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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

proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of

AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of

the software and the application of the results obtained.

Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software

may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO

WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION,

ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE.

200 Wheeler Road

Burlington, MA 01803-5501

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

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

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

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

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

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.

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

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

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

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

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.

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.

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

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.

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

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

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

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

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

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

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

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

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

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

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

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

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:

Where:

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

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:

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.

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/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

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

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

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).

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).

The GERG2008 equation-of-state model is the basis for the GERG2008

property method.

The equation of state is based on a multi-fluid approximation explicit in the

reduced Helmholtz free energy:

(1)

mixture density, temperature, and molar composition are:

(2)

(3)

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

)

(8)

(9)

Where:

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

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:

, with

, where

, with

, where

, and

Cross-Interactions

The previous equations are valid for dimerization and cross-dimerization if

these mixing rules are applied:

and j are in the same class of compounds). Many values are present in the

Aspen Physical Property System.

Chemical Theory

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

The chemical reaction for the general case of a mixture of dimerizing

components i and j is:

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 .

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.

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)

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)

represents the true partial pressure of the hexamer, then the equilibrium

constant is defined as:

(4)

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)

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.

If you assume the ideal gas law for a mixture containing HF, the apparent HF

mole fraction is:

(8)

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).

The apparent fugacity coefficient is related to the true fugacity coefficient and

mole fractions:

(10)

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)

From the fugacity coefficient, the Gibbs energy departure of the mixture or

pure apparent components can be calculated:

(12)

(12a)

For the enthalpy departure, the heat of reaction is considered. For an

arbitrary gas phase reaction:

(13)

(14)

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)

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)

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.

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.

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.

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

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.

Vcm =

Zm =

Where:

Vcij =

Tcij =

Zci =

kij = kji

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

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.

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.

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 =

The chemical reaction for the general case of a mixture of dimerizing

components i and j is:

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

association, the quantity V/na reflects the apparent contraction in an

associating mixture.

The heat of reaction due to each dimerization can be calculated:

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

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:

or parameters you entered.

Built-in correlations:

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

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.

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.

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..

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.

where ares is the molar residual Helmholtz energy of mixtures, R is the gas

constant, T is the temperature, is the molar density, and Zm is the

compressibility factor; ares is defined as:

where a is the Helmholtz energy of a mixture and aig is the Helmholtz energy

of a mixture of ideal gases at the same temperature, density and composition

xi. Once is known, any other thermodynamic function of interest can be

easily derived. For instance, the fugacity coefficient i is calculated as follows:

with

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

constant.

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

Enthalpy departure:

Entropy departure:

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-

sphere mixtures prior to bonding to form chains) and a bonding contribution

due to chain formation:

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:

copolymer component i and can be calculated from the segment weight

fraction within 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:

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

alternating, b) block, and c) random.

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:

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:

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

different segments to multi types of different segments within a copolymer

is straightforward.

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:

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:

Therefore,

That is,

The equations for the dispersion term are given as follows:

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).

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:

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

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

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,

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:

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:

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.

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

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

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

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

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

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

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

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.

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

a0 =

been made temperature-dependent)

kij =

kij = kji

a1

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 =

ci =

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

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

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:

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 =

ci =

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

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.

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.

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 =

Name/Element Limit Limit

TC Tci 5.0 2000.0 TEMPERATURE

5 8

PC pci 10 10 PRESSURE

References

O. Redlich and J.N.S. Kwong, "On the Thermodynamics of Solutions V. An

Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,

(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 =

b =

ai =

bi =

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

RKAKA1 ka,ij1 0 x -15.0 15.0 TEMPERATURE

RKAKB0 kb,ij0 0 x -5.0 5.0

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:

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).

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

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/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.

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:

b =

ai =

bi =

kij = kji

; ;

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

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/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-

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 =

c =

ai =

bi =

ci =

(for T Tci)

The latter equation is used to ensure bi-ci remains

positive in supercritical conditions.

g0i = bi (covolume)

g2i =

g1i =

ka,ij =

lij =

kb,ij =

ka,ij = ka,ji

lij = -lji

kb,ij = kb,ji

The binary parameters ka,ij, kb,ij, and lij are temperature-dependent. In most

cases, ka,ij0 and lij0 are sufficient to represent the system of interest.

VLE calculations are independent of c. However, c does influence the fugacity

values and can be adjusted to (liquid) molar volumes. For a wide temperature

range, adjust ci0 to the molar volume at 298.15K or at boiling temperature.

