Component and Thermodynamic

Data Input Manual

Volume II:
Thermodynamic Data

PRO/II 5.5 Edition

Component and Thermodynamic The software described in this guide is furnished under a license
Data Input Manual agreement and may be used only in accordance with the terms of
that agreement. Information in this document is subject to
change without notice. Simulation Sciences, Inc. assumes no
liability for any damage to any hardware or software component
or any loss of data that may occur as a result of the use of the
information contained in this manual.
Copyright Notice Copyright © 2001 Simulation Sciences, Inc. All rights reserved.
No part of this publication may be copied and/or distributed
without the express written permission of Simulation Sciences,
Inc., 601 Valencia Ave., Brea, CA 92823-6346.
Trademarks PRO/I, PIPEPHASE, NETOPT, and SIMSCI are registered marks
of Simulation Sciences, Inc.

Printed in the United States of America, September 2001.

 Contents

Chapter 1
Thermodynamic Data Overview
General Information. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-1-1
Notes Statement (optional) . . . . . . . . . . . . . . . . . . . . . . . . . . .II-1-12
Minimum Required User Input . . . . . . . . . . . . . . . . . . . . . . . .II-1-12
Order of Input . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-1-15
Thermodynamic Sets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-1-16
Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-1-21
Predefined Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-1-25
Multiple Thermodynamic Sets. . . . . . . . . . . . . . . . . . . . . . . . .II-1-28
Free-water Decant Considerations . . . . . . . . . . . . . . . . . . . . . .II-1-31
Vapor-liquid-liquid Equilibrium Considerations . . . . . . . . . . .II-1-34

Chapter 2
Application Guidelines
General Information. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-2-1
Refinery and Gas Processing Applications . . . . . . . . . . . . . . . .II-2-2
Natural Gas Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-2-5
Petrochemical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-2-8
Chemical and Environmental Applications . . . . . . . . . . . . . . .II-2-13
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-2-15

Chapter 3
Generalized Correlations
Ideal and Library Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-1
Grayson-Streed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-4
Chao-Seader . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-8
Modifications to GS and CS . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-11
Curl-Pitzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-15
Braun K10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-18
Johnson-Grayson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-21
Lee-Kesler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-23
API Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-3-26

Thermodynamic Data Input Manual II-iii

 Rackett Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-3-28
Costald Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-3-30
User-supplied K-value Data . . . . . . . . . . . . . . . . . . . . . . . . . . II-3-32

Chapter 4
Equations of State
Soave Modified Redlich-Kwong . . . . . . . . . . . . . . . . . . . . . . . . II-4-1
Peng-Robinson. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-4-7
Modified Soave-Redlich-Kwong and Peng-Robinson . . . . . . II-4-13
UNIWAALS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-4-23
Filling in Missing Parameters . . . . . . . . . . . . . . . . . . . . . . . . . II-4-27
Cubic Equation Of State Alpha Formulations . . . . . . . . . . . . . II-4-29
Benedict-Webb-Rubin-Starling . . . . . . . . . . . . . . . . . . . . . . . . II-4-33
Associating Hexamer Equation Of State . . . . . . . . . . . . . . . . . II-4-37
Lee-Kesler-Plocker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-4-41

Chapter 5
Liquid Activity Methods
NRTL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-1
UNIQUAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-7
UNIFAC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-13
Modifications to UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-21
Wilson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-29
Van Laar. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-34
Margules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-40
Regular Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-45
Flory-Huggins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-49
Filling in Missing Parameters . . . . . . . . . . . . . . . . . . . . . . . . . II-5-54
Henry’s Law for Non-condensible Components . . . . . . . . . . . II-5-60
Hayden-O’Connell Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . II-5-66
Truncated Virial Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . . . II-5-70
IDIMER Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-5-74
Redlich-Kister, Gamma Heat of Mixing . . . . . . . . . . . . . . . . . II-5-78

II-iv Contents
 Chapter 6
Special Packages
Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-6-1
Glycols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-6-12
Sour Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-6-17
GPA Sour Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-6-21
Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-6-24
User-added Subroutines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-6-29

Chapter 7
Solid Solubility Methods
Van’t Hoff Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-7-1
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-7-3
User-supplied Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-7-3
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-7-5

Chapter 8
Transport and Special Properties
Transport Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-8-1
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-8-8
Special Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-8-10
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-8-24

Chapter 9
Method-specific Pure Component Data
Method-specific Pure Component Data. . . . . . . . . . . . . . . . . . .II-9-1
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .II-9-6

Index

Thermodynamic Data Input Manual II-v

II-vi Contents
 Chapter 1
Thermodynamic Data Overview

This section provides an overview of the Thermodynamic Data Cat-

egory. 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. Fortunately, the ther-
modynamic data input requirements for most simulations are sim-
ple, 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:
THERMODYAMIC DATA
METHOD SYSTEM=SRK
The first statement “THERMODYNAMIC DATA” declares the
beginning of the Thermodynamic Data Category. The second state-
ment states that the predefined SRK system of thermodynamic gen-
erators be employed. The usage of each thermodynamic generator
is fully documented in individual sections.

Thermodynamic methods are bundled 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 best 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

Thermodynamic Data Input Manual II-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.

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.

II-1-2 Thermodynamic Data Overview

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
Category Heading Statement, Required
THERMODYNAMIC DATA None Chapter 1
Notes Statement, Optional
NOTES TEXT = notes line (up to 256 characters) “Notes Statement
(optional)” on
page 1-12
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, 1-25
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} Sets” on page 1-
{KVALUE (LLE) = option}, {L1KEY = i and L2KEY = j}, 16
{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
ENTROPY(VL)=NONE
or ENTROPY(V)=option, ENTROPY(L)=option,
TRANSPORT = NONE or
TRANSPORT = PURE or PETRO or TRAPP or
TACITE or U1 or U2 or U3 or U4 or U5
or
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

Thermodynamic Data Input Manual II-1-3

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
VISCOSITY(VL) = NONE
or VISCOSITY(VL) = PURE or PETRO or TRAPP or
U1 or U2 or U3 or U4 or U5
or VISCOSITY(V) = option, VISCOSITY(L) = option
and/or
CONDUCTIVITY(VL) = NONE
or CONDUCTIVITY(VL) = PURE or PETRO or TRAPP
or U1 or U2 or U3 or U4 or U5
or CONDUCTIVITY(V) = option,
CONDUCTIVITY(L) = option
and/or
SURFACE = NONE
or SURFACE = PURE or PETRO or PARACHOR or
U1or U2 or U3 or U4 or U5
DIFFUSIVITY(L) = NONE
or DIFFUSIVITY(L) = WILKE or DIFDATA
Method-specific Water Handling Options, Optional
WATER DECANT = ON or OFF, {GPSA}, “Free-water
SOLUBILITY = SIMSCI or KEROSENE or EOS, Decant
PROPERTY = SATURATED or STEAM Considerations”
on page 1-31
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 or ALCOHOL or GLYCOL or NONE or
bankid,
FILL = NONE or UNIFAC or UFT1 or REGULAR or
FLORY,
AZEOTROPE = SIMSCI or NONE or bankid,
{WRITE = fileid},
ALPHA = ACENTRIC or SIMSCI or 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.

( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

II-1-4 Thermodynamic Data Overview

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
Liquid-Liquid Equilibrium Options, Optional Chapter 5
KVALUE(LLE) BANK = SIMSCI or ALCOHOL or GLYCOL or NONE or
bankid,
FILL = NONE or UNIFAC or UFT1 or REGULAR or
FLORY,
AZEOTROPE = SIMSCI or NONE or bankid,
{WRITE = fileid},
ALPHA = ACENTRIC or SIMSCI or bankid
(default depends on method)
<optional data statements> ...
Solid-Liquid Equilibrium Options, Optional Chapter 7
KVALUE(SLE) FILL = VANTHOFF or ONE or FREE
SOLUTE i, j, ....
SOLDATA(tunit) i, j, c1, c2, c3/ ...

Diffusivity Options, Optional Chapter 7

DIFFUSIVITY(L)
DIFDATA(tunit) i, l, c1, c2, c3/ ...
Vapor Fugacity Options, Optional Chapter 5
PHI BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid,
<optional data statements> ...
Henry’s Law Options, Optional Chapter 5
HENRY BANK = SIMSCI or NONE or bankid
SOLUTE i, j, ...
HENDATA(punit, tunit) i, l, c1, c2, c3, c4 / ...
Density Options, Optional Chapters 4 & 5
DENSITY(VL) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid
or
DENSITY(V) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid
or
DENSITY(L) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid
<optional data statements> ...
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

Thermodynamic Data Input Manual II-1-5

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
Enthalpy Options, Optional Chapters 4 & 5
ENTHALPY(VL) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid,
HMIX = IDEAL or GAMMA or RK1 or RK2
or
ENTHALPY(V) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid
and/or
ENTHALPY(L) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid,
HMIX = NONE or GAMMA or RK1 or RK2
<optional data statements> ...
Entropy Options, Optional Chapters 4 & 5
ENTROPY(VL) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid
or
ENTROPY(V) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid
and/or
ENTROPY(L) BANK = SIMSCI or NONE or bankid,
ALPHA = ACENTRIC or SIMSCI or bankid
<optional data statements> ...
User-supplied K-value Data, Optional Chapter 3
(Use with KVALUE statements)
KVALUE(VLE or LLE)
KDATA CORR=icorr, LN or LOG or EXPFAC=ipos,
PREF(punit)=value
DATA=i, tmax, tmin, c1, ... c8/ ...
or
KDATA TABULAR=t1, t2, .../ i, p1, p2, .../ ..., PREF(punit)=value
Binary Interaction Data, Optional Chapters 4 & 5
(Use with KVALUE, PHI, DENSITY, ENTHALPY, or ENTROPY statements)
BWRS Equation of State Data, Optional
BWRS i, j, kij, / ...
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, / ...
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

II-1-6 Thermodynamic Data Overview

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
Hayden-O’Connell 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, ηi
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 i, j, aij, bij, cij, dij, eij, fij, gij, hij / ...
(K or KCAL or KJ)
or
RK2 i, j, aij, bij, cij, dij, eij, fij, gij, hij / ...
(K or KCAL or KJ)

Soave-Redlich-Kwong or Peng-Robinson Equation of State Interaction Chapter 4

Parameters, Optional
SRK(K or R) or i, j, kija, kijb, kijc / ...
PR(K or R)
or
SRKKD(K or R) i, j, kija, kijb, kijc / ...
or
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 i, j, aij, bij, cij, aji, bji, cji, αij, βij / ...
(K or KCAL or KJ) or
PRH
(K or KCAL or KJ)
or
SRKS(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

Thermodynamic Data Input Manual II-1-7

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
Liquid Phase Activity Binary Interaction Data Chapter 5
NRTL Data, Optional
NRTL3 i, j, bij, bji, αij / ...
(K or KCAL or KJ)
NRTL i, j, aij, bij, aji, bji, αij / ...
(K or KCAL or KJ)

NRTL6 i, j, aij, bij, aji, bji, α’ij, β’ij / ...

(K or KCAL or KJ)
NRTL8 i, j, aij, bij, cij, aji, bji, cji, α’ij, β’ij / ...
(K or KCAL or KJ)

UNIQUAC Data, Optional

UNIQUAC i, j, aij, aji / ...
(K or KCAL or KJ)
UNIQ4 i, j, aij, aji, bij, bji / ...
(K or KCAL or KJ)

Wilson Data, Optional

WILSON i, j, aij, aji / ...
(K or KCAL or
KJ or NODIME)
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, χij / ...
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 i, j, pres, temp, xi / ... Chapter 5
(basis, punit, tunit)
INFINITE(tunit) i, j, temp, γioo, γjoo / ... Chapter 5
MUTUAL i, j, temp, xiI, xjII / ... Chapter 5
(basis, tunit)
IDEAL i, j / ... Chapter 5
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

II-1-8 Thermodynamic Data Overview

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
Henry’s Law Data, Optional Chapter 5
SOLUTE i, {j, ...}
HENDATA i, l, c1, c2, c3, c4 / ...
(punit, tunit)
UNIFAC Group Contribution Data, Optional Chapter 5
(For K-value calculations only)
UNIFAC l, k, Alk, A kl / ...
(K or KCAL or KJ)
UNIFT1(K) l, k, alk, akl, blk, bkl, clk, ckl / ...
or
UNIFT2(K) l, k, alk, akl, blk, bkl, clk, ckl / ...
or
UNIFT3(K) l, k, alk, akl, blk, bkl, clk, ckl / ...
UNFV l, k, alk, akl / ...
(K or KCAL or KJ)
UNIWAALS Modified Group Contribution Interaction Data, Optional Chapter 4
UNIFT1(K) l, k, alk, akl, blk, bkl, clk, ckl / ...
UNIFAC l, k, Alk, A kl / ...
(K or KCAL or KJ)
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

Thermodynamic Data Input Manual II-1-9

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
Pure Component Alpha Formulations, Optional Chapter 4
(Used with PR, SRK, or UNIWAALS methods)
PA01 or SA01 or i, c1 / ...
VA01
PA02 or SA02 or i, c1, c2, c3 / ...
VA02
PA03 or SA03 or i, c1, c2 / ...
VA03
PA04 or SA04 or i, c1, c2 / ...
VA04
PA05 or SA05 or i, c1, c2 / ...
VA05
PA06 or SA06 or i, c1, c2, c3 / ...
VA06
PA07 or SA07 or i, c1 / ...
VA07
PA08 or SA08 or i, c1, c2, c3 / ...
VA08
PA09 or SA09 or i, c1, c2, c3 / ...
VA09
PA10 or SA10 or i, c1, c2 / ...
VA10
PA11 or SA11 or i, c1, c2 / ...
VA11
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 / ...
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

II-1-10 Thermodynamic Data Overview

Table 1-1: THERMODYNAMIC DATA Category of Input
Statement Keywords For details see
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 Data Transfer System and User-added Subroutines User’s Guide)
UDATA i, value / ...
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.

