COCO Help TEA

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TEA
Thermodynamics for engineering applications
TEA is a CAPE-OPEN compatible thermodynamics system. Such a system can be used in CAPE-
OPEN compatible environments, such as COCO, or any of the many for CAPE-OPEN compatible
main stream process engineering applications.
The property implementations in TEA are largely based on those in ChemSep. Parts of this document
are adapted from the ChemSep Book.
TEA's internal material objects are very similar to those in COFE, the same restrictions do apply.
Also the same transparency towards CAPE-OPEN thermodynamic standard versions 1.0 and 1.1
apply.
TEA exports both CAPE-OPEN thermodynamic standard versions 1.0 and 1.1 (depending on whether
it is loaded as version 1.0 Thermo Package or version 1.1 Property Package Manager).
TEA supports loading of external version 1.1 property packages (stand-alone or from a Property
Package Manager) as equilibrium server or as property calculation routine. TEA also supports version
1.0 stand-alone external equilibrium routines as well as stand-alone external version 1.0 and version
1.1 external property calculation routines.
Property packages and property package

templates
A Property Package is a collection of chemical compounds and calculation methods, specific to a
chemical engineering application. TEA differentiates between instances of Property Packages and
Property Package Templates.
Property package templates

Property package templates are configurations for a property package; you can use a property package
template to instantiate a property package.
You can configure the Property Package templates for TEA from within COCO (by using the Edit
Templates button, that is available when choosing Edit after selecting TEA in the Add Property
Package window), or by using the external configuration utility 'configureTEA.exe'.
To create a duplicate of a property package, start with creating a new one, and then use Load Existing
from the Package menu.
Property package templates are stored in the data file TEAconfig.dat (which is located in [the user's
application data folder]\COCO\data). Remove the user copy of TEAconfig.dat to revert to the default
copy.
Property packages
Once you have created a property package template, you can use it by adding a property package to a
simulation. At this point you will be asked what property package template to use for your simulation.
file://C:\Users\klaus\AppData\Local\Temp\~hhF65B.htm 2018/06/12
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Some simulation environments, like COCO, will allow you to edit the content of a property package.
In the case of TEA, this does not reflect on the property package templates. Also, changes made to the
property package template do not reflect on instantiated property packages.
When editing a property package, you can however reload the property package from a property
package template. To do so, select Load Existing from the Package menu. Vice versa, you can also
save the content of the current property package to a property package template. For this, select Store
As Template from the Package menu when editing the property package.
When editing your property package, you can select Check Validity from the Package menu to check
whether your package configuration is valid.
Some simulation environments do not allow you to edit a property package. In this case, it is likely
that the content of a property package is also not stored (using the CAPE-OPEN defined persistence
interface).
For this scenario, it is likely that each time you load your document, the property package is reloaded
from a template that has the same name (the name of the template that was originally used for the
document). In order to make changes to the document's property package, you will therefore need to
close the document, use the ConfigureTEA.exe utility to change the corresponding property package
template, and reload your document.
Documents that do not support editing and storing property packages depend on information in the
property package template data file "TEAconfig.data". Therefore, when transporting such a
simulation document between computers, make sure the "TEAconfig.dat" files for the current user are
the same.
Configuration
By default, the Simple configuration mode is used for editing property packages. To edit more
advanced features of your package, select any of the options under the Configure menu. Use Simple
from the Mode menu to return to simple mode.
For details on the configuration of property package (templates), see:
Compounds
Property calculations
Equilibrium calculations
Solid-only compounds
Options
Simple editing mode

In simple editing mode, pre-defined model sets are available. All that is required for a standard-
configuration of a Property Package is selection of compounds and a model set. This will select the
VLE equilibrium server, a standard set of properties, and corresponding property calculation methods.
Any more advanced modifications to the package set up can be done using the items in the Configure
menu. Changing advanced options will cause the model set to change to Custom. Re-selecting a
model set once in Custom configuration mode, will overwrite any existing property and model
selections.
Model sets
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Before selecting a model set, it is best to first add the desired compounds. This will prevent any
warnings or errors from being shown that would not be shown in case the compounds had already
been selected. Vice versa, when presence of particular compounds cause issues with the selected
model set, these warnings will only be at model selection if the compounds have already been added.
The pre-defined model sets can be divided into two groups: EOS (Equation of State) based models,
and Activity based models.
All models will use default calculation routines for the following properties: ideal gas enthalpy,
surface tension, viscosity, thermal conductivity, heat capacity, Gibbs free energy and molecular
weight. For all model sets, the COSTALD liquid density model is selected by default.
EOS based model sets

For EOS based model sets, vapor and liquid phase will use the same equation of state. The following
properties are based on the equation of state: compressibility factor, fugacity, enthalpy, entropy and
vapor density. The following model sets are available:
Peng Robinson: uses the Peng Robinson Equation of State for the vapor and liquid phase.
Soave Redlich Kwong: uses the Soave Redlich Kwong Equation of State for the vapor and
liquid phase.
Activity based model sets

All activity based model sets will use the ideal gas model for the vapor phase fugacity, density,
enthalpy and entropy. A compound-based default model will be selected for heat of vaporization.
Fugacity for the liquid phase will be defined by the DECHEMA model (which does not include the
saturated vapor fugacity or Poynting correction). The liquid excess entropy and enthalpy are based on
the activity coefficient. The following models are available for the liquid activity:
Wilson: uses the Wilson model for liquid phase activity

NRTL: uses the NRTL model for liquid phase activity
UNIFAC VLE: uses the UNIFAC VLE model for liquid phase activity
UNIQUAC: uses the UNIQUAC model for liquid phase activity
Chemical Theory (Prausnitz): uses the UNIQUAC-Q' model for liquid phase activity; the
liquid fugacities and enthalpies follow the Prausnitz formulation based on a liquid reference
fugacity. The vapor phase uses the Hayden O'Connel equation of state with the Chemical
Theory model. This model describes non-idealities resulting dimerization in the vapor phase,
such as for carboxylic acids.
Compounds
Compound selection
Compounds that are added to a property package (or -template), will appear in your simulation
document. Compound data in TEA is loaded from Pure Compound Data files (PCD files). A default
compound file "DefaultComponentLib.pcd" comes with TEA and is located in the data folder. Once
compounds have been loaded from a PCD file, they are stored in the property package configuration
data. Changing the PCD file content has no effect unless you reload the compounds.
To add or remove compounds to your simulation, you can use the Simple Configuration mode; here
you can add and remove compounds. For more advanced compound operations, select 'Compounds'
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from the Configure menu.
To add compounds, press the Add button. Compounds are listed for the specified PCD file. You can
filter the listed compounds by entering text in the filter box. Only compounds that contain that text in
either the compound name (or one of its alternative names) or formula will appear (in case of an exact
match, the compound will be selected as well). Alternative names for compounds are stored in the file
Synonyms.dat; when entering a filter, the closest matching alternative name will automatically be
selected for a compound. You can choose another synonym by clicking on the compound name. The
default compound name will also be shown. When adding the compound, the selected alternative
name will be used, unless the "Add using default name" check box is checked. When pressing Enter
or clicking OK, the selected compounds will be added. You can select more than one compound at a
time.
To remove compounds, select the compound you want to remove and click Delete. Repeat for each
compound to be removed.
To edit the pure compound data for a compound, select the compound and press Edit. The Constants
page allows access to compound constants. Expressions are accepted. The Temperature Correlation
page allows access to the temperature correlations. Functional form and parameter values can be
altered. Only a number of functional forms are available.
To rename a compound, click the name of the compound when it is selected.
The order of the compounds can be changed by selecting a compound and press Up or Down to
change the location of a compound in the list.
Some property models (optionally) require interaction parameters. Some property models require
group contribution data.
Compound dependent property calculations