The ai are calculated using the Extended Mathias Alpha Function, as described

in Soave Alpha Functions.

Warning: Using c1i and c2i can cause anomalous behavior in enthalpy and

heat capacity. Their use is strongly discouraged.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

TCRKU Tci TC x 5.0 2000.0 TEMPERATURE

PCRKU pci PC x 105 108 PRESSURE

OMGRKU i OMEGA x -0.5 2.0

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.

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:

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

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

SRKOMG i OMEGA x 0.5 2.0

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.

SRK-Kabadi-Danner

The SRK-Kabadi-Danner property model uses the SRK equation-of-state with

improved phase equilibrium calculations for mixtures containing water and

hydrocarbons. These improvements are achieved by using the Kabadi-Danner

mixing rules.

The form of the equation-of-state is:

Where:

Where:

;

The best values of kwj (w = water) were obtained from experimental data.

Results are given for seven homologous series.

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

Where:

molecule of hydrocarbon i.

gl is the group contribution parameter for groups constituting hydrocarbons.

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

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

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

SMLOMG i OMEGA x 0.5 2.0

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

Option Codes.

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

and j, for i,j 1 to 5.

p0 = Reference pressure

k = Number of components

Association Equilibria

Every association equilibrium reaction

(1)

(2)

(3)

(4)

By setting

(5)

(6)

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)

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)

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

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

for a calculation.

The compressibility factor is defined by the ratio between the number of

complexes and the number of monomers in the complexes.

(9)

(10)

Fugacity Coefficient

As is well-known from thermodynamics, the fugacity coefficient can be

calculated by

(11)

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)

complexes is considered. The quota of monomers i being integrated in a

complex of degree n is given by

(14)

and

(16)

(1)

(2)

(17)

(18)

(19)

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)

A similar expression for ga should hold as it does for the enthalpy departure

(eq. 20):

(21)

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)

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.

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.

The pure component parameters for the Peng-Robinson equation-of-state are

calculated as follows:

(1)

(2)

equation-of-state under these conditions:

(3)

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)

acentric factor:

(5)

Peng-Robinson alpha function is adequate for hydrocarbons and other

nonpolar compounds, but is not sufficiently accurate for polar compounds.

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

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

=

temperatures. Additional parameters are not needed.

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.

parameters.

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

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

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 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

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).

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

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

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

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)

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

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:

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

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.

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

calculated as:

(1)

(2)

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)

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)

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

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.

This is an extension of the Soave alpha function which provides a more

accurate fit of vapor pressure for polar compounds.

(8)

formulation, equations 5 and 6. For temperatures above critical, the Boston-

Mathias extrapolation is used, that is, equation 7 with:

(9)

(10)

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

RKAPOL for Redlich-Kwong-Aspen, SRKPOL for SRK and SRKKD, SRKMLP for

SRK-ML, RKSPOL for RKS-BM, or RKSSPO for RK-SOAVE.

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)

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

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

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

RKSMCP/3 c3,i 0 X

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)

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

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.

parameters.

This function is equivalent to the standard Soave alpha function if

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

used instead.

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

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

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

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

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.

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)

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)

contains the excess Gibbs energy at an infinite pressure:

(4)

Where:

(5)

cubic equation-of-state can be written as:

(6)

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.

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.

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:

(3)

and

(4)

With:

(5)

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)

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)

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)

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

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)

(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)

(6)

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

(7)

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:

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).

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

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)

(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)

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)

(7)

Wong and Sandler discovered the following mixing rule to satisfy equation 4

(using equations 6 and 7):

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.

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

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

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

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

Where:

xi = Mole fraction of ion i

xw = Mole fraction of water

Mw = Molecular weight of water (g/mol)

ni = Moles of ion i

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.

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

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

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

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.

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

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

Where:

contribution to i

component i

solvent mixture

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

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.

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

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).

(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:

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:

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

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.

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

Regression System (DRS). The parameter requirements of the model are

given in Electrolyte NRTL Activity Coefficient 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)

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.

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.

