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
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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:
There are also many additional features that permit the simulation of the
entire manufacturing processes.
operation models, data fitting tools, and analysis tools, such as sensitivity
studies.
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
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:
Search for tech tips, solutions and frequently asked questions (FAQs)
Send suggestions
Technical advisories
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
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;
Reid et al., 1987; Sandler, 1988, 1994; Van Krevelen, 1990; Van Ness, 1964;
Walas, 1985).
Thermodynamic properties
Transport properties
Viscosity
Thermal conductivity
Internal energy, or
Enthalpy, or
CV
CP
Surface tension
Diffusivity
Entropy
Density
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
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.
10
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.
12
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
Tait 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
Eyring-NRTL Mixture
Viscosity Model
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
13
Model
Description
Equations of State
Sanchez-Lacombe
Polymer SRK
SAFT
PC-SAFT
Copolymer PC-SAFT
f iv f il
(1.1)
Where:
f iv
fil
f i l1 f i l 2
(1.2)
Where:
f i l1
f i l2
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.
15
16
Property
method
Description
POLYFH
POLYNRTL
Property
method
Description
POLYUF
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
POLYSL
POLYSRK
POLYSAFT
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
Vapor
Departure
functions,
fugacity
coefficient, molar
volume
SAFT
(POLYSAFT)
17
Properties
Calculated
Model (Property
method)
Used For
PC-SAFT
(POLYPCSF)
Liquid
Vapor pressure
PLXANT
Antoine
Activity
Coefficient
Flory-Huggins (POLYFH)
Enthalpy, entropy
Vaporization
enthalpy
Density
Viscosity
18
Sanchez-Lacombe (POLYSL)
SAFT (POLYSAFT)
PC-SAFT (POLYPCSF)
Properties
Calculated
Model (Property
method)
Used For
Thermal
Conductivity
19
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
Click the Route ID that you want to change. From the list, select the new
route ID.
The new route ID is highlighted.
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.
20
Click Parameters.
The following folders appear:
o
Pure Component
Binary Interaction
Electrolyte Pair
Electrolyte Ternary
UNIFAC Group
Results
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
On the same component parameter form, click the name box and either
enter a name, or accept the default, and click OK.
Click the Parameters box, and click the name of the parameter.
Click Next
to proceed.
21
Click Estimation.
A Setup sheet appears.
Click the parameter tab in the object manager for the parameters you
want to estimate.
Click Next
to proceed.
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
Functional group
Formula
Select the method you want to use and define the molecule according to
the method selected.
Click Next
to proceed.
Click Data.
An object manager appears.
Click New.
A Create a new ID form appears.
MIXTURE
PURE-COMP
Following is a description for pure component data entry. Similar steps are
required for mixture data entry.
6
10 Click Next
to proceed.
References
Aspen Physical Property System Physical Property Methods and Models.
Cambridge, MA: Aspen Technology, Inc.
23
24
25
26
2 Equation-of-State Models
2 Equation-of-State Models
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
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
SAFT EOS
PC-SAFT EOS
28
2 Equation-of-State Models
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
il
yi
xi
= System temperature
ni
Zm
pV
, compressibility factor of the mixture
nRT
i
Equations 2.1 and 2.2 are identical except for the phase to which the
2 Equation-of-State Models
29
iv y i il xi
(2.4)
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
2 Equation-of-State Models
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)
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
Sm
Gm
Vm
H mig
S mig
Gmig
V ig
p ref
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
2 Equation-of-State Models
l
m
v
m
ig
m
ig
m
31
G
G
v
m
G mig
l
m
G mig
(2.14)
(2.15)
p( T ,Vm ) for Vm or by
H mig y i H i*,ig
in vapor phase
(2.16)
H mig xi H i*,ig
in liquid phase
(2.17)
Where:
32
Property
Name
Symbol
Description
PHIVMX
iv
PHILMX
il
HVMX
H mv
HLMX
H ml
SVMX
S mv
SLMX
S ml
2 Equation-of-State Models
Property
Name
Symbol
Description
GVMX
Gmv
GLMX
Gml
VVMX
Vmv
VLMX
Vml
PHIV
i*, v
PHIL
i*,l
HV
H i*,v
HL
H i*,l
SV
S i*,v
SL
S i*,l
GV
i*, v
GL
i*, l
VV
Vi *,v
VL
Vi *,l
DHVMX
H mv H mig
DHLMX
H ml H mig
DSVMX
S mv S mig
DSLMX
S ml S mig
DGVMX
Gmv Gmig
DGLMX
Gml Gmig
DHV
H i*, v H i*,ig
DHL
H i*,l H i*,ig
DSV
S i*,v S i*,ig
DSL
S i*,l S i*,ig
DGV
i*, v i*,ig
DGL
i*,l i*,ig
2 Equation-of-State Models
33
Model
Name
Phase(s)
Pure
Mixture
Properties Calculated
POLYSL
ESPLSL0
v and l
ESPLSL
v and l
ESPLRKS0
v and l
ESPLRKS
v and l
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
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
2 Equation-of-State Models
N r N 0 mN
The total volume of the system is:
V N 0 mN v *
Where:
v*
*
mN
~
N 0 mN
With
M
mv *
NM
V
Where:
= Mass density
1
~ ~
~ 2 P T ln1 ~ 1 ~ 0
m
(2.18)
~ T
T *
T
2 Equation-of-State Models
p
~
P *
P
~ *
(2.19)
35
Sanchez-Lacombe Parameters
T*
*
k
P*
*
v*
M
(2.20)
mv *
v*
= Boltzmann's constant
*,
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.
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.
36
2 Equation-of-State Models
*
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:
vij*
1 *
vii v *jj 1 ij
2
(2.25)
(2.26)
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.
v *p
Nseg Nseg
v *AB
Where:
and
2 Equation-of-State Models
37
v *AB
1 *
*
v AA v BB
(1 AB )
2
Where:
AB
*p
1
v *p
Nseg Nseg
*
AB
v *AB
A B
With:
*
*AB *AA BB
(1 k AB )
Where:
*
=
*AA and BB
k AB
1
A
mp
A mA
Where:
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
2 Equation-of-State Models
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*
XA
*AA
k iA
*p1 p2
*p1
p1
*p2
p2
Tr
T
Tref
Where:
Tref
2 Equation-of-State Models
39
vip*
Nseg
vip*
v *AA
iA
p1
v *p2
p2
dependence:
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
2 Equation-of-State Models
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
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:
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
2 Equation-of-State Models
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:
42
2 Equation-of-State Models
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
GE
a
ai , bi , xi , GE or AE
bRT
Where:
ai
bi
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 )
2 Equation-of-State Models
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
Tc , i
p c ,i
Tr ,i
= T / Tc ,i
p c for alkanes up to
about C20 (See works of Tsonopoulos & Tan, 1993; Teja et al., 1990). The
44
2 Equation-of-State Models
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.
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
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
2 Equation-of-State Models
45
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
2 Equation-of-State Models
the polymer SRK model. In this case, the mixture parameters of the selected
GE
Low-density polyethylene (Folie & Radosz, 1995; Xiong & Kiran, 1995)
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
2 Equation-of-State Models
47
N AV
md 3
6
Where:
= Molar density
N AV = Avogadro constant
This equation can be rewritten as:
mv o
(2.28)
With
v0
N AV 3
d
6
(2.29)
Where:
48
2 Equation-of-State Models
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,
(2.32)
Where:
2 Equation-of-State Models
49
a (T , V , N )
segments
The general expression for the Helmholtz free energy in SAFT is given by:
(2.33)
a seg m a hs a disp
(2.34)
a hs 4 3 2
RT
1 2
(2.35)
Dispersion Term
a disp
u
Dij
RT
kT
i
j
(2.36)
50
2 Equation-of-State Models
a chain
1 m ln g (d ) seg
RT
(2.37)
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
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
(2.41)
(2.42)
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,
2 Equation-of-State Models
v oo
51
uo / k
Segment energy,
Segment number, m
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
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
2 Equation-of-State Models
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
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
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
2 Equation-of-State Models
53
/ k ) and the
oo
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
oo
54
2 Equation-of-State Models
00
p
Nseg
00
A A
u 0p
Nseg
u A0
Nseg
m p M n X A rA
A
Where:
v 00
p
u 0p
2 Equation-of-State Models
55
mp
XA
v A00
u A0
rA
Mn
If parameters
0
v 00
p , u p and m p are provided for the polymer or oligomer, then
these have highest priority and are used for calculations. If they are not
known, usually in the case of copolymers, the user must provide
v A00 , u A0 and
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:
u ip0
Nseg
u ii0 u 0AA (1 k iA )
Where:
uip0
u ii0
0
u AA
u A0
k iA
56
2 Equation-of-State Models
u 0p1 p2
k p1 p2
u 0p1
p1
u 0p2
p2
Tr
T
Tref
Where:
Tref
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
2 Equation-of-State Models
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
These options are shown in priority order. For example, if the binary
parameters are provided for both polymer-solvent pairs and segment-solvent
pairs, the polymer-solvent parameters are used and the segment-solvent
pairs are ignored. If the user provides the binary parameters for segmentsolvent pairs only, the values for polymer-solvent pairs will be calculated.