For ideal gas heat capacity, and for all properties for which a per-compound calculation routine is
selected, the calculation method can be selected per compound. To change a calculation method for a
given compound, click on the compounds method as it is currently defined, and select the desired
method from the drop down list.
The ideal gas heat capacity is the bases of most enthalpy and entropy calculations. Two correlations
may be available for each compound (that can be inspected by editing a compound). If neither
correlation is available, a value of 3.5 times the gas constant may serve as a default approximation for
heat capacity (this is the theoretical value for two-atom gases with 5 degrees of freedom).
PCD Files
Pure Compound Data is stored in PCD files. TEA PCD files use the same format as ChemSep PCD
files. To add user compounds to a PCD file or create your own PCD files, one can use the PCDman
application that is installed with Chemsep LITE.
The default compounds are available from Chemsep1.pcd; the solid-only compounds are available
from solids.pcd.
PCDman
PCDman is very useful for creating a new entry in a PCD file; it comes with many features for
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importing data from the web or estimating data.
If PCDman is installed at your system, you can start it from TEA's Add Compounds dialog.
Interaction parameters
Some property models (optionally) require interaction parameters. Interaction parameters are
automatically loaded from the IPD files in the data\ipd folder when you add compounds to your
property package definition. Interaction parameters are stored with the property package definition, so
changing the content of IPD files has no effect unless you reload your compounds, or if you explicitly
select Import (which imports the selected item from a specified IPD file) or Import All, which imports
all unavailable data from a specified IPD file. Click the defaults to re-import all data from the default
IPD files.
Each data point comes with a numeric value, a source description and a comment. All of these are
optional (although some property models require all values to be present).
To add, remove or modify interaction parameters, choose Interaction Parameters from the Configure
menu. Select the model for which you want to modify the interaction parameters from the topmost
list. If the interaction parameters have a dimension (unit), select the desired dimension from the
second list. Conversion will take place automatically, so make sure to enter your data when the
correct dimension is selected. Expressions are accepted.
Click on an entry to change or remove it. To remove, either click Erase for the selected item, or set
the value to an empty string or "N/A". To remove all values at once, click Erase All.
Some interaction parameter sets are symmetric, and some require or allow the diagonal to be set.
Group contribution data

Some property models require group contribution data. Group contribution data consists of two parts:
a definition for each molecule from which groups it exists, and the data that define the groups. Group
contribution data, where available, are automatically loaded from the GC files in the data\ipd folder
when you add compounds to your property package definition. Group contribution data are stored
with the property package definition, so changing the content of GC files has no effect unless you
reload your compounds.
To define, for a compound, which sub-groups it exists of, choose Group Contributions from the
Configure menu. From the top-most drop down list, select the property model for which you want to
edit the data.
Select the desired compound, and click Add Subgroup to add a sub-group to a molecule definition.
Click on the count to change how many of these groups are present in a molecule. To remove a sub-
group from a molecule, select the sub-group and click Delete Sub-Group. As a check on the
correctness of the definition, the total molecular weight vs. the known molecular weight is displayed
at the bottom of the list of sub-groups for the selected molecule.
To edit the available groups, click Edit Groups. You can create new groups by clicking New Group.
To change the interaction parameters for groups, click on the parameter. Expressions are accepted. To
delete an existing group, click Delete.
To edit the available sub-groups, click Edit Sub-Groups on the Group Contributions page. Here, you
can add and remove groups, and set the parameters available for each group. To change a parameter
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value, click on the parameter value itself. Expressions are accepted.
Property Calculations
Choosing property models
To setup which models are used for your simulation, you will need to properly set up the property
package template that will be used for the simulation. Once the property package is instantiated, some
simulation environments will allow you to edit the property package, making changes to the selected
models. For other simulation engines that do not support editing and storing property package
content, you will need to modify the property package template and reload your simulation document.
The property calculations page of the property package (template) editing window allows you to
select which properties are available in your simulation, and which models will be used for it. Select
Properties from the Configure menu.
You can add properties to your property package (template) by clicking the Add Property button
(here, you can select multiple properties at the same time). To remove a property, select the property
and click Delete Property.
Equation of state can be selected for each phase type present. This is not a property, but allows for
calculating many properties, if you select the EOS calculation method for these properties. This is the
default property evaluation method if an equation of state is selected.
For each property that is present, an evaluation method for at least one phase must be present.
For some properties, consistency is forced. For example, you cannot choose different property models
for fugacity, fugacityCoefficient and logFugacityCoefficient, or for volume and density.
Derivatives
Unless mentioned otherwise, analytical derivatives w.r.t. mole fraction, temperature and pressure are
available for all internal property routines. Mole fraction derivatives are the ones in which the mole
fractions are not restricted to add up to unity. Mole fraction derivatives are never available for pure
compound properties.
External property calculation routines

You can load external property methods (registered implementations of
ICapeThermoCalculationRoutines for CAPE-OPEN version 1.0, or property packages (stand-alone or
from a property package manager) or stand-alone ICapeThermoPropertyRoutine objects for CAPE-
OPEN version 1.1) to your property package (template). Do do so, go to the "External Routines"
page, and click Add. To remove an imported routine, select the routine and click Remove.
Properties exported by an external property routine are automatically added to the property package
configuration. Only properties that appear in COCO's configuration files can be supported by TEA.
Property models
For the details on the various models, see the following sections:
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Equations of state
Activity
Bubble and dew points
Density, volume and compressibility factor
Enthalpy, EnthalpyF, EnthalpyNF
Internal energy
Entropy, EntropyF, EntropyNF
Fugacity
Gibbs free energy
Heat capacity
Heat of vaporization
K-values
Molecular weight
Surface tension
Thermal conductivity
Vapor pressure
Viscosity
Equations of state
Three types of equations of state may be selected in TEA; Ideal Gas, Virial, and Cubic EOS. From an
equation of state, a number of properties can be predicted, amongst which are fugacity, density,
compressibility factor and volume and enthalpy.
Ideal gas law

Virial equations of state
Cubic equations of state
Ideal gas law

The fugacity coefficient of an ideal gas mixture is unity (since the fugacity represents the deviation
from an ideal gas, and we use the natural logarithm of the fugacity as the fugacity coefficient). The
pressure relation for an ideal gas is:
Virial equations of state