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

T = Temperature

k = Boltzmann constant

Ix = Ionic strength (mole fraction scale)

xi = Mole fraction of component i

zi = Charge number of ion i

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:

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

(8)

The Debye-Hckel theory is based on the infinite dilution reference state for

ionic species in the actual solvent media. For systems with water as the only

solvent, the reference state is the infinite dilution aqueous solution. For

mixed-solvent systems, the reference state for which the Debye-Hckel

theory remains valid is the infinite dilution solution with the corresponding

mixed-solvent composition. However, the molecular weight Ms, the mass

density ds, and the dielectric constant s for the single solvent need to be

extended for mixed solvents; simple composition average mixing rules are

adequate to calculate them as follows:

(6a)

(7a)

(8a)

(8b)

(8c)

(8d)

Where:

xm = Mole fraction of the solvent m in the solution

Mm = Molecular weight of the solvent m

Vm l = Molar volume of the solvent mixture

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.

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

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 =

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:

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.

(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)

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)

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)

(27)

(28)

and,

(29)

(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)

(33)

activity coefficients of all three species can be determined.

(34)

(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)

(39)

(40)

Where:

(41)

(42)

(43)

(44)

(45)

(46)

(47)

(48)

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

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.

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.

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

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

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

conceptual segments

segments

A = Debye-Hckel parameter

= Average solvent molecular weight, g/mol

NA = Avogadros number

Qe = Absolute electronic charge

= Average solvent dielectric constant

ra = Born radius of anionic segment

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

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

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)

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:

effect

bonding effect

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.

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

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

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:

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.

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

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.

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.

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.

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

corresponding electrolyte component CA, as defined by the chemical equation

describing the dissociation of the electrolyte:

with

single electrolyte.

simple mixing rule is used:

composition fraction; they are defined as follows:

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.

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:

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.

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)

molecular and ionic 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.

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.

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)

and is related to the corresponding cationic and anionic activity coefficients C

and A by this expression:

(5)

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)

(7)

(8)

(9)

containing a single electrolyte component. For multi-electrolyte systems, the

symmetric reference state can be generalized from Eq. 3 as follows:

(10)

reference state is a molecular-component-free media.

The condition of infinite-dilution solution for ionic components can be written

as follows:

(11)

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:

(12)

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)

(21)

with

(22)

calculated as follows:

(23)

segments, the cationic segment, and the anionic segment can be calculated

out as follows:

(24

)

(25)

(26)

The local composition term for the logarithm of the activity coefficient of

component I , before normalization to a chosen reference state, is computed

as the sum of the individual segment contributions.

(27)

coefficients are given as follows:

(28)

(29)

(30)

Molecular components

Applying Eq. 1, the normalization for molecular components can be done as

follows:

(31)

component I,

(32)

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)

(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.

reference state

Applying Eq. 12, the unsymmetric activity coefficients for ionic components in

aqueous solutions can be normalized as follows:

(36)

(37)

solution:

(38)

(39)

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

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)

(44)

(45)

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)

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)

sum is over all solvent components in the solution.

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)

Applying Eq. 10, the symmetric activity coefficients for ionic components from

the long range contribution are given as follows:

(54)

(55)

(56)

Applying Eq. 12, the unsymmetric activity coefficients for ionic components

from the long range contribution in aqueous solutions are given as follows:

(57)

(58)

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:

(59)

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)

(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)

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.

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)

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)

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)

(75)

(76)

(77)

Applying Eq. 12, the unsymmetric activity coefficients for ionic components in

aqueous solutions can be carried out as follows:

(78)

(79)

aqueous solution:

(80)

(81)

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)

(xI0) in the solution. By this definition I* approaches unity as

xI approaches zero. The phase equilibrium relationship for Henry components

becomes:

(83)

The Henrys Law is available in all activity coefficient property methods. The

model calculates the Henrys constant for a dissolved gas component in all

solvent components in the mixture:

(84)

(85)

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)

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

G = exp(-)

Where:

I, J = Component index

i, j, m = Conceptual segment indexx, y-, y+, z

IR = Ilc = NRTL term for local composition interaction contribution to

I

I = Segment mole fraction 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

conceptual segments

segments

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

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

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

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

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.

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

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

component.

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.

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.

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 =

With:

zi = Charge of ion i

Qe = Electron charge

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

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.

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)

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

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)

The natural logarithm of the activity coefficient for ions is calculated from

equation 4a to give:

(5)

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

effects:

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

polynomial form:

form:

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

follows:

Applying:

(6)

(7)

(8)

(9)

So that:

(10)

Hckel constant for the osmotic coefficient, determined from:

(11)

Where:

NA = Avogadro's constant

dw = Water density

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)

By taking appropriate derivatives, expressions for B' can be derived for 1n

electrolytes:

(14)

(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:

(16)

(17)

Where:

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.

