conductivity models is:

w=fcn(T, p)
Where:

3 Transport Property Models 279


fcn = Correlation developed by IAPS
The models are only applicable to water. No parameters are required.

Li Mixing Rule
Liquid mixture thermal conductivity is calculated using Li equation (Reid
et.al., 1987):

Where:

The pure component liquid molar volume Vi*,l is calculated from the Rackett
model.

The pure component liquid thermal conductivity i*,l is calculated by the


General Pure Component Liquid Thermal Conductivity model.
Reference: R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases
and Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 550.

Riedel Electrolyte Correction


The Riedel model can calculate the correction to the liquid mixture thermal
conductivity of a solvent mixture, due to the presence of electrolytes:

Where:

lsolv = Thermal conductivity of the liquid solvent mixture,


calculated by the General Pure Component Liquid
Thermal Conductivity model using the Vredeveld
mixing rule
xcaa = Mole fraction of the apparent electrolyte ca
ac, aa = Riedel ionic coefficient
l
Vm = Apparent molar volume computed by the Clarke
density model
Apparent electrolyte mole fractions are computed from the true ion mole-
fractions and ionic charge number. They can also be computed if you use the
apparent component approach. A more detailed discussion of this method is
found in Electrolyte Calculation.

280 3 Transport Property Models


You must provide parameters for the Sato-Riedel model. This model is used
for the calculation of the thermal conductivity of solvent mixtures.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
CHARGE z 0.0
IONRDL a 0.0

THERMAL CONDUCTIVITY, MOLE-VOLUME


The behavior of this model can be changed using option codes (these codes
apply to the Vredeveld mixing rule).
Option Option Description
Code Value
1 0 Do not check ratio of KL max / KL min
1 Check ratio. If KL max / KL min > 2, set exponent to 1,
overriding option code 2.
2 0 Exponent is -2
1 Exponent is 0.4
2 Exponent is 1. This uses a weighted average of liquid thermal
conductivities.

General Pure Component Liquid Thermal


Conductivity
The Aspen Physical Property System has several submodels for calculating
pure component liquid thermal conductivity. It uses parameter TRNSWT/3 to
determine which submodel is used. See Pure Component Temperature-
Dependent Properties for details.
If TRNSWT/3 is This equation is used And this parameter is used
0 Sato-Riedel
100 DIPPR KLDIP
301 PPDS KLPDS
401 IK-CAPE KLPO
503 NIST ThermoML KLTMLPO
polynomial
510 NIST PPDS8 equation KLPPDS8

Sato-Riedel
The Sato-Riedel equation is (Reid et al., 1987):

Where:
Tbri = Tbi / Tci
Tri = T / Tci

3 Transport Property Models 281


Note: Reduced temperature Tr is always calculated using absolute
temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0
TC Tci 5.0 2000.0 TEMPERATURE
TB Tbi 4.0 2000.0 TEMPERATURE

PPDS
The equation is:

Linear extrapolation of *,l versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLPDS/1 C1i THERMAL-
CONDUCTIVITY
KLPDS/2 C2i 0
KLPDS/3 C3i 0
KLPDS/4 C4i 0
KLPDS/5 C5i 0 TEMPERATURE
KLPDS/6 C6i 1000 TEMPERATURE

NIST PPDS8 Equation


The equation is

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
KLPPDS8/1 C1i THERMAL-
CONDUCTIVITY
KLPPDS8/2, ..., 7 C2i , ..., C7i 0
KLPPDS8/8 TCi TEMPERATURE
KLPPDS8/9 nTerms 7
KLPPDS8/10 Tlower 0 TEMPERATURE
KLPPDS8/11 Tupper 1000 TEMPERATURE

DIPPR Liquid Thermal Conductivity


The DIPPR equation is:

282 3 Transport Property Models


Linear extrapolation of *,l versus T occurs outside of bounds.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
The DIPPR equation is used by PCES when estimating liquid thermal
conductivity.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLDIP/1 C1i x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLDIP/2, ... , 5 C2i , ..., C5i 0 x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLDIP/6 C6i 0 x TEMPERATURE
KLDIP/7 C7i 1000 x TEMPERATURE

NIST ThermoML Polynomial


The equation is:

Linear extrapolation of *,l versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLTMLPO/1 C1i x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLTMLPO/2, ... , C2i , ..., C4i 0 x THERMAL-
4 CONDUCTIVITY,
TEMPERATURE
KLTMLPO/5 nTerms 4 x
KLTMLPO/6 Tlower 0 x TEMPERATURE
KLTMLPO/7 Tupper 1000 x TEMPERATURE

IK-CAPE
The IK-CAPE equation is:

Linear extrapolation of *,l versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLPO/1 C1i x THERMAL-
CONDUCTIVITY

3 Transport Property Models 283


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLPO/2, ... , 10 C2i , ..., C10i 0 x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLPO/11 C11i 0 x TEMPERATURE
KLPO/12 C12i 1000 x TEMPERATURE

References
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1977), p. 533.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 550.

Solid Thermal Conductivity Polynomial


Thermal conductivity for solid pure components is calculated using the solid
thermal conductivity polynomial. For mixtures, the mole-fraction weighted
average is used.
For pure solids, thermal conductivity is calculated by:

For mixtures:

Linear extrapolation of i*,s versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KSPOLY/1 a THERMAL
CONDUCTIVITY
KSPOLY/2, 3, 4, 5 b, c, d, e 0 THERMAL
CONDUCTIVITY,
TEMPERATURE
KSPOLY/6 0 x TEMPERATURE

KSPOLY/7 1000 x TEMPERATURE

General Pure Component Vapor Thermal


Conductivity
The Aspen Physical Property System has several submodels for calculating
pure component low pressure vapor thermal conductivity. It uses parameter
TRNSWT/4 to determine which submodel is used. See Pure Component
Temperature-Dependent Properties for details.

284 3 Transport Property Models


If TRNSWT/4 is This equation is used And this parameter is
used
0 Stiel-Thodos
102 DIPPR KVDIP
301 PPDS KVPDS
401 IK-CAPE KVPO
503 NIST ThermoML KVTMLPO
polynomial

Stiel-Thodos
The Stiel-Thodos equation is:

Where:

i*,v(p = 0) can be obtained from the General Pure Component Vapor


Viscosity model.
Cpi*,ig is obtained from the General Pure Component Ideal Gas Heat Capacity
model.
R is the universal gas constant.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0

DIPPR Vapor Thermal Conductivity


The DIPPR equation for vapor thermal conductivity is:

Linear extrapolation of i*,v versus T occurs outside of bounds.


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
The DIPPR equation is used in PCES when estimating vapor thermal
conductivity.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVDIP/1 C1i x THERMAL
CONDUCTIVITY
KVDIP/2 C2i 0 x
KVDIP/3, 4 C3i, C4i 0 x TEMPERATURE
KVDIP/5 0 x
KVDIP/6 C6i 0 x TEMPERATURE
KVDIP/7 C7i 1000 x TEMPERATURE

If any of C2i through C4i are non-zero, absolute temperature units are
assumed for C1i through C4i. Otherwise, all coefficients are interpreted in user

3 Transport Property Models 285


input temperature units. The temperature limits are always interpreted in
user input units.