Hayden-O'Connell
Hayden and O'Connell have provided a method of predicting the second virial coefficient for multi-
compound vapour mixtures. The method is quite complicated (see Prausnitz et al., 1980) but is well
suited to ideal and non-ideal systems at low pressures. You must input the association parameters. A
library of association parameters is provided with TEA in the file HAYDENO.IPD.
Hayden-O'Connell with Chemical theory

This is an extension on the Hayden O'Connell virial model, which takes the association of molecules
into account (see Prausnitz et al., 1980). Since the mole fractions are a function of the association, an
iterative method (here Newton's method) must be used to obtain them in order to compute the virial
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coefficients.
Derivatives of compressibilities are determined by perturbation, and therefore all quantities derived
from that (volume, density, fugacity, enthalpy, ...)
Tsonopoulous
The two-term virial equation:
The method of Tsonopoulous for estimating virial coefficients is recommended for hydrocarbon
mixtures at low pressures. It is based on an earlier correlation due to Pitzer.
$\displaystyle $\textstyle =$
B_{ij}$
$\displaystyle
B^{(0)}_{ij}$
Binary interaction parameters kij must be supplied by the user. For paraffins, kij can be calculated
with:
Temperature Correlation
Temperature correlated values for the virial coefficient are available from TEA (PCD) data files.
Cubic equations of state
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Redlich Kwong
The Redlich Kwong (RK) equation is used in the Chao-Seader method of computing thermodynamic
properties.
with
and the mixing rules:
where kij is a binary interaction parameter; original RK:
Soave Redlich Kwong

Soave's modification of the Redlich Kwong (SRK) EOS is one of the most widely used methods of
computing thermodynamic properties. The SRK EOS is most suitable for computing properties of
hydrocarbon mixtures.
with
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API SRK EOS

Graboski and Daubert have modified the coefficients in the SRK EOS and provided a special relation
for hydrogen. This modification of the SRK EOS has been recommended by the American Petroleum
Institute (API), hence the name of this menu option. It uses the same equations as the SRK except for
the α:
and specially for hydrogen:
Peng Robinson EOS

The Peng-Robinson equation is another cubic EOS that owes its origins to the RK and SRK EOS. The
PR EOS, however, gives improved predictions of liquid phase densities.
with
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$\displaystyle
b$
Activity
Here we discuss the activity coefficient models available in TEA. For an in depth discussion of these
models see the standard references. For the calculation of activity coefficients and their derivatives
(for diffusion calculations) see also Kooijman and Taylor (1991).
Ideal
For an ideal system the activity coefficient of all species is unity, and thus, ln(γi) = 0.
Regular solution
The regular solution model is due to Scatchard and Hildebrand. It is probably the simplest model of
liquid mixtures. The activity coefficient is given by:
where δi is called the solubility parameter and Vi the molal volume of compound i (both read from the
PCD-file).
The Flory-Huggins corrected version is also available:
Margules
The "Three suffix" or two parameter form of the Margules equation is implemented in TEA:
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It can only be used for binary mixtures.
Van Laar
The Van Laar equation is
It can only be used for binary mixtures.
Wilson
The Wilson equation was proposed by G.M. Wilson in 1964. It is a "two parameter equation". That
means that two interaction parameters per binary pair are needed to estimate the activity coefficients
in a multi-compound mixture. For mixtures that do NOT form two liquids, the Wilson equation is, on
average, the most accurate of the methods used to predict equilibria in multi-compound mixtures.
However, for aqueous mixtures the NRTL model is usually superior.
The two interaction parameters are (λij-λii) and (λji-λjj) per binary pair of compounds. If interaction
parameters g are specified in temperature units (K), then
or if interaction parameters g are specified in energy units, then
or if interaction parameters g are specified temperature invariant, then
NRTL
The NRTL equation due to Renon and Prausnitz is a three parameter equation. Unlike the original
Wilson equation, it could also be used for liquid-liquid equilibrium calculations.
$\displaystyle
\tau_{ij}$
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The interaction parameters are (\lambdaij-\lambdaii), (\lambdaji-\lambdajj) and αij per binary (only
one α is required as αji = αij).
If interaction parameters g are specified in temperature units (K), then
or if interaction parameters g are specified in temperature invariant units, then
In addition, a temperature dependent modification of gij can be introduced. If specified, the above
equations are modified to, when specified in temperature units (K), then
The reference temperature in TEA is Tref = 298.15 K
UNIQUAC
UNIQUAC stands for Universal Quasi Chemical and is a very widely used model of liquid mixtures
that reduces, with certain assumptions, to almost all of the other models mentioned in the list. Like the
Wilson equation, it is a two parameter equation but is capable of predicting liquid-liquid equilibria as
well as vapour-liquid equilibria. Two types of UNIQUAC models are available Original and q-prime.
Original is to be used if you have obtained interaction parameters from DECHEMA. The q-prime (q')
form of UNIQUAC is recommended for alcohol mixtures. An additional pure compound parameter,
q', is needed. If q' equals the q value it reduces to the original method.
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$\displaystyle
\phi$
$\displaystyle \theta$
The interaction parameters are (λij-λii) and (λji-λjj) per binary. The parameters ri and qi are read from
the compound database (PCD file).
The coordination number z is taken as 10. In the q-prime mode, q' is used instead of q in the residual
part ln γir, whereas the combinatorial part ln γir uses q.
If interaction parameters g are specified in temperature units (K), then
UNIFAC
UNIFAC is a group contribution method that is used to predict equilibria in systems for which NO
experimental equilibrium data exist. The method is based on the UNIQUAC equation, but is
completely predictive in the sense that it does not require interaction parameters. Instead, these are
computed from group contributions of all the molecules in the mixture.
UNIFAC-VL is fitted to vapor-liquid equilibria. UNIFAC-LL is fitted to liquid-liquid equilibria.
ASOG
ASOG is a group contribution method similar to UNIFAC but based on the Wilson equation. It was
developed before UNIFAC but is less widely used because of the comparative lack of fitted group
interaction parameters.
Bubble and dew points
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Bubble point pressure, bubble point temperature, dew point pressure and dew point temperature are
offered for convenience. They can alternatively be obtained by performing equilibrium calculations
with a fixed vapor fraction of either zero or unity.
The only available calculation method for bubble and dew points is by using TEA's VLE equilibrium
routine. This method can only be selected if the TEA VLE equilibrium routine is the selected routine
for equilibrium calculations.
Density, volume and compressibility factor

The sections below discuss the various density models available in TEA.
Volume is always calculated as one over density.
Compressibility factor the ratio of pressure times volume and gas constant times temperature: PV/RT.
Compressibility factor is only available when using an equation of state.
Liquid mixture density