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.

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:

=

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

= 0.3524

= 1.6815

= 0.00520

Parameter Sources

Binary and ternary parameters for the Pitzer model for various electrolyte

systems are available from Pitzer's series on the thermodynamics of

electrolytes. These papers and the electrolyte parameters they give are:

Reference Parameters available

(Pitzer, 1973) 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.

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.

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:

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

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:

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

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 =

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

Three-Suffix Margules

This model can be used to describe the excess properties of liquid and solid

solutions. It does not find much use in chemical engineering applications, but

is still widely used in metallurgical applications. Note that the binary

parameters for this model do not have physical significance.

The equation is:

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

i = di

Parameter Name/ Symbol 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).

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

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:

Option codes can affect the performance of this model. See Option Codes for

Activity Coefficient Models for details.

The following table lists the parameters used by GMENRTLS and GMENRTLQ:

Parameter Symbol No. of Default MDS Units

Name Elements

Dielectric Constant Unary Parameters

CPDIEC 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

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.

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)

(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.

(3)

or

(4)

The activity coefficient needs to be normalized by choosing a reference state

for any molecular and ionic component, respectively.

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.

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.

For an electrolyte component ca, the pure fused salt state can be defined as

follows:

(6)

(7)

and is related to the corresponding cationic and anionic activity coefficients c

and a by this expression:

(8)

stoichiometric coefficient, and =c+a (one mole of salt releases moles of

ions in solution). They are given by the chemical equation describing the

dissociation of the electrolyte:

(9)

with

(10)

(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)

containing a single electrolyte component. For multi-electrolyte systems, the

symmetric reference state can be generalized from Eq. 6 as follows:

(16)

reference state is a molecular-component-free medium.

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)

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)

follows:

(24)

(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)

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.

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)

composition fraction, defined as follows:

(33)

(34)

(35)

(36)

(37)

(38)

(39)

(40)

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

(41)

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 ionic components with symmetric reference state, apply Eq. 16 to find:

(43)

(44)

(45)

(46)

(47)

(48)

For ionic components with infinite-dilution aqueous solution as reference

state, apply Eq. 18 to get:

(49)

(50)

coefficients at infinite dilution aqueous solution:

(51)

(52)

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)

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)

(59)

so that

(60)

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)

(62)

(63)

(64)

(65)

(66)

(67)

or

(68)

(69)

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.

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)

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

of species i.

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

as follows:

(73)

(74)

(75)

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.

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)

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)

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.

(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)

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)

Where:

K = Equilibrium constant

xw = Water mole fraction

ion)

component

i = Stoichiometric coefficient

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)

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.

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)

(90)

(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)

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

component and is the ideal Gibbs free energy of mixing. Once the

excess liquid functions are known, the thermodynamic properties of liquid

mixtures can be computed as follows:

(95)

(96)

(97)

where Hil and Hiig are the enthalpy and ideal gas enthalpy of component i at

the system conditions. Similarly, Gil and Giig are the Gibbs free energy and

ideal gas Gibbs free energy of component i at the system conditions. In Aspen

Plus, both Hiig and Giig are computed by the expressions:

(98

)

(99

)

where is the standard enthalpy 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)

solvents, Henry components and ionic components, respectively.

Solvents

The contribution from solvents can be written as follows:

(103)

(104)

(105)

(106)

(107)

(108)

component i, pisat is the vapor pressure of pure component at the system

temperature T, iv is the vapor fugacity coefficient of pure component at T

and pisat (normally calculated from an equation-of-state model), and

is the Poynting pressure correction from pisat to p,

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)

(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.

(124)

infinite dilution heat capacity polynomial. If the polynomial model parameters

follows:

(125)

(126)

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)

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

)

free energy of the solution calculated by the unsymmetric electrolyte NRTL

model at the limit of all molecular components approach zero, that is, the

excess enthalpy and excess Gibbs free energy of ion i at the same limit

condition.

Applying Eq. 127, the system enthalpy and Gibbs free energy with the

symmetric reference state can be expressed as:

(130)

(131)

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

(132)

(133)

Therefore, the enthalpy and Gibbs free energy of ionic components with the

symmetric reference state can be written as:

(134)

(135)

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.

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.

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

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 =

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

number of groups in the mixture.

The residual term is:

activity coefficient of group k in a mixture of groups corresponding to pure i.

The parameters k and ki are defined by:

With:

And:

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

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:

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.

