AspenPolymersPropertiesV8 0 Usr

Aspen Polymers
Polymer Characterization and Physical Properties
Version Number: V8.0

December 2012
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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
Sanchez-Lacombe EOS Model Parameters ............................................... 40
Contents
iii
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
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
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
Specifying the Polymer UNIFAC- FV Model ............................................. 119
iv
Contents
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 ........................................................................ 140
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
Contents
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 ......................................................... 184
POLYNRTL: Polymer Non-Random Two-Liquid Property Method .......................... 186
POLYUF: Polymer UNIFAC Property Method ..................................................... 188
POLYUFV: Polymer UNIFAC Free Volume Property Method ................................. 190
PNRTL-IG: Polymer NRTL with Ideal Gas Law Property Method........................... 192
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 ....................................................................................................... 197
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 .....................................................................203
Calculating Segment Properties From Functional Groups ................................... 203
Heat Capacity (Liquid or Crystalline) ..................................................... 203
Molar Volume (Liquid, Crystalline, or Glassy) ......................................... 204
Enthalpy, Entropy and Gibbs Energy of Formation .................................. 204
Glass Transition Temperature .............................................................. 205
Melt Transition Temperature ................................................................ 205
Viscosity Temperature Gradient ........................................................... 205
Rao Wave Function............................................................................. 205
Van Krevelen Functional Group Parameters ..................................................... 206
Bifunctional Hydrocarbon Groups ......................................................... 206
Bifunctional Oxygen-containing Groups ................................................. 209
Bifunctional Nitrogen-containing Groups................................................ 211
Bifunctional Nitrogen- and Oxygen-containing Groups............................. 212
Bifunctional Sulfur-containing Groups ................................................... 213
Bifunctional Halogen-containing Groups ................................................ 213
vi
Contents
C Tait Model Coefficients ....................................................................................217

D Mass Based Property Parameters....................................................................219
E Equation-of-State Parameters .........................................................................221
Sanchez-Lacombe Unary Parameters .............................................................. 221
POLYSL Polymer Parameters................................................................ 221
POLYSL Monomer and Solvent Polymers................................................ 222
SAFT Unary Parameters ................................................................................ 224
POLYSAFT Parameters ........................................................................ 224
F Input Language Reference ..............................................................................227
Specifying Physical Property Inputs ................................................................ 227
Specifying Property Methods................................................................ 227
Specifying Property Data..................................................................... 229
Estimating Property Parameters ........................................................... 232
Index ..................................................................................................................233
Contents
vii
viii
Contents
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
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
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
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.
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
al., 1999; Chen & Mathias, 2002; Poling et al., 2001; Prausnitz et al., 1986;
1 Thermodynamic Properties of Polymer Systems
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
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:
Thermodynamic properties
Transport properties
Fugacity (or thermodynamic potential)
Viscosity
Gibbs free energy
Thermal conductivity
Internal energy, or
Enthalpy, or
CV
CP
Surface tension
Diffusivity
Entropy
Density
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).
10
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.
12
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
Calculates thermophysical properties of polymers using group

contribution
Tait Model
Calculates molar volume of polymers
Aspen Ideal Gas Property

Model
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
Transport property models

Modified Mark-Houwink/Van
Krevelen Model
Calculates viscosity of polymers
Aspen Polymer Mixture

Viscosity Model
Correlates liquid viscosity of polymer solutions and mixtures from

pure component liquid viscosity and mass fraction mixing rules
Van Krevelen Polymer

Solution Viscosity Model
Calculates liquid viscosity of polymer solutions
Eyring-NRTL Mixture
Viscosity Model
Correlates liquid viscosity of polymer solutions and mixtures from

pure component liquid viscosity and NRTL term to capture non-ideal
mixing behavior
Modified van Krevelen

Thermal Conductivity Model
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
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
Electrolyte-Polymer NRTL
Model
Integrates the electrolyte NRTL model and the polymer NRTL model.
It computes activity coefficients for polymers, solvents, and ionic
species
Flory-Huggins Model
Represents non-ideality of polymer systems. Based on the wellknown model developed by Flory and Huggins
Polymer UNIFAC and

Polymer UNIFAC-FV Models
Extends the UNIFAC group contribution method to polymer systems

taking into account polymer segments. They are predictive models
13
Model
Description
Equations of State
Sanchez-Lacombe
Tailors the well-known equation of state model, based on the lattice

theory, to polymer mixtures
Polymer SRK
Extends the SRK equation of state to cover polymer mixtures
SAFT
Provides a rigorous thermodynamic model for polymer systems

based on the perturbation theory of fluids
PC-SAFT
Provides an improved SAFT model based on perturbation theory
Copolymer PC-SAFT
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
(1.1)
Where:
f iv
= Fugacity of component i in the vapor phase
fil
= Fugacity of component i in the liquid phase
Similarly, the liquid-liquid equilibrium condition is:
f i l1 f i l 2
(1.2)
Where:
f i l1
= Fugacity of component i in the liquid phase 1
f i l2
= 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
14
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
15
transition and melting point temperatures. For molar volume, another

alternative is the Tait model (Danner & High, 1992).
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):
16
Property
method
Description
POLYFH
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.
POLYNRTL
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.
Property
method
Description
POLYUF
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.
POLYUFV
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.
PNRTL-IG
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.
POLYSL
Uses the Sanchez-Lacombe equation of state model for

thermodynamic property calculations.
POLYSRK
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.
POLYSAFT
Uses the statistical associating fluid theory (SAFT) equation of state

for thermodynamic property calculations.
POLYPCSF
Uses the perturbed-chain statistical associating fluid theory (PCSAFT) equation of state for thermodynamic property calculations.
PC-SAFT
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.
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
Model (Property
method)
Used For
Soave-Redlich-Kwong
All vapor properties: Fugacity

coefficient, enthalpy, entropy,
Gibbs free energy, density
Vapor
Departure
functions,
fugacity
coefficient, molar
volume
(All activity coefficient

property methods)
Sanchez-Lacombe (POLYSL)

Polymer SRK (POLYSRK)

SAFT
(POLYSAFT)

17
Properties
Calculated
Model (Property
method)
Used For
PC-SAFT
(POLYPCSF)
All vapor properties: fugacity

Copolymer PC-SAFT (PCSAFT)

Liquid
Vapor pressure
PLXANT
Antoine
Activity
Coefficient
Flory-Huggins (POLYFH)
Fugacity, Gibbs free energy,

enthalpy, entropy
Polymer NRTL (POLYNRTL)

enthalpy, entropy
Polymer UNIFAC (POLYUF)

enthalpy, entropy
UNIFAC free volume

(POLYUFV)

enthalpy, entropy
Watson for monomers, Van

Krevelen for polymers and
oligomers from segments
Enthalpy, entropy
Vaporization
enthalpy

property methods)

property methods)
Molar Volume
Rackett for monomers, Van

Krevelen for polymers and
oligomers from segments
Density
Tait molar model for

polymers and oligomers
property methods)
Departure
functions,
fugacity
coefficient, molar
volume
Viscosity
18
Sanchez-Lacombe (POLYSL)
All liquid properties: Fugacity

Polymer SRK (POLYSRK)

SAFT (POLYSAFT)

PC-SAFT (POLYPCSF)
All liquid properties: fugacity

Copolymer PC-SAFT (PCSAFT)
All liquid properties: fugacity


Viscosity Model
Liquid viscosity of polymer

solutions and mixture
Properties
Calculated
Model (Property
method)
Used For
Thermal
Conductivity

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.
19
To select a built-in property method for the entire flowsheet:

1
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:
1
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:
1
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:

1
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.
20
To enter pure model parameters:

1

Several subfolders appear.
Click Parameters.
The following folders appear:
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:
1
Click Pure Component.

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:

1
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:
1
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.
21
To use parameter estimation:

1

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
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:
1
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:
1

Click Molecular Structure.

22
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
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:
1
From the Data Browser, double-click Properties.
Click Data.
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
MIXTURE
PURE-COMP
Following is a description for pure component data entry. Similar steps are
required for mixture data entry.
6
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.
10 Click Next
to proceed.
References
Aspen Physical Property System Physical Property Methods and Models.
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23
Barton, A. F. M. (1990). CRC Handbook of Polymer-Liquid Interaction

Parameters and Solubility Parameters. Boca Raton, FL: CRC Press, Inc.
Behme, S., Sadowski, G., Song, Y., & Chen, C.-C. (2003). Multicomponent
Flash Algorithm for Mixtures Containing Polydisperse Polymers. AIChE J., 49,
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Bicerano J. (1993). Prediction of Polymer Properties. New York: Marcel
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Bokis, C. P., Orbey, H., & Chen, C.-C. (1999). Properly Model Polymer
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Brandup, J., Immergut, E. H., & Grulke, E. A. (Eds.) (1999). Polymer
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24
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25
Sandler, S. I. (1994). Models for Thermodynamic and Phase Equilibria

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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.
26
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.
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.
27
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.
28
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 l 2 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
(2.1)
f i l il xi p
(2.2)
With
ln i
1
RT
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
il
= Fugacity coefficient of component i in the liquid phase
yi
= Mole fraction of component i in the vapor phase
xi
= Mole fraction of component i in the liquid phase
= Vapor phase ( v ) or liquid phase ( l )
= Universal gas constant
= System temperature
= Total volume of the mixture
ni
= Mole number of component i
Zm
P , system pressure, calculated using an EOS model
pV
, compressibility factor of the mixture
nRT
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 i is obtained from the equation of

state, represented by 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:
il1 xil1 il2 xil2 (2.5)

and also to vapor-liquid-liquid equilibria:
iv y i il1 xil1 il2 x il2 (2.6)

Where:
il1 = Fugacity coefficient of component i in the liquid phase l1

il2 = Fugacity coefficient of component i in the liquid phase l 2
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:
30
Enthalpy departure:
V
RT
V
H mig p
dV RT ln ig
T Sm S
RT Z
(2.7)
m
Entropy departure:
ig
m
V p
R
V
S mig dV R ln ig
V
T v V
(2.8)
Gibbs free energy departure:
V
RT
V
G mig p
dV RT ln ig RT Z m 1
Molar volume:
Solve
(2.9)
p T ,Vm for Vm
Where:
Hm
= Molar enthalpy of the mixture
Sm
= Molar entropy of the mixture
Gm
= Molar Gibbs free energy of the mixture
Vm
= Molar volume of the mixture
H mig
= Molar ideal gas enthalpy of the mixture
S mig
= Molar ideal gas entropy of the mixture
Gmig
= Molar ideal gas Gibbs free energy of the mixture
V ig
p ref
= Reference pressure (1 atm)
RT
, molar ideal gas volume
p ref
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:
(2.10)
(2.11)
H H
S S (2.12)
H mv H mig H mv H mig
H ml H mig
S mv S mig
l
m
v
m
ig
m
ig
m
31

G
G
S ml S mig S ml S mig (2.13)

G mv G mig
G ml G mig
v
m
G mig
l
m
G mig
(2.14)
(2.15)
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:
H mig y i H i*,ig
in vapor phase
(2.16)
H mig xi H i*,ig
in liquid phase
(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:
32
Property
Name
Symbol
Description
PHIVMX
iv
Vapor fugacity coefficient of a component in a mixture
PHILMX
il
Liquid fugacity coefficient of a component in a mixture
HVMX
H mv
Vapor mixture molar enthalpy
HLMX
H ml
Liquid mixture molar enthalpy
SVMX
S mv
Vapor mixture molar entropy
SLMX
S ml
Liquid mixture molar entropy
Property
Name
Symbol
Description
GVMX
Gmv
Vapor mixture molar Gibbs free energy
GLMX
Gml
Liquid mixture molar Gibbs free energy
VVMX
Vmv
Vapor mixture molar volume
VLMX
Vml
Liquid mixture molar volume
PHIV
i*, v
Vapor pure component fugacity coefficient
PHIL
i*,l
Liquid pure component fugacity coefficient
HV
H i*,v
Vapor pure component enthalpy
HL
H i*,l
Liquid pure component enthalpy
SV
S i*,v
Vapor pure component entropy
SL
S i*,l
Liquid pure component entropy
GV
i*, v
Vapor pure component Gibbs free energy
GL
i*, l
Liquid pure component Gibbs free energy
VV
Vi *,v
Vapor pure component molar volume
VL
Vi *,l
Liquid pure component molar volume
DHVMX
H mv H mig
Vapor mixture molar enthalpy departure
DHLMX
H ml H mig
Liquid mixture molar enthalpy departure
DSVMX
S mv S mig
Vapor mixture molar entropy departure
DSLMX
S ml S mig
Liquid mixture molar entropy departure
DGVMX
Gmv Gmig
Vapor mixture molar Gibbs free energy departure
DGLMX
Gml Gmig
Liquid mixture molar Gibbs free energy departure
DHV
H i*, v H i*,ig
Vapor pure component molar enthalpy departure
DHL
H i*,l H i*,ig
Liquid pure component molar enthalpy departure
DSV
S i*,v S i*,ig
Vapor pure component molar entropy departure
DSL
S i*,l S i*,ig
Liquid pure component molar entropy departure
DGV
i*, v i*,ig
Vapor pure component molar Gibbs free energy departure
DGL
i*,l i*,ig
Liquid pure component molar Gibbs free energy departure
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
Model
Name
Phase(s)
Pure
Mixture
Properties Calculated
POLYSL
ESPLSL0
v and l
PHIV, PHIL, DHV, DHL, DSV,

DSL, DGV, DGL, VV, VL
ESPLSL
v and l
PHIVMX, PHILMX, DHVMX,

DHLMX, DSVMX, DSLMX,
DGVMX, DGLMX, VVMX, VLMX
ESPLRKS0
v and l

DSL, DGV, DGL, VV
ESPLRKS
v and l

DGVMX, DGLMX, VVMX
ESPLSFT0
v and l

ESPLSFT
v and l

ESPCSFT0
v and l

ESPCSFT
v and l

ESPSAFT0
v and l

ESPSAFT
v and l

POLYSRK
POLYSAFT
POLYPCSF
PC-SAFT
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:
34
N r N 0 mN
The total volume of the system is:
V N 0 mN v *
Where:
v*
= Volume of a lattice site
m = Number of segments per chain

Sanchez and Lacombe defined a reduced density as the fraction of occupied
lattice sites:
*
mN
~
N 0 mN
With
M
mv *
NM
V
Where:
* = Scale factor for density
= Mass density
M = Molecular weight (for polymer components this is the number average

molecular weight)
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
1
~ ~
~ 2 P T ln1 ~ 1 ~ 0
m
(2.18)
Where the reduced quantities are defined by:
~ T
T *
T
p
~
P *
P
~ *
(2.19)
35
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:
m = Number of segments per chain

*
= Characteristic interaction energy per segment
v*
= Closed-packed volume of a segment
= Boltzmann's constant
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
36
*
mix
1
v
*
mix
(2.21)
*
v mix
i j vij*
i
* *
ij ij
(2.22)
1
i (2.23)
mmix
i mi
wi
i* vi*
i
wj
j *v *
j j
(2.24)
Where:
= Volume fraction of component I
wi = Weight fraction of component i

The cross parameters are calculated by:
vij*
1 *
vii v *jj 1 ij
2
ij* ii* *jj 1 k ij
(2.25)
(2.26)
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
v *AB
Where:
and
= Volume fractions of the segments that form the copolymer

(calculated using an equation similar to the third Sanchez-
37
Lacombe mixing rule given by Equation 2.24)

Nseg
= Number of distinct segment types present in the copolymer

chain, and
v *AB
1 *
*
v AA v BB
(1 AB )
2
Where:
v *AA and v *BB = Characteristic volume parameters of the segments A and B
AB
= Factor that accounts for differences in molecular size
Similarly, for the energy parameter of the copolymer:
*p
1
v *p
Nseg Nseg
*
AB
v *AB
A B
With:
*
*AB *AA BB
(1 k AB )
Where:
*
=
*AA and BB
k AB
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.
38
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
ii* *AA (1 k iA )
Where:
ip*
= Cross energy parameter for a solvent-copolymer pair
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
*AA
= Energy parameter of segment type A in the copolymer, determined

from data on the homopolymer A
k iA
= Binary parameter for a solvent-segment pair, determined from VLE

or LLE data of the solvent (i)- homopolymer (A) solution
The cross energy parameter for a copolymer-copolymer pair in the mixture

*p1 p2 (1 k p1 p2 ) *p1 *p2

Where:
*p1 p2
= Cross energy parameter for a copolymer-copolymer pair
k p1 p2 = Binary parameter for a copolymer-copolymer pair
*p1
= Energy parameter of pure copolymer
p1
*p2
p2
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
Where:
Tref
= Reference temperature and the default value = 298.15 K
39
Similarly, the cross volume parameter for solvent-copolymer pairs and

copolymer-copolymer pairs can be calculated as:
vip*
Nseg
(vii* v *AA )(1 iA ) / 2
v *p1 p2 (1 p1 p2 )(v *p1 v *p2 ) / 2

Where:
vip*
= Cross volume parameter for a solvent-copolymer pair
v *AA
= Volume parameter of segment type A in the copolymer, determined

from data on the homopolymer A
iA
= Binary parameter for a solvent-segment pair, determined from VLE

or LLE data of the solvent (i)- homopolymer (A) solution
v *p1 p2 = Cross volume parameter for a copolymer-copolymer pair
p1 p2 = Binary parameter for a copolymer-copolymer pair

v *p1
= Volume parameter of pure copolymer
p1
v *p2
= Volume parameter of pure copolymer
p2
The binary interaction parameter,
ij , allows complex temperature
dependence:
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:
40
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
SLTSTR
T*
---
---
---
TEMP
Unary
SLPSTR
P*
---
---
---
PRESSURE
Unary
SLRSTR
---
---
---
DENSITY
Unary
SLKIJ/1
a ij
0.0
---
---
---
Binary,
Symmetric
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
SLKIJ/2
bij
0.0
---
---
---
Binary,
Symmetric
SLKIJ/3
c ij
0.0
---
---
---
Binary,
Symmetric
SLKIJ/4
d ij
0.0
---
---
---
Binary,
Symmetric
SLKIJ/5
e ij
0.0
---
---
---
Binary,
Symmetric
SLKIJ/6
Tref
298.15
---
---
TEMP
Binary,
Symmetric
SLETIJ/1
aij'
0.0
---
---
---
Binary,
Symmetric
SLETIJ/2
bij'
0.0
---
---
---
Binary,
Symmetric
SLETIJ/3
cij'
0.0
---
---
---
Binary,
Symmetric
SLETIJ/4
d ij'
0.0
---
---
---
Binary,
Symmetric
SLETIJ/5
eij'
0.0
---
---
---
Binary,
Symmetric
SLETIJ/6
Tref
0.0
---
---
TEMP
Binary,
Symmetric
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
41
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 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:
42
E
GE
G EOS
ln xi ln i x i ln i
RT
RT
i
i
Where:
E
= Excess Gibbs free energy from an EOS model
G EOS
= Mixture fugacity coefficient
= Fugacity coefficient of component i in a mixture
= Activity coefficient of component i in a mixture
GE
= 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
ai
= Cubic EOS parameter of component i
bi
= Cubic EOS parameter of component i
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:
RT
a (T )
v b v (v b )
Holderbaum and Gmehling Approach
43
GE
a
a
b
xi i 1546
.
xi ln
bRT
RTbi
bi
RT
i
i
For the co-volume parameter, b, the linear mixing rule
b xi bi was used.
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
GE
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
bi 0.08664
ai 0.42748
RTc ,i
p c ,i
R 2Tc2,i
p c ,i
i [1 c1 (1 Tr0,i.5 ) c2 (1 Tr0,i.5 ) 2 c3 (1 Tr0,i.5 ) 3 ] 2

Where:
Tc , i
= Critical temperature of component i
p c ,i
= Critical pressure of component i
Tr ,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 Tc and
p c for alkanes up to
about C20 (See works of Tsonopoulos & Tan, 1993; Teja et al., 1990). The
44
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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
TCRKS
Tc
TC
7000
---
TEMP
Unary
PCRKS
pc
PC
105
108
---
PRESSURE
Unary
RKSMCP/1
c1
---
---
---
Unary
RKSMCP/2
c2
---
---
---
---
Unary
RKSMCP/3
c3
---
---
---
---
Unary
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 Tc 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
46
GE
term in
the polymer SRK model. In this case, the mixture parameters of the selected
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
47
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)
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
N AV
md 3
6
of the fluid (segment packing fraction) is defined as:

(2.27)
Where:
= 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
(2.28)
With
v0
N AV 3
d
6
(2.29)
Where:
= Constant equal to 0.74048
v 0 = Segmental molar volume at closed-packing (the volume occupied by a

mole of closely packed segments), in units of cc per mole of
segments
0
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
oo
at T=0, denoted v . This parameter will be referred to as the segment

volume. Chen and Kreglewski (1977) solved the Barker-Henderson integral
48
equation of the diameter d (which depends on the square-well potential), and

proposed the following expression between
v o and v oo :
3u o
(2.30)
v v 1 C exp
kT
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
u u o 1
kT
(2.31)
Where:
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:
a res (T , V , N ) a(T , V , N ) a ideal (T , V , N )
(2.32)
Where:
49
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
a seg represents segment-segment interactions (hard-sphere repulsions
and attractive or dispersion forces)
a chain is due to the presence of covalent chain-forming bonds among the
segments
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
(2.33)
Segment contribution per mole of molecules

The segment contribution
a seg m a hs a disp
a seg per mole of molecules is given by:
(2.34)
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
(2.35)
Dispersion Term
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
50
a chain
1 m ln g (d ) seg
RT
(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
Where
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
segments are approximated by hard spheres, and thus,
g( d )seg can be
approximated by the hard-sphere radial distribution function (Carnahan &

Starling, 1972):
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
(2.39)
Compressibility Factor
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:
Pv
1 Z seg Z chain Z assoc
RT
(2.40)
Where:
i
j
4 2 2
u
Z seg m
jD
ij
3
kT
i
j
1
Z chain
5
2
2
1 m
1 1 1
2
The contribution from association,

and thus this term will be zero.
(2.41)
(2.42)
Z 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
51
uo / k
Segment energy,
Segment number, m
Estimated parameters for these fluids are given in Appendix E.
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
2 3
a hs
6 2 3 1 2 3 3 1 2 3
ln
1
0
3
2
RT
3 2
3 1 3
With
N Av
x i mi d ii k
6
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
3d
2
22
1
d ii
ii
2
2
3
1 3
2 1 3 2
1 3
2
hs
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:
52
Dispersion Energy Mixing Rule
v
kT
x x m m v
x x m m
i
kT
u ij
ij
ij
With
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,
uo / 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 , uo / 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
53
equation of state. However, the advantage of SAFT is the behavior of its

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
oo
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:
m
Mn
(2.43)
m 0.70402 0.046647 M n
(2.44)
mv oo 11.888 0.55187 M n
(2.45)
uo
210.0 26.886 exp 0.013341M n
k
(2.46)
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
v oo are cm3 / mole , and the units of

uo / k are in Kelvin. The last two equations given above suggest that as M n
components in a simulation. The units of
oo
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
54
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 CS 2 ;
40 for CO2 ; and 88 for SO2 .
oo
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
00
the segments are the segment ratio (r), the segment volume ( v ), and
segment energy ( u ). The binary parameter, k ij , can be regressed for
0
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.