Thermodynamic Data Input Manual II-1-11

Notes Statement (optional)
NOTES TEXT = notes line
The NOTES statement in the Thermodynamic Data Section pro-
vides a TEXT keyword that specifies the actual note.

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.

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 thermo 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.

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 1-25) is
sufficient. This takes the form:
THERMODYNAMIC DATA
METHOD SYSTEM=system id

Where the “system id” is selected from Table 1-5.

II-1-12 Thermodynamic Data Overview

 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
...

Thermodynamic Data Input Manual II-1-13

 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
...

II-1-14 Thermodynamic Data Overview

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 1-2. Some general guidelines are discussed later in this sec-
tion. More detailed descriptions of the various statements can be
found in later sections.
Table 1-2: Thermodynamic Data Order of Input
Statement Comments Chapter
THERMODYNAMIC Section heading, required as the first statement in the 1
DATA section.
METHOD Required as the first statement in defining each set of 1 to 5
methods.
WATER Optional. Method-specific water options that apply only
to the current method.
<property> Optional. Any KVALUE, ENTHALPY,K ENROPY, DENSITY,
TRANSPORT, HENRY, or PHI statement that applies to a
method declared on the METHOD statement.
<binary data> Optional. Additional binary interaction data statements
associated with the <property> statement.
<alpha data> Optional. Additional alpha data statements associated
with the <property> statement.
<component data> Optional. Any pure component data statements (Tc, Pc, 9
etc.) that apply to the current <property> statement.
<property>
...
METHOD Optional additional sets of thermodynamic methods
...

The Thermodynamic Data Category must begin with the THER-

MODYNAMIC 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.

Thermodynamic Data Input Manual II-1-15

 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.

Thermodynamic 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 following 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 1-25 and “Soave
Modified Redlich-Kwong” on page 4-1.

II-1-16 Thermodynamic Data Overview

 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 1-28.)
Table 1-3 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.

Thermodynamic Data Input Manual II-1-17

Table 1-3: Thermodynamic Generators
Method Description K-values Enthalpy Entropy Density Phi
Generalized Correlation Methods (see Chapter 3)
IDEAL Ideal 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 Chao- VLE(fw) — — — —
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 Density — — — L —
COSTALD COSTALD Liquid — — — L —
Density
LIBRARY Library Liquid Entropy — — L — —
Equation of State Methods (see Chapter 4)
SRK Soave-Redlich-Kwong VLE1(fw) VL VL V2 yes

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 Panagiotopoulos VLLE VL VL V2 yes

& 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

II-1-18 Thermodynamic Data Overview

Table 1-3: Thermodynamic Generators
Method Description K-values Enthalpy Entropy Density Phi
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)
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 Volume VLLE — — — —
option
WILSON Wilson equation VLE — — — —
VANLAAR van Laar equation VLLE — — — —
MARGULES Margules equation VLLE — — — —
REGULAR Regular solution VLLE — — — —
theory VLE(fw)
FLORY Flory Huggins VLLE — — — —
HOCV Hayden-O’Connell — V V V yes
vapor fugacity
TVIRIAL Truncated virial vapor — — — — yes
fugacity
IDIMER IDIMER vapor fugacity — V V V yes

Thermodynamic Data Input Manual II-1-19

Table 1-3: Thermodynamic Generators
Method Description K-values Enthalpy Entropy Density Phi
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 van’t Hoff solubilities SLE — — — —
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 1-4: Features that Require Entropy

Feature
COMPRESSOR
EXPANDER
GIBBS Reactor
HCURVE Entropy Tables
EXERGY

II-1-20 Thermodynamic Data Overview

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 1-5. 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.

Thermodynamic Data Input Manual II-1-21

 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 1-3
KVALUE(LLE) to 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 1-3) 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 1-3 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.

II-1-22 Thermodynamic Data Overview

 ENTHALPY This entry is used to select a method fromTable 1-3
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
1-3 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 1-4.

Note: Not all systems available on the SYSTEM entry declare an

entropy method, and the ENTROPY entry still may be required.
Refer to Table 1-4 to determine which features require an entropy
method.
PHI This entry specifies the method from Table 1-3
used to compute pure component and mixture
vapor fugacity coefficients (φi). 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-O’Connell Vapor
Fugacity” on page 5-66 and “Truncated Virial Vapor
Fugacity” on page 5-70.
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 “Henry’s Law for Non-
condensible Components” on page 5-60.

Thermodynamic Data Input Manual II-1-23

 RVPMETHOD, These options are used to specify the
TVPMETHOD thermodynamic 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 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
v3.3 calculation methods and v3.3 properties.
These properties are KVIS, CLOU, POUR, FLPT,
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 a unique identifier and may contain up
to 12 alphanumeric characters, excluding delimiters
and embedded blanks. See “Multiple
Thermodynamic Sets” on page 1-28.

II-1-24 Thermodynamic Data Overview

 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 1-5, 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, &
DENSITY(V)=SRK, DENSITY(L)=API

Thermodynamic Data Input Manual II-1-25

 Input Overview
Table 1-5 shows the predefined systems available and the property
methods used for each one.

Table 1-5: 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 SAT’D SAT’D — IDEAL SAT’D
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 UNIWAAL UNIW UNIW UNIW API
BRWS VLE1 BRWS BRWS BRWS BRWS BRWS BRWS

HEXAMER VLLE HEXAMER HEXA HEXA HEXA HEXA API

LKP VLLE1 LKP LKP LKP LKP LKP API
1 May decant free water 2 GS preferred to CS 3 VLLE available, but not recommended

II-1-26 Thermodynamic Data Overview

Table 1-5: Systems of Thermodynamic Methods
Methods for Evaluating Properties

VLE or Enthalpy Density

SYSTEM VLLE K-values vapor liquid Entropy vapor liquid
Liquid Activity Methods
NRTL VLLE NRTL SAT’D SAT’D — IDEAL SAT’D
UNIQUAC VLLE UNIQUAC SAT’D SAT’D — IDEAL SAT’D
UNIFAC VLLE UNIFAC SAT’D SAT’D — IDEAL SAT’D
UFT1 VLLE UFT1 SAT’D SAT’D — IDEAL SAT’D
UFT2 VLLE UFT2 SAT’D SAT’D — IDEAL SAT’D
UFT3 VLLE UFT3 SAT’D SAT’D — IDEAL SAT’D
UNFV VLLE UNFV SAT’D SAT’D — IDEAL SAT’D
WILSON VLE WILSON SAT’D SAT’D — IDEAL SAT’D
VANLAAR VLLE VANLAAR SAT’D SAT’D — IDEAL SAT’D
MARGULES VLLE MARGULES SAT’D SAT’D — IDEAL SAT’D
REGULAR VLLE REGULAR SAT’D SAT’D — IDEAL SAT’D
FLORY VLLE FLORY SAT’D SAT’D — IDEAL SAT’D
Special Packages
ALCOHOL VLLE NRTL SRKM SAT’D SRKM SRKM SAT’D
GLYCOL VLLE SRKM SRKM SRKM SRKM SRKM API
SOUR VLLE3 SOUR SRKM SAT’D SRKM SRKM SAT’D

GPSWATER VLLE3 GPSWATER SRKM SAT’D SRKM SRKM SAT’D

AMINE VLLE3 AMINE SRKM AMINE SRKM SRKM SAT’D

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

Thermodynamic Data Input Manual II-1-27

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:

● 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
a 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.

II-1-28 Thermodynamic Data Overview

 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 bub-
ble point flash calculation (as appropriate) using the new enthalpy
method. The RESET unit operation in PRO/II 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.

Thermodynamic Data Input Manual II-1-29

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
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
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 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 find two liquid
phases.

II-1-30 Thermodynamic Data Overview

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 1-3 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.

The GPSA method is based on the GPSA Data Book, Figure 20-3.
This option is useful for natural gas mixtures at pressures above
2000 psia.
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.

Note: A WATER statement may appear only after a METHOD

statement. Therefore water properties apply only to that thermo-
dynamic set.
For example, in the following thermodynamic data section the
water solubility in hydrocarbon is calculated via the API kerosene
solubility curve for thermodynamic set SRK only:
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, SET=SRK
WATER SOLUBILITY=KEROSENE
METHOD SYSTEM=GS, SET=GS

Thermodynamic Data Input Manual II-1-31

 Input Description
Water Handling Statement
WATER DECANT=ON or OFF, GPSA,
SOLUBILITY=SIMSCI or KEROSENE or EOS,
PROPERTY=SATURATED or STEAM

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 / (XΘ π)
where: P0 is the partial pressure of water,
XΘ is the solubility of water in the liquid
hydrocarbon phase,
π 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 GPSA Data Book, Figure 20-3, instead of the steam
tables. This option is useful for natural gas mixtures at
pressures above 2000 psia.
SOLUBILITY This statement selects the method for 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.

II-1-32 Thermodynamic Data Overview

 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

components other than those listed above, or containing NONLIB
components, the program estimates the correlation parameters for
these components and prints a warning message.

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.
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.
STEAM The basis for computing water properties
is the Keenan and Keyes equation of state
for water. It is recommended when water is
present as a superheated vapor.

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 predefined
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 state-
ment.

Thermodynamic Data Input Manual II-1-33

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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
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 1-6).

● by including the VLLE qualifier when using the KVALUE

entry to declare the method used to calculate equilibrium
K-values (Table 1-6).

● by including both a KVALUE(VLE) and KVALUE(LLE)

entry to declare the method used to calculate equilibrium
K-values (Table 1-6).

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

II-1-34 Thermodynamic Data Overview

 VLLE are the same as for VLE method sets. Table 1-6 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 1-6: 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
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.

Thermodynamic Data Input Manual II-1-35

 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

Table 1-7: 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

BWRS binary interactions

RK1 / RK2 interaction coefficients
COSTALD component critical properties
RACKETT component Rackett properties
HENRY Henry’s Law solubility data

II-1-36 Thermodynamic Data Overview

 Table 1-7: Available Databanks
BANK= Method Type of Data
binary coefficients for specific
ALCOHOL NRTL
components
binary interactions and pure
GLYCOL SRKM
component alphas
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 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.

Thermodynamic Data Input Manual II-1-37

 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

II-1-38 Thermodynamic Data Overview

 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:

VLE Interface LLE Interface

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:

VLE Interface LLE Interface

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 5-54 for liquid activity meth-
ods.

Thermodynamic Data Input Manual II-1-39

 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

or thermodynamic system or K-value generator to
KVALUE(VLLE) be used in the problem. The VLLE systems and
K-value generators available are given in Table
1-6.
L1KEY The L1KEY and L2KEY optional entries identify
and the most prevalent components expected in
L2KEY the first 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.

II-1-40 Thermodynamic Data Overview

Examples
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

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

Thermodynamic Data Input Manual II-1-41

 UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3, W=4
ADIA DP=0.0
END

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

II-1-42 Thermodynamic Data Overview

 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 program, 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

Thermodynamic Data Input Manual II-2-1

 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.

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 GPSA
Data Book, Figure 20-3 for the water vapor pressure. The GPSA
values should be used for natural gas systems above 2000 psia (136
atmospheres).
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
in the water phase. It uses interaction parameters for the water and
hydrocarbons based on the amount of water present in each phase.

II-2-2 Application Guidelines

 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 different
assay and characterization methods before employing other thermo-
dynamic methods. The API method should be used for calculating
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.

Thermodynamic Data Input Manual II-2-3

 For FCCU main fractionators, the petroleum fractions are much
more hydrogen deficient than are crude fractions. Since most char-
acterization correlations are derived from crude petroleum data, it is
expected that the results will be less accurate than for crude frac-
tions.

Recommended
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.

II-2-4 Application Guidelines

 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 give excellent answers.
The interaction parameters for hydrogen, carbon dioxide, nitrogen,
and hydrogen sulfide are estimated using general correlations when
user-supplied interaction parameters are not available. The BWRS
method should be used with more caution, since it does not extrapo-
late 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

Thermodynamic Data Input Manual II-2-5

 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
SRKS other 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.

II-2-6 Application Guidelines

 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. At least one amine and water must be
present when using the package.

Thermodynamic Data Input Manual II-2-7

 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.

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 den-
sities.

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.

II-2-8 Application Guidelines

 Recommended
Methods Comments

SRK / PR / BWRS Good for systems containing only similar hydrocarbon

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 temper-
atures, and is better than API if any light components such as meth-
ane are present. For systems at high temperatures with all aromatic
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, but
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

Thermodynamic Data Input Manual II-2-9

 availability of all critical parameters to ensure getting good results.
It is not necessary to use the VLLE option unless polar components,
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 / UNIQUAC Use these liquid activity methods for extraction
systems, 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

II-2-10 Application Guidelines

 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.

Thermodynamic Data Input Manual II-2-11

 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 / UNIQUAC Use either of these methods for all non-ideal systems.
Use 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
SRKS quantities 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 / UNIQUAC Use when valid user-supplied interaction data are
available.

HF Systems
A special equation of state, HEXAMER, has been created for sys-
tems containing molecules that hexamerize in the vapor phase. This

II-2-12 Application Guidelines

 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

Thermodynamic Data Input Manual II-2-13

 .

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 / UNIQUAC Use either of these methods for all non-ideal systems.
Use 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
SRKS non-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 accurate
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 conjunction 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, or are often

II-2-14 Application Guidelines

 available in the SIMSCI databank. In order to model the systems
accurately, the user should supply temperature-dependent values 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
2.1: You are required to model a hydrocarbon-water mixture
which 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

Thermodynamic Data Input Manual II-2-15

 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

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.

