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Copyright (c) 2008 by Aspen Technology, Inc. All rights reserved. Aspen Physical Property System, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered trademarks of Aspen Technology, Inc., Cambridge, 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. Aspen Technology, Inc. 200 Wheeler Road Burlington, MA 01803-5501 USA Phone: (1) (781) 221-6400 Toll Free: (1) (888) 996-7100 URL: http://www.aspentech.com

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Contents

1 Introduction .........................................................................................................5 Units for Temperature-Dependent Parameters .................................................... 6 Pure Component Temperature-Dependent Properties .......................................... 7 Extrapolation Methods .................................................................................... 9 2 Thermodynamic Property Models .......................................................................11 Equation-of-State Models ...............................................................................14 ASME Steam Tables .............................................................................15 BWR-Lee-Starling................................................................................16 Benedict-Webb-Rubin-Starling ..............................................................17 Hayden-O'Connell................................................................................20 HF Equation-of-State ...........................................................................22 Ideal Gas ...........................................................................................26 Lee-Kesler..........................................................................................26 Lee-Kesler-Plcker...............................................................................28 NBS/NRC Steam Tables........................................................................29 Nothnagel ..........................................................................................30 Peng-Robinson....................................................................................32 Standard Peng-Robinson ......................................................................34 Peng-Robinson-MHV2 ..........................................................................36 Predictive SRK (PSRK) .........................................................................36 Peng-Robinson-Wong-Sandler ...............................................................36 Redlich-Kwong ....................................................................................37 Redlich-Kwong-Aspen ..........................................................................37 Redlich-Kwong-Soave ..........................................................................38 Redlich-Kwong-Soave-Boston-Mathias....................................................40 Redlich-Kwong-Soave-Wong-Sandler .....................................................42 Redlich-Kwong-Soave-MHV2 .................................................................42 Schwartzentruber-Renon ......................................................................42 Soave-Redlich-Kwong ..........................................................................44 SRK-Kabadi-Danner.............................................................................46 SRK-ML .............................................................................................48 VPA/IK-CAPE Equation-of-State.............................................................49 Peng-Robinson Alpha Functions .............................................................54 Huron-Vidal Mixing Rules......................................................................64 MHV2 Mixing Rules ..............................................................................66 Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules ...........................67 Wong-Sandler Mixing Rules ..................................................................69 Activity Coefficient Models ..............................................................................71 Bromley-Pitzer Activity Coefficient Model ................................................71 Chien-Null ..........................................................................................74 Constant Activity Coefficient .................................................................76

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COSMO-SAC .......................................................................................76 Electrolyte NRTL Activity Coefficient Model ..............................................79 ENRTL-SAC ........................................................................................92 Hansen ..............................................................................................97 Ideal Liquid ........................................................................................98 NRTL (Non-Random Two-Liquid)............................................................98 Using NRTL-SAC................................................................................ 104 Pitzer Activity Coefficient Model ........................................................... 105 Polynomial Activity Coefficient............................................................. 117 Redlich-Kister ................................................................................... 118 Scatchard-Hildebrand ........................................................................ 119 Three-Suffix Margules ........................................................................ 120 UNIFAC Activity Coefficient Model ........................................................ 121 UNIFAC (Dortmund Modified) .............................................................. 123 UNIFAC (Lyngby Modified) .................................................................. 124 UNIQUAC Activity Coefficient Model ..................................................... 125 Van Laar Activity Coefficient Model ...................................................... 126 Wagner Interaction Parameter ............................................................ 127 Wilson Activity Coefficient Model.......................................................... 128 Wilson Model with Liquid Molar Volume................................................. 129 Vapor Pressure and Liquid Fugacity Models ..................................................... 131 Extended Antoine/Wagner/PPDS/IK-CAPE Liquid Vapor Pressure Model ..... 131 API Sour Model ................................................................................. 136 Braun K-10 Model ............................................................................. 136 Chao-Seader Pure Component Liquid Fugacity Model .............................. 137 Grayson-Streed Pure Component Liquid Fugacity Model .......................... 137 Kent-Eisenberg Liquid Fugacity Model................................................... 138 Maxwell-Bonnell Vapor Pressure Model ................................................. 139 Solid Antoine Vapor Pressure Model ..................................................... 139 DIPPR/Watson/PPDS/IK-CAPE Heat of Vaporization Model ................................. 139 DIPPR Heat of Vaporization Equation.................................................... 140 Watson Heat of Vaporization Equation .................................................. 140 PPDS Heat of Vaporization Equation ..................................................... 141 IK-CAPE Heat of Vaporization Equation................................................. 141 NIST TDE Watson Heat of Vaporization Equation .................................... 142 Clausius-Clapeyron Equation ............................................................... 142 Molar Volume and Density Models ................................................................. 143 API Liquid Volume ............................................................................. 143 Brelvi-O'Connell ................................................................................ 144 Clarke Aqueous Electrolyte Volume ...................................................... 145 COSTALD Liquid Volume..................................................................... 147 Debye-Hckel Volume ........................................................................ 149 Liquid Constant Molar Volume Model .................................................... 150 Rackett/DIPPR/PPDS/IK-CAPE Liquid Molar Volume ................................ 150 Rackett/Campbell-Thodos Mixture Liquid Volume ................................... 155 Modified Rackett Liquid Molar Volume................................................... 156 Aspen/DIPPR/IK-CAPE Solid Molar Volume ............................................ 157 Liquid Volume Quadratic Mixing Rule.................................................... 159 Heat Capacity Models ..................................................................................160 Aqueous Infinite Dilution Heat Capacity ................................................ 160 Criss-Cobble Aqueous Infinite Dilution Ionic Heat Capacity ...................... 161 DIPPR/PPDS/IK-CAPE Liquid Heat Capacity ........................................... 161 Aspen/DIPPR/Barin/PPDS/IK-CAPE Ideal Gas Heat Capacity .................... 165

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Contents

Aspen/DIPPR/Barin/IK-CAPE Solid Heat Capacity ................................... 168 Solubility Correlations .................................................................................. 170 Henry's Constant...............................................................................171 Water Solubility ................................................................................ 172 Hydrocarbon Solubility ....................................................................... 172 Other Thermodynamic Property Models .......................................................... 173 Cavett ............................................................................................. 173 Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity ... 174 Electrolyte NRTL Enthalpy................................................................... 176 Electrolyte NRTL Gibbs Free Energy ..................................................... 178 Liquid Enthalpy from Liquid Heat Capacity Correlation ............................ 179 Enthalpies Based on Different Reference States ..................................... 180 Helgeson Equations of State ............................................................... 184 Quadratic Mixing Rule ........................................................................ 187 3 Transport Property Models ...............................................................................188 Viscosity Models.......................................................................................... 190 Andrade Liquid Mixture Viscosity ......................................................... 190 Andrade/DIPPR/PPDS/IK-CAPE Pure Component Liquid Viscosity .............. 191 API Liquid Viscosity ........................................................................... 195 API 1997 Liquid Viscosity.................................................................... 195 Aspen Liquid Mixture Viscosity............................................................. 196 ASTM Liquid Mixture Viscosity ............................................................. 196 Chapman-Enskog-Brokaw/DIPPR/PPDS/IK-CAPE Vapor Viscosity .............. 197 Chapman-Enskog-Brokaw-Wilke Mixing Rule ......................................... 200 Chung-Lee-Starling Low-Pressure Vapor Viscosity .................................. 202 Chung-Lee-Starling Viscosity .............................................................. 204 Dean-Stiel Pressure Correction ............................................................ 206 IAPS Viscosity for Water..................................................................... 206 Jones-Dole Electrolyte Correction......................................................... 207 Letsou-Stiel ...................................................................................... 209 Lucas Vapor Viscosity ........................................................................ 209 TRAPP Viscosity Model ....................................................................... 211 Twu Liquid Viscosity .......................................................................... 211 Viscosity Quadratic Mixing Rule ........................................................... 213 Thermal Conductivity Models ........................................................................ 213 Chung-Lee-Starling Thermal Conductivity ............................................. 214 IAPS Thermal Conductivity for Water.................................................... 215 Li Mixing Rule ................................................................................... 216 Riedel Electrolyte Correction ............................................................... 216 Sato-Riedel/DIPPR/IK-CAPE Liquid Thermal Conductivity......................... 217 Solid Thermal Conductivity Polynomial ................................................. 220 Stiel-Thodos/DIPPR/PPDS/IK-CAPE Vapor Thermal Conductivity ............... 221 Stiel-Thodos Pressure Correction Model ................................................ 223 Vredeveld Mixing Rule........................................................................ 224 TRAPP Thermal Conductivity Model ...................................................... 224 Wassiljewa-Mason-Saxena Mixing Rule ................................................. 225 Diffusivity Models ........................................................................................226 Chapman-Enskog-Wilke-Lee (Binary) ................................................... 226 Chapman-Enskog-Wilke-Lee (Mixture).................................................. 227 Dawson-Khoury-Kobayashi (Binary) ..................................................... 228 Dawson-Khoury-Kobayashi (Mixture) ...................................................228

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Nernst-Hartley .................................................................................. 229 Wilke-Chang (Binary)......................................................................... 230 Wilke-Chang (Mixture) ....................................................................... 231 Surface Tension Models................................................................................ 232 Liquid Mixture Surface Tension ............................................................ 232 API Surface Tension........................................................................... 233 IAPS Surface Tension for Water........................................................... 233 Hakim-Steinberg-Stiel/DIPPR/PPDS/IK-CAPE Liquid Surface Tension......... 233 Onsager-Samaras ............................................................................. 237 Modified MacLeod-Sugden .................................................................. 238 4 Nonconventional Solid Property Models ...........................................................239 General Enthalpy and Density Models............................................................. 239 General Density Polynomial ................................................................ 240 General Heat Capacity Polynomial........................................................ 240 Enthalpy and Density Models for Coal and Char ............................................... 241 General Coal Enthalpy Model............................................................... 244 IGT Coal Density Model ...................................................................... 250 IGT Char Density Model...................................................................... 250 5 Property Model Option Codes ...........................................................................252 Option Codes for Transport Property Models.................................................... 252 Option Codes for Activity Coefficient Models .................................................... 253 Option Codes for Equation of State Models...................................................... 255 Soave-Redlich-Kwong Option Codes............................................................... 258 Option Codes for K-Value Models................................................................... 259 Option Codes for Enthalpy Models.................................................................. 260 Option Codes for Gibbs Energy Models ........................................................... 261 Option Codes for Liquid Volume Models .......................................................... 263 Index ..................................................................................................................264

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Contents

1 Introduction

This manual describes the property models available in the Aspen Physical Property System and defines the parameters used in each model. The description for each model lists the parameter names used to enter values on the Properties Parameters forms. This manual also lists the pure component temperature-dependent properties that the Aspen Physical Property System can calculate from a model that supports several equations or submodels. See Pure Component TemperatureDependent Properties (below). Many parameters have default values indicated in the Default column. A dash () indicates that the parameter has no default value and you must provide a value. If a parameter is missing, calculations stop. The lower limit and upper limit for each parameter, when available, indicate the reasonable bounds for the parameter. The limits are used to detect grossly erroneous parameter values. The property models are divided into the following categories: 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.

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Categories of Models

Category Thermodynamic Property Models Sections Equation-of-State Models Activity Coefficient Models (Including Electrolyte Models) Vapor Pressure and Liquid Fugacity Models Heat of Vaporization Models Molar Volume and Density Models Heat Capacity Models Solubility Correlations Other Viscosity 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

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.

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1 Introduction

The following table lists the pure component temperature-dependent properties that the Aspen Physical Property System can calculate from a 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

Property Solid Volume Liquid Volume Submodel-Selection Default DIPPR Parameter Element Equation Number Available Submodels Number THRSWT/1 THRSWT/2 Aspen, DIPPR, IK-CAPE 100 Aspen, DIPPR, PPDS, IK-CAPE 105/116

Liquid Vapor Pressure THRSWT/3 Heat of Vaporization THRSWT/4 Solid Heat Capacity THRSWT/5

Aspen, Wagner, 101/115 BARIN, PPDS, IK-CAPE Aspen, DIPPR, PPDS, IK-CAPE 106

Aspen, DIPPR, BARIN, 100 IK-CAPE DIPPR, PPDS, BARIN, IK-CAPE 100/114

Liquid Heat Capacity THRSWT/6 Ideal Gas Heat Capacity Second Virial Coefficient Liquid Viscosity Vapor Viscosity Liquid Thermal Conductivity Vapor Thermal Conductivity Liquid Surface Tension

Aspen, DIPPR, BARIN, 107 PPDS, IK-CAPE DIPPR Aspen, DIPPR, PPDS, IK-CAPE Aspen, DIPPR, PPDS, IK-CAPE Aspen, DIPPR, PPDS, IK-CAPE Aspen, DIPPR, PPDS, IK-CAPE Aspen, DIPPR, PPDS, IK-CAPE 104 101 102 100 102 106

Equations 114 through 116 are used as the default only for water.

Which equation is actually used to calculate the property for a given component depends on which parameters are available. If parameters are available for more than one equation, the Aspen Physical Property System uses the parameters that were entered or retrieved first from the databanks.

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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) submodelselection parameter, and the transport properties use the TRNSWT (transport switch) submodel-selection parameter. 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) 0 1 to 116 200 301 to 302 400 401 to 404 501 to 515 Submodel Aspen DIPPR BARIN PPDS or property-specific methods PML IK-CAPE NIST

All built-in databank components have model-selection parameters (THRSWT, TRNSWT) that are set to use the correct equations that are consistent with the available parameters. For example, suppose that parameters for the DIPPR equation 106 are available for liquid surface tension. For that component, TRNSWT element 5 is set to 106 in the databank. If you are retrieving data from an in-house or user databank, you should store the appropriate values for THRSWT and TRNSWT in the databank, using the appropriate equation number. Otherwise, the Aspen Physical Property System will search for the parameters needed for the Aspen form of the equations. If a component is available in more than one databank, the Aspen Physical Property System uses the data and equations based on the databank list order on the Components Specifications Selection sheet. For example, suppose the databank search order is ASPENPCD, then PURE10, and that the Aspen Physical Property System cannot find the parameters for a particular submodel (equation) in the ASPENPCD databank. If the PURE10 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 Properties 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 Properties Parameters Pure-Components 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

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1 Introduction

Set the fourth element of the THRSWT parameter to 106, and the 1-3 and 5-8 elements to 0. If you want to set the other temperature-dependent properties to use what is defined for that component in the databank, leave the element blank. The following table lists the available DIPPR equations and the corresponding equation (submodel) number.

Equation Number 100 101 102 103 104 105 106 107 114 116 Equation Form

For equations 114 and 116, t = 1-Tr. Note: Reduced temperature Tr is always calculated using absolute temperature units. This chapter describes the Aspen, DIPPR, BARIN, IK-CAPE, and PPDS 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-versustemperature curve, or the ln(property)-versus-temperature curve for models expressed in logarithmic form, at the upper or lower temperature limit. For temperatures beyond the limit, it uses a linear model with this slope which meets the curve from the equation at the temperature limit. Thus the model is:

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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.

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.

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1 Introduction

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

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

Equation-of-State Models

Property Model ASME Steam Tables BWR-Lee-Starling Benedict-Webb-Rubin-Starling Hayden-O'Connell HF equation-of-state Ideal Gas Lee-Kesler Lee-Kesler-Plcker NBS/NRC Steam Tables Nothnagel Peng-Robinson Standard Peng-Robinson Peng-Robinson-Wong-Sandler Peng-Robinson-MHV2 Predictive SRK Model Name(s) ESH2O0,ESH2O ESBWRS, ESBWRS0 ESHOC0,ESHOC ESHF0, ESHF ESIG0, ESIG ESLK ESLKP0,ESLKP ESSTEAM0,ESSTEAM ESNTH0,ESNTH ESPR0, ESPR ESPRSTD0,ESPRSTD ESPRWS0,ESPRWS ESPRV20,ESPRV2 Phase(s) Pure VL VL V V V VL VL VL V VL VL VL VL X X X X X X X X X X X X X X Mixture X X X X X X X X X X X X X

ESBWR0, ESCSTBWR V L

ESRKSV10, ESRKSV1 V L

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Property Model Redlich-Kwong Redlich-Kwong-Aspen Redlich-Kwong-Soave Redlich-Kwong-Soave-BostonMathias Redlich-Kwong-Soave-WongSandler Redlich-Kwong-Soave-MHV2 Schwartzentruber-Renon Soave-Redlich-Kwong SRK-Kabadi-Danner SRK-ML Peng-Robinson Alpha functions RK-Soave Alpha functions Huron-Vidal mixing rules MHV2 mixing rules PSRK mixing rules Wong-Sandler mixing rules

Phase(s) Pure V VL VL VL X X X X X X X X X X X X X

Mixture X X X X X X X X X X X X X X X

ESRKSML0, ESRKSML V L

Property Model Bromley-Pitzer Chien-Null Constant Activity Coefficient COSMO-SAC Electrolyte NRTL ENRTL-SAC Hansen Ideal Liquid NRTL-SAC Pitzer Polynomial Activity Coefficient Redlich-Kister Scatchard-Hildebrand Three-Suffix Margules UNIFAC UNIFAC (Lyngby modified) UNIFAC (Dortmund modified) UNIQUAC van Laar Wagner interaction parameter Model Name GMPT2 GMCHNULL GMCONS COSMOSAC GMELC ENRTLSAC HANSEN GMIDL NRTLSAC GMPT1 GMPOLY GMREDKIS GMXSH GMMARGUL GMUFAC GMUFLBY GMUFDMD GMUQUAC GMVLAAR GMWIP Phase(s) Pure L L S L L L1 L2 L L L L L1 L2 L L LS LS L LS L L1 L2 L L1 L2 L L1 L2 L L1 L2 L S Mixture X X X X X X X X X X X X X X X X X X X X X

NRTL(Non-Random-Two-Liquid) GMRENON

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Phase(s) Pure L L

Mixture X X

Property Model Extended Antoine/Wagner API Sour Braun K-10 Chao-Seader Grayson-Streed Kent-Eisenberg Maxwell-Bonnell Solid Antoine Model Name PL0XANT SWEQ BK10 PHL0CS PHL0GS ESAMINE PL0MXBN PS0ANT Phase(s) Pure L L1 L2 L L L L L L L1 L2 S X X X X X Mixture X X X

Property Model DIPPR/Watson/PPDS/IK-CAPE Clausius-Clapeyron Equation Model Name DHVLWTSN DHVLWTSN Phase(s) Pure L L X X Mixture

Property Model API Liquid Volume Brelvi-O'Connell Clarke Aqueous Electrolyte Volume COSTALD Liquid Volume Debye-Hckel Volume Liquid Constant Molar Volume Rackett / DIPPR/ PPDS / IKCAPE Liquid Volume Rackett/Campbell-Thodos Mixture Liquid Volume Modified Rackett Aspen/DIPPR/IK-CAPE Solid Molar Volume Model Name VL2API VL1BROC VAQCLK VL0CTD,VL2CTD VAQDH VL0CONS VL0RKT,VL2RKT VL2RKT VL2MRK VS0POLY Phase(s) Pure L L L L L L L L L S L X X X X X X Mixture X X X X X X X X

Property Model Aqueous Infinite Dilution Heat Capacity Polynomial Criss-Cobble Aqueous Infinite Dilution Ionic Heat Capacity Model Name Phase(s) Pure L L Mixture X X

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13

Phase(s) Pure L V X X

Mixture X

Aspen / DIPPR / Barin / PPDS / IK-CAPE Ideal Gas Heat Capacity Aspen / DIPPR / Barin / IK-CAPE HS0POLY Solids Heat Capacity

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

Other Models

Property Model Cavett Liquid Enthalpy Departure BARIN Equations for Gibbs Energy, Enthalpy, Entropy and Heat Capacity Electrolyte NRTL Enthalpy Electrolyte NRTL Gibbs Energy Model Name DHL0CVT, DHL2CVT Phase(s) Pure L SLV X X Mixture X

L L L LV L LV

X X

X X X X X X

Liquid Enthalpy from Liquid Heat DHL0DIP Capacity Correlation Enthalpies Based on Different Reference States Helgeson Equations of State Quadratic Mixing Rule DHL0HREF

Equation-of-State Models

The Aspen Physical Property System has the following built-in equation-ofstate property models. This section describes the equation-of-state property models available.

Model ASME Steam Tables BWR-Lee-Starling Benedict-Webb-Rubin-Starling Hayden-O'Connell HF Equation-of-State Huron-Vidal mixing rules Ideal Gas Lee-Kesler Type Fundamental Virial Virial Virial and association Ideal and association Mixing rules Ideal Virial

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Model Lee-Kesler-Plcker MHV2 mixing rules NBS/NRC Steam Tables Nothnagel Peng-Robinson Standard Peng-Robinson Peng-Robinson Alpha functions Peng-Robinson-MHV2 Peng-Robinson-Wong-Sandler Predictive SRK PSRK mixing rules Redlich-Kwong Redlich-Kwong-Aspen Standard Redlich-Kwong-Soave Redlich-Kwong-Soave-Boston-Mathias Redlich-Kwong-Soave-MHV2 Redlich-Kwong-Soave-Wong-Sandler RK-Soave Alpha functions Schwartzentruber-Renon Soave-Redlich-Kwong SRK-Kabadi-Danner SRK-ML VPA/IK-CAPE equation-of-state Wong-Sandler mixing rules

Type Virial Mixing rules Fundamental Ideal Cubic Cubic Alpha functions Cubic Cubic Cubic Mixing rules Cubic Cubic Cubic Cubic Cubic Cubic Alpha functions Cubic Cubic Cubic Cubic Ideal and association 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 STEAMTA 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.

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15

BWR-Lee-Starling

The Benedict-Webb-Rubin-Lee-Starling equation-of-state is the basis of the BWR-LS property method. It is a generalization by Lee and Starling of the virial equation-of-state for pure fluids by Benedict, Webb and Rubin. The equation is used for non-polar components, and can manage hydrogencontaining systems. General Form:

Where:

Mixing Rules:

Where:

Default TC VC OMEGA 0 0

i ij ij

Binary interaction parameters BWRKV and BWRKT are available in the Aspen Physical Property System for a large number of components. (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.

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Benedict-Webb-Rubin-Starling

The Benedict-Webb-Rubin-Starling equation-of-state is the basis of the BWRS property method. It is a modification by Han and Starling of the virial equation-of-state for pure fluids by Benedict, Webb and Rubin. This equationof-state can be used for hydrocarbon systems that include the common light gases, such as H2S, CO2 and N2. The form of the equation-of-state is:

Where:

17

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. If the values of these parameters are not given, 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 phaseequilibrium data such as VLE data.

Parameter Name/ Element BWRSTC BWRSVC BWRSOM BWRSA/1 BWRSA/2 BWRSA/3 SymbolDefault MDS Lower Upper Units Limit Limit x x x x x x 5.0 0.5 2000.0 TEMPERATURE MOLE-VOLUME MOLE-VOLUME PRESSURE * MOLEVOL^2 PRESSURE * TEMPERATURE^2 * MOLE-VOLUME^2 MOLE-VOLUME^2 MOLE-VOLUME^2 PRESSURE * MOLEVOL^3 MOLE-VOLUME^3 PRESSURE * TEMPERATURE^2 * MOLE-VOLUME^3 PRESSURE * TEMPERATURE^3 * MOLE-VOLUME^2 PRESSURE * TEMPERATURE * MOLEVOLUME^3 2.0

Tci Vci

TC VC OMEGA fcn(i ,Vci , Tci) fcn(i ,Vci , Tci) fcn(i ,Vci , Tci)

0.001 3.5

i

B0 i A0i C0 i

i

bi ai

fcn(i ,Vci , Tci) fcn(i ,Vci , Tci) fcn(i ,Vci , Tci) fcn(i ,Vci , Tci) fcn(i ,Vci , Tci)

x x x x x

i

ci

BWRSA/9

D0 i

BWRSA/10

di

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SymbolDefault

E0 i

BWRAIJ

kij

Parameter B0 i A0i C0 i D0 i E0 i bi ai di Methane 0.723251 7520.29 2.71092x10 1.07737x10 0.925404 2574.89 47489.1 0.468828 4.37222x108 1.48640

8 10

Ethane 0.826059 13439.30 2.95195x10 2.57477x10 3.112060 22404.50 702189.0 0.909681 6.81826x109 2.99656

9 11

Propane 0.964762 18634.70 7.96178x10 4.53708x10 5.462480 40066.40 1.50520x10 2.014020 2.74461x1010 4.56182

7 9 11

n-Butane 1.56588 32544.70 1.37436x1010 3.33159x1011 2.30902x1012 9.140660 71181.80 3.64238x107 4.009850 7.00044x1010 7.54122

3.01122x1010

1.46819x1013

2.56053x1013

i

ci

i

Parameter B0 i A0i C0 i D0 i E0 i bi ai di

n-Pentane 2.44417 51108.20 2.23931x10 1.01769x10 16.607000 162185.00 3.88521x10 7.067020 1.35286x1011 11.85930

7 10 12

n-Hexane 2.66233 45333.10 5.26067x10 5.52158x10 29.498300 434517.00 3.27460x10 9.702300 3.18412x1011 14.87200

7 10 12

n-Heptane 3.60493 77826.90 6.15662x10 7.77123x10 27.441500 359087.00 8351150.0 21.878200 3.74876x1011 24.76040

10 12

n-Octane 4.86965 81690.60 9.96546x1010 7.90575x1012 3.46419x1013 10.590700 131646.00 1.85906x108 34.512400 6.42053x1011 21.98880

3.90860x1013

6.26433x1014

6.36251x1012

i

ci

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).

