Aspen Polymers Vol2 V7 Tutorial

Aspen Polymers
User Guide Volume 2: Physical Property Methods & Models
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Version Number: V7.0 July 2008

Copyright (c) 2008 by Aspen Technology, Inc. All rights reserved. Aspen Polymers, Aspen Custom Modeler, Aspen Dynamics, Aspen Plus, Aspen Properties, aspenONE, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered trademarks of Aspen Technology, Inc., Burlington, MA. All other brand and product names are trademarks or registered trademarks of their respective companies. This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of the software and the application of the results obtained. Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION, ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE. 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
Contents
Introducing Aspen Polymers ...................................................................................1 About This Documentation Set ......................................................................... 1 Related Documentation ................................................................................... 2 Technical Support .......................................................................................... 3 1 Thermodynamic Properties of Polymer Systems..................................................5 Properties of Interest in Process Simulation ....................................................... 5 Properties for Equilibria, Mass and Energy Balances................................... 6 Properties for Detailed Equipment Design ................................................ 6 Important Properties for Modeling........................................................... 6 Differences Between Polymers and Non-polymers ............................................... 7 Modeling Phase Equilibria in Polymer-Containing Mixtures .................................... 9 Vapor-Liquid Equilibria in Polymer Solutions ............................................. 9 Liquid-Liquid Equilibria in Polymer Solutions ............................................11 Polymer Fractionation ..........................................................................12 Modeling Other Thermophysical Properties of Polymers.......................................12 Available Property Models...............................................................................13 Equation-of-State Models .....................................................................14 Liquid Activity Coefficient Models ...........................................................15 Other Thermophysical Models ...............................................................15 Available Property Methods.............................................................................16 Thermodynamic Data for Polymer Systems .......................................................19 Specifying Physical Properties .........................................................................19 Selecting Physical Property Methods.......................................................19 Creating Customized Physical Property Methods.......................................20 Entering Parameters for a Physical Property Model ...................................20 Entering a Physical Property Parameter Estimation Method........................21 Entering Molecular Structure for a Physical Property Estimation .................22 Entering Data for Physical Properties Parameter Optimization ....................23 References ...................................................................................................23 2 Equation-of-State Models ..................................................................................27 About Equation-of-State Models ......................................................................27 Phase Equilibria Calculated from EOS Models.....................................................29 Vapor-Liquid Equilibria in Polymer Systems .............................................30 Liquid-Liquid Equilibria in Polymer Systems .............................................30 Other Thermodynamic Properties Calculated from EOS Models.............................30 Physical Properties Related to EOS Models in Aspen Polymers ..............................32 Sanchez-Lacombe EOS Model .........................................................................34 Pure Fluids .........................................................................................34 Fluid Mixtures Containing Homopolymers ................................................36 Extension to Copolymer Systems...........................................................37
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iii
Sanchez-Lacombe EOS Model Parameters ...............................................40 Specifying the Sanchez-Lacombe EOS Model ...........................................42 Polymer SRK EOS Model.................................................................................42 Soave-Redlich-Kwong EOS ...................................................................43 Polymer SRK EOS Model Parameters ......................................................45 Specifying the Polymer SRK EOS Model ..................................................47 SAFT EOS Model ...........................................................................................47 Pure Fluids .........................................................................................47 Extension to Fluid Mixtures ...................................................................52 Application of SAFT..............................................................................53 Extension to Copolymer Systems...........................................................55 SAFT EOS Model Parameters .................................................................57 Specifying the SAFT EOS Model .............................................................59 PC-SAFT EOS Model.......................................................................................59 Sample Calculation Results ...................................................................60 Application of PC-SAFT.........................................................................62 Extension to Copolymer Systems...........................................................63 PC-SAFT EOS Model Parameters ............................................................65 Specifying the PC-SAFT EOS Model ........................................................66 Copolymer PC-SAFT EOS Model .......................................................................67 Description of Copolymer PC-SAFT.........................................................67 Copolymer PC-SAFT EOS Model Parameters ............................................76 Option Codes for PC-SAFT ....................................................................78 Sample Calculation Results ...................................................................79 Specifying the Copolymer PC-SAFT EOS Model ........................................82 References ...................................................................................................83 3 Activity Coefficient Models ................................................................................87 About Activity Coefficient Models .....................................................................87 Phase Equilibria Calculated from Activity Coefficient Models.................................88 Vapor-Liquid Equilibria in Polymer Systems .............................................88 Liquid-Liquid Equilibria in Polymer Systems .............................................90 Other Thermodynamic Properties Calculated from Activity Coefficient Models .........90 Mixture Liquid Molar Volume Calculations .........................................................92 Related Physical Properties in Aspen Polymers...................................................93 Flory-Huggins Activity Coefficient Model ...........................................................94 Flory-Huggins Model Parameters ...........................................................97 Specifying the Flory-Huggins Model........................................................98 Polymer NRTL Activity Coefficient Model ...........................................................98 Polymer NRTL Model ............................................................................99 NRTL Model Parameters ..................................................................... 102 Specifying the Polymer NRTL Model ..................................................... 103 Electrolyte-Polymer NRTL Activity Coefficient Model ......................................... 103 Long-Range Interaction Contribution .................................................... 105 Local Interaction Contribution ............................................................. 107 Electrolyte-Polymer NRTL Model Parameters.......................................... 111 Specifying the Electrolyte-Polymer NRTL Model...................................... 114 Polymer UNIFAC Activity Coefficient Model ...................................................... 114 Polymer UNIFAC Model Parameters ...................................................... 117 Specifying the Polymer UNIFAC Model .................................................. 117 Polymer UNIFAC Free Volume Activity Coefficient Model.................................... 117 Polymer UNIFAC-FV Model Parameters ................................................. 119
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Contents
Specifying the Polymer UNIFAC- FV Model ............................................ 119 References ................................................................................................. 119 4 Thermophysical Properties of Polymers ..........................................................121 About Thermophysical Properties................................................................... 121 Aspen Ideal Gas Property Model .................................................................... 123 Ideal Gas Enthalpy of Polymers ........................................................... 124 Ideal Gas Gibbs Free Energy of Polymers .............................................. 124 Aspen Ideal Gas Model Parameters ...................................................... 125 Van Krevelen Liquid Property Models.............................................................. 127 Liquid Enthalpy of Polymers ................................................................ 128 Liquid Gibbs Free Energy of Polymers................................................... 130 Heat Capacity of Polymers .................................................................. 131 Liquid Enthalpy and Gibbs Free Energy Model Parameters ....................... 131 Van Krevelen Liquid Molar Volume Model ........................................................ 136 Van Krevelen Liquid Molar Volume Model Parameters ............................. 137 Tait Liquid Molar Volume Model ..................................................................... 140 Tait Model Parameters ....................................................................... 141 Van Krevelen Glass Transition Temperature Correlation .................................... 141 Glass Transition Correlation Parameters................................................ 142 Van Krevelen Melt Transition Temperature Correlation...................................... 142 Melt Transition Correlation Parameters ................................................. 143 Van Krevelen Solid Property Models ............................................................... 143 Solid Enthalpy of Polymers ................................................................. 143 Solid Gibbs Free Energy of Polymers .................................................... 144 Solid Enthalpy and Gibbs Free Energy Model Parameters........................ 144 Solid Molar Volume of Polymers........................................................... 144 Solid Molar Volume Model Parameters .................................................. 145 Van Krevelen Group Contribution Methods ...................................................... 145 Polymer Property Model Parameter Regression ................................................ 146 Polymer Enthalpy Calculation Routes with Activity Coefficient Models .................. 147 References ................................................................................................. 150 5 Polymer Viscosity Models ................................................................................151 About Polymer Viscosity Models..................................................................... 151 Modified Mark-Houwink/van Krevelen Model.................................................... 152 Modified Mark-Houwink Model Parameters ............................................ 154 Specifying the MMH Model .................................................................. 158 Aspen Polymer Mixture Viscosity Model .......................................................... 158 Multicomponent System ..................................................................... 158 Aspen Polymer Mixture Viscosity Model Parameters ................................ 159 Specifying the Aspen Polymer Mixture Viscosity Model ............................ 161 Van Krevelen Polymer Solution Viscosity Model................................................ 161 Quasi-Binary System ......................................................................... 161 Properties of Pseudo-Components........................................................ 162 Van Krevelen Polymer Solution Viscosity Model Parameters ..................... 163 Polymer Solution Viscosity Estimation .................................................. 164 Polymer Solution Glass Transition Temperature ..................................... 165 Polymer Viscosity at Mixture Glass Transition Temperature...................... 166 True Solvent Dilution Effect ................................................................ 167 Specifying the van Krevelen Polymer Solution Viscosity Model ................. 167 Eyring-NRTL Mixture Viscosity Model.............................................................. 167
Multicomponent System ..................................................................... 168 Eyring-NRTL Mixture Viscosity Model Parameters ................................... 169 Specifying the Eyring-NRTL Mixture Viscosity Model ............................... 169 Polymer Viscosity Routes in Aspen Polymers ................................................... 170 References ................................................................................................. 170 6 Polymer Thermal Conductivity Models.............................................................171 About Thermal Conductivity Models ............................................................... 171 Modified van Krevelen Thermal Conductivity Model .......................................... 173 Modified van Krevelen Thermal Conductivity Model Parameters ................ 174 Van Krevelen Group Contribution for Segments ..................................... 176 Specifying the Modified van Krevelen Thermal Conductivity Model ............ 179 Aspen Polymer Mixture Thermal Conductivity Model ......................................... 180 Specifying the Aspen Polymer Mixture Thermal Conductivity Model ........... 180 Polymer Thermal Conductivity Routes in Aspen Polymers .................................. 181 References ................................................................................................. 181 A Physical Property Methods ..............................................................................183 POLYFH: Flory-Huggins Property Method ........................................................ 183 POLYNRTL: Polymer Non-Random Two-Liquid Property Method .......................... 185 POLYUF: Polymer UNIFAC Property Method ..................................................... 187 POLYUFV: Polymer UNIFAC Free Volume Property Method ................................. 189 PNRTL-IG: Polymer NRTL with Ideal Gas Law Property Method .......................... 191 POLYSL: Sanchez-Lacombe Equation-of-State Property Method ......................... 193 POLYSRK: Polymer Soave-Redlich-Kwong Equation-of-State Property Method ..... 195 POLYSAFT: Statistical Associating Fluid Theory (SAFT) Equation-of-State Property Method ...................................................................................................... 196 POLYPCSF: Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) Equationof-State Property Method ............................................................................. 198 PC-SAFT: Copolymer PC-SAFT Equation-of-State Property Method..................... 200 B Van Krevelen Functional Groups .....................................................................202 Calculating Segment Properties From Functional Groups ................................... 202 Heat Capacity (Liquid or Crystalline) .................................................... 202 Molar Volume (Liquid, Crystalline, or Glassy)......................................... 203 Enthalpy, Entropy and Gibbs Energy of Formation .................................. 203 Glass Transition Temperature.............................................................. 204 Melt Transition Temperature ............................................................... 204 Viscosity Temperature Gradient........................................................... 204 Rao Wave Function ............................................................................ 204 Van Krevelen Functional Group Parameters ..................................................... 205 Bifunctional Hydrocarbon Groups ......................................................... 205 Bifunctional Oxygen-containing Groups................................................. 208 Bifunctional Nitrogen-containing Groups ............................................... 210 Bifunctional Nitrogen- and Oxygen-containing Groups............................. 211 Bifunctional Sulfur-containing Groups................................................... 212 Bifunctional Halogen-containing Groups ................................................ 212
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Contents
C Tait Model Coefficients ....................................................................................215 D Mass Based Property Parameters....................................................................217 E Equation-of-State Parameters .........................................................................218 Sanchez-Lacombe Unary Parameters ............................................................. 218 POLYSL Polymer Parameters ............................................................... 218 POLYSL Monomer and Solvent Polymers ............................................... 219 SAFT Unary Parameters ............................................................................... 220 POLYSAFT Parameters........................................................................ 220 F Input Language Reference ..............................................................................223 Specifying Physical Property Inputs................................................................ 223 Specifying Property Methods ............................................................... 223 Specifying Property Data .................................................................... 225 Estimating Property Parameters .......................................................... 227 Index ..................................................................................................................228
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Introducing Aspen Polymers
Aspen Polymers (formerly known as Aspen Polymers Plus) is a generalpurpose process modeling system for the simulation of polymer manufacturing processes. The modeling system includes modules for the estimation of thermophysical properties, and for performing polymerization kinetic calculations and associated mass and energy balances. Also included in Aspen Polymers are modules for: Characterizing polymer molecular structure Calculating rheological and mechanical properties Tracking these properties throughout a flowsheet
There are also many additional features that permit the simulation of the entire manufacturing processes.
About This Documentation Set

The Aspen Polymers User Guide is divided into two volumes. Each volume documents features unique to Aspen Polymers. This User Guide assumes prior knowledge of basic Aspen Plus capabilities or user access to the Aspen Plus documentation set. If you are using Aspen Polymers with Aspen Dynamics, please refer to the Aspen Dynamics documentation set. Volume 1 provides an introduction to the use of modeling for polymer processes and discusses specific Aspen Polymers capabilities. Topics include: Polymer manufacturing process overview - describes the basics of polymer process modeling and the steps involved in defining a model in Aspen Polymers. Polymer structural characterization - describes the methods used for characterizing components. Included are the methodologies for calculating distributions and features for tracking end-use properties. Polymerization reactions - describes the polymerization kinetic models, including: step-growth, free-radical, emulsion, Ziegler-Natta, ionic, and segment based. An overview of the various categories of polymerization kinetic schemes is given. Steady-state flowsheeting - provides an overview of capabilities used in constructing a polymer process flowsheet model. For example, the unit
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operation models, data fitting tools, and analysis tools, such as sensitivity studies. Run-time environment - covers issues concerning the run-time environment including configuration and troubleshooting tips.
Volume 2 describes methodologies for tracking chemical component properties, physical properties, and phase equilibria. It covers the physical property methods and models available in Aspen Polymers. Topics include: Thermodynamic properties of polymer systems describes polymer thermodynamic properties, their importance to process modeling, and available property methods and models. Equation-of-state (EOS) models provides an overview of the properties calculated from EOS models and describes available models, including: Sanchez-Lacombe, polymer SRK, SAFT, and PC-SAFT. Activity coefficient models provides an overview of the properties calculated from activity coefficient models and describes available models, including: Flory-Huggins, polymer NRTL, electrolyte-polymer NRTL, polymer UNIFAC. Thermophysical properties of polymers provides and overview of the thermophysical properties exhibited by polymers and describes available models, including: Aspen ideal gas, Tait liquid molar volume, pure component liquid enthalpy, and Van Krevelen liquid and solid, melt and glass transition temperature correlations, and group contribution methods. Polymer viscosity models describes polymer viscosity model implementation and available models, including: modified MarkHouwink/van Krevelen, Aspen polymer mixture, and van Krevelen polymer solution. Polymer thermal conductivity models - describes thermal conductivity model implementation and available models, including: modified van Krevelen and Aspen polymer mixture.
Related Documentation
A volume devoted to simulation and application examples for Aspen Polymers is provided as a complement to this User Guide. These examples are designed to give you an overall understanding of the steps involved in using Aspen Polymers to model specific systems. In addition to this document, a number of other documents are provided to help you learn and use Aspen Polymers, Aspen Plus, and Aspen Dynamics applications. The documentation set consists of the following:
Installation Guides
Aspen Engineering Suite Installation Guide
Aspen Polymers Guides

Aspen Polymers User Guide, Volume 1
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Aspen Polymers User Guide, Volume 2 (Physical Property Methods & Models) Aspen Polymers Examples & Applications Case Book
Aspen Plus Guides

Aspen Plus User Guide Aspen Plus Getting Started Guides
Aspen Physical Property System Guides

Aspen Physical Property System Physical Property Methods and Models Aspen Physical Property System Physical Property Data
Aspen Dynamics Guides

Aspen Dynamics Examples Aspen Dynamics User Guide Aspen Dynamics Reference Guide
Help
Aspen Polymers has a complete system of online help and context-sensitive prompts. The help system contains both context-sensitive help and reference information. For more information about using Aspen Polymers help, see the Aspen Plus User Guide.
Technical Support
AspenTech customers with a valid license and software maintenance agreement can register to access the online AspenTech Support Center at: http://support.aspentech.com This Web support site allows you to: Access current product documentation Search for tech tips, solutions and frequently asked questions (FAQs) Search for and download application examples Search for and download service packs and product updates Submit and track technical issues Send suggestions Report product defects Review lists of known deficiencies and defects
Registered users can also subscribe to our Technical Support e-Bulletins. These e-Bulletins are used to alert users to important technical support information such as: Technical advisories
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Product updates and releases
Customer support is also available by phone, fax, and email. The most up-todate contact information is available at the AspenTech Support Center at http://support.aspentech.com.
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1 Thermodynamic Properties of Polymer Systems
This chapter discusses thermodynamic properties of polymer systems. It summarizes the importance of these properties in process modeling and outlines the differences between thermodynamic properties of polymers and those of small molecules. Topics covered include: Properties of Interest in Process Simulation, 5 Differences Between Polymers and Non-polymers, 7 Modeling Phase Equilibria in Polymer-Containing Mixtures, 9 Modeling Other Thermophysical Properties of Polymers, 12 Available Property Models, 13 Available Property Methods, 16 Thermodynamic Data for Polymer Systems, 19 Specifying Physical Properties, 19
Properties of Interest in Process Simulation

Steady-state or dynamic process simulation is, in most instances, a form of performing simultaneous mass and energy balances. Rigorous modeling of mass and energy balances requires the calculation of phase and chemical equilibria and other thermophysical properties. In addition to the steps governed by equilibrium, there are rate-limited chemical reactions, and mass and heat transfer limited unit operations in a given process. Therefore, a fundamental understanding of the reaction kinetics and transport phenomena involved is a prerequisite for its modeling. In process modeling, in addition to the properties needed for performing mass and energy balances and evaluating time dependent characteristics, detailed equipment design requires the calculation of additional thermophysical properties for equipment sizing. For detailed discussion of all these issues, please refer to references available in the literature (Bicerano, 1993; Bokis et
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al., 1999; Chen & Mathias, 2002; Poling et al., 2001; Prausnitz et al., 1986; Reid et al., 1987; Sandler, 1988, 1994; Van Krevelen, 1990; Van Ness, 1964; Walas, 1985).
Properties for Equilibria, Mass and Energy Balances

Often chemical and phase equilibria play the most fundamental role in mass and energy balance calculations. There are two ways of calculating chemical and phase equilibria. The classical route is to evaluate fugacities or activities of the components in the different phases, and find, at given conditions, the compositions that obey the equilibrium requirement of equality of fugacities for all components in all phases. Fugacities or activities are quantities related to Gibbs free energy, and often it is more convenient to evaluate a fugacity coefficient or an activity coefficient rather than the fugacity and activity directly. Chapter 2 and Chapter 3 provide details on the calculation of these quantities. Another method of calculating chemical and phase equilibria consists of searching for the minimum total of the mixture Gibbs free energies for the different phases involved. This is the Gibbs free energy minimization. This technique can be used to calculate simultaneous phase and chemical equilibria. Gibbs free energy minimization is discussed in Aspen Physical Property System Physical Property Methods and Models. In performing energy balances, the interest is in changes in the energy content of a system, a section of a plant or a single unit, in a process. Depending upon the nature of the system, either an enthalpy H (usually for flow systems such as heat exchangers, flash towers in which pressure changes are modest) or an internal energy U (for systems such as closed batch reactors) balance is performed. These balances are often expressed as heat duty of a unit, yet the data on substances are usually measured as constant pressure heat capacity (H / T ) p , or as constant volume heat capacity (U T )V where T is the temperature, p is the pressure, and V is the volume. Consequently, it is necessary to calculate temperature derivatives of enthalpy and internal energy.
Properties for Detailed Equipment Design

Mixture density is required for equipment sizing. To calculate the efficiency of pumps and turbines, entropy is needed. Entropy is usually derived from enthalpy and Gibbs free energy. For detailed heat-exchanger design, viscosity and thermal conductivity of the mixture are needed. In detailed rating or design of column trays or packing, surface tension may be needed in addition to viscosity. Finally, diffusion coefficients are used to calculate mass transfer rates.
Important Properties for Modeling

The most important properties for process simulation are:
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Thermodynamic properties Fugacity (or thermodynamic potential) Gibbs free energy Internal energy, or Enthalpy, or Entropy Density
Transport properties Viscosity Thermal conductivity Surface tension Diffusivity
CV
CP
Differences Between Polymers and Non-polymers

The word polymer derives from the Greek words poly many and meros part. A polymer consists of a large number of segments (repeating units of identical structure). Because of their structure, polymers exhibit thermodynamic properties significantly different than those of standard molecules (solvents, monomers, other additive solutes), consequently different property models are required to describe their behavior. For example, polymers being orders of magnitude larger molecules, have substantially more spatial conformations than the small molecules. This affects equilibrium properties such as the entropy of mixing, as well as nonequilibrium properties like viscosity. Unlike conventional molecules, polar interactions (between dipoles, quadrapoles etc., also called London-van-derWaals or dispersion forces) among the segments of a single molecule play a role in thermodynamic behavior of polymers and their mixtures. Moreover, when polymer molecules interact with conventional small molecules, due to their large size, only a fraction of segments of the polymer molecule may be involved rather than the whole molecule. All these segment-segment and segment-conventional molecule interactions are influenced by the spatial conformations mentioned above. Besides the different spatial conformations a single polymer molecule can have, they also exhibit chain length distributions, isomerism for each chain length due to distributions of branching and co-monomer composition, and stereo chemical configuration of segments in a chain. Detailed discussion of these issues is beyond the scope of this document. However, excellent sources are available in the literature (Bicerano 1993; Brandup & Immergut, 1989; Cotterman & Prausnitz, 1991; Folie & Radosz, 1995; Fried, 1995; Ko et al., 1991; Kroschwitz, 1990; Sanchez, 1992; Van Krevelen, 1990). A simplified overview is presented here from a modeling point of view.
Polymer Polydispersity
When modeling polymer phase equilibrium, one must take into account the basic polymer characteristics briefly mentioned above. First, no polymer is pure. Rather, a polymer is a mixture of components with differing chain
length, chain composition, and degree of branching. In other words, polymers are polydisperse. For the purposes of property calculations, this makes a polymer a mixture of an almost infinite number of components. In the calculation of phase equilibria of polymer solutions, some physical properties of the solution, such as vapor pressure depression, can be related to average polymer structure properties. On the other hand, physical properties of the polymer itself, for example distribution of the polymer over different phases or fractionation, cannot be related to the average polymer structure properties. It is also impossible to take each individual component into account; therefore, compromise approximations are made to incorporate information about polydispersity in polymer process modeling (Behme et al., 2003). Long-chain polymers have very low vapor pressures and are considered nonvolatile. Short-chain polymers may be volatile, and these species can be treated as oligomers as discussed later in this section. The nonvolatile nature of polymers must be taken into account in developing models to describe polymer phase behavior, or when a model developed for conventional molecules is extended for use with polymers. Polymers cannot exhibit a critical point either, since they decompose before they reach their critical temperatures. In the pure condensed phase, polymers can be a liquid-like melt, amorphous solid, or a semi-crystalline solid. Due to their possible semi-crystalline nature in the solid state, polymeric materials may exhibit two major types of transition temperatures from solid to liquid. A completely amorphous solid is characterized by glass transition temperature, Tg , at which it turns into melt from amorphous solid. A semi-crystalline polymer is not completely crystalline, but still contains unordered amorphous regions in its structure. Such a polymer, upon heating, exhibits both a Tg and a melting temperature, Tm , at which phase transition of crystalline portion of the polymer to melt occurs. Thus, a semi-crystalline polymer may be treated as a glassy solid at temperatures below Tg , a rubbery solid between Tg and
Tm , and a melt above Tm .
The knowledge of state of aggregation of polymer in the condensed phase is important because all thermophysical characteristics change from one condensed state to another. For example, monomers and solvents are soluble in melt and in amorphous solid polymer, but crystalline areas are inert and do not participate in phase equilibrium. Other thermodynamic properties such as heat capacity, density, etc. are also significantly different in each phase. Another very important characteristic of the polymers is their viscoelastic nature, which affects their transport properties enormously. The models to characterize viscosity of polymers or diffusion of other molecules in polymers must, therefore, be unique. Oligomers In process modeling, we also deal with oligomers. An oligomer is a substance that contains only a few monomeric segments in its structure, and its thermophysical properties are somewhere between a conventional molecule and a polymer. They can be considered like a heavy hydrocarbon molecule,
and they act like one. In most cases they can be simulated as a heavy conventional molecule. Aspen Polymers (formerly known as Aspen Polymers Plus) permits a substance to be defined as oligomer, apart from standard molecules and polymers.
Modeling Phase Equilibria in Polymer-Containing Mixtures

In modeling phase equilibrium of polymer mixtures, there are two broad categories of problems that are particularly important. The first is the solubility of monomers, other conventional molecules used as additives, and solvents in a condensed phase containing polymers. The second is the phase equilibrium when two polymer-containing condensed phases are in coexistence.
Vapor-Liquid Equilibria in Polymer Solutions

A good example of the first case is the devolatilization of monomers, solvents and other conventional additives from a polymer. The issue here is to determine the extent of solubility of conventional molecules in the polymer at a given temperature and pressure. The polymer may be a melt, an amorphous solid, or a semi-crystalline solid. An amorphous polymer is treated as a pseudo-liquid. If the polymer is semicrystalline, then one would compute overall solubility based on the solubility in the amorphous polymer and the fraction of amorphous polymer in the total polymer phase. This problem is somewhat similar to a vapor-liquid equilibrium (VLE) of conventional systems. The thermodynamic model selected can be tested by investigating pressure-composition phase diagrams of polymer-solvent pairs at constant temperature. For example:
PIB-N-Pentane Binary System (Data from compilation of Wohlfarth, 1994)
Usually a flash algorithm is used to model the devolatilization process. Proven vapor-liquid equilibrium flash algorithms have been widely used for polymer systems. In these flash algorithms calculations can be done with a number of options such as specified temperature and pressure, temperature and vapor fraction (dew point or bubble point), pressure and vapor fraction, pressure and heat duty, and vapor fraction and heat duty. It is important to stress that in such calculations polymers are considered nonvolatile while solvents, monomers and oligomers are distributed between vapor and liquid phases. Another example in this category is modeling of a polymerization reaction carried out in a liquid solvent with monomer coming from the gas phase. It is important to know the solubility of the monomer gas in the reaction solution, as this quantity directly controls the polymerization reaction kinetics in the liquid phase. In such a case, the mixture may contain molecules of a conventional solvent, dissolved monomer, other additive molecules, and the polymer either as dissolved in solution or as a separate particle phase swollen with solvent, monomer and additive molecules. Interactions of various conventional molecules in the solution with the co-existing polymer molecules have direct effect on the solubility of the monomer gas in the solution. Again, the phase equilibrium problem can be considered as a VLE (polymer dissolved in solution) or as a vapor-liquid-liquid equilibrium (VLLE; polymer in a separate phase swollen with conventional molecules).
Liquid-Liquid Equilibria in Polymer Solutions

Liquid-liquid phase equilibrium (LLE)between two polymer containing phases is also important in modeling polymer processes. The overall thermodynamic behavior of two co-existing liquid phases is shown here:
LCST-UCST Behavior of Polymer Mixtures (Folie & Radosz, 1995)
In the figure, the space under the saddle is the region where liquid-liquid phase split occurs. Above that region, only a single homogeneous fluid phase exists. Various two-dimensional temperature-composition projections are also shown in the figure. In these projections, several phase behavior types common in polymer-solvent systems are indicated. For example, at certain pressures, polymer-solvent mixtures exhibit two distinctly different regions of immiscibility. These regions are characterized by the upper critical solution temperature (UCST) and the lower critical solution temperature (LCST). UCST characterizes the temperature below which a homogeneous liquid mixture splits into two distinct phases of different composition. This phase behavior is rather common, and it is observed in many kinds of mixtures of conventional molecules and polymers. LCST represents the temperature above which a formerly homogeneous liquid mixture splits into two separate liquid phases. This thermally induced phase separation phenomenon is observed in mixtures of conventional molecules only when strong polar interactions exist (such as aqueous solutions). However, for polymer-solvent mixtures the existence of a LCST is the rule, not the exception (Sanchez, 1992). In polymerization processes, especially those carried out at high pressures in the gas phase, such as LDPE production, it is important to estimate the boundaries of these regions of immiscibility. It is directly pertinent to modeling of reaction kinetics whether the reactive mixture remains a homogeneous fluid phase or splits into two liquid phases.
11
Polymer Fractionation
Another process where LLE behavior plays a role is polymer fractionation. A classical method of fractionating a polydisperse polymer is to dissolve the polymer completely in a 'good' solvent and then progressively add small amounts of a poor solvent (or antisolvent). Upon addition of the antisolvent, a second phase, primarily consisting of lowest-molecular weight polymers, will form. The system can be modeled as an LLE system. Existing liquid-liquid equilibrium and vapor-liquid-liquid equilibrium flash algorithms cannot be applied to solve these LLE systems with nonvolatile polymers, unless the polymers are treated as oligomers with 'some' volatility. These flash algorithms are based on solving a set of nonlinear algebraic equations derived from the isofugacity relationship for each individual component. Such an isofugacity relationship cannot be mathematically established for nonvolatile polymer components. In such cases, using the Gibbs free energy minimization technique usually offers a more robust way of estimating the number of existing phases and their compositions.
Modeling Other Thermophysical Properties of Polymers

Correlations for other important thermophysical properties of pure polymers such as heat capacity, density, and viscosity are essentially empirical in nature. Van Krevelen developed an excellent group contribution methodology to predict a wide variety of thermophysical properties for polymers, using polymer molecular structure, in terms of functional groups, and polymer compositions (Van Krevelen, 1990). These relations are basically applicable to random linear copolymers. Group contribution techniques cannot be applied to polymers containing exotic structural units, if no experimental data is available for estimating contributions for functional groups not studied previously. To overcome these limitations, Bicerano developed a new generation of empirical quantitative structure-property relationships in terms of topological variables (Bicerano, 1993). Correlations for predicting thermophysical properties of polymer mixtures are not well established. Typically, pure component properties are first estimated for polymers, monomers, and solvents by various techniques. Properties of polymer solutions are then calculated with mass fraction or segment-based molar fraction mixing rules. This methodology seems to work well for calorimetric properties and volumetric properties. On the other hand, different empirical mixing rules are needed for transport properties. This is because polymers are viscoelastic, while conventional components exhibit Newtonian behavior, which poses a challenge in developing mixing rules for viscosity of polymer-solvent mixtures.
Available Property Models

Aspen Polymers contains several key property models specifically developed for polymer systems. These models consist of two classes: Solution thermodynamic models for polymer phase equilibrium calculations (activity coefficient models and equations of state) Models for other thermophysical properties (molar volume, enthalpy and heat capacity, entropy, Gibbs free energy, and transport properties)
These models, which are described individually in later chapters, have been incorporated into several physical property methods. A summary of the available thermodynamic and transport property models is provided here:
Model Description
Enthalpy, Gibbs free energy, heat capacity, and density models Van Krevelen Models Tait Model Aspen Ideal Gas Property Model Transport property models Modified Mark-Houwink/Van Krevelen Model Aspen Polymer Mixture Viscosity Model Van Krevelen Polymer Solution Viscosity Model Eyring-NRTL Mixture Viscosity Model Modified van Krevelen Thermal Conductivity Model Aspen Polymer Mixture Thermal Conductivity Model Activity coefficient models Polymer NRTL Model Extends the non-random two liquid theory to polymer systems. It accounts for interactions with polymer segments and is well suited for copolymers Integrates the electrolyte NRTL model and the polymer NRTL model. It computes activity coefficients for polymers, solvents, and ionic species Represents non-ideality of polymer systems. Based on the wellknown model developed by Flory and Huggins Extends the UNIFAC group contribution method to polymer systems taking into account polymer segments. They are predictive models Calculates viscosity of polymers Correlates liquid viscosity of polymer solutions and mixtures from pure component liquid viscosity and mass fraction mixing rules Calculates liquid viscosity of polymer solutions Correlates liquid viscosity of polymer solutions and mixtures from pure component liquid viscosity and NRTL term to capture non-ideal mixing behavior Calculates thermal conductivity of polymers Uses the modified van Krevelen thermal conductivity model with existing Aspen Plus thermal conductivity models to calculate thermal conductivity of mixture containing polymers Calculates thermophysical properties of polymers using group contribution Calculates molar volume of polymers Extends the ideal gas model to calculate the ideal gas properties of polymers. It is used together with equations of state to calculate thermodynamic properties of polymer systems
Electrolyte-Polymer NRTL Model Flory-Huggins Model Polymer UNIFAC and Polymer UNIFAC-FV Models Equations of State
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Model Sanchez-Lacombe Polymer SRK SAFT PC-SAFT Copolymer PC-SAFT
Description Tailors the well-known equation of state model, based on the lattice theory, to polymer mixtures Extends the SRK equation of state to cover polymer mixtures Provides a rigorous thermodynamic model for polymer systems based on the perturbation theory of fluids Provides an improved SAFT model based on perturbation theory A complete PC-SAFT model applicable to complex fluids, including normal fluids, water and alcohols, polymers and copolymers, and their mixtures.
Phase equilibrium calculations are the most important aspect of thermodynamics. The basic relationship for every component in the vapor and liquid phases of a mixture at equilibrium is:
f iv = f il
Where:
(1.1)
fiv f il
= Fugacity of component i in the vapor phase = Fugacity of component i in the liquid phase
Similarly, the liquid-liquid equilibrium condition is:
f i l1 = f i l2
Where:
(1.2)
f i l1 f i l2
= Fugacity of component i in the liquid phase 1 = Fugacity of component i in the liquid phase 2
Applied thermodynamics provides two methods for representing the fugacities from the phase equilibrium relationship: equation-of-state models and liquid activity coefficient models.
Equation-of-State Models
In modeling polymer systems at high pressures, the activity coefficient models suffer from certain shortcomings. For example, most of them are applicable only to incompressible liquid solutions, and they fail to predict the LCST type phase behavior that necessitates pressure dependence in a model (Sanchez, 1992). To overcome these difficulties an equation of state (EOS) is needed. Another advantage of using an equation of state is the simultaneous calculation of enthalpies and phase densities along with phase equilibrium from the same model. The literature describes many polymer-specific equations-of-state. Currently, the most widely used EOS for polyolefin systems are the Sanchez-Lacombe EOS (Sanchez & Lacombe, 1976, 1978), Statistical Associating Fluid Theory EOS (SAFT) (Chapman et al., 1989; Folie & Radosz, 1995; Huang & Radosz,
1990, 1991; Xiong & Kiran, 1995), and Perturbed-Chain Statistical Associating Fluid Theory EOS (PC-SAFT) (Gross & Sadowski, 2001, 2002). In addition, well-known cubic equations-of-state for systems with small molecules are being extended for polymer solutions (Kontogeorgis et al., 1994; Orbey et al., 1998a, 1998b; Saraiva et al., 1996). Presently, Aspen Polymers offers Sanchez-Lacombe EOS, an extension of the Soave-RedlichKwong (SRK) cubic equation of state to polymer-solvent mixtures (Polymer SRK EOS), the SAFT EOS, and the PC-SAFT EOS. The Sanchez-Lacombe, SAFT, and PC-SAFT equations of state are polymer specific, whereas the polymer SRK model is an extension of a conventional cubic EOS to polymers. Polymer specific equations of state have the advantage of describing polymer components of the mixture more accurately. The Sanchez-Lacombe, SAFT, and PC-SAFT equations of state are implemented in Aspen Polymers for modeling systems containing homopolymers as well as copolymers. The details of the individual EOS models are given in Chapter 2.
Liquid Activity Coefficient Models

In general, the activity coefficient models are versatile and accommodate a high degree of solution nonideality into the model. On the other hand, when applied to VLE calculations, they can only be used for the liquid phase and another model (usually an equation of state) is needed for the vapor phase. They are used for the calculation of fugacity, enthalpy, entropy and Gibbs free energy but are rather cumbersome for evaluation of calorimetric and volumetric properties. Usually other empirical correlations are used in parallel for the calculations of densities when an activity coefficient model is used in phase equilibrium modeling. Many activity coefficient models can be used in polymer process modeling. Aspen Polymers offers the Flory-Huggins model (Flory, 1953), the NonRandom Two-Liquid Activity Coefficient model adopted to polymers (Chen, 1993), the Polymer UNIFAC model, and the UNIFAC free volume model (Oishi & Prausnitz, 1978). The two UNIFAC models are predictive while the FloryHuggins and Polymer-NRTL model are correlative. Between the correlative models, the Flory-Huggins model is only applicable to homopolymers because its parameter is polymer-specific. The Polymer-NRTL model is a segmentbased model that allows accurate representation of the effects of copolymer composition and polymer chain length. The details of the individual activity coefficient models are given in Chapter 3.
Other Thermophysical Models

Aspen Polymers offers models for the calculations of enthalpy, Gibbs free energy, entropy, molar volume (density), viscosity, and thermal conductivity of pure polymers. It also extends the existing Aspen Ideal Gas Property Model to cover polymers, oligomers, and segments. Van Krevelen (1990) physical property models are used to evaluate enthalpy, Gibbs free energy, and molar volume in both liquid and solid states, glass transition and melting point temperatures. For molar volume, another alternative is the Tait model (Danner & High, 1992).
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Aspen Polymers offers methods for estimation of zero-shear viscosity of polymer melts, for concentrated polymer solutions, and also for polymer solutions and mixtures over the entire range of composition. Melt viscosity is calculated using the modified Mark-Houwink/Van Krevelen model (Van Krevelen, 1990). Concentrated polymer solution viscosity is calculated using the van Krevelen polymer solution viscosity model. Liquid viscosity of polymer solutions and mixtures is correlated using the Aspen polymer viscosity mixture model (Song et al., 2003). Aspen Polymers offers a modified van Krevelen model to calculate thermal conductivity of polymers. Liquid thermal conductivity of polymer solutions and mixtures is calculated using the modified van Krevelen model for polymers with existing Aspen Plus models for non-polymer components. When an equation of state is used for calculation of enthalpy, entropy and Gibbs free energy, it provides only departure values from ideal gas behavior (departure functions). Therefore, in estimating these properties from an equation of state, the ideal gas contribution must be added to the departure functions obtained from the equation of state model. For this purpose, the ideal gas model already available in Aspen Plus for monomers and solvents was extended to polymers and oligomers and made available in Aspen Polymers.
Available Property Methods

Following the Aspen Physical Property System, the methods and models used to calculate thermodynamic and transport properties in Aspen Polymers are packaged in property methods. Each property method contains all the methods and models needed for a calculation. A unique combination of methods and models for calculating a property is called a route. For details on the Aspen Physical Property System, see the Aspen Physical Property System Physical Property Methods and Models documentation. You can select a property method from existing property methods in Aspen Polymers or create a custom-made property method by modifying an existing property method. The property methods already available in Aspen Polymers are listed here (Appendix A lists the entire physical property route structure for all polymer specific property methods):
Property method POLYFH Description Uses the Flory-Huggins model for solution thermodynamic property calculations and van Krevelen models for polymer thermophysical property calculations. The Soave-Redlich-Kwong equation-of-state is used to calculate vapor-phase properties of mixtures. Uses the polymer NRTL model for solution thermodynamic property calculations and van Krevelen models for polymer thermophysical property calculations. The Soave-Redlich-Kwong equation-of-state is used to calculate vapor-phase properties of mixtures.
POLYNRTL
Property method POLYUF
Description Uses the polymer UNIFAC model for solution thermodynamic property calculations and van Krevelen models for polymer thermophysical property calculations. The Soave-Redlich-Kwong equation-of-state is used to calculate vapor-phase properties of mixtures. Uses the polymer UNIFAC model with a free volume correction for solution thermodynamic property calculations and van Krevelen models for polymer thermophysical property calculations. The Soave-Redlich-Kwong equation-of-state is used to calculate vaporphase properties of mixtures. Uses the ideal-gas equation-of-state to calculate vapor-phase properties of mixtures. This is a modified version of the standard POLYNRTL property method. Uses the Sanchez-Lacombe equation of state model for thermodynamic property calculations. Uses an extension of the Soave-Redlich-Kwong equation of state to polymer systems, with the MHV1 mixing rules and the polymer NRTL excess Gibbs free energy model, for thermodynamic property calculations. Uses the statistical associating fluid theory (SAFT) equation of state for thermodynamic property calculations. Uses the perturbed-chain statistical associating fluid theory (PCSAFT) equation of state for thermodynamic property calculations. Uses the perturbed-chain statistical associating fluid theory (PCSAFT) equation of state for thermodynamic property calculations. The association term is included and no mixing rules are used for copolymers.
POLYUFV
PNRTL-IG
POLYSL POLYSRK
POLYSAFT POLYPCSF PC-SAFT
The following table describes the overall structure of the property methods in terms of the properties calculated for the vapor and liquid phases. Additionally, the models used for the property calculations are given.
Properties Calculated Vapor Departure functions, fugacity coefficient, molar volume Soave-Redlich-Kwong (All activity coefficient property methods) Sanchez-Lacombe (POLYSL) All vapor properties: Fugacity coefficient, enthalpy, entropy, Gibbs free energy, density Model (Property method) Used For
All vapor properties: Fugacity coefficient, enthalpy, entropy, Gibbs free energy, density All vapor properties: Fugacity coefficient, enthalpy, entropy, Gibbs free energy, density All vapor properties: Fugacity coefficient, enthalpy, entropy, Gibbs free energy, density
Polymer SRK (POLYSRK)
SAFT (POLYSAFT)
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Properties Calculated
Model (Property method) PC-SAFT (POLYPCSF) Copolymer PC-SAFT (PCSAFT)
Used For All vapor properties: fugacity coefficient, enthalpy, entropy, Gibbs free energy, density All vapor properties: Fugacity coefficient, enthalpy, entropy, Gibbs free energy, density
Liquid Vapor pressure PLXANT Activity Coefficient Antoine (All activity coefficient property methods) Flory-Huggins (POLYFH) Polymer NRTL (POLYNRTL) Polymer UNIFAC (POLYUF) UNIFAC free volume (POLYUFV) Vaporization enthalpy Watson for monomers, Van Krevelen for polymers and oligomers from segments (All activity coefficient property methods) Molar Volume Rackett for monomers, Van Krevelen for polymers and oligomers from segments Tait molar model for polymers and oligomers (All activity coefficient property methods) Departure functions, fugacity coefficient, molar volume Sanchez-Lacombe (POLYSL) All liquid properties: Fugacity coefficient, enthalpy, entropy, Gibbs free energy, density Density Fugacity, Gibbs free energy, enthalpy, entropy Fugacity, Gibbs free energy, enthalpy, entropy Fugacity, Gibbs free energy, enthalpy, entropy Fugacity, Gibbs free energy, enthalpy, entropy Enthalpy, entropy
Polymer SRK (POLYSRK)
All liquid properties: Fugacity coefficient, enthalpy, entropy, Gibbs free energy, density All liquid properties: Fugacity coefficient, enthalpy, entropy, Gibbs free energy, density All liquid properties: fugacity coefficient, enthalpy, entropy, Gibbs free energy, density All liquid properties: fugacity coefficient, enthalpy, entropy, Gibbs free energy, density Liquid viscosity of polymer solutions and mixture
SAFT (POLYSAFT)
PC-SAFT (POLYPCSF)
Copolymer PC-SAFT (PCSAFT) Viscosity Aspen Polymer Mixture Viscosity Model
Properties Calculated Thermal Conductivity
Model (Property method) Aspen Polymer Mixture Thermal Conductivity Model
Used For Liquid thermal conductivity of polymer solutions and mixtures
Thermodynamic Data for Polymer Systems

The data published in the literature for pure polymers and for polymer solutions is very limited in comparison to the enormous amount of vaporliquid equilibrium data available for mixtures of small molecules (Wohlfarth, 1994). The AIChE-DIPPR handbooks of polymer solution thermodynamics (Danner & High, 1992) and diffusion and Thermal Properties of Polymers and Polymer Solutions (Caruthers et al., 1998) provide computer databases for pure polymer pressure-volume-temperature data, finite concentration VLE data, infinite dilution VLE data, binary liquid-liquid equilibria data, and ternary liquid-liquid equilibria data. The DECHEMA polymer solution data collection contains data for VLE, solvent activity coefficients at infinite dilution, and liquid-liquid equilibrium (Hao et al., 1992). Another data source for polymer properties is the compilation of Wohlfarth (1994). Wohlfarth compiled VLE data for polymer systems in three groups: vapor pressures of binary polymer solutions (or solvent activities), segmentbased excess Gibbs free energies of binary polymer solutions, and weight fraction Henry-constants for gases and vapors in molten polymers. In another useful source, Barton (1990) presented a comprehensive compilation of cohesion parameters for polymers as well as polymer-liquid Flory-Huggins interaction parameter . Finally, Polymer Handbook (Brandup & Immergut, 1989; Brandup et al., 1999) brought together data and correlations for many properties of polymers and polymer solutions.
Specifying Physical Properties

Following is an explanation of common procedures for working with physical properties in Aspen Polymers.
Selecting Physical Property Methods

For an Aspen Polymers simulation, you must specify the physical property method(s) to be used. Aspen Polymers provides many built-in property methods. You can either select one of these built-in property methods, or customize your own property method. Additionally, you can choose a property method for the entire flowsheet, part of a flowsheet, or a unit.
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To select a built-in property method for the entire flowsheet: From the Data Browser, double-click Properties. From the Properties folder, click Specifications. On the Specifications sheet, specify Process type and Base method. You can also specify property methods for flowsheet sections. Once you have chosen a built-in property method, the property routes and models used are resolved for you. You can use any number of property methods in a simulation.
Creating Customized Physical Property Methods

Occasionally, you may prefer to construct new property methods customized for your own modeling needs. To create customized property methods: From the Data Browser, click Properties. From the Properties folder, click Property Methods. An object manager appears. Click New. In the Create new ID dialog box, enter property method ID and click OK. Now you are ready to customize Routes and/or Models used in the property method you created. In general, to create a custom-made property method you select a base method and modify it. To customize routes: On the, Routes sheet, select a base method to be modified for customization. A Property versus Route ID table is automatically filled in depending on your choice. Click the Route ID that you want to change. From the list, select the new route ID. The new route ID is highlighted. To customize the models: Click the Models tab. In the Models form, from the Property versus Model name table, click the model name to be replaced and select the new model name from the list. The new model name is highlighted.
Entering Parameters for a Physical Property Model

Frequently you need to enter pure model parameters for a pure-component or mixture physical property model. To enter pure model parameters: From the Data Browser, click Properties.
Several subfolders appear. Click Parameters. The following folders appear:

o o o o o o o
Pure Component Binary Interaction Electrolyte Pair Electrolyte Ternary UNIFAC Group UNIFAC Group Binary Results
Following is a description of pure component parameter entry. Other parameter entries are completed in a similar manner. To enter component parameters: Click Pure Component. An object manager appears. Click New. A New Pure Component Parameters form appears. Use the New Pure Component Parameters form to select the type of the pure component parameter. The selections are: Scalar (default) T-dependent correlation Nonconventional
To prepare a New Pure Component Parameters form: Select the type of the parameter (for example, click Scalar). On the same component parameter form, click the name box and either enter a name, or accept the default, and click OK. The parameter form is ready for parameter entry. To enter a parameter: Click the Parameters box, and click the name of the parameter. Click the Units box. Enter the proper unit for the parameter. Click the Component column. Enter the parameter value. Click Next to proceed.
Entering a Physical Property Parameter Estimation Method

If a parameter value for a physical property model is missing, you can request property parameter estimation. To use parameter estimation: From the Data Browser, click Properties.
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Several subfolders appear. Click Estimation. A Setup sheet appears. There are three estimation options available in the Setup sheet: Do not estimate any parameters (default) Estimate all missing parameters Estimate only the selected parameters
o o o o
Pure component scalar parameters Pure component temperature-dependent property correlation parameters Binary interaction parameters UNIFAC group parameters
In the default option, no parameters are estimated during the simulation. If you select the second option, all missing parameters are estimated according to a preset hierarchy of the Aspen Plus simulator. If you select either of these first two options, the task is complete and you can continue by clicking Next . If you select the option to estimate only selected parameters, you must complete additional steps: In the object manager, click Estimate only the selected parameters option. All parameter types are selected automatically. Clear all parameter types that you do not want estimated. Click the parameter tab in the object manager for the parameters you want to estimate. Fill in the parameter form by selecting the names of components, parameters, and estimation methods etc. from the lists. Click Next to proceed.
Entering Molecular Structure for a Physical Property Estimation