II-2-16 Application Guidelines

 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
PROD OVHD=3, BTMS=4,24446
PSPEC TOP=20.8, DPCOL=2.1678
ESTI MODEL=CONV
END

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

Thermodynamic Data Input Manual II-2-17

 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
PROD OVHD=2, BTMS=3,700
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

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

II-2-18 Application Guidelines

 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
PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, &
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

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

Thermodynamic Data Input Manual II-2-19

 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
PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, &
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

II-2-20 Application Guidelines

 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, ENTROPY=LIBRARY
STREAM DATA
. . .

General Information
The IDEAL method calculates K-values, vapor and liquid densities,
and vapor and liquid enthalpies. The LIBRARY method calculates
liquid entropies. These methods should be used with pure compo-
nent streams and streams with very similar components — for
instance:

o-xylene / m-xylene / p-xylene / ethylbenzenestyrene.

Thermodynamic Data Input Manual II-3-1

 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 Liquid entropies

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
Liquid entropies - Pure component liquid entropies
Suggested application ranges
Pressure - Low pressures
Two liquid phase behavior
Free-water decant - Not supported
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.

The METHOD Statement

METHOD SYSTEM=IDEAL, ENTROPY(L)=LIBRARY ...
or
METHOD KVALUE=IDEAL, ENTHALPY=IDEAL,
DENSITY=IDEAL, ENTROPY(L)=LIBRARY

SYSTEM Selects a combination of compatible thermodynamic

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

II-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 = χ 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
V and/or L) phase calculations.
DENSITY Selects the method for density calculations. IDEAL
(VL or methods may be selected for liquid and/or vapor
V and/or L) phase calculations.
ENTROPY (L) Selects the method for entropy calculations. LIBRARY
methods may be selected for liquid phase
calculations only.

Examples
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-3-3

 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

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

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.

II-3-4 Generalized Correlations

 Table 3-2: Attributes of Grayson-Streed Methods
Properties predicted by GS methods
K-values

Required pure component properties1

Molecular weight Liquid molar volume
Critical temperature Acentric factor
Critical pressure Solubility parameter
Suggested application ranges
Pressure < 3000 psia
Temperature 0 - 800 F
Two liquid phase behavior
Free-water decant - Supported
VLLE - Not supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
METHOD SYSTEM=GS, ...
or
METHOD KVALUE=GS, ...

SYSTEM Selects a combination of compatible

thermodynamic 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.

Thermodynamic Data Input Manual II-3-5

 Water Handling Options (optional)

WATER DECANT=ON or OFF, GPSA,

SOLUBILITY=SIMSCI or KEROSENE or EOS
PROPERTY=SATURATED or STEAM
The GS K-value generator supports the free-water decant option.
Refer to “Free-water Decant Considerations” on page 1-31 for a
description of these input options.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
MOLVOL(unit) i, value / ...
ACENTRIC i, value / ...
SOLUPARA i, value / ...
...
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
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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=GS
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

II-3-6 Generalized Correlations

 3.6: For the same problem, use GS K-values, Lee-Kesler
enthalpies and densities.
THERMO DATA
METHOD KVALUE=GS, ENTHALPY=LK, DENSITY=LK

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.
TITLE PROB=GS, PROJ=THERMO
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=GS
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-3-7

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

Required pure component properties1

Molecular weight Liquid molar volume
Critical temperature Acentric factor
Critical pressure Solubility parameter
Suggested application ranges
C2 & Higher H2 & C1
Pressure - < 2000 psia < 8000 psia
Temperature - 0 to 800 F -100 to 500F
Two liquid phase behavior
Free-water decant - Supported
VLLE - Not supported
1 Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

II-3-8 Generalized Correlations

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

SYSTEM Selects a combination of compatible

thermodynamic 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.

Water Handling Options (optional)

WATER DECANT=ON or OFF, GPSA,
SOLUBILITY=SIMSCI or KEROSENE or EOS
PROPERTY=SATURATED or STEAM
The CS K-value generator supports the free-water decant option.
Refer to “Free-water Decant Considerations” on page 1-31, for a
description of these input options.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
MOLVOL(unit) i, value / ...
ACENTRIC i, value / ...
SOLUPARA i, value / ...
...
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”.

Thermodynamic Data Input Manual II-3-9

Examples
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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=CS
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

3.9: For the same problem, use CS K-values, Lee-Kesler

enthalpies and densities.
THERMO DATA
METHOD KVALUE=CS, ENTHALPY=LK, DENSITY=LK

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.
TITLE PROB=GS, PROJ=THERMO
DESC THERMO MANUAL PROBLEM
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
PROP STREAM=1, TEMP=100, PRES=1000, COMP=20/40/40

II-3-10 Generalized Correlations

 UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3, W=4
TPSPEC TEMP=100
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
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.

Thermodynamic Data Input Manual II-3-11

 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

Required pure component properties1

Molecular weight Acentric factor
Critical temperature Water solubility parameter (IGS only)
Critical pressure
Suggested application ranges
Pressure - < 3000 psia
Temperature - 0 to 800 F
Two liquid phase behavior
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 supplied by the user for non-
library components.

Input Description
The METHOD Statement

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, ...

SYSTEM Selects a combination of compatible thermodynamic

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.

II-3-12 Generalized Correlations

 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.

Water Handling Options (optional)

These options are not valid when the VLLE option is active.
WATER DECANT=ON or OFF, GPSA,
SOLUBILITY=SIMSCI or KEROSENE or EOS
PROPERTY=SATURATED or STEAM
The IGS, GSE, and CSE K-value generators support the free-water
decant option. Refer to “Free-water Decant Considerations” on
page 1-31, for a description of these input options.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
MOLVOL(unit) i, value / ...
ACENTRIC i, value / ...
SOLUPARA i, value / ...
WDELT
...
Properties may be supplied that are active only when a specific
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
3.11: Using the IGS methods, model a 50/50 mix of propane
and normal butane at 100 psia and 100 F. By choosing the
IGS “system”, Curl-Pitzer enthalpies are invoked.
TITLE PROB=IGS, PROJ=THERMO
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=IGS
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=1000, COMP=50/50

Thermodynamic Data Input Manual II-3-13

 UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3
TPSPEC TEMP=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

3.12: For the same problem, use GSE K-values, Lee-Kesler

enthalpies and densities.
THERMO DATA
METHOD KVALUE=GSE, ENTHALPY=LK, DENSITY=LK

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.
TITLE PROB=GS, PROJ=THERMO
COMPONENT DATA
LIBID 1,H2O/ 2,C3/ 3,NC4
THERMO DATA
METHOD SYSTEM(VLLE)=IGS, SET=RIGOROUS
METHOD SYSTEM=IGS, SET=DECANTING
WATER DECANT=ON, GPSA, SOLUBILITY=KEROSENE, &
PROPERTY=STEAM
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=1000, COMP=20/40/4
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

II-3-14 Generalized Correlations

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

Required pure component properties1

Critical temperature
Critical pressure
Acentric factor
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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, ...

Thermodynamic Data Input Manual II-3-15

 SYSTEM Selects a combination of compatible
thermodynamic 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
(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 entropies
by providing both an ENTROPY(V) and ENTROPY(L)
entry.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
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 glo-
bally 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
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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4

II-3-16 Generalized Correlations

 THERMO DATA
METHOD SYSTEM=CS
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

3.15: For the same problem, specify CP enthalpies and entropies

explicitly.
THERMO DATA
METHOD KVALUE=CS, ENTHALPY=CP, ENTROPY=CP, &
DENSITY=API

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
DESC THERMO MANUAL PROBLEM
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
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-3-17

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

Required pure component properties1

Molecular weight Acentric factor
Critical temperature Normal boiling point
Critical pressure
Suggested application ranges
Pressure - 0 to 100 psia
Temperature - 100 to 1200 F
Composition - C6 & Heavier
Two liquid phase behavior
Free-water decant - Supported
VLLE - Not supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

II-3-18 Generalized Correlations

 Input Description
The METHOD Statement
METHOD SYSTEM=BK10, ...
or
METHOD KVALUE=BK10, ...

SYSTEM Selects a combination of compatible thermodynamic

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.
KVALUE Selects the method for K-value calculations. Only VLE
K-value calculations are available with the BK10
method.

Water Handling Options (optional)

WATER DECANT=ON or OFF, GPSA,
SOLUBILITY=SIMSCI or KEROSENE or EOS
PROPERTY=SATURATED or STEAM
The BK10 K-value generator supports the free-water decant option.
Refer to “Free-water Decant Considerations” on page 1-31, for a
description of these input options.

Method-specific Pure Component Properties (optional)

NBP(unit) i, value / ...
TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
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
3.17: Using the BK10 method, model a 50/50 mix of propane
and normal butane at 100 psia and 100 F. By choosing the
SYSTEM=BK10, Johnson-Grayson enthalpies are
invoked.
TITLE PROB=BK10, PROJ=THERMO
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL

Thermodynamic Data Input Manual II-3-19

 COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=BK10
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

3.18: For the same problem, use BK10 K-values, Lee-Kesler

enthalpies and densities.
THERMO DATA
METHOD KVALUE=BK10, ENTHALPY=LK, DENSITY=LK

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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,H2O/ 2,C3/ 3,NC4
THERMO DATA
METHOD SYSTEM=BK10
WATER DECANT=ON, GPSA, &
SOLUBILITY=KEROSENE, PROPERTY=STEAM
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=1000, COMP=20/40/40
UNIT OPERATION
FLASH UID=DRUM
FEED 1
PROD V=2, L=3, W=4
TPSPEC TEMP=100
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

II-3-20 Generalized Correlations

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

Required pure component properties1

Critical temperature
Critical pressure
Normal boiling point
1
Automatically supplied for library and petroleum components. must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
METHOD SYSTEM=BK10, ...
or
METHOD ..., ENTHALPY(VL)=JG, ...
or
ENTHALPY(V)= JG and/or ENTHALPY(L)=JG

Thermodynamic Data Input Manual II-3-21

 SYSTEM Selects a combination of compatible
thermodynamic property generators. When
SYTEM=BK10 is chosen, Johnson-Grayson
vapor and liquid enthalpies are assumed.
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, although this is not
recommended.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
NBP(unit) i, value / ...
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-specific Pure Component Data”.

Examples
3.20: Using the BK10 system, model a 50/50 mix of propane
and normal butane at 100 psia and 100 F. By choosing the
BK10 “system”, Johnson-Grayson enthalpies are invoked.
TITLE PROB=JG, PROJ=THERMO
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=BK10
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=D101
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

II-3-22 Generalized Correlations

 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.
Refer to the PRO/II Reference Manual for additional limitations.

Table 3-8: Attributes of the Lee-Kesler Methods

Properties predicted by LK methods
Enthalpies
Entropies
Densities
Suggested application ranges
Composition - C8 & lighter (for liquid density method)

Required pure component properties1

Critical temperature
Critical pressure
Normal boiling point
1 Automatically supplied for library and petroleum components. must be supplied by the user for
non-library components.

Thermodynamic Data Input Manual II-3-23

 Input Description
The METHOD Statement
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
(VL or V and/or L default both vapor and liquid (VL) densities are
calculated using the same method. You may
select different methods for the vapor and liquid
densities by providing both a DENSITY(V) and
DENSITY(L) entry.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
NBP(unit) i, value / ...
...
The Lee-Kesler method requires Tc, Pc, NBP and ideal gas enthalp-
ies. 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”.

II-3-24 Generalized Correlations

Examples
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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=SRK, ENTHALPY=LK
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

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

Thermodynamic Data Input Manual II-3-25

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.

Table 3-9: Attributes of API Methods

Properties predicted by API methods
Liquid densities
Required pure component properties1
Critical temperature
Critical pressure
Normal boiling point
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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
METHOD ..., DENSITY(L)=API, ...

SYSTEM Selects a combination of compatible thermodynamic

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

II-3-26 Generalized Correlations

 Method-specific Pure Component Properties (optional)
TC(unit) i, value / ...
PC(unit) i, value / ...
NBP(unit) i, value / ...
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
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
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=D121
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END
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

Thermodynamic Data Input Manual II-3-27

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.
Refer to the PRO/II Reference Manual for additional limitations.

Table 3-10: Attributes of RACKETT Methods

Properties predicted by RACKETT methods
Liquid densities

Required pure component properties1

Critical temperature Rackett parameter
Critical pressure Critical compressibility factor
1
Automatically supplied for some library and petroleum components. Must be supplied by the user for
non-library components.

Input Description
The METHOD Statement
METHOD ..., DENSITY(L)=RACKETT, ...

DENSITY(L) Selects the method for liquid density calculations.

Method-specific Pure Component Properties (optional)

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

II-3-28 Generalized Correlations

 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
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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=SRK, DENSITY(L)=RACKETT
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

3.27: For the same problem, specify SRK K-values, SRK

enthalpies, entropies, Lee-Kesler vapor densities, and
RACKETT liquid densities explicitly.
THERMO DATA
METHOD KVALUE=SRK, ENTHALPY=SRK, &
ENTROPY=SRK, DENSITY(V)=LK, &
DENSITY(L)=RACKETT

Thermodynamic Data Input Manual II-3-29

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

Required pure component properties1

Critical temperature Critical volume
Acentric factor
1
Automatically supplied for some library and petroleum components. Must be supplied by the user for
non-library components.

Input Description
The METHOD Statement
METHOD . ..., DENSITY(L)=COSTALD, ...

DENSITY(L) Selects the method for liquid density calculations.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
ACENTRIC i, value / ...
VC(unit) i, value / ...
...
The COSTALD method requires Tc, the acentric factor, and critical
volumes. Tc and w may be overridden here for a specific method

II-3-30 Generalized Correlations

 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 however, a characteristic volume
is back calculated in order to provide a correct specific gravity for
the pseudocomponent. For a further description of these input
parameters, see Chapter 9, “Method-specific Pure Component
Data”.