All mixture density derivatives are determined by perturbation, except for the Amagat method.
Mixture liquid densities are calculated with one of the following models
Equation of State
If an equation of state is selected for the liquid phase, density can be calculated using the equation of
state.
Amagat's law (Ideal)
Amagat's law calculated mixture density by ideally mixing the volumes for the available compounds:
See the section below for the pure compound liquid densities ρiL.
Rackett
This method requires compound critical temperatures, pressures, mole weights and Rackett
parameters (for which critical compressibilities are used if unknown):
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If the reduced temperature, Tr, is greater than unity the formula above is evaluated for Tr = 1.
Yen-Woods
Mixture critical temperature, volume, and compressibility are calculated with the "normal" mixing
rules. If the mixture reduced temperature, Tr = T / Tc,m, is greater than unity the density is evaluated
using Tr = 1.
COSTALD (Hankinson-Thompson)
Mixture density is calculated by the COSTALD method of Hankinson and Thomson (AIChE J, 25,
653, 1979) and Thomson et al. (AIChE J, 28, 671, 1982):
If the reduced temperature is larger than unity, the following is evaluated using unity for the reduced
temperature:
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where
a=-1.52816 e=-0.296123
b= 1.43907 f= 0.386914
c=-0.81446 g=-0.0427258
d= 0.190454 h=-0.0480645
The density equals the inverse of the liquid molar volume.
This method should be used for reduced temperatures from 0.25 up to the critical point.
Pure compound liquid density

Pure compound liquid densities are required by some of the above mixture liquid density routines,
and are only valid in this context. If an external density calculation routine is used, pure compound
liquid densities are evaluated fore each compound by setting the mole fraction of that compound to
unity and the remaining mole fractions to zero, and evaluate mixture density.
Pure compound liquid densities are computed with one of the following methods. Depending on the
choice of mixture liquid density (see above), the choices for pure compound mixture density may be
limited in order to be consistent.
All derivatives are determined by perturbation, except for the EOS method.
The temperature correlation for pure compound liquid density is a polynomial of which the
parameters are available through TEA's PCD data files.
Rackett
The Rackett method for pure compound liquid density:
Hankinson-Thompson
As for liquid mixture density, but with pure compound parameters.
Per compound
When selecting the Per Compound routine, the above methods can be selected on a per-compound
basis in the compounds tab.
Equation of State
As for liquid mixture density.
Vapor density
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The only available vapor density methods use the selected vapor equation of state.
Solid density
The only available mixture solid density calculation routine is Amagat's law (see above for liquid).
The only available compound solid density calculation routine is temperature correlation.
Overall density
Overall density is not available.
Overall volume
Overall volume can be calculated through summation over the available phases.
Enthalpy
Ideal
In this model the enthalpy is computed from the ideal gas contribution:
For liquids, the latent heat of vaporization is subtracted from the ideal gas contribution:
Excess
This model includes the ideal enthalpy as above. In addition to that, excess enthalpy is included:
Prausnitz
The liquid enthalpy for the Prausnitz model is consistent with the liquid reference fugacity of the
Prausnitz model fugacity calculations:
EOS
This model includes the ideal vapor enthalpy as above. In addition to that, the temperature derivative
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of the fugacity coefficients from the selected equation of state is subtracted from the ideal part:
Pressure and temperature derivatives are determined by perturbation.
Solids
For solids, currently the only enthalpy model is ideal enthalpy:
Here, the solid phase heat capacity is used (configured per compound). The solid state reference
enthalpy at reference temperature is zero for solid-only compounds; these compounds have their
reference state in the solid phase. This means the heat of formation - Hform as used below in
enthalpyF - must also be at the solid reference state. Other solids are currently not supported.
Overall
The overall enthalpy can be calculated from summation over the available phases, taking into account
the phase fractions.
EnthalpyF
EnthalpyF, as opposed to enthalpy, contains the enthalpy of formation:
For EnthalpyF, the same models are available as for Enthalpy.
EnthalpyNF
EnthalpyNF is defined as enthalpy for which enthalpy of formation is not included. In TEA it can be
calculated and is treated synonymous for Enthalpy.
Excess Enthalpy
From activity coefficient
The only available excess enthalpy model is for the liquid phase: by calculation from the temperature
derivatives of the activity coefficient model.
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Pressure and temperature derivatives are determined by perturbation.
Entropy
Ideal entropy is determined from
where for the vapor phase,
For the heat capacity Cp, the Temperature Correlation is used.
For the liquid phase,
For compound for which T > TC, the heat of vaporization is taken to be zero, and Psat,i is taken to be
equal to P, so that SLi,ideal reduces to SVi,ideal.
EOS
When using an equation of state, departure entropy can be determined from fugacity coefficient and
its temperature derivative:
For both vapor and liquid, the vapor ideal entropy is used in the above, since the saturated vapor
pressure and heat of vaporization are accounted for in the fugacity terms.
From activity coefficient

If an activity model is used for the liquid phase, excess entropy can be determined from the activity
coefficient and its temperature derivative:
The ideal entropy for the liquid phase is used in the above.
From fugacity coefficient
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When not using an equation of state, the equation for determining entropy from fugacity (as used for
equations of state) still holds:
Again, for both vapor and liquid, the vapor ideal entropy is used in the above, since the saturated
vapor pressure and heat of vaporization are accounted for in the fugacity terms. Any fugacity
calculation method can be used with this routine.
Temperature and pressure derivatives for the above entropy calculations are determined by
perturbation.
Solids
For solid compounds, only ideal entropy is currently available. By default, the assumption is that the
solids do not mix within the phase (representing multiple separate solid phases within an overall solid
phase):
Alternatively you can select ideal mixing for the solid phase:
Here, Θi represents the (ideal) volume fraction of compound i (evaluated from mole fractions and
pure compound solid densities).
The reference state entropy for solid-only compounds is zero for the solid state at reference pressure
and temperature, and the solid compound heat capacity is configured per compound. Other solids are
currently not supported.
The solid compound entropy is mixed ideally:
For these compounds, the absolute entropy needs to be in the solid phase for the calculation of
EntropyF (see below).
EntropyF
EntropyF, as opposed to entropy, includes the absolute entropy:
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For EntropyF, the same models are available as for Entropy.
The absolute entropy Si,abs for each compound is tabulated in TEA's PCD data files.
EntropyNF
EntropyNF is defined as entropy that is sure not to include entropy of formation. In TEA, this
property is available and synonymous to Entropy.
Fugacity
EOS
Fugacities are calculated from the selected equation of state. This model is recommended for mixtures
of hydrocarbons and light gases (hydrogen, carbon dioxide, nitrogen, etc.) at low and high pressures.
It is not recommended for non-ideal chemical mixtures at low pressures.
From Activity Coefficient