If a particular component is not in the component databank, or its structure is to be defined for a particular physical property estimation method, then you need to supply the molecular structure information. There are several ways to provide this information: From the Data Browser, click Properties. Several subfolders appear. Click Molecular Structure. An object manager appears. All of the components selected for the current simulation are listed in the object manager. Click the name of the component structure you want to enter. Click Edit.
A Molecular Structure Data Browser appears. Three options are available in the data-browser as forms for structure definition:
o o o
General (default form) Functional group Formula
Select the method you want to use and define the molecule according to the method selected. Click Next to proceed.
Entering Data for Physical Properties Parameter Optimization

If data is available for a particular physical property, this data can be used to fit a property model available in Aspen Polymers. In order to accomplish this data fit, first the data must be supplied to the system: From the Data Browser, double-click Properties. Click Data. An object manager appears. Click New. A Create a new ID form appears. Enter a name for the data form or accept the default. In the same form, select the data type:
o o
MIXTURE PURE-COMP
Following is a description for pure component data entry. Similar steps are required for mixture data entry. Select a property from the Property list. Select a component from the Component list. Click the Data tab. Enter the data in proper units. Note that the numbers in the first row in the data form indicate estimated standard deviation in each piece of data. They are automatically filled in, but you can edit those figures if necessary. Click Next to proceed.
References
Aspen Physical Property System Physical Property Methods and Models. Cambridge, MA: Aspen Technology, Inc. Barton, A. F. M. (1990). CRC Handbook of Polymer-Liquid Interaction Parameters and Solubility Parameters. Boca Raton, FL: CRC Press, Inc.
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Behme, S., Sadowski, G., Song, Y., & Chen, C.-C. (2003). Multicomponent Flash Algorithm for Mixtures Containing Polydisperse Polymers. AIChE J., 49, 258-268. Bicerano J. (1993). Prediction of Polymer Properties. New York: Marcel Dekker, Inc. Bokis, C. P., Orbey, H., & Chen, C.-C. (1999). Properly Model Polymer Processes. Chem. Eng. Prog., 39, 39-52. Brandup, J., & Immergut, E. H. (Eds.) (1989). Polymer Handbook, 3rd Ed. New York: John Wiley & Sons. Brandup, J., Immergut, E. H., & Grulke, E. A. (Eds.) (1999). Polymer Handbook, 4th Ed. New York: John Wiley & Sons. Caruthers, J. M., Chao, K.-C., Venkatasubramanian, V., Sy-Siong-Kiao, R., Novenario, C. R., & Sundaram, A. (1998) . Handbook of Diffusion and Thermal Properties of Polymers and Polymer Solutions. New York: American Institute of Chemical Engineers. Chapman, W. G., Gubbins, K. E., Jackson, G., & Radosz, M. (1989). Fluid Phase Equilibria, 52, 31. Chen, C.-C. (1993). A Segment-Based Local Composition Model for the Gibbs Energy of Polymer Solutions. Fluid Phase Equilibria, 83, 301-312. Chen, C.-C. (1996). Molecular Thermodynamic Model for Gibbs Energy of Mixing of Nonionic Surfactant Solutions. AIChE Journal, 42, 3231-3240. Chen, C.-C., & Mathias, P. M. (2002). Applied Thermodynamics for Process Modeling. AIChE Journal, 48, 194-200. Cotterman, R. L., & Prausnitz, J. M. (1991). Continuous Thermodynamics for Phase-Equilibrium Calculations in Chemical Process Design. In Kinetics and Thermodynamic Lumping of Multicomponent Mixtures. New York: Elsevier. Danner R. P., & High, M. S. (1992). Handbook of Polymer Solution Thermodynamics. New York: American Institute of Chemical Engineers. Flory, P. J. (1953). Principles of Polymer Chemistry. London: Cornell University Press. Folie, B., & Radosz, M. (1995). Phase Equilibria in High-Pressure Polyethylene Technology. Ind. Eng. Chem. Res., 34, 1501-1516. Fried, J. R. (1995). Polymer Science and Technology. Englewood Cliffs, NJ: Prentice-Hall International. Gross, J., & Sadowski, G. (2001). Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain Molecules. Ind. Eng. Chem. Res., 40, 1244-1260. Gross, J., & Sadowski, G. (2002). Modeling Polymer Systems Using the Perturbed-Chain Statistical Associating Fluid Theory Equation of State. Ind. Eng. Chem. Res., 41, 1084-1093. Hao W., Elbro, H. S., & Alessi, P. (1992). Part 1: Vapor-Liquid Equilibrium; Part 2: Solvent Activity Coefficients at Infinite Dilution; Part 3: Liquid-Liquid Equilibrium, Chemistry Data Series, Vol. XIV. In Polymer Solution Data Collection. Frankfurt: DECHEMA.
Huang, S. H., & Radosz, M. (1990). Equation of State for Small, Large, Polydisperse, and Associating Molecules. Ind. Eng. Chem. Res., 29, 2284. Huang, S. H., & Radosz, M. (1991). Equation of State for Small, Large, Polydisperse, and Associating Molecules: Extension to Fluid Mixtures. Ind. Eng. Chem. Res., 30, 1994. Ko, G. H., Osias, M., Tremblay, D. A., Barrera, M. D., & Chen, C.-C. (1991). Process Simulation in Polymer Manufacturing. Computers & Chemical Engineering, 16, S481-S490. Koningsveld, R., & Kleintjens, L. A. (1971). Liquid-Liquid Phase Separation in Multicomponent Polymer Systems. X. Concentration Dependence of the PairInteraction Parameter in the System Cyclohexane-Polystyrene. Macromolecules, 4, 637-641. Kontogeorgis, G. M., Harismiadis, V. I., Frendenslund, Aa., & Tassios, D. P. (1994). Application of the van der Waals Equation of State to Polymers. I. Correlation. Fluid Phase Equilibria, 96, 65-92. Kroschwitz, J. I. (Ed.). (1990). Concise Encyclopedia of Polymer Science and Engineering. New York: Wiley. Oishi, T., & Prausnitz, J. M. (1978). Estimation of Solvent Activity in Polymer Solutions Using a Group Contribution Method. Ind. Eng. Chem. Process Des. Dev., 17, 333-335. Orbey, H., Bokis, C. P., & Chen, C.-C. (1998a). Polymer-Solvent Vapor-Liquid Equilibrium: Equations of State versus Activity Coefficient Models. Ind. Eng. Chem. Res., 37, 1567-1573. Orbey, H., Bokis, C. P., & Chen, C.-C. (1998b). Equation of State Modeling of Phase Equilibrium in the Low-Density Polyethylene Process: The SanchezLacombe, Statistical Associating Fluid Theory, and Polymer-Soave-RedlichKwong Equation of State. Ind. Eng. Chem. Res., 37, 4481-4491. Poling, B. E., Prausnitz, J. M., & OConnell, J. P. (2001). The Properties of Gases and Liquids, 5th Ed. New York: Mc Graw-Hill. Prausnitz, J. M., Lichtenthaler, R. N., & de Azevedo, E. G. (1986). Molecular Thermodynamics of Fluid Phase Equilibria, 2nd Ed, Englewood Cliffs, NJ: Prentice-Hall. Qian, C., Mumby, S. J., & Eichinger, B. E. (1991). Phase Diagram of Binary Polymer Solutions and Blends. Macromolecules, 24, 1655-1661. Reid, R. C., Prausnitz, J. M., & Poling, B. E. (1987). The Properties of Gases and Liquids, 4th Ed. New York: McGraw-Hill. Sanchez, I. C., & Lacombe, R. H. (1976). An Elementary Molecular Theory of Classical Fluids. Pure Fluids. J. Phys. Chem., 80, 2352-2362. Sanchez, I. C., & Lacombe, R. H. (1978). Statistical Thermodynamics of Polymer Solutions. Macromolecules, 11, 1145-1156. Sanchez, I. C. (1992). Polymer Phase Separation. In Encyclopedia of Physical Science and Technology, 13. New York: Academic Press. Sandler, S. I. (1994). Models for Thermodynamic and Phase Equilibria Calculations. New York: Marcel-Dekker.
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Sandler, S. I. (1988). Chemical and Engineering Thermodynamics, 2nd Ed. New York: J. Wiley & Sons. Saraiva A., Kontogeorgis, G. M., Harismiadis, V. I., Fredenslund, Aa., & Tassios, D. P. (1996). Application of the van der Waals Equation of State to Polymers IV. Correlation and Prediction of Lower Critical Solution Temperatures for Polymer Solutions. Fluid Phase Equilibria, 115, 73-93. Song, Y., Mathias, P. M., Tremblay, D., & Chen, C.-C. (2003). Viscosity Model for Polymer Solutions and Mixtures. Ind. Eng. Chem. Res., 42, 2415. Van Ness, H. C. (1964). Classical Thermodynamics of Non-Electrolyte Solutions. Oxford: Pergamon Press. Van Krevelen, D. W. (1990). Properties of Polymers, 3rd Ed. Amsterdam: Elsevier. Walas, S. M. (1985). Phase Equilibria in Chemical Engineering. Boston: Butterworth-Heinemann. Wohlfarth, C. (1994). Vapor-Liquid Equilibrium Data of Binary Polymer Solutions: Vapor Pressures, Henry-Constants and Segment-Molar Excess Gibbs Free Energies. Amsterdam: Elsevier. Xiong, Y., & Kiran, E. (1995). Comparison of Sanchez-Lacombe and SAFT Model in Predicting Solubility of Polyethylene in High-Pressure Fluids. J. of Applied Polymer Science, 55, 1805-181.
2 Equation-of-State Models
This chapter discusses thermodynamic properties of polymer systems from equation-of-state models (EOS) used in Aspen Polymers (formerly known as Aspen Polymers Plus). EOS models are used to calculate molar volumes, fugacity coefficients, enthalpy, entropy, and Gibbs free energy departures, for both pure components and mixtures. Topics covered include: About Equation-of-State Models, 27 Phase Equilibria Calculated from EOS Models, 29 Other Thermodynamic Properties Calculated from EOS Models, 30 Physical Properties Related to EOS Models in Aspen Polymers, 32 Sanchez-Lacombe EOS Model, 34 Polymer SRK EOS Model, 42 SAFT EOS Model, 47 PC-SAFT EOS Model, 59 Copolymer PC-SAFT EOS Model, 67
About Equation-of-State Models

In modeling polymer systems at high pressures, activity coefficient models suffer from certain shortcomings. For example, most of them are applicable only to incompressible liquid solutions, and they fail to predict the lower critical solution temperature (LCST) type phase behavior that necessitates pressure dependence in a model (Sanchez, 1992). In contrast to activity coefficient models, equations-of-state models do not suffer from these shortcomings. EOS models are able to predict both upper critical solution temperature (UCST) and LCST types of phase behavior in polymer solutions. EOS models are valid over the entire fluid region, from the dilute-gas to the dense-liquid region, and, therefore, are not limited to incompressible liquids. Thus, unlike activity coefficient models, EOS are able to evaluate the physical properties of any fluid phase, liquid and/or vapor, such as fugacity coefficient, molar volume, enthalpy, entropy, and Gibbs free energy departures. In addition, EOS are developed as pure-component models and subsequently extended to mixtures, thus providing information for both pure components and mixtures.
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There are a large number of equations of state for polymers and polymer solutions in the literature, which can be classified in the following categories: Cell models Lattice models Hole models Tangent sphere models
Detailed discussions of these models are beyond the scope of this chapter. Refer to available literature for this purpose (Lambert et al., 2000; Rodgers, 1993; Wei & Sadus, 2000). Currently, the most widely used EOS for polymer systems are the: Sanchez-Lacombe EOS (Sanchez & Lacombe, 1976, 1978) Statistical Associating Fluid Theory EOS (SAFT) (Chapman et al., 1989; Huang & Radosz, 1990, 1991) Perturbed-Chain Statistical Associating Fluid Theory EOS (PC-SAFT) (Gross & Sadowski, 2001, 2002a) Copolymer PC-SAFT (Gross and Sadowski, 2001, 2002a, 2002b; Gross et al., 2003; Becker et al., 2004; Kleiner et al., 2006)
Although many details are different, these segment-based polymer equations of state that were derived from statistical thermodynamics share a common formulation. That is, each pure component in the polymer mixture is characterized by three segment-based parameters: segment number, segment size or volume, and segment energy. In addition, well-known cubic equations-of-state for systems with small molecules are being extended for polymer solutions (Kontogeorgis et al., 1994; Orbey et al., 1998a, 1998b; Saraiva et al., 1996). Presently, Aspen Polymers offers: Sanchez-Lacombe EOS An extension of the Soave-Redlich-Kwong (SRK) cubic equation of state to polymer-solvent mixtures (Polymer SRK EOS) SAFT EOS PC-SAFT EOS Copolymer PC-SAFT EOS
The Sanchez-Lacombe, SAFT, and PC-SAFT equations of state are polymer specific, whereas the polymer SRK model is an extension of a conventional cubic EOS to polymer systems. Copolymer PC-SAFT is a complete PC-SAFT model applicable to complex fluids, including normal fluids, water and alcohols, polymers and copolymers, and their mixtures. Polymer specific equations of state have the advantage of describing polymer components of the mixture more accurately; these EOS models are implemented in Aspen Polymers for modeling systems containing homopolymers as well as copolymers. The details of the individual EOS models are given in the following sections.
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Phase Equilibria Calculated from EOS Models

Phase equilibrium calculations, as given by Equations 1.1 and 1.2, are critical for accurate simulations (For more information, see Chapter 1.):
f i v = f i l for vapor-liquid equilibria (1.1) f i l1 = f i l2 for liquid-liquid equilibria (1.2)

The equation of state can be related to the fugacity through fundamental thermodynamic equations:
f i v = iv y i p f i l = il xi p
With
(2.1) (2.2)
1 ln i = RT
p ni
RT dV ln Z m T ,V ,n j i V
(2.3)
Where:
iv
= Fugacity coefficient of component i in the vapor phase = Fugacity coefficient of component i in the liquid phase = Mole fraction of component i in the vapor phase = Mole fraction of component i in the liquid phase =
il
yi xi
P , system pressure, calculated using an EOS model
R T
V
= Vapor phase ( v ) or liquid phase ( l ) = Universal gas constant = System temperature = Total volume of the mixture = Mole number of component i = =
ni Zm
n
Z=
pV , compressibility factor of the mixture nRT

i
n
i
, total mole number of the mixture
Equations 2.1 and 2.2 are identical except for the phase to which the variables apply. The fugacity coefficient state, represented by
is obtained from the equation of
p in Equation 2.3.
29
Vapor-Liquid Equilibria in Polymer Systems

The relationship for vapor-liquid equilibrium (VLE) is obtained by substituting Equations 2.1 and 2.2 in Equation 2.1 and dividing by p :
iv y i = il xi
(2.4)
In principle, Equation 2.4 applies to each component in the mixture. In practice, however, the polymer components in VLE are considered nonvolatile. Therefore, fugacity coefficients are needed from the equation of state only for solvents, monomers and oligomers. The mole fraction of the polymers in the liquid phase at VLE can be determined by the mass balance condition.
Liquid-Liquid Equilibria in Polymer Systems

The liquid-liquid phase equilibrium (LLE) in polymer systems is also important in modeling polymer processes, and the calculation is more complicated than that in VLE as the polymer components are present in two-coexisting liquid phases. From Equation 2.2, the equation-of-state model can be applied to liquid-liquid equilibria:
il xil = il xil
1 1 2 1 1
(2.5)
and also to vapor-liquid-liquid equilibria:
iv y i = il xil = il xil
2
(2.6)
Where:
il
= =
Fugacity coefficient of component i in the liquid phase l1 Fugacity coefficient of component i in the liquid phase l 2
il
xil1 = Mole fraction of component i in the liquid phase l1 xil2 = Mole fraction of component i in the liquid phase l 2
It is important to address the fact that fugacity coefficients in all phases are calculated from the same equation of state model. They are all functions of composition, temperature, and pressure.
Other Thermodynamic Properties Calculated from EOS Models

The equation of state can be related to other properties through fundamental thermodynamic equations. These properties (called departure functions) are
relative to the ideal gas properties of the same mixture at the same condition: Enthalpy departure:
(H
V RT V ig H m = p dV RT ln ig V V
+ T Sm S
Entropy departure:
ig m
) + RT (Z
(2.7)
m
1)
(S
V p R V ig S m = dV + R ln ig V T v V
(2.8)
Gibbs free energy departure:
(G

V RT V ig Gm = p dV RT ln ig + RT (Z m 1) V V
(2.9)
Molar volume:
Solve p (T ,Vm ) for Vm
Where:
Hm Sm Gm Vm
ig Hm
= Molar enthalpy of the mixture = Molar entropy of the mixture = Molar Gibbs free energy of the mixture = Molar volume of the mixture = Molar ideal gas enthalpy of the mixture = Molar ideal gas entropy of the mixture = Molar ideal gas Gibbs free energy of the mixture =
ig Sm
ig Gm
V ig p ref
RT , molar ideal gas volume p ref
= Reference pressure (1 atm)
The departure functions given by the previous equations are calculated from the same equation of state and apply to both vapor and liquid phases. They also apply to both pure components and mixtures. Once the departure functions are known from the equation of state, the thermodynamic properties of a system (pure or mixture) in both vapor and liquid phases can be computed as follows:
v ig v ig Hm = Hm + Hm Hm
l ig Hm = Hm l m ig Hm
( + (H
) )
(2.10) (2.11)
31
v ig v ig S m = S m + S m S m (2.12)
l ig Sm = Sm v ig Gm = Gm
l ig Gm = Gm
( ) + (S S ) (2.13) + (G G ) (2.14) + (G G ) (2.15)

l m ig m v m ig m
l m ig m
Vapor and liquid volume are computed by solving p( T ,Vm ) for Vm or by using an empirical correlation. The molar ideal gas properties of the mixture are computed by the summation over the components in the mixture. For instance, the molar ideal gas enthalpy of the mixture in both vapor and liquid phases is calculated as follows:
ig H m = y i H i*,ig i ig H m = xi H i*,ig i
in vapor phase in liquid phase
(2.16) (2.17)
Where:
H i*,ig = Ideal gas molar enthalpy of component i

The ideal gas properties for non-polymer components are well established in the Aspen Plus databanks and related results are retrieved automatically when an equation-of-state model is chosen in a calculation (for details, see Aspen Physical Property System Physical Property Methods and Models). Aspen Polymers extends the Aspen ideal gas property model to handle polymer components in the mixture. For a detailed description of the Aspen Ideal Gas Property Model, see Chapter 4.
Physical Properties Related to EOS Models in Aspen Polymers

The following properties are related to equation-of-state models in Aspen Polymers:
Property Name PHIVMX PHILMX HVMX HLMX SVMX Symbol Description Vapor fugacity coefficient of a component in a mixture Liquid fugacity coefficient of a component in a mixture Vapor mixture molar enthalpy Liquid mixture molar enthalpy Vapor mixture molar entropy
iv il
v Hm l Hm v Sm
Property Name SLMX GVMX GLMX VVMX VLMX PHIV PHIL HV HL SV SL GV GL VV VL DHVMX DHLMX DSVMX DSLMX DGVMX DGLMX DHV DHL DSV DSL DGV DGL
Symbol
l Sm v Gm l Gm v Vm l Vm
Description Liquid mixture molar entropy Vapor mixture molar Gibbs free energy Liquid mixture molar Gibbs free energy Vapor mixture molar volume Liquid mixture molar volume Vapor pure component fugacity coefficient Liquid pure component fugacity coefficient Vapor pure component enthalpy Liquid pure component enthalpy Vapor pure component entropy Liquid pure component entropy Vapor pure component Gibbs free energy Liquid pure component Gibbs free energy Vapor pure component molar volume Liquid pure component molar volume Vapor mixture molar enthalpy departure Liquid mixture molar enthalpy departure Vapor mixture molar entropy departure Liquid mixture molar entropy departure Vapor mixture molar Gibbs free energy departure Liquid mixture molar Gibbs free energy departure Vapor pure component molar enthalpy departure Liquid pure component molar enthalpy departure Vapor pure component molar entropy departure Liquid pure component molar entropy departure Vapor pure component molar Gibbs free energy departure Liquid pure component molar Gibbs free energy departure
i*,v i*,l
H i*,v H i*,l S i*,v S i*,l
i*,v i*,l
Vi*,v Vi*,l
v ig Hm Hm l ig Hm Hm
v ig Sm Sm l ig Sm Sm v ig Gm Gm l ig Gm Gm
H i*,v H i*,ig H i*,l H i*,ig S i*,v S i*,ig S i*,l S i*,ig
i*,v i*,ig i*,l i*,ig
33
The following table provides an overview of the equation-of-state models available in Aspen Polymers. This table lists the Aspen Physical Property System model names, and their possible use in different phase types, for pure components and mixtures. Details of individual models are presented in the next sections of this chapter.
EOS Models POLYSL Model Name ESPLSL0 ESPLSL POLYSRK ESPLRKS0 ESPLRKS POLYSAFT ESPLSFT0 ESPLSFT POLYPCSF ESPCSFT0 ESPCSFT PC-SAFT ESPSAFT0 ESPSAFT Phase(s) v and l v and l v and l v and l v and l v and l v and l v and l v and l v and l Pure X X X X X Mixture X X X X X Properties Calculated PHIV, PHIL, DHV, DHL, DSV, DSL, DGV, DGL, VV, VL PHIVMX, PHILMX, DHVMX, DHLMX, DSVMX, DSLMX, DGVMX, DGLMX, VVMX, VLMX PHIV, PHIL, DHV, DHL, DSV, DSL, DGV, DGL, VV PHIVMX, PHILMX, DHVMX, DHLMX, DSVMX, DSLMX, DGVMX, DGLMX, VVMX PHIV, PHIL, DHV, DHL, DSV, DSL, DGV, DGL, VV, VL PHIVMX, PHILMX, DHVMX, DHLMX, DSVMX, DSLMX, DGVMX, DGLMX, VVMX, VLMX PHIV, PHIL, DHV, DHL, DSV, DSL, DGV, DGL, VV, VL PHIVMX, PHILMX, DHVMX, DHLMX, DSVMX, DSLMX, DGVMX, DGLMX, VVMX, VLMX PHIV, PHIL, DHV, DHL, DSV, DSL, DGV, DGL, VV, VL PHIVMX, PHILMX, DHVMX, DHLMX, DSVMX, DSLMX, DGVMX, DGLMX, VVMX, VLMX
An X indicates applicable to Pure or Mixture.
Sanchez-Lacombe EOS Model

This section describes the Sanchez-Lacombe equation-of-state (EOS) model for polymers and polymer solutions. This EOS is used through the POLYSL property method.
Pure Fluids
According to the lattice theory of Sanchez and Lacombe (1976), a pure fluid is viewed as a mixture of molecules and holes, confined on the sites of a lattice. Each segment of the chain, as well as each hole, occupies one lattice site. The
total number of lattice sites for a binary mixture of N m-mers and N 0 empty sites is:
N r = N 0 + mN
The total volume of the system is:
V = (N 0 + mN )v *
Where:
v*
= Volume of a lattice site = Number of segments per chain
Sanchez and Lacombe defined a reduced density as the fraction of occupied lattice sites:
~ =
With
* mN = N 0 + mN
M mv *
* =
NM V
= Scale factor for density = Mass density molecular weight)
Where:
M = Molecular weight (for polymer components this is the number average
Sanchez and Lacombe used the Flory-Huggins expression for the combinatorial entropy of a binary mixture on an incompressible lattice, replacing one component with holes. For the energy, they only considered segment-segment interactions (in other words, segment-hole and hole-hole pair interactions were set equal to zero), and assumed that the segments and the holes are randomly distributed in the lattice. They developed an expression for the Gibbs free energy of a chain fluid on a lattice. By minimizing the Gibbs free energy expression, Sanchez and Lacombe derived the SL EOS: Sanchez-Lacombe EOS Equation
~ ~ 2 + P + T ln(1 ) + 1 ~
1 ~ = 0 m
(2.18)
Where the reduced quantities are defined by:
35
~ T T = * T
p ~ P= * P
~ =
(2.19)
The scale factors, T * , P* and
are related to lattice variables by:
Sanchez-Lacombe Parameters
T* =
*
k
P* =
*
v
*
* =
M (2.20) mv *
In the above expressions:
= Number of segments per chain = Characteristic interaction energy per segment = Closed-packed volume of a segment = Boltzmann's constant
*
v*
A pure fluid is characterized completely by three molecular parameters:
*,
v * , and m, or equivalently, the scale factors T * , P * , and * . These

parameters are obtained by fitting pure component experimental data, usually data along the saturation curve. Some additional characteristics of the SL EOS are: The SL EOS has an explicit size or shape dependency through the molecular parameter m. Thus, it takes into account the chain-like structure of long-chain molecules, such as heavy paraffins and polymers. SL is more accurate than most cubic equations of state of the van der Waals type (Redlich-Kwong, Peng-Robinson, Redlich-Kwong-Soave, etc.) in calculating liquid volumes. SL is not accurate at the critical point of pure fluids; the vapor-liquid equilibrium coexistence curve predicted by the SL EOS is too sharp near critical conditions. Therefore, when experimental vapor pressure data are being regressed, temperatures closer than 15-20C of the critical point should be omitted. Unlike most cubic EOS, the SL EOS does not satisfy a corresponding states principle, except for large molecules (m ) . This is related directly to the fact that the repulsive part of the EOS scales with molecular size through the parameter m. For polymer molecules, m is very large. This means that polymeric liquids of high molecular weight satisfy a corresponding states principle. Since vapor pressure data are unavailable for polymer liquids, the molecular parameters are determined by fitting experimental liquid volume data.
Fluid Mixtures Containing Homopolymers

The SL EOS for multicomponent fluid mixtures containing homopolymers is identical to the pure-component equation, Equation 2.18 (Sanchez & Lacombe, 1978). The difference is that the parameters become composition
dependent through mixing rules. These mixing rules are written in terms of volume fractions, rather than mole fractions: Sanchez-Lacombe Mixing Rules
* mix =
1 v
i
* mix

i j i j
j
* * ij ij
(2.21)
* * v mix = i j vij
(2.22)
1 = i (2.23) mmix i mi
wi i* vi* i = wj *v * j j j
Where:
(2.24)
= Volume fraction of component I
wi = Weight fraction of component i

The cross parameters are calculated by:
* vij =
1 * vii + v * (1 ij ) jj 2
(2.26)
(2.25)
* * ij = ii * (1 k ij ) jj
In two expressions above, kij and
ij
are binary interaction parameters that
are fitted to experimental VLE and LLE data. Both parameters are symmetric. If no data are available, they are set equal to zero. The SL EOS is able to predict the thermodynamic properties of multicomponent mixtures through pure-component and binary interaction parameters only.
Extension to Copolymer Systems

The same equation, Equation 2.18, is used for mixtures containing copolymers. The pure-component parameters for copolymers can be input directly or can be calculated in terms of the relative composition of the segments or repeat units that form the copolymer. The mixing rule for the closed-packed volume parameter of the copolymer is: Pure Parameters
v* = p
Nseg Nseg

A B
B v* AB
37
Where:
and
= Volume fractions of the segments that form the copolymer (calculated using an equation similar to the third SanchezLacombe mixing rule given by Equation 2.24) = Number of distinct segment types present in the copolymer chain, and
Nseg
v* = AB
1 * * v AA + v BB (1 AB ) 2
Where:
v * and v * = Characteristic volume parameters of the segments A and B AA BB
AB
1 = * vp
* p
= Factor that accounts for differences in molecular size
Similarly, for the energy parameter of the copolymer:

Nseg Nseg

A B
B * v* AB AB
With:
* * = * BB (1 k AB ) AB AA
Where:
* AA
k AB
and
* BB
= =
Characteristic energy parameters for the segments A and B Correction to the geometric-mean rule
Finally, for the molecular size of the copolymer:

Nseg 1 = A mp A mA
Where:
m A = Characteristic size parameter of segment A in the copolymer

The characteristic parameters * , v * , and m for the segments A and B are obtained from data on the homopolymers A and B, respectively. McHugh and coworkers (Hasch et al., 1992) have shown that the correction terms AB and k AB have little effect on calculated copolymer phase behavior. For this reason, these two binary parameters are not used in the model and have not been made available for user input. The SL EOS is able to predict UCST and LCST types of phase immiscibility. If parameters T * , P* , and are provided for the polymer or oligomer, then these have highest priority and are used for calculations. If they are not known, usually in the case of copolymers, the user must provide these parameters for the segments that compose the copolymer.
*
Binary Parameters
There are three types of binary parameters: solvent-solvent, solvent-segment and segment-segment. Assuming the binary parameter between different segments is zero, the cross energy parameter for a solvent-copolymer pair can be calculated as:
* ip = Nseg
X
A
* * ii AA (1 k iA )
Where:
* ip
= Cross energy parameter for a solvent-copolymer pair = Segment mole fraction or weight fraction of segment type A in the copolymer. The default is the segment mole fraction and the segment weight fraction can be selected via Option Code in Aspen Plus = Energy parameter of segment type A in the copolymer, determined from data on the homopolymer A = Binary parameter for a solvent-segment pair, determined from VLE or LLE data of the solvent (i)- homopolymer (A) solution
XA
* AA
k iA
The cross energy parameter for a copolymer-copolymer pair in the mixture can be calculated as:
* p = (1 k p p ) * * p p p
1 2 1 2 1
Where:
* p p
= Cross energy parameter for a copolymer-copolymer pair
1 2
k p1 p2 = Binary parameter for a copolymer-copolymer pair
* p
* p
= Energy parameter of pure copolymer p1 = Energy parameter of pure copolymer p 2
The binary interaction parameter, k ij , allows complex temperature dependence:
k ij = aij + bij / Tr + cij ln Tr + d ij Tr + eij Tr2

with
Tr =
T Tref
= Reference temperature and the default value = 298.15 K
Where:
Tref
39
Similarly, the cross volume parameter for solvent-copolymer pairs and copolymer-copolymer pairs can be calculated as:
* vip = Nseg
X
A
* (vii + v * )(1 iA ) / 2 AA
v *1 p2 = (1 p1 p2 )(v *1 + v * 2 ) / 2 p p p
Where:
* vip
= Cross volume parameter for a solvent-copolymer pair = Volume parameter of segment type A in the copolymer, determined from data on the homopolymer A = Binary parameter for a solvent-segment pair, determined from VLE or LLE data of the solvent (i)- homopolymer (A) solution
v* AA
iA
v *1 p2 = Cross volume parameter for a copolymer-copolymer pair p
p p
v *1 p v*2 p
= Binary parameter for a copolymer-copolymer pair = Volume parameter of pure copolymer p1 = Volume parameter of pure copolymer p 2
1 2
The binary interaction parameter, dependence:
ij , allows complex temperature
' ' ' ' ' ij = aij + bij / Tr + cij ln Tr + d ij Tr + eij Tr2
Similar to pure component parameters, if the user provides the binary parameters for solvent-copolymer pairs, then these have highest priority and are used directly for calculations. However, if the user provides the binary parameters for solvent-segment pairs, the values for solvent-copolymer pairs will be calculated.
Sanchez-Lacombe EOS Model Parameters

The following table lists the Sanchez-Lacombe model parameters implemented in Aspen Polymers:
Parameter Name / Element SLTSTR SLPSTR SLRSTR SLKIJ/1 SLKIJ/2 Symbol Default Lower Limit ----------Upper Limit ----------MDS Units Keyword TEMP PRESSURE DENSITY ----Comments
T* P*
------0.0 0.0
X X X X X
Unary Unary Unary Binary, Symmetric Binary,
*
aij bij
Parameter Name / Element SLKIJ/3 SLKIJ/4 SLKIJ/5 SLKIJ/6 SLETIJ/1 SLETIJ/2 SLETIJ/3 SLETIJ/4 SLETIJ/5 SLETIJ/6
Symbol
Default
Lower Limit
Upper Limit
MDS
Units Keyword
Comments
Symmetric
cij d ij e ij Tref
' aij ' bij ' cij ' d ij ' eij
0.0 0.0 0.0 298.15 0.0 0.0 0.0 0.0 0.0 0.0
---------------------
---------------------
X X X X X X X X X X
------TEMP ----------TEMP
Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric
Tref
Parameter Input and Regression

All three unary parameters, SLTSTR, SLPSTR, and SLRSTR can be: Specified for each polymer or oligomer component Specified for segments that compose a polymer or oligomer component
These options are shown in priority order. For example, if parameters are provided for a polymer component and for the segments, the polymer parameters are used and the segment parameters are ignored. If the user provides the parameters for segments only, the values for polymers will be calculated from the segment parameters. Both binary parameters, SLKIJ and SLETIJ, can be: Specified for each polymer-solvent pair Specified for each segment-solvent pair
These options are also shown in priority order. For example, if the binary parameters are provided for both polymer-solvent pairs and segment-solvent pairs, the polymer-solvent parameters are used and the segment-solvent pairs are ignored. If the user provides the binary parameters for segmentsolvent pairs only, the values for polymer-solvent pairs will be calculated. Appendix E lists pure component parameters for some solvents (monomers) and homopolymers. If the pure parameters are not available for components in a calculation, the user can perform an Aspen Plus Regression Run (DRS) to obtain these pure component parameters. For non-polymer components, the
41
pure component parameters are usually obtained by fitting experimental vapor pressure and liquid molar volume data. To obtain pure homopolymer (or segment) parameters, experimental data on liquid density should be regressed. Once the pure component parameters are available for a homopolymer, ideal-gas heat capacity parameters, CPIG, should be regressed for the same homopolymer using experimental liquid heat capacity data (for details on ideal-gas heat capacity for polymers, see Aspen Ideal Gas Property Model section in Chapter 4). In addition to pure component parameters (SLTSTR, SLPSTR, and SLRSTR), the binary parameters (SLKIJ and SLETIJ) for each solvent-solvent pair or each solvent-polymer (segment) pair can be regressed using vapor-liquid equilibrium (VLE) data in the form of TPXY data in Aspen Plus. Note: In a Data Regression Run, a polymer component must be defined as an OLIGOMER type, and the number of each type of segment that forms the oligomer (or polymer) must be specified.
Missing Parameters
If the user does not provide all three unary parameters for a defined component or segment, the following nominal values are assumed: SLTSTR = 415 (K) SLPSTR = 3000 (bar) SLRSTR = 736 (kmol/cum)
Specifying the Sanchez-Lacombe EOS Model

See Specifying Physical Properties in Chapter 1.
Polymer SRK EOS Model

This section describes the Polymer SRK equation-of-state model available in the POLYSRK physical property method. The polymer SRK EOS model is an extension of the popular cubic SRK EOS to mixtures containing polymers. From a modeling point of view, this model is considered similar to the PSRK EOS model available in Aspen Plus for conventional mixtures. Like the PSRK model, for mixture applications this model uses a Huron-Vidal-type mixing rule that incorporates an excess energy (Gibbs or Helmholtz) term. The detailed discussion of these types of mixing rules can be found elsewhere (see Aspen Physical Property System Physical Property Methods and Models, see also Orbey, et al., 1998a and 1998b; Fischer & Gmehling, 1996). Here, the basic characteristics of the model are summarized from a modeling perspective. The excess Gibbs free energy can be written from an EOS using rigorous thermodynamics, and it can be equated to the same property from an activity coefficient model:
E GE G EOS = ln xi ln i xi ln i = RT RT i i
Where:
E G EOS = Excess Gibbs free energy from an EOS model
i i
GE
= Mixture fugacity coefficient = Fugacity coefficient of component i in a mixture = Activity coefficient of component i in a mixture = Excess Gibbs free energy from an activity coefficient model
The above equality can only be written at a selected reference pressure. A reference for pressure is needed since the Gibbs free energy from an EOS is pressure dependent but the same term from an activity coefficient is not. Thus, an algebraically explicit equality can only be established at a single reference pressure. The usual alternatives for the reference pressure are either p = 0 or p = . There is much debate as to which selection is better (Fischer & Gmehling, 1996; Orbey & Sandler, 1995, 1997), and it is beyond the scope of this documentation. In general, the combination of an EOS with an activity coefficient model by equating the Gibbs free energy terms leads to a general functional relation between a and b parameters of a cubic EOS in the form:
a = ai , bi , xi , GE or AE bRT
Where:
= Cubic EOS parameter of a mixture = Cubic EOS parameter of a mixture = Cubic EOS parameter of component i = Cubic EOS parameter of component i
ai bi
AE = Excess Helmholtz free energy
Soave-Redlich-Kwong EOS
The functional form depends on the selection of reference pressure. Holderbaum and Gmehling (1991) used this approach for the SRK EOS to develop the following relation at the limit of low (atmospheric) pressure:
p=
RT a (T ) v b v (v + b)
Holderbaum and Gmehling Approach
43
GE b a a = xi i 1546 . + xi ln bi RTbi bRT RT i i

For the co-volume parameter, b, the linear mixing rule b =
x b was used.
i i i
With the Holderbaum and Gmehling approach (see previous equation), this completely defines a and b parameters of the SRK EOS for any mixture, provided that an activity coefficient model is selected to represent the molar excess Gibbs free energy term . In the original PSRK EOS, the UNIFAC predictive model was used for this purpose. For the polymer SRK model here, the POLYNRTL model proposed for polymer mixtures is used (for details, see the Polymer-NRTL Activity Coefficient Model section in Chapter 3). Consequently, the same mixture interaction parameters used in the POLYNRTL model are used in the polymer SRK model, only this time in the EOS format. In modeling polymer containing mixtures with the polymer SRK EOS, one needs values of the critical temperature, the critical pressure, and component-specific constants of Mathias and Copeman (1983) for each constituent of the mixture to evaluate pure component ai and bi 's. (For more details on the Mathias-Copeman constants for the SRK EOS, See Aspen Physical Property System Physical Property Methods and Models). Only the final results are presented here: Mathias-Copeman Constants
GE
bi = 0.08664
ai = 0.42748
RTc ,i p c ,i
R 2Tc2i , p c ,i
i = [1 + c1 (1 Tr0,i.5 ) + c 2 (1 Tr0,i.5 ) 2 + c3 (1 Tr0,i.5 ) 3 ] 2

Where:
Tc ,i p c ,i Tr ,i
= Critical temperature of component i = Critical pressure of component i =
T / Tc ,i
c1 , c 2 , c3 = Mathias-Copeman constants of a component

For conventional components, values of the pure component constants are readily available and stored in the Aspen Plus databanks. For oligomers and polymers, these parameters are not available. To overcome this drawback, some estimation techniques have been suggested by several researchers based on the available experimental values for about
Tc and p c for alkanes up to
C20 (See works of Tsonopoulos & Tan, 1993; Teja et al., 1990). The
user needs to supply these constants for the polymers and oligomers using the guidelines given in the Polymer SRK EOS Model Parameters section on page 45. Most two-parameter cubic equations of state (SRK, Peng-Robinson, etc.) cannot predict the molar volumes in the liquid phase accurately. To overcome this difficulty, the Rackett model is used to overwrite the liquid molar volume predictions of the EOS in PSRK property method in Aspen Plus. In the case of the polymer SRK EOS, the van Krevelen liquid molar volume model (See Chapter 4) is used for the polymer and oligomer components; the Rackett equation is still used for conventional components. Mixture liquid molar volumes are calculated using the ideal-mixing assumption. For details, see Mixture Liquid Molar Volume Calculations in Chapter 3.
Polymer SRK EOS Model Parameters

To use the polymer SRK EOS, several pure component parameters are required, including the critical constants Tc , c and the Mathias-Copeman constants. The following tables show the polymer SRK EOS model unary parameters implemented in Aspen Polymers. The conventional components are available from the Aspen Plus data bank. For oligomers and polymers, the user needs to provide them using unary parameter forms.
Parameter Name / Element TCRKS PCRKS RKSMCP/1 RKSMCP/2 RKSMCP/3 Symbol Default Lower Limit 2 Upper Limit 7000 MDS Units Keyword TEMP PRESSURE ------Comments
Tc pc
c1 c2
TC PC 0 -----
----X X X
Unary Unary Unary Unary Unary
105
-------
108
-------
c3
Critical Constants for Polymers

Polymers are not supposed to vaporize, and, therefore, for the critical temperature of the polymers a high value is recommended (typically
Tc > 1000 K ). For the same reason, a relatively low critical pressure is needed
p < 10 6 N / m 2
). For all of the Mathias-Copeman parameters for oligomers ( c and polymers, zero is recommended due to unavailability of information on polymer vapor pressure, though the user may overwrite them. For oligomers, critical temperatures lower than those used for polymers and critical pressures higher than that of polymers could be used. Depending upon the magnitude of these choices, some oligomer may appear in the vapor phase. For the selection of these constants for oligomers, the works of Tsonopoulos and Tan (1993) and Teja et al. (1990) can be used as a
45
guideline. The c and c profiles obtained by Tsonopoulos and by Teja for alkane hydrocarbons are shown here:
In some cases, the choices for the critical constants for polymers and oligomers may affect the VLE calculations significantly. This largely depends on the nature of the solvents present and the temperature and pressure at which the phase calculations are made. None of the parameters listed previously are automatically supplied by Aspen Polymers for oligomers and polymers. The user needs to enter them using unary parameter forms. The default option for the excess energy model used in the polymer SRK model is the polymer NRTL activity coefficient model. Therefore, the same binary interaction parameters needed for the polymer NRTL model are required in this application. The polymer NRTL model is described in Chapter 3. The user may overwrite this choice by creating a custom property method selecting another activity coefficient model for the evaluation of term in the polymer SRK model. In this case, the mixture parameters of the selected
GE
GE
model need to be supplied.
Specifying the Polymer SRK EOS Model

SAFT EOS Model

This section describes the Statistical Associating Fluid Theory (SAFT). This equation-of-state model is used through the POLYSAFT property method. The SAFT EOS is a rigorous thermodynamic model for polymer systems based on the perturbation theory of fluids. The equation of state accounts explicitly for the molecular repulsions, the chain connectivity, dispersion (attractive) forces, and specific interactions via hydrogen bonding. TheSAFT EOS was developed by Gubbins and co-workers (Chapman et al., 1990), and was first used for engineering calculations by Huang and Radosz (1990, 1991). This EOS currently represents a state-of-the-art engineering tool for the thermodynamic properties and phase equilibria correlation and prediction of polymer-containing systems. Recent research efforts by various research groups worldwide have demonstrated the applicability of SAFT to a variety of polymer systems . Among others, these include: Low-density polyethylene (Folie & Radosz, 1995; Xiong & Kiran, 1995) Polystyrene (Pradham et al., 1994) Poly(ethylene-propylene) copolymer (Chen et al., 1992) Polyisobutylene (Gregg et al., 1994) Poly(ethylene-methyl acrylate) copolymers (Lee et al., 1996) Poly(ethylene-acrylic acid) copolymers (Hasch & McHugh, 1995; Lee et al., 1994)
The above researchers, together with others in the field of polymer thermodynamics, have found that the SAFT equation of state is able to correlate accurately the thermodynamic properties and phase behavior of both pure-components and their mixtures. In addition, SAFT has shown remarkable predictive capability, which is a very important feature for modeling industrial applications. Although SAFT of Huang and Radosz (1990, 1991) is a homopolymer model, the version implemented in Aspen Polymers has some features that make the model convenient to use for copolymer property modeling.
Pure Fluids
The SAFT model is a molecularly-based equation of state, which means that it evaluates the properties of fluids based on interactions at the molecular level. This way the model is able to separate and quantify the effects of molecular structure and interactions on bulk properties and phase behavior. Examples of such effects are: Molecular size and shape (e.g., chain length) Association energy (e.g., hydrogen bonding)
47
Attractive (e.g., dispersion) energy
In developing any equation of state based on theoretical considerations, a model fluid has to be selected. In the case of SAFT, Chapman et al. (1990) chose a model fluid that is a mixture of equal-sized spherical segments interacting with square-well potential. To make the model fluid more realistic, two kinds of bonds where also considered between the segments: covalentlike bonds that form chain molecules, and hydrogen bonds. As a result, the model fluid can represent a wide variety of real fluids such as: Small nearly-spherical species (methane, ethane, etc.) Chain molecules (alkanes, polymers) Associating species (alkanols)
Reduced density term The reduced density
of the fluid (segment packing fraction) is defined as:
N AV
6
md 3
(2.27)
Where:
m d
= Molar density = Number of segments in each molecule = Effective segment diameter (temperature dependent)
N AV = Avogadro constant
This equation can be rewritten as:
= mv o
With
(2.28)
v0 =
N AV 3 d 6
(2.29)
Where:
= Constant equal to 0.74048 mole of closely packed segments), in units of cc per mole of segments
0
v 0 = Segmental molar volume at closed-packing (the volume occupied by a

From the previous two equations, it follows that v is temperature dependent, since it depends on the temperature dependent diameter d. Thus, it is convenient to define a temperature-independent segmental molar volume at T=0, denoted v . This parameter will be referred to as the segment volume. Chen and Kreglewski (1977) solved the Barker-Henderson integral equation of the diameter d (which depends on the square-well potential), and proposed the following expression between
oo
v o and v oo :
3u o v = v 1 C exp kT (2.30)
o oo
In the above equation, u / k is the square-well depth, a temperatureindependent energy parameter, referred to as the segment energy, in Kelvins. Chen and Kreglewski (1977) set the constant C=0.12, and used the following temperature dependence of the dispersion energy of interaction between segments: Chen and Kreglewski temperature dependence of dispersion energy
e u = u o 1 + kT
Where:
(2.31)
e/k = Constant (values will be provided later) SAFT was proposed by Gubbins, Radosz, and co-workers (Chapman et al., 1990). The main idea in SAFT is perturbation theory. In perturbation theory, the fluid is simulated using a reference fluid. The reference fluid is usually a well-understood and well-described fluid (such as the hard-sphere fluid). Any deviations between the properties of the real and the reference fluid are referred to as perturbations. These authors used a reference fluid that incorporates both the chain length (molecular size and shape) and the molecular association (whenever applicable). (In most pre-existing engineering equations of state, the much simpler hard-sphere fluid had been used as the reference fluid). To derive the equation of state for the reference fluid, Chapman et al. (1990) needed expressions for the Helmholtz free energy for the chain and association effects. These researchers used Wertheims expressions for chain and hydrogen bonding, which are based on cluster expansion theory (Wertheim, 1984; 1986a,b). (As a reminder, equation of state developers often derive expressions for the Helmholtz free energy for convenience reasons. Most properties of interest, such as the system pressure, can be easily obtained via simple algebraic differentiation of the Helmholtz free energy.) As mentioned above, the reference equation of state in SAFT accounts for the hard-sphere, chain, and association effects. The effects of other kinds of intermolecular forces, such as dispersion forces, are usually weaker, and are treated through a perturbation term. Chapman et al. (1990) used an expression similar to that of Alder et al. for the square-well potential (Alder et al., 1972). The statistical associating fluid theory results in an expression of the residual Helmholtz free energy,
a res per mole, defined as:

(2.32)
a res (T , V , N ) = a(T , V , N ) a ideal (T , V , N )

Where:
a(T ,V , N )
= Total Helmholtz energy per mole at the same temperature and volume as:
a ideal (T , V , N ) = Ideal-gas Helmholtz energy per mole

In SAFT, the residual Helmholtz free energy contributions:
a res is a sum of three
49
and attractive or dispersion forces) segments
a seg represents segment-segment interactions (hard-sphere repulsions a chain is due to the presence of covalent chain-forming bonds among the a assoc is present when the fluid exhibits hydrogen bonding interactions
among the segments
The general expression for the Helmholtz free energy in SAFT is given by:
a res = a seg + a chain + a assoc