Examples
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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMO DATA
METHOD SYSTEM=SRK, DENSITY(L)=COSTALD
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

3.29: For the same problem, specify SRK K-values, SRK

enthalpies, entropies, Lee-Kesler vapor densities, and
COSTALD liquid densities explicitly.
THERMO DATA
METHOD KVALUE=SRK, ENTHALPY=SRK, &
ENTROPY=SRK, DENSITY(V)=LK, &
DENSITY(L)=COSTALD

Thermodynamic Data Input Manual II-3-31

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, only
LLE K-value data may be supplied. KDATA may be supplied in
either tabular or correlation forms.

Table 3-12: Attributes of User-Supplied K-value Data

Properties predicted by K-value Data
K-values
Required pure component properties
None
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported

II-3-32 Generalized Correlations

 Input Description
The METHOD Statement
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(punit)=value, DATA=i, tmax, tmin, c1, ...c8/ ...
or
KDATA TABU=t1, t2, .../ i, p1, p2, .../ ..., PREF(punit)=value

Note: If KVALUE(VLE)=DATA is used, all components of phase

type VL or VLS must have KDATA information. 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.

Thermodynamic Data Input Manual II-3-33

 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, only LLE KDATA may be supplied.

Examples
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
PROP STREAM=1, TEMP=90, PRES=50, COMP=50/50/50
UNIT OPERATIONS
FLASH UID=1
FEED 1
PROD L=2
BUBB PRES=50
END

II-3-34 Generalized Correlations

 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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4/ 3,H20
THERMO DATA
METHOD SYSTEM=SRKM
KVALUE
KDATA TABU=50,100,150,6.0387,10.822,18.773, PREF=100
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/40/10
UNIT OPERATION
FLASH UID=FD23
FEED 1
PROD V=2, L=3
TPSPEC PRES=75
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-3-35

II-3-36 Generalized Correlations
 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
LIBID 1,IC4/ 2,NC4/ 3,NC5
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 (see“Modified Soave-Redlich-Kwong and Peng-Robinson” on
page 4-13).

Thermodynamic Data Input Manual II-4-1

 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

Required pure component properties1

Molecular weight Acentric factor
Critical temperature Ideal vapor enthalpy
Critical pressure
Suggested application ranges
Pressure - 0 to 5000 psia
Temperature - -460 to 1200 F
Two liquid phase behavior
Free-water decant - Supported
VLLE - Not recommended
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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.
KVALUE Selects the method for K-value calculations. Only
VLE K-value calculations are recommended with
the SRK method.
ENTHALPY Selects the method for enthalpy calculation. By
(VL or V and/or L) default, both vapor and liquid enthalpies use this
method.

II-4-2 Equations of State

 ENTROPY Selects the method for entropy calculation. By
(VL or V and/or L) default, both vapor and liquid entropies use this
method.
DENSITY (V) Selects the method for vapor density.

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
SRK(K or R) i, j, kija, kijb, kijc/ ...
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.

Thermodynamic Data Input Manual II-4-3

 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.
bankid This option selects the user-created databank
named “bankid” that is created and maintained
by the LIBMGR 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

Temperature units may be K (default) or R.
SA01 to These entries permit various formulations of the pure
SA11 component Alpha correlations. See “Cubic Equation Of State
Alpha Formulations” on page 4-29, 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,

ALPHA=ACENTRIC or SIMSCI or bankid

SRK(K or R) i, j, kija, kijb, kijc/ ...

SA01to SA11 i, c1, c2, c3/ ...
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.

II-4-4 Equations of State

 See above under K-value Data for format and definition of these
entries.

Water Handling Options (optional)

WATER DECANT=ON or OFF, GPSA,
SOLUBILITY=SIMSCI or KEROSENE or EOS
PROPERTY=SATURATED or STEAM
The SRK K-value generator supports the free-water decant option.
Refer to “Free-water Decant Considerations” on page 1-31 for a
description of these input options.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
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
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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=SRK
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-4-5

 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,&
DENSITY(V)=SRK, DENSITY(L)=API

4.3: Use the SOUR thermo methods but apply SRK to vapor
density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=SRK
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...

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 4-29.
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

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.
TITLE PROB=SRK, PROJ=THERMO
COMPONENT DATA
LIBID 1,C3/ 2,NC4/ 3,H2O/ 4,NH3/ 5,CO2
THERMO DATA
METHOD SYSTEM=SRK

II-4-6 Equations of State

 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
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50/2/2/2
UNIT OPERATION
FLASH UID=F1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Peng-Robinson
Typical Usage

...
COMPONENT DATA
LIBID 1,IC4/ 2,NC4/ 3,NC5
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).

Thermodynamic Data Input Manual II-4-7

 Table 4-2: Attributes of the PR Equation of State
Properties predicted by PR
K-values Vapor densities
Enthalpies Liquid densities (not recommended)
Entropies

Required pure component properties1

Molecular weight Ideal vapor enthalpy
Critical pressure Acentric factor
Critical temperature
Suggested application ranges
Pressure - 0 to 5000 psia
Temperature - -460 to 1200 F
Two liquid phase behavior
Free-water decant - Supported
VLLE - Not recommended
1 Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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.

SYSTEM Selects a combination of consistent

thermodynamic 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.
ENTHALPY Selects the method for enthalpy calculation. By
(VL or V and/or L) default, both vapor and liquid enthalpies use this
method.

II-4-8 Equations of State

 ENTROPY Selects the method for entropy calculation. By
(VL or V and/or L) default, both vapor and liquid entropies use this
method.
DENSITY (V) Selects the method for vapor density.

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.

K-value Data (optional)

KVALUE BANK=PROCESS or SIMSCI or NONE or bankid,
FILL=NONE or GOR or GAO or CPHC
ALPHA=ACENTRIC or SIMSCI or bankid
PR(K or R) i, j, kija, kijb, kijc/ ...
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.
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.

Thermodynamic Data Input Manual II-4-9

 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.
bankid This option selects the user-created
databank named “bankid” that is created
and maintained by the LIBMGR 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

Temperature units may be K (default) or R.
PA01 to PA11 These entries permit various formulations of the pure
component Alpha correlations. See “Cubic Equation Of
State Alpha Formulations” on page 4-29, 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,
ALPHA=ACENTRIC or SIMSCI or bankid
PR(K or R) i, j, kija, kijb, kijc/ ...
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 for-
mulations independently.

II-4-10 Equations of State

 See above under K-value Data for format and definition of these
entries.

Water Handling Options (optional)

WATER DECANT=ON or OFF, GPSA,
SOLUBILITY=SIMSCI or KEROSENE or EOS
PROPERTY=SATURATED or STEAM
The PR K-value generator supports the free-water decant option.
Refer to “Free-water Decant Considerations” on page 1-31 for a
description of these input options.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
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
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
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=PR
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
UNIT OPERATION
FLASH UID=F203
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-4-11

 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...

4.9: Use the SOUR thermo methods but apply PR to vapor

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

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

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 4-29.
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

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.

II-4-12 Equations of State

 TITLE PROB=PR, PROJ=THERMO
DESC THERMO MANUAL PROBLEM
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
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50/2/2/2
UNIT OPERATION
FLASH UID=F209
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Modified Soave-Redlich-Kwong and Peng-Robinson

Typical Usage

...
COMPONENT DATA
LIBID 1,IC4/ 2,NC4/ 3,NC5
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.

Thermodynamic Data Input Manual II-4-13

 Table 4-3: Attributes of the Modified SRK and PR Equations of State
Properties predicted by Modified SRK and PR Equations
K-values Vapor densities
Entropies Liquid densities (not recommended)
Enthalpies

Required pure component properties1

Molecular weight Ideal vapor enthalpy
Critical temperature Acentric factor (needed only if ACENTRIC
Critical pressure alpha formulation is selected)
Suggested application ranges
Pressure - 0 to 5000 psia
Temperature - -460 to 1200 F
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1 Automatically
supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement

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.

II-4-14 Equations of State

 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.

Thermodynamic Data Input Manual II-4-15

 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 densities are
assumed.
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.

K-value Data (optional)

KVALUE(VLE or LLE or VLLE) BANK=SIMSCI or NONE or bankid,
FILL=NONE or GOR or GAO or CPHC
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, αij, βij/ ...
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/ ...

II-4-16 Equations of State

 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.
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.
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.
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.

Thermodynamic Data Input Manual II-4-17

 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.
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 or KJ. αij
and βij 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
Temperature units may be K (default) or R.
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:

II-4-18 Equations of State

 kij = kija + kijb / T + kijc /T 2
Temperature units may be K (default) or R.
SA01 to SA11 These entries permit various formulations of the pure
PA01 to PA11 component Alpha correlations. See “Cubic Equation Of
State Alpha Formulations” on page 4-29 for further
details.

Enthalpy, Entropy, and Density Data (optional)

ENTHALPY BANK=SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC or bankid

ENTROPY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

DENSITY 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, αij, βij/ ...
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 automatically
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.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...

Thermodynamic Data Input Manual II-4-19

 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
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE,VALUE=0.5
END

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

4.15: Use the SOUR thermo methods but apply PRM to vapor
density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=PRM...

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.

II-4-20 Equations of State

 THERMODYNAMIC DATA
METHOD SYSTEM=SRKM
KVALUE
SRKM 1, 2, 0.01, -0.02/ 2, 3, 0.025, 0.04

4.17: 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 4-29.
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...

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
LIBID 1,C3/ 2,NC4/ 3,H2O
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
PROP STREAM=1, TEMP=100, PRES=100, COMP=1,50/ 2,40/ 3,10
UNIT OPERATION
FLASH UID=F101
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-4-21

 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
LIBID 1,C3/ 2,NC4/ 3,H2O
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
ENTROPY BANK=NONE, ALPHA=ACENTRIC
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
ENTROPY BANK=NONE, ALPHA=ACENTRIC
WATER DECANT=ON
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=1,50/ 2,40/ 3,10
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

II-4-22 Equations of State

UNIWAALS
Typical Usage

...
COMPONENT DATA
LIBID 1,IC4/ 2,NC4/ 3,NC5
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
K-values Vapor densities
Enthalpies Liquid densities
Entropies

Required pure component properties1

Molecular weight Acentric factor
Critical temperature Ideal vapor enthalpy
Critical pressure
Suggested application ranges
Low to mid temperatures
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1 Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Thermodynamic Data Input Manual II-4-23

 Input Description
The METHOD Statement
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.

SYSTEM Selects a combination of consistent

thermodynamic 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.

K-value Data (optional)

KVALUE(VLE and/or LLE or VLLE)
BANK=SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC or bankid
UFT1(K) m, k, amk, akm, b mk, bkm, cmk, ckm/ ...
UNIFAC(K or KCAL or KJ) m, k, A mk, Akm/...
VA01 to VA11 i, c1, c2, c3/ ...

Note: The UFT1, UNIFAC and VAxx statements must follow the
KVALUE statement.

BANK This option selects one or more banks from which to

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

II-4-24 Equations of State

 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 This option selects the user-created databank
named “bankid” that is created and
maintained by the LIBMGR program.
UFT1 This statement allows entry of the temperature
and/or dependent Lyngby modification of the UNIFAC method
UNIFAC (UFT1) and non-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 or KJ.
VA01 to These entries permit various formulations of the pure
VA11 component Alpha correlations. See “Cubic Equation Of
State Alpha Formulations” on page 4-29 for further
details.

Enthalpy, Entropy, and Density Data (optional)

ENTHALPY BANK=SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC or bankid

ENTROPY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid
DENSITY BANK=SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC or bankid

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

UNIFAC(K or KCAL or KJ) m, k, A mk, Akm/...
VA01 to VA11 i, c1, c2, c3/ ...
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 UNIWAALS,
you can supply these parameters independently.

Thermodynamic Data Input Manual II-4-25

 See above under K-value Data for format and definition of these
entries.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
Properties may be supplied that are active only when a specific
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
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

4.21: For the same problem, use explicitly specified

UNIWAALS K-values, enthalpies, entropies, and vapor
densities. Specify API liquid densities.

II-4-26 Equations of State

 THERMODYNAMIC DATA
METHOD KVALUE=UNIWAAL, ENTHALPY=UNIWAAL, &
ENTROPY=UNIWAAL, DENSITY(V)=UNIWAAL, &
DENSITY(L)=API

4.22: For the previous example, also supply parameters for the
Twu-Bluck-Cunningham alpha formulation for
components 1 and 2, propane and butane. See “Cubic
Equation Of State Alpha Formulations” on page 4-29.
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

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 has an extensive facility to backfill missing binary interac-
tion data between hydrocarbons for cubic equations of state (i.e.,
SRK, PR, and their modifications). Table 4-5 shows the methods
developed by SIMSCI that can be used for estimating binary inter-
action parameters.

Thermodynamic Data Input Manual II-4-27

 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
The METHOD Statement
METHOD SYSTEM=SRK or PR or SRKM or PRM or SRKS
or SRKP or PRP, ...
or
METHOD KVALUE=SRK or PR or SRKM or PRM or SRKS
or SRKP or PRP, ...

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

II-4-28 Equations of State

 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
LIBID 1,IC4/ 2,NC4/ 3,NC5
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 will use all data supplied
on the SAxx, PAxx, or VAxx statements. The constants to be sup-
plied on the SAxx, PAxx, or VAxx statements can be regressed from

Thermodynamic Data Input Manual II-4-29

 experimental data using REGRESSTM. Components 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.

ALPHA This option allows access to the databank for alpha

formulations for components not given on SAxx, PAxx, or
VAxx statements.
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.