PPDS
The equation is:

Linear extrapolation of i*,v versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVPDS/1 C1i THERMAL-
CONDUCTIVITY
KVPDS/2 C2i 0 THERMAL-
CONDUCTIVITY
KVPDS/3 C3i 0 THERMAL-
CONDUCTIVITY
KVPDS/4 C4i 0 THERMAL-
CONDUCTIVITY
KVPDS/5 C5i 0 TEMPERATURE
KVPDS/6 C6i 1000 TEMPERATURE

IK-CAPE Polynomial

Linear extrapolation of i*,v versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVPO/1 C1i x THERMAL-
CONDUCTIVITY
KVPO/2, ... , 10 C2i, ..., C10i 0 x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KVPO/11 C11i 0 x TEMPERATURE
KVPO/12 C12i 1000 x TEMPERATURE

NIST ThermoML Polynomial

Linear extrapolation of i*,v versus T occurs outside of bounds.

286 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVTMLPO/1 C1i x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KVTMLPO/2, ... , C2i, ..., C4i 0 x THERMAL-
4 CONDUCTIVITY,
TEMPERATURE
KVTMLPO/5 nTerms 4 x
KVTMLPO/6 Tlower 0 x TEMPERATURE
KVTMLPO/7 Tupper 1000 x TEMPERATURE

References
R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquid,
4th ed., (New York: McGraw-Hill, 1987), p. 494.

Stiel-Thodos Pressure Correction Model


The pressure correction to a pure component or mixture thermal conductivity
at low pressure is given by:

Where:

rm =

The parameter Vmv can be obtained from Redlich-Kwong.

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.

Vredeveld Mixing Rule


Liquid mixture thermal conductivity is calculated using the Vredeveld equation
(Reid et al., 1977):

3 Transport Property Models 287


Where:
wi = Liquid phase weight fraction of component i

i*,l = Pure component liquid thermal conductivity of component i

Where n is determined from two option codes on model KL2VR:


If option code 1 is Then n is determined by
0 (default) Option code 2, always
1
Option code 2, unless . In this case n is
set to 1.

If option code 2 is Then n is


0 (default) -2
1 0.4
2 1 (This uses a weighted average of liquid thermal
conductivities.)

For most systems, the ratio of maximum to minimum pure component liquid
thermal conductivity is between 1 and 2, where the exponent -2 is
recommended, and is the default value used.

Pure component liquid thermal conductivity i*,l is calculated by the General


Pure Component Liquid Thermal Conductivity model.
Reference: R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of
Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1977), p. 533.

TRAPP Thermal Conductivity Model


The general form for the TRAPP thermal conductivity model is:

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.

288 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0
TCTRAP Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PCTRAP pci PC x 10 10 PRESSURE
VCTRAP Vci VC x 0.001 3.5 MOLE-VOLUME
ZCTRAP Zci ZC x 0.1 1.0
OMGRAP i OMEGA x -0.5 3.0

References
J.F. Ely and H.J. M. Hanley, "Prediction of Transport Properties. 2. Thermal
Conductivity of Pure Fluids and Mixtures," Ind. Eng. Chem. Fundam., Vol. 22,
(1983), pp. 9097.

Wassiljewa-Mason-Saxena Mixing Rule


The vapor mixture thermal conductivity at low pressures is calculated from
the pure component values, using the Wassiljewa-Mason-Saxena equation:

Where:

i*,v = Calculated by the General Pure Component Vapor


Thermal Conductivity model

i*,v(p = 0) = Obtained from the General Pure Component Vapor


Viscosity model

You must supply parameters for i*,v(p = 0) and i*,v.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), pp. 530531.

Diffusivity Models
The Aspen Physical Property System has seven built-in diffusivity models. This
section describes the diffusivity models available.

3 Transport Property Models 289


Model Type
Chapman-Enskog-Wilke-Lee (Binary) Low pressure vapor
Chapman-Enskog-Wilke-Lee (Mixture) Low pressure vapor
Dawson-Khoury-Kobayashi (Binary) Vapor
Dawson-Khoury-Kobayashi (Mixture) Vapor
Nernst-Hartley Electrolyte
Wilke-Chang (Binary) Liquid
Wilke-Chang (Mixture) Liquid

Chapman-Enskog-Wilke-Lee (Binary)
The binary diffusion coefficient at low pressures is calculated using
the Chapman-Enskog-Wilke-Lee model:

Dijv=Djiv
Where:

The collision integral for diffusion is:

D =

The binary size and energy parameters are defined as:

ij =

ij =

A parameter is used to determine whether to use the Stockmayer or


Lennard-Jones potential parameters for /k (energy parameter ) and
(collision diameter). To calculate , the dipole moment p, and either the
Stockmayer parameters or Tb and Vb are needed.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi 1.0 5000.0
-24
MUP pi 0.0 5x10 DIPOLEMOMENT
TB Tbi 4.0 2000.0 TEMPERATURE
VB Vb 0.001 3.5 MOLE-VOLUME
OMEGA i -0.5 2.0

STKPAR/1 (i/k)ST fcn(Tbi, Vbi, pi) x TEMPERATURE

290 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
STKPAR/2 iST fcn(Tbi, Vbi, pi) x LENGTH

LJPAR/1 (i/k)LJ fcn(Tci, i) x TEMPERATURE

LJPAR/2 iLJ fcn(Tci, pci, i) x LENGTH

References
R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquids,
4th ed., (New York: McGraw-Hill, 1987), p. 587.

Chapman-Enskog-Wilke-Lee (Mixture)
The diffusion coefficient of a gas into a gas mixture at low pressures is
calculated using an equation of Bird, Stewart, and Lightfoot by default (option
code 0):

If the first option code is set to 1, Blanc's law is used instead:

The binary diffusion coefficient Dijv(p = 0) at low pressures is calculated using


the Chapman-Enskog-Wilke-Lee model. (See Chapman-Enskog-Wilke-Lee
(Binary).)
You must provide parameters for this model.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DVBLNC 1 x

DVBLNC is set to 1 for a diffusing component and 0 for a non-diffusing


component.

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:

3 Transport Property Models 291


Dijv=Djiv

Dijv(p = 0) is the low-pressure binary diffusion coefficient obtained from the


Chapman-Enskog-Wilke-Lee 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):

If the first option code is set to 1, Blanc's law is used instead:

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.

292 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DVBLNC 1

DVBLNC is set to 1 for a diffusing component and 0 for a nondiffusing


component.

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:

The diffusivity for molecular species is calculated by the Wilke-Chang


(Mixture) model.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
CHARGE z 0.0
IONMOB/1 l1 AREA, MOLES
IONMOB/2 l2 0.0 AREA, MOLES,
TEMPERATURE

When IONMOB/1 is missing, the Nernst-Hartley model uses a nominal value


of 5.0 and issues a warning. This parameter should be specified for ions, and
not allowed to default to this value.

3 Transport Property Models 293


References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis
Horwood, Ltd, 1985).