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
00
p
Nseg
00
A A
u 0p
Nseg
u A0
Nseg
m p M n X A rA
A
Where:
v 00
p
= Average segment volume for the copolymer
u 0p
= 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

copolymer; the default is the segment mole fraction and the
segment weight fraction can be selected via Option Code in
Aspen Plus
v A00
= Segment volume for segment A, determined from data on the

homopolymer A
u A0
= Segment energy for segment A, determined from data on the

homopolymer A
rA
= Segment ratio parameter for segment A, determined from data on

the homopolymer A
Mn
= Number average molecular weight of the copolymer
If parameters
0
v 00
p , u p and m p are provided for the polymer or oligomer, then
known, usually in the case of copolymers, the user must provide
v A00 , u A0 and
rA for the segments that compose the copolymer.
Binary Parameters
u ip0
Nseg
u ii0 u 0AA (1 k iA )
Where:
uip0
u ii0
u i0 , energy parameter for pure solvent i
0
u AA
u A0
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 0p1 p2 (1 k p1 p2 ) u 0p1 u 0p2

Where:
56
u 0p1 p2
= Cross energy parameter for a copolymer-copolymer pair
k p1 p2
= Binary parameter for a copolymer-copolymer pair
u 0p1
p1
u 0p2
p2

dependence:

with
Tr
T
Tref
Where:
Tref

will be calculated.
SAFT EOS Model Parameters

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

Three unary parameters, SAFTR, SAFTU, and SAFTV can be:
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:
These options are shown in priority order. For example, if the binary
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
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.
58

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:
60
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
Decane - Ethane at 238C

PC-SAFT, kij=0
120
SAFT, kij=0
100
Raemer,Sage,1962
80
P (bar)
60
40
20
0
0.0
0.2
0.4
xEthane
0.6
Ethane-Decane VLE at 238 C. Predictions using
0.8
1.0
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
62
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
Nseg
Nseg
Nseg
m p M n X A rA
A
Where:
= Average segment diameter for the copolymer
= Average segment energy for the copolymer
mp
= Average segment number for the copolymer
Nseg = Number of distinct segment types present in the copolymer
XA

copolymer; the default is the segment mole fraction and the
segment weight fraction can be selected via Option Code in
Aspen Plus
63
= Segment diameter for segment A, determined from data on the

homopolymer A
= Segment energy for segment A, determined from data on the

homopolymer A
rA
= Segment ratio parameter for segment A, determined from data on

the homopolymer A
Mn
If parameters
p , p and m p are provided for the polymer or oligomer, then
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
ii AA (1 k iA )
Where:
ip
ii
i , energy parameter for pure solvent i
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

p1 p2 (1 k p1 p2 ) p1 p2
Where:
p1 p2 = Cross energy parameter for a copolymer-copolymer pair

k p1 p2 = Binary parameter for a copolymer-copolymer pair
64
p1
p1
p2
p2

dependence:

with
T
Tref
Tr
Where:
Tref

will be calculated.
PC-SAFT EOS Model Parameters

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

Three unary parameters, PCSFTR, PCSFTU, and PCSFTV can be:
65
These options are shown in priority order. For example, if property

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:
These options are shown in priority order. For example, if the binary
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
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.
Specifying the PC-SAFT EOS Model

66
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
where
hc
disp
assoc
polar
, and
(2.47)
polar are contributions due to hard-chain fluids,
dispersion, association, and polarity, respectively.

The generated function is defined as follows:
a res
d
( Z m 1)
RT 0
where a
(2.48)
is the molar residual Helmholtz energy of mixtures, R is the gas

constant, T is the temperature, is the molar density, and Z m is the
res
compressibility factor; a
res
is defined as:
a res a (T , , xi ,...) a ig (T , , xi ,...)
(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
ig
interest can be easily derived. For instance, the fugacity coefficient i is

calculated as follows:
67

ln i
xi
xj
x
j
T , , x j i
j
Z m 1 ln Z m
T , , xk j
(2.50)
with

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 mig RT T
( Z m 1)
T
(2.52)
Entropy departure:
S mig R T
ln Z m R ln ref
T
(2.53)
Gibbs free energy departure:
p
Gmig RT Z m 1 ln Z m RT ln ref
p
(2.54)
The following thermodynamic conditions must be satisfied:
p
Gmig RT xi ln i RT ln ref
i
p
G mig H m H mig T S m S mig
(2.55)
(2.56)
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
(2.57)
hs is the contribution from

chain
hard-sphere mixtures on a per-segment basis, and
is the contribution
where m is the mean segment in the mixture,
68
due to chain formation. Both m and
hs are well-defined for mixtures
containing polymers, including copolymers; they are given by the following

equations:
m x i mi
(2.58)
hs
31 2
23
23
ln(
1
0
3
2
2
(1 3 ) 3 (1 3 )
mi mi
(2.59)
(2.60)
xi mi z i d in ,
6 i
z i
n 0, 1, 2, 3
mi
mi
(2.62)

d i i 1 0.12 exp 3 i
kT
where
(2.61)
(2.63)
mi , i , and i , are the segment number, the segment diameter,
and the segment energy parameter of the segment type in the copolymer
component i , respectively. The segment number
mi is calculated from the
segment ratio parameter ri :
mi ri M i
(2.64)
M i is the total molecular weight of the segment type in the

copolymer component i and can be calculated from the segment weight
where
fraction within the copolymer:
M i wi M i
(2.65)
wi is the weight fraction of the segment type in the copolymer

component i , and M i is the molecular weight of the copolymer component i .
where
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 )
(2.66)
1 1
with

i ,i
(2.67)
69
hs
i , j
d i d j
1
(d i , j )
(1 3 ) d i d j
3 2
d i d j
2
(1 )
d d
j
3
2 22
(1 ) 3
3
(2.68)
where Bi ,i is defined as the bonding fraction between the segment type
within the copolymer component i , is the number

hs
of the segment types within the copolymer component i , and g i , j (d i , j ) is
and the segment type
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
(2.70)
m m m
(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
or
adjacent
sequences. Therefore:
B B B 0, B 1
(2.72)
hs
chain (m 1) ln g
(d )
(2.73)
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:
ma
m
(2.75)
The bonding fraction of each pair of types can be written as follows:
B Cz2 , B Cz 2 , B B Cz z
70
(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:
B z2 , B z 2 , 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 ... mr
m
; there are no
adjacent sequences for the same type of segments. Therefore,
m
, 1
(m 1)
(2.80)
m
, 1,
(m 1)
(2.81)
B 0, 1
(2.82)
B 0,
(2.83)
B B , 1 B1,
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:
m 1
, 1,2,...
m 1
(2.85)
1
, 1
m 1
(2.86)
B 0, 1
(2.87)
71
B 0,
(2.88)
B B B , 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
in the copolymer. The

probability of finding a segment of type is the fraction of segments z
a segment of type
and a segment of type
in the copolymer:
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,
C z z 1
(2.92)
1 1
That is,
Put
(2.93)
z z
C into Equation 2.91, we obtain:
z z
z z
, , 1,2,...
(2.94)
Dispersion term
The equations for the dispersion term are given as follows:
disp 2I 1 X m C1 I 2Y
72
(2.95)
i , j
X xi x j mi m j z i z j
ij
kT
3
i , j
i , j
Y xi x j mi m j z i z j
ij
kT
3
i , j
(2.96)
(2.97)
I 1 ( , m ) al (m ) l 1
(2.98)
l 1
7
I 2 ( , m ) bl (m ) l 1
(2.99)
l 1
Z hc
C1 1 Z hc
2 (4 )
(20 27 12 2 )
1 m
(1 m )
4
(1 )
(1 )(2 )2
(2.100)
a l a1l
m 1
m 1 m 2
a 2l
a 3l
m
m m
(2.101)
bl b1l
m 1
m 1 m 2
b2 l
b 3l
m
m m
(2.102)
3
where
(2.103)
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
1
( i j )
2
(2.104)
i , j (1 i , j )( i j )1 / 2
(2.105)
In above equations, the model constants
a1l , a 2l , a3l , 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
i
Ai
X Ai 1
ln X Ai

2
2
(2.106)
A
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
1
1 x j N Bi X
B j
(2.107)
Ai B j
with
Ai B j
(d i , j )
hs
i , j
Ai B j
3
i , j
Ai B j
exp
kT
(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
A B
Ai B j
Ai B j
( AB ) i
( AB )i
( AB ) j
i j
( i j ) / 2
(2.109)
( AB ) j
(2.110)
i
i
where
and
are the effective association volume and the
association energy between the association-site types A and B , of the
segment type in the copolymer component i , respectively.
( AB)
( AB )
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 ,
N Ai N i
M i wi M i
M
M
in the
in the
(2.111)
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
where
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:
X Ai 1
assoc xi N i ln X Ai

2
2
i
A
X Ai
1
1 x j N j X
B j
Ai B j
(2.112)
(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
74
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 Ai X Bi ) ( X Ai X Bi ) 1
2
X Ai
1
1 x j N j X
j
X Bi
B j
A j
Ai B j
(2.115)
1
1 x j N j X
j
(2.114)
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)
X Ai 1
assoc 2 xi N i ln X Ai

2
2
i
(2.119)
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
i2 2j
2 I 2 ( )
2
z i z j ( x p ) i ( x p ) j 3
x i x j mi m j
9 (kT ) 2 ij
d i , j
(2.121)
(2.122)
i2 2j k2
5 2 2 I 3 ( )
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 d d d
162 (kT ) 3 ijk
i , j j , k i , k
(2.123)
d i , j ( d i d j ) / 2
(2.124)
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 i , respectively. Both
2
i
/ kTd
3
i , j
2
i
/ kT and
are dimensionless. In terms of them, we can have:
2
2
2
I 2 x i x j mi m j z i z j ( x p ) i ( x p ) j i
9
ij
kT
2
j
kTd i , j
(2.125)
5 2
I 3 x i x j x k mi m j m k z i z j z k ( x p ) i ( x p ) j ( x p ) k
162 ijk
2
i
kT
2
j
kT
k2
kTd i , j d j ,k d i ,k
(2.126)
Rushbrooke et al. (1973) have shown that

2
1 0.3618 * 0.3205 * 0.1078 *

I 2 ( )
(1 0.5236 * ) 2
I 3 ( * )
1 0.62378 * 0.11658 *
1 0.59056 * 0.20059 *
(2.127)
(2.128)
In terms of
(2.129)
, I 2 ( ) and I 3 ( ) are computed by the expressions:
1 0.69099 1.16904 2 0.75097 3

I 2 ( )
(1 ) 2
I 3 ( )
(2.130)
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
effective association volume
and the association energy
polar species, two additional parameters are the dipole moment
( AB )
( AB )
. For a
and the
segment dipolar fraction x p .
76
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
(2.132)
with
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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
PCSFTM
Unary
Unary
PCSFTU
/k
TEMP
Unary
PCSFTR
Unary
PCSFAU
AB / k
TEMP
Unary
PCSFAV
AB
Unary
---
---
---
DIPOLE
MOMENT
Unary
PCSFXP
xp
---
---
---
---
Unary
PCSKIJ/1
ai , j
0.0
Binary,
Symmetric
PCSKIJ/2
bi , j
0.0
Binary,
Symmetric
PCSKIJ/3
ci , j
0.0
Binary,
Symmetric
PCSKIJ/4
d i , j
0.0
Binary,
Symmetric
PCSKIJ/5
e i , j
0.0
Binary,
Symmetric
PCSKIJ/6
Tref
298.15
TEMP
Binary,
Symmetric
PCSFTV
PCSFMU
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.
78
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
Temperature (C)
UCST
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).
80
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
Pressure bar
60
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
82
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86
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.
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.
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 x i i f i *,l
Where:
f il
Fugacity of component i in the liquid phase
xi
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
f i *,l
In the equation above, the activity coefficient,
i , represents the deviation of
the mixture from ideality, and the liquid phase reference fugacity, f i
*, l
, 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
88
(3.1)
iv , is computed from an equation of

state (see Chapter 2).The liquid activity coefficient, i , is computed from an
The vapor phase fugacity coefficient,
activity coefficient model.
Liquid Phase Reference Fugacity
The liquid phase reference fugacity, f i
f i *,l i*,v p i*,l i*,l
*, l
, is generally expressed as:
(3.2)
With
1
i*,l exp
RT
pi*,l
Vi*,l dp
(3.3)
Where:
i*,v
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
pi*,l
Liquid vapor pressures of component i at the system temperature
i*,l
Poynting correction of component i for pressure
Vi *,l
Liquid molar volume of component i at T and p
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*,l , becomes H i (the
Henry's constant for component i in the mixture).

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
equilibrium relationship for dissolved gases becomes:
iv y i p xi i* H i
(3.5)
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 (3.7)

Where:
il1 = Activity coefficient of component i in the liquid phase l1

il2 = Activity coefficient of component i in the liquid phase l 2
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:
GmE ,l RT xi ln i
(3.8)
90
Excess molar liquid enthalpy:
H mE ,l RT 2 xi
i
ln i
T
(3.9)
Excess molar liquid entropy:
ln i
S mE ,l R xi ln i T
T (3.10)
i
Where:
G mE ,l =
Excess molar liquid Gibbs free energy of the mixture
H mE ,l =
Excess molar liquid enthalpy of the mixture
S mE ,l
Excess molar liquid entropy of the mixture
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:
1 (nGmE ,l )
RT ni T , p ,n
j i
ln i
(3.11)
With
id
nGmE ,l Gmixing Gmixing
id
Gmixing
ni ln xi
i
(3.12)
(3.13)
Where:
= Total mole number of the mixture
ni
= Mole number of component i in the mixture
G mixing
= 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
id
Gmixing
= Ideal Gibbs free energy of mixing
Once the excess liquid functions are known, the thermodynamic properties of
liquid mixtures can be computed as follows:
H ml xi H i*,l H mE ,l
(3.14)
Gml xi i*,l GmE ,l RT xi ln xi

i
S ml
1
H ml G ml
T
(3.15)
(3.16)
91
Where:
H ml
G ml
S ml
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
i*, l for polymers, oligomers, and segments. For more information, see
and
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:
Vml Vms x pV p*,l

p
With
Vms Rackett ( x s' , T , p )
x s' x s / x s
s
x x
s
Where:
92
Vml
Liquid mixture molar volume
Vms
Liquid polymer-free mixture molar volume
V p*,l
Liquid molar volume of a polymer or oligomer component in the

mixture
xp
Liquid mole fraction of a polymer or oligomer component in the

mixture
xs
Liquid mole fraction of a solvent component in the mixture
x s'
Liquid mole fraction of a solvent component in the polymer-free

mixture
The liquid polymer-free mixture molar volume, Vm , is calculated using the

s
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*,l , is calculated using either the van Krevelen
model or the Tait model. For more information, see Chapter 4.
Related Physical Properties in