II-4-30 Equations of State

 SA01 to SA11 These entries permit various formulations of the pure
or component alpha correlations. Statements that have an
“S” prefix may be used with any form of the Soave-
PA01 to PA11
Redlich- Kwong equation of state, those with “P” apply to
or the Peng-Robinson equation of state, while those
VA01 to VA11 statements prefixed with “V” apply to the UNIWAALS
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 α = [ 1 + C1 ( 1 – T r )] Soave (1972)
C3 2
02 α = [ C1 + C2 ( 1 – T r ) ] Peng-Robinson (1980)
C2
03 α = 1 + ( 1 – T r )  C 1 + -----  Soave (1979)
 Tr 

C2
04 α = exp [ C 1 ( 1 – T r ) ] Boston-Mathias (1980)
2 ( C2 – 1 ) 2C 2
05 α = Tr exp [ C 1 ( 1 – T r )] Twu (1988)
C3 ( C 2 – 1 ) C2C3 Twu-Bluck-Cunningham
06 α = Tr exp [ C 1 ( 1 – T r )] (1990) (Recommended
by SimSci)
2C 1 (C r + 1 ) ⁄ 2 
07 α = exp  --------------- ( 1 – T r ) Alternative for form (04)
 1 + C1 

C3 C2
08 α = T r exp [ C 1 ( 1 – T r ) ] Alternative for form (06)

0.5 0.5 2 0.5 2 0.5 3 2

09 α = [ 1 + C1 ( 1 – Tr ) + C2 ( 1 – Tr ) + C3 ( 1 – Tr ) + C3 ( 1 – Tr ) ] ] Mathias-Copeman (1983)

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

0.5 2 Melhem-Saini-Goodwin
11 α = exp [ C 1 ( 1 – T r ) + C 2 ( 1 – Tr ) ] (1989)

Thermodynamic Data Input Manual II-4-31

 Enthalpy, Entropy, and Density Data (optional)
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.
See above under K-value Data for format and definition of these
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.

II-4-32 Equations of State

Examples
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
METHOD KVALUE=SRK, ENTHALPY=SRK, &
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
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
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
LIBID 1,IC4/ 2,NC4/ 3,NC5
THERMO DATA
METHOD SYSTEM=BRWS
STREAM DATA
. . .

Thermodynamic Data Input Manual II-4-33

 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
K-values Vapor densities
Enthalpies Liquid densities
Entropies

Required pure component properties1

Molecular weight Acentric factor
Critical temperature Ideal vapor enthalpy
Critical volume
Suggested application ranges
Pressure - 0 to 2000 psia
Temperature - -460 to 200 F
Components - C1 & heavier
Two liquid phase behavior
Free-water decant - Supported
VLLE - Not supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

The METHOD Statement

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

SYSTEM Selects a combination of consistent

thermodynamic property generators. When
SYSTEM=BWRS is chosen, BWRS K-values,
BWRS enthalpies, BWRS entropies, BWRS liquid
and vapor densities are assumed.

II-4-34 Equations of State

 KVALUE Selects the method for K-value calculations. Only
VLE K-value calculations are available with the
BRWS method.
ENTHALPY Selects the method for enthalpy calculation. By
(VL or V and/or L) default, both vapor and liquid enthalpies use this
method.
ENTROPY Selects the method for entropy calculation. By
(VL or V and/or L) default, both vapor and liquid entropies use this
method.
DENSITY Selects the method for density calculation. By
(VL or V and/or L) default, both liquid and vapor densities use this
method.

K-value Data (optional)

KVALUE BANK=SIMSCI or NONE or bankid
BWRS i, j, kij/ ...

Note: The BWRS statements must follow the KVALUE state-

ment.

BANK This option selects one or more banks from which to retrieve
vapor and/or liquid phase binary interaction data.
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.
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, Entropy, and Density Data (optional)

ENTHALPY BANK=SIMSCI or NONE or bankid

ENTROPY BANK=SIMSCI or NONE or bankid

DENSITY BANK=SIMSCI or NONE or bankid

BWRS i, j, kij ...

Thermodynamic Data Input Manual II-4-35

 BWRS 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 BWRS, you can
supply these parameters independently.

See above under K-value Data for format and definition of these
entries.

Water Handling Options (optional)

WATER DECANT=ON or OFF, GPSA,
SOLUBILITY=SIMSCI or KEROSENE or EOS
PROPERTY=SATURATED or STEAM
The BWRS K-value generator supports the free-water decant
option. Refer to “Free-water Decant Considerations” on page 1-31
for a description of these input options.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
Properties may be supplied that are active only when a specific
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,
see Chapter 9, “Method-specific Pure Component Data”.

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
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/50

II-4-36 Equations of State

 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
API liquid densities.
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-

1. Twu, C.H., J.E. Coon, and J. Cunningham, 1993, “An Equation of State
for Hydrogen Fluoride”, Fluid Phase Equilibria, 86, 47-62.

Thermodynamic Data Input Manual II-4-37

 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
K-values Vapor densities
Enthalpies Liquid densities (not recommended)
Entropies

Required pure component properties1

Molecular weight Acentric factor
Critical temperature Ideal vapor enthalpy
Critical volume
Suggested application ranges
Components - Only 1 hexamerizing component and no H2O
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1 Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

The METHOD Statement

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, ...

SYSTEM Selects a combination of consistent

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

II-4-38 Equations of State

 ENTROPY Selects the method for entropy calculation. By
(VL or V and/or L) default, both vapor and liquid entropies use this
method.
DENSITY (V) Selects the method for vapor density.

Note: If DENSITY=HEXAMER without the “V” qualifier is

used, liquid density will also be calculated from the HEXAMER
equation of state. This method is not recommended for this pur-
pose.

K-value Data (optional)

KVALUE BANK=SIMSCI or NONE or bankid,
HEXA(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...

Note: The HEXA statements must follow the KVALUE state-

ment.

BANK This option selects one or more banks from which to

retrieve vapor and/or liquid phase binary group
contribution data.
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.
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, Entropy, and Density Data (optional)

ENTHALPY BANK=SIMSCI or NONE or bankid

ENTROPY BANK=SIMSCI or NONE or bankid

DENSITY BANK=SIMSCI or NONE or bankid

HEXA(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...

Thermodynamic Data Input Manual II-4-39

 HEXAMER 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 HEXAMER,
you can supply these parameters independently.

See above under K-value Data for format and definition of these
entries.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
Properties may be supplied that are active only when a specific
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
see Chapter 9, “Method-specific Pure Component Data”.

Examples
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

II-4-40 Equations of State

 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
LIBID 1,IC4/ 2,NC4/ 3,NC5
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 4-33).
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.

Thermodynamic Data Input Manual II-4-41

 Table 4-9: Attributes of the LKP Method
Properties predicted by LKP
K-values Vapor densities
Enthalpies Liquid densities
Entropies

Required pure component properties1

Molecular weight Acentric factor
Critical temperature Ideal vapor enthalpy
Critical volume Specific gravity
Suggested application ranges
Temperature - Below reduced temperatures of 0.96
Components - Light hydrocarbons
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1 Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

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

SYSTEM Selects a combination of consistent

thermodynamic 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.

II-4-42 Equations of State

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

K-value Data (optional)

KVALUE(VLE or LLE or VLLE) BANK=SIMSCI or NONE or bankid
LKP i, j, kij / ...

Note: The LKP 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.
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.
SRK 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.

Thermodynamic Data Input Manual II-4-43

 Enthalpy, Entropy, and Density Data (optional)
ENTHALPY BANK= SIMSCI or NONE or bankid

ENTROPY BANK= SIMSCI or NONE or bankid

DENSITY 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.

See above under K-value Data for format and definition of these
entries.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
Properties may be supplied that are active only when a specific
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,
see Chapter 9, “Method-specific Pure Component Data”.

Examples
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.
TITLE PROB=SRK, PROJ=THERMO
DESC THERMO MANUAL PROBLEM
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,C3/ 2,NC4
THERMODYNAMIC DATA
METHOD SYSTEM=LKP
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50

II-4-44 Equations of State

 UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

4.30: For the same problem, explicitly specify LKP K-values,

enthalpies, entropies, and vapor densities. Specify API
liquid densities.
THERMODYNAMIC DATA
METHOD KVALUE=LKP, ENTHALPY=LKP, ENTROPY=LKP, &
DENSITY(V)=LKP, DENSITY(L)=API

4.31: Use the SOUR thermo methods but apply LKP to vapor
density.
THERMODYNAMIC DATA
METHOD SYSTEM=SOUR, DENSITY(V)=LKP

Thermodynamic Data Input Manual II-4-45

II-4-46 Equations of State
 Chapter 5
Liquid Activity Methods

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.

Thermodynamic Data Input Manual II-5-1

 Table 5-1: Attributes of NRTL methods
Properties predicted by NRTL methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
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 BWRS or UNIWAAL or
Acentric factor HOCV

Vapor pressure When used with POYNTING=ON

Liquid molar volume
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

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

SYSTEM Selects a combination of consistent

thermodynamic property generators. When
SYSTEM=NRTL is chosen, NRTL K-values,
LIBRARY enthalpies, IDEAL liquid densities and
IDEAL vapor densities are default.
KVALUE Selects the method for K-value calculations. Both
VLE and LLE K-value calculations are available
with the NRTL method. The VLLE option
automatically selects both. See “Vapor-liquid-
liquid Equilibrium Considerations” on page 1-34
for more details on liquid-liquid equilibrium
calculations.

II-5-2 Liquid Activity Methods

 PHI Selects the option used to calculate pure
component and mixture vapor phase fugacity
coefficients (φi). 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, BWRS and
UNIWAAL (see Chapter 4) and HOCV (the
Hayden-O’Connell method), TVIRIAL (the
Truncated Virial method) and the IDIMER
method. See “Hayden-O’Connell Vapor Fugacity”
on page 5-66, “Truncated Virial Vapor Fugacity”
on page 5-70, and “IDIMER Vapor Fugacity” on
page 5-74, 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 “Henry’s
Law for Non-condensible Components” on page
5-60 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 5-78, 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=SIMSCI or ALCOHOL or NONE or bankid,
FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR,
AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid

NRTL3(K or KCAL or KJ) i, j, bij, bji, αij / ...

and/or
NRTL(K or KCAL or KJ) i, j, aij, bij, aji, bji, αij / ...
and/or
NRTL6(K or KCAL or KJ) i, j, aij, bij, aji, bji, α’ij, β’ij / ...
and/or
NRTL8(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, α’ij, β’ij / ...
and/or
AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ...
and/or
INFINITE(tunit) i, j, temp, γioo , γjoo / ...
and/or

Thermodynamic Data Input Manual II-5-3

 MUTUAL(basis, tunit) i, j, temp, xiI, xjII / ...
and/or
IDEAL i, j / ...

Note: The NRTL3, NRTL, NRTL6, NRTL8, 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.
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 one or more banks from
which to retrieve vapor and/or liquid phase
binary interaction data.
SIMSCI Selects the SimSci standard
databank (default).
ALCOHOL Selects the Alcohol databank.
This databank contains binary
coefficients for systems with
alcohols, water and other polar
components.
NONE This option disables all data
retrieval from databanks for
interaction parameters.

II-5-4 Liquid Activity Methods

 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 5-
54, 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
NRTL and/or interaction data parameters for the NRTL liquid
NRTL6 and/or activity coefficient method. The statements can
NRTL8 be mixed in order to enter the data in the most
convenient form. The binary parameters aij, bij,
cij, aji, bji, cji, α’ij, and β’ij are related to the liquid
activity coefficients gi by the following equations:


∑ τ ji Gji xj x j G ij 
∑ xk τ kj G kj
- + ∑ --------------------  τ ij – ---------------------------
ln γ i = ------------------------
j k 
 
∑ Gki xk j ∑ k j k  G x  ∑ Gkj x k 
k k k

b c
τ ij = a ij + -----ij- + -----ij (when unit is K)
T T2

b ij c ij
τ ij = a ij + ------ - (when unit is KCAL or KJ)
- + -----------
RT 2 2
R T

Thermodynamic Data Input Manual II-5-5

 G j i = exp ( – α ji τj i ) and αij = α’ij + β’ij T

AZEOTROPE These statements are used to enter data for

and/or INFINITE binary pairs. This data will be regressed to the
and/or MUTUAL coefficients for the liquid activity method used to
generate the K-values. Multiple 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
IDEAL parameters to zero.

Data input using the NRTL3, NRTL, NRTL6, NRTL8, 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 5-
54, for further details.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
...

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”. Note that
only the vapor pressure has any direct effect on the calculation of K-
values. The vapor pressure may only be supplied globally for all
sets in the Component Data Category. Tc, Pc and the acentric factor
will have an impact on the K-values if a cubic equation of state is
chosen for vapor phase fugacities. Molar volume will have an
impact on the Poynting correction factor.

Examples
5.1: 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

II-5-6 Liquid Activity Methods

 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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.2
END

5.2: For the same problem, use NRTL K-values, IDEAL

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

UNIQUAC
Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
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.

Thermodynamic Data Input Manual II-5-7

 Table 5-2: Attributes of UNIQUAC Methods
Properties predicted by UNIQUAC methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
van der Waals area
and volume
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 BWRS or UNIWAAL or
Acentric factor HOCV
van der Waals area
and volume
Vapor pressure When used with POYNTING=ON
Liquid molar volume
van der Waals area
and volume
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

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

SYSTEM Selects a combination of consistent

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

II-5-8 Liquid Activity Methods

 KVALUE Selects the method for K-value calculations. Both
VLE and LLE K-value calculations are available
with the UNIQUAC method. The VLLE option
automatically selects both. See “Vapor-liquid-
liquid Equilibrium Considerations” on page 1-34
for more details on liquid-liquid equilibrium
calculations.
PHI Selects the option used to calculate pure
component and mixture vapor phase fugacity
coefficients (φi). 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, BWRS and UNIWAAL
(see Chapter 4) and HOCV (the Hayden-O'Connell
method), TVIRIAL (the Truncated Virial method)
and the IDIMER method. See “Hayden-O’Connell
Vapor Fugacity” on page 5-66, “Truncated Virial
Vapor Fugacity” on page 5-70, “IDIMER Vapor
Fugacity” on page 5-74, 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 “Henry’s Law for
Non-condensible Components” on page 5-60 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 5-78, 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=SIMSCI or NONE or bankid,
FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR,
AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid

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, punit, tunit) i, j, pres, temp, xi / ...
and/or

Thermodynamic Data Input Manual II-5-9

 INFINITE(tunit) i, j, temp, γioo, γjoo / ...
and/or
MUTUAL(basis, tunit) i, j, temp, xiI, xjII / ...
and/or
IDEAL i, j / ...