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:

With:

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.

The equations for the "temperature-dependent UNIFAC" (Larsen et al., 1987)

are similar to the original UNIFAC:

With:

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

defined as:

With:

constant:

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.

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.

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

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

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.

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 =

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).

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:

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

i = gi

This model is recommended for dilute solutions.

Parameter Name/ Symbol Default MDS 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.

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 =

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.

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.

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

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

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.

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

Model Type

Solid Antoine Vapor pressure

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

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:

Parameter Symbol Default MDS Lower Upper Units

Name/ Element Limit Limit

PLXANT/1 C1i x PRESSURE,

TEMPERATURE

PLXANT/2 C2i 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.

Barin

See Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity

for details about this submodel.

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.

temperature units.

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

TC Tci TEMPERATURE

PC pci PRESSURE

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

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:

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

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):

Where:

Tri = T / Tci

pri*,l = pi*,l / pci

LNVPEQ/2 and LNVPEQ/3 are the lower and upper temperature limits,

respectively.

In equations 1-4, if elements 4, 7, or 8 are non-zero, absolute temperature

units are assumed for all elements.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

LNVP1/1, ...,8 C1i, ..., C8i x PRESSURE

TEMPERATURE

LOGVP1/1, ..., 8 C1i, ..., C8i x PRESSURE

TEMPERATURE

LNPR1/1, ..., 8 C1i, ..., C8i x PRESSURE

TEMPERATURE

LOGPR1/1, ..., 8 C1i, ..., C8i x PRESSURE

TEMPERATURE

LNPR2/1,2 C1i, C2i x

LNVPEQ/1 (equation

number)

LNVPEQ/2 Tlower 0 X TEMPERATURE

TC Tci TEMPERATURE

PC pci PRESSURE

NIST TDE Polynomial for Liquid Vapor Pressure

This equation can be used for calculating vapor pressure when parameter

PLTDEPOL is available.

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/3 C3i 0 X

References

Reid, Prausnitz, and Poling, The Properties of Gases and Liquids, 4th ed.,

(New York: McGraw-Hill, 1987).

Harlacher and Braun, "A Four-Parameter Extension of the Theorem of

Corresponding States," Ind. Eng. Chem. Process Des. Dev., Vol. 9, (1970), p.

479.

W. Wagner, Cryogenics, Vol. 13, (1973), pp. 470-482.

D. Ambrose, M. B. Ewing, N. B. Ghiassee, and J. C. Sanchez Ochoa "The

ebulliometric method of vapor-pressure measurement: vapor pressures of

benzene, hexafluorobenzene, and naphthalene," J. Chem. Thermodyn. 22

(1990), p. 589.

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

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).

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.

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:

=

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.

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:

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.

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:

Where:

R' = Alcohol substituted alkyl groups

The equilibrium constants are given by:

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.

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.

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:

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

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

If THRSWT/4 Then this equation is used And this parameter is

is used

505 NIST TDE Watson equation DHVLTDEW

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

temperature units.

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

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:

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

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

DHVLWT/1 vapHi*(T1) 5x104 5x108 MOLE-ENTHALPY

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

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:

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

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:

using the slope at the temperature bound

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

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:

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

equation of state

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.

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

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:

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)):

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:

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.

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:

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.

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

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

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

Reference

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

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.

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

(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

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.

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)

Parameter Applicable Symbol Default Units

Name/Element Components

VLCLK/1 Cation-Anion MOLE-VOLUME

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.

Reference

C.C. Chen, private communication.

The equation for the COSTALD liquid volume model is:

Where:

VmR,0 and VmR, are functions or Tr for

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.

temperature units.

Mixing Rules:

Where:

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

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:

coefficients (Pitzer, 1979)

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).

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.

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

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:

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.

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

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:

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:

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

This equation can be used when parameter DNLTMLPO is available.

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

Rackett

The Rackett equation is:

Where:

Tr = T / Tci

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

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

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

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

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

Parameter Symbol Default MDS Lower Upper Units

Name/ Limit Limit

Element

DNLCOSTD/1 Voi x VOLUME

DNLCOSTD/2 0 x

DNLCOSTD/4 Tlower 0 x TEMPERATURE

DNLCOSTD/5 Tupper 1000 x TEMPERATURE

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

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

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.

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

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

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 =

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

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.

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:

Where:

Tc =

kij =

ZmRA =

Zi*,RA =

Vcm =

Tr = T / Tc

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.