Liquid fugacity is calculated from
where PFi is the Poynting correction for compound i, Pi* is the saturated vapor pressure for
compound i and φi* is the fugacity coefficient of the vapor phase for compound i at liquid
composition and liquid temperature and saturated vapor pressure.
This option should be used when dealing with non-ideal fluid mixtures. It is not suitable for high
pressures.
DECHEMA
This is a simplified form of the complete "From Activity Coefficient" model in which the Poynting
correction factor is assumed equal to unity.
This is the form of the K-value model used in the DECHEMA compilations of equilibrium data when
used with the Ideal gas equation of state and the Antoine equation for vapor pressure.
Prausnitz
TEA Page 23 of 43
The saturated vapor fugacity, Poynting factor and vapor pressure are all combined into a liquid
reference fugacity fi0. Values of the reference fugacity are calculated using a temperature dependent
function for which the shape is equal to the Extended Antoine equation:
The parameters A through G must be supplied by the user; this can be done by editing the compound
in the TEA package configuration dialog. For a number of chemicals, the parameter values are given
by the data file prausnitz_e_antoine.lib in the data sub folder of the COCO installation folder.
Parameter values for the compounds in this file will be automatically loaded.
Gibbs free energy

Gibbs free energy, for all phases, is calculated from:
G=H-TS
for which enthalpy and entropy need to be available.
For the overall phase, Gibbs free energy can be calculated by summation over the existing phases,
taking phase fraction into account.
If TEA's internal calculation routines for enthalpy and entropy are used, the Gibbs energy will not
include the formation terms (heat of formation and entropy of formation).
Heat capacity
For all phases, the consistent way to calculate heat capacity (including mixing enthalpy terms) is to
calculate it from enthalpy. This is the default calculation routine for heat capacity. Other methods are
described below.
Liquid heat capacity

The mixture liquid heat capacity is the molar average of the compound liquid heat capacities.
The parameters for the temperature correlation for liquid heat capacity are available through TEA's
PCD data files.
Corresponding states
Liquid heat capacity can be computed from a corresponding states method and the ideal gas capacity.
Rowlinson (1969, see A140) proposed a Lee-Kesler heat capacity departure function which was later
modified to:
TEA Page 24 of 43
If the reduced temperature exceeds 0.98, a value of 0.98 is used instead.
Temperature derivatives are determined by perturbation.
Vapor heat capacity

The mixture vapor heat capacity is the molar average of the compound vapor heat capacities.
The parameters for the temperature correlation for vapor heat capacity are available through TEA's
PCD data files.
Solid heat capacity

The mixture solid heat capacity is the molar average of the compound solid heat capacities. The solid
heat capacities are configured per compound.
The parameters for the temperature correlation for solid heat capacity are available through TEA's
PCD data files.
Temperature Correlation for liquid phase
If solid phase heat capacity data is not available, the liquid heat capacity temperature correlation can
be selected for the solid phase. The parameters for the temperature correlation for liquid heat capacity
are available through TEA's PCD data files.
Ideal gas contribution
If solid and liquid phase heat capacity data are not available, the ideal vapor heat capacity temperature
correlation can be selected for the solid phase. The parameters for the temperature correlation for
vapor heat capacity are available through TEA's PCD data files.
Zero contribution
For compounds that do not appear in the solid phase, zero contribution is a safe selection for solid
heat capacity.
Heat of vaporization
The heat of vaporization routines are specified per compound in the compounds tab, if the heat of
vaporization calculations are enabled.
When the EOS method is selected for liquid enthalpy, heat of vaporization is not required for
calculating liquid enthalpy.
For any other internal enthalpy liquid method, heat of vaporization is required. Three models are
available:
TEA Page 25 of 43
The parameters for the temperature correlation for heat of vaporization are available through TEA's
PCD data files.
Pitzer
The Pitzer correlation for heat of vaporization:
Clausius Clapeyron
The relation between vapor pressure and heat of vaporization is given by
The approximation ∆z = 1 is made, and a valid routine for vapor pressure must be selected.
Internal Energy
Internal Energy, for all phases, is calculated from:
U=H-PV
for which enthalpy and volume need to be available.
For the overall phase, internal energy can be calculated by summation over the existing phases, taking
phase fraction into account.
If TEA's internal calculation routines for enthalpy and volume are used, the internal energy will not
include the formation terms (heat of formation).
K-Values
In TEA, when using CAPE-OPEN version 1.0, K-values are only available for phase "VaporLiquid".
Composition derivatives are not supported.
For CAPE-OPEN version 1.1, K-values are a regular two-phase property.
The only internal routine calculates log(K-values) for phase 1 and phase 2 as log(fugacity
coefficient,phase 2) minus log(fugacity coefficient,phase 1). So logFugacityCoefficient must be
available for both phases.
Molecular weight
The only internal calculation routine for molecular weight calculates the molecular weight of each
TEA Page 26 of 43
phase by summing up the product of mole fraction and molecular weight of each compound in that
phase.
Surface tension
In TEA, when using CAPE-OPEN version 1.0, surface tension is only available between vapor and
liquid. Because two-phase qualifiers are not well defined, external objects may specify both "Liquid"
and "VaporLiquid" for the phase specifier of surfaceTension. Composition derivatives are not
supported for version 1.0; however, COFE's material objects will translate a call for
surfaceTension.DmolFraction properly when TEA is loaded as version 1.1 property package and a
PMC specifies "Liquid" as phase identifier.
For CAPE-OPEN version 1.1, surface tension is a regular two-phase property.
None of the formulas below take any of the vapor properties into account.
Mixture surface tension

All surface tension derivatives are obtained by perturbation.
Ideal
Winterfeld et al.
This method by Winterfeld et al. (1978) is DIPPR 7C procedure:
Digulio-Teja
This method evaluates the compound surface tensions at the compounds normal boiling points (σb,i)
and computes the mixture critical temperature, normal boiling temperature and the mixture surface
tension at normal boiling temperature with the following mixing rules:
TEA Page 27 of 43
Then it corrects the σb,m with:
Pure compound surface tension

Pure compound surface tension is required by the internal mixture surface tension routines, and can
only be used with these routines. If mixture surface tension is calculated by an external calculation
routine, pure compound surface tension is obtained by using the same external routine and making a
call for each compound in which compositions are set as to have only that compound present.
Compound surface tensions are only determined for temperatures below the compound's critical
temperature, otherwise it is assumed that the compound does not contribute to the mixture surface
tension (to prevent numerical difficulties, implemented as σi = 1e-10). The following methods are
available.
The parameters for the temperature correlation for liquid surface tension of pure compounds are
available through TEA's PCD data files.
Brock-Bird
This is DIPPR procedure 7A:
Lielmezs-Herrick
This method by Lielmezs and Herrick (1986) uses the Temperature Correlation but evaluates it at the
reduced normal boiling temperature and corrects the resulting σr with:
Per compound
TEA Page 28 of 43
Thermal conductivity
All thermal conductivity derivatives are determined by perturbation.
Pure compound thermal conductivities are only available for use with internal mixture thermal
conductivity routines. They cannot be used if no internal mixture routine is selected. For CAPE-
OPEN version 1.1 external calculations, pure compound thermal conductivities are evaluated for each
compound as mixture thermal conductivities with composition set to unity for that compound and
zero for all other compounds.
Liquid Mixture Thermal Conductivity