Note: The UNIQUAC, UNIQ4, 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.
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 one or more banks from which
to retrieve vapor and/or liquid phase binary
interaction data.
SIMSCI Selects the SimSci standard
databank (default).
NONE This option disables all data
retrieval from databanks for
interaction parameters.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.

II-5-10 Liquid Activity Methods

 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 5-54, 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.
UNIQUAC This statement allows entry of the binary
and/or interaction data parameters for the UNIQUAC
UNIQ4 liquid activity coefficient 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
γi by the following equations:
C R
ln γ i = ln γ i + ln γ i
M
ϕ Z θ ϕi
∑ Xj lj
C
ln γ i = ln -----i + --- q i ln -----i + l i – -----
xi 2 ϕi θi
j=1
 
 M M 
 θ j τ ij 
= q i  1 – ln ∑ θj τj i – ∑ ----------------------
R
ln γ i -
 M 
 
∑ θk τkj
j=1 j=1


k=1

U
τ ij = exp  – ------i-j (when unit is K)
 T

U
τ ij = exp  – ------i-j (when the unit is KCAL or KJ)
 RT

U i j = a ij + b ij T

xiqi Z
θ i = ------------------
- l j = --- ( r j – q j ) – ( r j – 1 )
M 2
∑ xiqi
i 1
xiri
ϕ i = -----------------
-
M

∑ xjrj
j 1
A wi V wi
q i = ------------------
- - , Z = 10
r i = ------------
9 15.17
2.5 ×10

Thermodynamic Data Input Manual II-5-11

 AZEOTROPE These statements are used to enter data for binary
and/or INFINITE pairs. This data will be regressed to the
and/or MUTUAL coefficients for the liquid activity method used to
generate the K-values. Multiple 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
IDEAL parameters to zero.
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).

Data input using the UNIQUAC, UNQ4, AZEOTROPE, 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 5-54, for further details.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
VANDERWAALS i, value / ...
...
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”. Note that
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.

II-5-12 Liquid Activity Methods

Examples
5.3: 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
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/25/20/5
UNIT OPERATION
FLASH UID=DRUM
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.2
END

5.4: For the same problem, use UNIQUAC K-values, IDEAL

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

UNIFAC
Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
THERMO DATA
METHOD SYSTEM=UNIFAC
STREAM DATA
. . .

Thermodynamic Data Input Manual II-5-13

 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 5-3: Attributes of UNIFAC Methods

Properties predicted by UNIFAC methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
Structural groups
Structure van der
Waals area and
volume parameters
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 BWRS or UNIWAAL or
Structural groups HOCV
Van der Waals
area and volume
Vapor pressure When used with POYNTING=ON
Liquid molar volume
Structural groups
Van der Waals
area and volume
Suggested application ranges
Pressure - up to 10 atmospheres
Temperature - 32-300 F
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

II-5-14 Liquid Activity Methods

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

SYSTEM Selects a combination of consistent

thermodynamic property generators. When
SYSTEM=UNIFAC is chosen, UNIFAC K-values,
LIBRARY enthalpies, IDEAL liquid densities and
IDEAL vapor densities are default.
KVALUE Selects the method for K-value calculations. Both
VLE and LLE K-value calculations are available
with the UNIFAC method. The VLLE option
automatically selects both. See “Vapor-liquid-
liquid Equilibrium Considerations” on page 1-34
for more details on liquid-liquid equilibrium
calculations.
PHI Selects the option used to calculate pure
component and mixture vapor phase fugacity
coefficients (φi). 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, BWRS and
UNIWAAL (see Chapter 4) and HOCV (the Hayden-
O'Connell method), TVIRIAL (the Truncated Virial
method) and the IDIMER method. See “Hayden-
O’Connell Vapor Fugacity” on page 5-66,
“Truncated Virial Vapor Fugacity” on page 5-70,
and “IDIMER Vapor Fugacity” on page 5-74, 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 “Henry’s Law for
Non-condensible Components” on page 5-60 for
further details.

Thermodynamic Data Input Manual II-5-15

 Note: A heat of mixing option, HMIX, is available for the
enthalpy method selected. See “Redlich-Kister, Gamma Heat of
Mixing” on page 5-78, 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=SIMSCI or NONE or bankid,
AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid

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

and/or
AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ...
and/or
INFINITE(tunit) i, j, temp, γioo, γjoo / ...
and/or
MUTUAL(basis, tunit) i, j, temp, xiI, xjII / ...
and/or
IDEAL i, j / ...

Note: The UNIFAC, 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.
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.

II-5-16 Liquid Activity Methods

 BANK This option selects one or more banks from which
to retrieve vapor and/or liquid phase binary
interaction data.
SIMSCI Selects the SimSci standard
databank (default).
NONE This option disables all data
retrieval from databanks for
interaction parameters.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.
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).
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 A lk and
Akl are related to the liquid activity coefficients γi
by the following equations:
C R
ln γ i = ln γ i + ln γ i

where:
Φ Φ Z Φi Φi
ln γ i = ln ------i + 1 – ------i – --- q i  ln  ------ + 1 – ------ 
C
xi xi 2   θi  θi 

Thermodynamic Data Input Manual II-5-17

 xiri xiqi
Φ i = ------------------
- , θ i = -------------------
NOC NOC

∑ xjrj ∑ xjqj
j=1 j=1

NK NK

∑ ∑ νkQ k
i i
ri = νk Rk , qi =
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

∑ νk ( ln Γk – ln Γk )
R i i
ln ( γ i ) =
k=1

 
 
  NK  NK θ Ψ 
   m mk 
ln ( Γ k ) = Q k 1 – ln ∑ θ m Ψ mk – ∑ ----------------------------
   NK 
 m = 1  n–1 


∑ θn Ψ nm

n=1

A nm
Ψ nm = exp  – --------- (where unit is K)
 T 

A nm
Ψ nm = exp  – --------- (where unit is KCAL or KJ)
 RT 

Q m Xm
θ nm = -----------------------
-
NK

∑ Qn Xn
n=1

NO C

∑ νm xj
j

j=1
X m = -------------------------------
-
NK NOC

∑ ∑ νnxj
j

n = 1j = 1

Anm = group interaction parameter for the

interaction between m and n.

II-5-18 Liquid Activity Methods

 Data are available in PRO/II databanks for many
structural groups as shown in Table 5-4.
AZEOTROPE These statements are used to enter data for binary
and/or INFINITE pairs. This data will be regressed to the
and/or MUTUAL coefficients for the liquid activity method used to
generate the K-values. Multiple 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
IDEAL parameters to zero.

Data input using the UNIQUAC, AZEOTROPE, INFINITE,

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

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
VANDERWAALS i, value / ...
...
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”. Note that
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.

Thermodynamic Data Input Manual II-5-19

 Table 5-4: Available UNIFAC Interaction Parameters

UNIFAC INTERACTION PARAMETERS

AVAILABLE IN PROII

. No interactions
V VLE interactions - ( 634)
L LLE interactions - ( 208)
* Both VLE and LLE - ( 91)
$ Both VLE and T - ( 48)
@ VLE - LLE and T - ( 103)
T TEMP dependent - ( 1)
11 --- *
20 --- @ *
21 --- V V .
27 --- . . . .
30 --- * V @ V .
40 --- V . V V V .
43 --- . . V V .V .
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 . . $ @ L V @ V . @ * $ @ . V
150 --- . . V . .
. . . V V . . . . V . V . V . . . . V . . V V V V . . .
151 --- . . . . .
. . . . . . . . . . . . . . . V . V V V . . . . . . . . V
153 --- . V V . .
. . . . . . . . . . . . . . . . . . V . . V V V . V . V . .
161 --- $ V $ V .
$ . . V $ $ $ V $ $ $ V V $ $ $ V V $ $ . $ V $ $ V . $ V V V
162 --- @ * @ V V
* V . * $ $ @ V $ @ @ . V @ @ @ * L @ @ . @ * @ @ * * @ . . . $
168 --- @ * @ V .
. . . V $ $ @ . $ @ @ V V @ @ @ * V @ @ . @ * @ @ * * $ . V V $ @
170 --- . V V V .
. . . . . . . . . V V . V V . V . V V V . V V V V V . . . . . V V V
171 --- * . * . .
L . . L . . . . . V * . V . L * . L * V . * * * . . . L . . . . * * .
203 --- . . V . .
V . . V . . . . . . V . V . . . . V V V . V V . V . . . . . . V V V . .
247 --- V . V . .
. . . V . . . . . V V . V . V V . . * * . * * V . . . . V . . V V V . . .
250 --- . V V . .
. . . . . . . . . . . . . . . V V V V V . V V . . . . . V . . . V . . . . .
251 --- . . V . .
. . . . . . . . . . . . . . . . . . V V . V V . . . . . . . . V V . . . . . .
260 --- V . V . .
. . . . V V . . . V . . . . . . . . V . . V V V . . . . . . . . V . . . . . . .
270 --- V . V . .
. . . . V V . . . . . . . . . . . . V . . V V . . . . . . . . . . V . . . . . . V
281 --- . . . . .
. . . V . . . . . . . . . . . . . . V V . V . . . . . . . . . . . . . . . . . . . .
287 --- . . V . .
. . . . . V . . V V . . . . . . . . V V . V V . . . . V . . . V . V . . . . . . . . V
290 --- . . V . .
. . . . . . . . . . . . . . . . . . V . . V . . . V . . . . . V . . . . . . . . . . V .
300 --- V . V . .
. . . . . . . . . V 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 . . . . V . V V . . . . . . . . . . .
330 --- . . . . .
. . . . . . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . . . . . . . . .
340 --- . . . . .
. . . . . . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . . . . . . . . . V
350 --- . . . . .
. . . . . . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . . . . . . . . . V V
360 --- . . . . .
. . . . . . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . . . . . . . . . V V V
385 --- L * * . .
. . . V . . * . . V * . V . . . L . * . . * * * V * L . . . . V * . . L . V V . . . . . . . . . . . .
388 --- . . V . .
. . . . . . . . . . V . V . V . V . V V . V V V V . . . . . . . V V . . . . . . . . . . . . . . . . . V
| | | | |
| | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | |
| | | | |
| | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | |
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 3 3 3 3 3 3 3
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 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 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 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
5.5: 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

II-5-20 Liquid Activity Methods

 STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/40/10
UNIT OPERATION
FLASH UID=F2
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.6: For the same problem, use UNIFAC K-values, IDEAL

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

Modifications to UNIFAC
Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
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.

Thermodynamic Data Input Manual II-5-21

 Table 5-5: Attributes of Modified UNIFAC Methods
Properties predicted by UNIFAC methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
van der Waals area and
volume
(UFT1,UFT2,UFT3 only)
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 BWRS or UNIWAAL or
Acentric factor HOCV
Van der Waals area and
volume (UFT1,UFT2,UFT3
only)
Vapor pressure When used with POYNTING=ON
Liquid molar volume
Van der Walls area and
volume (UFT1,UFT2,UFT3
only)
Suggested application ranges
Pressure - up to 10 atmospheres
Temperature - 70-300 F
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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},..

II-5-22 Liquid Activity Methods

 SYSTEM Selects a combination of consistent thermodynamic
property 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 enthalpies, IDEAL liquid
densities and IDEAL vapor densities are
default.
UFT3 When SYSTEM=UF3 is chosen, UFT3 K-
values, LIBRARY enthalpies, IDEAL liquid
densities and IDEAL vapor densities are
default.
UNFV When SYSTEM=UNFV is chosen, UNFV
K-values, LIBRARY enthalpies, IDEAL
liquid densities and IDEAL vapor
densities are default.
KVALUE Selects the method for K-value calculations. Both VLE and
LLE 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 1-34 for more details on liquid-
liquid equilibrium calculations.
PHI Selects the option used to calculate pure component and
mixture vapor phase fugacity coefficients (φi). 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, BWRS and UNIWAAL (see Chapter 4)
and HOCV (the Hayden-O'Connell method), TVIRIAL (the
Truncated Virial method) and the IDIMER method. See
“Hayden-O’Connell Vapor Fugacity” on page 5-66,
“Truncated Virial Vapor Fugacity” on page 5-70, and
“IDIMER Vapor Fugacity” on page 5-74 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 “Henry’s Law for Non-condensible
Components” on page 5-60 for further details.

Thermodynamic Data Input Manual II-5-23

 Note: A heat of mixing option, HMIX, is available for the
enthalpy method selected. See “Redlich-Kister, Gamma Heat of
Mixing” on page 5-78, for further information on the use of this
option.

K-value Data (optional)

UFT1-Lyngby modified UNIFAC

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON,
MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY,
BANK=SIMSCI or NONE or bankid,
AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid

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

and/or
UFT2-Dortmund modified UNIFAC
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON,
MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY,
BANK=SIMSCI or NONE or bankid,
AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid

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

and/or
UFT3-Modified UNIFAC
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON,
MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY,
BANK=SIMSCI or NONE or bankid,
AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid

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

and/or
UNFV-Free Volume modification
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON,
MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY,
BANK=SIMSCI or NONE or bankid,
AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid

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

and/or
AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ...
and/or
INFINITE(tunit) i, j, temp, γioo , γjoo / ...
and/or

II-5-24 Liquid Activity Methods

 MUTUAL(basis, tunit) i, j, temp, xiI, xjII / ...
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.