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

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:

difference required for the circle equation:

Finally, the equation of the circle is used to determine any point (T,V) for

0.99Tc < T < T00:

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:

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:

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:

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

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

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.

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

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:

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

assumed for C1i through C6i . Otherwise, user input units for temperature are

used. The temperature limits are always interpreted in user input units.

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:

Name Components

IONTYP Ions Ion Type 0

SO25C Anions MOLE-ENTROPY

Cations MOLE-ENTROPY

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

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

= Enthalpy of vaporization

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

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.

The DIPPR equation is used to calculate liquid heat capacity when parameter

THRSWT/6 is 100.

The DIPPR equation is:

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.)

The PPDS equation is used to calculate liquid heat capacity when parameter

THRSWT/6 is 301.

The PPDS equation is:

Linear extrapolation occurs for Cp*,l versus T outside of bounds.

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

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:

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:

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

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

CPLPO/12 C12i 1000 X TEMPERATURE

THRSWT parameters.

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:

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:

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

THRSWT parameters.

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.

The ideal gas heat capacity polynomial is available for components stored in

ASPENPCD, AQUEOUS, and SOLIDS databanks. This model is also used in

PCES.

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.

NIST ThermoML Polynomial

This equation can be used when parameter CPITMLPO is available.

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

The DIPPR ideal gas heat capacity equation 107 by Aly and Lee 1981 is:

(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.

The DIPPR ideal gas heat capacity equation 127 is:

(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:

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

The equation is:

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.

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:

The Aspen equation is:

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:

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

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.)

The equation is:

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

IK-CAPE Heat Capacity Polynomial

The equation is:

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) =

HiA(T, P) =

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.

renormalized.

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:

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

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:

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

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.

Reference

C. Tsonopoulos, Fluid Phase Equilibria, 186 (2001), 185-206.

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:

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

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)

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:

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

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

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

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

range. CPLXP2 stores liquid parameters for the second temperature range.

TEMPERATURE, ENTHALPY, ENTROPY

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.

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

(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.)

usual for components in activity coefficient models:

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

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 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:

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

*,ig

CPIG Molecular Solutes Cp,i

*,ig

Water, Solvents Cp,w

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.

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.

(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.)

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.

capacity polynomial. If the polynomial model parameters are not available,

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:

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

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.

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.

Correlation

Liquid enthalpy is directly calculated by integration of liquid heat capacity:

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

298.15 K

See General Pure Component Heat of Vaporization for parameter requirement

and additional details.

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

=

(Hml-Hmig) = Enthalpy departure of mixture

For supercritical components, declared as Henry's components, the enthalpy

departure is calculated as follows:

For subcritical components:

Hml-Hmig =

HmE,l =

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.

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.

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

p = System pressure

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:

Where:

Hiref,ig = Ideal gas enthalpy of formation for liquid state at

298.15K

Giref,ig = Ideal gas Gibbs free energy of formation for liquid

state at 298.15K

Note that we cannot default the liquid reference enthalpy and Gibbs free

energy to zero, as is the case for WILS-LR, because it will cause inconsistency

with the enthalpy of components that use ideal-gas reference state. The

default values used result in the enthalpies of all components being on the

same basis. In fact, if you enter values for Hiref,l and Giref,l for a liquid-

reference state component you must make sure that they are consistent with

each other and are consistent with the enthalpy basis of the remaining

components in the mixture. If you enter a value for Hiref,l, you should also

enter a value for Giref,l to ensure consistency.

When the liquid-reference state is used, the ideal gas enthalpy at

temperature T is not calculated from the integration of the ideal gas heat

capacity equation (see Ideal Gas as Reference State section below). For

consistency, it is calculated from liquid enthalpy as follows:

Where:

Ticon,l = Temperature of conversion from liquid to vapor

enthalpy for component i

temperature of Tcon,l

conversion temperature and vapor pressure pi*,l

pi*,l = Liquid vapor pressure of component i

= 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

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:

Where:

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

reference state.

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.

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 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

Enthalpy reference state RSTATE for a component. Value of 1 denotes 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.

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:

Where:

Where:

water)

= Born coefficient

Pr = Reference pressure (1 bar)

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

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:

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.

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.

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

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

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

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

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

Model Type

Twu liquid viscosity Liquid

Viscosity quadratic mixing rule Liquid

The liquid mixture viscosity is calculated by the modified Andrade equation:

Where:

kij =

mij =

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

*,l

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

The Andrade equation is:

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

and Ci. Otherwise, all coefficients are interpreted in user input temperature

units. The temperature limits are always interpreted in user input units.