Ideal
The ideal liquid thermal conductivity mixing:
DIPPR 9I
The DIPPR procedure 9I for liquid thermal conductivity mixing:
DIPPR 9H
The DIPPR procedure 9H for liquid thermal conductivity mixing:
where wi is the weight fraction of compound i.
High pressure correction
For all liquid thermal conductivity mixing models, a correction is applied when the pressure is larger
than 35 bar:
TEA Page 29 of 43
This is DIPPR procedure 9G-1 where the mixture parameters are computed by the ideal mixing rules.
Pure compound liquid thermal conductivity

The parameters for the temperature correlation for liquid thermal conductivity of pure compounds are
available through TEA's PCD data files. If the reduced temperature exceeds 0.99, a value of 0.99 is
used.
Pachaiyappan et al.
for straight chain hydrocarbons:
otherwise:
If the reduced temperature exceeds 0.99, a value of 0.99 is used. If the critical temperature is below
273.15 K, a value of 3 is used for b.
Sato-Riedel
Here, the reduced boiling temperature Tb,r is substituted by a default value of 0.65 if the normal
boiling temperature is not available. If the reduced temperature exceeds 1, a value of 1 is used.
DIPPR procedure 9E
The Latini et al. procedure (DIPPR procedure 9E) for liquid thermal conductivity of pure compounds:
TEA Page 30 of 43
$\displaystyle
A$
where parameters A*, α, β and γ depend on the class of the compound:

Family A* α β γ
Saturated hydrocarbons 0.0035 1.2 0.5 0.167
Olefins 0.0361 1.2 1.0 0.167
Cycloparaffins 0.0310 1.2 1.0 0.167
Aromatics 0.0346 1.2 1.0 0.167
Alcohols, phenols 0.00339 1.2 0.5 0.167
Acids (organic) 0.00319 1.2 0.5 0.167
Ketones 0.00383 1.2 0.5 0.167
Esters 0.0415 1.2 1.0 0.167
Ethers 0.0385 1.2 1.0 0.167
Refrigerants:
R20, R21, R22, R23 0.562 0.0 0.5 -0.167
Others 0.494 0.0 0.5 -0.167
If the reduced temperature exceeds 0.99, a value of 0.99 is used.
Per compound
Vapor Mixture Thermal Conductivity

Ideal
The mixture vapour thermal conductivity is computed from the pure compound thermal conductivities
as follows:
Kinetic theory
This is DIPPR procedure 9D:
TEA Page 31 of 43
where interaction parameters φij are computed from:
Note that the compound viscosities are required for this evaluation.
High pressure correction
If the system pressure is larger than 1 atmosphere a correction is applied according to DIPPR
procedure 9C-1. Mixture parameters are computed using the ideal mixing rules. Critical and reduced
densities are computed from:
If the reduced density is below 0.5, then
else, if the reduced density is below 2, then
otherwise
The high pressure thermal conductivity correction is then calculated from:
which must be added to the calculated thermal conductivity for low pressure.
TEA Page 32 of 43
Pure compound vapor thermal conductivity

The parameters for the temperature correlation for vapor thermal conductivity of pure compounds are
available through TEA's PCD data files.
DIPPR procedure 9B-3
DIPPR procedure 9B-3 for pure compound thermal conductivity:
This method is recommended for linear molecules.
This method is suitable for mono-atomic gases only.
Misic-Thodos 2
This method is used for methane and cyclic compounds.
This method should be used when Tr < 1. A warning is produced if this is not the case.
Misic-Thodos 1
This method is used for all compounds but methane and cyclic compounds.
TEA Page 33 of 43
Per compound
Vapor Pressure
The vapor pressure routines are specified per compound in the compounds tab, if the vapor pressure
calculations are enabled.
Antoine
The Antoine Equation is:
Note the natural logarithm. This option should be selected if you are using activity coefficient models
with parameters from the DECHEMA series. Antoine parameters are available in the TEA PCD data
files.
Extended Antoine
The Extended Antoine equation incorporated in TEA's thermodynamic routines is:
The parameters A through G must be supplied by the user.
The temperature correlation for vapor pressure is given by
Parameters A through E are available in the TEA PCD data files.
Riedel
The Riedel equation is best suited to non-polar mixtures:
TEA Page 34 of 43
Lee-Kesler
Lee and Kesler used a Pitzer expansion to obtain:
where
$T_r=T/T_{Ci}$
Both the Riedel and Lee-Kesler models are recommended for hydrocarbon mixtures in particular.
Viscosity
Pure compound viscosities are only available for use with internal mixture viscosity routines. They
cannot be used if no internal mixture routine is selected. For CAPE-OPEN version 1.1 external
calculations, pure compound viscosities are evaluated for each compound as mixture viscosities with
composition set to unity for that compound and zero for all other compounds.
Liquid mixture viscosity

Liquid mixture viscosity is calculate through logarithmic mixing:
where zi are either the mole fractions (for molar averaging) or alternatively the weight fractions for
mass averaging.
For mass averaging, composition derivatives are approximate due to normalization of the mass
fractions.
Pure compound liquid viscosity

The parameters for the temperature correlation for liquid viscosity of pure compounds are available
through TEA's PCD data files.
TEA Page 35 of 43
Letsou-Stiel
The Letsou-Stiel method (1973) for liquid viscosity of pure compounds:
If the temperature is above the critical temperature of the compound, vapor viscosity is used instead.
Reid et al
The simple temperature correlation given in Reid et al. (RPS liquid viscosity, see A439) can also be
used:
The parameters A and B are available through TEA's PCD data files.
Per compound
Vapor mixture viscosity

All vapor mixture viscosity derivatives are determined by perturbation.
Wilke
Mixture vapour viscosities are computed using:
where the interaction parameters φij are calculated by Wilke's (1950) method:
\begin{displaymath}\phi_{ij} = ({1 + \sqrt{ \eta_i / \eta_j } (M_i / M_j)^{1/4})^2\over\sqrt{ 8 (1 + M_i / M_j) } }\end{displaymath}
Brokaw
Mixture vapour viscosities are computed using:
TEA Page 36 of 43
where the interaction parameters φij are calculated by Brokaw's method:

$\textstyle
=$
$\textstyle
=$
$\textstyle
=$
If the Lennard-Jones energy parameter, ε, and the Stockmayers polar parameter, δ, are known, S is
calculated from:
Otherwise, it is approximated by S = 1.
ε and δ can be estimated from:

$\textstyle
=$
$\textstyle
=$
where µ is the dipole moment in C*m and Vb the volume change of boiling in m3/kmol.
Pressure correction
Vapour viscosities are a function of pressure and a correction is normally applied. Mixture properties
are computed with the "normal" mixing rules:
$\textstyle
=$
$\textstyle
=$
$\textstyle
=$
$\textstyle
=$
$\textstyle
=$
$\textstyle
=$
TEA Page 37 of 43
where ρ is the vapour mixture molar density.
Pure compound vapor viscosity