19

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:

, where

Cross-Interactions

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

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= 0 unless a special solvation contribution can be justified (for example, i and j are in the same class of compounds). Many values are present in the Aspen Physical Property System.

Chemical Theory

When a compound with strong association is present in a mixture, the entire mixture is treated according to the chemical theory of dimerization. The chemical reaction for the general case of a mixture of dimerizing components i and j is:

with In this case, molar volume is equal to V/nt. This represents true total volume over the true number of species nt. However, the reported molar volume is V/na. This represents the true total volume over the apparent number of species na. If dimerization does not occur, na is defined as the number of species. V/na reflects the apparently lower molar volume of an associating gas mixture. The chemical equilibrium constant for the dimerization reaction on pressure basis Kp, is related to the true mole fractions and fugacity coefficients:

Where: yi and yj yij = True mole fractions of monomers = True mole fraction of dimer

21

i

Kij

= True fugacity coefficient of component i = Equilibrium constant for the dimerization of i and j, on a pressure basis =

ij

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 .

Default MDS Lower Limit 0.0 X 5.0 105 10

-11

Parameter Name/ Symbol Element TC PC RGYR MUP HOCETA Tci pci rigyr pi

-9 -24

0.0

The binary parameters HOCETA for many component pairs are available in the Aspen Physical Property System. These parameters are retrieved automatically when you specify any of the following property methods: NRTLHOC, UNIF-HOC, UNIQ-HOC, VANL-HOC, and WILS-HOC.

References

J.G. Hayden and J.P. O'Connell, "A Generalized Method for Predicting Second Virial Coefficients," Ind. Eng. Chem., Process Des. Dev., Vol. 14,No. 3, (1974), 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

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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) If p1 represents the true partial pressure of the HF monomer, and p6 represents the true partial pressure of the hexamer, then the equilibrium constant is defined as: (4)

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)

23

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

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)

Equation 10 represents a correction to the ideal mixing term of the fugacity. The ratio of the true number of species to the apparent number of species is similar to the correction applied in equation 2. Since the ideal gas law is assumed, the apparent fugacity coefficient is given by the equation. All variables on the right side are known. (11)

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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)

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

All components are assumed to be ideal. The enthalpy departure is equal to the heat of reaction, per apparent number of moles: (16)

(17)

From the Gibbs energy departure and enthalpy departure, the entropy departure can be calculated: (18) Temperature derivatives for the thermodynamic properties can be obtained by straightforward differentiation.

Usage

The HF equation-of-state should only be used for vapor phase calculations. It is not suited for liquid phase calculations.

25

The HF equation-of-state can be used with any activity coefficient model for nonelectrolyte VLE. Using the Electrolyte NRTL model and the data package MHF2 is strongly recommended for aqueous mixtures (de Leeuw and Watanasiri, 1993).

Parameter Name/Element ESHFK/1 ESHFK/2 ESHFK/3 ESHFK/4 Symbol C0 C1 C2 C3 Default 43.65 -8910 0 0 MDS Lower Limit Upper Limit Units

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.

Ideal Gas

The ideal gas law (ideal gas equation-of-state) combines the laws of Boyle and Gay-Lussac. It models a vapor as if it consisted of point masses without any interactions. The ideal gas law is used as a reference state for equationof-state calculations, and can be used to model gas mixtures at low pressures (without specific gas phase interactions). The equation is: p = RT / Vm

Lee-Kesler

This equation-of-state model is based on the work of Lee and Kesler (1975). In this equation, the volumetric and thermodynamic properties of fluids based on the Curl and Pitzer approach (1958) have been analytically represented by a modified Benedict-Webb-Rubin equation-of-state (1940). The model calculates the molar volume, enthalpy departure, Gibbs free energy departure, and entropy departure of a mixture at a given temperature, pressure, and composition for either a vapor or a liquid phase. Partial

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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) Z(1) = = Compressibility factor of a simple fluid ( = 0) 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 Tc Pc Parameter Name Default TCLK PCLK TC PC Definition Critical temperature Critical pressure

27

Symbol

References

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

Lee-Kesler-Plcker

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

Where:

The fo and fR parameters are functions of the BWR form. The fo parameter is for a simple fluid, and fR is for reference fluid n-octane.

= =

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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 Name/ Element TCLKP PCLKP VCLKP OMGLKP LKPZC Symbol Default MDS Lower Limit x x x x x 0.001 -0.5 0.1 3.5 2.0 0.5 5.0 Upper Limit 2000.0 Units

Zci kij

LKPKIJ

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.

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.

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. They are the most accurate steam tables in the Aspen Physical Property System. The STMNBS2 model uses the same equations as STEAMNBS but with different root search method. The STEAMNBS method is

29

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, VANLNTH, and WILS-NTH. It is recommended for systems that exhibit strong vapor phase association. The model incorporates the chemical theory of dimerization to account for strong association and solvation effects, such as those found in organic acids, like acetic acid. The equation-of-state is:

Where: b =

bij nc

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

The chemical equilibrium constant for the dimerization reaction on pressure basis Kp is related to the true mole fractions and fugacity coefficients:

Where: yi and yj yij = = = = True mole fractions of monomers True mole fraction of dimer True fugacity coefficient of component i Equilibrium constant for the dimerization of i and j, on a pressure basis

i

Kij

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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:

The heat of reaction for the mixed dimerization of components i and j is by default the arithmetic mean of the heats of reaction for the dimerizations of the individual components. Parameter factor to this value: is a small empirical correction

The sum of the contributions of all dimerization reactions, corrected for the ratio of apparent and true number of moles, is added to the molar enthalpy departure:

The equilibrium constants can be computed using either built-in calculations or parameters you entered. Built-in correlations: The pure component parameters b, d, and p are stored in the Aspen Physical Property System for many components. Parameters you entered:

In this method, you enter Ai, Bi, Ci, and Di on the Properties Parameters Unary.T-Dependent form. The units for Kii is pressure-1; use absolute units for temperature. If you enter Kii and Kjj, then Kij is computed from If you enter Ai, Bi, Ci, and Di, the equilibrium constants are computed using the parameters you entered. Otherwise the equilibrium constants are computed using built-in correlations.

Parameter Name/Element TC TB PC NTHA/1 NTHA/2 Symbol Default Tci Tbi pci bi di 0.33 Lower Limit 5.0 4.0 10

5

8

1.0 3.0

31

Symbol Default pi Ai Bi Ci Di 0 0 0 0 0

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.

Peng-Robinson

The Peng-Robinson equation-of-state is the basis for the PENG-ROB and PRBM property methods. The model has been implemented with choices of different alpha functions (see Peng-Robinson Alpha Functions) and has been extended to include advanced asymmetric mixing rules. Note: You can choose any of the available alpha functions, but you cannot define multiple property methods based on this model using different alpha functions within the same run. By default, the PENG-ROB property method uses the literature version of the alpha function and mixing rules. The PR-BM property method uses the Boston-Mathias alpha function and standard mixing rules. These default

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property methods are recommended for hydrocarbon processing applications such as gas processing, refinery, and petrochemical processes. Their results are comparable to those of the property methods that use the standard Redlich-Kwong-Soave equation-of-state. When advanced alpha function and asymmetric mixing rules are used with appropriately obtained parameters, the Peng-Robinson model can be used to accurately model polar, non-ideal chemical systems. Similar capability is also available for the Soave-Redlich-Kwong model. The equation for the Peng-Robinson model is:

Where: b c a a0 = = = a0+a1 = (the standard quadratic mixing term, where kij has been made temperature-dependent) kij = kij = kji a1

(an additional, asymmetric term used to model highly non-linear systems) lij = In general, ai bi ci = = = .

For best results, the binary parameters kij and lij must be determined from regression of phase equilibrium data such as VLE data. The Aspen Physical Property System also has built-in kij and lij for a large number of component pairs in the EOS-LIT databank. These parameters are used automatically with the PENG-ROB property method. Values in the databank can be different than

33

those used with other models such as Soave-Redlich-Kwong or RedlichKwong-Soave, and this can produce different results. The model has option codes which can be used to customize the model, by selecting a different alpha function and other model options. See PengRobinson Alpha Functions for a description of the alpha functions. See Option Codes for Equation of State Models (under ESPR) for a list of the option codes.

Parameter Name/Element PRTC PRPC OMGPR PRZRA PRKBV/1 PRKBV/2 PRKBV/3 PRKBV/4 PRKBV/5 PRLIJ/1 PRLIJ/2 PRLIJ/3 PRLIJ/4 PRLIJ/5 Symbol Tci pci Default MDS TC PC x x Lower Limit 5.0 10

5

8

Units TEMPERATURE PRESSURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE

i

zRA kij(1) kij(2) kij(3) Tlower Tupper lij(1) lij(2) lij(3) Tlower Tupper

-0.5

2.0

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.

Standard Peng-Robinson

The Standard Peng-Robinson equation-of-state is the original formulation of the Peng-Robinson equation of state with the standard alpha function (see Peng-Robinson Alpha Functions). It is recommended for hydrocarbon processing applications such as gas processing, refinery, and petrochemical processes. Its results are comparable to those of the standard RedlichKwong-Soave equation of state. Note: You can choose any of the available alpha functions, but you cannot define multiple property methods based on this model using different alpha functions within the same run. The equation for this model is:

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Where: b a ai bi kij = = = = =

The model has option codes which can be used to customize the model, by selecting a different alpha function and other model options. See PengRobinson Alpha Functions for a description of the alpha functions. See Option Codes for Equation of State Models (under ESPRSTD) for a list of the option codes. For best results, the binary parameter kij must be determined from regression of phase equilibrium data such as VLE data. The Aspen Physical Property System also has built-in kij for a large number of component pairs in the EOSLIT databank. These parameters are used automatically with the PENG-ROB property method. Values in the databank can be different than those used with other models such as Soave-Redlich-Kwong or Redlich-Kwong-Soave, and this can produce different results.

Parameter Name/Element TCPRS PCPRS OMGPRS PRKBV/1 PRKBV/2 PRKBV/3 PRKBV/4 PRKBV/5 Symbol Tci pci Default MDS TC PC 0 0 0 0 1000 x x x x x x x Lower Limit 5.0 10 5

i

kij(1) kij(2) kij(3) Tlower Tupper

OMEGA x

-0.5

2.0

References

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

35

Peng-Robinson-MHV2

This model uses the Peng-Robinson equation-of-state for pure compounds. The mixing rules are the predictive MHV2 rules. Several alpha functions can be used in the Peng-Robinson-MHV2 equation-of-state model for a more accurate description of the pure component behavior. The pure component behavior and parameter requirements are described in Standard PengRobinson, or in Peng-Robinson Alpha Functions. The MHV2 mixing rules are an example of modified Huron-Vidal mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For more details, see MHV2 Mixing Rules.

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

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Redlich-Kwong

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

Where: = b ai bi = =

Parameter Name/Element TC PC

Default MDS

5

8

References

O. Redlich and J.N.S. Kwong, "On the Thermodynamics of Solutions V. An Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44, (1979), pp. 223 244.

Redlich-Kwong-Aspen

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

37

For best results, binary parameters kij must be determined from phaseequilibrium data regression, such as VLE data.

Parameter Name/Element TCRKA PCRKA OMGRKA RKAPOL RKAKA0 RKAKA1 RKAKB0 RKAKB1 Symbol Tci pci Default MDS TC PC 0 0 0 0 0 x x x x x x x Lower Limit 5.0 105 -0.5 -2.0 -5.0 -15.0 -5.0 -15.0 Upper Limit 2000.0 108 2.0 2.0 5.0 15.0 5.0 15.0 Units TEMPERATURE PRESSURE TEMPERATURE TEMPERATURE

i i

ka,ij0 ka,ij1 kb,ij0 kb,ij1

OMEGA x

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

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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. The model uses option codes which are described in Soave-Redlich-Kwong Option Codes. For best results, binary parameters kij must be determined from phaseequilibrium 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. 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 Name/Element TCRKSS Symbol Tci Default MDS TC x Lower Limit 5.0 Upper Limit 2000.0 Units TEMPERATURE

39

Parameter Name/Element PCRKSS OMRKSS RKSKBV/1 RKSKBV/2 RKSKBV/3 RKSKBV/4 RKSKBV/5 RKSLBV/1 RKSLBV/2 RKSLBV/3 RKSLBV/4 RKSLBV/5

Symbol pci

Units PRESSURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE

i

kij(1) kij(2) kij(3) Tk,lower Tk,upper lij(1) lij(2) lij(3) Tl,lower Tl,upper

OMEGA x

References

G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-ofstate," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 1203. J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures and Temperatures by the Use of a Cubic Equation-of-state," Ind. Eng. Chem. Res., Vol. 28, (1989), pp. 1049 1955. A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For RedlichKwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723.

Redlich-Kwong-Soave-Boston-Mathias

The Redlich-Kwong-Soave-Boston-Mathias equation-of-state is the basis for the RKS-BM property method. It is the Redlich-Kwong-Soave equation-ofstate with the Boston-Mathias alpha function (see Soave Alpha Functions). It is recommended for hydrocarbon processing applications, such as gasprocessing, refinery, and petrochemical processes. Its results are comparable to those of the Peng-Robinson-Boston-Mathias equation-of-state. Note: You can choose any of the available alpha functions, but you cannot define multiple property methods based on this model using different alpha functions within the same run. The equation is: p =

Where:

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b ai bi

= = =

kij = kji ; ;

The parameter ai is calculated by the standard Soave formulation at supercritical temperatures. If the component is supercritical, the BostonMathias extrapolation is used (see Soave Alpha Functions). The model uses option codes which are described in Soave-Redlich-Kwong Option Codes. For best results, binary parameters kij must be determined from phaseequilibrium data regression (for example, VLE data).

Parameter Name/Element TCRKS PCRKS OMGRKS RKSKBV/1 RKSKBV/2 RKSKBV/3 RKSKBV/4 RKSKBV/5 RKSLBV/1 RKSLBV/2 RKSLBV/3 RKSLBV/4 RKSLBV/5 Symbol Tci pci Default MDS TC PC 0 0 0 0 1000 0 0 0 0 1000 x x x x x x x x x x x x Lower Limit 5.0 105 -0.5 -5.0 Upper Limit 2000.0 108 2.0 5.0 Units TEMPERATURE PRESSURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE

i

kij(1) kij(2) kij(3) Tk,lower Tk,upper lij(1) lij(2) lij(3) Tl,lower Tl,upper

OMEGA x

References

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

41

Redlich-Kwong-Soave-Wong-Sandler

This equation-of-state model uses the Redlich-Kwong-Soave equation-of-state for pure compounds. The predictive Wong-Sandler mixing rules are used. Several alpha functions can be used in the Redlich-Kwong-Soave-WongSandler equation-of-state model for a more accurate description of the pure component behavior. The pure component behavior and parameter requirements are described in Standard Redlich-Kwong-Soave, and in Soave Alpha Functions. Note: You can choose any of the available alpha functions, but you cannot define multiple property methods based on this model using different alpha functions within the same run. The Wong-Sandler mixing rules are an example of modified Huron-Vidal mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For more details, see Wong-Sandler Mixing Rules.

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:

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a b

= =

c ai bi ci

= = = =

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 cio to the molar volume at 298.15K or at boiling temperature. Warning: Using c1i and c2i can cause anomalous behavior in enthalpy and heat capacity. Their use is strongly discouraged.

Parameter Name/Element TCRKU PCRKU OMGRKU RKUPP0 RKUPP1 RKUPP2 RKUC0 RKUC1 RKUC2 RKUKA0 RKUKA1 RKUKA2 Symbol Tci pci Default MDS TC PC 0 0 0 0 0 0 0 0 x x x x x x x x x x x Lower Limit 5.0 105 -0.5 Upper Limit 2000.0 108 2.0 Units TEMPERATURE PRESSURE TEMPERATURE TEMPERATURE

i

q0i q1i q2i c0i c1i c2i ka,ij0 ka,ij1 ka,ij2

OMEGA x

43

Default MDS 0 0 0 0 0 0 x x x x x x

Lower Limit

Upper Limit

ka,ij2, lij2,

and kb,ij2.

For polar components (dipole moment >> 0), if you do not enter q0i, the system estimates q0i, q1i, q2i from vapor pressures using the Antoine vapor pressure model. If you do not enter at least one of the binary parameters ka,ij0, ka,ij2, lij0, lij2, kb,ij0, or kb,ij2 the system estimates ka,ij0, ka,ij2, lij0, and lij2 from the UNIFAC or Hayden O'Connell models.

References

G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-ofstate," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203. J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures and Temperatures by the Use of a Cubic Equation-of-State," Ind. Eng. Chem. Res., Vol. 28, (1989), pp. 1049 1955. A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For RedlichKwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723.

Soave-Redlich-Kwong

The Soave-Redlich-Kwong equation-of-state is the basis of the SRK property method. This model is based on the same equation of state as the RedlichKwong-Soave model. However, this model has several important differences. 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.

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Where:

Where: ; ;

The enthalpy, entropy, Gibbs energy, and molar volume of water are calculated from the steam tables. The total properties are mole-fraction averages of these values with the properties calculated by the equation of state for other components. Fugacity coefficient is not affected. For best results, the binary parameter kij must be determined from phase equilibrium data regression (for example, VLE data). The Aspen Physical Property System also has built-in kij for a large number of component pairs in the SRK-ASPEN databank. 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.

45

Parameter Name/ Element SRKTC SRKPC SRKOMG SRKZRA SRKKIJ/1 SRKKIJ/2 SRKKIJ/3 SRKKIJ/4 SRKKIJ/5 SRKLIJ/1 SRKLIJ/2 SRKLIJ/3 SRKLIJ/4 SRKLIJ/5

Symbol Default

Units

Tci pci

TEMPERATURE PRESSURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE

i

zRA kij(1) kij(2) kij(3) Tlower Tupper lij(1) lij(2) lij(3) Tlower Tupper

References

G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-ofstate," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203. A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For RedlichKwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723. P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules for multicomponent mixtures: the problem of invariance," Fluid Phase Equilibria, Vol 67, (1991), pp. 31-44.

SRK-Kabadi-Danner

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

Where:

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

Best Fit Values of kwj for Different Homologous Series with Water

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

Where:

Gi is the sum of the group contributions of different groups which make up a molecule of hydrocarbon i.

Group l CH4 CH3 CH2 > CH >C< CH2 (cyclic) > CH (cyclic) CH = CH (cyclic) gl , atm m6 x 105 1.3580 0.9822 1.0780 0.9728 0.8687 0.7488 0.7352 0.6180

47

This value is obtained from very little data. Might not be reliable. The model uses option codes which are described in Soave-Redlich-Kwong Option Codes. SRK-Kabadi-Danner uses the same parameters as SRK, with added interaction parameters. Do not specify values for the SRKLIJ parameters when using SRK-KD.

Parameter Name/ Element SRKTC SRKPC SRKOMG SRKWF SRKZRA SRKKIJ/1 SRKKIJ/2 SRKKIJ/3 SRKKIJ/4 SRKKIJ/5 Symbol Default MDS Lower Limit x x x x x x x x x x 5.0 105 0.5 Upper Limit 2000.0 108 2.0 Units

Tci pci

TC PC OMEGA 0 RKTZRA 0 0 0 0 0

i

Gi zRA kij(1) kij(2) kij(3) Tlower Tupper

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 standard Soave-RedlichKwong model with two exceptions: kij may not equal kji; they are unsymmetric, and a different set of parameters are used, as shown below. The lij are calculated from the equation lij = kji - kij

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Parameter Name/ Element SRKTCML SRKPCML SRKOMGML SRKZRAML SRKKIJML/1 SRKKIJML/2 SRKKIJML/3 SRKKIJML/4 SRKKIJML/5

Symbol Default

Units

Tci pci

i

zRA kij(1) kij(2) kij(3) Tlower Tupper

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 zin = = Apparent concentration True concentration, for component i and degree of association n=1, 2, 4, 6

zMij p0 k

= = =

True concentration of cross-dimers of components i and j, for i,j 1 to 5. Reference pressure Number of components

49

Association Equilibria

Every association equilibrium reaction (1) (2) is described by the equilibrium constants (3)

(4)

By setting (5)

(6) their temperature dependence can be reproduced. To evaluate the true concentration of every complex zin, the following nonlinear systems of equations are to be solved: Total mass balance: The sum of true concentrations is unity.

(7)

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

(8)

Thus, a system of k nonlinear equations for k unknowns zi1 has been developed. After having solved it, all the zin and zMij can be determined using

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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)

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)

to evaluate ha, a mixture consisting of N monomers integrated in the complexes is considered. The quota of monomers i being integrated in a complex of degree n is given by

51

(14)

and (16)

respectively. For the reactions mentioned above: (1) (2) the enthalpies of reaction are (17) (18)

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

(20)

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

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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)

Default MDS 0 0 0 0 0 0 X X X X X X

Lower Limit

Upper Limit

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.

53

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)

These expressions are derived by applying the critical constraints to the equation-of-state under these conditions: (3) The parameter is a temperature function. It was originally introduced by Soave in the Redlich-Kwong equation-of-state. This parameter improves the correlation of the pure component vapor pressure. Note: You can choose any of the alpha functions described here, but you cannot define multiple property methods based on this model using different alpha functions within the same run. This approach was also adopted by Peng and Robinson: (4) Equation 3 is still represented. The parameter mi can be correlated with the acentric factor: (5) Equations 1 through 5 are the standard Peng-Robinson formulation. The Peng-Robinson alpha function is adequate for hydrocarbons and other nonpolar compounds, but is not sufficiently accurate for polar compounds. Note: Reduced temperature Tr is always calculated using absolute temperature units.

Parameter Name/Element TCPR PCPR OMGPR Symbol Tci pci Default MDS TC PC X X Lower Limit 5.0 10

5

8

OMEGA X

-0.5

2.0

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Boston-Mathias Extrapolation

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

Where mi is computed by equation 5, and equation 4 is used for subcritical temperatures. Additional parameters are not needed.

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

Where Tr is the reduced temperature; Xi, Yi and Zi are substance dependent parameters. This function is equivalent to the standard Peng-Robinson alpha function if

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

55

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 L(0) M N L

(0) (0)

(1)

M(1) N

(1)

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

Where the L, M, and N are substance-dependent parameters that must be determined from regression of pure-component vapor pressure data or other data such as liquid heat capacity.

Parameter Name/Element PRTWUP/1 PRTWUP/2 PRTWUP/3 Symbol L M N Default MDS 0 0 X X X Lower Limit Upper Limit Units

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 PengRobinson 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 Name/Element TCPR PCPR Symbol Tci pci Default MDS TC PC X X Lower Limit 5.0 105 Upper Limit 2000.0 108 Units TEMPERATURE PRESSURE

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Default MDS 0 0 X X X

Lower Limit

Upper Limit

Units

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)

Default MDS TC PC 0 0 X X X X X

5

8

OMEGA X

-0.5

2.0

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 Properties | Property Methods | Model form.

Alpha function Standard PR/ Boston-Mathias Extended GibbonsLaughton Twu Generalized alpha function Twu alpha function Model name ESPR0, ESPR ESPRWS0, ESPRWS ESPRV20, ESPRV2 ESPR0, ESPR ESPR0, ESPR ESPR0, ESPR First Option code 1 0 0 0 2 3 4 Standard Peng Robinson ESPRSTD0, ESPRSTD

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Model name ESPRWS0, ESPRWS ESPRV20, ESPRV2 ESPRWS0, ESPRWS ESPRV20, ESPRV2

References

J. F. Boston and P.M. Mathias, "Phase Equilibria in a Third-Generation Process Simulator" in Proceedings of the 2nd International Conference on Phase Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin, (17-21 March 1980) pp. 823-849. D.-Y. Peng and D.B. Robinson, "A New Two-Constant Equation-of-state," Ind. Eng. Chem. Fundam., Vol. 15, (1976), pp. 59-64. P.M. Mathias and T.W. Copeman, "Extension of the Peng-Robinson Equationof-state To Complex Mixtures: Evaluation of the Various Forms of the Local Composition Concept",Fluid Phase Eq., Vol. 13, (1983), p. 91. J. Schwartzentruber, H. Renon, and S. Watanasiri, "K-values for Non-Ideal Systems:An Easier Way," Chem. Eng., March 1990, pp. 118-124. G. Soave, "Equilibrium Constants for a Modified Redlich-Kwong Equation-ofstate," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203. C.H. Twu, J. E. Coon, and J.R. Cunningham, "A New Cubic Equation of State," Fluid Phase Equilib., Vol. 75, (1992), pp. 65-79. C.H. Twu, D. Bluck, J.R. Cunningham, and J.E. Coon, "A Cubic Equation of State with a New Alpha Function and a New Mixing Rule," Fluid Phase Equilib., Vol. 69, (1991), pp. 33-50.