The segment contribution
(2.33)
Segment contribution per mole of molecules
a seg = m(a hs + a disp ) (2.34)
a seg per mole of molecules is given by:
The two contributions represent the segmental hard-sphere and dispersion interactions. These two quantities are given by: Hard-Sphere Term
a hs 4 3 2 = RT (1 )2
Dispersion Term
(2.35)
a disp u = Dij RT kT i j
(2.36)
The hard-sphere term is the well-known Carnahan-Starling expression for the hard-sphere fluid (Carnahan & Starling, 1972). The dispersion term is a fourth-order perturbation expansion of the Helmholtz free energy, initially fitted by Alder et al. (1972) to molecular dynamics simulation data for the square-well fluid. In the dispersion term, Dij are universal constants. In SAFT, Huang and Radosz (1990) used the
Dij constants that were proposed
by Chen and Kreglewski (1977), who re-fitted Alders expression to very accurate experimental data for argon. The chain and association terms in SAFT are the result of Wertheims thermodynamic theory of polymerization. This section does not deal with associating species, and, therefore, the association term will be neglected. The chain term, which represents the Helmholtz free energy increment due to the formation of covalent bonds, is given by the following expression (Chapman et al., 1990): Chain Term
a chain = (1 m ) ln g (d ) seg RT
Where
(2.37)
g( d )seg is the value of the segmental radial distribution function at a seg distance equal to the effective segment diameter d. In other words, g ( d ) is
the radial distribution function at the surface of the segment, or the contact value. As explained by Chapman et al. (1990) and Huang and Radosz (1990), this equation is derived from the association theory by replacing the hydrogen bonds with covalent, chain-forming bonds. As mentioned above, in SAFT, the can be segments are approximated by hard spheres, and thus, g ( d ) approximated by the hard-sphere radial distribution function (Carnahan & Starling, 1972):
seg
g (d ) seg g (d ) hs
1 1 2 = (1 )3
(2.38)
Therefore, the chain contribution to the free energy in SAFT can be rewritten as:
1 1 a chain 2 = (1 m ) ln RT (1 )3
Compressibility Factor
(2.39)
The compressibility factor Z can be easily obtained by taking the molar volume derivative of the residual Helmholtz free energy; the resulting SAFT equation of state has the form:
Z=
Pv = 1 + Z seg + Z chain + Z assoc RT
(2.40)
Where:
seg
i j 4 2 2 u = m + jDij 3 kT i j (1 )
(2.41)
Z chain
5 2 2 = (1 m ) (1 )1 1 2
(2.42)
The contribution from association, Z and thus this term will be zero.
assoc
, is not considered for the time being,
The SAFT equation of state presented above has been used to correlate vapor pressures and liquid densities of over 100 real fluids by Huang and Radosz (1990). For each fluid, three parameters were fitted to the experimental data: Segment volume, v
oo
Segment energy, u / k Segment number, m
Estimated parameters for these fluids are given in Appendix E.
51
Extension to Fluid Mixtures

Huang and Radosz (1991) extended the SAFT equation of state to treat multicomponent fluid mixtures. In doing so, they took advantage of the fact that SAFT was based on theoretical arguments and, therefore, the extension of the equation of state from pure components to mixtures is straightforward, based on statistical mechanical considerations. For the extension of the hard-sphere term to mixtures, Huang and Radosz (1991) used the theoretical result of Mansoori et al. for the Helmholtz free energy of a mixture of hard spheres, which is given by the following expression (Mansoori et al., 1971): Helmholtz free energy of a mixture of hard spheres
3 2 ( )3 6 ( 2 ) + 3 1 2 3 3 1 2 ( 3 ) a hs = 0 2 2 ln (1 3 ) 2 RT ( 3 ) 3 (1 3 )
With
k =
N Av
6
xi mi (d ii )k
i
Note that the Helmholtz free energy equation reduces to the same result for pure components, as given by the segment contribution equation and the hard-sphere equation, given by Equation 2.32, in the limit of xi of unity. In a similar fashion, the chain contribution for fluid mixtures is a direct extension of the pure-component result:
a chain hs = xi (1 mi ) ln g ii (d ii ) RT i
Where gii is the radial distribution function of two species i in a mixture of spheres, evaluated at the hard-sphere contact. This value was derived from statistical mechanics by Mansoori et al. (1971), and has the form:
g ii (d ii )
seg
g ii (d ii ) =
hs
3d 2 22 1 d + ii + 2 ii 3 1 3 2 (1 3 )2 2 (1 3 )
2
For the dispersion (attractive) term in SAFT, Huang and Radosz (1991) used several approaches for its extension to fluid mixtures. One of these approaches, the conformal solution approach (which has been considered by most researchers who have applied SAFT to engineering calculations) is discussed here. According to the conformal solution, or van der Waals onefluid (vdW1) theory, a fluid mixture is approximated by a hypothetical pure fluid having the same molecular energy and size (volume). The vdW1 theory leads to the vdW1 mixing rules. For the energy parameter in SAFT, the vdW1 mixing rule is: Dispersion Energy Mixing Rule
u = kT
With
x x m m
i j i i j i j i i j
(v ) kT x x m m (v )
u ij
o j o j ij
ij
(v )
o
ij
vo =
( )
1/ 3
i
+ vo
( )
1/ 3
j
u ij = u ii u jj (1 k ij )
Where kij is an empirical binary parameter, fitted to experimental VLE or LLE data. In the absence of mixture data, kij is equal to zero. Finally, the molecular size is taken into account via the segment number m. For mixtures, it is calculated as:
m = x i mi
i
Application of SAFT
Huang and Radosz (1991) have proposed a comprehensive parameterization of the SAFT equation of state based on the work by Topliss (1985), which facilitates the coding of the SAFT individual terms and their derivatives with respect to density and composition. This approach has been followed in Aspen Polymers. All individual terms and their derivatives are provided in the Huang and Radosz (1991) paper, and will not be reproduced here. To apply SAFT to real fluid systems, three pure-component (unary) parameters need to be provided for each species: Segment volume, v
oo
Segment energy, u / k Segment number, m
These parameters are estimated by fitting vapor-pressure and liquid-density experimental data for the pure components. Huang and Radosz (1990) have evaluated pure-component parameters for about 100 species; these parameters are also tabulated in Appendix E for convenience. In case the component of interest is not included in the list of components with already available parameters, the user needs to set up a regression run (DRS), and use vapor-pressure and liquid density experimental data to estimate the necessary parameters v
oo
, u / k , and m.
For the components that Huang and Radosz (1991) regressed experimental data and obtained parameters, they reported percent average absolute deviations in vapor pressures and liquid densities. The quality of their fit is very good, as can be usually expected for a reasonable, three parameter equation of state. However, the advantage of SAFT is the behavior of its
53
parameters. This means that the SAFT unary parameters follow expected trends, which makes their estimation possible in the absence of experimental data. This is very important because engineers are often dealing with polydisperse, poorly defined pseudocomponents of real fluid mixtures, whose parameters cannot be fitted due to the absence of experimental information. The fact that the parameter values are well-behaved and suggest predictable trends upon increasing the molar mass of components in the same homologous series gives SAFT a predictive capability in the absence of experimental data. SAFT Parameter Generalization To understand this important concept better, it helps to remember what the three SAFT parameters represent. The segment energy ( u / k ) and the segment volume ( v ) are segmental parameters, which suggests that they should remain fairly constant between components in the same homologous series. The third parameter (m) represents the number of segments on the chain; this implies that m should be proportional to the molecular mass. In the case of normal alkanes, Huang and Radosz proposed the following generalized correlations for the pure-component parameters:
oo o
r=
m Mn
(2.43) (2.44) (2.45) (2.46)
m = 0.70402 + 0.046647 M n mv oo = 11.888 + 0.55187 M n uo = 210.0 26.886 exp[ 0.013341M n ] k
In the above expression, r is the ratio of the size parameter m divided by the polymer number-average molecular weight, M n . This is a more convenient parameterization for SAFT, since the size of the polymer (and thus the size parameter m) changes during polymerization. Entering the r parameter instead of the size parameter m gives more flexibility to the user. Note, the r parameter cannot be used for conventional components. It can only be used for polymers, oligomers, and segments. Equations 2.442.46 are implemented for calculating missing parameters of components in a simulation. The units of v
oo
are cm / mole , and the units of

oo o
uo / k are in Kelvin. The last two equations given above suggest that as M n
becomes a very large number (polymer components), v and u / k will assume some limiting values. Huang and Radosz (1991) also have proposed generalized correlations for other kinds of organic compounds, such as polynuclear aromatics, n-alkylbenzenes, and others. These can be found in the original reference, and will not be reproduced here. As mentioned earlier, the temperature dependence of the energy u in SAFT is given by the Chen and Kreglewski equation, Equation 2.31. In that equation, the parameter e/k is a constant that was related to the acentric factor and the critical temperature by Chen and Krewlewski (1977). Since, in SAFT, the
energy parameter is between segments rather than components, Huang and Radosz set e/k=10 for all components. They only proposed a few exceptions for some small molecules: e/k=0 for argon; 1 for methane, ammonia, and water; 3 for nitrogen; 4.2 for carbon monoxide; 18 for chlorine; 38 for 40 for CO2 ; and 88 for SO2 . The three unary parameters v , u / k , and m for each component represent the necessary user input to apply SAFT to real fluid systems (together with the value of e/k). For fine-tuning of mixture phase behavior, the binary parameter ij can be regressed to available phase equilibrium data from the literature and/or the lab. Huang and Radoszs (1990, 1991) version of SAFT is a homopolymer EOS model. We have implemented an empirical way of treating copolymers in Aspen Polymers using SAFT. The user can enter or regress both purecomponent parameters and the binary parameter on the segment basis, rather than the polymer molecule itself. The parameters to be regressed for the segments are the segment ratio (r), the segment volume ( v ), and segment energy ( u ). The binary parameter, k ij , can be regressed for segment-solvent pairs, instead of polymer-solvent pairs. Aspen Polymers then uses a segment mole fraction or weight fraction average mixing rule to calculate the copolymer SAFT pure-component parameters and the binary parameter for copolymer-solvent pairs based on the segment parameters and the copolymer composition. The details are described next.
0 00
oo o
CS2 ;

The same expressions are used for mixtures containing copolymers. The pure-component parameters for copolymers can be input directly or calculated in terms of the relative composition of the segments or repeat units that form the copolymer. The mixing rules for the characteristic parameters of the copolymer are: Pure Parameters
v 00 = p u0 = p
Nseg
X
A A
00 A A
Nseg
0 uA
m p = M n X A rA
A
Nseg
Where:
v 00 p u0 p
= Average segment volume for the copolymer = Average segment energy for the copolymer
55
mp
= Average segment number for the copolymer
Nseg = Number of distinct segment types present in the copolymer

XA
= Segment mole fraction or weight fraction of segment type A in the copolymer; the default is the segment mole fraction and the segment weight fraction can be selected via Option Code in Aspen Plus = Segment volume for segment A, determined from data on the homopolymer A = Segment energy for segment A, determined from data on the homopolymer A = Segment ratio parameter for segment A, determined from data on the homopolymer A = Number average molecular weight of the copolymer
00 0
00 vA
u0 A
rA
Mn
If parameters v p , u p and m p are provided for the polymer or oligomer, then these have highest priority and are used for calculations. If they are not known, usually in the case of copolymers, the user must provide v A , u A and
00 0
rA for the segments that compose the copolymer.
Binary Parameters
0 u ip =
Nseg
X
A
0 0 u ii u AA (1 k iA )
Where:
0 u ip 0 u ii
= Cross energy parameter for a solvent-copolymer pair = =
u i0 , energy parameter for pure solvent i u0 A
u0 AA k iA
= Binary parameter for a solvent-segment pair; it is determined from VLE or LLE data of the solvent (i)- homopolymer (A) solution
u 01 p2 = (1 k p1 p2 ) u 01 u 0 2 p p p
Where:
u 01 p2 p
= Cross energy parameter for a copolymer-copolymer pair = Binary parameter for a copolymer-copolymer pair = Energy parameter of pure copolymer p1 = Energy parameter of pure copolymer p 2
k p1 p2
u 01 p u 02 p

with
Tr =
T Tref
Where:
Tref
SAFT EOS Model Parameters

The following tables list the SAFT EOS model name and model parameters implemented in Aspen Polymers:
Parameter Name / Element SAFTM SAFTV SAFTU SAFTR SFTEPS SFTKIJ/1 SFTKIJ/2 SFTKIJ/3 SFTKIJ/4 Symbol Default Lower Limit ------------------Upper Limit ------------------MDS Units Keyword --MOLEVOLUME TEMP ------------Comments
--------10.0 0.0 0.0 0.0 0.0
X X X X --X X X X
Unary Unary Unary Unary Unary Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric
v
r
oo
uo / k
e/k
aij bij cij d ij
57
SFTKIJ/5 SFTKIJ/6
e ij Tref
0.0 298.15
-----
-----
X X
--TEMP
Binary, Symmetric Binary, Symmetric

Three unary parameters, SAFTR, SAFTU, and SAFTV can be: Specified for each polymer or oligomer component Specified for segments that compose a polymer or oligomer component
These options are shown in priority order. For example, if property parameters are provided for a polymer component and for the segments, the polymer parameters are used and the segment parameters are ignored. If the user provides the parameters for segments only, the values for polymers will be calculated. For each non-polymer component, these three parameters, SAFTM, SAFTV, and SAFTU must be specified. Note that SAFTR cannot be used for nonpolymer components and can only be used for polymers, oligomers, and segments. The parameter SFTEPS has a default value of 10, which applies to most species, including polymers, oligomers, and segments (see text for some exceptions) The binary parameter, SFTKIJ, can be: Specified for each polymer-solvent pair Specified for each segment-solvent pair
These options are shown in priority order. For example, if the binary parameters are provided for both polymer-solvent pairs and segment-solvent pairs, the polymer-solvent parameters are used and the segment-solvent pairs are ignored. If the user provides the binary parameters for segmentsolvent pairs only, the values for polymer-solvent pairs will be calculated. Appendix E lists pure component parameters for some solvents (monomers) and homopolymers. If the pure parameters are not available for components in a calculation, the user can perform an Aspen Plus Regression Run (DRS) to obtain these pure component parameters. For non-polymer components, the pure component parameters are usually obtained by fitting experimental vapor pressure and liquid molar volume data. To obtain pure homopolymer (or segment) parameters, experimental data on liquid density should be regressed. Once the pure component parameters are available for a homopolymer, ideal-gas heat capacity parameters, CPIG, should be regressed for the same homopolymer using experimental liquid heat capacity data (for details on ideal-gas heat capacity for polymers, see Aspen Ideal Gas Property Model in Chapter 4). In addition to pure component parameters, SAFTU, SAFTV, and SAFTM or SAFTR, the binary parameter, SFTKIJ, for each solventsolvent pair or each solvent-polymer (segment) pair, can be regressed using vapor-liquid equilibrium (VLE) data in the form of TPXY data in Aspen Plus.
Note: In a Data Regression Run, a polymer component must be defined as an OLIGOMER type, and the number of each type of segment that forms the oligomer (or polymer) must be specified.
Missing Parameters
If the user does not provide all three unary parameters for a defined conventional component or segment, the following approximated values are assumed: SAFTV and SAFTU will be calculated from Equations 2.45 and 2.46, respectively. For a conventional component, SAFTM will be calculated from Equation 2.44. For a segment, SAFTR will be set to a nominal value of 0.046647.
Specifying the SAFT EOS Model

PC-SAFT EOS Model

This section describes the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT). This equation-of-state model is used through the POLYPCSF property method. The PC-SAFT EOS model was developed by Gross and Sadowski (2001, 2002). It was based on the well-established SAFT EOS, with some modifications on the expressions for the dispersion forces. PC-SAFT represents an improved version of the very successful SAFT EOS. Therefore, its applicability includes fluid systems of small and/or large molecules over a wide range of temperature and pressure conditions. The big advantage of this EOS method is that it can represent the thermodynamic properties of polymer systems very well. In addition, it is better than other chain equations of state (Sanchez-Lacombe, SAFT) in describing the properties of conventional chemicals. In fact, its accuracy is comparable to, and often better than, the Peng-Robinson EOS or other similar cubic equations of state for small molecules. The perturbation term in SAFT takes into account the attractive (dispersion) interactions between molecules. In PC-SAFT, Gross and Sadowski used the Barker-Henderson second-order perturbation theory of spherical molecules and extended it to chain molecules. The idea is that the perturbation theory concept applies to segments that are connected to chains rather than between disconnected segments, which is the case in SAFT. This is equivalent to considering attractive (dispersion) interactions between the connected segments instead of disconnected ones. For example:
59
SAFT
PC-SAFT
This concept offers a more realistic picture of how chain molecules, such as hydrocarbons, oligomers, and polymers, behave in a solution. In SAFT, the perturbation (attractive) contribution is a series expansion in terms of reciprocal temperature, and each coefficient depends on density and composition. PC-SAFT expresses the attractive term of the equation as a sum of two terms (first- and second-order perturbation terms):
A A A pert = 1 + 2 RT RT RT
Where A denotes the Helmholtz free energy. The Helmholtz free energy is used frequently in statistical thermodynamics to express equations of state because most properties of interest, such as the system pressure, can be obtained by proper differentiation of A. The coefficients A1 and A2 have a dependence on density and composition, as well as molecular size. Gross and Sadowski (2000) obtained all the necessary constants that appear in the coefficients of the previous equation by regression of thermophysical properties of pure n-alkanes. They are reported in their original publication and thus they will not be reproduced here. Similarly to SAFT, there are three pure-component parameters for each chemical substance: Segment number, m Segment diameter, Segment energy,
These parameters are obtained by fitting experimental vapor pressure and liquid molar volume data for pure components. Also, a k ij binary interaction parameter is used to fit phase equilibrium binary data; this parameter defaults to zero if not supplied.
Sample Calculation Results

From the work of Gross and Sadowski, we can draw the following conclusions: PC-SAFT has better predictive capability for the VLE of hydrocarbon systems than SAFT. PC-SAFT has better predictive capability for the VLE of polymer/solvent solutions at low pressures than SAFT.
It also can predict the LLE of polymer solutions at high pressures better than SAFT. Although PC-SAFT somewhat overpredicts the critical point of pure substances, the predicted critical point is much closer to the measured value in PC-SAFT than in SAFT. The correlative capability of PC-SAFT is superior, especially for the phase equilibria of polymer solutions at high pressures.
The following figures demonstrate some of these remarks:
Methane-Butane VLE at 21.1 C. Predictions using
k ij =0.
61
120 100 80
PC-SAFT, kij=0 SAFT, kij=0 Raemer,Sage,1962
P (bar)
60 40 20 0 0.0 0.2 0.4
xEthane
0.6
0.8
1.0
Ethane-Decane VLE at 238 C. Predictions using
k ij =0.
Application of PC-SAFT
Each species must have a set of three pure-component parameters (segment number, m, segment diameter, , and segment energy, ) so the PC-SAFT EOS can calculate all its thermodynamic properties. A databank called POLYPCSF contains both pure and binary parameters available from literature; it is must be used with the property method POLYPCSF. The pure parameters available for segments are stored in the SEGMENT databank. For components not found in the databanks, a pure-component multiproperty parameter fit must be performed. In this case, you must create a Data Regression run type, create data sets for the vapor pressure, the liquid density, and the liquid heat capacity of the species of interest, and then create a regression case that regresses the PC-SAFT pure component parameters. Note: Always supply starting values for the PC-SAFT parameters in the data regression. Pure component parameters have been provided by Gross and Sadowski (2002) for selected polymers. They have also shown that PC-SAFT parameters follow well-behaved trends (similar to SAFT). Therefore, the parameters for a linear polyethylene can be estimated by extrapolating those of n-alkanes. The following generalized expressions are proposed by Gross and Sadowski (2001):
= 4.072
r = m / M n = 0.02434
/ k = 269.67K
In the above expression, r is the ratio of the size parameter m divided by the polymer number-average molecular weight, M n . This is a more convenient
parameterization for PC-SAFT, since the size of the polymer (and thus the size parameter m) is often unknown until after polymerization. Entering the r parameter instead of the size parameter m gives more flexibility to the user. Note, the r parameter cannot be used for conventional components. It can only be used for polymers, oligomers, and segments. The previous equation is implemented for calculating the missing parameters of components in a simulation. The current version of PC-SAFT by Gross and Sadowski (2001, 2002) is a homopolymer EOS model. We have implemented an empirical way of treating copolymers in Aspen Polymers using PC-SAFT. The user can enter or regress both pure-component parameters and the binary parameter on the segment basis, rather than the polymer molecule itself. The parameters to be regressed for the segments are the segment ratio, r, the segment diameter, , and the segment energy, /k. The binary parameter, k ij , can be regressed for segment-solvent pairs, instead of polymer-solvent pairs. A segment mole fraction /or weight fraction average mixing rule is then used by Aspen Polymers to calculate the copolymer PC-SAFT pure-component parameters and the binary parameter for copolymer-solvent pairs based on the segment parameters and the copolymer composition. The details are described next.

The same expressions are used for mixtures containing copolymers. The pure-component parameters for copolymers can be input directly or calculated in terms of the relative composition of the segments or repeat units that form the copolymer. The mixing rules for the characteristic parameters of the copolymer are: Pure Parameters
p = p =
Nseg
X
A A
Nseg
m p = M n X A rA
A
Nseg
Where:
p p
mp
= Average segment diameter for the copolymer = Average segment energy for the copolymer = Average segment number for the copolymer
Nseg = Number of distinct segment types present in the copolymer
63
XA
= Segment mole fraction or weight fraction of segment type A in the copolymer; the default is the segment mole fraction and the segment weight fraction can be selected via Option Code in Aspen Plus = Segment diameter for segment A, determined from data on the homopolymer A = Segment energy for segment A, determined from data on the homopolymer A = Segment ratio parameter for segment A, determined from data on the homopolymer A = Number average molecular weight of the copolymer
A A
rA
Mn
If parameters
p , p and m p
are provided for the polymer or oligomer, then
these have highest priority and are used for calculations. If they are not known, usually in the case of copolymers, the user must provide A , A and
rA for the segments that compose the copolymer.
Binary Parameters
ip =
Nseg
X
A
ii AA (1 k iA )
Where:
ip ii
AA
k iA
= Cross energy parameter for a solvent-copolymer pair = =
i , energy parameter for pure solvent i

A
= Binary parameter for a solvent-segment pair; it is determined from VLE or LLE data of the solvent (i)- homopolymer (A) solution
p p = (1 k p p ) p p
1 2 1 2 1
Where:
p p
= Cross energy parameter for a copolymer-copolymer pair
1 2
k p1 p2 = Binary parameter for a copolymer-copolymer pair
= Energy parameter of pure copolymer p1
= Energy parameter of pure copolymer p 2

with
Tr =
T Tref
Where:
Tref
PC-SAFT EOS Model Parameters

The following table lists the PC-SAFT EOS model parameters implemented in Aspen Polymers:
Parameter Name / Element PCSFTM PCSFTV PCSFTU PCSFTR PCSKIJ/1 PCSKIJ/2 PCSKIJ/3 PCSKIJ/4 PCSKIJ/5 PCSKIJ/6 Symbol Default Lower Limit --------------------Upper Limit --------------------MDS Units Keyword ----TEMP ------------TEMP Comments
--------0.0 0.0 0.0 0.0 0.0 298.15
X X X X X X X X X X
Unary Unary Unary Unary Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric
/k
r
aij bij cij d ij e ij Tref
65

Three unary parameters, PCSFTR, PCSFTU, and PCSFTV can be: Specified for each polymer or oligomer component Specified for segments that compose a polymer or oligomer component
These options are shown in priority order. For example, if property parameters are provided for a polymer component and for the segments, the polymer parameters are used and the segment parameters are ignored. If the user provides the parameters for segments only, the values for polymers will be calculated. For each non-polymer component, these three parameters (PCSFTM, PCSFTU, and PCSFTV) must be specified. Note that PCSFTR cannot be used for nonpolymer components and can only be used for polymers, oligomers, and segments. The binary parameter, PCSKIJ, can be: Specified for each polymer-solvent pair Specified for each segment-solvent pair
These options are shown in priority order. For example, if the binary parameters are provided for both polymer-solvent pairs and segment-solvent pairs, the polymer-solvent parameters are used and the segment-solvent pairs are ignored. If the user provides the binary parameters for segmentsolvent pairs only, the values for polymer-solvent pairs will be calculated. The databank POLYPCSF contains both unary and binary PC-SAFT parameters available from literature; it must be used with the POLYPCSF property method. If the pure parameters are not available for components in a calculation, the user can perform an Aspen Plus Regression Run (DRS) to obtain these pure component parameters. For non-polymer components, the pure component parameters are usually obtained by fitting experimental vapor pressure and liquid molar volume data. To obtain pure homopolymer (or segment) parameters, experimental data on liquid density should be regressed. Once the pure component parameters are available for a homopolymer, ideal-gas heat capacity parameters, CPIG, should be regressed for the same homopolymer using experimental liquid heat capacity data (for details on ideal-gas heat capacity for polymers, see Aspen Ideal Gas Property Model in Chapter 4). In addition to pure component parameters, PCSFTU, PCSFTV, and PCSFTM or PCSFTR, the binary parameter, PCSKIJ, for each solvent-solvent pair or each solvent-polymer (segment) pair, can be regressed using vapor-liquid equilibrium (VLE) data in the form of TPXY data in Aspen Plus. Note: In a Data Regression Run, a polymer component must be defined as an OLIGOMER type, and the number of each type of segment that forms the oligomer (or polymer) must be specified.
Specifying the PC-SAFT EOS Model

Copolymer PC-SAFT EOS Model

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

Fundamental equations
The copolymer PC-SAFT model is based on the perturbation theory. The underlying idea is to divide the total intermolecular forces into repulsive and attractive contributions. The model uses a hard-chain reference system to account for the repulsive interactions. The attractive forces are further divided into different contributions, including dispersion, polar and association. Using a generated function, , the copolymer PC-SAFT model in general can be written as follows:
= hc + disp + assoc +
hc disp assoc
polar
(2.47)
polar
where , , , and are contributions due to hard-chain fluids, dispersion, association, and polarity, respectively. The generated function is defined as follows:
d a res = ( Z m 1) RT 0
res
(2.48)
where a
is the molar residual Helmholtz energy of mixtures,

res
constant,
T is the temperature, is the molar density, and Z m is the

is defined as:
R is the gas
compressibility factor; a
a res = a(T , , xi ,...) a ig (T , , xi ,...)

ig
(2.49)
where a is the Helmholtz energy of a mixture and a is the Helmholtz energy of a mixture of ideal gases at the same temperature, density and composition xi . Once is known, any other thermodynamic function of interest can be easily derived. For instance, the fugacity coefficient i is calculated as follows:
67
ln i = + x i
with
xj x j T , ,x j i j
+ Z m 1 ln Z m T , , xk j
(2.50)
Z m = 1 +
where
T , xi
(2.51)
is a partial derivative that is always done to the mole fraction xi
stated in the denominator, while all other mole fractions are considered constant. Applying
to Equations 2.7, 2.8, and 2.9, departure functions of enthalpy,
entropy, and Gibbs free energy can be obtained as follows: Enthalpy departure:
(H
(S
ig H m = RT T + ( Z m 1) T
(2.52)
Entropy departure:
p ig S m ) = R T + ln Z m R ln ref p T p ig Gm ) = RT [ + (Z m 1) ln Z m ] + RT ln ref p p ig Gm = RT xi ln i + RT ln ref p i
(2.53)
Gibbs free energy departure:
(G
(2.54)
The following thermodynamic conditions must be satisfied:
(G
(2.55) (2.56)
(G
ig ig ig Gm = H m H m T S m S m
) (
) (
Hard-chain fluids and chain connectivity

In PC-SAFT model, a molecule is modeled as a chain molecule by a series of freely-jointed tangent spheres. The contribution from hard-chain fluids as a reference system consists of two parts, a nonbonding contribution (i.e., hardsphere mixtures prior to bonding to form chains) and a bonding contribution due to chain formation:
hc = m hs + chain
where hard-sphere mixtures on a per-segment basis, and
(2.57)
m is the mean segment in the mixture, hs is the contribution from
chain
is the contribution
due to chain formation. Both m and are well-defined for mixtures containing polymers, including copolymers; they are given by the following equations:
hs
m = x i mi
i
(2.58)
hs
23 23 1 31 2 = + + 2 0 ln(1 3 ) 0 (1 3 ) 3 (1 3 ) 2 3
(2.59) (2.60)
m i = m i
n =
z i =
xi mi z i d in ,
i
n = 0, 1, 2, 3
(2.61)
mi mi
(2.62)
d i = i 1 0.12 exp 3 i kT
where mi ,
(2.63)
i , and i , are the segment number, the segment diameter, and the segment energy parameter of the segment type in the copolymer
component i , respectively. The segment number mi is calculated from the
segment ratio parameter ri :
mi = ri M i
where M i is the total molecular weight of the segment type
(2.64)
in the
copolymer component i and can be calculated from the segment weight fraction within the copolymer:
M i = wi M i
where wi is the weight fraction of the segment type
(2.65)
in the copolymer
component i , and M i is the molecular weight of the copolymer component
i.
Following Sadowski and co-workers work (Gross et al., 2003; Becker et al., 2004), the contribution from the chain connectivity can be written as follows:
chain = xi (mi 1) Bi ,i ln g ihs,i (d i ,i )

i
(2.66)
=1 =1
with
B
=1 =1
i ,i
=1
(2.67)
69
d i d j 1 + g ihs , j (d i , j ) = (1 3 ) d i + d j
3 2 d i d j + 2 (1 ) d +d j 3 i
2 22 (1 ) 3 3
(2.68)
where Bi ,i is defined as the bonding fraction between the segment type and the segment type within the copolymer component i , is the number of the segment types within the copolymer component i , and
g ihs , j (d i , j ) is the radial distribution function of hard-sphere mixtures at

contact. However, the calculation for Bi ,i depends on the type of copolymers. We start with a pure copolymer system which consists of only two different types of segments and ; Equation 2.66 becomes:
hs hs hs chain = (m 1)[B ln g (d ) + ( B + B ) ln g (d ) + B ln g (d )]
(2.69)
with
B + B + B + B = 1 m = m + m
(2.70) (2.71)
We now apply Equations 2.69-2.71 to three common types of copolymers; a) alternating, b) block, and c) random. For an alternating copolymer, m = m ; there are no sequences. Therefore:
or
adjacent (2.72) (2.73)
B = B = B = 0, B = 1
hs chain = (m 1) ln g (d )
For a block copolymer, there is only one
pair and the number of
and
pairs depend on the length of each block; therefore:
B =
m 1 m 1 1 , B = , B = , B = 0 m 1 m 1 m 1
(2.74)
For a random copolymer, the sequence is only known in a statistical sense. If the sequence is completely random, then the number of adjacent pairs is proportional to the product of the probabilities of finding a segment of type and a segment of type in the copolymer. The probability of finding a segment of type
is the fraction of
segments z in the copolymer: (2.75)
z =
ma m
The bonding fraction of each pair of types can be written as follows:

2 2 B = Cz , B = Cz , B = B = Cz z
(2.76)
where C is a constant and can be determined by the normalization condition set by Equation 2.70; the value for C is unity. Therefore:
2 2 B = z , B = z , B = B = z z
(2.77)
A special case is the Sadowskis model for random copolymer with two types of segments only (Gross et al., 2003; Becker et al., 2004). In this model, the bonding fractions are calculated as follows: When z < z
B = B =
m m 1
, B = 1 B B , B = 0
(2.78)
When z < z
B = B =
m , B = 0 B = 1 B B m 1
(2.79)
The generalization of three common types of copolymers from two types of different segments to multi types of different segments within a copolymer is straightforward. For a generalized alternative copolymer, m = m = ... = m r =
; there are no
adjacent sequences for the same type of segments. Therefore,
B = B =
m , = +1 (m 1) m , = 1, = (m 1)
(2.80)
(2.81) (2.82) (2.83)
B = 0, > + 1 B = 0,
B = B , +1 + B1, =
=1 =1 =1
m( 1) m =1 + (m 1) (m 1)
(2.84)
For a generalized block copolymer, there is only one pair for each adjacent type of segment pairs ( ) and the number of pairs for a same type depends on the length of the block; therefore:
B =
m 1 , = 1,2,... m 1
(2.85) (2.86) (2.87)
B =
1 , = +1 m 1
B = 0, > + 1
71
B = 0, <
(2.88)
1
B = B + B , +1 =
=1 =1 =1 =1
1 (m 1) + 1 = 1 m 1 =1
(2.89)
For a generalized random copolymer, the sequence is only known in a statistical sense. If the sequence is completely random, then the number of adjacent pairs is proportional to the product of the probabilities of finding a segment of type in the copolymer:
and a segment of type
in the copolymer. The
probability of finding a segment of type
is the fraction of
segments z
z =
m , = 1,2,... m
(2.90)
The bonding fraction of each pair of types can be written as follows:
B = Cz z
, = 1,2,...
(2.91)
where C is a constant and can be determined by the normalization condition set by Equation 2.67. Therefore,
B
=1 =1
= C z z = 1
=1 =1
(2.92)
That is,
C=
z z
=1 =1
(2.93)
Put C into Equation 2.91, we obtain:
B =
z z
z z
=1 =1
, , = 1,2,...
(2.94)
Dispersion term
The equations for the dispersion term are given as follows:
disp = 2I 1 X m C1 I 2Y
i , j X = x i x j m i m j z i z j kT ij 3 i , j
(2.95) (2.96)
i , j Y = x i x j m i m j z i z j kT ij
3 i , j
(2.97)
I 1 ( , m ) = al (m ) l 1
l =1
7
(2.98)
I 2 ( , m ) = bl (m ) l 1
l =1
(2.99)
1
Z hc C1 = 1 + Z hc +
2 (4 ) (20 27 + 12 2 ) = 1 + m + (1 m ) 4 (1 ) [(1 )(2 )]2

2 3
(2.100)
al = a1l + bl = b1l +
m 1 m 1 m 2 a 2l + a 3l m m m m 1 m 1 m 2 b2l + b 3l m m m
(2.101)
(2.102) (2.103)
= 3
where
i , j
and
i , j
are the cross segment diameter and energy
parameters, respectively; only one adjustable binary interaction parameter, i , j is introduced to calculate them:
i , j = ( i + j )
i , j = (1 i , j )( i j )1 / 2
1 2
(2.104) (2.105)
In above equations, the model constants a1l , a 2l , a 3l , b1l , b2l , and b3l are fitted to pure-component vapor pressure and liquid density data of n-alkanes (Gross and Sadowski, 2001).
Association term for copolymer mixtures 2B model

The association term in PC-SAFT model in general needs an iterative procedure to calculate the fraction of a species (solvent or segment) that are bounded to each association-site type. Only in pure or binary systems, the fraction can be derived explicitly for some specific models. We start with general expressions for the association contribution for copolymer systems as follows:
assoc = xi N A ln X A
i i
X Ai 1 + 2 2
A
(2.106)
where A is the association-site type index, N i is the association-site number of the association-site type A on the segment type in the copolymer component i , and X
Ai
is the mole fraction of the segment type
73
in the copolymer component i that are not bonded with the associationsite type A ; it can be estimated as follows:
X Ai =
with
1 1 + x j N Bi X
j B j
Ai B j
(2.107)
Ai B j
=g
hs i , j
(d i , j )
Ai B j
3 i , j
Ai B j exp kT
1
A B
(2.108)
where i j is the cross effective association volume and i j is the cross association energy; they are estimated via simple combination rules:
A B
Ai B j
( AB ) i
( AB ) j
i j ( i + j ) / 2
(2.109)
Ai B j
( AB ) +
i
( AB ) j
2
( AB) ( AB)
(2.110)
i i and are the effective association volume and the where association energy between the association-site types A and B , of the segment type in the copolymer component i , respectively.
The association-site number of the site type A on the segment type copolymer component i is equal to the number of the segment type copolymer component i ,
in the in the
N Ai = N i =
M i wi M i = M M
(2.111)
where N i is the number of the segment type
in the copolymer
component i and M is the molecular weight of the segment type
. In
other words, the association-site number for each site type within a segment is the same; therefore, we can rewrite Equations 2.107 and 2.108 as follows:
assoc = xi N i ln X A
i
X Ai 1 + 2 2
Ai B j
(2.112)
X Ai =
1 1 + x j N j X
j B j
(2.113)
To calculate X i , Equation 2.113 has to be solved iteratively for each association-site type associated with a species in a component. In practice, further assumption is needed for efficiency. The commonly used model is the so-called 2B model (Huang and Radosz, 1990). It assumes that an associating species (solvent or segment) has two association sites, one is designed as the
site type A and another as the site type B . Similarly to the hydrogen bonding, type A treats as a donor site with positive charge and type B as an acceptor site with negative charge; only the donor-acceptor association bonding is permitted and this concept applies to both pure systems (selfassociation such as water) and mixtures (both self-association and crossassociation such as water-methanol). Therefore, we can rewrite Equations 2.112 and 2.113 as follows:
assoc = xi N i ln( X A X B ) ( X A + X B ) + 1
i i i i
1 2
(2.114)
X Ai =
1 1 + x j N j X
j B j
Ai B j
(2.115)
X Bi =
1 1 + x j N j X
j A j
Bi A j
(2.116)
It is easy to show that
Bi A j
Ai B j
(2.117)
Therefore
X Ai = X Bi
(2.118) (2.119)
assoc
X Ai 1 ln X Ai = 2 x i N i + 2 2 i
X Ai =
1 1 + x j N j X
j A j
Ai B j
(2.120)
Polar term
The equations for the polar term are given by Jog et al (2001) as follows:
polar
2 1 3 / 2
(2.121)
i2 2 2 I 2 ( ) j 2 = x x m m j z i z j ( x p ) i ( x p ) j 3 2 i j i 9 (kT ) ij d i , j 3 =
(2.122)
2 2 2
i j k 5 2 2 I 3 ( ) x x x m m j mk z i z j z k ( x p ) i ( x p ) j ( x p ) k 3 i j k i 162 (kT ) ijk d i , j d j ,k d i ,k

(2.123) (2.124)
d i , j = (d i + d j ) / 2
75
In the above equations, I 2 ( ) and I 3 ( ) are the pure fluid integrals and i and ( x p ) i are the dipole moment and dipolar fraction of the segment type within the copolymer component
2 i
/ kTd
3 i , j
) are dimensionless. In terms of them, we can have:

2 j kTd 3 i , j
i , respectively. Both i2 / kT and

2 2 I 2 x i x j m i m j z i z j ( x p ) i ( x p ) j i 2 = kT 9 ij
(2.125)
3 =
5 2 I 3 xi x j x k mi m j mk z i z j z k ( x p ) i ( x p ) j ( x p ) k 162 ijk
2 j kT
2 i kT
k2 kTd i , j d j ,k d i ,k
2
(2.126)
Rushbrooke et al. (1973) have shown that
1 0.3618 * 0.3205 * + 0.1078 * I 2 ( ) = (1 0.5236 * ) 2

*
(2.127)
I 3 ( ) =
*
1 + 0.62378 * 0.11658 * 1 0.59056 * + 0.20059 *
2 2
(2.128)
* =
(2.129)
In terms of
, I 2 ( ) and I 3 ( )
are computed by the expressions: (2.130)
1 0.69099 1.16904 2 + 0.75097 3 I 2 ( ) = (1 ) 2 I 3 ( ) = 1 + 1.19133 0.42523 2 1 1.12789 + 0.73166 2
(2.131)
Copolymer PC-SAFT EOS Model Parameters

Pure parameters. Each non-association species (solvent or segment) must have a set of three pure-component parameter; two of them are the segment diameter and the segment energy parameter . The third parameter for a solvent is the segment number m and for a segment is the segment ratio parameter r . For an association species, two additional parameters are the and the association energy effective association volume polar species, two additional parameters are the dipole moment
( AB )
( AB )
. For a and the
segment dipolar fraction x p .
Binary parameters
There are three types of binary interactions in copolymer systems: solventsolvent, solvent-segment, and segment-segment. The binary interaction parameter i , j allows complex temperature dependence:
i , j = ai , j + bi , j / Tr + ci , j ln Tr + d i , j Tr + ei , j Tr2
with
(2.132)
Tr =
T Tref
(2.133)
where Tref is a reference temperature and the default value is 298.15 K. The following table lists the copolymer PC-SAFT EOS model parameters implemented in Aspen Plus:
Parameter Name / Element
PCSFTM PCSFTV PCSFTU PCSFTR PCSFAU PCSFAV PCSFMU PCSFXP PCSKIJ/1 PCSKIJ/2 PCSKIJ/3 PCSKIJ/4 PCSKIJ/5 PCSKIJ/6
Symbol
Default
Lower Limit
----
Upper Limit
----
MDS
Units Keyword
TEMP TEMP DIPOLE MOMENT -- TEMP
Comments
----0.0 0.0 0.0 0.0 0.0 298.15
X X X X X X X X X X X X X X
Unary Unary Unary Unary Unary Unary Unary Unary Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric
/k
r
AB / k AB
xp ai , j bi , j ci , j d i , j e i , j Tref
Parameter input and regression

Since the copolymer PC-SAFT is built based on the segment concept, the unary (pure) parameters must be specified for a solvent or a segment. Specifying a unary parameter for a polymer component (homopolymer or copolymer) will be ignored by the simulation. For a non-association and non-
77
polar solvent, three unary parameters PCSFTM, PCSFTU, and PCSFTV must be specified. For a non-association and non-polar segment, these three unary parameters PCSFTR, PCSFTU, and PCSFTV must be specified. For an association species (solvent or segment), two additional unary parameters PCSFAU and PCSFAV must be specified. For a polar species (solvent or segment), two additional unary parameters PCSFMU and PCSFXP must be specified. The binary parameter PCSKIJ can be specified for each solvent-solvent pair, or each solvent-segment pair, or each segment-segment pair. By default, the binary parameter is set to be zero. A databank called PC-SAFT contains both unary and binary PC-SAFT parameters available from literature; it must be used with the PC-SAFT property method. The unary parameters available for segments are stored in the SEGMENT databank. If unary parameters are not available for a species (solvent or segment) in a calculation, the user can perform an Aspen Plus Data Regression Run (DRS) to obtain unary parameters. For non-polymer components (mainly solvents), the unary parameters are usually obtained by fitting experimental vapor pressure and liquid molar volume data. To obtain unary parameters for a segment, experimental data on liquid density of the homopolymer that is built by the segment should be regressed. Once the unary parameters are available for a segment, the ideal-gas heat capacity parameter CPIG may be regressed for the same segment using experimental liquid heat capacity data for the same homopolymer. In addition to unary parameters, the binary parameter PCSKIJ for each solvent-solvent pair, or each solvent-segment pair, or each segment-segment pair, can be regressed using vapor-liquid equilibrium (VLE) data in the form of TPXY data in Aspen Plus. Note: In Data Regression Run, a homopolymer must be defined as an OLIGOMER type, and the number of the segment that builds the oligomer must be specified.
Option Codes for PC-SAFT

The copolymer PC-SAFT has three option codes. Option code 1. The user can use this option code to specify the copolymer type. The default type is the random copolymer (0). Other types are the alternative copolymer (1) and the block copolymer (2). All other values are assigned to the random copolymer. Option code 2. This option code is restricted to the Sadowskis copolymer model in which a copolymer must be built only by two different types of segments (Gross and Sadowski, 2003; Becker et al., 2004). In order to use the Sadowskis copolymer model, this option code must be set to one. Option code 3. The user can use this option code to turn off the association term from the copolymer PC-SAFT model by setting a non-zero value.
Sample Calculation Results

In Figure 1, Aspen Plus applies the PC-SAFT EOS model to calculate both vapor-liquid and liquid-liquid equilibria for methanol-cyclohexane mixtures at p = 1.013 bar. This mixture exhibits an azeotropic vapor-liquid equilibrium at higher temperatures and shows a liquid-liquid equilibrium at lower temperatures. Both pure and binary parameters used are taken directly from the paper by Gross and Sadowski (2002b). The results show that the PC-SAFT model with the association term included can correlate phase equilibrium data well for associating mixtures.
Figure 1. Isobaric vapor-liquid and liquid-liquid equilibria of methanolcyclohexane at p = 1.013 bar. Experimental data are taken from Jones and Amstell (1930) and Marinichev and Susarev (1965).
Figure 2 shows a model calculation for HDPE-Hexane mixtures. This system exhibits both lower critical solution temperature (LCST) and upper critical solution temperature (UCST) at p = 50 bar. The pure parameters are taken directly from papers Gross and Sadowski (2001; 2002a). The binary parameter between hexane and ethylene segment is set to 0.012. The phase equilibrium calculations are carried by Flash3 block with Gibbs flash algorithm in Aspen Plus.
79
Liquid-liquid equilibria of HDPE-Hexane

250
200 UCST
Temperature (C)
150
100
50 LCST
0 0 0.1 0.2 0.3 0.4 0.5 0.6
HDPE weight fraction

Figure 2. Liquid-liquid equilibria of HDPE-Hexane mixtures in a weight fraction-pressure plot by PC-SAFT EOS model. It shows both lower critical solution temperature (LCST) and upper critical solution temperature (UCST).
Figure 3 shows the vapor-liquid equilibrium of the mixture water-acetone at p = 1.703 bar. The dashed line represents PC-SAFT calculations where water is treated as an associating component and acetone as a polar component; the cross association in the mixture is not considered ( ij = 0.15 ). The solid line represents PC-SAFT calculations where the cross association between water and acetone is accounted for ( ij = 0.055 ) using a simple approach by Sadowski & Chapman et al. (2006). In this approach, the association energy and effective volume parameters of the non-associating component (acetone) are set to zero and to the value of the associating component (water), respectively. Further, the polar component is represented by the three purecomponent parameters without using the dipolar model.
Figure 3. Vapor-liquid equilibrium of the mixture water-acetone at p = 1.703 bar. Experimental data are taken from Othmer and Morley (1946).
81
Figure 4 shows the liquid-liquid equilibria of polypropylene (PP)-n-pentane at three temperatures in a pressure-weight fraction plot. The weight average molecular weight of PP is M w = 50.4 kg / mol , M w / M n = 2.2 . Both pure and binary parameters used are taken directly from the paper by Gross and Sadowski (2002a).
Liquid-liquid equilibria of PP-n-Pentane

80
70
60
Pressure bar
50
40
30
PC-SAFT Data (T=187 C)

20
Data (T=177 C) Data (T=197 C)
10
0 0 0.05 0.1 0.15 0.2 0.25 0.3
PP weight fraction
Figure 4. Liquid-liquid equilibria of PP-n-Pentane at three different temperatures. Comparison of experimental cloud points (Martin et al., 1999) to PC-SAFT calculations ( ij monodisperse at
= 0.0137 ). The polymer was assumed to be
M w = 50.4 kg / mol .
Specifying the Copolymer PC-SAFT EOS Model