Wilke-Chang (Binary)
The Wilke-Chang model calculates the liquid diffusion coefficient of
component i in a mixture at finite concentrations:

Dijl = Djil
The equation for the Wilke-Chang model at infinite dilution is:

Where i is the diffusing solute and j the solvent, and:

j = Association factor of solvent. 2.26 for water, 1.90


for methanol, 1.50 for ethanol, 1.20 for propyl
alchohols and n-butanol, and 1.00 for all other
solvents.
Vbi = Liquid molar volume at Tb of solvent i

jl = Liquid viscosity of the solvent. This can be obtained


from the General Pure Component Liquid Viscosity
model. You must provide parameters for one of
these models.

l = Liquid viscosity of the complete mixture of n


components
xi, xj = Apparent binary mole fractions. If the actual mole
fractions are then

Parameter Symbol Default Lower Upper Units


Name/Element Limit Limit
MW Mj 1.0 5000.0
*,l
VB Vbi 0.001 3.5 MOLE-VOLUME

294 3 Transport Property Models


References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 598600.

Wilke-Chang (Mixture)
The Wilke-Chang model calculates the infinite-dilution liquid diffusion
coefficient of component i in a mixture.
The equation for the Wilke-Chang model is:

With:

Where:

j = Association factor of solvent. 2.26 for water, 1.90 for


methanol, 1.50 for ethanol, 1.20 for propyl alchohols
and n-butanol, and 1.00 for all other solvents.
nl = Mixture liquid viscosity of all nondiffusing
components. This can be obtained from the General
Pure Component Liquid Viscosity model. You must
provide parameters for one its submodels.
The parameter DLWC specifies which components diffuse. It is set to 1 for a
diffusing component and 0 for a non-diffusing component.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
MW Mj 1.0 5000.0
*,l
VB Vbi 0.001 3.5 MOLE-VOLUME
DLWC 1

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.

Surface Tension Models


The Aspen Physical Property System has the following built-in surface tension
models.This section describes the surface tension models available.
Model Type
Liquid Mixture Surface Tension Liquid-vapor

3 Transport Property Models 295


Model Type
API Liquid-vapor
IAPS Water-stream
General Pure Component Liquid Surface Liquid-vapor
Tension
Onsager-Samaras Electrolyte Correction Electrolyte liquid-vapor
Modified MacLeod-Sugden Liquid-vapor

Liquid Mixture Surface Tension


The liquid mixture surface tension is calculated using a general weighted
average expression (R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties
of Gases and Liquids, 4th. ed., New York: McGraw-Hill, 1987, p. 643):

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.

API Surface Tension


The liquid mixture surface tension for hydrocarbons is calculated using the
API model. This model is recommended for petroleum and petrochemical
applications. It is used in the CHAO-SEA, GRAYSON, LK-PLOCK, PENG-ROB,
and RK-SOAVE property models. The general form of the model is:

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.

296 3 Transport Property Models


The mixture surface tension is then calculated as a mole-fraction-weighted
average of these surface tensions.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TB Tbi 4.0 2000.0 TEMPERATURE
SG SG 0.1 2.0
TC Tci 5.0 2000 TEMPERATURE

IAPS Surface Tension for Water


The IAPS surface tension model was developed by the International
Association for Properties of Steam. It calculates liquid surface tension for
water and steam. This model is used in option sets STEAMNBS and STEAM-
TA.
The general form of the equation for the IAPS surface tension model is:

w=fcn(T, p)
Where:
fcn = Correlation developed by IAPS
The model is only applicable to water. No parameters are required.

General Pure Component Liquid Surface


Tension
The Aspen Physical Property System has several submodels for calculating
liquid surface tension. It uses parameter TRNSWT/5 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If TRNSWT/5 is This equation is used And this parameter is
used
0 Hakim-Steinberg-Stiel
106 DIPPR SIGDIP
301 PPDS SIGPDS
401 IK-CAPE polynomial SIGPO
equation
505 NIST TDE Watson SIGTDEW
equation
511 NIST TDE expansion SIGISTE
512 NIST PPDS14 Equation SIGPDS14

Hakim-Steinberg-Stiel
The Hakim-Steinberg-Stiel equation is:

Where:

3 Transport Property Models 297


Qpi =

mi =

The parameter i is the Stiel polar factor.


Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
TC Tci 5.0 2000.0 TEMPERATURE
PC pci PRESSURE

OMEGA i -0.5 2.0

CHI i 0

DIPPR Liquid Surface Tension


The DIPPR equation for liquid surface tension is:

Where:
Tri = T / Tci

Linear extrapolation of i*,l versus T occurs outside of bounds.


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
The DIPPR model is used by PCES when estimating liquid surface tension.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
SIGDIP/1 C1i SURFACE-
TENSION
SIGDIP/2, ..., 5 C2i, ..., C5i 0
SIGDIP/6 C6i 0 TEMPERATURE
SIGDIP/7 C7i 1000 TEMPERATURE

PPDS
The equation is:

Linear extrapolation of i*,l versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SIGPDS/1 C1i SURFACE-
TENSION

298 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SIGPDS/2 C2i 0
SIGPDS/3 C3i 0
SIGPDS/4 C4i 0 TEMPERATURE
SIGPDS/5 C5i 1000 TEMPERATURE

NIST PPDS14 Equation


This equation is the same as the PPDS equation above, but it uses its own
parameter set which includes critical temperature.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SIGPDS14/1 C1i x N/m
SIGPDS14/2 C2i 0 x
SIGPDS14/3 C3i 0 x
SIGPDS14/4 Tci x TEMPERATURE
SIGPDS14/5 C4i 0 x TEMPERATURE
SIGPDS14/6 C5i 1000 x TEMPERATURE

IK-CAPE Polynomial
The IK-CAPE equation is:

Linear extrapolation of i*,l versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SIGPO/1 C1i x SURFACE-
TENSION
SIGPO/2, ..., 10 C2i, ..., C10i 0 x SURFACE-
TENSION
TEMPERATURE
SIGPO/11 C11i 0 x TEMPERATURE
SIGPO/12 C12i 1000 x TEMPERATURE

NIST TDE Watson Equation


This equation can be used when parameter SIGTDEW is available.

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
SIGTDEW/1 C1i x

3 Transport Property Models 299


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SIGTDEW/2, 3, 4 C2i, C3i, C4i 0 x
SIGTDEW/5 Tc x TEMPERATURE
SIGTDEW/6 nTerms 4 x
SIGTDEW/7 Tlower 0 x TEMPERATURE
SIGTDEW/8 Tupper 1000 x TEMPERATURE

NIST TDE Expansion


This equation can be used when parameter SIGISTE is available.

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
SIGISTE/1 C1i x N/m
SIGISTE/2, 3, 4 C2i, C3i, C4i 0 x N/m
SIGISTE/5 Tci x TEMPERATURE
SIGISTE/6 nTerms 4 x
SIGISTE/7 Tlower 0 x TEMPERATURE
SIGISTE/8 Tupper 1000 x TEMPERATURE

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th. ed., (New York: McGraw-Hill, 1987), p. 638.