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 one or more banks from which to
retrieve vapor and/or liquid phase binary interaction data.
SIMSCI Selects the SimSci standard
databank (default).
NONE This option disables all data
retrieval from databanks for
interaction parameters.

Thermodynamic Data Input Manual II-5-25

 bankid This option selects a user-
created databank named
“bankid” that is created and
maintained with the LIBMGR
program.
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).
UNIFAC This statement allows entry of the group interaction data
parameters for the UNIFAC liquid activity coefficient
method. See “UNIFAC” on page 5-13 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 from:
Similar to the UNIFAC method except
T
A mk = a mk + b m k ( T – T o ) + c mk  T ln -----o + T – T o
 T 

where:
T o = 298.25K

2⁄3
c ω ω ri xi
ln γ i = ln -----i + 1 – -----i , ω i = -------------------------
xi xi NOC
2⁄3
∑ rj x j
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:

II-5-26 Liquid Activity Methods

 Similar to the UNIFAC method, except
2
A mk = a mk + b m k T + c m k T

ω ω Zq i ln Φ Φ
ln γ i = ln -----i + 1 – -----i – --------  -----------i + 1 – ------i
c
xi xi 2  θi θi 

3⁄4
ri xi
ω i = -------------------------
NOC
3⁄4
∑ 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 m k T + c m k 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 γ i = ln γ i + ln γ i + ln γi

  V˜ i 
1⁄3   ------
˜
- – 1 
FV
˜
 V i – 1   Vm 
ln γ i = 3C i ln  -------------------
⁄
- – C i  ---------------------
 V˜ m – 1
1 3
 1 – ----------- 
1
 1 ⁄ 3
 V˜ i 
NK
Vi
V˜ i = --------------------- 1
-,
∑ νk Rk
i
15.17br' i r’i = ------
Mi
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)

Thermodynamic Data Input Manual II-5-27

 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 activity method used to generate the K-values. Multiple
and/or statements may be used to enter data with different units
MUTUAL 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 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
5-54, for further details.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
VANDERWAALS i, value / ...
...
Properties may be supplied that are active only when a specific
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.

II-5-28 Liquid Activity Methods

Examples
5.7: 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
LIBID 1,DIPE/ 2,IPA/ 3,H2O

THERMO DATA
METHOD SYSTEM=UFT1
STREAM
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.8: For the same problem, use UFT2 K-values, IDEAL

enthalpies and liquid densities and SRK vapor densities..
THERMO DATA
METHOD KVALUE=UFT2, ENTHALPY=IDEAL, &
DENSITY(L)=IDEAL, DENSITY(V)=SRK

Wilson
Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
THERMO DATA
METHOD SYSTEM=WILSON
STREAM DATA
. . .

Thermodynamic Data Input Manual II-5-29

 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 5-6: Attributes of WILSON Methods

Properties predicted by WILSON methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
Liquid molar volume
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 BWRS or UNIWAAL or
Acentric factor HOCV
Liquid molar volume
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1 Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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.

II-5-30 Liquid Activity Methods

 PHI Selects the option used to calculate pure component
and mixture vapor phase fugacity coefficients (φi). 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, BWRS and
UNIWAAL (see Chapter 4) and HOCV (the Hayden-
O’Connell method), TVIRIAL (the Truncated Virial
method) and the IDIMER method. See “Hayden-
O’Connell Vapor Fugacity” on page 5-66, “Truncated
Virial Vapor Fugacity” on page 5-70, and “IDIMER
Vapor Fugacity” on page 5-74 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 “Henry’s Law for Non-
condensible Components” on page 5-60 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 5-78 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 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
AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ...
and/or
INFINITE(tunit) I, j, temp, γioo , γj oo / ...
and/or
MUTUAL(basis, tunit) i, j, temp, xiI, xjII / ...
and/or
IDEAL i, j / ...

Note: The WILSON, AZEOTROPE, INFINITE, MUTUAL and/

or IDEAL statements must follow the KVALUE statement.

Thermodynamic Data Input Manual II-5-31

 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).
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 5-54 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).
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 γi by the following
equations:
N N
xk A k i
ln γ i = 1 – ln ∑ xj Aij – ∑ ---------------------
N
-

∑ xj Akj
j=1 k=1

j 1

II-5-32 Liquid Activity Methods

 where:

Vj
L
– a ij (when unit is K)
A i j = -----L- exp  ---------
 T 
Vi

Vj
L
– a ij (when unit is KCAL or KJ)
A i j = -----L- exp  ---------
Vi RT

Ai j = a i j (when unit is NODIME)

and V Li is the liquid molar volume of component i.

AZEOTROPE These statements are used to enter data for binary
and/or pairs. These data will be regressed to the coefficients
INFINITE for 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 WILSON, AZEOTROPE, 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 5-54 for further details.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
...
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”. Note that
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.

Thermodynamic Data Input Manual II-5-33

Examples
5.9: Using the WILSON system, model a 50/40/10 mix of
DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=WILSON
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,DIPE/ 2,IPA/ 3,H2O
THERMO DATA
METHOD SYSTEM=WILSON
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/40/10
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.10: For the same problem, use WILSON K-values, IDEAL

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

Van Laar
Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
THERMO DATA
METHOD SYSTEM=VANLAAR
STREAM DATA
. . .

II-5-34 Liquid Activity Methods

 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 5-7: Attributes of VANLAAR Methods

Properties predicted by VANLAAR methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
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 BWRS or UNIWAAL or
Acentric factor HOCV

Vapor pressure When used with POYNTING=ON

Liquid molar volume
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

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

SYSTEM Selects a combination of compatible

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

Thermodynamic Data Input Manual II-5-35

 KVALUE Selects the method for K-value calculations. Both
VLE and LLE K-value calculations are available with
the VANLAAR method. The VLLE option
automatically selects both. See “Vapor-liquid-liquid
Equilibrium Considerations” on page 1-34 for more
details on liquid-liquid equilibrium calculations.
PHI Selects the option used to calculate pure
component and mixture vapor phase fugacity
coefficients (φi). 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, BWRS and UNIWAAL (see Chapter
4) and HOCV (the Hayden-O'Connell method),
TVIRIAL (the Truncated Virial method) and the
IDIMER method. See “Hayden-O’Connell Vapor
Fugacity” on page 5-66, “Truncated Virial Vapor
Fugacity” on page 5-70, and “IDIMER Vapor
Fugacity” on page 5-74 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 “Henry’s Law for
Non-condensible Components” on page 5-60 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 5-78 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, FILL=NONE or
UNIFAC or UFT1 or FLORY or REGULAR,
AZEOTROPE=SIMSCI or NONE or bankid,
WRITE=fileid

VANLAAR I, j, aij, aji / ...

and/or
AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ...
and/or
INFINITE(tunit) I, j, temp, γioo , γj oo / ...

II-5-36 Liquid Activity Methods

 and/or
MUTUAL(basis, tunit) i, j, temp, xiI, xjII / ...
and/or
IDEAL i, j / ...

Note: The VANLAAR, 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.
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.
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 5-54 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.

Thermodynamic Data Input Manual II-5-37

 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).
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 coefficients γi by the following
equations:
N N N N
1 a ij
ln γ i = ∑ a il Z l – ∑ a ij Z i Z j – ---
2 ∑ ∑ aj k -----
-Z Z
a ji j k
i=1 j=1 j = 1k = 1
j, k ≠ i

where:
a li
x l  ------
a il
Z l = -------------------------
-
N
a il
∑ xj  ----- 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,

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 5-54 for further details.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
...
Properties may be supplied that are active only when a specific
method is used. For a further description of these input parameters,

II-5-38 Liquid Activity Methods

 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
5.11: Using the VANLAAR system, model a 50/40/10 mix of
DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=VANLAAR
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,DIPE/ 2,IPA/ 3,H2O
THERMO DATA
METHOD SYSTEM=VANLAAR
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/40/10
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.12: For the same problem, use VANLAAR K-values, IDEAL

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

Thermodynamic Data Input Manual II-5-39

Margules
Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
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 5-8: Attributes of MARGULES Methods

Properties predicted by MARGULES methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
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 BWRS or UNIWAAL or
Acentric factor HOCV

Vapor pressure When used with POYNTING=ON

Liquid molar volume
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

II-5-40 Liquid Activity Methods

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

SYSTEM Selects a combination of compatible thermodynamic

property generators. When SYSTEM=MARGULES is
chosen, MARGULES 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. Both
VLE and LLE K-value calculations are available with
the Margules method. The VLLE option automatically
selects both. See “Vapor-liquid-liquid Equilibrium
Considerations” on page 1-34 for more details on
liquid-liquid equilibrium calculations.
PHI Selects the option used to calculate pure component
and mixture vapor phase fugacity coefficients (φi). 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, BWRS and
UNIWAAL (see Chapter 4) and HOCV (the Hayden-
O'Connell method) and TVIRIAL (the Truncated Virial
method). See “Hayden-O’Connell Vapor Fugacity” on
page 5-66, “Truncated Virial Vapor Fugacity” on page
5-70, and “IDIMER Vapor Fugacity” on page 5-74 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 “Henry’s Law for Non-
condensible Components” on page 5-60 for further
details.

Note: A heat of mixing option, HMIX, is available for the

enthalpy method selected. See “Henry’s Law for Non-condensible
Components” on page 5-60 for further information on the use of
this option.

Thermodynamic Data Input Manual II-5-41

 K-value Data (optional )
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON,
MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY,
FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR,
AZEOTROPE=SIMSCI or NONE or bankid, WRITE=fileid

MARGULES I, j, aij, aji, dij / ...

and/or
AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ...
and/or
INFINITE(tunit) I, j, temp, γioo , γj oo / ...
and/or
MUTUAL(basis, tunit) i, j, temp, xiI, xjII / ...
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.
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.
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 5-54 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.

II-5-42 Liquid Activity Methods

 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).
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 coefficients γi by the
following equations:
2 2
ln γi = ( 1 – x i ) [ A i + 2 ( B i – A i – D i )x i + 3D i x i ]

where:
N

Ai = ∑ xj aij
j=1

Bi = ∑ xj aji
j=1

Di = ∑ xj dij
j=1

d ij = d j i

AZEOTROPE These statements are used to enter data for binary

and/or pairs. This data will be regressed to the coefficients
INFINITE for the liquid activity method used to generate the K-
and/or values. Multiple statements may be used to enter
MUTUAL data 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 MARGULES, AZEOTROPE, 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 5-54 for further details.

Thermodynamic Data Input Manual II-5-43

 Method-specific Pure Component Properties (optional)
TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
...
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”. 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
5.13: Using the MARGULES system, model a 50/40/10 mix of
DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=MARGULES
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,DIPE/ 2,IPA/ 3,H2O
THERMO DATA
METHOD SYSTEM=MARGULES
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/40/10
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.14: For the same problem, use MARGULES K-values,

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

II-5-44 Liquid Activity Methods

Regular Solution

Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
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 5-9: Attributes of REGULAR Methods

Properties predicted by REGULAR methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
Liquid molar volume
Solubility parameter
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 BWRS or UNIWAAL or
Acentric factor HOCV
Liquid molar volume
Solubility parameter
Two liquid phase behavior
Free-water decant - Supported
VLLE - Supported
1Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Thermodynamic Data Input Manual II-5-45

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

SYSTEM Selects a combination of compatible thermodynamic

property generators. When SYSTEM=REGULAR is
chosen, REGULAR 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. Both VLE
and LLE K-value calculations are available with the
Regular method. The VLLE option automatically
selects both. See “Vapor-liquid-liquid Equilibrium
Considerations” on page 1-34 for more details on
liquid-liquid equilibrium calculations.
PHI Selects the option used to calculate pure component
and mixture vapor phase fugacity coefficients (φi). 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, BWRS and
UNIWAAL (see Chapter 4) and HOCV (the Hayden-
O'Connell method), TVIRIAL (the Truncated Virial
method) and the IDIMER method. See “Hayden-
O’Connell Vapor Fugacity” on page 5-66, “Truncated
Virial Vapor Fugacity” on page 5-70, and “IDIMER
Vapor Fugacity” on page 5-74 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 “Henry’s Law for Non-
condensible Components” on page 5-60 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 5-78 for further information on the use of this
option.

II-5-46 Liquid Activity Methods

 K-value Data (optional)
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON,
MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY

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.

The Regular Solution Method is derived from the Scatchard-Hilde-

brand equation where the liquid activity coefficient γi of a solution
is given by the following equations:
L 2
Vi ( δi – δm )
ln γ i = ------------------------------
-
RT
where:

VLi = Liquid molar volume of component i

δi = Solubility parameter of component i

and

∑ xi Vi δi
L

δ m = -------------------------
i=1
N

∑ xi Vi
L

i 1

Thermodynamic Data Input Manual II-5-47

 Method-specific Pure Component Properties (optional)
TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
SOLUPARA i, value / ...
...
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”. Note that
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
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 also
have an impact on the Poynting correction factor.

Examples
5.15: Using the REGULAR system, model a 50/40/10 mix of
DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=REGULAR
PRINT INPUT=ALL
COMPONENT DATA
LIBID 1,DIPE/ 2,IPA/ 3,H2O
THERMO DATA
METHOD SYSTEM=REGULAR
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/40/10
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

II-5-48 Liquid Activity Methods

 5.16: For the same problem, use REGULAR K-values, IDEAL
enthalpies and liquid densities and SRK vapor densities.
THERMO DATA
METHOD KVALUE=REGULAR, ENTHALPY=IDEAL, &
DENSITY(L)=IDEAL, DENSITY(V)=SRK

Flory-Huggins
Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
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.