The parameters for the temperature correlation for vapor viscosity of pure compounds are available
through TEA's PCD data files.
Kinetic Gas Theory
The pure compound vapor viscosity can be computed with the Chapman-Enskog kinetic theory (see
Hirschfelder et al. 1954 and A391-393):
$\textstyle
=$
$\textstyle
=$
$\textstyle
=$
where the collision integral constants are
Yoon and Thodos
The vapor pure compound viscosity may also be computed with the Yoon and Thodos method:
$\textstyle
=$
$\textstyle
=$
where the constants a through f are given by:

Hydrogen Helium Others
a=47.65 a=52.57 a=46.1
b=0.657 b=0.656 b=0.618
c=20.0 c=18.9 c=20.4
d=-0.858 d=-1.144 d=-0.449
TEA Page 38 of 43
e=19.0 e=17.9 e=19.4

f=-3.995 f=-5.182 f=-4.058
Per compound
Symbols
List of used symbols
Cubic EOS parameter
Cubic EOS parameters
Second virial coefficient, m3/mol
Number of compounds
Mass heat capacity, J/kg/K
Binary interaction coefficient (for EOS)
Molecular mass, kg/mol
Gas constant, 8.134 J/mol/K
Pressure, Pa
Vapour pressure, Pa
Vapour pressure, Pa
$P_i$
Parachor of compound i, m3 kg1/4 / s1/2
Poynting correction factor
UNIQUAC surface area parameter
Temperature, K
Reduced temperature, T / Tc
Normal boiling temperature, K
Molar volume, m3/mol
Molar volume at normal boiling point, m3/mol
Saturated molar volume, m3/mol
Weight fraction (of compound)
Liquid mole fraction (of compound)
Vapour mole fraction (of compound)
Compressibility factor
Racket parameter
Greek symbols
Attractive parameter in EOS
TEA Page 39 of 43
Acentric factor
EOS parameter
EOS parameter
Collision integral for viscosity
Activity coefficient
Stockmayer parameter
Molecular energy parameter, K
Thermal conductivity, W/m/K
Molar density, mol/m3
Viscosity, Pa s
Fugacity coefficient of compound i
Interaction parameter for viscosities
Pure fugacity coefficient at saturation
Surface tension, N/m
Surface tension at normal boiling point, N/m
Dipole moment, Debye
Superscripts
Liquid
Vapor, or gas
Vapor, or gas
Saturated liquid
Subscripts
At normal boiling point

Critical
Of compound i
Of compound j
Mixture
Reduced
Saturated liquid
Abbreviations
EOS Equation of State

RK Redlich-Kwong
SRK Soave Redlich-Kwong
PR Peng-Robinson
Equilibrium Calculations
TEA Page 40 of 43
Internal TEA equilibrium calculations

The only internal equilibrium calculation (or flash calculation) method supported is the VLE
equilibrium method. The VLE equilibrium method only calculates vapor-liquid equilibria.
The logFugacityCoefficient property must be present and configured if the VLE equilibrium model is
selected.
To calculate an equilibrium, the following CAPE-OPEN version 1.0 specifications are supported:
TP: pressure and temperature must be specified

TVF: temperature and vapor fraction must be specified
PVF: pressure and vapor fraction must be specified
PH: pressure and enthalpy must be specified
TH: temperature and enthalpy must be specified
HVF: enthalpy and vapor fraction must be specified
PS: pressure and entropy must be specified
TS: temperature and entropy must be specified
SVF: entropy and vapor fraction must be specified
PHF: pressure and enthalpyF must be specified
THF: temperature and enthalpyF must be specified
HFVF: enthalpyF and vapor fraction must be specified
PSF: pressure and entropyF must be specified
TSF: temperature and entropyF must be specified
SFVF: entropyF and vapor fraction must be specified
PU: pressure and internal energy must be specified
TU: temperature and internal energy must be specified
UVF: internal energy and vapor fraction must be specified
The reversed specifiers are also supported, e.g. PT, VFT, VFP, HP, HT, VFH, SP, ST, VFS, HFP,
HFT, VFHF, SFP, SFT, VFSF, UP, UT and VFU.
Note: no additional flash types are currently supported for enthalpyNF and entropyNF. However, the internal VL
equilibrium server will be able to calculate equilibria involving these properties when using version 1.1 thermo, when
using internal calculation routines for properties enthalpyNF and entropyNF
For CAPE-OPEN version 1.1, all combinations of specifications equivalent to the above are
supported. For the equilibrium type argument, only 'Unspecified' is currently supported.
Numeric details of the VLE equilibrium server

Primary calculations
Most of the equilibrium calculations are first attempted with the inside-out flash algorithms, based on:
Boston and Britt, "A radically different formulation and solution of the
single-stage flash problem", Computers and chemical engineering, vol 2 pp
109-122 (1978)
Parekh and Mathias, "Efficient flash calculations for chemical process
design - extension to the Boston-Britt Inside-Out flash algorithm to extreme
conditions and new flash types", Computers and chemical engineering, vol 22
pp 1371-1380 (1998)
If the primary calculation method fails, a backup calculation method will be attempted.
TEA Page 41 of 43
Backup calculation method
The backup method of calculation equilibria is based on a full Newton approach to solving all
equilibrium equations simultaneously. On the Options page of the property package configuration,
one can select either of the following initialization methods:
None: initialization uses the Wilson Ideal Solution model for K-values, but no iteration is
performed. The Wilson Ideal Solution model:
Wilson Ideal Solution Model: initialization uses the Wilson Ideal Solution model for K-values.
The equilibrium is first calculated using K-values with the Wilson model, and then with the
actually selected models.
Saturated Vapor Pressures: initialization uses the K-values based on:
When using the backup methods, the equilibrium is first calculated using these K-values, and
then with the actually selected models.
The backup equilibrium calculation is not used if the mixture contains solid-only compounds or
if mass-based vapor fraction is part of the flash constraints.
For the backup equilibrium calculation methods, during calculations with estimation of K-values,
simplified models for enthalpies and entropies calculations are used for phases that use a cubic
equation of state.
For enthalpy, the Ideal Enthalpy model is used. For entropy, the Ideal Entropy model is used. In both
cases, a default model is applied for the liquid heat capacity and heat of vaporization.
Cubic equations of state and pseudo properties
When using cubic equations of state, and when evaluating properties of a phase outside of its region
of existence, properties are returned that belong to the other phase. I.e. gas phase properties are
returned for the liquid phase in regions where liquid does not exist and vice versa. This may lead to
equilibrium calculation divergence or to invalid trivial solutions.
To prevent this from happening, cubic equations can return pseudo property values for these regions.
These pseudos properties (enabled by default) can be turned on or off from the property package
configuration window, on the Options page.
The pseudo property calculations for cubic equations of state are only applied during:
equilibrium calculations performed by an external equilibrium routine

equilibrium calculations performed by the internal equilibrium routine in case of multiple
compounds
External equilibrium calculations