The pure component parameters for the Redlich-Kwong equation-of-state are calculated as: (1)

(2)

These expressions are derived by applying the critical constraint to the equation-of-state under these conditions: (3) Note: You can choose any of the alpha functions described here, but you cannot define multiple property methods based on this model using different alpha functions within the same run. In the Redlich-Kwong equation-of-state, alpha is:

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(4)

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

Soave Modification

The parameter i is a temperature function introduced by Soave in the Redlich-Kwong equation-of-state to improve the correlation of the pure component vapor pressure: (5) Equation 3 still holds. The parameter mi can be correlated with the acentric factor: (6) Equations 1, 2, 3, 5 and 6 are the standard Redlich-Kwong-Soave formulation. The Soave alpha function is adequate for hydrocarbons and other nonpolar compounds, but is not sufficiently accurate for polar compounds.

Parameter Name/Element TCRKS PCRKS OMGRKS Symbol Tci pci Default MDS TC PC X X Lower Limit 5.0 10

5

8

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 reduces molecules should vanish for extremely high temperatures, and asymptotically to zero. Boston and Mathias derived an alternative function for temperatures higher than critical: (7) With di ci =

Where:

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mi Equation 5

= =

This is an extension of the Soave alpha function which provides a more accurate fit of vapor pressure for polar compounds. (8) For i=0, equation 8 reduces to the standard Redlich-Kwong-Soave formulation, equations 5 and 6. For temperatures above critical, the BostonMathias extrapolation is used, that is, equation 7 with: (9)

(10)

The Mathias alpha function is used in the Redlich-Kwong-Aspen model, which is the basis for the RK-ASPEN property method. This alpha function is also available as an option for SRK, SRKKD, SRK-ML, RK-SOAVE, and RKS-BM. See Soave-Redlich-Kwong Option Codes for more information.

Parameter Symbol Name/Element TCRKA PCRKA OMGRKA Tci pci Default MDS TC PC X X X Lower Limit 5.0 10

5

8

i i

OMEGA X

-0.5 -2.0

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)

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(13)

This alpha function is used in the Redlich-Kwong-UNIFAC model which is the basis for the SR-POLAR property method.

Parameter Name/Element TCRKU PCRKU OMGRKU RKUPP0 RKUPP1 RKUPP2 Symbol Tci pci Default MDS TC PC 0 0 X X X X X Lower Limit 5.0 10

5

8

i

p1,i p2,i p3,i

OMEGA X

-0.5

2.0

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-KwongSoave 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 Name/Element TCRKS PCRKS RKSMCP/1 RKSMCP/2 RKSMCP/3 Symbol Tci pci c1,i c2,i c3,i Default MDS TC PC 0 0 X X X X X Lower Limit 5.0 10

5

8

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)

61

(17)

Default MDS TC PC 0 0 X X X X X

5

8

i

p1,i p2,i p3,i

OMEGA X

-0.5

2.0

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

Where Tr is the reduced temperature; Xi, Yi and Zi are substance dependent parameters. This function is equivalent to the standard Soave alpha function if

This function is not intended for use in supercritical conditions. To avoid predicting negative alpha, when Tri>1 the Boston-Mathias alpha function is used instead.

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

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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 L(0) M N L

(0) (0)

(1)

M(1) N

(1)

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 Properties | Property Methods | Models sheet.

Alpha Function original RK standard RKS Model Name ESRK0, ESRK ESRKSTD0, ESRKSTD * First Option Code 1, 2 (default) 0 1 1 1 2 2 2 3 (default) 3 (default) 3 (default) 5 3 4

standard RKS/Boston-Mathias * ESRKSWS0, ESRKSWS ESRKSV10, ESRKV1 ESRKSV20, ESRKSV2 Mathias/Boston-Mathias Extended Mathias/BostonMathias Mathias-Copeman ESRKA0, ESRKA ESRKU0, ESRKU ESRKSW0, ESRKSW ESRKSV10, ESRKSV1 ESRKSV20, ESRKSV2 ESPRWS0, ESPRWS ESRKSV10, ESRKSV1 ESRKSV20, ESRKSV2 * * *

Schwartzentruber-RenonWatanasiri Twu generalized Gibbons-Laughton with Patel extension Mathias for T < Tc; BostonMathias for T > Tc

* ESRKSTD0, ESRKSTD, ESRKS0, ESRKS, ESSRK, ESSRK0, ESRKSML, ESRKSML0. The default alpha function (option code 2) for these models is the

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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 Equationof-state To Complex Mixtures: Evaluation of the Various Forms of the Local Composition Concept", Fluid Phase Eq., Vol. 13, (1983), p. 91. O. Redlich and J. N. S. Kwong, "On the Thermodynamics of Solutions V. An Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44, (1949), pp. 223244. J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures and Temperatures by the Use of a Cubic Equation-of-state," Ind. Eng. Chem. Res., Vol. 28, (1989), pp. 10491055. J. Schwartzentruber, H. Renon, and S. Watanasiri, "K-values for Non-Ideal Systems:An Easier Way," Chem. Eng., March 1990, pp. 118-124. G. Soave, "Equilibrium Constants for a Modified Redlich-Kwong Equation-ofstate," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203. C.H. Twu, W.D. Sim, and V. Tassone, "Getting a Handle on Advanced Cubic Equations of State", Chemical Engineering Progress, Vol. 98 #11 (November 2002) pp. 58-65.

Huron and Vidal (1979) used a simple thermodynamic relationship to equate the excess Gibbs energy to expressions for the fugacity coefficient as computed by equations of state: (1) Equation 1 is valid at any pressure, but cannot be evaluated unless some assumptions are made. If Equation 1 is evaluated at infinite pressure, the mixture must be liquid-like and extremely dense. It can be assumed that: (2) (3) Using equations 2 and 3 in equation 1 results in an expression for a/b that contains the excess Gibbs energy at an infinite pressure:

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(4)

Where: (5)

The parameters 1and 2depend on the equation-of-state used. In general a cubic equation-of-state can be written as: (6)

Values for 1and 2 for the Peng-Robinson and the Soave-Redlich-Kwong equations of state are:

Equation-of-state 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:

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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) The constants 1 and 2, which depend only on the equation-of-state (see Huron-Vidal Mixing Rules) occur in equations 2 and 4. Instead of using infinite pressure for simplification of equation 1, the condition of zero pressure is used. At p = 0 an exact relationship between the

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compacity and can be derived. By substitution the simplified equation q() is obtained, and equation 1 becomes: (6)

However, q() can only be written explicitly for = 5.8. Only an approximation is possible below that threshold. Dahl and Michelsen use a second order polynomial fitted to the analytical solution for 10 < < 13 that can be extrapolated to low alpha: (7) Since q()is a universal function (for each equation-of-state), the combination of equations 6 and 7 form the MHV2 mixing rule. Excess Gibbs energies, from any activity coefficient model with parameters optimized at low pressures, can be used to determine , if i, bi, and b are known. To compute b, a linear mixing rule is assumed as in the original Huron-Vidal mixing rules: (8) This equation is equivalent to the assumption of zero excess molar volume. The MHV2 mixing rule was the first successful predictive mixing rule for equations of state. This mixing rule uses previously determined activity coefficient parameters for predictions at high pressures. UNIFAC was chosen as a default for its predictive character. The Lyngby modified UNIFAC formulation was chosen for optimum performance (see UNIFAC (Lyngby Modified)). However, any activity coefficient model can be used when its binary interaction parameters are known. Like the Huron-Vidal mixing rules, the MHV2 mixing rules are not flexible in the description of the excess molar volume. The MHV2 mixing rules are theoretically incorrect at the low pressure limit. But the practical 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.

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:

67

(1)

The Helmholtz energy is calculated by integration. AE is obtained by: (2) Where both Ai* and Am are calculated by using equation 1. Ai* and Am are written in terms of equation-of-state parameters. The simplification of constant packing fraction (Vm / b) is used: (3)

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:

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

References

K. Fischer, "Die PSRK-Methode: Eine Zustandsgleichung unter Verwendung des UNIFAC-Gruppenbeitragsmodells," (Dsseldorf: VDI Fortschrittberichte, Reihe 3: Verfahrenstechnik, Nr. 324, VDI Verlag GmbH, 1993). T. Holderbaum and J. Gmehling, "PSRK: A Group Contribution Equation-ofstate based on UNIFAC," Fluid Phase Eq., Vol. 70, (1991), pp. 251-265.

These mixing rules use a relationship between the excess Helmholtz energy and equation-of-state. They do not use a relationship between equation-ofstate properties and excess Gibbs energy, as in the Huron-Vidal mixing rules. The pressure-explicit expression for the equation-of-state is substituted in the thermodynamic equation: (1)

The Helmholtz energy is obtained by integration, AE is obtained by: (2) Where both Ai* and Am are calculated by using equation 1. Ai* and Am are written in terms of equation-of-state parameters. Like Huron and Vidal, the limiting case of infinite pressure is used. This simplifies the expressions for Ai* and Am. Equation 2 becomes: (3)

69

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):

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

References

D. S. Wong and S. I. Sandler, "A Theoretically Correct New Mixing Rule for Cubic Equations of State for Both Highly and Slightly Non-ideal Mixtures," AIChE J., Vol. 38, (1992), pp. 671 680.

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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 Bromley-Pitzer Chien-Null Constant Activity Coefficient COSMO-SAC Electrolyte NRTL ENRTL-SAC Hansen Ideal Liquid NRTL (Non-Random-Two-Liquid) NRTL-SAC Pitzer Polynomial Activity Coefficient Redlich-Kister Scatchard-Hildebrand Three-Suffix Margules UNIFAC UNIFAC (Lyngby modified) UNIFAC (Dortmund modified) UNIQUAC Van Laar Wagner interaction parameter Wilson Wilson with Liquid Molar Volume Type Electrolyte Regular solution, local composition Arithmetic Regular solution Electrolyte Segment contribution, electrolyte Regular solution Ideal Local composition Segment contribution Electrolyte Arithmetic Arithmetic Regular solution Arithmetic Group contribution Group contribution Group contribution Local composition Regular solution Arithmetic Local composition 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

71

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:

The user must: Supply these elements using a Properties 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.

No. of Elements Default Units 1 1 5 5 5 5 5 5 5 5 0 0 0 0 0 0 0 0 0 0

Parameter Name Symbol Ionic Unary Parameters GMBPB GMBPD GMBPB0 GMBPB1 GMBPB2 GMBPB3 GMBPTH GMBPTH GMBPB0 GMBPB1

ion ion (0) (1) (2) (3) cc' aa' (0) (1)

Cation-Anion Parameters

Working Equations

The complete Pitzer equation (Frst and Renon, 1982) for the excess Gibbs energy is (see also equation 4):

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(1) Where: GE R T nw zi = = = = = = Excess Gibbs energy Gas constant Temperature Kilograms of water Charge number of ion i molality of ion i

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

B, C, and are interaction parameters, and f(I) is an electrostatic term as a function of ionic strength; these terms are discussed in Pitzer Activity Coefficient Model, which has a detailed discussion of the Pitzer model. The C term and the term are dropped from equation 1 to give the simplified Pitzer equation. (2)

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

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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:

Aij = aij + bij / T Subscripts i and j are component indices. The choice of model and parameters can be set for each binary pair constituting the process mixture by assigning the appropriate value to the ICHNUL parameter.

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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 Name/Element ICHNUL CHNULL/1 CHNULL/2 CHNULL/3 Symbol Default Lower Limit aij bij Vij 3 0 0 0 1 Upper Limit 6 Units

The parameter ICHNUL is used to identify the activity model parameters available for each binary pair of interest. The following values are allowed for ICHNUL:

75

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 Unary Scalar form. The equation is:

i = ai

Parameter Name/Element GMCONS Symbol Default MDS Upper Limit ai 1.0 x Lower Limit Units

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. CosmoSAC 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

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Where:

i iSG

i(m)

= Activity coefficient of component i = Staverman-Guggenheim model for combinatorial contribution to i = Segment activity coefficient of segment component i

m in

77

S(m)

pi(m) pi(m)

= Segment activity coefficient of segment solvent mixture = Sigma profile of component i = Sigma profile of solvent mixture = Surface charge density = Exchange energy between segments

m in

W(m,n) WHB(m,n)

z Vi Ai aeff Veff Aeff

m and n

= Hydrogen-bonding contribution to exchange energy between segments m and n = Coordination number, 10 = Molecular volume of component i = Molecular surface area of component i = Standard segment surface area, 7.50 2 = Standard component volume, 66.69 3 = Standard component surface area, 79.53 2 = Misfit energy constant

'

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

Parameter Symbol Name/Element CSACVL SGPRF1 SGPRF2 SGPRF3 SGPRF4 SGPRF5 Vi Ai pi(1-12) Ai pi(13-24) Ai pi(25-36) Ai pi(37-48) Ai pi(49-51) Default MDS Lower Limit x x x x x x Upper Limit Units VOLUME (3)

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:

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Option Code 1 2 3

Description COSMO-SAC model by Lin and Sandler (2002) COSMO-RS model by Klamt and Eckert (2000) Lin and Sandler model with modified exchange energy (Lin et al., 2002)

References

A. Klamt and F. Eckert, "COSMO-RS: A Novel and Efficient Method for the a Priori Prediction of Thermophysical Data of Liquids," Fluid Phase Equilibria 43, 172 (2000). 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).

The Electrolyte Non-Random Two Liquid (NRTL) model 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

79

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). Option codes can affect the performance of this model. See Option Codes for Activity Coefficient Models for details.

Parameter Symbol No. of Default MDS Units Name Elements Dielectric Constant Unary Parameters CPDIEC AB BB CB 1 1 1 0 298.15 TEMPERATURE

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Parameter Symbol No. of Default MDS Units Name Elements Dielectric Constant Unary Parameters Ionic Born Radius Unary Parameters RADIUS ri 1 Molecule-Molecule Binary Parameters NRTL/1 NRTL/2 NRTL/3 NRTL/4 NRTL/5 NRTL/6 ABB' AB'B BBB' BB'B 3x10-10 0 0 0 0 .3 0 0 0 0 0 0 0 0 0 0 0 .2 0 0 0 0 0 0 0 0 0 0 0 0 .2 .2 x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x LENGTH TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE

BB' = B'B

FBB' FB'B GBB'

GB'B Electrolyte-Molecule Pair Parameters GMELCC GMELCD GMELCE GMELCN GMELCC Cca,B CB,ca Dca,B DB,ca Eca,B EB,ca 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

ca,B = B,ca

Cca',ca'' Cca'',ca' Cc'a,c''a Cc''a,c'a

GMELCD

TEMPERATURE TEMPERATURE

GMELCE

GMELCN

Certain Electrolyte NRTL activity coefficient model parameters are used with reciprocal temperature terms: CPDIEC NRTL/2 GMELCD for electrolyte-electrolyte or electrolyte-molecule pairs

81

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).

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(1)

This leads to (2) Note: The notation using * to denote an unsymmetric reference state is wellaccepted in electrolyte thermodynamics and will be maintained here. The reader should be warned not to confuse it with the meaning of * in classical thermodynamics according to IUPAC/ISO, referring to a pure component property. In fact in the context of G or , the asterisk as superscript is never used to denote pure component property, so the risk of confusion is minimal. For details on notation, see Chapter 1 of Physical Property Methods.

References

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

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:

83

xi Ms A NA ds Qe

= = = = = = = = = = = = =

Mole fraction of component i Molecular weight of the solvent Debye-Hckel parameter Avogadro's number Mass density of solvent Electron charge Dielectric constant of the solvent Temperature Boltzmann constant Ionic strength (mole fraction scale) Mole fraction of component i Charge number of ion i "Closest approach" parameter

s

T k Ix xi zi

Taking the appropriate derivative of equation 3, an expression for the activity coefficient can then be derived. (6)

The Born equation is used to account for the Gibbs energy of transfer of ionic species from the infinite dilution state in a mixed-solvent to the infinite dilution state in aqueous phase. (7)

Where:

w

ri

= =

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

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extended for mixed solvents; simple composition average mixing rules are adequate to calculate them as follows: (6a) (7a)

(8a)

(8b)

(8c) (8d) Where: xm Mm Vml = = = = = = = Mole fraction of the solvent m in the solution Molecular weight of the solvent m Molar volume of the solvent mixture Dielectric constant of the solvent m Molar volume of water from the steam table. Sum of the mole fractions of all non-water solvents. Liquid molar volume for the mixture of all nonwater solvents. It is calculated using the Rackett equation.

m

Vw* xnws Vnwsl

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.

85

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

ji ji

Nonrandomness factor

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

Where: Gji,ki = =

ji,ki ji,ki

Nonrandomness factor

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:

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

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 effective local mole fractions: . These are then related to the (17) (18) (19) The reference Gibbs energy is determined for the reference states of completely dissociated liquid electrolyte and of pure solvent. The reference Gibbs energies per mole are then: (20) (21) (22) Where:

87

zc za

= =

The molar excess Gibbs energy can be found by summing all changes in residual Gibbs energy per mole that result when the electrolyte and solvent in their reference state are mixed to form the existing electrolyte system. The expression is: (23)

Using the previous relation for the excess Gibbs energy and the expressions for the residual and reference Gibbs energy (equations 17 to 19 and 20 to 22), the following expression for the excess Gibbs energy is obtained: (24)

The assumption of local electroneutrality applied to cells with central solvent molecules may be stated as: (25) Combining this expression with the expression for the effective local mole fractions given in equations 9 and 10, the following equality is obtained: (26) The following relationships are further assumed for nonrandomness factors: (27) (28) and, (29) It can be inferred from equations 9, 10, and 26 to 29 that: (30) (31) The binary parameters ca,B , ca,B and B,ca are now the adjustable parameters for an apparent binary system of a single electrolyte and a single solvent. The excess Gibbs energy expression (equation 24) must now be normalized to the infinite dilution reference state for ions: (32)

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(33)

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

89

(38)

Where: (41)

(42)

(43)

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(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.

91

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.

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

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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

93

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Where: I, J i, j, m, c, a m c a i, j = = = = = = = = = = = Component index Conceptual segment index Conceptual molecular segment, x, y-, y+, z Conceptual cationic segment Conceptual anionic segment m,c,a Unsymmetric activity coefficient of an ionic species I NRTL term Pitzer-Debye-Hckel term Flory-Huggins term Aqueous-phase infinite-dilution reference state Activity coefficient of conceptual segment i Total segment number of component I Mole fraction of component I Number of conceptual segment i containing in component I Segment mole fraction of conceptual segment i in mixtures NRTL binary non-randomness factor parameter for conceptual segments NRTL binary interaction energy parameter for conceptual segments Debye-Hckel parameter Closest approach parameter, 14.9 Ionic strength (segment mole fraction scale) Average solvent molecular weight, g/mol Average solvent density, g/cm3

i

rI xI rI,i xi

= = = = = = = = = = = =

ij ij

A

Ix

95

NA Qe

= = =

Avogadros number Absolute electronic charge Average solvent dielectric constant Water dielectric constant Born radius of cationic segment Born radius of anionic segment

w

rc ra

= = =

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 Segment (2) yx z 6.547 yz -2.000 y+ z 2.000 1.787 0.3 x y+ 1.643 1.834 0.2

12 21 12 = 21

NaCl is used as the reference electrolyte for the conceptual electrolyte segment e. The NRTL binary parameters between conceptual molecular segments and the electrolyte segment e are determined from literature data or preset as follows:

Segment (1) x Segment (2) e ye 12 -3 0.2 y+ e 12 -3 0.2 z e 8.885 -4.549 0.2

12 21 12 = 21

15 5 0.2

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)

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Others

References

C.-C. Chen and Y. Song, "Solubility Modeling with a Nonrandom Two-Liquid Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004). C.-C. Chen and Y. Song, "Extension of Nonrandom Two-Liquid Segment Activity Coefficient Model for Electrolytes," Ind. Eng. Chem. Res. 44, 8909 (2005).

Hansen

Hansen is a solubility parameter model and is commonly used in the solvent selection process. It is based on the regular solution theory and Hansen solubility parameters. This model has no binary parameters and its application merely follows the empirical guide like dissolves like. The Hansen model calculates liquid activity coefficients. The equation for the Hansen model is:

with

Where:

i

Vi

= Activity coefficient of component i = Molar volume of component i = Hansen solubility parameter of component i for nonpolar effect = Hansen solubility parameter of component i for polar effect = Hansen solubility parameter of component i for hydrogenbonding effect = Volume fraction of component i

id ip ih i

97

xi R T

The Hansen model does not require binary parameters. For each component, it has four input parameters.

Parameter Symbol Name/Element DELTAD DELTAP DELTAH HANVOL Default MDS x x x x Lower Upper Limit Limit Units PRESSURE^0.5 PRESSURE^0.5 PRESSURE^0.5 VOLUME

id ip ih

Vi

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 Other values Hansen volume input by user (default) 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

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

Where: Gij = = = = = 0 1

ij

ij

ii

Gii

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

cij 0.30 0.20 0.47 Mixtures Nonpolar substances; nonpolar with polar non-associated liquids; small deviations from ideality Saturated hydrocarbons with polar non-associated liquids and systems that exhibit liquid-liquid immiscibility 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 Name/Element NRTL/1 NRTL/2 NRTL/3 NRTL/4 NRTL/5 NRTL/6 Symbol Default MDS aij bij cij dij eij fij 0 0 0.30 0 0 0 x x x x x x Lower Limit -100.0 -30000 0.0 -0.02 Upper Limit 100.0 30000.0 1.0 0.02 Units TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE

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

99

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

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 (yand y+). In practice, these conceptual segments become the molecular descriptors used to represent the molecular surface characteristics of each solute or solvent molecule. Hexane, water, and acetonitrile are selected as the reference molecules for the hydrophobic, hydrophilic, and polar segments, respectively. The molecular parameters for all other solvents can be determined by regression of available VLE or LLE data for binary systems of solvent and the reference molecules or their substitutes. The treatment results in four component-specific molecular parameters: hydrophobicity X, hydrophilicity Z, and polarity Y- and Y+. The two types of polar segments, Yand 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

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G = exp(-) Where: I, J i, j, m = = = = = = = Component index Conceptual segment indexx, y-, y+, z Activity coefficient of component I Flory-Huggins term for combinatorial contribution to

I IC = IFH IR = Ilc I

pI sI and rI xI rI,m xi

Segment mole fraction of component I Effective component size parameter Empirical parameters for pI Total segment number of component I Mole fraction of component I Number of conceptual segment m containing in component I Segment mole fraction of conceptual segment i in mixtures NRTL binary non-randomness factor parameter for conceptual segments NRTL binary interaction energy parameter for conceptual segments

= = = = = = =

im im

101

The NRTL binary parameters between conceptual segments in NRTL-SAC are determined by available VLE and LLE data between reference molecules defined above.

Segment 1 x Segment 2 yx z 6.547 yz -2.000 y+ z 2.000 1.787 0.3 x y+ 1.643 1.834 0.2

12 21 12 = 21

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 NRTL-SAC 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 Name/ Element NRTLXY FHSIZE/1 FHSIZE/2 Symbol Default MDS Lower Limit 1E-15 -1E10 Upper Limit 1E15 1E10 Units Comment

rI,m sI

1.0 1.0

Option codes

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

The molecular parameters are identified for 62 solvents and published.

Solvent name ACETIC-ACID ACETONE ACETONITRILE ANISOLE rI,x rI,yrI,y+ rI,z

0.217

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Solvent name BENZENE 1-BUTANOL 2-BUTANOL N-BUTYL-ACETATE METHYL-TERT-BUTYL-ETHER CARBON-TETRACHLORIDE CHLOROBENZENE CHLOROFORM CUMENE CYCLOHEXANE 1,2-DICHLOROETHANE 1,1-DICHLOROETHYLENE 1,2-DICHLOROETHYLENE DICHLOROMETHANE 1,2-DIMETHOXYETHANE N,N-DIMETHYLACETAMIDE N,N-DIMETHYLFORMAMIDE DIMETHYL-SULFOXIDE 1,4-DIOXANE ETHANOL 2-ETHOXYETHANOL ETHYL-ACETATE ETHYLENE-GLYCOL DIETHYL-ETHER ETHYL-FORMATE FORMAMIDE FORMIC-ACID N-HEPTANE N-HEXANE ISOBUTYL-ACETATE ISOPROPYL-ACETATE METHANOL 2-METHOXYETHANOL METHYL-ACETATE

rI,x

rI,y-

rI,y+

rI,z

0.607 0.414 0.335 0.317 1.040 0.718 0.710 0.278 1.208 0.892 0.394 0.529 0.188 0.321 0.081 0.067 0.073 0.532 0.154 0.256 0.071 0.322 0.194 0.030 0.564 2.890 0.086 0.081 0.318 0.049 0.141 0.448 0.257 0.089 0.707 1.340 1.000 1.660 0.552 0.088 0.052 0.236 0.154 0.149 0.043 2.470 0.041 0.007 0.082 0.030 0.219

103

Solvent name 3-METHYL-1-BUTANOL METHYL-BUTYL-KETONE METHYLCYCLOHEXANE METHYL-ETHYL-KETONE METHYL-ISOBUTYL-KETONE ISOBUTANOL N-METHYL-2-PYRROLIDONE NITROMETHANE N-PENTANE 1-PENTANOL 1-PROPANOL ISOPROPYL-ALCOHOL N-PROPYL-ACETATE PYRIDINE SULFOLANE TETRAHYDROFURAN

rI,x

rI,y-

rI,y+

rI,z

0.419 0.673 1.162 0.247 0.673 0.566 0.197 0.025 0.898 0.474 0.375 0.351 0.514 0.205 0.210 0.235 0.040 0.555 0.223 0.030 0.070 0.134 0.135 0.322 0.036 0.224 0.224

0.314

0.485 0.305

1.216

0.457 0.320

0.304 0.287

0.316 1.000

0.557 0.766

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 NRTL-SAC

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. For more information about the model, see NRTL-SAC.

