SimCentral Simulation Platform Thermodynamics Reference Guide

SimCentral™ Simulation Platform
Thermodynamics Reference Guide
Version 4.1
December 2019
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Acknowledgements
CSPARSE
To analyze and report proper variable specification, SimCent ral Simulation Platform makes use of
CSPARSE, a library of direct methods for sparse linear systems by Timothy Davis. CSPARSE is free
software and is distribut ed under the GNU Lesser General Public License
(http://www.gnu.org/licenses/lgpl.html) as published by the Free Software Foundation.
The source code for CSPARSE is available at
http://people.sc.fsu.edu/~jburkardt/c_src/csparse/csparse.html.
KLU
SimCent ral Simulation Platform us es KLU as its linear equation solver. KLU is an open-source solver
package with a focus on solving sparse linear systems of equations. Timothy A. Davis distributes KLU as
part of the SuiteSparse software (http://www.suitesparse.com) under the GNU Lesser General Public
License and a University of Florida copyright.
SimCentral™ Simulation Platform Thermodynamics Reference Guide
Contents
Acknowledgements .................................................................................................................. 3
Chapter 1 Thermodynamic Methods by Type ................................................................... 9
Thermodynamic Methods by Type System Calculation Methods ................................................ 9
Liquid Density Calculation Methods ............................................................................................ 9
Equations of State................................................................................................................... 10
Liquid Activity Methods ............................................................................................................ 10
Generaliz ed Methods .............................................................................................................. 10
Special Data Packages ........................................................................................................... 10
Electrolytes............................................................................................................................. 10
Trans port Properties ............................................................................................................... 11
Chapter 2 Thermodynamics Methods by Name ............................................................. 13

Thermodynamics Methods by Name AP I - American Petroleum Institute Liquid Density ............ 13
Equations ......................................................................................................................... 13
Applications ...................................................................................................................... 13
Referenc es ....................................................................................................................... 13
Bosen-E ngels Method ............................................................................................................. 13
Reaction Submodels ......................................................................................................... 14
Configuring the Fluid in SimCentral Simulation Platform ....................................................... 15
Limitations ........................................................................................................................ 15
Referenc es ....................................................................................................................... 15
COS TALD Method .................................................................................................................. 16
Standard Equations ........................................................................................................... 16
Mixture Equations ............................................................................................................. 16
Compressed Liquids .......................................................................................................... 17
Applications ...................................................................................................................... 17
Referenc es ....................................................................................................................... 17
General Two-Parameter Equation of State................................................................................ 17
General Virial Equation of State ............................................................................................... 18
GS - Grayson-Streed Method................................................................................................... 18
Equations ......................................................................................................................... 18
Limitations ........................................................................................................................ 20
Referenc es ....................................................................................................................... 20
HOCV - Hay den-O'Connell ...................................................................................................... 21
Equations ......................................................................................................................... 21
Calculation of the Second Virial Coefficient ......................................................................... 22
Chemical Theory of Vapor Nonideality for Strongly Int eracting Substances ........................... 22
Vapor Enthalpy Corrections ............................................................................................... 23
Applications ...................................................................................................................... 26
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SimCentral™ Simulation Platform Thermodynamics Reference Guide Contents
Limitations ........................................................................................................................ 26
Referenc es ....................................................................................................................... 26
IF97 - IAPWS Industrial Formulation 1997 ................................................................................ 26
Equations ......................................................................................................................... 26
Applications ...................................................................................................................... 27
Limitations ........................................................................................................................ 27
Referenc es ....................................................................................................................... 28
IGS - Improved Grayson-Streed Method................................................................................... 28
Limitations ........................................................................................................................ 28
Referenc es ....................................................................................................................... 28
Library Correlations ................................................................................................................. 28
Trans port Properties for Pure Components ......................................................................... 29
Trans port Properties for Petroc omponents .......................................................................... 29
Mixing Rules for Transport Properties of a Mixture ............................................................... 29
NRTL - Non-Random Two-Liquid Method ................................................................................. 30
Equations ......................................................................................................................... 30
Applications ...................................................................................................................... 31
Referenc es ....................................................................................................................... 31
PR - Peng-Robinson ............................................................................................................... 31
Equations ......................................................................................................................... 31
Applications ...................................................................................................................... 32
Limitations ........................................................................................................................ 33
Referenc es ....................................................................................................................... 33
PRM - Peng-Robinson Modified Panagiotopolous-Reid ............................................................. 33
Equations ......................................................................................................................... 33
Applications ...................................................................................................................... 35
Limitations ........................................................................................................................ 36
Referenc es ....................................................................................................................... 36
Rackett Method....................................................................................................................... 36
Equations ......................................................................................................................... 36
Mixtures............................................................................................................................ 37
Applications ...................................................................................................................... 37
Referenc es ....................................................................................................................... 37
Redlich-Kwong Method (RK).................................................................................................... 37
Equations ......................................................................................................................... 37
Applications ...................................................................................................................... 38
Referenc es ....................................................................................................................... 38
Regular Solution Theory Method .............................................................................................. 39
Equations ......................................................................................................................... 39
Limitations ........................................................................................................................ 39
Referenc es ....................................................................................................................... 39
SRK - Soave-Redlich-K wong ................................................................................................... 39
Equations for Pure-Component Systems ............................................................................ 40
Equations for Multi-Component Systems ............................................................................ 40
Applications ...................................................................................................................... 42
Referenc es ....................................................................................................................... 42
SRKM - Soave-Redlich-Kwong Modified Panagiotopoulos-Reid ................................................. 42
Equations ......................................................................................................................... 43
Applications ...................................................................................................................... 45
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Contents SimCentral™ Simulation Platform Thermodynamics Reference Guide
Limitations ........................................................................................................................ 45
Referenc es ....................................................................................................................... 45
UNIFA C - Universal Functional Activity Coefficient Method ........................................................ 45
Equations ......................................................................................................................... 46
Modified UNIFA C (Dortmund) ............................................................................................ 48
Limitations ........................................................................................................................ 49
Referenc es ....................................................................................................................... 49
UNIQUA C - UNIversal QUAsi-Chemical Met hod ....................................................................... 50
Equations ......................................................................................................................... 50
Applications ...................................................................................................................... 52
Referenc es ....................................................................................................................... 52
Wilson Method ........................................................................................................................ 52
Equations ......................................................................................................................... 52
Applications ...................................................................................................................... 53
Limitations ........................................................................................................................ 53
Referenc es ....................................................................................................................... 53
Chapter 3 Special Topics ................................................................................................... 55

Opening SimCentral TDM ........................................................................................................ 55
Referenc e State ...................................................................................................................... 55
Effective Viscosity of Multiphas e Flow ...................................................................................... 55
Henry's Law............................................................................................................................ 56
Enthalpy Calculations for Liquid Activity Methods ...................................................................... 59
System Enthalpy Calculation Route .................................................................................... 60
Custom Enthalpy Calculation Rout es .................................................................................. 61
Ideal Gas Calculation Route ......................................................................................... 62
Saturated Liquid Calculation Route ............................................................................... 64
Departure Function............................................................................................................ 66
VLLE ...................................................................................................................................... 67
Equilibrium Calculations..................................................................................................... 67
VLE with a Bulk Liquid Phase............................................................................................. 69
Energy Balance................................................................................................................. 70
VLWE .................................................................................................................................... 71
Thermodynamic Libraries ........................................................................................................ 72
Managing Thermodynamic Libraries ......................................................................................... 72
Equation Forms for Temperature-dependent Properties in SimCentral TDM ............................... 74
Correlation 1 (Polynomial).................................................................................................. 76
Correlation 2 (Chebychev) ................................................................................................. 76
Correlation 3 (Polynomial in Reduc ed Temperature Form) ................................................... 77
Correlation 4 (Polynomial in (1-Tr) Form) ............................................................................ 78
Correlation 5 ..................................................................................................................... 79
Correlation 6 (Surface Tension).......................................................................................... 80
Correlation 12 (Inverse Temperature Correlation) ................................................................ 80
Correlation 13 ................................................................................................................... 81
Correlation 14 ................................................................................................................... 82
Correlation 15 ................................................................................................................... 82
Correlation 16 (Rackett)..................................................................................................... 83
Correlation 17 ................................................................................................................... 85
Correlation 18 ................................................................................................................... 85
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Correlation 19 ................................................................................................................... 86
Correlation 20 ................................................................................................................... 87
Correlation 21 ................................................................................................................... 88
Correlation 22 (Chebychev) ............................................................................................... 89
Correlation 23 ................................................................................................................... 90
Correlation 24 ................................................................................................................... 90
Correlation 25 ................................................................................................................... 91
Correlation 26 ................................................................................................................... 92
Correlation 27 ................................................................................................................... 93
Correlation 28 (Extended Antoine)...................................................................................... 93
Correlation 29 ................................................................................................................... 94
Correlation 30 ................................................................................................................... 95
Correlation 31 ................................................................................................................... 95
Correlation 32 ................................................................................................................... 96
Correlation 33 ................................................................................................................... 97
Correlation 34 ................................................................................................................... 97
Correlation 35 ................................................................................................................... 98
Correlation 36 ................................................................................................................... 99
Correlation 37 ................................................................................................................... 99
Correlation 38 (Viscosity Correlation)................................................................................ 100
Correlation 40 ................................................................................................................. 101
Correlation 41 ................................................................................................................. 102
Correlation 42 ................................................................................................................. 102
Correlation 43 (Kistiakowsky – Watson Equation for Latent Heat) ....................................... 103
Correlation 44 (Watson)................................................................................................... 104
Correlation 45 ................................................................................................................. 104
Correlation 46 (Zabransky-Ruzica-Majer).......................................................................... 105
Correlation 47 (Wagner – First Form) ............................................................................... 106
Correlation 48 (Wagner – Second Form)........................................................................... 107
Correlation 49 ................................................................................................................. 107
Correlation 53 ................................................................................................................. 108
Correlation 54 ................................................................................................................. 109
Converting UOMs for Correlation 38 ................................................................................. 110
Creating a Custom Library from PPDX Data ........................................................................... 110
Specifying an Ambient Temperature for the PPDX Data .......................................................... 111
Adding Units of Measures to the PPDXImport Tool.................................................................. 112
Appendix A Glossary of Terms ........................................................................................ 113
8 Version 4.1
C HAPTER 1
Thermodynamic Methods by Type
System Calculation Methods
You can select a system calculation method only for Compositional fluids.
Equations of State
 PR - Peng-Robinson on page 31
 PRM - Peng-Robinson Modified Panagiotopolous-Reid on page 33
 SRK - Soave-Redlich-K wong on page 39
 SRK M - Soave-Redlich-K wong Modified Panagiotopoulos-Reid on page 42
Generalized Methods
 GS - Grayson-Streed Method on page 18
 IGS - Improved Grayson-Streed Method on page 28
Liquid Activity Methods
 NRTL - Non-Random Two-Liquid Method on page 30
 Regular Solution Theory Method on page 39
 UNIQUA C - UNIversal QUAsi-Chemical Met hod on page 50
 Wilson Method on page 52
Liquid Density Calculation Methods

You can select a liquid density calculation met hod only for Compositional fluids that contain a liquid
phase.
Equations of State
You can use an equation of state as your liquid density calculation method only if you also use that
equation of state as your system calculation method. To us e one of the equations of s tate as your liquid
density calculation method, in the System list, select the equation of state, and then in the Liquid
Density list, select Use system method.
Note: In general, equations of state are not good at predicting liquid density. You may want t o use a
more suitable method to calculate liquid density.
Generalized Methods
 COSTALD Method on page 16
 Library Correlations on page 28
 Rack ett Method on page 36
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SimCentral™ Simulation Platform Thermodynamics Reference Guide Thermodynamic Methods by Type
Special Data Packages

 API - American Petroleum Institute Liquid Density on page 13
Equations of State
The following equations of state are available in SimCentral Simulation Platform:
 HOCV - Hayden-O'Connell on page 21
 PRM - Peng-Robinson Modified Panagiotopolous-Reid on page 33
 Redlich-K wong Method (RK) on page 37
 SRK M - Soave-Redlich-K wong Modified Panagiotopoulos-Reid on page 42
Liquid Activity Methods

The following liquid activity methods are available in SimCent ral Simulation Platform:
 NRTL - Non-Random Two-Liquid Method on page 30
 Regular Solution Theory Method on page 39
 UNIFA C - Universal Functional Activity Coefficient Method on page 45
 UNIQUA C - UNIversal QUAsi-Chemical Met hod on page 50
 Wilson Method on page 52
Generalized Methods
The following generalized methods are available in SimCentral Simulation Plat form:
 COSTALD Method on page 16
 GS - Grayson-Streed Method on page 18
 IGS - Improved Grayson-Streed Method on page 28
 Rack ett Method on page 36
Special Data Packages

The following special data packages are available in SimCentral Simulation Plat form:
 API - American Petroleum Institute Liquid Density on page 13
 IF97 - IAPWS Industrial Formulation 1997 on page 26
Note: SimCentral Simulation Platform uses the IF97 method only for Steam fluids. You cannot use
the IF97 method for Composi tional fluids.
Electrolytes
You can use the following method to handle electrolytes:
 Bosen-E ngels Method on page 13
10 Version 4.1
Thermodynamic Methods by Type SimCentral™ Simulation Platform Thermodynamics Reference Guide
Transport Properties
SimCent ral Simulation Platform us es the following method to calculate transport properties:
Version 4.1 11
C HAPTER 2
Thermodynamics Methods by Name
API - American Petroleum Institute Liquid Density
The API Liquid Density correlation is used to predict liquid densities, published in 1978 [1]. An initial
density is calculated at 60°F using the weight average of the components. The reduced temperature and
pressure of the stream at 60°F and 14. 7 psia are computed by using K ay's rule; for example, the reduced
temperature and pressure are assumed t o be a linear function of the liquid mole fraction. A density fac tor,
C, is then read from Figure 6A2.21 in the API Technical Data Book. A second correction factor is then
determined corresponding to the reduc ed temperature and pressure at the actual fluid conditions.
Equations
The actual liquid density is calculated according to:
 Cact  (1)
 act
L
  60L  
 C 60 
where:
 Lact= actual liquid density
 L60= liquid density at 60°F
Cact = actual correction factor
C60 = correction factor at 60°F
Applications
The API method works well for most hydrocarbon systems, provided that the reduced temperature is less
than 1.0.
References
1. American Petroleum Institute, 1978, Technical Data Book - Petroleum Refining, 5th Ed., 6-45 - 6-46.
Bosen-Engels Method
The Bosen-Engels method relies on a specialized configuration for Fluids within SimCentral Simulation
Platform. It uses the same thermodynamic calculations as the NRTL method but uses an additional
reaction submodel to include reaction equilibrium as part of the phase and composition calculations.
To use the Bosen-Engels method, you need a thermodynamic library that contains the property data for
the ionic and pure component species in your equilibrium reactions. The default SimSci library should
contain the required dat a for the pure component species, but you may need to create a custom library
with custom data banks that include binary interaction data and component properties for all ionic
species. See Managing Thermodynamic Libraries on page 72 and Creating a Custom Library from
PPDX Data on page 110 for more information.
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SimCentral™ Simulation Platform Thermodynamics Reference Guide Thermodynamics Methods by Name
To use the Bosen-Engels method, you also need a reaction submodel that defines the reaction kinetics
of your system. Typically, this includes equations for the rate constant and the reaction rates that you
develop from empirical data for the reaction system. See Reaction Submodels on page 14 for more
information.
Reaction Submodels
To properly use the Bosen-Engels methods you must create a reaction submodel that includes
equations for the rate constant and the reaction rates. The equations depend on the empirical reaction
data that you have gathered for your reaction system.
In most cases, you can use the following generic equilibrium reactions and equations to define your
reaction system. If your reaction contains more products or reactant s than the generic equilibrium
reaction, you must add more equations for eac h species so that your reaction submodel accurately
defines your reaction kinetics.
The following equations give a generic equilibrium reaction along with a generic equilibrium constant
equation.
aA  bB 
ka
 cC  dD
ln  ka T    A1 
B1
 C1 ln T   D1T  E1T 2
T
where
ka is the equilibrium constant
a , b , c, and d are the stoichiomet ric coefficients
A1 , B1, C1, D1 , and E1 are dimensionless coefficients
T is the temperat ure
We can calculate equilibrium constants for all the reactions in the system in this way. If your system
contains more than one equilibrium reaction, you should add equations and variables for all the
equilibrium constant equations to your reaction submodel.
For electrolyte reactions, we can simplify the products of the dissociation into a single complex consisting
of the ion and solvent molecules. For example, the reaction equation scheme for an H 2SO4 -H2O system
is as follows:
aH 2 SO4  bH 2O 
ka
 vC 
where
C± represents the combination of two different ions (H3O+ and SO4--*2H2O)
For simplicity, the model does not differentiate between positively and negatively charged complexes.
We can formulat e the equilibrium reaction with an equilibrium constant according t o the following
equation:
X Cv  Cv
ka T  
X a
H 2 SO4  Ha SO
2 4
 X b
 b
H 2O H 2O 
where
Xi is the liquid mole fraction of component i in the solution
i is the activity coefficient of component i
14 Version 4.1
Thermodynamics Methods by Name SimCentral™ Simulation Platform Thermodynamics Reference Guide
We can calculate ka according to the following equation, as before:
ln  ka T    A1 
B1
 C1 ln T   D1T  E1T 2
T
After you configure your reaction submodel with all the required rate constant equations and reaction
rate equations, you can then add it to a Fluid to use the reaction submodel in all model instances that use
the Fluid. You als o use the reaction submodel as a replac eable submodel in a reactor model, such as the
CNV R, EQR, CS TR, and PFR models in the Proc ess library, as well as in the Source from the
experimental Electrolytes library. The Source in the Electrolytes library propagates the reaction
submodel throughout the simulation. Please cont act SimSci Technical Support if you would like a copy of
the Electrolytes library.
Configuring the Fluid in SimCentral Simulation Platform

To successfully use the Bosen-Engels method, you must configure the Fluid in SimCentral Simulation
Platform so that it uses the correct thermodynamic method, calculations, and custom data banks.
To configure the Fluid:
1. In the Model Library, right-click the Fluid and then click Edit. The Fluid E ditor appears.
2. In the Methods area, in the System list, select Non-Random Two-Liquid (NRTL).
3. In the Binary Interaction Banks area, click Expand and then add the user data bank that contains
the binary interaction data for your electrolyte species to the list of data banks that the Fluid uses. We
recommend that you add your user dat a bank to the top of the list.
4. In the Enthalpy Route list, select Custom.
5. Select the Include Heat of Mixing (Excess Enthalpy in Liquid Enthalpy Calculations) check box
6. Select the Include Activity Coeffi cients in Fluid State check box.
7. In the Component Li st area, do the following for each component in the fluid:
a. In the Enthalpy Ba si s list, select Sat. Liquid.
b. In the Ref T column, verify that the reference temperature is 298.15 K (25°C).
c. In the Ref H column, enter the enthalpy of the liquid at 298.15 K (25°C). You may need to
calculate the value by subtracting the latent heat of vaporization from the ideal gas heat of
formation at 298. 15 K (25°C).
8. In the Model s area, in the Reaction box, type the name of the reaction submodel that you want to
use for the fluid.
9. In the Pure Component User Data Bank box, type the name of the user dat a bank that cont ains the
component property data for your electrolyte species.
Limitations
The Bosen-Engels method has the following limitation:
 Temperature: 0 to 240°C
 Concentration: 0 to 96 wt%
References
1. Bosen, A. and Engels, H., 1988, "Description of the phase equilibrium of sulfuric acid with the NRTL
equation and a solvation model in a wide concentration and temperat ure range", Fluid Phase
Equilibria, 43, 213-230.
Version 4.1 15
2. Nilges, J., 1991, "Vapor-liquid equilibrium of the system H2SO4-SO3", Fluid Phase Equilibria, 68,
247-261.
COSTALD Method
The Corresponding States Liquid Density model (COS TA LD) was developed to accurately predict the
liquid densities of liquid natural gas. It is a corresponding states model and is 98.8 % accurate in
predicting the densities of light hydrocarbon mixtures.
This model uses two characteristic paramet ers for each pure component in the mixture - a characteristic
volume, V , and a tuned acentric factor, SRK. The acentric factor is chosen such that the S RK (s ee "SRK
*
- Soave-Redlich-K wong" on page 39) equation of state best matches the vapor pressure dat a. Typically,
this tuned acent ric factor varies little in value from the standard acentric factor.
Standard Equations
The saturated volume is given by:
 Vr ,0 1  SRKV r , 
Vs
V*
4
Vr , 0  1   Ak (1  Tr ) k 3 , 0.25  Tr  0.95
k 1
3 k
 Bk Tr 
Vr ,   k 0  , 0.25  T  1.0
Tr  1.00001 r
where
Vs is the saturated molar volume
V* is the characteristic volume
Vr is the reduced volume
Ak and Bk are the COS TALD parameters
SRK is the SRK tuned acentric factor
Mixture Equations
For mixtures, the software uses the following mixing rules:
 
  xi x jVij*Tc ,ij 
 
 
i j
Tc ,m *
Vm
1  * 2 3  *1 3 
Vm*   xiVi  3  xiVi   xiVi 
*
4 i  i  i 

Vij*Tc,ij  Vi*Tc,iV j*Tc, j 
12
 SRK   xi SRK ,i

i
16 Version 4.1
where
subscript m refers to mixture properties
Compressed Liquids
For compressed pure liquids and liquid mixtures, the original work was extended by Thomson et al. in
1982, adding a pressure correction of the form:
  BP 
V  Vs 1  C ln   

  B  Psat  ,
where
B and C are constants dependent on composition
P is the pressure
Psat is the saturated vapor pressure obtained from a generalized pressure relationship
V is the molar volume
Applications
The COS TALD method is valid for aromatics and light hydrocarbons up to reduced tem peratures of 0.95.
*
The databanks contain the COS TALD characteristic volume V for many components. However, if the
characteristic volume for a pure component is not available, the soft ware uses the critical volume of the
pure component, Vc. If the characteristic volume for a petroleum or assay pseudocomponent is not
available, the software back-calculates a characteristic volume to provide a correct specific gravity for
the pseudocomponent.
References
1. Hankinson, R. W., and G. H. Thomson, 1979, A New Correlation for Saturated Densities of Liquids
and Their Mixtures, AIChE J., 25(4), 653.
2. Thomson, G. H., Brobst, K. R., and Hankinson, R. W., 1982, An Improved Correlation for Densities of
Compressed Liquids and Liquid Mixtures, AIChE J., 28(4), 671.
General Two-Parameter Equation of State

The generalized two-parameter cubic equation of state takes the form:
RT aT 
P  2

v  b  v  ubv  wb 2 
where:
P = pressure
R = the ideal gas constant
T = absolute temperat ure
v = molar volume
a = at the critical temperature a c, is the first derivative of pressure with volume set to zero
b = at the critical temperature b c, is the second derivative of pressure with volume set to zero
u , w = constants (typically integers)
Version 4.1 17
Different values for the constants u and w give different specialized equations of state, such as the van
der Waals equation, the P R - Peng-Robinson on page 31 equation, and the Redlich-K wong Method (RK)
on page 37 equation.
General Virial Equation of State

Virial equations of state are based on a selection of powers of the following expansion:
1 B C 
P  RT   2  3 
V V V 
where
P is the pressure
V is the molar volume
R is the universal gas constant
T is the temperat ure
B is the second virial coefficient
C is the third virial coefficient
The number of virial coefficients present in the equation depends on the type of virial equation of state
that you use. For example, the Hay den -O'Connel, BWRS, and Lee-K esler equations of state are all types
of virial equations of state and use different forms of the general virial equation of state in their
formulations.
Of the various types of virial equations of state, only the Hayden-O'Connell equation of state is currently
available in SimCentral Simulation Plat form. See HOCV - Hayden-O'Connell on page 21 for more
information.
GS - Grayson-Streed Method
2
The Grayson-Streed (GS ) method is based on the Chao-Seader method with special emphasis on
hydrogen. It represents an attempt by Grayson and Streed to extend the Chao-Seader approach to the
higher temperatures and pressures encountered in oil refining. Grayson and Streed also fit special
equations for the liquid fugacities of methane and hydrogen by using data available from hydrocracking
operations.
Equations
The Grayson-Streed method is based on a heterogeneous, asymmetric approach, in which the
distribution coefficient Ki is calculated as follows:
yi f i L* i iL* i
Ki    V
xi PiV i
where the three factors are calculated by using a different model:
 The pure liquid fugacity coefficient,  i L* , is calculated by using a specific corresponding states
method.
 The liquid activity coefficient, i , is calculated by using the regular solution model
 The vapor phase fugacity coefficient, i V , is computed from the Redlich-Kwong (RK ) cubic equation
of state.
18 Version 4.1
The Pure Liquid Fugacity Coefficient

The fugacity coefficient of pure liquid is calculated with a Curl and Pitzer corresponding state correlation,
that is, in terms of the reduced temperatu re, reduced pressure, and the acentric factor:
     
log iL*  log i( 0)   log i(1)
where  is the acentric factor. When the component at hand is hydrogen or methane, the acentric factor
is zero.
The first term on the right-hand side of the equation represents the fugacity coefficient of "simple
fluids". The second term is a correction accounting for departure of the properties of real fluids from those
of "simple fluids."
The quantity  i depends only on reduced temperature and reduced pressure. It was fitted with the
(0)
2
following function by Chao and Seader :
 
log i( 0)  A0 
A1
Tr
 A2Tr  A3Tr2  A4Tr3
 
 Pr A5  A6Tr  A7Tr2  Pr2  A8  A9Tr   log Pr 
where Tr and Pr are the reduced temperature and pressure of the component at hand.
1
Coefficients for this equation were det ermined by Grayson and Streed and they are present ed in
Table 1.
The quantity i similarly depends only on reduced temperature and reduc ed pressure and was fitted by
(1)
2
Chao and Seader :
 
log i(1)  4.23893  8.65808Tr 
1.22060
Tr
 3.15224Tr3  0.025Pr  0.6
Version 4.1 19
Activity coefficient from Regular Solution Theory

The liquid activity coefficient is calculated from the Hildebrand equation, assuming a "regular" liq uid
solution (no excess volume and no excess entropy).
 i  i   
2
ln  i  
RT
where
i is the molar volume of component i
 i is the solubility parameter of component i
 is the solubility parameter for the solution
The solubility parameter is calculated as follows:
 
 
x 
   i i    n i i i 
n n

i 1 i 1
  x j j 
 j 1 
The quantity  i is the volume fraction, that is, the ratio of t he molar volume of component i to the weighted
molar volume of the mixture.
Fugacity Coefficient in a Vapor Phase
The soft ware calculates the fugacity coefficients by using the same equations from the Redlich-K wong
equation of state. The Redlich-K wong equation of state is a specific case of the General Two-Parameter
Equation of State on page 17 in which u = 1 and w = 0 to get the following equation:
RT aT 
P  2

v  b  v  b 2 
Limitations
Grayson and Streed modified the Chao -Seader correlation in 1963 by fitting data over a wider range of
conditions and hence deriving different constants for the equations that give the fugacity coefficients of
the pure liquids. This method supplies special coefficients for hydrogen and met hane because typical
application temperat ures are far above the critical points of these two components. Grayson and
Streed's modifications have extended the application range for hydrocarbon systems up to 800°F and
3000 psia, but the lower limits imposed by Chao and Seader still apply:
 Pressure: Up to 3000 psia, but not exceeding 0.8 of the critical pressure of the system.
 Temperature: - 100°F to 800°F, and pseudo-reduced temperature, Tr , of the equilibrium liquid
mixture less than 0.93. The pseudo -reduced temperature is based on the molar average of the
critical temperat ures of the components.
 Concentration: Up to 20 mole percent of other dissolved gases in the liquid.
References
1. Grayson, H. G., and Streed, C. W., 1963, Vapor-Liquid Equilibria for High Temperature, High
Pressure Hydrocarbon-Hydrocarbon Systems, 6th World Congress, Frankfurt am Main, June 19 -26.
2. Chao, K. C., and Seader, J. D., 1961, A Generalized Correlation of Vapor-Liquid Equilibria in
Hydrocarbon Mixtures, AIChE J., 7(4), 598-605.
20 Version 4.1
3. Pitzer, K.S., Lippmann, D.J., Curl, R.F., Huggins, C. M, and Peterson, D.E., 1955, The Volumetric
and Thermodynamic Properties of Fluids, II. Compressibility Factor, Vapor pressure and entropy of
vaporization, J. Am. Chem. Soc., 77, 3433.
4. Pitzer, K.S., and Curl, R.F., 1957, The Volumetric and Thermodynamic Properties of Fluids, III. The
empirical Equation for the second Virial Coefficient, J. Am. Chem. Soc., 79, 2369.
5. Pitzer, K.S., and Hultgren G.O., 1958, The Volumetric and Thermodynamic Properties of Fluids, V.
Two Component Solutions, J. Am. Chem. Soc., 80, 4793-96.
HOCV - Hayden-O'Connell
The Hayden-O'Connell (HOCV) equation of state is a vapor-only equilibrium method similar to the Ideal
and Redlick-Kwong (RK) methods. It is designed to handle systems in which the components dimerize in
the vapor phase, such as carboxylic acids.
You cannot select this method as a System method for yo ur Fluid Ty pes. You can use it only in
conjunction with the LA CT methods. That is, when you select one of the LACT met hods in the System
list, you can select it in the Vapor Phase Equilibrium Method list.
Equations
The Hayden-O'Connell equation of state incorporates the chemical theory of dimerization. It is a virial
equation of state that accounts for the association and chemical bonding in the vapor phase in the
computation of the second virial coefficient. In this approach, we truncate the general virial equation of
state to the second virial coefficient term:
PV BP
Z  1
RT RT
where
B is the second virial coefficient that concerns interactions bet ween two molecules
B   yi y j Bij T 
i j
We can develop the relationship bet ween the fugacity coefficient and the vapor-phase P, V, and T
relations directly from the definitions of the fugacity and fugacity coefficient:
  f 
RT  ln  i    RT ln i 
  Pyi 
We can substitute the virial equation int o the preceding equation to produce an equation that requires
only an expression for the virial coefficients:
 n  P 
ln i    2  yi Bij   B   
 j 1   RT 
We use this equation when the vapor mixture does not contain one or more species of polar or dimerizing
compounds, such as carboxylic acids. At moderate densities (densities less than approximately one half
of the critical density), this equation provides a very good approximation.
Version 4.1 21
Calculation of the Second Virial Coefficient

The second virial coefficient is a correction to the ideal gas law to consider vapor-phase interactions. For
a simple system with only the classical electrostatic forces (that is, no polar or association contributions ),
the molecular interactions include bound, metastable bound, and free types, and we can include the
corresponding contributions to the virial coefficient. For the polar and association contributions, Hayden
1
and O'Connell developed correlations to account for the polar and associating components. They
correlated the polar (attractive) c ontribution t o the free contribution by empirically fitting data for polar and
non-associating compounds. They then correlated the association contribution to the bound contribution
as an equilibrium constant for the association reaction in terms of an association (or solvation for unlike
molecules) paramet er. They also developed suitable mixing rules for unlike pair interactions.
We can use the following necessary equations to calculate the virial coefficients for both polar and
nonpolar systems:
BijTotal  BijFree  BijDimerized
BijFree  BijFree, Nonpolar  BijFree,Polar
BijDimerized   BijD,Metastable  BijD ,Bound   BijD , Associative

1 2
Please see the references by Hayden and O'Connell and Prausnitz, et al. for details on the correlations
for each cont ribution.
Chemical Theory of Vapor Nonideality for Strongly Interacting

Substances
In systems that contain strongly interacting substances (such as those that contain carboxylic acids), the
two interacting molecules tend to form a pair of stable weak bonds (such as hydrogen bonds for acid
molecules in carboxylic acid systems). As a result, large negative deviations from vapor ideality occur
even at low pressures. To account for the dimerization, Hayden and O'Connell developed expressions
for the fugacity coefficients based on the thermody namics of chemical equilibrium.
The chemical theory postulates that there is a dimerization equilibrium of the following type:
i + j ⇌ ij
In this equilibrium reaction, i and j are tow monomer molecules (that may or may not be chemically
identical) that form a dimer ij . To describe this chemical equilibrium, we us e a chemical equilibrium
constant:
fij zijij
Kij  
fi f j zi z ji j P
where
f is the fugacity of the true molecular species (monomer or dimer)
z is the true mole fraction
" is the fugacity coefficient of the true molecular species
P is the total pressure
22 Version 4.1
The following equation gives the fugacity coefficient of component i:
zii
i 
yi
In this equation, zi and  i " refer to the monomer of species i while yi is the apparent mole fraction of
component i, where apparent means that we neglect dimerization. To use this equation, we must first
calculate the true fugacity coefficient,  i". We use the Lewis fugacity rule to calculate this value:
 
ln i 
BiF P
RT
where
Bi F is the free contribution to the second virial coefficient of component i
See Calc ulation of the Second Virial Coefficient on page 22 for more information.
After we calculate the true fugacity coefficient, we must then calculate the true mole fraction, zi . We
simultaneously solve both the material balanc es ( z = 1) and the chemical equilibria for all possible
dimerization reactions to calculate the zi value.
We use the following relation to find the chemical equilibrium constant, Kij :
BijD  2   ij 
Kij  
RT
0 for i  j
 ij  
1 for i  j
where
Bij D is the dimerization contribution to the second virial coefficient
 ij is the Kronecker delta
See Calc ulation of the Second Virial Coefficient on page 22 for more information.
Vapor Enthalpy Corrections

For a real vapor mixture, we can calculate the deviation from the ideal enthalpy by adding a departure
term to the equation for ent halpy:
HV  H IG  dep H V
where
dep HV is the molar ent halpy correction (that is, the departure term) for the vapor at T and P relative to the
ideal vapor at the same T and composition that we can calculate from an equation of state
HV is the enthalpy of the real vapor
HIG is the enthalpy of the ideal gas
Version 4.1 23
For the Hayden-O'Connell equation of state, we us e the following equation to calculat e the departure
term:
P  V  
 dep H V   V  T    dP
0
  T  P , y 
where
V is the molar volume of the vapor phas e
The evaluation of this integral depends on whether the mixture is associating or non-associating.
Non-Associating Mixtures
For non-associating mixtures, we use the virial equation to evaluate the integral for the departure term.
The following equation gives the result:
m m  d  Bij   
 dep H V  P  yi y j  Bij  T 
 i 1 j 1  dT  
 
where
m is the number of components in the mixture
Bij is the second virial coefficient
Associating Mixtures
For associating vapor mixtures where strong dimerization occurs ( ij >4.5 or ii<4.5), we base the molar
enthalpy on the stoichiometric (apparent) mole of vapor. We use the following equation to calculate the
enthalpy of the real vapor:
HV  H IG  H assoc
where
Hassoc is the enthalpy correction per stoichiometric (apparent ) mole of the vapor at T and P relative to the
ideal vapor at the same T and composition
There are two enthalpy corrections for strongly associating vapors. The dominant term, H , is due to
D
the combined enthalpies of reaction of the stoichiometric species to form the true species. The second
correction, H , accounts for the physical interactions of thes e true species.
F
H assoc  H D  H F
We determine the enthalpy changes due to dimerization from the van't Hoff relation. For a dimerization
reaction between species i and j , we use the following equation:
H ijD


d ln  Kij  
R 1
d 
T 
where
HD ij is the enthalpy of the reaction per mole of dimer i-j that forms.
24 Version 4.1
We obtain the following equation for H ij by substituting the expression for Kij from Chemical Theory of
D
Vapor Nonideality for Strongly Interacting Substances on page 22 into the general equation for the real
vapor:
 T d  Bij  
D
H   RT 1  D
D

ij
 Bij dT 
 
The total enthalpy correction due to chemical reactions is the sum of all the enthalpies of dimerization for
each i-j pair multiplied by the mole fraction of dimer i-j . Since this gives the enthalpy correction of one
mole of the true species, we multiply this quantity by the ratio of the true number of moles to the
stoichiometric number of moles. The following equation gives the results:
n  m i  T d  Bij   
D
H    at  RT  zij 1  D 

D
 nt   i 1 j 1  Bij dT  
 
We determine the ratio of the true number of moles to the stoichiometric number of moles from the
material balances over the true and stoichiometric species:
 nt  1
 a 
 nt   1 m  i m 
1     zij   z ji  
 2 i 1  j 1 j i  
We calculate the enthalpy correction due to the physical interactions of the true species, H , from the
F
virial equation of state and the general equation for the real vapor. However, the virial coefficients for the
F
true species are given by only the total free contribution, B ij . Therefore, we write the equation of state for
the associated mixture as follows:
PV  BF P 
 nt  nt  mix 
RT  RT 
This equation is consist with previous assumptions, for which we use the following equation to calculate
BF mix:
m m i
F
Bmix   zi BiiF   zij BijF
i 1 i 1 j 1
We apply this equation to the equation of state for the associated mixture to gi ve the following equation:
 d  Bmix
F
 
H  P  Bmix  T
F F
 dT 

The fully expanded form of this equation is as follows:
n  m  F d  BiiF   m i  d  BijF   
H   at  P  zi  Bii  T    zij  Bij  T 
F F
 nt   i 1  dT  i 1 j 1  dT  
  
where
Version 4.1 25
 nt 
 a
 nt  is the molar correction term, which yields a molar enthalpy correction that i s based on one
stoichiometric mole
Applications
The Hayden-O'Connell equation of state reliably predicts the solvation of polar compounds and
dimerization in the vapor phase, as occurs with mixtures that contain carboxylic acids.
Limitations
This equation of state provides a good approximation for systems at moderate densities. You should use
this equation of state only for densities less than approximately one half of the critical density.
As a rough rule, this equation of state is valid for the following pressure range:
 n 
 yi Pc,i
 T   i 1 
P  n 
 2  
  yiTc ,i 
 i 1 
where
Pc,i is the critical pressure of component i
Tc,i is the critical temperature of component i
n is the total number of components in the system
References
1. J.G. Hayden and J.P. O’Connell, "A generalized method for predicting second virial coefficients",
Ind. Eng. Chem. Process Des. Dev., Vol. 14, No 3 (1975), pp.209-216.
2. J. Prausnitz, T. Anderson, E. Grens, C. Eckert, R. Hsieh, J. O’Connell, "Computer Calculations for
Multicomponent Vapor-Liquid and Liquid-Liquid Equilibria", Prentice Hall, 1980.
IF97 - IAPWS Industrial Formulation 1997

The IAPWS Industrial Formulation 1997 includes steam tables that calculate the properties of water and
steam. SimCentral Simulation Plat form uses the August 2007 revision documented by The International
1
Association for the Properties of Water and Steam (IAPWS) .
Equations
1
The model details of the IF97 calculations, described in the PDF from IAPWS , are very verbose and are
not represented here. However, these det ails are not necessary to use IF97 as they are encapsulated
within the steam Fluid State model in SimCentral Simulation Platform.
The IAPWS Industrial Steam Tables are suitable for calculating the following properties for steam and
water, given a temperature and a pressure:
Variable Description
V Specific Volume
26 Version 4.1
H Specific enthalpy
U Specific internal energy
S Specific entropy
 Dynamic viscosity
Ps Saturation pressure as a function of temperature
Ts Saturation temperat ure as a function of pressure
The steam Fluid State model uses the IAPWS internal energy and entropy datums, which state that, at
the triple point (273.16 K, 611.657 Pa), the (saturated) specific liquid internal energy and the specific
entropy are set equal to zero. This results in an enthalpy of saturated liquid at triple point of 0.611783
J/kg.
Applications
Typical applications include industrial systems, like process steam distribution systems and industrial
boilers.
Limitations
The IF97 method, as used in SimCentral Simulation Platform, is valid between temperatures of 0°C and
800°C for pressures bet ween 0.000611 and 100 MPa (t he section labeled "1" in the graph below). This
method is also valid between temperatures of 800°C and 2000°C for pressures between 0. 000611 and
50 MPa (the section labeled "2" in the graph below).
Note: The following graph is a simplified version of Fig. 1 in the IF97 document referenced earlier. It has
been simplified in order to demonstrate the two ranges of pressure and temperat ure appropriat e for this
method.
Version 4.1 27
SimCent ral Simulation Platform us es the implementation of IF97 officially approved by the International
Association for the Properties of Water and Steam (IAPWS). Refer to the tables in the Reference
document for det ailed information on accuracy and uncertainty at specified temperatures and pressures.
References
1. The International Association for the Properties of Water and Steam. "Revised Release on the
IAPWS Industrial Formulation 1997 for the Thermodynamic Properties of Water and Steam." The
International Association for the Properties of Water and Steam. August 2007.
http://www.iapws.org/relguide/ IF97-Rev.pdf
IGS - Improved Grayson-Streed Method

The Improved Grayson-Streed (IGS ) method is an extension of the Grayson-Streed method to support a
rigorous three-phase calculation for hydrocarbon systems with an aqueous phas e.
For hydrocarbon-water mixtures, the GS - Grayson-Streed Method on page 18 and Erbar-modified
1
Grayson-Streed methods accurately predict the phase behavior of the hy droc arbon -rich phase, but do
not do as well in predicting the water-rich phase. To improve the predictions for the water -rich phase, IGS
uses a separate set of solubility parameters in the wat er-rich phase and improved liquid fugacity curves
for N2, H2S, H2O, CO, CO2, and O2 compared to the original work.
In addition, it was found that the Grayson -Streed (GS) liquid fugacity coefficient for the simple fluid
decreases rapidly as Tr increases above 2.5, and can in fact become negative. Therefore, IGS replaces
the liquid fugacity coefficient for the simple fluid with that for hydrogen at reduced temperatures of 2.5
and greater.
Compared to the IGS implementation in S IM4ME Thermo, we have modified the IGS method to match
the GS logic. This improves performance and robustness while maintaining the IGS method's
advantages when predicting three-phase conditions.
Limitations
The limitations for the IGS met hod are similar to those for the GS method:
 Pressure: Up to 3000 psia, but not exceeding 0.8 of the critical pressure of the system.
 Temperature: - 100°F to 800°F, and pseudo-reduced temperature, Tr , of the equilibrium liquid
mixture less than 0.93. The pseudo -reduced temperature is based on the molar averag e of the
critical temperat ures of the components.
 Concentration: Up to 20 mole percent of other dissolved gases in the liquid.
References
1. Erbar, J. H., and Edmister, W. C., 1963, Vapor-Liquid Equilibria for High Temperat ure, High
Pressure Hydrocarbon-Hydrocarbon Systems, 6th World Congress, Frankfurt am Main, June 19 -26.
Library Correlations
The component libraries in SimCentral TDM include temperature -dependent correlations that calculate
many component properties. You can specify a separate temperature -dependent correlation for each
transport property of a pure component. Each correlation has a unique set of correlation coefficients.
If you want to use your own data for the correlation coefficients or if you want to change the correlation
that SimCentral TDM uses to calculate a property value of a pure component, you must create a custom
component library in SimCentral TDM. See Managing Thermodynamic Libraries on page 72 for more
information.
28 Version 4.1
Transport Properties for Pure Components

For pure components, SimCentral Simulation Plat form uses the transport property values that
SimCent ral TDM calculates. The calculated value depends on the selected temperature -dependent
correlation for the trans port property and on the specified correlation coefficients. The TempDep tab in
SimCent ral TDM displays this data. See Equation Forms for Temperature-dependent Properties in
SimCent ral TDM for more information.
Transport Properties for Petrocomponents

When you characterize a petrocomponent, SimCentral TDM estimates the coefficients for the
temperature-dependent correlation for each transport property. It then calculates the transport property
values from these correlations and coefficients. SimCentral Simulation Platform uses these calculated
property values.
Mixing Rules for Transport Properties of a Mixture

SimCent ral Simulation Platform currently calculates the bulk transport properties of a mixture ( m) by
applying the following mixing rules to the pure-component property values. Thes e mixing rules require an
available property value for each pure component and pet rocomponent in the mixture.
Liquid Thermal Conductivity
m2   wi i2
i
where
wi is the weight fraction of component i
Vapor Thermal Conductivity
 y   MW 
13
i i i
m  i
 y  MW 
13
i i
i
Liquid Viscosity
3
 
m    xi i1 3 
 i 
Vapor Viscosity
 y   MW 
12
i i i
m  i
 y  MW 
12
i i
i
Surface Tension
 m   xi i
i
Version 4.1 29
NRTL - Non-Random Two-Liquid Method

Renon and Prausnitz [1] developed the non-random two-liquid equation to make use of the local
composition concept, while avoiding the inability of the Wilson equation to predict liquid -liquid phase
separation. The resulting equation has been quite successful in correlating a wide variety of systems.
Equations
The expression for the activity coefficients is:
 G x xG ji ji j 
 k xk kjGkj 
ln      ij 
j j ij

G x G x 
i
ki k j kj k  Gkj xk 
k k  k 
where
bij cij
 ij  aij    d ij ln T   eij T  f ij T ln T 
T T2 (temperature unit is K)
G ji  exp   ji ji 
 ij   ij   ijT
These equations require three parameters,  ij ,  ji , and ij = ji, for each binary. We can make these
parameters temperature dependent, as described in the preceding equations. If you want to represent  ij
with only one constant, empirical data shows that you obtain better results over a range of temperatures
if you use only b ij and a ij = cij = 0. The  parameter does not vary greatly from binary to binary, and you
can fix it at 0.3 for vapor-liquid systems or 0.2 for liquid-liquid systems to obtain satisfactory results.
For VLE, we use modified Raoult 's law to determine the vapor and liquid compositions :
yiP,i P  xi i Pi sat

where
yi is the vapor composition of component i
P,i is the fugacity coefficient for component i at pressure P
xi is the liquid composition of component i
i is the activity coefficient for component i
Pi sat is the saturation pressure for component i
For LLE, we use the relative activity coefficients to determine the compositions for eac h liquid phase:
xi i  xi i

where
xi ' is the composition of component i in the first liquid phase
i ' is the activity coefficient for component i in the first liquid phase
xi" is the composition of component i in the second liquid phase
i " is the activity coefficient for component i in the second liquid phase
30 Version 4.1
Applications
The NRTL liquid activity method works well for strongly non-ideal mixtures and for partially immiscible
systems.
We recommend that you do not use petro components in a fluid when you use the NRTL method.
Currently, there are no paramet ers for binaries that include petro components, so we treat them as ideal.
References
1. Renon, H., & Prausnitz, J. M. (1968). Local compositions in thermodynamic excess functions for
liquid mixtures. AIChE J., 14(1), 135-144.
2. Harris, R. E. (1972). DIS TILLA TION PRA CTICES-DIS TILLA TION DESIGNS US ING FLOWTRAN.
Chem. Eng. Prog., 68(10), 56.
PR - Peng-Robinson
The Peng-Robinson equation of state (PR) is a modification of the Redlich -Kwong equation of state and
was published by Peng and Robinson in 1976 [1]. It is similar to the Soave -Redlich-Kwong equation in
0.5
many respects. As with the SRK equation, the a c/Tr term in the Redlich-Kwong equation was replaced
with a more general temperature dependent term, a(Tr ).
This equation provides accurate predictions for mixtures of hydrocarbons, but does not accurately
predict the behavior of mixtures of polar components or hydrocarbons with light gases such as hydrogen.
However, the simplicity of the equation, and its accuracy for calculating vapor-liquid equilibrium for
hydrocarbon mixtures, allowed it to gain widespread industry popularity.
In addition to fugacity coefficients and K -values, the PR equation can also predict the enthalpy, entropy
and density for the liquid and vapor phases.
Equations
The PR expression is as follows:
RT aT  (1)
P  2

V  b  V  ubV  wb 2 
Note: u = 2 and w = -1
b   xibi (2)
i
0.07780RTc,i (3)
bi 
Pc,i
aT    xi x j ai a j  1  kij  (4)

12
i j
where
Tc,i = critical temperature of component i
Pc,i = critical pressure of component i
kij = binary interaction constant for components i and j
Version 4.1 31
The combination formula for calculation of a(Tr ) with the introduction of the term k ij was intended to
improve prediction of the mixture properties.
The remaining equations depend on your Alpha Selection for your Fluid Type in SimCentral Simulation
Platform. You can find the Alpha Selection list on the Fluid Editor, in the Methods section. It appears
only when you select an equation of state in the System list.
If you select Acentric Factor Formulation in the Alpha Selection list, the remaining equations follow
the same formulation as the SRK equation of state:
ai  ac ,i i Tr ,i , i 
0.42747RTc ,i 
2
ac ,i 
Pc ,i
 i Tr ,i , i   1  M i 1  Tr1,i2 
2
M i  0.480  1.574 i  0.176 i2

T
Tr ,i 
Tc ,i
where
i = acentric factor for component i
If you select Alpha Databanks in the Alpha Selection list, the remaining equations follow the PR
formulation for a i , but the alpha correlation that the software uses is different for each component and
depends on the alpha data in the data banks that you add to the Alpha Data Banks box.
ai  ac ,i i Tr ,i , i 
0.45725RTc ,i 
2
ac ,i 
Pc ,i
where
 i (Tr,i ,i ) depends on the data specified in the selected ALP HA data banks
Warning: If you use a custom ALPHA data bank, you should also use a binary interaction data bank that
contains adjusted binary interaction parameters that correspond to the alpha data in your custom ALPHA
data bank.
For PR, the default Alpha Selection is Acentric Factor Formulation. We recommend that you use the
default selection.
Applications
All light hydrocarbon proc esses such as natural gas processing and light ends processing in refinery gas
plants. For hydrogen-rich systems the accuracy for the hydrogen solubility may be improved by using a
different alpha formulation or one of the more advanced mixing rules.
Using the Peng-Robinson formulation for prediction of mixture properties involves two steps. First, the
component ac entric factor, a(Tr ), is "tuned" for each component such that the component vapor pressure
is accurately predicted. Sec ondly, the term k ij is determined from ex perimental data for the binary system
with components i and j such that the phase equilibria is matched.
32 Version 4.1
This equation has been found to give accurate predictions for nonpolar mixtures of hydrocarbons.
In addition to K-values, the PR equation may be used to predict the enthalpies, entropies and densities
for the liquid and vapor phases.
Limitations
The predicted liquid phase densities are not very accurate. The API Liquid Density method is suggested
as an alternative when liquid densities are important and the system in question falls within the intent of
the API density method.
PR does not give accurate predictions for systems of polar and nonpolar components. Hydrogen phase
behavior is approximat ed by Peng-Robinson by modification of the acentric factor.
References
1. Peng, D.Y. and D.B. Robinson; Ind. End. Fundam., 15; 59 (1 976)
PRM - Peng-Robinson Modified Panagiotopolous-Reid

The PRM method is a modified version of the PR - Peng-Robinson on page 31 equation of state.
First, we use the Panagiotopoulos-Reid modification by using an asymmetric mixing rule that contains
two adjustable interaction paramet ers, kij and k ji . This significantly improves the accuracy of predictions
for mixtures of polar and nonpolar components. Second, we use a SimSci modification of the mixing rule
and introduce two more adjustable parameters, cij and cji. This improves the prediction for polar-nonpolar
systems where the non-ideality is large or strongly asymmetric.
The thermodynamic databanks in SimCentral TDM supply these parameters for many binary systems of
chemicals to this modified mixing rule.
We also use an improved α correlation developed by SimSci, which provides more accurate vapor
pressure predictions than the original PR formulation for a wide variety of components.
In addition to fugacity coefficients, you can use the PRM method t o predict the ent halpies, entropies, and
densities for the liquid and vapor phases.
Equations
The PRM method uses the same formulation as the PR equation of state:
RT a T 
P  2
V  b  V  2bV  b2 
Note: This equation is the general two -parameter cubic equation of state when u = 2 and w = -1.
b   xibi
i
0.07780RTc,i
bi 
Pc,i
a T    xi x j aij
i j
For the mixing rule, that is, the a(T) formulation, the PRM method uses two modifications, the
Panagiotopoulos-Reid modification and a SimSci modification.
Version 4.1 33
The Panagiotopoulos -Reid modification introduces two adjustable parameters, k ij and kji:
aij   ai a j  1  kij    kij  k ji  xi 

12
kij  k ji
When k ij = k ji , the Panagiotopoulos-Reid mixing rule reduces to that of the P R equation of state.
We have tested this mixing rule for several systems:
 Low-pressure, non-ideal systems
 High-pressure systems
 Three-phase systems
 Systems with supercritical fluids
The results in all reported cases agree well with experimental data.
The SimSci modification introduces an additional two adjustable parameters, cij and cji :
   
cij
aij   ai a j  1  k    k  k   x
 
12
i
 ij ij ji
  xi  x j   
   
  xj  
c ji
a ji   ai a j  1  k    k  k    
12
 ji ji ij
  xi  x j   
   
For binary systems, this mixing rule is identical to the the Panagiotopoulos -Reid mixing rule when c12 =
c21 = 1.
The four adjustable parameters for this final form of the mixing rule are k ij , kji , cij, and cji. For binary,
nonpolar systems where the deviations from ideality are not large or are only weakly asymmetric, only
the two Panagiotopoulos -Reid parameters (k ij and k ji ) are sufficient to fit the data (that is, c12 = c21 = 1).
For non-binary systems for this case, the SimSci mixing rule is identical to the mixing rule propos ed by
2
Harvey and Prausnitz in 1989. For binary, polar and binary, polar -nonpolar systems where the
non-ideality is large or strongly asymmetric, you may need to include the SimSci parameters (c12 and
c21 ). For binary, polar systems, c12 generally equals c21 . For binary, polar-nonpolar systems, which have
the greatest deviation from ideality, c12 does not equal c21 .
34 Version 4.1
ai  ac ,i i Tr ,i , i 
0.42747RTc ,i 
2
ac ,i 
Pc ,i
 i Tr ,i , i   1  M i 1  Tr1,i2 
2
M i  0.480  1.574 i  0.176 i2

T
Tr ,i 
Tc ,i
where
kij = binary interaction constant for component i in j
kji = binary interaction constant for component j in i
If you select Alpha Databanks in the Alpha Selection list, the remaining equations follow the PR
ai  ac ,i i Tr ,i , i 
0.45725RTc ,i 
2
ac ,i 
Pc ,i
where
data bank.
For PRM, the default Alpha Selection is Alpha Databanks. We recommend that you use the default
selection.
Applications
The PRM equation of state is suitable for specific systems of polar and nonpolar compounds for which
the Panagiotopoulos-Reid parameters (k ij and kji ) and the SimSci parameters (cij and cji ) are available in
the thermodynamic databanks in SimCentral TDM or can be determined by regressing experimental
data. Some examples of these types of systems include:
 Three-phase separators
 Water-hy drocarbon systems, such as those found in FCC gas plants and hy drocrackers
Version 4.1 35
 Lube oil and solvent de-waxing units

 Natural gas systems that contain polar compounds such as methanol
Limitations
Due to the asymmetric nature of the Panagiotopoulos -Reid mixing rule, you may get slightly different
results for a system that has more than one instance of the same pure component compared to an
identical system that has only one instance of that pure component. For example, if you add two ethanol
components, ethanol-1 and ethanol-2, to a compositional Fluid Ty pe and you split the total ethanol
compositional fraction between them, SimCentral TDM may not calculate the same property values as a
similar compositional Fluid Type that includes only a single ethanol component . The variations between
two such Fluid Types is very small, but we recommend that you use the PRM met hod only for
compositional Fluid Types that have a single instance of each pure component.
If your Fluid Type contains a large number of petro components (>150), you should use this method with
caution. This situation is similar to splitting a single component into a large number of similar components
and has the same limitations as Fluid Types that include more than one instanc e of a pure component.
We recommend that you do not use the PRM method for compositional Fluid Types that contain a large
number of petro components.
The predicted liquid-phase densities are not very accurate. We recommend t hat you do not use the PRM
method to predict liquid-phase densities.
References
1. A. Z. Panagiotopoulos and R. C. Reid, "New Mixing Rule for Cubic Equations of State for Highly
Polar, Asymmetric Systems", Equations of State - Theories and Applications, 1986, pp. 571-582.
2. Harvey, A. H., and Prausnitz, J. M., "Thermodynamics of High-P ressure Aqueous Systems
Cont aining Gases and Salts", AIChE J., 1989, 35, pp. 635-644.
Rackett Method
You can use the Rackett method to predict liquid densities. The software cal culat es the liquid density by
using equations that relate the critical temperature, critical pressure, and Rackett parameter for the
mixture.
Equations
The soft ware calculates the saturated liquid density by using the following equations:
 RT   i
Vs ,i   c ,i  Z Ra ,i
 Pc ,i 
 1  1  Tr ,i 2 7 for Tr ,i  0.75

i   6.93026  103
1 . 6  for Tr ,i  0.75
 Tr ,i  0.655
where
Vs,i is the saturated liquid volume
ZRa,i is the Rackett parameter for component i
Tc,i and Pc,i are the critical temperature and pressure for component i, respectively
Tr,i is the reduced temperature for component i
36 Version 4.1
Mixtures
For mixtures, there are two ways to use the Rackett equation. The most straight forward way, which the
software calls the RA CKE TT method, is to use the equation in Equations on page 36 for the molar
volume of each pure component and then mix the volumes together linearly. A second approach is the
One-Fluid Rackett method in which the soft ware uses mixing rules to determine the effective critical
parameters for the mixture and then uses the equation to det ermine the mixture density. For most
mixtures, the difference bet ween these two methods will not be significant.
Applications
The databanks contain Rackett parameters for many components. However, if Rackett parameters are
not available, the soft ware uses the critical compressibility factor, zc. When the Rackett parameter is
missing for a petroleum or assay component, the software back -calculat es the missing parameter to
ensure that the specific gravity of the pseudocomponent is correct.
References
1. Rackett, H. G., 1970, Equation of State for Saturated Liquids, J. Chem. Eng. Data, 15, 514.
2. Spencer, C. F., and Danner, R. P., 1972, Improved Equation for Prediction of Saturated Liquid
Density, J. Chem. Eng. Data, 17, 236-241.
3. Spencer, C. F., and Adler, S. B., 1978, A Critical Review of Equations for P redicting Saturated Liquid
Density, J. Chem. Eng. Data, 23, 82-89.
Redlich-Kwong Method (RK)

The Redlich-Kwong equation of state is a specific case of the general two-parameter cubic equation of
state, where the constant u equals 1 and the constant w equals 0.
Equations
The Redlich-Kwong equation of state uses the following formulation:
RT a T 
P 
V  b  V V  b 
Version 4.1 37
Note: This equation is the general two -parameter cubic equation of state when u = 1 and w = 0.
b   xibi
i
0.08664RTc,i
bi 
Pc,i
i j
aij   ai a j 
1  k 
12
ij
a  a  T 
i c ,i i r ,i
0.42747RT 
2
ac ,i  c ,i
Pc ,i
i Tr ,i   Tr1 2
T
Tr ,i 
Tc ,i
where
kij = kji = binary interaction constant for components i and j
Applications
In most cases, the SRK equation of state is more appropriate to us e and yields better res ults than the RK
equation of state. We suggest that you use the RK equation of state over the SRK equation of state only
for simple systems that are nearly ideal. In general, the RK equation of state is appropriate for systems in
which the following is true for all components in the system.
P T

Pc 2Tc
Currently, you can use the RK equation of state only as a supplementary thermodynamic method for
your Fluid Ty pes. Specifically, you can select the RK equation of state only to calculate vapor phase
properties for compositional Fluid Types that use the NRTL method.
References
1. Redlich, O., and Kwong, N. S., "On the Thermody namics of Solutions. v: An Equation of State.
Fugacities of Gaseous Solutions", Chem. Rev., 1949, 44 (1), pp. 233-244.
38 Version 4.1
Regular Solution Theory Method

Hildebrand defined a regular solution as one in which the excess entropy vanishes when the solution is
mixed at constant temperature and constant volume. This is nearly the case for most solutions of
nonpolar compounds, provided that the molecules do not differ greatly in size. The attractive
intermolecular forces then primarily determine the excess Gibbs energy. Scatchard and Hildebrand
made a simple assumption relating mixture interactions to those in pure fluids; the result is a simple
theory in which the activity coefficients are a function of pure-component properties only. The important
property is the solubility parameter, which is related to the energy required to vaporize a liquid
component to an ideal gas state.
This method requires the following pure component properties:
 Vapor pressure
 Liquid molar volume
 Solubility parameter
Equations
The activity coefficient expression is:
2
 n 
 
RT ln  i  Vi  i    j j 
L
 j 1 
x j Lj
j  n
x
k 1
k
L
k
where:
i L is the liquid molar volume of component i
 i is the solubility parameter of component i
There are no adjustable parameters in the regular solution model. It is useful for mixtures of nonpolar
components, but it should not be used for highly non -ideal mixtures, especially if they contain polar
components. Solubility paramet ers have been tabulated for numerous compounds, and these
parameters are included for most components in the library.
Limitations
This method is not valid for polar components and solutions that contain fluorocarbons.
References
1. Hildebrand, J.H., Prausnitz, J. M. and Scott, R. L., 1970, Regular and Related S olutions, Van
Nostrand Reinhold Co., New York.
SRK - Soave-Redlich-Kwong
The Soave-Redlich-Kwong (SRK ) equation of state, published by Georgio Soave in 1972 [1], is a
0.5
modification of the Redlich-Kwong equation of state. Soave replaced the term a c/Tr in the
Redlich-Kwong equation with a more general temperature -dependent term, a(Tr ). This modification
improves the prediction of the vapor pressure of pure components which, in turn, should improve
prediction of multi-component vapor-liquid equilibrium.
Version 4.1 39
This equation provides accurate predictions for mixtures of hydrocarbons, but does not accurately
predict the behavior of mixtures of polar components or hydrocarbons with light gases such as hydrogen.
However, the simplicity of the equation, and its accuracy for calculating vapor-liquid equilibrium for
hydrocarbon mixtures, allowed it to gain widespread industry popularity.
In addition to fugacity coefficients and K-values, the SRK equation can also predict the enthalpy, entropy
and density for the liquid and vapor phases.
Equations for Pure-Component Systems

Equations:
RT aTr 
P 
V  b V V  b 
(1)
a Tr    Tr ac (2)
The values of a c and b are obtained from pure-component critical properties according to:
0.42747RTc 
2
ac  (3)
Pc
0.08664 RTc
b (4)
Pc
The alpha function,  (Tr ), is given as a function of reduced temperat ure and the acentric factor, :
 Tr   1  M 1  Tr1 2 
2
(5)
M  0.480  1.574  0.176 2 (6)
The variables used above are:
Tc Critical temperat ure
Pc Critical pressure
Tr Reduced temperature, Tr = T/Tc
 Acentric factor
The constants in the expression for M (Eq. 6) were obt ained from the reduction of vapor pressure data
for a limited number of common hydrocarbons.
Equations for Multi-Component Systems

The multi-component version of the SRK equation of state is the same as Eq. (1):
40 Version 4.1
RT aTr 
P  (1)
V  b V V  b 
The parameters a and b , however, are obtained through mixing rules. With i and j denoting the
component indices, we then have:
b   xibi (7)
i
0.08664RTc,i
bi  (8)
Pc,i
a   xi x j ai a j  1  kij 
0.5
(9)
i j
The above equations introduce a few new variables:
xi Mole fraction of component i
kij Binary interaction parameter for components i and j
The combination formula for calculation of a(T) with the introduction of the interaction parameter k ij is
intended to improve predictions for the mixture properties.
The standard component libraries provide binary interaction paramet ers kij for many pairs of library
components. The software also contains correlations for values for systems with hydrocarbons and N 2,
O2, H2, H2S, CO2, mercaptans, and other sulfur compounds. Some k ij values are also provided for
hydrocarbon splits such as ethane-ethylene and propane-propylene. SRK approximates hydrogen
phase behavior by modifying the acentric factor.
The interaction parameter k ij is determined from experimental VLE data for the binary system with
components i and j such that the phase equilibria behavior is matched.
ai  ac ,i i Tr ,i , i 
0.42747RTc ,i 
2
ac ,i 
Pc ,i
 i Tr ,i , i   1  M i 1  Tr1,i2 
2
M i  0.480  1.574 i  0.176 i2

T
Tr ,i 
Tc ,i
Version 4.1 41
where
If you select Alpha Databanks in the Alpha Selection list, the remaining equations follow the SRK
ai  ac ,i i Tr ,i , i 
0.42747RTc ,i 
2
ac ,i 
Pc ,i
where
data bank.
For SRK, the default Alpha Selection is Acentric Factor Formulation. We recommend that you use
the default selection.
Applications
The SRK EOS is suitable for most hydrocarbon processes, especially light hydrocarbon processes such
as natural gas processing and light ends processing in refinery gas plants.
References
1. Soave, G. "Equilibrium Constants from a Modified Redlich -Kwong Equation of State." Chem. Eng.
Sci., 27, 1972, 1197-1203.
SRKM - Soave-Redlich-Kwong Modified

Panagiotopoulos-Reid
The SRKM met hod is a modified version of the SRK - Soave-Redlich-K wong on page 39 equation of
state.
First, we use the Panagiotopoulos-Reid modification by using an asymmetric mixing rule that contains
two adjustable interaction paramet ers, kij and k ji . This significantly improves the accuracy of predictions
for mixtures of polar and nonpolar components. Second, we use a SimSci modification of the mixing rule
and introduce two more adjustable parameters, cij and cji. This improves the prediction for polar-nonpolar
systems where the non-ideality is large or strongly asymmetric.
The thermodynamic databanks in SimCentral TDM supply these parameters for many binary systems of
chemicals to this modified mixing rule.
We also use an improved α correlation developed by SimSci, which provides more accurate vapor
pressure predictions than the original PR formulation for a wide variety of components.
42 Version 4.1
In addition to fugacity coefficients, you can use the SRKM method to predict t he enthalpies, entropies,
and densities for the liquid and vapor phases.
Equations
The SRKM met hod uses the same formulation as the SRK equation of state:
RT aTr 
P 
V  b V V  b 
Note: This equation is the general two -parameter cubic equation of state when u = 1 and w = 0.
b   xibi
i
0.08664RTc,i
bi 
Pc,i
i j
For the mixing rule, that is, the a(T) formulation, the SRKM method uses two modifications, the
Panagiotopoulos-Reid modification and a SimSci modification.
The Panagiotopoulos -Reid modification introduces two adjustable parameters, k ij and kji:
aij   ai a j  1  kij    kij  k ji  xi 

12
kij  k ji
When k ij = k ji , the Panagiotopoulos-Reid mixing rule reduces to that of the S RK equation of state.
We have tested this mixing rule for several systems:
 Low-pressure, non-ideal systems
 High-pressure systems
 Three-phase systems
 Systems with supercritical fluids
The results in all reported cases agree well with experimental data.
The SimSci modification introduces an additional two adjustable parameters, cij and cji :
   
cij
aij   ai a j  1  k    k  k   x
 
12
i
 ij ij ji
  xi  x j   
   
  xj  
c ji
a ji   ai a j  1  k    k  k    
12
 ji ji ij
  xi  x j   
   
For binary systems, this mixing rule is identical to the the Panagiotopoulos -Reid mixing rule when c12 =
c21 = 1.
Version 4.1 43
The four adjustable parameters for this final form of the mixing rule are k ij , kji , cij, and cji. For binary,
nonpolar systems where the deviations from ideality are not large or are only weakly asymmetric, only
the two Panagiotopoulos -Reid parameters (k ij and k ji ) are sufficient to fit the data (that is, c12 = c21 = 1).
For non-binary systems for this case, the SimSci mixing rule is identical to the mixing rule propos ed by
2
Harvey and Prausnitz in 1989. For binary, polar and binary, polar -nonpolar systems where the
non-ideality is large or strongly asymmetric, you may need to include the SimSci parameters ( c12 and
c21 ). For binary, polar systems, c12 generally equals c21 . For binary, polar-nonpolar systems, which have
the greatest deviation from ideality, c12 does not equal c21 .
ai  ac ,i i Tr ,i , i 
0.42747RTc ,i 
2
ac ,i 
Pc ,i
 i Tr ,i , i   1  M i 1  Tr1,i2 
2
M i  0.480  1.574 i  0.176 i2

T
Tr ,i 
Tc ,i
where
If you select Alpha Databanks in the Alpha Selection list, the remaining equations follow the SRK
ai  ac ,i i Tr ,i , i 
0.42747RTc ,i 
2
ac ,i 
Pc ,i
where
data bank.
44 Version 4.1
For SRKM, the default Alpha Selection is Alpha Databanks. We recommend that you use the default
selection.
Applications
The SRKM met hod is suitable for systems of polar compounds for which the Panagiotopoulos -Reid
parameters (k ij and kji ) and the SimSci paramet ers (cij and cji ) are available in the thermodynamic
databanks in SimCentral TDM or can be determined by regressing experiment al data. Some examples
of these types of systems include:
 Three-phase separators
 Water-hy drocarbon systems, such as those found in FCC gas plants and hy drocrackers
 Lube oil and solvent dewaxing units
 Natural gas systems that contain polar compounds such as methanol
Limitations
Due to the asymmetric nature of the Panagiotopoulos -Reid mixing rule, you may get slightly different
results for a system that has more than one instance of the same pure component compared to an
identical system that has only one instance of that pure component. For example, if you add two ethanol
components, ethanol-1 and ethanol -2, to a compositional Fluid Ty pe and you split the total ethanol
compositional fraction between them, SimCentral TDM may not calculate the same property values as a
similar compositional Fluid Type that includes only a single ethanol component. The variations between
two such Fluid Types is very small, but we recommend that you use the SRKM method only for
compositional Fluid Types that have a single instance of each pure component.
If your Fluid Type contains a large number of petro components (>150), you should use this method with
caution. This situation is similar to splitting a single component into a large number of similar components
and has the same limitations as Fluid Types that include more than one instanc e of a pure component.
We recommend that you do not use the SRKM method for c ompositional Fluid Types that cont ain a large
number of petro components.
The predicted liquid-phase densities are not very accurat e. We recommend that you do not use the
SRKM method to predict liquid-phase densities.
References
1. A. Z. Panagiotopoulos and R. C. Reid, "New Mixing Rule for Cubic Equations of State for Highly
Polar, Asymmetric Systems", Equations of State - Theories and Applications, 1986, pp. 571-582.
2. Harvey, A. H., and Prausnitz, J. M., "Thermodynamics of High-P ressure Aqueous Systems
Cont aining Gases and Salts", AIChE J., 1989, 35, pp. 635-644.
UNIFAC - Universal Functional Activity Coefficient Method

The Universal Functional Activity Coefficient (UNIFAC) method was developed in 1975 by Fredenslund,
1
Jones, and Prausnitz . This method estimates activity coefficients based on the group contribution
2
concept following the Analytical Solution of Groups (ASOG) model proposed by Derr and Deal in 1969.
Interactions bet ween two molecules are assumed to be a function of group-group interactions. Although
there are thousands of chemical compounds of interest in chemical processing, the number of functional
groups is much smaller. Group-group interaction data are obtained from reduction of experimental dat a
for binary component pairs.
Version 4.1 45
The UNIFA C-CI option adds more UNIFA C group-group interaction parameters to the existing collection.
These parameters predict vapor-liquid equilibria (VLE ). The UNIFAC-CI methodology is based on
3
atom-atom connectivity indices and int eractions , which we us e in turn to predict missing UNIFAC
group-group interaction parameters. This methodology uses only currently available experimental data.
For systems that have existing experimental data, the accuracy of the VLE predicted with the original
UNIFA C parameters is similar to that predicted with the UNIFA C-CI parameters. However, in this
implementation, the UNIFA C-CI option predicts only the missing UNIFA C parameters. This allows the
UNIFA C model to calculate the VLE for systems for which it could not calculat e before.
The UNIFAC method requires the vapor pressure, van der Waals area, and van der Waals volume for
each component to successfully complete its calculations.
If SimCentral Simulation Platform cannot find component property data in any of the custom or default
data banks for the Fluid Type, it uses the UNIFAC data to calculate property information for that
component.
Equations
The UNIFA C method is based on the UNIQUA C model, which represents the excess Gibbs energy (and
the logarithm of the activity coefficient) as a combination of two effects. We therefore use the activity
coefficient of the NRTL equation:
ln  i   ln  iC   ln  iR 
Combinational Term
We compute the combinational term, ln(i ), directly from the UNIQUA C equation by using the van der
C
Waals area and volume paramet er, which SimCent ral Simulation Platform calculates from the individual
structural groups:
  z   
ln  iC   ln  i   qi ln  i   li  i
NOC
xl
 i 
j j
 xi  2 xi j 1
xi ri
i  NOC
xr
j 1
j j
xi qi
i  NOC
xq
j 1
j j
z
li   ri  qi    ri  1
2
NOG
ri  
k 1
i
k Rk
NOG
qi   Q
k 1
i
k k
where
NOC is the number of components
NOG is the number of different groups in the mixture
46 Version 4.1
z is the lattice coordination number, which typically equals 10

ki is the number of functional groups of type k in molecule i
Rk is the volume parameter of functional group k
Qk is the area parameter of functional group k
xi is the mole fraction of component i in the liquid phase
Group Volume and Area Parameters
We obtain the group volume and area parameters from the atomic and molecular structure.
Vwk
Rk 
15.17
Awk
Qk 
2.5 109
where
Vwk is the van der Waals volume of group k
Awk is the van der Waals area of group k
Residual Term
The following equation gives us the residual term, ln(i ):
R
ln   iR      ln     ln    
NOG
i i
k k k
k 1
where
k is the residual activity coefficient of group k in the mixture
ki is the residual activity coefficient of group k in a reference solution that contains only molecules of
group type i. This quantity is required so that i → 1 as xi → 1.
R
Residual Activity Coefficient

The following equation gives us the residual activity coefficient. You use this equation to find both k and
ki .
 
  NOG
 NOG
 
ln   k   Qk 1  ln    m mk    NOGm km 
 m1  m1



n 1
 n nm 

Version 4.1 47
The following equations give parameter m and mk:

Q Xm
m  NOG
m
Q X
n 1
n n
NOC

j 1
i
m xj
Xm  NOC NOG
 
j 1 n 1
i
n xj
 amk 
 mk  exp   
 RT 
where
a mk is the binary interaction parameter for groups m and k
We assume that the binary energy interaction parameter a mk is constant and not a function of
temperature. We have incorporat ed a large number of interaction parameters bet ween structural groups
as well as parameters for group size and shape int o the soft ware.
Modified UNIFAC (Dortmund)

The UNIFAC method provides good order -of-magnitude estimates. We can improve the accuracy of the
method by incorporating a temperature-dependent form for the binary group energy interaction
parameter.
Researchers at Dortmund developed a three -parameter, temperature-dependent form for the binary
7,8,9,10
interaction paramet er . For this modified method, the following equations give the
temperature-dependent form of Amk:
 Amk 
 mk  exp   
 RT 
Amk  amk  bmk T  cmk T 2
48 Version 4.1
The following equation gives the combinational part of the logarithm of the activity coefficient:
w  wi zqi  ln i   
ln   iC   ln  i  1   1 i 
 xi  xi 2  i Qi 
ri3 4 xi
wi  NOC
r
j 1
34
j xj
xi ri
i  NOC
xr
j 1
j j
xi qi
i  NOC
xq
j 1
j j
where
z is the lattice coordination number, which typically equals 10
Limitations
You should use the UNIFA C method only if the following conditions are met:
 Pressures are less than 10 atm.
 Temperat ures are in the range of 32 - 300°F.
 All components are well below their critical points.
References
1. Fredenslund, Aa., Jones, R.L., and Prausnitz, J.M., 1975, Group Contribution Estimation of Activity
Coefficients in Nonideal Liquid Mixtures, AIChE J., 27, 1086-1099.
2. Derr, E.L., and Deal, C.H., 1969, Analytical Solutions of Groups: Correlation of Activity Coefficients
Through Structural Group Parameters, Inst. Chem. Eng. Symp. Ser., 32(3), 40.
3. Gonzalez, H.E., Abildskov, J., Gani, R., Rousseaux, P., and Le Bert, B., 2007, A Method for
Prediction of UNIFA C Group Interaction Parameters, AIChE J., 53(6), 1620-1632.
4. Skjold-Jørgensen, S., Kolbe, B., Gmehling, J., and Rasmussen, P., 1979, VaporLiquid Equilibria by
UNIFA C Group Contribution. Revision and Extension, Ind. Eng. Chem. Proc. Des. Dev., 18(4),
714-722.
5. Gmehling, J., Rasmussen, P., and Fredenslund, Aa., 1983, Vapor-Liquid Equilibria by UNIFA C
Group Contribution. Revision and E xtension, Ind. Eng. Chem. Proc. Des. Dev., 22(10), 676 -678.
6. Hans en, H.K., Rasmussen, P., Fredenslund, Aa., Schiller, M., and Gmehling, J., 1991, VaporLiquid
Equilibria by UNIFAC Group Contribution. 5. Revision and Extension, Ind. Eng. Chem. Res., 30(10),
2352-2355.
E
7. Weidlich, V., and Gmehling, J., 1987, A Modified UNIFA C Model. 1. Prediction of VLE, h , and
-infinity, Ind. Eng. Chem. Res., 26, 1372-1381.
8. Gmehling, J., Li, J., and Schiller, M., 1993, A Modified UNIFAC Model. 2. Present Parameter Matrix
and Results for Different Thermodynamic Properties, Ind. Eng. Chem Res., 32(1) 178.
Version 4.1 49
9. Gmehling, J., Lohmann, J., Jakob, A., Li, J., Joh, R., 1998, A Modified UNIFA C Model. 3. Revision
and E xtension, Ind. Eng. Chem Res., 37,4876.
10. DDBS T. The UNIFA C Consortium. http://www.ddbst.com/unifac -consortium.html (accessed May 1,
2018).
UNIQUAC - UNIversal QUAsi-Chemical Method

The universal quasi-chemical equation was developed by Abrams and Prausnitz based on
statistical-mechanical considerations and the lattice-based quasichemical model of Guggenheim. As in
the Wilson (see "Wilson Method" on page 52) and NRTL (see " NRTL - Non-Random Two-Liquid Method"
on page 30) equations, it uses local compositions. However, it uses the local surface area fractions as
the primary composition variable instead of volume fractions. It characterizes each molecule i by a
volume parameter, ri , and a surface area parameter, q i .
The excess Gibbs energy (and therefore the logarithm of the activity coefficient) is divided into a
combinat orial and a residual part. The combinatorial part depends only on the sizes and shapes of the
individual molecules; it contains no binary paramet ers . The residual part, which accounts for the
energetic interactions, has two adjustable binary parameters. Like the NRTL (see "NRTL - Non-Random
Two-Liquid Met hod" on page 30) equation, the UNIQUAC equation is quite successful in correlating a
wide variety of systems.
Equations
The expression for the activity coefficient is:
 
ln  i   ln  iC  ln  iR 
  z   
ln  iC   ln  i   qi ln  i   li  i
M
x l
 i 
j j
 xi  2 xi j 1
 
    j ij 
 
M M
ln  iR  qi 1  ln   j ji    M 
  j 1  j 1  k kj 
 k 1

The following equations show how the UNIQUA C method calculates the variables in the activity
coefficient expression:
lj 
z
rj  q j   rj  1
2
xi ri
i  M
x r
j 1
j j
xi qi
i  M
x q
j 1
j j
where
i is the segment or volume fraction of molecules i
i is the area fraction of molecules i
50 Version 4.1
ri is the molecular volume (called the van der Waals volume)

q i is the molecular surfac e area(called the van der Waals area)
z = 10, because the average coordination number, that is, the number of molecules around a central
molecule, is usually taken to be 10
6
The UNIQUAC met hod estimates ri and q i by using the group cont ribution values of Bondi , R and Q:
ri   vk( i ) Rk
k
qi   vk(i )Qk
k
where
k(i) is the number of functional groups of type k in molecule i
Rk is the volume parameter for each functional group k
Qk is the surface area parameter for each functional group k
In the UNIQUA C method, there are "dimensionless" values of Rk and Qk. These values are based on the
6
van der Waals volume and surface values of B ondi , but are normalized by using the volume and
external area of the CH2 unit in polyethylene:
Awk
Qk 
2.5 109
Vwk
Rk 
15.17
where
Awk is the van der Waals area of molecule k
Vwk is the van der Waals volume of molecule k
The SimSci component library includes calculated ri and q i values for each component.
The UNIQUAC met hod uses the following equations to calculate the remaining variables in the activity
coefficient expression:
  U ij 
 ij  exp 
 T  (where Uij has a temperature unit of measure, for example, K)
  U ij 
 ij  exp 
 RT  (where Uij has an energy unit of measure, for example, kcal/kmol or kJ/kmol)
U ij  a ij bij T
where
Uij is the interaction parameter between components i and j
The UNIQUAC met hod requires two adjustable parameters,  ij and  ji (or equivalently Uij and Uji ), for
each binary pair; you can make these parameters temperature-dependent, as described in the preceding
equations. If you do not use temperat ure dependence for Uij , you can typically obtain better results over
a range of temperatures by using a ij and setting b ij to 0.
Version 4.1 51
Applications
The UNIQUAC met hod applies to a wide variety of non -electrolyte liquid mixtures that contain nonpolar
or polar components, such as hyrocarbons, alcohols, nitriles, ketones, aldehydes, organic acids, and
water. This includes partially miscible systems there of.
Because the UNIQUAC method uses only two adjustable binary parameters, it cannot always represent
high-quality data with accuracy. However, for many typical mixtures, it provides a satisfactory
description.
When you use t his thermodynamic method, you should ensure that the following properties are available
for each pure component that you are working wit h:
 Vapor pressure
 Van der Waals area
 Van der Waals volume
References
1. Abrams, D. S. and Prausnitz, J. M., 1975, Statistical Thermodynamics of Mixt ures: A New
Expression for the Excess Gibbs Free Energy of Partly or Completely Miscible Systems , AIChE J.,
21, 116-128.
2. Anderson, T. F. and Prausnitz, J. M., 1978, Application of the UNIQUA C Equation to Calculation of
Multicomponent Phase Equilibria. 1. VaporLiquid Equilibria, Ind. Eng. Chem. Proc. Des. Dev., 17,
552-561.
3. Anderson, T. F. and Prausnitz, J. M., 1978, Application of the UNIQUA C Equation to Calculation of
Multicomponent Phase Equilibria. 2. LiquidLiquid Equilibria, Ind. Eng. Chem. Proc. Des. Dev., 17,
561-567.
4. Maurer, G. and Prausnitz, J. M., 1978, On the Derivation and Extension of the UNIQUAC Equation,
Fluid Phase Equilibria, 2, 91-99.
5. Sandler, S.I., Chemical, Biochemical, and Engineering Thermodynamics , 4th ed., Wiley, 2006.
6. Bondi, A.A., Physical Properties of Molecular Crystals, Liquid and Glasses , John Wiley and Sons
Inc., 1968.
7. Kontogeorgis, G.M. and Folas, G.K., Thermodynamic Models for Industrial Applications: From
Classical and Advanced Mixing Rules to Association Theories , Wiley, 2010.
Wilson Method
The Wilson equation was the first to incorporate the concept of local composition. The basic idea is that,
because of differenc es in intermolecular forces, the composition in the neighborhood of a specific
molecule in solution will differ from that of the bulk liquid. The two parameters per binary are, at least in
principle, associated with the degree to which each molecule can produce a change in the composition of
its local environment.
Equations
The expression for the activity coefficient is:
 N  N x A
ln  i   1  ln   x j Aij    N k ki
 j 1  k 1  x j Akj
j 1
where:
52 Version 4.1
viL   aij 
Aij  L
exp 
vj  T  (where a ij has a temperature unit of measure, for example, K)
viL   aij 
Aij  L
exp 
vj  RT  (where a ij has an energy unit of measure, for example, kcal/kmol or kJ/kmol)
Aij  aij
(when a ij is dimensionless)
i is the liquid molar volume of component i.
L
a ij represents a characteristic energy of interaction between species i and j .

The Wilson method requires a ij values as inputs to the equations. By default, it uses the Azeotropic
databank to calculate these inputs.
Applications
The Wilson equation is useful for polar or associating components in nonpolar solvents and for
completely miscible liquids.
When you use t his thermodynamic method, you should ensure that the following properties are available
for each pure component that you are working wit h:
 Vapor pressure
 Liquid molar volume
While there is no explicit temperature dependence in the Wilson equation's parameters, the derivation is
such that you c an use the Wilson equation with some confidence over a wide range of temperatures. It is
also successful in correlating mixtures that contain polar components.
Limitations
The Wilson equation cannot describe local maxima or minima in the activity coefficient. However, its
single significant shortcoming is that it cannot mathematically predict the splitting of a liquid into two
partially miscible phases. It is therefore completely unsuitable for problems involving liquid-liquid
equilibria.
For liquid-liquid equilibria, you should use the non-random t wo-liquid (NRTL) equation (see "NRTL -
Non-Random Two-Liquid Method" on page 30) instead.
References
1. Holmes, M. H. and van Winkle, M., 1970, Wilson Equation Used to Predict Vapor Compositions, Ind.
Eng. Chem., 62(1), 2231.
2. Orye, R. V. and Prausnitz, J. M., 1965, Multicomponent Equilibria with the Wilson Equation, Ind.
Eng.Chem., 57(5), 1826.
3. Wilson, G. M., 1964, VaporLiquid Equilibrium XI. A New E xpression for the Excess Free Energy of
Mixing, J. Amer. Chem. Soc., 86, 127.
Version 4.1 53
C HAPTER 3
Special Topics
Opening SimCentral TDM
SimCent ral TDM is thermodynamic soft ware that you can us e to view and manage the thermodynamic
data that SimCentral Simulation Platform uses for its thermodynamic calculations. You can open
SimCent ral TDM directly from the SimCentral Simulation Platform UI or independently from the Windows
Start menu. Changes that you make to your thermodynamic data in SimCentral TDM are i mmediately
available in SimCentral Simulation Plat form.
To open SimCentral TDM from SimCentral Simulation Platform:
 On the Advanced tab, in the Thermo Data group, click Launch the Thermo Data Manager (TDM).
The SimCentral TDM UI appears.

To open SimCentral TDM from the Windows Start menu:
 On the Start menu, under the list of all programs, under SimSci SimCentral, select SimSci
SimCentral TDM.
The SimCentral TDM UI appears.
Reference State
For multi-component methods developed by SimSci, the reference states are as follows:
 Enthalpy: Ideal Gas Heat of Formation at 25°C and 1 bar
 Entropy: Ideal Gas at 1 K and 1 bar
IF97 - IAPWS Industrial Formulation 1997 on page 26 us es its own referenc e state as described in its
documentation.
Effective Viscosity of Multiphase Flow

SimCent ral Simulation Platform calculates the effective viscosity of multiphase flow by using the
1
following volumetric average proposed by Govier and Aziz :
eff  V V   L1 L1   L 2 L 2
where
V , L1 , and L2 are the viscosities of the vapor, liquid 1, and liquid 2 phases, respectively
V , L1 , and L2 are the vapor, liquid 1, and liquid 2 phase fractions of the mixture, respectively
Reference
1. Govier, G.W. and Aziz, K. The Flow of Complex Mixtures in Pipes; Van Nostrand Reinhold
Company: New York, 1972.
Version 4.1 55
SimCentral™ Simulation Platform Thermodynamics Reference Guide Special Topics
Henry's Law
When we use liquid activity (LACT) methods, the standard -state fugacity for a component is the fugacity
of the component as a pure liquid. This basis is not very useful for dissolved gas es, especially when they
are above their critical temperature. Therefore, it is more convenient to use a standard state defined at
infinit e dilution. We can use Henry’s Law to accomplish this. The Henry’s Law approach is also useful for
representing trac e solutes such as organic pollutants in water.
In SimCentral Simulation Platform, you can us e Henry's Law in conjunction with the following LACT
methods:
 Non-Random Two-Liquid (NRTL)
 UNIversal QUAsi-Chemical (UNIQUA C)
 Wilson
When you c onfigure a compositional Fluid Ty pe that uses one of the preceding thermodynamic methods,
you can specify whether SimCentral Simulation Platform uses Henry's Law to calculate the fugacity for
super-critical gasses. If you chose to use Henry's Law, you must specify the components in the Fluid
Type that SimCentral Simulation Plat form should treat as solute components. SimCent ral Simulation
Platform automatically designates components with critical temperat ures less than 400 K as solute
components. Please see Configuring a Fluid Type in the SimSci SimCentral Simulation Platform
Simulation Building Guide for more information.
Thermodynamically, the Henry's constant of a light gas (solute) i in a solvent j is defined as the
infinit e-dilution limit of the ratio of fugacity to mole fraction:
fi
H ij  lim
x j 1 x
i
xi 0
Unless the pressure is high or there is vapor phase association, we can replace the fugacity with the
component partial pressure, yi P, where yi is the component vapor mole fraction and P is the system
pressure.
SimCent ral Simulation Platform correlates Henry's constants to the following functional form:
ln H ij   C1   C3 ln T   C4 P
C2
T
where
T is the temperat ure, in Kelvin
P is the pressure, in kPa
Hij is Henry’s constant, in kPa/mole fraction
C1 , C2 , C3 , and C4 are correlation coefficients that SimCentral Simulation Platform can read from the
Henry data banks
Units of Measure Considerations for Henry's Law
It is important that the correlation coefficients, C1, C2 , C3, and C4, that are stored in the Henry data banks
be consistent with the assumption that T is in Kelvin, P is in kPa, and Hij represents kPa/mole fraction.
However, these coefficients have been regressed by using different units of measure ( UOM). Typically,
we can convert the coefficients from their original UOM system to the Kelvin -kPa basis. To be more
specific, the Henry correlation is available in the following form:
ln H ij ,UOM   C1   C3 ln TUOM   C4 PUOM

C2
TUOM
56 Version 4.1
Special Topics SimCentral™ Simulation Platform Thermodynamics Reference Guide
Here TUOM and PUOM represent temperature and pressure expressed in units of measure that may be
different from Kelvin and kPa. Moreover, we assume that Hij,UOM has the same pressure units of
measure as PUOM . Further, suppose that we can convert TUOM and PUOM to Kelvin and kPa, respectively,
with the following formulas:
TKelvin   T TUOM
PkPa   P PUOM
where
 T and  P represent conversion factors
Then, we can rewrite the Henry correlation in the following form:
ln H ij ,kPa   C1, Bank 

C2, Bank
 C3, Bank ln TKelvin   C4, Bank PkPa
TKelvin
The coefficients C1,Bank, ..., C4,Bank represent the values that are stored in the Henry bank. We obtain them
from the original coefficients as follows:
C1, Bank  C1  ln  P   C3 ln  T 
C2, Bank   T C2
C3, Bank  C3
C4
C4, Bank 
P
The following tables give the conversion factors  T and  P for various units of meas ure:
UOM T
K 1
R 0.55555556
UOM P
kPa 1
psia 6.89476
atm 101.325
2
kg/cm 98.0665
bar 100
mbar 0.1
2
dyne/cm 0.0001
Version 4.1 57
UOM P
in Hg 3.38639
MPa 1000
2
N/m 0.001
Pa 0.001
psf 0.0478803
torr 0.13332237
in H2O 0.24884327
mm H2O 0.00979698
ft H2O 2.98611
Example
In this example, TUOM is given in Rankine and PUOM is given in psia. Therefore,  T = 0.55555556 and  P
= 6.89476, as summarized in the following table.
Variable UOM Conversion Factor
TUOM R 0.55555556
PUOM psia 6.89476
The following table shows the resulting Henry correlation coefficients:
Coefficient Original UOM Ci,Bank
C1 152.4 142.575028
C2 -8000.0 -4444.44444
C3 -20.0 -20
C4 1.00E-03 1.45038E -04
Reference
1. Prausnitz, J.M., Lichtenthaler, R.N., and Gomes de Azevedo, E., 1986, Molec ular Thermodynamics
of Fluid Phase Equilibria, 2nd ed., Prentice Hall, Englewood Cliffs, NJ, Chapter 8.
58 Version 4.1
Enthalpy Calculations for Liquid Activity Methods

The liquid activity (LA CT) methods in SimCentral Simulation Platform all use t he same calculation routes
and equations to calculate the liquid and vapor enthalpy for pure components. The equations of state use
a different method and the descriptions in the following topics do not apply to the equations of state.
In the Fluid Editor for the LACT methods, in the Methods area, in the Enthalpy Route list, you can select
which type of ent halpy route that you want to use for your Fluid, System or Custom.
Version 4.1 59
System Enthalpy Calculation Route

The following diagram summarizes the enthalpy calculations that SimCentral Simulation Platform
performs when you use the system calculation route.
For this calculation route, all the calculations are based on the enthalpy of the vapor at 25°C, which
equals the heat of formation in the gas state at this temperat ure. We use this value in all the equatio ns
that SimCent ral Simulation Platform us es to calculate the enthalpy of the vapor. SimCentral Simulation
Platform calculates the ent halpy of the liquid directly from the enthalpy of the vapor by using the latent
heat of vaporization.
The calculations require temperature-dependent correlations for the latent heat of vaporization ( H ),
vap
the ideal gas heat capacity (cp ), and the departure function (dep H). The SimSci data bank contains
IG
default correlations for these variables. You can also supply your o wn correlations by using SimCentral
TDM.
Liquid Enthalpy Calculations
We base all calculations on the ent halpy of the vapor phase and the latent heat of vaporization:
H L T   HV T   H vap T 
60 Version 4.1
Vapor Enthalpy Calculations

We base all calculations below Tmax on the correlation for the ideal gas heat capacity:
HV T , P, y     yi HiIG T    dep H V T , P, y 
HiIG T   Hiref Tref    c pIG,i T  dT

T
Tref
H iIG T   H iref  25C    c pIG,i T  dT

T
25 C
Hiref  25C  HiF  IG,25C

where
dep HV is the departure function that computes the difference bet ween the enthalpy of the real gas and
the enthalpy in the ideal gas state. If you are using the ideal gas law as the vapor phase equilibrium
method, t he departure function becomes zero. See Departure Function on page 66 for more information.
cp IG is the correlation for the ideal gas heat capacity as a function of temperature. The SimSci data bank
contains a default correlation for the ideal gas heat capacity. You can also supply your own correlation by
using SimCentral TDM.
Tmax is the maximum temperat ure for whic h the correlation for the ideal gas heat capacity is valid.
IG
If the range for the correlation for the ideal gas heat capacity, cp , does not extend to the required
temperature, SimCentral Simulation Platform linearly extrapolates the value at the required temperature:
HV T   HV Tmax   T  Tmax   c pIG Tmax 
Note: This portion of the calculations is not shown in the summary diagram.
Custom Enthalpy Calculation Routes

When you select Custom as the Enthalpy Route for a Fluid, you can choose which ent halpy calculation
route you want to use for each component in your Fluid. In the Enthalpy Ba si s column for each
component, you can select one of the following options:
 System: This option uses the same reference state and c alculations as the system calculation rout e.
See System Enthalpy Calculation Rout e on page 60 for more information.
 Ideal Gas: This option uses a user-specified referenc e state and the ideal gas calculation route.
 Sat. Liquid: This option uses a user-specified reference state and the saturated liquid calculation
route.
Version 4.1 61
Ideal Gas Calculation Route

performs when you use the ideal gas calculation route.
For this calculation route, you must define bot h the reference temperature in the Ref T column and the
reference enthalpy in the Ref H column for that component. The Ref H value is dependent on the Ref T
value and you may need to calculat e its value outside of SimCentral Simulation Plat form. Please see
Changes to the Enthalpy Basis and Reference State for Components in the SimSci SimCentral
Simulation Platform Simulation Buildin g Guide for more information on how to change the referenc e
temperature and ent halpy.
All the calculations are based on the enthalpy of the vapor at the reference temperat ure, that is, the Ref
H value. We use this value in all the equations that SimCentral Simulation Platform uses to calculate the
enthalpy of the vapor. SimCent ral Simulation Platform calculates the enthalpy of the liquid directly from
the enthalpy of the vapor by using the latent heat of vaporization.
The calculations require temperature -dependent correlations for the latent heat of vaporization ( H ),
vap
the ideal gas heat capacity (cp ), and the departure function (dep H). If you specify a phase-change
IG
temperature, the calculations also require a temperat ure -dependent correlation for the liquid heat
L
capacity (cp ). The SimSci data bank contains default correlations for these variables. You can also
supply your own correlations by using SimCentral TDM.
62 Version 4.1

We base all calculations on the ent halpy of the vapor phase and the latent heat of vaporization:
H L T   HV T   H vap T 

T
Tref
where
dep HV is the departure function that computes the difference bet ween the enthalpy of the real gas and
the enthalpy in the ideal gas state. If you are using the ideal gas law as the vapor phase equilibrium
method, t he departure function becomes zero. See Departure Function on page 66 for more information.
cp,i IG is the correlation for the ideal gas heat capacity of component i as a function of temperature. The
SimSci data bank contains default correlations for the ideal gas heat capacity. You can also supply your
own correlations by using SimCentral TDM.
Tref is the Ref T value.
Hi ref (Tref ) is the Ref H value.
If you specify a phase-c hange temperature (that is, you enter a value in the Phase Ch T column),
SimCent ral Simulation Platform performs the phase change at the specified temperature and uses the
value of the latent heat of vaporization at the phase-c hange temperature in the calculations. It also uses
the liquid heat capacity to determine the enthalpy change from the phase -change temperature to the
required temperature (T).
H L T   HV Tphc   H vap Tphc    c pL T  dT

T
Tphc
 
HV Tphc    yi H iIG Tphc    dep H V Tphc 
HiIG Tphc   Hiref Tref    c pIG,i T  dT

Tphc
Tref
where
cp L is the correlation for the liquid heat capacity as a function of temperat ure. The SimSci data bank
Tphc is the Phase Ch T value.
L
If the range for the correlation for the liquid heat capacity, cp , does not extend to the required
H L T   HV Tphc   H vap Tphc    c pL T  dT  T  Tmax   c pL Tmax 

Tmax
Tphc
where
Tmax is the maximum temperat ure for whic h the correlation for the liquid heat capacity is valid.
Version 4.1 63

We base all calculations below Tmax on the correlation for the ideal gas heat capacity:

T
Tref
Tmax is the maximum temperat ure for whic h the correlation for the ideal gas heat capacity is valid.
IG

Saturated Liquid Calculat ion Route

performs when you use the saturated liquid calculation route.
For this calculation route, you must define bot h the reference temperature in the Ref T column and the
reference enthalpy in the Ref H column for that component. The Ref H value is dependent on the Ref T
value and you may need to calculat e its value outside of SimCentral Simulation Plat form. Please see
Changes to the Enthalpy Basis and Reference State for Components in the SimSci SimCentral
Simulation Platform Simulation Building Guide for more information on how to change the referenc e
temperature and ent halpy.
64 Version 4.1
All the calculations are based on the enthalpy of the liquid at the reference temperature, that is, the Ref H
value. We use this value in all the equations that SimCentral Simulation Plat form uses to calculate the
enthalpy of the liquid. SimCentral Simulation Platform calculates the enthalpy of the vapor directly from
the enthalpy of the liquid by using the latent heat of vaporizat ion.
L
The calculations require temperature -dependent correlations for the saturated liquid heat capacity ( cp ),
the latent heat of vaporiz ation (H ), and the ideal gas heat capacity (cp ). The SimSci data bank
vap IG
contains default correlations for these variables. You can also supply your own correlations by using
SimCent ral TDM.
We base all calculations below the critical temperature, TC, on the temperature-dependent correlation for
L
the saturated liquid heat capacity, cp .
 
H L T     xi  H iref Tref    c pL,i T  dT  
T
  Tref 
where
cp,i L is the correlation for the liquid heat capacity of component i as a function of temperature. The SimSci
data bank contains default correlations for the liquid heat capacity. You can also supply your own
correlations by using SimCent ral TDM.
Tref is the Ref T value.
Hi ref (Tref ) is the Ref H value.
If the range of the correlation for the liquid heat capacity does not extend to the required temperature,
SimCent ral Simulation Platform extrapolates the liquid enthalpy according to the following equati on:
HL T   H L Tmax   T  Tmax   cpL Tmax 

where
Tmax is the maximum temperat ure for whic h the correlation for the liquid heat capacity is valid
We base all c alculations below the critical temperature, T C, on the liquid heat capacity correlation and the
latent heat correlation:
 
HV T     xi  H iref Tref    c pL,i T  dT    H vap T 
T
  Tref 
where
Hvap (T) is the latent heat of vaporization at the required temperature. The SimSci data bank contains a
default correlation for this variable. You can also supply your own correlation by using SimCentral TDM.
If the range of these correlations does not extend to the required temperature, SimCentral Simulation
Platform extrapolates the values for bot h cp (T) and H (T) when it calculates the vapor enthalpy.
L vap
The latent heat value must be zero at the critical temperature so that HV (TC) equals HL(TC). If the latent
heat correlation does not extend to TC, SimCentral Simulation Platform extrapolates the latent heat value
to zero at this temperature.
Version 4.1 65
If you specify a phase-c hange temperature (that is, you enter a value in the Phase Ch T column),
SimCent ral Simulation Platform performs the phase change at the specified temperature and uses th e
value of the latent heat of vaporization at the phase-c hange temperature in the calculations. It also uses
the ideal gas heat capacity to determine the enthalpy change from the phase -change temperature to the
required temperature (T).
 
HV T     xi  H iref Tref    c pL,i T  dT    H vap Tphc    c pIG T  dT
Tphc T
  Tref  Tphc
where
cp IG is the correlation for the ideal gas heat capacity as a function of temperature. The SimSci data bank
Tphc is the Phase Ch T value.
We base all calculations above TC on the correlation for the ideal gas heat capacity:
HV T   H L TC    c pIG T  dT
T
TC
IG

where
Tmax is the maximum temperat ure for whic h the correlation for the ideal gas heat cap acity is valid
Departure Function
The departure function computes the difference between the fluid in the real state of interest and the
hypothetical ideal gas state. Mathematically, this function is equivalent to the following equation:
P  H 
 dep H V T , P, z      dP
0
 P T , z
In practice, there are several direct ways to evaluate this integral depending on the specific form of the
equation of state that your Fluid Type uses for the enthalpy calculations. You can use the Vapor Phase
Equilibrium Method list in the Methods section on the Fluid Editor to change the equation of state for
your Fluid Ty pe.
If you select Ideal Gas Law in the Vapor Phase Equilibrium Method list, the departure function
becomes zero.
If you select one of the following equations of state in the Vapor Phase Equilibrium Method list,
SimCent ral Simulation Platform evaluates the int egral according to the selected equation of state:
 Hayden-O'Connell (HOCV): See HOCV - Hayden-O'Connell on page 21 for more information.
 Redlich-Kwong (RK): SeeRedlich-K wong Method (RK) on page 37 for more information.
 Soave-Redlich-Kwong (S RK): See SRK - Soave-Redlich-K wong on page 39 for more information.
 Peng-Robinson (PR): See PR - Peng-Robinson on page 31 for more information.
66 Version 4.1
 SRK-Modified Panag.-Reid (SRKM): See SRK M - Soave-Redlich-K wong Modified

Panagiotopoulos-Reid on page 42 for more information.
 PR-Modi fied Panag.-Reid (PRM): See PRM - Peng-Robinson Modified Panagiotopolous -Reid on
page 33 for more information.
VLLE
In the Fluid Editor, in the Methods area, you can select Vapor/Liquid1/Liquid2 (VLLE) for the Phase s
option for compositional fluids. The vapor -liquid-liquid equilibrium (VLLE ) includes a vapor phase and
two immiscible liquid phases. You can use VLLE with the prototype Separator model in the Process
library, which is only visible in the Model Writing role.
Limitations
 You cannot use VLLE in high pressure systems.
 Currently, we do not support VLLE in Fluid Flow or Dynamics mode.
 You can use VLLE in the Column model. However, it currently does not support multi -stage
contactors.
Equilibrium Calculations
The following equation is the complete equation for VLE by using a liquid activity model.
ˆi yi P   i xiisat Pi satPi

where
ˆi Is the fugacity coefficient of component i in the gas mixture at T and P

yi is the mole fraction of component i in the vapor at equilibrium
P is the pressure of the system
i is the activity coefficient of component i in the liquid mixture at T and P
i sat is the fugacity coefficient of pure i at T and Psat
Pi sat is the saturation pressure of pure i at T
P i is the Poynting correction factor for component i
The activity coefficient is related to the excess Gibbs energy of solution of the liquid:
1    nG  
E
GiE
ln   i     
RT RT  ni 
  T , P , n j i
where
GE is the excess Gibbs energy of the solution compared to an ideal solution
The activity coefficient is a function of T, P, and x.
The Poynting correction factor corrects for the difference bet ween the system pressure and the
saturation pressure of each component. We use the following equation to calculate its value.
 P VL 
Pi  exp   sat i dP 
 Pi RT 
Version 4.1 67
where
Vi L is the partial liquid molar volume of component i in the mixture

We can simplify this expression to the following equation.
  P  Pi sat Vi L 
Pi  exp  
 RT 
 
We can furt her simplify this expression to the following equation is we use the pure component molar
volume instead of the partial molar volume.
  P  Pi sat Vi L 
Pi  exp  
 RT 
 
If the pressure is low, then we can assume that  and P are 1, which leads to the following simplified
equilibrium expression.
yi P   i xi Pi sat
We use this simplified equilibrium expression when we calculate the equilibrium when there are two
liquid phases present:
I
The following equation is the equilibrium between phases V and L :
yi P   iI xiI Pi sat
II
Similarly, the following equation is the equilibrium bet ween phases V and L :
yi P   iII xiII Pi sat

We can write the following equilibrium K-values for each phase pair:
yi  iI Pi sat
KiI  
xiI P
yi  iII Pi sat
KiII  
xiII P
We divide the two K-values to form the following equation.
KiI xiII  iI
 K I II
 
xiI  iII
i
KiII
68 Version 4.1
Therefore, we can write the following three equilibrium equations between the three pairs of phases:
yi  K iI xiI
yi  K iII xiII
xiII  K iI II xiI
Only two out of these three equations are independent. We can choose any two of the equilibrium
equations for the equation set and any choice from the three available pairs should lead to the identical
solution.
In principle, the activity coefficients are a function of only the phase where the component is found. For
example:
 iI   i T , P, x I 
 iII   i T , P, x II 
We assure consistency between the three-phase equilibrium equations by using a single, unique ()
function for each liquid phas e.
VLE with a Bulk Liquid Phase

If the two liquid phases exist in the molar ratio :(1-), then we can calculate the bulk average liquid
composition according to the following equation:
xi   xiI  1    xiII
We can then define a "pseudo K-value" bet ween the vapor composition and this bulk composition:
yi  K i xi
If we substitute for the xi terms by using the general relationship xi = yi /Ki , we have the following
equation:
yi  y   yi 

   iI   1     II 
Ki  Ki   Ki 
This simplifies to the following equation, which relates the pseudo K -value to the true K-values:
1  1   1 

 I   1     II 
Ki  Ki   Ki 
We can furt her simplify this equation by replacing the K-values with their definitions:
1  P   P 
     1     II sat 
Ki   i Pi    i Pi 
I sat
or
1 P   1  
 sat  I  II 
 i i 

Ki Pi
Version 4.1 69
This pseudo K-value for the bulk liquid phase is useful when setting up the equations for the flash
solution, but it has the disadvantage that it depends on the phase fractions as well as the phase
properties.
Energy Balance
The following equation gives the enthalpy of a liquid phase:
H  H ideal  H E
or
H  H ideal  H mix
where
H mix  H E
This is the sum of two terms, the enthalpy of an ideal solution and the excess enthalpy of a non-ideal
solution, which is also known as the heat of mixing.
H ideal   xi Hi
The following equation relat es excess enthalpy to the excess Gibbs free energy.
G E  H E  TS E
or
H E  G E  TS E
The following equation gives the entropy:
 G 
S   
 T  P, z
We substitute this into the enthalpy equation to get the following equation:
 G E 
H E  GE T  
 T  P , z
The following equation is an algebraically equivalent expression of the preceding equation.
  GE 
 
2   T 
H  T
E
 T 
 
  P, z
We use either ex pression depending on which one is most convenient to compute.
The following equation relat es the activity coefficients to the excess Gibbs energy.
GiE  RT ln  i 
70 Version 4.1
E
Since Gi is a partial molar property, we can rewrite this equation as follows:
GE
  xi ln   i 
RT
Therefore, the heat of mixing is inseparable from the liquid activity model.
VLWE
In the Fluid Editor, in the Methods area, you can select Vapor/Liquid/Water (VLWE) (Beta Version) for
the Phase s option for compositional fluids. The vapor-liquid-water equilibrium (VLWE) includes a vapor
phase, a liquid phase, and a water decant phase.
For most hydrocarbon-water mixtures found in refinery and g as plant operations, the free water phase
that forms is nearly immiscible with the hy drocarbon liquid phase. For such systems, we can model the
three-phase calculation by decanting the free water as a pure aqueous phase. This greatly simplifies the
VLLE calculations.
For the VLWE calculations, we assume that the water vapor forms an ideal mixture with the hydrocarbon
vapor phase. We predict the quantity of water in the vapor phase by using an equilibrium calculation,
which uses the following expressions for the K-value of water.
yw Pwsat
K wI  
xwI PxwI
yw Pwsat
K wII  
xwII PxwII
where
KwI is the K-value of water bet ween the vapor phase and the hydrocarbon liquid phase
KwII is the K-value of water bet ween the vapor phase and the free water phase
yw is the water composition in the vapor phase
xwI is the water composition in the hydrocarbon liquid phase, which is a measure of the water solubility in
the hydrocarbon liquid
xwII is the water composition in the free water phase
Pwsat is the water saturation pressure at the current temperature
P is the current pressure
We use the Industrial Formulation 1997 (IF97) steam tables from the International Association for the
I II
Properties of Water and Steam (IAPWS) to calculate Kw and Kw .
II II
For Kw , we assume that the free water phase is pure water ( xw = 1.0). The K-value equation reduces to
the following equation:
Pwsat
K wII 
P
Version 4.1 71
This K-value formulation allows the free water phase to form or disappear based on the system
sat
conditions. When the calculated water saturati on pressure is less than the system pressure ( Pw < P),
the free water phase forms. When the calculat ed water saturation pressure is greater than the system
sat II
pressure (Pw > P), the K-value is great er than 1.0 (Kw > 1.0). In this case, we must reduce the water
II
composition in the free water phase to a value less than 1.0 ( xw < 1.0) so that the value of the water
II
composition in the vapor (yw) does not exceed 1.0. When we reduce the xw value, the free water phase
effectively disappears.
When the free water phase is present, you can use the Separat or model in the Process library to decant
the water stream and separate the hydrocarbon liquid phase from the free water phase.
Limitations
 You cannot use VLWE in high pressure systems.
 You cannot use VLWE in cryogenic systems. The temperature must be above the freezing point of
water at all times.
 In Dy namics mode, the vapor phas e may not condense into a liquid phas e as expected.
 You can use VLWE in the Column model. Howe ver, testing is still in progress and we currently do not
officially support VLWE in the Column model.
 Currently, you can use only the API 68 Kerosene method to calculate the water solubility in the
I
hydrocarbon liquid phase (xw ).
Thermodynamic Libraries
Thermodynamic libraries contain all the thermodynamic data and coefficients that SimCent ral Simulation
Platform needs to calculate thermodynamic properties.
There are two types of thermodynamic libraries:
 Default Libraries: Currently there is only one standard thermodynamic library.
 Custom Libraries: These are thermodynamic libraries based on the default library in which a user
has changed the thermodynamic data and coefficients to meet their proc ess needs.
The thermodynamic librari es exist as .lb1 files in the %userprofile %\My Thermo Data folder. To use a
custom library in SimCentral Simulation Platform, you must add it to this folder. You can creat e and
manage custom libraries by using the SimSci SimCentral Thermodynamic Data Manager (TDM) that
comes along with the SimCent ral Simulation Platform software.
Managing Thermodynamic Libraries

This section describes how to create and manage custom thermodynamic libraries. You cannot change
the default library that comes with SimCentral Simulation Platform, System.lb1. If you want to modify the
thermodynamic data or coefficients in the default library, you must create a custom library based on the
default library.
Acti vity Directions
Opening SimSci Thermodynamic On the Windows Start menu, in the list of programs, under the
Data Manager (TDM) SimSci SimCentral folder, click SimSci SimCentral TDM. The
Thermo Data Manager appears.
72 Version 4.1
Opening the Thermo Data Manager In TDM, on the Help menu, click User Guide.
User Guide
The documentation presented here is intended to be a quick
primer on the creation and management of custom libraries.
Please see the Thermo Data Manager Us er Guide for more
detailed information regarding the procedures presented here
as well as the more advanced features of TDM.
Creating a custom library In TDM, on the File menu, click New. The New library file
dialog box appears. In the File Name box, scroll to the end of
the file path and change the asterisk (*) to the name that you
want to use for your custom library.
We recommend that you create your custom libraries in the
%userprofile %\My Thermo Data folder. SimCentral
Simulation Plat form can use only libraries that appear in this
folder.
Adding a unary data banks to a In TDM, in the Library Type area, select Unary. In the Unary
custom library Type list, select the type of data that you want to work with. In
the Regi stered Libraries tree, right-click the custom library,
and then click Add New Databank. The Databank Name
dialog box appears. In the Name box, type the name that you
want to use for the data bank and then click OK.
Adding a known component to a In TDM, in the Regi stered Libraries tree, right-click the data
unary data bank bank and then click Add Known Component. The Add
Known Component dialog box appears. In the Databank list,
select the default dat a bank that contains the component that
you want to add. Click the browse button . The Select
Component dialog box appears. Use the filters to locate the
component and then click it in the list of components. The
component alias now appears in the Alias box. Click OK.
Also, if you already know the SimSci alias for the component,
you can type the alias directly into the Alias box instead of
browsing for the component.
Modifying unary thermodynamic data In TDM, in the Regi stered Libraries tree, select the data bank
for which you want to modify the t hermodynamic data. In the list
of components in the data bank, select the check boxes for the
components for which you want to modify data. Use the tabs to
the right of the list of components to locate and change the
thermodynamic data. Save the library.
Adding a binary data bank to a In TDM, in the Library Type area, select Binary. In the Binary
custom library list, select the type of data that you want to work with. In the
Method list, select the thermodynamic method that you want to
work with. In the Registered Libraries tree, right -click the
custom library, and then click Add New Databank. The
Databank Name dialog box appears. In the Name box, type
the name that you want to use for the data bank and then click
OK.
Version 4.1 73
Adding components to a binary dat a In TDM, in the Registered Libraries tree, select the data bank.
bank On the Quick Entry tab, in the Select Components area, click
the Component i browse button . The Select
component alias now appears in the Component i box. Click
the Component j browse button . The Select
component alias now appears in the Component j box. Click
Get Data. In the Edi t Data table, enter data for the component
pair and then click Save Data.
Also, if you already know the SimSci aliases or SimSci IDs for
the components, you can select Alias or SimSciID, and then
type the alias names or IDs directly into the Component i and
Component j boxes instead of browsing for the components.
Modifying binary thermodynamic data In TDM, in the Regi stered Libraries tree, select the data bank
for which you want to modify the t hermodynamic data. In the list
of components in the data bank, select the check boxes for the
components for which you want to modify data. On the Data
tab, in the Reference Component list, select the component
that you want to use as component i. In the data table, change
the data as needed. Save the library.
Using a custom library in SimCentral Ensure that your custom library appears in the
Simulation Plat form %userprofile %\My Thermo Data folder. In SimCentral
Simulation Plat form, open the Fluid Editor for a compositional
fluid. In any of the Data Bank areas, click Expand and add your
custom data banks to the list of selected data banks.
Equation Forms for Temperature-dependent Properties in

SimCentral TDM
When you create a custom library in SimCentral TDM, you may want to adjust the
temperature-dependent property data for the components in your unary data banks.
In SimCentral TDM, you can find these temperature-dependent properties on the TempDep tab when
you select the component that you want to modify. There are a number of different equation forms that
you can choose from when you input your dat a. You should choose the equation form that best fits the
temperature-dependent data that you have on hand for the component.
The following table lists all the temperature dependent properties and the available equation forms that
you can use for each property. The values in the Correlations column correspond to the value that you
select in the Correlation No. list on the TempDep tab.
Property Correlations
Solid Heat Capacity 1, 2, 18
74 Version 4.1
Property Correlations
Vapor Pressure 14, 20, 21, 22, 47, 48
Saturated Liquid Enthalpy 35, 45, 46, 49, 54
Saturated Liquid Density 1, 2, 3, 4, 16, 29, 31, 32
Saturated Liquid Thermal Conductivity 1, 2, 3, 4, 16, 34, 37
Saturated Liquid Surface Tension 1, 2, 6, 15, 30
Saturated Liquid Viscosity 12, 13, 19, 20, 21, 38
Ideal Vapor Enthalpy 1, 2, 17, 23, 24, 25, 40, 41, 42
Latent Heat of Vaporization 3, 4, 5, 15, 36, 43, 44, 53
Saturated Vapor Thermal Conductivity 1, 2, 19, 25, 33
Saturated Vapor Viscosity 19, 26, 27
The following table lists the options that you can select on the TempDep tab, in the Properties area, to
specify each property.
Property UI Selection
Solid Heat Capacity The correlations for this property apply to both the
solid enthalpy and the solid density. For the solid
enthalpy, in the Enthalpy area, select Solid. For
the solid density, in the Density area, select
Solid.
Vapor Pressure In the Liquid area, select Vapor Pressure.
Saturated Liquid Enthalpy In the Enthalpy area, select Liquid.
Saturated Liquid Density In the Density area, select Liquid.
Saturated Liquid Thermal Conductivity In the Therm. Cond. area, select Liquid.
Saturated Liquid Surface Tension In the Liquid area, select Surface Tension.
Saturated Liquid Viscosity In the Vi scosity area, select Liquid.
Ideal Vapor Enthalpy In the Enthalpy area, select Ideal.
Latent Heat of Vaporization In the Liquid area, select Latent Heat.
Saturated Vapor Thermal Conductivity In the Therm. Cond. area, select Vapor.
Version 4.1 75
Property UI Selection
Saturated Vapor Viscosity In the Vi scosity area, select Vapor.
Correlation 1 (Polynomial)
The following table lists the identific ation numbers of this correlation with respect to some well -known
sources of thermodynamic data.
Source Correlation Number
SimSci 01
PPDS -
DIPP R 801 100
NIS T TDE -
DECHEMA IK-CAPE PPDX POLY: Polynom
The equation has the following form:

n
Prop   CiT i 1
i 1
You must use at least 1 coefficient with this correlation.

You can use up to 10 coefficients with this correlation.
You can use any temperature UOM when you input data for this correlation.
Usage
We recommend that you us e this correlation to calculate only the following properties:
 Ideal Vapor Enthalpy
 Liquid Density
 Liquid Thermal Conductivity
 Solid Heat Capacity
 Surface Tension
 Vapor Thermal Conductivity
References
1. Thermodynamics-Package for CAPE-A pplications. DECHE MA e.V. [Online] March 28, 2002, pp
7-10. http://dechema.de/dec hema_media/IK_CAPE_Equations -p-888.pdf
http://dechema.de/dechema_media/IK_CAPE _Equations -p-888. pdf (accessed May 1, 2018).
Correlation 2 (Chebychev)
76 Version 4.1
SimSci 02
PPDS -
DIPP R 801 -
NIS T TDE -
DECHEMA IK-CAPE PPDX -

n
Prop   Ci E  X i 1
i 1
E  X 1  1.0
E  X 2  X
E  X i  2 XE  X i1  E  X i 2 , for i  3, ..., n
2T  Tmax  Tmin 
X
Tmax  Tmin
Usage
 Liquid Density
 Surface Tension
Correlation 3 (Polynomial in Reduced Temperature Form)

SimSci 03
Version 4.1 77
PPDS -
DIPP R 801 -
NIS T TDE -

n 1
Prop   CiTr
i 1 F
i 1
T
Tr 
Cn
where
F is a factor that you enter in the F box on the TempDep tab, in the Coefficients area, in addition to the
available coefficients
The default value of F is 1.0.
You must use at least 3 coefficients with this correlation.
You can use any temperature UOM when you input data for this corr elation. However, Thermo Data
Manager converts T and Cn to Kelvin (K) before it calculates the property value.
Usage
 Latent Heat of Vaporization
 Liquid Density
Correlation 4 (Polynomial in (1-Tr) Form)

SimSci 04
PPDS -
DIPP R 801 -
NIS T TDE -
78 Version 4.1

n 1
 i 1
Prop   Ci 1  Tr 
F
i 1
T
Tr 
Cn
where
F is a factor that you enter in the F box on the TempDep tab, in the Coefficients area, in addition to the
available coefficients
The default value of F is 1.0.
You can use any temperature UOM when you input data for this correlation. However, Thermo Data
Manager converts T and Cn to Kelvin (K) before it calculates the property value.
Usage
 Liquid Density
Correlation 5
SimSci 05
PPDS -
DIPP R 801 -
NIS T TDE -
C1T C2
Prop 
 C3  T 
You must use 3 coefficients with this correlation.
Version 4.1 79
Usage
We recommend that you us e this correlation to calculate only the following property:
Correlation 6 (Surface Tension)

SimSci 06
PPDS -
DIPP R 801 -
NIS T TDE 08

n
Prop   Ci i
i 1
T
  1
TC
where
TC is the critical temperature in Kelvin (K ).
All temperat ures must be in units of Kelvin (K ).
Usage
 Surface Tension
Correlation 12 (Inverse Temperature Correlation)

SimSci 12
PPDS -
80 Version 4.1
DIPP R 801 -
NIS T TDE -

n
Ci
ln  Prop    i 1
i 1 T

The input temperature must be in absolute units (K or R).
Usage
 Liquid Viscosity
Correlation 13
SimSci 13
PPDS 9
DIPP R 801 -
NIS T TDE 27
Prop  C5 exp  C1 X 1 3  C2 X 4 3 
 C T 
X  3 
 T  C4 
Usage
Version 4.1 81
Correlation 14
SimSci 14
PPDS -
DIPP R 801 -
NIS T TDE -
ln  Prop   C1 
X
Tr
C2  C3 X  C4 X 2  C5 X 5 
X  1  Tr 
T
Tr 
TC
Thermo Data Manager converts temperatures to Kelvin (K) before it calculates the property value.
Usage
 Vapor Pressure
Correlation 15
SimSci 15
PPDS -
DIPP R 801 106
NIS T TDE -
DECHEMA IK-CAPE PPDX DIP 4: DIPP R function for HVAP

and S T
82 Version 4.1
Prop  C1 1  Tr 
X
X  C2  C3Tr  C4Tr2  C5Tr3
T
Tr 
TC
Manager converts temperat ures to Kelvin (K) before it calculates the property value. The C1 coefficient
has the same UOM as the calculated property.
Usage
 Surface Tension
References
Correlation 16 (Rackett)
The following table lists the identific ation numbers of this correlation with respect to some well-known
SimSci 16
PPDS -
DIPP R 801 105
NIS T TDE 10
DECHEMA IK-CAPE PPDX RACK: Rackett equation
C1
Prop 
C2X
C4
 T 
X  1  1    C5
 C3 
Version 4.1 83

You can use the following UOMs:
 The C1 coefficient has units of molar density
 The C3 coefficient has units of absolute temperature (K or R).
 The temperatures should be in Kelvin (K).

The C2 and C3 coefficients cannot equal zero.
This correlation is the same as the IK-CAPE RACK equation when C5 equals zero.
The NIS T TDE 10 equation imposes the following restrictions on the coefficients:
 C1 =  C
 C3 = TC
 C4 = 2/7
 C5 = -1
1
The original Rackett equation uses the same restrictions as the NIS T TDE 10 equation, but imposes the
following additional restriction.
 C2 = ZC
2
The modified Rackett equation uses the following restrictions:
 C1 = PC/(RTC)
 C3 = TC
 C4 = 2/7
 C5 = 0
These restrictions use the following nomenclature.
 C is the critical density
R is the universal gas constant
TC is the critical temperature
PC is the critical pressure
ZC is the critical compressibility factor
Usage
 Liquid Density
References
1. Rackett, H. G., 1970, Equation of State for Saturated Liquids, J.Chem. Eng. Dat a 15(4), 514-517.
2. Spencer, C. F. and Danner, R. P., 1972, Improved Equation for Prediction of Saturated Liquid
Density, J.Chem. Eng. Dat a 17(2), 236-241.
84 Version 4.1
Correlation 17
SimSci 17
PPDS -
DIPP R 801 107
NIS T TDE 20
DECHEMA IK-CAPE PPDX ALYL: Aly-Lee equation
C  C 
Prop  C1  C2T  C3C4 coth  4   C5C6 tanh  6 
T  T 
You can use the following UOMs:
 The C4 and C6 coefficients have units of temperature.
 The C2 coefficient has units of energy/mass/temperature.
 The temperatures can be in any UOM.

This correlation is the integrated form of the DIPP R 107 and IK-CAPE ALYL equations.
Usage
References
1. Aly, F. A.; Lee, L. L. Fluid Phase Equil. 1981, 6, 169-179.
Correlation 18
The following table lists the identific ation numbers of this cor relation with respect to some well-known
SimSci 18
PPDS -
Version 4.1 85
1
DIPP R 801 102
NIS T TDE -
DECHEMA IK-CAPE PPDX DIP 5: DIPP R function for KVAP

and V ISV
1 This correlation is the integrated form of the DIPPR 102 equation w hen DIPPR uses the equation for solid heat capacity. This
correlation is not the full integrated version of the DIPPR 102, but DIPPR currently uses only the first two coeffic ients for solid heat
capacity. Therefore, the first three coefficients of this correlation account for the integration of the first two coefficients of the DIPPR
102 equation.
C2T C3
Prop  C1 
 C4 C5 
1  T  T 2 
 
If you want to use the IK -CAPE DIP5 equation, set the C1 coefficient to zero.
Usage
References
Correlation 19
SimSci 19
PPDS -
DIPP R 801 102
NIS T TDE 19
DECHEMA IK-CAPE PPDX DIP 5: DIPP R function for KVAP

and V ISV
SUTH: Sutherland equation
86 Version 4.1
C1T C2
Prop 
 C3 C4 
1  T  T 2 
 
If you want to use the IK -CAPE SUTH equation, set the C2 coefficient to 0.5 and the C4 coefficient to
zero.
Usage
 Vapor Viscosity
References
Correlation 20
SimSci 20
PPDS -
DIPP R 801 101, 115
NIS T TDE 1, 2, 3, 4, 18
DECHEMA IK-CAPE PPDX KIRC: Kirchhoff equation

KIR1: extended Kirchhoff equation

C2 C C
ln  Prop   C1   C3 ln T   C4T C5  C6T 3  C7T 6  82  94  C10T 2
T T T
Version 4.1 87
If you want to use the NIS T TDE 1 equation, set the C5 coefficient to 1 and the C6 and C8 coefficients to
zero.
If you want to use the NIS T TDE 3 equation, set the C4 , C6, C7, and C9 coefficients to zero.
If you want to use the NIS T TDE 4 equation or the DIPP R 801 115 equation, set the C5 coefficient to 1
and the C6 , C7, C9 , and C10 coefficients to zero.
If you want to use the IK -CAPE KIRC equation, set the C2 coefficient to the -a 1 coefficient in the KIRC
equation and the C4 , C6 , C7 , C8 ,C9 , and C10 coefficients to zero.
If you want to use the IK -CAPE KIR1 equation, set the C6 , C7, C8 ,C9, and C10 coefficients to zero.
Usage
 Vapor Pressure
References
Correlation 21
SimSci 21
PPDS -
DIPP R 801 -
NIS T TDE 6
DECHEMA IK-CAPE PPDX ANTO: Antoine equation

C2 Prop
ln  Prop   C1   C4T  C5T 2  C6 ln T   C7 2
C3  T T
If you want to use the IK -CAPE ANTO equation, set the C2 coefficient to the -a 1 coefficient in the A NTO
equation and the C4 , C5 , C6 , and C7 coefficients to zero.
Usage
88 Version 4.1
 Vapor Pressure
References
1. Yaws, C.L., J.W. Miller, P.N. Shah, G.R. Schorr and P.M. Patel. Correlation Constants for Chemical
Compounds, Chem. Eng. Sci., Vol. 83, No. 24, pp. 153 - 162, 1976.
Correlation 22 (Chebychev)
SimSci 22
PPDS -
DIPP R 801 -
NIS T TDE -

n
T ln  Prop    Ci E  X i
i 1
E  X 1  1.0
E  X 2  X
E  X i  2 XE  X i1  E  X i 2 , for i  3, ..., n
2T  Tmax  Tmin 
X
Tmax  Tmin
Usage
 Vapor Pressure
Version 4.1 89
Correlation 23
SimSci 23
PPDS 21G
DIPP R 801 -
NIS T TDE 21

  C  C2  C42 X 
Prop  R C1  C3T  3 

  C4  T  
 2  C5  C6  C7  C8  C9  C4  T  ln  C4  T 
X 
C4
C4  C5  3C6  6C7  5  2C8  3C9  
 1  2C5  3C6  4C7  5C8  6C9  
2  C4  T 
C42  C4  C7  5  C8  3C9    C6  4C7  10  C8  2C9   

   
 C4  T  
2
4  C4  T  3 


C44  C4C9  C  6C9  
 8
4  
 C4  T   6  C4  T  5 
You must use at least 4 coefficients with this correlation. The C4 coefficient cannot equal zero.
Manager converts temperat ures to Kelvin (K) before it calculates the property value.
Usage
Correlation 24
90 Version 4.1
SimSci 24
PPDS -
DIPP R 801 128
NIS T TDE -
C3C4 C5C6 C7C8

Prop  C1  C2T   
C  C  C 
exp  4   1 exp  6   1 exp  8   1
T  T  T 
You must use at least 2 coefficients with this correlation. The C4 , C6 , and C8 coefficients cannot equal
zero.
Usage
Correlation 25
SimSci 25
PPDS -
DIPP R 801 -
NIS T TDE -
DECHEMA IK-CAPE PPDX CPL: Equation for the specific heat

capacity of liquids
ICP L: Equation for the specific heat
capacity of liquids

5
C6 C7
Prop   CiT 
i 1
 
i 1 T T2
Version 4.1 91

If you want to use the IK -CAPE CP L equation, set the C5 and C6 coefficients to zero.
If you want to use the IK -CAPE ICPL equation, set the C7 coefficient to zero.
Usage
References
Correlation 26
SimSci 26
PPDS -
DIPP R 801 -
NIS T TDE -
2.669 106 C1T

Prop 
 1.1645 0.52847 2.16178 0.2C42 
C22  0.14874  0.7732 X  2.43787 X  
X e e X 
T
X
C3
Usage
 Vapor Viscosity
92 Version 4.1
Correlation 27
SimSci 27
PPDS 5
DIPP R 801 -
NIS T TDE 23

1 6
Prop  C1Tr 1  C2TrC3 1  Tr  
T
Tr 
TC
Usage
 Vapor Viscosity
Correlation 28 (Extended Antoine)

SimSci 28
PPDS -
DIPP R 801 -
NIS T TDE -
DECHEMA IK-CAPE PPDX ANT1: extended Ant oine equation
Version 4.1 93
C2
ln  Prop   C1   C4T  C5 ln T   C6T C7
 T  C3

Usage
We recommend that you us e this correlation to calculate only the followi ng properties:
 Vapor Pressure
References
1. Yaws, C.L., J.W. Miller, P.N. Shah, G.R. Schorr and P.M. Patel. Correlation Constants for Chemical
Compounds, Chem. Eng. Sci., Vol. 83, No. 24, pp. 153–162, 1976.
7–10. http://dechema.de/dec hema_media/IK_CAPE_Equations -p-888.pdf
Correlation 29
SimSci 29
PPDS 17
DIPP R 801 -
NIS T TDE 29

2
C  C2 
1 7
Prop  1
C3
T
  1
TC
You must use 3 coefficients with this correlation. The C3 coefficient cannot equal zero.
The temperatures must be in Kelvin (K).
94 Version 4.1
Usage
 Liquid Density
Correlation 30
SimSci 30
PPDS 14
DIPP R 801 -
NIS T TDE 28
Prop  C1 1  Tr  2 1  C3 1  Tr 

C
T
Tr 
TC
Usage
 Surface Tension
Correlation 31
SimSci 31
PPDS -
DIPP R 801 119
NIS T TDE -
Version 4.1 95

1 2 5 16 43 110
Prop  C1  C2 3  C3 3  C4 3  C5 3
 C6 3
 C7 3
T
  1
TC
Usage
 Liquid Density
Correlation 32
SimSci 32
PPDS 10
DIPP R 801 116
NIS T TDE 5, 24
Prop  C1  C2 1  Tr   C3 1  Tr   C4 1  Tr   C5 1  Tr 
0.35 23 43
T
Tr 
TC
Usage
96 Version 4.1
 Liquid Density
Correlation 33
SimSci 33
PPDS 3
DIPP R 801 -
NIS T TDE 22
Tr
Prop 
C1  C2 X  C3 X 2  C4 X 3
1
X 
Tr
T
Tr 
TC
Usage
Correlation 34
SimSci 34
PPDS 8
DIPP R 801 123
Version 4.1 97
NIS T TDE 25
Prop  C1 1  C2 X  C3 X 2  C4 X 3 
X  1  Tr 
13
T
Tr 
TC
Usage
Correlation 35
SimSci 35
PPDS -
DIPP R 801 -
NIS T TDE -
Prop  RTC C1   C2 ln  X   C3 X  C4 X 2  C5 X 3  C6 X 4  C7 X 5 
X  1  Tr 
T
Tr 
TC
98 Version 4.1

Usage
 Liquid Enthalpy
Correlation 36
SimSci 36
PPDS 12
DIPP R 801 -
NIS T TDE 26
Prop  RTC C1 X  C2 X 2  C3 X 3  C4 X 6  C5 X 18 
X  1  Tr 
13
T
Tr 
TC
Usage
Correlation 37
SimSci 37
Version 4.1 99
PPDS -
DIPP R 801 -
NIS T TDE 16

2
 T  7
ln  Prop   C1  C2 1  
 C3 
Usage
We recommend that you us e this correlation to calculate only the following propert y:
Correlation 38 (Viscosity Correlation)

SimSci 38
PPDS -
DIPP R 801 100
NIS T TDE -
ln  Prop  C1  C2 ln  L   C3 ln VP   C4T  C5T 2  C6 ln T 

where
 L is the saturated liquid density in kmol/m 3
VP is the saturation vapor pressure in kPa
This equation supports only Kelvin (K ) and Rankine (R) temperature units.
You cannot use this correlation to model the saturated liquid density or the saturation vapor pressure
because this res ults in infinite recursions.
100 Version 4.1

You may have data for the coefficients that you have derived by using different UOMs for  L and VP than
3
the UOMs needed for this correlation (kmol/m and kPa, res pectively). In t his case, you must modify your
coefficients to align with the necessary UOMs. See Converting UOMs for Correlation 38 on page 110 for
more information on how to do this.
Usage
Correlation 40
SimSci 40
PPDS -
DIPP R 801 -
NIS T TDE 17
   C4 
  
 C3e T  
Prop  R  C1  C2T   H T  
 C4 
 
   1   1  
 
 2C5  8C6  ln 1  y   y C5 1    C6  7   
   1 y   1  y  
H T    C8  C9   
  2 5 y3 3 y5 y6  y7  C7  
C6 3 y  3  y  5  3   7 C6   
4
 
2
   
 C8  C 9  
 T  C9
 for T  C9
y   T  C8
 0 for T  C9

Usage
Version 4.1 101

References
1. Frenk el, M.; Kabo, G.J.; Marsh, K.N.; Roganov, G.N.; Wilhoit, R.C.,Thermodynamics of Organic
Compounds in the Gas State, TRC: College Station, 1994, Vol. II, p. 537
Correlation 41
SimSci 41
PPDS -
DIPP R 801 -
NIS T TDE -
C2  n 1 i 3 
Prop  C1   C3 ln  X     Ci X   
X  i 4 if n5
1
X
 T 
1  
 Cn 
4  n  10
You must use at least 2 coefficients with this correlation. However, you should use at least 3 coefficients
to make this correlation temperature dependent.
Usage
Correlation 42
SimSci 42
102 Version 4.1

PPDS -
DIPP R 801 -
NIS T TDE -

6
Prop   CiT   C7 ln  C8  T 
i 1
i 1

Usage
Correlation 43 (Kistiakowsky – Watson Equation for Latent Heat)

SimSci 43
PPDS -
DIPP R 801 -
NIS T TDE -

C2
 T T 
Prop  C1  C 
 TC  Tb 
where
TC is the critical temperature
Tb is the boiling point temperature
Version 4.1 103

Usage
Correlation 44 (Watson)
SimSci 44
PPDS -
DIPP R 801 -
NIS T TDE 9

n
ln  Prop   C1   CiTr ln 1  Tr 
i 2
i2
T
Tr 
TC
Usage
Correlation 45
SimSci 45
PPDS -
DIPP R 801 -
104 Version 4.1

NIS T TDE 7
CT 
n i 2
Prop  C1  C2TC log TC  T    i
i 3 i2
Usage
 Liquid Enthalpy
Correlation 46 (Zabransky-Ruzica-Majer)
SimSci 46
PPDS -
DIPP R 801 114
NIS T TDE -
 2 3 2
4
5 2  
6
Prop  C1  TC  C2 ln    C3  C2C4  C2C5  C4
2
 C4C5  C5 
 3 12 10 30 
T
  1
TC
Usage
Version 4.1 105

 Liquid Enthalpy
Correlation 47 (Wagner – First Form)

SimSci 47
PPDS -
DIPP R 801 -
NIS T TDE -
DECHEMA IK-CAPE PPDX WAGN: Wagner equation
T 
ln  Prop    C   C1  C2 3 2  C3 3  C4 6 
T 
P
Prop 
PC
T
  1
TC
where
P is the temperature-dependent property that you want to calculate
Manager converts temperat ures to Kelvin (K) and the critical pressure, PC, to the UOMs that you select
for the temperat ure-dependent property before it calculates the property value.
Usage
 Vapor Pressure
References
1. Wagner, W.,"New vapour pressure measurements for argon and nitrogen and a new method for
establishing rational vapour pressure equations." Cryogenics 1973, 13, 470-482.
106 Version 4.1

Correlation 48 (Wagner – Second Form)

SimSci 48
PPDS -
DIPP R 801 -
NIS T TDE -
T 
ln  Prop    C   C1  C2 3 2  C3 5 2  C4 5 
T 
P
Prop 
PC
T
  1
TC
where
P is the temperature-dependent property that you want to calculate
You can use any temperature UOM when you input data for this correlation. However, Thermo Dat a
Manager converts temperat ures to Kelvin (K) and the critical pressure, PC, to the UOMs that you select
for the temperat ure-dependent property before it calculates the property value.
Usage
 Vapor Pressure
References
1. Wagner, W.,"New vapour pressure measurements for argon and nitrogen and a new method for
establishing rational vapour pressure equations." Cryogenics 1973, 13, 470-482.
Correlation 49
Version 4.1 107

SimSci 49
PPDS -
DIPP R 801 -
NIS T TDE -
 2 3 5 2  
6
Prop  C1  TC  C2 log    C3  C2C4  C2C5  C4C5  C6
2

 3 15 30 
T
  1
TC
Usage
 Liquid Enthalpy
Correlation 53
SimSci 53
PPDS -
DIPP R 801 -
NIS T TDE -
108 Version 4.1

  C  0.21  
Prop  RTC  J1  J 2  1 
  0.25  
J1  6.537 X 1 3  2.467 X 5 6  77.521X 1.208  59.634 X  36.009 X 2  14.606 X 3
J 2  0.133 X 1 3  28.215 X 5 6  82.958 X 1.208  99.000 X  19.105 X 2  2.796 X 3
T
X  1
C2
Usage
Correlation 54
SimSci 54
PPDS -
DIPP R 801 -
NIS T TDE -
Prop  RC1  RC3 1.45 1  X   0.45ln  X   0.25C2G   H ideal
   
  3
1 2 X  1
 1  X 2 3  X 1 3 1  3 
G  17.111  X   1.742 ln  X   25.2   3 tan    ln 3 X 
3  2  3 X  1  
2
   
 
T
X  1
C3
where
Hideal is the ideal gas enthalpy
Version 4.1 109

You cannot use this correlation to model the ideal gas enthalpy because this res ults in infinite recursions.
Usage
 Liquid Enthalpy
Converting UOMs for Correlation 38

You may have coefficients for correlation 38 that you derived by using different UOMs for the saturated
liquid density and vapor pressure than the UOMs that Thermo Data Manager uses (kmol/m3 and kPa,
respectively). In this case, you must convert your coefficients before you use them in Thermo Data
Manager.
Because the coefficients will change by constant conversion factors, we can consolidate the changes
into only the first coefficient and therefore reduc e the number of coefficients that we need t o convert. The
following equations show the mathematical derivation of the conversion for C1 .
where
* is the saturated liquid density in the original units
P* is the saturation vapor pressure in the original units
f is the conversion factor that converts the original units for the saturated liquid density into kmol /m3
f VP is the conversion factor that converts the original units for the saturation vapor pressure into kPa
 L is the saturated liquid density in kmol/m 3
VP is the vapor pressure
Ci * is the coefficient that you determined by using the original units for saturated liquid density and
saturation vapor pressure
If we compare the converted equation to the equation for Correlation 38, we get the following
equivalences for the coefficients:
Creating a Custom Library from PPDX Data

If you have thermodynamic data in a PPDX neutral data file, you can import this data into SimCent ral
TDM. The PPDX data exists as an .ikc file. When you import the data from this .ikc file, the soft ware
creates the following:
 A corresponding .lib1 file in the %userprofile %\My Thermo Data folder.
The .lib1 file has the same name as the .ikc file. If an existing .lib1 file has the same name as the .ikc
file, you can choose to overwrit e that .lib1 file with the data in the .ikc file. You can immediately use
the data in this custom library in SimCentral Simulation Plat form.
 A detailed .rpt file in the same folder as the .ikc file.
The .rpt file contains detailed information on the data banks in the new .lib1 file and the exact data
that those data banks contain. You can open the .rpt file in any text editor, such as Notepad or
Notepad++.
110 Version 4.1

Note: You can produce PPDX files from the DE THERM software produced and distributed by
DECHEMA, the Aspen Plus soft ware produced and distributed by AspenTec h, or the DDB soft ware
produced and distributed by DDBS T. The PPDX file format was developed by members of the IK -CAPE
Cons ortium and is currently maintained by DE CHEMA.
To create a custom library from PPDX data:

1. Open SimCentral TDM.
2. On the File menu, on the Import submenu, select Import PPDX. The Select the PPDX (.ikc) File
dialog box appears.
3. In the Directorie s pane, brows e to and select the folder that cont ains the .ikc file that you want to
import. The File s pane updates wit h the files in that folder.
4. In the Files pane, select the .ikc file that you want to import, and then click OK.
SimCent ral TDM creates a new custom library with the same name as the .ikc file. If this custom
library already exists, you can choose to overwrite the custom library with the data in the .ikc file.
Specifying an Ambient Temperature for the PPDX Data

For some of the thermodynamic equations in a PPDX file, there is not an exact match between the
IK-CAPE equation and the equation implemented in SimCentral Simulation Plat form. For example,
IK-CAPE allows the Wilson parameters to be temperature -dependent, whereas SimCentral Simulation
Platform allows only constant parameters. To res olve this, the PPDXImport conversion tool evaluates
the terms that SimCentral Simulation Plat form does not support at an ambient temperature and then
uses that value for the constant term. The report (.rpt ) file created by the PPDXImport conversion tool
notes where this is done.
By default, the PPDXImport conversion tool uses an ambient temperature of 25°C (298.15 K). If this is
not appropriate for your process, you can supply your own ambient temperature by using a private
AMBIENT block in the .ikc file that you import.
To specify an ambient temperature for the PPDX data:
1. Open the .ikc file in a text editor, such as Notepad or Notepad++.
2. Ensure that your .ikc file includes the following lines of code. If any lines are missing, add them.
VERSION IKC-PPDX 1.7
PRIVATE
BLOCKS AMBIENT
END PRIVATE
AMBIENT
TEMPERATURE 60 F
END AMBIENT
...
...
3. In the AMBIENT block, at the TEMPERATURE paramet er, change the value and unit of measure to
meet your requirements.
4. Save the .ikc file.
Version 4.1 111

Adding Units of Measures to the PPDXImport Tool

The PPDX format has a very flexible structure for specifying units of measure (UOMs). It uses a table of
recognized unit conversions that are stored in the PP DXImport.uom file in the
%LocalAppData %\SimSci\SimCentral\TDM\Bin folder. If a desired UOM is missing, you can add it to
the PPDXImport.uom file. Depending on how SimCentral Simulation Plat form was installed, you may
need administrator permissions to change the PPDXImport.uom file.
We recommended that you make a backup copy of the PPDXImport.uom file before you make any
changes so that you can restore the original version if your changes have an undesirable result.
To add UOMs:
1. In the %LocalAppData %\SimSci\SimCentral\TDM\Bin folder, open the PPDXImport.uom file in a
text editor, such as Notepad or Not epad++.
There are comments at the beginning of this file that describe its format.
2. Locate a UOM that is similar to the UOM that you want to add and enter a new line of code below the
existing UOM. Type the name of the new UOM and its appropriate conversion factors in the same
format as the other UOMs.
3. Repeat Step 2 until you have added all the desired UOMs.
4. Save the file.
112 Version 4.1

A PPENDIX A
Glossary of Terms
The following terms are used in SimCentral, the product documentation, or the online help.
A
Application Ribbon
A horizontal ribbon that cont ains tabs to invoke Process, Fluid Flow and Dynamics simul ation actions;
set simulation view preferences; and display the product help.
Auto Solve
The automatic solution of portions of a simulation when sufficient information is available.
B
Badge
A symbol next to a SimCentral object that describes its state to the user. For ex ample, in the P roperties
Inspector and Simulation Manager, objects like model instances, variables, and equations have badges
to indicate an error status with tooltips that describe the nature of the er ror.
C
Calculated Variable
A variable with a value that is not specified by the user and with its specification box unchecked. The
solver determines the value of calculated variables.
Canvas
The graphical representation of the Flowsheet on which models are placed and connected to build a
simulation.
Client
The computer us ed to run the user interfac e and that connects to the server computer.
Condition
An object defined by the Model Writer within the Model Editor which evaluates a boolean expression
composed of parameters. When conditions are used in a simulation, they describe the variables,
equations, and submodels that are used by the model instance based on parameter selections made by
the Simulation Builder.
Connection
An object that provides the numeric al equivalence of variables that it connects. Connections between
model Instances wit h the same Port Type define variable streams that represent the material flowing
between the models. See Variable Connections and Paramet er Connections.
Connection Model
A library model that looks like a connector on the Canvas. Typical connection models are Pipes and
Streams.
Version 4.1 113

SimCentral™ Simulation Platform Thermodynamics Reference Guide Glossary of Terms
Connector
The graphical representation of a connection on the Canvas.
D
Description
Descriptive text provided by the Model Writer for models and their parameters, variables, and equations,
or by the Simulation Builder for model i nstances placed on the Canvas. Descriptions can normally be
viewed by mouse-over tooltips.
Dynamic Attribute
A variable attribute for a Dynamic simulation. Possible values are state variables, operated on by the
der() function, and time-derivative variables creat ed by the der() operator.
Dynamics Mode
A Simulation Mode that solves bot h algebraic and time-derivative equations over successive int egration
time steps.
E
Editor
See Model Editor, Port Editor, and Fluid Editor.
Enumerated Parameter
A type of parameter wit h text-based options that are selectable by the Simulation Builder.
Equation
An object that describes the mathematical relationship of variables and real parameters. Model Writers
add equations to Model Types through the Model Editor. Simulation Builders may also create
Flowsheet-level equations using the Simulation Manager.
External
An object defined by the Model Writer within the Model Editor that defines an external DLL in which
variable relationships reside.
F
Fluid Editor
A configuration editor used by Simulation B uilders to modify the fluids used by a simulation.
Fluid Flow Mode
A pressure-driven steady state Simulation Mode. Fluid Flow Mode is defined by the collection of variable
specifications which typically invoke a simultaneous net work solution.
Fluid State (Instance)
An instance of a Fluid State submodel whose variables represent the thermodynamic state of that fluid
instance through values such as temperature, pressure, and enthalpy.
Fluid State (Model Type)
A Model Type that represents fluid behavior. Used as a submodel in process equipment Model Ty pes.
Fluid Type
A Fluid Type describes the thermodynamic behavior assigned to model instances in a simulation.
114 Version 4.1

Glossary of Terms SimCentral™ Simulation Platform Thermodynamics Reference Guide
Free Variable
See Calc ulated Variable.
G
Grid
Visible, equally-s paced vertical and horizontal lines on the Canvas that can be used to align objects.
Group Box
An area within the Roles Manager, Properties Inspector, and editors to which columns are dragged to
group data. When empty, the Group Box reads "group by area" and "Drag a field here to group by that
field."
Guide Lines
A vertical or horizontal line that appears on the simulation Canvas when a model instance being moved
is adjacent to another. Used to help align model instances with one another.
H
History Manager
An editor that allows you to define the frequency and quantity of simulation data that you want to save for
historical reference.
I
Icon
The graphical symbol that defines the appearance of all Model Types, Port Types, and Fluid Types on
the Canvas.
Integer Parameter
A Parameter that contains integer values. Integer parameters, such as the number of ports, are used to
configure models.
Invariant Attribute
A Variable and Parameter attribute that indicates the value does not change when you revert a
simulation to an earlier snapshot.
K
Keyword View
The detailed information pane of t he Simulation Manager, which allows modification of a selected object.
L
Library
See Model Library.
M
Manager
See Simulation Manager, UOM Manager, Snapshot Manager, and Role Manager.
Mode
The solution mode of a simulation that includes a collection of predefined variable specifications and, in
some cases, special solvers.
Version 4.1 115

Model Editor
The configuration editor used by Model Writers to define Model Types.
Model (Instance)
The mathematical relations hips defined by a Model Type composed of paramet ers, variables, and
equations that define a specific unit operation, such as a valve or pump that exists within a Flowsheet.
Model Library
A collection of Model Types, Fluid Types, Curve Types, and Port Types residing in the Repository, or a
single simulation-specific Model Library residing with a simulation.
Model Library (Display)
A UI component that displays Model Libraries, shapes, and referenc es that can be dragged onto the
Canvas.
A paramet er that contains integer values. Integer parameters can be used to configure a model, such as
defining how many ports it has.
The act of writing a Model Type.
N
Not Solved Variable Attribute
A Variable attribute that indicates that the variable is invalid, stale, or otherwise incorrect and should not
be used. Not solved variables are indic ated in grey strike-through text.
P
Parameter
An object that repres ents the static values of a simulation. Model Writers can add parameters using the
Model Editor and Simulation Builders can add parameters through the Simulation Manager. See Real
Parameter, Enumerated Parameter, Integer Parameter and Fluid Type.
Parameter Connection
A parameter connection is defined in the Model Editor to directionally transfer parameter values through
port connections. Parameter connections of a special parameter type called FluidTy pe are used to
transfer fluid information to connected models.
Parameter Connection
A way of connecting parameters across ports and submodels to t rans fer parameter values, such as Fluid
Types.
Port Editor
The configuration editor used by Model Writers to define Port Ty pes.
Port Type
A defined collection of variables that define the stream connection information bet ween model instances
connected by identical Port Types.
Process Mode
Process Mode performs steady state simulations to create and improve process design
Profile
An object which graphically displays scalar and vector data.
116 Version 4.1

Properties Inspector
A model instance property view accessed through the Canvas or Simulation Manager that allows
Simulation Builders to inspect and configure model instances.
Q
Quick Filter
A disposable Simulation Manager filter created for the immediat e search of an object in the Simulation
Manager. Save it if you want to use it again.
R
Real Parameter
A parameter that contains real numerical values (not integers or enumerations) and is defined using
Variable Types. Real parameters can be used in equations, but are treated as a fixed value. A typical real
parameter could be Pi with the value 3.14159.
Repository
The storage location of simulations, Model Libraries, and Variable Types on the server to which all
SimCent ral users of that server have access.
Repository Manager
The UI component that displays simulations in the Repository.
Required Variable Attribute
A variable attribute for which a Simulation Builder must provide a numerical value.
Reset Snapshot
A function that resets only the calculated values of a previously captured Snapshot. The variable
specifications and real parameters of the simulation being reset are not changed.
Revert Snapshot
A function that reverts the variable specifications, both specified and calculated variable values, and real
parameter values of a previously captured Snapshots.
Ribbon
A set of controls at the top of the UI where common user operations are grouped.
Role
Your role wit hin SimCentral. You can select Model Writing, which is the creation and modification of
Model Types, or Simulation Building, which is the use of existing Model Types within a simulation.
Additional roles may be defined in the Role Manager.
Roles Manager
A manager used to modify default roles and add new roles.
S
Scenario Manager
An editor that allows you to manually script, automatically record and run simulation actions.
Set By User Variable Attribute
A Variable attribute that is set when the Simulation Builder enters a value for a specified variable.
Version 4.1 117

Shapes
Primitive drawing objects, such as squares or circles, that can be dragged from the Shapes Model
Library to the Canvas.
SimCentral Button
The SimCentral Button contains options to create, import, open, rename, copy, delete, and export
simulations.
SimCentral Server
The computer us ed to host the solver and the Repository.
Simulation
A collection of Flowsheets and their connected model instanc es that define a process.
Simulation Building
The act of building a simulation using existing Model Types.
Simulation Canvas
See Canvas.
Simulation Manager
A hierarchical view of a simulation that allows the Simulation B uilder to explore and modify the simulation
and its objects.
Snapshot
The collection of simulation dat a saved with the simulation that defines the variable specifications,
variable values, and real parameter values. A Snapshot is used to reset or revert a simulation state as it
existed at the point that it was saved.
Snapshot Manager
The UI component that lets you manage existing simulations and capture new ones.
Solver
The soft ware component that solves the mathematical relationships of a simulation.
Specified Variable
A variable with a value specified by the Simulation Builder and with its specification box checked. The
solver does not change the value of specified variables.
State Variable
A Variable with the dynamic attribut e "State Value," whose value is calculated by the evaluation and
integration of its time derivative.
Status Bar
The single line display at the bottom of the user interface which provides system status information.
Submodel
A Submodel is a model which is part of another model, such as a Fluid State submodel. Typically,
submodels are defined so that they can be reused across many different models.
T
118 Version 4.1

Theme
A collection of text, background, and highlighting colors that can be selected per user preference.
Themes include Dark, Light, and Windows.
Thermo Type
The implementation that SimCentral uses to determine the Fluid State's properties, suc h as SimSci
Thermodynamics, an external DLL, or a named set of Equations in the Fluid State Submodel.
Trend
An object which graphically displays the time-dependent behavior of a variable during a dynamic
simulation.
Types
See Model Types, Variable Types, Port Types, and Fluid Types.
U
UOM Categories
A sortable grouping of relat ed Variable Types for the purpose of updating their display UOM in a UOM
Slate.
UOM Manager
A manager used to create and manage UOM Slates.
UOM Slate
A collection of UOM settings for all Variable Types, typically representative of a specific count ry or
industry. SI is a standard UOM Slate which comes with SimCentral.
V
Version 4.1 119

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SimCentral™ Simulation Platform

Thermodynamics Reference Guide

Chapter 2 Thermodynamics Methods by Name ............................................................. 13

Chapter 3 Special Topics ................................................................................................... 55

Appendix A Glossary of Terms ........................................................................................ 113

Liquid Density Calculation Methods

Special Data Packages

Liquid Activity Methods

Special Data Packages

We can calculate ka according to the following equation, as before:

Configuring the Fluid in SimCentral Simulation Platform

 SRK   xi SRK ,i

General Two-Parameter Equation of State

General Virial Equation of State

The Pure Liquid Fugacity Coefficient

Activity coefficient from Regular Solution Theory

Calculation of the Second Virial Coefficient

BijTotal  BijFree  BijDimerized

BijFree  BijFree, Nonpolar  BijFree,Polar

BijDimerized   BijD,Metastable  BijD ,Bound   BijD , Associative

Chemical Theory of Vapor Nonideality for Strongly Interacting

The following equation gives the fugacity coefficient of component i:

Vapor Enthalpy Corrections

H    at  RT  zij 1  D 

IF97 - IAPWS Industrial Formulation 1997

U Specific internal energy

Ps Saturation pressure as a function of temperature

Ts Saturation temperat ure as a function of pressure

IGS - Improved Grayson-Streed Method

Transport Properties for Pure Components

Transport Properties for Petrocomponents

Mixing Rules for Transport Properties of a Mixture

NRTL - Non-Random Two-Liquid Method

yiP,i P  xi i Pi sat

xi i  xi i

aT    xi x j ai a j  1  kij  (4)

M i  0.480  1.574 i  0.176 i2

PRM - Peng-Robinson Modified Panagiotopolous-Reid

aij   ai a j  1  kij    kij  k ji  xi 

M i  0.480  1.574 i  0.176 i2

 Lube oil and solvent de-waxing units

Redlich-Kwong Method (RK)

Regular Solution Theory Method

Equations for Pure-Component Systems

a Tr    Tr ac (2)

M  0.480  1.574  0.176 2 (6)

The variables used above are:

Tc Critical temperat ure

Tr Reduced temperature, Tr = T/Tc

Equations for Multi-Component Systems

The above equations introduce a few new variables:

xi Mole fraction of component i

kij Binary interaction parameter for components i and j

M i  0.480  1.574 i  0.176 i2

SRKM - Soave-Redlich-Kwong Modified

aij   ai a j  1  kij    kij  k ji  xi 

M i  0.480  1.574 i  0.176 i2

UNIFAC - Universal Functional Activity Coefficient Method

z is the lattice coordination number, which typically equals 10

Residual Activity Coefficient

The following equations give parameter m and mk:

Modified UNIFAC (Dortmund)

UNIQUAC - UNIversal QUAsi-Chemical Method

ri is the molecular volume (called the van der Waals volume)