References
Alder, B. J., Young, D. A., & Mark, M. A. (1972). Studies in Molecular Dynamics. X. Corrections to the Augmented van der Waals Theory for the Square-Well Fluid. J. Chem. Phys., 56, 3013. Aspen Physical Property System Physical Property Methods and Models. Cambridge, MA: Aspen Technology, Inc. Behme, S., Sadowski, G., Song, Y., & Chen, C.-C. (2003). Multicomponent Flash Algorithm for Mixtures Containing Polydisperse Polymers. AIChE J., 49, 258. Becker, F., Buback, M., Latz, H., Sadowski, G., & Tumakaka, F. (2004). Cloud-Point Curves of Ethylene-(Meth)acrylate Copolymers in Fluid Ethene up to High Pressures and Temperatures Experimental Study and PC-SAFT Modeling. Fluid Phase Equilibria, 215, 263-282. Behme, S., Sadowski, G., Song, Y., & Chen, C.-C. (2003). Multicomponent Flash Algorithm for Mixtures Containing Polydisperse Polymers. AIChE J., 49, 258. Carnahan, N. F., & Starling, K. E. (1972). Intermolecular Repulsions and the Equation of State for Fluids. AIChE J., 18, 1184. Chapman, W. G., Gubbins, K. E., Jackson, G., & Radosz, M. (1989). Fluid Phase Equilibria, 52, 31. Chapman, W. G., Gubbins, K. E., Jackson, D., & Radosz, M. (1990). A New Reference Equation of State for Associating Liquids. Ind. Eng. Chem. Res., 29, 1709. Chen S.-J., Economou, I. G., & Radosz, M. (1992). Density-Tuned Polyolefin Phase Equilibria. 2. Multicomponent Solutions of Alternating Poly(EthylenePropylene) in Subcritical and Supercritical Solvents. Experiment and SAFT Model. Macromolecules, 25, 4987. Chen, S. S., & Kreglewski, A. (1977). Applications of the Augmented van der Waals Theory of Fluids I. Pure Fluids. Ber. Bunsenges. Phys. Chem., 81, 1048. Fischer, K., & Gmehling, J. (1996). Further development, status and results of the PSRK method for the prediction of vapor-liquid equilibria and gas solubilities. Fluid Phase Eq., 121, 185. Folie, B., & Radosz, M. (1995). Phase Equilibria in High-Pressure Polyethylene Technology. Ind. Eng. Chem. Res., 34, 1501. Gregg, C. J., Stein, F. P., & Radosz, M. (1994). Phase Behavior of Telechelic Polyisobutylene (PIB) in Subcritical and Supercritical Fluids. 1. Inter- and Intra-Association Effects for Blank, Monohydroxy, and Dihydroxy PIB(1K) in Ethane, Propane, Dimethyl Ether, Carbon Dioxide, and Chlorodifluoromethane. Macromolecules, 27, 4972. Gross, J., & Sadowski, G. (2001). Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain Molecules. Ind. Eng. Chem. Res., 40, 1244-1260.
83
Gross, J., & Sadowski, G. (2002a). Modeling Polymer Systems Using the Perturbed-Chain Statistical Associating Fluid Theory Equation of State. Ind. Eng. Chem. Res., 41, 1084-1093. Gross, J., & Sadowski, G. (2002b). Application of the Perturbed-Chain SAFT Equation of State to Associating Systems. Ind. Eng. Chem. Res., 41, 55105515. Gross, J., Spuhl, O., Tumakaka, F., & Sadowski, G. (2003). Modeling Copolymer Systems Using the Perturbed-Chain SAFT Equation of State. Ind. Eng. Chem. Res., 42, 1266-1274. Hasch, B. M., & McHugh, M. A. (1995). Calculating Poly(ethylene-co-acrylic acid)-Solvent Phase Behavior with the SAFT Equation of State. J. Pol. Sci.:B: Pol. Phys., 33, 715. Hasch, B. M, Meilchen, M. A., Lee, S.-H., & McHugh, M. A. (1992). HighPressure Phase Behavior of Mixtures of Poly(Ethylene-co-Methyl Acrylate) with Low-Molecular Weight Hydrocarbons. J. Pol. Sci., 30, 1365-1373. Holderbaum, T., & Gmehling, J. (1991). PSRK: A group contribution equation of state based on UNIFAC. Fluid Phase Eq., 70, 251. Huang, S. H., & Radosz, M. (1990). Equation of State for Small, Large, Polydisperse, and Associating Molecules. Ind. Eng. Chem. Res., 29, 2284. Huang, S. H., & Radosz, M. (1991). Equation of State for Small, Large, Polydisperse, and Associating Molecules: Extension to Fluid Mixtures. Ind. Eng. Chem. Res., 30, 1994. Jog, P. K., Sauer, S. G., Blaesing, J., & Chapman, W. G. (2001), Application of Dipolar Chain Theory to the Phase Behavior of Polar Fluids and Mixtures. Ind. Eng. Chem. Res., 40, 4641. Jones, D. C., & Amstell, S. (1930). J. Chem. Soc., 1316. Kleiner, M., Tumakaka, F., Sadowski, G., Dominik, A., Jain, S., Bymaster, A., & Chapman, W. G. (2006). Thermodynamic Modeling of Complex Fluids using PC-SAFT. Final Report for Consortium of Complex Fluids. Universitt Dortmund & Rice University. Kleiner, M., Tumakaka, F., Sadowski, G., Latz, H., & Buback, M. (2006).Phase Equilibria in Polydisperse and Associating Copolymer Solutions: Poly(ethaneco-(meth)acrylic acid) Monomer Mixtures. Fluid Phase Equilibria, 241, 113123. Kontogeorgis, G. M., Harismiadis, V. I., Frendenslund, Aa., & Tassios, D. P. (1994). Application of the van der Waals Equation of State to Polymers. I. Correlation. Fluid Phase Equilibria, 96, 65-92. Lambert, S. M., Song, Y., & Prausnitz, J. M. (2000). Equations of State for Polymer Systems. In J. V. Sengers, R. F. Kayer, C. J. Peters, and H. J. White, (Eds.), Equations of State for Fluids and Fluid Mixtures. (pp. 523-588) New York: Elsevier Science. Lee, S.-H., Hasch, B. M., & McHugh, M. A. (1996). Calculating Copolymer Solution Behavior with Statistical Associating Fluid Theory. Fluid Phase Equil., 117, 61.
Lee, S.-H., LoStracco, M. A., & McHugh, M. A. (1994). High-Pressure, Molecular-Weight Dependent Behavior of (Co)polymer-Solvent Mixtures: Experiments and Modeling. Macromolecules, 27, 4652. Mansoori, G. A., Carnahan, N. F., Starling, K. E., & Leland, T. W. J. (1971). J. Chem. Phys., 54, 1523. Marinichev, A.N., & Susarev, M.P. (1965). Zh. Prikl. Khim., 38, 1619. Martin, T. M., Lateef, A. A., & Roberts, C. B. (1999). Measurements and modeling of cloud point behavior for polypropylene/n-pentane and polypropylene/n-pentane/carbon dioxide mixtures at high pressures. Fluid Phase Equilibria, 154, 241. Mathias, P. M., & Copeman, T. W. (1983). Extension of the Peng-Robinson equation of state to complex mixtures: evaluation of the various forms of the local composition concept. Fluid Phase Eq., 13, 91. Orbey, H., Bokis, C. P., & Chen, C.-C. (1998a). Polymer-Solvent Vapor-Liquid Equilibrium: Equations of State versus Activity Coefficient Models. Ind. Eng. Chem. Res., 37, 1567-1573. Orbey, H., Bokis, C. P., & Chen, C.-C. (1998b). Equation of State Modeling of Phase Equilibrium in the Low-Density Polyethylene Process: The SanchezLacombe, Statistical Associating Fluid Theory, and Polymer-Soave-RedlichKwong Equation of State. Ind. Eng. Chem. Res., 37, 4481-4491. Orbey, H., & Sandler, S. I. (1995). On the combination of equation of state and excess free energy models. Fluid Phase Eq., 111, 53. Orbey, H., & Sandler, S. I. (1997). A comparison of Huron-Vidal type mixing rules of compounds with large size differences, and a new mixing rule. Fluid Phase Eq., 132, 1. Othmer, D. F., & Morley, F. R. (1946). Composition of Vapors from Boiling Binary Solutions Apparatus for Determinations under Pressure. Ind. Eng. Chem., 38, 751-757. Pradham, D., Chen, C.-K., & Radosz, M. (1994). Fractionation of Polystyrene with Supercritical Propane and Ethane: Characterization, Semibatch Solubility Experiments, and SAFT Simulations. Ind. Eng. Chem. Res., 33, 1984. Rodgers, P. A. (1993). Pressure-Volume-Temperature Relationships for Polymeric Liquids: A Review of Equations of State and Their Characteristic Parameters for 56 Polymers. J. of Applied Polymer Science, 48, 1061-1080. Rushbrooke, G. S., & Stell, G., Hoye, J. S. (1973), Molec. Phys., 26, 1199. Sanchez, I. C., & Lacombe, R. H. (1976). An Elementary Molecular Theory of Classical Fluids. Pure Fluids. J. Phys. Chem., 80, 2352-2362. Sanchez, I. C., & Lacombe, R. H. (1978). Statistical Thermodynamics of Polymer Solutions. Macromolecules, 11, 1145-1156. Sanchez, I. C. (1992). Polymer Phase Separation. In Encyclopedia of Physical Science and Technology, 13. New York: Academic Press. Saraiva A., Kontogeorgis, G. M., Harismiadis, V. I., Fredenslund, Aa., & Tassios, D. P. (1996). Application of the van der Waals Equation of State to Polymers IV. Correlation and Prediction of Lower Critical Solution Temperatures for Polymer Solutions. Fluid Phase Equilibria, 115, 73-93.
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Teja, A. S., Lee, R. J., Rosenthal, D.J., & Anselme, M. (1990). Correlation of the critical properties of alkanes and alkanols. Fluid Phase Eq., 56, 153. Topliss, R. J. (1985). Techniques to Facilitate the Use of Equations of State for Complex Fluid-Phase Equilibria. Ph.D. Dissertation, University of California, Berkeley. Tsonopoulos, C., & Tan, Z. (1993). The critical constants of normal alkanes from methane to polyethylene. II. Application of the Flory theory. Fluid Phase Eq., 83, 127. Wei, Y. S., & Sadus, R. J. (2000). Equations of State for Calculation of FluidPhase Equilibria. AIChE Journal, 46, 169. Wertheim, M. S. (1984). Fluids with Highly Directional Attractive Forces. II. Thermodynamic Perturbation Theory and Integral Equations. J. Stat. Phys., 35, 35. Wertheim, M. S. (1986a). Fluids with Dimerizing Hard Spheres, and Fluid Mixtures of Hard Spheres and Dispheres. J. Stat. Phys., 85, 2929. Wertheim, M. S. (1986b). Fluids with Highly Directional Attractive Forces. IV. Equilibrium Polymerization. J. Stat. Phys., 42, 477. Xiong, Y., & Kiran, E. (1995). Comparison of Sanchez-Lacombe and SAFT Model in Predicting Solubility of Polyethylene in High-Pressure Fluids. J. Appl. Pol. Sci., 55, 1805.
3 Activity Coefficient Models
This chapter discusses thermodynamic properties of polymer systems from activity coefficient models. Activity coefficient models are used in Aspen Polymers (formerly known as Aspen Polymers Plus) to calculate liquid activity coefficients, liquid excess Gibbs free energy, liquid excess enthalpy, and liquid excess entropy of mixtures. Topics covered include: About Activity Coefficient Models, 87 Phase Equilibria Calculated from Activity Coefficient Models, 88 Other Thermodynamic Properties Calculated from Activity Coefficient Models, 90 Mixture Liquid Molar Volume Calculations, 92 Related Physical Properties in Aspen Polymers, 93 Flory-Huggins Activity Coefficient Model, 94 Polymer NRTL Activity Coefficient Model, 98 Electrolyte-Polymer NRTL Activity Coefficient Model, 103 Polymer UNIFAC Activity Coefficient Model, 114 Polymer UNIFAC Free Volume Activity Coefficient Model, 117
About Activity Coefficient Models

In general, the activity coefficient models are versatile, accommodating a high degree of solution nonideality into the model. On the other hand, when applied to VLE calculations, they can only be used for the liquid phase and another model (usually an equation of state) is needed for the vapor phase. Activity coefficient models usually perform well for systems of polar compounds at low pressures and away from the critical region. They are the best way to represent highly non-ideal liquid mixtures at low pressures. They are used for the calculation of fugacity, enthalpy, entropy and Gibbs free energy. Usually an empirical correlation is used in parallel for the calculations of density when an activity coefficient model is used in phase equilibrium modeling.
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87
There are a large number of activity coefficient models for use in polymer process modeling. Aspen Polymers offers: Flory-Huggins model (Flory, 1953) Non-Random Two-Liquid (NRTL) Activity Coefficient model adopted to polymers (Chen, 1993) Polymer UNIFAC model UNIFAC free volume model (Oishi & Prausnitz, 1978) The two UNIFAC models are predictive while the Flory-Huggins and Polymer-NRTL models are correlative. Between the correlative models, the Flory-Huggins model is only applicable to homopolymers because its parameter is polymer-specific. The Polymer-NRTL model is a segmentbased model that allows accurate representation of the effects of copolymer composition and polymer chain length.
Phase Equilibria Calculated from Activity Coefficient Models

The activity coefficient model can be related to the fugacity of liquid phase through fundamental thermodynamic equation:
f i l = xi i f i *,l
Where:
f il
= = = =
Fugacity of component i in the liquid phase Mole fraction of component i in the liquid phase Activity coefficient of component i in the liquid phase Liquid phase reference fugacity of component i
xi
i
f i *,l
In the equation above, the activity coefficient,
i , represents the deviation of

*,l
the mixture from ideality, and the liquid phase reference fugacity, f i , is defined as that of the pure liquid i at the temperature and pressure of the mixture. The activity coefficient, i , is obtained from an activity coefficient model, as shown in the following sections.
Vapor-Liquid Equilibria in Polymer Systems

In the activity coefficient approach, the basic vapor-liquid equilibrium relationship is represented by:
iv y i p = xi i f i *,l
(3.1)
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The vapor phase fugacity coefficient,
iv , is computed from an equation of
state (see Chapter 2).The liquid activity coefficient, i , is computed from an activity coefficient model. Liquid Phase Reference Fugacity The liquid phase reference fugacity, f i , is generally expressed as:
*,l
f i *,l = i*,v p i*,l i*,l

With
(3.2)
i*,l = exp
Where:
1 RT
pi*, l
Vi *,l dp
(3.3)
i*,v
pi*,l
Fugacity coefficient of pure component i at the system temperature and the vapor pressure of component i, as calculated from the vapor phase equation of state Liquid vapor pressures of component i at the system temperature Poynting correction of component i for pressure Liquid molar volume of component i at T and p
= = =
i*,l
Vi *,l
However, Equations 3.2 and 3.3 are applicable only to solvents, light polymers and oligomers (volatile) in the mixture. For other components such as heavy polymers and oligomers (nonvolatile) and dissolved gases in the *,l mixture, the liquid phase reference fugacity, f i , has to be computed in different ways: For nonvolatile polymers or oligomers (used in Data Regression) : These components exist only in the liquid phase. Therefore, the vaporliquid equilibrium condition given by Equation 3.1 does not apply to them. Their mole fractions in the liquid phase at VLE can be determined by the mass balance condition. For dissolved gases: Light gases (such as O2 and N 2 ) are usually supercritical at the temperature and pressure of the solution. In this case pure component vapor pressure is meaningless and, therefore, cannot serve as the reference fugacity. The reference state for a dissolved gas is redefined to be at infinite dilution and at the temperature and pressure of the mixtures. The liquid phase reference fugacity, f i Henry's constant for component i in the mixture).
*, l
, becomes H i (the
The activity coefficient, i , is converted to the infinite dilution reference state through the relationship:
* = ( i )
i i
(3.4)
Where:
89
Infinite dilution activity coefficient of component i in the mixture
By this definition
*i approaches unity as x i approaches zero. The phase

(3.5)
equilibrium relationship for dissolved gases becomes:
iv y i p = xi i* H i
To compute H i , you must supply the Henry's constant for the dissolved-gas component i in each subcritical solvent component.
Liquid-Liquid Equilibria in Polymer Systems

The basic liquid-liquid-vapor equilibrium relationship is:
xil1 il1 f i*,l = xil2 il2 f i *,l = iv yi p
(3.6)
For liquid-liquid equilibria, the vapor phase term can be omitted, and the pure component liquid fugacity cancels out:
xil1 il1 = xil2 il2

Where:
(3.7)
il
= =
Activity coefficient of component i in the liquid phase Activity coefficient of component i in the liquid phase
l1 l2
il
xil1 = Mole fraction of component i in the liquid phase l1 xil2 = Mole fraction of component i in the liquid phase l 2
Unlike Equation 3.1 for vapor-liquid equilibria, Equation 3.7 applies to each component of mixtures in two-coexisting liquid phases.
Other Thermodynamic Properties Calculated from Activity Coefficient Models

The activity coefficient model can be related to other properties through fundamental thermodynamic equations. These properties (called excess liquid functions) are relative to the ideal liquid mixture at the same condition: Excess molar liquid Gibbs free energy:
E Gm ,l = RT xi ln i i
(3.8)
Excess molar liquid enthalpy:
E H m ,l = RT 2 xi i
ln i T
(3.9)
Excess molar liquid entropy:
ln i E S m ,l = R xi ln i + T T (3.10) i
Where:
E G m ,l =
E H m ,l =
Excess molar liquid Gibbs free energy of the mixture Excess molar liquid enthalpy of the mixture Excess molar liquid entropy of the mixture
E S m ,l
The excess liquid functions given by Equations 3.83.10 are calculated from the same activity coefficient model. In practice, however, the activity coefficient i is often derived first from the excess liquid Gibbs free energy of a mixture from an activity coefficient model:
E 1 ( nGm ,l ) RT ni T , p ,n j i
ln i =
With
(3.11)
E id nGm ,l = Gmixing Gmixing

id Gmixing = ni ln xi i
(3.12)
(3.13)
Where:
n
ni
G mixing
id Gmixing
= Total mole number of the mixture = Mole number of component i in the mixture = Liquid Gibbs free energy of mixing; it is defined as the difference between the Gibbs free energy of the mixture and that of the pure components = Ideal Gibbs free energy of mixing
Once the excess liquid functions are known, the thermodynamic properties of liquid mixtures can be computed as follows:
l E H m = xi H i*,l + H m ,l i
(3.14) (3.15)
l E Gm = xi i*,l + G m ,l + RT xi ln xi i i
l Sm =
1 l l H m Gm T
(3.16)
91
Where:
l Hm
l Gm l Sm
= = =
Liquid mixture molar enthalpy Liquid mixture molar Gibbs free energy Liquid mixture molar entropy Liquid pure component enthalpy Liquid pure component Gibbs free energy
H i*,l =
i*,l
In Equations 3.14 and 3.15, the first terms are the ideal mixing terms and the second terms come from the excess functions. The last term in Equation 3.15 represents the Gibbs free energy of mixing for ideal gases. For non-polymer components, Aspen Plus provides the standard correlation model such as the *,l *,l DIPPR method to calculate H i and i . For more information, see Aspen Physical Property System Physical Property Methods and Models. Aspen *,l Polymers provides the van Krevelen liquid property models to calculate H i and
i*,l
for polymers, oligomers, and segments. For more information, see
Chapter 4.
Mixture Liquid Molar Volume Calculations

In Aspen Plus, when an activity coefficient model or a cubic equation-of-state model is used, an empirical correlation method is used in parallel for calculating liquid density of both pure components and mixtures. This concept is extended to cover polymer and oligomer components and polymer mixtures in Aspen Polymers. The liquid molar default route uses the van Krevelen model or the Tait model to calculate the liquid molar volume of pure polymers, oligomers, and segments. The Rackett model is used to calculate the liquid molar volume of non-polymer components. The mixture liquid molar volume is calculated using the ideal mixing rule:
l s Vm = Vm + x pV p*,l p
With
s Vm = Rackett ( x s' , T , p)
x s' = x s / x s
s
x +x
s s p
=1
Where:
l Vm
= = = = = =
Liquid mixture molar volume Liquid polymer-free mixture molar volume Liquid molar volume of a polymer or oligomer component in the mixture Liquid mole fraction of a polymer or oligomer component in the mixture Liquid mole fraction of a solvent component in the mixture Liquid mole fraction of a solvent component in the polymer-free mixture
s
s Vm
V p*,l
xp xs x s'
The liquid polymer-free mixture molar volume, Vm , is calculated using the Rackett model. For more information, see Aspen Physical Property System Physical Property Methods and Models. The liquid molar volume of a polymer or oligomer component, V p , is calculated using either the van Krevelen model or the Tait model. For more information, see Chapter 4.
*,l
Related Physical Properties in Aspen Polymers

The following properties are related to activity coefficient models in Aspen Polymers:
Property Symbol Name GAMMA HLMX SLMX GLMX HLXS GLXS SLXS Description Liquid activity coefficient of a component in a mixture Liquid mixture molar enthalpy Liquid mixture molar entropy Liquid mixture molar Gibbs free energy Liquid mixture molar excess enthalpy Liquid mixture molar excess Gibbs free energy Liquid mixture molar excess entropy
i
l Hm
l Sm l Gm E H m ,l
E G m ,l E S m ,l
The following table provides an overview of the activity coefficient models available in Aspen Polymers. This table lists the Aspen Physical Property System model names, and their possible use in liquid phase for mixtures. Details of individual models are presented next.
Models Model Name Phase(s) Pure Mixture Properties Calculated
93
Flory-Huggins Polymer NRTL ElectrolytePolymer NRTL Polymer UNIFAC Polymer UNIFAC Free Volume
GMFH GMNRTLP GMEPNRTL GMPOLUF GMUFFV
l l l l l
X X X X X
GAMMA, HLXS, GLXS, SLXS GAMMA, HLXS, GLXS, SLXS GAMMA, HLXS, GLXS, SLXS GAMMA, HLXS, GLXS, SLXS GAMMA, HLXS, GLXS, SLXS
Flory-Huggins Activity Coefficient Model

This section describes the Flory-Huggins activity coefficient model available in the POLYFH physical property method. The Flory-Huggins model gives good results if the interaction parameter is known accurately at the particular physical states of the system, i.e., temperature, composition, and polymer molecular weight. According to the Flory-Huggins theory, the parameter should be independent of polymer concentration and of polymer molecular weight. In reality, it is shown to vary significantly with both. The model works well if the interaction parameter at a low solvent concentration is used to estimate the activity coefficient at a higher solvent concentration. However, extrapolations to low solvent concentrations using based on a higher solvent concentration can lead to significant errors. Finally, the Flory-Huggins model is not very accurate for polar systems, and unless it is used with a cubic-equation-of-state, it should not be used for phase equilibrium calculations at high pressures. Flory (1941) and Huggins (1941) independently derived an expression for the combinatorial entropy of mixing of polymer molecules with monomer molecules based on the lattice theory of fluids. This statistical approach, widely used for liquid mixtures, takes into account the unequal size of the molecules and the linkage between flexible segments on the polymer chains. The enthalpy of mixing and the energetic interactions between the molecules are quantified through an interaction parameter for each moleculemolecule pair. (See Polymer NRTL Activity Coefficient Model on page 98 for a relationship of to NRTL interaction parameters.) Consider a binary mixture with components differing significantly in molecular size: a polymer and a spherical solvent. To obtain the mixing properties of this system, Flory and Huggins applied a lattice model to this system. The combinatorial and non-combinatorial properties of the mixture are derived by arranging both polymer and solvent on the lattice. Each solvent molecule occupies one lattice site. Each polymer molecule is divided into m flexible segments and each segment occupies one lattice site.
Gibbs free energy of mixing Based on statistical arguments and several assumptions, the Gibbs free energy of mixing is derived as follows for a binary system:
2 Gmixing = 1 ln1 + ln 2 + 12 1 2 (n1 +n2 m ) RT m

With:
(3.17)
1 = 2 =
n1 n1 + mn2 (3.18) mn2 n1 + mn2
(3.19)
Where:
12
m
= Molecular interaction parameter = Number of segments in the polymer molecule = Number of moles of solvent in the mixture = Number of polymer molecules in the mixture = Mole fractions on a segment basis
n1 n2
1 , 2
If m is set equal to the ratio of molar volumes of polymer and solvent, then 1 and 2 are the volume fractions. If m is set equal to the ratio of molecular weight of polymer and solvent, then 1 and 2 are the weight fractions. Therefore, the Gibbs free energy of mixing equation, Equation 3.17, is a generalized form that can be expanded to three different equations with being the segment-based mole fraction, volume fraction or weight fraction, depending on how m is defined. These three equations can be accessed in the Flory-Huggins model using option codes. Option codes 1, 2, and 3, correspond to the weight basis, segment mole basis and volume basis, respectively. Option code 2 (segment basis) is the default. A large portion of experimental polymer solution phase equilibria data in the open literature are reported using a volume fraction basis. The volume fraction basis allows users to directly apply interaction parameters from literature to their simulation. There are, however, situations where neither the segment-based mole fraction basis nor the volume fraction basis are appropriate. This is the case for many industrial processes of polymer mixtures. In such situations composition is usually known on a weight basis. Unlike segment mole fraction, component weight fraction remains consistent regardless of how the polymer segments are defined. Multicomponent Mixtures
95
The derivation of Flory and Huggins has been extended to cover multiple components (Tompa, 1956):
Gmixing RT
= i ln i + ij i j ni mi m j <i i i i
(3.20)
From this equation, one can derive the activity coefficient of a component (for example, Equation 3.11):
ln i = ln
+ 1 mi xi
1 jk j k ij + mj k> j
(3.21)
Where:
xi
= =
Mole fraction of component I Interaction binary parameter
ij
In the above equations, note that
can be calculated on three different
basis: segment-based mole fraction, volume fraction, and weight fraction, as given in the next table for three option codes. However, mi is treated independently as a pure component characteristic size parameter regardless of what option basis is used for calculating i ; it is related to the degree of polymerization by:
mi = s i * Pi i
Where: =
(3.22) Degree of polymerization Empirical parameters
Pi
si and i =
si and i account for deviation of the component characteristic size from its
degree of polymerization. Users may use these parameters singly or in combination to adjust the component characteristic size. By default Pi is 1.0 for small molecules. The binary interaction parameter,
ij , accounts for the enthalpic effects on

(3.23)
mixing. It is strongly temperature dependent:
ij = aij + bij / Tr + cij ln Tr + d ij Tr + eij Tr2

with
Tr =
T Tref
= Reference temperature and the default value = 1 K for compatibility with previous releases.
Where:
Tref
A summary of equations for the three options for concentration basis of the Flory-Huggins model is given here :
Option 1 Description Mass Basis: Concentration Characteristic Size
wi Mi
= Mass fraction = Number average molecular
i =
weight for polymer/oligomer; molecular weight for conventional component 2 Segment mole fraction basis:
ni M i = wi njM j
j
mi = s i * Pi i
ni Pi
3
= Number of moles = Number average chain length
i =
ni Pi n j Pj
j
mi = s i * Pi i
Volume basis:
Vi vi wi
= Molar volume ( m
/ kmol )
3
= Specific volume ( m = Mass fraction
/ kg )
i =
niVi = n jV j
j
wi vi wjv j
j
mi = s i * Pi i
Note that for monomers and solvents, user.
Pi = POLDP = 1.0
unless changed by the
si
and
are defaulted to be unity for all components. For option code 2
(segment-based mole fraction), Equation 3.21 reduces to the original Flory-Huggins equation for the solvent activity coefficient.
Flory-Huggins Model Parameters

The following table lists the input parameters for the Flory-Huggins model. These parameters would normally be regressed from experimental data.
Parameter Name / Element FHCHI/1 FHCHI/2 FHCHI/3 FHCHI/4 FHCHI/5 FHCHI/6 Symbol Default Lower Limit -100 -1E6 -1E6 -1E6 -1E6 -1E6 Upper Limit 100 1E6 1E6 1E6 1E6 1E6 MDS Units Keyword ----------TEMP Comments
aij bij cij d ij eij
0.0 0.0 0.0 0.0 0.0 1.0
X X X X X X
Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric
Tref
97
FHSIZE/1 FHSIZE/2 POLDP*
si
1.0 1.0 1.0
1E-15 -1E10 1.0
1E15 1E10 1E10
X X ---
-------
Unary Unary Unary
i
Pi
The actual degree of polymerization is used for polymer components.
Specifying the Flory-Huggins Model

Polymer NRTL Activity Coefficient Model

This section describes the Polymer NRTL activity coefficient model available in the POLYNRTL physical property method. The polymer NRTL activity coefficient model is an extension of the NRTL model for low molecular weight compounds (Chen, 1993; Renon & Prausnitz, 1968). The main difference between this model and the Flory-Huggins model is that in the polymer NRTL activity coefficient model the binary interaction parameters are relatively independent of polymer concentration and polymer molecular weight. Furthermore, in the case of copolymers, the polymer NRTL binary parameters are independent of the relative composition of the repeat units on the polymer chain. This model can be used in a correlative mode at low and moderate pressures for a wide variety of fluids, including polar systems. The current model does not address the free volume term or the so-called equation-of-state term, and strong orientational interactions, such as hydrogen bonding, as part of the entropy of mixing. As a result, the models cannot be used to represent lower critical solution temperature. The polymer NRTL model is a segment-based local composition model for the Gibbs free energy of mixing of polymer solutions. It represents a synergistic combination of the Flory-Huggins description for the entropy of mixing molecules of different sizes and the Non-Random Two Liquid theory for the enthalpy of mixing solvents and polymer segments. It reduces to the wellknown NRTL equation if no polymers are present in the system. The NRTL model is known to be one of the most widely used activity coefficient models. It has been used to represent phase behavior of systems with nonelectrolytes and electrolytes. The polymer NRTL model is an extension of the NRTL model from systems of small molecules to systems with both small molecules and macromolecules. It requires the solventsolvent, solvent-segment, and segment-segment binary parameters. The solvent-solvent binary parameters can be readily obtained from systems of monomeric molecules. Many such solvent-solvent binary parameters are available in the literature. Furthermore, the solvent-segment binary
parameters have the desirable characteristic that they are relatively independent of temperature, chain length, and polymer concentration. The polymer NRTL model provides a flexible thermodynamic framework to correlate the phase behavior of polymer solutions. The model can be used to represent vapor-liquid equilibrium and liquid-liquid equilibrium of polymer systems.
Polymer NRTL Model

In the Polymer NRTL model (GMNRTLP), the Gibbs free energy of mixing of a polymer solution is expressed as the sum of the entropy of mixing, based on the Flory-Huggins equation, and the enthalpy of mixing, based on the NonRandom Two Liquid theory. The reference states for the polymer NRTL equation are pure liquids for solvents and a hypothetical segment aggregate state for polymers. In this hypothetical aggregate state, all segments are surrounded by segments of the same type. The following is the equation for the Gibbs free energy of mixing:
G mixing RT
NRTL H mixing
RT
FH S mixing
Gibbs free energy of mixing
G mixing RT
x G = n x G
j js j s s j j
js
js
x G + n r x G
j ji j p i ,p p i j j
ji
ji
+ nI ln I
I
With:
xi
X r = X r
I i,I I J j
J j,J
XI =
nI nJ
J
G ji = exp( ji ji )
ji =
I =
( g ji g ii )
RT
nI mI nJ mJ
J
Where:
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I and J = i and j = s p = = = = = = = = = = = = = =
Component based indices Segment based indices Solvent component Polymer component Number of mole of solvent component s Number of mole of polymer component p Segment based mole fraction for segment based species i Mole fraction of component I in component basis Number of segment type i in component I NRTL non-random factor Interaction parameter Energies of interaction between j-i pairs of segment based species Energies of interaction between i-i pairs of segment based species Number of moles of component I Volume fraction (approximated as segment mole fraction) of component I Ratio of polymer molar volume to segment molar volume of component I
ns np xi
XI
ri , I
ji ji
g ji
gii
nI I
mI
The species i and j can be solvent molecules or segments. The excess Gibbs free energy expression is obtained by subtracting the ideal Gibbs free energy of mixing from the Gibbs free energy of mixing equation:
E nGm ,l = ns RT s
x G x G
j js j j j
js
js
x G + n r x G
j ji j p i, p p i j j
ji
ji
+ nI ln I X I I
The activity coefficient of each component in the polymer solution can also be considered as the sum of two contributions:
ln I = ln INRTL + ln IFH
With:
ln IFH = ln I X I
+ 1 mI J J mJ
Where:
m J = Characteristic size of component J m J is related to the degree of polymerization by:
m J = s J * PJ J
Where:
PJ
Degree of polymerization Empirical parameters
s J and J =
s J and J account for deviation of the component characteristic size from its
degree of polymerization. These parameters can be used singularly or in combination to adjust the component characteristic size. By default PJ is 1.0 for small molecules. Solvent Activity Coefficient
ln
NRTL I =s
x G = x G
j js j k k
js
ks
xk Gkj kj x j Gsj k + sj j xk Gkj xk Gkj k k
Polymer Activity Coefficient
ln
NRTL I=p
x j G ji ji xk Gkj kj x j Gij j k = ri , p + ij i xk Gki j xk Gkj xk Gkj k k k
The activity coefficient of a polymer component given by this last equation needs to be further normalized so that
INRTL becomes unity as X p 1 =p
(i.e.,
pure polymer); it can be easily done as follows:
ln
NRTL I=p
x j G ji ji xk Gkj kj x j Gij j k = ri , p + ij xG j xk Gkj i xk Gkj k ki k k k x j , p G ji ji xk , pGkj kj x j , p Gij j k ri , p + ij x G j xk , p Gkj i xk , pGkj k , p ki k k k
With
xi , p =
r
j
ri , p
j, p
Where:
101
xi , p
= Segment mole fraction of type i in polymer component p
It is often useful for the case of homopolymers to establish a relationship between the NRTL interaction parameters and the Flory-Huggins parameter:
IJ =
JI G JI IJ G IJ + ( I + J G JI ) ( J + I G IJ )
= Solvent-polymer Flory-Huggins binary interaction parameter
Where:
IJ
NRTL Model Parameters

The polymer NRTL model requires two binary interaction parameters, ij and
ji , for the solvent-solvent interactions, the solvent-segment interactions,

and the segment-segment interactions. These binary interaction parameters become the correlation variables in representing the thermodynamic properties of polymer solutions. The binary interaction parameters have the following features: The model automatically retrieves the NRTL binary interaction parameters from the Aspen Plus databank for standard components when they are available. The binary parameters allow complex temperature dependence:
ij = aij +
bij T
+ eij ln T + f ijT
The non-randomness factor ij is allowed to be temperature dependent:
ij = cij + dij (T 27315) .

Typically, the temperature dependency is weak and ij is mainly influenced by cij . The default value for cij is 0.3, and ij increases as the association between molecules increases. The input parameters for the polymer NRTL model are summarized in the following table. These parameters are normally regressed from experimental data.
Parameter Name / Element NRTL/1 NRTL/2 NRTL/3 Symbol Default Lower Limit ------Upper Limit ------MDS Units Keyword --TEMP --Comments
a ij bij cij
0 0 0.3
X X X
Binary, Asymmetric Binary, Asymmetric Binary, Symmetric
NRTL/4 NRTL/5 NRTL/6 NRTL/7 NRTL/8 FHSIZE/1 FHSIZE/2 POLDP
dij eij f ij T min T max si
0 0 0 0 1000 1.0 1.0 1.0
----------1E-15 -1E10 1.0
----------1E15 1E10 1E10
X X X X X X X ---
1/TEMP --1/TEMP TEMP TEMP -------
Binary, Symmetric Binary, Asymmetric Binary, Asymmetric Unary Unary Unary Unary Unary
i
Pi
The number-average degree of polymerization is used for polymer and oligomer components. For monomers, unless changed by the user, Pi
= POLDP = 1.0 .
Specifying the Polymer NRTL Model

Electrolyte-Polymer NRTL Activity Coefficient Model

The Electrolyte-Polymer Non-Random Two-Liquid (EP-NRTL) activity coefficient model is an integration of the electrolyte NRTL model for electrolytes (Chen et al., 1982, 1999; Chen & Evans, 1986) and the polymer NRTL model (Chen, 1993) for oligomers and polymers. The model is used to compute activity coefficients for polymers, solvents, and ionic species (Chen & Song 2004). This integrated electrolyte-polymer NRTL model is designed to represent the excess Gibbs free energy of aqueous organic electrolytes and complex chemical systems with the presence of oligomers, polymers and electrolytes. The model incorporates the segment-based local composition concept of the polymer NRTL model into the electrolyte NRTL model. From the Gibbs free energy expression, one can compute activity coefficients for various species as functions of compositions and molecular structure of oligomers, polymers, solvents, and electrolytes. As an integrated model, the electrolyte-polymer NRTL model reduces to the electrolyte NRTL model in the absence of polymers or oligomers. The model reduces to the polymer NRTL model in the absence of electrolytes. Furthermore, the model reduces to the original NRTL model (Renon & Prausnitz, 1968) if neither electrolytes nor polymers or oligomers are present.
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As such, this model is a very versatile activity coefficient model. Note that this model does not address the solution nonideality of polyelectrolytes, which are further characterized by counterion condensation (Manning, 1979), an intramolecular phenomenon that closely resembles micelle formation. The excess Gibbs free energy expression for the electrolyte-polymer NRTL model contains three contributions: Long-range ion-ion interactions that exist beyond the immediate neighborhood of an ionic species Local interactions that exist at the immediate neighborhood of any species Entropy of mixing polymeric species as described by the Flory-Huggins equation.
The model uses pure liquid at the system temperature and pressure as the reference state for solvents. For ions, the reference state is at infinite dilution in water at the system temperature and pressure. In the case of mixedsolvent electrolytes, the Born equation is added to account for the Gibbs free energy of transfer of ionic species from the infinite dilution state in the mixed solvent to the infinite dilution state in aqueous phase (Mock et al., 1986). To account for the long-range ion-ion interactions, the model uses the unsymmetric Pitzer-Debye-Hckel (PDH) expression (Pitzer, 1973). To account for the local interactions, the model uses the segment-based local composition (lc) concept as given by the polymer NRTL expression. This local composition term is first developed as a symmetric expression that envisions a hypothetical reference state of pure, completely dissociated, segment-based liquid species. It is then normalized using infinite-dilution activity coefficient in water terms for each solute species, including ions, in order to obtain an expression based on the unsymmetric convention. The model retains the two fundamental assumptions regarding the local composition of electrolyte solutions: The like-ion repulsion assumption: this states that the local composition of cations around cations is zero (and likewise for anions around anions). Here cations refer to either monomeric cations or cationic segments. The same is true for anions. The local electroneutrality assumption: this states that the distribution of cations and anions around a central molecular species is such that the net local ionic charge is zero. As before, here cations and anions refer to either monomeric ones or ionic segments.
In summary, the integrated model has four terms, which are discussed later in this chapter: Pitzer-Debye-Hckel term Born term Local composition term Flory-Huggins term
*ex * g *ex , PDH g *ex , Born g *ex ,lc g *ex , FH GmE ,l g = = + + + RT RT RT RT RT RT
Note: Using * to denote an unsymmetric reference state is well accepted in electrolyte thermodynamics and will be maintained here. In this case, * does not refer to a pure component property, as it does in other sections of this document. Following this equation, the ionic activity coefficient is the sum of four terms, which are discussed later in this chapter: Pitzer-Debye-Hckel term activity coefficient Born term activity coefficient Local composition term activity coefficient Flory-Huggins term activity coefficient
ln I* = ln I*PDH + ln i* Born + ln I*lc + ln I*FH

Mean ionic activity coefficients and molality scale mean ionic activity coefficients can then be computed by the following expressions:
* ln =
1 * * c ln c + a ln a c + a
* * ln m = ln ln (1 + M B ( c + a )m / 1000 )
Where:
*
= Mean ionic activity coefficient = Molality scale mean ionic coefficient = Cationic stoichiometric coefficient = Anionic stoichiometric coefficient = Molecular weight of the solvent B
* m
c a
m
= Molality
Long-Range Interaction Contribution

The Pitzer-Debye-Hckel formula, normalized to mole fractions of unity for solvent and zero for electrolytes, is used to represent the long-range interaction contribution: Pitzer-Debye-Hckel Term
1000 g *ex , PDH = M RT B

With
4 A I x

3
1 ln 1 + I x 2
2 N A d A = 1 3 1000
Qe2 kT w
105
Ix =
x z
i
2 i i
Where: = Debye-Hckel parameter = Ionic strength (mole fraction scale)
= "Closest approach" parameter = Avogadro's number = Density of solvent = Electron charge = Dielectric constant of water
T k
= Temperature = Boltzmann constant = Segment-based mole fraction of component i (i can be a monomeric species or a segment) = Charge number of component i
Pitzer-Debye-Hckel Term Activity Coefficient Taking the appropriate derivative of the Pitzer-Debye-Hckel term, an expression for the activity coefficient can then be derived:
ln i*PDH
3 1 2 2 z i2 1000 z i2 I x 2 2 I x 2 1 2 = M A ln 1 + I x + 1 + I 12 B x 1
For oligomeric ions, we sum up the contributions from various ionic segments of species I:
* ln I PDH =
r
c
c, I
* ln c PDH +
r
a
a, I
* ln a ,PDH I
Where:
rc , I = Number of cationic segments in species I ra , I = Number of anionic segments in species I

Born Term The Born equation is used to account for the Gibbs free energy of transfer of ionic species from the infinite dilution state in a mixed-solvent to the infinite dilution state in aqueous phase:
Q2 g *ex , Born = e RT 2kT
x z2 1 1 i i 2 i 10 ri w
Where:
= Mixed-solvent dielectric constant = Born radius
Born Term Activity Coefficient The expression for the activity coefficient can be derived from the Born term:
ln
*Born i
Qe2 = 2kT
1 1 z i2 2 10 r w i
Local Interaction Contribution

The local interaction contribution is accounted for by the Non-Random Two Liquid theory. The basic assumption of the NRTL model is that the nonideal entropy of mixing is negligible compared to the heat of mixing, and, indeed, this is the case for electrolyte systems. This model was adopted because of its algebraic simplicity and its applicability to mixtures that exhibit liquid phase splitting. The model does not require specific volume or area data. The effective local mole fractions and of species j and i, respectively, in the neighborhood of i are related by:
X ji X ii
With
Xj = X i
G ji
X j = x jC j G ji = exp( ji ji )
ji =
( g ji g ii )
RT
=
Where:
Cj
z j for ions and unity for molecules
ji ji
g ji gii
= NRTL non-random factor = Interaction parameter = Energies of interaction between j-i pairs of segment based species = Energies of interaction between i-i pairs of segment based species and ). are energies of interaction between species j and i, and i and i, and
respectively. Both
ij
are inherently symmetric (
and
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Similarly,
X ji X ki
With
Xj = X k
G ji ,ki
G ji ,ki = e
ji , ki ji , ki
ji ,ki = ji,ki
g ji g ki RT
= Nonrandomness factor
Where:
Local Composition Term The local composition term for multicomponent systems is:
ex , g mixlc = rm , I X m RT I m
X
j k
G jm jm
k
X
j
Gkm
j
+ rc , I X c Ya
I c a
X X
j k k
G jc ,ac jc ,ac
k
X
j
Gkc ,ac
+ ra , I X a Yc
I a c
G ja ,ca ja ,ca
k
Gka ,ca
With
Ya =
Xa X a'
a'
Yc =
Xc X c'
c'
cm = Ya m,ca
a
am = Yc m,ca
c
Gcm = Ya Gca ,m
a
Gam = Yc Gca ,m
c
cm = am =
ln(Gcm )
cm
ln(Gam )
am
mc ,ac = cm ma ,ca = am mc ,ac = cm ca ,m ( ca ,m m ,ca ) mc ,ac
ma ,ca = am
ca ,m ( ca ,m m ,ca ) ma ,ca
Gmc ,ac = exp( mc ,ac mc ,ac ) = exp( cm mc,ac ) Gma ,ca = exp( ma ,ca ma ,ca ) = exp( am ma ,ca )
Where: j & k = Any species = Number of molecular segments in species I = Number of cationic segments in species I = Number of anionic segments in species I
rm , I rc , I ra , I
To compute the local composition term for the activity coefficients of polymeric species, we first compute local composition contributions for each of the segments. The segment contributions to the activity coefficients from molecular segments, cationic segments, and anionic segments are given in the next three equations.
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ln
lc m
X
j k
G jm jm
k
Gkm
X k Gkm' km' X m ' Gmm ' k + mm ' m ' X k G km ' X k Gkm' k k X k Gkc,ac kc,ac X c Gmc ,ac k + Ya mc ,ac c a X k Gkc,ac X k Gkc,ac k k X k Gka,ca ka,ca X a Gma ,ca k + Yc mc ,ca a c X k Gka,ca X k Gka,ca k k
1 ln clc = Ya zc a
X G X G
k k k k
kc , ac kc , ac
kc , ac
X k Gkm kB X m Gcm k + cm m X k G km X k Gkm k k X k Gka,ca ka,ca X a Gca ,ca k + Yc ' ca ,ca X k G ka ,ca a c X k Gka,ca k k
1 lc ln a = Yc za c
X G X G
k k k k
ka , ca ka , ca
ka ,ca
X k Gkm km X m G am k + am m X k G km X k Gkm k k X k Gkc,ac kc,ac X c G ac ,ac k + Ya ' ac ,ac X k Gkc ,ac c a X k Gkc,ac k k
Local Composition Term Activity Coefficient
The local composition term for the activity coefficient of a species I is then computed as the sum of the individual segment contributions:
lc lc ln Ilc = rc , I ln clc + ra , I ln a + rm , I ln m c a m
For electrolytes, we are interested in unsymmetric convention activity coefficients. Therefore, we need to compute infinite dilution activity coefficients for ionic segments and molecular segments. They are then used to compute the unsymmetric activity coefficients of oligomeric ions:
ln *lc = ln lc ln lc I I I
Flory-Huggins Term To account for the entropy of mixing from polymeric species, we also compute the Flory-Huggins term:
g ex , FH = x I ln I n I m I x RT I I I ln IFH = ln I x I
with
+ 1 mI J J mJ
m I = rm , I + rc , I + ra , I
m c a
I =
xI mI xJ mJ
J
Flory-Huggins Term Activity Coefficient The unsymmetric activity coefficients from the Flory-Huggins term are:
ln FH = ln m I + 1 m I I ln *FH = ln FH ln FH I I I
Electrolyte-Polymer NRTL Model Parameters

The adjustable parameters for the EP-NRTL model include the: Pure component dielectric constant coefficient of nonaqueous solvents and molecular segments Born radius of ionic monomeric species or ionic segments Segment-based NRTL parameters for molecule-molecule, moleculeelectrolyte, and electrolyte-electrolyte pairs
The pure component dielectric constant coefficients of nonaqueous solvents and Born radius of ionic species are required only for mixed-solvent electrolyte systems. The temperature dependency of the dielectric constant of solvent B is:
111
1 1 B (T ) = AB + BB T CB
Each type of NRTL parameter consists of both the nonrandomness factor, , and the energy parameter, . The temperature dependency relations of the NRTL parameters are: Molecule-Molecule Binary Parameters:
BB' = ABB' +
BBB' + FBB' ln(T ) + G BB'T T

Dca , B (T ref T ) T + Eca , B + ln ref T T T

Electrolyte-Molecule Pair Parameters:
ca , B = Cca , B + B,ca = CB,ca
DB,ca (T ref T ) T + + E B,ca + ln ref T T T
Electrolyte-Electrolyte Pair Parameters: For the electrolyte-electrolyte pair parameters, the two electrolytes must share either one common cation or one common anion:
ca ,c 'a = C ca ,c 'a +
Dca ,c 'a T
(T ref T ) T + E ca ,c 'a + ln ref T T
ca ' ,ca ' ' = Cca ' ,ca ' ' +

Where:
Dca ' ,ca ' ' T
(T ref T ) T + Eca ' ,ca ' ' + ln ref T T
T ref = Reference temperature (298.15K)

Note that all of these interacting species (c, a, B, etc.) should be only monomeric species or segments. The following table lists the EP-NRTL activity coefficient model parameters:
Parameter Name / Element Symbol Default Lower Limit Upper Limit MDS Units Keyword Comments
Dielectric Constant Parameters * CPDIEC/1 CPDIEC/2 CPDIEC/3
AB BB CB
ri
ABB '
--0.0 298.15
-------
-------
X X X
----TEMP
Unary Unary Unary
Ionic Born Radius Parameters RADIUS --1E-11 1E-9 --LENGTH Unary
Molecule-Molecule Binary Parameters NRTL/1 0 ----X --Binary, Asymmetric
Parameter Name / Element NRTL/2 NRTL/3 NRTL/4 NRTL/5 NRTL/6 NRTL/7 NRTL/8
Symbol
Default
Lower Limit ---------------
Upper Limit ---------------
MDS
Units Keyword TEMP ------1/TEMP TEMP TEMP
Comments
BBB'
0 0.3 --0 0 0 1000
X X --X X X X
Binary, Asymmetric Binary, Symmetric --Binary, Asymmetric Binary, Asymmetric Unary Unary
BB '
---
FBB ' G BB '
T min T max Cca , B Dca ,B E ca , B
Electrolyte-Molecule Pair Parameters ** GMELCC GMELCD GMELCE GMELCN 0.0 0.0 0.0 0.2 -100 -3E4 -100 0.01 100 3E4 100 5 X X X X --TEMP ----Binary, Asymmetric Binary, Asymmetric Binary, Asymmetric Binary, Symmetric
ca, B
Electrolyte-Electrolyte Pair Parameters GMELCC
C ca ,ca ' C ca ,c 'a
0.0 0.0 0.0 0.0 0.0 0.0 0.2 0.2
-100 -100 -3E4 -3E4 -100 -100 0.01 0.01
100 100 3E4 3E4 100 100 5 5
X X X X X X X X
----TEMP TEMP ---------
Binary, Asymmetric Binary, Asymmetric Binary, Asymmetric Binary, Asymmetric Binary, Asymmetric Binary, Asymmetric Binary, Symmetric Binary, Symmetric
GMELCD
Dca ' ,ca ' ' Dc 'a , c ' 'a
GMELCE
Eca ' ,ca ' ' Ec 'a , c ' 'a
GMELCN
ca ',ca '' c 'a ,c ''a