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The NRTL-SAC model in the Aspen Physical Property System is a liquid activity coefficient model called NRTLSAC. To specify it: 1. On the Properties | Specifications sheet, specify an activity coefficient model, such as NRTL. 2. Click the Properties | Property Methods folder. 3. In the Object Manager, click New. 4. In the Create New ID dialog box, enter a name for the NRTL-SAC method, such as NRTLSAC. 5. In the Base Property Method field, select NRTL. 6. Click the Models tab. 7. Change the Model Name for GAMMA from GMRENON to NRTLSAC. In order to use NRTL-SAC, all components must be defined as oligomers. Four conceptual segments also must be defined. On the Components | Polymers | Oligomers sheet, enter a number for at least one conceptual segment for each oligomer component, as required by the definition of an oligomer. These numbers are not used by NRTL-SAC. On the Properties | Parameters | Binary Interaction | NRTL-1 form, enter the binary parameters between conceptual segments. In the following example, the conceptual segments are named X, Y-, Y+, and Z.

Segment 1 X Segment 2 YAIJ AJI CIJ 1.643 1.834 0.2 X Z 6.547 0.2 YZ -2.000 0.3 Y+ Z 2.000 1.787 0.3 X Y+ 1.643 1.834 0.2

10.949 1.787

On the Properties | Parameters | Binary Interaction | NRTLXY-1 form, 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. The model can be used for aqueous electrolyte systems, up to 6 molal ionic strength. It cannot be used for systems with any other solvent or mixed solvents. 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.

105

The Pitzer model in the Aspen Physical Property System involves usersupplied parameters that are used in the calculation of binary and ternary parameters for the electrolyte system. Five elements (P1 through P5) account for the temperature dependencies of parameters (0), (1), (2), (3), C , , and . These parameters follow the temperature dependency relation:

The user must: Supply these elements for the binary parameters using a Properties | Parameters | Binary | T-Dependent form. Supply these elements for on the Properties | 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 Name GMPTB0 GMPTB1 GMPTB2 GMPTB3 GMPTC GMPTTH GMPTTH GMPTPS, GMPTP1, GMPTP2, GMPTP3, GMPTP4 GMPTB0 GMPTB1 Provides P1 - P5 for No. of Default MDS Units Elements 5 5 5 5 5 5 5 0 0 0 0 0 0 0 x x x x x x x x

Cation-Anion Parameters

C

Cation-Cation Parameters

cc' aa'

ijk

(0) (1)

5 5

0 0

x x

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Provides P1 - P5 for 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 r qij = = = (pair potential of mean force) With: zi Qe = = = = = Charge of ion i Electron charge Average electric potential for ion j Boltzmann's constant Temperature Distribution function Radius

j(r)

k T

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 R T nw mi = = = = = (molality of ion i) Excess Gibbs energy Gas constant Temperature Kilograms of water

107

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

The function f(I) is an electrostatic term that expresses the effect of longrange electrostatic forces between ions. This takes into account the hard-core effects of the Debye-Hckel theory. This term is discussed in detail in the following section. The parameters ij are second virial coefficients that account for the short-range forces between solutes i and j. The parameters ijk account for the interactions between solutes, i, j, k. For ion-ion interactions, ij is a function of ionic strength. For molecule-ion or moleculemolecule interactions this ionic strength dependency is neglected. The dependence of ijk on ionic strength is always neglected. The matrices ij and ijk are also taken to be symmetric (that is, ij = ji). Pitzer modified this expression for the Gibbs energy by identifying combinations of functions. He developed interaction parameters that can be evaluated using experimental data. He selected mathematical expressions for these parameters that best fit experimental data. Pitzer's model can be applied to aqueous systems of strong electrolytes and to aqueous systems of weak electrolytes with molecular solutes. These applications are discussed in the following section. In the Aspen Physical Property System, this model is applied using the reference state of infinite dilution solution in water for non-water molecular solutes and ionic species. The properties such as DHAQFM are obtained at 25 C and 1 atm.

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)

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zi

Charge of ion i

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

The difference between equations 3 and 4 is that Pitzer orders cation before anions. Frst and Renon do not. All summations are taken over all ions i and j (both cations and anions). This involves making the parameter matrices Bij, Cij, ij, and ijk symmetric, as follows: Second-order parameters are written Bij if i and j are ions of different sign. Bij = 0 if the sign of zi = sign of zj, and Bii = 0. Since cations are not ordered before anions, Bij = Bji. This eliminates the 2 in the second term in brackets in Pitzer's original expression (equation 3). Second-order parameters are written ij if i and j are ions of the same sign. Thus ij = 0 if the sign of zi is different from the sign of zj, and ii = 0 with ij = ji. Third-order parameters are written Cij if i and j are ions with different signs. Cij = 0 if the sign of zi = sign of zj, and Cii = 0 with Cij = Cji. The factor of 2 in the fifth bracketed term in Pitzer's original expression (equation 3) becomes 1/2 in equation 4. The matrix C is symmetric and ions to make the equation symmetric. is extended to all

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:

ijk is written for three different ions ijk = kij = jki , and ikk = 0. ijk = 0

109

(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:

The X parameters are calculated differently on the option code. For option code = 1, there is no unsymmetric mixing correction term:

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

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

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

I, the ionic strength, is defined as: (8) Taking the derivative of equation 7 with respect to I, gives:

111

(9)

So that: (10)

This equation is used in equation 6. In equations 7 and 9, is the usual DebyeHckel constant for the osmotic coefficient, determined from: (11)

b is an adjustable parameter, which has been optimized in this model to equal 1.2. B and B' need expressions so that equations 5 and 6 can completely be solved for the activity coefficients. The parameter B is determined differently for different electrolyte pairings. For 1-n electrolytes (1-1, 1-2, 2-1, and so on) the following expression gives the parameter B: (12)

with

1=2.0.

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

with

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

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(15)

After the activity coefficients are calculated, they can be converted to the mole fraction scale from the molality scale by the following relations: For solutes: (16)

Where:

m x

= =

Application of the Pitzer Model to Aqueous Electrolyte Systems with Molecular Solutes

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

iii = 6iii

However, molecule-molecule interactions were not taken into account by Pitzer and coworkers. So iii is an artificially introduced quantity.

113

The equations for activity coefficients and the Gibbs free energy are the same as equations 3 through 6.

Parameters

The Pitzer model in the Aspen Physical Property System involves usersupplied parameters. These parameters are used in the calculation of binary and ternary parameters for the electrolyte system. These parameters include 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)

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) 4/3(1) = = 0.4698 2.242

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0.00979

Perform the necessary conversions and enter the parameters as: = = = 0.3524 1.6815 0.00520

Parameter Sources

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

Reference (Pitzer, 1973) (Pitzer and Mayorga, 1973) Parameters available Binary parameters ((0), (1), C ) for 13 dilute aqueous electrolytes 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 Binary parameters for 2-2 electrolytes in water at 25C Binary and ternary parameters for mixed electrolytes, binary mixtures without a common ion, mixed electrolytes with three or more solutes Ternary parameters for systems mixing doubly and singly charged ions Parameters for phosphoric acid and its buffer solutions Parameters and thermodynamic properties for sulfuric acid Data for NaCl and aqueous NaCl solutions Rare earth chlorides, nitrates, and perchlorates Aqueous carbonate solutions, including mixtures of sodium carbonate, bicarbonate, and chloride Aqueous calcium chloride Saturated aqueous solutions, including mixtures of sodium chloride, potassium chloride, and cesium chloride

(Pitzer, 1975) (Pitzer and Silvester, 1976) (Pitzer, Roy and Silvester, 1977) (Silvester and Pitzer, 1977) (Pitzer, Silvester, and Peterson, 1978) (Peiper and Pitzer, 1982)

115

Parameters available Parameters for polynomial unsymmetric mixing term 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.

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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 HighTemperature 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 Properties | Specifications sheet, specify an activity coefficient model, such as NRTL. 2. Click the Properties | Property Methods folder. 3. In the Object Manager, click New. 4. In the Create New ID dialog box, enter a name for the new method. 5. In the Base Property Method field, select NRTL. 6. Click the Models tab. 7. Change the Model Name for GAMMA from GMRENON to GMPOLY.

Parameter Name/Element GMPLYP/1 GMPLYP/2 GMPLYP/3 Symbol ai1 ai2 ai3 Default 0 0 0 MDS x x x Lower Limit Upper Limit Units

117

Parameter Name/Element GMPLYP/4 GMPLYP/5 GMPLYP/6 GMPLYP/7 GMPLYP/8 GMPLYP/9 GMPLYP/10 GMPLYP/11 GMPLYP/12 GMPLYP/13 GMPLYP/14 GMPLYP/15 GMPLYO

Symbol bi1 bi2 bi3 ci1 ci2 ci3 di1 di2 di3 ei1 ei2 ei3 fi

Default 0 0 0 0 0 0 0 0 0 0 0 0

MDS x x x x x x x x x x x x x

Lower Limit

Upper Limit

Units

Note: If you specify GMPLYP on the Properties | Parameters | Pure Component | T-Dependent sheet, you can only enter the first 12 elements. If you want to specify values for elements 13 to 15, you should go to the Flowsheeting Options | Add-Input | Add After sheet in Aspen Plus or the Add-Input | Add-Input | Add After sheet in Aspen Properties, 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 16.

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 A1,ij A2,ij A3,ij = = = = Number of components aij / T + bij cij / T + dij eij / T + fij

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= = = = =

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

i = vi

Parameter Name/ Element GMRKTB/1 GMRKTB/2 GMRKTB/3 GMRKTB/4 GMRKTB/5 GMRKTB/6 GMRKTB/7 GMRKTB/8 GMRKTB/9 GMRKTB/10 GMRKTO Symbol aij bij cij dij eij fij gij hij mij nij vi Default 0 0 0 0 0 0 0 0 0 0 MDS x x x x x x x x x x x Lower Limit Upper Limit Units

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

Default

Units TEMPERATURE

119

Default

i

Vi*,CVT Vi*,l

GMSHXL

kij

0.0

-5

Three-Suffix Margules

This model can be used to describe the excess properties of liquid and solid solutions. It does not find much use in chemical engineering applications, but is still widely used in metallurgical applications. Note that the binary parameters for this model do not have physical significance. The equation is:

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

i = di

Parameter Name/ Symbol Element GMMRGB/1 GMMRGB/2 GMMRGB/3 GMMRGO aij bij cij di Default MDS 0 0 0 x x x x Lower Limit Upper Limit Units TEMPERATURE

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).

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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

ic + ln ir

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

and Where ki is the number of groups of type k in molecule i, and ng is the number of groups in the mixture. The residual term is:

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

With:

121

And:

m, ...)

The parameter UFGRP stores the UNIFAC functional group number and number of occurrences of each group. UFGRP is stored in the Aspen Physical Property System pure component databank for most components. For nondatabank components, enter UFGRP on the Properties Molecular Structure Functional Group sheet. See Physical Property Data, Chapter 3, for a list of the UNIFAC functional groups.

UNIFAC-PSRK

The PSRK property method uses GMUFPSRK, the UNIFAC-PSRK model, which is a variation on the standard UNIFAC model. UNIFAC-PSRK has special groups defined for the light gases CO2, H2, NH3, N2, O2, CO, H2S, and argon, and the group binary interaction parameters are temperature-dependent, 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.

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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:

Parameter Symbol Name/Element UFGRPD GMUFDQ GMUFDR UNIFDM/1 UNIFDM/2 UNIFDM/3 (k,k, m, Qk Rk amn,1 amn,2 amn,3

m, ...)

0 0 0

The parameter UFGRPD stores the group number and the number of occurrences of each group. UFGRPD is stored in the Aspen Physical Property System pure component databank. For nondatabank components, enter UFGRPD on the Properties Molecular Structure Functional Group sheet. See Physical Property Data, Chapter 3, for a list of the Dortmund modified UNIFAC functional groups.

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.

123

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:

Default MDS

m, ...)

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Parameter Symbol Name/Element GMUFLR UNIFLB/1 UNIFLB/2 UNIFLB/3 Rk amn,1 amn,2 amn,3

Default MDS 0 0 0

The parameter UFGRPL stores the modified UNIFAC functional group number and the number of occurrences of each group. UFGRPL is stored in the Aspen Physical Property System pure component databank. For nondatabank components, enter UFGRP on the Properties | Molecular Structure | Functional Group sheet. See Physical Property Data, Chapter 3, for a list of the Larsen modified UNIFAC functional groups. Reference: B. Larsen, P. Rasmussen, and Aa. Fredenslund, "A Modified UNIFAC Group-Contribution Model for Prediction of Phase Equilibria and Heats of Mixing," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 2274 2286.

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 '

li ti '

ij

z

= = 10

125

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

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

1000 K x

Absolute temperature units are assumed for elements 2 through 4 and 7 of UNIQ. The UNIQ-2 property method uses data set 2 for UNIQ. All other UNIQUAC methods use data set 1.

References

D.S. Abrams and J.M. Prausnitz, "Statistical Thermodynamics of liquid mixtures: A new expression for the Excess Gibbs Energy of Partly or Completely Miscible Systems," AIChE J., Vol. 21, (1975), p. 116. A. Bondi, "Physical Properties of Molecular Crystals, Liquids and Gases," (New York: Wiley, 1960). Simonetty, Yee and Tassios, "Prediction and Correlation of LLE," Ind. Eng. Chem. Process Des. Dev., Vol. 21, (1982), p. 174.

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

Where:

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zi

aij and bij are unsymmetrical. That is, aij may not be equal to aji, and bij may not be equal to bji.

Parameters Symbol Default MDS Name/Element VANL/1 VANL/2 VANL/3 VANL/4 aij bij cij dij 0 0 0 0 x x x x Lower Limit Upper Limit -50.0 -15000.0 -50.0 -15000.0 50.0 15000.0 50.0 15000.0 Units TEMPERATURE 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:

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The parameter

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

i = gi

This model is recommended for dilute solutions.

Parameter Name/ Symbol Default MDS Element GMWIPR/1 GMWIPR/2 GMWIPR/3 GMWIPB/1 GMWIPB/2 GMWIPB/3 GMWIPO GMWIPS ai bi ci dij eij fij gi 0 0 0 0 0 0 0 x x x x x x x x Lower Limit Upper Limit Units TEMPERATURE TEMPERATURE

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, WILSHF, 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:

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ln Aij

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

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

1000 K x

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

129

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 Rackett/DIPPR/IK-CAPE model. The extended form of ln Aij provides more flexibility in fitting phase equilibrium and enthalpy data. aij, bij, cij, dij, and eij are unsymmetrical. That is, aij may not be equal to aji, etc. The binary parameters aij, bij, cij, dij, and eij must be determined from data regression of VLE and/or heat-of-mixing data. There are no built in binary parameters for this model.

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

1000 K x

Pure component parameters for the Rackett model/DIPPR/IK-CAPE are also required. In the original formulation of the Wilson model, aij = cij = dij = eij = 0 and . Vj and Vi are calculated at 25C. If any of biA, ciA, and eiA are non-zero, absolute temperature units are assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are interpreted in input units. The temperature limits are always interpreted in input units. Reference: G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.

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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 Extended Antoine/Wagner/IK-CAPE API Sour Braun K-10 Chao-Seader Grayson-Streed Kent-Eisenberg Maxwell-Bonnell Solid Antoine Type Vapor pressure Vapor pressure Vapor pressure Fugacity Fugacity Fugacity Vapor pressure Vapor pressure

The Aspen Physical Property System has several submodels for calculating vapor pressure of a liquid. It uses parameter THRSWT/3 to determine which submodel is used. See Pure Component Temperature-Dependent Properties for details.

If THRSWT/3 is 0 200 301 302 400 401 501 502 Then this equation is used Extended Antoine BARIN Wagner PPDS Modified Wagner PML IK-CAPE NIST TDE Polynomial NIST Wagner 25

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:

131

Default MDS x x x x x

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.

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

Where: Tri = T / Tci pri*,l = pi*,l / pci Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds. Note: Reduced temperature Tr is always calculated using absolute temperature units.

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 Name/Element WAGNER/1 WAGNER/2 WAGNER/3 WAGNER/4 WAGNER/5 Symbol C1 i C2 i C3 i C4 i C5 i 0 0 0 0 Default MDS x x x x x TEMPERATURE Lower Limit Upper Limit Units

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Lower Limit

Upper Limit

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 Name/Element WAGNER25/1 WAGNER25/2 WAGNER25/3 WAGNER25/4 WAGNER25/5 WAGNER25/6 WAGNER25/7 WAGNER25/8 Symbol C1 i C2 i C3 i C4 i ln pci Tci Tlower Tupper 0 1000 0 0 0 0 Default MDS x x x x x x x x TEMPERATURE TEMPERATURE TEMPERATURE Lower Limit Upper Limit Units

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 Name/Element PLPO/1 Symbol C1 i Default MDS X Lower Upper Limit Limit Units PRESSURE TEMPERATURE

133

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 Name/Element LNVP1/1, ...,8 LOGVP1/1, ..., 8 LNPR1/1, ..., 8 LOGPR1/1, ..., 8 LNPR2/1,2 LOGPR2/1,2 Symbol C1i, ..., C8i C1i, ..., C8i C1i, ..., C8i C1i, ..., C8i C1i, C2i C1i, C2i Default MDS Lower Limit x x x x x x Upper Limit Units PRESSURE TEMPERATURE PRESSURE TEMPERATURE PRESSURE TEMPERATURE PRESSURE TEMPERATURE

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Default

Upper Limit

Units

0 1000

X X

This equation can be used for calculating vapor pressure when parameter PLTDEPOL is available.

Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds. If elements 2, 3, 6, or 8 are non-zero, absolute temperature units are assumed for all elements.

Parameter Name/Element PLTDEPOL/1 PLTDEPOL/2 PLTDEPOL/3 Symbol C1 i C2 i C3 i 0 0 0 0 1000 Default MDS X X X X X X TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE Lower Upper Limit Limit Units

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.

135

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 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 Above 60 C to 60 C 10 36 11 24 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.

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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: =

Lower Limit Upper Limit 5.0 105 -0.5 2000.0 108 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.

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:

5

2000.0 10

8

-0.5

2.0

References

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

137

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:

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

The apparent fugacities and partial molar enthalpies, Gibbs energies and entropies of H2S and CO2 are calculated by standard thermodynamic relationships. The chemical reactions are always considered. The values of the coefficients for the seven equilibrium constants (A1i, ... A5i) and for the two Henry's constants B1i and B2i are built into the Aspen Physical Property System. The coefficients for the equilibrium constants were determined by regression. All available data for the four amines were used: monoethanolamine, diethanolamine, disopropanolamine and diglycolamine. You are not required to enter any parameters for this model.

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References

R.L. Kent and B. Eisenberg, Hydrocarbon Processing, (February 1976), pp. 87-92.

The Maxwell-Bonnell model calculates vapor pressure using the MaxwellBonnell 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 Name/ Element PSANT/1 PSANT/2 PSANT/3 PSANT/4 PSANT/5 Symbol Default MDS Lower Limit Upper Limit Units

C1 i C2 i C3 i C4 i C5 i

0 0 1000

x x x x x

The Aspen Physical Property System has several submodels for calculating pure component heat of vaporization. It uses parameter THRSWT/4 to

139

determine which submodel is used. See Pure Component TemperatureDependent Properties for details.

If THRSWT/4 is 0 106 301 401 505 Then this equation is used Watson DIPPR PPDS IK-CAPE NIST TDE Watson equation

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

Where: Tri = T / Tci Note: Reduced temperature Tr is always calculated using absolute temperature units. Linear extrapolation of vapHi* versus T occurs outside of temperature bounds, using the slope at the temperature bound, except that vapHi* is zero for .

Parameter Symbol Name/Element DHVLDP/1 DHVLDP/6 DHVLDP/7 TC C1 i C6 i C7 i Tci Default MDS 0 1000 x x x x Lower Limit 5.0 Upper Limit 2000.0 Units MOLE-ENTHALPY TEMPERATURE TEMPERATURE 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:

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Where:

vapHi*(T1)

Linear extrapolation of vapHi* versus T occurs below the minimum temperature bound, using the slope at the temperature bound.

Parameter Name/Element TC DHVLWT/1 DHVLWT/2 DHVLWT/3 DHVLWT/4 DHVLWT/5 Symbol Tci Default Lower Limit 0.38 0 0 5.0 5x10 4.0 -2.0 -2.0 0.0

4

8

vapHi*(T1)

T1 ai bi Tmin

3500.0

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

where R is the gas constant. Linear extrapolation of vapHi* versus T occurs outside of temperature bounds, using the slope at the temperature bound.

Parameter Name/Element TC DHVLDS/1 DHVLDS/2 DHVLDS/3 DHVLDS/4 DHVLDS/5 DHVLDS/6 DHVLDS/7 Symbol Tci C1 i C2 i C3 i C4 i C5 i C6 i C7 i Default MDS Lower Limit 0 0 0 0 0 1000 5.0 Upper Limit 2000.0 Units TEMPERATURE TEMPERATURE 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:

141

Linear extrapolation of vapHi* versus T occurs outside of temperature bounds, using the slope at the temperature bound

Parameter Symbol Name/Element DHVLPO/1 C1 i Default MDS 0 X X Lower Limit Upper Limit Units MOLEENTHALPY MOLEENTHALPY TEMPERATURE TEMPERATURE TEMPERATURE

DHVLPO/11 DHVLPO/12

C11i C12i

0 1000

X X

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

Linear extrapolation of vapHi* versus T occurs outside of temperature bounds, using the slope at the temperature bound

Parameter Symbol Name/Element DHVLTDEW/1 C1 i DHVLTDEW/2, 3, C2i, C3i, C4i 4 DHVLTDEW/5 DHVLTDEW/6 DHVLTDEW/7 DHVLTDEW/8 Tci nTerms Tlower Tupper Default MDS 0 4 0 1000 X X X X X X Lower Limit Upper Limit Units TEMPERATURE TEMPERATURE TEMPERATURE

Clausius-Clapeyron Equation

The Aspen Physical Property System can calculate heat of vaporization using the Clausius Clapeyron equation:

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Where: = Slope of the vapor pressure curve calculated from the Extended Antoine equation Vapor molar volume calculated from the Redlich Kwong equation of state Liquid molar volume calculated from the Rackett equation

Vi*,v Vi*,l

= =

For parameter requirements, see Extended Antoine/Wagner, the Rackett model, and Redlich Kwong.

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 API Liquid Volume Brelvi-O'Connell Clarke Aqueous Electrolyte Volume COSTALD Liquid Volume Debye-Hckel Volume Liquid Constant Molar Volume Model Rackett/DIPPR/PPDS/IK-CAPE Liquid Molar Volume Rackett/Campbell-Thodos Mixture Liquid Volume Modified Rackett Aspen/DIPPR/IK-CAPE Solids Volume Liquid Volume Quadratic Mixing Rule Type Liquid volume Partial molar liquid volume of gases Liquid volume Liquid volume Electrolyte liquid volume Liquid volume Liquid volume/liquid density Liquid volume Liquid volume Solid volume Liquid volume

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

Where:

143

xp xr

Where: fcn = A correlation based on API Figure 6A3.5 (API Technical Data Book, Petroleum Refining, 4th edition)

At high density, the Ritter equation is used (adapted from Ritter, Lenoir, and Schweppe, Petrol. Refiner 37 [11] 225 (1958)):

Where SG is the specific gravity, Tb is the mean average boiling point in Rankine, T is the temperature of the system in Rankine, and the mass volume is produced in units of cubic feet per pound-mass. For real components, the mixture Rackett model is used:

Note: Reduced temperature Tr is always calculated using absolute temperature units. See the Rackett model for descriptions.

Parameter Name/Element TB API TC PC RKTZRA Symbol Default MDS Tb API Tc pc Z

RA

5

8

ZC

0.1

0.5

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:

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i A

The liquid molar volume of solvent is obtained from the Rackett model:

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

References

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

The 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: Vml Vsl Vel = = = Liquid molar volume for electrolyte solutions. Liquid molar volume for solvent mixtures. Liquid molar volume for electrolytes.

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

145

(2) Where: xw Vw* xnws = = = Mole fraction of water. Molar volume of water from the steam table. Sum of the mole fractions of all non-water solvents. Liquid molar volume for the mixture of all non-water solvents. It is calculated using the Rackett equation.