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:

outside bounds.

(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:

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

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

IK-CAPE Liquid Viscosity Model

The IK-CAPE liquid viscosity model includes both exponential and polynomial

equations.

Exponential

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

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

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

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.

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

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)

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

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 --- --- ---

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 --- --- ---

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.

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

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).

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MULOGF f 1.0 0.0 2.0

Institut Francais du Petrole Publications, 1995, p. 130.

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:

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

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

LJPAR/1 (i/k)LJ fcn(Tci, i) X TEMPERATURE

The equation for the DIPPR vapor viscosity model is:

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.

The equation is:

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

The equation is:

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.

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

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.

Polynomial

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

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:

Where:

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).

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

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.

Chung-Lee-Starling Low-Pressure Vapor

Viscosity

The low-pressure vapor viscosity by Chung, Lee, and Starling is:

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:

Vcij =

Tcij =

ij =

Mij =

ij =

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

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:

f1 =

f2 =

FC =

example, the Benedict-Webb-Rubin). 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 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 =

Tcij =

ij =

Mij =

ij =

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

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.

The residual vapor viscosity or the pressure correction to low pressure vapor

viscosity by Dean and Stiel is:

example, General Pure Component Vapor Viscosity). The dimensionless-

making factor is:

Tc =

M =

pc =

Vcm =

Zcm =

rm = Vcm / Vmv

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

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.

The Jones-Dole model calculates the correction to the liquid mixture viscosity

of a solvent mixture, due to the presence of electrolytes:

Where:

calculated by the Andrade model

apparent electrolyte ca

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

If these parameters are available Use this equation

IONMOB and IONMUB Jones-Dole

IONMUB Breslau-Miller

Carbonell

Miller equation is used instead.

Jones-Dole

The Jones-Dole equation is:

(1)

Where:

= Concentration of apparent electrolyte ca (2)

Aca = (4)

La = (5)

Lc = (6)

Bca = (7)

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)

Where the effective volume Vc is given by:

(9)

(9a)

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

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.

temperature units.

The general form for the model is:

l = (l)0 + (l)1

Where:

(l)0 =

(l)1 =

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.

The equation for the Lucas vapor viscosity model is:

The polar and quantum correction factors at high and low pressure are:

FP =

FQ =

FPi (p = 0) =

FQi (p = 0) = fcn(Tri), but is only nonunity for the quantum

gates i = H2, D2, and He.

temperature units.

The Lucas mixing rules are:

Tc =

pc =

M =

FP (p = 0) =

FQ (p = 0) =

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.

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.

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.

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.

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

(i=1) and 210 F (i=2), cSt

210 F, cSt

Tc = Critical temperature of reference fluid, Rankine

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

With i and j being components, the viscosity quadratic mixing rule is:

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 - -

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

Chung-Lee-Starling Thermal Conductivity

The main equation for the Chung-Lee-Starling thermal conductivity model is:

Where:

f1 =

f2 =

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:

Vcij =

Tcij =

ij =

Mij =

ij =

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

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.

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:

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.

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.

The Riedel model can calculate the correction to the liquid mixture thermal

conductivity of a solvent mixture, due to the presence of electrolytes:

Where:

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.

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

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.

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

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:

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

The equation is

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

The DIPPR equation is:

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

The equation is:

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:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

KLPO/1 C1i x THERMAL-

CONDUCTIVITY

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.

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:

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

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.

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:

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

The DIPPR equation for vapor thermal conductivity is:

(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

input temperature units. The temperature limits are always interpreted in

user input units.

PPDS

The equation is:

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

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

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.

The pressure correction to a pure component or mixture thermal conductivity

at low pressure is given by:

Where:

rm =

v(p = 0) can be obtained from the low pressure General Pure Component

Vapor Thermal Conductivity.

This model should not be used for polar substances, hydrogen, or helium.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

MW Mi 1.0 5000.0

TC Tci 5.0 2000.0 TEMPERATURE

PC 105 108 PRESSURE

VC Vci 0.001 3.5 MOLE-VOLUME

ZC Zci 0.1 0.5

References

R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquids,

4th ed., (New York: McGraw-Hill, 1987), p. 521.

Liquid mixture thermal conductivity is calculated using the Vredeveld equation

(Reid et al., 1977):

Where:

wi = Liquid phase weight fraction of component i

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.