Aspen Polymers
The following properties are related to activity coefficient models in Aspen
Polymers:
Property Symbol
Name
Description
GAMMA
Liquid activity coefficient of a component in a mixture
HLMX
H ml
SLMX
S ml
GLMX
Gml
HLXS
H mE ,l
Liquid mixture molar excess enthalpy
GLXS
G mE ,l
Liquid mixture molar excess Gibbs free energy
SLXS
S mE ,l
Liquid mixture molar excess entropy
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.
93
Models
Model
Name
Phase(s)
Pure
Mixture
Properties Calculated
Flory-Huggins
GMFH
GAMMA, HLXS, GLXS, SLXS
Polymer NRTL
GMNRTLP
ElectrolytePolymer NRTL
GMEPNRTL
Polymer UNIFAC
GMPOLUF
Polymer UNIFAC
Free Volume
GMUFFV
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
94
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
(3.17)
With:
n1
n1 mn2 (3.18)
mn2
n1 mn2
(3.19)
Where:
12
= Molecular interaction parameter
= Number of segments in the polymer molecule
n1
= Number of moles of solvent in the mixture
n2
= Number of polymer molecules in the mixture
1 , 2
= Mole fractions on a segment basis
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.
95
Multicomponent Mixtures
The derivation of Flory and Huggins has been extended to cover multiple
components (Tompa, 1956):
Gmixing
= i ln i + ij i j ni mi
j i
i mi
i
RT
(3.20)
From this equation, one can derive the activity coefficient of a component (for
example, Equation 3.11):
ln i ln
i
1 mi
xi
j
ij
jk j k
mj
k j
(3.21)
Where:
xi
Mole fraction of component I
ij
Interaction binary parameter
In the above equations, note that
i 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
(3.22)
Where:
=
Pi
si and i =
Degree of polymerization
Empirical parameters
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
mixing. It is strongly temperature dependent:
ij aij bij / Tr cij ln Tr d ij Tr eij Tr2
(3.23)
with
Tr
96
T
Tref
Where:
= Reference temperature and the default value = 1 K for
compatibility with previous releases.
Tref
A summary of equations for the three options for concentration basis of the
Flory-Huggins model is given here :
Option
Description
Mass Basis:
wi
Concentration
= Mass fraction
Mi
= Number average molecular
weight for polymer/oligomer;

molecular weight for conventional
component
2
= Number of moles
Pi
= Number average chain length
ni M i
wi
njM j
mi s i * Pi i
ni Pi
n j Pj
mi s i * Pi i
Segment mole fraction basis:
ni
Characteristic
Size
Volume basis:
3
Vi
= Molar volume ( m
/ kmol )
vi
= Specific volume ( m
wi
= Mass fraction
/ kg )
niVi
n jV j
j
Note that for monomers and solvents,

user.
si
and
wi vi
wjv j
Pi POLDP 1.0
mi s i * Pi i
unless changed by the
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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
FHCHI/1
a ij
0.0
-100
100
---
Binary,
Symmetric
FHCHI/2
bij
0.0
-1E6
1E6
---
Binary,
Symmetric
FHCHI/3
cij
0.0
-1E6
1E6
---
Binary,
Symmetric
FHCHI/4
d ij
0.0
-1E6
1E6
---
Binary,
Symmetric
97
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
FHCHI/5
eij
0.0
-1E6
1E6
---
Binary,
Symmetric
FHCHI/6
Tref
1.0
-1E6
1E6
TEMP
Binary,
Symmetric
FHSIZE/1
si
1.0
1E-15
1E15
---
Unary
FHSIZE/2
1.0
-1E10
1E10
---
Unary
POLDP*
Pi
1.0
1.0
1E10
---
---
Unary
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
98
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
x G
n
x G
j
js
RT
js
js
x G
n r
x G
j
ji
ji
i ,p
ji
nI ln I
I
With:
X r
X r
I i,I
xi
J j,J
XI
nI
nJ
J
G ji exp( ji ji )
99
ji
I
( g ji g ii )
RT
nI mI
nJ mJ
J
Where:
I and J =
Component based indices
i and j =
Segment based indices
Solvent component
Polymer component
ns
Number of mole of solvent component s
np
Number of mole of polymer component p
xi
Segment based mole fraction for segment based species i
XI
Mole fraction of component I in component basis
ri , I
Number of segment type i in component I
ji
NRTL non-random factor
ji
Interaction parameter
g ji
Energies of interaction between j-i pairs of segment based species
gii
Energies of interaction between i-i pairs of segment based species
nI
Number of moles of component I
Volume fraction (approximated as segment mole fraction) of

component I
mI
Ratio of polymer molar volume to segment molar volume of

component I
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:
nGmE ,l
ns
RT
s
x G
x G
j
js
js
ji
ji
js
nI ln I
I
XI
x G
n r
x G
i, p
ji
The activity coefficient of each component in the polymer solution can also be
considered as the sum of two contributions:
100
ln I ln INRTL ln IFH
With:
ln IFH ln I
XI
1 m I 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
s J and J =
Empirical parameters
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
x G
x G
j
ln
NRTL
I s
js
ks
js
k xk Gkj kj
x j Gsj
sj
xk Gkj
j xk Gkj
k
k
Polymer Activity Coefficient

ln
NRTL
Ip
x j G ji ji
k xk Gkj kj
x j Gij
j
ri , p
ij
xk Gki
xk Gkj
i
j 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
p becomes unity as X p 1
(i.e.,
pure polymer); it can be easily done as follows:
ln
NRTL
Ip
x j G ji ji
k xk Gkj kj
x j Gij
j
ri , p
ij
xk Gki
xk Gkj
i
j xk Gkj
k
k
k
x j , p G ji ji
k xk , pGkj kj
x j , pGij
j
ri , p
ij
xk , pGki
xk , pGkj
i
j xk , p Gkj
k
k
k
101
With
xi , p
ri , p
j, p
Where:
= Segment mole fraction of type i in polymer component p
xi , 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 GIJ
Where:
IJ
Solvent-polymer Flory-Huggins binary interaction parameter
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 /
102
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
Element
NRTL/1
a ij
---
---
---
Binary,
Asymmetric
NRTL/2
bij
---
---
TEMP
Binary,
Asymmetric
NRTL/3
cij
0.3
---
---
---
Binary,
Symmetric
NRTL/4
dij
---
---
1/TEMP
Binary,
Symmetric
NRTL/5
eij
---
---
---
Binary,
Asymmetric
NRTL/6
f ij
---
---
1/TEMP
Binary,
Asymmetric
NRTL/7
T min
---
---
TEMP
Unary
NRTL/8
T max
si
1000
---
---
TEMP
Unary
1.0
1E-15
1E15
---
Unary
FHSIZE/2
1.0
-1E10
1E10
---
Unary
POLDP
Pi
1.0
1.0
1E10
---
---
Unary
FHSIZE/1
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

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
103
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.
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:
104
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
Gm* E ,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
* m
= Molality scale mean ionic coefficient
= Cationic stoichiometric coefficient
= Anionic stoichiometric coefficient
MB
= Molecular weight of the solvent B
= 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

RT
MB
4 A I x
1
ln 1 I x 2
With
105
2N A d
A 1 3
1000
Ix
Qe2
w kT
x z
2
i i
Where:
= Debye-Hckel parameter
Ix
= Ionic strength (mole fraction scale)
= "Closest approach" parameter
NA
= Avogadro's number
= Density of solvent
Qe
= Electron charge
= Dielectric constant of water
= Temperature
= Boltzmann constant
xi
= Segment-based mole fraction of component i (i can be a monomeric

species or a segment)
zi
= 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:
2
2 z 2
1000
z 2 I 2 2I x 2
1
A i ln 1 I x 2 i x

1
1 I x 2

MB
1
ln
*PDH
i
For oligomeric ions, we sum up the contributions from various ionic segments
of species I:
ln I*PDH
c, I
ln c*PDH
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
106
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:
xi z i2
2
Qe2 1 1
g *ex, Born
i
10
RT
2kT w ri
Where:
= Mixed-solvent dielectric constant
ri
= Born radius
Born Term Activity Coefficient

The expression for the activity coefficient can be derived from the Born term:
ln i*Born
Qe2 1 1 z i2 2
10
2kT w ri
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 X
ji
and
X ii of species j and i, respectively,
in the neighborhood of i are related by:
X ji
X ii
Xj

Xi
G ji
With
X j x jC j
G ji exp( ji ji )
ji
( g ji g ii )
RT
Where:
Cj
ji
= NRTL non-random factor
z j for ions and unity for molecules
107
ji
= Interaction parameter
g ji
= Energies of interaction between j-i pairs of segment based species
gii
= Energies of interaction between i-i pairs of segment based species
g ji and g ii are energies of interaction between species j and i, and i and i,
ij are inherently symmetric ( g ji g ij and
respectively. Both g ij and
ji ij ).
Similarly,
X ji
X ki
Xj

Xk
G ji , ki
With
G ji ,ki e
ji ,ki
ji , ki ji , ki
g ji g ki
RT
Where:
ji,ki = Nonrandomness factor

Local Composition Term
The local composition term for multicomponent systems is:
ex ,lc
g mix
rm , I X m
RT
I
m
rc , I X c Ya
c
G jm jm
X
k
Gkm
X
j
G jc ,ac jc ,ac
Gkc ,ac
ra , I X a Yc
I
X
j
G ja ,ca ja ,ca
Gka ,ca
With
Ya
Xa
X a'
a'
108
Yc
Xc
X c'
c'
cm Ya m ,ca
a
am Yc m ,ca
c
Gcm Ya Gca ,m
a
G am Yc Gca ,m
c
cm
ln(Gcm )
cm
am
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
G mc ,ac exp( mc ,ac mc ,ac ) exp( cm mc ,ac )

G ma ,ca exp( ma ,ca ma ,ca ) exp( am ma ,ca )
Where:
j & k = Any species
rm, I
= Number of molecular segments in species I
rc , I
= Number of cationic segments in species I
ra , I
= Number of anionic segments in species 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.
109
ln
lc
m
G jm jm
Gkm
k X k Gkm' km'
X m ' Gmm '
mm '
X k Gkm '
m ' X k G km '
k
k
k X k Gkc,ac kc,ac
X c Gmc ,ac
Ya
mc ,ac
c
a
k X k Gkc,ac
k X k Gkc,ac
k X k Gka,ca ka,ca
X a Gma ,ca
Yc
mc ,ca
a
c
k X k Gka,ca
k X k Gka,ca
1
ln clc Ya
zc
a
X G
X G
k
kc , ac kc , ac
kc , ac
k X k Gkm kB
X m Gcm
cm
X k Gkm
m X k G km
k
k
k X k Gka,ca ka,ca
X a Gca ,ca
Yc '
ca ,ca
a c
k X k Gka,ca
k X k Gka,ca
1
ln alc Yc
za
c
X G
X G
k
ka ,ca ka ,ca
ka ,ca
k X k Gkm km
X m Gam
am
X k Gkm
m X k G km
k
k
k X k Gkc,ac kc,ac
X c Gac ,ac
Ya '
ac ,ac
c a
k X k Gkc,ac
k X k Gkc,ac
110
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:
ln Ilc rc , I ln clc ra , I ln alc rm, I ln mlc

c
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 *I lc ln lcI ln I lc
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
RT
I
x I I
ln IFH ln I
xI
1 m I J
J mJ
with
m I rm , I rc , I ra , I
m
x I mI
xJ mJ
J
Flory-Huggins Term Activity Coefficient

The unsymmetric activity coefficients from the Flory-Huggins term are:
ln I FH ln m I 1 m I
ln *I FH ln FH
ln I FH
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
111
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:
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
Electrolyte-Molecule Pair Parameters:
ca , B Cca , B
Dca ,B
(T ref T )
T
Eca , B
ln ref
T
T
T
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
ca ' ,ca ' ' Cca ' ,ca ' '
(T ref T )
T
E ca ,c 'a
ln ref
T
T
Dca ' ,ca ' '

T
(T ref T )
T
Eca ' ,ca ' '
ln ref
T
T
Where:
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
AB
---
---
---
---
Unary
CPDIEC/2
BB
0.0
---
---
---
Unary
CPDIEC/3
CB
298.15
---
---
Kelvin (no
conversion)
Unary
Ionic Born Radius Parameters
112
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
RADIUS
ri
---
1E-11
1E-9
---
LENGTH
Unary
Molecule-Molecule Binary Parameters

NRTL/1
ABB'
---
---
---
Binary,
Asymmetric
NRTL/2
BBB'
---
---
TEMP
Binary,
Asymmetric
NRTL/3
BB'
0.3
---
---
---
Binary,
Symmetric
NRTL/4
---
---
---
---
---
---
---
NRTL/5
FBB'
---
---
---
Binary,
Asymmetric
NRTL/6
G BB '
---
---
1/TEMP
Binary,
Asymmetric
NRTL/7
T min
---
---
TEMP
Unary
NRTL/8
T max
1000
---
---
TEMP
Unary
Electrolyte-Molecule Pair Parameters **

GMELCC
C ca , B
0.0
-100
100
---
Binary,
Asymmetric
GMELCD
Dca ,B
0.0
-3E4
3E4
TEMP
Binary,
Asymmetric
GMELCE
E ca , B
0.0
-100
100
---
Binary,
Asymmetric
GMELCN
ca, B
0.2
0.01
---
Binary,
Symmetric
Electrolyte-Electrolyte Pair Parameters

GMELCC
GMELCD
GMELCE
GMELCN
C ca ,ca '
0.0
-100
100
---
Binary,
Asymmetric
C ca ,c 'a
0.0
-100
100
---
Binary,
Asymmetric
Dca ' ,ca ' '
0.0
-3E4
3E4
TEMP
Binary,
Asymmetric
Dc 'a , c ' 'a
0.0
-3E4
3E4
TEMP
Binary,
Asymmetric
Eca ' ,ca ' '
0.0
-100
100
---
Binary,
Asymmetric
Ec 'a , c ' 'a
0.0
-100
100
---
Binary,
Asymmetric
ca ',ca ''
0.2
0.01
---
Binary,
Symmetric
c 'a ,c ''a
0.2
0.01
---
Binary,
Symmetric
If dielectric constant parameters are missing for a solvent, the dielectric constant
113
of water is automatically assigned.

**
If an electrolyte-molecule parameter is missing, the following defaults are used:

Electrolytewater
-4
Waterelectrolyte
Electrolytesolvent
-2
Solventelectrolyte
10
Electrolytesolute
-2
Soluteelectrolyte
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
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
114
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
z
1 i ln i 1 i
xi
xi 2 i
i
Where the molecular volume and surface fractions are:
z
qi
i nc
and i nc 2
z
j x j r j
j x j 2 q j
xi
xi ri
With:
nc = Number of components in the mixture
The coordination number z is set to 10.
The parameters ri and q i are calculated from the group volume and area
parameters:
ng
ng
ri ki Rk and q i ki Qk
Where:
ki =
Number of groups of type k in molecule i
ng
Number of groups in the mixture
The residual term is:

ng
ln iR ki ln k ln ki
Where:
ln k = Activity coefficient of a group at mixture composition
ki
= Activity coefficient of group k in a mixture of groups corresponding
115
to pure i
The parameters k and ki are defined by:
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 Qm
2
m
Xk
And:
mn e bmn / T
The parameter X k is the group mole fraction of group k in the liquid:
nc
Xk
116
kj
xj
j
nc
ng
mj
xj
Polymer UNIFAC Model Parameters

The input parameters for the Polymer UNIFAC model are given here:
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
UFGRP
v ki , v mi , ...
---
---
---
---
Unary
GMUFQ
Qk
---
---
---
---
Unary
GMUFR
Rk
---
---
---
---
Unary
GMUFB
bkn
---
---
---
---
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
117
is usually not significant for small molecules, it could be important for

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
z
1 i ln i 1 i
xi
xi 2 i
i
ng
ln iR ki ln k ln ki
Free-Volume Contribution
ln iFV
~ 13
1
V~
Vi 1
~ 13
i
3C i ln 1
Ci ~ 11 Vi
~3

V m
~
Vi
Vi
0.01517bri
~
Vm
V x
0.01517b r x
i
Where:
Ci
= 1.1
= 1.28
ri
= Volume parameter for component i
Vi
= Specific volume of component i, cubic meters per kilogram mole,

calculated from Rackett equation for solvents and from Tait equation
for polymers.
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,
118
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
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
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.
120
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.
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
4 Thermophysical Properties of Polymers
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
Symbol
Description
HL
H i*,l
GL
i*, l
SL
S i*,l
Liquid pure component entropy
VL
Vi *,l
Liquid pure component molar volume
TGVG
Tg
Glass Transition temperature
TMVG
Tm
Melt Transition temperature
HS
H i*, s
Solid pure component enthalpy
GS
i*, s
Solid pure component Gibbs free energy
VS
Vi *, s
Solid pure component molar volume
SS
S i*, s
Solid pure component entropy
Property Models
Model Name
Aspen Ideal Gas Property Model
122
Properties
Calculated
HIG, GIG,
CPIG
Van Krevelen/DIPPR Model
HL0DVK,
HL0DVKD
HL
Van Krevelen/DIPPR Model
GL0DVK
GL
Van Krevelen/Rackett Model
VL0DVK
VL
Tait/Rackett Model
VL0TAIT
VL
Van Krevelen Model
TG0DVK
TGVK
Van Krevelen Model
TM0DVK
TMVK
Van Krevelen/Standard Model
HS0DVK
HS
Van Krevelen/Standard Model
GS0DVK
GS
Van Krevelen/Rackett Model
VS0DVK
VS
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 T g 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
1
( H i*,l i*,l )
T
S i*, s
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
*,ig
= Ideal gas molar Gibbs free energy of polymers
H *,l H *,ig
= Polymer molar enthalpy departure, calculated from an

equation-of-state model
*,l *,ig
= Polymer molar Gibbs free energy departure, calculated from

an equation-of-state model
Both departure functions,
H *,l H *,ig and *,l *,ig , are calculated from the
same equation of state.
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
Cp
*,ig
dT
T ref
Where:
= Reference temperature (298.15 K)
T ref
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:
*,ig
(T )
T
*,ig
(T
ref
Cp
T
*,ig
T ref
dT T
T ref
Cp *,ig
dT
T
(T T ref ) S *,ig (T ref )

With
S *,ig (T ref )
H *,ig (T ref ) *,ig (T ref )

T ref
Where:
*,ig (T ref ) = Gibbs free energy of formation of the polymer at the ideal-gas
ref
state and T
124
= Entropy of formation of the polymer at the ideal-gas state
S *,ig (T ref )
and
T ref
In the ideal gas model, the quantities
H *,ig (T ref ) and *,ig (T ref ) 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 *,ig , is temperature-dependent and is implemented as
polynomial expressions:
Cp *,ig (T ) C1 C 2T C3T 2 C 4T 3 C5T 4 C 6T 5

C 7 T C8
or
Cp *,ig (T ) C 9 C10T C11
T C7
or
Cp*,ig (T )
C8 for T C8
Linearly extrapolated using slope at
Aspen Ideal Gas Model Parameters

The following table lists the parameters used in the ideal gas model:
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units Keyword
CPIG/1
C1
---
---
---
MOLE-HEAT-CAPACITY
CPIG/2,, 6
C 2 ,...,C 6
0.0
---
---
MOLE-HEATCAPACITY, TEMP
CPIG/7
C7
---
---
TEMP
CPIG/8
C8
1000
---
---
TEMP
CPIG/9
C9
---
---
---
MOLE-HEAT-CAPACITY
CPIG/10, 11
C10 ,C11
---
---
---
DHFVK
H *,ig T ref
---
5 1010
51010
---
MOLE-ENTHALPY
DGFVK
*,ig
---
5 1010
51010
---
MOLE-ENTHALPY
---
T ref
298.15
---
---
---
Kelvin

T
ref
Parameter Input
All three unary parameters, CPIG, DHFVK, and DGFVK can be:
Specified for each polymer or oligomer component; or
125
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
H *,A ig (T ref )
*,ig (T ref )
Nseg
*,A ig (T ref )
Cp *,ig (T )
Nseg
Cp *,A ig (T )
Where:
Nseg
Number of segment types in the copolymer
XA
Mole segment fraction of segment type A in the copolymer
T ref
Reference temperature (298.15 K)
H *,A ig (T ref ) = Ideal-gas enthalpy of formation of segment type A at T ref
*,A ig (T ref )
Cp *,A ig (T )
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 ) n k H k*,ig (T ref )

k
*,A ig (T ref ) n k k*,ig (T ref )

k
Where:
nk
126
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
k*,ig (T ref )
Ideal-gas Gibbs free energy of formation of functional group

k at
T ref , 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.
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
Gas
Ideal
as
Real G
DHFORM
DHFVK
Hi*,v(T)
H i*,ig T ref
vap H i* T
Enthalpy
sub H i* T ref
con H i* T ref
DHSUB
Liquid
s
Amorphou
Solid
H i*,l T ref
*, c
i
Hi*,l(T)
DHCON
SemiCrystalline
Solid
T
ref
H i*,l T melt
fus H i* T melt
H i*,c T melt
Crystalline
Solid
Tref
Tmelt
Temperature
The key variables are:

T
T
H i*,ig T ref
= Ideal gas heat of formation (DHFORM, DHFVK)
H i*,l
ref
= Liquid phase reference enthalpy
ref
= Crystal phase reference enthalpy
H i*,c
dep H i*,v
128
= Vapor phase enthalpy departure (DHV)
= Enthalpy of condensation (DHCON)

T = Enthalpy of sublimation (DHSUB)
T = Heat of fusion at the melting point
con H i* T ref
sub H i*
fus H i*
ref
melt
vap H i* T
= Heat of vaporization (DHVL)
H i*,v T
= Vapor-phase enthalpy (HV)
H i*,l T
= Liquid-phase enthalpy (HL)
H i*,l T melt
H i*,c T melt
= Enthalpy of amorphous solid phase or liquid phase at the

melting point
= Enthalpy of pure crystalline polymer at the melting point
T melt
= Melt transition temperature (TMVK)
T ref
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:
for
T Tm
H *, c x c H *,l (1 x c )
for
Tg T Tm
H *,c
for
T Tg
HL H *,l
With:
T Cp
T
*,l
*,l
ref
*,l
dT
T ref
H *,l (T ref ) H *,ig T ref con H * T ref
Cp
T
H *,c H *,c T ref
*,c
dT
ref
H *,c (T ref ) H *,ig T ref sub H * T ref

Where:
HL
= Net enthalpy of the polymer
H *,l
= Enthalpy of the polymer in the liquid phase
H *,c
= Enthalpy of the polymer in the crystalline phase
129
Tm
= Melt transition temperature of the polymer
Tg
= Glass transition temperature of the polymer
xc
= Mass-fraction crystallinity
T ref
= Heat of formation of the polymer at the ideal-gas state and
H *,ig T ref
T ref
con H * T ref
= Heat of condensation of the polymer at
sub H *
= Heat of sublimation of the polymer at
ref
T ref
T ref
Cp *,l
= Heat capacity of the polymer in the liquid phase
Cp *,c
= 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.
*
ref
Aspen Polymers uses the heat of condensation, con H T
, and heat of
sublimation, sub H T
*
ref
, as reference parameters to convert between the
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:
for
T Tm
*,c x c *,l (1 x c )
for
Tg T Tm
*,c
for
T Tg
GL *,l
With:
(T ) (T
*, l
*, l
T
ref
Cp dT T
*,l
T ref
T ref
Cp *,l
dT
T
(T T ref ) S *,l (T ref )
(T ) (T
*,c
*,c
T
ref
Cp dT T
*,c
T ref
*,l (T ref ) *,ig T ref con * T ref
130
T ref
Cp *,c
dT
T
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
*, l
*, c
= Gibbs free energy of the polymer in the crystalline phase
T ref
*,ig T ref
= Gibbs free energy of formation of the polymer at the idealgas state and
T ref
con * T ref
= Gibbs free energy of condensation of the polymer at
sub *
= Gibbs free energy of sublimation of the polymer at
ref
T ref
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
for
T l ,min T T l ,max
Cp *,c A c B cT C cT 2 D c T 3
for
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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units Keyword
CPLVK/1
Al
Calculated
---
---
MOLE-HEATCAPACITY
CPLVK/2
Bl
Calculated
---
---
CPLVK/3
Cl
---
---
CPLVK/4
Dl
---
---
CPLVK/5
T l ,min
---
---
TEMP
131
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units Keyword
CPLVK/6
T l , max
Ac
1000
---
---
TEMP
Calculated
---
---
MOLE-HEATCAPACITY
CPCVK/2
Bc
Calculated
---
---
CPCVK/3
Cc
---
---
CPCVK/4
Dc
---
---
CPCVK/5
T c , min
---
---
TEMP
CPCVK/6
T c , max
1000
---
---
TEMP
DHFVK
H *,ig T ref
---
5 1010
5 1010
---
MOLE-ENTHALPY
DHCON
con
5 1010
5 1010
---
MOLE-ENTHALPY
DHSUB
sub H * T ref
5 1010
5 1010
---
MOLE-ENTHALPY
DGFVK
*,ig T ref
---
5 1010
5 1010
---
MOLE-ENTHALPY
DGCON
con * T ref
-2.528E6
5 1010
5 1010
---
MOLE-ENTHALPY
DGSUB
sub *
5.074E6
5 1010
5 1010
---
MOLE-ENTHALPY
POLCRY
xc
0.0
---
---
TMVK
Tm
---
5000
TEMP
TGVK
Tg
---
5000
TEMP
---
T ref
298.15
---
---
---
Kelvin
CPCVK/1

H T
*
ref

T
ref
-7E6
1.7E7
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:
132
Calculated automatically using van Krevelen group contribution

techniques.
parameters are used and the segment parameters are ignored.