* **
If dielectric constant parameters are missing for a solvent, the dielectric constant of water is automatically assigned. If an electrolyte-molecule parameter is missing, the following defaults are used: Electrolytewater Water-4 8
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electrolyte Electrolytesolvent Solventelectrolyte Electrolytesolute Soluteelectrolyte -2 10 -2 10
Option Codes The primary version of EPNRTL implemented is for aqueous solutions; that is, for ions, the reference state is at infinite dilution in water. The version for handling mixed-solvent electrolyte systems is also available by using Option Codes in the Aspen Plus Interface.
Option Codes in EPNRTL model 0 1 Aqueous solutions Mixed-solvent solutions
Specifying the Electrolyte-Polymer NRTL Model

Polymer UNIFAC Activity Coefficient Model

This section describes the polymer UNIFAC activity coefficient model available in the POLYUF physical property method. The polymer UNIFAC model is an extension of the UNIFAC group contribution method for standard components to polymer systems (Fredenslund et al., 1975, 1977; Hansen et al., 1991). It is a predictive method of calculating phase equilibria, and, therefore, it should be used only in the absence of experimental information. The UNIFAC method yields fairly accurate predictions. It becomes less reliable, however, in the dilute regions, especially for highly non-ideal systems (systems that exhibit strong association or solvation). Although the UNIFAC approach is a good predictive method, it should not be used as a substitute to reducing good experimental data to calculate phase equilibria. In general, higher accuracy can be obtained from empirical models when these models are used with binary interaction parameters obtained from experimental data. Finally, the method is only applicable in the temperature range of 300-425 K (Danner & High, 1992). Extrapolation outside this range is not recommended. The group parameters are not temperature-dependent; consequently, predicted phase equilibria extrapolate poorly with respect to temperature.
The polymer UNIFAC model calculates liquid activity coefficients for the POLYUF property method. This UNIFAC model is the same as the UNIFAC model in Aspen Plus for monomer systems except that this model obtains functional group information from segments and polymer component attributes. The equation for the original UNIFAC liquid activity coefficient model is made up of a combinatorial and residual term:
ln = ln iC + ln iR
ln iC = ln
i
xi
+1
i
xi
z i ln + 1 i 2 i i
Where the molecular volume and surface fractions are:
z qi 2 i = nc and i = nc z x j rj xj 2 qj j j xi ri xi
With: nc = 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:
ri = ki Rk and q i = ki Qk
k k
ng
ng
Where:
ki =
ng =
Number of groups of type k in molecule i Number of groups in the mixture
The residual term is:
ln iR = ki ln k ln ki
k
ng
Where:
ln k = Activity coefficient of a group at mixture composition

ki
= Activity coefficient of group k in a mixture of groups corresponding to pure i
The parameters k and ki are defined by:
115
ng ng ln k = Qk 1 ln m mk ng m km m m n nm n
With:
z Qk 2 k = ng z X m 2 Qm m Xk
And:
mn = e b
mn
/T
The parameter X k is the group mole fraction of group k in the liquid:
Xk =
j nc j ng m
nc
kj
xj
mj
xj
Polymer UNIFAC Model Parameters

The input parameters for the Polymer UNIFAC model are given here:
Parameter Name / Element UFGRP GMUFQ GMUFR GMUFB Symbol Default Lower Limit --------Upper Limit --------MDS Units Keyword --------Comments
v ki , v mi , ...
Qk Rk bkn
---------
X X X X
Unary Unary Unary Unary
The parameter UFGRP stores the UNIFAC functional group number and number of occurrences of each group. UFGRP is stored in the Aspen Polymers segment databank for polymer segments, and in the Aspen Plus pure component databank for standard components. For non-databank components, enter UFGRP on the Properties Molec-Struct.Func-Group form. See Aspen Physical Property System Physical Property Data, for a list of the UNIFAC functional groups.
Specifying the Polymer UNIFAC Model

Polymer UNIFAC Free Volume Activity Coefficient Model

This section describes the polymer UNIFAC free volume activity coefficient model available in the POLYUFV physical property method. The polymer UNIFAC free volume activity coefficient model (UNIFAC-FV) is the same as the polymer UNIFAC model, with the exception that it contains a term to account for free-volume (compressibility) effects. Thus, the two methods have similar applicability (see Polymer UNIFAC Activity Coefficient Model on page 114). The UNIFAC-FV model can be used with more confidence for predictions at higher pressures than the polymer UNIFAC model. Nonetheless, both methods are predictive, and should not be used to substitute correlative models (such as Flory-Huggins or POLYNRTL) with fitted binary parameters. Oishi and Prausnitz (1978) modified the UNIFAC model (Fredenslund et al., 1975, 1977) to include "a contribution for free volume difference between the polymer and solvent molecules." Oishi and Prausnitz suggested that the UNIFAC combinatorial contribution does not account for the free volume differences between the polymer and solvent molecules. While this difference is usually not significant for small molecules, it could be important for
117
polymer-solvent systems. They added the free volume contribution derived from the Flory equation of state to the original UNIFAC model to arrive at the following expression for the weight fraction activity coefficient of a solvent in a polymer:
ln = ln iC + ln iR + ln iFV
ln iC = ln ln
ng R i
i
xi
+1
z ln i + 1 i xi 2 i i
= ki ln k ln ki
k
Free-Volume Contribution
ln iFV
~ Vi = ~ Vm =
~1 ~ 1 V V 3 1 ~ 1 = 3C i ln i 1 C i ~i 11 Vi 3 ~3 Vm Vm 1
Vi 0.01517bri
V x 0.01517b r x
i i i
Where:
Ci
b
= 1.1 = 1.28 = Volume parameter for component i = Specific volume of component i, cubic meters per kilogram mole, calculated from Rackett equation for solvents and from Tait equation for polymers.
ri
Vi
See Chapter 4 for a description of the Tait equation. The combinatorial and residual contributions, C and R , are identical to those in the polymer UNIFAC model (see Polymer UNIFAC Activity Coefficient Model on page 114). The Oishi-Prausnitz modification of UNIFAC is currently the most used method available to predict solvent activities in polymers. Required for the OishiPrausnitz method are the densities of the pure solvent and pure polymer at the temperature of the mixture and the structure of the solvent and polymer. The Tait equation is used to calculate molar volume for polymers (see Chapter 4 for a description of the Tait equation). Molecules that can be constructed from the groups available in the UNIFAC method can be treated. At present, groups are available to construct alkanes, alkenes, alkynes, aromatics, water, alcohols, ketones, aldehydes, esters, ethers, amines, carboxylic acids, chlorinated compounds, brominated
compounds, and a few other groups for specific molecules. The OishiPrausnitz method has been tested only for the simplest of these structures, and these groups should be used with care.
Polymer UNIFAC-FV Model Parameters

The UNIFAC free volume parameters are the same as those required for the polymer UNIFAC model (see Polymer UNIFAC Model Parameters on page 117). In addition, parameters for the Tait liquid molar volume model are required for free volume calculations (see Chapter 4 for a description of the Tait liquid molar volume model).
Specifying the Polymer UNIFAC- FV Model

References
Aspen Physical Property System Physical Property Methods and Models. Cambridge, MA: Aspen Technology, Inc. Flory, P. J. (1953). Principles of Polymer Chemistry. London: Cornell University Press. Chen, C.-C. (1993). A Segment-Based Local Composition Model for the Gibbs Energy of Polymer Solutions. Fluid Phase Equilibria, 83, 301-312. Chen, C.-C. (1996). Molecular Thermodynamic Model for Gibbs Energy of Mixing of Nonionic Surfactant Solutions. AIChE Journal, 42, 3231-3240. Chen, C-C., Britt, H. I., Boston, J. F., & Evans, L. B. (1982). Local Composition Model for Excess Gibbs Energy of Electrolyte Systems. AIChE J., 28, 588. Chen, C-C., & Evans, L. B. (1986). A Local Composition Model for the Excess Gibbs Energy of Aqueous Electrolyte Systems. AIChE J., 32, 444. Chen, C-C., Mathias, P. M., & Orbey, H. (1999). Use of Hydration and Dissociation Chemistries with the Electrolyte-NRTL Model. AIChE Journal, 45, 1576. Chen, C-C., Song Y. (2004). Generalized Electrolyte-NRTL Model for MixedSolvent Electrolyte Systems. AIChE Journal, 50, 1928. Danner, R. P., & High, M. S. (1992). Handbook of Polymer Solution Thermodynamics. New York: American Institute of Chemical Engineers. Flory, P. J. (1941). Thermodynamics of High Polymer Solutions. J. Chem. Phys., 9, 660. Fredenslund, Aa., Jones, R. L., & Prausnitz, J. M. (1975). AIChE J., 21, 1086. Fredenslund, Aa., Gmehling, J., & Rasmussen, P. (1977). Vapor-Liquid Equilibria using UNIFAC. Amsterdam: Elsevier.
119
Hansen, H. K., Rasmussen, P., Fredenslund, Aa., Schiller, M., & Gmehling, J. (1991). Vapor-Liquid Equilibria by UNIFAC Group Contribution. 5 Revision and Extension. Ind. Eng. Chem. Res., 30, 2352-2355. Huggins, M. L. (1941). Solutions of Long Chain Compounds. J. Phys. Chem., 9, 440. Manning, G.S. (1979). Counterion Binding in Polyelectrolyte Theory. Acc. Chem. Res., 12, 443. Mock, B., Evans, L. B., & Chen, C.-C. (1986). Thermodynamic Representation of Phase Equilibria of Mixed-Solvent Electrolyte Systems. AIChE Journal, 32, 1655. Oishi, T., & Prausnitz, J. M. (1978). Estimation of Solvent Activity in Polymer Solutions Using a Group Contribution Method. Ind. Eng. Chem. Process Des. Dev., 17, 333-335. Pitzer, K.S. (1973). Thermodynamics of Electrolytes. I. Theoretical Basis and General Equations. J. Phys. Chem., 77, 268. Renon, H., & Prausnitz, J. M. (1968). Local Compositions in Thermodynamic Excess Functions for Liquid Mixtures. AIChE J., 14, 135-144. Tompa, H. (1956). Principles of Polymer Chemistry. London: Butterworths.
4 Thermophysical Properties of Polymers
This chapter discusses thermophysical properties of polymers. These properties are needed when an equation-of-state model (see Chapter 2) or an activity coefficient model (see Chapter 3) is used to calculate thermodynamic properties of mixtures containing polymers. In general, Aspen Polymers (formerly known as Aspen Polymers Plus) provides various property models to estimate thermophysical properties of polymers; these models are implemented as polynomial expressions so that they can be used in a predictive mode (such as Van Krevelen Group Contribution Methods, explained on page 145), or in a correlative mode (in case experimental data are available for parameter estimation). Note that these models only apply to polymers, oligomers, and segments. Models for conventional components are already available in Aspen Plus. Topics covered include: About Thermophysical Properties, 121 Aspen Ideal Gas Property Model, 123 Van Krevelen Liquid Property Models, 127 Van Krevelen Liquid Molar Volume Model, 136 Tait Liquid Molar Volume Model, 140 Van Krevelen Glass Transition Temperature Correlation, 141 Van Krevelen Melt Transition Temperature Correlation, 142 Van Krevelen Solid Property Models, 143 Van Krevelen Group Contribution Methods, 145 Polymer Property Model Parameter Regression, 146 Polymer Enthalpy Calculation Routes with Activity Coefficient Models, 147
About Thermophysical Properties

As discussed in Chapter 1, due to their structure, polymers exhibit thermophysical properties significantly different than those of conventional
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121
components. Consequently, different property models are required to describe their behavior. Aspen Polymers provides models to estimate polymer enthalpy, Gibbs free energy and molar volume. These properties are essential for heat and mass balance calculations of mixtures containing polymers. Aspen Polymers also provides models to estimate some of the unique properties of polymer components (such as the glass transition temperature and melt transition temperature). The following tables list the properties available for polymers and the models available for calculating these properties in Aspen Polymers:
Property Name HL GL SL VL TGVG TMVG HS GS VS SS Symbol Description Liquid pure component enthalpy Liquid pure component Gibbs free energy Liquid pure component entropy Liquid pure component molar volume Glass Transition temperature Melt Transition temperature Solid pure component enthalpy Solid pure component Gibbs free energy Solid pure component molar volume Solid pure component entropy
H i*,l
i*,l
S i*,l Vi*,l Tg Tm H i*,s
i*,s
Vi*,s S i*,s
Property Models
Model Name
Properties Calculated
Aspen Ideal Gas Property Model Van Krevelen/DIPPR Model Van Krevelen/DIPPR Model Van Krevelen/Rackett Model Tait/Rackett Model Van Krevelen Model Van Krevelen Model Van Krevelen/Standard Model Van Krevelen/Standard Model Van Krevelen/Rackett Model HL0DVK, HL0DVKD GL0DVK VL0DVK VL0TAIT TG0DVK TM0DVK HS0DVK GS0DVK VS0DVK
HIG, GIG, CPIG HL GL VL VL TGVK TMVK HS GS VS
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For conventional components, standard models are already available in Aspen Plus, and, therefore, no details are presented here. (See Aspen Physical Property System Physical Property Methods and Models for more information). Instead, we focus on describing the calculation of thermophysical properties of polymers, oligomers, and segments. Polymer properties except Tg and Tm are calculated using different routes, depending on whether an equation-of-state model or an activity coefficient model is used. For instance, when an equation-of-state model is used, only the Aspen Ideal Gas Property Model is needed to calculate the polymer ideal gas properties to the departure functions. When an activity coefficient model is used, the van Krevelen property models (van Krevelen, 1990) are used to calculate polymer enthalpy, Gibbs free energy and molar volume. In most cases, the van Krevelen models provide separate correlations for the crystalline phase and the liquid phase. Depending on the temperature region being considered, above the melt transition temperature, between the melt and glass transition temperature, or below the glass transition temperature, one or both correlations may apply. When the temperature region is between the melt transition temperature and the glass transition temperature, the contribution of each correlation is determined by the degree of crystallinity, which is one of the models input parameters. Correlations for estimating the melt and glass transition temperature are also provided. The entropy of polymers in both liquid and solid phases is calculated using the rigorous thermodynamic equations:
S i*,l = S i*,s =
1 ( H i*,l i*,l ) T
1 ( H i*,s i*,s ) T
As the models presented in the remainder of this chapter relate only to polymers, oligomers, and segments, the index i is dropped for simplicity.
Aspen Ideal Gas Property Model

As shown in Chapter 2, equations of state provide information concerning ideal gas departure functions. Therefore, in estimating enthalpy, entropy, and Gibbs free energy with an equation of state, the ideal gas contribution must be added to the departure functions obtained from the equation of state. The ideal gas model already available in Aspen Plus for conventional components is extended to handle polymers and oligomers. First, we apply Equations 3.11 and 3.15 to pure polymer components to calculate the liquid enthalpy and Gibbs free energy of polymers:
H *,l = H *,ig (T ) + H *,l H *,ig
123
*,l = *,ig (T ) + ( *,l *,ig )

Where:
H *,ig
= Ideal gas molar enthalpy of polymers = Ideal gas molar Gibbs free energy of polymers = Polymer molar enthalpy departure, calculated from an equation-of-state model = Polymer molar Gibbs free energy departure, calculated from an equation-of-state model
*,l
*,ig
H *,l H *,ig
*,l *,ig
Both departure functions, H same equation of state.
H *,ig and *,l *,ig , are calculated from the
Ideal Gas Enthalpy of Polymers

The ideal gas enthalpy of a polymer at temperature T is given by the following equation:
T
*,ig
(T ) = H
*,ig
(T
ref
)+
T ref
Cp
*,ig
dT
Where:
T ref
= Reference temperature (298.15 K)
H *,ig (T ref
= Heat of formation of the polymer at the ideal-gas state and
T ref
= Ideal-gas heat capacity of the polymer
Cp *,ig
Ideal Gas Gibbs Free Energy of Polymers

Similarly, the ideal gas Gibbs free energy of a polymer at temperature T is given by the following equation:
T *,ig T *,ig
*,ig
(T ) =
(T
ref
)+
T ref
Cp
dT T
T ref
Cp *,ig dT T
(T T ref ) S *,ig (T ref )

With
S *,ig (T ref ) =
Where:
H *,ig (T ref ) *,ig (T ref ) T ref

= Gibbs free energy of formation of the polymer at the ideal-gas state and T
ref
*,ig (T ref )
S *,ig (T ref )
= Entropy of formation of the polymer at the ideal-gas state
and T
ref *,ig ref *,ig ref
In the ideal gas model, the quantities H (T ) and (T ) are constants for polymers and oligomers. They can be estimated using Van Krevelen Group Contribution Methods (see page 145). They can also be adjusted to fit the data of the polymer. However, the ideal-gas heat capacity of polymers, Cp , is temperature-dependent and is implemented as polynomial expressions:
*,ig
Cp *,ig (T ) = C1 + C 2T + C 3T 2 + C 4T 3 + C 5T 4 + C 6T 5 C 7 T C8
or
Cp *,ig (T ) = C 9 + C10T C11

or
T < C7
Cp*,ig (T )
Linearly extrapolated using slope at C8 for T > C8
Aspen Ideal Gas Model Parameters

The following table lists the parameters used in the ideal gas model:
Parameter Name / Element CPIG/1 CPIG/2,, 6 CPIG/7 CPIG/8 CPIG/9 CPIG/10, 11 DHFVK DGFVK --Symbol Default Lower Limit ------------Upper Limit ------------MDS Units Keyword
C1
--0.0 0 1000 -----
X X X X X X
-------
MOLE-HEAT-CAPACITY MOLE-HEATCAPACITY, TEMP TEMP TEMP MOLE-HEAT-CAPACITY MOLE-HEATCAPACITY, TEMP MOLE-ENTHALPY MOLE-ENTHALPY Kelvin
C 2 ,..., C 6 C7 C8 C9 C10 , C11

H *,ig (T ref
*,ig (T ref
T ref
) )
----298.15
5 1010
5 1010
---
51010
5 1010
---
Parameter Input
All three unary parameters, CPIG, DHFVK, and DGFVK can be: Specified for each polymer or oligomer component; or Specified for segments that compose a polymer or oligomer component
125
These options are shown in priority order. For example, if parameters are provided for a polymer component as well as for the segments, the polymer parameters are used and the segment parameters are ignored.
Parameters for Polymers

If parameters are specified for the polymeric component, then these values are used directly, independent of the polymer composition. Otherwise, the parameters of a polymer are calculated using the polymer composition (segment fraction) and the parameters of segments:
H *,ig (T ref ) =
Nseg
X
A A
*, H A ig (T ref )
*,ig (T ref ) =
Cp *,ig (T ) =
Where:
Nseg
X
A
*,ig (T ref ) A
Nseg
X
A
Cp *,ig (T ) A
Nseg
XA
= = =
Number of segment types in the copolymer Mole segment fraction of segment type A in the copolymer Reference temperature (298.15 K)
T ref
*, H A ig (T ref ) = Ideal-gas enthalpy of formation of segment type A at T ref
*,ig (T ref ) A
Cp *,ig (T ) A
= =
Ideal-gas Gibbs free energy of formation of segment type A at T

ref
Ideal-gas heat capacity of segment type A
Van Krevelen Group Contribution for Segments

If the parameters DHFVK and DGFVK are not entered for the segments, then these values are estimated using using Van Krevelen Group Contribution Methods (see page 145). That is, Aspen Polymers automatically retrieves functional group data of segments from the van Krevelen databank.
*, *, H A ig (T ref ) = nk H k ig (T ref ) k *, *,ig (T ref ) = nk k ig (T ref ) A k
Where:
nk
Number of occurrences of functional group k in the segment from the segment database or user-specified segment structure
*, H k ig (T ref ) = Ideal-gas enthalpy of formation of functional group k at T ref ,
from van Krevelen database

ref
*, k ig (T ref )
Ideal-gas Gibbs free energy of formation of functional group k at T , from van Krevelen database
In some cases, the parameters of functional groups may not be available in the databank. The contributions from these groups are ignored.
Ideal Gas Heat Capacity Parameters

CPIG parameters are required for the model. If your model uses polymers and oligomers contained in the polymer segment databank, the CPIG parameters are calculated automatically. However, if the values are not in the databank you must either estimate or regress the CPIG parameters.
Parameter Regression
You must estimate parameters if your polymer includes non-databank segments. You can perform an Aspen Plus Regression Run (DRS) to obtain these parameters. Additionally, you can use a DRS run to adjust the values for polymers that contain databank segments. This is useful for fitting available experimental data. Since the ideal-gas property model is used with an equation-of-state model, experimental data on liquid density of a polymer should be regressed first to obtain the EOS pure parameters for the polymer (or segments). In the data regression, these parameters can be: Specified for each oligomer component (polymer) Specified for each segment that composes an oligomer component (polymer)
Once the pure EOS parameters are available for a polymer, ideal-gas heat capacity parameters, CPIG, should be regressed for the same polymer using experimental liquid heat capacity data. Data on heat of formation and Gibbs free energy of formation, of the same polymer (segment), can then be used to obtain DHFVK and DGFVK by performing an Aspen Design Spec or Aspen Sensitivity. Note: In a Data Regression Run, a polymer component must be defined as an OLIGOMER type, and the number of each type of segment that forms the oligomer (or polymer) must be specified.
Van Krevelen Liquid Property Models

The activity coefficient and equation-of-state property methods calculate polymer liquid properties using a different structure. For example, equationof-state property methods normally use an ideal gas reference state to estimate polymer properties. However, activity coefficient property methods use a liquid reference state. In Aspen Polymers, the activity coefficient
127
property methods use simple polynomial equations to calculate polymer liquid properties of interest.
Liquid Enthalpy of Polymers

By design, Aspen Polymers uses the liquid-phase property routes to calculate the properties of both liquid- and solid-phase polymers present in the mixed substream. Liquid enthalpy of polymer components is calculated first. The enthalpy and heat capacity of amorphous solid polymers are continuous with the liquid-phase polymer properties across the melting point, so the models do not distinguish between amorphous solid and liquid polymer. Alternately, the crystalline polymer can be included in the CISOLID substream. The solid property model, described later in this chapter, is used to calculate the properties of polymer in the CISOLID substream. Temperature-Enthalpy Relationship The following figure summarizes the relationship between temperature and enthalpy for a polymer component:
dep H i*,v
DHFORM DHFVK
Gas Ideal as Real G
Hi*,v(T)
H i*,ig T ref
( )
( )
con H i* T ref
DHCON
s Amorphou Solid SemiCrystalline Solid Crystalline Solid
vap H i* (T )
sub H i* T ref
Enthalpy
DHSUB
( )
d Liqui
Hi*,l(T)
H i*,l T ref
( )
ref
H i*,l T melt fus H i* T melt
*,c i
(T )
Tref
H i*,c T melt
Tmelt Temperature
The key variables are:
H i*,ig T ref H i*,l H i*,c

ref
( ) (T ) (T )
ref
= Ideal gas heat of formation (DHFORM, DHFVK) = Liquid phase reference enthalpy = Crystal phase reference enthalpy = Vapor phase enthalpy departure (DHV)
dep H i*,v
con H i* T ref sub H i*

fus H i*
ref
( ) = Enthalpy of condensation (DHCON) (T ) = Enthalpy of sublimation (DHSUB) (T ) = Heat of fusion at the melting point
melt
vap H i* (T )
= Heat of vaporization (DHVL) = Vapor-phase enthalpy (HV) = Liquid-phase enthalpy (HL)
H i*,v (T ) H i*,l (T ) H i*,l T melt H i*,c T melt T melt T ref
)
)
= Enthalpy of amorphous solid phase or liquid phase at the melting point = Enthalpy of pure crystalline polymer at the melting point = Melt transition temperature (TMVK) = Reference temperature (298.15 K)
The crystalline polymer generally has a lower enthalpy and higher heat capacity than amorphous polymer. The van Krevelen enthalpy model accounts for this difference by using two sets of equations corresponding to the amorphous/liquid and crystalline phases. The net enthalpy is calculated using the mass fraction crystallinity and a mass-average mixing rule:
HL = H *,l = H *,c xc + H *,l (1 xc ) = H *,c

With:
for for for
T > Tm Tg T Tm T < Tg
H *,l = H *,l T ref +
( ) Cp
T T
ref
*,l
dT
H (T
*,l
ref
)=H
*,ig
(T ) +
ref T *,c T
ref
con
H * T ref
( ) ( )
H *,c = H *,c T ref +
( ) Cp
dT
H *,c (T ref ) = H *,ig T ref sub H * T ref

Where: HL
( )
= Net enthalpy of the polymer = Enthalpy of the polymer in the liquid phase = Enthalpy of the polymer in the crystalline phase
H *,l H *,c
129
Tm Tg
= Melt transition temperature of the polymer = Glass transition temperature of the polymer = Mass-fraction crystallinity = Reference temperature (298.15 K)
xc
T ref
H *,ig T ref
( )
= Heat of formation of the polymer at the ideal-gas state and
con H * T ref sub H * Cp *,l Cp *,c

ref
( ) (T )
T ref
= Heat of condensation of the polymer at T ref = Heat of sublimation of the polymer at T ref = Heat capacity of the polymer in the liquid phase = Heat capacity of the polymer in the crystalline phase
Note that superscript c refers to the crystalline state, superscript l refers to the liquid state, and the asterisk (*) refers to pure component properties. Aspen Polymers uses the heat of condensation, con H T
*
sublimation, sub H T
*
( ) , as reference parameters to convert between the

ref
( ) , and heat of
ref
ideal gas reference state and the condensed phase reference state.
Liquid Gibbs Free Energy of Polymers

The liquid Gibbs free energy of polymers can be calculated using a similar approach:
GL
= *,l = *,c xc + *,l (1 xc ) = *,c
for for for
With:
*,l (T ) = *,l (T ref ) +
T ref
*,l Cp dT T
T ref
Cp *,l dT T
(T T ref ) S *,l (T ref )
*,c (T ) = *,c (T ref ) +
T ref
*,c Cp dT T
T ref
Cp *,c dT T
*,l (T ref ) = *,ig (T ref ) + con * (T ref )
S *,l (T ref ) =
H *,l (T ref ) *,l (T ref ) T ref
*,c (T ref ) = *,ig (T ref ) sub * (T ref )

Where: GL = Net Gibbs free energy of the polymer = Gibbs free energy of the polymer in the liquid phase = Gibbs free energy of the polymer in the crystalline phase = Reference temperature (298.15 K) = Gibbs free energy of formation of the polymer at the idealgas state and T
ref
*,l
*,c
T ref
*,ig (T ref )
con * (T ref sub *

ref
) (T )
= Gibbs free energy of condensation of the polymer at T ref = Gibbs free energy of sublimation of the polymer at T ref
Heat Capacity of Polymers

The liquid- and crystalline-phase heat capacities for polymeric components are calculated using the polynomial expressions:
Cp *,l = A l + B l T + C l T 2 + D l T 3 Cp *,c = A c + B c T + C c T 2 + D c T 3
for for
T l ,min < T < T l ,max T c ,min < T < T c ,max
Liquid Enthalpy and Gibbs Free Energy Model Parameters

The following table lists the liquid enthalpy and Gibbs free energy model parameters:
Parameter Name / Element CPLVK/1 CPLVK/2 CPLVK/3 CPLVK/4 CPLVK/5 Symbol Default Lower Limit ----------Upper Limit ----------MDS Units Keyword
Al
Calculated Calculated 0 0 0
X X X X X
MOLE-HEATCAPACITY MOLE-HEATCAPACITY, TEMP MOLE-HEATCAPACITY, TEMP MOLE-HEATCAPACITY, TEMP TEMP
Bl
Cl
Dl T l ,min
131
Parameter Name / Element CPLVK/6 CPCVK/1 CPCVK/2 CPCVK/3 CPCVK/4 CPCVK/5 CPCVK/6 DHFVK DHCON DHSUB DGFVK DGCON DGSUB POLCRY TMVK TGVK ---
Symbol
Default
Lower Limit ---------------
Upper Limit ---------------
MDS
Units Keyword
T l , max Ac Bc Cc Dc T c ,min T c ,max H *,ig (T ref
1000 Calculated Calculated 0 0 0 1000
X X X X X X X --------------X X ---
TEMP MOLE-HEATCAPACITY MOLE-HEATCAPACITY, TEMP MOLE-HEATCAPACITY, TEMP MOLE-HEATCAPACITY, TEMP TEMP TEMP MOLE-ENTHALPY MOLE-ENTHALPY MOLE-ENTHALPY MOLE-ENTHALPY MOLE-ENTHALPY MOLE-ENTHALPY --TEMP TEMP Kelvin
con H * T ref sub H * T ref
( )
---7E6
5 1010
5 1010
5 1010
5 1010
5 1010
5 1010
( )
1.7E7 ---2.528E6 5.074E6 0.0 ----298.15
con * (T ref sub *

xc
ref
*,ig (T ref )
) (T )
5 1010
5 1010 5 1010
0 0 0 ---
5 1010
5 1010 5 1010
1 5000 5000 ---
Tm Tg T ref
The default values of these parameters are calculated using the van Krevelen group contribution model as given by Equations 4.74.10 later in this chapter.
Parameter Input
The parameters in the above table can be: Specified for each polymer or oligomer component Specified for segments that compose a polymer or oligomer component Calculated automatically using van Krevelen group contribution techniques.
These options are shown in priority order. For example, if parameters are provided for a polymer component and for the segments, the polymer parameters are used and the segment parameters are ignored.

If parameters are specified for the polymeric component, then these values are used directly, independent of the copolymer composition. Otherwise, the parameters of a copolymer are calculated using the copolymer composition and the parameters of segments:
H *,ig (T ref ) =
Nseg
X
A Nseg A
*, H A ig (T ref )
con H * (T ref ) = sub H * (T ref ) =
X
A
* con H A (T ref )
Nseg
X
A
* sub H A (T ref )
*,ig
(T
ref
)=
Nseg
X
A Nseg A
*,ig (T ref ) A
con * (T ref ) A sub * (T ref ) A
con * (T ref ) = sub * (T ref ) = Cp *,l (T ) = Cp (T ) =

*,c Nseg
X
A
Nseg
X
A
X
A Nseg
Cp *,l (T ) A Cp *,c (T ) A
X
A
Where:
Nseg
XA
= = = =
Number of segment types in the copolymer Mole segment fraction of segment type A in the copolymer Reference temperature (298.15 K) Ideal-gas enthalpy of formation of segment type A at T
ref
T ref
*, H A ig (T ref )
* con H A (T ref ) = Heat of condensation of segment type A at T ref
* sub H A (T ref ) = Heat of sublimation of segment type A at T ref
*,ig (T ref ) A
Ideal-gas Gibbs free energy of formation of segment type A at T

ref
133
con * (T ref ) = Gibbs free energy of condensation of segment type A at A T ref sub * (T ref ) = Gibbs free energy of sublimation of segment type A at T ref A Cp *,l A Cp *,c A
= = Heat capacity of segment type A in the liquid phase Heat capacity of segment type A in the crystalline phase

If you do not enter parameters for the segments, these values are estimated using using Van Krevelen Group Contribution Methods (see page 145). Aspen Polymers automatically retrieves functional group data for segments from the van Krevelen databank.
*, *, H A ig (T ref ) = nk H k ig (T ref ) k * * con H A (T ref ) = nk con H k (T ref ) k * * sub H A (T ref ) = nk sub H k (T ref ) k *, *,ig (T ref ) = nk k ig (T ref ) A k
(4.1) (4.2) (4.3)
(4.4) (4.5) (4.6)
* con * (T ref ) = n k con k (T ref ) A k * sub * (T ref ) = n k sub k (T ref ) A k
Where:
nk T ref
*, H k ig (T ref )
Number of occurrences of functional group k in the segment from the segment database or user-specified segment structure Reference temperature (298.15 K) Ideal-gas enthalpy of formation of functional group k at
= =
T ref , from van Krevelen database
* con H k (T ref ) = Heat of condensation of formation of functional group k at T ref , from van Krevelen database * sub H k (T ref ) = Heat of sublimation of formation of functional group k at T ref , from van Krevelen database
*, k ig (T ref )
Ideal-gas Gibbs free energy of formation of functional group k at T

ref
, from van Krevelen database
* con k (T ref ) * sub k (T ref )
= =
Gibbs free energy of condensation of formation of functional group k at T group k at T

ref ref
, from van Krevelen database
Gibbs free energy of sublimation of formation of functional , from van Krevelen database
In some cases, the parameters of functional groups are not available in the databank. The contributions from these groups are ignored. Missing parameters in heat capacity of segments are estimated using van Krevelens group contribution model:
*, A l = 0.64 nk Cp k l T ref k
( )
(4.7) (4.8) (4.9) (4.10)
*, B l = 0.0012 nk Cp k l T ref k *, A c = 0.106 nk Cp k c (T ref k *, B c = 0.003 nk Cp k c (T ref k
( )
) )
Where:
T ref
= Reference temperature (298.15 K)
*, Cp k l T ref
( )
*, Cp k c (T ref
)=
= Liquid molar heat capacity of functional group k at T ref , from van Krevelen database Crystalline molar heat capacity of functional group k at T from van Krevelen database
ref
You must estimate parameters if your polymer includes non-databank segments. You can perform an Aspen Plus Regression Run (DRS) to obtain heat capacity parameters. Additionally, you can use a DRS run to adjust the values for polymers that contain databank segments. This is useful for fitting available experimental data. In the data regression, these parameters can be: Specified for each oligomer component (polymer) Specified for each segment that composes an oligomer component (polymer)
135
Van Krevelen Liquid Molar Volume Model

The molar volume of a polymeric component depends on the temperature and the physical state of the polymer, as shown here:
Liquid Vl
us ho orp Am
Molar Volume
Vg
Glassy
Semi-crystalline Vc
lline Crysta
Tglass Temperature
Tmelt
The polymer molar volume model uses the temperature and user-specified crystallinity to determine the phase regime of the polymer. The molar volume is calculated using the following equations:
VL = V *,l
for for for
= V *,c xc + V *,l (1 xc ) = V *,c xc + V *, g (1 xc )

Where:
VL
= Net molar volume of the polymer
V *,l = Molar volume of the polymer in the liquid phase

V *,c = Molar volume of the polymer in the crystalline phase V *, g = Molar volume of the polymer in the glassy phase
xc
= Mass fraction crystallinity = Melt transition temperature = Glass transition temperature
Tm Tg
Superscripts l, c, and g refer to the liquid, crystalline, and glassy states respectively.
V *,l , V *,c , and V *, g are calculated from the following expressions: V *,l = (1 + B l T ) / A l
for
T l ,min < T < T l ,max T c ,min < T < T c ,max
(4.11) (4.12) (4.13)
V *,c = (1 + B c T ) / A c for
V *, g = (1 + B g T + C g Tg ) / A g for
T g ,min < T < T g ,max
Van Krevelen Liquid Molar Volume Model Parameters

The following table lists the van Krevelen liquid molar volume model parameters :
Parameter Name / Element DNLVK/1 DNLVK/2 DNLVK/3 DNLVK/4 DNCVK/1 DNCVK/2 DNCVK/3 DNCVK/4 DNGVK/1 DNGVK/2 DNGVK/3 DNGVK/4 DNGVK/5 POLCRY TMVK TGVK Symbol Default Lower Limit --------
Upper Limit --------------------------1 5000 5000
MDS
Units Keyword MOLEDENSITY 1/TEMP TEMP TEMP MOLEDENSITY 1/TEMP TEMP TEMP MOLEDENSITY 1/TEMP 1/TEMP TEMP TEMP --TEMP TEMP
Al
Calculated Calculated 0 1000 Calculated
X X X X X X X X X X X X X --X X
Bl
T l ,min T l ,max Ac
Bc
---------
Calculated 0 1000 Calculated
T c ,min T c ,max
Ag
----------0 0 0
Bg
Calculated Calculated 0 1000 0.0 ----
Cg
T g ,min T g ,max
xc
Tm Tg
The default values of these parameters are calculated using the van Krevelen group contribution model as given by Equations 4.144.16 later in this chapter.
137
Parameter Input
The parameters A , B , A , B , A , B , and C
l l c c g
can be:
Specified for each polymer or oligomer component on a mass or molar basis Specified for segments that compose a polymer or oligomer component on a molar basis Calculated automatically using van Krevelen group contribution techniques
These options are shown in priority order. For example, if parameters are provided for a polymer component and for the segments, the polymer parameters are used and the segment parameters are ignored. The mass based parameters take precedence over the molar based parameters.

If parameters are specified for the polymeric component, then these values are used directly, independent of the copolymer composition. Otherwise, the parameters of a copolymer are calculated using the copolymer composition and the parameters of segments:
*,l
Mn = M seg Mn M seg Mn M seg

Nseg
Nseg
X
A Nseg
*, VA l
V *,c = V *, g =
With
X
A Nseg
*, VA c
X
A
*, VA g
M seg =
Where:
X
A
MA
Nseg = Number of segment types in the copolymer Mn

= Number average molecular weight of the copolymer
M seg = Average molecular weight of segments in the copolymer

XA MA
*, VA l *, VA c
= Mole segment fraction of segment type A in the copolymer = Molecular weight of segment type A in the copolymer = Molar volume of segment type A in the copolymer in the liquid phase = Molar volume of segment type A in the copolymer in the crystalline phase
*, V A g = Molar volume of segment type A in the copolymer in the glassy
phase

If the parameters are not entered for the segments, then these values are estimated using Van Krevelen Group Contribution Methods (see page 145). The van der Walls molar volume of a segment is calculated from contributions of functional groups in the segment:
Vw = nk Vwk
k
Where:
Vw = Van der Waals molar volume of a segment
nk
= Number of occurrences of functional group k in the segment from the segment database or user-specified segment structure database
Vwk = Van der Waals volume of functional group k, from van Krevelen
The segment parameters A , B , A , B , A , B , and calculated by the following equations:
l l c c g
C g , are then
Al = A c = A g = Bl = Bc = B g =
g
1 1.3 Vw 0.001 1.3

(4.16)
(4.14) (4.15)
5.5 10 4 C = 1 1.3
In some cases, the parameters of functional groups are not available in the databank. The contributions from these groups are ignored.
If the parameters in Equations 4.114.13 are not available for components, and cannot be estimated by van Krevelen group contribution, the user can perform an Aspen Plus Regression Run (DRS) to obtain these parameters. In some cases, a DRS run can also be used to adjust these parameters to fit available experimental data. In the data regression, these parameters can be: Specified for each oligomer component (polymer) Specified for each segment that composes an oligomer component (polymer) Specified for each oligomer component on a molar basis or mass basis
139
Tait Liquid Molar Volume Model

The Tait molar volume model is an empirical correlation of the molar volume of polymer and oligomer components with temperature and pressure. This model is especially useful when the model parameters are available in the literature, or can be estimated through experimental data regression. Due to the empirical nature of the model, it should be used only within the ranges of temperature and pressure that were used to obtain the model parameters for each polymer or oligomer. The Tait model is applicable over a wide range of temperature and pressure, and it is particularly useful in cases where the effect of pressure is significant. In almost all cases, the average error with the Tait model was found to be within the reported experimental error (approximately 0.1%). The Tait equation is a P-V-T relationship for pure polymers, which gives the best representation of P-V-T data for most polymers (Danner & High, 1992). This empirical equation uses a polynomial expression for the zero pressure isobar. The Tait equation is used to calculate the molar volume of a polymer component as follows :
P V *,l = M n V (0, T )1 C ln 1 + B(T )
V (0, T ) = A0 + A1 (T 273.15) + A2 (T 273.15) 2 B (T ) = B0 exp[ B1 (T 273.15)]

Where: visit
V *,l Mn
C P T
= Molar volume of the polymer in = Polymer molecular weight
m 3 / kmol
V (0, T ) = Zero pressure isobar

= 0.0894 = Pressure in Pascals = Temperature in Kelvin
(P (T
lower
P Pupper T Tupper
lower
) )
A0 , A1 , A2 , B0 , B1 = Specific constants
Values for several common polymers are given in Appendix C.
Tait Model Parameters

The following table lists the Tait model parameters. These parameters may be entered on the T-Dependent correlation Input form located in the Pure Component subfolder. Note that the Tait model parameters have to be specified for a polymer or oligomer component.
Parameter Name / Element VLTAIT/1 VLTAIT/2 VLTAIT/3 VLTAIT/4 VLTAIT/5 VLTAIT/6 VLTAIT/7 VLTAIT/8 VLTAIT/9 Symbol Default Lower Limit ------------------Upper Limit ------------------MDS Units Keyword
A0 A1 A2
----------0
-------------------
MASS-VOLUME MASS-VOLUME TEMP MASS-VOLUME TEMP PRESSURE 1/TEMP PRESSURE PRESSURE TEMP TEMP
B0 B1 Plower
Pupper Tlower Tupper
1000
0 1000
If the parameters are not available for a polymer component, the user can perform an Aspen Plus Regression Run (DRS) to obtain these parameters. In some cases, a DRS run can also be used to adjust these parameters to fit available experimental data. Note: In a Data Regression Run, a polymer component must be defined as an OLIGOMER type, and the number of each type of segment that forms the oligomer (or polymer) must be specified.
Van Krevelen Glass Transition Temperature Correlation

The van Krevelen correlations for the glass transition temperature are as follows:
Tg , A = n k Yg , k / n k M k
k k
Tg =
Nseg
X A M AT g , A / X A M A
A A
Nseg
141
Where:
Tg , A nk Yg , k Mk Tg
= Glass transition temperature for segment type A = Number of occurrences of functional group k in the segment from the segment database or user-specified segment structure = Glass transition temperature of functional group k, from van Krevelen database = Molecular weight of functional group k = Glass transition temperature of the polymer
Nseg = Number of segment types in the copolymer

XA MA
= Mole segment fraction of segment type A in the copolymer = Molecular weight of segment type A
Yg ,k values for functional groups are given in Appendix B.
Glass Transition Correlation Parameters

The glass transition model parameters are given here:
Parameter Name / Element TGVK Symbol Default Lower Limit 0 0 Upper Limit 5000 5000 MDS Units Keyword TEMP TEMP
Tg , or Tg , A
-----
X X
Van Krevelen Melt Transition Temperature Correlation

The van Krevelen correlations for the glass transition temperature are:
Tm , A = nk Ym ,k / nk M k
k k
Tm =
Nseg
X
A
M ATm, A / X A M A
A
Nseg
Where:
Tm , A
= Melt transition temperature for segment type A
nk Ym ,k Mk Tm
= Number of occurrences of functional group k in the segment from the segment database or user-specified segment structure = Melt transition temperature of functional group k, from van Krevelen database = Molecular weight of functional group k = Melt transition temperature of the polymer
Nseg = Number of segment types in the copolymer

XA MA
= Mole segment fraction of segment type A in the copolymer = Molecular weight of segment type A
Ym ,k values for functional groups are given in Appendix B.
Melt Transition Correlation Parameters

The glass transition model parameters are given here:
Parameter Name / Element TMVK Symbol Default Lower Limit 0 0 Upper Limit 5000 5000 MDS Units Keyword TEMP TEMP
Tm , or
-----
X X
Tm , A
Van Krevelen Solid Property Models

The polymer properties at the solid state in Aspen Polymers can be calculated using the similar approach of that for the liquid state (see Van Krevelen Liquid Property Models on page 127).
Solid Enthalpy of Polymers

The solid enthalpy of a polymer component is calculated using the following equation:
HS = H *,c xc + H *,l (1 xc ) for
Tg T Tm
T < Tg
= H *,c
Where: HS
for
= Net enthalpy of the polymer
143
H *,l H *,c Tm Tg
= Enthalpy of the polymer in the liquid phase = Enthalpy of the polymer in the crystalline phase = Melt transition temperature of the polymer = Glass transition temperature of the polymer = Mass-fraction crystallinity
xc
For a detailed discussion of the above quantities, see Liquid Enthalpy of Polymers on page 128.
Solid Gibbs Free Energy of Polymers

The solid Gibbs free energy of a polymer component is calculated using the following equation:
GS
= *,c xc + *,l (1 xc ) = *,c
for for
Tg T Tm
T < Tg
Where: GS = Net Gibbs free energy of the polymer = Gibbs free energy of the polymer in the liquid phase = Gibbs free energy of the polymer in the crystalline phase
*,l *,c
For a detailed discussion of the above quantities, see Liquid Gibbs Free Energy of Polymers on page 130.
Solid Enthalpy and Gibbs Free Energy Model Parameters

The van Krevelen solid property model parameters are the same as those required for the van Krevelen liquid property models. For a detailed discussion, see Liquid Enthalpy and Gibbs Free Energy Model Parameters on page 131.
Solid Molar Volume of Polymers

The solid molar volume of a polymer component is calculated using the following equation: VS
= V *,c xc + V *,l (1 xc ) = V *,c xc + V *, g (1 xc )
for for
Tg T Tm T < Tg
Where:
VS
= Net molar volume of the polymer in the solid state
V *,l = Molar volume of the polymer in the liquid phase
V *,c = Molar volume of the polymer in the crystalline phase V *, g = Molar volume of the polymer in the glassy phase
xc
= Mass fraction crystallinity
*,l *,c
For a detailed discussion of V , V Molar Volume Model on page 136.
, and
V *, g , see Van Krevelen Liquid
Solid Molar Volume Model Parameters

The van Krevelen solid molar volume model parameters are the same as those required for the van Krevelen liquid molar volume model. For a detailed discussion, see Van Krevelen Liquid Molar Volume Model Parameters on page 137.
Van Krevelen Group Contribution Methods

Based on the group contribution concept, the van Krevelen models use the properties of functional groups to estimate heat capacity ( Cp , Cp molar volume ( V , V , V polymers and oligomers.
*,l *,c *, g *,l *,c
), and
), for polymer segments, and, thereafter, of
In Aspen Polymers, a polymer is defined in terms of its repeating units or segments. The van Krevelen models use the following approach to estimate properties for a system containing polymers: First, the segment properties are estimated using the properties of the functional groups that make up the segment(s). For example, for heat capacity, Cp, the segment property is calculated as the sum of the functional group values using:
* Cp * = nk Cp k k
Where subscript k refers to the functional group. Correlations for other properties are given in Appendix B. If you are retrieving the segments from the SEGMENT databank, you do not need to supply functional groups. If you are not retrieving the segments from SEGMENT, or wish to override their databank functional group definition, you must supply their molecular structure in terms of van Krevelen functional groups. Next, the polymer properties are calculated using the properties of polymer segments, number average degree of polymerization, and segment composition. Finally, mixture properties for the whole component system (polymer, monomer, and solvents) are calculated.
145
The following table illustrates this approach for acrylonitrile-butadiene-styrene (ABS). The van Krevelen functional groups available in Aspen Polymers are given in Appendix B.
Polymer ABS Segments Butadiene-R Functional Groups
CH2 CH CH CH<
CH2 CH CH CH<
Styrene-R
CH2 CH
CH2 CH<
Acrylonitrile-R
CH2 CH C N
CH2 CH C N
Polymer Property Model Parameter Regression

As stated earlier in this chapter, the polymer property models, including Aspen Ideal Gas Property Model, van Krevelen Liquid and Solid Property Models, and Tait Liquid Molar Volume Model, are implemented as polynomial expressions in Aspen Polymers so that they can be used in a predictive mode (such as Van Krevelen Group Contribution Methods, explained on page 145), or in a correlative mode (in case experimental data are available for parameter estimation). Therefore, all polymer property model parameters can be adjusted to fit available experimental data. The user can perform an Aspen Plus Regression Run (DRS) to obtain these parameters. These parameters can be: Specified for each oligomer component (polymer) Specified for each segment that composes an oligomer component (polymer) Specified for each oligomer component on a molar basis or mass basis
Note: The Tait model parameters have to be specified for an oligomer component (polymer). In a Data Regression Run, a polymer component must be defined as an OLIGOMER type, and the number of each type of segment that forms the oligomer (or polymer) must be specified.
Polymer Enthalpy Calculation Routes with Activity Coefficient Models

When an activity coefficient model is used, Aspen Polymers 2006 will provide three new routes, DHL00P, DHL01P, and DHL09P, to calculate the liquid pure component enthalpy departure. In the Aspen Physical Property System, a route is defined as a unique combination of methods and models for calculating a property. The polymer mixture enthalpy is calculated from the ideal gas mixture enthalpy and the liquid mixture enthalpy departure as follows:
l ig l ig E H m = H m + ( H m H m ) = xi H i*,l + H m ,l i l ig E H m H m = xi (H i*,l H i*,ig ) + H m ,l i
H i*,l = H i*,ig + ( H i*,l H i*,ig )

or
HLMX = HIGMX + DHLMX = xi HLi + HLXS

i
DHLMX = xi DHLi + HLXS

i
HL = HIG + DHL
Where:
Name HLMX HIGMX DHLMX HLXS HL HIG DHL Symbol
l Hm ig Hm
Description Liquid mixture molar enthalpy Ideal gas mixture molar enthalpy Liquid mixture molar enthalpy departure Liquid mixture molar excess enthalpy Liquid pure component molar enthalpy Ideal gas pure component molar enthalpy Liquid pure component molar enthalpy departure
l ig Hm Hm
E H m ,l
H i*,l H i*,ig H i*,l H i*,ig
For an activity coefficient model, the calculation procedure for HLMX and HL is constituted in a unique route, respectively. The ideal gas pure or mixture molar enthalpy is automatically calculated using the same Aspen model
147
regardless of the route used for HLMX or HL. HLXS is calculated directly from the activity coefficient model. The new routes for the liquid pure component enthalpy departure are embedded in new routes for both HLMX and HL to ensure that both HLMX and HL are directly dependent on DHL. Changing the route for DHL will affect both HLMX and HL simultaneously. The route structure also insures that HLMX will reduce to HL when there is only a single component in the mixture (HLXS = 0). For polymer/oligomer components, all three routes apply the same van Krevelen model to calculate the liquid pure component enthalpy departure. The difference lies in the way to calculate the liquid pure component enthalpy departure for conventional components. DHL00P uses Ideal gas law, Extended Antoine model, and Watson model to calculate the enthalpy departure. DHL01P uses Redlich-Kwong model, Extended Antoine model, and Watson model. And DHL09P uses the DIPPR liquid heat capacity correlation model. For PNRTL-IG, the default route is DHL00P and for all other activity coefficient models, the default route is DHL01P. Use DHL09P to calculate the liquid pure component enthalpy or heat capacity from the DIPPR correlation model for conventional components. The following tables list the routes available in Aspen Polymers for liquid pure component enthalpy and polymer mixture enthalpy calculations with activity coefficient models:
Routes available for liquid pure component enthalpy (HL)

Route ID HLDVK0 Route ID for DHL DHL00P Description Using Ideal gas law, Extended Antoine model and Watson model for conventional components and van Krevelen model for polymer components. Using Redlich-Kwong model (RK), Extended Antoine model and Watson model for conventional components and van Krevelen model for polymer components Using DIPPR model for conventional components and van Krevelen model for polymer components. Using Ideal gas law, Extended Antoine model and Watson model for conventional components and van Krevelen model for polymer components. Using Redlich-Kwong model (RK), Extended Antoine model, and Watson model for conventional components and van Krevelen model for polymer components Using DIPPR model for conventional components and van Krevelen model for polymer components.
HLDVK1 (default)
DHL01P
DHL09P HLDVK
HL0DVKRK
HL0DVKD
HL0DVKRK is the default route for HL in Aspen Polymers 2004.1 and earlier releases.
Routes available for polymer mixture enthalpy (HLMX) in POLYNRTL

Route ID Route ID for DHL Description
Route ID HLMXP1 (default) HLMXP2
Route ID for DHL DHL01P
Description Using Redlich-Kwong model (RK), Henrys law, Extended Antoine model, Watson model, van Krevelen model, and polymer-NRTL model Using Redlich-Kwong model (RK), Extended Antoine model, Watson model, van Krevelen model, and polymer-NRTL model Using Redlich-Kwong model (RK), Henrys law, Extended Antoine model, Watson model, van Krevelen model, and polymer-NRTL model
DHL01P
HLMXPRK
HLMXPRK is the default route for HLMX in Aspen Polymers 2004.1 and earlier releases.
Routes available for polymer mixture enthalpy (HLMX) in POLYFH

Route ID HLMXFH1 (default) HLMXFH2 Route ID for DHL DHL01P Description Using Redlich-Kwong model (RK), Henrys law, Extended Antoine model, Watson model, van Krevelen model, and polymer-FH model Using Redlich-Kwong model (RK), Extended Antoine model, Watson model, van Krevelen model, and polymer-FH model Using Redlich-Kwong model (RK), Henrys law, Extended Antoine model, Watson model, van Krevelen model, and polymer-FH model
DHL01P
HLMXFHRK
HLMXFHRK is the default route for HLMX in Aspen Polymers 2004.1 and earlier releases.
Routes available for polymer mixture enthalpy (HLMX) in POLYUF

Route ID HLMXUF1 (default) HLMXUF2 Route ID for DHL DHL01P Description Using Redlich-Kwong model (RK), Henrys law, Extended Antoine model , Watson model, van Krevelen model, and polymer-UNIFAC model Using Redlich-Kwong model (RK), Extended Antoine model, Watson model, van Krevelen model, and polymer-UNIFAC model Using Redlich-Kwong model (RK), Henrys law, Extended Antoine model, Watson model, van Krevelen model, and polymer-UNIFAC model
DHL01P
HLMXPURK
HLMXPURK is the default route for HLMX in Aspen Polymers 2004.1 and earlier releases.
Routes available for polymer mixture enthalpy (HLMX) in POLYUFV

Route ID Route ID for DHL Description
149
Route ID HLMXFV1 (default) HLMXFV2
Route ID for DHL DHL01P
Description Using Redlich-Kwong model (RK), Henrys law, Extended Antoine model, Watson model, van Krevelen model, and polymer-UNIFAC-Free-Volume model Using Redlich-Kwong model (RK), Extended Antoine model, Watson model, van Krevelen model, and polymer-UNIFAC-Free-Volume model Using Redlich-Kwong model (RK), Henrys law, Extended Antoine model, Watson model, van Krevelen model, and polymer-UNIFAC-Free-Volume model
DHL01P
HLMXFVRK
HLMXFVRK is the default route for HLMX in Aspen Polymers 2004.1 and earlier releases.
Routes available for polymer mixture enthalpy (HLMX) in PNRTL-IG

Route ID HLMXP00 (default) HLMXP02 HLMXP Route ID for DHL DHL00P Description Using Ideal gas law, Henrys law, Extended Antoine model, Watson model, van Krevelen model, and polymer-NRTL model Using Ideal gas law, Extended Antoine model, Watson model, van Krevelen model, and polymer-NRTL model Using Ideal gas law, Extended Antoine model, Watson model, van Krevelen model, and polymer-NRTL model
DHL00P
HLMXP is the default route for HLMX in Aspen Polymers 2004.1 and earlier releases.
References
Aspen Physical Property System Physical Property Methods and Models. Cambridge, MA: Aspen Technology, Inc. Bicerano, J. (1993). Prediction of Polymer Properties. New York: Marcel Dekker, Inc. Danner, R. P., & High, M. S. (1992). Handbook of Polymer Solution Thermodynamics. New York: American Institute of Chemical Engineers. Van Krevelen, D. W. (1990). Properties of Polymers, 3rd Ed. Amsterdam: Elsevier.
5 Polymer Viscosity Models
This chapter describes the polymer viscosity models in Aspen Polymers (formerly known as Aspen Polymers Plus). Polymer melt viscosity is calculated using the Modified Mark-Houwink/van Krevelen model. Viscosity of polymer solutions and mixtures over the entire range of composition is calculated using the Aspen polymer mixture viscosity model. Polymer solution viscosity can also be calculated using the van Krevelen polymer solution viscosity model or the Eyring-NRTL mixture viscosity model. Topics covered include: About Polymer Viscosity Models, 151 Modified Mark-Houwink/van Krevelen Model, 152 Aspen Polymer Mixture Viscosity Model, 158 Van Krevelen Polymer Solution Viscosity Model, 161 Eyring-NRTL Mixture Viscosity Model, 167 Polymer Viscosity Routes in Aspen Polymers, 170
About Polymer Viscosity Models

The modified Mark-Houwink/van Krevelen model is used to calculate the zeroshear viscosity of polymer melts. The effects of temperature and polymer molecular weight on viscosity are considered. The model can be used correlatively (in the presence of viscosity data for regression) or predictively, as proposed by van Krevelen. The Aspen polymer mixture viscosity model is used with good accuracy to correlate data over the entire concentration range, from pure polymer melt to polymer at infinite dilution. The EyringNRTL mixture viscosity model is also applicable to polymer mixture systems. For polymer solutions, the effect of polymer concentration can also be considered using the van Krevelen polymer solution viscosity model. The following tables provide an overview of the available models for polymer systems in Aspen Polymers:
Property Name MUL Symbol Description Liquid viscosity of a component in a mixture
i*,l
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151
MULMX
Liquid viscosity of a mixture
Viscosity Models Modified Mark-Houwink/ van Krevelen Model Aspen Polymer Mixture Viscosity Model Van Krevelen Polymer Solution Viscosity Model Eyring-NRTL Mixture Viscosity Model
Model Name MUL0MH MUPOLY MUL2VK EYRING
Pure X __ __ __
Mixture __ X X X
Properties Calculated MUL MULMX MULMX MULMX
Modified Mark-Houwink/van Krevelen Model

The polymer melt viscosity varies with the polymer structural characteristics, state conditions, and shear history. Currently, the melt viscosity model available in Aspen Polymers considers the effects of polymer structure, polymer molecular weight and molecular weight averages, and temperature. This model combines two zero-shear viscosity correlations. The modified Mark-Houwink equation correlates polymer molecular weight and temperature effect; the van Krevelen method estimates viscosity-temperature function based on functional group properties. The Andrade/DIPPR model is used to calculate viscosity for conventional components (Andrade, 1930) Polymer melt viscosity increases as polymer molecular weight increases. The classical Mark-Houwink equation correlates the viscosity-molecular weight dependency with a power-law expression. Polymer melt viscosity is also a strong function of temperature; it decreases as the temperature increases. Modified Mark-Houwink Expression The Modified Mark-Houwink (MMH) equation uses an Arrhenius expression to account for the viscosity-temperature relationship of polymers:
*,l i
M = ref w M ref
= =
Tref T
E T exp 1 T RT ref
Where:
i*,l ref
Zero-shear viscosity of a polymer component Zero-shear viscosity of the polymer at the specified reference temperature and molecular weight
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Mw = M ref = Tref =
Weight average molecular weight for the polymer Reference molecular weight of the polymer Reference temperature Exponential factor accounting for the polymer molecular weight effect. This is a two parameter vector where
(1) (2)
M cr =
is used for M w > M cr is used for M w M cr
Critical molecular weight of polymer, at which viscosity-molecular weight dependency changes. It corresponds to the polymer weightaverage molecular weight at the turning point of a log 0 vs.
log M w plot. For example:
E
R T
= = = =
Activation energy of viscous flow Universal gas constant Absolute temperature Empirical temperature exponent
The weight average molecular weight, M w , of the polymer can be retrieved from the polymer attribute MWW or calculated from its number average molecular weight and polydispersity index:
M w = M n * PDI
Where:
Mn =
Number average molecular weight of the polymer
153
PDI =
Polydispersity index of the polymer
The value for critical molecular weight is available for a limited number of POLYMER databank polymers (Van Krevelen, 1990). If the critical molecular weight for a polymer component is not available from the databank, you must supply it.
Modified Mark-Houwink Model Parameters

The following table lists the MMH model parameters:
Parameter Name / Element MULMH/1 MULMH/2 MULMH/3 MULMH/4 MULMH/5 MULMH/6 MULMH/7 CRITMW HMUVK Symbol Default Lower Limit Upper Limit MDS Units Keyword VISCOSITY MOLEENTHALPY ------TEMP ---(MOLEENTHALPY)1
/3
Comments
ref
E
--0 3.4 1.0 0 ---------
10 10
0 0 0 -5.0 200 5000 1.0 10-10
1010 1010
20.0 20.0 5.0 5000
-------------------
Unary Unary Unary Unary Unary Unary Unary Unary Unary
(1) (2)
Tref M ref
M cr
1010 1010
1010
H Tg
PDI
TGVK POLPDI*
--1.0
0 1.0
5000 1000
-----
TEMP ---
Unary Unary
MULMH must be created as a new parameter to enter data for it. Values for MULMH must be entered in SI units. Only required for Data Regression (DRS) runs and oligomer components or when weight-average molecular weight is not included in the list of polymer component attributes.

All unary parameters have to be specified for each polymer or oligomer component. The parameters E and Except
are related to the effect of temperature on
viscosity. The parameters
and M cr are related to polymer molecular weight. M cr , values for E , , and can be regressed from experimental
data and entered for any polymer or oligomer. Therefore, if viscosity data is available for a given polymer component, a Data Regression (DRS) simulation will return the MMH equation parameters. Note: In DRS runs, the polymer must be treated as an oligomer and the number of each type of segment that forms the oligomer must also be specified. In order to calculate the weight average molecular weight of the polymer in a DRS run, the polydispersity index of the polymer has to be specified using the pure component property POLPDI.
Van Krevelen Viscosity-Temperature Correlation

If no MMH parameters are supplied to the MMH expression the Arrhenius term drops out:
*,l i
M = cr (T ) w M cr
We set M ref = M cr . In this case, the
cr (T )
term is estimated using the van
Krevelen viscosity-temperature correlation. The van Krevelen viscosity-temperature correlation estimates the
cr
based
on polymer structural information and glass transition temperature. The following figure shows the viscosity-temperature relationship for a number of common polymer components:
cr
vs. T Graphical Correlation (Hoftyzer & Van Krevelen, 1976)
The zero-shear viscosity of various polymers exhibits similar
trends. If
T 1.2T g , all the polymers follow a Williams-Landel-Ferry (WLF) relationship
155
(Williams et al., 1955). At higher temperatures, different polymers follow different paths. Van Krevelen modeled this behavior using a group contribution method. The principles of the van Krevelen method can be summarized as follows: The viscosity-temperature relationship of different polymer components can be represented by a number of master curves. These master curves are functions of three parameters: the polymer glass transition temperature, Tg , the critical mass viscosity at T = 1.2Tg cr (1.2Tg ) , and a
structural parameter, A. A new transport property called the viscosity-temperature gradient, H , is defined. Each functional group of a polymer molecule has a unique value for H that is mole-additive with respect to functional groups and segments.
H is used to compute cr (1.2Tg ) and A.
The van Krevelen master curves, which correlate the polymer viscositytemperature relationship, are shown here:
cr
vs. T Master Curves (Hoftyzer & Van Krevelen, 1976)
These master curves simulate the polymer viscosity-temperature behavior of the previous graphical correlation figure. The van Krevelen method calculates the critical mass viscosity at given temperature cr (T ) through the following
steps: 1 Compute the component viscosity-temperature gradient from van Krevelen functional group values. Aspen Polymers uses the following mixing rules to compute polymer component viscosity-temperature gradient from van Krevelen functional groups: For segments:
Ngrp
H,A =
n H
k k
,k
/MA
For polymers and oligomers:
H =
Nseg
X
A
M A H,A / X A M A
A
Nseg
Where:
H , A = Viscosity-temperature gradient of segment type A

Ngrp = Number of types of groups in a segment
= Number of occurrences of group k in a segment database
nk
H ,k = Viscosity-temperature gradient of group k, from van Krevelen

MA
= Molecular weight of segment type A = Viscosity-temperature gradient of a polymer
Nseg = Number of types of segments in a polymer
XA
2
= Mole segment fraction of segment type A in a polymer
E () , the activation energy of viscous flow at high temperature, is

calculated from the polymer component viscosity-temperature gradient:
3 E () = H
With E () computed from group quantity, the following two parameters that affect polymer melt viscosity are estimated using the following equations: The critical mass viscosity at T = 1.2T g is calculated using the WLF equation:
log cr (1.2T g ) = E () 1 E () 2.3 RTg
(0.052 8.5 10 5 T g ) Tg
1.4
The structural parameter A is calculated using the following equation:
A=
Tg may be provided for polymer components. If Tg is not supplied, the

van Krevelen estimate is used. 4 Given values for Tg / T and A, the value for the reduced viscosity is obtained from the master curves shown in the previous figure and where:
Tg cr (T ) A 1 = log T cr (1.2Tg )
cr (1.2Tg )
is known from the previous step, therefore the final
157
value for
cr (T )
can be calculated.
Specifying the MMH Model

Aspen Polymer Mixture Viscosity Model

Viscosity of polymer solutions,, and mixtures in general, depends on composition, molecular weight, temperature, and shear rate. Although a great deal of effort has been spent to describe the viscosity of dilute polymer solutions (intrinsic viscosity) as well as that of polymer melts, relatively little attention has been paid to the broad range of polymer composition between these extremes. It is this region, however, that is import when describing reacting mixtures. Aspen polymer mixture viscosity model (Song et al., 2003) can be used to correlate the entire concentration range from pure polymer melt to polymer at infinite dilution. This correlative model is essentially a new mixing rule for calculating the mixture viscosity from the pure component viscosities. It assumes that the viscosities of both pure polymer and nonpolymeric components (solvents) are already available as input. This model uses two binary parameters to capture non-ideal mixing behavior. Our testing indicates that this model is very effective for polymeric and conventional chemical systems.
Multicomponent System
The Aspen polymer mixture viscosity model is applicable to mixtures containing any number of components containing polymers. It expresses the zero-shear viscosity of the mixture as follows:
ln = wi ln
l i
*,l i
1/ 3 + k ij wi w j ln ij + wi w j (lij ln ij ) j >i i j i
Where:
l i*,l
wi k ij lij
= Zero shear viscosity of the mixture = Zero shear viscosity of component i = Weight fraction of component i = Symmetric binary parameter, k ji = k ij = Antisymmetric binary parameter, l ji = l ij
ln ij = Cross binary term from viscosities of pure components
The first term is the linear mixing, the second term is the binary symmetricquadratic mixing, and the last term is the binary antisymmetric mixing. The cross binary term is chosen as follows:
ln ij =| ln i*,l ln *,l | j
Therefore, ln ij 0 when
i*,l *,l . The antisymmetric mixing term j
satisfies the invariant condition when a component is divided into two or more identical subcomponents (Mathias et al., 1991).
Binary Parameters
There are two binary parameters, one symmetric, k ij , and one antisymmetric,
lij . Both binary parameters allows complex temperature dependence:

' ' ' ' ' lij = aij + bij / Tr + cij ln Tr + d ij Tr + eij Tr2
with
Tr =
T Tref
Where:
Tref
Aspen Polymer Mixture Viscosity Model Parameters

The binary parameters for the Aspen polymer mixture viscosity model are listed here:
Parameter Name / Element MUKIJ/1 MUKIJ/2 MUKIJ/3 MUKIJ/4 MUKIJ/5 MUKIJ/6 Symbol Default Lower Limit ------------Upper Limit ------------MDS Units Keyword ------------Comments
aij bij cij d ij eij Tref
0 0 0 0 0 298.15
X X X X X X
Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric Binary, Symmetric
159
MULIJ/1
' aij
---
---
---
Binary, Antisymmetr ic Binary, Antisymmetr ic Binary, Antisymmetr ic Binary, Antisymmetr ic Binary, Antisymmetr ic Binary, Antisymmetr ic
MULIJ/2
' bij
---
---
---
MULIJ/3
' cij
---
---
---
MULIJ/4
' d ij
---
---
---
MULIJ/5
' eij
---
---
---
MULIJ/6
Tref
298.15
---
---
---

Both binary parameters, k ij and l ij , have to be specified for each componentcomponent pair. Their default values are zero. If viscosity data is available for a polymer solution or a binary mixture, a Data Regression (DRS) simulation will return both binary parameters, k ij and l ij . Note: In DRS runs, the polymer must be treated as an oligomer and the number of each type of segment that forms the oligomer must also be specified.
Polymer Solution Viscosity Correlation

For polymer-solvent solutions, the Aspen polymer mixture viscosity model reduces to:
ln l = (1 w p ) ln s*,l + w p ln *,l p + [k12 + l12 (1 2 w p )](1 w p ) w p ln 12

ln 12 = (ln *,l ln s*,l ) / 2 p
Where:
l s*,l
*,l p
= Zero shear viscosity of the polymer-solvent solution = Zero shear viscosity of the solvent = Zero shear viscosity of the polymer
wp
k12 l12
= Weight fraction of the polymer = Symmetric binary parameter = Antisymmetric binary parameter
Specifying the Aspen Polymer Mixture Viscosity Model

Van Krevelen Polymer Solution Viscosity Model

The viscosity of concentrated polymer solutions exhibits characteristics similar to those of polymer melts. The influence of parameters such as molecular mass, temperature and shear rate on viscosity are largely similar. The viscosity of a polymer solution is also a function of polymer concentration. A discontinuity is observed in polymer solution viscosity versus concentration profile at the so-called critical concentration. A solution is considered concentrated when the polymer weight concentration exceeds the critical concentration, typically at five percent by weight. Historically, a clear distinction has been made in the literature between dilute polymer solutions and concentrated polymer solutions with regard to viscosity. In concentrated solutions, solvents reduce the solution viscosity by reducing the glass transition temperature, Tg , and through dilution effects. This model extends the van Krevelen binary polymer solution viscosity correlations to multicomponent mixtures. The solution is treated as a quasibinary mixture of polymer and solvent. For mixtures without polymeric components, the Letsou-Stiel corresponding state correlation is used.
Quasi-Binary System
The van Krevelen binary polymer solution viscosity model in Aspen Polymers treats a multicomponent polymer mixture as a quasi-binary system consisting of a pseudo-polymer component and a pseudo-solvent component. The pseudo-polymer component is a blend of all polymers and oligomers in the mixture that possesses properties averaged across the components present. The pseudo-solvent component is composed of all present non-polymeric species. The properties of the pseudo-solvent are averaged across the conventional species in the system.
161
Properties of Pseudo-Components
A weight-average mixing rule is used to compute pseudopolymer properties: Weight-average mixing rule
Npol
QB =
i =1
Npol
wi Qip /
w
i =1
Where:
QB
= Property of the pseudo-polymer (the superscript B stands for the pseudo-polymer) represents any of the following quantities:
B 0 = Zero-shear viscosity of the pseudo-polymer. The above mixing
Npol = Total number of polymeric components in the system
QB
rule for the pseudo-polymer viscosity is derived from the influence of polydispersity on zero-shear viscosity (Flory, 1943)
B H = Van Krevelen viscosity-temperature gradient of the pseudopolymer. H is additive for van Krevelen groups. The viscosity-
temperature gradient of the blend equals the weight-averaged viscosity-temperature gradient of all polymeric species
TgB = Glass transition temperature of the pseudo-polymer. The weightaverage mixing rule is derived for TgB by extending the Bueche
formula to polymer mixtures, with an assumption that the K constant is the same for all polymers (Bueche, 1962)
B = Power-law exponential factor that accounts for the real solvent

dilution effects
Q pi
Property of polymer component i, and represents any of the following quantities: component viscosity models. It is a function of polymer molecular weight, temperature and polymer structure estimated from the van Krevelen group contribution method (See Chapter 4) specified or estimated from the van Krevelen group contribution method (see Chapter 4)
0i = Zero-shear viscosity of polymer i, computed from pure
H i = Van Krevelen viscosity-temperature gradient of polymer i. It is Tgi = Glass transition temperature of polymer i. Tg values are user
= Power-law exponent for solvent dilution of polymer i. i is correlated to the molecular weight exponential factor by / 15 usually varies from 4.0 to 5.6. For more information . on , see Van Krevelen Viscosity-Temperature Correlation on page 155.
The same mixing rule applies to the solvent mixture for the properties of the pseudo-solvent:
QS =
Nsol
i =1
Nsol
wi Qsi /
w
i =1
Where:
QS
= Property of the pseudo-solvent (the superscript S stands for pseudo-component solvent) represents any of the following quantities:
Nsol = Total number of solvent components in the system
QS
TgS = Glass transition temperature of the pseudo-solvent component. The mixing rule for TgS is an extension of the Bueche formula
(Bueche, 1962)
K S = Constant related to the component volume expansion coefficient
Qsi
= Property of solvent component i and represents any of the following quantities:
Tgi = Glass transition temperature of solvent component i. In situations when the solvent Tg values are not available, user may use
component melting point for estimation: Tg 2 / 3Tm . Tg values must be specified to for each solvent
K i = Constant related to the component volume expansion coefficient:

Ki 1s gs 1 p gp
, 1 is the volume expansion coefficient above Tg ,
and g is the volume expansion coefficient below Tg . K i is defined as a solvent parameter. Typically, K i has a value between 1.0 and 3.0. If there is no data available to estimate K i , a default value of 2.5 is suggested With the above mixing rules, the two pseudo-component properties needed to compute solution viscosity are available. The van Krevelen binary solution model is applied to the quasi-binary solution to obtain the mixture viscosity.
Van Krevelen Polymer Solution Viscosity Model Parameters

The parameters for the van Krevelen polymer solution viscosity model are listed here:
Parameter Name / Element MULVK/1 Symbol Default Lower Limit 0 Upper Limit 10 MDS Units Keyword Comments
Ki
2.5
---
---
Unary
163
MULVK/2 TGVK
i Tg
5.1 ---
1 0
100 5000
-----
--TEMP
Unary Unary
Polymer Solution Viscosity Estimation

In a binary solution of polymer and solvent, the solution viscosity decreases as the solvent concentration increases. This is caused by: Decrease of the viscosity of the pure polymer as a result of a decrease of the glass transition temperature Real dilution effect, which causes the viscosity of the solution to fall between that of the pure polymer and that of the pure solvent
For these reasons, the concentration dependency and temperature dependency of solution viscosity are strongly related. Polymer viscosity is much more significant than solvent viscosity. Therefore, in the van Krevelen solution viscosity model, the solvent viscosity is neglected. To calculate the binary polymer solution viscosity, the van Krevelen model estimates Tg of the polymer mixture, calculates the mixture viscosity at given temperature with the mixture glass point, then applies the true solvent dilution effect. The Tg effect and the real dilution effect are imposed on the polymer viscosity only. The polymer viscosity-temperature relationship is described in graphical form in the van Krevelen polymer melt viscosity correlation in the figure cr vs T Graphical Correlation (see page 155). The steps used to calculate viscosity in the van Krevelen solution viscosity model are illustrated here:
Polymer Solution Glass Transition Temperature

Polymer viscosity varies with glass transition temperature. Addition of a solvent to the polymer lowers the glass transition temperature to the mixture glass point, Tgm , and, therefore, lowers the polymer viscosity. This is the socalled plasticizer effect. A theoretical treatment of the plasticizer effect has been developed by Bueche who gave the following equation for the glass transition temperature of a plasticized polymer (Bueche, 1962):
165
T =
m g
TgB wB + K S TgS wS wB + K S wS
= Glass transition temperature of the mixture (superscript m stands for the mixture) =
Npol
Where:
Tgm
wB
Total weight fraction of polymer in the mixture, wB =
w
i =1 i
wS
Total weight fraction of solvent in the mixture, wS =
Nsol i =1
Polymer Viscosity at Mixture Glass Transition Temperature

For a polymer-solvent binary mixture, the undiluted polymer viscosity at the mixture glass point is calculated from the van Krevelen viscosity-temperature relationship:
Tgm log , A = f T (1.2Tg )
Where:
= Viscosity of the undiluted polymer with a new glass temperature Viscosity of the undiluted polymer at its own glass temperature
(1.2Tg ) =
f A
= Van Krevelen graphical correlation for polymer melt viscosity = Structural factor related to the viscosity-temperature gradient of the polymer H by:
A=
(H )
2.303RTg
For a quasi-binary system, the structural factor of pseudo-polymer, A B , is used in the van Krevelen viscosity-temperature relationship. A B is calculated using the pseudo-polymer properties:
log
B (1.2TgB )
* B
Tgm , AB = f T
A =
B
(H )
B 3
2.303RT gB
where
B (1.2T gB )
is solved from the van Krevelen zero shear viscosity
graphical correlation of the pseudo-polymer
0B :
TgB B log B ,A = f T (1.2TgB )
0B
True Solvent Dilution Effect

The influence of the solvent concentration can be described by a power-law equation:
0m = * w p
For a quasi-binary system, the mixture viscosity is:

* 0m = B wB
B
Where:
0m p
B
= Zero shear viscosity of the mixture = Exponential factor that accounts for polymer concentration = Exponential factor that accounts for the pseudo-polymer concentration
Specifying the van Krevelen Polymer Solution Viscosity Model

Eyring-NRTL Mixture Viscosity Model

The Eyring-NRTL viscosity model (Novak et al., 2004) is a segment-based mixture model for correlating the viscosity of polymer mixtures, including copolymers. It represents a synergistic combination of the Eyring theory for fluid diffusion and flow and the NRTL model for local composition interaction. The segment-based approach provides a more physically realistic model for large molecules like polymers when diffusion and flow is viewed to occur by a sequence of individual segment jumps into vacancies rather than jumps of the entire large molecules. This model uses NRTL binary parameters to capture non-ideal mixing behavior.
167
Multicomponent System
The Eyring-NRTL mixture viscosity model is applicable to mixtures containing any number of components containing polymers. It expresses the zero-shear viscosity of the mixture as follows:
ln = xi ln
l i
*,l i
x j G ji ji j + xi i x j G ji j
With:
xi
X r = X r
I i,I I J j
J j,J
G ji = exp( ji ji )
Where:
l i*,l
I and J i and j
= = = = = = = = =
Zero shear viscosity of the mixture Zero shear viscosity of component i Component based indices Segment based indices Segment based mole fraction for segment based species i Mole fraction of component I in component basis Number of segment type i in component I NRTL non-random factor Interaction parameter
xi
XI
ri , I
ji ji
Binary Parameters
The binary parameter,
ij , allows complex temperature dependence:
ij = aij + bij / Tr + cij ln Tr + d ij Tr + eij Tr2

with
Tr =
T Tref
Where:
Tref
Eyring-NRTL Mixture Viscosity Model Parameters

The parameters for the Eyring-NRTL mixture viscosity model are listed here:
Parameter Name / Element PVISC VNRTL/1 VNRTL /2 VNRTL /3 VNRTL /4 VNRTL /5 VNRTL /6 VNRTL /7 Symbol Default Lower Limit ----------------Upper Limit ----------------MDS Units Keyword VISCOSITY --------------Comments
i*,l
aij bij cij d ij eij
--0 0 0 0 0 0.3 298.15
X X X X X X X X
Unary Binary, Antisymmetric Binary, Antisymmetric Binary, Antisymmetric Binary, Antisymmetric Binary, Antisymmetric Binary, Symmetric Binary, Antisymmetric
ij
Tref

The input for pure component viscosity,
i*,l , is optional. By default, the pure
component viscosity is automatically calculated by the modified MarkHouwink/van Krevelen model. The binary parameters in ij and ij have to be specified for solvent-solvent pairs and solvent-segment pairs for data input or data regression. Their default values are zero. Note: In DRS runs, the polymer must be treated as an oligomer and the number of each type of segment that forms the oligomer must also be specified.
Specifying the Eyring-NRTL Mixture Viscosity Model

169
Polymer Viscosity Routes in Aspen Polymers

Aspen Polymers offers two routes, MULMX13 and MULMXVK, for calculating the polymer mixture viscosity. MULMX13 directly refers the Aspen polymer mixture viscosity model, MUPOLY, and is the default route employed by all polymer property methods. MULMXVK directly refers the van Krevelen polymer solution viscosity model, MUL2VK, and can be chosen as an option. A summary of routes appears in the following table:
Route MULMX13 Model Name MUPOLY Applicability default Property Methods POLYFH, POLYNRTL, POLYUF, POLYUFV, POLYSL, POLYSRK, POLYSAFT, POLYPCSF
MULMXVK
MUL2VK
optional
References
Andrade, E. N. da Costa (1930). Nature, 125, 309, 582. Bueche. F. (1962). Physical Properties of Polymers. New York: Wiley. Flory, P. J. (1943). J. Amer. Chem. Soc., 65, 372. Hoftyzer, P. J., & Van Krevelen, D. W. (1976). Angew. Makromol. Chem., 54, 1. Kim, D.-M., & Nauman, E. B. (1992). J. Chem. Eng. Data, 37, 427. Mathias, P. M., Klotz, H. C., & Prausnitz, J. M. (1991). Fluid Phase Equilibria, 67, 31. Novak, L. T., Chen, C.-C., & Song, Y. (2004). A Segment-Based Eyring-NRTL Viscosity Model for Mixtures Containing Polymers. Ind. Eng. Chem Res., 43, 6231. Song, Y., Mathias, P. M., Tremblay, D., & Chen, C.-C. (2003). Viscosity Model for Polymer Solutions and Mixtures. Ind. Eng. Chem Res., 42, 2415. Van Krevelen, D. W. (1990). Properties of Polymers, 3rd. Ed. Amsterdam: Elsevier. Van Krevelen, D. W., & Hoftyzer, P.J. (1976). Angew. Makromol. Chem., 52, 101. Williams, M. L., Landel, R. F., & Ferry, J. D. (1955). J. Am. Chem. Soc., 77, 3701.
6 Polymer Thermal Conductivity Models
This chapter describes the polymer thermal conductivity models in Aspen Polymers (formerly known as Aspen Polymers Plus). Polymer thermal conductivity is calculated using the modified van Krevelen thermal conductivity model. The Aspen polymer mixture thermal conductivity model is used to calculate the thermal conductivity of mixtures containing polymers. Topics covered include: About Thermal Conductivity Models, 171 Modified van Krevelen Thermal Conductivity Model, 173 Aspen Polymer Mixture Thermal Conductivity Model, 180 Polymer Thermal Conductivity Routes in Aspen Polymers, 181
About Thermal Conductivity Models

The thermal conductivity of a polymeric component generally depends on both temperature and pressure, as well as on the physical state of the polymer. The physical state and temperature dependence is depicted in the following figure:
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171
crystalline
Thermal Conductivity
semi-crystalline
glassy
rubbery liquid
Tg
Tm
Temperature
In the figure, T g and Tm are the polymer glass and melt transition temperatures respectively. The top boundary of the semi-crystalline region is the crystalline thermal conductivity curve. The bottom boundary of the semicrystalline region is separated into two curves. To the left of the glass transition temperature is the glass thermal conductivity curve, and to the right is the liquid thermal conductivity curve. Based on this description, the modified van Krevelen thermal conductivity model is used to calculate the thermal conductivity of polymers. Additionally, the effects of temperature and pressure are considered. The model can be used correlatively (in the presence of thermal conductivity data for regression) or predictively, as proposed by van Krevelen. The Aspen polymer mixture thermal conductivity model is used to calculate the polymer mixture thermal conductivity. The following tables provide an overview of the available models for polymer systems in Aspen Polymers:
Property Name KL KLMX Symbol Description Liquid thermal conductivity of a component in a mixture Liquid thermal conductivity of a mixture
*,l i
Thermal Conductivity Models Modified van Krevelen/DIPPR Modified van Krevelen/TRAPP Aspen Polymer Thermal Conductivity Mixture Model
Model Name
Pure
Mixture
Properties Calculated KL KL KLMX
KL0VKDP KL0VKTR KLMXVKTR
X X __
__ __ X
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Modified van Krevelen Thermal Conductivity Model

The polymer thermal conductivity is calculated using the following equation:
KL = *,l i = *,c + *,l (1 ) i i = *,c + *, g (1 ) i i

Where:
for for for
T > Tm Tg < T Tm T Tg
KL = Net thermal conductivity of the polymer
*,l i *,c i *, g i
= Thermal conductivity of the polymer in the liquid phase = Thermal conductivity of the polymer in the crystalline phase = Thermal conductivity of the polymer in the glassy phase = Crystalline weighting fraction
The superscripts l, c, and g refer to the liquid, crystalline, and glassy curves, respectively. The crystalline weighting fraction is given by Eirmann (1962):
3xc
2+
*,c i *, g ,l i
*,c + xc 1 *,i g ,l i
(6.1)
With
*, g ,l i
= *,l i = *, g i
for for
Tg < T Tm T Tg
Where:
xc
= Mass fraction crystallinity
Modified van Krevelen Equation The thermal conductivities for the liquid, crystalline and glassy states are calculated using the modified van Krevelen equation:
*, = *,,ref F i i
(6.2)
With
173
= 1 + A
T Tref + B Tref 1 1 + C ln T T T T T ref ref ref P Pref T Tref P Pref + E + D P T P ref ref ref
(6.3)
Where:
= l, c, or g = Thermal conductivity of the polymer for state = Thermal conductivity of the polymer for state temperature and pressure = Reference temperature for state = Reference pressure for state
*, i
*,,ref i Tref Pref
at the reference
A , B , C , D , E , and F are dimensionless constants.
Modified van Krevelen Thermal Conductivity Model Parameters

The following table lists the modified van Krevelen thermal conductivity model parameters:
Parameter Name / Element Symbol Default Lower Limit Upper Limit MDS Units Keyword Comments
KLVKL/1 KLVKL/2 KLVKL/3 KLVKL/4 KLVKL/5 KLVKL/6 KLVKL/7 KLVKL/8 KLVKL/9 KLVKC/1 KLVKC/2 KLVKC/3
l *,,ref i
--0 0 0 0 0 1 298.15 101325 --0 0
10-6 -1000 -1000 -1000 -1000 -1000 -100 2 1000 10-6 -1000 -1000
1000 1000 1000 1000 1000 1000 100 1000 1010 1000 1000 1000
---------------------
THERMALCONDCTIVITY ------------TEMP PRESSURE THERMALCONDCTIVITY -----
Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary
Al Bl Cl Dl El Fl
l Tref l Pref c *,,ref i
Ac Bc
-----
Parameter Name / Element
Symbol
Default
Lower Limit
Upper Limit
MDS
Units Keyword
Comments
KLVKC/4 KLVKC/5 KLVKC/6 KLVKC/7 KLVKC/8 KLVKC/9 KLVKG/1 KLVKG/2 KLVKG/3 KLVKG/4 KLVKG/5 KLVKG/6 KLVKG/7 KLVKG/8 KLVKG/9 POLCRY TGVK TMVK
Cc
Dc Ec Fc
c Tref c Pref g *,,ref i
0 0 0 1 298.15 101325 --0 0 0 0 0 1 298.15 101325 0 -----
-1000 -1000 -1000 -100 2 1000 10-6 -1000 -1000 -1000 -1000 -1000 -100 2 1000 0 0 0
1000 1000 1000 100 1000 1010 1000 1000 1000 1000 1000 1000 100 1000 1010 1 5000 5000
-----------------
--------TEMP PRESSURE THERMALCONDCTIVITY ------------TEMP PRESSURE --TEMP TEMP
Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary Unary
Ag Bg
----------------X X
Cg
Dg Eg Fg
g Tref g Pref
xc
Tg
Tm
Parameter Input
The unary parameters can be: Specified for each polymer or oligomer component Specified for segments that compose a polymer or oligomer component
These options are shown in priority order. For example, if the model parameters are provided for a polymer component and for the segments, the polymer parameters are used and the segment parameters are ignored.

If parameters are specified for the polymeric component, then these values are used directly, independent of the copolymer composition. Otherwise, the polymer component thermal conductivity is calculated as the mass average of the segment contributions:
175
*, = i
Nseg
X
A
*, A M A A / X A M A A
Nseg
Where:
Nseg
XA MA
= Number of segment types in the copolymer = Mole segment fraction of segment type A in the copolymer = Molecular weight of segment type A in the copolymer = Thermal conductivity of segment type A in state using Equation 6.2
*, A
, estimated

If
*,,ref i
is missing for a segment, all parameters for that segment in state
are estimated using van Krevelen group contributions (van Krevelen, 1990). The first step is to estimate the segment reference temperature Tref . For liquid and glassy states, the segment reference temperatures are calculated from:
l g Tref = Tref = TgVK = nk Yg ,k / nk M k k k
Segment Reference Temperature

Similarly, the segment reference temperature in crystalline state is calculated from:
c VK Tref = Tm = n k Ym,k / n k M k k k
Where:
nk
TgVK
VK Tm
= Number of occurrences of functional group k in the segment from the segment database or user-specified segment structure = Van Krevelen estimate of segment glass transition temperature = Van Krevelen estimate of segment melt transition temperature = Glass transition contribution of functional group k from van Krevelen database = Melt transition contribution of functional group k from van Krevelen database = Molecular weight of functional group k
Yg , k Ym ,k Mk
Note that van Krevelen group parameters are used to calculate Tref even if the user has provided component or segment TGVK and TMVK parameter values.
Segment Thermal Conductivity at 298K

In order to estimate the segment reference thermal conductivity, the segment thermal conductivity at 298.15 K,
VK 298 , is calculated first:
VK 298
Cp VK 298 UR VK 298 = L VK 298 VK 298 V V

=
Where: L
5 x10 11 m (constant)
Cp VK 298 V VK 298
= Van Krevelen estimate of segment molar heat capacity at 298.15 K (J/mol.K) = Van Krevelen estimate of segment molar volume at 298.15 K
(m 3 /mol)
UR VK 298 = Van Krevelen estimate of segment Rao wave function at 298.15 10 / 3 1/3 /s .mol) K (m
The segment heat capacity, molar volume, and Rao function at 298.15 K are calculated from van Krevelen group contributions:
*, Cp VK 298 = nk Cp k l k
V VK 298 = 1.6 n k Vwk

k
UR VK 298 = nk URk
k
Where:
*, Cp k l
= Liquid heat capacity contribution of functional group k from van Krevelen database = Van der Walls volume contribution of functional group k from van Krevelen database = Rao wave function contribution of functional group k from van Krevelen database
VK 298
Vwk URk
Note that van Krevelen group parameters are used to calculate Cp
and
V VK 298 even if the user has provided component or segment CPLVK, CPLVKM, *,l DNLVK, or DNLVKM parameter values. Also, either Cp k , Vwk , or URk are
missing for any group comprising a segment, K.
VK 298
is set equal to 0.20 W/m-
177
Segment Reference Thermal Conductivity

Liquid and Glassy States The next step is to calculate the segment thermal conductivity at the reference temperature. First, we examine liquid and glassy states. Van Krevelen (1990) presents a generalized curve relating the thermal conductivity for liquid and glassy polymer, at an arbitrary temperature, to that at the glass transition temperature:
T (T ) = g T (Tg ) g
(6.4)
Bicerano (1993) fit van Krevelen's curve to a pair of equations: one applicable for the glassy region (below T g ), and the other applicable in the liquid region (above T g ):
(T ) T = (Tg ) Tg
0.22
for
T Tg (glass) (6.5) T > Tg (liquid)

(6.6)
(T ) T = 1.2 0.2 (Tg ) Tg
for
Since the segment thermal conductivity at 298.15 K is known, these expressions can be inverted to provide an estimate for T g , and
( )
equivalently,
*, ref
for a segment: if
*,l , g = ref
VK 298
298.15 1.2 0.2 VK T g
TgVK
< 298.15 K
(6.7)
*,l , g = ref
VK 298
298.15 T VK g
0.22
if
TgVK
298.15 K
(6.8)
Crystalline Polymer For crystalline polymer, we use the following expression from van Krevelen (1990) relating liquid and crystalline thermal conductivity:
c c = 1 + 5.8 l 1 l
Where:
(6.9)
c l
= Density of crystalline state = Density of liquid state
Applying this expression at the segment melt temperature (the reference temperature for crystalline thermal conductivity), noting that the density ratio can be replaced by a molar volume ratio, and simplifying, we obtain:
V l (Tm ) c (Tm ) = 5.8 c V (T ) 4.8 l (Tm ) m

Where:
(6.10)
Vc Vl
= =
Segment molar volume at Tm and crystalline state Segment molar volume at Tm and liquid state
Van Krevelen (1990) relates the molar volumes at an arbitrary temperature for liquid and crystalline polymer to the segment van der Waals volume, VW :
V l (T ) = VW 1.6 + 10 3 (T 298.15) (6.11) Vc

3
[ (T ) = VW [1.435 + 0.45 10
(T 298.15)
(6.12)
The liquid thermal conductivity at the melting point can be related to the thermal conductivity at the glass point using Equation 6.6. The final expression for the crystalline reference thermal conductivity is therefore:
*,c ref
VK 298
T VK 1.2 0.2 m T VK g
VK 2.392 + 3.64 10 3 (Tm 298.15) 1.435 + 0.45 10 3 (T VK 298.15) m
(6.13)
Other Parameters
No adequate method exists for estimating the pressure dependence of polymer thermal conductivity. Therefore, the estimated value of parameters
D and E is zero for all three polymer states. For liquid and glassy polymer, the estimated values of A , B , C , and F are set in order to
be consistent with Equations 6.5 and 6.6. For crystalline polymer, we assume no temperature dependence, and so reference pressure,
A c = B c = C c = 0 , and F c = 1 . The
Pref , is set equal to 101325 Pa in all cases.
Specifying the Modified van Krevelen Thermal Conductivity Model

179
Aspen Polymer Mixture Thermal Conductivity Model

The Aspen polymer mixture thermal conductivity model (KLMXVKTR) is used to calculate the thermal conductivity of mixtures containing polymers. This model uses the Vredeveld mixing rules for calculating the mixture thermal conductivity from the pure component thermal conductivities. It assumes that both pure polymer and non-polymeric components (solvents) are already available as input. For polymer components, it uses the modified van Krevelen model previously described for calculating thermal conductivity. For non-polymer components, it uses the TRAPP model to calculate the thermal conductivity. Since the TRAPP model directly calculates the thermal conductivity of a polymer-free mixture, the Vredeveld mixing rule is written as:
xs M s xpM p + s (*,l ) 2 *,s ( x ' ) 2 p p l = xi M i i
1 / 2
With
x s' =
xs xs
s
Where:
l
*,l p
= = = = = =
Thermal conductivity of the mixture Thermal conductivity of polymer component p in the mixture Thermal conductivity of the polymer-free mixture, calculated using the TRAPP model Mole fraction of non-polymer component s in the polymer-free mixture Mole fraction of component i Molecular weight of component I
*,s ( x ' )
x s' xi Mi
Specifying the Aspen Polymer Mixture Thermal Conductivity Model

Polymer Thermal Conductivity Routes in Aspen Polymers

Aspen Polymers offers two routes, KLMXVKDP and KMXVKTR, for calculating the polymer mixture thermal conductivity. The KMXVKTR route directly refers the Aspen polymer mixture thermal conductivity model described previously. The KLMXVKDP route uses the Vredeveld mixing rule to combine the modified van Krevelen thermal conductivity model for polymer components and the Sato-Reidel/DIPPR model for non-polymer components:
xM i*,l i2 ( ) l = i i xM i i i
Where:
1 / 2
l *,l i
xi Mi
= Thermal conductivity of the mixture = Thermal conductivity of component i = Mole fraction of component i = Molecular weight of component i; it is the number average molecular weight for polymer components
The routes differ in the manner in which the thermal conductivity of nonpolymer components is handled. The Sato-Reidel/DIPPR model includes only the temperature dependence, and should be used at low pressures. The TRAPP model is a corresponding states model that includes both temperature and pressure dependences, and is applicable to the high pressure region as well. The following table provides a summary of the available routes:
Route KLMXVKDP Model Name KL0VKDP Applicability Low pressure (less than 20 bar) Property Methods POLYFH, POLYNRTL, POLYUF, POLYUFV POLYSL, POLYSRK, POLYSAFT, POLYPCSF
KLMXVKTR
KLMXVKTR
High pressure (greater than 20 bar)
References
Aspen Physical Property System Physical Property Methods and Models. Cambridge, MA: Aspen Technology, Inc.
181
Bicerano, J. (1993). Prediction of Polymer Properties. New York: Marcel Dekker. Eirmann, V. K. (1962). Bestimmung der wrmeleitfhigkeit des amorphen und des kristallinen anteils von polythylen. Kolloid-Zeitschrift & Zeitschrift fr Polymere, 180, 163-164. Van Krevelen, D. W. (1990). Properties of Polymers, 3rd. Ed. Amsterdam: Elsevier.
A Physical Property Methods
This appendix documents the physical property route structure for the polymer specific property methods: POLYFH: Flory-Huggins Property Method, 183 POLYNRTL: Polymer Non-Random Two-Liquid Property Method, 185 POLYUF: Polymer UNIFAC Property Method, 187 POLYUFV: Polymer UNIFAC Free Volume Property Method, 189 PNRTL-IG: Polymer NRTL with Ideal Gas Law Property Method, 191 POLYSL: Sanchez-Lacombe Equation-of-State Property Method, 193 POLYSRK: Polymer Soave-Redlich-Kwong Equation-of-State Property Method, 195 POLYSAFT: Statistical Associating Fluid Theory (SAFT) Equation-of-State Property Method, 196 POLYPCSF: Perturbed-Chain Statistical Associating Fluid Theory (PCSAFT) Equation-of-State Property Method, 198 PC-SAFT: Copolymer PC-SAFT Equation-of-State Property Method, 200
For each property method the property models used in the route calculations are described.
POLYFH: Flory-Huggins Property Method

The following table lists the physical property route structure for the POLYFH property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX Route ID PHIVMX01 HVMX01 GVMX01 SVMX01 VVMX01 Model Name ESRK ESRK ESRK ESRK ESRK Description Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong
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183
MUVMX KVMX DVMX PHIV HV GV SV VV DV MUV KV
MUVMX02 KVMX02 DVMX02 PHIV01 HV02 GV01 SV01 VV01 DV01 MUV01 KV01
MUV2DNST KV2STLTH DV1DKK ESRK0 ESRK0 ESRK0 ESRK0 ERSK0 DV0CEWL MUV0BROK KV0STLTH
Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Chapman-Enskog-Wilke-Lee Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name PHILMX Route ID PHILMXFH Model Name GMFH, WHENRY, HENRY1, PL0XANT, ESRK0, VL0RKT, VL1BROC GMFH, WHENRY, HENRY1, VL1BROC, DHL02PH GMFH, GL0DVK GMFH, WHENRY, HENRY1, VL1BROC, DHL02PH, GL0DVK VL2VKRK MUPOLY, MULMH KLMX DLMX PHIL HL GL SL VL DL MUL KLMXVKDP DLMX02 PHIL04 HLDVKRK GLDVK SLDVK VLDVK DL01 MULMH KL0VKDP, KL2VR DL1WCA PL0XANT, ESRK0, VL0RKT HL0DVKRK* GL0DVK HL0DVKRK*, GL0DVK VL0DVK, VL0RKT DL0WCA MUL0MH Description Flory-Huggins, HENRY, Extended Antoine, RedlichKwong, Rackett, BreviO'Connell Flory-Huggins, van Krevelen, HENRY, Redlich-Kwong, Rackett, Brevi-O'Connell Flory-Huggins, van Krevelen, DIPPR Flory-Huggins, van Krevelen, DIPPR
HLMX
HLMXFHRK
GLMX SLMX
GLMXFH SLMXFHRK
VLMX MULMX
VLMXVKRK MULMX13
Ideal mixing, van Krevelen, Rackett Aspen, Modified MarkHouwink/van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, Sato-Riedel/DIPPR Wilke-Chang-Andrade Extended Antoine, RedlichKwong, Rackett van Krevelen, Redlich-Kwong, Ideal gas van Krevelen, DIPPR van Krevelen, Redlich-Kwong, Ideal gas van Krevelen, Rackett Wilke-Chang-Andrade Modified Mark-Houwink, Andrade
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Liquid Property Name KL Route ID KL0VKDP Model Name KL0VKDP Description Modified van Krevelen, SatoRiedel/DIPPR
Optional van Krevelen/DIPPR model, HL0DVKD, available (see Pure Component Liquid Enthalpy Models in Chapter 4).
Solid Property Name HSMX GSMX SSMX VSMX HS GS SS VS Route ID HSMXDVK GSMXDVK SSMXDVK VSMXDVK HSDVK GSDVK SSDVK VSDVK Model Name HS0DVK GS0DVK HS0DVK, GS0DVK VS0DVK, VS0POLY HS0DVK GS0DVK HS0DVK, GS0DVK VS0DVK, VS0POLY Description Ideal mixing, van Krevelen Ideal mixing, van Krevelen Ideal mixing, van Krevelen van Krevelen, Polynomial van Krevelen van Krevelen van Krevelen van Krevelen, Polynomial
POLYNRTL: Polymer NonRandom Two-Liquid Property Method

The following table lists the physical property route structure for the POLYNRTL property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX MUVMX KVMX Route ID PHIVMX01 HVMX01 GVMX01 SVMX01 VVMX01 MUVMX02 KVMX02 Model Name ESRK ESRK ESRK ESRK ESRK MUV2DNST KV2STLTH Description Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Dean-Stiel Stiel-Thodos
185
DVMX PHIV HV GV SV VV DV MUV KV
DVMX02 PHIV01 HV02 GV01 SV01 VV01 DV01 MUV01 KV01
DV1DKK ESRK0 ESRK0 ESRK0 ESRK0 ERSK0 DV0CEWL MUV0BROK KV0STLTH
Dawson-Khoury-Kobayashi Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Chapman-Enskog-Wilke-Lee Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name PHILMX Route ID PHILMXP Model Name GMNRTLP, WHENRY, HENRY, PL0XANT, ESRK0, VL0RKT, VL1BROC GMNRTLP, WHENRY, HENRY1, VL1BROC, DHL02PH GMNRTLP, GL0DVK GMNRTLP, WHENRY, HENRY1, VL1BROC, DHL02PH, GL0DVK VL2VKRK MUPOLY, MULMH Description Polymer NRTL, HENRY, Extended Antoine, RedlichKwong, Rackett, BreviO'Connell Polymer-NRTL, van Krevelen, HENRY, Redlich-Kwong, Rackett, Brevi-O'Connell Polymer NRTL, van Krevelen, DIPPR Polymer NRTL, van Krevelen, HENRY, Redlich-Kwong, BreviO'Connell Ideal mixing, van Krevelen, Rackett Aspen, Modified MarkHouwink/van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, Sato-Riedel/DIPPR Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power Law Mixing Extended Antoine, RedlichKwong, Rackett van Krevelen, Redlich-Kwong, Ideal gas van Krevelen, DIPPR van Krevelen, DIPPR van Krevelen, Rackett Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, SatoRiedel/DIPPR
HLMX
HLMXPRK
GLMX SLMX
GLMXP SLMXPRK
VLMX MULMX
VLMXVKRK MULMX13
KLMX DLMX SIGLMX PHIL HL GL SL VL DL MUL KL
KLMXVKDP DLMX02 SIGLMX01 PHIL04 HLDVKRK GLDVK SLDVK VLDVK DL01 MULMH KL0VKDP
KL0VKDP, KL2VR DL1WCA SIG2HSS PL0XANT, ESRK0, VL0RKT HL0DVKRK* GL0DVK HL0DVK*, GL0DVK VL0DVK, VL0RKT DL0WCA MUL0MH KL0VKDP
POLYUF: Polymer UNIFAC Property Method

The following table lists the physical property route structure for the POLYUF property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX MUVMX KVMX DVMX PHIV HV GV SV VV Route ID PHIVMX01 HVMX01 GVMX01 SVMX01 VVMX01 MUVMX02 KVMX02 DVMX02 PHIV01 HV02 GV01 SV01 VV01 Model Name ESRK ESRK ESRK ESRK ESRK MUV2DNST KV2STLTH DV1DKK ESRK0 ESRK0 ESRK0 ESRK0 ERSK0 Description Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong
187
Vapor MUV KV MUV01 KV01 MUV0BROK KV0STLTH Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name PHILMX Route ID PHILMPUF Model Name GMPOLUF, WHENRY, HENRY, PL0XANT, ESRK0, VL0RKT, VL1BROC GMPOLUF, WHENRY, HENRY1, VL1BROC, DHL02PH GMPOLUF, GL0DVK GMPOLUF, WHENRY, HENRY1, VL1BROC, DHL02PH, GL0DVK VL2VKRK MUPOLY, MULMH Description Polymer UNIFAC, HENRY, Extended Antoine, RedlichKwong, Rackett, BreviO'Connell Polymer UNIFAC, van Krevelen, HENRY, RedlichKwong, Rackett, BreviO'Connell Polymer UNIFAC, van Krevelen, DIPPR Polymer UNIFAC, van Krevelen, HENRY, RedlichKwong, Rackett, BreviO'Connell Ideal mixing, van Krevelen, Rackett Aspen, Modified MarkHouwink/ van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, SatoRiedel/DIPPR Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power Law Mixing Extended Antoine, RedlichKwong, Rackett van Krevelen, Redlich-Kwong, Ideal gas van Krevelen, DIPPR van Krevelen, DIPPR van Krevelen, Rackett Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, SatoRiedel/DIPPR
HLMX
HLMXPURK
GLMX SLMX
GLMXPUF SLMXPURK
VLMX MULMX
VLMXVKRK MULMX13
KLMX
KLMXVKDP
KL0VKDP, KL2VR
DLMX SIGLMX PHIL HL GL SL VL DL MUL KL
DLMX02 SIGLMX01 PHIL04 HLDVKRK GLDVK SLDVK VLDVK DL01 MULMH KL0VKDP
DL1WCA SIG2HSS PL0XANT, ESRK0, VL0RKT HL0DVKRK* GL0DVK HL0DVK*, GL0DVK VL0DVK, VL0RKT DL0WCA MUL0MH KL0VKDP
POLYUFV: Polymer UNIFAC Free Volume Property Method

The following table lists the physical property route structure for the POLYUFV property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX MUVMX KVMX DVMX PHIV HV GV SV VV MUV KV Route ID PHIVMX01 HVMX01 GVMX01 SVMX01 VVMX01 MUVMX02 KVMX02 DVMX02 PHIV01 HV02 GV01 SV01 VV01 MUV01 KV01 Model Name ESRK ESRK ESRK ESRK ESRK MUV2DNST KV2STLTH DV1DKK ESRK0 ESRK0 ESRK0 ESRK0 ERSK0 MUV0BROK KV0STLTH Description Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Redlich-Kwong Chapman-Enskog-Brokaw Stiel-Thodos
Liquid
189
Property Name PHILMX
Route ID PHILMUFV
Model Name GMUFFV, WHENRY, HENRY, PL0XANT, ESRK0, VL0RKT, VL1BROC, VL0TAIT GMUFFV, WHENRY, HENRY1, VL1BROC, DHL02PH GMUFFV, GL0DVK GMUFFV, WHENRY, HENRY1, VL1BROC, DHL02PH, GL0DVK VL2VKRK MUPOLY, MULMH
Description UNIFAC-FV, HENRY, Extended Antoine, RedlichKwong, Rackett, BreviO'Connell UNIFAC-FV, van Krevelen, HENRY, Redlich-Kwong, Rackett, Brevi-O'Connell UNIFAC-FV, van Krevelen, DIPPR UNIFAC-FV, van Krevelen, HENRY, Redlich-Kwong, Rackett, Brevi-O'Connell Tait/van Krevelen, Rackett Aspen, Modified MarkHouwink/ van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, SatoRiedel/DIPPR Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power Law Mixing Extended Antoine, RedlichKwong, Rackett van Krevelen, RedlichKwong, Ideal gas van Krevelen, DIPPR van Krevelen, DIPPR van Krevelen, Rackett Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, Sato-Riedel/DIPPR
HLMX
HLMXFVRK
GLMX SLMX
GLMXUFV SLMXFVRK
VLMX MULMX
VLMXVKRK MULMX13
KLMX
KLMXVKDP
KL0VKDP, KL2VR
DLMX02 SIGLMX01 PHIL04 HLDVKRK GLDVK SLDVK VLDVK DL01 MULMH KL0VKDP
DL1WCA SIG2HSS PL0XANT, ESRK0, VL0RKT HL0DVKRK* GL0DVK HL0DVK*, GL0DVK VL0DVK, VL0RKT DL0WCA MUL0MH KL0VKDP
Solid Property Name HSMX GSMX SSMX Route ID HSMXDVK GSMXDVK SSMXDVK Model Name HS0DVK GS0DVK HS0DVK, GS0DVK Description Ideal mixing, van Krevelen Ideal mixing, van Krevelen Ideal mixing, van Krevelen
VSMX HS GS SS VS
VSMXDVK HSDVK GSDVK SSDVK VSDVK
VS0DVK, VS0POLY HS0DVK GS0DVK HS0DVK, GS0DVK VS0DVK, VS0POLY
van Krevelen, Polynomial van Krevelen van Krevelen van Krevelen van Krevelen, Polynomial
PNRTL-IG: Polymer NRTL with Ideal Gas Law Property Method

The following table lists the physical property route structure for the PNRTLIG property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX MUVMX KVMX DVMX PHIV HV GV SV VV DV MUV KV Route ID PHIVMX00 HVMX00 GVMX00 SVMX00 VVMX00 MUVMX02 KVMX02 DVMX02 PHIV0 HV00 GV00 SV00 VV00 DV01 MUV01 KV01 Model Name ESIG ESIG ESIG ESIG ESIG MUV2DNST KV2STLTH DV1DKK ESIG0 ESIG0 ESIG0 ESIG0 ESIG0 DV0CEWL MUV0BROK KV0STLTH Description Ideal gas law Ideal gas law Ideal gas law Ideal gas law Ideal gas law Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi Ideal gas law Ideal gas law Ideal gas law Ideal gas law Ideal gas law Chapman-Enskog-Wilke-Lee Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name Route ID Model Name Description
191
Liquid Property Name PHILMX Route ID PHILMXPI Model Name GMNRTLP, WHENRY, HENRY, PL0XANT, ESIG0, VL0RKT, VL1BROC GMNRTLP, WHENRY, HENRY1, VL1BROC, DHL01PH GMNRTLP, GL0DVK GMNRTLP, WHENRY, HENRY1, VL1BROC, DHL01PH, GL0DVK VL2VKRK MUPOLY, MULMH Description Polymer NRTL, HENRY, Extended Antoine, Ideal gas law, Rackett, Brevi-O'Connell Polymer NRTL, van Krevelen, Ideal gas, Rackett, BreviO'Connell Polymer NRTL, van Krevelen, DIPPR Polymer NRTL, van Krevelen, Ideal gas, Rackett, BreviO'Connell Ideal mixing, van Krevelen, Rackett Aspen, Modified MarkHouwink/van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, SatoRiedel/DIPPR Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power law mixing Extended Antoine, Ideal gas law van Krevelen, DIPPR van Krevelen, DIPPR van Krevelen, DIPPR van Krevelen, Rackett Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, SatoRiedel/DIPPR
HLMX
HLMXP
GLMX SLMX
GLMXP SLMXP
VLMX MULMX
VLMXVKRK MULMX13
KLMX
KLMXVKDP
KL0VKDP, KL2VR
DLMX02 SIGLMX01 PHIL00 HLDVKD GLDVK SLDVK VLDVK DL01 MULMH KL0VKDP
DL1WCA SIG2HSS PL0XANT, ESIG0, VL0RKT HL0DVKD* GL0DVK HL0DVK*, GL0DVK VL0DVK, VL0RKT DL0WCA MUL0MH KL0VKDP
Solid Property Name HSMX GSMX SSMX Route ID HSMXDVK GSMXDVK SSMXDVK Model Name HS0DVK GS0DVK HS0DVK, GS0DVK Description Ideal mixing, van Krevelen, Ideal mixing, van Krevelen Ideal mixing, van Krevelen
Solid VSMX HS GS SS VS VSMXDVK HSDVK GSDVK SSDVK VSDVK VS0DVK, VS0POLY HS0DVK GS0DVK HS0DVK, GS0DVK VS0DVK, VS0POLY van Krevelen, Polynomial van Krevelen van Krevelen van Krevelen van Krevelen, Polynomial
POLYSL: Sanchez-Lacombe Equation-of-State Property Method

The following table lists the physical property route structure for the POLYSL property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX MUVMX KVMX DVMX PHIV HV GV SV VV DV MUV KV Route ID PHIVMXSL HVMXSL GVMXSL SVMXSL VVMXSL MUVMX02 KVMX02 DVMX02 PHIVSL HVSL GVSL SVSL VVSL DV01 MUV01 KV01 Model Name ESPLSL ESPLSL ESPLSL ESPLSL ESPLSL MUV2DNST KV2STLTH DV1DKK ESPLSL0 ESPLSL0 ESPLSL0 ESPLSL0 ESPLSL0 DV0CEWL MUV0BROK KV0STLTH Description Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Chapman-Enskog-Wilke-Lee Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name PHILMX HLMX GLMX Route ID PHILMXSL HLMXSL GLMXSL Model Name ESPLSL ESPLSL ESPLSL Description Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe
193
Liquid Property Name SLMX VLMX MULMX KLMX DLMX SIGLMX PHIL HL GL SL VL DL MUL KL Route ID SLMXSL VLMXSL MULMX13 KLMXVKTR DLMX02 SIGLMX01 PHILSL HLSL GLSL SLSL VLSL DL01 MULMH KL0VKTR Model Name ESPLSL ESPLSL MUPOLY, MULMH KLMXVKTR DL1WCA SIG2HSS ESPLSL0 ESPLSL0 ESPLSL0 ESPLSL0 ESPLSL0 DL0WCA MUL0MH KL0VKTR Description Sanchez-Lacombe Sanchez-Lacombe Aspen, Modified Mark-Houwink/van Krevelen, Andrade Vredeveld mixing , Modified van Krevelen, TRAPP Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power Law Mixing Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Sanchez-Lacombe Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, TRAPP
POLYSRK: Polymer SoaveRedlich-Kwong Equation-ofState Property Method

The following table lists the physical property route structure for the POLYSRK property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX MUVMX KVMX DVMX PHIV HV GV SV VV DV MUV KV Route ID PHIVMXPS HVMXPS GVMXPS SVMXPS VVMXPS MUVMX02 KVMX02 DVMX02 PHIVPS HVPS GVPS SVPS VVPS DV01 MUV01 KV01 Model Name ESPLRKS ESPLRKS ESPLRKS ESPLRKS ESPLRKS MUV2DNST KV2STLTH DV1DKK ESPLRKS0 ESPLRKS0 ESPLRKS0 ESPLRKS0 ESPLRKS0 DV0CEWL MUV0BROK KV0STLTH Description Polymer SRK Polymer SRK Polymer SRK Polymer SRK Polymer SRK Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi Polymer SRK Polymer SRK Polymer SRK Polymer SRK Polymer SRK Chapman-Enskog-Wilke-Lee Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name PHILMX HLMX GLMX SLMX VLMX MULMX KLMX DLMX SIGLMX Route ID PHILMXPS HLMXPS GLMXPS SLMXPS VLMXVKRK MULMX13 KLMXVKTR DLMX02 SIGLMX01 Model Name ESPLRKS ESPLRKS ESPLRKS ESPLRKS VL2VKRK MUPOLY, MULMH KLMXVKTR DL1WCA SIG2HSS Description Polymer SRK Polymer SRK Polymer SRK Polymer SRK Ideal mixing, van Krevelen, Rackett Aspen, Modified MarkHouwink/van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, TRAPP Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power Law Mixing
195
Liquid PHIL HL GL SL VL DL MUL KL PHILPS HLPS GLPS SLPS VLDVK DL01 MULMH KL0VKTR ESPLRKS0 ESPLRKS0 ESPLRKS0 ESPLRKS0 VL0DVK, VL0RKT DL0WCA MUL0MH KL0VKTR Polymer SRK Polymer SRK Polymer SRK Polymer SRK van Krevelen, Rackett Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, TRAPP
POLYSAFT: Statistical Associating Fluid Theory (SAFT) Equation-of-State Property Method

The following table lists the physical property route structure for the POLYSAFT property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX Route ID PHIVMXSF HVMXSF GVMXSF SVMXSF Model Name ESPLSFT ESPLSFT ESPLSFT ESPLSFT Description SAFT SAFT SAFT SAFT
VVMX MUVMX KVMX DVMX PHIV HV GV SV VV DV MUV KV
VVMXSF MUVMX02 KVMX02 DVMX02 PHIVSF HVSF GVSF SVSF VVSF DV01 MUV01 KV01
ESPLSFT MUV2DNST KV2STLTH DV1DKK ESPLSFT0 ESPLSFT0 ESPLSFT0 ESPLSFT0 ESPLSFT0 DV0CEWL MUV0BROK KV0STLTH
SAFT Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi SAFT SAFT SAFT SAFT SAFT Chapman-Enskog-Wilke-Lee Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name PHILMX HLMX GLMX SLMX VLMX MULMX KLMX DLMX SIGLMX PHIL HL GL SL VL DL MUL KL Route ID PHILMXSF HLMXSF GLMXSF SLMXSF VLMXSF MULMX13 KLMXVKTR DLMX02 SIGLMX01 PHILSF HLSF GLSF SLSF VLSF DL01 MULMH KL0VKTR Model Name ESPLSFT ESPLSFT ESPLSFT ESPLSFT ESPLSFT MUPOLY, MULMH KLMXVKTR DL1WCA SIG2HSS ESPLSFT0 ESPLSFT0 ESPLSFT0 ESPLSFT0 ESPLSFT0 DL0WCA MUL0MH KL0VKTR Description SAFT SAFT SAFT SAFT SAFT Aspen, Modified Mark-Houwink/ van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, TRAPP Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power Law Mixing SAFT SAFT SAFT SAFT SAFT Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, TRAPP
Solid Property Name PHILMX HLMX Route ID PHILMXSF HLMXSF Model Name ESPLSFT ESPLSFT Description SAFT SAFT
197
GLMX SLMX VLMX MULMX KLMX DLMX
GLMXSF SLMXSF VLMXSF MULMX13 KLMXVKTR DLMX02
ESPLSFT ESPLSFT ESPLSFT MUPOLY, MULMH KLMXVKTR DL1WCA
SAFT SAFT SAFT Aspen, Modified Mark-Houwink/ van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, TRAPP Wilke-Chang-Andrade
POLYPCSF: Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) Equation-ofState Property Method
The following table lists the physical property route structure for the POLYPCSF property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX MUVMX KVMX DVMX PHIV HV GV SV VV DV MUV KV Route ID PHIVMXPC HVMXPC GVMXPC SVMXPC VVMXPC MUVMX02 KVMX02 DVMX02 PHIVPC HVPC GVPC SVPC VVPC DV01 MUV01 KV01 Model Name ESPCSFT ESPCSFT ESPCSFT ESPCSFT ESPCSFT MUV2DNST KV2STLTH DV1DKK ESPCSFT0 ESPCSFT0 ESPCSFT0 ESPCSFT0 ESPCSFT0 DV0CEWL MUV0BROK KV0STLTH Description PCSAFT PCSAFT PCSAFT PCSAFT PCSAFT Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi PCSAFT PCSAFT PCSAFT PCSAFT PCSAFT Chapman-Enskog-Wilke-Lee Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name Route ID Model Name Description
Liquid Property Name PHILMX HLMX GLMX SLMX VLMX MULMX KLMX DLMX SIGLMX PHIL HL GL SL VL DL MUL KL Route ID PHILMXPC HLMXPC GLMXPC SLMXPC VLMXPC MULMX13 KLMXVKTR DLMX02 SIGLMX01 PHILPC HLPC GLPC SLPC VLPC DL01 MULMH KL0VKTR Model Name ESPCSFT ESPCSFT ESPCSFT ESPCSFT ESPCSFT MUPOLY, MULMH KLMXVKTR DL1WCA SIG2HSS ESPCSFT0 ESPCSFT0 ESPCSFT0 ESPCSFT0 ESPCSFT0 DL0WCA MUL0MH KL0VKTR Description PCSAFT PCSAFT PCSAFT PCSAFT PCSAFT Aspen, Modified Mark-Houwink/van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, TRAPP Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power Law Mixing PCSAFT PCSAFT PCSAFT PCSAFT PCSAFT Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, TRAPP
199
PC-SAFT: Copolymer PC-SAFT Equation-of-State Property Method

The following table lists the physical property route structure for the PC-SAFT property method:
Vapor Property Name PHIVMX HVMX GVMX SVMX VVMX MUVMX KVMX DVMX PHIV HV GV SV VV DV MUV KV Route ID PHIVMXPA HVMXPA GVMXPA SVMXPA VVMXPA MUVMX02 KVMX02 DVMX02 PHIVPA HVPA GVPA SVPA VVPA DV01 MUV01 KV01 Model Name ESPSAFT ESPSAFT ESPSAFT ESPSAFT ESPSAFT MUV2DNST KV2STLTH DV1DKK ESPSAFT0 ESPSAFT0 ESPSAFT0 ESPSAFT0 ESPSAFT0 DV0CEWL MUV0BROK KV0STLTH Description Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Dean-Stiel Stiel-Thodos Dawson-Khoury-Kobayashi Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Chapman-Enskog-Wilke-Lee Chapman-Enskog-Brokaw Stiel-Thodos
Liquid Property Name PHILMX HLMX GLMX SLMX VLMX MULMX KLMX DLMX SIGLMX PHIL Route ID PHILMXPA HLMXPA GLMXPA SLMXPA VLMXPA MULMX13 KLMXVKTR DLMX02 SIGLMX01 PHILPA Model Name ESPSAFT ESPSAFT ESPSAFT ESPSAFT ESPSAFT MUPOLY, MULMH KLMXVKTR DL1WCA SIG2HSS ESPSAFT0 Description Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Aspen, Modified Mark-Houwink/van Krevelen, Andrade Vredeveld mixing, Modified van Krevelen, TRAPP Wilke-Chang-Andrade Hakim-Steinberg-Stiel, Power Law Mixing Copolymer PCSAFT
Liquid Property Name HL GL SL VL DL MUL KL Route ID HLPA GLPA SLPA VLPA DL01 MULMH KL0VKTR Model Name ESPSAFT0 ESPSAFT0 ESPSAFT0 ESPSAFT0 DL0WCA MUL0MH KL0VKTR Description Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Copolymer PCSAFT Wilke-Chang-Andrade Modified Mark-Houwink/van Krevelen, Andrade Modified van Krevelen, TRAPP
201
B Van Krevelen Functional Groups
This appendix lists the methods used to calculate segment and polymer property parameters and the van Krevelen functional group parameters used in these calculations. These functional groups are used by the van Krevelen property models.
Calculating Segment Properties From Functional Groups

The van Krevelen property models use functional groups to calculate segment property parameters, which are in turn used to calculate polymer property parameters. The functional group parameters listed in Van Krevelen Functional Group Parameters on page 205 are used to calculate segment properties using the following correlations:
Heat Capacity (Liquid or Crystalline)

*, Cp*,l (T ref ) = nk Cpk l (T ref ) k *, Cp *,c (T ref ) = nk Cp k c (T ref k
Where:
Cp *,l
= Liquid heat capacity of a segment
Cp *,c = Crystalline heat capacity of a segment T ref nk

*, Cpk l
= Reference temperature (298.15 K) = Number of occurrences of functional group k in a segment = Liquid heat capacity for functional group k in Van Krevelen Functional Group Parameters on page 205
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*, Cpk c = Crystalline heat capacity for functional group k in Van Krevelen
Functional Group Parameters on page 205
Molar Volume (Liquid, Crystalline, or Glassy)

V * = nk Vk*
k
Vk* = Vwk * ( A + B * T + C * Tg )
Where:
V*
Vk* Vwk
T
= Molar volume of a segment (liquid, crystalline, or glassy) = Molar volume of functional group k (liquid, crystalline, or glassy) = Van der Waals volume of functional group k in Van Krevelen Functional Group Parameters on page 205 = Temperature = Glass transition temperature
Tg
A, B, and C = Empirical constants and vary by phase
Enthalpy, Entropy and Gibbs Energy of Formation

*, H *,ig (T ref ) = n k H k ig (T ref k
*, S *,ig (T ref ) = nk S k ig (T ref k
*,ig (T ref ) = H *,ig (T ref ) + T ref S *,ig (T ref )

Where:
H *,ig (T ref
ref
S *,ig
*,ig
*, H k ig
) (T ) (T ) (T )
ref ref
= Ideal gas heat of formation of a segment = Ideal gas entropy of formation of a segment = Ideal gas Gibbs energy of formation of a segment = Ideal gas heat of formation of functional group k in Van Krevelen Functional Group Parameters on page 205 = Ideal gas entropy of formation of functional group k in Van Krevelen Functional Group Parameters on page 205
*, S k ig T ref
( )
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203
Glass Transition Temperature

Tg
n Y = n M
k k k k
g ,k
Where:
Tg Yg , k Mk
= Glass transition temperature of a segment = Glass transition parameter of functional group k in Van Krevelen Functional Group Parameters on page 205 = Molecular weight of functional group k
Melt Transition Temperature

Tm
n Y = n M
k k k k
m,k
Where:
Tm Ym ,k
= Melt transition temperature of a segment = Melt transition parameter of functional group k in Van Krevelen Functional Group Parameters on page 205
Viscosity Temperature Gradient

H = nk H ,k / M
k
Where:
= Viscosity-temperature gradient of a segment Functional Group Parameters on page 205
H ,k = Viscosity-temperature gradient of functional group k in Van Krevelen

M = Molecular weight of a segment
Rao Wave Function

UR(T ref ) = nk URk (T ref )
k
Where:
UR (T ref )
= Rao wave function of a segment
URk (T ref ) = Rao wave function of functional group k in Van Krevelen

Functional Group Parameters on page 205
Van Krevelen Functional Group Parameters

This section shows the functional group parameters used to calculate segment properties. Function groups are listed by category: Hydrocarbon and hydrogen-containing groups Oxygen-containing groups Nitrogen-containing groups Sulfur-containing groups Halogen-containing groups
Source: Van Krevelen, D.W. (1990). Properties of Polymers, 3rd Ed. Amsterdam: Elsevier.
Bifunctional Hydrocarbon Groups

The following table shows the bifunctional hydrocarbon group parameters. Estimated values appear in italic.
Yg,k 103 (g K/mol) Ym,k 103 (g K/mol) Sk*,ig(Tref) J/mol.K
Functional Group
CH2 CH(CH3) CH(CH3) CH(C5H9) CH(C6H11) CH(C6H5) C(CH3)2 C(CH3)(C6H5)

(sym) (asym)
100 101 102 103 104 105 106 107
14.03 10.23 25.35 30.4 28.05 20.45 46.5 28.05 20.45 46.5
-22,000 102
2,700 5,700
420
57.85 -48,700 215 57.85 -48,700 215
8,000 13,000 1060 8,000 13,000 1,060
82.14 53.28 110.8 147.5 -73,400 548 96.17 63.58 121.2 173. 9 118,40 680 0 90.12 52.62 101.2 144.15 84,300 287 42.08 30.67 68.0 81.2 -72,000 330
30,70 4,60 45,763 2,180 0 0 41,30 5,50 51,463 2,600 0 0 36,10 48,000 3600 0 8,500 12,100 1620 5,10 0 2,85 0
104.1 62.84 122.7 167.5 61,000 402 4
51,00 6,10 54,000 4,160 0 0
H,k 103 ( /
Grou p No.
880 1,85 0 1,85 0
URk cm10/3(s
205
Cpk*,c(Tref) J/mol.K
Cpk*,l(Tref) J/mol.K
Hk*,ig(Tref) J/mol
Vw cm3/mol
Mk g/mol
l)
Yg,k 103 (g K/mol) Ym,k 103 (g K/mol)
Sk*,ig(Tref) J/mol.K
Functional Group
CH CH CH CH
CH C(CH3) CH C(CH3)
(trans)
(cis) (trans) (cis)
108 109 110 111 112 113 114 115 116 117
26.04 16.94 37.3 26.04 16.94 37.3
42.8 42.8
76,000 76 70,000 83
3,800 8,000
760
7,400 11,000 760 8,100 10,000 1,190 9,100 13,000 1,190 ----------
40.06 27.16 60.05 74.22 42,000 183 40.06 27.16 60.05 74.22 36,000 190 24.02 16.1 ------230,00 -50 0
C C
(cis) (trans)
82.14 53.34 103.2 147.5 -96,400 578 82.14 53.34 103.2 147.5 102,40 585 0 76.09 43.32 78.8 76.09 43.32 78.8 76.09 43.32 78.8 113.1 113.1 113.1 100,00 180 0 100,00 180 0 100,00 180 0
2,90 19,00 31,000 2,180 0 0 27,00 2,90 45,000 2,180 0 0 29,00 38,000 3200 0 25,00 31,000 ---0 ---------4,10 0 3,50 0 3,45 0
CH3
118 104.1 65.62 126.8 166.8 33,000 394 4 6,15 54,00 67,000 4,820 0 0
CH3
119 90.12 54.47 102.75 140.1 66,500 287 5,50 35,00 45,000 4,010 0 0 31,70 4,98 43,700 3,620 0 0 31,70 4,98 43,700 3,620 0 0 5,86 25,00 47,000 4,040 0 0 65,00 9,10 85,000 6,820 0 0 8,20 70,00 99,000 6,400 0 0
CH3 CH2 CH2 CH2

CH2
(sym) (asym) 120 121 122 123 124 90.12 53.55 104.15 143.5 78,000 282 90.12 53.55 104.15 143.5 78,000 282 104.1 63.78 129.5 173.9 56,000 384 4 178,00 166.2 462 96.87 182.95 256.6 0 1 152.1 200,00 86.64 157.6 226.2 360 8 0
CH2
H,k 103 ( /
Grou p No.
1,40 0 1,40 0 2,15 0 2,15 0 1,24 0
URk cm10/3(s
Hk*,ig(Tref) J/mol
Vw cm3/mol
Mk g/mol
l)
Yg,k 103 (g K/mol) Ym,k 103 (g K/mol)
Functional Group
125
228.2 130 2
236
339
299,00 538 0
118,0 173,00 12,6 9,900 00 0 50
Other Hydrogen-containing Groups

The following table shows the other hydrogen-containing group parameters:
Sk*,ig(Tref) J/mol.K Gro up No. 126 127 128 129 130 131
Yg,k 103 ( K/
CH3 C2H5 nC3H7 iC3H7 tC4H9 CH
15.03 29.06 43.09 43.09 57.11 13.02
13.67 23.90 34.13 34.12 44.34 6.78
30.9 56.25 81.6 77.4 99.0 15.9
36.9 67.3 97.7 94.75 118.1 20.95
-46,000 -68,000 -90,000 -94,700
95 197 299 310
2,900 5,600 8,300 10,90 0 13,60 0 5,100
1,519 3,952 6,774 14,51 9 20,12 9 11,48 1
810 1,230 1,650 1,870 2,290 250
425 118,000 -2,700 120
C CH2 CH C C CH C CH C
132 133 134 135 136 137 138 139
12.01 14.01 13.02 12.01 12.01 25.03 13.02 12.01
3.33 11.94 8.47 5.01 6.96 13.48 8.05 8.05
6.2 22.6 18.65 10.5 ---29.15 -------
7.4 21.8 21.8 15.9 ---37.3 -------
20,000 23,000 38,000 50,000
140 30 38 50
2,700 ---1,900 3,300 -------------
9,063 ---4,000 4,481 -------------
0 0 380 0 ---380 -------
147,000 -20 88,000 88
112,500 -32.5 115,000 -25
H,k 103 ( /
Functional Group
1,400 2,280 3,160 3,250 4,130 460
40 ---745 255 ---1,000 -------
URk cm10/3(s 1/3 mol)

207
l)
Cpk*,l(Tref)
Hk*,ig(Tref)
l)
Vw cm3/mol
J/mol.K
Ym,k 103 ( K/
Mk g/mol
J/mol
l)
H,k 103 ( /
Grou p No.
URk cm10/3(s
Hk*,ig(Tref) J/mol
Vw cm3/mol
Mk g/mol
l)
Yg,k 103 ( K/
C C C C
(cis) (trans)
140 141
24.02 24.02
10.02 10.02
21.0 21
31.8 31.8
100,000 100 94,000 107
-------
-------
0 ----
CHar
142
13.02
8.06
15.4
22.2
12,500
26
----
----
----
Car
143
12.01
5.54
8.55
12.2
25,000
38
----
----
----
144 145 146
69.12 83.15 77.10
45.56 56.79 45.84
95.2 105.6 85.6
126.5 5 152.9 5 123.2
-70,700
428
28,00 0 38,60 0 33,40 0 48,20 0 29,20 0
34,28 1 39,98 1 42,30 0 63,96 3 41,96 3
1,930 2,350 3,350
560 115,700 87,000 167
147
74.08
38.28
65.0
93.0
125,000 204
3,200
148
75.08
40.80
71.85
103.2
112,500 192
2,390
Bifunctional Oxygen-containing Groups

The following table shows the bifunctional oxygen-containing group parameters:
J/mol.K
H,k 103 ( / 480 H,k 10970 1,45 0
Functional Group
Ym,k 103 ( K/
Mk g/mol
Gro up No.
510 510
830
400
4,140 5,000 4,640
3,300
3,700
Yg,k 103 ( K/
Functional Group
Grou p No. 149
O C O O C O
16.00
3.71/ [5.1]1 11.7
16.8
35.6
120,000 132,000 337,000
70
4,000
13,50 0 12,00 0 30,00 0
400
150
28.01
23.05
52.8
40
9,000 12,50 0
900
151
44.01
15.2
46
65.0
116
1,250
URk cm10/3(s
l)
Cpk*,c(Tref)
Hk*,ig(Tref) J/mol
Vw cm3/mol
J/mol.K
Sk*,ig(Tref)
Ym,k 103 ( K/
Mk g/mol
l)
l)
Hk*,ig(Tref) J/mol
l)
Vw cm3/mol
l)
Yg,k 103 ( K/
Functional Group
O C O
(acrylic) 152 44.01 17.0 46 65.0
337,000 457,000 584,070 178,700 395,700 127,700 237,000 262,000
116
12,50 0 20,00 0 22,00 0 13,00 0 ------38,00 0 10,70 0
30,00 0 30,00 0 35,00 0 37,50 0 30,72 4 13,36 2 50,00 0 32,70 0
1,45 0 3,15 0 2,42 0 539 1,58 7 908 4,17 0 1,38 0
H,k 10-
Grou p No.
1,250
O C O O C O C O CH(OH) CH(COOH) CH(HC=O) COO O CH2 O O
153
60.01
18.9/ [23.0]1 27 14.82 26.52 21.92 58.52 17.63
63
100.6
186
1,600
154 155 156 157 158 159
72.02 30.03 58.04 42.14 120.1 0 46.03
63 32.6 65.6 ---124.8 58.95
114 65.75 119.8 5 ---178.1 101.6
156 170 238 146 296 242
2,150 1,050 1,990 ---5,350 1,680
Other Oxygen-containing Groups

The following table shows the other oxygen-containing group parameters:
Cpk*,c(Tref) J/mol.K Cpk*,l(Tref) J/mol.K Sk*,ig(Tref) J/mol.K
Yg,k 103 ( K/
Functional Group
OH OH C H O C OH O
160 161
17.01 8.04 93.10 51.36
17.0 95.8
44.8 157.9
50 176,000 -76,000 230
-------
1,477 39,47 7 1,881
289 3,48 9 658
H,k 10-
Grou p No.
630 4,730
162
29.02 15.14
----
----
26 125,000 118 393,000
----
----
163
45.02 19.74
50
98.9
----
19,24 3
1,33 7
1,530

209
l)
Vw cm3/mol
Hk*,ig(Tref) J/mol
Ym,k 103 ( K/
Mk g/mol
l)
URk cm10/3(s
l)
Vw cm3/mol
Hk*,ig(Tref) J/mol
Ym,k 103 ( K/
Mk g/mol
l)
Bifunctional Nitrogen-containing Groups

The following table shows the bifunctional nitrogen-containing group parameters:
Gro up No. 164 165 166 167 Sk*,ig(Tref) J/mol.K
Yg,k 103 ( K/
NH CH(CN) CH(NH2) NH
15.0 2 39.0 4 29.0 4 91.1 1
8.08 21.48 17.32 51.4
14.25 40.6 36.55 93.05
31.8 ------144.9
58,000
120
7,000 16,40 5 ---36,00 0
18,00 0 25,71 7 15,08 8 56,00 0
680 ---562 3,88 0
H,k 10H,k 10-3(g/mol)
Functional Group
875 1,750 ---4,975
120,300 91.5 8,800 222. 5
158,000 300
Other Nitrogen-containing Groups

The following table shows the other nitrogen-containing group parameters:
Yg,k 103 ( K/
Functional Group
NH2 N
168 169
16.0 2 14.0 1
10.54 4.33
20.95 17.1
---44.0
11,500 97,000
102. 5 150
-------
3,607 10,38 0
Ym,k 103 ( K/
Mk g/mol
Gro up No.
312 ----
---65
Nar
170
14.0 1 26.0 2 92.1 2 90.1 0
----
----
----
69,000
50
----
----
----
----
C N NH2 N
171 172 173
14.7 53.86 47.65
25 99.75 95.9
------157.1
123,000 111,500
28.5 282. 5
----------
1,824 41,60 7 48,38 0
---3,51 2 ----
1,400 ---4,165
197,000 330
l)
Vw cm3/mol
Hk*,ig(Tref) J/mol
l)
l)
Vw cm3/mol
Hk*,ig(Tref) J/mol
Ym,k 103 ( K/
Mk g/mol
l)
Bifunctional Nitrogen- and Oxygencontaining Groups

The following table shows the bifunctional nitrogen- and oxygen-containing group parameters:
Yg,k 103 (g.K/mol) Gro up Functional Group No. Sk*,ig(Tref) J/mol.K
C NH O O C NH O NH C NH O CH(NO2) O C NH
174
43.03
19.56
[18.1]1
38
90.1
-74,000
160
15,000 45,000
1,65 0 2,13 0 2,33 0 ----
1,70 0 1,80 0 2,00 0 ----
175
59.03
23
58
125.7
-240 279,000
20,000 43,500
176 177
58.04 59.03
27.6 23.58
50 57.5
121.9 ----
-16,000 -44,200
280 263
20,000 60,000 -------
178
119.1 2
62.88
116. 8
203.2
26,000
340
7,000
98,000
4,85 0
5,80 0
Other Nitrogen- and Oxygen-containing Groups

The following table shows the other nitrogen- and oxygen-containing group parameters:
Yg,k 103 (g.K/mol) Sk*,ig(Tref) J/mol.K Ym,k 103 (g.K/mol) Cpk*,c(Tref) J/mol.K Cpk*,l(Tref) J/mol.K
O C NH2 O C N NO2
181 180 179
44.0 3
22.2
----
----
----
----
----
20,721 ----
H,k 10----
Functional Group
Group No.
----
42.0 2 46.0 1
16.0
----
----
----
----
----
48,380 ----
965
16.8
41.9
----
143 41,500
----
----
----
URk cm10/3(s
211
Vw cm3/mol
Mk g/mol
Hk*,ig(Tref) J/mol
URk cm10/3(s
Ym,k 103 (g.K/mol)
Vw cm3/mol
Mk g/mol
Hk*,ig(Tref) J/mol
H,k 10-
Bifunctional Sulfur-containing Groups

The following table shows the bifunctional sulfur-containing group parameters:
Yg,k 103 (g.K/mol) Sk*,ig(Tref) J/mol.K
Functional Group
Group No. 182 183 184
S S S SO2 S CH2 S
32.06 64.12 64.06 78.15
10.8 22.7 20.3 31.8
24.05 48.1 50 73.45
44.8 89.6 ---120.0
40,000 46,000
-24 -28
8,000
22,500 ----
550 1,100 1,250 1,980
16,000 30,000 ---32,000 56,000 -------------
152 282,000 58,000 54
185
Other Sulfur-containing Groups

The following table shows the other sulfur-containing group parameters:
H,k 10-3(g/mol) ---Yg,k 103 (g.K/mol) Cpk*,c(Tref) J/mol.K Hk*,ig(Tref) J/mol J/mol.K
Functional Group
Group No. 186
SH
33.07
14.81
46.8
52.4
13,0 00
-33
----
----
----
Bifunctional Halogen-containing Groups

The following table shows the bifunctional halogen-containing group parameters:
Functional Group
Group No. 187 188 189 190 191
CHF CF2 CHCl CCl2 CH CCl
32.02 50.01 48.48 82.92 60.49
13.0 15.3 19.0 27.8 25.72
37.0 49.0 42.7 60.4 56.25
41.95 49.4 60.75 87.0 77.1
114 197,700 128 370,000 -51,700 111 -78,000 122 39,000 79
12,400 17,400 ---10,500 25,500 ---19,400 27,500 2,330 22,000 29,000 ---15,200 32,000 ----
950 1,050 1,600 2,350 1,900
Ym,k 103 (g.K/mol)
H,k 103 (g/mol) (J/mol)1/3
Vw cm3/mol
Mk g/mol
Hk*,ig(Tref) J/mol
URk cm10/3(s
Ym,k 103 (g.K/mol)
Sk*,ig(Tref)
Vw cm3/mol
Mk g/mol
Ym,k 103 (g.K/mol)
H,k 103 (g/mol) (J/mol)1/3
Vw cm3/mol
Mk g/mol
Hk*,ig(Tref) J/mol
Yg,k 103 (g.K/mol)
Ym,k 103 (g.K/mol)
Functional Group
Group No. 192 193 194 195 196
CFCl CHBr CBr2 CHI CI2
66.47 92.93
21.57 21.4
54.7 41.9 58.8 38.0 51.0
68.2 -------------
125 224,000 -16,700 106 -8,000 37,300 112 79
28,000 32,000 ----------------------------------------
H,k 103 (g/mol) (J/mol)1/3 H,k 103 (g/mol) (J/mol)1/3 -------------
1,700 1,760 2,640 -------
171.84 32.5 139.93 27.1 265.83 44.0
100,000 58
Other Halogen-containing Groups

The following table shows the other halogen-containing group parameters:
Functional Group
Group No. 197 198 199 200 201 202 203 204
F CF3 CHF2 CH2F Cl CCl3 CHCl2 CH2Cl
19.00 69.01 51.02 33.03 35.46
6.0 21.33 18.8 16.2 12.2
21.4 70.4 58.4 46.75 27.1 87.5 69.8 52.45 105.9 26.3 85.1 68.2 51.65 22.4
21.0 70.4 62.95 51.4 39.8 126.8
-6 195,000 122 565,000 108 392,700 96 217,000 -49,000 -9 113 127,000
9,000
11,000 ----
530 1,580 1,480 1,410 1,265 3,615 2,865 2,145 5,365 1,300 3,940 3,060 2,180 ----
19,500 36,500 ---21,400 28,400 ---11,700 16,700 ---17,500 22,000 2,080 39,500 51,000 ---36,900 49,500 4,410 20,200 27,700 2,500 46,500 60,000 5,280 35,000 11,500 -----------------------------
118.38 40 83.93 49.48 31.3 22.5
100.55 100,700 102 70.2 152.9 ----------------71,700 93 51,000 171
Cl 205 Br CBr3 CHBr2 CH2Br I

206 207 208 209 210
111.55 55.3 79.92 14.6
-14,000 -14 -22,000 98 -30,700 92 -36,000 88 40,000 -41
251.76 47.1 172.85 36.0 93.94 24.8
126.91 20.4