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 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.

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.

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.

The vapor mixture thermal conductivity at low pressures is calculated from

the pure component values, using the Wassiljewa-Mason-Saxena equation:

Where:

Thermal Conductivity model

Viscosity model

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.

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:

D =

ij =

ij =

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

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

STKPAR/2 iST fcn(Tbi, Vbi, pi) 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):

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

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:

Dijv=Djiv

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):

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.

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

DVBLNC 1

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:

(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

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, 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:

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

from the General Pure Component Liquid Viscosity

model. You must provide parameters for one of

these models.

components

xi, xj = Apparent binary mole fractions. If the actual mole

fractions are then

Name/Element Limit Limit

MW Mj 1.0 5000.0

*,l

VB Vbi 0.001 3.5 MOLE-VOLUME

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:

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.

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

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

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.

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.

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

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.

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:

Qpi =

mi =

Parameter Symbol Default Lower Upper Units

Name/Element Limit Limit

TC Tci 5.0 2000.0 TEMPERATURE

PC pci PRESSURE

CHI i 0

The DIPPR equation for liquid surface tension is:

Where:

Tri = T / Tci

(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.

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:

Parameter Symbol Default MDS Lower Upper Units

Name/Element Limit Limit

SIGPDS/1 C1i SURFACE-

TENSION

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

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:

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

This equation can be used when parameter SIGTDEW is available.

Name/Element Limit Limit

SIGTDEW/1 C1i x

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

This equation can be used when parameter SIGISTE is available.

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:

by the General Pure Component Liquid Surface

Tension model

xcaa = Mole fraction of the apparent electrolyte ca

to apparent electrolyte ca

For each apparent electrolyte ca, the contribution to the surface tension

correction is calculated as:

(2)

Where:

ccaa =

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:

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.

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).

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.

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

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:

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.

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

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

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.

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:

wij = Mass fraction of the jth constituent in

component i

h is = Specific enthalpy of solid component i

component i

Name/Element Limit Limit

DHFGEN/J fhjs x 0 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.

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

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

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:

of carbon in carbonates and the loss of hydrogen

present in the water constitution of clays

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

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

m = Mineral-matter-free basis

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.

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:

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:

BOIEC/1 a1i 151.2

BOIEC/2 a2i 499.77

Parameter Name/Element Symbol Default

BOIEC/3 a3i 45.0

BOIEC/4 a4i -47.7

BOIEC/5 a5i 27.0

BOIEC/6 a6i -189.0

Dulong Correlation:

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

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

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:

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

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

Parameter Name/Element Symbol Default

HCOMB chid 0

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:

liquid, the heat of vaporization at 298.15 K is needed in the conversion. The

The complete oxidation of carbon is based on the reaction

The complete oxidation of sulfur (pyritic and organic sulfur) is based on the

calculated by:

The complete oxidation of nitrogen is based on the reaction

is calculated by:

Direct Correlation: Normally small, relative to its heat of combustion. An error

of 1% in the heat of a combustion-based correlation produces about a 50%

error when it is used to calculate the heat of formation. For this reason, the

following direct correlation was developed, using data from the Penn State

Data Base. It has a standard deviation of 112.5 Btu/lb, which is close to the

limit, due to measurement in the heat of combustion:

Where:

Parameter Name/Element Symbol Default

HFC/1 a1i 1810.123

HFC/2 a2i -502.222

HFC/3 a3i 329.1087

HFC/4 a4i 121.766

HFC/5 a5i -542.393

HFC/6 a6i 1601.573

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

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

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

The cubic temperature equation is:

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.

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

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

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.

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.

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.

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):

DENIGT/1 a1i 0.4397

DENIGT/2 a2i 0.1223

DENIGT/3 a3i -0.01715

DENIGT/4 a4i 0.001077

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.

5 Property Model Option

Codes

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

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

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

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

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

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

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)

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

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

finding

ESPRWS, ESPRWS0, 1 0 ASPEN Boston/Mathias alpha function

ESPRV1, ESPRV10,

ESPRV2, ESPRV20,

ESPSAFT, ESPSAFT0 1 0 Random copolymer (default)

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)

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

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)

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.

Models

Model Option Value Descriptions

Name Code

BK10 1 0 Treat pseudocomponents as paraffins (default)

1 Treat pseudocomponents as aromatics

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

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)

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

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

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)

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

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

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