Vnwsl =

(5) Where: xca = Apparent mole fraction of electrolyte ca 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: (6)

Where: nca zc zfactor nc na = = = = = Number of moles of apparent electrolyte ca Charge of c zc if c and a have the same number of charges; otherwise 1. Number of moles of cation c 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

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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: (7)

t

= = = =

Liquid volume per number of true species Liquid volume per number of apparent species, Vml of equation 1 Number of apparent species Number of true species

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: (8)

Parameter Name/Element VLCLK/1 VLCLK/2 Applicable Components Cation-Anion Cation-Anion Aca Symbol Default 0.020 Units MOLE-VOLUME MOLE-VOLUME

If VLCLK/1 is missing, it is calculated based on VLBROC and CHARGE. If VLBROC is missing, the default value of -0.12x10-2 is used. See 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:

147

Where: VmR,0 and VmR, are functions or Tr for For , there is a linear interpolation between the liquid density at Tr = 0.95 and the vapor density at Tr = 1.05. This model can be used to calculate saturated and compressed liquid molar volume. The compressed liquid molar volume is calculated using the Tait equation:

Note: Reduced temperature Tr is always calculated using absolute temperature units. Mixing Rules:

Where:

To improve results, the Aspen Physical Property System uses a special correlation for water when this model is used. Changing the VSTCTD and OMGCTD parameters for water will not affect the results of the special correlation.

Parameter Name/Element TC VSTCTD OMGCTD Symbol Default MDS Tci Vr*,CTD VC X Lower Limit 5.0 0.001 -0.5 Upper Limit 2000.0 3.5 2.0 Units TEMPERATURE MOLE-VOLUME

OMEGA X

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.

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Debye-Hckel Volume

The Debye-Hckel model calculates liquid molar volume for aqueous electrolyte solutions. The equation for the Debye-Hckel volume model is:

Where: Vk is the molar volume for water and is calculated from the ASME steam table. Vk is calculated from the Debye-Hckel limiting law for ionic species. It is assumed to be the infinite dilution partial volume for molecular solutes.

Where: Vk zk Av b I mk

= = = = =

Partial molar ionic volume at infinite dilution Charge number of ion k Debye-Hckel constant for volume 1.2 the ionic strength, with

Molarity of ion k

Av is computed as follows:

w w

= =

Density of water (kg / m3) Dielectric constant of water (Fm-1), a function of pressure and temperature (Bradley and Pitzer, 1979)

Applicable Components Symbol Default 0 Units MOLE-VOLUME

149

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 VLCONS Default 1 MDS x Units MOLE-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 0 100-116 301 401 503 504 514 515 Rackett DIPPR PPDS IK-CAPE NIST ThermoML Polynomial NIST TDE expansion NIST TDE Rackett NIST COSTALD And this parameter is used RKTZRA DNLDIP DNLPDS VLPO DNLTMLPO DNLEXSAT DNLRACK DNLCOSTD

For liquid molar volume of mixtures, the Rackett mixture equation is always used by default. This is not necessarily consistent with the pure component molar volume or density. If you need consistency, select route VLMX26 on the Properties | Property Methods form. This route calculates mixture molar volume from the mole-fraction average of pure component molar volumes. Many of these equations calculate density first, and return calculate liquid molar volume based on that density:

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DIPPR

DIPPR equation 105 is the default DIPPR equation for most substances:

This equation is similar to the Rackett equation. DIPPR equation 116 is the default equation for water.

= 1 - T / Tc

Other DIPPR equations, such as equation 100, may be used for some substances. Check the value of THRSWT/2 to determine the equation used. See Pure Component Temperature-Dependent Properties for details about DIPPR equations. In either case, linear extrapolation of temperature bounds.

Parameter Name/Element DNLDIP/1 DNLDIP/2 DNLDIP/3 DNLDIP/4 DNLDIP/5 DNLDIP/6 DNLDIP/7

Lower Upper Limit Limit Units MOLE-DENSITY TEMPERATURE TEMPERATURE TEMPERATURE

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

PPDS

The PPDS equation is:

Linear extrapolation of

Parameter Name/Element MW

Default MDS Lower Limit 1.0 Upper Limit 5000.0 Units

Symbol Mi

151

IK-CAPE

The IK-CAPE equation is:

Parameter Symbol Name/Element VLPO/1 VLPO/2, ..., 10 C1 i C2i, ..., C10i Default MDS 0 X X Lower Limit Upper Limit Units MOLEVOLUME MOLEVOLUME TEMPERATURE TEMPERATURE TEMPERATURE

VLPO/11 VLPO/12

C11i C12i

0 1000

X X

This equation can be used when parameter DNLTMLPO is available.

Default MDS 0 X X

Lower Limit

Upper Limit

4 0 1000

X X X

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Rackett

The Rackett equation is:

Where: Tr = T / Tci Note: Reduced temperature Tr is always calculated using absolute temperature units.

Parameter Name/ Element TC PC RKTZRA Symbol Default MDS Lower Limit x 5.0 10

5

8

Units

ZC

TEMPERATURE PRESSURE

0.1

1.0

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

Parameter Name/ Element DNLRACK/1 DNLRACK/2 DNLRACK/3 DNLRACK/4 DNLRACK/5 DNLRACK/6 Symbol Default MDS Lower Limit x x x x x x Upper Limit Units

2/7 0 0 1000

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

153

Parameter Name/ Element DNLCOSTD/1 DNLCOSTD/2 DNLCOSTD/3 DNLCOSTD/4 DNLCOSTD/5 Symbol Default MDS Lower Limit x x x x x Upper Limit Units

Voi

0 0 1000

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

Parameter Name/ Element DNLEXSAT/1 DNLEXSAT/2 Symbol Default MDS Lower Limit x x x x x x x Upper Limit Units

ci

C1 i

0 6 0 1000

DNLEXSAT/3, C2i, ..., C6i ..., DNLEXSAT/7 DNLEXSAT/8 DNLEXSAT/9 DNLEXSAT/10 DNLEXSAT/11 Tci nTerms Tlower Tupper

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.

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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

Parameter Name/ Element TC PC VCRKT RKTZRA RKTKIJ Symbol Default MDS Lower Limit x x x 5.0 10

5

8

Units

VC ZC

155

Campbell-Thodos

The Campbell-Thodos model uses the same equation and parameters as the Rackett model, above, except that ZmRAis allowed to vary with temperature: ZmRA =

Campbell-Thodos also uses separately-adjustable versions of the critical parameters. Tmin and Tmax define the temperature range where the equation is applicable.

Parameter Name/ Element RACKET/1 RACKET/2 RACKET/3 RACKET/4 RACKET/5 Symbol Default MDS Lower Limit x x x x 0.1 0 Upper Limit 1.0 0.11 Units

The Campbell-Thodos model is used when RACKET/3 is set to a value less than 0.11. The default value, 2/7, indicates that the standard Rackett equation should be used. When Campbell-Thodos is not used, RACKET/3 should be kept at its default value of 2/7 for all components.

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

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= = = = T / Tc

Parameter Name/Element MRKZRA/1 MRKZRA/2 MRKZRA/3 MRKKIJ/1 Symbol Default ai bi ci Aij RKTZRA 0 0 MDS x x x x Lower Limit 0.1 Upper Limit 0.5 Units

MRKKIJ/2 MRKKIJ/3

Bij Cij

0 0

x 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 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 0 100 401 503 Aspen DIPPR IK-CAPE NIST ThermoML polynomial And this parameter is used VSPOLY DNSDIP VSPO DNSTMLPO

157

Aspen Polynomial

The equation for the Aspen solids volume polynomial is:

Parameter Name VSPOLY/1 Applicable Components Salts, CI solids Symbol C1 i C2i, ..., C5i C6 i C7 i MDS x x x x Default 0 0 1000 Units MOLE-VOLUME TEMPERATURE MOLE-VOLUME TEMPERATURE MOLE-VOLUME TEMPERATURE MOLE-VOLUME TEMPERATURE

VSPOLY/2, ..., 5 Salts, CI solids VSPOLY/6 VSPOLY/7 Salts, CI solids Salts, CI solids

IK-CAPE Equation

The IK-CAPE equation is:

Parameter Symbol Name/Element VSPO/1 VSPO/2, ..., 10 C1 i C2i, ..., C10i Default MDS 0 X X Lower Limit Upper Limit Units MOLEVOLUME MOLEVOLUME TEMPERATURE TEMPERATURE TEMPERATURE

VSPO/11 VSPO/12

C11i C12i

0 1000

X X

DIPPR

The DIPPR equation is:

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.

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Default MDS 0 x x

Lower Limit

Upper Limit

DNSDIP/6 DNSDIP/7

C6 i C7 i

0 1000

x x

Default MDS 0 x x Lower Limit Upper Limit Units MOLEDENSITY MOLEDENSITY, TEMPERATURE TEMPERATURE TEMPERATURE

i*,s

Symbol C1 i

8 0 1000

x x x

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

Option Codes

Option Code Value 1 0 1 2 0 1 Descriptions Use normal pure component liquid volume model for all components (default) Use steam tables for water Use mole basis composition (default) Use mass basis composition

Parameter

Parameter Name/Element VLQKIJ Symbol Kij Default MDS x Lower Limit Upper Limit Units

159

This model is not part of any property method. To use it, you will need to define a property method on the Properties | Property Methods form. Specify the route VLMXQUAD for VLMX on the Routes sheet of this form, or the model VL2QUAD for VLMX on the Models sheet.

The Aspen Physical Property System has five built-in heat capacity models. This section describes the heat capacity models available.

Model Aqueous Infinite Dilution Heat Capacity Polynomial Criss-Cobble Aqueous Infinite Dilution Ionic Heat Capacity Aspen/DIPPR/Barin/PPDS/IK-CAPE Ideal Gas Heat Capacity Aspen/DIPPR/Barin/IK-CAPE Solid Heat Capacity Type Electrolyte liquid Electrolyte liquid

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 Name/Element CPAQ0/1 CPAQ0/2,,6 CPAQ0/7 CPAQ0/8 Applicable Components Symbol Default Units 0 0 1000 TEMPERATURE and HEAT CAPACITY TEMPERATURE and HEAT CAPACITY TEMPERATURE TEMPERATURE

Ions, molecular solutes C1i Ions, molecular solutes C2i, ..., C6i Ions, molecular solutes C7i Ions, molecular solutes C8i

If any of C4i through C6i is non-zero, absolute temperature units are assumed for C1i through C6i . Otherwise, user input units for temperature are used. The temperature limits are always interpreted in user input units.

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

Parameter Applicable Symbol Name Components IONTYP SO25C Ions Anions Cations

Default

Ion Type 0

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 100 200 301 401 403 503 506 DIPPR Barin PPDS IK-CAPE heat capacity polynomial IK-CAPE liquid heat capacity NIST ThermoML polynomial NIST TDE equation And this parameter is used CPLDIP CPLXP1, CPLXP2 CPLPDS CPLPO CPLIKC CPLTMLPO CPLTDECS

The DIPPR/PPDS/IK-CAPE 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 below) is available. The component is not supercritical (HENRY-COMP).

The model uses a specific method (see Methods in Property Calculation Methods and Routes):

161

Where = Reference enthalpy calculated at Tref = Ideal gas enthalpy = Vapor enthalpy departure = Enthalpy of vaporization Tref is the reference temperature; it defaults to 298.15 K. You can enter a different value for the reference temperature. This is useful when you want to use this model for very light components or for components that are solids at 298.15K. Activate this model by specifying the route DHL09 for the property DHL on the Properties Property Methods Routes sheet. For equation of state property method, you must also modify the route for the property DHLMX to use a route with method 2 or 3, instead of method 1. For example, you can use the route DHLMX00 or DHLMX30. You must ascertain that the route for DHLMX that you select contains the appropriate vapor phase model and heat of mixing calculations. Click the View button on the form to see details of the route. Optionally, you can specify that this model is used for only certain components. The properties for the remaining components are then calculated by the standard model. Use the parameter COMPHL to specify the components for which this model is used. By default, all components with the CPLDIP or CPLIKC parameters use this model.

The DIPPR equation is used to calculate liquid heat capacity when parameter THRSWT/6 is 100. The DIPPR equation is:

Parameter Symbol Name/Element CPLDIP/1 C1 i Default MDS x Lower Limit Upper Units Limit MOLE-HEATCAPACITY, TEMPERATURE MOLE-HEATCAPACITY, TEMPERATURE

CPLDIP/2, ..., 5

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ref

MDS x x

Lower Limit

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:

Where R is the gas constant. Linear extrapolation occurs for Cp*,l versus T outside of bounds.

Parameter Symbol Name/Element CPLPDS/1 CPLPDS/2 CPLPDS/3 CPLPDS/4 CPLPDS/5 CPLPDS/6 CPLPDS/7 CPLPDS/8 C1 i C2 i C3 i C4 i C5 i C6 i C7 i C8 i Default 0 0 0 0 0 0 1000 MDS x x Lower Limit Upper Units Limit TEMPERATURE 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:

163

Upper Limit

CPLIKC/5

C5 i

CPLIKC/6 CPLIKC/7

C6 i C7 i

0 1000

x x

If C5i is non-zero, absolute temperature units are assumed for C2i through C5i. Otherwise, user input units for temperature are used. The temperature limits are always interpreted in user input units. When THRSWT/6 is 401, the IK-CAPE heat capacity polynomial is used.The equation is:

Parameter Symbol Name/Element CPLPO/1 CPLPO/2,,10 CPLPO/11 CPLPO/12 C1 i C2i, ..., C10i C11i C12i

Lower Limit

Upper Limit

See Pure Component Temperature-Dependent Properties for details on the 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:

Parameter Symbol Name/Element CPLTMLPO/1 CPLTMLPO/6 CPLTMLPO/7 C1 i nTerms Tlower CPLTMLPO/2,,5 C2i, ..., C5i

Default MDS 0 5 0 X X X X

Lower Limit

Upper Limit

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Lower Limit

Upper Limit

Units TEMPERATURE

When THRSWT/6 is 506, the TDE equation is used to calculate liquid heat capacity:

Lower Limit

Upper Limit

CPLTDECS/2,,4 C2i, ..., C4i CPLTDECS/5 CPLTDECS/6 CPLTDECS/7 CPLTDECS/8 CPLTDECS/9 B Tci nTerms Tlower Tupper

See Pure Component Temperature-Dependent Properties for details on the THRSWT parameters.

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 0 107 200 301 401 503 513 Ideal gas heat capacity polynomial DIPPR Barin PPDS IK-CAPE heat capacity polynomial NIST ThermoML polynomial NIST Aly-Lee And this parameter is used CPIG CPIGDP CPIXP1, CPIXP2, CPIXP3 CPIGDS CPIGPO CPITMLPO CPIALEE

These equations are also used to calculate ideal gas enthalpies, entropies, and Gibbs energies.

165

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 Name/ Element CPIG/1 Symbol Default MDS Lower Upper Units Limit Limit MOLE-HEAT-CAPACITY, TEMPERATURE MOLE-HEAT-CAPACITY, TEMPERATURE TEMPERATURE TEMPERATURE MOLE-HEAT-CAPACITY, TEMPERATURE

C1 i

0 0 1000

CPIG/2, ..., 6 C2i, ..., C6i CPIG/7 CPIG/8 CPIG/9, 10, 11 C7 i C8 i C9i, C10i, C11i

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.

This equation can be used when parameter CPITMLPO is available.

Symbol

Default MDS

C1 i

0 6 0 1000

x x x x x

CPITMLPO /2, C2i, ..., C6i ..., 6 CPITMLPO/7 CPITMLPO /8 CPITMLPO /9 nTerms Tlower Tupper

DIPPR

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

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(Other DIPPR equations may sometimes be used. See Pure Component Temperature-Dependent Properties for details.)

Parameter Symbol Name/Element CPIGDP/1 CPIGDP/2 CPIGDP/3 CPIGDP/4 CPIGDP/5 CPIGDP/6 CPIGDP/7 C1 i C2 i C3 i C4 i C5 i C6 i C7 i Default MDS Lower Limit 0 0 0 0 0 1000 x x x x x x x Upper Limit Units MOLE-HEATCAPACITY MOLE-HEATCAPACITY TEMPERATURE MOLE-HEATCAPACITY TEMPERATURE TEMPERATURE TEMPERATURE

Absolute temperature units are assumed for C3i and C5i. The temperature limits are always interpreted in user input units.

NIST Aly-Lee

This equation is the same as the DIPPR Aly and Lee equation above, but it uses a different parameter set. Note that elements 6 and 7 of the CPIALEE parameter are not used in the equation.

Parameter Symbol Name/Element CPIALEE/1 CPIALEE/2 CPIALEE/3 CPIALEE/4 CPIALEE/5 CPIALEE/8 CPIALEE/9 C1 i C2 i C3 i C4 i C5 i C6 i C7 i Default MDS Lower Limit 0 0 0 0 0 1000 x x x x x x x Upper Limit Units MOLE-HEATCAPACITY MOLE-HEATCAPACITY TEMPERATURE MOLE-HEATCAPACITY TEMPERATURE TEMPERATURE 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:

167

Parameter Symbol Name/Element CPIGDS/1 CPIGDS/2, , 8 CPIGDS/9 CPIGDS/10 C1 i C2i, ..., C8i C9 i C10i Default MDS 0 0 1000 Lower Limit Upper Limit Units TEMPERATURE TEMPERATURE TEMPERATURE

The equation is:

Parameter Symbol Name/Element CPIGPO/1 CPIGPO/2,,10 CPIGPO/11 CPIGPO/12 C1 i C2i, ..., C10i C11i C12i Default MDS 0 0 1000 X X X X Lower Limit Upper Limit Units MOLE-CAPACITY MOLE-CAPACITY TEMPERATURE TEMPERATURE 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.

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.

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Aspen solid heat capacity CPSPO1 polynomial DIPPR Barin IK-CAPE heat capacity polynomial NIST ThermoML polynomial CPSDIP CPSXP1, CPSXP2, , CPSXP7 CPSPO CPSTMLPO

The enthalpy, entropy, and Gibbs energy of solids are also calculated from these equations:

The Aspen equation is:

Parameter Name CPSPO1/1 CPSPO1/7 CPSPO1/8 Applicable Symbol Components Solids, Salts C1i Solids, Salts C7i Solids, Salts C8i MDS x x x x Default 0 0 1000 Units

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.

DIPPR

The DIPPR equation is:

Parameter Symbol Name/Element CPSDIP/1 C1 i Default MDS x Lower Limit Upper Units Limit MOLE-HEATCAPACITY, TEMPERATURE MOLE-HEATCAPACITY, TEMPERATURE TEMPERATURE TEMPERATURE

CPSDIP/2,...,5

CPSDIP/6 CPSDIP/7

C6 i C7 i

0 1000

x x

169

(Other DIPPR equations may sometimes be used. See Pure Component Temperature-Dependent Properties for details.)

The equation is:

Parameter Symbol Name/Element CPSTMLPO/1 CPSTMLPO/6 CPSTMLPO/7 CPSTMLPO/8 C1 i nTerms Tlower Tupper Default 5 0 1000 MDS x x x x x Lower Limit Upper Units Limit J/K^2/mol J/K^2/mol TEMPERATURE TEMPERATURE

The equation is:

Parameter Symbol Name/Element CPSPO/1 CPSPO/2,,10 CPSPO/11 CPSPO/12 C1 i C10i C11i C12i Default MDS 0 0 1000 X X X X Lower Limit Upper Limit Units MOLE-CAPACITY MOLE-CAPACITY TEMPERATURE TEMPERATURE TEMPERATURE

Solubility Correlations

The Aspen Physical Property System has three built-in solubility correlation models. This section describes the solubility correlation models available.

Model Henry's constant Water solubility Hydrocarbon solubility Type Gas solubility in liquid Water solubility in organic liquid Hydrocarbon solubility in water-rich liquid

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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)

The parameter

is obtained from the Brelvi-O'Connell model. pA*,l is is obtained from the appropriate activity

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. See Physical Property Data, Chapter 1, for details.

Parameter Name/Element VC HENRY/1 HENRY/2 HENRY/3 HENRY/4 HENRY/5 HENRY/6 HENRY/7 Symbol Default MDS VcA aiA biA ciA diA TL TH eiA 0 0 0 0 2000 0 x x x x x x x Lower Upper Units Limit Limit 0.001 3.5 MOLE-VOLUME PRESSURE, TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE 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.

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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 Name/ Element WATSOL/1 WATSOL/2 WATSOL/3 WATSOL/4 WATSOL/5 Symbol Default MDS Lower Limit -10.0 -0.05 0.0 4.0 Upper Limit 33.0 0.05 500 1000 Units

C1 i C2 i C3 i C4 i C5 i

-10000.0 3000.0

Hydrocarbon Solubility

This model calculates solubility of hydrocarbon in a water-rich liquid phase. The model is used automatically when you model a hydrocarbon-water system with the dirty-water option. See Free-Water Immiscibility Simplification in Free-Water and Rigorous Three-Phase Calculations for details. The expression for the liquid mole fraction of the ith hydrocarbon species in water is:

No extrapolation is used with this equation. The parameters for about 40 components are stored in the Aspen Physical Property System pure component databank.

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Symbol Default

Units

C1 i C2 i C3 i C4 i C5 i

100000.0 TEMPERATURE 100000.0 -100.0 0.0 4.0 100.0 500 1000 TEMPERATURE TEMPERATURE TEMPERATURE

For Hydrocarbons and pseudocomponents, the default values are estimated by the method given by API Procedure 9A2.17 at 25 C. Absolute temperature units are assumed for elements 2 and 3. The temperature limits are always interpreted in user input units.

Reference

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

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:

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5

8

0.1

0.5

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

The following equations are used when parameters from the Aspen Physical Property System inorganic databank are retrieved. Gibbs energy: (1) Enthalpy: (2) Entropy: (3) Heat capacity: (4)

refers to an arbitrary phase which can be solid, liquid, or ideal gas. For each

phase, multiple sets of parameters from 1 to n are present to cover multiple temperature ranges. The value of the parameter n depends on the phase. (See tables that follow.) When the temperature is outside all these temperature ranges, linear extrapolation of properties versus T is performed using the slope at the end of the nearest temperature bound. The four properties Cp, H, S, and G are interrelated as a result of the thermodynamic relationships:

There are analytical relationships between the expressions describing the properties Cp, H, S, and G (equations 1 to 4). The parameters an,i to hn,i can occur in more than one equation. The Aspen Physical Property System has other models which can be used to calculate temperature-dependent properties which the BARIN equations can

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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 THRSWT/3 THRSWT/5 THRSWT/6 THRSWT/7 Then the BARIN equations are used to calculate Liquid vapor pressure Solid heat capacity Liquid heat capacity Ideal gas heat capacity

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 /Element Limit CPSXPn/1 CPSXPn/2 CPSXPn/3 CPSXPn/4 CPSXPn/5 CPSXPn/6 CPSXPn/7 CPSXPn/8 CPSXPn/9 CPSXPn/10 Tn,ls Tn,hs an,is bn,is cn,is dn,is en,i

s

Upper Limit

0 0 0 0 0 0 0

x x x x x x x x x x

n is 1 through 7. CPSXP1 vector stores solid parameters for the first temperature range. CPSXP2 vector stores solid parameters for the second temperature range, and so on. TEMPERATURE, ENTHALPY, ENTROPY

Liquid Phase

The parameters in range n are valid for temperature: Tn,ll < T < Tn,hl When you specify this parameter, be sure to specify at least elements 1 through 3.

Parameter Name Symbol Default MDS Lower /Element Limit CPLXPn/1 CPLXPn/2 CPLXPn/3 CPLXPn/4 CPLXPn/5 CPLXPn/6 CPLXPn/7 CPLXPn/8 Tn,ll Tn,hl an,i

l

Upper Limit

0 0 0 0 0

x x x x x x x x

l

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Parameter Name Symbol Default MDS Lower /Element Limit CPLXPn/9 CPLXPn/10 gn,il hn,il 0 0 x x

Upper Limit

Units

n is 1 through 2. CPLXP1 stores liquid parameters for the first temperature range. CPLXP2 stores liquid parameters for the second temperature range. TEMPERATURE, ENTHALPY, ENTROPY

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 /Element Limit CPIXPn/1 CPIXPn/2 CPIXPn/3 CPIXPn/4 CPIXPn/5 CPIXPn/6 CPIXPn/7 CPIXPn/8 CPIXPn/9 CPIXPn/10 Tn,lig Tn,h an,i cn,i

ig ig

Upper Limit

0 0 0 0 0 0 0

x x x x x x x x x x

bn,iig

ig

ig

hn,iig

n is 1 through 3. CPIXP1 vector stores ideal gas parameters for the first temperature range. CPIXP2 vector stores ideal gas parameters for the second temperature range, and so on. TEMPERATURE, ENTHALPY, ENTROPY

The equation for the electrolyte NRTL enthalpy model 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.)

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Hs*,l is the enthalpy contribution from a non-water solvent. It is calculated as usual for components in activity coefficient models: Hs*,l(T) = Hs*,ig + DHVs(T,p) - Hs,vap(T). The term DHVs(T,p) = Hs*,v - Hs*,ig is the vapor enthalpy departure contribution to liquid enthalpy; option code 5 determines how this is calculated. The property Hk is calculated from the infinite dilution aqueous phase heat capacity polynomial model, by default. If polynomial model parameters are not available, it is calculated from the Criss-Cobble model for ions and from Henry's law for molecular solutes. The subscript k can refer to a molecular solute defined as a Henry's component (i), or a cation (c), or an anion (a):

Hm*E is excess enthalpy and is calculated from the electrolyte NRTL activity coefficient model. See Criss-Cobble model and Henry's law model for more information. Option codes can improve the performance of this model when using mixed solvents and Henry components. See Option Codes for Enthalpy Models for details.