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

at
T ref
133
con *A (T ref ) = Gibbs free energy of condensation of segment type A at

T ref
sub *A (T ref ) = Gibbs free energy of sublimation of segment type A at T ref
Cp *,A l
Heat capacity of segment type A in the liquid phase
Cp *,A c
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 ) n k H k*,ig (T ref )
(4.1)
con H A* (T ref ) n k con H k* (T ref )
(4.2)
sub H A* (T ref ) nk sub H k* (T ref )
(4.3)
*,A ig (T ref ) n k k*,ig (T ref ) (4.4)

k
con *A (T ref ) n k con k* (T ref )
(4.5)
sub *A (T ref ) n k sub k* (T ref )
(4.6)
Where:
nk
Number of occurrences of functional group k in the

segment from the segment database or user-specified
segment structure
T ref
H k*,ig (T ref )
Ideal-gas enthalpy of formation of functional group k at
con H k* (T ref ) = Heat of condensation of formation of functional group k at

sub H k* (T ref ) = Heat of sublimation of formation of functional group k at
k*,ig (T ref )
134
Ideal-gas Gibbs free energy of formation of functional

group k at
con k* (T ref )
sub k* (T ref )
Gibbs free energy of condensation of formation of

functional group k at
Gibbs free energy of sublimation of formation of functional

group k at
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 n k Cp k*,l T ref
(4.7)
B l 0.0012 n k Cp k*,l T ref
(4.8)
(4.9)
(4.10)
A c 0.106 n k Cp k*,c T ref

k
B c 0.003 n k Cp k*,c T ref

k
Where:
T ref
Cp k*,l T ref
Cp k*,c T ref
= Liquid molar heat capacity of functional group k at

van Krevelen database
T ref , from
Crystalline molar heat capacity of functional group k at

from van Krevelen database
T 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:

(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
Molar Volume
Vl
us
ho
p
r
o
Am
Vg
Semi-crystalline
Glassy
Vc
lline
Crysta
Tglass
Tmelt
Temperature
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:
for
T Tm
V *, c x c V *,l (1 x c )
for
Tg T Tm
V *,c x c V *, g (1 x c )
for
T Tg
VL V *,l
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
136
xc
= Mass fraction crystallinity
Tm
= Melt transition temperature
Tg
= Glass transition temperature
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
(4.11)
V *, c (1 B c T ) / A c for
T c ,min T T c ,max
(4.12)
V *, g (1 B g T C g Tg ) / A g for
T g ,min T T g ,max
(4.13)
Van Krevelen Liquid Molar Volume Model

Parameters
The following table lists the van Krevelen liquid molar volume model
parameters :
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
DNLVK/1
Al
Calculated
---
---
MOLEDENSITY
DNLVK/2
Bl
Calculated
---
---
1/TEMP
DNLVK/3
T l ,min
---
---
TEMP
DNLVK/4
1000
---
---
TEMP
DNCVK/1
T l ,max
Ac
---
---
MOLEDENSITY
DNCVK/2
Bc
Calculated
---
---
1/TEMP
DNCVK/3
T c ,min
---
---
TEMP
DNCVK/4
T c ,max
Ag
1000
---
---
TEMP
---
---
MOLEDENSITY
Bg
Calculated
---
---
1/TEMP
---
---
1/TEMP
DNGVK/1
DNGVK/2
Calculated
Calculated
DNGVK/3
Cg
Calculated
DNGVK/4
T g ,min
---
---
TEMP
DNGVK/5
T g ,max
1000
---
---
TEMP
POLCRY
xc
0.0
---
---
TMVK
Tm
---
5000
TEMP
TGVK
Tg
---
5000
TEMP
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 Al , B l , A c , B c , A g ,
B g , and 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
parameters are used and the segment parameters are ignored. The mass
based parameters take precedence over the molar based parameters.

parameters of a copolymer are calculated using the copolymer composition
and the parameters of segments:
V *,l
V *,c
Mn
M seg
Nseg
Mn
M seg
Nseg
Mn
M seg
Nseg
V *, g
V A*,l
V A*, c
V A*, g
With
M seg
Nseg
MA
Where:
Nseg = Number of segment types in the copolymer
Mn
M seg = Average molecular weight of segments in the copolymer
138
XA
= Mole segment fraction of segment type A in the copolymer
MA
= Molecular weight of segment type A in the copolymer
V A*,l
= Molar volume of segment type A in the copolymer in the liquid phase
V A*,c
= 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 n k Vwk
k
Where:
Vw = Van der Waals molar volume of a segment

= Number of occurrences of functional group k in the segment from the
segment database or user-specified segment structure
nk
Vwk = Van der Waals volume of functional group k, from van Krevelen
database
The segment parameters Al , B l , A c , B c , A g ,

calculated by the following equations:
Al Ac A g
1
1.3 Vw
(4.14)
Bl Bc B g
0.001
1 .3
(4.15)
Cg
5.5 10 4
1
1.3
B g , and C g , are then
(4.16)
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:

(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
= Molar volume of the polymer

in
Mn
= Polymer molecular weight
m 3 / kmol
V (0, T ) = Zero pressure isobar

C
= 0.0894
= Pressure in Pascals
= Temperature in Kelvin
P
T
lower
P Pupper
lower
T Tupper
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
140
Component subfolder. Note that the Tait model parameters have to be

specified for a polymer or oligomer component.
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units Keyword
VLTAIT/1
A0
---
---
---
---
MASS-VOLUME
VLTAIT/2
A1
---
---
---
---
MASS-VOLUME
TEMP
VLTAIT/3
A2
---
---
---
---
MASS-VOLUME
TEMP
VLTAIT/4
B0
---
---
---
---
PRESSURE
VLTAIT/5
B1
---
---
---
---
1/TEMP
VLTAIT/6
Plower
---
---
---
PRESSURE
VLTAIT/7
Pupper
1000
---
---
---
PRESSURE
VLTAIT/8
Tlower
---
---
---
TEMP
VLTAIT/9
Tupper
1000
---
---
---
TEMP
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.
Van Krevelen Glass Transition

Temperature Correlation
The van Krevelen correlations for the glass transition temperature are as
follows:
Tg , A n k Y g , k / n k M k
k
Tg
Nseg
Nseg
X A M AT g , A / X A M A
Where:
Tg , A
= Glass transition temperature for segment type A
141
nk
= Number of occurrences of functional group k in the segment from

the segment database or user-specified segment structure
Yg ,k
= Glass transition temperature of functional group k, from van

Krevelen database
Mk
= Molecular weight of functional group k
Tg
XA
MA
= Molecular weight of segment type A
Y g ,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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
TGVK
T g , or
---
5000
TEMP
Tg , A
---
5000
TEMP
Van Krevelen Melt Transition

Temperature Correlation
The van Krevelen correlations for the glass transition temperature are:
Tm , A n k Ym ,k / nk M k
k
Tm
Nseg
Nseg
X A M ATm, A / X A M A
Where:
142
Tm, A
= Melt transition temperature for segment type A
nk

Ym , k
= Melt transition temperature of functional group k, from van

Krevelen database
Mk
Tm
XA
MA
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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
TMVK
Tm , or
---
5000
TEMP
Tm, A
---
5000
TEMP
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 x c H *,l (1 x c ) for
H *,c
for
Tg T Tm
T Tg
Where:
HS
= Net enthalpy of the polymer
H *,l
= Enthalpy of the polymer in the liquid phase
H *,c
= Enthalpy of the polymer in the crystalline phase
143
Tm
Tg
xc
= Mass-fraction crystallinity
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 x c *,l (1 x c )
for
Tg T Tm
*,c
for
T Tg
Where:
GS
= Net Gibbs free energy of the polymer
*, l
= Gibbs free energy of the polymer in the liquid phase
*, c
= Gibbs free energy of the polymer in the crystalline phase
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 x c V *,l (1 x c )
for
Tg T Tm
V *,c x c V *, g (1 x c )
for
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
144
V *, g = Molar volume of the polymer in the glassy phase

xc
For a detailed discussion of V , V

Molar Volume Model on page 136.
*, l
*, c
, 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
molar volume ( V
*,l
*, l
, Cp *, c ), and
, V *, c , V *, g ), for polymer segments, and, thereafter, of
polymers and oligomers.

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 * n k 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.
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.
145
Polymer
Segments
ABS
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

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:

(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
146
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:
H ml H mig ( H ml H mig ) xi H i*,l H mE ,l

i
H ml H mig xi H i*,l H i*,ig H mE ,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
Symbol
Description
HLMX
H ml
HIGMX
H mig
Ideal gas mixture molar enthalpy
DHLMX
H ml H mig
Liquid mixture molar enthalpy departure
HLXS
H mE ,l
Liquid mixture molar excess enthalpy
HL
H i*,l
Liquid pure component molar enthalpy
HIG
H i*,ig
Ideal gas pure component molar enthalpy
DHL
H i*,l H i*,ig
Liquid pure component molar enthalpy departure
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
regardless of the route used for HLMX or HL. HLXS is calculated directly from
the activity coefficient model.
147
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
Route ID for DHL
Description
HLDVK0
DHL00P
Using Ideal gas law, Extended Antoine model and

Watson model for conventional components and van
Krevelen model for polymer components.
HLDVK1
(default)
DHL01P
Using Redlich-Kwong model (RK), Extended Antoine

model and Watson model for conventional components
and van Krevelen model for polymer components
DHL09P
Using DIPPR model for conventional components and van

HLDVK
Using Ideal gas law, Extended Antoine model and

Watson model for conventional components and van
HL0DVKRK

model, and Watson model for conventional components
and van Krevelen model for polymer components
HL0DVKD
Using DIPPR model for conventional components and van

HL0DVKRK is the default route for HL in Aspen Polymers 2004.1 and earlier
releases.
Routes available for polymer mixture enthalpy (HLMX) in

POLYNRTL
148
Route ID
Route ID for DHL
Description
HLMXP1
(default)
DHL01P
Using Redlich-Kwong model (RK), Henrys law, Extended

Antoine model, Watson model, van Krevelen model, and
polymer-NRTL model
Route ID
Route ID for DHL
Description
HLMXP2
DHL01P

model, Watson model, van Krevelen model, and
polymer-NRTL model
HLMXPRK

polymer-NRTL model
HLMXPRK is the default route for HLMX in Aspen Polymers 2004.1 and
earlier releases.

POLYFH
Route ID
Route ID for DHL
Description
HLMXFH1
(default)
DHL01P

polymer-FH model
HLMXFH2
DHL01P

polymer-FH model
HLMXFHRK

polymer-FH model
HLMXFHRK is the default route for HLMX in Aspen Polymers 2004.1 and
earlier releases.

POLYUF
Route ID
Route ID for DHL
Description
HLMXUF1
(default)
DHL01P

Antoine model , Watson model, van Krevelen model, and
polymer-UNIFAC model
HLMXUF2
DHL01P

HLMXPURK

HLMXPURK is the default route for HLMX in Aspen Polymers 2004.1 and
earlier releases.

POLYUFV
Route ID
Route ID for DHL
Description
HLMXFV1
(default)
DHL01P

polymer-UNIFAC-Free-Volume model
149
Route ID
Route ID for DHL
Description
HLMXFV2
DHL01P

HLMXFVRK

HLMXFVRK is the default route for HLMX in Aspen Polymers 2004.1 and
earlier releases.

PNRTL-IG
Route ID
Route ID for DHL
Description
HLMXP00
(default)
DHL00P
Using Ideal gas law, Henrys law, Extended Antoine

polymer-NRTL model
HLMXP02
DHL00P
Using Ideal gas law, Extended Antoine model, Watson

model, van Krevelen model, and polymer-NRTL model
HLMXP
Using Ideal gas law, Extended Antoine model, Watson

model, van Krevelen model, and polymer-NRTL model
HLMXP is the default route for HLMX in Aspen Polymers 2004.1 and earlier
releases.
References
Bicerano, J. (1993). Prediction of Polymer Properties. New York: Marcel
Dekker, Inc.
Danner, R. P., & High, M. S. (1992). Handbook of Polymer Solution
Van Krevelen, D. W. (1990). Properties of Polymers, 3rd Ed. Amsterdam:
Elsevier.
150
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.
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
Symbol
Description
MUL
i*,l
Liquid viscosity of a component in a mixture
MULMX
Liquid viscosity of a mixture
151
Viscosity Models
Model Name
Pure
Mixture
Properties
Calculated
Modified Mark-Houwink/
van Krevelen Model
MUL0MH
__
MUL

Viscosity Model
MUPOLY
__
MULMX
Van Krevelen Polymer

MUL2VK
__
MULMX
Eyring-NRTL Mixture
Viscosity Model
EYRING
__
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
exp 1
RT Tref
Where:
152
i*,l =
Zero-shear viscosity of a polymer component
ref =
Zero-shear viscosity of the polymer at the specified reference

temperature and molecular weight
Mw =
Weight average molecular weight for the polymer
M ref =
Reference molecular weight of the polymer
Tref
Reference temperature
Exponential factor accounting for the polymer molecular weight

effect. This is a two parameter vector where
(1) is used for M w M cr

( 2) is used for M w M cr
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:
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
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
153
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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
MULMH/1
ref
---
10 10
10 10
---
VISCOSITY
Unary
MULMH/2
10 10
---
MOLEENTHALPY
Unary
MULMH/3
(1)
3.4
20.0
---
---
Unary
MULMH/4
( 2)
1.0
20.0
---
---
Unary
MULMH/5
-5.0
5.0
---
---
Unary
MULMH/6
Tref
---
200
5000
---
TEMP
Unary
MULMH/7
M ref
---
5000
10 10
---
---
Unary
CRITMW
M cr
---
1.0
10 10
---
--
Unary
HMUVK
---
10-10
1010
---
(MOLEENTHALPY)1
Unary
/3
TGVK
Tg
---
5000
---
TEMP
Unary
POLPDI*
PDI
1.0
1.0
1000
---
---
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
are related to the effect of temperature on
and M cr are related to polymer molecular weight.

M cr , values for E , , and can be regressed from experimental
viscosity. The parameters

Except
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.
154
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
T trends. If
T 1.2T g , all the polymers follow a Williams-Landel-Ferry (WLF) relationship

(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:
155
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 1.2T g 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
H ,k / M A
For polymers and oligomers:
Nseg
Nseg
X A M A H, A / X A M A
Where:
156
H , A = Viscosity-temperature gradient of segment type A

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

database
MA
= 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:
E () H 3
3
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 ()
(0.052 8.5 10 5 T g )
Tg
1.4
The structural parameter A is calculated using the following equation:
1 E ()
2.3 RT g
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
cr (1.2Tg )
T
cr (1.2Tg ) is known from the previous step, therefore the final

value for
cr (T ) can be calculated.
157
Specifying the MMH Model


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
*,l
i
1/ 3
k ij wi w j ln ij wi w j l ij ln ij
j i
i
j i
Where:
= Zero shear viscosity of the mixture
i*,l = Zero shear viscosity of component i

wi
= Weight fraction of component i
k ij
= Symmetric binary parameter, k ji k ij
l 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:
158
ln ij
| ln i*,l ln *,j l |
2
Therefore, ln ij 0 when
i*,l *,j l . The antisymmetric mixing term
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,
l ij . Both binary parameters allows complex temperature dependence:

l ij 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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
MUKIJ/1
a ij
---
---
---
Binary,
Symmetric
MUKIJ/2
bij
---
---
---
Binary,
Symmetric
MUKIJ/3
c ij
---
---
---
Binary,
Symmetric
MUKIJ/4
d ij
---
---
---
Binary,
Symmetric
MUKIJ/5
eij
---
---
---
Binary,
Symmetric
MUKIJ/6
Tref
298.15
---
---
---
Binary,
Symmetric
MULIJ/1
aij'
---
---
---
Binary,
Antisymmetric
159
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
MULIJ/2
bij'
---
---
---
Binary,
Antisymmetric
MULIJ/3
cij'
---
---
---
Binary,
Antisymmetric
MULIJ/4
d ij'
---
---
---
Binary,
Antisymmetric
MULIJ/5
eij'
---
---
---
Binary,
Antisymmetric
MULIJ/6
Tref
298.15
---
---
---
Binary,
Antisymmetric

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 .
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 *,p l
[k12 l12 (1 2 w p )](1 w p ) w p ln 12
ln12 (ln *,p l ln s*,l ) / 2

Where:
= Zero shear viscosity of the polymer-solvent solution
s*,l = Zero shear viscosity of the solvent
160
*,p l
= Zero shear viscosity of the polymer
wp
= Weight fraction of the polymer
k12
= Symmetric binary parameter
l12
= Antisymmetric binary parameter
Specifying the Aspen Polymer Mixture

Viscosity Model
Aspen Polymer Mixture Viscosity Model (MUPOLY) requires the pure
component liquid viscosities to be calculated by another model before the
mixture liquid viscosity can be calculated. To ensure this prerequisite, the
route MULMX13 was created particularly for this model. MULMX13 is the
default route for MULMX in all polymer property methods. However, this
model is not limited to polymer systems and it can also be used for nonpolymer systems. To use this model in the non-polymer property methods,
specify or change the route for MULMX to MULMX13 rather than changing the
mixture liquid viscosity model to MUPOLY directly.
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 /
i 1
Where:
QB
= Property of the pseudo-polymer (the superscript B stands for the

pseudo-polymer)
Npol = Total number of polymeric components in the system
QB
represents any of the following quantities:
0B = Zero-shear viscosity of the pseudo-polymer. The above mixing
rule for the pseudo-polymer viscosity is derived from the

influence of polydispersity on zero-shear viscosity (Flory, 1943)
H B = Van Krevelen viscosity-temperature gradient of the pseudopolymer. H is additive for van Krevelen groups. The viscositytemperature gradient of the blend equals the weight-averaged
viscosity-temperature gradient of all polymeric species
TgB = Glass transition temperature of the pseudo-polymer. The weightB

average mixing rule is derived for Tg 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:
0i = Zero-shear viscosity of polymer i, computed from pure
component viscosity models. It is a function of polymer molecular

weight, temperature and polymer structure
H i = Van Krevelen viscosity-temperature gradient of polymer i. It is
estimated from the van Krevelen group contribution method (See

Chapter 4)
Tgi = Glass transition temperature of polymer i. Tg values are user

specified or estimated from the van Krevelen group contribution
method (see Chapter 4)
= 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.
162
The same mixing rule applies to the solvent mixture for the properties of the
pseudo-solvent:
QS
Nsol
Nsol
wi Qsi /
i 1
i 1
Where:
QS
= Property of the pseudo-solvent (the superscript S stands for

pseudo-component solvent)
Nsol
= Total number of solvent components in the system
QS
represents any of the following quantities:
TgS = Glass transition temperature of the pseudo-solvent component.

S
The mixing rule for Tg 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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
MULVK/1
Ki
2.5
10
---
---
Unary
163
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
MULVK/2
5.1
100
---
---
Unary
TGVK
Tg
---
5000
---
TEMP
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:
164
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, Tg , and, therefore, llowers
owers the polymer viscosity. This is the soso
m
called plasticizer effect

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 plast
plasticized
icized polymer (Bueche, 1962):
165
T
m
g
TgB wB K S TgS wS
wB K S wS
Where:
Tgm
= Glass transition temperature of the mixture (superscript m stands

for the mixture)
wB
Npol
Total weight fraction of polymer in the mixture, wB
i 1
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:
*
log
1.2T g
T gm
f
, A
T
Where:
= Viscosity of the undiluted polymer with a new glass temperature
1.2T g = Viscosity of the undiluted polymer at its own glass temperature

f
= Van Krevelen graphical correlation for polymer melt viscosity
= Structural factor related to the viscosity-temperature gradient of

the polymer H by:
2.303 RTg
For a quasi-binary system, the structural factor of pseudo-polymer, AB , is

used in the van Krevelen viscosity-temperature relationship. AB is calculated
using the pseudo-polymer properties:
*
log B B B
1.2Tg
A
B
166
Tgm B
f
,A
T
B 3
2.303RT gB
where
B (1.2TgB )
is solved from the van Krevelen zero shear viscosity
graphical correlation of the pseudo-polymer
0B
log B
1.2TgB
0B :
TgB B
f
,A
T
True Solvent Dilution Effect

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

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. It 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 non-polymeric components
(solvents) are already available as input.
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
*,l
i
x j G ji ji
j
xi
i
x j G ji
j
With:
X r
X r
I i,I
xi
J j,J
G ji exp( ji ji )
Where:
Zero shear viscosity of the mixture
i*,l
Zero shear viscosity of component i
I and J
Component based indices
i and j
Segment based indices
xi
Segment based mole fraction for segment based species i
XI
Mole fraction of component I in component basis
ri , I
Number of segment type i in component I
ji
NRTL non-random factor
ji
Interaction parameter
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
168
Eyring-NRTL Mixture Viscosity Model

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

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.
specified.
Specifying the Eyring-NRTL Mixture

Viscosity Model
Although the Eyring-NRTL Mixture Viscosity Model (EYRING) was primarily
developed for polymer systems, it can also be used for non-polymer systems.
It requires the pure component liquid viscosities to be calculated by another
model before the mixture liquid viscosity can be calculated. To ensure this
prerequisite, the route MULMX15 was created particularly for this model. To
use this model in a property method, specify or change the route for MULMX
to MULMX15 rather than changing the mixture liquid viscosity model to
EYRING directly.
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
Model Name
Applicability
Property Methods
MULMX13
MUPOLY
default
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.
170
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.
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:
6 Polymer Thermal Conductivity Models
171
Thermal Conductivity
crystalline
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
Symbol
Description
KL
*,i l
Liquid thermal conductivity of a component in a mixture
KLMX
Liquid thermal conductivity of a mixture
Thermal Conductivity
Models
Model Name
Pure
Mixture
Properties
Calculated
Modified van
Krevelen/DIPPR
KL0VKDP
__
KL
Modified van
Krevelen/TRAPP
KL0VKTR
__
KL
Aspen Polymer Thermal

Conductivity Mixture Model
KLMXVKTR
__
KLMX
172
Modified van Krevelen Thermal

Conductivity Model
The polymer thermal conductivity is calculated using the following equation:
for
T Tm
*,i c *,i l (1 )
for
Tg T Tm
*,i c *,i g (1 )
for
T Tg
KL *,i l
Where:
KL = Net thermal conductivity of the polymer
*,i l = Thermal conductivity of the polymer in the liquid phase

*,i c = Thermal conductivity of the polymer in the crystalline phase
*,i g = 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):
3 xc
*, c
i
*, g ,l
i
*, c
xc 1 *,i g ,l
i
(6.1)
With
*,i g ,l
*,i l
for
Tg T Tm
*,i g
for
T Tg
Where:
xc
Modified van Krevelen Equation

The thermal conductivities for the liquid, crystalline and glassy states are
calculated using the modified van Krevelen equation:
*,i *,i ,ref F
(6.2)
With
173
T Tref
B Tref 1 1 C ln T
1 A
T
T T
T
ref
ref
ref
P Pref
T Tref P Pref
E
T P
ref
ref
ref
(6.3)
Where:
= l, c, or g
*,i
= Thermal conductivity of the polymer for state
*,i ,ref
= Thermal conductivity of the polymer for state

temperature and pressure
Tref
= Reference temperature for state
Pref
= Reference pressure for state
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
l
*,i , ref
---
10-6
1000
---
THERMALCONDCTIVITY
Unary
KLVKL/2
Al
-1000
1000
---
---
Unary
KLVKL/3
Bl
-1000
1000
---
---
Unary
KLVKL/4
Cl
-1000
1000
---
---
Unary
KLVKL/5
Dl
-1000
1000
---
---
Unary
KLVKL/6
El
-1000
1000
---
---
Unary
KLVKL/7
Fl
-100
100
---
---
Unary
KLVKL/8
Trefl
298.15
1000
---
TEMP
Unary
KLVKL/9
Prefl
101325
1000
1010
---
PRESSURE
Unary
KLVKC/1
c
*,i , ref
---
10-6
1000
---
THERMALCONDCTIVITY
Unary
KLVKC/2
Ac
-1000
1000
---
---
Unary
KLVKC/3
Bc
-1000
1000
---
---
Unary
174
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
KLVKC/4
Cc
-1000
1000
---
---
Unary
KLVKC/5
Dc
-1000
1000
---
---
Unary
KLVKC/6
Ec
-1000
1000
---
---
Unary
KLVKC/7
Fc
-100
100
---
---
Unary
KLVKC/8
Trefc
298.15
1000
---
TEMP
Unary
KLVKC/9
Prefc
101325
1000
1010
---
PRESSURE
Unary
KLVKG/1
g
*,i , ref
---
10-6
1000
---
THERMALCONDCTIVITY
Unary
KLVKG/2
Ag
-1000
1000
---
---
Unary
KLVKG/3
Bg
-1000
1000
---
---
Unary
KLVKG/4
Cg
-1000
1000
---
---
Unary
KLVKG/5
Dg
-1000
1000
---
---
Unary
KLVKG/6
Eg
-1000
1000
---
---
Unary
KLVKG/7
Fg
-100
100
---
---
Unary
KLVKG/8
Trefg
298.15
1000
---
TEMP
Unary
KLVKG/9
Prefg
101325
1000
1010
---
PRESSURE
Unary
POLCRY
xc
---
---
Unary
TGVK
Tg
---
5000
TEMP
Unary
TMVK
Tm
---
5000
TEMP
Unary
Parameter Input
The unary parameters can be:
These options are shown in priority order. For example, if the model
polymer parameters are used and the segment parameters are ignored.

polymer component thermal conductivity is calculated as the mass average of
the segment contributions:
175
*,i
Nseg
X
A
Nseg
*,
A M A A / X A M A
A
Where:
Nseg
= Number of segment types in the copolymer
XA
MA
= Molecular weight of segment type A in the copolymer
*,A
= Thermal conductivity of segment type A in state

using Equation 6.2
, estimated
Van Krevelen Group Contribution for

Segments
If
*,i ,ref
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:
Trefl Trefg TgVK n k Yg ,k / nk M k

k
Segment Reference Temperature

Similarly, the segment reference temperature in crystalline state is calculated
from:
Trefc TmVK n k Ym ,k / n k M k
k
Where:
176
nk

TgVK
= Van Krevelen estimate of segment glass transition temperature
TmVK
= Van Krevelen estimate of segment melt transition temperature
Yg ,k
= Glass transition contribution of functional group k from van

Krevelen database
Ym , k
= Melt transition contribution of functional group k from van

Krevelen database
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
Cp VK 298 UR VK 298
L VK 298 VK 298
V
V
VK 298 , is calculated first:
Where:
L
Cp VK 298
= Van Krevelen estimate of segment molar heat capacity at

298.15 K (J/mol.K)
V VK 298
= Van Krevelen estimate of segment molar volume at 298.15 K
UR VK 298
= Van Krevelen estimate of segment Rao wave function at 298.15
5 x10 11 m (constant)
(m 3 /mol)
K
(m10 / 3 /s1/3 .mol)
The segment heat capacity, molar volume, and Rao function at 298.15 K are
calculated from van Krevelen group contributions:
Cp VK 298 n k Cp k*,l
k
V VK 298 1.6 nk Vwk

k
UR VK 298 n k URk
k
Where:
Cp k*,l
= Liquid heat capacity contribution of functional group k from van

Krevelen database
Vwk
= Van der Walls volume contribution of functional group k from van

Krevelen database
URk
= Rao wave function contribution of functional group k from van

Krevelen database
Note that van Krevelen group parameters are used to calculate
Cp VK 298 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 UR k 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 )
Tg
T
g
T
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
(T )
T
1.2 0.2
Tg
Tg
for
T Tg (glass) (6.5)
for
T Tg (liquid)
(6.6)
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,
*,refl , g
*,ref
for a segment:
VK 298
298.15
1.2 0.2 VK
T
*,refl , g
VK 298
298.15
T VK
g
0.22
if
if
TgVK
TgVK
298.15 K
< 298.15 K
(6.7)
(6.8)
Crystalline Polymer
For crystalline polymer, we use the following expression from van Krevelen
(1990) relating liquid and crystalline thermal conductivity:
c
l 1
5
.
8
l
(6.9)
Where:
178
= 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
4.8
5.8 c
l Tm
V
(6.10)
Where:
Vc
Segment molar volume at
Tm and crystalline state
Vl
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 :
(T ) VW 1.435 0.45 10
V l (T ) VW 1.6 10 3 (T 298.15) (6.11)

Vc
(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
TmVK
1.2 0.2 VK
T
g
2.392 3.64 10 3 (TmVK 298.15)

(6.13)
1.435 0.45 10 3 (T VK 298.15)
m
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,
Ac 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

179

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
2
*, s ( x ' )
p ( p )
l

i xi M i
1 / 2
With
x s'
xs
xs
s
Where:
Thermal conductivity of the mixture
*,pl
Thermal conductivity of polymer component p in the mixture
*, s ( x ' ) = Thermal conductivity of the polymer-free mixture, calculated

using the TRAPP model
x s'
Mole fraction of non-polymer component s in the polymer-free

mixture
xi
Mole fraction of component i
Mi
Molecular weight of component I
Specifying the Aspen Polymer Mixture

180
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
( i )
l i
xi M i

i
1 / 2
Where:
= Thermal conductivity of the mixture
*,i l
= Thermal conductivity of component i
xi
= Mole fraction of component i
Mi
= 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
Model Name
Applicability
Property
Methods
KLMXVKDP
KL0VKDP
Low pressure
(less than 20 bar)
POLYFH,
POLYNRTL,
POLYUF,
POLYUFV
KLMXVKTR
KLMXVKTR
High pressure
(greater than 20
bar)
POLYSL,
POLYSRK,
POLYSAFT,
POLYPCSF
References
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.
182
A Physical Property Methods
This appendix documents the physical property route structure for the
polymer specific property methods:
POLYFH: Flory-Huggins Property Method, 184
POLYNRTL: Polymer Non-Random Two-Liquid Property Method, 186
POLYUF: Polymer UNIFAC Property Method, 188
POLYUFV: Polymer UNIFAC Free Volume Property Method, 190
PNRTL-IG: Polymer NRTL with Ideal Gas Law Property Method, 192
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, 197
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.
183
POLYFH: Flory-Huggins
Property Method
The following table lists the physical property route structure for the POLYFH
property method:
Vapor
Property
Name
Route ID
Model Name
Description
PHIVMX
PHIVMX01
ESRK
Redlich-Kwong
HVMX
HVMX01
ESRK
Redlich-Kwong
GVMX
GVMX01
ESRK
Redlich-Kwong
SVMX
SVMX01
ESRK
Redlich-Kwong
VVMX
VVMX01
ESRK
Redlich-Kwong
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
Dawson-Khoury-Kobayashi
PHIV
PHIV01
ESRK0
Redlich-Kwong
HV
HV02
ESRK0
Redlich-Kwong
GV
GV01
ESRK0
Redlich-Kwong
SV
SV01
ESRK0
Redlich-Kwong
VV
VV01
ERSK0
Redlich-Kwong
DV
DV01
DV0CEWL
Chapman-Enskog-Wilke-Lee
MUV
MUV01
MUV0BROK
Chapman-Enskog-Brokaw
KV
KV01
KV0STLTH
Stiel-Thodos
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMXFH
GMFH, WHENRY,
HENRY1, PL0XANT,
ESRK0, VL0RKT,
VL1BROC
Flory-Huggins, HENRY,
Extended Antoine, RedlichKwong, Rackett, BreviO'Connell
HLMX
HLMXFHRK
GMFH, WHENRY,
HENRY1,
VL1BROC,
DHL02PH
Flory-Huggins, van Krevelen,

HENRY, Redlich-Kwong,
Rackett, Brevi-O'Connell
GLMX
GLMXFH
GMFH, GL0DVK

DIPPR
SLMX
SLMXFHRK
GMFH, WHENRY,
HENRY1,
VL1BROC,
DHL02PH, GL0DVK

DIPPR
Liquid
184
Liquid
Property
Name
Route ID
Model Name
Description
VLMX
VLMXVKRK
VL2VKRK
Ideal mixing, van Krevelen,

Rackett
MULMX
MULMX13
MUPOLY,
Aspen, Modified MarkHouwink/van Krevelen,

Andrade
MULMH
KLMX
KLMXVKDP
KL0VKDP, KL2VR
Vredeveld mixing, Modified van

Krevelen, Sato-Riedel/DIPPR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
PHIL
PHIL04
PL0XANT, ESRK0,
VL0RKT
Extended Antoine, RedlichKwong, Rackett
HL
HLDVKRK
HL0DVKRK*
van Krevelen, Redlich-Kwong,

Ideal gas
GL
GLDVK
GL0DVK
van Krevelen, DIPPR
SL
SLDVK
HL0DVKRK*,
GL0DVK

Ideal gas
VL
VLDVK
VL0DVK, VL0RKT
van Krevelen, Rackett
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Modified Mark-Houwink,
Andrade
KL
KL0VKDP
KL0VKDP
Modified van Krevelen, SatoRiedel/DIPPR
Optional van Krevelen/DIPPR model, HL0DVKD, available (see Pure Component

Liquid Enthalpy Models in Chapter 4).
Solid
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
Ideal mixing, van Krevelen
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK,
GS0DVK
VSMX
VSMXDVK
VS0DVK,
VS0POLY
van Krevelen, Polynomial
HS
HSDVK
HS0DVK
van Krevelen
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK,
GS0DVK
van Krevelen
VS
VSDVK
VS0DVK,
VS0POLY
185
POLYNRTL: Polymer NonRandom Two-Liquid Property

Method
The following table lists the physical property route structure for the
POLYNRTL property method:
Vapor
Property
Name
Route ID
Model Name
Description
PHIVMX
PHIVMX01
ESRK
Redlich-Kwong
HVMX
HVMX01
ESRK
Redlich-Kwong
GVMX
GVMX01
ESRK
Redlich-Kwong
SVMX
SVMX01
ESRK
Redlich-Kwong
VVMX
VVMX01
ESRK
Redlich-Kwong
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIV01
ESRK0
Redlich-Kwong
HV
HV02
ESRK0
Redlich-Kwong
GV
GV01
ESRK0
Redlich-Kwong
SV
SV01
ESRK0
Redlich-Kwong
VV
VV01
ERSK0
Redlich-Kwong
DV
DV01
DV0CEWL
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMXP
GMNRTLP,
WHENRY, HENRY,
PL0XANT, ESRK0,
VL0RKT, VL1BROC
Polymer NRTL, HENRY,

HLMX
HLMXPRK
GMNRTLP,
WHENRY, HENRY1,
VL1BROC, DHL02PH
Polymer-NRTL, van Krevelen,

GLMX
GLMXP
GMNRTLP, GL0DVK
Polymer NRTL, van Krevelen,

DIPPR
SLMX
SLMXPRK
GMNRTLP,
WHENRY, HENRY1,
VL1BROC,
DHL02PH, GL0DVK

HENRY, Redlich-Kwong, BreviO'Connell
VLMX
VLMXVKRK
VL2VKRK

Rackett
Liquid
186
Liquid
Property
Name
Route ID
Model Name
Description
MULMX
MULMX13
MUPOLY, MULMH

Andrade
KLMX
KLMXVKDP
KL0VKDP, KL2VR

Krevelen, Sato-Riedel/DIPPR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
Hakim-Steinberg-Stiel, Power
Law Mixing
PHIL
PHIL04
PL0XANT, ESRK0,
VL0RKT
HL
HLDVKRK
HL0DVKRK*

Ideal gas
GL
GLDVK
GL0DVK
van Krevelen, DIPPR
SL
SLDVK
HL0DVK*, GL0DVK
van Krevelen, DIPPR
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Krevelen, Andrade
KL
KL0VKDP
KL0VKDP

Solid
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK,
GS0DVK
VSMX
VSMXDVK
VS0DVK,
VS0POLY
HS
HSDVK
HS0DVK
van Krevelen
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK,
GS0DVK
van Krevelen
VS
VSDVK
VS0DVK,
VS0POLY
187
POLYUF: Polymer UNIFAC

Property Method
The following table lists the physical property route structure for the POLYUF
property method:
Vapor
Property
Name
Route ID
Model Name
Description
PHIVMX
PHIVMX01
ESRK
Redlich-Kwong
HVMX
HVMX01
ESRK
Redlich-Kwong
GVMX
GVMX01
ESRK
Redlich-Kwong
SVMX
SVMX01
ESRK
Redlich-Kwong
VVMX
VVMX01
ESRK
Redlich-Kwong
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIV01
ESRK0
Redlich-Kwong
HV
HV02
ESRK0
Redlich-Kwong
GV
GV01
ESRK0
Redlich-Kwong
SV
SV01
ESRK0
Redlich-Kwong
VV
VV01
ERSK0
Redlich-Kwong
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMPUF
GMPOLUF,
WHENRY, HENRY,
PL0XANT, ESRK0,
VL0RKT, VL1BROC
Polymer UNIFAC, HENRY,

HLMX
HLMXPURK
GMPOLUF,
WHENRY, HENRY1,
VL1BROC,
DHL02PH
Polymer UNIFAC, van

Krevelen, HENRY, RedlichKwong, Rackett, BreviO'Connell
GLMX
GLMXPUF
GMPOLUF, GL0DVK
Polymer UNIFAC, van

Krevelen, DIPPR
SLMX
SLMXPURK
GMPOLUF,
WHENRY, HENRY1,
VL1BROC,
DHL02PH, GL0DVK
Polymer UNIFAC, van

Krevelen, HENRY, RedlichKwong, Rackett, BreviO'Connell
VLMX
VLMXVKRK
VL2VKRK

Rackett
Liquid
188
Liquid
Property
Name
Route ID
Model Name
Description
MULMX
MULMX13
MUPOLY, MULMH
Aspen, Modified MarkHouwink/ van Krevelen,

Andrade
KLMX
KLMXVKDP
KL0VKDP, KL2VR
Vredeveld mixing, Modified

van Krevelen, SatoRiedel/DIPPR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
Law Mixing
PHIL
PHIL04
PL0XANT, ESRK0,
VL0RKT
HL
HLDVKRK
HL0DVKRK*

Ideal gas
GL
GLDVK
GL0DVK
van Krevelen, DIPPR
SL
SLDVK
HL0DVK*, GL0DVK
van Krevelen, DIPPR
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Krevelen, Andrade
KL
KL0VKDP
KL0VKDP

Solid
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK,
GS0DVK
VSMX
VSMXDVK
VS0DVK,
VS0POLY
HS
HSDVK
HS0DVK
van Krevelen
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK,
GS0DVK
van Krevelen
VS
VSDVK
VS0DVK,
VS0POLY
189
POLYUFV: Polymer UNIFAC

Free Volume Property Method
The following table lists the physical property route structure for the POLYUFV
property method:
Vapor
Property
Name
Route ID
Model Name
Description
PHIVMX
PHIVMX01
ESRK
Redlich-Kwong
HVMX
HVMX01
ESRK
Redlich-Kwong
GVMX
GVMX01
ESRK
Redlich-Kwong
SVMX
SVMX01
ESRK
Redlich-Kwong
VVMX
VVMX01
ESRK
Redlich-Kwong
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIV01
ESRK0
Redlich-Kwong
HV
HV02
ESRK0
Redlich-Kwong
GV
GV01
ESRK0
Redlich-Kwong
SV
SV01
ESRK0
Redlich-Kwong
VV
VV01
ERSK0
Redlich-Kwong
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMUFV
GMUFFV, WHENRY,
HENRY, PL0XANT,
ESRK0, VL0RKT,
VL1BROC, VL0TAIT
UNIFAC-FV, HENRY,
HLMX
HLMXFVRK
GMUFFV, WHENRY,
HENRY1, VL1BROC,
DHL02PH
UNIFAC-FV, van Krevelen,

GLMX
GLMXUFV
GMUFFV, GL0DVK

DIPPR
SLMX
SLMXFVRK
GMUFFV, WHENRY,
HENRY1, VL1BROC,
DHL02PH, GL0DVK

VLMX
VLMXVKRK
VL2VKRK
Tait/van Krevelen, Rackett
MULMX
MULMX13
MUPOLY, MULMH
Aspen, Modified MarkHouwink/ van Krevelen,

Andrade
Liquid
190
Liquid
Property
Name
Route ID
Model Name
Description
KLMX
KLMXVKDP
KL0VKDP, KL2VR

DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
Hakim-Steinberg-Stiel,
Power Law Mixing
PHIL
PHIL04
PL0XANT, ESRK0,
VL0RKT
HL
HLDVKRK
HL0DVKRK*
van Krevelen, RedlichKwong, Ideal gas
GL
GLDVK
GL0DVK
van Krevelen, DIPPR
SL
SLDVK
HL0DVK*, GL0DVK
van Krevelen, DIPPR
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Krevelen, Andrade
KL
KL0VKDP
KL0VKDP
Modified van Krevelen,

Sato-Riedel/DIPPR
Optional van Krevelen/DIPPR model, HL0DVKD, available (see Pure

Component Liquid Enthalpy Models in Chapter 4).
Solid
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK,
GS0DVK
VSMX
VSMXDVK
VS0DVK,
VS0POLY
HS
HSDVK
HS0DVK
van Krevelen
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK,
GS0DVK
van Krevelen
VS
VSDVK
VS0DVK,
VS0POLY
191
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
Route ID
Model Name
Description
PHIVMX
PHIVMX00
ESIG
Ideal gas law
HVMX
HVMX00
ESIG
Ideal gas law
GVMX
GVMX00
ESIG
Ideal gas law
SVMX
SVMX00
ESIG
Ideal gas law
VVMX
VVMX00
ESIG
Ideal gas law
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIV0
ESIG0
Ideal gas law
HV
HV00
ESIG0
Ideal gas law
GV
GV00
ESIG0
Ideal gas law
SV
SV00
ESIG0
Ideal gas law
VV
VV00
ESIG0
Ideal gas law
DV
DV01
DV0CEWL
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMXPI
GMNRTLP, WHENRY,
HENRY, PL0XANT,
ESIG0, VL0RKT,
VL1BROC
Polymer NRTL, HENRY,

Extended Antoine, Ideal gas
law, Rackett, Brevi-O'Connell
HLMX
HLMXP
GMNRTLP, WHENRY,
HENRY1, VL1BROC,
DHL01PH

Ideal gas, Rackett, BreviO'Connell
GLMX
GLMXP
GMNRTLP, GL0DVK

DIPPR
SLMX
SLMXP
GMNRTLP, WHENRY,
HENRY1, VL1BROC,
DHL01PH, GL0DVK

Ideal gas, Rackett, BreviO'Connell
VLMX
VLMXVKRK
VL2VKRK

Rackett
MULMX
MULMX13
MUPOLY, MULMH

Andrade
Liquid
192
Liquid
Property
Name
Route ID
Model Name
Description
KLMX
KLMXVKDP
KL0VKDP, KL2VR

DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
law mixing
PHIL
PHIL00
PL0XANT, ESIG0,
VL0RKT
Extended Antoine, Ideal gas

law
HL
HLDVKD
HL0DVKD*
van Krevelen, DIPPR
GL
GLDVK
GL0DVK
van Krevelen, DIPPR
SL
SLDVK
HL0DVK*, GL0DVK
van Krevelen, DIPPR
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Krevelen, Andrade
KL
KL0VKDP
KL0VKDP

Solid
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK, GS0DVK
VSMX
VSMXDVK
VS0DVK, VS0POLY
HS
HSDVK
HS0DVK
van Krevelen
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK, GS0DVK
van Krevelen
VS
VSDVK
VS0DVK, VS0POLY
POLYSL: Sanchez-Lacombe
Equation-of-State Property
Method
The following table lists the physical property route structure for the POLYSL
property method:
193
Vapor
Property
Name
Route ID
Model Name
Description
PHIVMX
PHIVMXSL
ESPLSL
Sanchez-Lacombe
HVMX
HVMXSL
ESPLSL
Sanchez-Lacombe
GVMX
GVMXSL
ESPLSL
Sanchez-Lacombe
SVMX
SVMXSL
ESPLSL
Sanchez-Lacombe
VVMX
VVMXSL
ESPLSL
Sanchez-Lacombe
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIVSL
ESPLSL0
Sanchez-Lacombe
HV
HVSL
ESPLSL0
Sanchez-Lacombe
GV
GVSL
ESPLSL0
Sanchez-Lacombe
SV
SVSL
ESPLSL0
Sanchez-Lacombe
VV
VVSL
ESPLSL0
Sanchez-Lacombe
DV
DV01
DV0CEWL
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMXSL
ESPLSL
Sanchez-Lacombe
HLMX
HLMXSL
ESPLSL
Sanchez-Lacombe
GLMX
GLMXSL
ESPLSL
Sanchez-Lacombe
SLMX
SLMXSL
ESPLSL
Sanchez-Lacombe
Liquid
194
VLMX
VLMXSL
ESPLSL
Sanchez-Lacombe
MULMX
MULMX13
MUPOLY,
MULMH
Aspen, Modified Mark-Houwink/van

Krevelen, Andrade
KLMX
KLMXVKTR
KLMXVKTR
Vredeveld mixing , Modified van

Krevelen, TRAPP
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
Hakim-Steinberg-Stiel, Power Law

Mixing
PHIL
PHILSL
ESPLSL0
Sanchez-Lacombe
HL
HLSL
ESPLSL0
Sanchez-Lacombe
GL
GLSL
ESPLSL0
Sanchez-Lacombe
SL
SLSL
ESPLSL0
Sanchez-Lacombe
VL
VLSL
ESPLSL0
Sanchez-Lacombe
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Krevelen, Andrade
KL
KL0VKTR
KL0VKTR
Modified van Krevelen, TRAPP
Solid
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK,
GS0DVK
VSMX
VSMXDVK
VS0DVK,
VS0POLY
HS
HSDVK
HS0DVK
van Krevelen
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK,
GS0DVK
van Krevelen
VS
VSDVK
VS0DVK,
VS0POLY
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
Route ID
Model Name
Description
PHIVMX
PHIVMXPS
ESPLRKS
Polymer SRK
HVMX
HVMXPS
ESPLRKS
Polymer SRK
GVMX
GVMXPS
ESPLRKS
Polymer SRK
SVMX
SVMXPS
ESPLRKS
Polymer SRK
VVMX
VVMXPS
ESPLRKS
Polymer SRK
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIVPS
ESPLRKS0
Polymer SRK
HV
HVPS
ESPLRKS0
Polymer SRK
GV
GVPS
ESPLRKS0
Polymer SRK
SV
SVPS
ESPLRKS0
Polymer SRK
VV
VVPS
ESPLRKS0
Polymer SRK
DV
DV01
DV0CEWL
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
195
Liquid
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMXPS
ESPLRKS
Polymer SRK
HLMX
HLMXPS
ESPLRKS
Polymer SRK
GLMX
GLMXPS
ESPLRKS
Polymer SRK
SLMX
SLMXPS
ESPLRKS
Polymer SRK
VLMX
VLMXVKRK
VL2VKRK

Rackett
MULMX
MULMX13
MUPOLY,
MULMH
Aspen, Modified MarkHouwink/van Krevelen, Andrade
KLMX
KLMXVKTR
KLMXVKTR

Krevelen, TRAPP
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
Law Mixing
PHIL
PHILPS
ESPLRKS0
Polymer SRK
HL
HLPS
ESPLRKS0
Polymer SRK
GL
GLPS
ESPLRKS0
Polymer SRK
SL
SLPS
ESPLRKS0
Polymer SRK
VL
VLDVK
VL0DVK,
VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Krevelen, Andrade
KL
KL0VKTR
KL0VKTR
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK, GS0DVK
VSMX
VSMXDVK
VS0DVK, VS0POLY
HS
HSDVK
HS0DVK
van Krevelen
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK, GS0DVK
van Krevelen
VS
VSDVK
VS0DVK, VS0POLY
Solid
196
POLYSAFT: Statistical
Associating Fluid Theory
(SAFT) Equation-of-State
Property Method
POLYSAFT property method:
Vapor
Property
Name
Route ID
Model Name
Description
PHIVMX
PHIVMXSF
ESPLSFT
SAFT
HVMX
HVMXSF
ESPLSFT
SAFT
GVMX
GVMXSF
ESPLSFT
SAFT
SVMX
SVMXSF
ESPLSFT
SAFT
VVMX
VVMXSF
ESPLSFT
SAFT
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIVSF
ESPLSFT0
SAFT
HV
HVSF
ESPLSFT0
SAFT
GV
GVSF
ESPLSFT0
SAFT
SV
SVSF
ESPLSFT0
SAFT
VV
VVSF
ESPLSFT0
SAFT
DV
DV01
DV0CEWL
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMXSF
ESPLSFT
SAFT
HLMX
HLMXSF
ESPLSFT
SAFT
GLMX
GLMXSF
ESPLSFT
SAFT
SLMX
SLMXSF
ESPLSFT
SAFT
VLMX
VLMXSF
ESPLSFT
SAFT
MULMX
MULMX13
MUPOLY,
MULMH
Aspen, Modified Mark-Houwink/

van Krevelen, Andrade
KLMX
KLMXVKTR
KLMXVKTR

Krevelen, TRAPP
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
Liquid
197
Liquid
Property
Name
Route ID
Model Name
Description
SIGLMX
SIGLMX01
SIG2HSS
Law Mixing
PHIL
PHILSF
ESPLSFT0
SAFT
HL
HLSF
ESPLSFT0
SAFT
GL
GLSF
ESPLSFT0
SAFT
SL
SLSF
ESPLSFT0
SAFT
VL
VLSF
ESPLSFT0
SAFT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Krevelen, Andrade
KL
KL0VKTR
KL0VKTR
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMXSF
ESPLSFT
SAFT
HLMX
HLMXSF
ESPLSFT
SAFT
GLMX
GLMXSF
ESPLSFT
SAFT
SLMX
SLMXSF
ESPLSFT
SAFT
Solid
VLMX
VLMXSF
ESPLSFT
SAFT
MULMX
MULMX13
MUPOLY,
MULMH
Aspen, Modified Mark-Houwink/

van Krevelen, Andrade
KLMX
KLMXVKTR
KLMXVKTR

Krevelen, TRAPP
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
POLYPCSF: Perturbed-Chain
Statistical Associating Fluid
Theory (PC-SAFT) Equation-ofState Property Method
POLYPCSF property method:
Vapor
198
Property
Name
Route ID
Model Name
Description
PHIVMX
PHIVMXPC
ESPCSFT
PCSAFT
Vapor
Property
Name
Route ID
Model Name
Description
HVMX
HVMXPC
ESPCSFT
PCSAFT
GVMX
GVMXPC
ESPCSFT
PCSAFT
SVMX
SVMXPC
ESPCSFT
PCSAFT
VVMX
VVMXPC
ESPCSFT
PCSAFT
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIVPC
ESPCSFT0
PCSAFT
HV
HVPC
ESPCSFT0
PCSAFT
GV
GVPC
ESPCSFT0
PCSAFT
SV
SVPC
ESPCSFT0
PCSAFT
VV
VVPC
ESPCSFT0
PCSAFT
DV
DV01
DV0CEWL
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
Route ID
Model Name
Description
Liquid
Property
Name
PHILMX
PHILMXPC
ESPCSFT
PCSAFT
HLMX
HLMXPC
ESPCSFT
PCSAFT
GLMX
GLMXPC
ESPCSFT
PCSAFT
SLMX
SLMXPC
ESPCSFT
PCSAFT
VLMX
VLMXPC
ESPCSFT
PCSAFT
MULMX
MULMX13
MUPOLY,
MULMH

Krevelen, Andrade
KLMX
KLMXVKTR
KLMXVKTR

Krevelen, TRAPP
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS

Mixing
PHIL
PHILPC
ESPCSFT0
PCSAFT
HL
HLPC
ESPCSFT0
PCSAFT
GL
GLPC
ESPCSFT0
PCSAFT
SL
SLPC
ESPCSFT0
PCSAFT
VL
VLPC
ESPCSFT0
PCSAFT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Modified Mark-Houwink/van Krevelen,

Andrade
KL
KL0VKTR
KL0VKTR
199
Solid
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK, GS0DVK
VSMX
VSMXDVK
VS0DVK,
VS0POLY
HS
HSDVK
HS0DVK
van Krevelen
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK, GS0DVK
van Krevelen
VS
VSDVK
VS0DVK,
VS0POLY
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
200
Property
Name
Route ID
Model Name
Description
PHIVMX
PHIVMXPA
ESPSAFT
Copolymer PCSAFT
HVMX
HVMXPA
ESPSAFT
Copolymer PCSAFT
GVMX
GVMXPA
ESPSAFT
Copolymer PCSAFT
SVMX
SVMXPA
ESPSAFT
Copolymer PCSAFT
VVMX
VVMXPA
ESPSAFT
Copolymer PCSAFT
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
PHIV
PHIVPA
ESPSAFT0
Copolymer PCSAFT
HV
HVPA
ESPSAFT0
Copolymer PCSAFT
GV
GVPA
ESPSAFT0
Copolymer PCSAFT
SV
SVPA
ESPSAFT0
Copolymer PCSAFT
VV
VVPA
ESPSAFT0
Copolymer PCSAFT
DV
DV01
DV0CEWL
MUV
MUV01
MUV0BROK
KV
KV01
KV0STLTH
Stiel-Thodos
Liquid
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMXPA
ESPSAFT
Copolymer PCSAFT
HLMX
HLMXPA
ESPSAFT
Copolymer PCSAFT
GLMX
GLMXPA
ESPSAFT
Copolymer PCSAFT
SLMX
SLMXPA
ESPSAFT
Copolymer PCSAFT
VLMX
VLMXPA
ESPSAFT
Copolymer PCSAFT
MULMX
MULMX13
MUPOLY,
MULMH

Krevelen, Andrade
KLMX
KLMXVKTR
KLMXVKTR

Krevelen, TRAPP
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS

Mixing
PHIL
PHILPA
ESPSAFT0
Copolymer PCSAFT
HL
HLPA
ESPSAFT0
Copolymer PCSAFT
GL
GLPA
ESPSAFT0
Copolymer PCSAFT
SL
SLPA
ESPSAFT0
Copolymer PCSAFT
VL
VLPA
ESPSAFT0
Copolymer PCSAFT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Modified Mark-Houwink/van Krevelen,

Andrade
KL
KL0VKTR
KL0VKTR
Property
Name
Route ID
Model Name
Description
HSMX
HSMXDVK
HS0DVK
GSMX
GSMXDVK
GS0DVK
SSMX
SSMXDVK
HS0DVK, GS0DVK
VSMX
VSMXDVK
VS0DVK,
VS0POLY
HS
HSDVK
HS0DVK
van Krevelen
Solid
GS
GSDVK
GS0DVK
van Krevelen
SS
SSDVK
HS0DVK, GS0DVK
van Krevelen
VS
VSDVK
VS0DVK,
VS0POLY
201
202
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 206 are used to calculate segment
properties using the following correlations:
Heat Capacity (J/kmol.K) (Liquid or

Crystalline)
Cp *,l T ref nk Cpk*, l T ref

k
Cp *,c T ref n k 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
= Number of occurrences of functional group k in a segment
B Van Krevelen Functional Groups
203
= Liquid heat capacity for functional group k in Van Krevelen

Functional Group Parameters on page 206
Cp k*,l
Cpk*,c = Crystalline heat capacity for functional group k in Van Krevelen

Molar Volume (m3/kmol) (Liquid,

Crystalline, or Glassy)
V * n k Vk*
k
Vk* Vwk * ( A B * T C * Tg )
Where:
V*
= Molar volume of a segment (liquid, crystalline, or glassy)
Vk*
= Molar volume of functional group k (liquid, crystalline, or glassy)
Vwk
= Van der Waals volume of functional group k in Van Krevelen

= Temperature
Tg
= Glass transition temperature
A, B, and C = Empirical constants and vary by phase
Enthalpy (J/kmol), Entropy (J/kmol.K) and

Gibbs Energy (J/kmol) of Formation
H *,ig T ref n k H k*,ig T ref

k
S *,ig T ref n k S k*,ig T ref
*,ig T ref H *,ig T ref T ref S *,ig T ref

Where:
T
T
T
H *,ig T ref
S *,ig
*,ig
H k*,ig
204
ref
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 206
S k*,ig T ref
= Ideal gas entropy of formation of functional group k in Van

Krevelen Functional Group Parameters on page 206
Glass Transition Temperature (K)

Tg
n Y
n M
k
g ,k
Where:
Tg
= Glass transition temperature of a segment
Yg ,k
= Glass transition parameter of functional group k in Van Krevelen

Mk
Melt Transition Temperature (K)

Tm
n Y
n M
k
m ,k
Where:
Tm
= Melt transition temperature of a segment
Ym , k
= Melt transition parameter of functional group k in Van Krevelen

Viscosity Temperature Gradient (J/kmol)1/3

H nk H ,k / M
k
Where:
= Viscosity-temperature gradient of a segment
H ,k = Viscosity-temperature gradient of functional group k in Van Krevelen

= Molecular weight of a segment
Rao Wave Function (m3/kmol)(m/s)1/3

UR(T ref ) n kURk (T ref )
k
Where:
205
UR(T ref )
= Rao wave function of a segment
URk (T ref ) = Rao wave function of functional group k in Van Krevelen

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

URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional Group
Mk
g/mol
The following table shows the bifunctional hydrocarbon group parameters.

Estimated values appear in italic.
100
14.03
10.23
25.35
30.4
-22,000
102
2,700
5,700
420
880
101
28.05
20.45
46.5
57.85
-48,700
215
8,000
13,000
1060
1,850
102
28.05
20.45
46.5
57.85
-48,700
215
8,000
13,000
1,060
1,850
103
82.14
53.28
110.8
147.5
-73,400
548
30,700
45,763
2,180
4,600
CH(C6H11)
104
96.17
63.58
121.2
173. 9
-118,400 680
41,300
51,463
2,600
5,500
CH(C6H5)
105
90.12
52.62
101.2
144.15
84,300
287
36,100
48,000
3600
5,100
C(CH3)2
106
42.08
30.67
68.0
81.2
-72,000
330
8,500
12,100
1620
2,850
C(CH3)(C6H5)
107
104.14
62.84
122.7
167.5
61,000
402
51,000
54,000
4,160
6,100
CH2
CH(CH3)
(sym)
CH(CH3)
(asym)
CH(C5H9)
206
CH CH
(cis)
CH CH
(trans)
CH C(CH3)
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Vw
cm3/mol
Group
No.
Mk
g/mol
Functional Group
108
26.04
16.94
37.3
42.8
76,000
76
3,800
8,000
760
1,400
109
26.04
16.94
37.3
42.8
70,000
83
7,400
11,000
760
1,400
110
40.06
27.16
60.05
74.22
42,000
183
8,100
10,000
1,190
2,150
111
40.06
27.16
60.05
74.22
36,000
190
9,100
13,000
1,190
2,150
112
24.02
16.1
----
----
230,000
-50
----
----
----
1,240
113
82.14
53.34
103.2
147.5
-96,400
578
19,000
31,000
2,180
2,900
114
82.14
53.34
103.2
147.5
-102,400 585
27,000
45,000
2,180
2,900
115
76.09
43.32
78.8
113.1
100,000
180
29,000
38,000
3200
4,100
116
76.09
43.32
78.8
113.1
100,000
180
25,000
31,000
----
3,500
117
76.09
43.32
78.8
113.1
100,000
180
----
----
----
3,450
118
104.14
65.62
126.8
166.8
33,000
394
54,000
67,000
4,820
6,150
119
90.12
54.47
102.75
140.1
66,500
287
35,000
45,000
4,010
5,500
120
90.12
53.55
104.15
143.5
78,000
282
31,700
43,700
3,620
4,980
121
90.12
53.55
104.15
143.5
78,000
282
31,700
43,700
3,620
4,980
122
104.14
63.78
129.5
173.9
56,000
384
25,000
47,000
4,040
5,860
123
166.21
96.87
182.95
256.6
178,000
462
65,000
85,000
6,820
9,100
124
152.18
86.64
157.6
226.2
200,000
360
70,000
99,000
6,400
8,200
(cis)
CH C(CH3)
(trans)
C C
(cis)
(trans)
CH3
CH3
CH3
CH2
(sym)
CH2
(asym)
CH2
CH2
CH2
207
236
299,000
538
9,900
URk cm10/3
/
(s1/3.mol)
173,000
H,k
(g/mol)
(J/mol)1/3
118,000
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
339
Ym,k
(g.K/mol)
130
Yg,k
(g.K/mol)
228.22
Cpk*,c(Tref)
J/mol.K
Group
No.
125
Vw
cm3/mol
Mk
g/mol
Functional Group
12,650
Other Hydrogen-containing Groups

URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk (T )
J/mol.K
ref
*,c
Group
No.
Vw
cm3/mol
Functional
Group
Mk
g/mol
The following table shows the other hydrogen-containing group parameters:
CH3
126
15.03
13.67
30.9
36.9
-46,000
95
2,900
1,519
810
1,400
C2H5
127
29.06
23.90
56.25
67.3
-68,000
197
5,600
3,952
1,230
2,280
nC3H7
128
43.09
34.13
81.6
97.7
-90,000
299
8,300
6,774
1,650
3,160
iC3H7
129
43.09
34.12
77.4
94.75
-94,700
310
10,900
14,519
1,870
3,250
tC4H9
130
57.11
44.34
99.0
118.1
-118,000
425
13,600
20,129
2,290
4,130
CH
131
13.02
6.78
15.9
20.95
-2,700
120
5,100
11,481
250
460
132
12.01
3.33
6.2
7.4
20,000
140
2,700
9,063
40
CH2
133
14.01
11.94
22.6
21.8
23,000
30
----
----
----
CH
134
13.02
8.47
18.65
21.8
38,000
38
1,900
4,000
380
745
135
12.01
5.01
10.5
15.9
50,000
50
3,300
4,481
255
136
12.01
6.96
----
----
147,000
-20
----
----
----
----
137
25.03
13.48
29.15
37.3
88,000
88
----
----
380
1,000
CH
138
13.02
8.05
----
----
112,500
-32.5
----
----
----
----
139
12.01
8.05
----
----
115,000
-25
----
----
----
----
CH C
208
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Group
No.
Cpk*,c(Tref)
J/mol.K
Vw
cm3/mol
Mk
g/mol
Functional
Group
140
24.02
10.02
21.0
31.8
100,000
100
----
----
510
141
24.02
10.02
21
31.8
94,000
107
----
----
----
510
CHar
142
13.02
8.06
15.4
22.2
12,500
26
----
----
----
830
Car
143
12.01
5.54
8.55
12.2
25,000
38
----
----
----
400
144
69.12
45.56
95.2
126.55
-70,700
428
28,000
34,281
1,930
4,140
145
83.15
56.79
105.6
152.95
-115,700
560
38,600
39,981
2,350
5,000
146
77.10
45.84
85.6
123.2
87,000
167
33,400
42,300
3,350
4,640
147
74.08
38.28
65.0
93.0
125,000
204
48,200
63,963
3,200
3,300
148
75.08
40.80
71.85
103.2
112,500
192
29,200
41,963
2,390
3,700
C C
(cis)
C C
(trans)
Bifunctional Oxygen-containing Groups
16.00
150
28.01
3.71/
[5.1]1
11.7
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk (T )
J/mol.K
ref
Cpk (T )
J/mol.K
ref
*,l
149
*,c
Group
No.
Vw
cm3/mol
Functional
Group
Mk
g/mol
The following table shows the bifunctional oxygen-containing group

parameters:
16.8
35.6
-120,000
70
4,000
13,500
480
400
23.05
52.8
-132,000
40
9,000
12,000
970
900
209
O C
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Vw
cm3/mol
Group
No.
Mk
g/mol
Functional
Group
151
44.01
15.2
46
65.0
-337,000
116
12,500
30,000
1,450
1,250
152
44.01
17.0
46
65.0
-337,000
116
12,500
30,000
1,450
1,250
O C O
O
153
60.01
63
100.6
-457,000
186
20,000
30,000
3,150
1,600
154
72.02
27
63
114
-584,070
156
22,000
35,000
2,420
2,150
CH(OH)
155
30.03
14.82
32.6
65.75
-178,700
170
13,000
37,500
539
1,050
CH(COOH)
156
58.04
26.52
65.6
119.85
-395,700
238
----
30,724
1,587
1,990
CH(HC=O)
157
42.14
21.92
----
----
-127,700
146
----
13,362
908
----
158
120.10
58.52
124.8
178.1
-237,000
296
38,000
50,000
4,170
5,350
159
46.03
17.63
58.95
101.6
-262,000
242
10,700
32,700
1,380
1,680
O
O C
(acrylic)
C O C
O
18.9/
[23.0]1
COO
O CH2 O
Other Oxygen-containing Groups
OH
OH
C H
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional Group
Mk
g/mol
The following table shows the other oxygen-containing group parameters:
160
17.01
8.04
17.0
44.8
-176,000
50
----
1,477
289
630
161
93.10
51.36
95.8
157.9
-76,000
230
----
39,477
3,489
4,730
162
29.02
15.14
----
----
-125,000
26
----
1,881
658
----
163
45.02
19.74
50
98.9
-393,000
118
----
19,243
1,337
1,530
O
C OH
O
210
Bifunctional Nitrogen-containing Groups

URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional
Group
Mk
g/mol
The following table shows the bifunctional nitrogen-containing group

parameters:
NH
164
15.02
8.08
14.25
31.8
58,000
120
7,000
18,000
680
875
CH(CN)
165
39.04
21.48
40.6
----
120,300
91.5
16,405
25,717
----
1,750
CH(NH2)
166
29.04
17.32
36.55
----
8,800
222.5
----
15,088
562
----
167
91.11
51.4
93.05
144.9
158,000
300
36,000
56,000
3,880
4,975
NH
Other Nitrogen-containing Groups
NH2
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional
Group
Mk
g/mol
The following table shows the other nitrogen-containing group parameters:
168
16.02
10.54
20.95
----
11,500
102.5
----
3,607
312
----
169
14.01
4.33
17.1
44.0
97,000
150
----
10,380
----
65
Nar
170
14.01
----
----
----
69,000
50
----
----
----
----
C N
171
26.02
14.7
25
----
123,000
-28.5
----
1,824
----
1,400
NH2
172
92.12
53.86
99.75
----
111,500
282.5
----
41,607
3,512
----
173
90.10
47.65
95.9
157.1
197,000
330
----
48,380
----
4,165
211
Bifunctional Nitrogen- and Oxygencontaining Groups
C NH
174
43.03
175
59.03
176
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
38
90.1
-74,000
160
15,000
45,000
1,650
1,700
23
58
125.7
-279,000
-240
20,000
43,500
2,130
1,800
58.04
27.6
50
121.9
-16,000
280
20,000
60,000
2,330
2,000
177
59.03
23.58
57.5
----
-44,200
263
----
----
----
----
178
119.12
62.88
116.8
203.2
26,000
340
7,000
98,000
4,850
5,800
O
O C NH
19.56
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional Group
Mk
g/mol
The following table shows the bifunctional nitrogen- and oxygen-containing

group parameters:
[18.1]1
O
NH C NH
O
CH(NO2)
O
C
NH
Other Nitrogen- and Oxygen-containing Groups

URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional Group
Mk
g/mol
The following table shows the other nitrogen- and oxygen-containing group
parameters:
O
C
179
44.03
22.2
----
----
----
----
----
20,721
----
----
180
42.02
16.0
----
----
----
----
----
48,380
----
965
181
46.01
16.8
41.9
----
-41,500
143
----
----
----
----
NH2
O
C
N
NO2
212
Bifunctional Sulfur-containing Groups

URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Group
No.
Cpk*,l(Tref)
J/mol.K
Vw
cm3/mol
Mk
g/mol
Functional
Group
Cpk*,c(Tref)
J/mol.K
The following table shows the bifunctional sulfur-containing group

parameters:
182
32.06
10.8
24.05
44.8
40,000
-24
8,000
22,500
----
550
S S
183
64.12
22.7
48.1
89.6
46,000
-28
16,000
30,000
----
1,100
SO2
184
64.06
20.3
50
----
-282,000
152
32,000
56,000
----
1,250
185
78.15
31.8
73.45
120.0
58,000
54
----
----
----
1,980
S CH2
Other Sulfur-containing Groups
186
SH
33.07
14.81
46.8
52.4
13,000
-33
----
----
----
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional Group
Mk
g/mol
The following table shows the other sulfur-containing group parameters:
----
Bifunctional Halogen-containing Groups

URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional
Group
Mk
g/mol
The following table shows the bifunctional halogen-containing group

parameters:
CHF
187
32.02
13.0
37.0
41.95
-197,700
114
12,400
17,400
----
950
CF2
188
50.01
15.3
49.0
49.4
-370,000
128
10,500
25,500
----
1,050
CHCl
189
48.48
19.0
42.7
60.75
-51,700
111
19,400
27,500
2,330
1,600
CCl2
190
82.92
27.8
60.4
87.0
-78,000
122
22,000
29,000
----
2,350
CH CCl
191
60.49
25.72
56.25
77.1
39,000
79
15,200
32,000
----
1,900
213
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Vw
cm3/mol
Group
No.
Mk
g/mol
Functional
Group
CFCl
192
66.47
21.57
54.7
68.2
-224,000
125
28,000
32,000
----
1,700
CHBr
193
92.93
21.4
41.9
----
-16,700
106
----
----
----
1,760
CBr2
194
171.84
32.5
58.8
----
-8,000
112
----
----
----
2,640
CHI
195
139.93
27.1
38.0
----
37,300
79
----
----
----
----
CI2
196
265.83
44.0
51.0
----
100,000
58
----
----
----
----
Other Halogen-containing Groups

URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Group
No.
Vw
cm3/mol
Functional
Group
Mk
g/mol
The following table shows the other halogen-containing group parameters:
197
19.00
6.0
21.4
21.0
-195,000
-6
9,000
11,000
----
530
CF3
198
69.01
21.33
70.4
70.4
-565,000
122
19,500
36,500
----
1,580
CHF2
199
51.02
18.8
58.4
62.95
-392,700
108
21,400
28,400
----
1,480
CH2F
200
33.03
16.2
46.75
51.4
-217,000
96
11,700
16,700
----
1,410
Cl
201
35.46
12.2
27.1
39.8
-49,000
-9
17,500
22,000
2,080
1,265
CCl3
202
118.38
40
87.5
126.8
-127,000
113
39,500
51,000
----
3,615
CHCl2
203
83.93
31.3
69.8
100.55
100,700
102
36,900
49,500
4,410
2,865
CH2Cl
204
49.48
22.5
52.45
70.2
-71,700
93
20,200
27,700
2,500
2,145
205
111.55
55.3
105.9
152.9
51,000
171
46,500
60,000
5,280
5,365
Br
206
79.92
14.6
26.3
----
-14,000
-14
35,000
11,500
----
1,300
CBr3
207
251.76
47.1
85.1
----
-22,000
98
----
----
----
3,940
CHBr2
208
172.85
36.0
68.2
----
-30,700
92
----
----
----
3,060
CH2Br
209
93.94
24.8
51.65
----
-36,000
88
----
-----
----
2,180
210
126.91
20.4
22.4
----
40,000
-41
----
----
----
----
Cl
214
URk cm10/3
/
(s1/3.mol)
H,k
(g/mol)
(J/mol)1/3
Ym,k
(g.K/mol)
Yg,k
(g.K/mol)
Sk*,ig(Tref)
J/mol.K
Hk*,ig(Tref)
J/mol
Cpk*,l(Tref)
J/mol.K
Cpk*,c(Tref)
J/mol.K
Vw
cm3/mol
Group
No.
Mk
g/mol
Functional
Group
CI3
211
392.74
64.4
73.4
----
140,000
17
----
----
----
----
CHI2
212
266.84
47.5
60.4
----
77,300
38
----
----
----
----
CH2I
213
140.94
30.6
47.75
----
18,000
61
----
-----
----
----
215
216
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:
Polymer
A 0 (m 3 /kg)
A 1 (m 3 /kg.K)
A 2 (m 3 /kg.K 2 )
B0 (Pa)
B1 (1/K)
P
Range
(Mpa)
T
Range
(K)
BR
1.0969E-03
7.6789E-07
-2.2216E-10
1.7596E+08
4.3355E-03
0.1-283
277-328
HDPE
1.1567E-03
6.2888E-07
1.1268E-09
1.7867E+08
4.7254E-03
0.1-200
415-472
I-PB
1.1561E-03
6.1015E-07
8.3234E-10
1.8382E+08
4.7833E-03
0.0-196
407-514
I-PMMA
7.9770E-04
5.5274E-07
-1.4503E-10
2.9210E+08
4.1960E-03
0.1-200
328-463
I-PP
1.2033E-03
4.8182E-07
7.7589E-10
1.4236E+08
4.0184E-03
0.0-196
447-571
LDPE
1.1004E-03
1.4557E-06
-1.5749E-09
1.7598E+08
4.6677E-03
0.1-200
398-471
LLDPE
1.1105E-03
1.2489E-06
-4.0642E-10
1.7255E+08
4.4256E-03
0.1-200
420-473
PAMIDE
7.8153E-04
3.6134E-07
2.7519E-10
3.4019E+08
3.8021E-03
0.0-177
455-588
PBMA
9.3282E-04
5.7856E-07
5.7343-10
2.2569E+08
5.3116E-03
0.1-200
295-473
PC
7.9165E-04
4.4201E-07
2.8583E-10
3.1268E+08
3.9728E-03
0.0-177
430-610
PCHMA
8.7410E-04
4.9035E-07
3.2707E-10
3.0545E+08
5.5030E-03
0.1-200
383-472
PDMS
1.0122E-03
7.7266E-07
1.9944E-09
8.7746E+07
6.2560E-03
0.0-100
298-343
PHENOXY
8.3796E-04
3.6449E-07
5.2933E-10
3.5434E+08
4.3649E-03
0.0-177
349-574
PIB
1.0890E-03
2.5554E-07
2.2682E-09
1.9410E+08
3.9995E-03
0.0-100
326-383
PMMA
8.2396E-04
3.0490E-07
7.0201E-10
2.9803E+08
4.3789E-03
0.1-200
387-432
PMP
1.2078E-03
5.1461E-07
9.7366E-10
1.4978E+08
4.6302E-03
0.0-196
514-592
POM
8.3198E-04
2.7550E-07
2.2000E-09
3.1030E+08
4.4652E-03
0.0-196
462-492
POMS
9.3905E-04
5.1288E-07
5.9157E-11
2.4690E+08
3.6633E-03
0.1-180
413-471
PS-1
9.3805E-04
3.3086E-07
6.6910E-10
2.5001E+08
4.1815E-03
0.1-200
389-469
PTFE
4.6867E-04
1.1542E-07
1.1931E-09
4.0910E+08
9.2556E-03
0.0-392
604-646
PVAC
8.2832E-04
4.7205E-07
1.1364E-09
1.8825E+08
3.8774E-03
0.0-100
337-393
Range of experimental data used in the determination of equation constants.
217
Source: Danner R. P., & High, M. S. (1992). Handbook of Polymer Solution

Thermodynamics. New York: American Institute of Chemical Engineers. p. 3B5.
218
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
Mass Based
Parameter
Description
CPCVK
CPCVKM
Crystalline heat capacity
CPLVK
CPLVKM
Liquid heat capacity
DGCON
DGCONM
Standard free energy of condensation
DGFORM
DGFVKM
Standard free energy on formation at 25C
DBSUB
DGSUBM
Standard free energy of sublimation
DHCON
DHCONM
Standard enthalpy of condensation
DHFVK
DHFVKM
Standard enthalpy of formation at 25C
DHSUB
DHSUBM
Standard enthalpy of sublimation
DNCVK
DNCVKM
Crystalline density
DNGVK
DNGVKM
Glass density
DNLVK
DNLVKM
Liquid density
D Mass Based Property Parameters
219
220
D Mass Based Property Parameters
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
T*, K
P*, bar
*, kg/m3
T range, K
P, up to bar
HDPE
649
4250
904
426-473
1000
LDPE
673
3590
887
408-471
1000
PDMS
476
3020
1104
298-343
1000
PBMA
627
4310
1125
307-473
2000
PHMA
697
4260
1178
398-472
2000
PIB
643
3540
974
326-383
1000
PMMA
696
5030
1269
397-432
2000
POMS
768
3780
1079
412-471
1600
PS
735
3570
1105
388-468
2000
PVAC
590
5090
1283
308-373
800
E Equation-of-State Parameters
221
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:
222
Alias
Component
T*, K
P*, bar
*, kg / m3
CCl4
Carbon Tetrachloride
535
8126
1788
CHCl3
Chloroform
512
4560
1688
CH3Cl
Methyl chloride
487
5593
1538
CO2
Carbon dioxide
277
7436
1629
CS2
Carbon disulfide
567
5157
1398
CH4
Methane
224
2482
500
CH4O
Methanol
468
12017
922
C3H3N
Acrilonitrile
527
5930
868
C3H6O
Acetone
484
5330
917
C3H6O2
Ethyl formate
466
4965
1076
C6H7N
Aniline
614
6292
1115
C3H8O
Propanol
420
8856
972
C3H8O
Isopropyl alcohol
399
8532
975
CH3NO2
Nitromethane
620
9251
1490
C2HCl3
1,1,1-Trichloroethylene
516
3779
1518
C2H2Cl2
1,1-Dichloroethylene
488
5117
1722
C2H4
Ethylene
291
3339
660
C2H4O2
Acetic acid
562
8613
1164
C2H6
Ethane
315
3273
640
C2H6O
Ethanol
413
10690
963
C3H8
Propane
371
3131
690
C4H8O
Methyl ethyl ketone
513
4468
913
C4H8O2
Ethyl acetate
468
4580
1052
C4H10
n-Butane
403
3222
736
C4H10
Isobutane
398
2878
720
C4H10O
Tert-butyl alcohol
448
6931
952
C4H10O
Diethyl ether
431
3627
870
C5H5N
Pyridine
566
5492
1079
C5H10
Cyclopentane
491
3800
867
C5H12
n-Pentane
441
3101
755
C5H12
Isopentane
424
3080
765
C5H12
Neopentane
415
2655
744
C6H5Cl
Chlorobenzene
585
4367
1206
C6H6
Benzene
523
4438
994
C6H6O
Phenol
530
7934
1192
Alias
Component
T*, K
P*, bar
*, kg / m3
C6H14
n-Hexane
476
2979
775
C6H12
Cyclohexane
497
3830
902
C6H12O2
n-Butyl acetate
498
3942
1003
C7H8
Toluene
543
4023
966
C7H16
n-Heptane
487
3090
800
C8H8
Styrene
563
3684
870
C8H10
p-Xylene
561
3810
949
C8H10
m-Xylene
560
3850
952
C8H10
o-Xylene
571
3942
965
C8H18
n-Octane
502
3080
815
C9H20
n-Nonane
517
3070
828
C10H18
trans-Decalin
621
3151
935
C10H18
cis-Decalin
631
3334
960
C10H22
n-Decane
530
3040
837
C11H24
n-Undecane
542
3030
846
C12H26
n-Dodecane
552
3009
854
C13H28
n-Tridecane
560
2989
858
C14H10
Phenanthrene
801
3769
1013
C14H30
n-Tetradecane
570
2959
864
C17H36
n-Heptadecane
596
2867
880
C20H42
n-Eicosane
617
3067
961
H2O
Water
623
26871
1105
H2S
Hydrogen Sulfate
382
6129
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.
223
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:
224
Alias
Component
T range,
K
v oo , cm 3 / mol
uo / k, K
N2
Nitrogen
---
19.457
1.0
123.53
AR
Argon
---
16.29
1.0
150.86
CO
Carbon Monoxide
72-121
15.776
1.221
111.97
CO2
Carbon Dioxide
218-288
13.578
1.417
216.08
CL2
Chlorine
180-400
22.755
1.147
367.44
CS2
Carbon Disulfide
278-533
23.622
1.463
396.05
SO2
Sulfur Dioxide
283-413
22.611
1.133
335.84
CH4
Methane
92-180
21.576
1.0
190.29
C2H6
Ethane
160-300
14.460
1.941
191.44
C3H8
Propane
190-360
13.457
2.696
193.03
C4H10
n-Butane
220-420
12.599
3.458
195.11
C5H12
n-Pentane
233-450
12.533
4.091
200.02
C6H14
n-Hexane
243-493
12.475
4.724
202.72
C7H16
n-Heptane
273-523
12.282
5.391
204.61
C8H18
n-Octane
303-543
12.234
6.045
206.03
C9H20
n-Nonane
303-503
12.240
6.883
203.56
C10H22
n-Decane
313-573
11.723
7.527
205.46
C12H26
n-Dodecane
313-523
11.864
8.921
205.93
C14H30
n-Tetradecane
313-533
12.389
9.978
209.40
C16H34
n-Hexadecane
333-593
12.300
11.209
210.65
C20H42
n-Eicosane
393-573
12.0
13.940
211.25
C28H58
n-Octacosane
449-704
12.0
19.287
209.96
C36H74
n-Hexatriacontane
497-768
12.0
24.443
208.74
C44H90
n-Tetratetracontane
534-725
12.0
29.252
207.73
C5H10
Cyclopentane
252-483
12.469
3.670
226.70
C6H12
Methyl-cyclopentane
263-503
13.201
4.142
223.25
C7H14
Ethyl-cyclopentane
273-513
13.766
4.578
229.04
C8H16
Propyl-cyclopentane
293-423
14.251
5.037
232.18
C9H18
Butyl-cyclopentane
314-578
14.148
5.657
230.61
C10H20
Pentyl-cyclopentane
333-483
13.460
6.503
225.56
C6H12
Cyclohexane
283-513
13.502
3.970
236.41
C7H14
Methylcyclohexane
273-533
15.651
3.954
248.44
C8H16
Ethylcyclohexane
273-453
15.503
4.656
243.16
Alias
Component
T range,
K
v oo , cm 3 / mol
uo / k, K
C9H18
Propylcyclohexane
313-453
15.037
5.326
238.51
C10H20
Butylcyclohexane
333-484
14.450
6.060
234.30
C11H22
Pentylcyclohexane
353-503
14.034
6.804
230.91
C6H6
Benzene
300-540
11.421
3.749
250.19
C7H8
Methyl-benzene
293-533
11.789
4.373
245.27
C8H10
Ethyl-benzene
293-573
12.681
4.719
248.79
C9H12
n-Propyl-benzene
323-573
12.421
5.521
238.66
C10H14
n-Butyl-benzene
293-523
12.894
6.058
238.19
C8H10
m-Xylene
309-573
12.184
4.886
245.88
C12H10
Biphenyl
433-653
12.068
6.136
280.54
C10H8
Naphthalene
373-693
13.704
4.671
304.80
C11H10
1-Methyl-naphthalene
383-511
13.684
5.418
293.45
C12H12
1-Ethyl-naphthalene
393-563
12.835
6.292
276.18
C13H14
1-n-Propyl-naphthalene
403-546
13.304
6.882
266.82
C14H16
1-n-Butyl-naphthalene
413-566
13.140
7.766
252.11
C14H10
Phenanthrene
373-633
16.518
5.327
352.00
C14H10
Anthracene
493-673
16.297
5.344
352.65
C16H10
Pyrene
553-673
18.212
5.615
369.38
C2H6O
Dimethyl-ether
179-265
11.536
2.799
207.83
C3H8O
Methyl-ethyl-ether
266-299
10.065
3.540
203.54
C4H10O
methyl-n-propyl-ether
267-335
10.224
4.069
208.13
C4H10O
Diethyl-ether
273-453
10.220
4.430
191.92
C12H10O
Phenyl-ether
523-633
12.100
6.358
276.13
C3H9N
Trimethylamine
193-277
14.102
3.459
196.09
C12H10O
Triethylamine
323-368
11.288
5.363
201.31
C3H6O
Acetone
273-492
7.765
4.504
210.92
C4H8O
Methy-ethyl ketone
257-376
11.871
4.193
229.99
C5H10O
Methyl-n-propyl ketone
274.399
11.653
4.644
230.40
C5H10O
Diethyl-ketone
275-399
10.510
4.569
235.24
C2H4
Ethylene
133-263
18.157
1.464
212.06
C3H6
Propylene
140-320
15.648
2.223
213.90
C4H8
1-Butene
203-383
13.154
3.162
202.49
C6H12
1-Hexene
213-403
12.999
4.508
204.71
CH3CL
Chloromethane
213-333
10.765
2.377
238.37
CH2CL2
Dichloromethane
230-333
10.341
3.114
253.03
CHCL3
Trichloromethane
244-357
10.971
3.661
240.31
CCL4
Tetrachloromethane
273-523
13.730
3.458
257.46
C2H5CL
Chloroethane
212-440
11.074
3.034
229.58
C3H7CL
1-Chloropropane
238-341
11.946
3.600
229.14
C4H7CL
1-Chlorobutane
262-375
12.236
4.207
227.88
C6H11CL
1-Chlorohexane
306-435
12.422
5.458
225.82
C6H5CL
Chlorobenzene
273-543
13.093
3.962
276.72
225
Alias
Component
T range,
K
v oo , cm 3 / mol
uo / k, K
PE
Polyethylene (MW=25000)
413-473
12.0
1165.77
210.0
P(E&P)
Polypropylene
263-303
12.0
822.68
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.
226
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
cid-list
henryid
227
Input Language Description for Property Methods
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
Primary property method name (See Available Property

Methods in Chapter 1).
sectionid-list
List of flowsheet section IDs.
FREE-WATER
Free water phase property method name (Default=STEAMTA).
SOLU-WATER
Method for calculating the K-value of water in the organic

phase.
HENRY-COMPS
SOLU-WATER=0
Water solubility correlation is used, vapor

phase fugacity for water calculated by
free water phase property method
SOLU-WATER=1
Water solubility correlation is used, vapor

phase fugacity for water calculated by
primary property method
SOLU-WATER=2
Water solubility correlation is used with a

correction for unsaturated systems,
vapor phase fugacity for water calculated
by primary property method
SOLU-WATER=3
Primary property method is used. This

method is not recommended for waterhydrocarbon systems unless waterhydrocarbon interaction parameters are
available. (Default)
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.
228
henryid
Henry's constant component list ID
cid-list
List of component IDs
Input Language Example for Property Methods
HENRY-COMPS HC INI1
PROPERTIES POLYNRTL HENRY-COMPS=HC
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.
229
Input Language Description for Property Data
230
PROP-LIST
Used to enter parameter names and data set numbers.
PVAL
Used to enter the PROP-LIST parameter values.
BPVAL
Used to enter the PROP-LIST binary parameter values.
COMP-LIST
Used to enter component IDs.
CVAL
Used to enter the COMP-LIST parameter values.
BCVAL
Used to enter the COMP-LIST binary parameter values.

paramname
Parameter name
setno
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)
cid
Component ID
cid1
Component ID of first component of binary

pair
cid2
Component ID of second component of binary

pair
value-list
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.
cid-list
List of component ID
Input Language Example for Property Data
PROP-DATA
IN-UNITS SI
PROP-LIST
PVAL HOPOLY
PVAL COPOLY
PROP-DATA
IN-UNITS SI
PROP-LIST
PVAL HOPOLY
PVAL COPOLY
PVAL ABSEG
PVAL ASEG
PVAL BSEG
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
MW
1.0
1.0
192.17
76.09
116.08
DHCONM
-3.64261D4
-3.64261D4
PROP-DATA
IN-UNITS SI
PROP-LIST GMRENB
BPVAL MCH ASEG -92.0
BPVAL ASEG MCH 430.0
/ TB
/ 2000.0
/ 2000.0
/
/
/
/
/
/
DHSUB
8.84633D4
8.84633D4
/
/
/
TMVK
1.0
1.0
/ TGVK
/ 0.0
/ 0.0
GMRENC
0.2
0.2
231
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
Option=ALL
Estimate all missing parameters (default)
method
Polymer property estimation method name
SEG-id
Segment ID defined in the component list
groupno
Functional group number (group ID taken from Appendix B)
nooccur
Number of occurrences of the group
Input Language Example for Property Parameter Estimation
ESTIMATE ALL
STRUCTURES
VANKREV ABSEG
VANKREV BSEG
COOVANKREV ABSEG
COO-
232
115 1
151 2 / 100 2
115 1
/ 151 2 / 100 2
;-(C6H4)-COO-CH2-CH2;-(C6H4)-COO-CH2-CH2-
Index
A
ABS 145
Acrylonitrile-butadiene-styrene 145
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 111
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
model 11719
Polymer UNIFAC model 11517
properties available 93
property models 13, 15
thermodynamic property
calculations 90
vapor-liquid equilibria
calculations 88
Adding
data for parameter optimization
23
Index
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 22429
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
233
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
activity coefficient 107
equation 107
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
234
Diffusion coefficients 6
Dilution effect 167
Dissolved gas 89
E
e-bulletins 3
adjustable parameters 112
applicability 104
assumptions 104
Born term 107
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 106
model 10314
model parameters 113
Pitzer-Debye-Hckel term 106
specifying model 114
terms 105
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
temperature relationship 128
Entropy
calculation 203
departure 31
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
Index
liquid-liquid equilibria
calculations 30
model overview 27
models available 2786, 34
parameters for 21823
PC-SAFT model 5966
phase equilibria calculations 29
30
Polymer SRK model 4247
properties available 32
property models 14
SAFT model 4759
Sanchez-Lacombe model 3442
thermodynamic property
calculations 3032
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
21
property parameters 229
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
parameters 169
specifying 169
F
Flory-Huggins
applicability 94
binary interaction parameter 96
concentration basis 97
Index
equation 111
for multiple components 96
Gibbs free energy of mixing 95
interaction parameter 94
model 9498
model parameters 97
property method (POLYFH) 184
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
Glass transition
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
235
H
Heat capacity
calculation 202
ideal gas 125
of polymers 131
parameters 127
Helmholtz free energy 49, 60
help desk 3
I
Ideal gas
departure functions 123
enthalpy 124
Gibbs free energy 124
heat capacity 125
heat capacity parameters 127
model 12327
molar mixture properties 32
property model 15
Input language
for physical properties 22429
property data 226
property methods 224
property parameter estimation
229
Interaction contribution
local 107
long range 106
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
of polymers 123, 128
pure component model 147
236
Liquid Gibbs free energy

of polymers 130
Liquid molar volume
mixture calculations 92
model parameters (Tait) 140
model parameters (van
Krevelen) 137
Tait model 14041
Van Krevelen model 13639
Liquid Van Krevelen model 12735
Liquid-liquid equilibrium 30, 90
Liquid-liquid phase equilibrium 11
LLE 11, 30, 90
Local composition
equation 108
Local interaction contribution 107
Long range interaction contribution
106
Lower critical solution temperature
11
M
Mark-Houwink
equation 152
Mark-Houwink/van Krevelen
model 15258
model applicability 151
Mass balance 6
Mass-based property parameters
217
Melt transition
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
Index
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
Copolymer PC-SAFT EOS 67
Electrolyte-Polymer NRTL activity
coefficient 10314
equation of state 2786
167
Flory-Huggins activity coefficient
9498
ideal gas 12327
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 11517
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 13639
Van Krevelen melt transition
temperature 142
Index
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
237
electrolyte-electrolyte 112
electrolyte-molecule 112
entering for components 21
entering for property models 20
estimating for property models
21
estimating property 229
for Electrolyte-Polymer NRTL
model 113
for equation of state models
21823
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)
140
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 103
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) 221
for SAFT model 57
for Sanchez-Lacombe (POLYSL)
218
for Sanchez-Lacombe model 36,
4042
238
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 215
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
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
Index
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
comparison to SAFT 60
copolymer model 67
for copolymer systems 63
implementation 62
model 5966
model parameters 65
property method (POLYPCSF)
198200
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 224
route structure 183
specifying 1923
Pitzer-Debye-Hckel
equation 106
Plasticizer effect 165
PNRTL-IG 17, 19293
Polydispersity 7
POLYFH 16, 18485
Polymer mixture thermal
Index
Polymer mixture viscosity model

about 15861
applicability 151, 158
Eyring-NRTL 151
parameters 159
specifying 161
Polymer NRTL
activity coefficients 101
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) 19293
model 98103
property method (POLYNRTL)
18687
Polymer solution
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 115
for solvent activity 118
free volume model 11719
free volume model parameters
119
free volume property method
(POLYUFV) 19091
239
model 11517
modification for free volume 117
property method (POLYUF) 188
89
specifying free volume model
119
Polymer viscosity
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
240
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 110
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, 18687
POLYPCSF
about 17
route structure 198200
POLYSAFT
about 17
POLYSL
about 17
POLYSRK 17, 19596
POLYUF 17, 18889
POLYUFV 17, 19091
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
Index
vapor-liquid-liquid equilibria 10
Process simulation See Process
Modeling
Properties See also Thermophysical
properties, See also
Thermodynamic properties
calculating segment from
estimating parameters 229
for activity coefficient models 93
for energy balance 6
for EOS models 32
for equilibria 6
for equipment design 6
for mass balance 6
for polymers 122
input language 22429
mass-based 217
modeling thermophysical 12
of interest in modeling 5
of polymer solution viscosity
components 162
of polymers 526, 12150
specifying 1923
specifying data 226
thermodynamic 526
thermophysical 12150
Property methods
available 1619
customizing 20
input language 224
liquid phase calcualtions 18
PC-SAFT 17, 200
PNRTL-IG 17, 19293
POLYFH 16, 18485
POLYNRTL 16, 18687
POLYPCSF 17, 198200
POLYSAFT 17, 196200
POLYSL 17, 19395
POLYSRK 17, 19596
POLYUF 17, 18889
POLYUFV 17, 19091
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
Index
estimating parameters 21
167
Flory-Huggins 9498
for activity coefficients 13, 15,
87120
for density 13, 15
for enthalpy 13, 15
for equations of state 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
15258
mixture thermal conductivity 180
optimizing 23
PCSAFT 5966
polymer mixture viscosity 158
61
Polymer NRTL 98103
Polymer UNIFAC 11517
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 13639
Van Krevelen melt transition
temperature 142
viscosity 16167
Van Krevelen solid 143
conductivity 17379
Pseudo-components 162
Q
Quasi-binary systems 161
241
R
Rao function
calculation 204
from van Krevelen group
contribution 177
Reduced viscosity 157
Regressing
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
183200
for thermal conductivity 181
for viscosity 170
S
SAFT
applicability 47
comparison to PC-SAFT 60
for fluid mixtures 52
for pure fluids 47
implementation 5355
model 4759
model parameters 57, 221
property method (POLYSAFT)
196200
required parameters 53
specifying model 59
Sanchez-Lacombe
characteristics 36
equation 35
for fluid mixtures 36
242
for homopolymers 36
for pure fluids 34
model 3442
model parameters 4042, 218
molecular parameters 36
property method (POLYSL) 193
95
specifying model 42
Sato-Reidel/DIPPR model 181
Segments
calculating properties from
reference temperature (thermal
conductivity) 176
reference thermal conductivity
178
thermal conductivity at 298K 177
(ideal gas) 126
(liquid molar volume) 139
(liquid) 134
(thermal conductivity) 176
Semi-crystalline solid 8
Simulation See Process Modeling
Soave-Redlich-Kwong See Polymer
SRK
Solid enthalpy
of polymers 143
Solid Gibbs free energy
of polymers 144
Solid molar volume
model parameters (van
Krevelen) 145
of polymers 144
Solids
amorphous 8
semi-crystalline 8
Solution viscosity See also Polymer
solution viscosity model
Solutions
critical concentration 161
viscosity estimation 164
Index
Solvent
dilution effect 167
Specifying
data for parameter optimization
23
Electrolyte-Polymer NRTL model
114
model 169
Flory-Huggins model 98
model 158
mixture thermal conductivity
model 180
molecular structure for property
estimation 22
parameter estimates for property
models 21
20
PC-SAFT model 66
physical properties 1923
physical properties (input
language) 224
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 226
property methods 19
SAFT model 59
Sanchez-Lacombe model 42
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 140
Index
model coefficients 215

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
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
Thermodynamic data
for polymer systems 19
Thermodynamic properties See
also Properties
243
activity 6
calculated from activity
coefficient models 90
calculated from EOS models 30
32
density 6
enthalpy 6
enthalpy departure 31
entropy 6
entropy departure 31
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 11517
UNIFAC free volume
applicability 117
Upper critical solution temperature
11
V
Van der Waals
for fluid mixture 52
244
volume 203
Van Krevelen
equation for thermal conductivity
173
functional group parameters
20514
group contribution 145
group contribution for polymers
156
liquid model 12735
liquid model parameters 131
liquid molar volume model 136
39
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
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
model 15258
model overview 151
models list 151
of mixtures 6
Index
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
model 16167
Van Krevelen temperature
correlation 155
zero-shear 16, 156
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 156
Z
Zero-shear viscosity
estimation methods 16
of mixtures 158, 168
of polymers 156
Index
245

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Aspen Polymers

Polymer Characterization and Physical Properties

Version Number: V8.0

Specifying the Sanchez-Lacombe EOS Model ........................................... 42

References .................................................................................................. 119

Eyring-NRTL Mixture Viscosity Model Parameters.................................... 169

C Tait Model Coefficients ....................................................................................217

Introducing Aspen Polymers

Characterizing polymer molecular structure

Calculating rheological and mechanical properties

Tracking these properties throughout a flowsheet

About This Documentation Set

Polymer manufacturing process overview - describes the basics of

Polymer structural characterization - describes the methods used for

Polymerization reactions - describes the polymerization kinetic models,

Steady-state flowsheeting - provides an overview of capabilities used

Introducing Aspen Polymers

Run-time environment - covers issues concerning the run-time

Volume 2 describes methodologies for tracking chemical component

Thermodynamic properties of polymer systems describes polymer

Equation-of-state (EOS) models provides an overview of the

Activity coefficient models provides an overview of the properties

Thermophysical properties of polymers provides and overview of

Polymer viscosity models describes polymer viscosity model

Polymer thermal conductivity models - describes thermal conductivity

Aspen Polymers Guides

Introducing Aspen Polymers

Aspen Polymers User Guide, Volume 2

Aspen Plus Guides

Aspen Physical Property System Guides

Aspen Dynamics Guides

Access current product documentation

Search for and download application examples

Search for and download service packs and product updates

Submit and track technical issues

Report product defects

Review lists of known deficiencies and defects

Registered users can also subscribe to our Technical Support e-Bulletins.

Introducing Aspen Polymers

Product updates and releases

Introducing Aspen Polymers

This chapter discusses thermodynamic properties of polymer systems. It

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

1 Thermodynamic Properties of Polymer Systems

Properties for Equilibria, Mass and Energy

T V where T is the temperature, p is the pressure, and V is

the volume. Consequently, it is necessary to calculate temperature

Properties for Detailed Equipment Design

Important Properties for Modeling

1 Thermodynamic Properties of Polymer Systems

Fugacity (or thermodynamic potential)

Gibbs free energy

Differences Between Polymers

1 Thermodynamic Properties of Polymer Systems

length, chain composition, and degree of branching. In other words, polymers

Tg and Tm , and a melt above Tm .

The knowledge of state of aggregation of polymer in the condensed phase is