TEA supports loading a CAPE-OPEN version 1.1 stand-alone ICapeThermoEquilibriumRoutine, or a
CAPE-OPEN version 1.1 property package (stand-alone or from a property package manager) as
equilibrium calculation server. To do so, click Import on the Equilibrium page of the property
package configuration window.
All phases exported by the equilibrium routine will be exported by TEA. Only one vapor phase is
TEA Page 42 of 43
allowed. Internal TEA phase identifiers will be mapped to those as exported by the external routine on
each call.
All TEA compounds must be known by the external routine. If the external routine does not export
compounds, all compounds are assumed to be known. If it does export compounds, compounds will
automatically be mapped between TEA internal names and those as exported by the external routine,
at each call.
If the object selected as external equilibrium calculation routine exports properties as well, these
property calculations can be selected by using calculation routine "Equilibrium server". This is
subsequently the default routine for all properties supported by the external routine.
Phase identifiers
When using internal or external equilibrium calculations, the exported identifiers can be modified.
Select a phase on the Equilibrium page, and click the Rename button. If the property package that you
are modifying will ever be used using the CAPE-OPEN version 1.0 standard, it is advised to name the
vapor phase "Vapor", the liquid phases "Liquid", "Liquid1", etc, and the solid phases "Solid",
"Solid1", etc. The only phase identifiers officially supported by the CAPE-OPEN version 1.0 standard
are "Vapor", "Liquid" and "Solid".
Solid-Only Compounds
Solid only compounds are compounds that can only occur in the solid phase. These compounds are
taken into account in the equilibrium calculations in a simplified manner, without the requirement to
calculate fugacities for these compounds.
As these solids cannot appear in the vapor or in the liquid phase, the reference state of these
compounds for enthalpy and entropy calculations in the solid phase, at reference temperature 298.15
K and reference pressure 101325 Pa. This choice of reference state makes that compounds for which
no vapor or liquid data is available can still be configured.
Please mind that for consistent property values, the heat of formation, the absolute entropy and the
Gibbs free energy of formation for these compounds in the PCD data files should therefore also be in
the solid phase, at reference temperature 298.15 K and reference pressure 101325 Pa.
Typically, for solid-only compounds, the following compound data needs to be available:
name
chemical formula (optional)
CAS registry number (optional)
molecular weight
solid phase heat capacity temperature correlation
solid phase density temperature correlation
heat of formation, absolute entropy (required when properties entropyF and enthalpyF are to be
used)
Currently, the only solids supported in TEA are solid-only compounds. The solid-only compounds
that come with TEA are available from solids.pcd.
Property package options
TEA Page 43 of 43
General options
The general options include the name and the description of the property package. They are found at
the General page (select General from the Configure menu).
The name of a property package template will appear as a set of choices when adding a property
package to a simulation. Depending on the simulation environment, the name and description of the
property package are shown in the configuration.
Numerical options
The numeric options include all the options that reflect on numeric methods that are applied by the
property calculations and equilibrium calculations. They are found at the Options page.
For all property derivatives that are determined by perturbation, the relative temperature, relative
pressure and composition perturbation magnitude are adjustable. All perturbation distances default to
0.001. If you have trouble with the precision of perturbed derivatives, try adjusting these values to be
smaller.
The default relative tolerance on iterative processes (cubic equations of state, equilibrium
calculations) is 10-6. This might be too strict if models are imported that use their own tolerance, and
use a lower value. Lowering the tolerance might cause invalid bubble and dew points.
The maximum number of iterations (default: 75) applies to equilibrium calculations mainly.
In a number of models as well in equilibrium calculations by internal methods, you can adjust below
which a compound is considered absent from the mixture. Make sure this value (10-15 by default) is
lower in magnitude than the tolerance value, or mass balances will likely fail.
For the values of estimation method for equilibrium calculations, see the description of the internal
VLE equilibrium server.
When using cubic equations of state, and when evaluating properties of a phase outside of its region
of existence, properties are returned that belong to the other phase. I.e. gas phase properties are
returned for the liquid phase in regions where liquid does not exist and vice versa. This may lead to
unwanted solutions. To prevent this from happening, pseudo property calculations can be enabled
(default). In this case, pseudo properties are returned for the cubic equation of state dependent
variables, as described in Mathias, Boston and Watanasiri, "Effective utilisation of
Equations of State for Thermodynamic Properties in Process Simulations", AIChEJ,
vol 30, no.2, pp 182-186 (1984)
The pseudo property calculations for cubic equations of state are only applied during:
equilibrium calculations performed by an external equilibrium routine

equilibrium calculations performed by the internal equilibrium routine in case of multiple
compounds
By default, trivial solutions are not allowed. This means that azeotrope calculations will likely fail.
When allowing trivial solutions, it is best to use the pseudo properties for cubic equations of state
(which does not apply to fugacity calculations imported from external property calculation routines).

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TEA Page 1 of 43

Property packages and property package

Property package templates

For details on the configuration of property package (templates), see:

Simple editing mode

EOS based model sets

Activity based model sets

Wilson: uses the Wilson model for liquid phase activity

from the Configure menu.

To rename a compound, click the name of the compound when it is selected.

Compound dependent property calculations

importing data from the web or estimating data.

Group contribution data

value, click on the parameter value itself. Expressions are accepted.

External property calculation routines

Ideal gas law

Ideal gas law

Virial equations of state

Hayden-O'Connell with Chemical theory

Cubic equations of state

and the mixing rules:

where kij is a binary interaction parameter; original RK:

Soave Redlich Kwong

and the mixing rules:

API SRK EOS

and specially for hydrogen:

Peng Robinson EOS

and the mixing rules:

The Flory-Huggins corrected version is also available:

It can only be used for binary mixtures.

It can only be used for binary mixtures.

or if interaction parameters g are specified in energy units, then

or if interaction parameters g are specified temperature invariant, then

If interaction parameters g are specified in temperature units (K), then

or if interaction parameters g are specified in energy units, then

or if interaction parameters g are specified in temperature invariant units, then

or if interaction parameters g are specified in energy units, then

or if interaction parameters g are specified in temperature invariant units, then

The reference temperature in TEA is Tref = 298.15 K

If interaction parameters g are specified in temperature units (K), then

or if interaction parameters g are specified in energy units, then

or if interaction parameters g are specified in temperature invariant units, then

UNIFAC-VL is fitted to vapor-liquid equilibria. UNIFAC-LL is fitted to liquid-liquid equilibria.

Bubble and dew points

Density, volume and compressibility factor

Volume is always calculated as one over density.

Liquid mixture density

Amagat's law (Ideal)

The density equals the inverse of the liquid molar volume.

Pure compound liquid density

The Rackett method for pure compound liquid density:

As for liquid mixture density, but with pure compound parameters.

As for liquid mixture density.

Pressure and temperature derivatives are determined by perturbation.

For EnthalpyF, the same models are available as for Enthalpy.

Pressure and temperature derivatives are determined by perturbation.

where for the vapor phase,

For the heat capacity Cp, the Temperature Correlation is used.

For the liquid phase,

From activity coefficient

From fugacity coefficient

The solid compound entropy is mixed ideally: