Thermo

SimSci
PRO/II 9.3
Thermodynamic Data
Keyword Manual
May 2014
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Table of Contents
Table of Contents
Chapter 1
Thermodynamic Data Overview
General Information. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
Keyword Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-3
Minimum Required User Input . . . . . . . . . . . . . . . . . . . . . . . . . .1-14
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-14
Order of Input . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-16
Notes Statement (optional). . . . . . . . . . . . . . . . . . . . . . . . . .1-17
Thermodynamic Method Sets . . . . . . . . . . . . . . . . . . . . . . . . . . .1-18
Available Thermodynamic Property Generators. . . . . . . . . .1-20
Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-23
Predefined Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-26
Input Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-27
Multiple Thermodynamic Sets. . . . . . . . . . . . . . . . . . . . . . . . . . .1-30
The Default Method Set . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-30
Method Set Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . .1-31
Avoiding Inconsistent Methods. . . . . . . . . . . . . . . . . . . . . . .1-31
Multiple Method Sets in Distillation Columns . . . . . . . . . . .1-31
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-32
Free-water Decant Considerations. . . . . . . . . . . . . . . . . . . . . . . .1-33
User-Added Water Enthalpy Methods . . . . . . . . . . . . . . . . .1-34
Vapor-liquid-liquid Equilibrium Considerations . . . . . . . . . . . . .1-38
Chapter 2
Application Guidelines
General Information. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1
Refinery and Gas Processing Applications . . . . . . . . . . . . . . . . . .2-2
PRO/II Thermodynamic Data Keyword Manual ToC-1

Water Handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-2
Low Pressure Crude Systems . . . . . . . . . . . . . . . . . . . . . . . . . 2-3
High Pressure Crude Systems, FCCU, and Main Coker
Fractionators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-3
Reformers and Hydrofiners . . . . . . . . . . . . . . . . . . . . . . . . . . 2-4
Lube Oil and Solvent De-asphalting Units . . . . . . . . . . . . . . . 2-4
Natural Gas Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-5
Glycol Dehydration Systems . . . . . . . . . . . . . . . . . . . . . . . . . 2-6
Sour Water Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-6
Amine Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-7
Petrochemical Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-8
Light Hydrocarbon Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 2-8
Aromatic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-9
Aromatic/Non-aromatic Systems . . . . . . . . . . . . . . . . . . . . . . 2-9
Non-hydrocarbon Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 2-10
Alcohol Dehydration Systems . . . . . . . . . . . . . . . . . . . . . . . 2-12
HF Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-12
Chemical and Environmental Applications. . . . . . . . . . . . . . . . . 2-13
Non-Ionic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-13
Carboxylic Acid Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-14
Environmental Applications . . . . . . . . . . . . . . . . . . . . . . . . . 2-14
Solid Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-15
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-15
Chapter 3
Generalized Correlations
Ideal and Library Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-2
Grayson-Streed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-5
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-5
Chao-Seader. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-8
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-8
Modifications to GS and CS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-11
ToC-2
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-11
Curl-Pitzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-15
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-15
Braun K10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-18
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-18
Johnson-Grayson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-21
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-21
Lee-Kesler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-23
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-23
API Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-26
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-26
Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-26
Rackett Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-28
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-28
Costald Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-30
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-30
Peneloux Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-32
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-32
User-supplied K-value Data. . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-34
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-34

General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-35
Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-35
Chapter 4
Equations of State
Soave Modified Redlich-Kwong . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1
Peng-Robinson. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-7
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-7
Modified Soave-Redlich-Kwong and Peng-Robinson . . . . . . . . 4-13
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-13
UNIWAALS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-22
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-22
Filling in Missing Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-27
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-27
Cubic Equation Of State Alpha Formulations . . . . . . . . . . . . . . . 4-28
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-28
K-value Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-29
Benedict-Webb-Rubin-Starling . . . . . . . . . . . . . . . . . . . . . . . . . . 4-34
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-34
Associating Hexamer Equation Of State . . . . . . . . . . . . . . . . . . . 4-39
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-39
Lee-Kesler-Plocker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-43
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-43
ToC-4
Predictive Peng-Robinson 78. . . . . . . . . . . . . . . . . . . . . . . . . . . .4-47
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-47
Predictive Soave-Redlich-Kwong (PSRK) . . . . . . . . . . . . . . . . .4-53
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-53
Chapter 5
Special Packages
Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-1
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-1
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-1
Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-2
Glycols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-14
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-14
Sour Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-19
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-19
GPA Sour Water. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-22
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-22
Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-26
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-26
User-added Subroutines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-32
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-32
CAPE-OPEN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-34
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-34

Chapter 6
Liquid Activity Methods
NRTL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1
UNIQUAC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-7
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-7
UNIFAC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-12
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-12
Modifications to UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-20
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-20
Wilson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-28
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-28
Van Laar. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-32
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-32
Margules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-38
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-38
Regular Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-43
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-43
Flory-Huggins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-48
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-48
ToC-6
Filling in Missing Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . .6-52
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-52
Henrys Law for Non-condensible Components . . . . . . . . . . . . .6-57
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-57
Henrys Law Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-62
Hayden-OConnell Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . . .6-64
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-64
Truncated Virial Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . . . . .6-68
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-68
IDIMER Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-71
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-71
Redlich-Kister, Gamma Heat of Mixing . . . . . . . . . . . . . . . . . . .6-75
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-75
Chapter 7
Solid Solubility Methods
Van't Hoff Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-1
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-1
User-supplied Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-4
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-4

Chapter 8
Transport and Special Properties
Transport Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-1
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-1
Input Description for Transport Properties . . . . . . . . . . . . . . . 8-2
Examples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-8
Special Stream Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-10
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-10
Chapter 9
Method-specific Pure Component Data
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9-11
Index
ToC-8
Chapter 1
Thermodynamic Data Overview
This chapter provides an overview of the Thermodynamic Data
Category. Detailed documentation, along with examples of
common usage of all the thermodynamic features, follows in
Chapters 2 through 9.
General Information
The program offers many thermodynamic methods and options
ranging from the simple to the very complex. However, the thermo-
dynamic data input requirements for most simulations are simple,
requiring only a few input statements. For example, to use the
Soave-modification to the Redlich-Kwong equation of state in a
flowsheet requires only two lines of code in the keyword file:
Example: THERMODYAMIC DATA
METHOD SYSTEM=SRK
The first statement THERMODYNAMIC DATA declares the begin-

ning of the Thermodynamic Data Category. The second statement
states that the predefined SRK system of thermodynamic generators
be employed. The usage of each thermodynamic generator is fully
documented in individual sections.
Thermodynamic methods are packed into sets or systems, each
containing a group of methods for performing all necessary thermo-
dynamic calculations. Most applications require only one set, but
complex flowsheets may be modeled better with several. The pro-
gram allows a maximum of 100 different sets of thermodynamic
methods in each input file.
When an input file includes only one set of methods, all unit opera-
tions use that set for all calculations. When an input file contains
PRO/II Thermodynamic Data Keyword Manual 1-1

two or more of these, one set serves as the default. If one set is not
explicitly specified as the default, then the program chooses the first
thermodynamic set in the input file as the default. Unit operations
that do not explicitly specify a set of methods use the default.
The SIMSCI databanks contain an extensive collection of pure
component data and binary interaction data for equations of state
and liquid activity methods. Additional special databanks for alco-
hol and glycol components are available.
Vapor-liquid, rigorous vapor-liquid-liquid, solid-liquid equilibria,
and electrolyte calculations can all be handled by the program using
suitable thermodynamic methods. In addition, the program can
compute enthalpies, entropies, flowing densities, and transport
properties.
Special water handling options may be declared locally within each
set of methods. Method-specific options apply only to calculations
controlled by the set of methods that contains the options. Options
exist to compute water enthalpy using a user-added subroutine as an
alternative to a built-in property generator.
Usually, all component data are retrieved from the component
libraries or are estimated for stream assay cuts and PETRO compo-
nents (petroleum pseudocomponents). Other component data, such
as for NONLIB components (those components missing from the
component databank), are usually supplied in the Component Data
Category of input. These data are global, applying to all calcula-
tions in the problem. Each set of methods optionally may include
additional method-specific data that override the data obtained from
other sources such as the SIMSCI databank, but which apply only
to calculations controlled by the methods set containing the data.
Method-specific data include selected pure component properties
(e.g., critical temperature and pressure) and multi-component data
such as binary interaction parameters.
1-2 Thermodynamic Data Overview

Keyword Summary
Table 1-1 summarizes the entries on the METHOD statement,
where calculation methods ( or property generators) are associated
with individual properties.
Table 1-2 summarizes the other available statements that may sup-
ply addional input data for for individual properties and property
generators.
Table 1-1: Thermodynamic Data METHOD Statement

Statement Keywords For details see
Category Heading Statement, Required
THERMODYNAMIC DATA None II-1-1
The METHOD Statement, Required
Selecting a Pre-defined System of Methods
METHOD SYSTEM(VLE or VLLE)= option, Predefined
{KVALUE (SLE)= option}, {L1KEY= i and L2KEY = j}, Systems on page
{KVALUE(VLE or LLE or VLLE)=option, 1-26
ENTHALPY = option, DENSITY=option,
ENTROPY=option}, { RVPMETHOD}, (TVPMETHOD}
{PHI=option}, {HENRY},
{PROPERTY = method}, {SET = setid, DEFAULT}
TRANSPORT = NONE or
TRANSPORT = PURE or PETRO or TRAPP or
TACITE or U1 or U2 or U3 or U4 or U5
Selecting Individual Methods
METHOD SET= setid, {DEFAULT} Thermodynamic
KVALUE (VLE) = option, {KVALUE (SLE)= option} Method Sets on
{KVALUE (LLE) = option}, {L1KEY = i and L2KEY = j}, page 1-18
{PHI=option}, {HENRY},
or
KVALUE(VLLE) =option, {L1KEY = i and L2KEY = j},
{KVALUE (SLE) = option}, {PHI = option}, {HENRY},
ENTHALPY(VL) = option,
or
ENTHALPY(V) = option and ENTHALPY(L) = option,
{RVPMETHOD}, {TVPMETHOD},
{PROPERTY=method}
DENSITY(VL) = option,
or DENSITY(V) = option and DENSITY(L) = option
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults;
Underlined keywords are defaults.

Table 1-1: Thermodynamic Data METHOD Statement
ENTROPY(VL)=NONE
or ENTROPY(V)=option, ENTROPY(L)=option,
{RVPMETHOD}, (TVPMETHOD}
TRANSPORT = NONE or
TRANSPORT = PURE or PETRO or TRAPP or TACITE or
U1 or U2 or U3 or U4 or U5
or
METHOD VISCOSITY(VL) = NONE
or VISCOSITY(VL) = PURE or PETRO or TRAPP or U1
or U2 or U3 or U4 or U5
or VISCOSITY(V) = PURE or PETRO or TRAPP or BW
or U1 or U2 or U3 or U4 or U5
and/or VISCOSITY(L) = PURE or PETRO or TRAPP
or KVIS or LBC or TWUB or APIT or
U1 or U2 or U3 or U4 or U5
and/or
METHOD CONDUCTIVITY(VL) = NONE
or CONDUCTIVITY(VL) = PURE or PETRO or TRAPP
or CONDUCTIVITY(V) = PURE or PETRO or TRAPP
and/or CONDUCTIVITY(L) = PURE or PETRO or
TRAPP or LATINI or API96 or API96H U1 or U2 or
U3 or U4 or U5
and/or
METHOD SURFACE = NONE
or SURFACE = PURE or PETRO or PARACHOR or
API82 or API82H or U1 or U2 or U3 or U4 or U5
METHOD DIFFUSIVITY(L) = NONE
or DIFFUSIVITY(L) = WILKE or DIFDATA

Table 1-2: Thermodynamic Input Category Data Statements
Category Heading Statement, Required
THERMODYNAMIC DATA None II-1-1
Notes Statement, Optional
NOTES TEXT = notes line (up to 256 characters) II-1-14
The METHOD Statement, Required
Selecting a Pre-defined System of Methods
METHOD SYSTEM(VLE or VLLE)= option, . . . See Table 1-1 1-26
Method-specific Water Handling Options, Optional
WATER DECANT = ON or OFF, {GPSA}, WICHERT Free-water
SOLUBILITY = SIMSCI or EXTSIMSCI or KEROSENE Decant
or EOS or LUBE or NAPH or APIKERO Considerations
or PARA or GASO or JP3 or JP-4, on page 2-1-33
PROPERTY = SATURATED or STEAM or IF97
TRANSPORT = IF97 or SIMSCI
ENTHALPY= PROPMETHOD or USER
Property Statements, Optional
Vapor-Liquid Equilibrium Options, Optional
KVALUE(VLE) POYNTING = OFF or ON, Chapter 5
MOLVOL = STANDARD or RACKETT or RCK2
or LIBRARY,
BANK = SIMSCI and/or ALCOHOL and/or GLYCOL
and/or bankid or NONE
or BANK=PROII_9.3:SIMSCI, and/or
PROII_9.3:ALCOHOL, and/or PROII_9.3:GLYCOL
and/or bankid or NONE}
FILL = NONE or GAO or GOR or CPHC or UNIFAC
or CIUNIFAC or UFT1 or REGULAR or FLORY, etc.
or FILL=PR and ALPHA=ACEN
AZEOTROPE = SIMSCI or NONE or bankid,
{WRITE = fileid},
{ALPHA = ACENTRIC or SIMSCI or bankid},
{COMP = SIMSCI, LIBRARY1:USER1, LIBRARY1:bankid...},
{PURE = LIBRARY1:USER1, and/or LIBRARY1:USER2
and/or LIBRARY1:bankid...}
(default depends on method)
<optional data statements> ...

Note: Only the STANDARD option is available for molar liquid volume (MOLVOL) calculations
when the WILSON K-value method is selected.
Note: The ALPHA=ACEN entry is required with FILL=PR to ensure that the fill calculations use
the same alpha formulation as the base PR method, since by default the PRH method uses
ALPHA=SIMSCI.
Note: PURE=LIBRARY1:USER1 entry is required to set databank search order for BWRS Coeffi-
cients for Pure Components.
Liquid-Liquid Equilibrium Options, Optional Chapter 5

KVALUE(LLE) {BANK = SIMSCI or ALCOHOL or GLYCOL or NONE
or BANK=PROII_9.3:SIMSCI, and/or PROII_9.3:ALCOHOL,
and/or PROII_9.3:GLYCOL LIBRARY1:USER1,
LIBRARY1:USER2, LIBRARY1:bankid...},
FILL = NONE or UNIFAC or CIUNIFAC or UFT1 or
REGULAR or FLORY,
AZEOTROPE = SIMSCI or NONE or bankid,
{WRITE = field},
{COMP = SIMSCI, LIBRARY1:USER1, LIBRARY1:bankid...}
(default depends on method)
Solid-Liquid Equilibrium Options, Optional Chapter 7
KVALUE(SLE) FILL = VANTHOFF or ONE or FREE
SOLUTE i, j, ....
SOLDATA(utemp) i, j, c1, c2, c3/ ...
Diffusivity Options, Optional Chapter 7
DIFFUSIVITY(L)
DIFDATA(utemp) i, l, c1, c2, c3/ ...
Vapor Fugacity Options, Optional Chapter 5
PHI {BANK= SIMSCI or NONE or BANK=PROII_9.3:SIMSCI,
LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...}
{PURE = LIBRARY1:USER1, and/or LIBRARY1:USER2, and/
or LIBRARY1:bankid...}
Henrys Law Options, Optional Chapter 5

HENRY {BANK= SIMSCI or NONE} or { BANK=PROII_9.3:SIMSCI,
LIBRARY1:USER1, LIBRARY1:USER2,
LIBRARY1:bankid...}
SOLUTE i, j, ...
HENDATA(upres, utemp) i, l, c1, c2, c3, c4 / ...
Density Options, Optional Chapters 4 & 5
DENSITY(VL) {BANK = SIMSCI or NONE } or {
BANK=PROII_9.3:SIMSCI, LIBRARY1:USER1,
{COMP = SIMSCI, LIBRARY1:USER1, LIBRARY1:bankid...}
or
DENSITY(V) {BANK = SIMSCI or NONE or
or
DENSITY(L) {BANK = SIMSCI or NONE } or { BANK=PROII_9.3:SIMSCI,
LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...},

Enthalpy Options, Optional Chapters 4 & 5
ENTHALPY(VL) {BANK = SIMSCI or NONE } or { BANK=PROII_9.3:SIMSCI,
HMIX = IDEAL or GAMMA or RK1 or RK2
or
ENTHALPY(V) {BANK = SIMSCI or NONE} or { BANK=PROII_9.3:SIMSCI,
LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid..},
and/or
ENTHALPY(L) {BANK = SIMSCI or NONE} or { BANK=PROII_9.3:SIMSCI,
HMIX = NONE or GAMMA or RK1 or RK2
Entropy Options, Optional Chapters 4 & 5
ENTROPY(VL) {BANK = SIMSCI or NONE } or { BANK=PROII_9.3:SIMSCI,
and/or
ENTROPY(V) {BANK = SIMSCI or NONE} or { BANK=PROII_9.3:SIMSCI,
and/or

ENTROPY(L) {BANK = SIMSCI or NONE or
LIBRARY1:USER2, DIPPR, bankid...},
User-supplied K-value Data, Optional Chapter 3
(Use with KVALUE statements shown)
KVALUE(VLE or LLE)
KDATA CORR=icorr, LN or LOG or EXPFAC=ipos,
PREF(upres)=value
DATA=i, tmax, tmin, c1, ... c8/ ...
or
KDATA TABULAR=t1, t2, .../ i, p1, p2, .../ ..., PREF(upres)=value
Binary Interaction Data, Optional (Use with Chapters 4 & 5

KVALUE, PHI, DENSITY, ENTHALPY, or ENTROPY statements)
BWRS Equation of State Data, Optional
BWRS i, j, aij, bij / ...
HEXAMER Equation of State Data, Optional
HEXA(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...
LKP Equation of State Data, Optional
LKP i, j, kij, / ...
Hayden-OConnell Data, Optional
(For vapor fugacity, vapor density, vapor enthalpy, and vapor entropy)
HOCV i, i, nii, / i, j, nij, / ...
Truncated Virial Data, Optional
(For vapor fugacity)
TVIRIAL i, i
IDIMER Data, Optional
(For vapor fugacity, vapor density, vapor enthalpy, and vapor entropy)
IDIMER i, i, Aii, Bii / i, j, Aij, Bij / ...

Redlich-Kister Excess Properties Data, Optional
(Currently for heat of mixing only)
RK1(K or KCAL or KJ) i, j, aij, bij, cij, dij, eij, fij, gij, hij / ...
or
RK2 (K or KCAL or KJ) i, j, aij, bij, cij, dij, eij, fij, gij, hij / ...
Note: UOM is K or KCAL/KMOL or KJ/KMOL.

Soave-Redlich-Kwong or Peng-Robinson Equation of State Chapter 4
Interaction Parameters, Optional
SRK(K or R) or i, j, kija, kijb, kijc / ...
PR(K or R) or
SRKKD(K or R) or i, j, kija, kijb, kijc / ...
SRKP(K or R) or i, j, kija, kjia, kijb, kjib, kijc, kjic / ...
PRP(K or R) or
SRKM(K or R) or i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...
PRM(K or R)or
SRKH (K or KCAL or KJ) or i, j, aij, bij, cij, aji, bji, cji, ij, ij / ...
PRH (K or KCAL or KJ) or
SRKS(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...
Note: UOM for SRKH & PRH is K or KCAL/KMOL or KJ/KMOL.

Liquid Phase Activity Binary Interaction Data Chapter 5
NRTL Data, Optional
NRTL3(K or KCAL or KJ) i, j, bij, bji, ij / ...
NRTL(K or KCAL or KJ) i, j, aij, bij, aji, bji, ij / ...
NRTL6(K or KCAL or KJ) i, j, aij, bij, aji, bji, ij, ij / ...
NRTL8(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, ij, ij / ...
NRTL10 (K) i, j, aij, bij, dij, eij, aji, bji, dji, eji, ij, ij / ...
NRTL14 (K) i, j, aij, bij, cij, dij, eij, fij, aji, bji, cji, dji, eji, fji, ij, ij / ...
Note: UOM for NRTL3,NRTL,NRTL6 & NRTL8 is K or KCAL/KMOL or KJ/KMOL.

UNIQUAC Data, Optional
UNIQUAC (K or KCAL i, j, aij, aji / ...
or KJ)
UNIQ4 (K or KCAL or KJ) i, j, aij, aji, bij, bji / ...
Note: UOM is K or KCAL/KMOL or KJ/KMOL or NONE.


Wilson Data, Optional
WILSON (K or KCAL or i, j, aij, aji / ...
KJ or NODIME)
Note: UOM is K or KCAL/KMOL or KJ/KMOL or NONE.

Van Laar Data, Optional
VANLAAR i, j, aij, aji / ...
Margules Data, Optional
MARGULES i, j, aij, aji, dij / ...
Flory-Huggins Data, Optional
FLORY i, j, ij / ...
Other Binary Data for Liquid Activity Methods
(For use with liquid activity methods, such as all forms of NRTL, UNIQUAC, Wilson, van
Laar, and the Margules methods.)
AZEOTROPE (basis, upres, i, j, pres, temp, xi / ... Chapter 5
utemp)
INFINITE(utemp) i, j, temp, ioo, joo / ... Chapter 5
MUTUAL (basis, utemp) i, j, temp, xiI, xjII / ... Chapter 5
IDEAL i, j / ... Chapter 5
Henrys Law Data, Optional Chapter 5
SOLUTE i, {j, ...}
HENDATA (upres, utemp) i, l, c1, c2, c3, c4 / ...
UNIFAC Group Contribution Data, Optional Chapter 5

(For K-value calculations only)
UNIFAC (K or KCAL or KJ) l, k, Alk, Akl / ...
UNIFT1(K) or l, k, alk, akl, blk, bkl, clk, ckl / ...
UNIFT2(K) or l, k, alk, akl, blk, bkl, clk, ckl / ...
UNIFT3(K) l, k, alk, akl, blk, bkl, clk, ckl / ...
UNFV (K or KCAL l, k, alk, akl / ...

or KJ)
Note: UOM for UNIFAC & UNFV is K or KCAL/KMOL or KJ/KMOL.

UNIWAALS Modified Group Contribution Interaction Data, Chapter 4
Optional

UNIFT1(K) l, k, alk, akl, blk, bkl, clk, ckl / ...
UNIFAC (K or KCAL or KJ) l, k, Alk, Akl / ...

NOTE: UOM for UNIFAC is K or KCAL/KMOL or KJ/KMOL
Pure Component Alpha Formulations, Optional Chapter 4
(Use with PR, SRK, or UNIWAALS methods)
PA01 or SA01 or VA01 i, c1 / ...
PA02 or SA02 or VA02 i, c1, c2, c3 / ...
PA03 or SA03 or VA03 i, c1, c2 / ...
PA04 or SA04 or VA04 i, c1, c2 / ...
PA05 or SA05 or VA05 i, c1, c2 / ...
PA06 or SA06 or VA06 i, c1, c2, c3 / ...
PA07 or SA07 or VA07 i, c1 / ...
PA08 or SA08 or VA08 i, c1, c2, c3 / ...
PA09 or SA09 or VA09 i, c1, c2, c3 / ...

PA10 or SA10 or VA10 i, c1, c2 / ...
PA11 or SA11 or VA11 i, c1, c2 / ...
Special Property Methods Data, Optional Chapter 8

property(qualifier) {GAMMA=value, REFINDEX=value,
REFVALUE(unit)=value}, {NCFILL=ncfill},
{NCBLEND=ncblend}
DATA(unit) i, datvalue / ...
INDEX i, indvalue / ...

Method-specific Pure Component Data, Optional Chapter 9
TC(unit) i, value / ...
PC(unit) i, value / ...
VC(unit) i, value / ...
ZC i, value / ...
ACENTRIC i, value / ...
NBP(unit) i, value / ...
MOLVOL(unit) i, value / ...
DIPOLE(unit) i, value / ...
RADIUS(unit) i, value / ...
SOLUPARA i, value / ...
RACKETT i, value / ...
WDELT i, value / ...
PARACHOR i, value / ...
PENELOUX i, value / ...
User-added Subroutine Data, Optional Chapters 6 & 8
(See the PRO/II User-added Subroutine User Guide)
UDATA i, value / ...

Minimum Required User Input
General Information
The program offers a multitude of user choices and data entry
options for the Thermodynamic Data Category. However, the input
requirements to define the thermodynamic properties for the vast
majority of applications are minimal. In most cases, selecting a
predefined system (see Predefined Systems on page 1-26) is
sufficient. This takes the form:
THERMODYNAMIC DATA
METHOD SYSTEM=system id
Where the system id is selected from Table 1-6.

Some unit operations require transport properties to be selected on
the METHOD statement. This is not defaulted with the SYSTEM
selection, and instead must be chosen separately. The simplest way
to do this is to use the TRANSPORT keyword which selects a group
of consistent property generators for viscosity, thermal conductivity
and surface tension. Once the TRANSPORT keyword is supplied,
the program uses a suitable default. The choices are given in
Transport Properties on page 8-1. The input takes the form:
THERMODYNAMIC DATA
METHOD SYSTEM=system id, TRANSPORT
or
THERMODYNAMIC DATA
METHOD SYSTEM=system id, TRANSPORT=transport id
Note: The DIFFUSIVITY entry is not included with the

TRANSPORT groupings and must be entered separately when the
DISSOLVER unit operation is present in the flowsheet and the
Treybal method is used to calculate the mass transfer coeffi-
cient.

Examples
Typical input file segments based on recommendations given in
Chapter 2, Application Guidelines, are provided below. The Ther-
modynamic Data Category is highlighted.
1. A petroleum refinery crude fractionator using the Grayson-
Streed system :
...
COMPONENT DATA
LIBID 1,H2O / 2,C2 / 3,C3 / 4,IC4 / 5,NC4 / 6,IC5 / 7,NC5
THERMODYNAMIC DATA
METHOD SYSTEM=GS
STREAM DATA
...
2. A deethanizer using Peng-Robinson. Transport properties are

selected to support tray rating calculations:
...
COMPONENT DATA
LIBID 1,N2 / 2,C1 / 3,C2 / 4,C3 / 5,IC4 / 6,NC4 / &
7,IC5 / 8,NC5 / 9,NC6 / 10,NC7
THERMODYNAMIC DATA
METHOD SYSTEM=PR, TRANSPORT=PURE
STREAM DATA
...
3. A three phase distillation tower containing MEK, water and tol-

uene using NRTL:
...
COMPONENT DATA
LIBID 1,MEK / 2,H2O / 3,TOLUENE
THERMODYNAMIC DATA
METHOD SYSTEM(VLLE)=NRTL
STREAM DATA
...
4. Gas sweetening with MEA:

...
COMPONENT DATA
LIBID 1,CO2 / 2,H2S / 3,C1 / 4,C2 / 5,C3 / 6, IC4 / 7,NC4 / &
8,IC5 / 9,NC5 / 10,NC6 / 11, NC7 / 12,H2O / 13,MEA
THERMODYNAMIC DATA
METHOD SYSTEM=AMINE
STREAM DATA
...

Order of Input
The order of appearance of statements in the input file is significant,
and the statements should always be given in the order shown in
Table 1-3. Some general guidelines are discussed later in this sec-
tion. More detailed descriptions of the various statements can be
found in later sections.
Table 1-3: Thermodynamic Data Order of Input
Statement Comments Chapter
THERMO DATA Section heading, required as the first statement in a 1-18
thermodynamic method set.
METHOD Required as the first statement in defining each set of 1-18
methods. A METHOD statement must be the first
statement in the THERMODYNAMIC DATA section of
keyword input.
WATER Optional. Method-specific water options that apply only 1-33
to the current method.
<property Optional. Any KVALUE, ENTHALPY, K ENTROPY, 6-8
statement> DENSITY, TRANSPORT, HENRY, or PHI statements 6-57
that apply to a method declared on the METHOD (see specific
statement. methods)
<binary data> Optional. Additional binary interaction data statements 4-27
associated with the preceding <property> statement.
<alpha data> Optional. Additional alpha data statements associated 4-28
with the preceding <property> statement.
<component data> Optional. Any pure component data statements (Tc, Pc, 9-1
etc.) that apply to the preceding <property> statement.
<specl property Optional. First statement in the definition of an 8-1
data>... additional property. May also be a data statement for a 8-10
special property.
NOTES Optional. One NOTES statement is allowed per 1-17
METHOD set. Up to 4096 characters of descriptive text
is allowed.
METHOD . . . Optional. First statement in the definition of an 1-1
additional thermodynamic method set.
The Thermodynamic Data Category must begin with the THERMO-

DYNAMIC DATA heading statement. This must be followed by the
definition of one or more thermodynamic system.
Each system begins with a METHOD statement that declares a
method for every thermodynamic property required by the problem.
The entries on this statement activate the required property calcula-
tions. Available entries include SYSTEM, KVALUE, ENTHALPY,

ENTROPY, DENSITY, TRANSPORT, PHI, and HENRY. If a
method is not specified for a property, that property will not be cal-
culated.
Most of the property methods have built-in databanks that contain
the required data. When desired, the user may supply additional
data or overwrite the default SimSci data by including optional
property statements and data statements. The property statements
(SYSTEM, KVALUE, ENTHALPY, ENTROPY, DENSITY,
HENRY, TRANSPORT and PHI) can appear in any order. Each
may be followed by optional data statements that supply pure com-
ponent data or binary interaction data for that property. These sub-
sequent data statements must appear immediately after the property
statement they affect and apply only to that property statement.
The exception is that data entered after the KVALUE property state-
ment serve as default values for all other properties that use the
same method (as the KVALUE method). For example, using SYS-
TEM=SRK selects the SRK method for computing K-values,
enthalpy, entropy, and vapor density. Binary interaction parameters
(Kijs) supplied for calculating K-values also act as default values
when calculating enthalpy, entropy, and vapor density.
Notes Statement (optional)

NOTES TEXT = notes line
The NOTES statement in the Thermodynamic Data Section provides
a TEXT keyword that accepts the actual descriptive text that com-
prises the note. Each METHOD set may include one NOTE statement.
NOTES This statement must be placed along with the METHOD statement
of the specific thermodynamic set to which the information
pertains. One NOTES statement is allowed per thermodynamic set.
TEXT This entry specifies the actual notes line(s). The Notes Data can be
specified in multiple lines. Only the first 4096 characters Ar stored.
The rest will be discarded.
An example of information added through NOTES statements

about the thermodynamic sets used in a simulation follows:
THERMODYNAMIC DATA
$Example with Set ID
METHOD SYSTEM=PR, DENSITY(L)=LK, SET=PR01
NOTES TEXT= This is the default METHOD set used in the &
simulation.
$Example without Set ID
METHOD SYSTEM=SRK

NOTES TEXT= The SRK method is defined for use with the &
hot key flash in PROVISION.
Thermodynamic Method Sets

In the program, property generators predicting K-values, enthalpy,
density, and, optionally, entropy and transport properties are
grouped together to form thermodynamic sets. By fixing the com-
position of a stream and two independent stream variables (such as
pressure and temperature, or pressure and enthalpy), the program
can fully calculate all of the thermodynamic properties for that
stream with the generators defined in that set.
Each set is headed by a METHODS statement and continues until the
next METHODS or STREAM DATA statement. For example, the fol-
lowing input section defines a thermodynamic set:
...
THERMODYNAMIC DATA
METHOD SYSTEM=SRK
STREAM DATA
...
It uses the SRK predefined system to calculate all of the stream

properties. See Predefined Systems on page 1-26 and Soave
Modified Redlich-Kwong on page 4-1.
In the following example, several different generators are assem-
bled to create a single set:
...
THERMODYNAMIC DATA
METHOD KVALUE=NRTL, PHI=SRK, &
ENTHALPY(V)=SRK, ENTHALPY(L)=IDEAL, &
TRANSPORT=PURE, RVPMETHOD, SET=01
NOTES TEXT= This thermo set is used for RVP calcs.
KVALUE
NRTL 1,3,,-51.2,,2216,.200
STREAM DATA
...
In this case, NRTL liquid activity coefficients coupled with SRK

vapor phase fugacities are used in combination to establish K-val-
ues. Vapor enthalpies are calculated via SRK, liquid enthalpies via
pure component saturated liquid enthalpies, and transport properties
via pure component blending. This thermodynamic set is defined as
set 01, and is used for RVP calculations.

Each unit operation that calculates stream properties has at least one
associated thermodynamic set. The product streams, internal
streams, and external feeds (feed streams defined on a PROPERTY
statement rather than from other unit operations) all use that set for
calculating the relevant thermodynamic properties. Some units,
such as columns and heat exchangers, have multiple internal
streams, and provision is made to allow multiple sets to be used
within the same unit operation. (See Multiple Thermodynamic
Sets on page 1-30.)
Table 1-4 shows all of the available thermodynamic property gener-
ators. Also given in this table are chapter numbers to refer to for
more information on each generator. A complete description of all
keywords relevant to that generator is provided in that chapter.

Available Thermodynamic Property Generators
Table 1-4: Thermodynamic Generators
Method Description K-values Enthalpy Entropy Density Phi
Generalized Correlation Methods (see Chapter 3)
IDEAL Ideal and library VLE VL VL
GS Grayson-Streed VLE(fw)
CS Chao-Seader VLE(fw)
IGS Improved Grayson- VLLE
Streed VLE(fw)
GSE Erbar Improved VLE(fw)
Grayson-Streed
CSE Erbar Improved VLE(fw)
Chao-Seader
CP Curl-Pitzer VL VL
BK10 Braun K10 VLE(fw)
JG Johnson-Grayson VL
LK Lee-Kesler VL VL VL
API API Liquid Density L
RACKETT Rackett Liquid L
Density
COSTALD COSTALD Liquid L
Density
Equation of State Methods (see Chapter 4)
SRK Soave-Redlich- VLE1(fw) VL VL V2 yes
Kwong
PR Peng-Robinson VLE1(fw) VL VL V2 yes
SRKKD SRK Kabadi-Danner VLLE VL VL V2 yes
SRKH SRK Huron-Vidal VLLE VL VL V2 yes
SRKP SRK Panagio- VLLE VL VL V2 yes

topoulos & Reid
SRKM SRKP Modified VLLE VL VL V2 yes
SRKS SRK Simsci VLLE VL VL V2 yes
PRH PR Huron-Vidal VLLE VL VL V2 yes
PRP PR Panagiotopoulos & VLLE VL VL V2 yes

Reid
PRM PRP Modified VLLE VL VL V2 yes

UNIWAAL UNIWAALS VLLE VL VL V2 yes
BRWS Benedict-Webb- VLE(fw) VL VL VL yes

Rubin-Starling
HEXAMER Associating EOS for VLLE VL VL VL yes
HF systems
LKP Lee-Kesler-Plocker VLLE VL VL VL yes
VLE(fw)
PPR78 Predictive Peng- VLE1(fw) VL VL V2 yes
Robinson
PSRK Predictive Soave- VLE1 VL VL V2 yes
Redlich-Kwong
Liquid Activity Methods (see Chapter 5)
NRTL NRTL VLLE
UNIQUAC UNIQUAC VLLE
UNIFAC UNIFAC VLLE
UFT1 UNIFAC Lyngby VLLE
UFT2 UNIFAC Dortmund VLLE
UFT3 Modified UNIFAC VLLE
UNFV UNIFAC Free VLLE
Volume option
WILSON Wilson equation VLE
VANLAAR van Laar equation VLLE
MARGULE Margules equation VLLE
REGULAR Regular solution VLLE
theory VLE(fw)
FLORY Flory Huggins VLLE
HOCV Hayden-OConnell V V V yes
vapor fugacity
TVIRIAL Truncated virial yes
vapor fugacity
IDIMER IDIMER vapor V V V yes
fugacity

Special Packages (see Chapter 6)
ALCOHOL Alcohol package VLLE
GLYCOL Glycol package VLLE
SOUR Sour water package VLLE1
GPSWATER GPA sour water VLLE1

package
AMINE Amine package VLLE1 L
U1 - U15 User-supplied VLLE VL VL VL

subroutines
Additional Thermodynamic Generators
VANTHOFF vant Hoff SLE
solubilities
SOLDATA User-supplied SLE
solubility data
DATA K-value data VLLE
Symbols
VLLE - Vapor-liquid-liquid equilibrium
VLE - Vapor-liquid equilibrium
VLE(fw) - Vapor-liquid equilibrium with free water decant
SLE - Solid-liquid equilibrium
V - Applicable to vapor phase
L - Applicable to liquid phase
VL - Applicable to both vapor and liquid phases
Notes
1 - VLLE available, but not recommended
2 - Liquid density available, but not recommended
3 - GS is preferred to CS
Table 1-5: Features that Require Entropy

Feature
COMPRESSOR
EXPANDER
GIBBS Reactor
HCURVE Entropy Tables
EXERGY

Input Description
METHOD SYSTEM{VLE or VLLE}=method,
KVALUE(SLE)=method},
{KVALUE(VLE or LLE or VLLE)=method,
ENTHALPY=method, DENSITY=method,
ENTROPY=method}, {PHI=method},
{HENRY},{RVPMETHOD, TVPMETHOD},
TRANSPORT=option}, {property(qualifier)=method,
REFPROP=SIMSCI} SET=setid, {DEFAULT}...
NOTES TEXT = Notes line (up to 256 characters)
or
METHOD KVALUE{VLE or LLE or VLLE}=method,
KVALUE(SLE)=method}, ENTHALPY=method,
DENSITY=method, ENTROPY=method},
{PHI=method}, {HENRY}, {RVPMETHOD,
TVPMETHOD}, {TRANSPORT=option},
{property(qualifier)=method, REFPROP=SIMSCI}
SET=setid ,{DEFAULT}...
NOTES TEXT = Notes line (up to 256 characters)
SYSTEM This entry selects a predefined system of

thermodynamic property methods as tabulated in Table
1-6. There are no default methods. If the SYSTEM entry
is missing, the user must select individual methods
using the KVALUE, ENTHALPY, ENTROPY, and
DENSITY entries described below. SYSTEM property
methods may be overridden individually with the
additional use of the KVALUE, ENTHALPY,
ENTROPY, and DENSITY entries. Methods for other
properties usually are optional, but may be required in a
specific problem.
The optional qualifier on the SYSTEM entry indicates
which equilibrium calculations apply to the problem.
Omitting the qualifier is the same as specifying VLE.
VLE This qualifier indicates that the
methods included in the selected
system apply to vapor-liquid
equilibrium calculations (normally, a
single liquid phase is present). It is the
default.
VLLE Include this qualifier to indicate that
the selected system of methods apply
to vapor-liquid- liquid equilibria
calculations. When used, the program
rigorously models the equilibrium
between the two liquid phases. If
omitted, VLE is the default.

KVALUE(VLE) This entry is used to select a method from Table 1-4 to
KVALUE(LLE) calculate vapor-liquid and liquid-liquid phase
equilibrium K-values. The VLE qualifier may be
omitted since it is the default. The METHOD statement
must include KVALUE(VLE) when the SYSTEM entry
is missing.
or
KVALUE(VLLE) This entry may be used instead of KVALUE(VLE) and
KVALUE(LLE) when both use the same generators.
KVALUE(SLE) When a problem includes solid phase components, this
optional entry declares the method (chosen from Table
1-4) used to determine solid-liquid equilibria. Use of
this entry does not eliminate the need to declare either a
VLE or VLLE K-value method. See Chapter 7, Solid
Solubility Methods.
DENSITY This entry is used to select a method from Table 1-4 to
perform vapor and liquid density calculations when no
SYSTEM entry is present. Omitting the qualifier or
specifying VL as the qualifier indicates that the selected
method applies to all liquid and vapor phases. To apply
different methods for vapor and liquid calculations, use
both DENSITY(V) and DENSITY(L). Refer to Chapter
2, Application Guidelines, for recommendations on
which density method to use.
Note: Correlations and data for solid phase component density

are supplied in the Component Data Category.
ENTHALPY This entry is used to select a method fromTable 1-4 to
perform vapor and liquid enthalpy calculations when no
SYSTEM entry is present. Omitting the qualifier or
specifying VL as the qualifier indicates that the selected
method applies to all liquid and vapor phases. To apply
different methods for vapor and liquid calculations, use
both ENTHALPY(V) and ENTHALPY(L).
Note: Correlations and data for solid phase component enthalpy

are supplied in the Component Data Category.
ENTROPY This entry is used to select the method from Table 1-4
used for vapor and liquid entropy calculations.
Specifying VL or omitting the qualifier indicates that
the selected method applies to all liquid and vapor
phases. Use both ENTROPY(V) and ENTROPY(L) to
apply different methods to vapor and liquid calculations.
This entry usually is optional, but may be required when
a problem includes any of the unit operations or options
shown in Table 1-5.

Note: Not all systems available on the SYSTEM entry declare an
entropy method, and the ENTROPY entry still may be required.
Refer to Table 1-5 to determine which features require an entropy
method.
PHI This entry specifies the method from Table 1-4 used to
compute pure component and mixture vapor fugacity
coefficients (i). It is available only when using a liquid
activity method to calculate equilibrium K-values. A
fugacity method generally is used for high pressure
applications. The default is PHI=IDEAL. See Hayden-
OConnell Vapor Fugacity on page 6-64 and
Truncated Virial Vapor Fugacity on page 6-68.
HENRY The HENRY option applies pre-stored or user-supplied
Henry's Law data to model dissolved gases in a liquid
solution. This option is available only when using a
liquid activity method for K-value calculations. This
method employs linear mixing rules to compute ln(H).
See Henrys Law for Non-condensible Components
on page 6-57.
RVPMETHOD, These options are used to specify the thermodynamic
TVPMETHOD method to be used for RVP and TVP calculations. If
either RVPMETHOD or TVPMETHOD appears, the
other method defaults to that method specified. If
neither RVPMETHOD nor TVPMETHOD is specified,
then the stream RVP and TVP are calculated by the
thermodynamic method used in generating that stream.
TRANSPORT This entry requests the calculation of all transport
properties, including vapor and liquid viscosities, vapor
and liquid thermal conductivities, and liquid surface
tension values. Alternatively, use one or more of the
options described below to select transport property
methods individually. The program does not calculate
transport properties unless requested by the presence of
these entries. Entering TRANSPORT with no argument
is the same as using TRANSPORT=PURE. See
Transport Properties on page 8-1.
property This entry requests the calculation of special refinery
properties. See Special Stream Properties on page 8-
10.
REFPROP This keyword is used to supply the default methods for
calculating special stream refinery properties. The
SIMSCI option is used to specify the PRO/II software
v3.3 calculation methods and v3.3 properties. These
properties are KVIS, CLOU, POUR, FLPO (CC,OC),
SULF, and CETA.

SET This entry supplies a label that uniquely identifies the
method set. When a problem includes more than one
method set, each set must have an assigned label. The
labels allow each unit operation to select a specific set of
thermodynamic methods. The setid is an unique
identifier and may contain up to 12 alphanumeric
characters, excluding delimiters and embedded blanks.
See Multiple Thermodynamic Sets on page 1-30.
NOTES This statement must be placed along with the METHOD
statement of the specific thermodynamic set to which
the information pertains. One NOTES statement is
allowed per thermodynamic set.
TEXT This entry specifies the actual notes line(s). The Notes
Data can be specified in multiple lines, but only the first
256 characters will be scanned and the rest will be
discarded.
Predefined Systems
General Information
The use of predefined systems is a convenient, shortcut method of
specifying thermodynamic sets. A predefined system may be
selected by using the SYSTEM keyword. This option uses a single
entry to declare several property methods at once.
In general, each predefined system includes methods for computing
K-values, vapor and liquid enthalpies, and vapor and liquid densi-
ties. Predefined systems using generalized and equation of state
methods and special package systems also include an entropy prop-
erty method. Predefined liquid activity systems do not include an
entropy method.
As an example, the following METHOD statement uses the SRK
system of thermodynamic generators (see Soave Modified
Redlich-Kwong on page 4-1, for keyword definitions):
METHOD SYSTEM=SRK
From Table 1-6, we can see that this is equivalent to the following
METHOD statement:
METHOD KVALUE=SRK, ENTHALPY=SRK, ENTROPY=SRK, &
DENSITY(V)=SRK, DENSITY(L)=API
or even more explicitly:
METHOD KVALUE=SRK, &
ENTHALPY(V)=SRK, ENTHALPY(L)=SRK, &
ENTROPY(V)=SRK, ENTROPY(L)=SRK, &

Input Overview
Table 1-6 shows the predefined systems available and the property
methods used for each one.
Table 1-6: Systems of Thermodynamic Methods

Methods for Evaluating Properties
VLE or Enthalpy Density
SYSTEM VLLE K-values vapor liquid Entropy vapor liquid
Generalized Correlation Methods
IDEAL VLE IDEAL SATD SATD IDEAL SATD
GS VLE1 GS CP CP CP SRK API
CS2 VLE1 CS CP CP CP SRK API
IGS VLLE1 IGS CP CP CP SRK API
GSE VLE1 GSE CP CP CP SRK API
CSE VLE1 CSE CP CP CP SRK API
BK10 VLE1 BK10 JG JG CP IDEAL API
Equation of State Methods

SRK VLE1,3 SRK SRK SRK SRK SRK API
PR VLE1,3 PR PR PR PR PR API
SRKKD VLLE SRKKD SRKKD SRKKD SRKKD SRKKD API

SRKH VLLE SRKH SRKH SRKH SRKH SRKH API
SRKP VLLE SRKP SRKP SRKP SRKP SRKP API
SRKM VLLE SRKM SRKM SRKM SRKM SRKM API
SRKS VLLE SRKS SRKS SRKS SRKS SRKS API
PRH VLLE PRH PRH PRH PRH PRH API
PRP VLLE PRP PRP PRP PRP PRP API
PRM VLLE PRM PRM PRM PRM PRM API
UNIWAAL VLLE UNIWAAL UNIW UNIW UNIW UNIW API
BRWS VLE1 BRWS BRWS BRWS BRWS BRWS BRWS
HEXAMER VLLE HEXAMER HEXA HEXA HEXA HEXA API

LKP VLLE 1 LKP LKP LKP LKP LKP API
1 May decant free water 2 GS preferred to CS 3 VLLE available, but not recommended

PPR78 VLE1,3 PPR78 PPR78 PPR78 PPR78 PPR78 API
PSRK VLE3 PSRK PSRK PSRK PSRK PSRK API

1 May decant free water 2 GS preferred to CS 3 VLLE available, but not recommended

NRTL VLLE NRTL SATD SATD IDEAL SATD
UNIQUAC VLLE UNIQUAC SATD SATD IDEAL SATD
UNIFAC VLLE UNIFAC SATD SATD IDEAL SATD
UFT1 VLLE UFT1 SATD SATD IDEAL SATD
UNFV VLLE UNFV SATD SATD IDEAL SATD
WILSON VLE WILSON SATD SATD IDEAL SATD
VANLAAR VLLE VANLAAR SATD SATD IDEAL SATD
MARGULES VLLE MARGUL SATD SATD IDEAL SATD
REGULAR VLLE REGULAR SATD SATD IDEAL SATD
FLORY VLLE FLORY SATD SATD IDEAL SATD
Special Packages
ALCOHOL VLLE NRTL SRKM SATD SRKM SRKM SATD
GLYCOL VLLE SRKM SRKM SRKM SRKM SRKM API
SOUR VLLE3 SOUR SRKM SATD SRKM SRKM SATD
GPSWATER VLLE3 GPSWAT SRKM SATD SRKM SRKM SATD
AMINE VLLE3 AMINE SRKM AMINE SRKM SRKM SATD

1 2 3
May decant free water GS preferred to CS VLLE available, but not recommended

Multiple Thermodynamic Sets
General Information
In most cases, each problem includes a single set of methods for
calculating all thermodynamic properties. However, a flowsheet
may contain widely varying process conditions that dictate the use
of more than one set. To facilitate this, the program allows up to 100
methods in each problem.
All method sets defined in the Thermodynamic Data Category are
available for use in the remainder of the problem. When a single
method set is present, all unit operations use that set. When two or
more sets appear, each unit operation may select any of the defined
sets. Some units may use more than one set. For example, in
PRO/II software:
A rigorous heat exchanger may use one method set for the
shell side and a second for the tube side.
A chemicals column is known to have two liquid phases on
only two trays. To prevent the CHEMDIST algorithm from
performing CPU intensive three phase calculations on all
trays, a VLLE set is declared on those two trays, and a VLE
set is declared for the remainder.
The following hierarchy of defaulting governs the selection of ther-
modynamic methods applied to stream calculations.
1. Product streams use the thermodynamic methods of the unit
operation from which they flow.
2. Feed streams that are not products of unit operations use the
thermodynamic methods of the unit operations they feed.
3. In all other cases, a stream use either the default methods set or
the set assigned to it in the input file.
The Default Method Set

One set of thermodynamic methods serves as the default set. When
an unit operation does not explicitly specify a method set, the
default set prevails. Normally, the program assumes the first set
declared in the Thermodynamics Data Category is the default set;
however, the use may declare any set as the default by including the
DEFAULT keyword on the METHOD statement of that set.
Note: Only one default set may exist in each problem.

Method Set Requirements
When an input file contains two or more thermodynamic method
sets, each set must be assigned a unique label (identifier). The label
allows individual unit operations to select a desired set.
Each method set is a complete set; that is, it contains declared meth-
ods for all required properties.
Avoiding Inconsistent Methods

Improper use of multiple thermodynamic methods can cause seri-
ous discontinuities that produce erroneous results. For example,
both the SRK and Curl-Pitzer methods are based on deviations from
ideal gas values. However, they predict different enthalpy values for
a mixture at any given temperature and pressure. Thus, an adiabatic
flash using the SRK method predicts an incorrect temperature value
for a feed stream with a Curl-Pitzer enthalpy. The stream enthalpy
first should be reset by performing an isothermal, dew point, or
bubble point flash calculation (as appropriate) using the new
enthalpy method. The RESET unit operation in PRO/II software is
provided just for that purpose.
Multiple Method Sets in Distillation Columns

For rigorous column calculations, provision exists to consider the
column as comprised of sections, with different method sets used in
the sections. This option requires great care to ensure that the data
sets interface smoothly, without discontinuities when moving from
one section to another. Changes in enthalpy methods will nearly
always cause unrealistic temperature and flow profiles.

Examples
1.1: A hydrocarbon-water mixture is modeled using both VLE
and rigorous VLLE thermodynamics.
TITLE PROB=SETS
COMPONENT DATA
LIBID 1,C3/2,NC4/3,H2O
THERMODYNAMIC DATA
METHOD SYSTEM(VLE)=SRK, SET=2PHASE, DEFAULT
WATER DECANT=OFF
METHOD SYSTEM(VLLE)=SRKM, SET=3PHASE
STREAM DATA
PROP STREAM=1, TEMP=60, PRES=250, COMP=50/40/10
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3
TPSPEC PRES=160
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
METHOD SET=2PHASE
FLASH UID=F1
FEED 1
PROD V=4, L=5, W=6
TPSPEC PRES=160
RATE, VALUE=0.5
METHOD SET=3PHASE
END
The first thermodynamic set, identified as 2PHASE, uses the pre-

defined SRK set to calculate all thermodynamic properties. The use
of the VLE argument (which is the default) implies that, although
you can decant a pure water phase, you cannot perform rigorous liq-
uid-liquid equilibrium calculations. The declared SYSTEM (in this
example, SRK) allows a WATER statement (i.e., non-rigorous
LLE). Other systems (such as liquid activity methods) do not allow
a WATER statement.
The second set, identified as 3PHASE, uses the predefined
SRKM set. This method is better suited than SRK for rigorous three
phase calculations. The VLLE argument implies that all equilib-
rium calculations using this set will attempt to rigorously model two
liquid phases. A WATER statement is not allowed.

Free-water Decant Considerations
General Information
Free-water decant is useful when handling mixtures that form water
as a nearly pure immiscible phase. Such systems are common in
hydrocarbon-water mixtures in refinery and gas processing plants.
For engineering purposes, it may be assumed that the water phase is
pure. This reduces the computational time required to solve these
problems with rigorous VLLE models. See Table 1-4 for K-value
generators that support free-water decant. When free-water decant
is not supported for a particular thermodynamic set, the WATER
statement is disregarded by the program.
When the free-water decant option is turned on, water properties
except transport are calculated from the Keenan and Keyes steam
tables. By default, all values are calculated as if the water were at
saturated conditions, which saves a significant amount of CPU
time. If superheated steam is present, the PROPERTIES=STEAM
option should be selected. This will calculate steam properties
based on the full Keenan and Keyes equation of state for water.
Note: If the WATER option is used, the predefined system or K-

value method in use must be able to handle free water decant, or
else the WATER statement is ignored. When any of the pre-
defined or K-value generators SRK, PR, GS, CS, GSE, CSE,
IGS, LKP, BK10 or BWRS are selected, free water decant is
automatically activated. If water is to be treated as any other
component, or in a rigorous manner, WATER DECANT=OFF
must be selected. The WATER statement applies only for that
particular METHOD statement.
The GPSA method is based on the 12th edition of GPSA Data
Book, Figure 20-4. This option is useful for natural gas mixtures at
pressures above 2000 psia. The WICHERT method is based on the
article with the title New charts provide accurate estimations for
water content of sour natural gas by Gordon C.Wichert and
Edward Wichert from the Oil and Gas Journal dated Oct. 27, 2003.
The sour gas nomograph method uses H2S mole fraction, CO2
mole fraction, system temperature, and system pressure as inputs
and predicts the water content of the sour gas. This method is rec-
ommended for low pressures.

When the free-water decant option is turned off, water properties
are calculated from the prevailing property generators. Beware that
many of the standard generators (i.e., SRK, PR and GS), are poorly
suited for calculating properties of highly polar, non-hydrocarbons
such as water.
User-Added Water Enthalpy Methods

When the enthalpy generator of a thermodynamic method is set to a
user-added subroutine, it can be used for water enthalpy as well as
for all other properties. For example, the METHOD statement may
declare ENTHALPY(VL)=U6. This specifies user-added subrou-
tine UKHS6 to compute vapor and liquid enthalpies. Adding a
WATER statement normally forces water enthalpy to be computed
from a built-in water property method. Using the ENTHALPY=
USER entry on the WATER statement instructs PRO/II to use the
declared user-added subroutine (in this example, UKHS6) to com-
pute water enthalpies. Note the user-added method must be used
for both vapor and liquid phase enthalpy calculations.Note also the
user-added method used for water enthalpy always will be the same
user-added method used for the enthalpies of all the other compo-
nents.
.
Note: A WATER statement may appear only after a METHOD

statement. Therefore, the property options on the WATER state-
ment apply only to that thermodynamic set.
For example, the following WATER statement calculates water sol-
ubility in hydrocarbon using the API kerosene solubility curve (API
Technical Data book figure 9A1.4). It computes all enthalpies using
user-added subroutine UKHS6 (ENTH=USER on the WATER
statement refers to ENTHALPY(VL)=U6 on the METHOD state-
ment). The WATER statement options apply only to thermody-
namic set SRK only, as shown in this sample input:
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, SET=SRK, ENTHALPY(VL)= U6
WATER SOLUBILITY=KEROSENE, &
ENTHALPY=USER
...
METHOD SYSTEM=GS, SET=GS

Input Description
Water Handling Statement
WATER DECANT = ON or OFF, GPSA, WICHERT
SOLUBILITY= SIMSCI or EXTSIMSCI or KEROSENE or EOS or
LUBE or NAPH or APIKERO or PARA or GASO or
JP3 or JP-4,
PROPERTY= SATURATED or STEAM or IF97,
TRANSPORT = IF97 or SIMSCI,
ENTHALPY= PROPMETHOD or USER
DECANT This turns the water decant option on or off.

ON This is the default when SRK, PR, GS, CS, GSE, CSE, IGS, LKP,
BK10 or BWRS methods are used. Water is treated as a non-
rigorous component that may be decanted as a pure aqueous
phase. The hydrocarbon phase has some water dissolved in it
according to the calculated solubility. K-values for water are
computed from:
Kw = P0 / (X )
where: P0 is the partial pressure of water,
X is the solubility of water in the liquid
hydrocarbon phase,
is the system pressure.
OFF Water is treated as a regular component and all other entries on
the WATER statement are ignored.
GPSA When DECANT=ON is selected, the presence of this keyword
requests the calculation of water partial pressures based on the
12th edition of GPSA Data Book, Figure 20-4, instead of the
steam tables. This option is useful for natural gas mixtures at
pressures above 2000 psia.
WICHERT When DECANT=ON is selected, the presence of this keyword
requests the calculation of water partial pressures based on the
WICHERT method. This method is based on the article with the
title New charts provide accurate estimations for water content
of sour natural gas by Gordon C.Wichert and Edward Wichert
from the Oil and Gas Journal dated Oct. 27, 2003. This method is
recommended for low pressures
SOLUBILITY This statement selects the method or computing water solubility

in the hydrocarbon phase.
SIMSCI This is the default. Water solubility calculations are based on the
solubility of water in the following individual components:

Library components in the Paraffin, Naphthalene, Unsaturated
and Aromatic classes, carbon disulfide, methyl mercaptan,
ammonia, argon, carbon dioxide, helium, hydrogen chloride,
hydrogen sulfide, nitrogen, nitrous oxide, oxygen, sulfur dioxide,
and air. For pseudocomponents, the water solubility is calculated
as a function of the Watson K-factor.
Note When the SIMSCI option is used in a problem containing com-

ponents other than those listed above, or containing NONLIB com-
ponents, the program estimates the correlation parameters for these
components and prints a warning message.
EXTSIMSCI When SIMSCI method is used for calculating Solubility of water
in hydrocarbon, it has a limitation for temperatures below 0 deg
C. If tried below 0 Deg C, SIMSCI method defaults to one value.
In such a case, make use of SIMSCI (Extrapolation method) to
get the extrapolated values in this temperature region.
KEROSENE Water solubility calculations are based on the data for the
solubility of water in kerosene, as presented in the API Technical
Data Book, Figure 9A1.4.
EOS The water solubility in the hydrocarbon phase is calculated from
the water K-value computed by the equation of state method.
Water-hydrocarbon interaction parameters are retrieved from the
databanks or estimated using the Kabadi-Danner method.
The following water solubility methods are from API Procedure
9A1.3 (1999). They calculate the solubility of water in various
liquid hydrocarbon mixtures.
Table 1-7: Properties of Water Solubility Fluids

Watson
Keyword Mixture API Molecular Characterization
Gravity Weight Factor
LUBE lube oil 29.3 425 12.4
NAPH Naphtha 54.3 147 12.2
APIKERO Kerosene 42.0 173 11.8
PARA Paraffin oil 28.8 350 12.1
GASO Gasoline 68.6 95 12.2
JP3 JP-3 fuel 54.7 112 11.7
JP4 JP-4 fuel 51.5 125 11.8

Additional entries on the WATER statement follow.
PROPERTY This option allows for the selection of the water
properties calculation basis.
SATURATED This is the default. Water properties are based on
vapor/liquid curves. This option is adequate for
most problems, and requires the least computing
time.
or The basis for computing water properties is the
Keenan and Keyes equation of state for water. It is
STEAM
recommended when water is present as a
superheated vapor.
or
IF97 This option uses the Industrial Formulation 1997
steam tables from the International Association for
the Properties of Water and Steam to compute water
properties.
TRANSPORT When IF97 Steam Table properties are in use, this
option allows transport properties (viscosities,
thermal conductivities and surface tension) to be
calculated using either IF97 methods or the pure
component library method.
IF97 This is there by default when PROPERTY is equal
to IF97. The water transport properties for pure
water and steam phases will be calculated using
IF97 methods. This entry will be ignored if
PROPERTY entry is not equal to IF97.
SIMSCI In PRO/II 9.3 and earlier versions, this method is
provided to duplicate water and steam transport
property results. Water transport properties will be
generated from pure component library values.
These transport properties are not pressure
dependent.
ENTHALPY Selects either a built-in water enthalpy generator or
a user-added subroutine.
PROPM Thermodynamic method systems that support a
WATER decant statement also have a built-in
property generator to compute the enthalpy of pure
water when water DECANT=ON. The default
PROPMETHOD option specifies using that built-in
property generator.

or A METHOD statement may declare a user-added
subroutine to calculate enthalpy. For example,
USER METHOD ENTH(VL)=U6 specifies user-added
subroutine UKHS6. as the enthalpy calculation
method. Normally, with DECANT=ON, water is
excluded and water enthalpies are computed using
the default PROPMETHOD.
The ENTHALPY=USER option instructs PRO/II to
use the user-added subroutine specified on the
METHOD statement to compute water enthalpies.
This essentially ignores the internal water enthalpy
generator.
Chapter 16, User-added Thermodynamic Property Methods, of

the User-Added Subroutine User Guide provides instructions for
creating and installing user-added thermodynamic subroutines that
perform enthalpy and other calculations.
Examples
1.2: SRK is used to model the phase behavior of a
hydrocarbon/ water mixture.
TITLE PROJECT=MANUAL, USER=SIMSCI, PROB=HC-WATER
COMPONENT DATA
LIBID 1,H2O/ 2,C3/ 3,NC4/ 4,NC5/ 5,NC6
THERMODYNAMIC DATA
METHOD SYSTEM=SRK
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=20/20/20/20/20
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
Vapor-liquid-liquid Equilibrium Considerations

General Information
Declaring a VLLE set
The program provides a number of methods that can rigorously cal-
culate vapor-liquid-liquid equilibrium. Most unit operation modules
support this capability. The user must specifically request VLLE
calculations on the METHOD statement in one of three ways:

by including the VLLE qualifier when using the SYSTEM
entry (Table 1-8).
by including the VLLE qualifier when using the KVALUE
entry to declare the method used to calculate equilibrium
K-values (Table 1-8).
by including both a KVALUE(VLE) and KVALUE(LLE)
entry to declare the method used to calculate equilibrium
K-values (Table 1-8).
When entering K-value data, VLE and LLE data are entered on sep-
arate KVALUE(VLE) and KVALUE(LLE) property statements
respectively. See Chapters 3 and 4. All other input requirements for
VLLE are the same as for VLE method sets. Table 1-8 lists the
method systems that support rigorous VLLE modeling.
Often, not all the unit operations in a problem perform VLLE calcu-
lations, making it desirable to include both VLE and VLLE meth-
ods sets in a single problem. The user may define separate method
sets for the VLE and VLLE methods. Unit operations that use the
VLE method will not attempt VLLE calculation, substantially
reducing computational time.
Table 1-8: VLLE Predefined Systems and K-value Generators

K-value Method System
SRK1 AMINE SRK1 NRTL
SRKM NRTL SRKM UNIQUAC
SRKKD UNIQUAC SRKKD UNIFAC
SRKH UNIFAC SRKH UFT1
SRKP UFT1 SRKP UFT2
SRKS UFT2 SRKS UFT3
PR1 UFT3 PR1 UNFV

PRM UNFV PRM VANLAAR
PRP MARGULES PRP REGULAR
UNIWAALS REGULAR UNIWAALS FLORY
IGS FLORY IGS ALCOHOL
LKP SOUR LKP GLYCOL
HEXAMER GPSWATER HEXAMER SOUR
AMINE GPSWATER
PPR78 PPR78

Table 1-8: VLLE Predefined Systems and K-value Generators
K-value Method System
PSRK PSRK
1
VLLE available, but not recommended.
Liquid-liquid equilibrium (LLE) calculations are a subset of VLLE.

For example, a VLLE methods set must be declared when modeling
a liquid-liquid extraction (LLEX) unit operation.
Table 1-9: Available Databanks

BANK= Method Type of Data
VLE and LLE interaction
SIMSCI NRTL
coefficients
VLE and LLE interaction
UNIQUAC
coefficients
SRK
PR
binary
SRKH
interactions
PRH and pure
component
SRKM
alpha values
PRM
SRKP
PRP
SRKK
SRKS
PPR78
BWRS binary interactions
RK1 / RK2 interaction coefficients
COSTALD component critical properties
RACKETT component Rackett properties
HENRY Henrys Law solubility data
binary coefficients for specific
ALCOHOL NRTL
components
binary interactions and pure
GLYCOL SRKM
component alphas

Table 1-9: Available Databanks
BANK= Method Type of Data
NONE omit all databank data
AZEOTROPE= Method Type of Data
All liquid activity azeotropic data for pairs of
SIMSCI
methods components
NONE omit all azeotropic databank data
The following example shows three equivalent input sections that

declare VLLE phase behavior. Each of these files uses the NRTL
binary interaction parameters as supplied in the SIMSCI databank.
THERMODYNAMIC DATA
METHOD SYSTEM(VLLE)=NRTL
THERMODYNAMIC DATA
METHOD KVALUE(VLLE)=NRTL, ENTHALPY=LIBRARY
THERMODYNAMIC DATA
METHOD KVALUE(VLE)=NRTL, KVALUE(LLE)=NRTL, &
ENTHALPY=LIBRARY
The user may specify any number of the available databanks by
using the BANK option on each property statement or the AZEO-
TROPE option for azeotropic data. BANK=SIMSCI is the default
specification for all properties except for GLYCOL and ALCOHOL
package K-values. The program searches the databanks in the order
they appear on the PROPERTY statement, and automatically
retrieves any data required for the property method (specified on the
METHOD statement).
Any data supplied in the Component Data Category of input or on
data statements in the Thermodynamic Data Category of input are
used instead of the data retrieved from the databanks. The
BANK=NONE entry suppresses all databank operations.
The following thermodynamic data section,
METHOD KVALUE=NRTL, ...
KVALUE BANK=SIMSCI, ALCOHOL
searches the SIMSCI databank, then the ALCOHOL databank for
VLE interaction parameters.

Specifying Key Components
Specifying VLLE equilibrium on the METHOD statement allows
the use of the two optional entries, L1KEY and L2KEY. These two
entries allow the user to specify the dominant component in the L1
and L2 phases. If these entries are missing, the program estimates
the key components during each K-value evaluation. The most
dense stream forms the L2 or W phase. If one of the liquids is an
aqueous phase, water will (in the majority of cases) be designated
as the L2KEY component.
Specifying Separate VLE and LLE Models

When specifying different K-value methods for VLE and LLE cal-
culations, or supplying different interaction parameters for VLE and
LLE calculations using the same method, some thermodynamic
inconsistency is necessarily introduced. Unfortunately, model
parameters regressed to VLE data seldom do an adequate job of
modeling LLE, and vice-versa. Using different VLE and LLE meth-
ods of data can overcome this problem. The user should be aware,
however, that for a system that exists in all three phases, V, L1, L2,
the L1 and L2 phases will be in equilibrium according to the LLE
method data. The V-L1 and V-L2 equilibria, according to the VLE
method/data, are averaged to give compromise V-bulk L equilib-
rium. Each L phase may not necessarily be at its bubble point, or in
equilibrium with the vapor phase, at the final conditions of pressure,
temperature and individual phase composition.
In the following example, the first thermodynamic set uses the
SRKM equation of state. The second set uses conventional SRK.
...
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, SET=SRK_VLE
METHOD SYSTEM=SRKM, SET=SRK_VLLE
STREAM DATA
...
When retrieving interaction parameters from the SIMSCI databank,
the program follows some special rules to minimize these inconsis-
tencies:
If no KVALUE(VLE) or KVALUE(LLE) statements are given (i. e.,
all data are retrieved from the SIMSCI databank), the program
searches the LLE databank for interaction parameters first, and the
VLE databank second for all data. Thus all phases will be governed
by the same set of coefficients as follows:

VLE Interface LLE Interface
LLE databank LLE databank
VLE databank VLE databank
Set interaction parameter Set interaction parameter
to zero to zero
If a KVALUE(VLE) statement is given, but KVALUE(LLE) is not

given, the interaction parameters for the VLE and LLE interfaces
are searched for in the following order:
KVALUE (VLE) statement KVALUE (VLE) statement
LLE databank LLE databank
VLE databank VLE databank
Use FILL option for missing Use FILL option for missing
parameters if requested parameters if requested
Set interaction parameter Set interaction parameter
to zero to zero
If a KVALUE(LLE) statement is given, the interaction parameters

are searched for in the following order:

KVALUE (VLE) statement KVALUE (VLE) statement
VLE databank LLE databank
Use FILL option for missing VLE databank
parameters if requested
Set interaction parameter Use FILL option for missing
to zero parameters if requested
Set interaction parameter
to zero
For more information on the use of the FILL option, see Filling in
Missing Parameters on page 4-27 for equations of state and Fill-
ing in Missing Parameters on page 6-52 for liquid activity meth-
ods.
Input Description
The METHOD Statement
METHOD SYSTEM(VLLE)=method, {L1KEY=i, L2KEY=j,}...

or
METHOD KVALUE(VLLE)=method, {L1KEY=i, L2KEY=j}, ...
or
METHOD KVALUE(VLE)=method, and
KVALUE(LLE)=method, {L1KEY=i, L2KEY=j,}...
SYSTEM(VLLE) This selects the VLLE predefined thermodynamic

or system or K-value generator to be used in the
KVALUE(VLLE) problem. The VLLE systems and K-value
generators available are given in Table 1-8.
L1KEY The L1KEY and L2KEY optional entries identify
and the most prevalent components expected in the first
L2KEY liquid phase and in the second liquid phase. These
entries are optional, and the program will estimate
the key components if they are not given. In the
majority of cases, water (when present) is
designated as the L2KEY component. Designation
of the two key components is suggested for
partially miscible systems containing little or no
water.
Note: While it is not necessary to designate the key components,

it is strongly recommended. Three-phase calculations are time
consuming. The algorithm uses an immiscible pair of components
to initialize the distribution of components between liquid phases.
Specifically declaring the key components instead of relying on
the calculations to find an appropriate pair significantly reduces
the time required to reach a solution.
K-value Data (Optional)

KVALUE(VLE) BANK=SIMSCI or NONE, ...
and
KVALUE(LLE) BANK=SIMSCI or NONE, ...
Note: When used for entering K-value data, VLE and LLE data
must be entered on separate property statements. See Chapters 3
through 6 for details on format and definition of the data entries.
Examples
E-1.3: A mixture of furfural, cyclohexane, heptane and nonane at
85 F and 1.5 atmospheres is to be modeled using NRTL
thermodynamics. This system forms two liquid phases. To
avoid arbitrary allocation of key components by the
calculation algorithm, the key components are designated
by the user. The explicit declaration of the dominant
components ensures that the Liquid2 stream contains the

cyclohexane-rich phase, while the Liquid1 stream contains
the furfural-rich liquid.
TITLE PROB=VLLE
COMPONENT DATA
LIBID 1,FURFURAL/2,CYHEXANE/3,HEPTANE/4,NONANE
THERMODYNAMIC DATA
METHOD SYSTEM(VLLE)=NRTL, L1KEY=1,L2KEY=2
STREAM DATA
PROP STREAM=1, TEMP=85, PRES(ATM)=1.5, &
COMP=35/25/20/10
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3, W=4
ADIA DP=0.0
END
E-1.4: A small amount of formic acid and benzene is present in

an aqueous stream. Note that, as the key components are
not specified by the user, the L2KEY component (i.e., the
dominant component in the second liquid product) is
designated to be water.
TITLE PROBLEM=VLLE
COMPONENT DATA
LIBID 1,BENZENE/2,FORMIC/3,H2O/4,BENZOIC
THERMODYNAMIC DATA
METHOD SYSTEM(VLLE)=NRTL, TRANS=PURE, PHI=HOCV
KVALUE(VLE) FILL=UNIF
KVALUE(LLE) FILL=UNIF
STREAM DATA
PROP STREAM=1, TEMP=86, PRES=21.3, RATE(M)=162.6, &
COMP(M)=1,0.1001/2,1.9059/3,160.6/4,0.0002, NORMALIZE
UNIT OPERATION
FLASH UID=F1

FEED 1
PROD V=2, L=3, W=4
ADIA DP=0.0
END
E-1.5: A mixed alcohol/water feed is modeled using the VLE

NRTL method. The NRTL binary interaction data are
obtained from the ALCOHOL databank.
TITLE PROBLEM=VLLE
COMPONENT DATA
LIBID 1,DIPE/ 2,IPA/ 3,H2O/ 4,BUTANOL
THERMODYNAMIC DATA
METHOD KVALUE(VLE)=NRTL, ENTH(V)=SRKM,
ENTH(L)=IDEA, DENS(V)=SRKM, DENS(L)=IDEA, &
SET=SET01, DEFAULT
KVALUE(VLE) BANK=ALCOHOL, SIMSCI
STREAM DATA
PROP STREAM=1, PRES=20, TEMP=150, RATE(M)=1000, &
COMP(M)=1,20/2,60/3,900/4,20, NORMALIZE
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3

ADIA DP=0.0
END

Chapter 2
Application Guidelines
This section presents simple heuristic rules for selecting suitable

methods for performing thermodynamic property calculations.
Note: Although these rules were developed specifically for the

PRO/II software, the general guidelines still apply to fluid flow
applications. However, the examples at the end of this section
were developed specifically for this program.
General Information
Usually, there are several thermodynamic methods suitable for any
given application. The user always should try to determine which
methods give the best representation of the whole flowsheet, while
trying to select the simplest, most appropriate thermodynamic
options. The user should bear in mind that the best thermodynamic
method is the one that gives the best agreement with reality. When
laboratory or actual operating data are available, it may be neces-
sary to try several options and compare the results to obtain the best
possible model.
The following guidelines are divided into four basic categories of
applications. These are:
Refinery and Gas Processing
Natural Gas
Petrochemical
Chemical and Environmental
For each application, the various types of unit operations encoun-
tered have recommended thermodynamic methods.

Refinery and Gas Processing Applications
Water Handling
For most systems containing water, it is perfectly satisfactory to use
the default water decant option with the simpler hydrocarbon ther-
modynamic methods. These are:
SRK, PR, CS, GS, CSE, GSE, IGS, BK10, BWRS.
For each of these methods, the amount of water dissolved in the
hydrocarbon phase is calculated using either the SIMSCI or the
KEROSENE correlation. The SIMSCI method is based on the solu-
bility of water in the pure components, while the KEROSENE cor-
relation is based on the solubility of water in kerosene, given in the
API Technical Data Book, Figure 9A1.4. In addition, SRK and PR
can use the EOS method for calculating the water solubility. See
Table 1-7 on page 2-1-36 for other water solubility options.
The remaining water may be decanted as a pure liquid water stream.
The properties of this pure water stream can be calculated using sat-
urated water properties or by using the full Keynan and Keyes equa-
tion of state for water. The Keynan and Keyes equation should be
used if water is present as super-heated vapor.
The program uses the vapor pressure of water at the temperature of
the system to calculate the amount of water in the vapor phase. The
user can select either the (default) built-in steam tables or the 12th
edition of GPSA Data Book, Figure 20-4 for the water vapor pres-
sure or the WICHERT method. The GPSA values should be used
for natural gas systems above 2000 psia (136 atmospheres). The
WICHERT method is based on the the article with the title New
charts provide accurate estimations for water content of sour natural
gas by Gordon C.Wichert and Edward Wichert from the Oil and
Gas Journal dated Oct. 27, 2003.This method is recommended for
low pressures.
For systems where the solubility of hydrocarbon in water is signifi-
cant, a more accurate method should be used. The Kabadi-Danner
modification to the SRK equation of state (SRKKD) is recom-
mended. This method may be selected by using either
SYSTEM(VLLE)=SRKKD or KVALUE(VLLE)=SRKKD on the
METHOD statement. The SRKKD method performs rigorous
vapor-liquid-liquid equilibrium calculations to predict the amount
of water in the hydrocarbon phase and the amount of hydrocarbon
2-2 Application Guidelines

in the water phase. It uses interaction parameters for the water and
hydrocarbons based on the amount of water present in each phase.
Low Pressure Crude Systems

Vacuum towers and atmospheric crude towers are representatives of
low pressure crude systems. These units generally exhibit nearly
ideal behavior, and simpler methods can be used very successfully.
The accuracy of the results depends much more on the characteriza-
tion of the crude feed than on the thermodynamic method chosen.
The BK10 method usually is adequate and quicker than more com-
plex general hydrocarbon methods such as GS, SRK or PR. The
user may wish to solve the unit with BK10 as a first attempt, and
then use a more complex method if the results are not satisfactory.
If the results do not agree with plant data, the user should try differ-
ent assay and characterization methods before employing other
thermodynamic methods. The API method should be used for cal-
culating the liquid density.
Thermal cracking is a common source of error when modeling vac-
uum units. A laboratory analysis of the vacuum tower overhead
product can be used to estimate the amount of light ends to be added
to the feed stream in order to correctly model the column. In lieu of
a direct analysis, methane can be added to the feed and adjusted
until the temperature profiles match the plant data.
Recommended
Methods Comments
BK10 Fast and easy to use, and gives acceptable answers.

GS / IGS / GSE Comparable to BK10 for low pressure systems. Substituting
LK for CP enthalpies may improve answer.
SRK / PR The results will be somewhat better than with BK10 near the
top of the tower where light ends may predominate. May
require more CPU time than BK10.
High Pressure Crude Systems, FCCU, and Main Coker Fractionators

Towers above atmospheric pressure usually contain greater concen-
trations of lighter components and therefore require more complex
thermodynamic methods. BK10 has been used extensively in the
past for these types of applications, but PR, SRK, GSE, IGS, and
GS can be expected to give better answers. The user should remem-
ber that the characterization of the petroleum fractions is more

important than the thermodynamic method for obtaining good
agreement with plant data. The API method should be used for the
liquid density.
For Fluidised Catalytic Cracker Unit (FCCU) main fractionators,
the petroleum fractions are much more hydrogen deficient than are
crude fractions. Since most characterization correlations are derived
from crude petroleum data, it is expected that the results will be less
accurate than for crude fractions.
Recommend
ed Methods Comments
GS / GSE / IGS Usually faster than SRK or PR, but less accurate in the
presence of a high concentration of light components.
Substituting LK for CP enthalpies may improve the answers.
SRK / PR Use SRK or PR if light crudes dominate the top of the tower.
Reformers and Hydrofiners

These units contain streams with a high hydrogen content. For the
SRK and PR methods the component databanks contain extensive
binary interaction parameters for component pairs involving hydro-
gen. The API method should be used for the liquid density.
Historically, GS has been used successfully with hydrogen rich sys-
tems. In general, SRKM and PRM should give better results with
the improvement in interaction parameters over previous versions.
Recommended
Methods Comments
SRKM / PRM Recommended because of the high concentration of

hydrogen present.
Lube Oil and Solvent De-asphalting Units

These units generally have non-ideal components present and
require a more complex thermodynamic method. SRKM or PRM is
recommended, but the answers will only be as good as the interac-
tion parameters supplied by the user for the non-ideal components.
This complex method should not be used unless such data are avail-
able. If no specific data are available, SRKM yields results compa-
rable to SRK, and the general SRK or PR method should be used.
The API method should be used for the liquid density.

Recommended
Methods Comments
SRKM / PRM Recommended when using user-supplied interaction data

for non-ideal components.
SRK / PR Use in place of SRKM or PRM when no user-supplied
interaction data are available. These methods require less
CPU time than SRKM or PRM.
Natural Gas Systems

For systems with less than 5 percent N2, CO2 or H2S, general equa-
tions of state such as SRK, PR, or BWRS provide excellent
answers. The interaction parameters for hydrogen, carbon dioxide,
nitrogen, and hydrogen sulfide are estimated using general correla-
tions when user-supplied interaction parameters are not available.
The BWRS method should be used with more caution, since it does
not extrapolate as well as SRK or PR into the supercritical region.
For systems with higher concentrations of the sour gases, the
default interaction parameters may not produce the best possible
answers. A general equation of state should still be used, but the
user should supply better interaction parameters to obtain good
results.
The default water decant option is usually acceptable. However, for
high pressure systems where the solubility of hydrocarbon in water
is significant and the solubility correlations of water in hydrocarbon
break down, the Kabadi-Danner modification to SRK should be
used with the VLLE option. The Kabadi-Danner option as imple-
mented has been extended to include nitrogen, hydrogen, carbon
dioxide, carbon monoxide, and hydrogen sulfide as specific compo-
nents. Petroleum fraction components are approximately identified
as paraffins, olefins, aromatics, or naphthenes, according to their
Watson characterization parameters, when suitable interaction
parameters are supplied by the user.
For systems containing non-hydrocarbon components (such as
methanol and glycol acting as inhibitors), more complex mixing
rules must be used to obtain good results. The SRKM and PRM
methods work well for these systems, but the user must ensure that
all the relevant interaction data are entered. These methods auto-
matically access the SIMSCI databank to retrieve all available inter-
action data, but the user may have to supply additional data if the

data for a component pair are not in the bank. The VLLE option
must be specified on the METHOD statement if two liquid phases
are expected.
Use the COSTALD method to calculate the liquid density for
Tr < 0.95. This option is not the default method and must be specif-
ically requested.
Recommended
Methods Comments
SRK / PR / BWRS These methods give good results for most hydrocarbon and
hydrocarbon-water systems.
SRKKD Use SRKKD(VLLE) for high pressure systems containing
hydrocarbons and water. SRKKD uses more CPU time than
SRK. Do not use SRKKD if other polar components, such
as methanol, are present.
SRKM / PRM / Use these methods for systems containing water and other
SRKS polar components, such as methanol. Always use the VLLE
option with these methods for this type of system.
SRKP / PRP Simpler versions of SRKM and PRM. These methods are
not as good as SRKM or PRM and do not significantly
reduce CPU time.
Glycol Dehydration Systems

The GLYCOL bank of interaction parameters for the SRKM
method has been created for these systems. This bank is a sub-sec-
tion of the general SRKM interaction bank, and the data have been
fitted over a narrow range of typical temperatures and pressures for
TEG, and, to a lesser extent, EG, and DEG dehydration systems.
Invoking the GLYCOL system automatically retrieves the GLY-
COL interaction parameters.
Recommended
Methods Comments
GLYCOL The program includes special interaction coefficients for

typical TEG, and, to a lesser extent, EG, and DEG
dehydration systems.
Sour Water Systems

There are two methods available for the prediction of vapor-liquid
equilibrium. They are identified on the METHODS statement as
SOUR and GPSWATER.

SOUR
This method is based on a combination of the API/EPA SWEQ
(Sour Water EQuilibrium) model for sour water components (H2O,
H2S, CO2 and NH3) and SRKM for all other components. The rec-
ommended range of application is:
Temperature (F) 68 < T < 300 F
Pressure P < 1500 psia
Composition xwtNH3 + xwtCO2+ xwtH2S< 0.30
where xi is the weight fraction in the aqueous phase.
In general, this method is recommended over the GPSWATER

when CPU time is a consideration.
GPSWATER
This method is based on the GPSWAT program for calculating sour
water equilibrium. The GPSWAT method is used for generating K-
values for sour water components (H2O, H2S, CO2, NH3, CO,
CS2, COS, MeSH and EtSH). All other components are calculated
using SRKM. The recommended range of application is:
Temperature (F) 68 < T < 600 F
Pressure P < 2000 psia
Composition xwtNH3 < 0.40
Sour gas partial pressure PCO2+ PH2S < 1200 psia
The GPSWATER method is valid for a broader range of applica-

tions than the SOUR method, but requires significantly more com-
putation time.
Amine Systems
The AMINE package is used for generating K-values for aqueous
amine systems and sour gases including H2S, CO2, H2O, MEA,
DEA, DGA, DIPA, and MDEA. All other component K-values are
calculated using SRKM. Water and exactly one amine must be pres-
ent when using the package.
Data for the equilibrium constants are provided for MEA, DEA,
DGA, DIPA, and MDEA. However, the DIPA data are not recom-
mended for use in final designs. For MDEA, the model is modified
to include composition effects.

Dimensionless residence time corrections to amine K-value calcula-
tions may be specified by the user. These corrections are only
appropriate for systems involving MDEA or DGA. For all other
amines, the entry is ignored if it appears. The user can override the
default value of 0.3 under the KVALUE keyword in the THERMO
DATA section in order to better fit the plant data. A RESI value of
1.0 corresponds to an equilibrium model.
The data package may be used over the ranges of concentrations
and acid gas loadings typically encountered in gas processing. This
includes the temperatures and pressures for the contactor and regen-
erator. MEA processes have been successfully applied in the 25-100
psig operating range. However, DEA does not perform well under
these conditions and is generally used at higher pressures. Typi-
cally, contactor pressures for MEA contactors may range from 100
to 500 psig, with DEA systems ranging from 100 to 1000 psig. The
amine regenerators are generally operated at temperatures less than
275 F, with a typical temperature being 255 F. Amine solution
strengths for MEA and DEA are generally within 15-25 wt% and
25-35 wt%, respectively.
The AMINE package accounts for heats of reactions by applying a
correction to IDEAL saturated liquid enthalpies. SRKM is also used
for actual vapor densities and IDEAL values are used for liquid
densities.
Petrochemical Applications
Light Hydrocarbon Systems
SRK, PR, or BWRS is recommended for most light-hydrocarbon,
petrochemical applications.
When solubility of water in hydrocarbon and hydrocarbon in water
becomes important, as it would at high pressure, SRKKD(VLLE) is
recommended.
Use the COSTALD method for liquid density. This option is not the
default and must be requested specifically.

Recommended
Methods Comments
SRK / PR / Good for systems containing only similar hydrocarbon

BWRS types (e.g., all paraffins). Water may be decanted as a pure
aqueous phase.
SRKKD Use SRKKD for more accurate results with hydrocarbon-
water systems. SRKKD uses more CPU time than SRK.
Aromatic Systems
For systems containing all aromatic components, use the ideal
method at low pressures as these systems are very close to ideal.
For systems at pressures above 2 atmospheres, use GS, SRK, or PR
for a more accurate result.
The liquid density can be calculated using the ideal, the default API,
or the COSTALD methods. The COSTALD method has data for
many aromatic components, will give good results at higher tem-
peratures, and is better than API if any light components such as
methane are present. For systems at high temperatures with all aro-
matic components, the API method is as good and uses less CPU
time. The ideal method is best at lower temperatures and should not
be used if the temperature is significantly higher than the boiling
point of any one component.
Recommended
Methods Comments
IDEAL Recommended for systems at low pressures below 2 atm.

GS / SRK/ PR Recommended for systems at pressures above 2 atm.
IDEAL / API / Recommended for liquid density.
COSTALD
Aromatic/Non-aromatic Systems
Traditionally, these systems are difficult to model accurately.How-
ever, new equation-of-state mixing rules and alpha formulations can
give excellent results when appropriate interaction parameters and
alpha parameters are available. The SIMSCI databank includes a
large number of interaction parameters, but the user should verify
the availability of all critical parameters to ensure getting good

results. It is not necessary to use the VLLE option unless polar com-
ponents, such as water, are present.
For aromatic / non-aromatic extraction systems (e.g., DMF extrac-
tion of butadiene), use a liquid activity method such as NRTL.
Equations of state using the advanced mixing rules can model this
system as well but require more CPU time to obtain the same
results. As with all systems of this type, the results are only as good
as the supplied data. The SIMSCI databank has a large amount of
interaction data stored for the advanced mixing rules and the NRTL
and UNIQUAC liquid activity methods. However, the user must
ensure that all important interactions are covered in order to get
good results. The liquid activity methods have an advantage over
equations of state, since they can use the UNIFAC FILL option to
estimate any missing binary interaction parameters.
Systems that include light gases can be modeled using the HENRY
option in conjunction with the liquid activity methods. This is
acceptable when the light gases are present in small quantities.
However, if the gases are present in large quantities, it is better to
employ an equation of state using one of the advanced mixing rule
methods. These calculate the solubilities of the gases more rigor-
ously.
Recommended
Methods Comments
SRKM / PRM / Use any of these methods for aromatic / non-aromatic

SRKH / PRH systems. Also use them for extraction systems at high
pressure, or when large quantities of supercritical gases are
present.
NRTL / Use these liquid activity methods for extraction systems,
UNIQUAC such as the extraction of butadiene using DMF. Use the
Henry option to model any supercritical gases present in
small quantities. Use the UNIFAC FILL option to estimate
missing binary pairs.
Non-hydrocarbon Systems
These systems typically contain oxygen, halogen, or nitrogen deriv-
atives of hydrocarbon components and tend to be highly non-ideal.
For low pressure systems, use a liquid activity coefficient method.
For single phase systems, the WILSON, NRTL, and UNIQUAC
methods are equally good. The Wilson method is the simplest and
requires the least amount of computer time. Simpler methods, such

as VANLAAR and MARGULES, are not as good, since they often
do not model the more non-ideal systems accurately.
For systems containing two liquid phases, the NRTL or UNIQUAC
method should be used. The SIMSCI databank contains a large
number of binary interaction coefficients for both VLE and LLE
systems. In order to get good results, the user must ensure that all
significant binaries are supplied in the input. The UNIFAC FILL
option can be used to fill in any missing binary data, but should be
used only if interaction data are available for most of the binary
pairs. If the user has no data, the SYSTEM= UNIFAC option can be
used, since it has group interaction data available for both VLE and
LLE applications.
For high pressure systems, the program offers several methods for
modeling the vapor phase fugacity. These methods should be used
only if the system pressure is significantly higher than the pressure
at which the interaction coefficients were regressed. Interaction
coefficients regressed from high pressure data may already include
any vapor phase non-ideality in the liquid phase interaction coeffi-
cients. The user should always determine whether or not any user-
supplied interaction parameters include vapor phase fugacity. All of
the parameters in the SIMSCI databank except for components such
as carboxylic acids were regressed without a vapor phase fugacity
method. For systems with carboxylic acids such as acetic acid, it
would therefore be appropriate to use PHI=HOCV.
Supercritical gases present in small quantities can be modeled using
the Henry option. If they are present in large quantities, or if the
system is at high pressures (usually greater than 10 atmospheres),
an equation of state using one of the advanced mixing rules should
be selected. These are the SRKH, PRH, SRKM, PRM, SRKS,
SRKP and PRP methods. The SRKM, SRKS or PRM methods are
recommended for the non-hydrocarbon systems discussed here.

Recommended
Methods Comments
WILSON Use WILSON for slightly non-ideal systems. Use the

HENRY option to model small amounts of non-
condensible gases. Use the UNIFAC FILL option to fill in
missing binary interaction data.Do not use WILSON for
VLLE systems.
NRTL / Use either of these methods for all non-ideal systems. Use
UNIQUAC the Henry option to model small amounts of non-
condensible gases. Both methods model VLLE systems as
well as VLE systems. Use the UNIFAC FILL option to fill
in missing binary interaction data.
SRKM / PRM / Use for systems at higher pressure or when large quantities
SRKS of non-condensible gases are present. Can be used for VLE
and VLLE systems.
SRKH / PRH Can be used as comparable alternatives to SRKS, SRKM
and PRM.
SRKP / PRP SRKS / SRKH / PRH / SRKM / PRM normally yield better
results than SRKP and PRP in these applications.
Alcohol Dehydration Systems

A special bank of interaction coefficients for the NRTL method has
been created for alcohol dehydration systems. The coefficients are
applicable over a much narrower range than the general NRTL bank
coefficients. The user may specify either BANK=ALCOHOL on
the KVALUE statement or SYSTEM=ALCOHOL on the
METHOD statement. The SYSTEM=ALCOHOL option calculates
the vapor enthalpy and density using the SRKM method.
Recommended
Methods Comments
ALCOHOL Use for all alcohol dehydration systems.

NRTL / Use when valid user-supplied interaction data are available.
UNIQUAC
HF Systems
A special equation of state, HEXAMER, has been created for sys-
tems containing molecules that hexamerize in the vapor phase. This
method is recommended for HF systems such as the HF alkylation

process, and for the manufacture of refrigerants and other haloge-
nated compounds using HF.
Chemical and Environmental Applications

Non-Ionic Systems
Non-ionic systems typically contain oxygen, halogen, or nitrogen
derivatives of hydrocarbon components and tend to be highly non-
ideal. For low pressure systems, use a liquid activity coefficient
method. For single liquid phase systems, the WILSON, NRTL, and
UNIQUAC methods are equally good. The Wilson method is the
simplest and requires the least amount of computer time. Simpler
methods such as VANLAAR and MARGULES are less applicable,
since they often do not model the more non-ideal systems accu-
rately.
The NRTL or UNIQUAC method should be used for systems con-
taining two liquid phases. The SIMSCI bank contains a large num-
ber of binary interaction coefficients for both VLE and LLE
systems. In order to get good results, the user must ensure that all
significant binaries are included in the input. The UNIFAC FILL
option can be used to estimate any missing binary data but should
be used only if interaction data are available for most of the binary
pairs. If the user has no data, the SYSTEM=UNIFAC option can be
used, since it has group interaction data available for both VLE and
LLE systems.
The program offers several methods for modeling the vapor phase
fugacity in high pressure systems. These should be used only if the
system pressure is significantly higher than the pressure at which
the interaction coefficients were regressed. Interaction coefficients
regressed from high pressure data may already include any vapor
phase non-ideality in the liquid phase interaction coefficients.
Supercritical gases present in small quantities may be modeled
using the Henry option. If they are present in large quantities or if
the system is at high pressures, an advanced equation of state such
as SRKH, PRH, SRKM, PRM, SRKS SRKP, and PRP should be
selected

.
Recommended
Methods Comments
WILSON Use WILSON for slightly non-ideal systems. Use the

Henry option to model small quantities of non-condensible
gases.Do not use WILSON for VLLE systems.
NRTL / Use either of these methods for all non-ideal systems. Use
UNIQUAC the Henry option to model small quantities of non-
condensible gases. Both methods model VLLE systems as
well as VLE systems. Use the UNIFAC FILL option to
estimate missing binary interaction data.
SRKM / PRM / Use at higher pressures or when large quantities of non-
SRKS condensible gases are present. All three of these methods
can be used for VLE and VLLE systems.
SRKP / PRP These methods often yield less satisfactory results than the
SRKH, PRH, SRKM, SRKS, and PRM methods in these
applications.
Carboxylic Acid Systems

Carboxylic acids form dimers in the vapor phase. To obtain accu-
rate values for vapor fugacity, enthalpy, and density, use the
Hayden-O'Connell method to calculate the vapor phase properties.
Note that HOCV vapor phase fugacities must be used in conjunc-
tion with a liquid activity method.
Recommended
Methods Comments
HOCV The Hayden-O'Connell method produces the best values

for vapor phase properties in these applications. Use the
PHI=HOCV, ENTHALPY(V)=HOCV,
DENSITY(V)=HOCV options on the METHOD
statement.
Environmental Applications
These systems usually involve stripping dilute pollutants out of
water. The normal liquid activity methods, such as NRTL, do not
usually model these very dilute systems with sufficient accuracy. A
better approach is to use Henry's Law data for the components in
water. The Henry's Law data can be obtained from data sources,
such as the U.S. Environmental Protection Agency( EPA), or are
often available in the SIMSCI databank. In order to model the sys-
tems accurately, the user should supply temperature-dependent val-

ues for the Henry data whenever possible. Non-temperature
dependent data often over-predict the required amount of stripping
steam.
Solid Applications
Solid-liquid equilibria for most systems can be represented by the
van't Hoff (ideal) solubility method or by using user-supplied solu-
bility data. In general, for those systems where the solute and sol-
vent components are chemically similar and form a near ideal
solution, the van't Hoff method is appropriate. For non-ideal sys-
tems, solubility data should be supplied. For most organic crystalli-
zation systems, which are very near ideal in behavior, the van't Hoff
SLE method provides good results. The VLE behavior can usually
be adequately represented by IDEAL or VANLAAR methods.
Examples
E-2.1: This example models a hydrocarbon-water mixture that
contains less than 10% of water. The SRK method is
chosen.
TITLE PROB=HC-WATER
PRINT INPUT=ALL
COMP DATA
LlBID 1,H2O/2,C2/3,NC4/4,NC5/5,NC6
THERMO DATA
METHOD SYSTEM=SRK
WATER DECANT=ON
STREAM DATA
PROP STREAM=1,TEMP=100,PRES=100, &
COMP=40/100/100/100/100
UNIT OPERATIONS
FLASH
FEED 1
PROD V=2,L=3,W=4
ISOT TEMP=100,PRES=100
END

E-2.2 Refinery Application: A mixture of topped crude and
dissolved steam is to be modeled. The BK10 method gives
satisfactory results for this low pressure crude application.
TITLE PROB=VACUUM
DIMEN METRIC, PRES=MMHG
COMP DATA
LIBID 1,H2O/ 2,C2/ 3,C3
THERMO DATA
METHOD SYSTEM=BK10
STREAM DATA
PROP STREAM=1, TEMP=330, PRES=8000, RATE(V)=99.37, &
ASSAY=LV
TBP STREAM=1, PRES(MMHG)=760, &
DATA=0,257/ 5,324/ 10,380/ 20,399/ 30,435/ 40,455/ &
50,505/ 60,541/ 70,596/ 75,634
SPGR AVERAGE=0.9833, STREAM=1
PROP STREAM=2, TEMP=30, PRES=8000, RATE(V)=3.0, &
COMP=2,75/ 3,25
PROP STREAM=3, TEMP=330, PRES=8000, RATE(W)=318, &
COMP=1,100
PROP STREAM=4, TEMP=355, PRES=8500, PHASE=V, &
RATE(W)=908, COMP=1,100
UNIT OPERATIONS
MIXER
FEED 1,2,3
PROD L=5
COLUMN
PARA TRAY=2
FEED 5,1/ 4,2
PROD OVHD=6, BTMS=7,100
VAPOR 1,300/ 2,50
TEMP 1,355/ 2,371
HEAT 1,1
PRES 1,98/ 2,115
SPEC STREAM=7, RATE(V), VALUE=50.88
VARY HEAT=1
END
E-2.3 Sour Water Application: A sour water stream containing

CO2, H2S, NH3 and HCN is to be modeled. The amount
of HCN in the feed is small, and its distribution between
the liquid and vapor phases is not important. Either the
SOUR or GPSWAT methods could be used. However, an
examination of the feed shows that the sum of the weight
fractions of the sour gases exceeds 0.30. The GPSWAT
method is therefore preferred over the SOUR method.

TITLE PROB=SOUR
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,N2/ 2,CH4/ 3,H2S/ 4,NH3/ &
5,CO2/6,HCN/7,H2O
THERMODYNAMIC DATA
METHODS SYSTEM=GPSWAT
STREAM DATA
PROP STREAM=1, TEMP=120, PRES=25, PHASE=L, &
COMP(W)=1,2/ 2,3/3,8000/4,4000/ &
5,1200/6,0.238/7,25584.7
PROP STREAM=2, PRES=50, PHASE=V, COMP(M)=7,2000
UNIT OPERATIONS
COLUMN
PARA TRAY=7, IO=25, DAMP=0.5
FEED 1,1/ 2,7, NOTSEP
PSPEC TOP=20.8, DPCOL=2.1678
ESTI MODEL=CONV
END
E-2.4 Natural Gas Application: You wish to study a natural gas

stream that contains less than 1 percent of N2. Therefore,
the SRK equation of state method is used along with the
COSTALD liquid density method to model this
application.
TITLE PROB=LNG
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,N2/ 2,CH4/ 3,C2/ 4,C3/ &
5,NC4/ 6,NC5/ 7,NC6
THERMODYNAMIC DATA
METHODS SYSTEM=SRK, DENSITY(L)=COSTALD
STREAM DATA
PROP STREAM=1, TEMP=10, PRES=50, PHASE=V, &
COMP(M)=1,2.6/2,93.7/3,1.94/4,0.95/ &
5,0.38/6,0.23/7,0.2
UNIT OPERATIONS
PHASE ENVELOPE
EVALUATE STREAM=1, LFRAC=0.90, IPLOT=OFF
END

E-2.5 Petrochemical Application: A binary aromatic mixture of
n-methyl-formamide (NMF) and tert-butylformamide
(TBUTFORM) is to be modeled at a pressure of 3
atmospheres. The SRK K-value method provides good
results for aromatic systems above 2 atmospheres. The
COSTALD liquid density method provides good results
for aromatic systems at low temperatures.
TITLE PROB=AROM
PRINT INPUT=ALL
COMP DATA
LIBID 1,NMF/ 2,TBUTFORM
THERMO DATA
METHOD SYSTEM=SRK, DENS(L)=COSTALD
STREAM DATA
PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, &
COMP=1,25/ 2,75
UNIT OPERATIONS
COLUMN
PARA TRAY=10, CHEM=40, DAMP=0.6
FEED 1,5
COND TYPE=BUBB, PRES(ATM)=3
PSPEC PTOP(ATM)=3, DPCOL=0.5
DUTY 1,1,10/ 2,10,10
SPEC RRATIO, VALUE=5
SPEC STREAM=3, COMP=2, FRAC, VALUE=0.9
VARY DUTY=1,2
ESTI MODEL=CONV
END

E-2.6 Chemical and Environmental Application: A water-
hydrocarbon stream is to be flashed at 1 atmosphere. The
presence of acetic and acrylic acids in the stream
necessitates the use of the Hayden-O'Connell vapor
fugacity method to account for the vapor phase dimer
formation. The NRTL method will be used to calculate
VLE equilibria. The HENRY option is selected to model
the supercritical components.
TITLE PROB=ACIDS
PRINT INPUT=ALL
COMP DATA
LIBID 1,H2O/ 2,O2/ 3,N2/ 4,C3/ 5,IC4/ 6,NC4/ &
7,NC5/ 8,ACETIC/ 9,ACRYLIC
THERMO DATA
METHOD SYSTEM=NRTL, PHI=HOCV, ENTH(V)=HOCV , &
DENS(V)=HOCV, HENRY
KVALUE BANK=SIMSCI, POYNTING=YES, FILL=IDEAL
HENRY BANK=SIMSCI
SOLUTE 2,3
STREAM DATA
COMP=1,0.80/ 2,2.0E-02/ 3,0.04/ 4,2E-02/ 5,5.0E-02/ &
6,0.05/ 7,1.0E-03/ 8,0.01/ 9,0.01
UNIT OPERATIONS
FLASH
FEED 1
PROD L=2, V=3
ISOT TEMP(C)=90, DP=0.0
END
E-2.7 Solid Application: Urea is to be precipitated from an

aqueous solution. Some library properties for urea and
water such as vapor pressure and heat capacity are
overridden with user-supplied values. The urea-water
mixture is non-ideal and so user solubility data are
supplied.

TITLE PROB=SOLIDS
PRINT INPUT=ALL
COMP DATA
LIBID 1,UREA/ 2,H2O
PHASE VLS=1
ATTR COMP=1, PSD(MIC)=147,208,295,417,589,833,1168
TTP(K) 1,4.0585E+02
PTP(PA) 1,9.31306E+01
FORMATION(V,J/KG,MOLE) 1,-2.458E+08,-1.582E+08
HFUS(J/KG,MOLE) 1,1.479E+07
VP(L,PA,K) CORR=20, LN, DATA=1, &
3.6805E+02,2.981E+02,2.8209E+01,-1.05E+04, &
1.0272E-01,0.0,0.0,0.0
LATENT(J,KG/K,MOLE) CORR=1, DATA=1, &
2.981E+02,2.981E+02,8.7864E+07,0.0, &
0.0,0.0,0.0,0.0
CP(S,J/KG,K,MOLE) CORR=1, DATA=1, &
4.0E+02,8.0E+01,1.725E+04,2.318E+02, &
7.9E-02,0.0,0.0,0.0
DENS(S,K,KG/M3,WT) CORR=1, DATA=1, &
300.0,20.0,1335.036
SVTB 1,-7.701601E-03
SLTB 1,1.889548E+02
SLTM 1,1.639447E+01
HVTB 1,-9.317743E-03
HLTB 1,8.7864E+04
HLTM 1,7.127574E+03
THERMO DATA
METHOD SYSTEM(VLE)=VANLAAR, KVALUE(SLE)=SOLDATA
KVALUE(VLE)
VANLAAR 1,2,0.8255,100.0
KVALUE(SLE)
SOLUTE 1
SOLDATA(K) 1,2,0.0,-1310.37,0.533619
STREAM DATA
COMP=1,25/ 2,75
UNIT OPERATIONS
CRYSTALLIZER
FEED 1
PROD OVHD=2, BTMS=3
RATING VOLUME=200
OPER SOLU=1, SOLVENT=2, TEMP=20, DP=0.0
GROWTH KG(M/S)=1.0E-07, GEXP=0.2
NUCLEATION KB=8.0E+13, RPM=100
END

Chapter 3
Generalized Correlations
These general purpose data generators may be used for a variety of

industrial applications but are primarily applicable to systems of
non-polar hydrocarbons. The program also allows the user to input
K-value data directly.
Ideal and Library Methods

Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=IDEAL
STREAM DATA
. . .
General Information
The IDEAL method calculates K-values, vapor and liquid densities,
and vapor and liquid enthalpies. LIBRARY methods to calculate
liquid entropies were discontinued starting with PRO/II software
version 4.1. These methods should be used with pure component
streams and streams with very similar components; for instance:
o-xylene / m-xylene / p-xylene / ethylbenzenestyrene.

Table 3-1: Attributes of IDEAL and LIBRARY Methods
Properties predicted by IDEAL and LIBRARY methods
K-values Liquid enthalpies
Liquid densities Vapor enthalpies
Vapor densities
Required pure component properties1
K-values - Vapor pressure correlations
Liquid enthalpy - Liquid enthalpy correlations
Vapor enthalpy - Liquid enthalpy and heat of vaporization
correlations
Liquid densities - Liquid density correlations
Vapor densities - Molecular weight
Suggested application ranges
Pressure - Low pressures
Two liquid phase behavior
Free-water - Not supported
decant
VLLE - Not supported
1 Automatically supplied for library and petroleum components. Must be
supplied by the user for non-library components.
Input Description
The THERMODYNAMIC DATA statement and the METHOD
statement are discussed in full in Chapter 1, Thermodynamic Data
Overview. The keywords relevant to the IDEAL method are dis-
cussed here.

METHOD SYSTEM=IDEAL, ...
or
METHOD KVALUE=IDEAL, ENTHALPY=IDEAL,
DENSITY=IDEAL
SYSTEM Selects a combination of compatible thermodynamic

property generators. When SYSTEM=IDEAL is chosen,
IDEAL K-values, densities, and enthalpies are assumed.
3-2 Generalized Correlations

KVALUE Selects the method for K-value calculations. Only VLE K-
value calculations are available with the IDEAL method.
Pure component vapor pressures and Raoult's law:
Pi = i Pisat
are used to calculate K-values.
ENTHALPY Selects the method for enthalpy calculations. IDEAL
(VL or methods may be selected for liquid and/or vapor phase
V and/or L) calculations.
DENSITY Selects the method for density calculations. IDEAL

(VL or methods may be selected for liquid and/or vapor phase
V and/or L) calculations.
Examples
E-3.1: Using the IDEAL methods, model a 50/50 mix of propane
and normal butane at 50 psia and 100 F. By choosing the
IDEAL system, Curl-Pitzer enthalpies are invoked.
TITLE PROB=IDEAL, PROJ=THERMO
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,IC4/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=IDEAL
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

E-3.2: For the same problem, explicitly declare IDEAL K-values,
enthalpies, IDEAL vapor density, and API liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE=IDEAL, ENTHALPY=IDEAL, &
DENSITY(V)=IDEAL, DENSITY(L)=API
E-3.3: For the same problem, use SRK for K-values and
enthalpies, and IDEAL densities.
THERMO DATA
METHOD KVALUE=SRK, ENTHALPY=SRK, DENSITY=IDEAL
or
THERMO DATA
METHOD SYSTEM=SRK, DENSITY=IDEAL
E-3.4: For the same problem, use SRK for everything except
liquid enthalpies. Use the IDEAL method instead for
liquid enthalpy calculations.
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, ENTHALPY(L)=IDEAL

Grayson-Streed
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=GS
STREAM DATA
. . .
General Information
The Grayson-Streed method calculates K-values. It is generally use-
ful for light to mid-range refinery hydrocarbons. It is also useful for
vacuum column and coker simulations when API87 is used. Refer
to the PRO/II Reference Manual for additional limitations.
Table 3-2: Attributes of Grayson-Streed Methods
Properties predicted by GS methods
K-values
Molecular weight Liquid molar volume
Critical temperature Acentric factor
Critical pressure Solubility parameter

Pressure < 3000 psia
Temperature 0 - 800 F
Free-water decant - Supported
1Automatically supplied for library and petroleum components. Must be supplied
by the user for non-library components.
Input Description
METHOD SYSTEM=GS, ...
or
METHOD KVALUE=GS, .

..

property generators. When SYSTEM=GS is chosen, GS
K-values, Curl-Pitzer (CP) enthalpies, CP entropies, API
liquid densities, and SRK vapor densities are assumed.
KVALUE Selects the method for K-value calculations. Only VLE
K-value calculations are available with the GS method.
Water Handling Options (optional)
WATER DECANT=ON or OFF, GPSA, WICHERT

SOLUBILITY=SIMSCI or EXTSIMSCI or KEROSENE
or EOS
(see Table 1-7 on page 2-1-36 for other options)
PROPERTY=SATURATED or STEAM
The GS K-value generator supports the free-water decant option.
Refer to Free-water Decant Considerations on page 1-33 for a
description of these input options.
Method-specific Pure Component Properties (optional)

...
Properties may be supplied that are active only when a specific
method is used. For a further description of these input parameters,
see Chapter 9, Method-specific Pure Component Data.
Examples
E-3.5: Using the GS methods, model a 50/50 mix of propane and
normal butane at 50 psia and 100 F. By choosing the GS
system, Curl-Pitzer enthalpies are invoked.
TITLE PROB=GS, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=GS
STREAM DATA
UNIT OPERATION

FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-3.6: For the same problem, use GS K-values, Lee-Kesler

enthalpies and densities.
THERMO DATA
METHOD KVALUE=GS, ENTHALPY=LK, DENSITY=LK
E-3.7: The same system as in Example 3.5 now contains 20%

water at a higher pressure. Use the GPSA Data Book,
water solubility by the API Technical Data Book, Fig.
9A1.4. Pure water properties are calculated using the
Keenan and Keyes steam tables.
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=GS
STREAM DATA
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

Chao-Seader
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=CS
STREAM DATA
. . .
General Information
The Chao-Seader method calculates K-values. It is generally useful
for light to mid-range refinery hydrocarbons. SimSci recommends
that the Grayson-Streed method (GS) be used in preference to CS.
Refer to the PRO/II Reference Manual for additional limitations.
Table 3-3: Attributes of the Chao-Seader Methods

Properties predicted by CS Methods
K-values - Chao-Seader

Molecular weight Liquid molar volume
Critical pressure Solubility parameter

C2 & Higher H2 & C1
Pressure - < 2000 psia < 8000 psia

Temperature - 0 to 800 F -100 to 500F

Input Description
METHOD SYSTEM=CS, ...
or
METHOD KVALUE=CS, ...

property generators. When SYSTEM=CS is chosen,
CS K-values, Curl-Pitzer (CP) enthalpies, CP
entropies, API liquid densities, and SRK vapor
densities are assumed.
KVALUE Selects the method for K-value calculations. Only
VLE K-value calculations are available with the CS
method.

or EOS
The CS K-value generator supports the free-water decant option.
Refer to Free-water Decant Considerations on page 1-33, for a

...
Examples
E-3.8: Using the CS methods, model a 50/50 mix of propane and
normal butane at 100 psia and 100 F. By choosing the CS
system, Curl-Pitzer enthalpies are invoked.
TITLE PROB=CS, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4

THERMO DATA
METHOD SYSTEM=CS
STREAM DATA
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-3.9: For the same problem, use CS K-values, Lee-Kesler

THERMO DATA
METHOD KVALUE=CS, ENTHALPY=LK, DENSITY=LK
E-3.10: The system in Example 3.8 now contains 20% water at a

higher pressure. Use the GPSA Data Book charts, water
solubility by the API Technical Data Book, Fig. 9A1.4.
Pure water properties are calculated using the Keenan and
Keyes steam tables.
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,H2O/ 2,C3/ 3,NC4
THERMO DATA
METHOD SYSTEM=CS
WATER DECANT=ON, GPSA, SOLUBILITY=KEROSENE, &
PROPERTY=STEAM
STREAM DATA
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3, W=4
TPSPEC TEMP=100
RATE, VALUE=0.5
END

Modifications to GS and CS
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=IGS
STREAM DATA
. . .
General Information
The Erbar modification to the Chao-Seader and Grayson-Streed
methods offers improved liquid fugacity coefficients for N2, H2S
and CO2. These methods do not support rigorous three-phase calcu-
lations, but they do support free water decant. The Improved Gray-
son-Streed method has better liquid fugacity coefficients for N2,
H2S, CO, CO2, H2O, and O2. This method supports a rigorous
three phase calculation but can also be used with the free water
decant option turned on.
These methods are generally useful for petroleum refinery applica-
tions. Refer to the PRO/II Reference Manual for additional limita-
tions.
Table 3-4: Attributes of the Modified GS and CS Methods

Properties predicted by modified GS and CS Methods
K-values (VLE) - Erbar modified Grayson-Streed
Erbar modified Chao-Seader
Improved Grayson-Streed
K-values (VLLE) - Improved Grayson-Streed

Molecular weight Acentric factor
Critical temperature Water solubility parameter (IGS only)
Critical pressure
Pressure - < 3000 psia
Temperature - 0 to 800 F

Table 3-4: Attributes of the Modified GS and CS Methods
Properties predicted by modified GS and CS Methods
Free-water decant - Supported by GSE, CSE and IGS
VLLE - Not supported by GSE and CSE
Supported by IGS
1Automatically supplied for library and petroleum components. Must be
Input Description
Improved Grayson-Streed
METHOD SYSTEM(VLE or VLLE)=IGS, ...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=IGS, ...
Erbar modifications to Grayson-Streed and Chao-Seader

METHOD SYSTEM=GSE or CSE, ...
or
METHOD KVALUE=GSE or CSE, ...

property generators. When SYSTEM=IGS, GSE or CSE is
chosen, GS K-values, Curl-Pitzer (CP) enthalpies, CP
entropies, API liquid densities, and SRK vapor enthalpies
are default.
KVALUE Selects the method for K-value calculations. Only VLE K-
value calculations are available with the GSE and CSE
methods. The IGS method supports VLLE as well.

These options are not valid when the VLLE option is active.
or EOS
The IGS, GSE, and CSE K-value generators support the free-water
decant option. Refer to Free-water Decant Considerations on
page 1-33, for a description of these input options.

WDELT
...
method is used. For IGS, the water solubility parameter, WDELT, is
applied asymmetrically to the water phase. For a further description
of these input parameters, see Chapter 9, Method-specific Pure
Component Data.
Examples
E-3.11: Using the IGS methods, model a 50/50 mix of propane
IGS system, Curl-Pitzer enthalpies are invoked.
TITLE PROB=IGS, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=IGS
STREAM DATA
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3
TPSPEC TEMP=50
RATE, VALUE=0.5
END
E-3.12: For the same problem, use GSE K-values, Lee-Kesler

THERMO DATA
METHOD KVALUE=GSE, ENTHALPY=LK, DENSITY=LK

E-3.13: The Improved Grayson-Streed (IGS) method, compare the
results using rigorous VLLE calculations with those
obtained using the water decant option. Use all the
defaults for the water decant option. Both thermodynamic
systems will be tried in the same run by assigning different
thermodynamic sets to the two flash units.
COMPONENT DATA
THERMO DATA
METHOD SYSTEM(VLLE)=IGS, SET=RIGOROUS
METHOD SYSTEM=IGS, SET=DECANTING
WATER DECANT=ON, GPSA, SOLUBILITY=KEROSENE, &
PROPERTY=STEAM
STREAM DATA
UNIT OPERATION
FLASH UID=DEC
FEED 1
PROD V=2D, L=3D, W=4D
TPSPEC TEMP=100
SPEC STREAM=2D, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
METHOD SET=DECANTING
FLASH UID=RIG
FEED 1
PROD V=2R, L=3R, W=4R
TPSPEC TEMP=100
SPEC STREAM=2R, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
METHOD SET=RIGOROUS
END

Curl-Pitzer
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=SRKM, ENTHALPY=CP
STREAM DATA
. . .
General Information
The Curl-Pitzer method calculates enthalpies and entropies. It is
generally useful for refinery hydrocarbons Refer to the PRO/II Ref-
erence Manual for additional limitations.
Table 3-5: Attributes of CP Methods

Properties predicted by CP methods
Enthalpies
Entropies
Critical temperature
Critical pressure
Acentric factor
1Automatically
supplied for library and petroleum components. Must be
Input Description
METHOD SYSTEM=GS or CS or IGS or GSE or CSE or BK10, ...
or
METHOD ..., ENTHALPY(VL)=CP,
or
ENTHALPY(V)= CP and/or ENTHALPY(L)=CP,
ENTROPY(VL)=CP, ...
or
ENTROPY(V)=CP and/or ENTROPY(L)=CP, ...

property generators. Selecting GS, CS, IGS, GSE or CSE
will cause Curl-Pitzer enthalpies and entropies to be
used. Selecting BK10 will cause CP entropies to be used.
ENTHALPY Selects the method for enthalpy calculations. By default
(VL or V and/or L) both vapor and liquid (VL) enthalpies are calculated
using the same method. You may select different
methods for the vapor and liquid enthalpies by providing
both an ENTHALPY(V) and ENTHALPY(L) entry.
ENTROPY Selects the method for entropy calculations. By default
(VL or V and/or L) both vapor and liquid (VL) entropies are calculated using
the same method. You may select different methods for
the vapor and liquid entropies by providing both an
ENTROPY(V) and ENTROPY(L) entry.

...
The Curl-Pitzer method requires Tc, Pc, acentric factors and ideal
enthalpies. Tc, Pc and acentric factors may be overridden here for a
specific method set. The ideal enthalpies may only be specified
globally for all sets in the Component Data Category. For a further
description of these input parameters, see Chapter 9, Method-spe-
cific Pure Component Data.
Examples
E-3.14: Using the CS system, model a 50/50 mix of propane and
normal butane at 100 psia and 100 F. By choosing the CS
system, Curl-Pitzer enthalpies and entropies are
invoked.
TITLE PROB=CP, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=CS
STREAM DATA
UNIT OPERATION

FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-3.15: For the same problem, specify CP enthalpies and entropies

explicitly.
THERMO DATA
METHOD KVALUE=CS, ENTHALPY=CP, ENTROPY=CP, &
DENSITY=API
E-3.16: For the same problem, use Curl-Pitzer methods in the

vapor phase and IDEAL methods in the liquid phase for
enthalpy and entropy calculations. For liquid density, use
API and for vapor density, use the IDEAL method.
TITLE PROB=CP, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD KVALUE=CS, ENTHALPY(V)=CP, &
ENTHALPY(L)=IDEAL, ENTROPY(V)=CP, DENSITY(L)=API, &
DENSITY(V)=IDEA
STREAM DATA
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

Braun K10
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=BK10
STREAM DATA
. . .
General Information
The Braun K10 method calculates K-values. It is generally useful
for heavy refinery hydrocarbons at low pressures. Refer to the
PRO/II Reference Manual for additional limitations.
Table 3-6: Attributes of the Braun K10 Methods
Properties predicted by BK10 method
K-values
Critical temperature Normal boiling point
Critical pressure
Pressure - 0 to 100 psia
Temperature - 100 to 1200 F
Composition - C6 & Heavier
1
Automatically supplied for library and petroleum components. Must be
Input Description
METHOD SYSTEM=BK10, ...
or

METHOD KVALUE=BK10, ...

property generators. When SYSTEM=BK10 is
chosen, BK10 K-values, Johnson-Grayson (JG)
enthalpies, Curl-Pitzer (CP) entropies, IDEAL vapor
densities, and API liquid densities are assumed.
VLE K-value calculations are available with the
BK10 method.

or EOS
The BK10 K-value generator supports the free-water decant option.
Refer to Free-water Decant Considerations on page 1-33, for a

...
Examples
E-3.17: Using the BK10 method, model a 50/50 mix of propane
SYSTEM=BK10, Johnson-Grayson enthalpies are
invoked.
TITLE PROB=BK10, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=BK10
STREAM DATA

UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-3.18: For the same problem, use BK10 K-values, Lee-Kesler

THERMO DATA
METHOD KVALUE=BK10, ENTHALPY=LK, DENSITY=LK
E-3.19: The system in Example 3.17 now contains 20% water at a

higher pressure. Calculate water partial pressures using
the GPSA Data Book, water solubilities using the API
Technical Data Book, and, because of the conditions, pure
water properties using the Keenan and Keyes steam tables.
TITLE PROB=BK10, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=BK10
WATER DECANT=ON, GPSA, &
SOLUBILITY=KEROSENE, PROPERTY=STEAM
STREAM DATA
UNIT OPERATION
FLASH UID=DRUM
FEED 1
PROD V=2, L=3, W=4
TPSPEC TEMP=100
RATE, VALUE=0.5
END

Johnson-Grayson
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=SRKM, ENTHALPY=JG
STREAM DATA
. . .
General Information
The Johnson-Grayson method calculates enthalpies. It is generally
useful for heavy refinery hydrocarbons. When using the Johnson-
Grayson enthalpy method, it is recommended that the Johnson-
Grayson method be used for both liquid and vapor phases.Refer to
the PRO/II Reference Manual for additional limitations.
Table 3-7: Attributes of JG Methods

Properties predicted by JG methods
Enthalpies
Critical pressure
Normal boiling point
1Automatically
supplied for library and petroleum components. must be
Input Description
METHOD SYSTEM=BK10, ...
or
METHOD ..., ENTHALPY(VL)=JG, ...
or
ENTHALPY(V)= JG and/or ENTHALPY(L)=JG

property generators. When SYTEM=BK10 is chosen,
Johnson-Grayson vapor and liquid enthalpies are
assumed.
ENTHALPY (VL or V and/or L) Selects the method for enthalpy
calculations. By default both vapor and liquid (VL)
enthalpies are calculated using the same method. You may
select different methods for the vapor and liquid
enthalpies by providing both an ENTHALPY(V) and
ENTHALPY(L) entry, although this is not recommended.

The Johnson-Grayson method requires Tc, Pc, and NBP. Tc, Pc, and
NBP may be overridden here for a specific method set. For a further
description of these input parameters, see Chapter 9, Method-spe-
cific Pure Component Data.
Examples
E-3.20: Using the BK10 system, model a 50/50 mix of propane
BK10 system, Johnson-Grayson enthalpies are invoked.
TITLE PROB=JG, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=BK10
STREAM DATA
UNIT OPERATION
FLASH UID=D101
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-3.21: For the same problem, specify JG enthalpies explicitly.

THERMO DATA

METHOD KVALUE=BK10, ENTHALPY=JG, ENTROPY=CP, &
DENSITY=API
Lee-Kesler
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=SRKM, ENTHALPY=LK
STREAM DATA
. . .
General Information
The Lee-Kesler method calculates enthalpies, entropies and densi-
ties. It is generally useful for refinery hydrocarbons. The liquid den-
sity method is not recommended for hydrocarbons heavier than C8.
Table 3-8: Attributes of the Lee-Kesler Methods

Properties predicted by LK methods
Enthalpies
Entropies
Densities
Composition - C8 & lighter (for liquid density method)
Critical pressure
1

Input Description
METHOD ENTHALPY(VL)=LK,
or ENTHALPY(V)= LK and/or ENTHALPY(L)=LK,
ENTROPY(VL)=LK, ...
or ENTROPY(V)= LK and/or ENTROPY(L)=LK, ...
DENSITY(VL)=LK, ...
or DENSITY(V)= LK and/or DENSITY(L)=LK, ...
ENTHALPY Selects the method for enthalpy calculations. By

(VL or V and/or L) default both vapor and liquid (VL) enthalpies are
calculated using the same method. You may select
different methods for the vapor and liquid enthalpies
by providing both an ENTHALPY(V) and
ENTHALPY(L) entry.
ENTROPY Selects the method for entropy calculations. By
(VL or V and/or L) default both vapor and liquid (VL) entropies are
calculated using the same method. You may select
different methods for the vapor and liquid entropy by
providing both an ENTROPY(V) and ENTROPY(L)
entry.
DENSITY Selects the method for density calculations. By default
(VL or V and/or L both vapor and liquid (VL) densities are calculated
methods for the vapor and liquid densities by
providing both a DENSITY(V) and DENSITY(L)
entry.

...
The Lee-Kesler method requires Tc, Pc, NBP and ideal gas enthal-
pies. Tc, Pc and NBP may be overridden here for a specific method
set. The ideal gas enthalpies may only be specified globally for all
sets in the Component Data Category. For a further description of
these input parameters, see Chapter 9, Method-specific Pure Com-
ponent Data.

Examples
E-3.22: Using the SRK system and Lee-Kesler enthalpies, model a
50/50 mix of propane and normal butane at 100 psia and
100 F. By choosing the SRK system, SRK entropies,
vapor densities, and API liquid densities are invoked.
TITLE PROB=LK, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=SRK, ENTHALPY=LK
STREAM DATA
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-3.23: For the same problem, specify SRK K-values, LK

enthalpies, entropies and densities explicitly.
THERMO DATA
METHOD KVALUE=SRK, ENTHALPY=LK, &
ENTROPY=LK, DENSITY=LK

API Liquid Density
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=SRKM, DENSITY(L)=API
STREAM DATA
. . .
General Information
The API method calculates liquid densities. It is generally useful for
refinery hydrocarbons. Refer to the PRO/II Reference Manual for
additional limitations.
Input Description
Table 3-9: Attributes of API Methods
Properties predicted by API methods
Liquid densities
Critical pressure
1Automatically

METHOD SYSTEM=SRK or SRKKD or SRKH or SRKP or
SRKM or PR or PRH or PRP or PRM or BK10 or GS
or IGS or CS or UNIWAAL or GLYCOL or PPR78
or
METHOD ..., DENSITY(L)=API, ...

property generators. When one of the above systems is
chosen, API liquid densities are assumed.
DENSITY(L) Selects the method for liquid density calculations.

The API method requires Tc, Pc, and NBP. Tc, Pc and NBP may be
overridden here for a specific method set. For a further description
of these input parameters, see Chapter 9, Method-specific Pure
Component Data.
Examples
E-3.24: Using the SRK system, model a 50/50 mix of propane and
normal butane at 100 psia and 100 F. By choosing
SYSTEM= SRK, API liquid densities are automatically
invoked.
TITLE PROB=API, PROJ=THERMO
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=SRK
STREAM DATA
UNIT OPERATION
FLASH UID=D121
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-3.25: For the same problem, specify SRK K-values, SRK
enthalpies, SRK entropies, SRK vapor densities, and API
liquid densities explicitly.
THERMO DATA
METHOD KVALUE=SRK, ENTHALPY=SRK, &
ENTROPY=SRK, DENSITY(V)=LK, &
DENSITY(L)=API

Rackett Liquid Density
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=SRKM, DENSITY(L)=RACKETT
STREAM DATA
. . .
General Information
The RACKETT method calculates liquid densities. It is generally
useful for refinery hydrocarbons as well as non-hydrocarbons.
Table 3-10: Attributes of RACKETT Methods

Properties predicted by RACKETT methods
Liquid densities

Critical temperature Rackett parameter
Critical pressure Critical compressibility factor
1Automatically supplied for some library and petroleum components. Must be
Input Description
METHOD ..., DENSITY(L)=RACKETT, ...

TC(unit) i, value /...
PC(unit) i, value /...
RACKETT i, value /...
ZC i, value /...

The RACKETT method requires Tc, Pc, the Rackett parameter, and
the critical compressibility factor. Either RACKETT or Zc may be
provided. If both are given, the Rackett parameter is used. Tc, Pc,
RACKETT and Zc may be overridden here for a specific method
set. For a further description of these input parameters, see Chapter
9, Method-specific Pure Component Data.
Examples
E-3.26: Using the SRK system and RACKETT liquid densities,
model a 50/50 mix of propane and normal butane at 100
psia and 100 F. The DENSITY(L)=RACKETT overrides
the default API liquid densities.
TITLE PROB=RACKETT, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=SRK, DENSITY(L)=RACKETT
STREAM DATA
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

enthalpies, entropies, Lee-Kesler vapor densities, and
RACKETT liquid densities explicitly.
THERMO DATA
DENSITY(L)=RACKETT

Costald Liquid Density
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=SRKM, DENSITY(L)=COSTALD
STREAM DATA
. . .
General Information
The COSTALD method calculates liquid densities. It is generally
useful for aromatics and other light refinery hydrocarbons up to
reduced temperatures of 0.95. Refer to the PRO/II Reference Man-
ual for additional limitations.
Table 3-11: Attributes of COSTALD Methods

Properties predicted by COSTALD methods
Liquid densities

Critical temperature Critical volume
Acentric factor
1
Automatically supplied for some library and petroleum components. Must be
Input Description
METHOD . ..., DENSITY(L)=COSTALD, ...

...

The COSTALD method requires Tc, the acentric factor, and critical
volumes. Tc and w may be overridden here for a specific method
set. The parameter Vc is used by COSTALD as a characteristic
volume, not a critical volume, and is retrieved (along with Tc and
the acentric factor) from the COSTALD databank. Pure component
critical volumes will however be used when the characteristic vol-
ume is not supplied or is missing from the COSTALD databank.
For petroleum and assay components, a characteristic volume is
back calculated in order to provide a correct specific gravity for the
pseudocomponent. For a further description of these input parame-
ters, see Chapter 9, Method-specific Pure Component Data.
Examples
E-3.28: Using the SRK system, and COSTALD liquid densities,
model a 50/50 mix of propane and normal butane at 100
psia and 100 F. The DENSITY(L)=COSTALD overrides
the default (API) liquid densities.
TITLE PROB=COSTALD, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=SRK, DENSITY(L)=COSTALD
STREAM DATA
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

enthalpies, entropies, Lee-Kesler vapor densities, and
COSTALD liquid densities explicitly.
THERMO DATA
DENSITY(L)=COSTALD

Peneloux Density
Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=SRKM, DENSITY(L)=SRKPENELOUX or
PRPENELOUX , & DENSITY(V)=SRKPENELOUX or
PRPENELOUX
STREAM DATA
. . .
General Information
The SRK/PR Peneloux methods calculate the liquid and Vapor den-
sities. They are generally useful for aromatics and other refinery
hydrocarbons. Refer to the PRO/II online Reference Manual for
additional information.
Input Description
METHOD . ..., DENSITY(L)=SRKPENELOUX or
PRPENELOUX, ...

PENELOUX (unit) i, value / ...
...
Table 3-12: Attributes of SRK/PR Peneloux Methods

Properties predicted by SRK/PR Peneloux Methods
Liquid densities, Vapor Densities
Required pure component properties
Acentric factor
Critical Pressure
Peneloux Parameter

General Information
The required pure component properties are automatically supplied
for some of the library and petroleum components but must be sup-
plied by the user for the non-library components.
DENSITY(L) selects the method for liquid density calculations.
DENSITY(V) selects the method for vapor density calculations.
The SRK/PR Peneloux methods require Tc, Pc, the acentric factor,
and the Peneloux Parameter values to calculate the liquid and vapor
densities. If required, these values can be overridden by the user for
a specific method set. Calculations in SRK-Peneloux method are
based on EOS SRK alpha formulation and mixing rules. On top of
that, Peneloux parameters are applied to calculate the density. Sim-
ilarly, calculations in PR-Peneloux method are based on PR alpha
formulation and mixing rules.
Examples
E-3.32: Using the SRK system and SRK Peneloux liquid and
Vapor densities, model a 50/50 mix of propane and
normal butane at 100 psia and 100 F. DENSITY(L)=
SRKPENELOUX overrides the default (API) liquid
densities.
TITLE PROB=PENELOUX, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=SRK, DENSITY(L)= SRKPENELOUX,
DENSITY(V)= SRKPENELOUX
STREAM DATA
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-3.33: Using the SRK system and PR Peneloux Liquid and Vapor
densities, model a 50/50 mix of propane and normal
butane at 100 psia and 100 F.

DENSITY(V)=PRPENELOUX overrides the default for
vapor densities.
TITLE PROB=PENELOUX, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1, C3/ 2, NC4
THERMO DATA
METHOD SYSTEM=SRK, DENSITY (L) =PRPENELOUX .
DENSITY (V) =PRPENELOUX
STREAM DATA
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
User-supplied K-value Data

Typical Usage
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMODYNAMIC DATA
METHOD KVALUE=DATA
KVALUE(VLE)
KDATA TABU=50, 100, 150/ 1, 0.4, 0.6, 0.7/ &
2, 0.3, 0.4, 10.8/ 3, 0.5, 0.7, 0.9, PREF=50
or
COMPONENT DATA
LIBID 1,IC4/ 2,NC4/ 3,NC5
THERMODYNAMIC DATA
METHOD KVALUE=DATA
KVALUE(VLE)
KDATA TABU=50, 100, 150/ 1, 0.4, 0.6, 0.7, PREF=50
STREAM DATA
. . .

General Information
All K-value data supplied by the user may be chosen as the primary
VLE or LLE K-value method by designating DATA as the K-value
method on the METHOD statement. K-value data may also be used
as a secondary K-value method, overriding some or all of the values
generated by the principal K-value method. VLE or LLE K-value
data may be supplied. However, if a VLLE method is selected, both
LLE and VLE K-value data may be supplied. KDATA may be sup-
plied in either tabular or correlation forms.
Table 3-13: Attributes of User-Supplied K-value Data

Properties predicted by K-value Data
K-values
None
Free-water decant - Not supported
VLLE - Supported
Input Description
METHOD KVALUE(VLE)=DATA, ...
or
METHOD KVALUE(VLE)=DATA, KVALUE(LLE)=method, ...
or
METHOD KVALUE(LLE)=DATA, SYSTEM(VLLE)=method, ...
or
METHOD KVALUE(LLE)=DATA, KVALUE(VLE)=method, ...
K-value Data (required)

KVALUE(VLE or LLE)
KDATA CORR=icorr, LN or LOG or EXPFAC=ipos,
PREF(upres)=value, DATA=i, tmax, tmin, c1, ...c8/ ...
or
KDATA TABU=t1, t2, .../ i, p1, p2, .../ ..., PREF(upres)=value

Note: If KVALUE(VLE)=DATA is used, all components of phase
type VL or VLS must have KDATA information.
Note: If KVALUE(LLE)=DATA is used, all component of phase
type VL, VLS, or LS must have KDATA information.
KDATA This statement allows entry of K-value data in either tabular or

correlation forms.
CORR Selects the correlation form of the supplied K-value data. icorr
is one of the 29 available correlation forms. See Volume I,
Component Properties, for further details on data entry for thes
equation-based correlations.
TABU Selects the tabular form of the supplied K-value data. See
Volume I, Component Properties, for further details on data
entry for tabular based data. Tabular data will interpolated using:
a
ln ( K ) = --- + b
T
where a and b are constants, and T is Kelvin.

PREF This keyword is required and provides the reference pressure at
which K-value data are being supplied. K-value data at any other
pressure P will be calculated using the following equations:
For VLE: PREF
K ( P ) = K ( PREF ) ---------------
P
For LLE: K ( P ) = K ( PREF )
Note: Supplied KDATA will apply to VLE by default. If VLLE

methods are used, both LLE or VLE KDATA may be supplied.
Examples
E-3.30: Using tabular data, predict the bubble point temperature at
50 psia for an equal molar mixture of propane, n-butane
and n-pentane. The K-value data to be entered are as
follows:
Temperature 50F 100F 150F

propane 2.2492 2.08300 1.9088
n-butane 0.58776 0.68216 0.76869
n-pentane 0.16308 0.23487 0.32252
TITLE PROB=KDATA BP

COMPONENT DATA
LIBID 1, C3/2, NC4 /3, NC5
THERMODYNAMIC DATA
METHOD SYST=DATA, ENTH=PR, DENS(V)=PR,
DENS(L)=API
KVALUE
KDATA TABU= 50, 100, 150 / &
1, 2.2492, 2.08300, 1.9088 / &
2, 0.58776,0.68216, 0.76869 / &
3, 0.16308, 0.23487, 0.32252, PREF=50
STREAM DATA
UNIT OPERATIONS
FLASH UID=1
FEED 1
PROD L=2
BUBB PRES=50
END

E-3.31: Using the SRKM method for VLE K-values, supply VLE
K-values for H2O in a 50/40/10 mixture of propane, n-
butane, and water at 100 F and 100 psia.
TITLE PROB=KDATA, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4/ 3,H20
THERMO DATA
METHOD SYSTEM=SRKM
KVALUE
KDATA TABU=50,100,150/ 1,6.0387,10.822,18.773, PREF=100
STREAM DATA
UNIT OPERATION
FLASH UID=FD23
FEED 1
PROD V=2, L=3
TPSPEC PRES=75
RATE, VALUE=0.5
END

Chapter 4
Equations of State
Historically, equations of state have been successfully applied to

petroleum and refining hydrocarbon systems and light gases.
Recent advances in mixing rules and alpha forms have extended
their applicability to many non-ideal systems.
Soave Modified Redlich-Kwong

Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=SRK
STREAM DATA
. . .
General Information
The Soave modified Redlich-Kwong equation of state predicts K-
values, enthalpies, entropies, and vapor densities. It is most often
used in gas and refining processes. Without significant modifica-
tion, it is generally not useful for highly non-ideal systems. Liquid
densities and VLLE behavior can be predicted with the SRK equa-
tion of state, but are not recommended without using an advanced
form (seeModified Soave-Redlich-Kwong and Peng-Robinson on
page 4-13).

Table 4-1: Attributes of the Soave-Redlich-Kwong Equation of State
Properties predicted by SRK
K-values Vapor densities
Enthalpies Liquid densities (not recommended)
Entropies
Critical temperature Ideal vapor enthalpy
Critical pressure
Temperature - -460 to 1200 F
VLLE - Not recommended
1
Input Description
METHOD SYSTEM=SRK, ...
or
METHOD KVALUE=SRK, ENTHALPY=SRK,
ENTROPY=SRK, DENSITY(V)=SRK,
DENSITY(L)=API,...
Note: DENSITY(L)=SRK is supported but not recommended.
KVALUE(VLLE)=SRK is supported but not recommended.
SYSTEM Selects a combination of consistent thermodynamic

property generators. When SYSTEM=SRK is chosen,
SRK K-values, SRK enthalpies, SRK entropies, API
liquid densities, and SRK vapor densities are assumed.
K-value calculations are recommended with the SRK
method.
ENTHALPY Selects the method for enthalpy calculation. By default,
(VL or V and/or L) both vapor and liquid enthalpies use this method.
ENTROPY Selects the method for entropy calculation. By default,

(VL or V and/or L) both vapor and liquid entropies use this method.
4-2 Equations of State

DENSITY (V) Selects the method for vapor density.
MEOH=ON Selects the Methanol hydrocarbon correlation to
calculate the Binary Interaction Parameters
Note: If DENSITY=SRK without the V qualifier is used, liquid

density will also be calculated from the SRK equation of state.
This method is not recommended for this purpose.
K-value Data (optional)

KVALUE BANK=PROCESS or SIMSCI or NONE or bankid,
FILL=NONE or GAO or GOR or CPHC,
ALPHA = ACENTRIC or SIMSCI or bankid,
COMP = SIMSCI or PROCESS or bankid
SRK(K or R) i, j, kija, kijb, kijc, kijd/ ...
SA01to SA11 i, c1, c2, c3/ ...
Note: The SRK and SAxx statements must follow the KVALUE
statement.
BANK This option selects one or more banks from which to retrieve
vapor and/or liquid phase binary interaction data.
PROCESS Selects the SimSci PROCESS databank.
SIMSCI Selects the SimSci standard databank (default).
NONE This option disables all data retrieval from databanks for
interaction parameters.
bankid This option selects the user-created databank named

bankid that is created and maintained by the LIBMGR
program.
FILL Selects the method used for estimating values for hydrocarbon/
hydrocarbon binary interaction data missing from the input file
and any selected databank libraries. This option is not valid for
all modified equations of state. See Filling in Missing
Parameters on page 4-27 for further information on the
methods given below.
NONE This option disables estimation of any missing binary
interaction data(default).
GOR This option estimates binary interaction parameters

between methane and ethane and heavier hydrocarbons.
GAO This option estimates binary interaction parameters

between methane through propane and heavier
hydrocarbons.
CPHC This option estimates binary interaction parameters for all
hydrocarbon pairs.

ALPHA This option allows access to the databank for alpha
formulations.
ACENTRIC Uses the original Soave acentric form for alpha (default).
SIMSCI Selects the SimSci alpha form and values supplied from the
SIMSCI databank.
program.
COMP Selects order of component libraries and databanks, when
searching for pure components required for the current Thermo
system. Properties missing from this databanks will be taken
from global component data search order.
SIMSCI Selects the SimSci standard databank.
program.
SRK This statement allows entry of the binary interaction parameters
(kijs) for the SRK equation of state. Entries correspond to the
following temperature-dependent correlation:
kij = kija + kijb/T + kijc/T2 + kijd*T

Temperature units may be K (default) or R.
SA01 to SA11 These entries permit various formulations of the pure
component Alpha correlations. See Cubic Equation Of
State Alpha Formulations on page 4-28, for further details.
Enthalpy, Entropy, and Density Data (optional)

ENTHALPY BANK=PROCESS or SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid,
ENTROPY BANK=PROCESS or SIMSCI or NONE or bankid,
ALPHA=ACENTRIC or SIMSCI or bankid,
DENSITY BANK=PROCESS or SIMSCI or NONE or bankid,
SRK(K or R) i, j, kija, kijb, kijc, kijd/ ...
SA01to SA11 i, c1, c2, c3/ ...
COMP Selects order of component libraries and databanks when
searching for pure components required for the current Thermo system.
Properties missing from this databanks will be taken from global
component data search order.

Bankid This option selects the user-created databank named

bankid that is created and maintained by the LIBMGR program.
SRK interaction parameters and alpha formulations may be pro-
vided for enthalpy, entropy, and density methods. Normally, these
data are provided for the K-value method and are automatically car-
ried over for other properties using the same method, i.e., SRK. If,
however, the K-value method is not SRK, you can supply the inter-
action parameters and/or alpha formulations independently.
See above under K-value Data for format and definition of these
entries.

or EOS
The SRK K-value generator supports the free-water decant option.

...
Examples
E-4.1: Using the SRK method with default interaction parameters
and using acentric factors for alpha formulation, calculate
the temperature of a 50/50 mix of propane and normal
butane at 50 psia and 50% vaporization.
TITLE PROB=SRK, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4

THERMODYNAMIC DATA
METHOD SYSTEM=SRK
STREAM DATA
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-4.2: For the same problem, explicitly specify SRK K-values,

enthalpies, entropies, and vapor densities. Specify API
liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE=SRK, ENTHALPY=SRK, ENTROPY=SRK,&
E-4.3: Use the SOUR thermo methods but apply SRK to vapor
density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=SRK
E-4.4: Supply SRK kij binaries for components 1-2 and 2-3. Note
that unless binary 1-3 is available in the databank, the kij
will have a value of 0.0. Note that the SRK statement must
follow the KVALUE statement even though there are no
additional entries on the KVALUE statement.
THERMODYNAMIC DATA
METHOD SYSTEM=SRK
KVALUE
SRK 1,2,0.01/ 2,3,0.025...
E-4.5: For the previous example, also supply parameters for the
Twu-Bluck-Cunningham alpha formulation for
components 1 and 3. See Cubic Equation Of State Alpha
Formulations on page 4-28.
THERMODYNAMIC DATA
METHOD SYSTEM=SRK
KVALUE SRK 1,2,0.01/ 1,3,0.025
SA06 1,0.75,0.93,1.6/ 3,0.61,0.81,2.1

E-4.6: For the previous example, use alpha parameters from the
PROCESS instead of the default SIMSCI databank for
entropy calculations. Also, supply parameters for the Twu
alpha formulation for entropy calculations for components
1 and 3.
COMPONENT DATA
LIBID 1,C3/ 2,NC4/ 3,H2O/ 4,NH3/ 5,CO2
THERMO DATA
METHOD SYSTEM=SRK
KVALUE
SRK 1,2,0.01/ 1,3,0.025
SA06 1,0.75,0.93,1.6/ 3,0.61,0.81,2.1
ENTROPY BANK=SIMSCI, ALPHA=SIMSCI
SA05 1,0.7,0.85/ 3,0.6,0.71
STREAM DATA
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
Peng-Robinson
Typical Usage
...
COMPONENT DATA
THERMODYNAMIC DATA
METHOD SYSTEM=PR
STREAM DATA
. . .
General Information
The Peng-Robinson (PR) equation of state predicts K-values,
enthalpies, entropies, and vapor densities. It is most often used for
gas and refining processes. Without significant modification, it is
generally not useful for highly non-ideal systems. Liquid densities

and VLLE behavior predictions are not recommended without
using an advanced form of the PR equation of state (see Modified
Soave-Redlich-Kwong and Peng-Robinson on page 4-13).
Table 4-2: Attributes of the PR Equation of State

Properties predicted by PR
Entropies
Molecular weight Ideal vapor enthalpy
Critical pressure Acentric factor
Free-water - Supported
decant
1
Input Description
METHOD SYSTEM=PR, ..
or
METHOD KVALUE=PR, ENTHALPY=PR, ENTROPY=PR,
DENSITY(V)=PR, DENSITY(L)=API,...
Note: DENSITY(L)=PR is supported but not recommended.

KVALUE(VLLE)=PR is supported but not recommended.

property generators. When SYSTEM=PR is chosen,
PR K-values, PR enthalpies, PR entropies, API liquid
densities, and SRK vapor densities are assumed.
KVALUE Selects the method for K-value calculations. VLE and
VLLE are both supported, but only VLE K-value
calculations are recommended with the PR method.



MEOH=ON Selects the Methanol hydrocarbon correlation to
calculate the Binary Interaction Parameters
Note: If DENSITY=PR without the V qualifier is used, liquid

density will also be calculated from the PR equation of state. This
method is not recommended for this purpose.

KVALUE BANK=PROCESS or SIMSCI or NONE or bankid,
FILL=NONE or GOR or GAO or CPHC
PR(K or R) i, j, kija, kijb, kijc, kijd/ ...
PA01to PA11 i, c1, c2, c3/ ...
Note: The PR and PAxx statements must follow the KVALUE

statement.
BANK This option selects one or more banks from which to retrieve vapor
and/or liquid phase binary interaction data.
program.
hydrocarbon binary interaction data missing from the input file and
any selected databank libraries. This option is not valid for all
modified equations of state. See Filling in Missing Parameters on
page 4-27 for further information on the methods given below.

hydrocarbons.
hydrocarbon pairs.

formulations.
SIMSCI Selects the SimSci alpha form and values supplied from the
SIMSCI databank.
program.
searching for pure components required for the current
Thermo system. Properties missing from this databanks
will be taken from global component data search order.
program.
PR This statement allows entry of the binary interaction parameters
(kijs) for the PR equation of state. Entries correspond to the
following temperature-dependent correlation:
kij = kija + kijb/T + kijc/T2+ kijd*T

PA01 to PA11 These entries permit various formulations of the pure
component Alpha correlations. See Cubic Equation Of
State Alpha Formulations on page 4-28, for further
details.

ENTHALPY BANK=PROCESS or SIMSCI or NONE or bankid,
ENTROPY BANK=PROCESS or SIMSCI or NONE or bankid,
DENSITY BANK=PROCESS or SIMSCI or NONE or bankid,
PR(K or R) i, j, kija, kijb, kijc, kijd/ ...

PA01to PA11 i, c1, c2, c3/ ...
PR interaction parameters and alpha formulations may be selected
for enthalpy, entropy, and density methods. Normally, these features
are selected for the K-value method and are automatically carried
over for these other methods. If, however, the K-value method is
not SRK, you can supply the interaction parameters and/or alpha
formulations independently. See above under K-value Data for for-
mat and definition of these entries.

or EOS
The PR K-value generator supports the free-water decant option.

...
Examples
E-4.7: Using the PR method with default interaction parameters and
using acentric factors for alpha formulation, calculate the
temperature of a 50/50 mix of propane and normal butane at 50 psia
and 50% vaporization.
TITLE PROB=PR, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=PR
STREAM DATA
UNIT OPERATION
FLASH UID=F203
FEED 1

PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-4.8: For the same problem, explicitly specify PR K-values, enthalpies,

entropies, and vapor densities. Specify API liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE=PR, ENTHALPY=PR, ENTROPY=PR,&
DENSITY(V)=PR, DENSITY(L)=API...
E-4.9: Use the SOUR thermo methods but apply PR to vapor density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=PR
E-4.10: Supply PR kij binaries for components 1-2 and 2-3. Note that
unless binary 1-3 is available in the databank, the kij will have a
value of 0.0. Note that the PR statement must follow the KVALUE
statement even though there are no additional entries on the
KVALUE statement.
THERMODYNAMIC DATA
METHOD SYSTEM=PR
KVALUE
PR 1, 2, 0.01/ 2, 3, 0.025
E-4.11: For the previous example, also supply parameters for the Twu-
Bluck-Cunningham alpha formulation for components 1 and 3. See
Cubic Equation Of State Alpha Formulations on page 4-28.
THERMODYNAMIC DATA
METHOD SYSTEM=PR
KVALUE
PR 1, 2, 0.01/ 2, 3, 0.025
PA06 1, 0.75, 0.93, 1.6/ 3, 0.61, 0.81, 2.1
E-4.12: For the previous example, use binary parameters from the
PROCESS databank instead of the default SIMSCI databank for
entropy calculations. Also, supply parameters for the Twu alpha
formulation for entropy calculations for components 1 and 3.
TITLE PROB=PR, PROJ=THERMO
PRINT INPUT=ALL

COMPONENT DATA
LIBID 1,C3/ 2,NC4/ 3,H2O/ 4,NH3/ 5,CO2
THERMO DATA
METHOD SYSTEM=PR
KVALUE
PR 1, 2, 0.01/ 1, 3, 0.025
PA06 1, 0.75, 0.93, 1.6/ 3, 0.61, 0.81, 2.1
ENTROPY BANK=SIMSCI, ALPHA=SIMSCI
PA05 1, 0.7, 0.85/ 3, 0.6, 0.71
STREAM DATA
UNIT OPERATION
FLASH UID=F209
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
Modified Soave-Redlich-Kwong and Peng-Robinson

Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=SRKM
STREAM DATA
. . .
General Information
The modified SRK and PR equations of state predict K-values,
enthalpies, entropies, and vapor densities. They are most often used
in gas and refining processes and are generally useful for non-ideal
systems. VLLE behavior can be predicted with the modified SRK
and PR equations of state. Liquid densities can also be predicted but
are not recommended.
Table 4-3: Attributes of the Modified SRK and PR Equations of State

Properties predicted by Modified SRK and PR Equations

Entropies Liquid densities (not recommended)
Enthalpies
Molecular weight Ideal vapor enthalpy
Critical temperature Acentric factor (needed only if ACENTRIC
Critical pressure alpha formulation is selected)

VLLE - Supported
1Automatically
Input Description
Modified Panagiotopoulos-Reid modifications to SRK

METHOD SYSTEM(VLE or VLLE)=SRKM, ...
or METHOD KVALUE(VLE and/or LLE or VLLE)=SRKM,
ENTHALPY=SRKM, ENTROPY=SRKM,
DENSITY(V)=SRKM, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKM is supported but not recommended.
Huron-Vidal modifications to SRK

METHOD SYSTEM(VLE or VLLE)=SRKH, ...
or METHOD KVALUE(VLE and/or LLE or VLLE)=SRKH,
ENTHALPY=SRKH, ENTROPY=SRKH,
DENSITY(V)=SRKH, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKH is supported but not recommended.
SimSci modifications to SRK

METHOD SYSTEM(VLE or VLLE)=SRKS, ...
or METHOD KVALUE(VLE and/or LLE or VLLE)=SRKS,
ENTHALPY=SRKS, ENTROPY=SRKS,
DENSITY(V)=SRKS, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKS is supported but not recommended.

Panagiotopoulos-Reid modifications to SRK
METHOD SYSTEM(VLE or VLLE)=SRKP, ...
or METHOD KVALUE(VLE and/or LLE or VLLE)=SRKP,
ENTHALPY=SRKP, ENTROPY=SRKP,
DENSITY(V)=SRKP, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKP is supported but not recommended.
Kabadi-Danner modifications to SRK

METHOD SYSTEM(VLE or VLLE)=SRKKD, ...
or METHOD KVALUE(VLE and/or LLE or VLLE)=SRKKD,
ENTHALPY=SRKKD, ENTROPY=SRKKD,
DENSITY(V)=SRKKD, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKKD is supported but not recommended.
Modified Panagiotopoulos-Reid modifications to PR

METHOD SYSTEM(VLE or VLLE)=PRM, ...
or METHOD KVALUE(VLE and/or LLE or VLLE)=PRM,
ENTHALPY=PRM, ENTROPY=PRM,
DENSITY(V)=PRM, DENSITY(L)=API, ...
Note: DENSITY(L)=PRM is supported but not recommended.
Huron-Vidal modifications to PR
METHOD SYSTEM(VLE or VLLE)=PRH, ...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=PRH,
ENTHALPY=PRH, ENTROPY=PRH,
DENSITY(V)=PRH, DENSITY(L)=API, ...
Note: DENSITY(L)=PRH is supported but not recommended.
Panagiotopoulos-Reid modifications to PR
METHOD SYSTEM(VLE or VLLE)=PRP, ...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=PRP,
ENTHALPY=PRP, ENTROPY=PRP,
DENSITY(V)=PRP, DENSITY(L)=API, ...
Note: DENSITY(L)=PRP is supported but not recommended.

SYSTEM Selects a combination of consistent thermodynamic property
generators. When SYSTEM=SRKM (or SRKS or SRKH or
SRKP or SRKKD or PRM or PRH or PRP) is chosen, SRKM (or
SRKS or SRKH or SRKP or SRKKD or PRM or PRH or PRP)
K-values, enthalpies, entropies, vapor densities, and API liquid
KVALUE Selects the method for K-value calculations. Both VLE and LLE
K-value calculations are available with the modified SRK and
PR methods. The VLLE option automatically selects
both.SRKM (or PRM) selects the modified Panagiotopoulos-
Reid SRK (or PR) method, SRKS selects the SimSci modified
SRK method, SRH (or PRH) selects the Huron-Vidal modified
SRK (or PR) method, SRP (or PRP) selects the
Panagiotopoulos-Reid modified SRK (or PR), and SRKKD
selects the Kabadi-Danner modified SRK.

KVALUE(VLE or LLE or VLLE) BANK=SIMSCI or NONE or bankid,
ALPHA = SIMSCI or ACENTRIC or bankid,
SRKM or PRM(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...
or
SRKS(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...
or
SRKH or PRH(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, ij, ij/ ...
or
SRKP or PRP(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic/...
or
SRKKD(K or R) i, j, kija, kijb, kijc/ ...
SA01 to SA11 or PA01 to PA11 i, c1, c2, c3/ ...
Note: UOM for SRKH and PRH is K or KCAL/KMOL or KJ/

KMOL
Note: If used for calculating K-values, the SRKM or PRM or

SRKH or PRH or SRKP or PRP or SRKKD or SRKS and SAxx
or PAxx statements must follow the KVALUE statement.
BANK This option selects one or more databanks from which to

retrieve vapor and/or liquid phase binary interaction data.

bankid This option selects the user-created databank named bankid
that is created and maintained by the LIBMGR program.
The SRKM and SRKS databanks are the only databanks that
contain extensive binary interaction parameter data. The
databanks for the advanced PR equations of state are
especially limited in the binary interaction data they contain.
Providing binary interaction parameters regressed from
experimental data is highly recommended when using
advanced SRK and PR equations of state for non-ideal
components.
FILL Selects the method used for estimating values for
hydrocarbon/hydrocarbon binary interaction data missing
from the input file and any selected databank libraries. This
option is not valid for all modified equations of state. See
Filling in Missing Parameters on page 4-27 for further
information on the methods given below.
GOR This option estimates binary interaction parameters between
methane and ethane and heavier hydrocarbons.
GAO This option estimates binary interaction parameters between
methane through propane and heavier hydrocarbons.
hydrocarbon pairs.
formulations.
SIMSCI Selects the SimSci alpha form and values
supplied from the SIMSCI databank (default).
ACENTRIC Uses the original Soave acentric form for alpha
(default).
bankid This option selects the user-created databank
named bankid that is created and maintained
by the LIBMGR program.
Thermo system. Properties missing from this databanks will
be taken from global component data search order.
SRKM This statement allows entry of the binary interaction
or parameters (kijs) for the SRKM or PRM equation of
PRM state.Entries correspond to the following temperature
dependent correlation:

kij = kija + kijb / T + kijc / T2
Temperature units may be K (default) or R. The cij's are

additional non-ideal interactions.
SRKS This statement allows entry of the binary interaction
parameters (kijs) for the SRKS equation of state. Entries
correspond to the following temperature dependent
correlation:
kij = kija + kijb / T + kijc / T 2
Temperature units may be K (default) or R. The cij's are

additional non-ideal interactions.
SRKH This statement allows entry of the binary interaction
or parameters (kijs) for the SRKH or PRH equation of state.
PRH Entries correspond to the following temperature dependent
correlation:
kij = aij + bijl / T + kijl / T2
Temperature units may be K (default) or KCAL/KMOL or KJ/

KMOL. ij and ij are two-parameter interactions.
SRKP This statement allows entry of the binary interaction

or parameters (kijs) for the SRKP or PRP equation of state.
PRP Entries correspond to the following temperature dependent
correlation:
kij = kija + kijb / T + kijc / T2

SRKKD This statement allows entry of the binary interaction
parameters (kijs) for the SRKKD equation of state. Entries
correspond to the following temperature dependent
correlation:
kij = kija + kijb / T + kijc /T 2

PA01 to PA11 component Alpha correlations. See Cubic Equation Of State
Alpha Formulations on page 4-28 for details.

ENTHALPY BANK=SIMSCI or NONE or bankid,
ENTROPY BANK=SIMSCI or NONE or bankid,

DENSITY BANK=SIMSCI or NONE or bankid,

SRKM or PRM(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...
or SRKS(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...
or SRKH or PRH(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, ij, ij/ ...
or SRKP or PRP(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic/...
or SRKKD(K or R) i, j, kija, kijb, kijc/ ...
SA01 to SA11 or PA01 to PA11 i, c1, c2, c3/ ...

All these interaction parameters and alpha formulations may be
selected for enthalpy, entropy, and density methods. Normally,
these features are selected for the K-value method and are automat-
ically carried over for these other methods. If, however, the K-value
method is not any of the modified SRK or PR methods, you can
supply the interaction parameters and/or alpha formulations inde-
pendently. See above under K-value Data for format and definition
of these entries.

...
Examples
E-4.13: Using the SRKM method with default interaction
parameters, model a 50/40/10 mix of propane, normal
butane, and water at 50 psia and 50% vaporization.
TITLE PROB=SRKM
COMPONENT DATA
LIBID 1,C3/ 2,NC4/ 3,H2O
THERMODYNAMIC DATA
METHOD SYSTEM(VLLE)=SRKM
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=1,50/ 2,40/ 3,10
UNIT OPERATION
FLASH UID=FL2
FEED 1
PROD V=2, L=3
TPSPEC PRES=50

RATE,VALUE=0.5
END
E-4.14: For the same problem, explicitly specify SRKKD K-

values, enthalpies, entropies, and vapor densities. Specify
API liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE(VLLE)=SRKKD, ENTHALPY=SRKKD, &
ENTROPY=SRKKD, DENSITY(V)=SRKKD, &
DENSITY(L)=API
E-4.15: Use the SOUR thermo methods but apply PRM to vapor
density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=PRM...
E-4.16: Supply SRKM kij binaries for components 1-2 and 2-3.
Note that unless binary 1-3 is available in the databank,
the kij will have a value of 0.0. Note that the SRKM
statement must follow the KVALUE statement even
though there are no additional entries on the KVALUE
statement.
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM
KVALUE
SRKM 1, 2, 0.01, -0.02/ 2, 3, 0.025, 0.04
components 1 and 3. See Cubic Equation Of State Alpha
Formulations on page 4-28.
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM
KVALUE
SRKM 1,2,0.01,-0.02/2,3,0.025,0.04
SA06 1,0.75,0.93,1.6/3,0.61,0.81,2.1...
E-4.18: For the previous example, supply binary interaction

parameters for component pairs 1-2 and 1-3. Disable all
entropy binary interaction data except those input directly.
Also, supply Twu alpha parameters for entropy

calculations for components 1 and 3, and use the acentric
databank to supply values for component 2.
TITLE PROB=SRKM
PRINT INPUT=ALL
COMPONENT DATA
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM $,ENTROPY=SRKH
KVALUE
SRKM 1,2,0.01/2,3,0.025
SA06 1,0.75,0.93,1.6/3,0.61,0.81,2.1
ENTROPY BANK=NONE, ALPHA=ACENTRIC
$ SRKH(KJ) 1,2,0.06/1,3,0.10
$ SA05 1,0.7,0.85/3,0.6,0.71
STREAM DATA
UNIT OPERATION
FLASH UID=F101
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-4.19: For the previous example, compare the results obtained

from using rigorous VLLE calculations with those
obtained from using the water decant option. Take all the
defaults for the water handling option. Both
thermodynamic systems will be tried in the same run by
assigning different thermodynamic sets.
TITLE PROB=SRKM
PRINT INPUT=ALL
COMPONENT DATA
THERMODYNAMIC DATA
METHOD SYSTEM(VLLE)=SRKM, SET=RIGOROUS
KVALUE
SRKM 1,2,0.01
SA06 1,0.75,0.93,1.6/3,0.61,0.81,2.1
METHOD SYSTEM=SRK, SET=DECANTING
KVALUE
SRK 1,2,0.01
SA06 1,0.75,0.93,1.6/3,0.61,0.81,2.1

WATER DECANT=ON
STREAM DATA
UNIT OPERATION
FLASH UID=RIG
FEED 1
PROD V=2R, L=3R, W=4R
TPSPEC PRES=100 $,TEMP=100
SPEC STREAM=2R, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
METHOD SET=RIGOROUS
FLASH UID=DEC
FEED 1
PROD V=2D, L=3D, W=4D
TPSPEC PRES=100 $,TEMP=100
SPEC STREAM=2D, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
METHOD SET=DECANTING
END
UNIWAALS
Typical Usage
...
COMPONENT DATA
THERMODYNAMIC DATA
METHOD SYSTEM=UNIWAAL
STREAM DATA
. . .
General Information
The UNIWAALS equation of state predicts K-values, enthalpies,
entropies, and vapor and liquid densities. It is most often useful for
highly non-ideal systems if group contribution parameters are sup-
plied either from the built-in databanks or by the user. VLLE behav-
ior can also be predicted with the UNIWAALS equation of state.
Table 4-4: Attributes of the UNIWAALS Equation of State

Properties predicted by UNIWAALS

Enthalpies Liquid densities
Entropies
Critical pressure
Low to mid temperatures
VLLE - Supported
1
Input Description
METHOD SYSTEM(VLE or VLLE)=UNIWAAL, ...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=UNIWAAL,
ENTHALPY=UNIWAAL, ENTROPY=UNIWAAL,
DENSITY(V)=UNIWAAL, DENSITY(L)=API, ...
Note: DENSITY(L)=UNIWAAL is also supported, but is not rec-

ommended.

property generators. When SYSTEM=UNIWAAL is
chosen, UNIWAAL K-values, enthalpies, entropies,
and API liquid densities are assumed.
KVALUE Selects the method for K-value calculations. Both VLE
and LLE K-value calculations are available with the
UNIWAAL method. The VLLE option automatically
selects both.

KVALUE(VLE and/or LLE or VLLE)
BANK=SIMSCI or NONE or bankid,
UFT1(K) m, k, amk, akm, bmk, bkm, cmk, ckm/ ...

UNIFAC(K or KCAL or KJ) m, k, Amk, Akm/...
VA01 to VA11 i, c1, c2, c3/ ...
Note: The UFT1, UNIFAC, and VAxx statements must follow the
KVALUE statement. UOM for UNIFAC is K (default) or KCAL/
KMOL or KJ/KMOL.
vapor and/or liquid phase binary group contribution data.
NONE This option disables all data retrieval from databanks
for interaction parameters.
bankid that is created and maintained by the
LIBMGR program.
ALPHA This option allows access to the databank for alpha formulations.
SIMSCI Selects the SimSci alpha form and values supplied from
the SIMSCI databank (default).
ACENTRIC Uses the original Soave acentric form for alpha.
bankid
system. Properties missing from this databanks will be taken from
global component data search order.
program.
UFT1 This statement allows entry of the temperature dependent Lyngby
and/or modification of the UNIFAC method (UFT1) and non-
UNIFAC temperature dependent UNIFAC group contribution data for
groups m and k for the UNIWAAL equation of state. UFT1 entries
correspond to the following temperature dependent correlation:
Amk = amk + bmk(T-To) + cmk(T ln{To / T} + T - To)
For UNIFAC, units may be K (default) or KCAL/KMOL or KJ/

KMOL.
VA01 to These entries permit various formulations of the pure component
VA11 Alpha correlations. See Cubic Equation Of State Alpha
Formulations on page 4-28 for further details.



UFT1(K) m, k, amk, akm, bmk, bkm, cmk, ckm/ ...

UNIFAC(K or KCAL or KJ) m, k, Amk, Akm/...
VA01 to VA11 i, c1, c2, c3/ ...
Note: UOM for UNIFAC is K or KCAL/KMOL or KJ/KMOL
UNIWAALS UFT1 and UNIFAC binary group contribution data

and alpha formulations VA01-VA11 may be selected for enthalpy,
entropy, and density methods. Normally, these features are selected
for the K-value method and are automatically carried over for these
other methods. If, however, the K-value method is not UNI-
WAALS, you can supply these parameters independently.
entries.

...
method is used. If UFT1 and/or UNIFAC data are specified, van der
Waals area and volume data (VANDERWAALS) may also be input.
However, VANDERWAALS data may only be specified globally
for all thermodynamic sets in the Component Data Category. For a
further description of these input parameters see Chapter 9,
Method-specific Pure Component Data.
Examples
E-4.20: Using the UNIWAALS method with default group
contribution data, calculate the temperature of a 50/50 mix

of propane and normal butane at 50 psia and 50%
vaporization.
TITLE PROB=UNIWAAL
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=UNIWAAL
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/50
UNIT OPERATION
FLASH UID=FL30
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-4.21: For the same problem, use explicitly specified

UNIWAALS K-values, enthalpies, entropies, and vapor
densities. Specify API liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE=UNIWAAL, ENTHALPY=UNIWAAL, &
ENTROPY=UNIWAAL, DENSITY(V)=UNIWAAL, &
DENSITY(L)=API
components 1 and 2, propane and butane. See Cubic
Equation Of State Alpha Formulations on page 4-28.
THERMODYNAMIC DATA
METHOD KVALUE=UNIWAAL, ENTHALPY=UNIWAAL, &
ENTROPY=UNIWAAL, DENSITY(V)=UNIWAAL, &
DENSITY(L)=API
KVALUE
VA06 1,0.34,0.85,2.54/ 2,0.19,0.87,2.96
E-4.23: Use the SOUR thermo methods but apply UNIWAAL to

vapor density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=UNIWAAL

Filling in Missing Parameters
Typical Usage
...
COMPONENT DATA
LIBID 1,C1/ 2,C2/ 3,C3/ 4,NC4/ 5,C5
THERMO DATA
METHOD SYSTEM=SRK
KVALUE FILL=GAO $ or GOR or CPHC
STREAM DATA
. . .
General Information
PRO/II software has an extensive facility to backfill missing binary
interaction data between hydrocarbons for cubic equations of state
(i.e., SRK, PR, and their modifications). Table 4-5 shows the meth-
ods developed by SIMSCI that can be used for estimating binary
Table 4-5: FILL options available for Cubic Equations of State

FILL Options Description
GOR Provides cubic equation of state binary interaction
parameters between methane and ethane and heavier
hydrocarbons. This method is based on correlations of
existing experimental data.
GAO Provides cubic equation of state binary interaction
parameters between methane, ethane, and propane and
heavier hydrocarbons. This method is based on a modified
Gao et al approach.
CPHC Provides cubic equation of state binary interaction
parameters for all hydrocarbon pairs. This method is based
on the work of Chueh and Prausnitz.
Input Description
METHOD SYSTEM=SRK or PR or SRKM or PRM or SRKS

or SRKP or PRP or PPR78, ...
or METHOD KVALUE=SRK or PR or SRKM or PRM or SRKS
or SRKP or PRP or PPR78, ...
SYSTEM One of the cubic equations of state shown above must be

selected if one of the three hydrocarbon/hydrocarbon FILL
options is used.
KVALUE Selects the method for K-value calculations. Only the above
cubic equations of state can be used with the hydrocarbon/
hydrocarbon FILL option.
K-value Data
KVALUE FILL=NONE or GOR or GAO or CPHC
FILL This selects the method used for estimating values for
hydrocarbon/hydrocarbon binary interaction data missing from
the input file and any selected databank libraries. Missing
parameters are regressed using the option selected to fit the
previously specified K-value cubic equation of state method. A
description of the FILL options shown in Table 4-5.
The options are ordered such that each subsequent method in the
table generates more and more binary interaction parameters, so
they provide a spectrum of results that can be selected based on
the goodness of fit to the specific production data being
modeled.
Cubic Equation Of State Alpha Formulations

Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=SRKM
KVALUE
SA06 2, 0.19, 0.87, 2.96
STREAM DATA
. . .
General Information
The pure component alpha formulations are used for methods based
on the cubic equation of state. The alpha function controls pure

component properties (vapor pressure, enthalpies and entropy) as
opposed to the interaction parameter (kij), which controls the mix-
ture properties.
Alpha formulations are available with all cubic equations of state.
The SAxx entries are associated with SRK and modified SRK equa-
tions of state. The PAxx entries are associated with the PR and mod-
ified PR equations of state. The VAxx entries are associated with
the UNIWAAL equation of state. PRO/II software will use all data
supplied on the SAxx, PAxx, or VAxx statements. The constants to
be supplied on the SAxx, PAxx, or VAxx statements can be
regressed from experimental data using REGRESSTM. Compo-
nents not entered here will default to the method selected on the
ALPHA entry.
K-value Data
KVALUE ALPHA=SIMSCI or ACENTRIC or bankid, ...
...,
SA01 or PA01 or VA01 i, c1/ ...
or
SA02 or PA02 or VA02 i, c1, c2, c3/ ...
or
SA03 or PA03 or VA03 i, c1, c2/ ...
or
SA04 or PA04 or VA04 i, c1, c2/ ...
or
SA05 or PA05 or VA05 i, c1, c2/ ...
or
SA06 or PA06 or VA06 i, c1, c2, c3/ ...
or
SA07 or PA07 or VA07 i, c1/ ...
or
SA08 or PA08 or VA08 i, c1, c2, c3/ ...
or
SA09 or PA09 or VA09 i, c1, c2, c3/ ...
or
SA10 or PA10 or VA10 i, c1, c2/ ...
or
SA11 or PA11 or VA11 i, c1, c2/ ...
Note: The SAxx, PAxx and VAxx statements must follow the
KVALUE statement.

formulations for components not given on SAxx, PAxx,
or VAxx statements.
program.
component alpha correlations. Statements that have an
or
S prefix may be used with any form of the Soave-
PA01 to PA11 Redlich- Kwong equation of state, those with P apply
or to the Peng-Robinson equation of state, while those
statements prefixed with V apply to the UNIWAALS
VA01 to VA11
equation of state. For each component i, c1, c2, and c3 are
dimensionless coefficients that define the alpha
correlation for that component.
Table 4-6 gives the equations for the eleven alpha formulations that
are available.
Table 4-6: Alpha Formulations SA01 to SA22 or PA01 to PA11 or VA01 to VA11
xx = Equation Reference
0.5 2
01 = 1 + C1 1 Tr Soave (1972)

C3 2
= C1 + C2 1 Tr
02 Peng-Robinson (1980)

C2
03 = 1 + ( 1 T r ) C 1 + ------- Soave (1979)
Tr
C2
= exp [ C 1 1 T r
04 Boston-Mathias (1980)
2 ( C2 1 ) 2C 2
exp [ C 1 1 T r
05 Twu (1988)
= Tr

C2 C Twu-Bluck-Cunningham
C3 ( C2 1 ) 3
06 (1990) (Recommended
= Tr exp C 1 1 T r
by SimSci)

2C 1 ( Cr + 1 ) 2
= exp ---------------- 1 T r
07 Alternative for form (04)
1 + C1
C3 C 2
08 = T exp C 1 T Alternative for form (06)
r r
09 Mathias-Copeman
0.5 0.5 2 0.5 3 2
= 1 + C1 1 Tr + C2 1 Tr + C3 1 Tr (1983)

0.5 2
10 = 1 + C1 1 Tr + C 2 ( 1 T r ) ( 0.7 T r ) Mathias (1983)

2 Melhem-Saini-Goodwin
0.5
11 = exp C 1 ( 1 T r ) + C 2 1 T r (1989)


ENTHALPY ALPHA=SIMSCI or ACENTRIC or bankid, ...
ENTROPY ALPHA=SIMSCI or ACENTRIC or bankid, ...
DENSITY ALPHA=SIMSCI or ACENTRIC or bankid, ...
SA01 to SA11i, c1, c2, c3/ ...

or
PA01 to PA11i, c1, c2, c3/ ...
or
VA01 to VA11i, c1, c2, c3/ ...
Alpha formulations SA01-SA11 or PA01-PA11 or VA01-VA11 may
be selected for enthalpy, entropy, and density methods. Normally,
these features are selected for the K-value method and are automat-
ically carried over for these other methods. If, however, the K-value
method is not the same as the enthalpy or entropy or density meth-
ods, you can supply these parameters independently.
entries.
Vapor Phase Fugacity Data (optional)

Available only when liquid activity methods are used.
PHI ALPHA=SIMSCI or ACENTRIC or bankid, ...
SA01 to SA11 i, c1, c2, c3/ ...

PA01 to PA11 i, c1, c2, c3/ ...
VA01 to VA11 i, c1, c2, c3/ ...
Alpha formulations SA01-SA11 or PA01-PA11 or VA01-VA11 may
be selected for vapor phase fugacities when liquid activity methods
are used. See above under K-value Data for format and definition of
these entries.
Examples
E-4.24: Using the SRK method with default data, model a 50/50
mix of propane and normal butane at 50 psia and 50%
vaporization. Supply parameters for the Twu-Bluck-
Cunningham alpha formulation SA06 for components 1
and 2, propane and butane.
TITLE PROB=ALPHA
COMPONENT DATA

LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
ENTROPY=SRK, DENSITY(V)=SRK, &
DENSITY(L)=API
KVALUE
SA06 1, 0.34, 0.85, 2.54/ 2, 0.19, 0.87, 2.96
STREAM DATA
UNIT OPERATION
FLASH UID=FL2
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1,
RATE, VALUE=0.5
END

Benedict-Webb-Rubin-Starling
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=BRWS
STREAM DATA
. . .
General Information
The Benedict-Webb-Rubin-Starling equation of state predicts K-
values, enthalpies, entropies, and vapor and liquid densities. It is
most often useful for light to heavy refinery hydrocarbons. Rigor-
ous two liquid phase behavior is not supported with the BWRS
equation of state.
Table 4-7: Attributes of the BWRS Equation of State

Properties predicted by BWRS
Entropies
Critical volume
Components - C1 & heavier
1

METHOD SYSTEM=BWRS, ...
or
METHOD KVALUE=BWRS, ENTHALPY=BWRS,
ENTROPY=BWRS, DENSITY=BWRS, ...

property generators. When SYSTEM=BWRS is
chosen, BWRS K-values, BWRS enthalpies, BWRS
entropies, BWRS liquid and vapor densities are
assumed.
K-value calculations are available with the BRWS
method.

DENSITY Selects the method for density calculation. By default,

(VL or V and/or L) both liquid and vapor densities use this method.

KVALUE BANK=SIMSCI or NONE or bankid
PURE=bankid
BWRS i, j, aij, bij/ ...
Note: BWRS statements must follow the KVALUE statement.
bankid This selects the user-created databank named bankid that is
created and maintained by the LIBMGR program.
PURE This option selects one or more banks from which pure
component BWRS parameters are retrieved.
created and maintained by TDM.

PURE This option selects one or more banks from which pure
component BWRS parameters are retrieved.
created and maintained by TDM.
BWRS This statement allows entry of interaction parameters for
component pairs that use the BWRS equation of state. Each entry
includes the component ID number for each component in the
pair, followed by the interaction parameter value.

ENTHALPY BANK=SIMSCI or NONE or bankid
PURE=bankid
ENTROPY BANK=SIMSCI or NONE or bankid

PURE=bankid
DENSITY BANK=SIMSCI or NONE or bankid

PURE=bankid
BWRS i, j, aij, bij ...

BWRS binary interaction data may be selected for enthalpy,
entropy and density methods. Normally, these features are selected
other methods. If, however, the K-value method is not BWRS, you
can supply these parameters independently.
entries.

or EOS

The BWRS K-value generator supports the free-water decant
option. Refer to Free-water Decant Considerations on page 1-33
for a description of these input options.

...
method is used. However, ideal vapor enthalpy data may only be
specified globally for all thermodynamic sets in the Component
Data Category. For a further description of these input parameters,
Examples
4.25: Using the BWRS method with default binary interaction
data, model a 50/50 mix of propane and normal butane at
50 PSIA AND 50% vaporization.
TITLE PROB=BWRS
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=BWRS
STREAM DATA
COMP=50/50
UNIT OPERATION
FLASH UID=DRUM
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1,&
RATE, VALUE=0.5
END
4.26: For the same problem, use explicitly specified BWRS K-

values, enthalpies, entropies, and vapor densities. Specify
THERMODYNAMIC DATA
METHOD KVALUE=BWRS, ENTHALPY=BWRS, &

ENTROPY=BWRS, DENSITY(V)=BWRS, &
DENSITY(L)=API
4.27: Use the SOUR thermo methods but apply BWRS to vapor
density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=BWRS...

Associating Hexamer Equation Of State
Typical Usage
...
COMPONENT DATA
LIBID 1,IBTE/ 2,IC4/ 3,HF
THERMO DATA
METHOD SYSTEM=HEXAMER
STREAM DATA
. . .
General Information
The HEXAMER equation of state1 predicts K-values, enthalpies,
entropies, and vapor densities. It is most often useful for HF alkyla-
tion and refrigerant synthesis. Rigorous two liquid phase behavior
is supported with the HEXAMER equation of state.
Table 4-8: Attributes of the HEXAMER Equation of State

Properties predicted by HEXAMER
Entropies
Critical volume
Components - Only 1 hexamerizing component and no H2O

VLLE - Supported
1
1. Twu, C.H., J.E. Coon, and J. Cunningham, 1993, An Equation of State

for Hydrogen Fluoride, Fluid Phase Equilibria, 86, 47-62.

METHOD SYSTEM(VLE or VLLE)=HEXAMER, ...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=HEXAMER,
ENTHALPY=HEXAMER, ENTROPY=HEXAMER,
DENSITY(V)=HEXAMER, DENSITY(L)=API, ...

generators. When SYSTEM=HEXAMER is chosen,
HEXAMER K-values, HEXAMER enthalpies, HEXAMER
entropies, HEXAMER vapor densities, and API liquid densities
are assumed.
VLLE K-value calculations are available with the
HEXAMER method.

Note: If DENSITY=HEXAMER without the V qualifier is

used, liquid density will also be calculated from the HEX-
AMER equation of state. This method is not recommended
for this purpose.

KVALUE BANK=SIMSCI or NONE or bankid,
Note: The HEXA statements must follow the KVALUE state-

ment.
vapor and/or liquid phase binary group contribution data.

COMP Selects order of component libraries and databanks, when
HEXA This statement allows entry of interaction parameters for
component pairs that use the Associating Hexamer equation of
state. Each entry includes the component ID number for each
of the two components in the pair, followed by the interaction
parameters.

ENTHALPY BANK=SIMSCI or NONE or bankid
ENTROPY BANK=SIMSCI or NONE or bankid
HEXAMER binary interaction data may be selected for enthalpy,
entropy, and density methods. Normally, these features are selected
other methods. If, however, the K-value method is not HEXAMER,
you can supply these parameters independently.
entries.

...
Data Category. For a further description of these input parameters

Examples
E-4.28: The HEXAMER equation of state is used to model a
hydrocarbon stream containing HF.
TITLE PROJ=MANUAL, PROB=HEXAMER
DIME LIQV=BBL, TIME=DAY, XDEN=API
COMPONENT DATA
LIBID 1,C3/ 2,IC4/ 3,NC4/ 4,IC5/ 5,HF/ 6,NC7
THERMODYNAMIC DATA
METHOD SYSTEM=HEXAMER, SET=SET01, DEFAULT
METHOD SYSTEM(VLLE)=HEXAMER, &
L1KEY=1, L2KEY=5, SET=SET02
STREAM DATA
PROP STREAM=F, TEMP=140, PRES=169, RATE(LV)=65952, &
COMP(V)=17.1/58.4/9.8/1.1/2.1/11.5
PROP STREAM=REFL, TEMP=86, PRES=158, RATE=56250, &
COMP=0.59/0.39/0.02
UNIT OPERATION
COLUMN UID=12C2, NAME=ISOSTRIPPER
PARA TRAY=49, IO=30
FEED F,7/ REFL,1
PROD OVHD=DF, BTMS=1, 20600, VDRAW=IR, 9, 167672
DUTY 1,42,1200/ 2,49,1000
PRES 1,161/ 7,164/ 49,174
ESTI MODEL=CONV
SPEC STREAM=IR, COMP=2, RATE, RATIO, STREAM=F, &
RATE, VALUE=O.75
SPEC TRAY=1, TEMP, VALUE=114.8
VARY DUTY=2, DRAW=IR
FLASH UID=F1, NAME=CONDENSER
FEED DF
PROD L=DF1, W=HF1
ISO PRES=50, TEMP=85
METHOD SET=SET02
END

Lee-Kesler-Plocker
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=LKP
STREAM DATA
. . .
General Information
The LKP method is derived from a corresponding states approach
combined with the Benedict-Webb-Rubin-Starling (BWRS) equa-
tion of state (see Benedict-Webb-Rubin-Starling on page 4-34).
The LKP method predicts K-values, enthalpies, entropies, and
vapor and liquid densities. It is most often used for light hydrocar-
bons and for reformer systems containing high quantities of hydro-
gen. VLLE behavior can also be predicted with the LKP method.
Table 4-9: Attributes of the LKP Method
Properties predicted by LKP
Entropies

Critical volume Specific gravity
Temperature - Below reduced temperatures of 0.96
Components - Light hydrocarbons
VLLE - Supported

Input Description
METHOD SYSTEM(VLE or VLLE)=LKP, ...
or
METHOD KVALUE(VLE or VLLE)=LKP, ENTHALPY=LKP,
ENTROPY=LKP, DENSITY=LKP

property generators. When SYSTEM=LKP is chosen,
LKP K-values, LKP enthalpies, LKP entropies, LKP
liquid and vapor densities are assumed.
KVALUE Selects the method for K-value calculations. Both VLE
and LLE K-value calculations are available with the
LKP method. The VLLE option automatically selects
both.
(VL or V and/or L) both vapor and liquid (VL) enthalpies are calculated
methods for the vapor and liquid enthalpies by
providing both an ENTHALPY(V) and
ENTHALPY(L) entry.
(VL or V and/or L) both vapor and liquid (VL) entropies are calculated
providing both an ENTROPY(V) and ENTROPY(L)
entry.
DENSITY Selects the method for density calculation. By default,
(VL or V and/or L) both vapor and liquid (VL) densities are calculated
providing both an DENSITY(V) and DENSITY(L)
entry.

KVALUE(VLE or LLE or VLLE) BANK=SIMSCI or NONE or bankid
COMP = SIMSCI or PROCESS or
bankid
LKP i, j, kij / ...
Note: The LKP statements must follow the KVALUE statement.

COMP Selects order of Component Libraries and Databanks, while
system. Properties missing from this databanks will be taken from
global component data search order
that is created and maintained by the LIBMGR program
LKP This statement allows entry of the interaction parameters for
component pairs that use the Lee-Kesler-Plocker method. Each
entry includes the component ID number for each of the two
components in the pair, followed by the interaction parameter
value.

ENTHALPY BANK= SIMSCI or NONE or bankid
ENTROPY BANK= SIMSCI or NONE or bankid


LKP i, j, kij / ...

LKP binary interaction data may be selected for enthalpy, entropy,
and density methods. Normally, these features are selected for the
K-value method and are automatically carried over for these other
methods. If, however, the K-value method is not LKP, you can sup-
ply these parameters independently.
entries.

...

Data Category. For a further description of these input parameters,
Examples
E-4.29: Using the LKP method, calculate the temperature of a 50/
50 mix of propane and normal butane at 50 psia and 50%
vaporization.
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=LKP
STREAM DATA
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-4.30: For the same problem, explicitly specify LKP K-values,

liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE=LKP, ENTHALPY=LKP, ENTROPY=LKP, &
DENSITY(V)=LKP, DENSITY(L)=API
E-4.31: Use the SOUR thermo methods but apply LKP to vapor
density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=LKP

Predictive Peng-Robinson 78
Typical Usage
...
COMPONENT DATA
THERMODYNAMIC DATA
METHOD SYSTEM= PPR78
STREAM DATA
. . .
General Information
The Predictive Peng-Robinson 78 (PPR78) equation of state pre-
dicts K-values, enthalpies, entropies, and vapor densities. It is used
for the prediction of phase equilibria of binary mixtures in both the
subcritical and critical regions very accurately. This method has
been applied to mixtures containing alkanes, aromatics, napthenes,
carbon dioxide, hydrogen sulfide, and nitrogen. The present imple-
mentation is limited to PPR78 model - supported groups only. For
unsupported components, the calculations for kij interaction param-
eters will be defaulted to PR EOS. Liquid densities and VLLE
behavior predictions are not recommended without using an
advanced form of the PR equation of state ( See Peng-Robinson
on page 4-7.).

Table 4-10: Attributes of the PPR78 Equation of State
Properties predicted by PR
Entropies

Molecular weight Ideal vapour enthalpy
Critical pressure Acentric Factor
Critical temprature
1
Input Description
METHOD SYSTEM= PPR78, ...
or
METHOD KVALUE=PPR78, ENTHALPY=PPR78,
ENTROPY=PPR78, DENSITY(V)=PPR78,
DENSITY(L)=API,........
Note: DENSITY(L)=PPR78 is supported but not recommended.

KVALUE(VLLE)=PPR78 is supported but not recommended.

property generators. When SYSTEM=PPR78 is
chosen, PPR78 K-values, PPR78 enthalpies, PPR78
entropies, API liquid densities, and PPR78 vapor
calculations are recommended with the PPR78 method.

Note: If DENSITY=PPR78 without the V qualifier is used, liq-

uid density will also be calculated from the PPR78 equation of
state. This method is not recommended for this purpose.

KVALUE BANK= SIMSCI or NONE or bankid,
program.
hydrocarbon binary interaction data missing from the input file and
any selected databank libraries. This option is not valid for all
modified equations of state. See Filling in Missing Parameters on
page 4-27. for further information on the methods given below.

hydrocarbons.
hydrocarbon pairs.
Example
E-4.32: Using the PPR78 method with default interaction
parameters and using acentric factors for alpha
formulation, calculate the temperature of a 50/50 mix of
propane and normal butane at 50 psia and 50%
vaporization.
TITLE PROB=PPR78, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=PPR78
STREAM DATA
UNIT OPERATION
FLASH UID=F203
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

E-4.33: For the same problem, explicitly specify PPR78 K-values,
liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE=PPR78, ENTHALPY=PPR78, ENTROPY=PPR78,&
DENSITY(V)=PPR78, DENSITY(L)=API...
E-4.34: Use the SOUR thermo methods but apply PR to vapor

density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=PPR78
The table below shows the 15 PPR78 groups defined for reference:
Table 4-11: PPR78 Method Supported Groups
Group No. Group Name IPS UNIFAC
Group
1 CH3 900
2 CH2 901
3 CH 902
4 C 903
5 CH4 2011
6 C 2 H6 None : Must
Convert Ethane
to PPR78 group
6.
7 CHaro 1200
8 Caro 1222
9 Cfused Aromatic 1201
Rings
10 CH2, Cyclic 1000
11 CH , Cyclic 1001
(for CHcyclic)
1002
(for Ccyclic)
12 CO2 2111
13 N2 2199

Table 4-11: PPR78 Method Supported Groups
Group No. Group Name IPS UNIFAC
Group
14 H2 S 2077
15 SH 1531
16 H20 1622

Predictive Soave-Redlich-Kwong (PSRK)
Typical Usage
...
COMPONENT DATA
THERMODYNAMIC DATA
METHOD SYSTEM= PSRK
STREAM DATA
. . .
General Information
PSRK is a group contribution equation of state based on a combina-
tion of the Soave-Redlich-Kwong equation of state and a mixing
rule whose parameters are determined by the UNIFAC method.
This model can be used for VLE-predictions over a large tempera-
ture and pressure range and is easily extended to mixtures contain-
ing supercritical compounds.

Table 4-12: Attributes of the PSRK Equation of State
Properties predicted by PSRK
Entropies

Molecular weight Ideal vapour enthalpy
Critical pressure Acentric Factor
Critical temprature
1
Input Description
METHOD SYSTEM= PSRK, ...
or
METHOD KVALUE=PSRK, ENTHALPY=PSRK,
ENTROPY=PSRK, DENSITY(V)=PSRK,
DENSITY(L)=API,........
Note: DENSITY(L)=PSRK is supported but not recommended.

KVALUE(VLLE)=PSRK is supported but not recommended.

property generators. When SYSTEM=PSRK is chosen,
PSRK K-values, PSRK enthalpies, PSRK entropies,
API liquid densities, and PSRK vapor densities are
assumed.
calculations are recommended with the PSRK method.

Note: If DENSITY=PSRK without the V qualifier is used, liq-

uid density will also be calculated from the PSRK equation of
state. This method is not recommended for this purpose.

KVALUE ALPHA= SIMSCI or NONE or bankid,

formulations.
SIMSCI Selects the SimSci alpha form and values supplied
from the SIMSCI databank.
program.
Example
E-4.35: Using the PSRK method, calculate the temperature of a 50/
50 mix of propane and normal butane at 50 psia and 50%
vaporization.
TITLE PROB=PPR78, PROJ=THERMO
PRINT INPUT=ALL
COMPONENT DATA

LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=PSRK
STREAM DATA
UNIT OPERATION
FLASH UID=F203
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-4.36: For the same problem, explicitly specify PSRK K-values,

liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE=PSRK, ENTHALPY=PSRK, ENTROPY=PSRK,&
DENSITY(V)=PSRK, DENSITY(L)=API...
E-4.37: Use the SOUR thermo methods but apply PSRK to vapor
density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=PSRK

Chapter 5
Special Packages
Several special thermodynamic packages have been incorporated
into the program. These packages have been developed for particu-
lar applications containing systems of components commonly
found in refining or chemicals processing. Systems available
include alcohols, glycols, sour water and amines.
Alcohols
Typical Usage
...
COMPONENT DATA
LIBID 1,ETOH/ 2, MEOH/ 3, H2O
THERMO DATA
METHOD SYSTEM=ALCOHOL
STREAM DATA
. . .
General Information
The ALCOHOL package is used to predict VLE and/or LLE phase
behavior. This method does not support free water decant. This sys-
tem uses a special set of NRTL binary interaction data for systems
containing alcohols, water, and other polar components.
The ALCOHOL package is generally useful for applications
involving alcohols, especially for azeotropic distillation common in
alcohol dehydration plants. Refer to the PRO/II Reference Manual
for information.

Input Description
Table 5-1: Attributes of the ALCOHOL Package
Properties predicted by the ALCOHOL method
K-values

Vapor pressure PHI=IDEAL and POYNTING=OFF
Vapor pressure PHI=SRK or PR or SRKM or PRM or SRH or
Critical temperature PRH or SRP or PRP or SRKS or SRKKD or
Critical pressure HOCV or PPR78 or BWRS or UNIWAAL
Acentric factor
Vapor pressure When used with POYNTING=ON
Liquid molar volume
Pressure - up to 1500 psia
Temperature - 122-230 F (H2O-Alcohol),
150-230 F (Other systems)
Components - Alcohols, water, other polar components
VLLE - Supported

METHOD SYSTEM(VLE or VLLE)=ALCOHOL,
PHI=IDEAL, {HENRY}
or
METHOD KVALUE(VLE and/or LLE or VLLE)=ALCOHOL,
ENTHALPY(V)=SRKM, ENTHALPY(L)=IDEAL,
ENTROPY=SRKM, DENSITY(V)=SRKM,
DENSITY(L)=IDEAL, PHI=IDEAL, {HENRY}, ...

generators. When SYSTEM=ALCOHOL is chosen, NRTL K-
values, SRKM vapor enthalpies, IDEAL liquid enthalpies, SRKM
entropies, IDEAL liquid densities, and SRKM vapor densities are
default. Interaction parameters are defaulted to the ALCOHOL
databank.
5-2 Special Packages

K-value calculations are available with the ALCOHOL package.
The VLLE option automatically selects both. See Vapor-liquid-
liquid Equilibrium Considerations on page 1-38 for more details
on liquid-liquid equilibrium calculations.
PHI Selects the option used to calculate pure component and mixture
vapor phase fugacity coefficients (i). A vapor fugacity method
should generally be selected for high pressure applications. The
options are the equations of state methods SRK, PR, SRKM,
PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, PPR78, BWRS
and UNIWAAL (see Chapter 4) and HOCV (the Hayden-
O'Connell method), TVIRIAL (the Truncated Virial method) and
the IDIMER method. See Hayden-OConnell Vapor Fugacity
on page 6-64; Truncated Virial Vapor Fugacity on page 6-68;
and IDIMER Vapor Fugacity on page 6-71 for details on these
last three options. The default is PHI=IDEAL.
HENRY This option selects Henry's Law data (either user-supplied or from
databanks) to model dissolved gases in a liquid solution. See
IDIMER Vapor Fugacity on page 6-71 for further details.
Note: A heat of mixing option, HMIX, is available for the

enthalpy method selected. See Redlich-Kister, Gamma Heat of
Mixing on page 6-75 for further information on the use of this
option.

K-value Data (Optional)
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON,
MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY,
BANK=ALCOHOL and SIMSCI or NONE or bankid,
FILL=NONE or UNIFAC or CIUNIFAC or UFT1 or FLORY or
REGULAR,
AZEOTROPE=SIMSCI or NONE or bankid, WRITE=fileid
NRTL3(K or KCAL or KJ) i, j, bij, bji, aij / ...

and/or
NRTL(K or KCAL or KJ) i, j, aij, bij, aji, bji, a ij / ...
and/or
NRTL6(K or KCAL or KJ) i, j, aij, bij, aji, bji, ij, ij /...
and/or
NRTL8(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, ij, ij/...
and/or
NRTL10(K) i, j, aij, bij, dij, eij, aji, bji, dji, eji, ij,
ij/....
and/or
NRTL14(K) i, j, aij, bij, cij, dij, eij, fij, aji, bji, cji, dji, eji,
fji, ij, ij/....
and/or
AZEOTROPE(basis, upres, utemp) i, j, pres, temp, xi / ...
and/or
INFINITE(utemp) i, j, temp, ioo, joo / ...
and/or
MUTUAL(basis, utemp) i, j, temp, xiI, xiII / ...
and/or
IDEAL i, j/ ...
Note: The NRTL3, NRTL, NRTL6, NRTL8, NRTL10, NRTL14

AZEOTROPE, INFINITE, MUTUAL and/or IDEAL statements
must follow the KVALUE statement. UOM for
NRTL3,NRTL,NRTL6 & NRTL8 is K or KCAL/KMOL or KJ/
KMOL.
POYNTING This option selects whether to apply the Poynting correction

to fugacities of components in the liquid phase. The default is
OFF unless a PHI method is selected, in which case the
default is ON.
MOLVOL This selects the method used to calculate the liquid molar
volume necessary for computing the Poynting correction
factor. Options are:

STANDARD The default. Selects the standard method for
calculating the liquid molar volume at
standard conditions (25 C, 1 atm).
RACKETT Selects the Rackett liquid density method.
RCK2 Selects the Rackett 2 liquid density method.
LIBRARY Selects the LIBRARY liquid density method.
BANK This option selects the alcohol databank from which to retrieve vapor
ALCOHOL Selects the ALCOHOL databank. This databank contains
binary coefficients for a special set of components including
many alcohols, water and other polar components. See Table
5-2 for the components available in this databank and Figure
5-1 for the binary interaction data available. This is the
default databank when SYSTEM=ALCOHOL or
KVALUE=ALCOHOL is selected.
SIMSCI Selects the SIMSCI databank. If selected, this should follow
the ALCOHOL entry. The program will search the
ALCOHOL databank first for NRTL interaction parameters,
then attempt to find missing parameters in the SIMSCI
databank.
bankid This option selects a user-created databank named bankid
that is created and maintained with the LIBMGR program.
FILL This selects the method used for estimating values for binary
interaction data missing from the input file and any selected
databank libraries. See Filling in Missing Parameters on
page 6-52 for further details on these options.
AZEOTROPE This selects the azeotrope databank used for retrieving azeotropic
data for binary pairs. Current options are SIMSCI (default) or NONE
or bankid.
WRITE This option writes the binary interaction parameters for the liquid
activity coefficient K-value method to a file. The format of this file is
suitable for inclusion into an input file.
fileid This name identifies the file containing the binary interaction data. It
may be any valid file name allowed on the particular operating
system being used, but must not include a suffix. The program will
automatically add a suffix (e.g., .FIL on PCs).

NRTL3 This statement allows entry of the binary interaction data parameters
and/or for the NRTL K-value method used in the ALCOHOL package. The
NRTL statements can be mixed in order to enter the data in the most
and/or convenient form. The binary parameters aij, bij, cij, dij, eij, fij, aji, bji,
NRTL6 cji, dji, eji, fji, ij and ij are related to the liquid activity coefficients
and/or i by the following equations:
NRTL8
and/or
NRTL10
and/or
NRTL14
j ji G ji x j x j G ij k x k kj G kj
In i = ----------------------- + ------------------- ij --------------------------
k G ki x k k G kj x k k G kj x k
j
When unit is K:
b ij c ij
ij = a ij + ----- + -----2 + d ij InT + e ij T + f ij TInT
T T
When unit is KCAL/KMOL or KJ/KMOL:

b ij c ij
ij = a ij + ------- + -----------
- + d ij In ( RT ) + e ij RT
RT R 2 T 2
+ f ij RTIn ( RT )
G ij = exp ( ji ij ), ji = ' ji + ' ji T
AZEOTROPE These statements are used to enter data for binary pairs. This data
and/or will be regressed to the coefficients for the liquid activity method
INFINITE used to generate the K-values. Multiple statements may be used to
and/or enter data with different units, or the data can be entered on a single
statement.
MUTUAL
and/or This statement sets the binary interaction parameters to zero.
IDEAL
Data input using the NRTL3, NRTL, NRTL6, NRTL8, NRTL10,

NRTL14, AZEOTROPE, INFINITE, MUTUAL and IDEAL state-
ments are used in preference to any data retrieved from the data-
banks or estimated using FILL options. See Filling in Missing
Parameters on page 6-52 for further details.

ENTHALPY(V) BANK=SIMSCI or NONE or bankid
ALPHA=SIMSCI or ACENTRIC or bankid,

COMP = SIMSCI or PROCESS or bankid.
DENSITY(V) BANK=SIMSCI or NONE or bankid,

SRKM(K or R)i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...
SA01 to SA11 i, c1, c2, c3/ ...
BANK Selects databank from which to retrieve binary

interaction data.
SIMSCI Selects the SimSci standard databank(default).
bankid This option selects a user-created databank named
bankid that is created and maintained with the
LIBMGR program.
formulations.
ACENTRIC Uses original Soave acentric form for alpha (default).
LIBMGR program.
COMP Selects order of component libraries and databanks
when searching for pure components required for the
current Thermo system. Properties missing from this
databanks will be taken from global component data
search order.
PROCESS Selects the SimSci PROCESS databank
program.
Note: The SRKM and SAxx statements may follow each

ENTHALPY(V), ENTROPY or DENSITY(V) STATEMENT.

Table 5-2: ALCOHOL Databank Components
Component Formula LIBID
Water H2O H2O
Alcohols
Methanol CH4O MEOH
Ethanol C2H6O ETOH
N-propanol C3H8O NPRA
Isopropanol C3H8O IPA
C4H10O IBA
N-butanol
C4H10O SBA
Isobutanol
C5H12O TBA
Sec-butanol C5H12O 3M1BA
Tert-butanol
3-Methyl-1 butanol
N-Pentanol
Ethers
Isopropyl Ether C6H14O IPE, DIPE,
Ethyl Ether C4H10O DEE
Methyl Ether C2H6O DME
Acids
Acetic Acid C2H4O2 HAC, HDAC
Formic Acid CH2O2 HFOR
Ketones
Methyl Ethyl C4H8O MEK
Ketone C3H6O DMK
Acetone
Esters
Ethyl Acetate C4H8O2 EOQC
Methyl Formate C2H4O2 MFOR
Miscellaneous
Acetaldehyde C2H4O ACH
Sulfolane C4H8O2S SULFLN
Light Gases
Hydrogen H2 H2
Nitrogen N2 N2
Oxygen O2 O2
Carbon Dioxide CO2 CO2

Table 5-2: ALCOHOL Databank Components
Component Formula LIBID
Hydrocarbons
Isopentane C5H12 IC5
N-Pentane C5H12 NC5
Cyclopentane C5H10 CP
2 Methylpentane C6H14 2MP
C6H12 1HEXENE
1-Hexene
C6H14 NC6
N-Hexane
C6H12 MCP
Methylcyclopentane C6H6 C6H6
Benzene C6H12 CH
Cyclohexane C7H16 24DMP
2-4 CYH16 3MHX
Dimethylpentane
3-Methylhexane C7H14 1T2MCP
1-Trans-2- C7H16 NC7
Dimethyl- C7H14 MCH
cyclopentane C7H8 TOLU
C8H18 24DMHX
N-Heptane
Methylcyclohexane
C8H16 1T2C4MCP
Toluene
2-4 Dimethylhexane
1-Trans-2-Cis-4-Tri-
Methylcyclopentane

Figure 5-1: Binary Interaction Data (a)

VP
...
see Chapter 9, Method-specific Pure Component Data. Note that
only vapor pressure has any direct effect on the calculation of liquid
activity coefficients. Tc, Pc and the acentric factor will have an
impact if a cubic equation of state is chosen for vapor phase fugaci-
ties. Molar volume will have an impact on the Poynting correction
factor.

Figure 5-2: Binary Interaction Data (b)

Figure 5-3: Binary Interaction Data (c)
Examples
E-5.1: Using the ALCOHOL system, model a 50/25/20/5 mix of
water, benzene, ethanol and cyclohexane at 50 psia and
20% vaporization. Use SRK for vapor phase fugacity
calculations, and supply NRTL binary interaction data.
TITLE PROB=ALCOHOL
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,H2O/2,BENZENE/3,ETOH/4,CHEN
THERMO DATA
METHOD SYSTEM=ALCOHOL, PHI=SRK
KVALUE FILL=UNIFAC, POYNTING=ON
NRTL 1,2,5.256,219.685,-5.645,288.34,0.2/ &
1,3,1.015,536.264,0.4985,-456.0,0.1448/ &
2,3,-2.748,1472.24,-0.449,440.51,0.5355
STREAM DATA
COMP=50/25/20/5

UNIT OPERATION
FLASH UID=FL2B
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.2
END
E-5.2: For the same problem, use ALCOHOL K-values, IDEAL

enthalpies and liquid densities and SRK vapor densities.
THERMO DATA
METHOD KVALUE=ALCOHOL, ENTHALPY=IDEAL, &
DENSITY(L)=IDEAL, DENSITY(V)=SRK, PHI=SRK

Glycols
Typical Usage
...
COMPONENT DATA
LIBID 1,H2O/ 2, CH/ 3, TEG
THERMO DATA
METHOD SYSTEM=GLYCOL
STREAM DATA
. . .
General Information
The GLYCOL package is used to predict VLE and/or LLE phase
behavior. This method does not support free water decant. It uses a
special set of SRKM binary interaction data and alpha parameters
for systems containing glycol, water, and other components.
The GLYCOL package is generally useful for applications involv-
ing triethylene glycol, and to a lesser extent, diethylene glycol, and
ethylene glycol. It is useful especially for TEG dehydration plants.
Refer to the PRO/II Reference Manual for information.
Table 5-3: Attributes of the GLYCOL Package

Properties predicted by GLYCOL method
K-values
Critical pressure
Temperature - 80-400 F
Components - A glycol or water must be present
VLLE - Supported
1 Automatically

Input Description
METHOD SYSTEM(VLE or VLLE)=GLYCOL
or
METHOD KVALUE(VLE and/or LLE or VLLE)=GLYCOL,
ENTHALPY(V)=SRKM, ENTHALPY(L)=SRKM,
DENSITY(L)=API,...
and
KVALUE BANK=GLYCOL

generators. When SYSTEM=GLYCOL is chosen, SRKM K-
values, SRKM vapor enthalpies, IDEAL liquid enthalpies,
SRKM entropies, IDEAL liquid densities, and SRKM vapor
densities are default.
KVALUE Selects the method for K-value calculations. Both VLE and
LLE K-value calculations are available with the SRKM
method, which is used by the GLYCOL package. The VLLE
option automatically selects both. See Vapor-liquid-liquid
Equilibrium Considerations on page 1-38 for more details on
liquid-liquid equilibrium calculations.

KVALUE(VLE or LLE or VLLE)
BANK=GLYCOL and SIMSCI or NONE or bankid,
SRKM(K or R)i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...
SA01 to SA11 i, c1, c2, c3/ ...
Note: If used for calculating K-values, the SRKM and SAxx

statements must follow the KVALUE statement.
BANK This option selects the GLYCOL databank from which to

GLYCOL Selects the GLYCOL databank. This databank contains
binary coefficients and alpha parameters for a special set of
components including many glycols, water and other
components. See Table 5-4 for the components available in
this databank. This is the default databank when
SYSTEM=GLYCOL or KVALUE=GLYCOL is selected.

SIMSCI Selects the SimSci standard databank. If selected this should
follow the GLYCOL entry. The program will search the
GLYCOL databank first for SRKM interaction parameters,
then attempt to find missing parameters in the SIMSCI
databank.
formulations.
SIMSCI Selects the SimSci alpha formulation and values supplied
from the SimSci databank (default).
ACENTRIC Uses original Soave acentric form for alpha (default).
program.
SRKM This statement inputs binary interaction parameters and
and/or alpha formulation data for the SRKM method used to
SA01 to SA11 calculate K-values for the GLYCOL package. See
Modified Soave-Redlich-Kwong and Peng-Robinson on
page 4-13 for further details.




SRKM(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...
SA01 to SA11 i, c1, c2, c3/ ...

selected for enthalpy, entropy, and density methods. Normally for
the GLYCOL package, these features are selected for the K-value
method and are automatically carried over for these other methods.
However, you can supply the interaction parameters and/or alpha
formulations independently.
entries.
Table 5-4: Components Available for GLYCOL Package
Gas Component Formula LIBID
Hydrogen H2 H2
Nitrogen N2 N2
Oxygen O2 O2
Carbon Dioxide CO2 CO2
H2S H2S
Hydrogen Sulfide
CH4 C1
Methane
C2H6 C2
Ethane C3H8 C3
Propane C4H10 IC4
Isobutane C4H10 NC4
N-butane
Liquid Components Formula LIBID
Isopentane C5H12 IC5
Pentane C5H12 NC5
Hexane C6H14 NC6
Heptane C7H16 NC7
C6H12 CH
Cyclohexane
C7H14 MCH
Methylcyclohexane
C8H16 ECH
Ethylcyclohexane C6H6 BNZN
Benzene C7H8 TOLU
Toluene C8H10 OXYL
O-xylene C8H10 MXYL
M-xylene C8H10 PXYL
P-xylene C8H10 EBZN
Ethylbenzene
Liquid Components Formula LIBID

Table 5-4: Components Available for GLYCOL Package
Ethylene Glycol C2H6O2 EG
Diethylene Glycol C4H10O3 DEG
Triethylene Glycol C6H14O4 TEG
Water H2O H2O

...
Examples
E-5.3: Using the GLYCOL system, model a 50/25/20/5 mix of
water, benzene, ethanol and TEG at 50 psia and 20%
vaporization. Supply SRKM binary interaction data.
TITLE PROB=GLYCOL
COMPONENT DATA
LIBID 1,H2O/2,BENZENE/3,ETOH/4,TEG
THERMO DATA
METHOD SYSTEM=GLYCOL
KVALUE
SRKM 2,4,0.05,0.0,0.0,0.3,0.07,0.0,0.0,0.3
STREAM DATA
COMP=50/25/20/5
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC TEMP=100
RATE, VALUE=0.2
END
E-5.4: For the same problem, use K-values and IDEAL liquid
densities.
THERMO DATA
METHOD KVALUE=GLYCOL, ENTHALPY=SRKM, &
DENSITY(L)=IDEAL, DENSITY(V)=SRKM

Sour Water
Typical Usage
...
COMPONENT DATA
LIBID 1,H2O/ 2, NH3/ 3, CO2
THERMO DATA
METHOD SYSTEM=SOUR
STREAM DATA
. . .
General Information
The SOUR package is used to predict VLE and/or LLE phase
tem uses the API/EPA SWEQ (Sour Water EQuilibrium) method
developed by Grant Wilson to model sour water components NH3,
H2S, CO2, and H2O. SRKM generates phase equilibria for all other
components.
The SOUR package is generally useful for applications involving
sour water containing less than 30% by weight of sour components.
Table 5-5: Attributes of the SOUR Package

Properties predicted by SOUR method
K-values

Critical pressure

Components - xwtNH3 + xwtCO2+ xwtH2S< 0.30
(H2O, NH3, and one acid gas required)

VLLE - Supported

Input Description
METHOD SYSTEM(VLE or VLLE)=SOUR,...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=SOUR,
DENSITY(L)=IDEAL, ...

generators. When SYSTEM=SOUR is chosen, SOUR K-values,
SRKM vapor enthalpies, IDEAL liquid enthalpies, SRKM
entropies, IDEAL liquid densities, and SRKM vapor densities
are default.
VLLE K-value calculations are available with the SOUR
package.



SA01 to SA11 i, c1, c2, c3/ ...

selected for enthalpy, entropy, and density methods. Normally, for
the SOUR package, these features are selected for the K-value
method and are automatically carried over for these other methods.
However, you can supply the interaction parameters and/or alpha
formulations independently.
BANK This option selects the databank from which to

retrieve vapor and/or liquid phase binary interaction
data.

NONE This option disables all data retrieval from

databanks for interaction parameters.
LIBMGR program.
formulations.
SIMSCI Selects the SimSci alpha formulation and values
supplied from the SimSci databank (default).
ACENTRIC Uses original Soave acentric form for alpha
(default).
LIBMGR program.
COMP Selects order of component libraries and databanks
when searching for pure components required for
the current Thermo system. Properties missing from
this databanks will be taken from global component
data search order.
bankid that is created and maintained by the
LIBMGR program.
SRKM These statements input binary interaction parameters and
SA01 to SA11 calculate vapor enthalpies, vapor densities and liquid and
vapor entropies for the SOUR package. See Modified
Soave-Redlich-Kwong and Peng-Robinson on page 4-13
for further details.

...

Examples
E-5.5: Using the SOUR system, model a 80/5/10/5 mix of water,
H2S, CO2 and NH3 at 50 psia and 20% vaporization.
TITLE PROB=SOUR
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,H2O/2,H2S/3,CO2/4,NH3
THERMO DATA
METHOD SYSTEM=SOUR
STREAM DATA
COMP=80/5/10/5
UNIT OPERATION
FLASH UID=FL7
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1,&
RATE, VALUE=0.2
END
E-5.6: For the same problem, supply SRKM vapor enthalpy

interaction data for component pairs 1-2 and 1-4.
THERMO DATA
METHOD SYSTEM=SOUR
ENTHALPY(V)
SRKM 1, 2, 0.38, -26.7, 7, 0.0, 1.64, 0.3, -168, 10011, 0.3/ &
1, 4, -0.08, -54, 0.0, 2.5, -0.18, -28, 0.0, 0.5
GPA Sour Water

Typical Usage
...
COMPONENT DATA
LIBID 1, H2O/2, H2S/3, CO2/4, NH3
THERMO DATA
METHOD SYSTEM=GPSWATER
STREAM DATA
. . .

General Information
The GPSWATER package predicts VLE and/or LLE phase behavior
for Sour Water systems. This method does not support free water
decant. It uses the Gas Processors Association GPSWAT method to
model sour water components H2O, NH3, H2S, CO, CS2, MeSH,
EtSH and CO2. SRKM is used for all other components.
The GPSWATER package is generally valid for a wider range of
applications involving sour water than the SOUR package (See
Sour Water on page 5-19).
Table 5-6: Attributes of GPSWATER Package
Properties predicted by GPSWATER method
K-values

Critical pressure
Components - xwtNH3 < 0.40, PCO2+ PH2S < 1200 psia
(H2O, NH3, H2S, and CO2 required)

VLLE - Supported
1
Input Description
METHOD SYSTEM(VLE or VLLE)=GPSWATER,...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=GPSWATER,


generators. When SYSTEM=GPSWATER is chosen,
GPSWATER K-values, SRKM vapor enthalpies, IDEAL liquid
enthalpies, SRKM entropies, IDEAL liquid densities, and
SRKM vapor densities are default.
VLLE K-value calculations are available with the GPSWATER
package.

SA01 to SA11 i, c1, c2, c3/ ...

selected for enthalpy, entropy, and density methods. Normally, for
the GPSWATER package, these features are selected for the K-
value method and are automatically carried over for these other
methods. However, you can supply the interaction parameters and/
or alpha formulations independently.
BANK This option selects the databank from which to retrieve vapor
SIMSCI Selects the SimSci standard databank
(default).
bankid This option selects a user-created databank
named bankid that is created and
maintained with the LIBMGR program.
formulations.

SIMSCI Selects the SimSci alpha formulation and
values supplied from the SimSci databank
(default).
(default).
named bankid that is created and
maintained with the LIBMGR program.
bankid This option selects the user-created
databank named bankid that is created
and maintained by the LIBMGR program.
SRKM This statement inputs binary interaction parameters and
SA01 to SA11 calculate vapor enthalpies, vapor densities and liquid and
vapor entropies for the GPSWATER package. See
Modified Soave-Redlich-Kwong and Peng-Robinson on
page 4-13 for further details.

...
Examples
E-5.7: Using the GPSWATER system, model a 80/5/10/5 mix of
water, H2S, CO2 and NH3 at 50 psia and 20%
vaporization.
TITLE PROB=GPSWATER
COMPONENT DATA
LIBID 1,H2O/2,H2S/3,CO2/4,NH3
THERMO DATA
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100,&
COMP=80/5/10/5

UNIT OPERATION
FLASH UID=F405
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.2
END
E-5.8: For the same problem, supply SRKM enthalpy interaction

data for component pairs 1-2 and 1-4.
THERMO DATA
ENTHALPY(V)
SRKM 1, 2, 0.38, -26, 0.0, 1.6, 0.3, -168, 10011, 0.3/ &
1, 4, -0.08, -54, 0.0, 2.5,- 0.18, -28, 0.0, 0.5
Amines
Typical Usage
...
COMPONENT DATA
LIBID 1, H20/2, H2S/3, MEA/4, C1
THERMO DATA
METHOD SYSTEM=AMINE
STREAM DATA
...
General Information
The AMINE package is used to predict VLE and/or LLE phase
tem uses the Kent-Eisenberg model for reaction equilibria with
MEA, DEA, or DIPA and an additional residence time correction
for MDEA or DGA. A correction is applied to IDEAL liquid
enthalpies to account for heats of reaction. The DIPA data are not
recommended for final design purposes.
The AMINE package is generally useful for gas sweetening pro-
cesses with a single amine. Only one amine at a time is allowed.
Table 5-7: Attributes of the AMINE Package
Properties predicted by the AMINE method
K-values

Critical temperature Critical pressure Acentric factor
MEA DEA DGA MDEA DIPA
Pressure, psig 25-500 100-1000 100-1000 100-1000 100-1000
Temperature, F <275 <275 <275 <275 <275
Concentration, wt.% ~15-25 ~25-35 ~55-65 ~50 ~30
Acid gas loading, 0.5-0.6 0.45 0.50 0.4 0.4
(mol gas/mol
amine)
VLLE - Supported
1
Input Description
METHOD SYSTEM(VLE or VLLE)=AMINE,...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=AMINE,
ENTHALPY(V)=SRKM, ENTHALPY(L)=AMINE,

property generators. When SYSTEM=AMINE is chosen,
AMINE K-values, SRKM vapor enthalpies, AMINE liquid
enthalpies, SRKM entropies, IDEAL liquid densities, and
SRKM vapor densities are default.
VLLE K-value calculations are available with the AMINE
package.

KVALUE(VLE or LLE or VLLE)RESI=0.3
RESI Specifies the dimensionless residence time correction for

systems involving MDEA or DGA. The default value is
0.3. A RESI value of 1.0 corresponds to an equilibrium
model. For amines MEA, DEA or DIPA, the entry is
ignored if it appears.
Note: If used for correcting the dimensionless residence time for

systems involving MDEA or DGA, the RESI statement must fol-
low the KVALUE statement.



SA01 to SA11 i, c1, c2, c3/ ...

selected for enthalpy, entropy, and density methods. You can supply
the interaction parameters and/or alpha formulations independently.
BANK This option selects the databank from which to retrieve vapor
with the LIBMGR program.
ALPHA This option allows access to the databank for alpha formulations.
SIMSCI Selects the SimSci alpha formulation and values
supplied from the SIMSCI databank (default).
(default).
COMP Selects order of component libraries and
databanks when searching for pure components
required for the current Thermo system.
Properties missing from this databanks will be
taken from global component data search order.

bankid This option selects the user-created databank
named bankid that is created and maintained by
the LIBMGR program.
SRKM This statement inputs binary interaction parameters and alpha
and/or formulation data for the SRKM method used to calculate vapor
SA01 to enthalpies, vapor densities and liquid and vapor entropies for the
SA11 AMINE package. See Modified Soave-Redlich-Kwong and
Peng-Robinson on page 4-13 for further details.

...
Examples
E-5.9: Using the AMINE system, model a mix of water, H2S,
CO2, MEA, and NH3 at 50 psia and 20% vaporization.
TITLE PROB=AMINE
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,H2O/2,H2S/3,CO2/4,NH3/5,MEA
THERMO DATA
METHOD SYSTEM=AMINE
STREAM DATA
COMP=30/5/10/5/50
UNIT OPERATION
FLASH UID=FL3
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.2
END
E-5.10: For the same problem, use MDEA and supply a residence
time correction factor of 1.0.
COMPONENT DATA
LIBID 1,H2O/2,H2S/3,CO2/4,NH3/5,MDEA
THERMO DATA

METHOD SYSTEM=AMINE
KVALUE RESI=1.0

User-added Subroutines
Typical Usage
COMPONENT DATA
LIBID 1,IC4/ 2, NC4/ 3, H2O
THERMO DATA
METHODKVALUE=U1, ENTHALPY=U2, DENSITY=U3
STREAM DATA
General Information
User-added subroutines can be supplied to calculate equilibrium K-
values and to generate liquid and/or vapor enthalpy data, liquid and/
or vapor entropy data and liquid and/or vapor density data.
Table 5-8: Attributes of User-Added Subroutines
Properties predicted by User-Added Subroutines
K-values Liquid/vapor entropies
Liquid/vapor densities Liquid/vapor enthalpies

As required by the subroutine
VLLE - Supported
1 Automatically supplied for library and petroleum components. Must
be supplied by the user for non-library components.
Input Description
METHOD
KVALUE(VLE and/or LLE or VLLE)=U1 or U2 or ... U15,
ENTHALPY(VL or V and/or L)=U1 or U2 or ... U15,
ENTROPY(VL or V and/or L)=U1 or U2 or ... U15,
DENSITY(VL or V and/or L)=U1 or U2 or ... U15
KVALUE Selects a user-added method for K-value calculations. Both

VLE and LLE K-value calculations are available when
supplying user-added subroutines. The VLLE option
and/or
automatically selects both.

ENTHALPY Selects a user-added method for liquid/vapor enthalpy,
and/or liquid/vapor entropy, and liquid/vapor density calculations.
ENTROPY See the PRO/II User-Added Subroutine User Guide for
and/or information about implementing these subroutines.
DENSITY

KVALUE(VLE or LLE or VLLE)
UDATA i, value /...
Note: If used for calculating K-values, the UDATA statement
must follow the KVALUE statement.
UDATA This statement supplies method-specific data that is used by user-

added subroutines to calculate equilibrium K-values. See the
PRO/II User-added Subroutine User Guide for more
information.

ENTHALPY
ENTROPY
DENSITY
UDATA i, value /...
See K-value Data (above) for format and definition of these entries.
Examples
E-5.11: Using a user-supplied liquid enthalpy method U1 and the
GLYCOL package, model a 50/25/20/5 mix of water,
benzene, ethanol and TEG at 50 psia and 20%
vaporization. Supply data for U1 for components 2 and 4.
TITLE PROB=UASENTH
COMPONENT DATA
LIBID 1,H2O/2,BENZENE/3,ETOH/4,TEG
THERMO DATA
METHOD SYSTEM=GLYCOL, ENTHALPY(L)=U1
ENTHALPY(L)
UDATA 2,2.5/4,3.0
STREAM DATA
COMP=50/25/20/5
UNIT OPERATION
FLASH UID=FL3D
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, RATE, VALUE=0.2
END

CAPE-OPEN
Typical Usage
. . .
COMPONENT DATA
LIBID 1,PROPANE/2,BENZENE/3,METHANE, &
BANK=PROCESS,SIMSCI
THERMODYNAMIC DATA
METHOD SYSTEM=CO, PID=SIMSCI.THERMOSYSTEM.1, &
PNAME=COC3C6C1SRK, SET=CO01 . . .
. . .
The PRO/II CAPE-OPEN thermodynamics capability enables users

to add a third party CAPE-OPEN property packages to perform
thermodynamic property calculations for streams on flow sheet.
CAPE-OPEN standards are the uniform standards for interfacing
process modeling software components developed specifically for
the design and operation of chemical processes. These standards
allow integration of different software components like Unit Opera-
tions and Thermodynamic Property Packages from different ven-
dors into a single simulation.
Input Description
The Method Statement
METHOD SYSTEM=CO, PID=SIMSCI.THERMOSYSTEM.1, &

PNAME=COC3C6C1SRK

property generators. When SYSTEM = CO is chosen, all
property calculations and flash calculations will done in
property package.
PID Program Id of COM identifier for property package. This is
to identify and instantiate the property package on
computer system
PNAME If CAPE-OPEN thermodynamics is thermo system, it
gives package name. If it is a property package, PNAME
will be NULL

Examples
E-5.12 Multiple METHOD Sets
TITLE =CAPE-OPEN
DESC TEST SAMPLE CAPEOPEN THERMO
DIMENSION SI, STDTEMP=273.15, STDPRES=101.325
SEQUENCE SIMSCI
CALCULATION RVPBASIS=APIN, TVP=310.93
COMPONENT DATA
LIBID 1,PROPANE/2,BENZENE/3,METHANE, &
BANK=PROCESS,SIMSCI
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, SET=SRK01, DEFAULT
METHOD SYSTEM=CO, &
PID=SIMSCI.THERMOSYSTEM.1, &
PNAME=COC3C6C1SRK, SET=CO01
METHOD SYSTEM=CO, &
PID=COPROPPACK.CPROPPACK, &
PNAME=NULL, SET=CO02
STREAM DATA
PROPERTY STREAM=S1, TEMPERATURE=250, &
PRESSURE=1400, PHASE=M, &
RATE(M)=300, COMPOSITION(M)=1,1/2,1/3,1, &
NORMALIZE, SET=DEFAULT
UNIT OPERATIONS
FLASH UID=F1
FEED S1
PRODUCT V=S2, L=S3
ADIABATIC
END

Chapter 6
These are primarily applicable to highly non-ideal systems, particu-

larly non-hydrocarbons. These methods are also useful for predict-
ing VLLE behavior.
NRTL
Typical Usage
...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
THERMO DATA
METHOD SYSTEM=NRTL
STREAM DATA
. . .
General Information
The Non-Random Two Liquid (NRTL) liquid activity method is
used to predict VLE and/or LLE phase behavior. This method does
not support free water decant.
The NRTL method is generally useful for non-ideal applications,
especially for partially immiscible systems. Refer to the PRO/II
Reference Manual for additional information.

Table 6-1: Attributes of NRTL methods
Properties predicted by NRTL methods
K-values

Vapor pressure When used with PHI=SRK or PR or SRKM
Critical temperature or PRM or SRH or PRH or SRP or PRP or
Critical pressure SRKS or SRKKD or PPR78 or BWRS or
Acentric factor UNIWAAL or HOCV
Liquid molar volume
VLLE - Supported
Input Description
METHOD SYSTEM(VLE or VLLE)=NRTL, PHI=IDEAL,
{HENRY},...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=NRTL,
PHI=IDEAL, {HENRY},..

generators. When SYSTEM=NRTL is chosen, NRTL K-
values, LIBRARY enthalpies, IDEAL liquid densities and
IDEAL vapor densities are default.
LLE K-value calculations are available with the NRTL
method. The VLLE option automatically selects both. See
Vapor-liquid-liquid Equilibrium Considerations on page 38
for more details on liquid-liquid equilibrium calculations.
6-2 Liquid Activity Methods

PHI Selects the option used to calculate pure component and
mixture vapor phase fugacity coefficients (i). A vapor
fugacity method should generally be selected for high pressure
applications. The options are the equations of state methods
SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS,
SRKKD,PPR78, BWRS and UNIWAAL (see Chapter 4) and
HOCV (the Hayden-O'Connell method), TVIRIAL (the
Truncated Virial method) and the IDIMER method. See
Hayden-OConnell Vapor Fugacity on page 64, Truncated
Virial Vapor Fugacity on page 68, and IDIMER Vapor
Fugacity on page 71, for details on these last three options.
The default is PHI=IDEAL.
HENRY This option selects Henry's Law data (either user-supplied or
from databanks) to model dissolved gases in a liquid solution.
See Henrys Law for Non-condensible Components on
page 57 for further details.

Mixing on page 75, for further information on the use of this
option.
BANK=SIMSCI or ALCOHOL or NONE or bankid,
REGULAR,
AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid
NRTL3(K or KCAL or KJ) i, j, bij, bji, ij / ...

and/or
NRTL(K or KCAL or KJ) i, j, aij, bij, aji, bji, ij / ...
and/or
NRTL6(K or KCAL or KJ) i, j, aij, bij, aji, bji, ij, ij / ...
and/or
NRTL8(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, ij, ij / ...
and/or
NRTL10(K) i, j, aij, bij, dij, eij, aji, bji, dji, eji, ij,
ij/....
and/or
NRTL14(K) i, j, aij, bij, cij, dij, eij, fij, aji, bji, cji, dji,
eji, fji, ij, ij/....
and/or
INFINITE(utemp) i, j, temp, ioo , joo / ...
and/or

MUTUAL(basis, utemp) i, j, temp, xiI, xjII / ...
and/or
IDEAL i, j / ...
Note: The NRTL3, NRTL, NRTL6, NRTL8, NRTL10, NRTL14,

AZEOTROPE, INFINITE, MUTUAL and/or IDEAL statements
must follow the KVALUE statement. UOM for
NRTL3,NRTL,NRTL6 & NRTL8 is K or KCAL/KMOL or KJ/
KMOL.
POYNTING This option selects whether to apply the Poynting

correction to fugacities of components in the liquid phase.
The default is OFF unless a PHI method is selected, in
which case the default is ON.
calculating the liquid molar volume at standard
conditions (25 C, 1 atm).
BANK This selects one or more banks that supply vapor and/or
liquid phase binary interaction data.
ALCOHOL Selects the Alcohol databank. This databank contains
binary coefficients for systems with alcohols, water
and other polar components.
LIBMGR program.
binary interaction data missing from the input file and any
selected databank libraries. See Filling in Missing
Parameters on page 52, for further details on these
options.
AZEOTROPE This selects the azeotrope databank used for retrieving
azeotropic data for binary pairs. Current options are
SIMSCI (default) or NONE or bankid.

WRITE This option writes the binary interaction parameters for the
liquid activity coefficient K-value method to a file. The
format of this file is suitable for inclusion into an input file.
fileid This name identifies the file containing the binary
interaction data. It may be any valid file name allowed on
the particular operating system being used, but must not
include a suffix. The program will automatically add a
suffix (e.g., .FIL on PCs).
NRTL3 and/or This statement allows entry of the binary interaction data
NRTL and/or parameters for the NRTL liquid activity coefficient
NRTL6 and/or method. The statements can be mixed in order to enter the
NRTL8and/or data in the most convenient form. The binary parameters
aij, bij, cij, aji, bji, cji, ij, and ij are related to the liquid
NRTL10and/or
NRTL14 activity coefficients gi by the following equations:
j ji G ji x j x j G ij k x k kj G kj
In i = ----------------------- + ------------------- ij --------------------------
k G ki x k k G kj x k k G kj x k
j
When unit is K:
b ij c ij
ij = a ij + ----- + -----2 + d ij InT + e ij T + f ij TInT
T T
When unit is KCAL/KMOL or KJ/KMOL:
b ij c ij
ij = a ij + ------- + -----------
- + d ij In ( RT ) + e ij RT
RT R 2 T 2
+ f ij RTIn ( RT )
G ji = exp ( ji ji ) and ij = ij + ij T
AZEOTROPE These statements are used to enter data for binary pairs.
and/or This data will be regressed to the coefficients for the liquid
INFINITE and/ activity method used to generate the K-values. Multiple
or MUTUAL statements may be used to enter data with different units or
the data can be entered on a single statement.
and/or This statement sets the binary interaction parameters to
IDEAL zero.
Data input using the NRTL3, NRTL, NRTL6, NRTL8, NRTL10,

NRTL14, AZEOTROPE, INFINITE, MUTUAL and IDEAL state-
ments is used in preference to any data retrieved from the databanks
or estimated using FILL options. See Filling in Missing Parame-
ters on page 52, for further details.

...
method is used. For a further description of these input parameters
only vapor pressure has any direct effect on the calculation of K-
values. Vapor pressure may only be supplied globally for all sets in
the Component Data Category. Tc, Pc and the acentric factor have
an impact on the K-values if a cubic equation of state is chosen for
vapor phase fugacities. Molar volume has an impact on the
Poynting correction factor.
Examples
E-6.1: Using the NRTL system, model a 50/40/10 mix of DIPE,
IPA and water at 50 psia and 50% vaporization.
TITLE PROB=NRTL
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,H2O/ 2,BENZENE/ 3,ETOH/ 4,CHEN
THERMO DATA
METHOD SYSTEM=NRTL, PHI=SRK
KVALUE FILL=UNIFAC, POYNTING=ON
NRTL 1,2, 5.256, 219.685, -5.645, 288.34, 0.2 / &
1,3, 1.015, 536.264, 0.4985, -456.0, 0.1448 / &
2,3, -2.748, 1472.24, -0.449, 440.51, 0.5355
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP= 50/ 25/ 20/ 5
UNIT OPERATION
FLASH UID=F204
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.2
END
E-6.2: For the same problem, use NRTL K-values, IDEAL
THERMO DATA
METHOD KVALUE=NRTL, ENTHALPY=IDEAL, &
DENSITY(L)=IDEAL, DENSITY(V)=SRK

UNIQUAC
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=UNIQUAC
STREAM DATA
. . .
General Information
The UNIQUAC liquid activity method is used to predict both VLE
and VLLE phase behavior. This method does not support free water
decant.
The UNIQUAC method is generally useful for highly non-ideal
applications, especially for partially immiscible systems. Refer to
the PRO/II Reference Manual for additional information.
Table 6-2: Attributes of UNIQUAC Methods

Properties predicted by UNIQUAC methods
K-values

van der Waals area
and volume
van der Waals area
and volume
Liquid molar volume
van der Waals area
and volume
VLLE - Supported

Input Description
METHOD SYSTEM(VLE or VLLE)=UNIQUAC,
PHI=IDEAL, {HENRY},...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=UNIQUAC,

generators. When SYSTEM=UNIQUAC is chosen, UNIQUAC
K-values, LIBRARY enthalpies, IDEAL liquid densities and
IDEAL vapor densities are default.
K-value calculations are available with the UNIQUAC method.
liquid Equilibrium Considerations on page 38 for more details on
on page 64, Truncated Virial Vapor Fugacity on page 68,
IDIMER Vapor Fugacity on page 71, for details on these last
three options. The default is PHI=IDEAL.
Henrys Law for Non-condensible Components on page 57 for
further details.

option.

REGULAR,

UNIQUAC(K or KCAL or KJ) i, j, aij, aji / ...
and/or
UNIQ4(K or KCAL or KJ) i, j, aij, aji, bij, bji / ...
and/or
AZEOTROPE(basis, upres, utemp)i, j, pres, temp, xi / ...
and/or
and/or
and/or
IDEAL i, j / ...
Note: The UNIQUAC, UNIQ4, AZEOTROPE, INFINITE,

MUTUAL and/or IDEAL statements must follow the KVALUE
statement. UOM for UNIQUAC and UNIQ4 is K or KCAL/
KMOL or KJ/KMOL.

STANDARD The default. Selects the standard method for calculating
the liquid molar volume at standard conditions (25 C, 1
atm).
BANK This option selects one or more banks from which to
bankid that is created and maintained with the LIBMGR
program.
binary interaction data missing from the input file and any
selected databank libraries. See Filling in Missing
Parameters on page 52, for further details on these
options.

UNIQUAC This statement allows entry of the binary interaction data
and/or parameters for the UNIQUAC liquid activity coefficient
UNIQ4 method. The statements can be mixed in order to enter the
data in the most convenient form. The binary parameters
aij, bij, aji and bji are related to the liquid activity
coefficients i by the following equations:
C R
ln i = ln i + ln i
M
C Z i
ln i = ln -----i + --- q i ln -----i + l i -----
xi 2 i i Xj lj
j=1

M M

j ij
= q i 1 ln
R
ln i j ji -----------------------
M
j=1 j=1

k kj
k=1
U ij (when unit is K)
ij = exp -------
T
U ij (when unit is KCal/KMol or

ij = exp ------- KJ/KMol)
RT
U ij = a ij + b ij T
xi qi Z
i = ------------------
- l j = --- ( r j q j ) ( r j 1 )
M 2
xi qi
i=1
xi ri
i = -----------------
M
-
xj rj
j=1
A wi V wi
q i = ------------------9- r i = ------------- , Z = 10
2.5 10 15.17
and/or This data will be regressed to the coefficients for the liquid
INFINITE and/ activity method used to generate the K-values. Multiple
or MUTUAL statements may be used to enter data with different units or
IDEAL zero.

include a suffix. The program will automatically add a
Data input using the UNIQUAC, UNQ4, AZEOTROPE, INFI-

NITE, MUTUAL and IDEAL statements is used in preference to
any data retrieved from the databanks or estimated using FILL
options. See Filling in Missing Parameters on page 52, for further
details.

VANDERWAALS i, value / ...
...
of these properties, only the van der Waals area and volume
(VANDERWAALS) has any direct effect on the calculation of
liquid activity coefficients, but may only be supplied in the
Component Data Category. The vapor pressure also has a direct
effect on K-values, but may only be supplied globally for all sets in
the Component Data Category. Tc, Pc and the acentric factor will
have an impact if a cubic equation of state is chosen for vapor phase
fugacities. Molar volume will have an impact on the Poynting
correction factor.
Examples
E-6.3: Using the UNIQUAC system, model a 50/40/10 mix of
DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=UNIQUAC
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,H2O/ 2,BENZENE/ 3,ETOH/ 4,CHEN
THERMO DATA
METHOD SYSTEM=UNIQUAC
STREAM DATA

COMP=50/25/20/5
UNIT OPERATION
FLASH UID=DRUM
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.2
END
E-6.4: For the same problem, use UNIQUAC K-values, IDEAL

THERMO DATA
METHOD KVALUE=UNIQUAC, ENTHALPY=IDEAL, &
UNIFAC
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=UNIFAC
STREAM DATA
. . .
General Information
The UNIFAC liquid activity method is used to predict both VLE
and VLLE phase behavior. This method does not support free water
decant.
The UNIFAC group contribution method is generally useful for
non-ideal applications at low pressures. It is generally restricted to
components with 10 or fewer different structural groups and sys-
tems containing low molecular weight polymers. Refer to the
PRO/II Reference Manual for additional information.
Table 6-3: Attributes of UNIFAC Methods

Properties predicted by UNIFAC methods
K-values

Structural groups
Structure van der
Waals area and
volume parameters
Structural groups UNIWAAL or HOCV
Van der Waals
area and volume
Liquid molar volume
Structural groups
Van der Waals
area and volume
Pressure - up to 10 atmospheres
VLLE - Supported
Input Description
METHOD SYSTEM(VLE or VLLE)=UNIFAC, PHI=IDEAL,
{HENRY},...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=UNIFAC,
PHI=IDEAL, {HENRY},..

generators. When SYSTEM=UNIFAC is chosen, UNIFAC K-
values, LIBRARY enthalpies, IDEAL liquid densities and IDEAL
vapor densities are default.

K-value calculations are available with the UNIFAC method. The
VLLE option automatically selects both. See Vapor-liquid-liquid
Equilibrium Considerations on page 38 for more details on liquid-
liquid equilibrium calculations.
options are the equations of state methods SRK, PR, SRKM, PRM,
SRKH, PRH, SRKP, PRP, SRKS, SRKKD, PPR78, BWRS and
UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell
method), TVIRIAL (the Truncated Virial method) and the IDIMER
method. See Hayden-OConnell Vapor Fugacity on page 64,
Truncated Virial Vapor Fugacity on page 68, and IDIMER
Vapor Fugacity on page 71, for details on these last three options.
The default is PHI=IDEAL.
further details.

option.

UNIFAC(K or KCAL or KJ) l, k, Alk, Akl / ...

and/or
and/or
and/or
and/or
IDEAL i, j / ...
Note: The UNIFAC, AZEOTROPE, INFINITE, MUTUAL and/

or IDEAL statements must follow the KVALUE statement. UOM
for UNIFAC is K or KCAL/KMOL or KJ/KMOL.

to fugacities of components in the liquid phase. The default
is OFF unless a PHI method is selected, in which case the
default is ON.
LIBMGR program.
azeotropic data for binary pairs. Current options are SIMSCI
(default) or NONE or bankid.
interaction data. It may be any valid file name allowed
on the particular operating system being used, but must
not include a suffix. The program will automatically
add a suffix (e.g., .FIL on PCs).
UNIFAC This statement allows entry of the group interaction data
parameters for the UNIFAC liquid activity coefficient
method. The statements can be mixed in order to enter the
data in the most convenient form. The group parameters Alk
and Akl are related to the liquid activity coefficients i by the
following equations:
C R
ln i = ln i + ln i
where:
i Z i i
ln i = ln ------i + 1 ------ --- q i ln ------ + 1 ------
C
xi xi 2 i i

xi ri xi qi
------------------
i = NOC -, i = -------------------
NOC
xj rj xj qj
j=1 j=1
NK NK
i i
ri = k Rk , qi = k Qk
k=1 k=1
Rk = volume parameter for group k

Qk = surface area parameter for group k
vki = number of type k groups in component i
xi = liquid mole fraction of component i
Z = coordination number (Z = 10)
NK = number of groups in molecule i
NK
R i i
ln ( i ) = k ( ln k ln k )
k=1

NK NK
ln ( k ) = Q k 1 ln m mk ---------------------------
m mk
-
NK
m = 1 n1

n nm

n=1
A nm (where unit is K)
nm = exp ---------
T
A nm (where unit is KCal/KMol or KJ/

nm = exp --------- KMol)
RT
NOC
j
m xj
Qm Xm j=1
nm = -----------------------
NK
- X m = -------------------------------
NK NOC
-
j
Qn Xn n xj
n=1 n = 1j = 1
Anm = group interaction parameter for the
interaction between m and n.
Data are available in PRO/II databanks for many
structural groups as shown in Table 6-4.
and/or This data will be regressed to the coefficients for the
INFINITE and/ liquid activity method used to generate the K-values.
or MUTUAL Multiple statements may be used to enter data with
different units or the data can be entered on a single
statement.

IDEAL zero.
Data input using the UNIQUAC, AZEOTROPE, INFINITE,

MUTUAL and IDEAL statements is used in preference to any data
retrieved from the databanks.

...
of these properties, only the van der Waals area and volume
(VANDERWAALS) has any direct effect on the calculation of
liquid activity coefficients, but may only be supplied in the
Component Data Category. The vapor pressure also has a direct
effect on K-values, but may only be supplied globally for all sets in
the Component Data Category. Tc, Pc and the acentric factor will
have an impact if a cubic equation of state is chosen for vapor phase
fugacities. Molar volume will have an impact on the Poynting
correction factor.
Table 6-4: Available UNIFAC Interaction Parameters
UNIFAC INTERACTION PARAMETERS

AVAILABLE IN PROII
11 --- * . No interactions
20 --- @ * V VLE interactions - ( 634)
21 --- V V . L LLE interactions - ( 208)
27 --- . . . . * Both VLE and LLE - ( 91)
30 --- * V @ V . $ Both VLE and T - ( 48)
40 --- V . V V . V @ VLE - LLE and T - ( 103)
43 --- . . V V . V . T TEMP dependent - ( 1)
46 --- V . V . . V . .
50 --- . . $ V . . . . V
52 --- . . $ V . . . . . V
55 --- * * @ V . . . . V V .
56 --- . . V V . V . . . . . .
59 --- . . $ . . . . . V V V . .
60 --- @ V @ V V $ V . V V $ . V V
70 --- @ * @ V . @ . V V . $ V V V @
73 --- V . V . . V . . V . . . . . V V

76 --- V V V . . V . . V . V V . . V V V
81 --- @ . @ V . @ . . . V . V . . @ V . V
84 --- @ . @ V . V . . . . . . . $ @ @ . V @
86 --- @ . @ V . V . . . . . L . $ @ @ V V @ .
87 --- * V * V . . . . . V V V . V V * V V V V V
88 --- * . * . . V . . V . . . . . V V V V V V V .
90 --- @ * @ V V @ V V * $ $ @ V $ @ @ V V @ @ @ * *
110 --- @ V @ V . @ V . * $ $ V . $ @ @ V V @ @ @ V V @
114 --- . . V . . . . . V . . . .
V . . . . . . . . . V V
120 --- @ * @ V . @ V V * $ $ @ V
@ $ @ @ V V @ $ @ * V @ .
122 --- * * * V . * V V V V V * V
* V * * V V * V * * V * . *
130 --- @ * @ V . @ V V V . V @ V
@ V @ @ V V @ @ @ * * @ V @ *
140 --- . . @ V . . . . V V V $ .
@ . V @ V V V V @ * V @ V @ * @
141 --- L . * . . . . . V . . . .
* . * V . V V V . * V * V * * * V
143 --- . L * . . . . . . . . * .
. . . . . . V . . V . * . * * * . V
144 --- V * @ . . . . . . . T * .
V . V . V . . $ @ L V @ . @ * $ @ . V
150 --- . . V . . . . . V V . . .
. . V . V . V . . . . V . V V V V . . .
151 --- . . . . . . . . . . . . .
V . . . . . . . V . V V . . . . . . . .
153 --- . V V . . . . . . . . . .
. . . . . . . . . . . V . V V V . V . V
161 --- $ V $ V . $ . . V $ $ $ V
$ $ $ $ V V $ $ $ V V $ . $ V $ $ V . $
162 --- @ * @ V V * V . * $ $ @ V
@ $ @ @ . V @ @ @ * L @ . @ * @ @ * * @
168 --- @ * @ V . . . . V $ $ @ .
@ $ @ @ V V @ @ @ * V @ . @ * @ @ * * $
170 --- . V V V . . . . . . . . .
V . V V . V V . V . V V . V V V V V . .
171 --- * . * . . L . . L . . . .
V . V * . V . L * . L * . * * * . . . L
203 --- . . V . . V . . V . . . .
V . . V . V . . . . V V . V V . V . . .
247 --- V . V . . . . . V . . . .
* . V V . V . V V . . * . * * V . . . .
250 --- . V V . . . . . . . . . .
V . . . . . . . V V V V . V V . . . . .
251 --- . . V . . . . . . . . . .
V . . . . . . . . . . V . V V . . . . .
260 --- V . V . . . . . . V V . .
. . V . . . . . . . . V . V V V . . . .
270 --- V . V . . . . . . V V . .
. . . . . . . . . . . V . V V . . . . .
| | | | | | | | | | | | |
| | | | | | | | | | | | | | | | | | | |
| | | | | | | | | | | | |
| | | | | | | | | | | | | | | | | | | |
1 1 1 1 1 1 1 1 1
1 1 2 2 2 3 4 4 4 5 5 5 5 5 6 7 7 7 8 8 8 8 8 9 1 1 2 2 3 4 4 4 4
0 1 0 1 7 0 0 3 6 0 2 5 6 9 0 0 3 6 1 4 6 7 8 0 0 4 0 2 0 0 1 3 4
281 --- . . . . . . . . V . . . .
V . . . . . . . . . . V . V . . . . . .
287 --- . . V . . . . . . . V . .
V V V . . . . . . . . V . V V . . . . V
290 --- . . V . . . . . . . . . .
. . . . . . . . . . . V . V . . . V . .
300 --- V . V . . . . . . . . . .
V . V V . V V V . V . V . V V V V V V V
320 --- V . V . . V . . . . . . .
. . V V . V . V V . . V . V V V . V V .
330 --- . . . . . . . . . . . . .
. . . . . . . . . . . V . . . . . . . .
340 --- . . . . . . . . . . . . .
. . . . . . . . . . . V . . . . . . . .
350 --- . . . . . . . . . . . . .
. . . . . . . . . . . V . . . . . . . .
360 --- . . . . . . . . . . . . .
. . . . . . . . . . . V . . . . . . . .
385 --- L * * . . . . . V . . * .
. . V * . V . . . L . * . * * * V * L .
388 --- . . V . . . . . . . . . .
V . . V . V . V . V . V . V V V V . . .
| | | | | | | | | | | | |
| | | | | | | | | | | | | | | | | | | |
| | | | | | | | | | | | |
| | | | | | | | | | | | | | | | | | | |
1 1 1 1 1 1 1 1 1
1 1 2 2 2 3 4 4 4 5 5 5 5 5 6 7 7 7 8 8 8 8 8 9 1 1 2 2 3 4 4 4 4
0 1 0 1 7 0 0 3 6 0 2 5 6 9 0 0 3 6 1 4 6 7 8 0 0 4 0 2 0 0 1 3 4

151 --- V . No interactions
153 --- . . V VLE interactions - ( 634)
161 --- V V V L LLE interactions - ( 208)
162 --- . . . $ * Both VLE and LLE - ( 91)
168 --- . V V $ @ $ Both VLE and T - ( 48)
170 --- . . . V V V @ VLE - LLE and T - ( 103)
171 --- . . . . * * . T TEMP dependent - ( 1)
203 --- . . . V V V . .
247 --- V . . V V V . . .
250 --- V . . . V . . . . .
251 --- . . . V V . . . . . .
260 --- . . . . V . . . . . . .
270 --- . . . . . V . . . . . . V
281 --- . . . . . . . . . . . . . .
287 --- . . . V . V . . . . . . . . V
290 --- . . . V . . . . . . . . . . V .
300 --- . . . V . V . . . V . . . . . . .
320 --- . . . V . V V . . . . . . . . . . .
330 --- . . . . . . . . . . . . . . . . . . .
340 --- . . . . . . . . . . . . . . . . . . . V
350 --- . . . . . . . . . . . . . . . . . . . V V
360 --- . . . . . . . . . . . . . . . . . . . V V V
385 --- . . . V * . . L . V V . . . . . . . . . . . .
388 --- . . . . V V . . . . . . . . . . . . . . . . . V
| | | | | | | | | | | | | | | | | | | | | | | |
| | | | | | | | | | | | | | | | | | | | | | | |
1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 3 3 3 3 3 3 3
5 5 5 6 6 6 7 7 0 4 5 5 6 7 8 8 9 0 2 3 4 5 6 8
0 1 3 1 2 8 0 1 3 7 0 1 0 0 1 7 0 0 0 0 0 0 0 5
Examples
E-6.5: Using the UNIFAC system, model 50/40/10 mix of DIPE,
IPA, and water at 50 psia and 50%vaporization.
TITLE PROB=UNIFAC
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,DIPE/ 2,IPA/ 3,H2O
THERMO DATA
METHOD SYSTEM=UNIFAC
STREAM DATA
COMP=50/40/10
UNIT OPERATION
FLASH UID=F2
FEED 1
PROD V=2, L=3
TPSPEC PRES=50

RATE, VALUE=0.5
END
6.6: For the same problem, use UNIFAC K-values, IDEAL

THERMO DATA
METHOD KVALUE=UNIFAC, ENTHALPY=IDEAL, &
Modifications to UNIFAC
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=UFT1
STREAM DATA
. . .
General Information
The modified UNIFAC liquid activity methods are used to predict
both VLE and VLLE phase behavior. These methods do not support
free water decant.
The modified UNIFAC group contribution methods are generally
useful for non-ideal applications at low pressures. The Lyngby
modification UFT1, the Dortmund modification UFT2, and UFT3
modified methods can be used if temperature dependent UNIFAC
data is available. The UNFV free volume data method is designed
to model polymer solutions and should not be used for non-polymer
systems. Refer to the PRO/II Reference Manual for additional infor-
mation.
Table 6-5: Attributes of Modified UNIFAC Methods

Properties predicted by UNIFAC methods
K-values

van der Waals area and
volume
(UFT1,UFT2,UFT3
only)
Van der Waals area and
volume
(UFT1,UFT2,UFT3 only)
Liquid molar volume
Van der Walls area and
volume
(UFT1,UFT2,UFT3 only)
Pressure - up to 10 atmospheres
VLLE - Supported
Input Description
METHOD SYSTEM(VLE or VLLE)=UF1 or UFT2 or UFT3 or
UNFV, PHI=IDEAL, {HENRY},...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=UF1 or UFT2 or
UFT3 or UNFV, PHI=IDEAL,{HENRY},..

generators. The options available are:

UFT1 When SYSTEM=UFT1 is chosen, UFT1 K-values, LIBRARY
enthalpies, IDEAL liquid densities and IDEAL vapor densities are
default.
UFT2 When SYSTEM=UFT2 is chosen, UFT2 K-values, LIBRARY
default.
UFT3 When SYSTEM=UF3 is chosen, UFT3 K-values, LIBRARY
default.
UNFV When SYSTEM=UNFV is chosen, UNFV K-values, LIBRARY
default.
K-value calculations are available with the UFT1, UFT2, UFT3
AND UNFV methodS. The VLLE option automatically selects
both. See Vapor-liquid-liquid Equilibrium Considerations on
page 38 for more details on liquid-liquid equilibrium calculations.
options are the equations of state methods SRK, PR, SRKM, PRM,
SRKH, PRH, SRKP, PRP, SRKS, SRKKD, PPR78, BWRS and
UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell
method), TVIRIAL (the Truncated Virial method) and the
IDIMER method. See Hayden-OConnell Vapor Fugacity on
page 64, Truncated Virial Vapor Fugacity on page 68, and
IDIMER Vapor Fugacity on page 71 for details on these last
further details.

option.
UFT1-Lyngby modified UNIFAC


and/or
UFT2-Dortmund modified UNIFAC


and/or
UFT3-Modified UNIFAC

and/or
UNFV-Free Volume modification

and/or
and/or
INFINITE(utemp) i, j, temp, ioo , joo / ...
and/or
and/or
IDEAL i, j / ...

Note: The AZEOTROPE, INFINITE, MUTUAL and/or IDEAL
statements may be used with the UFT1, UFT2, UFT3 and UNFV
methods. The data statements must follow the KVALUE state-
ment. UNIFAC data statements may be used with any of the mod-
ified UNIFAC methods if non-temperature dependent data are
entered. The UNIFT1, UNIFT2, UNIFT3 and/or UNFV data
statements may not be mixed, i.e., they may not follow the
same KVALUE statement. UFT1, UFT2, and UFT3 are aliases
for the UNIFT1, UNIFT2, and UNIFT3 data keywords. UOM for
UNIFAC coefficients is K or KCAL/KMOL or KJ/KMOL.

to fugacities of components in the liquid phase. The default is
OFF unless a PHI method is selected, in which case the
default is ON.
RCK2 Selects the Rackett 2 liquid density method
LIBMGR program.
WRITE This option writes the binary interaction parameters for
the liquid activity coefficient K-value method to a file.
The format of this file is suitable for inclusion into an
input file.

interaction data. It may be any valid file name allowed
on the particular operating system being used, but must
not include a suffix. The program will automatically
add a suffix (e.g., FIL on PCs).
UNIFAC This statement allows entry of the group interaction data
parameters for the UNIFAC liquid activity coefficient
method. See UNIFAC on page 12 for further details.
UFT1 This selects the Lyngby modification of the UNIFAC method.
The data entered are the temperature-dependent group
interaction parameters alk, blk and clk. The liquid activity for
each component is calculated similar to the UNIFAC method
except:
T
A mk = a mk + b mk ( T T o ) + c mk T ln -----o + T T o
T
where: T o = 298.25K
23
c i ri xi
ln i = ln -----i + 1 ----- , i = -------------------------
NOC
xi xi
23
rj xj
j=1
UFT2 This statement allows entry of the temperature-dependent
group interaction data for the Dortmund modification of the
UNIFAC method. The liquid activity coefficients are
calculated from the following equations:
Similar to the UNIFAC method, except
2
A mk = a mk + b mk T + c mk T
i Zq i ln i i
ln i = ln -----i + 1 ----- -------- ----------- + 1 ------
c
xi x i 2 i i
34
ri xi
i = -------------------------
NOC
34
rj xj
j=1
UFT3 This selects temperature-dependent group interaction data for
a modification of the UNIFAC method. The liquid activity
coefficients are computed using the equations following:
Similar to the UNIFAC method, except
3
A mk = a mk + b mk T + c mk T

UNFV This option is for entering free volume data for polymer
systems. This model uses the same liquid activity coefficient
combinatorial and residual terms as UNIFAC, in addition to a
free volume effect term. The liquid activity equations are
given by:
C R FV
ln i = ln i + ln i + ln i
V i
13 ------

- 1
FV V i 1 m
V
ln i = 3C i ln 1 3 -
------------------- C i ---------------------
V m 1 1 ----------1
-
V 1 3
i
NK
Vi
V i = ---------------------- , 1 i
15.17br' i r' i = ------
Mi k Rk
k=1
Vi wi + Vj wj
V m = -------------------------------------------------- , b = 1.28
15.17b ( r' i w i + r' j w j )
where:
Vi = volume per gram of solvent i
Mi = molecular weight of solvent i
Wi = weight fraction of component i
Ci = number of degrees of freedom per molecule of
solvent i (=3.3)
and/or INFINITE This data will be regressed to the coefficients for the
and/or MUTUAL liquid activity method used to generate the K-values.
Multiple statements may be used to enter data with
statement.
IDEAL zero.
Data input using the UNIFAC, UFT1, UFT2, UFT3, UNFV, AZEO-
TROPE, INFINITE, MUTUAL and IDEAL statements is used in
preference to any data retrieved from the databanks or estimated
using FILL options. See Filling in Missing Parameters on
page 52, for further details.


...
method is used. VANDERWAALS may be supplied only if UNFV
is used. For a further description of these input parameters see
Chapter 9, Method-specific Pure Component Data. Note that of
these properties, only the van der Waals area and volume
(VANDERWAALS) has any direct effect on the calculation of liq-
uid activity coefficients, but may only be supplied in the Compo-
nent Data Category. The vapor pressure also has a direct effect on
K-values, but may only be supplied globally for all sets in the Com-
ponent Data Category. Tc, Pc and the acentric factor will have an
impact if a cubic equation of state is chosen for vapor phase fugaci-
ties. Molar volume will have an impact on the Poynting correction
factor.
Examples
E-6.7: Using the UFT1 liquid activity method, model a 50/40/10
mix of DIPE, IPA and water at 50 psia and 50%
vaporization.
TITLE PROB=UFT1
PRINT INPUT=ALL
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=UFT1
STREAM
COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-6.8: For the same problem, use UFT2 K-values, IDEAL

enthalpies and liquid densities and SRK vapor densities..
THERMO DATA
METHOD KVALUE=UFT2, ENTHALPY=IDEAL, &

Wilson
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=WILSON
STREAM DATA
. . .
General Information
The WILSON liquid activity method is used to predict VLE phase
behavior. This method does not support free water decant.
The WILSON liquid activity method is generally useful for slightly
non-ideal applications. Refer to the PRO/II Reference Manual for
additional information.
Table 6-6: Attributes of WILSON Methods

Properties predicted by WILSON methods
K-values
Liquid molar volume
Liquid molar volume
VLLE - Supported

Input Description
METHOD SYSTEM(VLE)=WILSON, PHI=IDEAL, {HENRY},..
or
METHOD KVALUE(VLE)=WILSON, PHI=IDEAL, {HENRY}, ...
SYSTEM Selects a combination of compatible thermodynamic property

generators. When SYSTEM=WILSON is chosen, WILSON K-
values, LIBRARY vapor enthalpies, IDEAL vapor densities,
IDEAL liquid densities, and LIBRARY liquid enthalpies are
default.
KVALUE Selects the method for K-value calculations. Only VLE K-value
calculations are available with the WILSON method.
on page 64, Truncated Virial Vapor Fugacity on page 68, and
from databanks) to model dissolved gases in a liquid solution. See
further details.

Mixing on page 75 for further information on the use of this
option.
K-value Data (optional )

KVALUE(VLE)POYNTING=OFF or ON, MOLVOL=STANDARD or
RACKETT or RCK2 or LIBRARY, FILL=NONE or
UNIFAC or CIUNIFAC or UFT1 or FLORY or
REGULAR,
AZEOTROPE=SIMSCI or NONE or bankid,
WRITE=fileid
WILSON(K or KCAL or KJ or NODIME) I, j, aij, aji / ...

and/or

and/or
INFINITE(utemp) I, j, temp, ioo , j oo / ...
and/or
and/or
IDEAL i, j / ...
Note: The WILSON, AZEOTROPE, INFINITE, MUTUAL and/

or IDEAL statements must follow the KVALUE statement. UOM
for WILSON is K or KCAL/KMOL or KJ/KMOL/NONE.

default is ON.
atm).
page 52 for further details on these options.
fileid This name identifies the file containing the binary interaction
data. It may be any valid file name allowed on the particular
operating system being used, but must not include a suffix.
The program will automatically add a suffix (e.g., .FIL on
PCs).
WILSON This statement allows entry of the binary interaction data for
the WILSON liquid activity coefficient method.

The statements can be mixed in order to enter the data in the most
convenient form. If the NODIME option is used, however, different unit
statements cannot be mixed. The binary parameters aij and aij are related
to the liquid activity coefficients i by the following equations:
N N
x k A ki
ln i = 1 ln xj Aij ---------------------
N
-
j=1 k=1
xj Akj
j=1
where:
Vj
L
a ij (when unit is K)
A ij = -----L- exp ---------
Vi T
Vj
L
a ij (when unit is KCAL/KMOL
A ij = -----L- exp --------- or KJ/KMOL)
Vi RT
A ij = a ij (when unit is NODIME)
and VLi is the liquid molar volume of component i.
and/or These data will be regressed to the coefficients for the liquid
INFINITE activity method used to generate the K-values. Multiple
and/or statements may be used to enter data with different units, or
MUTUAL
and/or IDEAL This statement sets the binary interaction parameters to zero.
Data input using the WILSON, AZEOTROPE, INFINITE,

retrieved from the databanks or estimated using FILL options. See
Filling in Missing Parameters on page 52 for further details.

...
method is used. For a further description of these input parameters
of these properties only the molar volume (MOLVOL) has any
direct effect on the calculation of liquid activity coefficients. The
vapor pressure also has a direct effect on K-values, but may only be
supplied globally for all sets in the Component Data Category. Tc,

Pc and the acentric factor will have an impact if a cubic equation of
state is chosen for vapor phase fugacities. Molar volume will also
have an impact on the Poynting correction factor.
Examples
E-6.9: Using the WILSON system, model a 50/40/10 mix of
TITLE PROB=WILSON
PRINT INPUT=ALL
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=WILSON
STREAM DATA
COMP=50/40/10
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-6.10: For the same problem, use WILSON K-values, IDEAL

enthalpies and liquid densities and SRK vapor densities..
THERMO DATA
METHOD KVALUE=WILSON, ENTHALPY=IDEAL, &
Van Laar
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=VANLAAR
STREAM DATA
. . .

General Information
The VANLAAR liquid activity method is used to predict VLE and
VLLE phase behavior. This method does not support free water
decant.
The VANLAAR liquid activity method is generally useful for
slightly non-ideal applications. Refer to the PRO/II Reference Man-
ual for additional information.
Table 6-7: Attributes of VANLAAR Methods

Properties predicted by VANLAAR methods
K-values

Liquid molar volume
VLLE - Supported
Input Description
METHOD SYSTEM(VLE or VLLE)=VANLAAR,
or
METHOD KVALUE(VLE and/or LLE or VLLE)=VANLAAR,
PHI=IDEAL, {HENRY}, ....

generators. When SYSTEM=VANLAAR is chosen, VANLAAR
K-values, LIBRARY vapor enthalpies, IDEAL vapor densities,
default.

K-value calculations are available with the VANLAAR method.
liquid Equilibrium Considerations on page 38 for more details
PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, PPR78,
BWRS and UNIWAAL (see Chapter 4) and HOCV (the
Hayden-O'Connell method), TVIRIAL (the Truncated Virial
method) and the IDIMER method. See Hayden-OConnell
Vapor Fugacity on page 64, Truncated Virial Vapor Fugacity
on page 68, and IDIMER Vapor Fugacity on page 71 for
details on these last three options. The default is PHI=IDEAL.

option.

KVALUE(VLE OR LLE OR VLLE)
POYNTING=OFF or ON, MOLVOL=STANDARD or
RACKETT or RCK2 or LIBRARY, FILL=NONE or
UNIFAC or CIUNIFAC or UFT1 or FLORY or
REGULAR,
AZEOTROPE=SIMSCI or NONE or bankid,
WRITE=fileid
VANLAAR I, j, aij, aji / ...

and/or
and/or
and/or
and/or
IDEAL i, j / ...

Note: The VANLAAR, AZEOTROPE, INFINITE, MUTUAL
and/or IDEAL statements must follow the KVALUE statement.

default is ON.
page 52 for further details on these options.
include a suffix. The program will automatically add a suffix
(e.g., .FIL on PCs).
VANLAAR This statement allows entry of the binary interaction data for
the VANLAAR liquid activity coefficient method. The
binary parameters aij and aij are related to the liquid activity
N N N N
1 a ij
ln i = ail Zl a ij Z i Z j ---
2 ajk -----
-Z Z
a ji j k
i=1 j=1 j = 1k = 1
j, k i
where:

xl
Z l = -------------------------
N
-
a
xj -----
il
-
a li
j=1
AZEOTROPE These statements are used to enter data for binary

and/or pairs. This data will be regressed to the coefficients for
INFINITE the liquid activity method used to generate the K-
and/or values. Multiple statements may be used to enter data
MUTUAL with different units, or the data can be entered on a
single statement.
and/or This statement sets the binary interaction parameters
IDEAL to zero.
Data input using the VANLAAR, AZEOTROPE, INFINITE,


...
see Chapter 9, Method-specific Pure Component Data. The vapor
pressure also has a direct effect on K-values, but may only be sup-
plied globally for all sets in the Component Data Category. Tc, Pc
and the acentric factor will have an impact if a cubic equation of
state is chosen for vapor phase fugacities. Molar volume will have
an impact on the Poynting correction factor.
Examples
E-6.11: Using the VANLAAR system, model a 50/40/10 mix of
TITLE PROB=VANLAAR
PRINT INPUT=ALL
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=VANLAAR
STREAM DATA

COMP=50/40/10
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-6.12: For the same problem, use VANLAAR K-values, IDEAL

THERMO DATA
METHOD KVALUE=VANLAAR, ENTHALPY=IDEAL, &

Margules
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=MARGULES
STREAM DATA
. . .
General Information
The MARGULES liquid activity method is used to predict VLE and
VLLE phase behavior. This method does not support free water
decant.
The MARGULES liquid activity method is generally useful for
slightly non-ideal applications. Refer to the PRO/II Reference Man-
ual for additional information.
Table 6-8: Attributes of MARGULES Methods

Properties predicted by MARGULES methods
K-values

Liquid molar volume
VLLE - Supported

Input Description
METHOD SYSTEM(VLE or VLLE)=MARGULES, PHI=IDEAL,
{HENRY},...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=MARGULES,
PHI=IDEAL, {HENRY}, ...

generators. When SYSTEM=MARGULES is chosen,
MARGULES K-values, LIBRARY vapor enthalpies, IDEAL
vapor densities, IDEAL liquid densities, and LIBRARY liquid
enthalpies are default.
LLE K-value calculations are available with the Margules
method. The VLLE option automatically selects both. See
Vapor-liquid-liquid Equilibrium Considerations on page 38
for more details on liquid-liquid equilibrium calculations.
PHI Selects the option used to calculate pure component and mixture vapor
phase fugacity coefficients (i). A vapor fugacity method should
generally be selected for high pressure applications. The options are
the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH,
SRKP, PRP, SRKKD, PPR78, BWRS and UNIWAAL (see Chapter 4)
and HOCV (the Hayden-O'Connell method) and TVIRIAL (the
Truncated Virial method). See Hayden-OConnell Vapor Fugacity
IDIMER Vapor Fugacity on page 71 for details on these last three
options. The default is PHI=IDEAL.

enthalpy method selected. See Henrys Law for Non-condensible
Components on page 57 for further information on the use of this
option.

REGULAR,
AZEOTROPE=SIMSCI or NONE or bankid, WRITE=fileid
MARGULES I, j, aij, aji, dij / ...

and/or

and/or
and/or
and/or
IDEAL i, j / ...
Note: The MARGULES, AZEOTROPE, INFINITE, MUTUAL

and/or IDEAL statements must follow the KVALUE statement.
POYNTING This option selects whether to apply the Poynting correction to

fugacities of components in the liquid phase. The default is
OFF unless a PHI method is selected, in which case the default
is ON.
volume necessary for computing the Poynting correction factor.
Options are:
atm).
FILL This selects a method for estimating binary interaction data
missing from the input file and any selected databank libraries.
See Filling in Missing Parameters on page 52 for further
details on these options.
liquid activity coefficient K-value method to a file. The format
of this file is suitable for inclusion into an input file.
fileid This name identifies a file containing binary interaction data. It
may be any valid file name allowed on the operating system,
but must not include a suffix. The program automatically adds a
MARGULES This statement allows entry of the binary interaction data for
the MARGULES liquid activity coefficient method. The binary
parameters aij, aji and dij are related to the liquid activity
2 2
ln i = ( 1 x i ) [ A i + 2 ( B i A i D i )x i + 3D i x i ]
where:

N N N
Ai = xj aij Bi = xj aji Di = xj dij

j=1 j=1 j=1
d ij = d ji
and/or This data will be regressed to the coefficients for the
INFINITE liquid activity method used to generate the K-values.
and/or Multiple statements may be used to enter data with
MUTUAL
statement.
IDEAL zero.
Data input using the MARGULES, AZEOTROPE, INFINITE,


...
see Chapter 9, Method-specific Pure Component Data. The vapor
state is chosen for vapor phase fugacities. Molar volume will have
an impact on the Poynting correction factor.
Examples
E-6.13: Using the MARGULES system, model a 50/40/10 mix of
TITLE PROB=MARGULES
PRINT INPUT=ALL
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=MARGULES
STREAM DATA
COMP=50/40/10

UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-6.14: For the same problem, use MARGULES K-values,

IDEAL enthalpies and liquid densities and SRK vapor
densities..
THERMO DATA
METHOD KVALUE=MARGULES, ENTHALPY=IDEAL, &

Regular Solution
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=REGULAR
STREAM DATA
. . .
General Information
The REGULAR liquid activity method is used to predict VLE and
VLLE phase behavior. It is generally useful for slightly non-ideal
applications. Refer to the PRO/II Reference Manual for additional
information.
Table 6-9: Attributes of REGULAR Methods

Properties predicted by REGULAR methods
K-values

Liquid molar volume
Solubility parameter
Liquid molar volume
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied

Input Description
METHOD SYSTEM(VLE or VLLE)=REGULAR,
or
METHOD KVALUE(VLE and/or LLE or VLLE)=REGULAR,

generators. For example, choosing SYSTEM=REGULAR sets
REGULAR K-values, LIBRARY vapor enthalpies, IDEAL vapor
densities, IDEAL liquid densities, and LIBRARY liquid
enthalpies as defaults.
K-value calculations are available with the Regular method. The
VLLE option automatically selects both. See Vapor-liquid-liquid
Equilibrium Considerations on page 38 for more details on
further details.

option.


Thermo system. Properties missing from this databanks
will be taken from global component data search order.
program.
The Regular Solution Method is derived from the Scatchard-Hil-

debrand equation where the liquid activity coefficient i of a solu-
tion is given by the following equations:
L 2
Vi ( i m )
ln i = ----------------------------------
RT
where:
VLi = Liquid molar volume of component i
i = Solubility parameter of component i
and
N
L
xi Vi
i---------------------------
=1
m = N
L
xi Vi
i=1

...
only two of these properties (MOLVOL and SOLUPARA) have any
direct effect on the calculation of liquid activity coefficients, but
may only be supplied in the Component Data Category. The vapor
state is chosen for vapor phase fugacities. Molar volume will also
have an impact on the Poynting correction factor.
Examples
E-6.15: Using the REGULAR system, model a 50/40/10 mix of
TITLE PROB=REGULAR
PRINT INPUT=ALL
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=REGULAR
STREAM DATA
COMP=50/40/10
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-6.16: For the same problem, use REGULAR K-values, IDEAL

THERMO DATA
METHOD KVALUE=REGULAR, ENTHALPY=IDEAL, &

Flory-Huggins
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=FLORY
STREAM DATA
. . .
General Information
The FLORY-HUGGINS liquid activity method is used to predict
VLE and VLLE phase behavior. This method does not support free
water decant.
The FLORY-HUGGINS liquid activity method is generally useful
for mixtures of components that differ vastly in size, e.g., polymer
solutions. Refer to the PRO/II Reference Manual for additional
information.
Table 6-10: Attributes of FLORY Methods

Properties predicted by FLORY methods
K-values

Liquid molar volume
Liquid molar volume
VLLE - Supported

Input Description
METHOD SYSTEM(VLE or VLLE)=FLORY, PHI=IDEAL,
{HENRY},...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=FLORY,

generators. When SYSTEM=FLORY is chosen, FLORY K-
values, LIBRARY vapor enthalpies, IDEAL vapor densities,
default.
K-value calculations are available with the Margules method.
liquid Equilibrium Considerations on page 38 for more details
PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, PPR78,
BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-

option.

COMP=SIMSCI or PROCESS or bankid

WRITE=fileid
FLORY I, j, cij / ..
.
POYNTING This option selects whether to apply the Poynting correction to

fugacities of components in the liquid phase. The default is OFF
unless a PHI method is selected, in which case the default is
ON.
volume necessary for computing the Poynting correction factor.
Options are:
liquid activity coefficient K-value method to a file. The format
of this file is suitable for inclusion into an input file.
fileid This name identifies the file containing the binary interaction
data. It may be any valid file name allowed on the particular
operating system being used, but must not include a suffix. The
program will automatically add a suffix (e.g., .FIL on PCs).
FLORY This statement allows entry of the c binary interaction
parameters for the Flory-Huggins liquid activity coefficient
method. It should be noted that ij = ji Therefore, the order of
the indices (i,j or j,i) is unimportant. The binary parameters are
related to the liquid activity coefficients by the following
equation:
n n n

ln j = 1 + ln -----i m i
xi ij j jk j k
ji j k>j
where: xi, i, and mi are the mole fraction, volume fraction,

number of segments of component i.

The volume fraction is defined by:
xi vi
i = ---------------
n
-
xi vi
i
where:
vi = the liquid molar volume of component i.
The number of segments is calculated as:
vi
m i = ----------
v min
where:
vmin = the smallest molar volume in the system.
Missing parameters are estimated as:
v min 2
jk = ---------- ( j k )
RT
where:
j and k are solubility parameters of components j and k,
respectively.

...
only two of these properties (MOLVOL and SOLUPARA) have any
direct effect on the calculation of liquid activity coefficients. The
vapor pressure also has a direct effect on K-values. Tc, Pc and the
acentric factor will have an impact if a cubic equation of state is
chosen for vapor phase fugacities. Molar volume will also have an
impact on the Poynting correction factor.

Examples
E-6.17: Using the FLORY-HUGGINS system, model a 50/40/10
mix of DIPE, IPA, and water at 50 psia and 50%
vaporization.
TITLE PROB=FLORY
PRINT INPUT=ALL
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=FLORY
STREAM DATA
COMP=50/40/10
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-6.18: For the same problem, use FLORY K-values, IDEAL

THERMO DATA
METHOD KVALUE=FLORY, ENTHALPY=IDEAL, &
Filling in Missing Parameters

Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=NRTL
KVALUE FILL=UNIFAC
STREAM DATA
. . .

General Information
The program has an extensive facility to backfill missing binary
interaction data for liquid activity methods. If liquid activity coeffi-
cients are unavailable, they may be estimated automatically if
mutual solubility, infinite dilution or azeotropic data are supplied. If
none of these is available, the program seeks to find azeotropic data
in the SIMSCI databank. If these data are unavailable, the FILL
option can be used to estimate the required coefficients using group
contribution methods (UNIFAC or CIUNIFAC or UFT1), regular
solution theory, or Flory-Huggins. If none of these methods are pos-
sible, the program then sets the binary interaction parameters to
zero. For solid-liquid equilibria, the FILL option may be used to
estimate solubility data missing from the databank, or not given by
the user. Missing values may be estimated using the ideal (vant
Hoff) solubility equation, or the solubilities may be set to 1.0 (com-
pletely soluble), or solvents missing solubility data may be ignored
in the solubility calculation.
Table 6-11: Attributes of the FILL Option

Properties predicted by FILL
Binary interaction parameters (liquid activity methods)
Binary solubilities (solid-liquid equilibria)

None FILL=NONE or VANTHOFF or ONE or
FREE
Solubility parameters and FILL=REGULAR or FLORY
liquid molar volumes
UNIFAC structure and group FILL=UNIFAC or UFT1
area and volume data
UNIFAC structure with CI FILL=CIUNIFAC
databank
Input Description
METHOD SYSTEM=NRTL or UNIQUAC or WILSON or
VANLAAR or MARGULES
...
or

METHOD KVALUE=NRTL or UNIQUAC or WILSON or VANLAAR
or MARGULES or SOLDATA
...
SYSTEM A liquid activity method system must be chosen if the FILL

option is to be used.
KVALUE Selects the method for K-value calculations. Only liquid
activity methods and the user-supplied solubility method
SOLDATA can be used with the FILL option.
K-value Data
KVALUE(VLE)FILL=NONE or UNIFAC or CIUNIFAC or UFT1 or
REGULAR or FLORY,
AZEOTROPE=SIMSCI or NONE or bankid
or
KVALUE(LLE)FILL=NONE or UNIFAC or CIUNIFAC or UFT1 or
REGULAR or FLORY,
AZEOTROPE=SIMSCI or NONE or bankid
or
KVALUE(SLE)FILL=VANTHOFF or ONE or FREE
FILL This statement is used to supply parameters missing for the

calculation of liquid activity coefficients. The FILL option
regresses the missing parameters from the option selected to
fit the previously specified K-value liquid activity method.
The FILL options are detailed in Table5-. It should be noted
that, of the VLE and LLE FILL options, only FILL=UNIFAC
or CIUNIFAC will produce LLE parameters that are different
from the VLE parameters. The VANTHOFF or ONE or
FREE fill options may only be used if the KVALUE(SLE)=
SOLDATA statement has been specified.
If the FILL=UNIFAC or CIUNIFAC or UFT1 option is
selected, and a component has no defined UNIFAC structure
or includes a group that is missing its area and volume
parameters, then a warning message is issued. The FILL
option then sets the interaction parameters to zero for any pair
containing that component. The UNIFAC component
structure and UNIFAC group area and volume data can be
supplied in the COMPONENT DATA section. See Volume I,
UNIFAC Structural Groups for more information on
entering UNIFAC structural data.
The UNIFAC "CI" bank is a self-contained VLE bank. Most
In CI-UNIFAC, main group interaction parameters data for
UNIFAC structural groups is taken from CI bank.
AZEOTROPE This statement is used to supply parameters missing for the
calculation of liquid activity coefficients. By default, the
AZEOTROPE option regresses the missing parameters from
the azeotropic databank.

Table 6-12: Data Estimation Options
Entry KVALUE( ) DESCRIPTION
FILL=
NONE No Estimates For Missing Data.
UNIFAC VLE, LLE UNIFAC group contribution method.
CIUNIFAC VLE, LLE UNIFAC method along with CI
databank
UFT1 VLE, LLE Modified UNIFAC method
REGULAR VLE, LLE Regular Solution Theory
FLORY VLE, LLE Flory Huggins method
ONE SLE Missing binary solubilities set to 1.0
(i.e., all unspecified solids are
completely soluble).
VANTHOFF SLE Missing binary solubilities calculated
with the vant Hoff equation
FREE SLE Solvents missing binary solubility
data are ignored in the solubility
calculation.
AZEOTROPE=
SIMSCI VLE, LLE Estimates for missing data made
from azeotropic data.
NONE No estimates for missing data.
bankid Estimates for missing data made
from user-created databank.
Examples
E-6.19: Using the VLLE NRTL liquid activity method, and the
Henrys Law option, determine the solubility of O2 in a
methanol/ethanol/benzene/water/IPA system.
NRTL binary interaction parameters are provided for the
ethanol-IPA and benzene-ethanol pairs. Data are provided
for the azeotrope formed between ethanol and water.
Mutual solubility data are provided between water and
benzene, while infinite dilution data are given for the
methanol-water pair.
The pairs ethanol-methanol and methanol-IPA are defined
as ideal pairs in the liquid phase. Supply data for the O2-
IPA pair via a HENDATA statement, and retrieve data for

the other pairs from the SIMSCI databank. Use the
FILL=UNIFAC option to estimate any missing
parameters.
TITLE PROB=MISSING PARAMETERS
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,MEOH/ 2,H2O/ 3,ETOH/ 4,BENZENE/ 5,IPA/ 6,O2
THERMO DATA
METHOD SYSTEM(VLLE)=NRTL, HENRY
KVALUE(VLE) FILL=UNIFAC
INFI 1, 2, 70.0, 1.79, 2.16
MUTU(W) 2, 4, 20.0, 5.823E-04, 1.732E-03
AZEO(W,F) 2, 3, 1.013, 172.7, 4.61E-02
NRT3(KCAL) 3, 5, 48.9, 49.3, 3.96E-01
NRTL(K) 4, 3, -2.75, 1472.2, -4.5E-01, 440.5, 5.34E-01
KVALUE(LLE) FILL=UNIFAC
IDEAL 1, 3/ 1, 5
HENRY
SOLUTE 6
HENDATA 6, 5, -36, 2000, 6.5
STREAM DATA
COMP=10/50/20/10/7/3
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

Henrys Law for Non-condensible Components
Typical Usage
...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, 02
THERMO DATA
METHOD SYSTEM=NRTL, HENRY
STREAM DATA
. . .
General Information
The HENRY option is used to predict gas solubilities, especially for
modeling supercritical components using a liquid activity method.
It is especially useful for environmental applications such as model-
ing trace organics in aqueous streams.
Table 6-13: Attributes of the Henrys Law Option

Properties predicted by HENRY
K-values
Vapor pressure
Components Supercritical gases, trace organics in water
Free-water decant Not supported
VLLE The HENRY option only calculates gas solubilities.
However, VLLE methods may also be used.

Input Description
METHOD SYSTEM=NRTL or UNIQUAC or UNIFAC or UFT1 or
UFT2 or UFT3 or UNFV or WILSON or VANLAAR or
MARGULES or REGULAR or FLORY,
HENRY, . . .
or
METHOD KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or
MARGULES or REGULAR or FLORY,
HENRY, . . .
SYSTEM A liquid activity method system must be chosen if the

HENRY option is to be used.
activity methods can be used with the HENRY option.
HENRY This option selects Henrys Law data (either user-supplied or
This option is only available when using a liquid activity
method for K-value calculations. Table 6-14 shows some of
the binary gas-solvent pairs available in PRO/II software.
Some additional Henrys Law data for hydrofluorocarbons
(HFCs) and chlorofluorocarbons (CFCs) are also available in
the databanks.

Table 6-14: Henrys Law Package Available Pairs
Gas Components
Hydrogen Chloride
Carbon Monoxide
Cartoon Disulfide
Hydrogen Sulfide
Carbon Dioxide
Sulfur Dioxide
Nitrous Oxide
Liquid
Methanethiol
Hydrogen
Acetylene
Propylene
Ammonia
Isobutane
Ethandiol
N-butane
Components
Ethylene
Nitrogen
Methane
Propane
Oxygen
Helium
Ethane
Argon
Water X X X X X X X X X X X X X X X X X X X X X
Acetic Acid X X X X X
Formic Acid X X X X
m-cresol X X
Methanol X X X X X X X X X X
Ethanol X X X X X X X
n-propanol X X X X X X X
isopropanol X X X X X X X
n-butanol X X X X X X
sec-butanol X X X X
tert-butanol X X X X
3-methyl-1butanol X X X X
n-pentanol X X X X
Ethylene Glycol X X
Triethylene Glycol X X X X X X X X X X
Acetaldehyde X X X X
Methyl ether X X X X
Ethyl ether X X X X
Isopropyl ether X X X X
Tetrahydrofuran X
Dibenzofuran X
Methyl formate X X X X
Methyl acetate X X X X
Ethyl acetate X X X X

Gas Components
Hydrogen Chloride
Carbon Monoxide
Cartoon Disulfide
Hydrogen Sulfide
Carbon Dioxide
Sulfur Dioxide
Nitrous Oxide
Liquid
Methanethiol
Hydrogen
Propylene
Acetylene
Ammonia
Ethandiol
Isobutane
N-butane
Components
Nitrogen
Ethylene
Methane
Propane
Oxygen
Helium
Ethane
Argon
Isopentane X X X X
n-pentane X X X X X
2-methylpentane X X X X
n-hexane X X X X X
2-4 X X X X
dimethylpentane
3-methylhexane X X X X
n-heptane X X X X X X
2-4- X X X X
dimethylhexane
n-octane X X
n-nonane X X
n-decane X X X X X X
n-dodecane X
n-tetradecane X
n-hexadecane X X X X X X X X X
Eicosane X
Docosane X
Dotriacontane X
Cyclopentane X X X X
Methylcyclopentane X X X X
Cyclohexane X X X X
Methylcyclohexane X X X X X
1-T-2-DMCP X X X X
1-T-2-C-4MCP X X X X
Bicyclohexyl X X X X X
1-hexene X X X X
Freon 113 X X
Benzene X X X X X
Chlorobenzene X X

Gas Components
Hydrogen Chloride
Carbon Monoxide
Cartoon Disulfide
Hydrogen Sulfide
Carbon Dioxide
Sulfur Dioxide
Nitrous Oxide
Liquid
Methanethiol
Hydrogen
Propylene
Acetylene
Ammonia
Ethandiol
Isobutane
N-butane
Components
Nitrogen
Ethylene
Methane
Propane
Oxygen
Helium
Ethane
Argon
Toluene X X X X X X
m-xylene X X X
1-C1-naphthalene X X X X X
Diphenylmethane X X X X
1,3,5-tri-C1- X
benzene
9,10 X
dihydrophenanthren
e
Tetralin X
2-ethylanthracene X
9-methylanthracene X
Hydrogen fluoride X X X
Acetone X X X X X X
Methyl ethyl ketone X X X X
Methyl n-butyl X
ketone
Methyl propyl X
ketone
n-methyl-2- X X X X X X
pyrrolidone
Quinoline X X
Sulfolane X X X X
Hydrogen chloride X
Ammonia X X
Chloride X

Henrys Law Data
HENRY BANK=SIMSCI or NONE or bankid
SOLUTE i, j, ...
HENDATA(upres, utemp) i, l, C1, C2, C3, C4 / ...
BANK This option selects one or more databanks from which to retrieve
Henrys Law data. Options available are:
SIMSCI Selects the SIMSCI standard databank (default).
Henrys Law data.
If the data for any component designated as a Henry component is
missing from the supplied databank and is not supplied via a
HENDATA statement, the Henrys law constant is obtained by
extrapolation of the component vapor pressure data.
SOLUTE This statement is used to enter the component ID numbers for the
components to be treated as solutes.
HENDATA This statement allows entry of the Henry coefficients for solute i in
solvent l. Coefficients C1, C2, C3, and C4 apply to Henrys
Law constant Hi (and the K-value) by the following equations
for one or more solutes in a pure solvent:
C2
ln ( H i ) = C 1 + ------ + C 3 ln ( T ) + C 4 ( P )
T
and Hi
K i = -----
P
For a mixture of solvents, the following mixing rules are used for
determining Hi,mix and Ki:
N
ln ( H i, mix ) = xl ln ( Hi, l )
l=1
and Hi
K i = -----
P

VP
...
Vapor pressure data may only be specified globally for all thermo-
dynamic sets in the Component Data Category in tabular or equa-
tion form. For a further description of these input parameters, see
Chapter 9, Method-specific Pure Component Data.
Examples
E-6.20: Using the NRTL liquid activity method, and the Henrys
Law option determine the solubility of CO in a methanol/
water system. Data for the CO-methanol pair are supplied
via a HENDATA statement, while data for the other pairs
are retrieved from the SIMSCI databank.
TITLE PROB=HENRY
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,N2/ 2,CO/ 3,H2O/ 4,MEOH
THERMO DATA
METHOD SYSTEM=NRTL, HENRY
HENRY
SOLUTE 1, 2
HENDATA 2, 4, 152.4, -8000, -20, 0
STREAM DATA
COMP=2/3/70/25
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

Hayden-OConnell Vapor Fugacity
Typical Usage
...
COMPONENT DATA
LIBID 1, ACETIC/ 2, ACRYLIC/ 3, H2O
THERMO DATA
METHOD SYSTEM=NRTL, PHI=HOCV, &
ENTHALPY(V)=HOCV, DENSITY(V)=HOCV
KVALUE FILL=UNIFAC
STREAM DATA
. . .
General Information
The HOCV method predicts vapor fugacities, vapor enthalpies,
vapor entropies and vapor densities. It is especially useful for sys-
tems where dimers form in the vapor phase, e.g., carboxylic acid
systems. A liquid activity method must be used in conjunction with
the HOCV method.
Table 6-15: Attributes of the HOCV Vapor Fugacity Method

Properties predicted by HOCV
Vapor fugacities Hayden-OConnell Vapor Fugacity:
vapor enthalpies
Critical temperature Dipole moment
Critical pressure Radius of gyration
van der Waals area and PHI=HOCV
volume
Components - Carboxylic acids, polar components
VLLE - HOCV only calculates vapor phase properties,
but VLLE methods may be used with HOCV
methods.
1

Input Description
MARGULES or REGULAR or FLORY, PHI=HOCV,
ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV,
DENSITY(V)=HOCV, . . .
or
MARGULES or REGULAR or FLORY, PHI=HOCV,
ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV,
DENSITY(V)=HOCV, . . .
SYSTEM A liquid activity method system must be chosen if the HOCV

method is to be used.
activity methods can be used with the HOCV method.
PHI Selects the HOCV method for vapor phase fugacities,
and/or and/or enthalpies and/or entropies and/or densities.
ENTHALPY(V)
and/or
ENTROPY(V)
and/or
DENSITY(V)

KVALUE POYNTING=ON or OFF, MOLVOL=STANDARD
or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE
or bankid, FILL=NONE or UNIFAC or CIUNIFAC or UFT1 or
FLORY or REGULAR.
POYNTING Selecting this option applies the Poynting correction

to fugacities of liquid phase components. The default
is OFF unless a PHI method is selected, which sets
the default ON.
MOLVOL This selects the method used to calculate the liquid
molar volume necessary for computing the Poynting
correction factor. Options are:

Vapor Fugacity Data
PHI BANK=SIMSCI or NONE or bankid,
HOCV i, i, nii/ i, j, nij/ . . .
Note: The HOCV statements must follow the PHI statement.
BANK This option selects one or more databanks from which to

retrieve vapor phase binary interaction data.
program.
HOCV This statement supplies interaction data for the Hayden-
OConnell vapor fugacity method. This method may be used for
components forming dimers, particularly carboxylic acids. nii is
the association parameter for component i while nij is the
solvation parameter for components i and j.
Enthalpy, Entropy and Density Data

ENTHALPY(V) BANK=SIMSCI or NONE or bankid,
ENTROPY(V) BANK=SIMSCI or NONE or bankid,
DENSITY(V) BANK=SIMSCI or NONE or bankid,
HOCV i, i, nii/ i, j, nij/ . . .
HOCV vapor interaction data may be selected for enthalpy, entropy
and density methods. Normally, these features are selected for the
vapor fugacity method and are automatically carried over for these
other methods. If, however, the vapor fugacity method is not
HOCV, you can supply these parameters independently.
See above under Vapor Fugacity Data for format and definition of
these entries.

RADIUS i, value / ...
...
method is used. VANDERWAALS must be supplied in the Compo-
nent Data Category. For a further description of these input parame-
ters, see Chapter 9, Method-specific Pure Component Data.
Examples
E-6.21: Using the HOCV vapor fugacity method with the NRTL
liquid activity method, model a 50/50 mix of acetic and
acrylic acids at 100 psia and 100 F.
TITLE PROB=HOCV
COMPONENT DATA
LIBID 1,ACETIC/ 2,ACRYLIC
THERMO DATA
ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV, &
DENSITY(V)=HOCV
STREAM DATA
COMP=50/50
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-6.22: For the same problem, use HOCV for vapor fugacities and
SRK for vapor enthalpies, entropies and densities. Specify
THERMODYNAMIC DATA
ENTHALPY(V)=SRK, ENTROPY(V)=SRK, &
DENSITY(V)=HOCV, DENSITY(L)=API

Truncated Virial Vapor Fugacity
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=NRTL, PHI=TVIRIAL
STREAM DATA
. . .
General Information
The TVIRIAL method predicts vapor fugacities. It is useful for sys-
the TVIRIAL method.
Table 6-16: Attributes of the TVIRIAL Vapor Fugacity Method

Vapor fugacities

Critical pressure Dipole moment
Critical volume
Components - Carboxylic acids
VLLE - TVIRIAL only calculates vapor phase
properties, but VLLE methods may be used with
TVIRIAL methods.

Input Description
MARGULES or REGULAR or FLORY, PHI=TVIRIAL
or
MARGULES or REGULAR or FLORY, PHI=TVIRIAL

TVIRIAL method is to be used.
activity methods use the TVIRIAL method.
PHI Selects the TVIRIAL method for vapor phase fugacities.

FLORY
or REGULAR.

Vapor Fugacity Data

PHI COMP = SIMSCI or PROCESS or bankid
TVIRIAL i, i
Note: The TVIRIAL statements must follow the PHI statement.

searching for pure components required for the current thermo
system. properties missing from this databanks will be taken
TVIRIAL This statement supplies interaction data for the Truncated Virial
vapor fugacity method. This method may be used for
components forming dimers, particularly carboxylic acids. i is
the Truncated Virial Coefficient for component i.

...
Examples
E-6.23: Using the TVIRIAL vapor fugacity method with the
NRTL liquid activity method, model a 75/25 mix of
ethanol and cyclohexane at 5 atm and 115 C.
TITLE PROB=TVIRIAL
PRINT INPUT=ALL
DIME METRIC, PRES=ATM, TEMP=C
COMPONENT DATA
LIBID 1,ETHANOL/ 2,CYHX
THERMO DATA
METHOD SYSTEM=NRTL, PHI=TVIRIAL
KVALUE POYNTING=ON
NRT6(K) 1, 2, -.1429, 472.71, -.01, 748.33, 0.3681, 2.871E-4
PHI
TVIRIAL 1, 1.0/ 2, 0.0
STREAM DATA
COMP=75/25
UNIT OPERATION
FLASH UID=FL1
FEED 1

PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
E-6.24: For the same problem, use TVIRIAL for vapor fugacities
and SRK for vapor enthalpies, entropies and densities.
Specify API liquid densities.
THERMODYNAMIC DATA
METHOD SYSTEM=NRTL, PHI=TVIRIAL, &
ENTHALPY(V)=SRK, ENTROPY(V)=SRK, &
IDIMER Vapor Fugacity

Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=NRTL, PHI=IDIMER, &
ENTHALPY(V)=IDIMER, DENSITY(V)=IDIMER
KVALUE FILL=UNIFAC
STREAM DATA
. . .
General Information
The IDIMER method predicts vapor fugacities, vapor enthalpies,
vapor entropies and vapor densities. It is especially useful for sys-
the IDIMER method.
Table 6-17: Attributes of the IDIMER Vapor Fugacity Method

Vapor fugacities Vapor densities
vapor enthalpies Vapor entropies

None
Components - Carboxylic acids, polar components
VLLE - IDIMER only calculates vapor phase properties,
but VLLE methods may be used with IDIMER
methods.
1
Input Description
MARGULES or REGULAR or FLORY, PHI=IDIMER,
ENTHALPY(V)=IDIMER, ENTROPY(V)=IDIMER,
DENSITY(V)=IDIMER, . . .
or
MARGULES or REGULAR or FLORY, PHI=IDIMER,
ENTHALPY(V)=IDIMER, ENTROPY(V)=IDIMER,
DENSITY(V)=IDIMER, . . .

IDIMER method is to be used.
liquid activity methods can be used with the IDIMER
method.
PHI Selects the IDIMER method for vapor phase
and/or fugacities, and/or enthalpies and/or entropies and/or
ENTHALPY( densities.
V)
and/or
ENTROPY(V)
and/or
DENSITY(V)


FLORY or REGULAR
.

Vapor Fugacity Data

PHI BANK=SIMSCI or NONE or bankid
IDIMER(utemp, upres, log or ln)i, i, Aii, Bii/ i, j, Aij, Bij/ . . .
Note: The IDIMER statements must follow the PHI statement.
BANK This option selects one or more databanks from which to retrieve
vapor phase binary interaction data.
IDIMER This statement supplies interaction data for the IDIMER vapor
fugacity method. This method may be used for components
forming dimers, particularly carboxylic acids. Aii and Bii are the
association parameter for component i, while Aii and Bii are the
solvation parameter for components i and j.
Enthalpy, Entropy and Density Data

ENTHALPY(V) BANK=SIMSCI or NONE or bankid
ENTROPY(V) BANK=SIMSCI or NONE or bankid
DENSITY(V) BANK=SIMSCI or NONE or bankid
IDIMER(utemp, upres, log or ln) i, i, Aii, Bii/ i, j, Aij, Bij/ . . .
IDIMER vapor interaction data may be selected for enthalpy,
entropy and density methods. Normally, these features are selected

for the vapor fugacity method and are automatically carried over for
these other methods. If, however, the vapor fugacity method is not
IDIMER, you can supply these parameters independently.
See above under Vapor Fugacity Data for format and definition of
these entries.
Examples
6.25: Use the IDIMER vapor fugacity method with the NRTL
liquid activity method for a mix of associating acids.
TITLE PROB=IDIMER
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1, HFOR/ 2, ACETIC/ 3, HPRP
THERMO DATA
METHOD SYSTEM=NRTL, PHI=IDIMER, &
ENTHALPY(V)=IDIMER, ENTROPY(V)=IDIMER, &
DENSITY(V)=IDIMER
PHI BANK=SIMSCI
IDIME(K, MMHG, LOG) 1,1,-10.743,3083.0
IDIME(K, MMHG, LOG) 2,2,-10.421,3166.0
IDIME(K, MMHG, LOG) 3,3,-10.843,3316.0
IDIME(K, MMHG, LOG) 1,2,-10.356,3193.0
STREAM DATA
COMP=0.477/0.094/0.729
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

Redlich-Kister, Gamma Heat of Mixing
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=NRTL
ENTHALPY(L) HMIX=RK1
KVALUE FILL=UNIFAC
STREAM DATA
. . .
General Information
The Redlich-Kister and Gamma heat of mixing methods apply a
correction to IDEAL enthalpy data. A liquid activity method must
be used in conjunction with the Redlich-Kister or Gamma methods.
Table 6-18: Attributes of the Redlich-Kister, Gamma Heat of Mixing

Properties predicted by RK1, RK2, GAMMA
Liquid enthalpy heat of mixing corrections
None
Free-water decant - N/A
VLLE - N/A
Input Description
MARGULES or REGULAR or FLORY
or
MARGULES or REGULAR or FLORY, . . . ,
ENTHALPY(L)=IDEAL, . . .

Gamma method is to be used.
activity methods can be used with the Gamma method.
ENTHALPY(L) Selects the IDEAL liquid enthalpy method for use with the
Redlich-Kister or Gamma heat of mixing methods.
Enthalpy Data
HMIX=NONE or RK1 or RK2 or GAMMA
RK1(K or KCAL or KJ) i, j, aij, bij, cij, dij, eij, fij, gij, hij/ . . .
or
RK2(K or KCAL or KJ) i, j, aij, bij, cij, dij, eij, fij, gij, hij/ . . .
Note: UOM for WILSON is K or KCAL/KMOL or KJ/KMOL.
BANK This option selects one or more databanks from which to retrieve vapor
phase binary interaction data.
HMIX This statement selects the heat of mixing method to be applied to the liquid
enthalpy method.
NONE No mixing enthalpy correction is applied (default).
RK1 or This option selects different formulations of the Redlich-
RK2 Kister correlation.
GAMMA The heat of mixing is calculated through activity coefficient

derivatives with respect to temperature.
RK1 The RK1 or RK2 statements are used to supply interaction parameters for
or the Redlich-Kister heat of mixing correlation methods RK1 and RK2. The
RK2 statement given here must correspond to the entry on the ENTHALPY
property data statement. The statements RK1 and RK2 are exclusive of
each other and cannot be mixed in the same property data section. The
Redlich-Kister equation for the excess heat of mixing is given as:
when unit is K:
EX
---------- = --1-
H 2 3 4 5 6 7
RT T xi xj ( aij + bij X + cij X + d ij X + e ij X + f ij X + g ij X + h ij X )
i j
when unit is KCAL/KMOL or KJ/KMOL:

EX
H 1 2 3 4 5 6 7
---------- = -------
RT RT xi xj ( aij + bij X + cij X + d ij X + e ij X + f ij X + g ij X + h ij X )
i j
where
X = xi xj (form 1 of Redlich-Kister)
xi xj (form 2 of Redlich-Kister)
X = --------------
xi + xj
Examples
6.26: Using the NRTL liquid activity method, and correcting for
the heat of mixing using the Redlich-Kister method RK1,
model a 50/50 mix of acetic and acrylic acids at 100 psia
and 100 F.
TITLE PROB=RK1
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1, ACETIC/ 2, ACRYLIC
THERMO DATA
METHOD SYSTEM=NRTL, PHI=HOCV
STREAM DATA
COMP=50/50
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END
6.27: For the same problem, use TVIRIAL for vapor fugacities
and specify API liquid densities.
THERMODYNAMIC DATA
METHOD SYSTEM=NRTL, PHI=TVIRIAL, DENSITY(L)=API

Chapter 7
Solid Solubility Methods
The program provides a number of methods for handling solids,

including the van't Hoff solubility method which calculates solid-
liquid equilibrium K-values.
Van't Hoff Solubility

Typical Usage
...
COMPONENT DATA
LIBID 1,H2O/ 2,TOLUENE/ 3,PXYLENE
THERMODYNAMIC DATA
METHOD SYSTEM=IDEAL, KVALUE(SLE)=VANTHOFF
STREAM DATA
. . .
General Information
The VANTHOFF solubility method is used to calculate solid-liquid
equilibrium K-values for nearly ideal non-electrolyte systems using
the van't Hoff ideal solubility equation.

Table 7-1: Attributes of the VANTHOFF Method
Properties predicted by the VANTHOFF method
SLE K-values

Triple point temperature
VLLE - N/A
Input Description
METHOD KVALUE(SLE)=VANTHOFF, ...
KVAL Selects the method for K-value calculations. Only

UE SLE K-value calculations are available with the
VANTHOFF method.
The solubility of solute i in solvent l at temperature T is given by:

H m T C p T t C p T
ln x i = ----------- ---- 1 + ---------- ---- 1 ---------- ln ----t
RT T t R T R T
where:
Hm= enthalpy change of melting at Tt
Cp= heat capacity change of melting at Tt
Tt= triple point temperature
In practice, the more easily accessible solid melting temperature is

usually used instead of the triple point temperature.
7-2 Solid Solubility Methods

Examples
7.1: Use the VANTHOFF method for a system containing p-
xylene.
TITLE PROJECT=MANUAL, PROB=VANTHOFF
PRINT INPUT=ALL
COMP DATA
LIBID 1,TOLU/ 2,PXYLENE/ 3,MXYLENE/ 4,OXYLENE/ 5,EBZN/ &
6,ETLN/ 7,C3, BANK=SIMSCI
ATTR COMP=2, PSD(MIC)=0., 10., 25., 50., 75., 100., &
250., 500., 1000., 5000., 10000.
THERMO DATA
METHOD SYSTEM=IDEAL, KVALUE(SLE)=VANTHOFF, &
TRANSPORT=PURE
STREAM DATA
...
END
7.2: For the same problem, use the VANLAAR method for
VLE calculations.
THERMO DATA
METHOD SYSTEM(VLE)=VANLAAR, &
KVALUE(SLE)=VANTHOFF, TRANSPORT=PURE

User-supplied Solubility
Typical Usage
...
COMPONENT DATA
LIBID 1,H2O/ 2,NACL/ 3,CACL2
THERMODYNAMIC DATA
METHOD SYSTEM=IDEAL, KVALUE(SLE)=SOLDATA
KVALUE(SLE)
SOLUTE 2,3
SOLDATA 2,1,-2.3/ 3,1,1.937,-1213
STREAM DATA
. . .
General Information
The SOLDATA solubility method is used to calculate solid-liquid
equilibrium K-values using user-supplied solubility data.
Table 7-2: Attributes of the SOLDATA Method

Properties predicted by the SOLDATA method
K-values

None
VLLE - N/A
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
METHOD KVALUE(SLE)=SOLDATA, ...
KVALUE Selects the method for K-value calculations. Only SLE K-value
calculations are available with the SOLDATA method.
K-value Data
KVALUE(SLE) FILL=VANTHOFF or ONE or FREE
SOLUTE i, j, k,...
SOLDATA(utemp) i, l, c1, c2, c3 { , tmin, tmax}.
FILL The fill option selects the method used to estimate binary interaction
data missing from the selected databank and not given via SOLDATA
statements. The options available are:
VANTHOFF van't Hoff ideal solubility equation. This is the default.
ONE Missing binary solubilities set to 1.0 (i.e., all
unspecified solids completely soluble).
FREE If a solvent k is missing binary solubility data for a
solute, the solvent is ignored in the solubility
calculation. That is, the solvent mole fractions are
normalized to a k-free basis.
SOLUTE Specifies the solutes i, j, k ... in the system.
SOLDATA This statement supplies the molar solubility of a solute
i in a mixture of i and solvent l, as a function of
temperature according to the following equations:
c2
ln x il = c 1 + ----- + c 3 ln T
T
The solubility of i in a multi-component stream is given as:

NOC
ln ( x i, mix ) = xl ln ( xi, l )
l = 1
li
The temperature units (utemp) may only be given in Kelvin or degrees

Rankine.
Note: When the SOLDATA method is used for calculating the

solid-liquid equilibrium K-values, the KVALUE(SLE) statement
must be utilized. The SOLUTE and SOLDATA statements must
follow the KVALUE(SLE) statement. The SOLDATA statement
supplies values used for equilibrium calculations.

Note:While only 3 coefficients are recognized on the SOL-
DATA statement, a total of five floating point values are
allowed. The final two values are the minimum and maxi-
mum applicable temperatures, respectively.
Examples
7.3: Use the SOLDATA method and supplied solubility data,
for a system containing p-xylene. Binary interaction data
not supplied via SOLDATA statements are retrieved from
the van't Hoff method by the selection of the
FILL=VANTHOFF option.
TITLE PROJECT=MANUAL,PROB=SOLDATA
PRINT INPUT=ALL
COMP DATA
LIBID 1,TOLU/2,PXYLENE/3,MXYLENE/4,OXYLENE/5,EBZN/ &
6,ETLN/7,C3, BANK=SIMSCI
ATTR COMP=2, PSD(MIC)=0., 10., 25., 50., 75., 100., &
250., 500., 1000., 5000., 10000.
THERMO DATA
METHOD SYSTEM=IDEAL, KVALUE(SLE)=SOLDATA, &
TRANSPORT=PURE
KVALUE(SLE) FILL=VANTHOFF
SOLUTE 2
SOLDATA 2,1,-0.6,0.02,0.01
STREAM DATA
...
END
7.4: For the same problem, use SRK for VLE calculations and
set all missing binary interaction data for SLE calculations
equal to 1.0.
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, KVALUE(SLE)=SOLDATA, &
TRANSPORT=PURE
KVALUE(SLE) FILL=ONE

Chapter 8
Transport and Special Properties
The program provides a number of methods for calculating trans-

port properties, and many stream properties such as kinematic vis-
cosities, cloud point, flash point temperature, and sulfur content.
The first part of this chapter describes transport property input
options. The second part of the chapter discusses keyword input
options for other stream properties, including special properties and
refinery inspection properties.
Transport Properties
Typical Usage
...
COMPONENT DATA
LIBID 1,C3/ 2,IC4/ 3,NC4
THERMO DATA
METHOD SYSTEM=SRK, TRANSPORT=PURE
STREAM DATA
. . .
General Information
The TRANSPORT keyword is used to provide transport properties,
including liquid and vapor viscosities, liquid and vapor thermal
conductivities, and liquid surface tension values. Liquid diffusivi-
ties may be computed by selecting the DIFFUSIVITY(L) keyword.

Table 8-1: Attributes of the TRANSPORT Method
Properties predicted by the SHELL, PURE and PETRO methods
Liquid/vapor viscosities Liquid/vapor thermal conductivities
Liquid surface tensions
Properties predicted by the SIMSCI and API methods
Liquid viscosities
Properties predicted by the TRAPP method
Liquid/vapor viscosities Liquid/vapor thermal conductivities
Properties predicted by the TACITE method
Liquid viscosities Liquid/vapor thermal conductivities
Varies with method and property; see the PRO/II Reference Manual
for more information
1 Automatically supplied for library and petroleum components.
Must be supplied by the user for non-library components.
Input Description for Transport Properties

METHOD . . .,
TRANSPORT= NONE (this is the default for all transport properties)

or TRANSPORT=PURE or PETRO or TRAPP or TACITE
or U1 or U2 ... or U5,
or
{DIFFUSIVITY(L)=NONE or DIFFUSIVITY(L)=WILKE or DIFDATA,
VISCOSITY(VL)= NONE
or VISCOSITY(VL)= PURE or PETRO or TRAPP or U1 or U2 or ...U5,
or VISCOSITY(V)=PURE or PETRO or TRAPP or BW or U1 or U2 ... or U5
or API or AGA8 or GERG or NIST 23
and/or
VISCOSITY(L)= PURE or PETRO or TRAPP or TWUB or APIT or KVIS
or LBC or U1 or U2 ... or U5 or SIMSCI or API or GERG or NIST 23
CONDUCTIVITY(VL)= NONE
or CONDUCTIVITY(VL)= PURE or PETRO or TRAPP or LATINI or U1 or
U2 or ... U5,
or CONDUCTIVITY(V)= PURE or PETRO or TRAPP or LATINI or U1 or U2
or ... U5,
and/or
CONDUCTIVITY(L)= PURE or PETRO or TRAPP or LATINI or API96 or
API96H or U1 or U2 or ... U5,
8-2 Transport and Special Properties

SURFACE(L)= NONE
or SURFACE(L)=PURE or PETRO or PARACHOR / API82Hor API82 or
NIST or GERG or { U1 or U2 ... or U5}
Table 8-2: Available Transport Property Methods
TRANSPORT
The TRANSPORT keyword selects the method set used to calculate of
transport properties including liquid and vapor viscosities, liquid and vapor
thermal conductivities, and liquid surface tension values. When the
TRANSPORT keyword is absent, no transport calculations occur. Begin-
ning with PRO/II 9.1, when the thermodynamic system is Tacite, the
default transport method is TACITE. When the TRANSPORT keyword is
present, the available options are:
NONE Suppresses all calculations of transport properties

PURE This option applies simple mixing rules to the temperature-
dependent pure component values available in the selected
databanks to calculate mixture transport properties.
Saturation values are used and no pressure corrections
apply. This method is the default if only the TRANSPORT
keyword is present.
PETRO This option uses predictive correlations that apply to bulk
hydrocarbon mixtures. Pressure corrections apply.
TRAPP This option uses a one fluid conformal TRAPP model to
calculate vapor and liquid viscosities and thermal
conductivities for hydrocarbons. The PETRO method is
used to calculate surface tension.
TACITE This option uses the Lohrenz-Bray-Clark (LBC) liquid
viscosity method, the PETRO conductivity methods, and
the PARACHOR method for surface tension. Starting with
PRO/II 9.1, it is the default when TACITE is the active
thermodynamic system.
U1-U5 This option selects one of the up to 5 user-defined
subroutines that are available to compute transport
properties.
Viscosity Data
VISCOSITY(VL or V and/or L)
This keyword requests the calculation of vapor and liquid viscosities. The
options available with this keyword are:

databanks to calculate mixture transport properties.
apply. This option is available for both vapor and liquid
viscosity calculations.
hydrocarbon mixtures. Pressure corrections apply. This
option is available for both vapor and liquid viscosity
calculations.
TRAPP This option uses a one fluid conformal solution model to
calculate vapor and liquid viscosities.
KVIS This option calculates the viscosity from the values of the
kinematic viscosity and the density. For purposes of this
calculation, the density is computed with the API method.
In order to use this option, a KVIS method must be declared
on the METHOD statement. This option is only available
with the VISCOSITY(L) keyword.
LBC This is the Lohrenz-Bray-Clark prediction method for
calculating liquid viscosities.
U1-U5 This option selects one of the 5 supported user-defined
properties. This option is available for both vapor and
liquid viscosity calculations.
SIMSCI This option uses SimSci developed liquid viscosity values.
This was known as the Twu method in PROCESS. This
option is available only with the VISCOSITY(L) keyword.
API This option uses liquid viscosities from the API Technical
Data Book. This option is available only with the
VISCOSITY(L) keyword.
BW Bromley-Wilkey correlation (Procedure 11B2.1) suitable
for gaseous mixtures at low pressure. Available only for
vapor viscosity calculations.
TWUB Applies the recommended Twu-Bulls mixing rule in the
API Technical Data Book to the SIMSCI (Twu) method.
This option is available for liquid viscosity.
APIT For liquid viscosities only, this option applies the Twu-
Bulls mixing rule to the viscosity nomograph in the API
Technical Data Book.
Conductivity Data
CONDUCTIVITY (VL or V and/or L)
This keyword requests the calculation of vapor and liquid thermal
conductivities. The options available with this keyword are:

databanks to calculate mixture thermal conductivity
properties. Saturation values are used, and no pressure
corrections apply. This option is available for both vapor
and liquid conductivity calculations.
hydrocarbon mixtures. Pressure corrections apply. This
option is available for both vapor and liquid conductivity
calculations.
TRAPP This option uses a one fluid conformal solution model to
calculate vapor and liquid conductivities.
LATINI Uses the Latini correlation to predict thermal conductivity
for polar and non-polar systems. Available for both liquid
and vapor phases.
API96 Updated correlation taken from the 1996 API Technical
Data Book Figure 12A3.1. Available only for liquid phase
thermal conductivities.
API96H Same as the API (1982) method above, but uses API
Procedure 12A4.1 to correct correlation 12A3.1. This
yields results similar to the API96 method. Available only
for liquid phase thermal conductivities.
properties. This option is available for both vapor and
liquid thermal conductivity calculations.
Surface Tension Data

SURFACE(L) This keyword selects the calculation method for liquid
surface tensions. Options available are:
databanks to calculate mixture viscosity properties.
apply.
hydrocarbon mixtures. Pressure corrections apply.
API82 Uses the 1982 API Procedure 10A3.2 to predict liquid
surface tension of petroleum fractions at low pressure.
API82H (or) Uses the 1982 API Procedure 10A2.2 (Weinaug-Katz
PARACHOR equation) to predict surface tension of defined hydrocarbon
mixtures at high pressures. Group contributions for
calculating Parachor come from Quayle.

properties.
Diffusivity Data
DIFFUSIVITY (L) This specifies a diffusivity method. Diffusivity is not
calculated when this entry is missing. Available method
options are:
WILKE This argument specifies using the Wilke-Chang correlation.
It is the default method used when the DIFFUSIVITY(L)
entry is present without the argument that identifies the
calculation method.
DIFDATA This option requires the user to provide DIFFUSIVITY and
DIFDATA statements after the METHOD statement. The
DIFDATA statement supplies the data to use in the
diffusivity calculations.
DIFDATA(utemp)i, j, c1, c2, c3/ ...
This statement supplies the diffusivity of a solute i in a mixture of
components i and j.
Diffusivity is a measure of the rate at which a solute diffuses through
a given area in a given time period under a concentration gradient.
The dimensions of diffusivity are always in m2/sec. The diffusivity is
given as a function of temperature according to the following
equation:
ln Dij = c1 + c2 / T + c3 ln T
where T is in absolute units (K or R).
Note: PRO/IIcurrently allows calculating of liquid diffusivities

only when using a KVALUE(SLE) method. Any DIFDATA statements
follow the DIFFUSIVITY(L) statement.

Features that Require Transport Properties
The TRANSPORT, VISCOSITY, CONDUCTIVITY, SURFACE and DIFFU-
SIVITY statements usually are optional. However, they are are
required when certain features or unit operations are used. Table 8-3
lists the PRO/II software features that require transport properties.
Table 8-3: Features that Require Transport Properties

Feature Property
Stream Output TRANSPORT
Transport properties option
HCURVE TRANSPORT
Transport properties tables
COLUMN
Tray vapor/liquid transport properties TRANSPORT
printout
Sieve tray sizing/rating VISCOSITY(VL)
Packed columns VISCOSITY(L)1 & SURFACE(L)2
HXRIG VISCOSITY(VL) &
CONDUCTIVITY(VL)
PIPE VISCOSITY(VL) & SURFACE(L)3
ROTARY DRUM FILTER VISCOSITY(VL) & SURFACE(L)
FILTERING CENTRIFUGE VISCOSITY(VL) & SURFACE(L)
DISSOLVER DIFFUSIVITY(L)
MASSTRANS not specified
1 If a liquid viscosity method is not explicitly defined, the viscosity contribution
to the correlation is omitted.
2 Surface
tension is required when the NORTON method is used for efficient
capacity and HETP calculations.
3 Surface tension used for two-phase flow.
User-supplied Viscosity, Conductivity, and Surface Tension Data

(optional)
VISCOSITY
CONDUCTIVITY
SURFACE
UDATA i, value/...
UDATA This statement supplies method-specific data that will be used by

the user-added subroutine for the calculation of viscosity,
conductivity, or surface tension values. See the PRO/II User-
added Subroutine User Guide for more information.

VISCOSITY
CONDUCTIVITY
SURFACE
...
Note: These required pure component properties are all temperature

dependent and may not be supplied in the Thermodynamic Data Cate-
gory. They may only be supplied globally in the Component Data Cate-
gory. See Component Properties in Volume I, for details on format and
entry.
The following data may be supplied in the Thermodynamic Data
Category of input:
PARACHOR i, value/...
PENELOUX(volunit) i, value/...
Examples
Example 8.1: In this example, of using a METHOD statement, an
HCURVE unit operation is used to generate heating
curves and transport property tables for a crude feed
stream.
TITLE PROBLEM=TRANSPORT
DIMEN ENGLISH, LIQV=BBL
PRINT RATE=M,STREAM=ALL,INPUT=ALL,TBP
COMPONENT DATA
LIBID 1,ETHANE/ 2,PROPANE/ 3,IBUTANE/ 4,BUTANE/ 5,PENTANE
TBPCUTS 115,300,6/ 400,10/ 650,8/ 800,4/ 1500,6
THERMODYNAMIC DATA
METHOD KVAUE(VLE)=BK10, ENTH(V)=JG, ENTH(L)=JG, &
ENTR(V)=CP, ENTR(L)=CP, DENS(V)=IDEA, &
DENS(L)=API, TRANS=PETRO
STREAM DATA
PROP STREAM=1,TEMP=375, PRES=300, PHASE=M, &
RATE(V)=3125, ASSAY=LV
D86 STREAM=1, PRES(MMHG)=760, TEMP=F, &
DATA=8,135/25,210/43,370/67,565/75,665/82,800/92,990
API STREAM=1, AVG=45.37, &
DATA=11.6,80.01/21.6,62.9/41.7,50.6/61.9,38.2/83.8,27.5
MW STREAM=1, AVG=162.9, &
DATA=24.2,99.5/40.5,135/55,184.7/74.8,334.8/100,789
LIGHT STREAM=1, PERCENT(W)=10.4, &
COMP(M)=1,0.1/2,1.4/3,0.65/4,3.15/5,5.1, NORMALIZE
UNIT OPERATIONS
HCURVE UID=HC1, NAME=HEATING CRV
ADIA STREAM=1, TEMP=375, 690, PRES=300, 50, POINTS=20
PROP TRANSPORT
END

Example 8.2: Using the van't Hoff method, calculate the amount of
p-xylene dissolved in 10 ft3 of water at 40 F. Note that the
WILKE option on the METHOD statement is used to
calculate the p-xylene diffusivity.
TITLE PROB=DIFFUSIVITY
COMPONENT DATA
LIBID 1,H2O/2,PXYLENE/3,ETHANE, BANK=SIMSCI
ATTR COMP=2, PSD(MIC)=0., 50., 200., 1000., 5000.
THERMO DATA
METHOD SYSTEM(VLE)=SRKM, &
KVALUE(SLE)=VANTHOFF, TRANSPORT=PURE, &
DIFFUSIVITY(L)=WILKE
STREAM DATA
PROP STREAM=1, TEMP=40, PRES(PSIG)=0, COMP(M)=1,10/3, 0.5
SOLID STREAM=1, COMP(M)=2,100
UNIT OPERATION
DISSOLVER UID=DIS
FEED 1
PROD OVHD=2, BTMS=3
PRINT CSD
RATING VOLUME(FT3)=10
OPERATION SOLUTE=2, SOLVENT=1, DP=0
END

Special Stream Properties
Special stream properties are supported in addition to transport
properties. PRO/II defines many special properties that often are
referred to as named properties, pre-defined properties, or
refinery inspection properties. The keywords for these properties
are listed in Table 8-4. Additionally, PRO/II supports user-defined
special properties, often referred to as user properties, numbered
special properties, or simply SPROPs. This section discusses
input options for all of these. Chapter 9 explains how to supply
method-specific pure component data.
Typical Usage
...
COMPONENT DATA
THERMO DATA
METHOD SYSTEM=system, ... propkw(options)=method ...
Optional method-specific property data statements
property(qualifier, basis) {GAMMA=value, REFINDEX=value &
REFVALUE(uprop)=propvalue, NCFILL=ncfill, &
NCBLEND=ncblend}
{ DATA i, datavalue {/ i, datavalue ...} or
INDEX i, indexvalue {/ i, indexvalue ...}}
Optional method-specific pure component data statements.

compProp icno, value { / icno, value / ... }
STREAM DATA
. . .
propkw These optional keyword entries on the METHOD

statement each identify a specific special property
and specify a calculation method for it. Many of the
keywords provide options in parenthesis to further
specify the property. For example, Research Octane
offers options C for unleaded or and L for leaded. It
also allows setting the basis as mole, weight, or liq-
uid volume; e.g., ROM(C, LV)= SIMSCI. Table 8-5
lists all available special property key words.and all
their entries.

property Optional property data statements supply data for
individual property methods.These statements must
appear immediately after the METHOD statement to
which they apply. Table 8-6 lists all available prop-
erty statements and all their entries.
DATA These statements supply values of a property for
INDEX each component. A modified syntax is used for
KVIS only. When used, these must appear immedi-
ately below the property statement to which they
apply. These are discussed in more detail starting on
page 8-27.
compProp Optional data statements that supply pure compo-
nent property data for use in individual property
methods. The component properties that may be
supplied are listed in Table 9-2 on page 9-9
General Information
The program provides numerous methods to compute special
stream refinery properties. These properties include KVIS which cal-
culates liquid kinematic viscosities, CLOUD and FLPO (CC,OC)
(cloud and flash point temperatures respectively), and SULF (sulfur
content). To include a special property in a simulation, use the
appropriate key word entry on the METHOD statement to designate
a calculation method. Use additional property statements to supply
optional data for the calculations. The keyword associated with
each stream refinery special properties available are given in Table
8-4.
Table 8-4: Keywords for Special Stream Refinery Properties
Keyword Property
KVIS Kinematic viscosity
POUR Pour point temperature
CLOU Cloud point temperature
FRZP Freeze point temperature
CFPP Cold filter plug point
FLPO (CC,OC) Flash point temperature (formerly FLPT) OC
selects open cup, CC is closed cup)
RON Research octane number
MON Motor octane number
IBP Initial boiling point

Keyword Property
FBP Final boiling point
RCR Ramsbottom carbon
TAN Total acid number
OLEF Olefinic content
CETA Cetane index {alternate kewyord CETI}
CETN Cetane number
REFR Refractive index
ANIL Aniline point
AROM Aromatics content
WTAR Weight aromatic content
NAPH Naphthene content
WTNA Weight naphthenic content
PARA Paraffin content
WTPA Weight paraffinic content
NPHL Naphthalene content
H2 Hydrogen content
CARB Carbon content
CHRA Carbon-hydrogen ratio
SMOK Smoke point
LUMI Luminometer number
SULF Sulfur content
MERC Mercaptan content
ASUL Aliphatic sulfur content
NITR Nitrogen content
OXYG Oxygen content
CCR Conradson carbon residue
NICK Nickel content
VANA Vanadium content
IRON Iron content
ASPH Asphaltene content
PHEN Phenol content
ANEU Neutralize number
BROM Bromine number
MEAB Mean average boiling point temperature

Keyword Property
CABP Cubic average boiling point temperature
MOAB Molal average boiling point temperature
VABP Volume average boiling point temperature
WABP Weight average boiling point temperature
NHV Heat of combustion
WAX Wax content
ASH Ash content
NOAC Noack volatility
SOFT Softening point
PENET Penetration index
SPROP User-defined special property

Input Description
For all stream property entries on the METHOD statement, the gen-
eral form is:
METHOD ..., property(option, basis)=method, ...
The available options, basis, and methods for each property are
listed in Table 8-5. .
Table 8-5: Special Refinery Property Entries for the METHOD

Statement
Property Options Basis Method
KVIS M or WT SIMSCI or INDEX or
or LV USINDEX or USFORM or
CHEVRON or MAXWELL or
REFUTAS
POUR M or WT INDEX (alias SIMSCI) or
or LV USINDEX or
USFORM or
API99 (alias AP2B)
CLOU M or WT SIMSCI or INDEX or
or LV USINDEX or
USFORM or
API99 (alias AP2B)
FRZP M or WT INDEX or USINDEX or
or LV USFORM or
API99 (alias AP2B)
CFPP M or WT INDEX or USINDEX or
or LV USFORM
FLPO CC, OC M or WT NELSON or INDEX or
(formerly or LV USINDEX or
FLPT) USFORM or API87 or API07
(alias AP2B)
RON C or L M or WT INDEX or SUM or SIMSCI or
or LV USINDEX or USFORM
MON C or L M or WT INDEX or SUM or SIMSCI or
IBP M or WT SIMSCI (alias SUM)
or LV
FBP M or WT SIMSCI (alias SUM)
or LV
RCR M or WT INDEX or SUM or

Statement
TAN M or WT INDEX or SUM or
OLEF MONO, ISO, M or WT INDEX or SUM or
CYCLIC or LV USINDEX or USFORM
CETA M or WT ASTM (alias D976) or API99
or LV {alias AP2B}
CETN M or WT INDEX or SUM or
REFR C20 M or WT INDEX or SUM or API99 or
REFR C70 M or WT INDEX or SUM or
ANIL M or WT SUM or USFORM or API99
or LV {aliasAP2B}
AROM MONO, DI, TRI, M or WT INDEX or SUM or
TETRA, PENTA, or LV USINDEX or USFORM
HEPTA, TOTAL or
RING
WTAR WT SUM or USFORM
NAPH M or WT INDEX or SUM or
WTNA WT SUM or USFORM
PARA NORM, ISO, M or WT INDEX or SUM or
ALKY, POLY, or or LV USINDEX or USFORM
TOTAL
WTPA WT SUM or USFORM
NPHL M or WT SUM or USFORM
or LV
H2 WT INDEX or SUM or
USINDEX or USFORM
CARB WT INDEX or SUM or
USINDEX or USFORM
CHRA WT INDEX or SUM or
USINDEX or USFORM
SMOK M or WT INDEX or SUM or
or LV USINDEX or USFORM or
API99 {alias AP2B}
LUMI WT INDEX or SUM or D1740 or
USINDEX or USFORM

Statement
Note: The D1740 method calculates the Luminometer number (LUMI) from
the Smoke Point (SMOK). Therefore, it requires the SMOK entry to be
provided on the METHOD statement and data supplied. Otherwise, the
LUMI number is reported as missing.
SULF FRAC or PCT or M or WT INDEX or SUM or
LV or LV USINDEX or USFORM
ASUL WT SUM or USFORM
MERC WT SUM or USFORM
NITR TOTA or BASI or WT INDEX or SUM or
NONB USINDEX or USFORM
OXYG WT INDEX or SUM or
USINDEX or USFORM
CCR M or WT INDEX or SUM or
or LV USINDEX or
USFORM
NICK WT INDEX or SUM or
USINDEX or USFORM
SODI WT INDEX or SUM or
USINDEX or USFORM
VANA WT INDEX or SUM or
USINDEX or USFORM
IRON WT SUM or USFORM
ASPH C5 or C7 WT INDEX or SUM or
USINDEX or USFORM
ANEU WT or LV SUM or USFORM
BROM WT or LV SUM or USFORM
MEAB API
CABP API
MOAB API
VABP API
WABP API
NHV API
WAX WT INDEX or SUM or
USINDEX or USFORM
ASH WT INDEX or SUM or
USINDEX or USFORM
NOAC WT INDEX or SUM or
USINDEX or USFORM

Statement
PENET M or WT INDEX or SUM or
PHEN WT SUM or USFORM
SOFT WT or LV SUM or USFORM
SPROP i M or WT INDEX or SUM or
For example, when specifying the SIMSCI mixing method for KVIS
using the default liquid volume basis, the entry on the METHOD
statement becomes:
METHOD ..., KVIS=SIMSCI, ...
When specifying the INDEX mixing method for leaded research
octane number (RON) and using the default weight basis, the RON
entry on the METHOD statement becomes:
METHOD ..., RON(L, WT)=INDEX, ...
Specifying Default Stream Refinery Property Methods
REFPROP This keyword declares a default method for calculating special

stream refinery properties. A separate REFPROP entry is
supported for each refinery property. The declared method must
be available for the specified property.
The SIMSCI option specifies the PRO/II software v3.3
calculation methods for PRO/II software v3.3 properties. Those
properties are KVIS, CLOU, POUR, FLPO (CC,OC), SULF,
and CETA.
The current version of PRO/II supports a much larger slate of
special properties. However, the method designated by the
REFPROP entry applies only to the properties listed above. It
usually is more desireable to explicitly declare a calculation
method for each property
Property Methods available for each Special Property

The available mixing methods for special refinery properties are
described below. Not all these methods are available for every spe-
cial property (see Table 8-5).
INDEX This mixing method sums the individual component indices on

a weight or molar or liquid volume basis. The individual
component index is calculated from the property itself using the
following relationship:

1.0
log ( INDEX ) = ------------------------ log ( VALUE ) + CONSTANT
GAMMA
The value of the CONSTANT for a particular property is

calculated from the values supplied at a reference point
(GAMMA, REFINDEX, REFVALUE) given using the data
statement (see below for a description of these keywords).
SUM This mixing method sums the actual individual component
property values.
SIMSCI These mixing rules are available only for cloud point (CLOUD)
and kinematic viscosity (KVIS). They mixing sum the
component property index values. A different formula than the
one shown in equation (1) is used to convert to data values to
indices.
Research and Motor Octane Numbers (RON and MON)
support a different SIMSCI correlation that also is accessed
using this key word, and is described below.
The CLOUD conversion equation is:
GAMMA CPF + 460.0

( INDEX ) = ------------------------------------------------------------------------------------------
exp ( 6.39693 9.21034 GAMMA )
For CLOUD, GAMMA defaults to a value of 0.05.
For KVIS, the SIMSCI conversion equations are:
For 0.2 <KVIS < 10000 cS:

2
Index = 72.0509 22.1322 ln ( KVIS ) + 4.35618 ln ( KVIS )
3 4
0.458592 ln ( KVIS ) + 0.0184378 ln ( KVIS )
For KVIS <= 0.2 cS:
I ndex = 36.021172 ln ( KVIS ) + 63.01676
For KVIS >= 10000 cS:
Index = 1.8928559 ln ( KVIS ) + 29.552456
For RON and MON calculations:

SIMSCI developed a new methodology for computing RON
and MON in 1997. Full discussion is available in the original
publication (see Reference 8-a). This method calculates the
octane number of a cut (ncut) by blending the octanes of its
components:

n cut = xi xj nij
i j
1
where n ij = --- ( n i + n j ) ( 1 ij )
2
ij is the binary interaction coefficient
between components i and j
8-a: Estimate Octane Numbers Using An Enhanced
Method, C.H. Twu and J. E. Coon, Hydrocarbon
Processing, March, 1997, pg 65-68.
CHEVRON Converts kinematic viscosity in centiStokes.to an index that is
blended on a liquid volume basis.
ln ( KVIS )
Index = -------------------------------------------
ln ( 1000 KVIS )
Index ln ( 1000 )
KVIS = exp --------------------------------------------
( 1 Index )
MAXWELL Converts kinematic viscosity in centiStokes.to an index that is
blended on a liquid volume basis.
Index = 59.58959 21.8373 ln ( ln ( KVIS +0.8 ) )
KVIS = exp exp (------------------------------------------------

Index 59.58959 )- 0.8
21.8373
REFUTAS Converts kinematic viscosity in centiStokes.to an index that is
blended on a weight basis.
Index = 10.975 + 14.535 ( ln ( ( ln ( KVIS + 0.8 ) ) ) )

( Index 10.975 )
KVIS = exp exp ------------------------------------------- 0.8
14.535
NELSON The Nelson method is an alternate method used to calculate the
flash point temperature.
API The FLPO (CC,OC), MEAB, CABP, MOAB, NHV, VABP,
WABP, and NHV properties all may be calculated using
methods based on the API Technical Data Book.

API99 This keyword represents different API procedures for different
alias AP2B properties. All the procedures are from the API 1999 technical
book.
ANIL=API99 Procedure API 2B9.1
CETI{alias CETA}=API99 Procedure API 2B13.1
CLOU=API99 Procedure API 2B12.1
FLPO{formerly FLPT}= API99 Procedure API 2B7.1
FRZP= API99 Procedure API2B11.1
POUR= API99 Procedure API 2B8.1
SMOK= API99 Procedure API 2B10.1
REFR(20)= API99 Procedure API 2B5.1
{API 99 does not apply to REFR(C70)}
D1740 The LUMI property may be calculated using the ASTM D1740
method. The Luminometer number (LUMI) is calculated from
the Smoke Point (SMOK) for the D1740 method only.
Therefore the SMOK entry must be provided on the METHOD
statement and data supplied if the LUMI property is required
when the D1740 method is selected. Otherwise, the LUMI
number will be reported as missing.
SYMS This method is available only for the RON and MON. Because
it is proprietary, it is not described here.
USFORM, These options select a user-added method for the property. The
USINDEX USFORM option requires that the FORTRAN routine
SPUSER.FOR be in PROCALC.EXE and PROOUT.EXE. The
USINDEX option requires that the FORTRAN routine
CVUSER.FOR be compiled and linked into PROIN.EXE,
PROCALC.EXE and PROOUT.EXE. See the PRO/II User-
Added Subroutine User Guide for more information.
Note: The USINDEX option requires that DATA or INDEX values or

NCFILL option be provided for the property.

Special Property Data
Additional input statements are available for each special property.
They supply additional data for use by each special property
method declared on the METHOD statement.
property(qualifier, basis) {GAMMA=value, REFINDEX=value, &
REFVALUE(ukvis)=value, {NCFILL=ncfill}, {NCBLEND=ncblend}
for User-defined Special Properties:
SPROP(ubasis, ufrac, idno) {GAMMA=value, REFINDEX=value, &
REFVALUE(unit)=value},{NAME=text24}
DATA i, datavalue {/ i, datavalue ...}
INDEX i, indexvalue {/ i, indexvalue ...}
for KVIS only:

KVIS(M or WT or LV) {GAMMA=value, REFINDEX=value, &
REFVALUE(ukvis)=value, {NCFILL=ncfill}, {NCBLEND=ncblend}
DATA(utemp, ukvis) t1, t2, /i, p1, p2, /...
INDEX(utemp) t1, t2, /i, p1, p2, /...
The entries and options for each special refinery property are given
in Table 8-6.
Table 8-6: Special Property Data Statements
Property Options Basis1 UoM NCFILL NCBLEND
KVIS M or WT or kvis-unit SIMSCI or MISS or ZERO
LV ZERO or or EXCL
NOFILL or
API
POUR M or WT or temp API or ZERO MISS or ZERO
LV or NOFILL or EXCL
CLOU M or WT or temp ZERO or MISS or ZERO
LV NOFILL or EXCL
FZPT M or WT or temp ZERO or MISS or ZERO
LV NOFILL or EXCL
CFPP M or WT or temp ZERO or MISS or ZERO
LV NOFILL or EXCL
FLPO M or WT or temp ZERO or MISS or ZERO
(CC,OC) LV NOFILL or EXCL
RON C or L M or WT or ZERO or MISS or ZERO
LV NOFILL or EXCL
1 Properties with bases frac, ppm, or pct, may use any one of these three bases.
The displayed basis frac, ppm or pct indicates the default for that property.

MON C or L M or WT or ZERO or MISS or ZERO
LV NOFILL or EXCL
CETA GAMMA, ZERO or MISS or ZERO
REFI, and NOFILL or EXCL
REFV not
allowed
CETN M or WT or ZERO or MISS or ZERO
LV NOFILL or EXCL
REFR C20 M or WT or GAMMA, ZERO or MISS or ZERO
LV REFI, NOFILL or or EXCL
REFV API
REFR C70 M or WT or GAMMA, ZERO or MISS or ZERO
LV REFI, NOFILL or EXCL
REFV
ANIL M or WT or GAMMA, ZERO or MISS or ZERO
LV REFI, and NOFILL or EXCL
REFV not
allowed
AROM TOTA or M or WT or ZERO or MISS or ZERO
RING LV, frac NOFILL or or EXCL
SIMSCI
OLEF MONO M or WT or ZERO or
LV, frac NOFILL or
SIMSCI
WTAR GAMMA, ZERO or MISS or ZERO
REFV not
allowed
NAPH M or WT or ZERO or MISS or ZERO
LV, frac NOFILL or EXCL
or SIMSCI
PARA TOTA or M or WT ZERO or MISS or ZERO
ISO or LV, frac NOFILL or or EXCL
SIMSCI
WTNA GAMMA, ZERO or MISS or ZERO
REFV not
allowed
1
Properties with bases frac, ppm, or pct, may use any one of these three bases.

WTPA GAMMA, ZERO or MISS or ZERO
REFV not
allowed
NPHL M or WT M or WT or GAMMA, ZERO or MISS or ZERO
or LV LV REFI, and NOFILL or EXCL
REFV not
allowed
H2 WT, frac SIMSCI MISS or ZERO
ZERO or EXCL
or NOFILL
CARB WT, frac SIMSCI MISS or ZERO
ZERO or EXCL
or NOFILL
CHRA WT SIMSCI MISS or ZERO
ZERO or EXCL
or NOFILL
SMOK M or WT or NELSON or MISS or ZERO
LV ZERO or or EXCL
SIMSCI
or NOFILL
LUMI M or WT or GAMMA, ZERO or MISS or ZERO
LV REFI, and NOFILL or EXCL
REFV not
allowed
SULF M or WT or ZERO or MISS or ZERO
MERC WT, frac GAMMA, ZERO or MISS or ZERO
REFV not
allowed
ASUL WT GAMMA, ZERO or MISS or ZERO
REFV not
allowed
NITR TOTA or TOTA or ZERO or MISS or ZERO
BASI or BASI or NOFILL or EXCL
NONB NONB
OXYG WT, frac ZERO or MISS or ZERO
NOFILL or EXCL
1
Properties with bases frac, ppm, or pct, may use any one of these three bases.

CCR M or WT or ZERO or MISS or ZERO
NICK WT, frac ZERO or MISS or ZERO
NOFILL or EXCL
VANA WT, frac ZERO or MISS or ZERO
NOFILL or EXCL
IRON WT GAMMA, ZERO or MISS or ZERO
REFV not
allowed
ASPH C5 or C7 WT, frac ZERO or MISS or ZERO
NOFILL or EXCL
PHEN WT GAMMA, ZERO or MISS or ZERO
REFV not
allowed
ANEU WT or LV GAMMA, ZERO or MISS or ZERO
REFV not
allowed
BROM WT or LV GAMMA, ZERO or MISS or ZERO
REFV not
allowed
WAX WT, frac ZERO or MISS or ZERO
NOFILL or EXCL
ASH WT, frac ZERO or MISS or ZERO
NOFILL or EXCL
SOFT WT or LV WT or LV GAMMA, ZERO or MISS or ZERO
REFV not
allowed
IBP temp SIMSCI
FBP temp SIMSCI
PENET M or WT M or WT or ZERO or MISS or ZERO
or LV LV NOFILL or EXCL
1 Properties with bases frac, ppm, or pct, may use any one of these three bases.

Note: For the properties NOAC, MEAB, CABP, MOAB, VABP, WABP,
and NHV no individual component data entries are possible. These
properties do not require a special methods data statement.
The program provides default values for GAMMA, REFINDEX, and
REFVALUE for properties CLOU, POUR, FLSH, and KVIS only. These
default values are given in Table 8-7.
Table 8-7: Default GAMMA, REFI, and REFV values

for CLOU, POUR, FLSH, KVIS
property GAMMA REFINDEX REFVALUE
CLOU 0.05 10000 333.15 (degrees K)
POUR 0.08 10000 333.15 (degrees K)
FLSH -0.06 10000 255.372 (degrees K)
KVIS -3.5 71.5 1.0 (centistoke)
User-Defined Special Properties

For user-defined special refinery properties, the data statements are:
SPROP(basis, ufrac, idno) {GAMMA=value, &
REFINDEX=value, REFVALUE=value, NAME=text24}
DATA i, datavalue {/ i, datavalue ... }

INDEX i, indexvalue {/ i, indexvalue ...}
SPROP The user-defined special refinery property

basis, may be supplied on a molar, weight, or liquid volume
(M, WT, or LV) basis.
ufrac Data may be represented as fraction (default, FRAC), percent
(PCT), or part per million (PPM).
idno This integer value must uniquely identify the property, and may be
any number between 1 and 9999. The total number of SPROPs
defined in any one simulation must be less than or equal to 60.
NAME This entry is valid only for SPROP statements to supply a
descriptive name for the user-defined special stream property. It
allows up to 24 alphanumeric characters including embedded
blanks, but excluding delimiters. It serves only as a description of
the user-defined stream property in the stream report, and does not
have to be unique.

The following keyword descriptions apply to all the property data
statements listed in Table 8-6:
GAMMA, These entries must be supplied when the INDEX or

REFINDEX, SIMSCI stream mixing method is chosen on the METHOD
REFVALUE statement. These entries are used to determine the inter-
relationship between a property value and its corresponding
index value. The equations used to convert from data value
to index depends on the property. These equations (1-3) are
given on page 8-18.
NCFILL Estimates refinery properties for narrow cuts generated
from assay streams or PETRO components. For all special
refinery properties except NOAC, MEAB, CABP, MOAB,
VABP, WABP, and NHV, properties for narrow cuts may be
estimated using the ZERO or NOFILL options.
ZERO Any missing data is set to 0.0.
NOFILL Any missing data is flagged with a warning message
before being set to 0.0.
SIMSCI This fill option is available for KVIS, SMOK, H2, CARB,
CHRA, RON, and MON property methods. For KVIS, the
Twu method is used to fill in missing data. For H2 and
CARB, the missing data are estimated from the carbon-
hydrogen ratio. For CHRA, the missing data are estimated
from the Twu correlation for the number of carbon and
hydrogen atoms.
NELSON This fill option is available for the SMOK method.
API This fill option is available for KVIS, POUR, REFR
methods.
KSLA This fill option uses KSLA (option 26) methods to supply
missing values.
NCBLEND There are three options for filling in missing data when
assay streams are blended. For all special refinery properties
except NOAC, MEAB, CABP, MOAB, VABP, WABP, and
NHV the fill options for blending streams are ZERO,
EXCLUDE, and MISSING.
ZERO Missing property data for narrow assay cuts is set to 0.0
EXCLUDE The narrow cuts in the assay with no data are excluded from
the blend when calculating the blended narrow cut property.
MISSING The blended narrow cut property data is set to missing if any
narrow cut in the blend has missing data.

DATA, These entries are used to provide data or index values for stream
INDEX special properties on a component basis. The unit qualifier on the
DATA entry need not be consistent with property qualified on the
REFVALUE keyword. The kvisunit qualifier for kinematic
viscosity may be either CST (centistokes), IN/S (inch per second), or
ST (stokes). If the unit qualifier is not given, the property unit
defaults to input units based on the special property units. A data and
an index entry cannot be given for the same component. The data
and index values are related by the equations (1), (2) and (3) above.
t1, These are the temperatures at which kinetic viscosity data and/or
t2 index values will be supplied. The utemp qualifier applies to t1 and
t2 for temperatures. A maximum of two temperatures may be
entered. If t2 is not given, it is set equal to t1. t1 and t2 must be the
same for entries on the DATA and INDEX keywords in the same
KVIS statement.
i This number provides the component id number.
p1 , These entries provide the kinematic viscosity data or index values at
p2 temperatures t1 and t2. If only one temperature (t1) is given, p2
entries are not allowed and are set internally equal to p1.
Most of the special properties shown in Table 8-6 may be defined

on a molar (M) or weight (WT) or liquid volume (LV) basis.
The following section describes the other unique qualifiers avail-
able for RON, MON, AROM, NITR, ASPH, and REFR:
For RON and MON:
L Leaded : 3 ml of lead tetraethyl added.
C Unleaded.
For AROM:
TOTA Total aromatic content.
RING Aromatic ring content.
For NITR:
TOTA Total nitrogen content.
BASIC Basic nitrogen content.
NONB Non-basic content.
For ASPH:
C5 Measurements taken using a pentane-based
solvent.
C7 Measurements taken using a heptane-based
solvent.
For REFR:
C20 Measurements taken at 20C.
C70 Measurements taken at 70C.

Examples
Example 8.3: Estimate the kinematic viscosity, pour point
temperature, carbon to hydrogen ratio, carbon content,
refractive index, hydrogen content and smoke point
temperature for an assay stream at 100 F and 15 psig. Use
the SIMSCI fill methods for KVIS, CARB, CHRA, and H2.
Use the NELSON fill method for SMOK, and the API fill
method for POUR and REFR.
TITLE PROB=SPECIAL
DIME LIQVOL=BBL
COMPONENT DATA
LIBID 1,H2O/ 2,C2/ 3,C3/ 4,IC4/ 5,NC4/ 6,PENTANE
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM, KVIS=INDEX, POUR=INDEX, &
CHRA=SUM, CARB=SUM, REFR=SUM, H2=SUM, &
SMOK=SUM
KVIS NCFILL=SIMSCI
POUR NCFILL=API
CARB NCFILL=SIMSCI
REFR NCFILL=API
H2 NCFILL=SIMSCI
SMOK NCFILL=NELSON
CHRA NCFILL=SIMSCI
STREAM DATA
PROP STREAM=1, TEMP=375, PRES=300, ASSAY=LV, &
RATE(LV)=3125
API STREAM=1, DATA=11.6,80.01/ 21.6,62.9/ 41.7,50.6/ &
61.9,38.2/ 3.8,27.5, AVG=45.37
LIGHT STREAM=1, PERC(LV)=10.4, &
COMP(LV)=2, 0.1/ 1.4/ 0.65/ 3.15/ 5.0, NORM
D86 STREAM=1, DATA= 8, 135/ 25, 210/ 43, 370/ 67, 565/ &
5, 665/ 82, 800/ 92, 990
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
ISO TEMP=100, PRES=15
END

Chapter 9
Method-specific Pure Component Data
Thermodynamic property calculations require various pure compo-
nent data, such as critical temperature, critical pressure, and liquid
molar volume. Data normally are found in the libraries or supplied
in the Component Data Category. Additionally, users may supply
pure component data in the Thermodynamic Data section. This
allows using different pure component data for each property
declared in each thermodynamic METHOD set. This chapter
describes such usage.
Usage Syntax
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM= system, property=propmethod, ...
property1 statement (see Table 8-6)
compProp statement (see Table 9-1)
...
compProp statement (see Table 9-1)
STREAM DATA
...
Typical Usage
...
THERMO DATA
METHOD SYSTEM=SRK
KVALUE . . .
TC 1, 373 . . .
STREAM DATA
. . .

General Information
The exact component data requirements of thermodynamic property
calculations depend on the property being computed and the ther-
modynamic methods that are selected. For example, the Soave
modified Redlich-Kwong equation of state requires pure compo-
nent critical temperatures, pressures and acentric factors, but not
normal boiling points. Components chosen from the SimSci
library or characterized from assay data normally contain all
required component data. For non-library components, users must
provide all the pure component property data required by the ther-
modynamic method(s) selected.
A property generator is a set of calculation methods that calculate
values for one or more thermodynamic (stream) properties. This
includes basic generators, such as K-value generators, transport
property generators, named stream refinery properties, and num-
bered user-defined special properties (SPROPs).
All thermodynamic data generators listed in the left-most column of
Table 9-2 accept user-supplied data. In the extreme, different pure
component data may be supplied for each property calculated in
each thermodynamic METHOD set.
Input Description
Supplying Pure Component Data In A METHOD Set
...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM= system, property=propmethod, ...
property1 data statement (see Table 8-6)
{DATA . . . or INDEX . . . }
compProp1 data statement (see Table 9-1)
...
compPropn data statement (see Table 9-1)
...
{DATA . . . or INDEX . . . }
compProp1 data statement (see Table 9-1)
...
compPropn data statement (see Table 9-1)
...
STREAM DATA
...
9-2 Method-specific Pure Component Data

Method Statement Entries
property Each property entry on a METHOD statement associ-
ates a calculation method or property generator
(propmethod) with one stream property.
A property entry is available on the METHOD statement for
every thermodynamic property. These include equilibrium
properties such as k-values, transport properties such as liquid
surface tension or diffusivity, general properties such as den-
sity, entropy and enthalpy, stream refinery inspection properties
such as KVIS, RON or ASPH, and user-defined special properties
(SPROPs). Refer to Table 1-1 on page 1-3 for a summary of
available entries on the METHOD statement.
propmethod Associates a calculation method with a property.
This method dictates which component data are
required (allowed as user input data) for the prop-
erty associated with the method.
Each property generator has its own specific data requirements.
In Table 9-1, column 1 (Method) lists all the available property
generators that can be specified by propmethod entries on a
METHOD statement. The remaining columns of the table indi-
cate which component properties are used by the generator.
Property Data Statements

property1 Each property declared on a METHOD statement
property2 has associated data statements. These statements
supply data to the method (propmethod) that calcu-
lates property values. Usually they are optional.
See Table 1-2, Thermodynamic Input Category Data State-
ments, on page 1-5 for a summary of most data statements.
Data statements for special properties are listed in Table 8-6,
Special Property Data Statements, on page 8-21.
The data statements (represented here by the property1,
property2 entries) must appear immediately after the METHOD
statement to which they apply. However, these statements do
not provide pure component data. A property statement must be
used (as a place holder) before pure component data statements
can be used for the property generator. See Pure Component
Data Statements on page 9-4.
DATA or INDEX When used, these statements must appear after a spe-
cial property statement. See Special Property Data on page 8-21.

Pure Component Data Statements
compProp These data statements provide pure component data to
a property generator.
They can appear only after a property statement. Data supplied
on these statements are used in preference to data supplied else-
where (including data retrieved from data-banks). The hierar-
chy of data selection is discussed later, in the section
Hierarchy on page 9-5.
Table 9-1 lists all the available property generators and all the
pure component data that each generator uses. Table 1-2
includes
Table 9-2 associates a keyword with each pure component
property statement that provides pure component data.
Pure component data statements must be located immediately
after the property data statement for which they provide data.
Pure component data statements are valid only when the prop-
erty generator uses the pure component data.
Example:
A DENSITY(V)=SRK entry declares the vapor density calculation
method to be the Soave modified Redlich-Kwong equation of state
(SRK).
Table 9-1 shows the only pure component data used by the SRK
generator are critical temperature, critical pressure, and acentric
factor (Tc, Pc, and ). Table 9-2 associates a component data state-
ment keyword with each pure component property listed in Table 9-
1. Here are the associated keywords.
Component Data Symbol Keyword
critical temperature Tc TC
critical pressure Pc PC
acentric factor ACENTRIC
It should be clear that these component properties are the only ones
that apply when computing density with this generator. A partial
keyword listing supplying pure component data for components 1
and 2 could be:
...
THERMODYNAMIC DATA
METHOD . . . DENSITY(V)=SRK
DENSITY(V) . . .

TC(K) 1, 273.15 / 2, 400.0
PC(ATM) 1, 15.60 / 2, 21.0
ACENTRIC 1, 0.999 / 2, 0.876
...
Note the pure component data statements appear after the DENSITY
property statement. The pure component data is used only when
computing vapor density with this method. A different set of pure
component data could be supplied for computing vapor density in
another METHOD set.
Note: Pure component data statements must appear immediately

after a property statement. The component data statement,
property statement, and method statement must all refer to the
same property and method. Except for the K-value property, the
values supplied on a data statement apply only to that property
method calculation. They do not act as default values for any
other property calculations. However, if values are supplied on
the data statement only for the K-value property, these values
act as defaults for other property calculations that use the same
calculation method.
See Solid Component Properties and Component Properties in
the Component Data Keyword Manual for further details on format
and definition of these data entries.
Hierarchy
The hierarchy that governs the use of pure component data is:
1. Any method-specific data supplied on the data statements for
each property in each method set. This includes both pure com-
ponent data and property data statements. Only temperature-
independent data may be given in the Thermodynamic Data
Category.
2. Applicable default values supplied on data statements follow-
ing a KVALUE statement in the same method set.
3. Data supplied in the COMPONENT DATA section of keyword
input.
4. Data stored in the component libraries as selected using the
BANK option.
If data are still missing after steps 1-4 are completed, PRO/II issues
an error message and terminates after input processing is complete.
The PROVISION GUI displays the error messages and opens the
keyword input file for correction by the user. .

Table 9-1: Pure Component Data Required By Property Generators
General Property Generators
Tc Pc MV Vc Zc Zra vdW DM Rad NBP SP
Method
IDEAL
GS X X X X X
CS X X X X X
IGS X X X X X
GSE X X X X X
CSE X X X X X
CP X X X
BK10 X X X X
JG X X X
LK X X X
API C C C
RACKETT X X X
COSTALD X X X
LIBRARY
Method
SRK,SRKKD, X X X
SRKH
SRKP,SRKM, X X X
SRKS
PR,PRH,PRP, X X X
PRM, PPR78
UNIWAALS X X
BWRS X X X
HEXAMER X X X
TBC X X X
LKP X X X

Method
NRTL

Table 9-1: Pure Component Data Required By Property Generators
UNIQUAC, C
UNQ4
UNIFAC C
UFT 1/2/3 C
UNFV
WILSON X
VANLAAR
MARGULES
REGULAR X X
FLORY X X
HOCV X X X X
TVIRIAL X X
Special Packages
Method
ALCOHOL
GLYCOL X X X
SOUR
GPSWATER
AMINE
U1-U15
Method
VANTHOFF
SOLDATA
VISCOSITY
CONDUCT
SURFACE
Parachor(Tacite) for surface tension: Parachor and Exponent data is optional.
PRPeneloux and SRKPeneloux (Tacite) for Liquid Density: Peneloux data is optional.
Table 9-1B: Pure Component Data Required By Property Generators

SPGR
Data or VP H0 Hvap Hliq
Method API
IDEAL C C C C
GS C C

CS C C
IGS C C
GSE C C
CSE C C
CP C C C C
BK10 C
JG C
LK C C
API C
RACKETT C
COSTALD C
LIBRARY C
SPGR
Method Data or VP H0 Hvap Hliq
API
SRK,SRKKD, C C
SRKH
SRKP,SRKM, C C
SRKS
PR,PRH,PRP, C C
PRM, PPR78
UNIWAALS C C
BWRS C C
HEXAMER C C
TBC
LKP
Parachor(Tacite) for surface tension: Parachor and Exponent data is optional.
PRPeneloux and SRKPeneloux (Tacite) for Liquid Density: Peneloux data is optional.

SPGR
API
NRTL C C C C C
UNIQUAC, C C C C C
UNQ4
UNIFAC C C C C C
UFT 1/2/3 C C C C C

UNFV C C C C C
WILSON C C C C C
VANLAAR C C C C C
MARGULES C C C C C
REGULAR C C C C C
FLORY C C C C C
HOCV C
TVIRIAL C
Special Packages
SPGR
API
ALCOHOL C C C C C C
GLYCOL C C
SOUR C C
GPSWATER C C
AMINE C C
U1-U15 C
SPGR
API
VANTHOFF C
SOLDATA C
VISCOSITY X C
CONDUCT X C
SURFACE X C
Table 9-2: Data Card Keywords To Use for Property Headers in Table 9-1
Header Keyword Description Header Keyword Description
Tc TC Critical temperature VISCOSITY Liquid Viscosity
Pc PC Critical pressure CONDUCT Thermal conductivity
ACENTRIC Acentric factor SURFACE Surface tension
MV MOLVOL Liquid molar volume DENSITY (L) Liquid density
Vc VC Critical volume Data DATA or Special property

data/index values
Zc ZC Critical compressibility INDEX
factor

Zra RACKETT Rackett parameter X Users may supply the data either
globally or in Component Data
Category or locally for a given method
set in the Thermo-dynamic Data
Category.
vdW VANDERWAAL van der Waals area and CONDUCT Thermal conductivity
volume
DM DIPOLE Dipole moment SURFACE Surface tension
Rad RADIUS Radius of gyration
NBP NBP Normal boiling point C Users may supply these data only in the
(temperature) Component Data Category.
SP SOLUPARA Hildebrand solubility

parameter
H0 ENTHALPY (V) Ideal vapor enthalpy Exponent EXPO Constant for surface
tension calculation
Parachor PCHO Parachor for tacite Peneloux PENE Peneloux for Tacite
surface tension liquid density
Hvap LATENT Latent heat of A The user may supply these data or
vaporization index values either globally in the
Hliq ENTHALPY (L) Saturated liquid Component Data or Stream Data
enthalpies Categories or locally in the Thermo-
VP VP Vapor pressure dynamic Data Category for a given
method sets.
SpGr SPGR Specific gravity
API API API gravity
ETA Truncated virial

equation coefficients

Examples
9.1: Using SRKM, model a 50/50 mix of normal butane and normal
hexane at 50 psia and 50% vaporization. Input critical temperature
data for calculation of vapor densities for components propane and
n-butane. Note that the critical temperatures supplied on the TC
statement apply only to the vapor density calculations. They do not
act as default values for any other property calculations.
TITLE PROB=COMPDATA
COMPONENT DATA
LIBID 1,NC4/ 2,NC6
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM
DENSITY(V)
TC(K) 1,373.15/2,401.6
STREAM DATA
COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
RATE, VALUE=0.5
END

9.2: Using the same problem as above, supply the cloud point index for
component 1 and the cloud point temperature for component 2.
TITLE PROB=COMPDATA
CALCULATION COMPOSITIONAL, SINGLE
FCODE PIPE=BBM
DIMENSION ENGLISH
DEFAULT TAMBIENT=65, ROUGH(IN)=0.001, IDPIPE(IN)=32
SEGMENT DLVERTICAL=6, DLHORIZONTAL=150
COMPONENT DATA
LIBID 1,NC4/ 2,NC6
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM, CLOUD=SIMSCI
DENSITY(V)
TC(K) 1,373.15/2,401.6
CLOUD
INDEX 1,20
DATA 2,50
STRUCTURE DATA
SOURCE NAME=1, TEMP=100, PRES=100, &
COMP=50/50
PIPE LENGTH=3800, ECHG=-100
END

Index
A METHOD Statement , 4-40

Method-specific Pure Component Properties , 4-41
Alcohol Dehydration Systems , 2-12 Typical Usage , 4-39
Alcohols
ALCOHOL Databank Components , 5-8
Attributes of the ALCOHOL Package , 5-2 B
Enthalpy, Entropy, and Density Data , 5-6
Benedict-Webb-Rubin-Starling
Examples , 5-12
Attributes of , 4-34
K-value Data , 5-4
METHOD Statement , 5-2
Examples , 4-37
K-value Data , 4-35
Typical Usage , 5-1
Alpha Formulations
Typical Usage , 4-34
Examples , 4-32
Water Handling Options , 4-36
General Information , 4-28
Binary Interaction Data
K-value Data , 4-29
BWRS Equation of State Data , 1-9
Hayden-OConnell Data , 1-9
Vapor Phase Fugacity Data , 4-32
HEXAMER Equation of State Data , 1-9
Amine Systems , 2-7
IDIMER Data , 1-9
Amines LKP Equation of State Data , 1-9
Attributes of the AMINE Package , 5-26 Redlich-Kister Excess Properties Data , 1-10
Enthalpy, Entropy, and Density Data , 5-29 Truncated Virial Data , 1-9
Examples , 5-30
Braun K10
K-value Data , 5-28
METHOD Statement , 5-27 Examples , 3-19
API Liquid Density Typical Usage , 3-18
Attributes of , 3-26 Water Handling Options , 3-19
Examples , 3-27
Typical Usage , 3-26 C
Application Guidelines , 2-1
Chemical and Environmental Applications , 2-13 Carboxylic Acid Systems , 2-14
Examples , 2-15 CHAO-SEADER
Natural Gas Systems , 2-5 Examples , 3-9
Petrochemical Applications , 2-8 Method-specific Pure Component Properties , 3-9
Refinery and Gas Processing , 2-2 Chao-Seader
Aromatic Systems , 2-9 Attributes of , 3-8
Aromatic/Non-aromatic Systems , 2-9 METHOD Statement , 3-9
Associating Hexamer Equation Of State Typical Usage , 3-8
Enthalpy, Entropy, and Density Data , 4-41 Water Handling Options , 3-9
Examples , 4-42 Chemical and Environmental Applications
K-value Data , 4-40 Carboxylic Acid Systems , 2-14
PRO/II Thermodynamic Data Keyword Manual Index- 1

Environmental Applications , 2-14 Grayson-Streed Method , 3-6
Non-Ionic Systems , 2-13 Hayden-OConnell Vapor Fugacity , 6-67
Solid Applications , 2-15 Henrys Law , 6-63
Costald Liquid Density Ideal Methods , 3-3
Attributes of , 3-30 IDIMER Vapor Fugacity , 6-74
Examples , 3-31 Johnson-Grayson , 3-22
Input Description , 3-30, 3-32 Lee-Kesler , 3-25
METHOD Statement , 3-30, 3-32 Lee-Kesler-Plocker , 4-46
Method-specific Pure Component Properties , 3- Margules , 6-41
30, 3-32 Method-specific Pure Component Data , 9-11
Typical Usage , 3-30, 3-32 Minimum Required User Input , 1-15
Curl-Pitzer Modifications to GS and CS , 3-13
Attributes of , 3-15 Modifications to UNIFAC , 6-32
Examples , 3-16 Modified Soave-Redlich-Kwong and Peng-
METHOD Statement , 3-15 Robinson , 4-19
Method-specific Pure Component Properties , 3-16 Multiple Thermodynamic Sets , 1-32
Typical Usage , 3-15 Natural Gas Application , 2-17
NRTL , 6-6
Peng-Robinson , 4-11
E Petrochemical Application , 2-18
Rackett Liquid Density , 3-29
Entropy Redlich-Kister, Gamma Heat of Mixing , 6-77
Features that Require Entropy , 1-22 Refinery Application , 2-16
Regular Solution , 6-46
Environmental Applications , 2-14
Soave Modified Redlich-Kwong , 4-5
Equations of State , 4-1
Soave Redlich-Kwong , 4-5
Associating Hexamer Equation Of State , 4-39
Solid Application , 2-19
Benedict-Webb-Rubin-Starling , 4-34
Sour Water , 5-22
Cubic Equation Of State Alpha Formulations , 4-28
Sour Water Application , 2-16
Filling in Missing Parameters , 4-27
Special Properties , 8-28
Lee-Kesler-Plocker , 4-43
Transport Properties , 8-8
Modified SRK and PR , 4-13
Truncated Virial Vapor Fugacity , 6-70
Peng-Robinson , 4-7
UNIFAC , 6-19
Soave Modified Redlich-Kwong , 4-1
UNIQUAC , 6-11
UNIWAALS , 4-22
UNIWAALS , 4-25
Examples User-added Subroutines , 5-33, 5-35
Alcohol , 5-12
User-supplied K-value Data , 3-36
Alpha Formulations , 4-32
User-supplied Solubility , 7-6
API Liquid Density , 3-27 Van Laar , 6-36
Associating Hexamer Equation Of State , 4-42
Vant Hoff Solubility , 7-3
Benedict-Webb-Rubin-Starling , 4-37 Vapor-liquid-liquid Equilibrium
Braun K10 , 3-19 Considerations , 1-44
CHAO-SEADER , 3-9
Chemical and Environmental Application , 2-19
Costald Liquid Density , 3-31 F
Cubic Equation Of State Alpha Formulations , 4-32
Curl-Pitzer , 3-16 FCCU , 2-3
Filling in Missing Parameters for Liquid Activity Filling in Missing Parameters
Methods , 6-55
Attributes of the FILL Option for Liquid Activity
Flory-Huggins , 6-52 Methods , 6-53
Free-water Decant , 1-38 Cubic Equations of State FILL options , 4-27
Glycol , 5-18 Data Estimation Options for Liquid Activity
GPA Sour Water , 5-25 Methods , 6-55
Index- 2
Examples for Liquid Activity Methods , 6-55 GPA Sour Water
General Information for Liquid Activity Attributes of GPSWATER Package , 5-23
Methods , 6-53 Enthalpy, Entropy, and Density Data , 5-24
K-value Data for Cubic EOS , 4-28 Examples , 5-25
K-value Data for Liquid Activity Methods , 6-54 METHOD Statement , 5-23
METHOD Statement for Cubic EOS , 4-27 Method-specific Pure Component Properties , 5-25
METHOD Statement for Liquid Activity Typical Usage , 5-22
Methods , 6-53
Grayson-Streed
Typical Usage for Cubic EOS , 4-27
Attributes of , 3-5
Typical Usage for Liquid Activity Methods , 6-52
Flory-Huggins Typical Usage , 3-5
Attributes of FLORY Methods , 6-48 Water Handling Options , 3-6
Examples , 6-52
Grayson-Streed Method
K-value Data , 6-49
Examples , 3-6
METHOD Statement , 6-49 Method-specific Pure Component Properties , 3-6
Free-water Decant Considerations , 1-33 H
Examples , 1-38
General Information , 1-33 Hayden-OConnell Vapor Fugacity
Water Handling Statement , 1-35 Attributes of the HOCV Vapor Fugacity
Method , 6-64
Enthalpy, Entropy and Density Data , 6-66
G Examples , 6-67
K-value Data , 6-65
Generalized Correlations METHOD Statement , 6-65
API Liquid Density , 3-26 Method-specific Pure Component Properties , 6-67
Braun K10 , 3-18 Typical Usage , 6-64
Chao-Seader , 3-8 Vapor Fugacity Data , 6-66
Costald Liquid Density , 3-30 Henrys Law
Curl-Pitzer , 3-15 Attributes of the Henrys Law Option , 6-57
Grayson-Streed , 3-5 Examples , 6-63
Ideal and Library Methods , 3-1 Henrys Law Data , 6-62
Ideal Methods , 3-1 Henrys Law Package Available Pairs , 6-59
Johnson-Grayson , 3-21 METHOD Statement , 6-58
Lee-Kesler , 3-23 Method-specific Pure Component Properties , 6-63
Library Methods , 3-1 Typical Usage , 6-57
Modifications to GS and CS , 3-11 Hierarchy of Pure Component Data , 9-5
Rackett Liquid Density , 3-28
High Pressure Crude Systems , 2-3
Typical Usage , 3-1
Hydrofiners , 2-4
Glycol Dehydration Systems , 2-6
Glycols
Attributes of the GLYCOL Package , 5-14
I
Components Available for GLYCOL Package , 5- Ideal Method
17
Attributes of , 3-2
Examples , 5-18
Ideal Methods
K-value Data , 5-15
Examples , 3-3
Method-specific Pure Component Properties , 5-18 IDIMER Vapor Fugacity
Typical Usage , 5-14, 5-19
Enthalpy, Entropy and Density Data , 6-73

Examples , 6-74 UNIQUAC , 6-7
K-value Data , 6-72 Van Laar , 6-32
METHOD Statement , 6-72 Wilson , 6-28
Typical Usage , 6-71 Liquid Phase Activity Binary Interaction Data
Vapor Fugacity Data , 6-73 Flory-Huggins Data , 1-11
Input Description , 1-23 Henrys Law Data , 1-11
Margules Data, , 1-11
NRTL Data , 1-10
J Other Binary Data for Liquid Activity
Methods , 1-11
Johnson-Grayson UNIFAC Group Contribution Data , 1-11
Attributes of , 3-21 UNIQUAC Data , 1-10
Examples , 3-22 UNIWAALS Modified Group Contribution
Interaction Data , 1-11
Method-specific Pure Component Properties , 3-22 Van Laar Data , 1-11
Wilson Data , 1-11
Low Pressure Crude Systems , 2-3
Lube Oil Units , 2-4
L
Lee-Kesler M
Examples , 3-25 Main Coker Fractionators , 2-3
METHOD Statement , 3-24 Margules
Method-specific Pure Component Properties , 3-24 Attributes of MARGULES Methods , 6-38
Typical Usage , 3-23 Examples , 6-41
Lee-Kesler-Plocker K-value Data , 6-39
Attributes of , 4-43, 4-48, 4-51, 4-54 METHOD Statement , 6-39
Enthalpy, Entropy, and Density Data , 4-45 Method-specific Pure Component Properties , 6-41
Examples , 4-46 Typical Usage , 6-38
K-value Data , 4-44 METHOD Statement , 1-3, 1-5
METHOD Statement , 4-44, 4-48, 4-54
Method-specific Pure Component Data , 1-13, 9-1
Examples , 9-11
Library Method Hierarchy , 9-5
Attributes of , 3-2
Typical Usage , 9-1
Light Hydrocarbon Systems , 2-8
Method-specific Water Handling Options , 1-5
Minimum Required User Input , 1-14
Filling in Missing Parameters , 6-52
Modifications to GS and CS
Flory-Huggins , 6-48
Attributes of the Modified GS and CS Methods , 3-
Hayden-OConnell Vapor Fugacity , 6-64
11
Henrys Law , 6-57 Erbar modifications to Grayson-Streed and Chao-
IDIMER Vapor Fugacity , 6-71 Seader , 3-12
Margules , 6-38 Examples , 3-13
Modifications to UNIFAC , 6-20 Improved Grayson-Streed , 3-12
NRTL , 6-1 METHOD Statement , 3-12
Redlich-Kister, Gamma Heat of Mixing , 6-75 Method-specific Pure Component Properties , 3-13
Regular Solution , 6-43 Typical Usage , 3-11
Sadip , 6-52 Water Handling Options , 3-12
Truncated Virial Vapor Fugacity , 6-68 Modifications to UNIFAC
UNIFAC , 6-12
Index- 4
Attributes of Modified UNIFAC Methods , 6-20 Typical Usage , 6-1
Examples , 6-32
K-value Data , 6-22
METHOD Statement , 6-21 O
Method-specific Pure Component Properties , 6-
26, 6-31 Order of Input , 1-16
UFT1-Lyngby modified UNIFAC , 6-22
UFT2-Dortmund modified UNIFAC , 6-23 P
UFT3-Modified UNIFAC , 6-23
UNFV-Free Volume modification , 6-23 Peng-Robinson , 4-7
Modified SRK and PR Enthalpy, Entropy, and Density Data , 4-10
Enthalpy, Entropy, and Density Data , 4-18 Examples , 4-11
Examples , 4-19 K-value Data , 4-9
Huron-Vidal modifications to PR , 4-15 METHOD Statement , 4-8
Huron-Vidal modifications to SRK , 4-14 Method-specific Pure Component Properties , 4-11
Kabadi-Danner modifications to SRK , 4-15 Typical Usage , 4-7
K-value Data , 4-16 Water Handling Options , 4-11
METHOD Statement , 4-14 Petrochemical Applications
Method-specific Pure Component Properties , 4-19 Alcohol Dehydration Systems , 2-12
Modified Panagiotopoulos-Reid modifications to Aromatic Systems , 2-9
PR , 4-15 Aromatic/Non-aromatic Systems , 2-9
Modified Panagiotopoulos-Reid modifications to HF Systems , 2-12
SRK , 4-14
Light Hydrocarbon Systems , 2-8
Panagiotopoulos-Reid modifications to PR , 4-15
Non-hydrocarbon Systems , 2-10
SimSci modifications to SRK , 4-14
Predefined Systems , 1-26
Property Statements
Multiple Thermodynamic Sets , 1-30
Density Options , 1-7
Avoiding Inconsistent Methods , 1-31
Diffusivity Options , 1-6
Default Method Set , 1-30
Enthalpy Options , 1-8
Examples , 1-32
Entropy Options , 1-8
Henrys Law Options , 1-6
Method Set Requirements , 1-31
Liquid-Liquid Equilibrium Options , 1-6
Multiple Method Sets in Distillation Columns , 1-
31 Solid-Liquid Equilibrium Options , 1-6
Vapor Fugacity Options , 1-6
Vapor-Liquid Equilibrium Options , 1-5
N Pure Component Alpha Formulations , 1-12
Natural Gas Systems , 2-5

Amine Systems , 2-7 R
Glycol Dehydration Systems , 2-6
Sour Water Systems , 2-6 Rackett Liquid Density
Examples , 3-29
Non-hydrocarbon Systems , 2-10
Input Description , 3-28
Non-Ionic Systems , 2-13
Notes Statement , 1-5, 1-14 Method-specific Pure Component Properties , 3-28
NRTL Typical Usage , 3-28
Attributes of NRTL methods , 6-2 Redlich-Kister, Gamma Heat of Mixing
Examples , 6-6 Attributes of , 6-75
K-value Data , 6-3 Enthalpy Data , 6-76
Method-specific Pure Component Properties , 6-6 METHOD Statement , 6-75

Typical Usage , 6-75 User-added Subroutines , 5-32
Refinery and Gas Processing , 2-2 Special Properties , 8-10
Refinery and Gas Processing Applications Examples , 8-28
FCCU , 2-3 General Information , 8-11
High Pressure Crude Systems , 2-3 Keywords for Special Stream Refinery
Low Pressure Crude Systems , 2-3 Properties , 8-11
Lube Oil and Solvent De-asphalting Units , 2-4 METHOD Statement , 8-14
Main Coker Fractionators , 2-3 Special Property Methods Data , 8-21
Reformers and Hydrofiners , 2-4 Special Refinery Property Entries , 8-14
Water Handling , 2-2 Typical Usage , 8-10
Reformers , 2-4 Special Property Methods Data , 1-12

Regular Solution SRK or PR Equation of State Interaction
Parameters , 1-10
Attributes of REGULAR Methods , 6-43
Examples , 6-46 Systems of Thermodynamic Methods , 1-27
K-value Data , 6-44
Method-specific Pure Component Properties , 6-46 T
Thermodynamic Data
S Thermodynamic Generators , 1-20
Thermodynamic Sets , 1-18
Selecting Individual Methods , 1-3 Transport Properties , 8-1
Soave Redlich-Kwong , 4-1 Diffusivity Data , 8-3
Attributes of , 4-2 Examples , 8-8
Enthalpy, Entropy, and Density Data , 4-4 General Information , 8-1
Examples , 4-5 METHOD Statement , 8-2
K-value Data , 4-3 Method-specific Pure Component Properties , 8-8
METHOD Statement , 4-2 Typical Usage , 8-1
Method-specific Pure Component Properties , 4-5 User-supplied Conductivity Data , 8-7
Typical Usage , 4-1 User-supplied Surface Tension Data , 8-7
Water Handling Options , 4-5 User-supplied Viscosity Data , 8-7
Solid Applications , 2-15 Truncated Virial Vapor Fugacity
Solid Solubility Methods , 7-1 Attributes of the TVIRIAL Vapor Fugacity
User-supplied Solubility , 7-4 Method , 6-68
Examples , 6-70
Vant Hoff Solubility , 7-1
K-value Data , 6-69
Solvent De-asphalting Units , 2-4
Sour Water , 5-19 Method-specific Pure Component Properties , 6-70
Attributes of SOUR Package , 5-19 Typical Usage , 6-68
Enthalpy, Entropy, and Density Data , 5-20 Vapor Fugacity Data , 6-69
Examples , 5-22
Method-specific Pure Component Properties , 5-21 U
Sour Water Systems , 2-6
Special Packages UNIFAC
Alcohols , 5-1 Attributes of UNIfAC Methods , 6-12
Amines , 5-26 Available UNIFAC Interaction Parameters , 6-17
Glycols , 5-14 Examples , 6-19
GPA Sour Water , 5-22 K-value Data , 6-14
Sour Water , 5-19 METHOD Statement , 6-13
Index- 6
Method-specific Pure Component Properties , 6-17 General Information , 7-1
Typical Usage , 6-12 METHOD Statement , 7-2
UNIQUAC Typical Usage , 7-1
Attributes of UNIQUAC Methods , 6-7 Vapor-liquid-liquid Equilibrium Considerations , 1-38
Examples , 6-11 Available Databanks , 1-40
K-value Data , 6-8 Declaring a VLLE set , 1-38
Method-specific Pure Component Properties , 6-11 K-value Data , 1-44
Typical Usage , 6-7 METHOD Statement , 1-43
UNIWAALS , 4-22 Specifying Key Components , 1-42
Attributes of , 4-22 Specifying Separate VLE and LLE Models , 1-42
Enthalpy, Entropy, and Density Data , 4-25 VLLE Predefined Systems and K-value
Examples , 4-25 Generators , 1-39
K-value Data , 4-23
Method-specific Pure Component Properties , 4-25 W
Water Handling , 2-2
User-added Subroutine Data , 1-13
User-added Subroutines
Examples , 5-33, 5-35
K-value Data , 5-33
Typical Usage , 5-32, 5-34
Attributes of , 3-32, 3-35
Examples , 3-36
Input Description , 3-35
K-value Data (required) , 3-35
User-supplied Solubility
Examples , 7-6
K-value Data , 7-5
Typical Usage , 7-4
V
Van Laar
Attributes of VANLAAR Methods , 6-33
Examples , 6-36
K-value Data , 6-34
Vant Hoff Solubility
Examples , 7-3

Index- 8
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PRO/II Thermodynamic Data Keyword Manual ToC-1

PRO/II Thermodynamic Data Keyword Manual ToC-3

PRO/II Thermodynamic Data Keyword Manual ToC-5

PRO/II Thermodynamic Data Keyword Manual ToC-7

The first statement THERMODYNAMIC DATA declares the begin-

PRO/II Thermodynamic Data Keyword Manual 1-1

1-2 Thermodynamic Data Overview

Table 1-1: Thermodynamic Data METHOD Statement

PRO/II Thermodynamic Data Keyword Manual 1-3

1-4 Thermodynamic Data Overview

PRO/II Thermodynamic Data Keyword Manual 1-5

Liquid-Liquid Equilibrium Options, Optional Chapter 5

1-6 Thermodynamic Data Overview

PRO/II Thermodynamic Data Keyword Manual 1-7

1-8 Thermodynamic Data Overview

Binary Interaction Data, Optional (Use with Chapters 4 & 5

PRO/II Thermodynamic Data Keyword Manual 1-9

Note: UOM is K or KCAL/KMOL or KJ/KMOL.

Note: UOM for SRKH & PRH is K or KCAL/KMOL or KJ/KMOL.

Note: UOM for NRTL3,NRTL,NRTL6 & NRTL8 is K or KCAL/KMOL or KJ/KMOL.

Note: UOM is K or KCAL/KMOL or KJ/KMOL or NONE.

1-10 Thermodynamic Data Overview

Note: UOM is K or KCAL/KMOL or KJ/KMOL or NONE.

UNIFAC Group Contribution Data, Optional Chapter 5

UNIFT2(K) or l, k, alk, akl, blk, bkl, clk, ckl / ...

UNIFT3(K) l, k, alk, akl, blk, bkl, clk, ckl / ...

UNFV (K or KCAL l, k, alk, akl / ...

Note: UOM for UNIFAC & UNFV is K or KCAL/KMOL or KJ/KMOL.

PRO/II Thermodynamic Data Keyword Manual 1-11

UNIFAC (K or KCAL or KJ) l, k, Alk, Akl / ...

PA02 or SA02 or VA02 i, c1, c2, c3 / ...

PA03 or SA03 or VA03 i, c1, c2 / ...

PA04 or SA04 or VA04 i, c1, c2 / ...

PA05 or SA05 or VA05 i, c1, c2 / ...

PA06 or SA06 or VA06 i, c1, c2, c3 / ...

PA07 or SA07 or VA07 i, c1 / ...

PA08 or SA08 or VA08 i, c1, c2, c3 / ...

PA09 or SA09 or VA09 i, c1, c2, c3 / ...

PA11 or SA11 or VA11 i, c1, c2 / ...

Special Property Methods Data, Optional Chapter 8

1-12 Thermodynamic Data Overview

PRO/II Thermodynamic Data Keyword Manual 1-13

Where the system id is selected from Table 1-6.

Note: The DIFFUSIVITY entry is not included with the

1-14 Thermodynamic Data Overview

2. A deethanizer using Peng-Robinson. Transport properties are

3. A three phase distillation tower containing MEK, water and tol-

4. Gas sweetening with MEA:

PRO/II Thermodynamic Data Keyword Manual 1-15

The Thermodynamic Data Category must begin with the THERMO-

1-16 Thermodynamic Data Overview

Notes Statement (optional)

An example of information added through NOTES statements

PRO/II Thermodynamic Data Keyword Manual 1-17

Thermodynamic Method Sets

It uses the SRK predefined system to calculate all of the stream

In this case, NRTL liquid activity coefficients coupled with SRK

1-18 Thermodynamic Data Overview

PRO/II Thermodynamic Data Keyword Manual 1-19

SRKKD SRK Kabadi-Danner VLLE VL VL V2 yes

SRKH SRK Huron-Vidal VLLE VL VL V2 yes