Appendix E lists pure component parameters for some solvents (monomers)
and homopolymers. If the pure parameters are not available for components
in a calculation, the user can perform an Aspen Plus Regression Run (DRS) to
obtain these pure component parameters. For non-polymer components, the
pure component parameters are usually obtained by fitting experimental
vapor pressure and liquid molar volume data. To obtain pure homopolymer
(or segment) parameters, experimental data on liquid density should be
regressed. Once the pure component parameters are available for a
homopolymer, ideal-gas heat capacity parameters, CPIG, should be regressed
for the same homopolymer using experimental liquid heat capacity data (for
details on ideal-gas heat capacity for polymers, see Aspen Ideal Gas Property
Model in Chapter 4). In addition to pure component parameters, SAFTU,
SAFTV, and SAFTM or SAFTR, the binary parameter, SFTKIJ, for each solventsolvent pair or each solvent-polymer (segment) pair, can be regressed using
vapor-liquid equilibrium (VLE) data in the form of TPXY data in Aspen Plus.
58
2 Equation-of-State Models
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.
2 Equation-of-State Models
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,
60
2 Equation-of-State Models
It also can predict the LLE of polymer solutions at high pressures better
than SAFT.
2 Equation-of-State Models
k ij =0.
61
120
SAFT, kij=0
100
Raemer,Sage,1962
80
P (bar)
60
40
20
0
0.0
0.2
0.4
xEthane
0.6
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
2 Equation-of-State Models
Nseg
Nseg
Nseg
m p M n X A rA
A
Where:
mp
XA
2 Equation-of-State Models
63
rA
Mn
If parameters
these have highest priority and are used for calculations. If they are not
known, usually in the case of copolymers, the user must provide A , A and
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
ii
AA
k iA
p1 p2 (1 k p1 p2 ) p1 p2
Where:
64
p1
p1
p2
p2
2 Equation-of-State Models
T
Tref
Tr
Where:
= Reference temperature and the default value = 298.15 K
Tref
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
2 Equation-of-State Models
65
These options are shown in priority order. For example, if the binary
parameters are provided for both polymer-solvent pairs and segment-solvent
pairs, the polymer-solvent parameters are used and the segment-solvent
pairs are ignored. If the user provides the binary parameters for segmentsolvent pairs only, the values for polymer-solvent pairs will be calculated.
The databank POLYPCSF contains both unary and binary PC-SAFT parameters
available from literature; it must be used with the POLYPCSF property
method. If the pure parameters are not available for components in a
calculation, the user can perform an Aspen Plus Regression Run (DRS) to
obtain these pure component parameters. For non-polymer components, the
pure component parameters are usually obtained by fitting experimental
vapor pressure and liquid molar volume data. To obtain pure homopolymer
(or segment) parameters, experimental data on liquid density should be
regressed. Once the pure component parameters are available for a
homopolymer, ideal-gas heat capacity parameters, CPIG, should be regressed
for the same homopolymer using experimental liquid heat capacity data (for
details on ideal-gas heat capacity for polymers, see Aspen Ideal Gas Property
Model in Chapter 4). In addition to pure component parameters, PCSFTU,
PCSFTV, and PCSFTM or PCSFTR, the binary parameter, PCSKIJ, for each
solvent-solvent pair or each solvent-polymer (segment) pair, can be
regressed using vapor-liquid equilibrium (VLE) data in the form of TPXY data
in Aspen Plus.
Note: In a Data Regression Run, a polymer component must be defined as an
OLIGOMER type, and the number of each type of segment that forms the
oligomer (or polymer) must be specified.
66
2 Equation-of-State Models
hc disp assoc
where
hc
disp
assoc
polar
, and
(2.47)
a res
d
( Z m 1)
RT 0
where a
(2.48)
compressibility factor; a
res
is defined as:
(2.49)
2 Equation-of-State Models
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)
stated in the denominator, while all other mole fractions are considered
constant.
Applying
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)
p
Gmig RT Z m 1 ln Z m RT ln ref
p
(2.54)
p
Gmig RT xi ln i RT ln ref
i
p
(2.55)
(2.56)
hc m hs chain
(2.57)
68
2 Equation-of-State Models
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)
and the segment energy parameter of the segment type in the copolymer
component i , respectively. The segment number
mi ri M i
(2.64)
M i wi M i
(2.65)
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:
(2.66)
1 1
with
i ,i
2 Equation-of-State Models
(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)
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)
or
adjacent
sequences. Therefore:
B B B 0, B 1
(2.72)
hs
chain (m 1) ln g
(d )
(2.73)
m 1
m 1
1
, B
, B
, B 0
m 1
m 1
m 1
(2.74)
is the fraction of
segments
z in the copolymer:
ma
m
(2.75)
B Cz2 , B Cz 2 , B B Cz z
70
(2.76)
2 Equation-of-State Models
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)
m m ... mr
m
; there are no
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 Equation-of-State Models
(2.87)
71
B 0,
(2.88)
B B B , 1
1 1
1
(m 1) 1 1
m 1 1
(2.89)
in the copolymer:
m
, 1,2,...
m
(2.90)
B Cz z
, 1,2,...
(2.91)
C z z 1
(2.92)
1 1
That is,
Put
(2.93)
z z
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)
2 Equation-of-State Models
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
1
( i j )
2
(2.104)
i , j (1 i , j )( i j )1 / 2
(2.105)
assoc
xi N
i
Ai
X Ai 1
ln X Ai
2
2
(2.106)
A
2 Equation-of-State Models
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)
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 )
N Ai N i
M i wi M i
M
M
in the
in the
(2.111)
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)
74
2 Equation-of-State Models
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)
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 Equation-of-State Models
(2.124)
75
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
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)
I 3 ( * )
1 0.62378 * 0.11658 *
1 0.59056 * 0.20059 *
(2.127)
(2.128)
In terms of
(2.129)
(2.130)
1 1.19133 0.42523 2
1 1.12789 0.73166 2
(2.131)
( AB )
. For a
and the
76
2 Equation-of-State Models
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)
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
2 Equation-of-State Models
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.
78
2 Equation-of-State Models
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).
2 Equation-of-State Models
79
200
Temperature (C)
UCST
150
100
50
LCST
0
0
0.1
0.2
0.3
0.4
0.5
0.6
80
2 Equation-of-State Models
2 Equation-of-State Models
81
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
M w 50.4 kg / mol .
82
2 Equation-of-State Models
References
Alder, B. J., Young, D. A., & Mark, M. A. (1972). Studies in Molecular
Dynamics. X. Corrections to the Augmented van der Waals Theory for the
Square-Well Fluid. J. Chem. Phys., 56, 3013.
Aspen Physical Property System Physical Property Methods and Models.
Cambridge, MA: Aspen Technology, Inc.
Behme, S., Sadowski, G., Song, Y., & Chen, C.-C. (2003). Multicomponent
Flash Algorithm for Mixtures Containing Polydisperse Polymers. AIChE J., 49,
258.
Becker, F., Buback, M., Latz, H., Sadowski, G., & Tumakaka, F. (2004).
Cloud-Point Curves of Ethylene-(Meth)acrylate Copolymers in Fluid Ethene up
to High Pressures and Temperatures Experimental Study and PC-SAFT
Modeling. Fluid Phase Equilibria, 215, 263-282.
Behme, S., Sadowski, G., Song, Y., & Chen, C.-C. (2003). Multicomponent
Flash Algorithm for Mixtures Containing Polydisperse Polymers. AIChE J., 49,
258.
Carnahan, N. F., & Starling, K. E. (1972). Intermolecular Repulsions and the
Equation of State for Fluids. AIChE J., 18, 1184.
Chapman, W. G., Gubbins, K. E., Jackson, G., & Radosz, M. (1989). Fluid
Phase Equilibria, 52, 31.
Chapman, W. G., Gubbins, K. E., Jackson, D., & Radosz, M. (1990). A New
Reference Equation of State for Associating Liquids. Ind. Eng. Chem. Res., 29,
1709.
Chen S.-J., Economou, I. G., & Radosz, M. (1992). Density-Tuned Polyolefin
Phase Equilibria. 2. Multicomponent Solutions of Alternating Poly(EthylenePropylene) in Subcritical and Supercritical Solvents. Experiment and SAFT
Model. Macromolecules, 25, 4987.
Chen, S. S., & Kreglewski, A. (1977). Applications of the Augmented van der
Waals Theory of Fluids I. Pure Fluids. Ber. Bunsenges. Phys. Chem., 81, 1048.
Fischer, K., & Gmehling, J. (1996). Further development, status and results of
the PSRK method for the prediction of vapor-liquid equilibria and gas
solubilities. Fluid Phase Eq., 121, 185.
Folie, B., & Radosz, M. (1995). Phase Equilibria in High-Pressure Polyethylene
Technology. Ind. Eng. Chem. Res., 34, 1501.
Gregg, C. J., Stein, F. P., & Radosz, M. (1994). Phase Behavior of Telechelic
Polyisobutylene (PIB) in Subcritical and Supercritical Fluids. 1. Inter- and
Intra-Association Effects for Blank, Monohydroxy, and Dihydroxy PIB(1K) in
Ethane, Propane, Dimethyl Ether, Carbon Dioxide, and
Chlorodifluoromethane. Macromolecules, 27, 4972.
Gross, J., & Sadowski, G. (2001). Perturbed-Chain SAFT: An Equation of State
Based on a Perturbation Theory for Chain Molecules. Ind. Eng. Chem. Res.,
40, 1244-1260.
2 Equation-of-State Models
83
Gross, J., & Sadowski, G. (2002a). Modeling Polymer Systems Using the
Perturbed-Chain Statistical Associating Fluid Theory Equation of State. Ind.
Eng. Chem. Res., 41, 1084-1093.
Gross, J., & Sadowski, G. (2002b). Application of the Perturbed-Chain SAFT
Equation of State to Associating Systems. Ind. Eng. Chem. Res., 41, 55105515.
Gross, J., Spuhl, O., Tumakaka, F., & Sadowski, G. (2003). Modeling
Copolymer Systems Using the Perturbed-Chain SAFT Equation of State. Ind.
Eng. Chem. Res., 42, 1266-1274.
Hasch, B. M., & McHugh, M. A. (1995). Calculating Poly(ethylene-co-acrylic
acid)-Solvent Phase Behavior with the SAFT Equation of State. J. Pol. Sci.:B:
Pol. Phys., 33, 715.
Hasch, B. M, Meilchen, M. A., Lee, S.-H., & McHugh, M. A. (1992). HighPressure Phase Behavior of Mixtures of Poly(Ethylene-co-Methyl Acrylate)
with Low-Molecular Weight Hydrocarbons. J. Pol. Sci., 30, 1365-1373.
Holderbaum, T., & Gmehling, J. (1991). PSRK: A group contribution equation
of state based on UNIFAC. Fluid Phase Eq., 70, 251.
Huang, S. H., & Radosz, M. (1990). Equation of State for Small, Large,
Polydisperse, and Associating Molecules. Ind. Eng. Chem. Res., 29, 2284.
Huang, S. H., & Radosz, M. (1991). Equation of State for Small, Large,
Polydisperse, and Associating Molecules: Extension to Fluid Mixtures. Ind.
Eng. Chem. Res., 30, 1994.
Jog, P. K., Sauer, S. G., Blaesing, J., & Chapman, W. G. (2001), Application
of Dipolar Chain Theory to the Phase Behavior of Polar Fluids and Mixtures.
Ind. Eng. Chem. Res., 40, 4641.
Jones, D. C., & Amstell, S. (1930). J. Chem. Soc., 1316.
Kleiner, M., Tumakaka, F., Sadowski, G., Dominik, A., Jain, S., Bymaster, A.,
& Chapman, W. G. (2006). Thermodynamic Modeling of Complex Fluids using
PC-SAFT. Final Report for Consortium of Complex Fluids. Universitt
Dortmund & Rice University.
Kleiner, M., Tumakaka, F., Sadowski, G., Latz, H., & Buback, M. (2006).Phase
Equilibria in Polydisperse and Associating Copolymer Solutions: Poly(ethaneco-(meth)acrylic acid) Monomer Mixtures. Fluid Phase Equilibria, 241, 113123.
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(1994). Application of the van der Waals Equation of State to Polymers. I.
Correlation. Fluid Phase Equilibria, 96, 65-92.
Lambert, S. M., Song, Y., & Prausnitz, J. M. (2000). Equations of State for
Polymer Systems. In J. V. Sengers, R. F. Kayer, C. J. Peters, and H. J. White,
(Eds.), Equations of State for Fluids and Fluid Mixtures. (pp. 523-588) New
York: Elsevier Science.
Lee, S.-H., Hasch, B. M., & McHugh, M. A. (1996). Calculating Copolymer
Solution Behavior with Statistical Associating Fluid Theory. Fluid Phase Equil.,
117, 61.
84
2 Equation-of-State Models
2 Equation-of-State Models
85
Teja, A. S., Lee, R. J., Rosenthal, D.J., & Anselme, M. (1990). Correlation of
the critical properties of alkanes and alkanols. Fluid Phase Eq., 56, 153.
Topliss, R. J. (1985). Techniques to Facilitate the Use of Equations of State for
Complex Fluid-Phase Equilibria. Ph.D. Dissertation, University of California,
Berkeley.
Tsonopoulos, C., & Tan, Z. (1993). The critical constants of normal alkanes
from methane to polyethylene. II. Application of the Flory theory. Fluid Phase
Eq., 83, 127.
Wei, Y. S., & Sadus, R. J. (2000). Equations of State for Calculation of FluidPhase Equilibria. AIChE Journal, 46, 169.
Wertheim, M. S. (1984). Fluids with Highly Directional Attractive Forces. II.
Thermodynamic Perturbation Theory and Integral Equations. J. Stat. Phys.,
35, 35.
Wertheim, M. S. (1986a). Fluids with Dimerizing Hard Spheres, and Fluid
Mixtures of Hard Spheres and Dispheres. J. Stat. Phys., 85, 2929.
Wertheim, M. S. (1986b). Fluids with Highly Directional Attractive Forces. IV.
Equilibrium Polymerization. J. Stat. Phys., 42, 477.
Xiong, Y., & Kiran, E. (1995). Comparison of Sanchez-Lacombe and SAFT
Model in Predicting Solubility of Polyethylene in High-Pressure Fluids. J. Appl.
Pol. Sci., 55, 1805.
86
2 Equation-of-State Models
87
There are a large number of activity coefficient models for use in polymer
process modeling. Aspen Polymers offers:
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.
f i l x i i f i *,l
Where:
f il
xi
f i *,l
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.
iv y i p xi i f i*,l
88
(3.1)
*, l
(3.2)
With
1
i*,l exp
RT
pi*,l
Vi*,l dp
(3.3)
Where:
i*,v
pi*,l
i*,l
Vi *,l
However, Equations 3.2 and 3.3 are applicable only to solvents, light
polymers and oligomers (volatile) in the mixture. For other components such
as heavy polymers and oligomers (nonvolatile) and dissolved gases in the
*, l
mixture, the liquid phase reference fugacity, f i , has to be computed in
different ways:
*i i i
(3.4)
Where:
89
By this definition
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.
(3.6)
For liquid-liquid equilibria, the vapor phase term can be omitted, and the pure
component liquid fugacity cancels out:
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:
GmE ,l RT xi ln i
(3.8)
90
H mE ,l RT 2 xi
i
ln i
T
(3.9)
ln i
S mE ,l R xi ln i T
T (3.10)
i
Where:
G mE ,l =
H mE ,l =
S mE ,l
The excess liquid functions given by Equations 3.83.10 are calculated from
the same activity coefficient model. In practice, however, the activity
coefficient i is often derived first from the excess liquid Gibbs free energy of
a mixture from an activity coefficient model:
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:
ni
G mixing
id
Gmixing
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)
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.
With
x s' x s / x s
s
x x
s
Where:
92
Vml
Vms
V p*,l
xp
xs
x 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,
Description
GAMMA
HLMX
H ml
SLMX
S ml
GLMX
Gml
HLXS
H mE ,l
GLXS
G mE ,l
SLXS
S mE ,l
93
Models
Model
Name
Phase(s)
Pure
Mixture
Properties Calculated
Flory-Huggins
GMFH
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.
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
n1
n2
1 , 2
If m is set equal to the ratio of molar volumes of polymer and solvent, then
1 and 2 are the volume fractions.
If m is set equal to the ratio of molecular weight of polymer and solvent, then
1 and 2 are the weight fractions.
Therefore, the Gibbs free energy of mixing equation, Equation 3.17, is a
generalized form that can be expanded to three different equations with
being the segment-based mole fraction, volume fraction or weight fraction,
depending on how m is defined. These three equations can be accessed in the
Flory-Huggins model using option codes.
Option codes 1, 2, and 3, correspond to the weight basis, segment mole basis
and volume basis, respectively. Option code 2 (segment basis) is the default.
A large portion of experimental polymer solution phase equilibria data in the
open literature are reported using a volume fraction basis. The volume
fraction basis allows users to directly apply interaction parameters from
literature to their simulation. There are, however, situations where neither the
segment-based mole fraction basis nor the volume fraction basis are
appropriate. This is the case for many industrial processes of polymer
mixtures. In such situations composition is usually known on a weight basis.
Unlike segment mole fraction, component weight fraction remains consistent
regardless of how the polymer segments are defined.
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
ij
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,
(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 of moles
Pi
ni M i
wi
njM j
mi s i * Pi i
ni Pi
n j Pj
mi s i * Pi i
ni
Characteristic
Size
Volume basis:
3
Vi
= Molar volume ( m
/ kmol )
vi
= Specific volume ( m
wi
= Mass fraction
/ kg )
niVi
n jV j
j
si
and
wi vi
wjv j
Pi POLDP 1.0
mi s i * Pi i
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
98
G mixing
RT
NRTL
H mixing
RT
FH
S 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 =
i and j =
Solvent component
Polymer component
ns
np
xi
XI
ri , I
ji
ji
Interaction parameter
g ji
gii
nI
mI
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:
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.
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
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
INRTL
p becomes unity as X p 1
(i.e.,
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
IJ
JI G JI
IJ G IJ
I J G JI J I GIJ
Where:
IJ
ij and
ij aij
bij
T
eij ln T f ijT
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
POLDP 1.0 .
Electrolyte-Polymer NRTL
Activity Coefficient Model
The Electrolyte-Polymer Non-Random Two-Liquid (EP-NRTL) activity
coefficient model is an integration of the electrolyte NRTL model for
electrolytes (Chen et al., 1982, 1999; Chen & Evans, 1986) and the polymer
NRTL model (Chen, 1993) for oligomers and polymers. The model is used to
compute activity coefficients for polymers, solvents, and ionic species (Chen &
Song 2004).
This integrated electrolyte-polymer NRTL model is designed to represent the
excess Gibbs free energy of aqueous organic electrolytes and complex
chemical systems with the presence of oligomers, polymers and electrolytes.
The model incorporates the segment-based local composition concept of the
polymer NRTL model into the electrolyte NRTL model. From the Gibbs free
energy expression, one can compute activity coefficients for various species
103
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.
In summary, the integrated model has four terms, which are discussed later
in this chapter:
104
Pitzer-Debye-Hckel term
Born 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
ln *
1
c ln c* a ln a*
c a
ln * m ln * ln 1 M B c a m / 1000
Where:
* m
MB
= Molality
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
NA
= Avogadro's number
= Density of solvent
Qe
= Electron charge
= Temperature
= Boltzmann constant
xi
zi
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:
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:
ri
= Born radius
ln i*Born
Qe2 1 1 z i2 2
10
2kT w ri
ji
and
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
107
ji
= Interaction parameter
g ji
gii
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:
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
rm, I
rc , I
ra , I
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
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
ln I FH ln m I 1 m I
ln *I FH ln FH
ln I FH
I
111
1
1
B (T ) AB BB
T CB
Each type of NRTL parameter consists of both the nonrandomness factor, ,
and the energy parameter, . The temperature dependency relations of the
NRTL parameters are:
BB' ABB'
BBB'
FBB ' ln(T ) G BB 'T
T
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
ca ,c 'a C ca ,c 'a
Dca ,c 'a
(T ref T )
T
E ca ,c 'a
ln ref
T
T
(T ref T )
T
Eca ' ,ca ' '
ln ref
T
T
Where:
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
AB
---
---
---
---
Unary
CPDIEC/2
BB
0.0
---
---
---
Unary
CPDIEC/3
CB
298.15
---
---
Kelvin (no
conversion)
Unary
112
Parameter
Name /
Element
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
Comments
RADIUS
ri
---
1E-11
1E-9
---
LENGTH
Unary
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
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
GMELCD
GMELCE
GMELCN
C ca ,ca '
0.0
-100
100
---
Binary,
Asymmetric
C ca ,c 'a
0.0
-100
100
---
Binary,
Asymmetric
0.0
-3E4
3E4
TEMP
Binary,
Asymmetric
0.0
-3E4
3E4
TEMP
Binary,
Asymmetric
0.0
-100
100
---
Binary,
Asymmetric
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
-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
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
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 =
ng
ln iR ki ln k ln ki
Where:
ki
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
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.
117
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
Vi
118
References
Aspen Physical Property System Physical Property Methods and Models.
Cambridge, MA: Aspen Technology, Inc.
Flory, P. J. (1953). Principles of Polymer Chemistry. London: Cornell
University Press.
Chen, C.-C. (1993). A Segment-Based Local Composition Model for the Gibbs
Energy of Polymer Solutions. Fluid Phase Equilibria, 83, 301-312.
Chen, C.-C. (1996). Molecular Thermodynamic Model for Gibbs Energy of
Mixing of Nonionic Surfactant Solutions. AIChE Journal, 42, 3231-3240.
Chen, C-C., Britt, H. I., Boston, J. F., & Evans, L. B. (1982). Local
Composition Model for Excess Gibbs Energy of Electrolyte Systems. AIChE J.,
28, 588.
Chen, C-C., & Evans, L. B. (1986). A Local Composition Model for the Excess
Gibbs Energy of Aqueous Electrolyte Systems. AIChE J., 32, 444.
Chen, C-C., Mathias, P. M., & Orbey, H. (1999). Use of Hydration and
Dissociation Chemistries with the Electrolyte-NRTL Model. AIChE Journal, 45,
1576.
Chen, C-C., Song Y. (2004). Generalized Electrolyte-NRTL Model for MixedSolvent Electrolyte Systems. AIChE Journal, 50, 1928.
Danner, R. P., & High, M. S. (1992). Handbook of Polymer Solution
Thermodynamics. New York: American Institute of Chemical Engineers.
Flory, P. J. (1941). Thermodynamics of High Polymer Solutions. J. Chem.
Phys., 9, 660.
Fredenslund, Aa., Jones, R. L., & Prausnitz, J. M. (1975). AIChE J., 21, 1086.
Fredenslund, Aa., Gmehling, J., & Rasmussen, P. (1977). Vapor-Liquid
Equilibria using UNIFAC. Amsterdam: Elsevier.
119
Hansen, H. K., Rasmussen, P., Fredenslund, Aa., Schiller, M., & Gmehling, J.
(1991). Vapor-Liquid Equilibria by UNIFAC Group Contribution. 5 Revision and
Extension. Ind. Eng. Chem. Res., 30, 2352-2355.
Huggins, M. L. (1941). Solutions of Long Chain Compounds. J. Phys. Chem.,
9, 440.
Manning, G.S. (1979). Counterion Binding in Polyelectrolyte Theory. Acc.
Chem. Res., 12, 443.
Mock, B., Evans, L. B., & Chen, C.-C. (1986). Thermodynamic Representation
of Phase Equilibria of Mixed-Solvent Electrolyte Systems. AIChE Journal, 32,
1655.
Oishi, T., & Prausnitz, J. M. (1978). Estimation of Solvent Activity in Polymer
Solutions Using a Group Contribution Method. Ind. Eng. Chem. Process Des.
Dev., 17, 333-335.
Pitzer, K.S. (1973). Thermodynamics of Electrolytes. I. Theoretical Basis and
General Equations. J. Phys. Chem., 77, 268.
Renon, H., & Prausnitz, J. M. (1968). Local Compositions in Thermodynamic
Excess Functions for Liquid Mixtures. AIChE J., 14, 135-144.
Tompa, H. (1956). Principles of Polymer Chemistry. London: Butterworths.
120
4 Thermophysical Properties
of Polymers
About Thermophysical
Properties
As discussed in Chapter 1, due to their structure, polymers exhibit
thermophysical properties significantly different than those of conventional
121
Symbol
Description
HL
H i*,l
GL
i*, l
SL
S i*,l
VL
Vi *,l
TGVG
Tg
TMVG
Tm
HS
H i*, s
GS
i*, s
VS
Vi *, s
SS
S i*, s
Property Models
Model Name
122
Properties
Calculated
HIG, GIG,
CPIG
HL0DVK,
HL0DVKD
HL
GL0DVK
GL
VL0DVK
VL
Tait/Rackett Model
VL0TAIT
VL
TG0DVK
TGVK
TM0DVK
TMVK
HS0DVK
HS
GS0DVK
GS
VS0DVK
VS
S i*,l
1
( H i*,l i*,l )
T
S i*, s
1
( H i*, s i*, s )
T
123
H *,ig
*,ig
H *,l H *,ig
*,l *,ig
*,ig
(T ) H
*,ig
(T
ref
Cp
*,ig
dT
T ref
Where:
= Reference temperature (298.15 K)
T ref
H *,ig T ref
T ref
= Ideal-gas heat capacity of the polymer
Cp *,ig
*,ig
(T )
T
*,ig
(T
ref
Cp
T
*,ig
T ref
dT T
T ref
Cp *,ig
dT
T
S *,ig (T ref )
Where:
*,ig (T ref ) = Gibbs free energy of formation of the polymer at the ideal-gas
ref
state and T
124
S *,ig (T ref )
and
T ref
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,
polynomial expressions:
T C7
or
Cp*,ig (T )
C8 for T C8
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
---
---
---
MOLE-HEATCAPACITY, TEMP
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:
125
These options are shown in priority order. For example, if parameters are
provided for a polymer component as well as for the segments, the polymer
parameters are used and the segment parameters are ignored.
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
XA
T ref
*,A ig (T ref )
Cp *,A ig (T )
T ref
Where:
nk
126
k*,ig (T ref )
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:
Once the pure EOS parameters are available for a polymer, ideal-gas heat
capacity parameters, CPIG, should be regressed for the same polymer using
experimental liquid heat capacity data. Data on heat of formation and Gibbs
free energy of formation, of the same polymer (segment), can then be used
to obtain DHFVK and DGFVK by performing an Aspen Design Spec or Aspen
Sensitivity.
Note: In a Data Regression Run, a polymer component must be defined as an
OLIGOMER type, and the number of each type of segment that forms the
oligomer (or polymer) must be specified.
127
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
H i*,l
ref
ref
H i*,c
dep H i*,v
128
con H i* T ref
sub H i*
fus H i*
ref
melt
vap H i* T
H i*,v T
H i*,l T
H i*,l T melt
H i*,c T melt
T melt
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
Cp
T
*,c
dT
ref
H *,l
H *,c
129
Tm
Tg
xc
= Mass-fraction crystallinity
T ref
H *,ig T ref
T ref
con H * T ref
sub H *
ref
T ref
T ref
Cp *,l
Cp *,c
sublimation, sub H T
*
ref
ideal gas reference state and the condensed phase reference state.
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
*,c
*,c
T
ref
Cp dT T
*,c
T ref
130
T ref
Cp *,c
dT
T
S *,l (T ref )
*, l
*, c
T ref
*,ig T ref
= Gibbs free energy of formation of the polymer at the idealgas state and
T ref
con * T ref
sub *
ref
T ref
T ref
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
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units Keyword
CPLVK/1
Al
Calculated
---
---
MOLE-HEATCAPACITY
CPLVK/2
Bl
Calculated
---
---
MOLE-HEATCAPACITY, TEMP
CPLVK/3
Cl
---
---
MOLE-HEATCAPACITY, TEMP
CPLVK/4
Dl
---
---
MOLE-HEATCAPACITY, TEMP
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
---
---
MOLE-HEATCAPACITY, TEMP
CPCVK/3
Cc
---
---
MOLE-HEATCAPACITY, TEMP
CPCVK/4
Dc
---
---
MOLE-HEATCAPACITY, TEMP
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
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.
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
XA
T ref
H *,A ig (T ref )
T ref
*,A ig (T ref )
T ref
133
Cp *,A l
Cp *,A c
(4.1)
(4.2)
(4.3)
(4.5)
(4.6)
Where:
nk
T ref
H k*,ig (T ref )
k*,ig (T ref )
134
con k* (T ref )
sub k* (T ref )
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:
(4.7)
(4.8)
(4.9)
(4.10)
Where:
T ref
Cp k*,l T ref
Cp k*,c T ref
T ref , from
T ref ,
Parameter Regression
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:
135
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
136
xc
Tm
Tg
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)
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 ,
These options are shown in priority order. For example, if parameters are
provided for a polymer component and for the segments, the polymer
parameters are used and the segment parameters are ignored. The mass
based parameters take precedence over the molar based parameters.
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:
Mn
138
XA
MA
V A*,l
V A*,c
Vw n k Vwk
k
Where:
nk
Vwk = Van der Waals volume of functional group k, from van Krevelen
database
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
(4.16)
In some cases, the parameters of functional groups are not available in the
databank. The contributions from these groups are ignored.
Parameter Regression
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:
139
P
V *,l M n V (0, T )1 C ln 1
B(T )
V *,l
Mn
m 3 / kmol
= 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.
140
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
Parameter Regression
If the parameters are not available for a polymer component, the user can
perform an Aspen Plus Regression Run (DRS) to obtain these parameters. In
some cases, a DRS run can also be used to adjust these parameters to fit
available experimental data.
Note: In a Data Regression Run, a polymer component must be defined as an
OLIGOMER type, and the number of each type of segment that forms the
oligomer (or polymer) must be specified.
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
141
nk
Yg ,k
Mk
Tg
XA
MA
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
TGVK
T g , or
---
5000
TEMP
Tg , A
---
5000
TEMP
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
nk
Ym , k
Mk
Tm
XA
MA
Symbol
Default
Lower
Limit
Upper
Limit
MDS
Units
Keyword
TMVK
Tm , or
---
5000
TEMP
Tm, A
---
5000
TEMP
HS H *, c x c H *,l (1 x c ) for
H *,c
for
Tg T Tm
T Tg
Where:
HS
H *,l
H *,c
143
Tm
Tg
xc
= Mass-fraction crystallinity
GS
*,c x c *,l (1 x c )
for
Tg T Tm
*,c
for
T Tg
Where:
GS
*, l
*, c
For a detailed discussion of the above quantities, see Liquid Gibbs Free
Energy of Polymers on page 130.
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
144
*, c
, and V
*, g
*,l
*, l
, Cp *, c ), and
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
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
146
HL HIG DHL
Where:
Name
Symbol
Description
HLMX
H ml
HIGMX
H mig
DHLMX
H ml H mig
HLXS
H mE ,l
HL
H i*,l
HIG
H i*,ig
DHL
H i*,l H i*,ig
For an activity coefficient model, the calculation procedure for HLMX and HL is
constituted in a unique route, respectively. The ideal gas pure or mixture
molar enthalpy is automatically calculated using the same Aspen model
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:
Description
HLDVK0
DHL00P
HLDVK1
(default)
DHL01P
DHL09P
HLDVK
HL0DVKRK
HL0DVKD
HL0DVKRK is the default route for HL in Aspen Polymers 2004.1 and earlier
releases.
148
Route ID
Description
HLMXP1
(default)
DHL01P
Route ID
Description
HLMXP2
DHL01P
HLMXPRK
HLMXPRK is the default route for HLMX in Aspen Polymers 2004.1 and
earlier releases.
Description
HLMXFH1
(default)
DHL01P
HLMXFH2
DHL01P
HLMXFHRK
HLMXFHRK is the default route for HLMX in Aspen Polymers 2004.1 and
earlier releases.
Description
HLMXUF1
(default)
DHL01P
HLMXUF2
DHL01P
HLMXPURK
HLMXPURK is the default route for HLMX in Aspen Polymers 2004.1 and
earlier releases.
Description
HLMXFV1
(default)
DHL01P
149
Route ID
Description
HLMXFV2
DHL01P
HLMXFVRK
HLMXFVRK is the default route for HLMX in Aspen Polymers 2004.1 and
earlier releases.
Description
HLMXP00
(default)
DHL00P
HLMXP02
DHL00P
HLMXP
HLMXP is the default route for HLMX in Aspen Polymers 2004.1 and earlier
releases.
References
Aspen Physical Property System Physical Property Methods and Models.
Cambridge, MA: Aspen Technology, Inc.
Bicerano, J. (1993). Prediction of Polymer Properties. New York: Marcel
Dekker, Inc.
Danner, R. P., & High, M. S. (1992). Handbook of Polymer Solution
Thermodynamics. New York: American Institute of Chemical Engineers.
Van Krevelen, D. W. (1990). Properties of Polymers, 3rd Ed. Amsterdam:
Elsevier.
150
Symbol
Description
MUL
i*,l
MULMX
151
Viscosity Models
Model Name
Pure
Mixture
Properties
Calculated
Modified Mark-Houwink/
van Krevelen Model
MUL0MH
__
MUL
MUPOLY
__
MULMX
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.
*,l
i
M
ref w
M
ref
Tref
T
exp 1
RT Tref
Where:
152
i*,l =
ref =
Mw =
M ref =
Tref
Reference temperature
Absolute temperature
from the polymer attribute MWW or calculated from its number average
molecular weight and polydispersity index:
M w M n * PDI
Where:
Mn =
PDI =
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.
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.
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.
*,l
i
M
cr (T ) w
M cr
cr based
cr
T trends. If
155
structural parameter, A.
The van Krevelen master curves, which correlate the polymer viscositytemperature relationship, are shown here:
cr
steps:
1
H , A
H ,k / M A
Nseg
Nseg
X A M A H, A / X A M A
Where:
156
nk
MA
XA
2
E () H 3
3
log cr (1.2T g ) E ()
(0.052 8.5 10 5 T g )
Tg
1.4
1 E ()
2.3 RT g
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 (T ) can be calculated.
157
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:
k ij
l ij
158
ln ij
| ln i*,l ln *,j l |
2
Therefore, ln ij 0 when
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,
Tr
T
Tref
Where:
Tref
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
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
160
*,p l
wp
k12
l12
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
QB
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
Q pi
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
Nsol
QS
Ki
1s gs
1 p gp
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
Real dilution effect, which causes the viscosity of the solution to fall
between that of the pure polymer and that of the pure solvent
164
165
T
m
g
TgB wB K S TgS wS
wB K S wS
Where:
Tgm
wB
Npol
i 1
wS
Nsol
i 1
*
log
1.2T g
T gm
f
, A
T
Where:
2.303 RTg
*
log B B B
1.2Tg
A
B
166
Tgm B
f
,A
T
B 3
2.303RT gB
where
B (1.2TgB )
0B
log B
1.2TgB
0B :
TgB B
f
,A
T
0m * w p p
For a quasi-binary system, the mixture viscosity is:
0m B* w BB
Where:
0m
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:
i*,l
I and J
i and j
xi
XI
ri , I
ji
ji
Interaction parameter
Binary Parameters
The binary parameter,
Tr
T
Tref
Where:
Tref
168
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
component viscosity is automatically calculated by the modified MarkHouwink/van Krevelen model. The binary parameters in ij and ij have to
be specified for solvent-solvent pairs and solvent-segment pairs for data input
or data regression. Their default values are zero.
Note: In DRS runs, the polymer must be treated as an oligomer and the
number of each type of segment that forms the oligomer must also be
specified.
169
Model Name
Applicability
Property Methods
MULMX13
MUPOLY
default
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
171
Thermal Conductivity
crystalline
semi-crystalline
glassy
rubbery
liquid
Tg
Tm
Temperature
In the figure, T g and
Symbol
Description
KL
*,i l
KLMX
Thermal Conductivity
Models
Model Name
Pure
Mixture
Properties
Calculated
Modified van
Krevelen/DIPPR
KL0VKDP
__
KL
Modified van
Krevelen/TRAPP
KL0VKTR
__
KL
KLMXVKTR
__
KLMX
172
T Tm
*,i c *,i l (1 )
for
Tg T Tm
*,i c *,i g (1 )
for
T Tg
KL *,i l
Where:
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
(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
*,i ,ref
Tref
Pref
at the reference
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
parameters are provided for a polymer component and for the segments, the
polymer parameters are used and the segment parameters are ignored.
175
*,i
Nseg
X
A
Nseg
*,
A M A A / X A M A
A
Where:
Nseg
XA
MA
*,A
, estimated
*,i ,ref
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:
Trefc TmVK n k Ym ,k / n k M k
k
Where:
176
nk
TgVK
TmVK
Yg ,k
Ym , k
Mk
Tref even if
the user has provided component or segment TGVK and TMVK parameter
values.
VK 298
Cp VK 298 UR VK 298
L VK 298 VK 298
V
V
Where:
L
Cp VK 298
V VK 298
UR VK 298
5 x10 11 m (constant)
(m 3 /mol)
K
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
UR VK 298 n k URk
k
Where:
Cp k*,l
Vwk
URk
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
177
(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)
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
V l Tm
c Tm
4.8
5.8 c
l Tm
V
(6.10)
Where:
Vc
Vl
(T ) VW 1.435 0.45 10
(T 298.15)
(6.12)
The liquid thermal conductivity at the melting point can be related to the
thermal conductivity at the glass point using Equation 6.6. The final
expression for the crystalline reference thermal conductivity is therefore:
*,c
ref
VK 298
TmVK
1.2 0.2 VK
T
g
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
Ac B c C c 0 , and F c 1 . The
179
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:
*,pl
x s'
xi
Mi
180
xM
i*,l i2
( i )
l i
xi M i
i
1 / 2
Where:
*,i l
xi
Mi
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
Aspen Physical Property System Physical Property Methods and Models.
Cambridge, MA: Aspen Technology, Inc.
181
182
This appendix documents the physical property route structure for the
polymer specific property methods:
PNRTL-IG: Polymer NRTL with Ideal Gas Law Property Method, 192
POLYPCSF: Perturbed-Chain Statistical Associating Fluid Theory (PCSAFT) Equation-of-State Property Method, 198
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
GLMX
GLMXFH
GMFH, GL0DVK
SLMX
SLMXFHRK
GMFH, WHENRY,
HENRY1,
VL1BROC,
DHL02PH, GL0DVK
Liquid
184
Liquid
Property
Name
Route ID
Model Name
Description
VLMX
VLMXVKRK
VL2VKRK
MULMX
MULMX13
MUPOLY,
MULMH
KLMX
KLMXVKDP
KL0VKDP, KL2VR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
PHIL
PHIL04
PL0XANT, ESRK0,
VL0RKT
HL
HLDVKRK
HL0DVKRK*
GL
GLDVK
GL0DVK
SL
SLDVK
HL0DVKRK*,
GL0DVK
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Modified Mark-Houwink,
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
185
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
PHILMXP
GMNRTLP,
WHENRY, HENRY,
PL0XANT, ESRK0,
VL0RKT, VL1BROC
HLMX
HLMXPRK
GMNRTLP,
WHENRY, HENRY1,
VL1BROC, DHL02PH
GLMX
GLMXP
GMNRTLP, GL0DVK
SLMX
SLMXPRK
GMNRTLP,
WHENRY, HENRY1,
VL1BROC,
DHL02PH, GL0DVK
VLMX
VLMXVKRK
VL2VKRK
Liquid
186
Liquid
Property
Name
Route ID
Model Name
Description
MULMX
MULMX13
MUPOLY, MULMH
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*
GL
GLDVK
GL0DVK
SL
SLDVK
HL0DVK*, GL0DVK
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Modified Mark-Houwink/van
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
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
MUV
MUV01
MUV0BROK
Chapman-Enskog-Brokaw
KV
KV01
KV0STLTH
Stiel-Thodos
Property
Name
Route ID
Model Name
Description
PHILMX
PHILMPUF
GMPOLUF,
WHENRY, HENRY,
PL0XANT, ESRK0,
VL0RKT, VL1BROC
HLMX
HLMXPURK
GMPOLUF,
WHENRY, HENRY1,
VL1BROC,
DHL02PH
GLMX
GLMXPUF
GMPOLUF, GL0DVK
SLMX
SLMXPURK
GMPOLUF,
WHENRY, HENRY1,
VL1BROC,
DHL02PH, GL0DVK
VLMX
VLMXVKRK
VL2VKRK
Liquid
188
Liquid
Property
Name
Route ID
Model Name
Description
MULMX
MULMX13
MUPOLY, MULMH
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*
GL
GLDVK
GL0DVK
SL
SLDVK
HL0DVK*, GL0DVK
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Modified Mark-Houwink/van
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
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
MUV
MUV01
MUV0BROK
Chapman-Enskog-Brokaw
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,
Extended Antoine, RedlichKwong, Rackett, BreviO'Connell
HLMX
HLMXFVRK
GMUFFV, WHENRY,
HENRY1, VL1BROC,
DHL02PH
GLMX
GLMXUFV
GMUFFV, GL0DVK
SLMX
SLMXFVRK
GMUFFV, WHENRY,
HENRY1, VL1BROC,
DHL02PH, GL0DVK
VLMX
VLMXVKRK
VL2VKRK
MULMX
MULMX13
MUPOLY, MULMH
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*
GL
GLDVK
GL0DVK
SL
SLDVK
HL0DVK*, GL0DVK
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Modified Mark-Houwink/van
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
191
Route ID
Model Name
Description
PHIVMX
PHIVMX00
ESIG
HVMX
HVMX00
ESIG
GVMX
GVMX00
ESIG
SVMX
SVMX00
ESIG
VVMX
VVMX00
ESIG
MUVMX
MUVMX02
MUV2DNST
Dean-Stiel
KVMX
KVMX02
KV2STLTH
Stiel-Thodos
DVMX
DVMX02
DV1DKK
Dawson-Khoury-Kobayashi
PHIV
PHIV0
ESIG0
HV
HV00
ESIG0
GV
GV00
ESIG0
SV
SV00
ESIG0
VV
VV00
ESIG0
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
PHILMXPI
GMNRTLP, WHENRY,
HENRY, PL0XANT,
ESIG0, VL0RKT,
VL1BROC
HLMX
HLMXP
GMNRTLP, WHENRY,
HENRY1, VL1BROC,
DHL01PH
GLMX
GLMXP
GMNRTLP, GL0DVK
SLMX
SLMXP
GMNRTLP, WHENRY,
HENRY1, VL1BROC,
DHL01PH, GL0DVK
VLMX
VLMXVKRK
VL2VKRK
MULMX
MULMX13
MUPOLY, MULMH
Liquid
192
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
PHIL00
PL0XANT, ESIG0,
VL0RKT
HL
HLDVKD
HL0DVKD*
GL
GLDVK
GL0DVK
SL
SLDVK
HL0DVK*, GL0DVK
VL
VLDVK
VL0DVK, VL0RKT
DL
DL01
DL0WCA
Wilke-Chang-Andrade
MUL
MULMH
MUL0MH
Modified Mark-Houwink/van
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
Dawson-Khoury-Kobayashi
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
Chapman-Enskog-Wilke-Lee
MUV
MUV01
MUV0BROK
Chapman-Enskog-Brokaw
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
KLMX
KLMXVKTR
KLMXVKTR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
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
Modified Mark-Houwink/van
Krevelen, Andrade
KL
KL0VKTR
KL0VKTR
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
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
Dawson-Khoury-Kobayashi
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
Chapman-Enskog-Wilke-Lee
MUV
MUV01
MUV0BROK
Chapman-Enskog-Brokaw
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
MULMX
MULMX13
MUPOLY,
MULMH
KLMX
KLMXVKTR
KLMXVKTR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
Hakim-Steinberg-Stiel, Power
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
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
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
The following table lists the physical property route structure for the
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
Dawson-Khoury-Kobayashi
PHIV
PHIVSF
ESPLSFT0
SAFT
HV
HVSF
ESPLSFT0
SAFT
GV
GVSF
ESPLSFT0
SAFT
SV
SVSF
ESPLSFT0
SAFT
VV
VVSF
ESPLSFT0
SAFT
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
PHILMXSF
ESPLSFT
SAFT
HLMX
HLMXSF
ESPLSFT
SAFT
GLMX
GLMXSF
ESPLSFT
SAFT
SLMX
SLMXSF
ESPLSFT
SAFT
VLMX
VLMXSF
ESPLSFT
SAFT
MULMX
MULMX13
MUPOLY,
MULMH
KLMX
KLMXVKTR
KLMXVKTR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
Liquid
197
Liquid
Property
Name
Route ID
Model Name
Description
SIGLMX
SIGLMX01
SIG2HSS
Hakim-Steinberg-Stiel, Power
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
Modified Mark-Houwink/van
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
KLMX
KLMXVKTR
KLMXVKTR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
POLYPCSF: Perturbed-Chain
Statistical Associating Fluid
Theory (PC-SAFT) Equation-ofState Property Method
The following table lists the physical property route structure for the
POLYPCSF property method:
Vapor
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
Dawson-Khoury-Kobayashi
PHIV
PHIVPC
ESPCSFT0
PCSAFT
HV
HVPC
ESPCSFT0
PCSAFT
GV
GVPC
ESPCSFT0
PCSAFT
SV
SVPC
ESPCSFT0
PCSAFT
VV
VVPC
ESPCSFT0
PCSAFT
DV
DV01
DV0CEWL
Chapman-Enskog-Wilke-Lee
MUV
MUV01
MUV0BROK
Chapman-Enskog-Brokaw
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
KLMX
KLMXVKTR
KLMXVKTR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
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
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
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
Dawson-Khoury-Kobayashi
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
Chapman-Enskog-Wilke-Lee
MUV
MUV01
MUV0BROK
Chapman-Enskog-Brokaw
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
KLMX
KLMXVKTR
KLMXVKTR
DLMX
DLMX02
DL1WCA
Wilke-Chang-Andrade
SIGLMX
SIGLMX01
SIG2HSS
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
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
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.
Where:
Cp *,l
nk
203
Cp k*,l
Vk* Vwk * ( A B * T C * Tg )
Where:
V*
Vk*
Vwk
= Temperature
Tg
T
T
T
H *,ig T ref
S *,ig
*,ig
H k*,ig
204
ref
ref
ref
S k*,ig T ref
n Y
n M
k
g ,k
Where:
Tg
Yg ,k
Mk
n Y
n M
k
m ,k
Where:
Tm
Ym , k
Where:
Where:
205
UR(T ref )
Oxygen-containing groups
Nitrogen-containing groups
Sulfur-containing groups
Halogen-containing groups
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
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
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
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)
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
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
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
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
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
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
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
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
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
[18.1]1
O
NH C NH
O
CH(NO2)
O
C
NH
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
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
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
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
----
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
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
----
----
----
----
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
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
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
217
218
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
CPLVK
CPLVKM
DGCON
DGCONM
DGFORM
DGFVKM
DBSUB
DGSUBM
DHCON
DHCONM
DHFVK
DHFVKM
DHSUB
DHSUBM
DNCVK
DNCVKM
Crystalline density
DNGVK
DNGVKM
Glass density
DNLVK
DNLVKM
Liquid density
219
220
E Equation-of-State
Parameters
Sanchez-Lacombe Unary
Parameters
This section lists the POLYSL model parameters for polymers, monomers, and
solvents.
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
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
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
E Equation-of-State Parameters
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
E Equation-of-State Parameters
223
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
E Equation-of-State Parameters
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
E Equation-of-State Parameters
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
E Equation-of-State Parameters
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.
PROPERTIES
opsetname
keyword=value /
opsetname [sectionid-list] keyword=value /...
Optional keywords:
FREE-WATER
SOLU-WATER
HENRY-COMPS
HENRY-COMPS
cid-list
henryid
227
sectionid-list
FREE-WATER
SOLU-WATER
HENRY-COMPS
SOLU-WATER=0
SOLU-WATER=1
SOLU-WATER=2
SOLU-WATER=3
228
henryid
cid-list
HENRY-COMPS HC INI1
PROPERTIES POLYNRTL HENRY-COMPS=HC
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
230
PROP-LIST
PVAL
BPVAL
COMP-LIST
CVAL
BCVAL
Parameter name
setno
cid
Component ID
cid1
cid2
value-list
cid-list
List of component ID
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
ESTIMATE [option]
STRUCTURES
method SEG-id
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
method
SEG-id
groupno
nooccur
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
Polymer UNIFAC Free Volume
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
233
234
Diffusion coefficients 6
Dilution effect 167
Dissolved gas 89
E
e-bulletins 3
Electrolyte-Polymer NRTL
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
property model 13, 15
temperature relationship 128
Entropy
calculation 203
departure 31
excess molar liquid 91
in equipment design 6
of mixing 94, 98, 111
of polymers 123
EP-NRTL See Electrolyte-Polymer
NRTL
Equations of state
Copolymer PC-SAFT model 67
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
parameters for property models
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
for multicomponent systems 168
parameters 169
specifying 169
F
Flory-Huggins
activity coefficient 111
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
property model 13, 15
Glass transition
model parameters 142
Glass transition temperature
calculation 204
for amorphous solids 8
polymer mixture 166
polymer solution 165
Van Krevelen correlation 141
Group contribution
Van Krevelen method 145
Group contribution method
van Krevelen 145, 146
235
H
Heat capacity
calculation 202
ideal gas 125
of polymers 131
parameters 127
property model 13, 15
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
model parameters 125
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
model parameters 131
of polymers 123, 128
pure component model 147
236
Index
Index
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
Index
Index
239
model 11517
model parameters 117
modification for free volume 117
property method (POLYUF) 188
89
specifying free volume model
119
specifying model 117
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
model parameters 221
route structure 196200
POLYSL
about 17
model parameters 218
route structure 19395
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
functional groups 202
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
models available 122
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
Eyring-NRTL mixture viscosity
167
Flory-Huggins 9498
for activity coefficients 13, 15,
87120
for density 13, 15
for enthalpy 13, 15
for equations of state 14, 2786
for Gibbs free energy 13, 15
for heat capacity 13, 15
for ideal gas 15, 12327
for polymer thermal conductivity
17182
for polymer viscosity 15170
for solution thermodynamics 13
for thermophysical properties 13
for transport properties 13
Mark-Houwink/van Krevelen
15258
mixture thermal conductivity 180
optimizing 23
PCSAFT 5966
polymer mixture viscosity 158
61
Polymer NRTL 98103
Polymer UNIFAC 11517
Polymer UNIFAC Free Volume
11719
pure component liquid enthalpy
147
SAFT 4759
Sanchez-Lacome 3442
SRK 4247
Tait liquid molar volume 14041
Van Krevelen glass transition
temperature 141
Van Krevelen liquid 12735
Van Krevelen liquid molar
volume 13639
Van Krevelen melt transition
temperature 142
Van Krevelen polymer solution
viscosity 16167
Van Krevelen solid 143
Van Krevelen thermal
conductivity 17379
Pseudo-components 162
Q
Quasi-binary systems 161
241
R
Rao function
calculation 204
from van Krevelen group
contribution 177
Reduced viscosity 157
Regressing
Eyring-NRTL mixture viscosity
parameters 169
ideal gas parameters 127
liquid model parameters (van
Krevelen) 135
liquid molar volume parameters
139
Mark-Houwink parameters 154
PC-SAFT parameters 66
polymer mixture viscosity
parameters 160
polymer properties 146
SAFT parameters 58
Sanchez-Lacombe parameters 41
Tait model parameters 141
Routes
calculations for property models
183200
for thermal conductivity 181
for viscosity 170
S
SAFT
applicability 47
binary parameters 56
comparison to PC-SAFT 60
for copolymer systems 55
for fluid mixtures 52
for pure fluids 47
implementation 5355
model 4759
model parameters 57, 221
property method (POLYSAFT)
196200
required parameters 53
specifying model 59
Sanchez-Lacombe
binary parameters 39
characteristics 36
equation 35
for copolymer systems 37
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
functional groups 202
reference temperature (thermal
conductivity) 176
reference thermal conductivity
178
thermal conductivity at 298K 177
Van Krevelen group contribution
(ideal gas) 126
Van Krevelen group contribution
(liquid molar volume) 139
Van Krevelen group contribution
(liquid) 134
Van Krevelen group contribution
(thermal conductivity) 176
Semi-crystalline solid 8
Simulation See Process Modeling
Soave-Redlich-Kwong See Polymer
SRK
Solid enthalpy
model parameters 144
of polymers 143
Solid Gibbs free energy
model parameters 144
of polymers 144
Solid molar volume
model parameters (van
Krevelen) 145
of polymers 144
Solids
amorphous 8
semi-crystalline 8
Van Krevelen model 143
Solution viscosity See also Polymer
solution viscosity model
Van Krevelen model 16167
Solutions
critical concentration 161
glass transition temperature 165
viscosity estimation 164
Index
Solvent
dilution effect 167
Specifying
data for parameter optimization
23
Electrolyte-Polymer NRTL model
114
Eyring-NRTL mixture viscosity
model 169
Flory-Huggins model 98
Mark-Houwink/van Krevelen
model 158
mixture thermal conductivity
model 180
molecular structure for property
estimation 22
parameter estimates for property
models 21
parameters for property models
20
PC-SAFT model 66
physical properties 1923
physical properties (input
language) 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
Van Krevelen thermal
conductivity model 179
SRK See Polymer SRK
Statistical associating fluid theory
See PC-SAFT , See SAFT
support, technical 3
Surface tension 6
T
Tait
equation 140
liquid molar volume model 140
41
liquid molar volume model
parameters 140
Index
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 90
excess molar liquid enthalpy 90
excess molar liquid entropy 91
fugacity 6
Gibbs free energy 6
Gibbs free energy departure 31
ideal gas 32
internal energy 6
molar volume 31
of polymers 526
Thermophysical properties See also
Properties, See also Properties
estimating 145
modeling 12
of polymers 12150
overview 121
Transport properties
diffusivity 6
property models 13
surface tension 6
thermal conductivity 6
viscosity 6
TRAPP model 180
True solvent dilution effect 167
U
UCST 11
UNIFAC See also Polymer UNIFAC
polymer free volume model 117
19
polymer model 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
functional groups 20214
glass transition temperature 141
group contribution 145
group contribution for polymers
156
liquid model 12735
liquid model parameters 131
liquid molar volume model 136
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
Van Krevelen group contribution
for segments (ideal gas) 126
for segments (liquid molar
volume) 139
for segments (liquid) 134
for segments (thermal
conductivity) 176
Vapor-liquid equilibrium 9, 30, 88
Vapor-liquid-liquid equilibrium 10
Viscoelasticity 8
Viscosity
at mixture glass transition
temperature 166
critical mass 156
estimating 164
Eyring-NRTL mixture model 167
Mark-Houwink/van Krevelen
model 15258
model overview 151
models available 15170
models list 151
of mixtures 6
Index
Index
245