Parameter Name IONTYP SO25C Applicable Components Ions Cations Anions DHAQFM CPAQ0 DHFORM Ions, Molecular Solutes Ions, Molecular Solutes Molecular Solutes Water, Solvents CPIG Molecular Solutes Water, Solvents Symbol Ion Sc

,aq ,aq

(T=298) (T=298)

Sa

f Hk,aq

Cp,k

,aq

f Hi*,ig f Hw*,ig

Cp,i*,ig Cp,w*,ig

IONTYP is not needed if CPAQ0 is given for ions. DHFORM is not used if DHAQFM and CPAQ0 are given for molecular solutes (components declared as Henry's components). If CPAQ0 is missing, DHFORM and Henry's constants are used to calculate infinite dilution enthalpy for solutes. The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If CPIG/10 or CPIG/11 is non-zero, then absolute temperature units are assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature units are used for all elements of CPIG. User input temperature units are always used for other elements of CPIG.

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The equation for the NRTL Gibbs free energy model is:

The molar Gibbs free energy and the molar excess Gibbs free energy Gm* and Gm*E are defined with the asymmetrical reference state: as pure water and infinite dilution of molecular solutes and ions. (* refers to the asymmetrical reference state.) The ideal mixing term is calculated normally, where j refers to any component. The molar Gibbs free energy of pure water (or thermodynamic potential) w* is calculated from the ideal gas contribution. This is a function of the ideal gas heat capacity and the departure function. (here * refers to the pure component.)

The departure function is obtained from the ASME steam tables. 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:

Because f Hk ,aq and f Gk ,aq are based on a molality scale, and on mole fraction scale, the term RT ln(1000/Mw) is added. For molecular solutes,

k is based

G*E is calculated from the electrolyte NRTL activity coefficient model. See the Criss-Cobble model and Henry's law model for more information.

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Option codes can improve the performance of this model when using mixed solvents and Henry components. See Option Codes for Gibbs Energy Models for details.

Parameter Name IONTYP SO25C Applicable Components Ions Cations Anions DGAQFM CPAQ0 DGFORM Ions, Molecular Solutes Ions, Molecular Solutes Molecular Solutes Water, Solvents CPIG Molecular Solutes Water, Solvents Symbol Ion Sc

,aq ,aq

(T=298) (T=298)

Sa

f Gk,aq

Cp,k

,aq

f Gi f Gw

Cp,i*,ig Cp,w

*,ig

IONTYP and SO25C are not needed if CPAQ0 is given for ions. DGFORM is not needed if DHAQFM and CPAQ0 are given for molecular solutes. The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If CPIG/10 or CPIG/11 is non-zero, then absolute temperature units are assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature units are used for all elements of CPIG. User input temperature units are always used for other elements of CPIG.

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

Where: Hi*,ig Hi*,v - Hi*,ig = = = = Ideal gas enthalpy Vapor enthalpy departure from equation of state Heat of vaporization from Watson/DIPPR/IK-CAPE model Reference temperature, specified by user. Defaults to 298.15 K

vapHi*,l

Tref

See DIPPR/IK-CAPE Liquid Heat Capacity for parameter requirement and additional details.

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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 = = Hi*,ig (Hml-Hmig) = = Ideal gas enthalpy of pure component i Enthalpy departure of mixture Enthalpy of ideal gas mixture

For supercritical components, declared as Henry's components, the enthalpy departure is calculated as follows:

HA*,l-HA*,ig

H*,ig and H*,l can be calculated based on either saturated liquid or ideal gas as reference state as described in the sections that follow. For the WILS-LR property method, H*,ig and H*,l are calculated based on the saturated liquid reference state for all components. For the WILS-GLR property method, H*,ig and H*,l can be calculated based on the saturated liquid reference state for some components and the ideal gas

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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.

The saturated liquid enthalpy at temperature T is calculated as follows:

Where: Hiref,l Cp,i*,l = = Reference enthalpy for liquid state at Tiref,l Liquid heat capacity of component i

Where: Giref,l = = = = Reference Gibbs free energy for liquid state at Tiref,l Liquid fugacity coefficient of component i System pressure Reference pressure (=101325 N/m2)

i*,l

p p

ref

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 Giref,ig = = = = Ideal gas enthalpy of formation for liquid state at 298.15K Ideal gas Gibbs free energy of formation for liquid state at 298.15K Vapor enthalpy departure of component i Vapor Gibbs free energy departure of component i

Hi*,v Gi*,v

181

vapHi*

Note that we cannot default the liquid reference enthalpy and Gibbs free energy to zero, as is the case for WILS-LR, because it will cause inconsistency with the enthalpy of components that use ideal-gas reference state. The default values used result in the enthalpies of all components being on the same basis. In fact, if you enter values for Hiref,l and Giref,l for a liquidreference state component you must make sure that they are consistent with each other and are consistent with the enthalpy basis of the remaining components in the mixture. If you enter a value for Hiref,l, you should also enter a value for Giref,l to ensure consistency. When the liquid-reference state is used, the ideal gas enthalpy at temperature T is not calculated from the integration of the ideal gas heat capacity equation (see Ideal Gas as Reference State section below). For consistency, it is calculated from liquid enthalpy as follows:

Where: Ticon,l = = = = = Temperature of conversion from liquid to vapor enthalpy for component i Heat of vaporization of component i at temperature of Tcon,l Vapor enthalpy departure of component i at the conversion temperature and vapor pressure pi*,l Liquid vapor pressure of component i Ideal gas heat capacity of component i

pi*,l

Ticon,l is the temperature at which one crosses from liquid state to the vapor state. This is a user defined temperature that defaults to the system temperature T. Ticon,l may be selected such that heat of vaporization for component i at the temperature is most accurate. The vapor enthalpy is calculated from ideal gas enthalpy as follows:

Where:

Hi*,v(T, P)

Vapor enthalpy departure of pure component i at the system temperature and pressure

The liquid heat capacity and the ideal gas heat capacity can be calculated from the ASPEN, DIPPR, IK-CAPE, BARIN, NIST/TDE, or other available models. The heat of vaporization can be calculated from the Watson, DIPPR, IK-CAPE, NIST/TDE, 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.

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Parameter Symbol Name/Element RSTATE TREFHL DHLFRM DGLFRM TCONHL Tiref,l Hiref,l Giref,l Ticon,l

Default MDS 2 T

Lower Limit

Upper Limit

Enthalpy reference state given by RSTATE. 2 denotes saturated liquid as 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 WILSGLR property method, DHLFRM defaults to the equation above. For WILS-LR property method, DGLFRM defaults to zero (0). For WILSGLR 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 Tiref,ig Ticon,ig = = = = Reference state enthalpy for ideal gas at Tiref,ig Heat of formation of ideal gas at 298.15 K by default Reference temperature corresponding to Hiref,ig. Defaults to 298.15 K 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 liquid heat capacity and the ideal gas heat capacity can be calculated from the ASPEN, DIPPR, IK-CAPE, BARIN, NIST/TDE, or other available models. The heat of vaporization can be calculated from the Watson, DIPPR, IK-CAPE, NIST/TDE, or other available models. The enthalpy departure is

183

obtained from an equation of state that is being used in the property method. For WILS-LR and WILS-GLR, the ideal gas equation of state is used.

Parameter Symbol Name/Element RSTATE TREFHI DHFORM TCONHI Tiref,ig Hiref,ig Ticon,ig Default MDS 1 T Lower Limit Upper Limit Units TEMPERATURE MOLE ENTHALPY TEMPERATURE

Enthalpy reference state RSTATE for a component. Value of 1 denotes ideal gas. For components with TB 298.15 K, RSTATE defaults to 1 (ideal gas). TREFHI defaults to 298.15 K. For components with TB > 298.15 K, RSTATE defaults to 2 (liquid) and TREFHI does not apply to these components. See the Saturated Liquid as Reference State section for more details.

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:

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Where:

185

Where:

= = = = = =

Pressure constant for a solvent (2600 bar for water) Temperature constant for a solvent (228 K for water) Born coefficient Dielectric constant of a solvent Reference temperature (298.15 K) Reference pressure (1 bar)

Tr Pr

Parameter Symbol Name/Element AHGPAR/1, ... , a1, ..., a4 4 CHGPAR/1, ... , c1, c2 2 DHAQHG DGAQHG S25HG OMEGHG Default MDS 0 x 0 0 0 0 Lower Limit Upper Limit Units MOLE-ENTHALPY MOLE-ENTHALPY MOLE-ENTROPY MOLE-ENTHALPY

References

Tanger, J.C. IV and H.C. Helgeson, "Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Revised equation of state for the standard partial properties of ions and electrolytes," American Journal of Science, Vol. 288, (1988), p. 19-98. Shock, E.L. and H.C. Helgeson, "Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures:

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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.

187

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 Andrade Liquid Mixture Viscosity API Liquid Viscosity API 1997 Liquid Viscosity Model name MUL2ANDR Phase(s) Pure L L L L L L V V V VL X X X X Mixture X X X X X X X X

Aspen Liquid Mixture Viscosity MUASPEN ASTM Liquid Mixture Viscosity MUL2ASTM Chapman-Enskog-Brokaw /DIPPR/PPDS/IK-CAPE Chapman-Enskog-BrokawWilke Mixing Rule Chung-Lee-Starling Low Pressure Chung-Lee-Starling MUV0CEB MUV2BROK, MUV2WILK MUV0CLSL, MUV2CLSL MUV0CLS2, MUV2CLS2, MUL0CLS2, MUL2CLS2

Dean-Stiel Pressure Correction MUV0DSPC, MUV2DSPC IAPS Viscosity Jones-Dole Electrolyte Correction Letsou-Stiel Lucas MUV0H2O MUL0H2O MUL2JONS MUL0LEST, MUL2LEST MUV0LUC, MUV2LUC

V V L L L V

X X X X X

X X X X

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Phase(s) Pure VL X

Mixture X

X X Mixture X

Viscosity quadratic mixing rule MUL2QUAD Thermal conductivity Model name models Chung-Lee-Starling Thermal Conductivtity KV0CLS2, KV2CLS2, KL0CLS2, KL2CLS2

L Phase(s) Pure VL X

IAPS Thermal Conductivity for KV0H2O Water KL0H2O Li Mixing Rule Riedel Electrolyte Correction Sato-Riedel/DIPPR/PPDS/ IKCAPE KL2LI KL2RDL KL0SR, KL2SRVR

V L L L L V V VL

X X X X X X X

X X X X X

Stiel-Thodos/DIPPR/PPDS/ IK- KV0STLP CAPE Stiel-Thodos Pressure Correction TRAPP Thermal Conductivity KV0STPC, KV2STPC KV0TRAP, KV2TRAP, KL0TRAP, KL2TRAP KL2SRVR KV2WMSM Model name DV0CEWL DV1CEWL DV1DKK DV1DKK DL0NST, DL1NST DL0WC2 DL1WC Model name SIG2API SIG0HSS, SIG2HSS SIG0H2O

Vredeveld Mixing Rule Wassiljewa-Mason-Saxena mixing rule Diffusivity models Chapman-Enskog-Wilke-Lee Binary Chapman-Enskog-Wilke-Lee Mixture Dawson-Khoury-Kobayashi Binary Dawson-Khoury-Kobayashi Mixture Nernst-Hartley Electrolytes Wilke-Chang Binary Wilke-Chang Mixture Surface tension models API Surface Tension Hakim-Steinberg-Stiel/DIPPR /IK-CAPE IAPS surface tension

L V

X X

X X Mixture X X X X X X X Mixture X X

Phase(s) Pure V V V V L L

L Phase(s) Pure L L L L X X

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189

Phase(s) Pure L L

Mixture X X

Viscosity Models

The Aspen Physical Property System has the following built-in viscosity models:

Model Andrade Liquid Mixture Viscosity Andrade/DIPPR/PPDS/IK-CAPE API liquid viscosity API 1997 liquid viscosity Chapman-Enskog-Brokaw/DIPPR/IK-CAPE Type Liquid Pure component liquid Liquid Liquid Low pressure vapor, pure components

Chapman-Enskog-Brokaw-Wilke Mixing Rule Low pressure vapor, mixture Chung-Lee-Starling Low Pressure Chung-Lee-Starling Dean-Stiel Pressure correction IAPS viscosity Jones-Dole Electrolyte Correction Letsou-Stiel Lucas TRAPP viscosity Aspen Liquid Mixture Viscosity ASTM Liquid Mixture Viscosity Twu liquid viscosity Viscosity quadratic mixing rule Low pressure vapor Liquid or vapor Vapor Water or steam Electrolyte High temperature liquid Vapor Vapor or liquid Liquid Liquid Liquid Liquid

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

Where: kij =

mij

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If first option code of MUL2ANDR is 0 (Default) 1 Then fi is Mole fraction of component i 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 MUL2JONS DL0WCA DL1WCA DL0NST DL1NST Model Name Jones-Dole Electrolyte Viscosity model Wilke-Chang Diffusivity model (binary) Wilke-Chang Diffusivity model (mixture) Nernst-Hartley Electrolyte Diffusivity model (binary) 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 Name/Element ANDKIJ/1 ANDKIJ/2 ANDMIJ/1 ANDMIJ/2 Symbol Default MDS aij bij cij dij 0 0 0 0 Lower Limit Upper Limit Units

See the Andrade/DIPPR/IK-CAPE Pure Component Liquid Viscosity model for descriptions.

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 0 101 301 401 Andrade DIPPR PPDS And this parameter is used MULAND MULDIP MULPDS

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191

If TRNSWT/1 is This equation is used 404 508 509 NIST TDE equation NIST PPDS9

The Andrade equation is:

Linear extrapolation of ln(viscosity) versus 1/T occurs for temperatures outside bounds.

Parameter Name/Element MULAND/1 MULAND/2 MULAND/3 MULAND/4 MULAND/5 Symbol Default MDS Ai Bi Ci Tl Th 0.0 500.0 X X X X X Lower Limit Upper Limit Units VISCOSITY, TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE

If Bi or Ci is non-zero, absolute temperature units are assumed for Ai, Bi, and Ci. Otherwise, all coefficients are interpreted in user input temperature units. The temperature limits are always interpreted in user input units.

The equation for the DIPPR liquid viscosity model is:

Linear extrapolation of ln(viscosity) versus 1/T occurs for temperatures outside bounds. (Other DIPPR equations may sometimes be used. See Pure Component Temperature-Dependent Properties for details.)

Parameter Symbol Name/Element MULDIP/1 MULDIP/2, ..., 5 MULDIP/6 MULDIP/7 C1 i Default MDS Lower Limit X X X X Upper Limit Units VISCOSITY, TEMPERATURE TEMPERATURE TEMPERATURE 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.

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PPDS

The PPDS equation is:

Parameter Symbol Name/Element MULPDS/1 MULPDS/2 MULPDS/3 MULPDS/4 MULPDS/5 MULPDS/6 MULPDS/7 C1 i C2 i C3 i C4 i C5 i C6 i C7 i Default MDS Lower Limit Upper Limit Units TEMPERATURE TEMPERATURE VISCOSITY TEMPERATURE 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 Name/Element MULPPDS9/1 MULPPDS9/2 MULPPDS9/3 MULPPDS9/4 MULPPDS9/5 MULPPDS9/6 MULPPDS9/7 C5 i C1 i C2 i C3 i C4 i C6 i C7 i Default MDS Lower Limit Upper Limit Units Pa*S TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE TEMPERATURE

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

Exponential

Parameter Name/Element MULIKC/1 SymbolDefault MDS C1 i X Lower Limit Upper Limit Units VISCOSITY

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193

Lower Limit

Upper Limit

Absolute temperature units are assumed for C2i. The temperature limits are always interpreted in user input units.

Polynomial

Parameter Symbol Name/Element MULPO/1 C1 i Default MDS Lower Limit X X X X Upper Limit Units VISCOSITY VISCOSITY, TEMPERATURE TEMPERATURE TEMPERATURE

MULPO/2, ..., 10 C2i, ..., C10i 0 MULPO/11 MULPO/12 C11i C12i 0 1000

Linear extrapolation of viscosity versus T occurs for temperatures outside bounds. Absolute temperature units are assumed for C2i, C3i, and C4i. The temperature limits are always interpreted in user input units.

Parameter Symbol Name/Element MULNVE/1 MULNVE/5 MULNVE/6 C1 i C5 i C6 i MULNVE/2, 3, 4 C2i, C3i, C4i Default MDS Lower Limit 0 0 1000 X X X X Upper Limit Units TEMPERATURE TEMPERATURE 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.

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The liquid mixture viscosity is calculated using a combination of the API and Andrade/DIPPR 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 Andrade/DIPPR model is used.

Parameter Name/Element TB API Symbol Default MDS Tbi APIi Lower Limit 4.0 -60.0 Upper Limit 2000.0 500.0 Units TEMPERATURE

The liquid mixture viscosity is calculated using a combination of the API and Andrade/DIPPR 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 Andrade/DIPPR model is used.

Parameter Name/Element TB API Symbol Default MDS Tbi APIi Lower Limit 4.0 -60.0 Upper Limit 2000.0 500.0 Units TEMPERATURE

195

The liquid mixture viscosity is calculated by the equation:

Where: Xi kij lij = = = Mole fraction or weight fraction of component i Symmetric binary parameter (kij = kji) Antisymmetric binary parameter (lij = -lji)

See the Andrade/DIPPR/IK-CAPE Pure Component Liquid Viscosity model for descriptions. The binary parameters kij and lij allow accurate representation of complex liquid mixture viscosity. Both binary parameters default to zero.

Parameter Name/Element MUKIJ MULIJ Symbol Default MDS kij lij 0 0 Lower Limit -100.0 100.0 Upper Limit 100.0 100.0 Units

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 Absolute viscosity of the mixture (N-sec/sqm) Viscosity of component i (N-sec/sqm) Common logarithm (base 10) An adjustable parameter, typically in the range of 0.5 to 1.0

m i

log f

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The individual component viscosities are calculated by the Andrade, DIPPR, or IK-CAPE equation. 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 Name/Element MULOGF Symbol Default MDS f 1.0 Lower Limit 0.0 Upper Limit 2.0 Units

"Petroleum Refining, 1 Crude Oil, Petroleum Products, Process Flowsheets", 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 TemperatureDependent Properties for details.

If TRNSWT/2 is This equation is used 0 102 301 302 401 402 503 Chapman-EnskogBrokaw DIPPR PPDS PPDS kinetic theory IK-CAPE polynomial equation IK-CAPE Sutherland equation NIST ThermoML polynomial And this parameter is used MUVDIP MUVPDS MUVCEB MUVPO MUVSUT MUVTMLPO

Chapman-Enskog-Brokaw

The equation for the Chapman-Enskog model is:

Where:

A parameter is used to determine whether to use the Stockmayer or Lennard-Jones potential parameters for /k (energy parameter) and (collision diameter). To calculate , the dipole moment p and either the Stockmayer parameters or Tb and Vb are needed. The polarity correction is from Brokaw.

197

Parameter Symbol Default Name/Element MW MUP STKPAR/1 STKPAR/2 LJPAR/1 LJPAR/2 Mi pi (i/k)

ST

-24

i) i)

fcn(Tci, pci,

The equation for the DIPPR vapor viscosity model is:

When necessary, the vapor viscosity is extrapolated beyond this temperature range linearly with respect to T, using the slope at the temperature limits. (Other DIPPR equations may sometimes be used. See Pure Component Temperature-Dependent Properties for details.) PCES uses the DIPPR equation in estimating vapor viscosity.

Parameter Name/Element MUVDIP/1 MUVDIP/2 MUVDIP/3, 4 MUVDIP/5 MUVDIP/6 MUVDIP/7 Symbol C1 i C2 i C3i, C4i C6 i C7 i Default MDS Lower Limit 0 0 0 0 1000 X X X X X X Upper Limit Units VISCOSITY TEMPERATURE TEMPERATURE 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:

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Symbol C1 i C2 i C3 i C4 i C5 i

Upper Limit

The equation is:

Symbol Mi C1 i C2 i C3 i C4 i C5 i

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

Parameter Name/Element MUVSUT/1 MUVSUT/2 MUVSUT/3 Symbol C1 i C2 i C3 i Default MDS Lower Limit 0 0 X X X Upper Limit Units VISCOSITY TEMPERATURE TEMPERATURE

199

Symbol C4 i

Upper Limit

Units 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

Upper Limit

Upper Limit

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.

The low pressure vapor mixture viscosity is calculated by the Wilke approximation of the Chapman-Enskog equation:

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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 Chapman- Enskog-Brokaw/DIPPR (or another) low pressure vapor viscosity model. Ensure that you supply parameters for

Parameter Name/ Element MW MUP Symbol Default

i*,v (p = 0).

Upper Limit 5000.0 5x10

-24

Units

Mi pi

DIPOLEMOMENT

201

Symbol

Default

Upper Limit

Units

(i/k)ST

TEMPERATURE LENGTH

iST

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.

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:

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Where: Vcij = = = = = 0 (in almost all cases) 0 (in almost all cases)

ij

Tcij

ij ij

Mij

ij

Parameter Name/Element TCCLS VCCLS MW MUP OMGCLS CLSK CLSKV CLSKT Symbol Default MDS Tci Vci Mi pi TC VC 0.0 0.0 0.0 x x x x x Lower Limit 5.0 0.001 1.0 0.0 -0.5 0.0 -0.5 -0.5 Upper Limit 2000.0 3.5 5000.0 5x10 2.0 0.5 -0.5 0.5

-24

i i ij ij

OMEGA x

The model specific parameters also affect the Chung-Lee-Starling Viscosity and the Chung-Lee-Starling Thermal Conductivity models.

203

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 = = =

The molar density can be calculated using an equation-of-state model (for example, the Benedict-Webb-Rubin). The parameter pr is the reduced dipolemoment:

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:

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Where: Vcij = = = = = 0 (in almost all cases) 0 (in almost all cases)

ij

Tcij

ij ij

Mij

ij

Lower Limit 5.0 0.001 1.0 0.0 -0.5 0.0 -0.5 -0.5

Upper Limit 2000.0 3.5 5000.0 5x10 2.0 0.5 -0.5 0.5

-24

i i ij ij

The model specific parameters affect the results of the Chung-Lee-Starling Thermal Conductivity and Low Pressure Viscosity models as well.

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 427.

205

The residual vapor viscosity or the pressure correction to low pressure vapor viscosity by Dean and Stiel is:

Where v (p = 0) is obtained from a low pressure viscosity model (for example, Chapman-Enskog-Brokaw). The dimensionless-making factor

is:

Tc M pc

= = =

Vcm Zcm

= = = Vcm / Vmv

Symbol Default MDS Mi Vci Lower Limit 1.0 0.001 Upper Limit 5000.0 3.5 Units MOLE-VOLUME

rm

Parameter Name/Element MW VC

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.

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The Jones-Dole model calculates the correction to the liquid mixture viscosity of a solvent mixture, due to the presence of electrolytes:

Where:

solv

cal

= =

Viscosity of the liquid solvent mixture, by default calculated by the Andrade/DIPPR model Contribution to the viscosity correction due to apparent electrolyte ca

The parameter solv can be calculated by different models depending on option code 3 for MUL2JONS:

Option Code Value 0 1 2 Solvent liquid mixture viscosity model Andrade liquid mixture viscosity model (default) Viscosity quadratic mixing rule Aspen liquid mixture viscosity model Use this equation Jones-Dole Carbonell

If these parameters are available IONMOB and IONMUB IONMUB

Breslau-Miller

When the concentration of apparent electrolyte exceeds 0.1 M, the BreslauMiller equation is used instead.

Jones-Dole

The Jones-Dole equation is: (1) Where: = Concentration of apparent electrolyte ca (2)

xcaa Aca

= =

(3) (4)

La

(5)

207

Lc Bca

= =

(6) (7)

When the electrolyte concentration exceeds 0.1 M, the Breslau-Miller equation is used instead. This behavior can be disabled by setting the second option code for MUL2JONS to 0.

Breslau-Miller

The Breslau-Miller equation is: (8) Where the effective volume Vc is given by: (9) for salts involving univalent ions (9a) for other salts

Carbonell

The Carbonell equation is: (10)

You must provide parameters for the model used for the calculation of the liquid mixture viscosity of the solvent mixture.

Parameter Name/Element CHARGE MW IONMOB/1 IONMOB/2 IONMUB/1 IONMUB/2 Symbol Default Lower Upper Limit Limit z M l1 l2 b1 b2 0.0 0.0 0,0 1.0 5000.0 Units AREA, MOLES AREA, MOLES, TEMPERATURE MOLE-VOLUME MOLE-VOLUME, TEMPERATURE

References

A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis Horwood, 1985).

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Letsou-Stiel

The Letsou-Stiel model calculates liquid viscosity at high temperatures for 0.76 Tr 0.98. This model is used in PCES. Note: Reduced temperature Tr is always calculated using absolute temperature units. The general form for the model is:

l = (l)0 + (l)1

Where: (l)0 (l)1 = = = =

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:

209

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.