213
Ym,k 103 (g.K/mol)
Vw cm3/mol
Mk g/mol
Hk*,ig(Tref) J/mol
Vw cm3/mol
Mk g/mol
Hk*,ig(Tref) J/mol
Yg,k 103 (g.K/mol)
Ym,k 103 (g.K/mol)
Functional Group
Group No. 211 212 213
CI3 CHI2 CH2I
392.74 64.4 266.84 47.5 140.94 30.6
73.4 60.4 47.75
----------
140,000 17 77,300 18,000 38 61
----------
-----------
----------
H,k 103 (g/mol) (J/mol)1/3
----------
Vw cm3/mol
Mk g/mol
Hk*,ig(Tref) J/mol
C Tait Model Coefficients
This appendix lists parameters available for the Tait molar volume calculations for selected polymers. These parameters are available in the POLYMER databank for the polymers listed:
B0 (Pa)
1.7596E+08 1.7867E+08 1.8382E+08 2.9210E+08 1.4236E+08 1.7598E+08 1.7255E+08 3.4019E+08 2.2569E+08 3.1268E+08 3.0545E+08 8.7746E+07 3.5434E+08 1.9410E+08
Polymer BR HDPE I-PB I-PMMA I-PP LDPE LLDPE PAMIDE PBMA PC PCHMA PDMS PHENOXY PIB
A 0 (m 3 /kg)
1.0969E-03 1.1567E-03 1.1561E-03 7.9770E-04 1.2033E-03 1.1004E-03 1.1105E-03 7.8153E-04 9.3282E-04 7.9165E-04 8.7410E-04 1.0122E-03 8.3796E-04 1.0890E-03
A1 (m3 /kg.K)
7.6789E-07 6.2888E-07 6.1015E-07 5.5274E-07 4.8182E-07 1.4557E-06 1.2489E-06 3.6134E-07 5.7856E-07 4.4201E-07 4.9035E-07 7.7266E-07 3.6449E-07 2.5554E-07
A 2 (m3 /kg.K 2 )
-2.2216E-10 1.1268E-09 8.3234E-10 -1.4503E-10 7.7589E-10 -1.5749E-09 -4.0642E-10 2.7519E-10 5.7343-10 2.8583E-10 3.2707E-10 1.9944E-09 5.2933E-10 2.2682E-09
B1 (1/K)
4.3355E-03 4.7254E-03 4.7833E-03 4.1960E-03 4.0184E-03 4.6677E-03 4.4256E-03 3.8021E-03 5.3116E-03 3.9728E-03 5.5030E-03 6.2560E-03 4.3649E-03 3.9995E-03
P Range (Mpa) 0.1-283 0.1-200 0.0-196 0.1-200 0.0-196 0.1-200 0.1-200 0.0-177 0.1-200 0.0-177 0.1-200 0.0-100 0.0-177 0.0-100
T Range (K) 277328 415472 407514 328463 447571 398471 420473 455588 295473 430610 383472 298343 349574 326383
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PMMA PMP POM POMS PS-1 PTFE PVAC
8.2396E-04 1.2078E-03 8.3198E-04 9.3905E-04 9.3805E-04 4.6867E-04 8.2832E-04
3.0490E-07 5.1461E-07 2.7550E-07 5.1288E-07 3.3086E-07 1.1542E-07 4.7205E-07
7.0201E-10 9.7366E-10 2.2000E-09 5.9157E-11 6.6910E-10 1.1931E-09 1.1364E-09
2.9803E+08 1.4978E+08 3.1030E+08 2.4690E+08 2.5001E+08 4.0910E+08 1.8825E+08
4.3789E-03 4.6302E-03 4.4652E-03 3.6633E-03 4.1815E-03 9.2556E-03 3.8774E-03
0.1-200 0.0-196 0.0-196 0.1-180 0.1-200 0.0-392 0.0-100
387432 514592 462492 413471 389469 604646 337393
Range of experimental data used in the determination of equation constants.
Source: Danner R. P., & High, M. S. (1992). Handbook of Polymer Solution Thermodynamics. New York: American Institute of Chemical Engineers. p. 3B5.
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D Mass Based Property Parameters
The Aspen Plus convention is to use mole based parameters for property model calculations. However, polymer property parameters are often more conveniently obtained on a mass basis. To satisfy the needs of users who may prefer the use of mass based parameters, in Aspen Polymers (formerly known as Aspen Polymers Plus) there is a corresponding mass based parameter for selected mole based parameters. The following table shows a list of model parameters and their mass-based counterparts. Note that the mass based parameters should only be used for polymers and oligomers, and not for segments.
Mole Based Parameter CPCVK CPLVK DGCON DGFORM DBSUB DHCON DHFVK DHSUB DNCVK DNGVK DNLVK Mass Based Parameter CPCVKM CPLVKM DGCONM DGFVKM DGSUBM DHCONM DHFVKM DHSUBM DNCVKM DNGVKM DNLVKM Description Crystalline heat capacity Liquid heat capacity Standard free energy of condensation Standard free energy on formation at 25C Standard free energy of sublimation Standard enthalpy of condensation Standard enthalpy of formation at 25C Standard enthalpy of sublimation Crystalline density Glass density Liquid density
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E Equation-of-State Parameters
This appendix lists unary parameters used with the: Sanchez-Lacombe (POLYSL) equation of state model SAFT (POLYSAFT) equation of state model
The parameters are not automatically retrieved from databanks. These parameters are not unique in any way. Users may generate them through experimental data regression for the components of interest.
Sanchez-Lacombe Unary Parameters

This section lists the POLYSL model parameters for polymers, monomers, and solvents.
POLYSL Polymer Parameters

The following table shows the Sanchez-Lacombe (POLYSL) unary parameters for polymers:
Polymer HDPE LDPE PDMS PBMA PHMA PIB PMMA POMS PS PVAC T*, K 649 673 476 627 697 643 696 768 735 590 P*, bar 4250 3590 3020 4310 4260 3540 5030 3780 3570 5090
*, kg/m3
904 887 1104 1125 1178 974 1269 1079 1105 1283
T range, K 426-473 408-471 298-343 307-473 398-472 326-383 397-432 412-471 388-468 308-373
P, up to bar 1000 1000 1000 2000 2000 1000 2000 1600 2000 800
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Source: Sanchez, I. C., & Lacombe, R. H. (1978). Statistical Thermodynamics of Polymer Solutions. Macromolecules, 11(6), pp. 11451156.
POLYSL Monomer and Solvent Polymers

The following table shows the Sanchez-Lacombe (POLYSL) unary parameters for monomers and solvents:
Formula CCl4 CHCl3 CH3Cl CO2 CS2 CH4 CH4O C3H3N C3H6O C3H6O2 C6H7N C3H8O C3H8O CH3NO2 C2HCl3 C2H2Cl2 C2H4 C2H4O2 C2H6 C2H6O C3H8 C4H8O C4H8O2 C4H10 C4H10 C4H10O C4H10O C5H5N C5H10 C5H12 C5H12 C5H12 C6H5Cl C6H6 C6H6O Component Carbon Tetrachloride Chloroform Methyl chloride Carbon dioxide Carbon disulfide Methane Methanol Acrilonitrile Acetone Ethyl formate Aniline Propanol Isopropyl alcohol Nitromethane 1,1,1-Trichloroethylene 1,1-Dichloroethylene Ethylene Acetic acid Ethane Ethanol Propane Methyl ethyl ketone Ethyl acetate n-Butane Isobutane Tert-butyl alcohol Diethyl ether Pyridine Cyclopentane n-Pentane Isopentane Neopentane Chlorobenzene Benzene Phenol T*, K 535 512 487 277 567 224 468 527 484 466 614 420 399 620 516 488 291 562 315 413 371 513 468 403 398 448 431 566 491 441 424 415 585 523 530 P*, bar 8126 4560 5593 7436 5157 2482 12017 5930 5330 4965 6292 8856 8532 9251 3779 5117 3339 8613 3273 10690 3131 4468 4580 3222 2878 6931 3627 5492 3800 3101 3080 2655 4367 4438 7934
*, kg / m3
1788 1688 1538 1629 1398 500 922 868 917 1076 1115 972 975 1490 1518 1722 660 1164 640 963 690 913 1052 736 720 952 870 1079 867 755 765 744 1206 994 1192
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Formula C6H14 C6H12 C6H12O2 C7H8 C7H16 C8H8 C8H10 C8H10 C8H10 C8H18 C9H20 C10H18 C10H18 C10H22 C11H24 C12H26 C13H28 C14H10 C14H30 C17H36 C20H42 H2O H2S
Component n-Hexane Cyclohexane n-Butyl acetate Toluene n-Heptane Styrene p-Xylene m-Xylene o-Xylene n-Octane n-Nonane trans-Decalin cis-Decalin n-Decane n-Undecane n-Dodecane n-Tridecane Phenanthrene n-Tetradecane n-Heptadecane n-Eicosane Water Hydrogen Sulfate
T*, K 476 497 498 543 487 563 561 560 571 502 517 621 631 530 542 552 560 801 570 596 617 623 382
P*, bar 2979 3830 3942 4023 3090 3684 3810 3850 3942 3080 3070 3151 3334 3040 3030 3009 2989 3769 2959 2867 3067 26871 6129
*, kg / m3
775 902 1003 966 800 870 949 952 965 815 828 935 960 837 846 854 858 1013 864 880 961 1105 1095
Evaluated from vapor-pressure and liquid-density data regression
Source: Sanchez, I. C., & Lacombe, R. H. (1978). Statistical Thermodynamics of Polymer Solutions. Macromolecules, 11(6), pp. 11451156.
SAFT Unary Parameters

This section lists the POLYSAFT model parameters for solvents and polymers.
POLYSAFT Parameters
The following table shows the SAFT (POLYSAFT) unary parameters for various non-associating fluids:
Formula Component T range, K
voo , cm3 / mol
uo / k, K
Formula N2 AR CO CO2 CL2 CS2 SO2 CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 C12H26 C14H30 C16H34 C20H42 C28H58 C36H74 C44H90 C5H10 C6H12 C7H14 C8H16 C9H18 C10H20 C6H12 C7H14 C8H16 C9H18 C10H20 C11H22 C6H6 C7H8 C8H10 C9H12 C10H14 C8H10
Component Nitrogen Argon Carbon Monoxide Carbon Dioxide Chlorine Carbon Disulfide Sulfur Dioxide Methane Ethane Propane n-Butane n-Pentane n-Hexane n-Heptane n-Octane n-Nonane n-Decane n-Dodecane n-Tetradecane n-Hexadecane n-Eicosane n-Octacosane n-Hexatriacontane n-Tetratetracontane Cyclopentane Methyl-cyclopentane Ethyl-cyclopentane Propyl-cyclopentane Butyl-cyclopentane Pentyl-cyclopentane Cyclohexane Methylcyclohexane Ethylcyclohexane Propylcyclohexane Butylcyclohexane Pentylcyclohexane Benzene Methyl-benzene Ethyl-benzene n-Propyl-benzene n-Butyl-benzene m-Xylene
T range, K ----72-121 218-288 180-400 278-533 283-413 92-180 160-300 190-360 220-420 233-450 243-493 273-523 303-543 303-503 313-573 313-523 313-533 333-593 393-573 449-704 497-768 534-725 252-483 263-503 273-513 293-423 314-578 333-483 283-513 273-533 273-453 313-453 333-484 353-503 300-540 293-533 293-573 323-573 293-523 309-573
v oo , cm3 / mol
19.457 16.29 15.776 13.578 22.755 23.622 22.611 21.576 14.460 13.457 12.599 12.533 12.475 12.282 12.234 12.240 11.723 11.864 12.389 12.300 12.0 12.0 12.0 12.0 12.469 13.201 13.766 14.251 14.148 13.460 13.502 15.651 15.503 15.037 14.450 14.034 11.421 11.789 12.681 12.421 12.894 12.184
m 1.0 1.0 1.221 1.417 1.147 1.463 1.133 1.0 1.941 2.696 3.458 4.091 4.724 5.391 6.045 6.883 7.527 8.921 9.978 11.209 13.940 19.287 24.443 29.252 3.670 4.142 4.578 5.037 5.657 6.503 3.970 3.954 4.656 5.326 6.060 6.804 3.749 4.373 4.719 5.521 6.058 4.886
uo / k, K
123.53 150.86 111.97 216.08 367.44 396.05 335.84 190.29 191.44 193.03 195.11 200.02 202.72 204.61 206.03 203.56 205.46 205.93 209.40 210.65 211.25 209.96 208.74 207.73 226.70 223.25 229.04 232.18 230.61 225.56 236.41 248.44 243.16 238.51 234.30 230.91 250.19 245.27 248.79 238.66 238.19 245.88
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Formula C12H10 C10H8 C11H10 C12H12 C13H14 C14H16 C14H10 C14H10 C16H10 C2H6O C3H8O C4H10O C4H10O C12H10O C3H9N C12H10O C3H6O C4H8O C5H10O C5H10O C2H4 C3H6 C4H8 C6H12 CH3CL CH2CL2 CHCL3 CCL4 C2H5CL C3H7CL C4H7CL C6H11CL C6H5CL PE P(E&P)
Component Biphenyl Naphthalene 1-Methyl-naphthalene 1-Ethyl-naphthalene 1-n-Propyl-naphthalene 1-n-Butyl-naphthalene Phenanthrene Anthracene Pyrene Dimethyl-ether Methyl-ethyl-ether methyl-n-propyl-ether Diethyl-ether Phenyl-ether Trimethylamine Triethylamine Acetone Methy-ethyl ketone Methyl-n-propyl ketone Diethyl-ketone Ethylene Propylene 1-Butene 1-Hexene Chloromethane Dichloromethane Trichloromethane Tetrachloromethane Chloroethane 1-Chloropropane 1-Chlorobutane 1-Chlorohexane Chlorobenzene Polyethylene (MW=25000) Polypropylene
T range, K 433-653 373-693 383-511 393-563 403-546 413-566 373-633 493-673 553-673 179-265 266-299 267-335 273-453 523-633 193-277 323-368 273-492 257-376 274.399 275-399 133-263 140-320 203-383 213-403 213-333 230-333 244-357 273-523 212-440 238-341 262-375 306-435 273-543 413-473 263-303
v oo , cm3 / mol
12.068 13.704 13.684 12.835 13.304 13.140 16.518 16.297 18.212 11.536 10.065 10.224 10.220 12.100 14.102 11.288 7.765 11.871 11.653 10.510 18.157 15.648 13.154 12.999 10.765 10.341 10.971 13.730 11.074 11.946 12.236 12.422 13.093 12.0 12.0
m 6.136 4.671 5.418 6.292 6.882 7.766 5.327 5.344 5.615 2.799 3.540 4.069 4.430 6.358 3.459 5.363 4.504 4.193 4.644 4.569 1.464 2.223 3.162 4.508 2.377 3.114 3.661 3.458 3.034 3.600 4.207 5.458 3.962 1165.77 822.68
uo / k, K
280.54 304.80 293.45 276.18 266.82 252.11 352.00 352.65 369.38 207.83 203.54 208.13 191.92 276.13 196.09 201.31 210.92 229.99 230.40 235.24 212.06 213.90 202.49 204.71 238.37 253.03 240.31 257.46 229.58 229.14 227.88 225.82 276.72 210.0 210.0
Source: Huang, S. H., & Radosz, M. (1990). Equation of State for Small, Large, Polydisperse, and Associating Molecules. Ind. & Eng. Chem. Res., 29, pp. 2284-2294.
F Input Language Reference
This appendix describes the input language for specify polymer physical property inputs only. A complete input language reference for Aspen Polymers (formerly known as Aspen Polymers Plus) is provided in Appendix D of the Aspen Polymers User Guide, Volume 1.
Specifying Physical Property Inputs

This section describes the input language for specifying physical property inputs.
Specifying Property Methods

Following is the input language used to specify property methods.
Input Language for Property Methods
PROPERTIES opsetname keyword=value / opsetname [sectionid-list] keyword=value /... Optional keywords: FREE-WATER SOLU-WATER
HENRY-COMPS
HENRY-COMPS
henryid
cid-list
Input Language Description for Property Methods
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The PROPERTIES paragraph is used to specify the property method(s) to be used in your simulation. In this paragraph properties may be specified for the entire flowsheet, for a flowsheet section, or for an individual unit operation block. Depending on the component system used, additional information may be required such as Henry's law information, water solubility correlation, freewater phase properties. The input language for specifying property methods is as follows. opsetname sectionid-list FREE-WATER SOLU-WATER Primary property method name (See Available Property Methods in Chapter 1). List of flowsheet section IDs. Free water phase property method name (Default=STEAMTA). Method for calculating the K-value of water in the organic phase. SOLU-WATER=0 Water solubility correlation is used, vapor phase fugacity for water calculated by free water phase property method Water solubility correlation is used, vapor phase fugacity for water calculated by primary property method Water solubility correlation is used with a correction for unsaturated systems, vapor phase fugacity for water calculated by primary property method Primary property method is used. This method is not recommended for waterhydrocarbon systems unless waterhydrocarbon interaction parameters are available. (Default)
SOLU-WATER=1
SOLU-WATER=2
SOLU-WATER=3
HENRY-COMPS
Henry's constant component list ID.
The HENRY-COMPS paragraph identifies lists of components for which Henry's law and infinite dilution normalization are used. There may be any number of HENRY-COMPS paragraphs since different lists may apply to different blocks or sections of the flowsheet. henryid cid-list Henry's constant component list ID List of component IDs
Input Language Example for Property Methods
HENRY-COMPS PROPERTIES
HC
INI1 HENRY-COMPS=HC
POLYNRTL
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Specifying Property Data

Following is the input language used to specify property data.
Input Language for Property Data
PROP-DATA PROP-LIST paramname [setno] / . . . PVAL cid value-list / value-list / . . . PROP-LIST paramname [setno] / . . . BPVAL cid1 cid2 value-list / value-list / . . . COMP-LIST cid-list CVAL paramname setno 1 value-list COMP-LIST cid2-list BCVAL paramname setno 1 cid1 value-list / 1 cid1 value-list / . . . Physical property models require data in order to calculate property values. Once you have selected the property method(s) to be used in your simulation, you must determine the parameter requirements for the models contained in the property method(s), and ensure that they are available in the databanks. If the model parameters are not available from the databanks, you may estimate them using the Property Constant Estimation System, or enter them using the PROP-DATA or TAB-POLY paragraphs. The input language for the PROP-DATA paragraphs is as follows. Note that only the general structure is given, for information on the format for the input parameters required by polymer specific models see the relevant chapter of this User Guide.
Input Language Description for Property Data
PROP-LIST PVAL BPVAL COMP-LIST CVAL BCVAL
Used to enter parameter names and data set numbers. Used to enter the PROP-LIST parameter values. Used to enter the PROP-LIST binary parameter values. Used to enter component IDs. Used to enter the COMP-LIST parameter values. Used to enter the COMP-LIST binary parameter values. paramname setno Parameter name Data set number. For CVAL and BCVAL the data set number must be entered. For setno > 1, the data set number must also be specified in a new property method defined using the PROP-REPLACE paragraph. (For PROP-LIST, Default=1) Component ID
cid
225
cid1 cid2 value-list
Component ID of first component of binary pair Component ID of second component of binary pair List of parameter values. For PROP-LIST, enter one value for each element of the property; for COMP-LIST, enter one value for each component in the cid-list. List of component ID
cid-list
Input Language Example for Property Data
PROP-DATA IN-UNITS SI PROP-LIST PVAL HOPOLY PVAL COPOLY PLXANT -40.0 0 0 0 0 0 0 0 1D3 -40.0 0 0 0 0 0 0 0 1D3 / TB / 2000.0 / 2000.0
PROP-DATA IN-UNITS SI PROP-LIST PVAL HOPOLY PVAL COPOLY PVAL ABSEG PVAL ASEG PVAL BSEG MW 1.0 1.0 192.17 76.09 116.08
PROP-DATA IN-UNITS SI PROP-LIST PVAL HOPOLY PVAL COPOLY DHCONM -3.64261D4 -3.64261D4 / / / DHSUB 8.84633D4 8.84633D4 / / / TMVK 1.0 1.0 / TGVK / 0.0 / 0.0
PROP-DATA IN-UNITS SI PROP-LIST GMRENB BPVAL MCH ASEG -92.0 BPVAL ASEG MCH 430.0 / / / GMRENC 0.2 0.2
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Estimating Property Parameters

Following is the input language used to estimate property parameters.
Input Language for Property Parameter Estimation
ESTIMATE [option] STRUCTURES method SEG-id
groupno nooccur / groupno nooccur /...
Input Language Description for Property Parameter Estimation
The main keywords for specifying property parameter estimation inputs are the ESTIMATE and the STRUCTURES paragraphs. A brief description of the input language for these paragraphs follows. For more detailed information please refer to the Aspen Physical Property System Physical Property Data documentation. option method SEG-id groupno nooccur Option=ALL Estimate all missing parameters (default)
Polymer property estimation method name Segment ID defined in the component list Functional group number (group ID taken from Appendix B) Number of occurrences of the group
Input Language Example for Property Parameter Estimation
ESTIMATE ALL STRUCTURES VANKREV VANKREV COOVANKREV COOABSEG BSEG ABSEG 115 1 115 1 151 2 / 100 2 / 151 2 / 100 2 ;-(C6H4); -COO-CH2-CH2-
;-(C6H4)-COO-CH2-CH2-
227
Index
A ABS 146 Acrylonitrile-butadiene-styrene 146 Activation energy 157 Activity coefficients Born 107 Electrolyte-Polymer NRTL model 10314 Flory-Huggins model 9498 Flory-Huggins term 111 for polymer activity 101 for polymer components 101 for solvents 101 ionic 105 liquid-liquid equilibria calculations 90 local composition term 110 mixture liquid molar volume calculations 92 model overview 87 models available 87120 models list 93 phase equilibria calculations 88 Pitzer-Debye-Hckel 106 Polymer NRTL model 98103 Polymer UNIFAC Free Volume model 11719 Polymer UNIFAC model 11417 properties available 93 property models 13, 15 thermodynamic property calculations 90 vapor-liquid equilibria calculations 88 Adding data for parameter optimization 23 molecular structure for property estimation 22 parameters for property models 20
property methods 20 Amorphous solid 8 Aspen polymer mixture viscosity model See Polymer mixture viscosity model Aspen Polymers activity coefficient models 87 120, 93 activity coefficient properties 93 available polymer properties 122 available property methods 16 19 available property models 1316, 122 EOS models 34 EOS properties 32 equation of state models 2786 input language for physical properties 22327 polymer thermal conductivity models 17182 polymer viscosity models 15170 thermal conductivity routes 181 viscosity models 151 viscosity routes 170 AspenTech support 3 AspenTech Support Center 3 B Binary antisymmetric mixing 159 Binary interaction parameters 96, 102 Binary parameters for Eyring-NRTL 168 for PC-SAFT EOS 64 for polymer mixture viscosity 159 for SAFT EOS 56 for Sanchez-Lacombe EOS 39 Binary symmetric-quadratic mixing 159 Born
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Index
activity coefficient 107 equation 106 C Calculating segment properties from functional groups 202 solution viscosity 164 Carnahan-Starling expression 50 Components liquid enthalpy model 147 Concentrated solution 161 Concentration basis 97 Copolymer PC-SAFT description 67 model 67 option codes 78 parameters 76 property method (PC-SAFT) 200 Critical concentration 161 constants 45 mass viscosity 156 molecular weight 154 Crystalline weighting fraction 173 Custom property methods 20 customer support 3 D Data for optimizing parameters 23 parameter estimation 21 thermodynamic 19 Density of mixtures 6 property model 13, 15 Departure functions about 30 ideal gas 123 Devolatilization of monomers 9 Diffusion coefficients 6 Dilution effect 167 Dissolved gas 89 E e-bulletins 3 Electrolyte-Polymer NRTL adjustable parameters 111 applicability 103 assumptions 104
Born term 106 excess Gibbs free energy 104 Flory-Huggins term 111 for multicomponent systems 108 ionic activity coefficient 105 local composition term 108 local interaction contribution 107 long range interaction contribution 105 model 10314 model parameters 112 Pitzer-Debye-Hckel term 105 specifying model 114 terms 104 Energy balance 6 Enthalpy See also Solid enthalpy, See also Liquid enthalpy calculation 203 departure 31 excess molar liquid 90 for amorphous polymer 129 for crystalline polymer 129 ideal gas 124 in systems 6 of mixing 94, 98 property model 13, 15 temperature relationship 128 Entropy calculation 203 departure 31 excess molar liquid 91 in equipment design 6 of mixing 94, 98, 111 of polymers 123 EP-NRTL See Electrolyte-Polymer NRTL Equations of state Copolymer PC-SAFT model 67 liquid-liquid equilibria calculations 30 model overview 27 models available 2786, 34 parameters for 21822 PC-SAFT model 5966 phase equilibria calculations 29 30 Polymer SRK model 4247 properties available 32 property models 13, 14 SAFT model 4759 Sanchez-Lacombe model 3442 thermodynamic property calculations 3032
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vapor-liquid equilibria calculations 30 Equilibria See also Phase equilibria calculating 6 liquid-liquid 11, 30, 90 polymer solutions 912 polymer systems 30, 88, 90 properties 6 vapor-liquid 9, 30, 88 vapor-liquid-liquid 10 Equipment design 6 Estimating parameters for property models 21 property parameters 227 solution viscosity 164 thermophysical properties 145 Excess liquid functions 90 molar liquid 90 molar liquid enthalpy 90 molar liquid entropy 91 Eyring-NRTL mixture viscosity model about 167 applicability 167 binary parameters 168 for multicomponent systems 168 parameters 169 specifying 169 F Flory-Huggins activity coefficient 111 applicability 94 binary interaction parameter 96 concentration basis 97 equation 111 for multiple components 96 Gibbs free energy of mixing 95 interaction parameter 94 model 9498 model parameters 97 property method (POLYFH) 183 85 specifying model 98 Fractionation 12 Fugacity 6 Functional groups
containing halogen 212 containing hydrocarbons 205 containing hydrogen 207 containing nitrogen 210 containing nitrogen and oxygen 211 containing oxygen 208 containing sulfur 212 parameters 20514 van Krevelen 20214 G Gas dissolved 89 Gibbs free energy See also Solid Gibbs free energy, See also Liquid Gibbs free energy calculation 203 departure 31 excess (EP-NRTL) 104 excess (NRTL) 100 excess (SRK) 42 ideal gas 124 minimization 6 of mixing (Flory-Huggins) 95 of mixing (Polymer NRTL) 99 of polymers 123 property model 13, 15 Glass transition model parameters 142 Glass transition temperature calculation 204 for amorphous solids 8 polymer mixture 166 polymer solution 165 Van Krevelen correlation 141 Group contribution Van Krevelen method 145 Group contribution method van Krevelen 145, 146 H Heat capacity calculation 202 ideal gas 125 of polymers 131 parameters 127 property model 13, 15 Helmholtz free energy 49, 60
Index
help desk 3 I Ideal gas departure functions 123 enthalpy 124 Gibbs free energy 124 heat capacity 125 heat capacity parameters 127 model 12327 model parameters 125 molar mixture properties 32 property model 15 Input language for physical properties 22327 property data 225 property methods 223 property parameter estimation 227 Interaction contribution local 107 long range 105 Interaction parameter 94 Internal energy 6 K KLMXVKDP 181 KLMXVKTR 180 KMXVKTR 181 L Lattice theory 34 LCST 11 Letsou-Stiel 161 Linear mixing 159 Liquid enthalpy model parameters 131 of polymers 123, 128 pure component model 147 Liquid Gibbs free energy model parameters 131 of polymers 130 Liquid molar volume mixture calculations 92 model parameters (Tait) 141 model parameters (van Krevelen) 137 Tait model 14041 Van Krevelen model 13640 Liquid Van Krevelen model 12735 Liquid-liquid equilibrium 30, 90
Liquid-liquid phase equilibrium 11 LLE 11, 30, 90 Local composition activity coefficient 110 equation 108 Local interaction contribution 107 Long range interaction contribution 105 Lower critical solution temperature 11 M Mark-Houwink equation 152 Mark-Houwink/van Krevelen model 15258 model applicability 151 model parameters 154 specifying model 158 Mass balance 6 Mass-based property parameters 217 Melt transition model parameters 143 Melt transition temperature calculation 204 Van Krevelen correlation 142 Melting temperature 8 Melts 8 Mixing binary antisymmetric 159 binary symmetric-quadratic 159 linear 159 Mixture density 6 thermal conductivity 6 viscosity 6 Mixture liquid molar volume calculations 92 Mixture viscosity See also EyringNRTL mixture viscosity model, See also Polymer mixture viscosity model Mixtures Eyring-NRTL viscosity model 167 glass transition temperature 166 thermal conductivity model 180 viscosity model 15861 Modeling See Process modeling Models activity coefficient 87120 Copolymer PC-SAFT EOS 67
231
Electrolyte-Polymer NRTL activity coefficient 10314 equation of state 2786 Eyring-NRTL mixture viscosity 167 Flory-Huggins activity coefficient 9498 ideal gas 12327 Mark-Houwink/van Krevelen 15258 mixture thermal conductivity 180 parameter regression 146 PC-SAFT EOS 5966 polymer mixture viscosity 158 61 Polymer NRTL activity coefficient 98103 Polymer SRK EOS 4247 polymer thermal conductivity 17182 Polymer UNIFAC activity coefficient 11417 Polymer UNIFAC Free Volume activity coefficient 11719 polymer viscosity 15170 pure component liquid enthalpy 147 SAFT EOS 4759 Sanchez-Lacombe EOS 3442 Tait liquid molar volume 14041 Van Krevelen glass transition temperature 141 Van Krevelen liquid 12735 Van Krevelen liquid molar volume 13640 Van Krevelen melt transition temperature 142 Van Krevelen polymer solution viscosity 16167 Van Krevelen solid 143 Van Krevelen thermal conductivity 17379 Modified Mark-Houwink equation 152 Molar liquid (excess) 90 Molar volume See also Liquid molar volume calculation 203 calculations for liquid mixture 92 for polymer (Tait) 140
for polymers (van Krevelen) 136 from EOS models 31 Molecular structure entering for property estimation 22 Molecular weight critical 154 weight average 153 Monomers devolatilization of 9 MULMX13 170 MULMXVK 170 N Non-random two liquid See NRTL Nonvolatility 8, 89 NRTL See also Electrolyte-Polymer NRTL, See also Polymer NRTL electrolye-polymer model 103 14 polymer model 98103 O Oligomers 8 ideal gas model 123 nonvolatility 89 P Parameters binary for Eyring-NRTL 168 binary for PC-SAFT 64 binary for polymer mixture viscosity 159 binary for SAFT 56 binary for Sanchez-Lacombe 39 binary interaction 96, 102 calculating segment properties 202 electrolyte-electrolyte 112 electrolyte-molecule 112 entering for components 21 entering for property models 20 estimating for property models 21 estimating property 227 for Electrolyte-Polymer NRTL model 112
Index
for equation of state models 21822 for Eyring-NRTL mixture viscosity model 169 for Flory-Huggins model 97 for glass transition 142 for ideal gas heat capacity 127 for ideal gas model 125 for liquid enthalpy 131 for liquid Gibbs free energy 131 for liquid molar volume (Tait) 141 for liquid molar volume (van Krevelen) 137 for Mark Houwink/van Krevelen model 154 for melt transition 143 for PC-SAFT model 65 for polymer mixture viscosity model 159 for Polymer NRTL model 102 for polymer solution viscosity model 163 for Polymer SRK model 45 for Polymer UNIFAC free volume model 119 for Polymer UNIFAC model 117 for polymers (ideal gas) 126 for polymers (van Krevelen liquid models) 133 for polymers (van Krevelen liquid molar volume model) 138 for polymers (van Krevelen thermal conductivity model) 175 for SAFT (POLYSAFT) 220 for SAFT model 57 for Sanchez-Lacombe (POLYSL) 218 for Sanchez-Lacombe model 36, 4042 for segments (ideal gas) 126 for segments (thermal conductivity) 176 for segments (van Krevelen liquid molar volume) 139 for segments (van Krevelen liquid) 134 for solid enthalpy 144 for solid Gibbs free energy 144 for solid molar volume (van Krevelen) 145 for Tait model 21516
for van Krevelen liquid model 131 for van Krevelen solid model 144 for van Krevelen thermal conductivity model 174 input for Eyring-NRTL mixture viscosity model 169 input for ideal gas model 125 input for Mark-Houwink model 154 input for PC-SAFT model 66 input for polymer mixture viscosity model 160 input for SAFT model 58 input for Sanchez-Lacombe model 41 input for van Krevelen liquid models 132 input for van Krevelen liquid molar volume model 138 input for van Krevelen thermal conductivity model 175 interaction 94 mass-based 217 missing for SAFT model 59 missing for Sanchez-Lacombe model 42 molecule-molecule 112 optimizing 23 regression 146 regression for Eyring-NRTL mixture viscosity model 169 regression for ideal gas model 127 regression for Mark-Houwink model 154 regression for PC-SAFT model 66 regression for polymer mixture viscosity model 160 regression for SAFT model 58 regression for Sanchez-Lacombe model 41 regression for Tait model 141 regression for van Krevelen liquid model 135 regression for van Krevelen liquid molar volume 139 Tait model 143 Van Krevelen estimation 145 PC-SAFT about 17 applicability 59 binary parameters 64
233
comparison to SAFT 60 copolymer model 67 for copolymer systems 63 implementation 62 model 5966 model parameters 65 property method (POLYPCSF) 19899 pure-component parameters 60 route structure 200 specifying model 66 Perturbation theory 49 Perturbed chain statistical associating fluid theory See PC-SAFT Phase equilibria calculated from activity coefficients 88 calculated from EOS models 29 30 modeling 9 Physical properties See also Properties for activity coefficient models 93 for EOS models 32 input language 223 route structure 183 specifying 1923 Pitzer-Debye-Hckel activity coefficient 106 equation 105 Plasticizer effect 165 PNRTL-IG 17, 19193 Polydispersity 7 POLYFH 16, 18385 Polymer mixture thermal conductivity model 180 Polymer mixture viscosity model about 15861 applicability 151, 158 binary parameters 159 Eyring-NRTL 151 for multicomponent systems 158 parameters 159 specifying 161 Polymer NRTL activity coefficients 100 applicability 98 binary interaction parameters 102
excess Gibbs free energy 100 for homopolymer 102 Gibbs free energy of mixing 99 ideal gas property method (PNRTL-IG) 19193 model 98103 model parameters 102 property method (POLYNRTL) 18587 specifying model 103 Polymer solution glass transition temperature 165 Polymer solution viscosity model about 16167 calculation steps 164 estimating values 164 for multicomponent mixtures 161 parameters 163 pseudo-component properties 162 quasi-binary system 161 specifying 167 Polymer SRK characteristics 42 cubic EOS parameters 43 equation 43 for polymer mixtures 44 model 4247 model parameters 45 property method (POLYSRK) 19596 specifying model 47 Polymer UNIFAC applicability 114 for solvent activity 118 free volume model 11719 free volume model parameters 119 free volume property method (POLYUFV) 18991 model 11417 model parameters 117 modification for free volume 117 property method (POLYUF) 187 89 specifying free volume model 119 specifying model 117 Polymer viscosity
Index
at mixture glass transition temperature 166 Polymers amorphous 8 available properties 122 available property methods 16 19 available property models 1316, 122 critical constants 45 critical molecular weight 154 differences from non-polymers 7 entropy 123 fractionation 12 Gibbs free energy 123 glass transition for mixtures 166 glass transition for solution 165 heat capacity 131 ideal gas enthalpy 124 ideal gas Gibbs free energy 124 ideal gas heat capacity 125 ideal gas model 123 liquid enthalpy 123, 128 liquid Gibbs free energy 130 melt 8 melt viscosity 152 melts 151 modeling considerations 7 modeling mixture phase equilibria 9 modeling thermophysical properties 12 molar volume (Tait) 140 molar volume (van Krevelen) 136 nonvolatility 8, 89 parameter regression 146 parameters for van Krevelen thermal conductivity model 175 polydispersity 7 semi-crystalline 8 solid enthalpy 143 solid Gibbs free energy 144 solid molar volume 144 solution viscosity 16, 158, 161, 164, 167 solution viscosity correlation 160 solutions 912 solvent activity 118 species 109 systems 30, 88, 90
temperature enthalpy relationship 128 thermodynamic data for systems 19 thermodynamic properties 526 thermophysical properties 121 50 Van Krevelen group contribution 156 viscoelasticity 8 weight average molecular weight 153 POLYNRTL 16, 18587 POLYPCSF about 17 route structure 19899 POLYSAFT about 17 model parameters 220 route structure 19699 POLYSL about 17 model parameters 218 route structure 19394 POLYSRK 17, 19596 POLYUF 17, 18789 POLYUFV 17, 18991 Process modeling liquid-liquid equilibria 11 phase equilibria for polymer mixtures 9 polymer fractionation 12 properties of interest 5 property methods available 16 19 property models available 1316 thermophysical polymer properties 12 vapor-liquid equilibria 9 vapor-liquid-liquid equilibria 10 Process simulation See Process Modeling Properties See also Thermophysical properties, See also Thermodynamic properties calculating segment from functional groups 202 estimating parameters 227 for activity coefficient models 93 for energy balance 6 for EOS models 32 for equilibria 6 for equipment design 6
235
for mass balance 6 for polymers 122 input language 22327 mass-based 217 modeling thermophysical 12 models available 122 of interest in modeling 5 of polymer solution viscosity components 162 of polymers 526, 12150 specifying 1923 specifying data 225 thermodynamic 526 thermophysical 12150 Property methods available 1619 customizing 20 input language 223 liquid phase calcualtions 18 PC-SAFT 17, 200 PNRTL-IG 17, 19193 POLYFH 16, 18385 POLYNRTL 16, 18587 POLYPCSF 17, 19899 POLYSAFT 17, 19699 POLYSL 17, 19394 POLYSRK 17, 19596 POLYUF 17, 18788, 18789 POLYUFV 17, 18991 properties calculated 17 selecting 19 vapor phase calcualtions 17 Property models available 1316 Copolymer PC-SAFT 67 Electrolyte-Polymer NRTL 103 14 entering molecular structure 22 entering parameters 20 estimating parameters 21 Eyring-NRTL mixture viscosity 167 Flory-Huggins 9498 for activity coefficients 13, 15, 87120 for density 13, 15 for enthalpy 13, 15 for equations of state 13, 14, 2786 for Gibbs free energy 13, 15
for heat capacity 13, 15 for ideal gas 15, 12327 for polymer thermal conductivity 17182 for polymer viscosity 15170 for solution thermodynamics 13 for thermophysical properties 13 for transport properties 13 Mark-Houwink/van Krevelen 15258 mixture thermal conductivity 180 optimizing 23 PCSAFT 5966 polymer mixture viscosity 158 61 Polymer NRTL 98103 Polymer UNIFAC 11417 Polymer UNIFAC Free Volume 11719 pure component liquid enthalpy 147 SAFT 4759 Sanchez-Lacome 3442 SRK 4247 Tait liquid molar volume 14041 Van Krevelen glass transition temperature 141 Van Krevelen liquid 12735 Van Krevelen liquid molar volume 13640 Van Krevelen melt transition temperature 142 Van Krevelen polymer solution viscosity 16167 Van Krevelen solid 143 Van Krevelen thermal conductivity 17379 Pseudo-components 162 Q Quasi-binary systems 161 R Rao function calculation 204 from van Krevelen group contribution 177 Reduced viscosity 157 Regressing
Index
Eyring-NRTL mixture viscosity parameters 169 ideal gas parameters 127 liquid model parameters (van Krevelen) 135 liquid molar volume parameters 139 Mark-Houwink parameters 154 PC-SAFT parameters 66 polymer mixture viscosity parameters 160 polymer properties 146 SAFT parameters 58 Sanchez-Lacombe parameters 41 Tait model parameters 141 Routes calculations for property models 18399 for thermal conductivity 181 for viscosity 170 S SAFT applicability 47 binary parameters 56 comparison to PC-SAFT 60 for copolymer systems 55 for fluid mixtures 52 for pure fluids 47 implementation 5355 model 4759 model parameters 57, 220 property method (POLYSAFT) 19699 required parameters 53 specifying model 59 Sanchez-Lacombe binary parameters 39 characteristics 36 equation 35 for copolymer systems 37 for fluid mixtures 36 for homopolymers 36 for pure fluids 34 model 3442 model parameters 4042, 218 molecular parameters 36 property method (POLYSL) 193 94 specifying model 42 Sato-Reidel/DIPPR model 181 Segments
calculating properties from functional groups 202 reference temperature (thermal conductivity) 176 reference thermal conductivity 178 thermal conductivity at 298K 177 Van Krevelen group contribution (ideal gas) 126 Van Krevelen group contribution (liquid molar volume) 139 Van Krevelen group contribution (liquid) 134 Van Krevelen group contribution (thermal conductivity) 176 Semi-crystalline solid 8 Simulation See Process Modeling Soave-Redlich-Kwong See Polymer SRK Solid enthalpy model parameters 144 of polymers 143 Solid Gibbs free energy model parameters 144 of polymers 144 Solid molar volume model parameters (van Krevelen) 145 of polymers 144 Solids amorphous 8 semi-crystalline 8 Van Krevelen model 143 Solution viscosity See also Polymer solution viscosity model Van Krevelen model 16167 Solutions critical concentration 161 glass transition temperature 165 viscosity estimation 164 Solvent dilution effect 167 Specifying data for parameter optimization 23 Electrolyte-Polymer NRTL model 114 Eyring-NRTL mixture viscosity model 169 Flory-Huggins model 98 Mark-Houwink/van Krevelen model 158
237
mixture thermal conductivity model 180 molecular structure for property estimation 22 parameter estimates for property models 21 parameters for property models 20 PC-SAFT model 66 physical properties 1923 physical properties (input language) 223 polymer mixture viscosity model 161 Polymer NRTL model 103 polymer solution viscosity model 167 Polymer SRK model 47 Polymer UNIFAC free volume model 119 Polymer UNIFAC model 117 property data 225 property methods 19 SAFT model 59 Sanchez-Lacombe model 42 Van Krevelen thermal conductivity model 179 SRK See Polymer SRK Statistical associating fluid theory See PC-SAFT , See SAFT support, technical 3 Surface tension 6 T Tait equation 140 liquid molar volume model 140 41 liquid molar volume model parameters 141 model coefficients 21516 technical support 3 Temperature enthalpy relationship 128 glass transition 8, 141 glass transition calculation 204 lower critical solution 11 melt transition 142 melt transition calculation 204
melting 8 polymer mixture glass transition 166 polymer solution glass transition 165 segment reference 176 segment thermal conductivity 177 upper critical solution 11 Van Krevelen viscosity correlation 155 viscosity gradient 204 Thermal conductivity for crystalline state 173 for equipment design 6 for glassy state 173 for liquid state 173 for segments at 298K 177 mixture model 180 model applicability 172 model overview 171 model parameters 174 models available 17182 modified van Krevelen equation 173 pressure dependence 179 routes in Aspen Polymersl 181 segment reference (crystalline state) 178 segment reference (glassy state) 178 segment reference (liquid state) 178 segment reference temperature 176 specifying mixture model 180 specifying van Krevelen model 179 temperature dependence 179 Van Krevelen model 17379 Thermodynamic data for polymer systems 19 Thermodynamic properties See also Properties activity 6 calculated from activity coefficient models 90 calculated from EOS models 30 32 density 6
Index
enthalpy 6 enthalpy departure 31 entropy 6 entropy departure 31 excess molar liquid 90 excess molar liquid enthalpy 90 excess molar liquid entropy 91 fugacity 6 Gibbs free energy 6 Gibbs free energy departure 31 ideal gas 32 internal energy 6 molar volume 31 of polymers 526 Thermophysical properties See also Properties, See also Properties estimating 145 modeling 12 of polymers 12150 overview 121 Transport properties diffusivity 6 property models 13 surface tension 6 thermal conductivity 6 viscosity 6 TRAPP model 180 True solvent dilution effect 167 U UCST 11 UNIFAC See also Polymer UNIFAC polymer free volume model 117 19 polymer model 11417 UNIFAC free volume applicability 117 Upper critical solution temperature 11 V Van der Waals for fluid mixture 52 volume 203 Van Krevelen equation for thermal conductivity 173 functional group parameters 20514 functional groups 20214 glass transition temperature 141
group contribution 145 group contribution for polymers 156 liquid model 12735 liquid model parameters 131 liquid molar volume model 136 40 liquid molar volume model parameters 137 melt transition temperature 142 model for thermal conductivity 17379 polymer solution viscosity model 16167 solid model 143 solid model parameters 144 solid molar volume model parameters 145 viscosity-temperature correlation 155 Van Krevelen group contribution for segments (ideal gas) 126 for segments (liquid molar volume) 139 for segments (liquid) 134 for segments (thermal conductivity) 176 Vapor-liquid equilibrium 9, 30, 88 Vapor-liquid-liquid equilibrium 10 Viscoelasticity 8 Viscosity at mixture glass transition temperature 166 critical mass 156 estimating 164 Eyring-NRTL mixture model 167 Mark-Houwink/van Krevelen model 15258 model overview 151 models available 15170 models list 151 of mixtures 6 of polymer mixtures 167 of polymer solutions 158 of solutions 161 polymer melt 152 polymer mixture model 15861 polymer solution 16 polymer solution correlation 160 reduced 157 routes in Aspen Polymers 170 temperature gradient calculation 204
239
Van Krevelen polymer solution model 16167 Van Krevelen temperature correlation 155 zero-shear 16, 155 VLE 9, 30, 88 VLLE 10 Volatility 8 Volume fraction basis 95 Vredeveld mixing rule 180 W web site, technical support 3 Weight average mixing rule 162 molecular weight 153 Weight fraction crystalline 173 Williams-Landel-Ferry 155 Z Zero-shear viscosity estimation methods 16 of mixtures 158, 168 of polymers 155
Index

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Aspen Polymers

User Guide Volume 2: Physical Property Methods & Models

Version Number: V7.0 July 2008

Introducing Aspen Polymers

About This Documentation Set

Aspen Polymers Guides

Aspen Plus Guides

Aspen Physical Property System Guides

Aspen Dynamics Guides

Product updates and releases

1 Thermodynamic Properties of Polymer Systems

Properties of Interest in Process Simulation

Properties for Equilibria, Mass and Energy Balances

Properties for Detailed Equipment Design

Important Properties for Modeling

Transport properties Viscosity Thermal conductivity Surface tension Diffusivity

Differences Between Polymers and Non-polymers

Tm , and a melt above Tm .

Modeling Phase Equilibria in Polymer-Containing Mixtures

Vapor-Liquid Equilibria in Polymer Solutions

PIB-N-Pentane Binary System (Data from compilation of Wohlfarth, 1994)

Liquid-Liquid Equilibria in Polymer Solutions

LCST-UCST Behavior of Polymer Mixtures (Folie & Radosz, 1995)

Modeling Other Thermophysical Properties of Polymers

Available Property Models

Model Sanchez-Lacombe Polymer SRK SAFT PC-SAFT Copolymer PC-SAFT

Similarly, the liquid-liquid equilibrium condition is:

Liquid Activity Coefficient Models

Other Thermophysical Models

Available Property Methods

Property method POLYUF

POLYSAFT POLYPCSF PC-SAFT

Polymer SRK (POLYSRK)

Model (Property method) PC-SAFT (POLYPCSF) Copolymer PC-SAFT (PCSAFT)

Polymer SRK (POLYSRK)

Copolymer PC-SAFT (PCSAFT) Viscosity Aspen Polymer Mixture Viscosity Model

Properties Calculated Thermal Conductivity

Model (Property method) Aspen Polymer Mixture Thermal Conductivity Model

Used For Liquid thermal conductivity of polymer solutions and mixtures

Thermodynamic Data for Polymer Systems

Specifying Physical Properties

Selecting Physical Property Methods

Creating Customized Physical Property Methods

Entering Parameters for a Physical Property Model

Several subfolders appear. Click Parameters. The following folders appear:

Entering a Physical Property Parameter Estimation Method

Entering Molecular Structure for a Physical Property Estimation

General (default form) Functional group Formula

Entering Data for Physical Properties Parameter Optimization

About Equation-of-State Models

Phase Equilibria Calculated from EOS Models

f i v = f i l for vapor-liquid equilibria (1.1) f i l1 = f i l2 for liquid-liquid equilibria (1.2)

P , system pressure, calculated using an EOS model

pV , compressibility factor of the mixture nRT

, total mole number of the mixture

is obtained from the equation of

Vapor-Liquid Equilibria in Polymer Systems

Liquid-Liquid Equilibria in Polymer Systems

and also to vapor-liquid-liquid equilibria:

Other Thermodynamic Properties Calculated from EOS Models

Gibbs free energy departure:

Solve p (T ,Vm ) for Vm

RT , molar ideal gas volume p ref

H i,v H i,ig H i,l H i,ig S i,v S i,ig S i,l S i,ig

i,v i,ig i,l i,ig