Onsager-Samaras
The Onsager-Samaras model calculates the correction to the liquid mixture
surface tension of a solvent mixture, due to the presence of electrolytes:
for salt concentration < 0.03 (1)
M

Where:

solv = Surface tension of the solvent mixture calculated


by the General Pure Component Liquid Surface
Tension model
xcaa = Mole fraction of the apparent electrolyte ca

ca = Contribution to the surface tension correction due


to apparent electrolyte ca
For each apparent electrolyte ca, the contribution to the surface tension
correction is calculated as:

300 3 Transport Property Models


(2)

Where:

solv = Dielectric constant of the solvent mixture

ccaa =

Vm l = Liquid molar volume calculated by the Clarke


model
Apparent electrolyte mole fractions are computed from the true ion mole-
fractions and ionic charge number. They are also computed if you use the
apparent component approach. See Apparent Component and True
Component Approaches in the Electrolyte Calculation chapter for a more
detailed discussion of this method.
Above salt concentration 0.03 M, the slope of surface tension vs. mole
fraction is taken to be constant at the value from 0.03 M.
You must provide parameters for the General Pure Component Liquid Surface
Tension model, used for the calculation of the surface tension of the solvent
mixture.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
CHARGE z 0.0

References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis,
Ltd. 1985).

Modified MacLeod-Sugden
The modified MacLeod-Sugden equation for mixture liquid surface tension can
be derived from the standard MacLeod-Sugden equation by assuming that the
density of the vapor phase is zero. The modified MacLeod-Sugden equation is:

Where:

i*,l = Surface tension for pure component i, calculated using


the General Pure Component Liquid Surface Tension
model.
Vi*,l = Liquid molar volume for pure component i, calculated
using the General Pure Component Liquid Molar Volume
model.

3 Transport Property Models 301


l
V = Mixture liquid molar volume, calculated using the
Rackett model.

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 3rd. ed., (New York: McGraw-Hill, 1977).

302 3 Transport Property Models


4 Nonconventional Solid
Property Models

This section describes the nonconventional solid density and enthalpy models
available in the Aspen Physical Property System. The following table lists the
available models and their model names. Nonconventional components are
solid components that cannot be characterized by a molecular formula. These
components are treated as pure components, though they are complex
mixtures.

Nonconventional Solid Property Models


General Enthalpy and Model name Phase(s)
Density Models
General density polynomial DNSTYGEN S
General heat capacity ENTHGEN S
polynomial
Enthalpy and Density Model name Phase(s)
Models for Coal and Char
General coal enthalpy model HCOALGEN S
IGT coal density model DCOALIGT S
IGT char density model DCHARIGT S

General Enthalpy and Density


Models
The Aspen Physical Property System has two built-in general enthalpy and
density models. This section describes the general enthalpy and density
models available:

General Density Polynomial


DNSTYGEN is a general model that gives the density of any nonconventional
solid component. It uses a simple mass fraction weighted average for the
reciprocal temperature-dependent specific densities of its individual
constituents. There may be up to twenty constituents with mass percentages.

4 Nonconventional Solid Property Models 303


You must define these constituents, using the general component attribute
GENANAL. The equations are:

Where:
wij = Mass fraction of the jth constituent in component i

ijs = Density of the jth consituent in component i

Parameter Symbol MDS Default Lower Upper Units


Name/Element Limit Limit
DENGEN/1, 5, 9, , 77 ai,j1 x MASS-ENTHALPY
and TEMPERATURE
DENGEN/2, 6, 10, , ai,j2 x 0 MASS-ENTHALPY
78 and TEMPERATURE
DENGEN/3, 7, 11, , ai,j3 x 0 MASS-ENTHALPY
79 and TEMPERATURE
DENGEN/4, 8, 12, , ai,j4 x 0 MASS-ENTHALPY
80 and TEMPERATURE

Use the elements of GENANAL to input the mass percentages of the


constituents. The structure of DENGEN 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.

General Heat Capacity Polynomial


ENTHGEN is a general model that gives the specific enthalpy of any
nonconventional component as a simple mass-fraction-weighted-average for
the enthalpies of its individual constituents. You may define up to twenty
constituents with mass percentages, using the general component attribute
GENANAL. The specific enthalpy of each constituent at any temperature is
calculated by combining specific enthalpy of formation of the solid with a
sensible heat change. (See Nonconventional Component Enthalpy Calculation
in Physical Property Methods.)
The equations are:

Where:

304 4 Nonconventional Solid Property Models


wij = Mass fraction of the jth constituent in
component i
h is = Specific enthalpy of solid component i

fhjs = Specific enthalpy of formation of constituent j

Cp s = Heat capacity of the jth constituent in


component i

Parameter Symbol MDS Default Lower Upper Units


Name/Element Limit Limit
DHFGEN/J fhjs x 0 MASS-ENTHALPY

HCGEN/1, 5, 9, , 77 ai,j1 x MASS-ENTHALPY


and
TEMPERATURE
HCGEN/2, 6, 10, , 78 ai,j2 x 0 MASS-ENTHALPY
and
TEMPERATURE
HCGEN/3, 7, 11, , 79 ai,j3 x 0 MASS-ENTHALPY
and
TEMPERATURE
HCGEN/4, 8, 12, , 80 ai,j4 x 0 MASS-ENTHALPY
and
TEMPERATURE

The elements of GENANAL are used to input the mass percentages of the
constituents. The structure for HCGEN is: Elements 1 to 4 are the four
coefficients for the first constituent, elements 5 to 8 are the coefficients for
the second constitutent, and so on, for up to 20 constituents.

Enthalpy and Density Models


for Coal and Char
Coal is modeled in the Aspen Physical Property System as a nonconventional
solid. Coal models are empirical correlations, which require solid material
characterization information. Component attributes are derived from
constituent analyses. Definitions of coal component attributes are given in the
Aspen Plus User Guide, Chapter 6.
Enthalpy and density are the only properties calculated for nonconventional
solids. This section describes the special models available in the Aspen
Physical Property System for the enthalpy and density of coal and char. The
component attributes required by each model are included. The coal models
are:
General coal enthalpy
IGT Coal Density
IGT Char Density

4 Nonconventional Solid Property Models 305


User models for density and enthalpy. See User Models for
Nonconventional Properties in Chapter 6 of Aspen Plus User Models, for
details on writing the subroutines for these user models.

Notation
Most correlations for the calculation of coal properties require proximate,
ultimate, and other analyses. These are converted to a dry, mineral-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

For hydrogen, the formula includes a correction for free-moisture hydrogen:

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:

wd = Correction factor for other losses, such as the loss


of carbon in carbonates and the loss of hydrogen
present in the water constitution of clays

306 4 Nonconventional Solid Property Models


The oxygen and organic sulfur contents are usually calculated by difference
as:

Where:
Cp = Heat capacity / (J/kgK)
cp = Heat capacity / (cal/gC)
h = Specific enthalpy

ch = Specific heat of combustion

fh = Specific heat of formation

Ro = Mean-maximum relectance in oil


T = Temperature/K
t = Temperature/C
w = Weight fraction

= 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

4 Nonconventional Solid Property Models 307


m = Mineral-matter-free basis

General Coal Enthalpy Model


The general coal model for computing enthalpy in the Aspen Physical Property
System is HCOALGEN. This model includes a number of different correlations
for the following:
Heat of combustion
Heat of formation
Heat capacity
You can select one of these correlations using an option code in the Methods
| NC-Props form. (See the Aspen Plus User Guide, Chapter 6). Use option
codes to specify a calculation method for properties. Each element in the
option code vector is used in the calculation of a different property.
The table labeled HCOALGEN Option Codes (below) lists model option codes
for HCOALGEN. The table is followed by a detailed description of the
calculations used for each correlation.
The correlations are described in the following section. The component
attributes are defined in Aspen Plus User Guide, Chapter 6.

Heat of Combustion Correlations


The heat of combustion of coal in the HCOALGEN model is a gross calorific
value. It is expressed in Btu/lb of coal on a dry mineral-matter-free basis.
ASTM Standard D5865-07a defines standard conditions for measuring gross
calorific value. (Earlier ASTM Standard D-2015 used the same conditions.)
Initial oxygen pressure is 20 to 40 atmospheres. Products are in the form of
ash; liquid water; and gaseous CO2, SO2, and NO2.
You can calculate net calorific value from gross calorific value by making a
deduction for the latent heat of vaporization of water.
Heat of combustion values are converted back to a dry, mineral-matter-
containing basis with a correction for the heat of combustion of pyrite. The
formula is:

The heat of combustion correlations were evaluated by the Institute of Gas


Technology (IGT). They used data for 121 samples of coal from the Penn
State Data Base (IGT, 1976) and 457 samples from a USGS report (Swanson,
et al., 1976). These samples included a wide range of United States coal
fields. The constant terms in the HCOALGEN correlations are bias corrections
obtained from the IGT study.
Boie Correlation:

Parameter Name/Element Symbol Default


BOIEC/1 a1i 151.2
BOIEC/2 a2i 499.77

308 4 Nonconventional Solid Property Models


Parameter Name/Element Symbol Default
BOIEC/3 a3i 45.0
BOIEC/4 a4i -47.7
BOIEC/5 a5i 27.0
BOIEC/6 a6i -189.0

Dulong Correlation:

Parameter Name/Element Symbol Default


DLNGC/1 a1i 145.44
DLNGC/2 a2i 620.28
DLNGC/3 a3i 40.5
DLNGC/4 a4i -77.54
DLNGC/5 a5i -16.0

Grummel and Davis Correlation:

Parameter Name/Element Symbol Default


GMLDC/1 a1i 0.3333
GMLDC/2 a2i 654.3
GMLDC/3 a3i 0.125
GMLDC/4 a4i 0.125
GMLDC/5 a5i 424.62
GMLDC/6 a6i -2.0

Mott and Spooner Correlation:

Parameter Name/Element Symbol Default


MTSPC/1 a1i 144.54
MTSPC/2 a2i 610.2
MTSPC/3 a3i 40.3
MTSPC/4 a4i 62.45
MTSPC/5 a5i 30.96
MTSPC/6 a6i 65.88
MTSPC/7 a7i -47.0

IGT Correlation:

4 Nonconventional Solid Property Models 309


Parameter Name/Element Symbol Default
CIGTC/1 a1i 178.11
CIGTC/2 a2i 620.31
CIGTC/3 a3i 80.93
CIGTC/4 a4i 44.95
CIGTC/5 a5i -5153.0

Revised IGT Correlation (Perry's, 7th ed., equation 27-7):

Parameter Name/Element Symbol Default


CIGT2/1 a1i 146.58
CIGT2/2 a2i 568.78
CIGT2/3 a3i 29.4
CIGT2/4 a4i -6.58
CIGT2/5 a5i -51.53

User Input Value of Heat Combustion


Parameter Name/Element Symbol Default
HCOMB chid 0

Standard Heat of Formation Correlations


There are two standard heat of formation correlations for the HCOALGEN
model:
Heat of combustion-based
Direct
Heat of Combustion-Based Correlation: This is based on the assumption that
combustion results in complete oxidation of all elements except sulfatic sulfur
and ash, which are considered inert. The numerical coefficients are
combinations of stoichiometric coefficients and heat of formation for CO2,
H2O, HCl, and NO2 at 298.15K:

For example, the complete oxidation of hydrogen is based on the reaction

, since the stable phase of water at 298.15 K is


liquid, the heat of vaporization at 298.15 K is needed in the conversion. The

numerical coefficient of is calculated by:

310 4 Nonconventional Solid Property Models


The complete oxidation of carbon is based on the reaction

, and the numerical coefficient of is calculated by:

The complete oxidation of sulfur (pyritic and organic sulfur) is based on the

reaction , and the numerical coefficient of is

calculated by:
The complete oxidation of nitrogen is based on the reaction

, and the numerical coefficient of is calculated by:

The complete oxidation of chlorine is based on the reaction

, and the numerical coefficient of

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

4 Nonconventional Solid Property Models 311


Parameter Name/Element Symbol Default
HFC/7 a7i 424.25
HFC/8 a8i -525.199
HFC/9 a9i -11.4805
HFC/10 a10i 31.585
HFC/11 a11i 13.5256
HFC/12 a12i 11.5
HFC/13 a13i -685.846
HFC/14 a14i -22.494
HFC/15 a15i -64836.19

Heat Capacity Kirov Correlations


The Kirov correlation (1965) considered coal to be a mixture of moisture, ash,
fixed carbon, and primary and secondary volatile matter. Secondary volatile
matter is any volatile matter up to 10% on a dry, ash-free basis; the
remaining volatile matter is primary. The correlation developed by Kirov
treats the heat capacity as a weighted sum of the heat capacities of the
constituents:

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

312 4 Nonconventional Solid Property Models


Parameter Name/Element Symbol Default
CP1C/7 ai,23

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

Cubic Temperature Equation


The cubic temperature equation is:

Parameter Name/Element Symbol Default


CP2C/1 a1i 0.438
CP2C/2 a2i

CP2C/3 a3i

CP2C/4 a4i

The default values of the parameters were developed by Gomez, Gayle, and
Taylor (1965). They used selected data from three lignites and a
subbituminous B coal, over a temperature range from 32.7 to 176.8C. This
correlation calculates heat capacity in cal/gram-C using temperature in C. The
parameters must be specified in appropriate units for this conversion.

HCOALGEN Option Codes


Option Code Option Code Calculation Parameter Component
Number Value Method Names Attributes
1 Heat of Combustion
1 Boie correlation BOIEC ULTANAL
SULFANAL
PROXANAL
2 Dulong DLNGC ULTANAL
correlation SULFANAL
PROXANAL
3 Grummel and GMLDC ULTANAL
Davis correlation SULFANAL
PROXANAL

4 Nonconventional Solid Property Models 313


Option Code Option Code Calculation Parameter Component
Number Value Method Names Attributes
1 Heat of Combustion
4 Mott and Spooner MTSPC ULTANAL
correlation SULFANAL
PROXANAL
5 IGT correlation CIGTC ULTANAL
PROXANAL
6 User input value HCOMB ULTANAL
PROXANAL
7 Revised IGT CIGT2 ULTANAL
correlation PROXANAL
2 Standard Heat of Formation
1 Heat-of- ULTANAL
combustion- SULFANAL
based correlation
2 Direct correlation HFC ULTANAL
SULFANAL
PROXANAL
3 Heat Capacity
1 Kirov correlation CP1C PROXANAL
2 Cubic CP2C
temperature
equation
4 Enthalpy Basis
1 Elements in their
standard states
at 298.15K and 1
atm
2 Component at
298.15 K

Default = 1 for each option code

Older Enthalpy Models


Three other versions of the correlation also exist.
HCJ1BOIE is similar to HCOALGEN with the first, second, and fourth option
codes set to 1. That is, it always uses the Boie correlation for heat of
combustion, the heat-of-combustion-based heat of formation correlation, and
elements as enthalpy basis. The option code of HCJ1BOIE is equivalent to the
third option code of HCOALGEN, selecting the heat capacity equation.
HCOAL-R8 and HBOIE-R8 are old versions of HCOALGEN and HCJ1BOIE,
respectively. They do not perform the dry/wet basis conversions correctly.
They are preserved for upward compatibility only and are not recommended
for use in any new simulations.

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.

314 4 Nonconventional Solid Property Models


IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data
Book, Section PMa. 44.1, 1976.
Kirov, N.Y., "Specific Heats and Total Heat Contents of Coals and Related
Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965),
pp. 29, 33.
Swanson, V.E. et al., Collection, Chemical Analysis and Evaluation of Coal
Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76
468.
R. H. Perry and D. W. Green, eds., Perry's Chemical Engineers' Handbook, 7th
ed., McGraw-Hill (1997), p. 27-5.

IGT Coal Density Model


The DCOALIGT model gives the true (skeletal or solid-phase) density of coal
on a dry basis. It uses ultimate and sulfur analyses. The model is based on
equations from IGT (1976):

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.

4 Nonconventional Solid Property Models 315


IGT Char Density Model
The DGHARIGT model gives the true (skeletal or solid-phase) density of char
or coke on a dry basis. It uses ultimate and sulfur analyses. This model is
based on equations from IGT (1976):

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

The densities of graphitic high-temperature carbons (including cokes) range


from 2.2x103 to 2.26x103 kg/m3. Densities of nongraphitic high-temperature
carbons (derived from chars) range from 2.0x103 to 2.2x103 kg/m3. Most of
the data used in developing this correlation were for carbonized coking coals.
Although data on a few chars (carbonized non-coking coals) were included,
none has a hydrogen content less than 2%. The correlation is probably not
accurate for high temperature chars.

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.

316 4 Nonconventional Solid Property Models


5 Property Model Option
Codes

The following tables list the model option codes available:


Option Codes for Transport Property Models
Option Codes for Activity Coefficient Models
Option Codes for Equation of State Models
Option Codes for K-value Models
Option Codes for Enthalpy Models
Option Codes for Gibbs Energy Models
Option Codes for Molar Volume Models

Option Codes for Transport


Property Models
Model Name Option Code Value Descriptions
SIG2HSS 1 1 Exponent in mixing rule (default)
-1,-2, Exponent in mixing rule
..., -9
SIG2ONSG 1 1 Exponent in mixing rule (default)
-1,-2, Exponent in mixing rule
..., -9
SIG2API 1 0 Use original API model for all
components
1 Use API model for
pseudocomponents, General Pure
Component Liquid Surface Tension
for real components, and take a
mole-fraction-weighted average of
the results.
MUL2API, MULAPI92 1 0 Release 9 method. First, the API, SG
of the mixture is calculated, then the
API correlation is used (default)
1 Pre-release 9 method. Liquid
viscosity is calculated for each

5 Property Model Option Codes 317


pseudocomponent using the API
method. Then mixture viscosity is
calculated by mixing rules.
MUL2ANDR, 1 0 Mixture viscosity weighted by mole
DL0WCA, DL1WCA, fraction (default)
DL0NST, DL1NST
1 Mixture viscosity weighted by mass
fraction

MUASPEN 1 0 Mixture viscosity weighted by mole


fraction (default)
1 Mixture viscosity weighted by mass
fraction
MUL2JONS 1 0 Mixture viscosity weighted by mole
fraction (default)
1 Mixture viscosity weighted by mass
fraction
2 0 Use Breslau and Miller equation
instead of Jones and Dole equation
when electrolyte concentration
exceeds 0.1 M.
1 Always use Jones and Dole equation
when the parameters are available.
3 0 Solvent liquid mixture viscosity from
Andrade liquid mixture viscosity
model (default)
1 Solvent liquid mixture viscosity from
quadratic mixing rule
2 Solvent liquid mixture viscosity from
Aspen liquid mixture viscosity model
MUL2CLS, 1 0 Original correlation
MUL2CLS2
1 Modified UOP correlation
MUL2QUAD 1 0 Use mole basis composition (default)
1 Use mass basis composition
KL2VR, KL2RDL 1 0 Do not check ratio of KL max / KL
min
1 Check ratio. If KL max / KL min > 2,
set exponent to 1, overriding option
code 2.
2 0 Exponent is -2
1 Exponent is 0.4
2 Exponent is 1. This uses a weighted
average of liquid thermal
conductivities.
KL0GLY, KL2GLY, 1 0 Use API 12A3.2-1 method for thermal
KL0HPR, KL2HPR, conductivity for most components
KL0HSRK, KL2HSRK (default)
1 Use API 12A1.2-1 method for thermal
conductivity for all components

318 5 Property Model Option Codes


Option Codes for Activity
Coefficient Models
Model Name Option Value Descriptions
Code
GMXSH 1 0 No volume term (default)
1 Includes volume term
WHENRY (Options used in calculating PHILMX)
1 1 Calculate WB with equal weighting (solutes)
2 Size - VC1/3
3 Area - VC2/3 (default)
4 Volume - VC
2 0 CalculateA for solvents
1 Set A = 1 (ln A = 0) for solvents
Electrolyte NRTL Activity Coefficient Model (GMELC and GMENRHG)
1 Defaults for pair parameters
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters default
to zero (default for GMELC)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
GMENRHG)
2 Not used
3 Solvent/solvent binary parameter values obtained
from
0 Scalar GMELCA, GMELCB and GMELCM (default
for GMELC)
1 Vector NRTL(8) (default for GMENRHG)
GMPT1, GMPT3 (Pitzer)
1 Defaults for pair mixing rule
-1 No unsymmetric mixing
0 Unsymmetric mixing polynomial (default)
1 Unsymmetric mixing integral
Symmetric and Unsymmetric Electrolyte NRTL Activity Coefficient Model (GMENRTLS and
GMENRTLQ)
1 PDH long-range term
0 Long-range term calculated (default)
1 Long-range term ignored
2 Water dielectric constant calculation
0 Calculated from Helgeson and Kirkham correlation
(1974) (default)
1 Calculated from parameter CPDIEC (as in
Electrolyte NRTL Activity Coefficient Model)
3 Water density calculation

5 Property Model Option Codes 319


Model Name Option Value Descriptions
Code
0 Calculated from steam table (default)
1 Calculated from DIPPR correlation model
COSMOSAC
1 Model choice
1 COSMO-SAC model by Lin and Sandler (2002)
(Default)
2 COSMO-RS model by Klamt and Eckert (2000)
3 Lin and Sandler model with modified exchange
energy (Lin et al., 2002)
Additional option codes for COSMOSAC are for features under development, but currently
inactive.
Hansen
1 0 Hansen volume input by user (default)
1 Hansen volume calculated by Aspen Plus
NRTLSAC (patent pending) for Segments/Oligomers, ENRTLSAC (patent pending)
1 0 Flory-Huggins term included (default)
1 Flory-Huggins term removed
NRTL-SAC (GMNRTLS)
1 0 Reference state for ions is unsymmetric: infinite
dilution in aqueous solution (default)
2 Reference state for ions is symmetric: pure fused
salts
2 0 Flory-Huggins term included (default)
1 Flory-Huggins term removed
3 0 Long-range interaction term included (default)
1 Long-range interaction term removed
4 Water dielectric constant calculation
0 Calculated from Helgeson and Kirkham correlation
(1974) (default)
1 Calculated from parameter CPDIEC (as in
Electrolyte NRTL Activity Coefficient Model)
5 Water density calculation
0 Calculated from steam table (default)
1 Calculated from DIPPR correlation model

Option Codes for Equation of


State Models
Model Name Option Value Descriptions
Code
ESBWRS, ESBWRS0 1 0 Do not use steam tables
1 Calculate properties (H, S, G, V) of water from
steam table (default; see Note)

320 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
2 0 Original RT-Opt root search method (default)
1 VPROOT/LQROOT Aspen Plus root search
method. Use this if the equation-oriented Aspen
Plus solution fails to converge and some streams
with missing phases show the same properties
for the missing phase as for another phase.
ESHOC, ESHOC0, 1 0 Hayden-O'Connell model. Use chemical theory
PHV0HOC only if one component has HOCETA=4.5 (default)
1 Always use the chemical theory regardless of
HOCETA values
2 Never use the chemical theory regardless of
HOCETA values
2 0 Check high-pressure limit. If exceeded, calculate
volume at cut-off pressure.
1 Ignore high-pressure limit. Calculate volume
model T and P.
ESPR, ESPR0, 1 0 ASPEN Boston/Mathias alpha function when Tr
ESPRSTD, >1, original literature alpha function otherwise.
ESPRSTD0 (default for ESPR)
1 Original literature alpha function (default for
ESPRSTD)
2 Extended Gibbons-Laughton alpha function
3 Twu Generalized alpha function
4 Twu alpha function
5 HYSYS alpha function
2 0 Standard Peng-Robinson mixing rules (default)
1 Asymmetric Kij mixing rule from Dow

3 0 Do not use steam tables (default)


1 Calculate water properties (H, S, G, V) from
steam table (see Note)
4 0 Do not use Peneloux liquid volume correction
(default)
1 Apply Peneloux liquid volume correction (See
SRK)
2 Apply volume correction to both liquid and vapor
phases
5 0 Use analytical method for root finding (default)
1 Use RTO numerical method for root finding

2 Use VPROOT/LQROOT numerical method for root


finding
ESPRWS, ESPRWS0, 1 0 ASPEN Boston/Mathias alpha function
ESPRV1, ESPRV10,
ESPRV2, ESPRV20,
ESPSAFT, ESPSAFT0 1 0 Random copolymer (default)

5 Property Model Option Codes 321


Model Name Option Value Descriptions
Code
1 Alternative copolymer
2 Block copolymer
2 0 Do not use Sadowski's copolymer model
1 Use Sadowski's copolymer model in which a
copolymer must be built only by two different
types of segments
3 0 Use association term (default)
1 Do not use association term
ESRKS, ESRKS0, See Soave-Redlich-Kwong Option Codes
ESRKSTD,
ESRKSTD0, ESSRK,
ESSRK0, ESRKSML,
ESRKSML0
ESRKSW, ESRKSW0 1 0 ASPEN Boston/Mathias alpha function (default)
1 Original literature alpha function
2 Grabowski and Daubert alpha function for H2
above TC ( = 1.202 exp(-0.30228xTri))
ESRKU, ESRKU0 1 Initial temperature for binary parameter
estimation
0 At TREF=25 C (default)
1 The lower of TB(i) or TB(j)
2 (TB(i) + TB(j))/2
100-999Value entered used as temperature in K
2 VLE or LLE UNIFAC
0 VLE (default)
1 LLE
3 Property diagnostic level flag (-1 to 8)
4 Vapor phase EOS used in generation of TPxy data
with UNIFAC
0 Hayden-O'Connell (default)
1 Redlich-Kwong
5 Do/do not estimate binary parameters
0 Estimate (default)
1 Set to zero
ESHF, ESHF0 1 0 Equation form for Log(k) expression:
log(K) = A + B/T + C ln(T) + DT (default)
1 log(K) = A + B/T + CT + DT2 + E log(P)
1 Original literature alpha function
2 Mathias-Copeman alpha function
3 Schwartzentruber-Renon alpha function (default)

322 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
ESRKSWS, 1 Equation form for alpha function
ESRKSWS0,
ESRKSV1,
ESRKSV10,
ESRKSV2,
ESRKSV20,
1 Original literature alpha function
2 Mathias-Copeman alpha function
3 Schwartzentruber-Renon alpha function (default)
ESSTEAM, ESSTEAM0 (STEAMNBS, STMNBS2)
1 0 ASME 1967 correlations
1 NBS 1984 equation of state (default)
2 NBS 1984 equation of state with alternate root
search method (STMNBS2)
2 0 Original fugacity and enthalpy calculations when
used with STMNBS2
1 Rigorous fugacity calculation from Gibbs energy
and corrected enthalpy departure with STMNBS2
root search method
2 Rigorous fugacity calculation from Gibbs energy
and corrected enthalpy departure with Aspen
Plus root search method (default)
ESGLY, ESGLY0 1 0 Cubic EOS analytical solution method
1 Numerical solution method
ESHPR, ESHPR0 1 0 Cubic EOS analytical solution method
1 Numerical solution method
2 0 Use modified Tc, Pc for H2 and He
1 Use unmodified Tc, Pc for H2 and He
3 0 No liquid volume translation
1 Translation volume estimated by COSTALD
2 Translation volume estimated by Rackett
4 0 HYSYS alpha function
1 Standard alpha function
ESHSPR, ESHSPR0 1 0 Cubic EOS analytical solution method
1 Numerical solution method
2 0 Use modified Tc, Pc for H2 and He
1 Use unmodified Tc, Pc for H2 and He
ESHSRK, ESHSRK0 1 0 Cubic EOS analytical solution method
1 Numerical solution method
2 0 Use modified Tc, Pc for H2 and He
1 Use unmodified Tc, Pc for H2 and He
3 0 No liquid volume translation
1 Translation volume estimated by COSTALD
2 Translation volume estimated by Rackett

5 Property Model Option Codes 323


Model Name Option Value Descriptions
Code
ESHSSRK, 1 0 Cubic EOS analytical solution method
ESHSSRK0
1 Numerical solution method
2 0 Use modified Tc, Pc for H2 and He
1 Use unmodified Tc, Pc for H2 and He
ESH2O, ESH2O0 1 0 ASME 1967 correlations (default)
1 NBS 1984 equation of state
2 NBS 1984 equation of state with alternate root
search method (STMNBS2)

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)

324 5 Property Model Option Codes


Option Value Description
Code
3 0 Do not calculate water properties from steam table (default for
Redlich-Kwong-Soave models)
1 Calculate properties (H, S, G, V) of water from steam table
(default for SRK models; see note 6)
4 0 Do not apply the Peneloux liquid volume correction (default for
SRK-ML and both Redlich-Kwong-Soave models)
1 Apply the liquid volume correction (default for Soave-Redlich-
Kwong and SRK-Kabadi-Danner, see Soave-Redlich-Kwong for
details)
2 Apply volume correction to both liquid and vapor phases
5 0 Use analytical method for root finding (default)
1 Use RTO numerical method for root finding
2 Use VPROOT/LQROOT numerical method for root finding
6 0 Use true logarithm in calculating properties (default for
Redlich-Kwong-Soave models)
1 Use smoothed logarithm in calculating properties (default for
SRK models)

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.

Option Codes for K-Value


Models
Model Option Value Descriptions
Name Code
BK10 1 0 Treat pseudocomponents as paraffins (default)
1 Treat pseudocomponents as aromatics

5 Property Model Option Codes 325


Option Codes for Enthalpy
Models
Model Name Option Value Descriptions
Code
DHL0HREF 1 1 Use Liquid reference state for all components (Default)
2 Use liquid and gaseous reference states based on the
state of each component
Electrolyte NRTL Enthalpy (HAQELC, HMXELC, and HMXENRHG)
1 Defaults for pair parameters
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters default to
zero (default for ELC models)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
HMXENRHG)
2 Vapor phase equation-of-state for liquid enthalpy of HF
0 Ideal gas EOS (default)
1 HF EOS for hydrogen fluoride
3 Solvent/solvent binary parameter values obtained
from:
0 Scalar GMELCA, GMELCB and GMELCM (default for ELC
models)
1 Vector NRTL(8) (default for HMXENRHG)
4 Enthalpy calculation method
0 Electrolyte NRTL Enthalpy (default for ELC models and
ELECNRTL property method)
1 Helgeson method (default for HMXENRHG)
5 Vapor phase enthalpy departure contribution to liquid
enthalpy. Hliq = Hig + DHV - Hvap; this option indicates
how DHV is calculated.
0 Do not calculate (DHV=0) (default)
1 Calculate using Redlich-Kwong equation of state
2 Calculate using Hayden-O'Connell equation of state
6 Method for calculating corresponding states (for
handling solvents that exist in both subcritical and
supercritical conditions)
0 Original method (default)
1 Corresponding state method. Calculates a pseudo-
critical temperature of the solvents and uses it
together with the actual critical temperatures of the
pure solvents to adjust the liquid enthalpy departure.
This results in a smoother transition of the liquid
enthalpy contribution when the component transforms
from subcritical to supercritical.
7 Method for handling Henry components and multiple
solvents

326 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
0 Pure liquid enthalpy calculated by aqueous infinite
dilution heat capacity; only water as solvent
1 Pure liquid enthalpy for Henry components calculated
using Henry's law; use this option when there are
multiple solvents.
HLRELNRT and HLRELELC
1 Defaults for pair parameters
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters default to
zero (default for HLRELELC)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
HLRENRTL)
2 Solvent/solvent binary parameter values obtained
from:
0 Scalar GMELCA, GMELCB and GMELCM (default)
1 Vector NRTL(8)
3 Mixture density model
0 Rackett equation with Campbell-Thodos modification
1 Quadratic mixing rule for molecular components (mole
basis)
HIG2ELC, HIG2HG
1 Enthalpy calculation method
0 Electrolyte NRTL Enthalpy (default for HIG2ELC)
1 Helgeson method (default for HIG2HG)
DHLELC
1 Steam table for liquid enthalpy of water
0 Use steam table for liquid enthalpy of water (default)
1 Use specified EOS model
2 Vapor phase equation-of-state for liquid enthalpy of HF
0 Use specified EOS model (default)
1 HF EOS for hydrogen fluoride
HAQPT1, HAQPT3 (Pitzer)
1 Defaults for pair mixing rule
-1 No unsymmetric mixing
0 Unsymmetric mixing polynomial (default)
1 Unsymmetric mixing integral
2 Standard enthalpy calculation
0 Standard electrolytes method (Pre-release 10)
1 Helgeson method (Default)
3 Estimation of K-stoic temperature dependency
0 Use value at 298.15 K
1 Helgeson Method (default)

5 Property Model Option Codes 327


Model Name Option Value Descriptions
Code
HS0POL1, GS0POL1, SS0POL1 (Solid pure component polynomials)
1 Reference temperature usage
0 Use standard reference temperature (default)
1 Use liquid reference temperature
PHILELC
1 Steam table for liquid enthalpy of water
0 Use steam table for liquid enthalpy of water (default)
1 Use specified EOS model
2 Vapor phase equation-of-state for liquid enthalpy of HF
0 Use specified EOS model (default)
1 HF EOS for hydrogen fluoride

Option Codes for Gibbs Free


Energy Models
Model Name Option Value Descriptions
Code
Electrolyte NRTL Gibbs Energy (GAQELC, GMXELC, and GMXENRHG)
1 Defaults for pair parameters
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters default
to zero (default for ELC models)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
GMXENRHG)
2 Vapor phase equation-of-state for liquid Gibbs
free energy of HF
0 Ideal gas EOS (default)
1 HF EOS for hydrogen fluoride
3 Solvent/solvent binary parameter values obtained
from
0 Scalar GMELCA, GMELCB and GMELCM (default
for ELC models)
1 Vector NRTL(8) (default for GMXENRHG)
4 Gibbs free energy calculation method
0 Electrolyte NRTL Gibbs free energy (default for
ELC models)
1 Helgeson method (default for GMXENRHG)
5 Vapor phase fugacity coefficient (PHIV)
calculation method.
0 Do not calculate (PHIV=1) (default)
1 Calculate using Redlich-Kwong equation of state

328 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
2 Calculate using Hayden-O'Connell equation of
state
6 Method for handling Henry components and
multiple solvents
0 Pure liquid Gibbs free energy calculated by
aqueous infinite dilution heat capacity; only water
as solvent
1 Pure liquid Gibbs free energy for Henry
components calculated using Henry's law; use
this option when there are multiple solvents.
GLRELNRT, GLRELELC
1 Defaults for pair parameters
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters default
to zero (default for GLRELELC)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
GLRENRTL)
2 Solvent/solvent binary parameter values obtained
from:
0 Scalar GMELCA, GMELCB and GMELCM (default)
1 Vector NRTL(8)
3 Mixture density model
0 Rackett equation with Campbell-Thodos
modification
1 Quadratic mixing rule for molecular components
(mole basis)
GIG2ELC, GIG2HG
1 Gibbs free energy calculation method
0 Electrolyte NRTL Gibbs free energy (default for
GIG2ELC)
1 Helgeson method (default for GIG2HG)
GAQPT1, GAQPT3 (Pitzer)
1 Defaults for pair mixing rule
-1 No unsymmetric mixing
0 Unsymmetric mixing polynomial (default)
1 Unsymmetric mixing integral
2 Standard Gibbs free energy calculation
0 Standard electrolytes method (Pre-release 10)
1 Helgeson method (Default)
3 Estimation of K-stoic temperature dependency
0 Use value at 298.15 K
1 Helgeson Method (default)

5 Property Model Option Codes 329


Option Codes for Liquid Volume
Models
Model Option Value Descriptions
Name Code
VL2QUAD 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
VAQCLK 1 0 Use Clarke model
1 Use liquid volume quadratic mixing rule
COSTALD liquid volume model for Aspen HYSYS property methods: VL2GLYCT,
VL0GLYCT (GLYCOL); VL2HPRCT, VL0HPRCT (HYSPR); VL2HSRKC, VL0HSRKC (HYSSRK)
1 0 Smoothly make liquid density change to equation of
state when Tr > 0.95
1 No smoothing of liquid density
2 0 Chueh-Prausnitz equation for pressure correction
1 Tait equation for pressure correction

330 5 Property Model Option Codes


Index

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