Note: Reduced temperature Tr is always calculated using absolute temperature units. The Lucas mixing rules are: Tc pc = =

M FP (p = 0) FQ (p = 0)

= = =

Parameter Name/Element TCLUC PCLUC ZCLUC MW MUP Symbol Default MDS Tci pci Zci Mi pi TC PC ZC x x x Lower Limit 5.0 10

5

8

-24

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.

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The general form for the TRAPP viscosity model is:

Where: is the mole fraction vector; fcn is a corresponding states The parameter correlation based on the model for vapor and liquid viscosity TRAPP, by the National Bureau of Standards (NBS, currently NIST) . The model can be used for both pure components and mixtures. The model should be used for nonpolar components only.

Parameter Name/Element MW TCTRAP PCTRAP VCTRAP ZCTRAP OMGRAP Symbol Default MDS Mi Tci pci Vci Zci TC PC VC ZC x x x x Lower Limit 1.0 5.0 10

5

8

OMEGA x

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.

211

Where: SG Tb SG T = = = = = = = = Specific gravity of petroleum fraction Normal boiling point of petroleum fraction, Rankine Specific gravity of reference fluid with normal boiling point Tb Temperature of petroleum fraction, Rankine Kinematic viscosity of petroleum fraction at T, cSt Kinematic viscosity of petroleum fraction at 100 F (i=1) and 210 F (i=2), cSt Kinematic viscosity of reference fluid at 100 F and 210 F, cSt Critical temperature of reference fluid, Rankine

i 1, 2

Tc

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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:

Option Codes

Option Code Value 1 0 1 Descriptions Use mole basis composition (default) Use mass basis composition

Parameter

Parameter Name/Element MLQKIJ Symbol Kij Default MDS x Lower Limit Upper Limit Units

The Aspen Physical Property System has eight built-in thermal conductivity models. This section describes the thermal conductivity models available.

Model Chung-Lee-Starling IAPS Li Mixing Rule Riedel Electrolyte Correction Sato-Riedel/DIPPR/IK-CAPE Solid Thermal Conductivity Polynomial Stiel-Thodos/DIPPR/IK-CAPE Stiel-Thodos Pressure Correction TRAPP Thermal Conductivity Vredeveld Mixing Rule Wassiljewa-Mason-Saxena Mixing Rule Type Vapor or liquid Water or steam Liquid mixture Electrolyte Liquid Solid Low pressure vapor Vapor Vapor or liquid Liquid mixture Low pressure vapor

213

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

Where: f1 f2 = = =

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:

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:

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Vcij

ij

Tcij

ij ij

Mij

ij

Lower Limit 5.0 0.001 1.0 0.0 -0.5 0.0 -0.5 -0.5

Upper Limit 2000.0 3.5 5000.0 5x10 2.0 0.5 -0.5 0.5

-24

i i ij ij

OMEGA x

The model-specific parameters also affect the results of the Chung-LeeStarling Viscosity models.

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 505, 523.

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)

215

Li Mixing Rule

Liquid mixture thermal conductivity is calculated using Li equation (Reid et.al., 1987):

Where:

The pure component liquid molar volume Vi*,l is calculated from the Rackett model. The pure component liquid thermal conductivity three models: Sato Riedel DIPPR IK-CAPE

See the Sato Riedel/DIPPR/IK-CAPE model for descriptions. 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:

lsolv

xcaa ac, aa

Thermal conductivity of the liquid solvent mixture, calculated by the Sato-Riedel model using the Vredeveld mixing rule Mole fraction of the apparent electrolyte ca Riedel ionic coefficient

= =

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Vml

Apparent electrolyte mole fractions are computed from the true ion molefractions and ionic charge number. They can also be computed if you use the apparent component approach. A more detailed discussion of this method is found in Electrolyte Calculation. You must provide parameters for the Sato-Riedel model. This model is used for the calculation of the thermal conductivity of solvent mixtures.

Parameter Name/Element CHARGE IONRDL Symbol z a Default 0.0 0.0 Lower Limit Upper Limit Units

THERMAL CONDUCTIVITY, MOLE-VOLUME The behavior of this model can be changed using option codes (these codes apply to the Vredeveld mixing rule).

Option Option Description Code Value 1 0 1 2 0 1 2 Do not check ratio of KL max / KL min Check ratio. If KL max / KL min > 2, set exponent to 1, overriding option code 2. Exponent is -2 Exponent is 0.4 Exponent is 1. This uses a weighted average of liquid thermal conductivities.

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 TemperatureDependent Properties for details.

If TRNSWT/3 is This equation is used 0 100 301 401 503 510 Sato-Riedel DIPPR PPDS IK-CAPE NIST ThermoML polynomial NIST PPDS8 equation And this parameter is used KLDIP KLPDS KLPO KLTMLPO KLPPDS8

Sato-Riedel

The Sato-Riedel equation is (Reid et al., 1987):

217

Parameter Name/Element MW TC TB Symbol Default MDS Mi Tci Tbi Lower Limit 1.0 5.0 4.0 Upper Limit 5000.0 2000.0 2000.0 Units TEMPERATURE TEMPERATURE

PPDS

The equation is:

Linear extrapolation of

Parameter Name/Element KLPDS/1 KLPDS/2 KLPDS/3 KLPDS/4 KLPDS/5 KLPDS/6

Default MDS 0 0 0 0 1000 Lower Limit Upper Limit Units THERMALCONDUCTIVITY TEMPERATURE TEMPERATURE

Symbol C1 i C2 i C3 i C4 i C5 i C6 i

The equation is

Default MDS 0 7

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The DIPPR equation is:

Linear extrapolation of

(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 Name/Element KLDIP/1 C1 i Default MDS x Lower Limit Upper Limit Units THERMALCONDUCTIVITY, TEMPERATURE THERMALCONDUCTIVITY, TEMPERATURE TEMPERATURE TEMPERATURE

KLDIP/2, ... , 5

KLDIP/6 KLDIP/7

C6 i C7 i

0 1000

x x

The equation is:

Linear extrapolation of

Default MDS x Lower Limit Upper Limit Units THERMALCONDUCTIVITY, TEMPERATURE THERMALCONDUCTIVITY, TEMPERATURE TEMPERATURE TEMPERATURE

KLTMLPO/2, ... , C2i , ..., C4i 0 4 KLTMLPO/5 KLTMLPO/6 KLTMLPO/7 nTerms Tlower Tupper 4 0 1000

x x x

IK-CAPE

The IK-CAPE equation is:

219

Linear extrapolation of

Parameter Symbol Name/Element KLPO/1 C1 i

Default MDS x x Lower Limit Upper Limit Units THERMALCONDUCTIVITY THERMALCONDUCTIVITY, TEMPERATURE TEMPERATURE TEMPERATURE

KLPO/11 KLPO/12

C11i C12i

0 1000

x x

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:

Linear extrapolation of

Parameter Name/Element KSPOLY/1 KSPOLY/2, 3, 4, 5

Lower Limit Upper Limit Units THERMAL CONDUCTIVITY THERMAL CONDUCTIVITY, TEMPERATURE TEMPERATURE TEMPERATURE

b, c, d, e

KSPOLY/6 KSPOLY/7

0 1000

x x

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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 0 102 301 401 503 Stiel-Thodos DIPPR PPDS IK-CAPE NIST ThermoML polynomial And this parameter is used KVDIP KVPDS KVPO KVTMLPO

Stiel-Thodos

The Stiel-Thodos equation is:

Where:

Cpi*,ig is obtained from the Ideal Gas Heat Capacity model. R is the universal gas constant.

Parameter Name/Element MW Symbol Default MDS Mi Lower Limit 1.0 Upper Limit 5000.0 Units

The DIPPR equation for vapor thermal conductivity is:

Linear extrapolation of

(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 Name/Element KVDIP/1 KVDIP/2 KVDIP/3, 4 KVDIP/5 C1 i C2 i C3i, C4i Default MDS 0 0 0 x x x x Lower Limit Upper Limit Units THERMAL CONDUCTIVITY TEMPERATURE

221

Lower Limit

Upper Limit

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:

Linear extrapolation of

Default 0 0 0 0 1000 MDS Lower Upper Limit Limit Units THERMALCONDUCTIVITY THERMALCONDUCTIVITY THERMALCONDUCTIVITY THERMALCONDUCTIVITY TEMPERATURE TEMPERATURE

IK-CAPE Polynomial

Linear extrapolation of

Parameter Name/Element KVPO/1 KVPO/2, ... , 10

Default MDS Lower Limit 0 x x Upper Units Limit THERMALCONDUCTIVITY THERMALCONDUCTIVITY, TEMPERATURE TEMPERATURE TEMPERATURE

KVPO/11 KVPO/12

C11i C12i

0 1000

x x

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Linear extrapolation of

Default MDS x Lower Limit Upper Limit Units THERMALCONDUCTIVITY, TEMPERATURE THERMALCONDUCTIVITY, TEMPERATURE TEMPERATURE TEMPERATURE

KVTMLPO/2, ... , C2i, ..., C4i 4 KVTMLPO/5 KVTMLPO/6 KVTMLPO/7 nTerms Tlower Tupper

4 0 1000

x x x

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

The parameter Vmv can be obtained from Redlich-Kwong. Conductivity model (Stiel-Thodos/DIPPR).

Parameter Name/Element MW TC PC VC ZC Symbol Default MDS Mi Tci Vci Zci

Lower Limit 1.0 5.0 10

5

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

Upper Limit 5000.0 2000.0 10

8

0.001 0.1

3.5 0.5

223

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 Pure component liquid thermal conductivity of component i

i*,l

If option code 1 is Then n is determined by 0 (default) 1 Option code 2, always Option code 2, unless set to 1. . In this case n is

If option code 2 is Then n is 0 (default) 1 2 -2 0.4 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 equations: Sato-Riedel DIPPR IK-CAPE

See the Sato-Riedel/DIPPR/IK-CAPE model for descriptions. 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:

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Where: = Cpi

*,ig

Mole fraction vector Ideal gas heat capacity calculated using the Aspen Physical Property System or DIPPR ideal gas heat capacity equations Corresponding states correlation based on the model for vapor and liquid thermal conductivity made by the National Bureau of standards (NBS, currently NIST)

fcn

The model can be used for both pure components and mixtures. The model should be used for nonpolar components only.

Parameter Name/Element MW TCTRAP PCTRAP VCTRAP ZCTRAP OMGRAP Symbol Default MDS Mi Tci pci Vci Zci TC PC VC ZC OMEGA x x x x x Lower Limit 1.0 5.0 10

5

8

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:

i*,v i*,v(p = 0)

= =

Calculated by the Stiel-Thodos model or the DIPPR thermal conductivity model (Stiel-Thodos/DIPPR) Obtained from the Chapman-Enskog-Brokaw model

225

Parameter Name/Element MW

i*,v(p = 0)

and

i*,v.

Upper Limit 5000.0 Units

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987), pp. 530531.

Diffusivity Models

The Aspen Physical Property System has seven built-in diffusivity models. This section describes the diffusivity models available.

Model Chapman-Enskog-Wilke-Lee (Binary) Chapman-Enskog-Wilke-Lee (Mixture) Dawson-Khoury-Kobayashi (Binary) Dawson-Khoury-Kobayashi (Mixture) Nernst-Hartley Wilke-Chang (Binary) Wilke-Chang (Mixture) Type Low pressure vapor Low pressure vapor Vapor Vapor Electrolyte Liquid Liquid

Chapman-Enskog-Wilke-Lee (Binary)

The binary diffusion coefficient at low pressures the Chapman-Enskog-Wilke-Lee model: is calculated using

Where:

ij

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ij

A parameter is used to determine whether to use the Stockmayer or Lennard-Jones potential parameters for /k (energy parameter ) and (collision diameter). To calculate , the dipole moment p, and either the Stockmayer parameters or Tb and Vb are needed.

Parameter Symbol Default Name/Element MW MUP TB VB OMEGA STKPAR/1 STKPAR/2 LJPAR/1 LJPAR/2 Mi pi Tbi Vb fcn(Tbi, Vbi, pi) fcn(Tbi, Vbi, pi) fcn(Tci, MDS Lower Upper Limit Limit x x x 1.0 0.0 4.0 0.001 -0.5 5000.0 5x10 3.5 2.0

-24

2000.0

i) i)

fcn(Tci, pci,

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 binary diffusion coefficient Dijv(p = 0) at low pressures is calculated using the Chapman-Enskog-Wilke-Lee model. (See Chapman-Enskog-Wilke-Lee (Binary).) You must provide parameters for this model.

227

Lower Limit

Upper Limit

Units

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 597.

Dawson-Khoury-Kobayashi (Binary)

The binary diffusion coefficient Dijv at high pressures is calculated from the Dawson-Khoury-Kobayashi model:

Dijv(p = 0) is the low-pressure binary diffusion coefficient obtained from the Chapman-Enskog-Wilke-Lee model. The parameters of-state model.

You must supply parameters for these two models. Subscript i denotes a diffusing component. j denotes a solvent.

Parameter Name/Element VC Symbol Default MDS Vci x Lower Limit 0.001 Upper Limit 3.5 Units 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):

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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 Name/Element DVBLNC Symbol Default MDS 1 Lower Limit Upper Limit Units

References

R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 597.

Nernst-Hartley

The effective diffusivity of an ion i in a liquid mixture with electrolytes can be calculated using the Nernst-Hartley model: (1)

Where: F xk zi = = = 9.65x107C/kmole (Faraday's number) Mole fraction of any molecular species k 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:

229

The diffusivity for molecular species is calculated by the Wilke-Chang (Mixture) model.

Parameter Name/Element CHARGE IONMOB/1 IONMOB/2 Symbol z l1 l2 Default 0.0 0.0 Lower Upper Limit Limit Units AREA, MOLES AREA, MOLES, TEMPERATURE

When IONMOB/1 is missing, the Nernst-Hartley model uses a nominal value of 5.0 and issues a warning. This parameter should be specified for ions, and not allowed to default to this value.

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:

Association factor of solvent. 2.26 for water, 1.90 for methanol, 1.50 for ethanol, 1.20 for propyl alchohols and n-butanol, and 1.00 for all other solvents. Liquid molar volume at Tb of solvent i Liquid viscosity of the solvent. This can be obtained from the Andrade/DIPPR model. You must provide parameters for one of these models. Liquid viscosity of the complete mixture of n components

Vbi

= =

jl l

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x i, x j

Apparent binary mole fractions. If the actual mole fractions are then

Parameter Name/Element MW VB

Symbol Mj Vbi*,l

Default

Units 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 liquid diffusion coefficient of component i in a mixture. The equation for the Wilke-Chang model is:

With:

Where:

j

nl

Association factor of solvent. 2.26 for water, 1.90 for methanol, 1.50 for ethanol, 1.20 for propyl alchohols and n-butanol, and 1.00 for all other solvents. Mixture liquid viscosity of all nondiffusing components. This can be obtained from the Andrade/DIPPR or another liquid mixture viscosity model. You must provide parameters for one of these models.

The parameter DLWC specifies which components diffuse. It is set to 1 for a diffusing component and 0 for a non-diffusing component.

Parameter Name/Element MW Symbol Mj Default Lower Limit 1.0 Upper Limit 5000.0 Units

231

Symbol Vbi*,l

Units MOLE-VOLUME

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 Liquid Mixture Surface Tension API IAPS Hakim-Steinberg-Stiel/DIPPR/IK-CAPE Onsager-Samaras Electrolyte Correction Modified MacLeod-Sugden Type Liquid-vapor Liquid-vapor Water-stream Liquid-vapor Electrolyte liquid-vapor 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):

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 models: Hakim-Steinberg-Stiel DIPPR

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IK-CAPE

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 option sets. The general form of the model is:

Where: fcn = A correlation based on API Procedure 10A32 (API Technical Data Book, Petroleum Refining, 4th edition)

Symbol Default MDS Tbi SG Tci Lower Limit 4.0 0.1 5.0 Upper Limit 2000.0 2.0 2000 Units TEMPERATURE TEMPERATURE

Parameter Name/Element TB SG TC

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 STEAMTA. The general form of the equation for the IAPS surface tension model is:

w=fcn(T, p)

Where: fcn = Correlation developed by IAPS

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 0 Hakim-Steinberg-Stiel And this parameter is used

233

If TRNSWT/5 is This equation is used 106 301 401 505 511 512 DIPPR PPDS IK-CAPE polynomial equation NIST TDE Watson equation NIST TDE expansion NIST PPDS14 Equation

And this parameter is used SIGDIP SIGPDS SIGPO SIGTDEW SIGISTE SIGPDS14

Hakim-Steinberg-Stiel

The Hakim-Steinberg-Stiel equation is:

Where: Qpi mi = =

The parameter

Parameter Name/Element TC PC OMEGA CHI

Symbol Tci pci Default 0 -0.5 2.0 Lower Limit 5.0 Upper Limit 2000.0 Units TEMPERATURE PRESSURE

i i

The DIPPR equation for liquid surface tension is:

Linear extrapolation of

(Other DIPPR equations may sometimes be used. See Pure Component Temperature-Dependent Properties for details.) The DIPPR model is used by PCES when estimating liquid surface tension. Note: Reduced temperature Tr is always calculated using absolute temperature units.

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Upper Limit

PPDS

The equation is:

Linear extrapolation of

Parameter Name/Element SIGPDS/1 SIGPDS/2 SIGPDS/3 SIGPDS/4 SIGPDS/5

Default MDS Lower Limit 0 0 0 1000 Upper Limit Units SURFACETENSION TEMPERATURE TEMPERATURE

Symbol C1 i C2 i C3 i C4 i C5 i

This equation is the same as the PPDS equation above, but it uses its own parameter set which includes critical temperature.

Parameter Name/Element SIGPDS14/1 SIGPDS14/2 SIGPDS14/3 SIGPDS14/4 SIGPDS14/5 SIGPDS14/6 Symbol C1 i C2 i C3 i Tci C4 i C5 i Default MDS Lower Limit 0 0 0 1000 x x x x x x Upper Limit Units N/m TEMPERATURE TEMPERATURE TEMPERATURE

IK-CAPE Polynomial

The IK-CAPE equation is:

Linear extrapolation of

235

SIGPO/11 SIGPO/12

C11i C12i

0 1000

x x

This equation can be used when parameter SIGTDEW is available.

Upper Limit

This equation can be used when parameter SIGISTE is available.

Upper Limit

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.

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Onsager-Samaras

The Onsager-Samaras model calculates the correction to the liquid mixture surface tension of a solvent mixture, due to the presence of electrolytes: for salt concentration < 0.03 (1) M Where:

solv

xcaa

= = =

Surface tension of the solvent mixture calculated by the Hakim-Steinberg-Stiel model Mole fraction of the apparent electrolyte ca Contribution to the surface tension correction due to apparent electrolyte ca

ca

For each apparent electrolyte ca, the contribution to the surface tension correction is calculated as: (2)

Where:

solv

ccaa

= =

Vml

Apparent electrolyte mole fractions are computed from the true ion molefractions and ionic charge number. They are also computed if you use the apparent component approach. See Apparent Component and True Component Approaches in the Electrolyte Calculation chapter for a more detailed discussion of this method. Above salt concentration 0.03 M, the slope of surface tension vs. mole fraction is taken to be constant at the value from 0.03 M. You must provide parameters for the Hakim-Steinberg-Stiel model, used for the calculation of the surface tension of the solvent mixture.

Parameter Name/Element CHARGE Symbol z Default 0.0 Lower Limit Upper Limit Units

References

A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis, Ltd. 1985).

237

Modified MacLeod-Sugden

The modified MacLeod-Sugden equation for mixture liquid surface tension can be derived from the standard MacLeod-Sugden equation by assuming that the density of the vapor phase is zero. The modified MacLeod-Sugden equation is:

Where:

i*,l

Vi*,l V

l

= Surface tension for pure component i, calculated using the Hakim-Steinberg-Stiel/DIPPR/IK-CAPE model. = Liquid molar volume for pure component i, calculated using the Rackett/DIPPR/IK-CAPE model. = 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).

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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 Density Models General density polynomial General heat capacity polynomial Enthalpy and Density Models for Coal and Char General coal enthalpy model IGT coal density model IGT char density model Model name DNSTYGEN ENTHGEN Model name HCOALGEN DCOALIGT DCHARIGT Phase(s) S S Phase(s) S S S

The Aspen Physical Property System has two built-in general enthalpy and density models. This section describes the general enthalpy and density models available:

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239

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 Density of the jth consituent in component i

Symbol MDS x x x x Default Lower Upper Limit Limit 0 0 0 Units MASS-ENTHALPY and TEMPERATURE MASS-ENTHALPY and TEMPERATURE MASS-ENTHALPY and TEMPERATURE MASS-ENTHALPY and TEMPERATURE

ijs

Parameter Name/Element

DENGEN/1, 5, 9, , 77 ai,j1 DENGEN/2, 6, 10, , 78 DENGEN/3, 7, 11, , 79 DENGEN/4, 8, 12, , 80 ai,j2 ai,j3 ai,j4

Use the elements of GENANAL to input the mass percentages of the constituents. The structure of DENGEN is: Elements 1 to 4 are the four coefficients for the first constituent, elements 5 to 8 are the coefficients for the second constitutent, and so on, for up to 20 constituents.

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:

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Where: wij hi s = = = = Mass fraction of the jth constituent in component i Specific enthalpy of solid component i Specific enthalpy of formation of constituent j Heat capacity of the jth constituent in component i

Symbol MDS Default 0 Lower Limit Upper Limit Units MASS-ENTHALPY MASS-ENTHALPY and TEMPERATURE MASS-ENTHALPY and TEMPERATURE MASS-ENTHALPY and TEMPERATURE MASS-ENTHALPY and TEMPERATURE

fhjs

Cps

fhjs

x x

HCGEN/1, 5, 9, , 77 ai,j1

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.

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

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241

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-matterfree basis. Only the organic portion of the coal is considered. Moisture corrections are made for all analyses except hydrogen, according to the formula:

Where: w w

d

= = =

The value determined for weight fraction 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 mineralmatter calculation. When information regarding the forms of sulfur is available, use the modified Parr formula to give a better approximation of the percent of inorganic material present. Because chlorine is usually small for United States coals, you can omit chlorine from the calculation. Correct analyses from a dry basis to a dry, mineral-matter-free basis, using the formula:

Where:

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wd

= Correction factor for other losses, such as the loss of carbon in carbonates and the loss of hydrogen present in the water constitution of clays

The oxygen and organic sulfur contents are usually calculated by difference as:

Where: Cp cp h = = = = = = = = = = Heat capacity / (J/kgK) Heat capacity / (cal/gC) Specific enthalpy Specific heat of combustion Specific heat of formation Mean-maximum relectance in oil Temperature/K Temperature/C Weight fraction Specific density

ch fh

Ro T t w

A C Cl FC H H2O MM N O So Sp St

Subscripts: = = = = = = = = = = = = Ash Carbon Chlorine Fixed carbon Hydrogen Moisture Mineral matter Nitrogen Oxygen Organic sulfur Pyritic sulfur Total sulfur

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243

S VM

= =

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 Properties Advanced NC-Props form. (See the Aspen Plus User Guide, Chapter 6). Use option codes to specify a calculation method for properties. Each element in the option code vector is used in the calculation of a different property. The table labeled HCOALGEN Option Codes (below) lists model option codes for HCOALGEN. The table is followed by a detailed description of the calculations used for each correlation. The correlations are described in the following section. The component attributes are defined in Aspen Plus User Guide, Chapter 6.

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 D-2015 defines standard conditions for measuring gross calorific value. 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-mattercontaining basis with a correction for the heat of combustion of pyrite. The formula is:

The heat of combustion correlations were evaluated by the Institute of Gas Technology (IGT). They used data for 121 samples of coal from the Penn State Data Base (IGT, 1976) and 457 samples from a USGS report (Swanson, et al., 1976). These samples included a wide range of United States coal fields. The constant terms in the HCOALGEN correlations are bias corrections obtained from the IGT study.

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Boie Correlation:

Dulong Correlation:

245

Symbol a7i

Default -47.0

IGT Correlation:

Parameter Name/Element HCOMB Symbol Default 0

chid

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:

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:

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Parameter Name/Element HFC/1 HFC/2 HFC/3 HFC/4 HFC/5 HFC/6 HFC/7 HFC/8 HFC/9 HFC/10 HFC/11 HFC/12 HFC/13 HFC/14 HFC/15

Symbol a1i a2i a3i a4i a5i a6i a7i a8i a9i a10i a11i a12i a13i a14i a15i

Default 1810.123 -502.222 329.1087 121.766 -542.393 1601.573 424.25 -525.199 -11.4805 31.585 13.5256 11.5 -685.846 -22.494 -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 j = = Component index 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.

247

Parameter Name/Element CP1C/1 CP1C/2 CP1C/3 CP1C/4 CP1C/5 CP1C/6 CP1C/7 CP1C/8 CP1C/9 CP1C/10 CP1C/11 CP1C/12 CP1C/13 CP1C/14 CP1C/15 CP1C/16 CP1C/17 CP1C/18 CP1C/19 CP1C/20

Symbol ai,11 ai,12 ai,13 ai,14 ai,21 ai,22 ai,23 ai,24 ai,31 ai,32 ai,33 ai,34 ai,41 ai,42 ai,43 ai,44 ai,51 ai,52 ai,53 ai,54

The cubic temperature equation is:

Default 0.438

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.

Option Code Option Code Calculation Number Value Method 1 Heat of Combustion 1 Boie correlation Parameter Names BOIEC Component Attributes ULTANAL SULFANAL PROXANAL

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Option Code Option Code Calculation Number Value Method 1 Heat of Combustion 2 Dulong correlation

Component Attributes ULTANAL SULFANAL PROXANAL ULTANAL SULFANAL PROXANAL ULTANAL SULFANAL PROXANAL ULTANAL PROXANAL ULTANAL PROXANAL ULTANAL SULFANAL ULTANAL SULFANAL PROXANAL PROXANAL

Grummel and GMLDC Davis correlation Mott and Spooner MTSPC correlation IGT correlation CIGTC

5 6

4 Enthalpy Basis 1 Elements in their standard states at 298.15K and 1 atm Component at 298.15 K

References

Gomez, M., J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965. IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data Book, Section PMa. 44.1, 1976. Kirov, N.Y., "Specific Heats and Total Heat Contents of Coals and Related Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965), pp. 29, 33. Swanson, V.E. et al., Collection, Chemical Analysis and Evaluation of Coal Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76 468.

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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 DENIGT/1 DENIGT/2 DENIGT/3 DENIGT/4 Symbol a1i a2i a3i a4i Default 0.4397 0.1223 -0.01715 0.001077

Reference

IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data Book, Section PMa. 44.1, 1976.

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):

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Parameter Name/Element Symbol DENIGT/1 DENIGT/2 DENIGT/3 DENIGT/4 a1i a2i a3i a4i

The densities of graphitic high-temperature carbons (including cokes) range from 2.2x103 to 2.26x103 kg/m3. Densities of nongraphitic high-temperature carbons (derived from chars) range from 2.0x103 to 2.2x103 kg/m3. Most of the data used in developing this correlation were for carbonized coking coals. Although data on a few chars (carbonized non-coking coals) were included, none has a hydrogen content less than 2%. The correlation is probably not accurate for high temperature chars.

References

I.M. Chang, B.S. Thesis, Massachusetts Institute of Technology, 1979. M. Gomez, J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965. IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data Book, Section PMa. 44.1, 1976. N.Y. Kirov, "Specific Heats and Total Heat Contents of Coals and Related Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965), pp. 29, 33. V.E. Swanson et al., Collection, Chemical Analysis and Evaluation of Coal Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76 468.

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The following tables list the model option codes available: Option Codes for Transport Property Models Option Codes for Activity Coefficient Models Option Codes for Equation of State Models Option Codes for K-value Models Option Codes for Enthalpy Models Option Codes for Gibbs Energy Models Option Codes for Molar Volume Models

Model Name SIG2HSS Option Value Code 1 1 -1,-2, ..., -9 SIG2ONSG 1 1 -1,-2, ..., -9 MUL2API, MULAPI92 1 0 Descriptions Exponent in mixing rule (default) Exponent in mixing rule Exponent in mixing rule (default) Exponent in mixing rule Release 9 method. First, the API, SG of the mixture is calculated, then the API correlation is used (default) Pre-release 9 method. Liquid viscosity is calculated for each pseudocomponent using the API method. Then mixture viscosity is calculated by mixing rules. Mixture viscosity weighted by mole fraction (default)

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Model Name

Descriptions Mixture viscosity weighted by mass fraction Mixture viscosity weighted by mole fraction (default) Mixture viscosity weighted by mass fraction Use Breslau and Miller equation instead of Jones and Dole equation when electrolyte concentration exceeds 0.1 M. Always use Jones and Dole equation when the parameters are available. Solvent liquid mixture viscosity from Andrade liquid mixture viscosity model (default) Solvent liquid mixture viscosity from quadratic mixing rule Solvent liquid mixture viscosity from Aspen liquid mixture viscosity model Original correlation Modified UOP correlation Use mole basis composition (default) Use mass basis composition Do not check ratio of KL max / KL min Check ratio. If KL max / KL min > 2, set exponent to 1, overriding option code 2. Exponent is -2 Exponent is 0.4 Exponent is 1. This uses a weighted average of liquid thermal conductivities.

MUL2JONS

0 1

Model Name GMXSH WHENRY Option Code 1 1 Value Descriptions 0 1 1 2 3 4 1 No volume term (default) Includes volume term Equal weighting Size - VC1/3 Area - VC2/3 (default) Volume - VC Defaults for pair parameters

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253

Model Name

Option Code

Value Descriptions 1 2 Pair parameters default to zero Solvent/solute pair parameters default to water parameters. Water/solute pair parameters default to zero (default for GMELC) Default water parameters to 8, -4. Default solvent/solute parameters to 10, -2 (default for GMENRTL and GMENRHG) Vapor phase equation-of-state for liquid enthalpy and Gibbs energy of HF 0 1 Ideal gas EOS (default) HF EOS for hydrogen fluoride Solvent/solvent binary parameter values obtained from 0 1 Scalar GMELCA, GMELCB and GMELCM (default for GMELC) Vector NRTL(8) (default for GMENRTL and GMENRHG) Enthalpy calculation method 0 1 Electrolyte NRTL Enthalpy (default for GMELC) Helgeson method (default for GMENRTL and GMENRHG) Vapor phase enthalpy departure contribution to liquid enthalpy. Hliq = Hig + DHV - Hvap; this option indicates how DHV is calculated. 0 1 2 Do not calculate (DHV=0) (default) Calculate using Redlich-Kwong equation of state Calculate using Hayden-O'Connell equation of state Method for calculating corresponding states (for handling solvents that exist in both subcritical and supercritical conditions) 0 1 Original method (default) 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. Defaults for pair mixing rule -1 0 1 No unsymmetric mixing Unsymmetric mixing polynomial (default) Unsymmetric mixing integral Defaults for pair mixing rule -1 0 No unsymmetric mixing Unsymmetric mixing polynomial (default)

GMPT1

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Model Name

Option Code 2

Value Descriptions 1 0 1 Unsymmetric mixing integral Standard enthalpy calculation Standard electrolytes method (Pre-release 10) Helgeson method (Default) Estimation of K-stoic temperature dependency 0 1 Use value at 298.15 K Helgeson Method (default) Reference temperature usage Model choice 1 2 3 COSMO-SAC model by Lin and Sandler (2002) (Default) COSMO-RS model by Klamt and Eckert (2000) Lin and Sandler model with modified exchange energy (Lin et al., 2002) Use standard reference temperature (default) Use liquid reference temperature Hansen volume input by user (default) Hansen volume calculated by Aspen Plus Flory-Huggins term included (default) Flory-Huggins term removed Steam table for liquid enthalpy of water 0 1 Use steam table for liquid enthalpy of water (default) Use specified EOS model Vapor phase equation-of-state for liquid enthalpy of HF 0 1 Use specified EOS model (default) HF EOS for hydrogen fluoride

1 COSMOSAC 1

Model Name Option Code Value 0 1 Descriptions Do not use steam tables Calculate properties (H, S, G, V) of water from steam table (default; see Note) ESBWRS, ESBWRS0 1

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Model Name

Option Code 2

Value 0 1

Descriptions Original RT-Opt root search method (default) 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. Hayden-O'Connell model. Use chemical theory only if one component has HOCETA=4.5 (default) Always use the chemical theory regardless of HOCETA values Never use the chemical theory regardless of HOCETA values Check high-pressure limit. If exceeded, calculate volume at cut-off pressure. Ignore high-pressure limit. Calculate volume model T and P. ASPEN Boston/Mathias alpha function when Tr >1, original literature alpha function otherwise. (default for ESPR) Original literature alpha function (default for ESPRSTD) Extended Gibbons-Laughton alpha function Twu Generalized alpha function Twu alpha function Standard Peng-Robinson mixing rules (default) Asymmetric Kij mixing rule from Dow Do not use steam tables (default) Calculate water properties (H, S, G, V) from steam table (see Note) Do not use Peneloux liquid volume correction (default) Apply Peneloux liquid volume correction (See SRK) Use analytical method for root finding (default) Use RTO numerical method for root finding Use VPROOT/LQROOT numerical method for root finding ASPEN Boston/Mathias alpha function

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Model Name ESRKS, ESRKS0, ESRKSTD, ESRKSTD0, ESSRK, ESSRK0, ESRKSML, ESRKSML0

Option Code

Value

ESRKSW, ESRKSW0 1

0 1 2

ASPEN Boston/Mathias alpha function (default) Original literature alpha function Grabowski and Daubert alpha function for H2 above TC ( = 1.202 exp(-0.30228xTri)) Initial temperature for binary parameter estimation

ESRKU, ESRKU0

1 0 1 2 >2 2 0 1 3 4 0 1 5 0 1

At TREF=25 C (default) The lower of TB(i) or TB(j) (TB(i) + TB(j))/2 Value entered used as temperature VLE or LLE UNIFAC VLE (default) LLE Property diagnostic level flag (-1 to 8) Vapor phase EOS used in generation of TPxy data with UNIFAC Hayden-O'Connell (default) Redlich-Kwong Do/do not estimate binary parameters Estimate (default) Set to zero Equation form for Log(k) expression: log(K) = A + B/T + C ln(T) + DT (default) log(K) = A + B/T + CT + DT2 + E log(P) Original literature alpha function Mathias-Copeman alpha function Schwartzentruber-Renon alpha function (default) Equation form for alpha function

ESHF, ESHF0

0 1 1 2 3

1 2 3 ESSTEAM, ESSTEAM0 1 0 1

Original literature alpha function Mathias-Copeman alpha function Schwartzentruber-Renon alpha function (default) ASME 1967 correlations NBS 1984 equation of state (default)

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Model Name

Option Code

Value 2

Descriptions NBS 1984 equation of state with alternate root search method (STMNBS2) ASME 1967 correlations (default) NBS 1984 equation of state NBS 1984 equation of state with alternate root search method (STMNBS2)

ESH2O, ESH2O0

0 1 2

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.

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 Code 1 Value 0 1 2 3 4 5 2 0 1 3 0 Description Standard SRK alpha function for Tr < 1, Boston-Mathias alpha function for Tr > 1 Standard SRK alpha function for all Grabovsky Daubert alpha function for H2 and standard SRK alpha function for others (default) Extended Gibbons-Laughton alpha function for all components (see notes 1, 2, 3) Mathias alpha function Twu generalized alpha function Standard SRK mixing rules (default except for SRK-KabadiDanner) Kabadi Danner mixing rules (default for SRK-Kabadi-Danner) (see notes 3, 4, 5) Do not calculate water properties from steam table (default for Redlich-Kwong-Soave models)

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Option Code

Value 1

Description Calculate properties (H, S, G, V) of water from steam table (default for SRK models; see note 6) Do not apply the Peneloux liquid volume correction Apply the liquid volume correction (default) Use analytical method for root finding (default) Use RTO numerical method for root finding Use VPROOT/LQROOT numerical method for root finding Use true logarithm in calculating properties (default for Redlich-Kwong-Soave models) Use smoothed logarithm in calculating properties (default for SRK models)

4 5

0 1 0 1 2

0 1

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.

Model Name BK10 Option Code 1 Value Descriptions 0 1 Treat pseudocomponents as paraffins (default) Treat pseudocomponents as aromatics

259

Model Name Option Code DHL0HREF 1 Value Descriptions 1 2 Use Liquid reference state for all components (Default) Use liquid and gaseous reference states based on the state of each component Defaults for pair parameters 1 2 Pair parameters default to zero Solvent/solute pair parameters default to water parameters. Water/solute pair parameters default to zero (default for ELC models) Default water parameters to 8, -4. Default solvent/solute parameters to 10, -2 (default for HMXENRTL and HMXENRHG) Vapor phase equation-of-state for liquid enthalpy and Gibbs energy of HF 0 1 3 0 1 4 0 1 5 Ideal gas EOS (default) HF EOS for hydrogen fluoride Solvent/solvent binary parameter values obtained from: Scalar GMELCA, GMELCB and GMELCM (default for ELC models) Vector NRTL(8) (default for HMXENRTL and HMXENRHG) Enthalpy calculation method Electrolyte NRTL Enthalpy (default for ELC models, HMXENRTL, and ELECNRTL property method) Helgeson method (default for HMXENRHG) Vapor phase enthalpy departure contribution to liquid enthalpy. Hliq = Hig + DHV - Hvap; this option indicates how DHV is calculated. 0 1 2 6 Do not calculate (DHV=0) (default) Calculate using Redlich-Kwong equation of state Calculate using Hayden-O'Connell equation of state Method for calculating corresponding states (for handling solvents that exist in both subcritical and supercritical conditions) 0 1 Original method (default) Corresponding state method. Calculates a pseudocritical temperature of the solvents and uses it together with the actual critical temperatures of the pure solvents to adjust the liquid enthalpy departure. This results in a smoother transition of the liquid enthalpy contribution when the component transforms from subcritical to supercritical.

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Value Descriptions Method for handling Henry components and multiple solvents 0 1 Pure liquid enthalpy calculated by aqueous infinite dilution heat capacity; only water as solvent Pure liquid enthalpy for Henry components calculated using Henry's law; use this option when there are multiple solvents. Defaults for pair parameters 1 2 Pair parameters default to zero Solvent/solute pair parameters default to water parameters. Water/solute pair parameters default to zero (default for HLRELELC) Default water parameters to 8, -4. Default solvent/solute parameters to 10, -2 (default for HLRENRTL) Solvent/solvent binary parameter values obtained from: 0 1 Scalar GMELCA, GMELCB and GMELCM (default) Vector NRTL(8) Mixture density model 0 1 Rackett equation with Campbell-Thodos modification Quadratic mixing rule for molecular components (mole basis) Enthalpy calculation method 0 1 Electrolyte NRTL Enthalpy (default for HIG2ELC) Helgeson method (default for HIG2HG) Steam table for liquid enthalpy of water 0 1 Use steam table for liquid enthalpy of water (default) Use specified EOS model Vapor phase equation-of-state for liquid enthalpy of HF 0 1 Use specified EOS model (default) HF EOS for hydrogen fluoride

HLRELNRT, HLRELELC 1

HIG2ELC, HIG2HG 1

DHLELC 1

Model Name Option Code 1 Value Descriptions Electrolyte NRTL Gibbs Energy (GMXENRTL, GAQELC, GMXELC, GMXENRHG) Defaults for pair parameters

261

Model Name

Option Code

Value Descriptions 1 2 Pair parameters default to zero Solvent/solute pair parameters default to water parameters. Water/solute pair parameters default to zero (default for ELC models) Default water parameters to 8, -4. Default solvent/solute parameters to 10, -2 (default for GMXENRTL and GMXENRHG) Vapor phase equation-of-state for liquid enthalpy and Gibbs energy of HF 0 1 Ideal gas EOS (default) HF EOS for hydrogen fluoride Solvent/solvent binary parameter values obtained from 0 1 Scalar GMELCA, GMELCB and GMELCM (default for ELC models) Vector NRTL(8) (default for GMXENRTL and GMXENRHG) Enthalpy calculation method 0 1 Electrolyte NRTL Enthalpy (default for ELC models) Helgeson method (default for GMXENRTL and GMXENRHG) Vapor phase enthalpy departure contribution to liquid enthalpy. Hliq = Hig + DHV - Hvap; this option indicates how DHV is calculated. 0 1 2 Do not calculate (DHV=0) (default) Calculate using Redlich-Kwong equation of state Calculate using Hayden-O'Connell equation of state Method for handling Henry components and multiple solvents 0 Pure liquid enthalpy calculated by aqueous infinite dilution heat capacity; only water as solvent Pure liquid enthalpy for Henry components calculated using Henry's law; use this option when there are multiple solvents. Defaults for pair parameters 1 2 Pair parameters default to zero Solvent/solute pair parameters default to water parameters. Water/solute pair parameters default to zero (default for GLRELELC) Default water parameters to 8, -4. Default solvent/solute parameters to 10, -2 (default for GLRENRTL) Solvent/solvent binary parameter values obtained from:

GLRELNRT, GLRELELC 1

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Model Name

Option Code

Value Descriptions 0 1 Scalar GMELCA, GMELCB and GMELCM (default) Vector NRTL(8) Mixture density model 0 1 Rackett equation with Campbell-Thodos modification Quadratic mixing rule for molecular components (mole basis) Enthalpy calculation method 0 1 Electrolyte NRTL Enthalpy (default for GIG2ELC) Helgeson method (default for GIG2HG)

GIG2ELC, GIG2HG 1

Model Name VL2QUAD Option Code 1 Value Descriptions 0 1 2 VAQCLK 1 0 1 0 1 Use normal pure component liquid volume model for all components (default) Use steam tables for water Use mole basis composition (default) Use mass basis composition Use Clarke model Use liquid volume quadratic mixing rule

263

Index

A Activity coefficient models 71 list of property models 71 Andrade/DIPPR viscosity model 191 Antoine/Wagner vapor pressure model 131 API 1997 Liquid Viscosity 195 API model 143, 195, 233 liquid viscosity 195 liquid volume 143 surface tension 233 API Sour model 136 Applications 76 metallurgical 76 Aqueous infinite dilution heat capacity model 160 Aspen Liquid Mixture Viscosity 196 model 196 Aspen polynomial equation 157 B Barin equations thermodynamic property model 174 Benedict-Webb-Rubin-Starling 17 property model 17 Braun K-10 model 136 Brelvi-O'Connell model 144 Bromley-Pitzer activity coefficient model 71 BWR-Lee-Starling property model 16 C Cavett thermodynamic property model 173 Chao-Seader fugacity model 137 Chapman-Enskog 197, 200, 226, 227

Brokaw/DIPPR viscosity model 197 Brokaw-Wilke mixing rule viscosity model 200 Wilke-Lee (binary) diffusion model 226 Wilke-Lee (mixture) diffusion model 227 Chien-Null activity coefficient model 74 Chung-Lee-Starling model 202, 204, 214 low pressure vapor viscosity 202 thermal conductivity 214 viscosity 204 Clarke electrolyte liquid volume model 145 Clausius-Clapeyron equation for heat of vaporization 142 Coal property models 241 Constant activity coefficient model 76 COSMO-SAC solvation model 76 COSTALD liquid volume model 147 Criss-Cobble aqueous infinite dilution ionic heat capacity model 161 D Dawson-Khoury-Kobayashi diffusion model 228 binary 228 mixture 228 DCOALIGT coal density model 250 Dean-Stiel pressure correction viscosity model 206 Debye-Huckel volume model 149 DGHARIGT char density model 250 Diffusivity models list 226 DIPPR 7 equations 7

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Index

DIPPR model 140, 150, 165, 191, 197, 217, 221, 233 heat of vaporization 140 ideal gas heat capacity 165 liquid surface tension 233 liquid thermal conductivity 217 liquid volume 150 surface tension 233 vapor thermal conductivity 221 vapor viscosity 197 viscosity 191, 197 DIPPR/IK-CAPE model 161 liquid heat capacity 161 DNSTYGEN nonconventional component density model 240 E Electrolyte models 145, 176, 178, 207, 216, 229, 237 Clarke liquid volume 145 electrolyte NRTL enthalpy 176 Gibbs energy 178 Jones-Dole viscosity 207 Nernst-Hartley diffusion 229 Onsager-Samaras surface tension 237 Riedel thermal conductivity 216 Electrolyte NRTL 79, 176, 178 activity coefficient model 79 enthalpy thermodynamic property model 176 Gibbs energy thermodynamic property model 178 eNRTL-SAC activity coefficient model 92 Enthalpies model based on different reference states 180 Enthalpy and density models for coal and char 241 ENTHGEN nonconventional component heat capacity model 240 Equation-of-state 14 property models 14 extrapolation 9 F Fugacity models list 131

G General models for nonconventional components 239, 240, 244 coal model for enthalpy 244 density polynomial model 240 enthalpy and density models list 239 heat capacity polynomial model 240 Grayson-Streed fugacity model 137 Group contribution activity coefficient models 121, 123, 124 Dortmund-modified UNIFAC 123 Lyngby-modified UNIFAC 124 UNIFAC 121 H Hakim-Steinberg-Stiel/DIPPR surface tension 233 Hansen solubility parameter model 97 Hayden-O'Connell 20 property model 20 HCOALGEN general coal model for enthalpy 244 Heat capacity models list 160 Heat of vaporization 139 model 139 Helgeson thermodynamic property model 184 Henry's constant solubility correlation model 171 HF equation of state 22 property model 22 Huron-Vidal mixing rules 64 I IAPS models for water 206, 215, 233 surface tension 233 thermal conductivity 215 viscosity 206 Ideal gas law 26 property model 26 Ideal gas/DIPPR heat capacity model 165 Ideal liquid activity coefficient model 98 IGT density model for 250

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265

char 250 coal 250 J Jones-Dole electrolyte correction viscosity model 207 K Kent-Eisenberg fugacity model 138 L Lee-Kesler Plcker property model 28 Lee-Kesler property model 26 Letsou-Stiel viscosity model 209 Li mixing rule thermal conductivity model 216 Liquid Constant Molar Volume Model 150 Liquid enthalpy 179 thermodynamic property model 179 Lucas vapor viscosity model 209 M Mathias alpha function 58 Mathias-Copeman alpha function 54, 58 Maxwell-Bonnell vapor pressure model 139 MHV2 mixing rules 66 Modified MacLeod-Sugden surface tension model 238 Modified Rackett model for molar volume 156 Molar volume and density models list 143 N Nernst-Hartley electrolyte diffusion model 229 Nonconventional solid property models 239 density 239 enthalpy 239 list of 239 Nothnagel 30 property model 30 NRTL 79

property model 79 NRTL-SAC 100 Using 104 O Onsager-Samaras electrolyte surface tension model 237 option codes activity coefficient models 253 enthalpy models 260 equation of state models 255 gibbs energy models 261 soave-redlich-kwong models 258 transport property models 252 P Peng-Robinson 32, 34, 36, 54 alpha functions 54 MHV2 property model 36 property model 34 Wong-Sandler property model 36 Physical properties 11, 14 models 11, 14 Pitzer activity coefficient model 105 Polynomial activity coefficient model 117 PPDS Heat of Vaporization Equation 141 PPDS Liquid Heat Capacity 163 Predictive Soave-Redlich-KwongGmehling mixing rules 67 Predictive SRK property model (PSRK) 36 Property models 5, 11, 14 equation-of-state list 14 list of 5 thermodynamic list 11 PSRK 36 property model 36 R Rackett mixture liquid volume model 155 Rackett/DIPPR pure component liquid volume model 150 Redlich-Kister activity coefficient model 118 Redlich-Kwong 37, 58 alpha function 58 property model 37

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Index

Redlich-Kwong-Aspen property model 37 Redlich-Kwong-Soave 40, 42, 44, 58 alpha function equations 58 alpha function list 58 Boston-Mathias property model 40 MHV2 property model 42 Soave-Redlich-Kwong property model 44 Wong-Sandler property model 42 Redlich-Kwong-Soave property model 38 Riedel electrolyte correction thermal conductivity model 216 S Sato-Riedel/DIPPR thermal conductivity model 217 Scatchard-Hildebrand activity coefficient model 119 Schwartzentruber-Renon property model 42 Soave-Redlich-Kwong property model 44 Solid Antoine vapor pressure models 139 Solid Thermal Conductivity Polynomial 220 Solids polynomial heat capacity model 168 Solubility correlation models 170 list 170 SRK-Kabadi-Danner property model 46 SRK-ML property model 48 Standard Peng-Robinson property model 34 Standard Redlich-Kwong-Soave property model 38 Steam tables 15, 29 NBS/NRC 29 property models 15 STEAMNBS property method 29 Stiel-Thodos pressure correction thermal conductivity model 223 Stiel-Thodos/DIPPR thermal conductivity model 221 Surface tension 232, 238

mixtures 232 models list 232 Modified MacLeod-Sugden 238 T Thermal conductivity 213, 220 models list 213 solids 220 thermo switch 7 Thermodynamic property 11, 173 list of additional models 173 models list 11 Three-suffix Margules activity coefficient model 120 THRSWT 7 Transport property 188 models list 188 transport switch 7 TRAPP 211, 224 thermal conductivity model 224 viscosity model 211 TRNSWT 7 Twu Liquid Viscosity 211 U UNIFAC 121, 123, 124 activity coefficient model 121 Dortmund modified activity coefficient model 123 Lyngby modified activity coefficient model 124 UNIQUAC 125 activity coefficient model 125 Units for Temperature-Dependent Properties 6 V Van Laar activity coefficient model 126 Vapor pressure model list 131 Viscosity 190 models 190 W Wagner Interaction Parameter activity coefficient model 127 Wagner vapor pressure model 131 Wassiljewa-Mason-Saxena mixing rule for thermal conductivity 225

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267

Water solubility model 172 Watson equation for heat of vaporization 140 Wilke-Chang diffusion model 230, 231 binary 230 mixture 231 WILS-GLR property method 180 WILS-LR property method 180 Wilson (liquid molar volume) activity coefficient model 129 Wilson activity coefficient model 128 Wong-Sandler mixing rules 69

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Index

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