Thermodynamic Data Input Manual II-5-49

 Table 5-10: Attributes of FLORY Methods
Properties predicted by FLORY methods
K-values

Required pure component properties1

Vapor pressure PHI=IDEAL and POYNTING=OFF
Liquid molar volume
Solubility parameter
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 BWRS or UNIWAAL or
Acentric factor HOCV
Liquid molar volume
Solubility parameter
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

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

SYSTEM Selects a combination of compatible

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

II-5-50 Liquid Activity Methods

 KVALUE Selects the method for K-value calculations. Both
VLE and LLE K-value calculations are available
with the Margules method. The VLLE option
automatically selects both. See “Vapor-liquid-
liquid Equilibrium Considerations” on page 1-34
for more details on liquid-liquid equilibrium
calculations.
PHI Selects the option used to calculate pure
component and mixture vapor phase fugacity
coefficients (φi). 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, BWRS and
UNIWAAL (see Chapter 4) and HOCV (the
Hayden-O'Connell method), TVIRIAL (the
Truncated Virial method) and the IDIMER method.
See “Hayden-O’Connell Vapor Fugacity” on page
5-66, “Truncated Virial Vapor Fugacity” on page 5-
70, and “IDIMER Vapor Fugacity” on page 5-74
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 “Henry’s Law for
Non-condensible Components” on page 5-60 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 5-78 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,
WRITE=fileid

FLORY I, j, cij / ..

Thermodynamic Data Input Manual II-5-51

 .

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.
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).
FLORY This statement allows entry of the c binary interaction
parameters for the Flory-Huggins liquid activity
coefficient method. It should be noted that χij = χji
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
ϕ
ln γ j = 1 + ln -----i – m i
xi ∑ χ i jϕ j – ∑ ∑ χ j kϕ j ϕ k
j≠i j k >j

II-5-52 Liquid Activity Methods

 where:
xi, φi, and mi are the mole fraction, volume fraction and
number of segments of component i.
The volume fraction is defined by:
xi vi
ϕ i = ---------------
-
n

∑ xivi
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 χ parameters are estimated as:
v min 2
χ jk = ---------- ( δ j – δ k )
RT

where:
δj and δk are solubility parameters of components j
and k, respectively.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
SOLUPARA i, value / ...
...
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”. Note that
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.

Thermodynamic Data Input Manual II-5-53

Examples
5.17: 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
LIBID 1,DIPE/ 2,IPA/ 3,H2O
THERMO DATA
METHOD SYSTEM=FLORY
STREAM DATA
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/40/10
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.18: For the same problem, use FLORY K-values, IDEAL

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

Filling in Missing Parameters

Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
THERMO DATA
METHOD SYSTEM=NRTL
KVALUE FILL=UNIFAC
STREAM DATA
. . .

II-5-54 Liquid Activity Methods

 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 UFT1), regular solution theory,
or Flory-Huggins. If none of these methods are possible, the pro-
gram 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 (van’t Hoff) solubility
equation, or the solubilities may be set to 1.0 (completely soluble),
or solvents missing solubility data may be ignored in the solubility
calculation.

Table 5-11: Attributes of the FILL Option

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

Required pure component properties1

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
1 Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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
...

Thermodynamic Data Input Manual II-5-55

 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 UFT1 or REGULAR or
FLORY,
AZEOTROPE=SIMSCI or NONE or bankid
or
KVALUE(LLE) FILL=NONE or UNIFAC 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 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 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.

II-5-56 Liquid Activity Methods

 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.

Thermodynamic Data Input Manual II-5-57

 Table 5-12: Data Estimation Options
KVALUE( ) DESCRIPTION
FILL=
NONE No Estimates For Missing Data.
UNIFAC VLE, LLE UNIFAC group contribution method.

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 van’t 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
5.19: Using the VLLE NRTL liquid activity method, and the
Henry’s 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

II-5-58 Liquid Activity Methods

 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
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=10/50/20/10/7/3
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-5-59

Henry’s 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 5-13: Attributes of the Henry’s Law Option

Properties predicted by HENRY
K-values

Required pure component properties1

Vapor pressure
Suggested application ranges
Components - Supercritical gases, trace organics in
water
Two liquid phase behavior
Free-water decant - Not supported
VLLE - The HENRY option only calculates gas
solubilities. However, VLLE methods
may also be used.
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

II-5-60 Liquid Activity Methods

 Input Description
The METHOD Statement
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
UFT2 or UFT3 or UNFV or WILSON or VANLAAR or
MARGULES or REGULAR or FLORY,
HENRY, . . .

SYSTEM A liquid activity method system must be chosen if

the HENRY option is to be used.
KVALUE Selects the method for K-value calculations. Only
liquid activity methods can be used with the
HENRY option.
HENRY This option selects Henry’s Law data (either user-
supplied or from databanks) to model dissolved
gases in a liquid solution. This option is only
available when using a liquid activity method for
K-value calculations. Table 5-14 shows some of
the binary gas-solvent pairs available in PRO/II.
Some additional Henry’s Law data for
hydrofluorocarbons (HFCs) and
chlorofluorocarbons (CFCs) are also available in
the databanks.

Thermodynamic Data Input Manual II-5-61

Table 5-14: Henry’s Law Package Available Pairs
Gas Components

Hydrogen Chloride
Carbon Monoxide

Hydrogen Sulfide

Cartoon Disulfide
Carbon Dioxide
Liquid

Sulfur Dioxide
Nitrous Oxide

Methanethiol
Hydrogen

Propylene
Isobutane
Ammonia

Acetylene

Ethandiol
N-butane
Nitrogen

Methane

Ethylene
Components

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

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

II-5-62 Liquid Activity Methods

Table 5-14: Henry’s Law Package Available Pairs
Gas Components

Hydrogen Chloride
Carbon Monoxide

Hydrogen Sulfide

Cartoon Disulfide
Carbon Dioxide
Liquid

Sulfur Dioxide
Nitrous Oxide

Methanethiol
Hydrogen

Propylene
Isobutane
Ammonia

Acetylene

Ethandiol
N-butane
Methane
Nitrogen

Ethylene
Components

Propane
Oxygen
Helium

Ethane
Argon
2-4 dimethylpentane X X X X
3-methylhexane X X X X
n-heptane X X X X X X
2-4- dimethylhexane X X X X

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
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-benzene X
9,10 dihydrophenanthrene X
Tetralin X
2-ethylanthracene X
9-methylanthracene X

Thermodynamic Data Input Manual II-5-63

Table 5-14: Henry’s Law Package Available Pairs
Gas Components

Hydrogen Chloride
Carbon Monoxide

Hydrogen Sulfide

Cartoon Disulfide
Carbon Dioxide
Liquid

Sulfur Dioxide
Nitrous Oxide

Methanethiol
Hydrogen

Propylene
Isobutane
Ammonia

Acetylene

Ethandiol
N-butane
Methane
Nitrogen

Ethylene
Components

Propane
Oxygen
Helium

Ethane
Argon
Hydrogen fluoride X X X
Acetone X X X X X X
Methyl ethyl ketone X X X X
Methyl n-butyl ketone X
Methyl propyl ketone X
n-methyl-2-pyrrolidone X X X X X X
Quinoline X X
Sulfolane X X X X
Hydrogen chloride X
Ammonia X X
Chloride X

Henry’s Law Data

HENRY BANK=SIMSCI or NONE or bankid
SOLUTE i, j, ...
HENDATA(punit, tunit) i, l, C1, C2, C3, C4 / ...

BANK This option selects one or more databanks from which

to retrieve Henry’s Law data. Options available are:
SIMSCI Selects the SIMSCI standard
databank (default).
NONE This option disables all data retrieval
from databanks for Henry’s Law data.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.
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 Henry’s
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.

II-5-64 Liquid Activity Methods

 HENDATA This statement allows entry of the Henry coefficients for
solute i in solvent l. The coefficients C1, C2, C3, and C4
are related to the Henry’s Law constant Hi (and the K-
value) by the following equations for one or more
solutes in a pure solvent:

C
ln ( H i ) = C 1 + -----2- + C 3 ln ( T ) + C 4 ( P )
T

and H
K i = -----i
P

For a mixture of solvents, the following mixing rules are

used for determining Hi,mix and Ki:
N

ln ( H i, m ix ) = ∑ xl ln ( Hi, l )
l=1

and H
K i = -----i
P

Method-specific Pure Component Properties (optional)

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”.

Thermodynamic Data Input Manual II-5-65

Examples
5.20: Using the NRTL liquid activity method, and the Henry’s
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
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=2/3/70/25
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Hayden-O’Connell 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
. . .

II-5-66 Liquid Activity Methods

 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 5-15: Attributes of the HOCV Vapor Fugacity Method

Properties predicted by HOCV
Vapor fugacities Hayden-O’Connell Vapor Fugacity:
vapor enthalpies

Required pure component properties1

Critical temperature PHI=HOCV
Critical pressure
van der Waals area and
volume
Dipole moment
Radius of gyration
Suggested application ranges
Components - Carboxylic acids, polar components
Two liquid phase behavior
Free-water decant - Not supported
VLLE - HOCV only calculates vapor phase
properties, but VLLE methods may be used
with HOCV methods.
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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, PHI=HOCV,
ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV,
DENSITY(V)=HOCV, . . .
or
METHOD KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or
UFT2 or UFT3 or UNFV or WILSON or VANLAAR or
MARGULES or REGULAR or FLORY, PHI=HOCV,
ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV,
DENSITY(V)=HOCV, . . .

Thermodynamic Data Input Manual II-5-67

 SYSTEM A liquid activity method system must be chosen if the
HOCV method is to be used.
KVALUE Selects the method for K-value calculations. Only liquid
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)

K-value Data (optional)

KVALUE POYNTING=ON or OFF, MOLVOL=STANDARD
or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE
or bankid, FILL=NONE or UNIFAC or UFT1 or FLORY
or REGULAR.

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.

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.

II-5-68 Liquid Activity Methods

 BANK This option selects one or more databanks from which
to retrieve vapor phase binary interaction data.
SIMSCI Selects the SIMSCI standard
databank (default).
NONE This option disables all data retrieval
from databanks for interaction
parameters.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.
HOCV This statement supplies interaction data for the
Hayden-O’Connell 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.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
VANDERWAALS i, value / ...
DIPOLE(unit) i, value / ...
RADIUS i, value / ...
...
Properties may be supplied that are active only when a specific
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”.

Thermodynamic Data Input Manual II-5-69

Examples
5.21: 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
METHOD SYSTEM=NRTL, PHI=HOCV, &
ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV, &
DENSITY(V)=HOCV
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.22: For the same problem, use HOCV for vapor fugacities and
SRK for vapor enthalpies, entropies and densities. Specify
API liquid densities.
THERMODYNAMIC DATA
METHOD SYSTEM=NRTL, PHI=HOCV, &
ENTHALPY(V)=SRK, ENTROPY(V)=SRK, &
DENSITY(V)=HOCV, DENSITY(L)=API

Truncated Virial Vapor Fugacity

Typical Usage

...
COMPONENT DATA
LIBID 1, ACETIC/ 2, ACRYLIC/ 3, H2O
THERMO DATA
METHOD SYSTEM=NRTL, PHI=TVIRIAL
STREAM DATA
. . .

II-5-70 Liquid Activity Methods

 General Information
The TVIRIAL method predicts vapor fugacities. It is 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 TVIRIAL method.

Table 5-16: Attributes of the TVIRIAL Vapor Fugacity Method

Properties predicted by HOCV
Vapor fugacities

Required pure component properties1

Critical temperature Acentric factor
Critical pressure Dipole moment
Critical volume
Suggested application ranges
Components - Carboxylic acids
Two liquid phase behavior
Free-water decant - Not supported
VLLE - TVIRIAL only calculates vapor phase
properties, but VLLE methods may be used
with TVIRIAL methods.
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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, PHI=TVIRIAL
or
METHOD KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or
UFT2 or UFT3 or UNFV or WILSON or VANLAAR or
MARGULES or REGULAR or FLORY, PHI=TVIRIAL

SYSTEM A liquid activity method system must be chosen if

the TVIRIAL method is to be used.
KVALUE Selects the method for K-value calculations. Only
liquid activity methods can be used with the
TVIRIAL method.

Thermodynamic Data Input Manual II-5-71

 PHI Selects the TVIRIAL method for vapor phase
fugacities.

K-value Data (optional)

KVALUE POYNTING=ON or OFF, MOLVOL=STANDARD
or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE
or bankid, FILL=NONE or UNIFAC or UFT1 or FLORY
or REGULAR.

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.

Vapor Fugacity Data

PHI
TVIRIAL i, ηi

Note: The TVIRIAL statements must follow the PHI statement.

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. ηi is the Truncated Virial
Coefficient for component i.

II-5-72 Liquid Activity Methods

 Method-specific Pure Component Properties (optional)
TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
DIPOLE(unit) i, value / ...
...
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
5.23: 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
PROP STREAM=1, TEMP=115, PRES=5, &
COMP=75/25
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.24: 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, &
DENSITY(V)=SRK, DENSITY(L)=API

Thermodynamic Data Input Manual II-5-73

IDIMER Vapor Fugacity
Typical Usage

...
COMPONENT DATA
LIBID 1, ACETIC/ 2, ACRYLIC/ 3, H2O
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-
tems where dimers form in the vapor phase, e.g., carboxylic acid
systems. A liquid activity method must be used in conjunction with
the IDIMER method.

Table 5-17: Attributes of the IDIMER Vapor Fugacity Method

Properties predicted by HOCV
Vapor fugacities Vapor densities
vapor enthalpies Vapor entropies

Required pure component properties1

None
Suggested application ranges
Components - Carboxylic acids, polar components
Two liquid phase behavior
Free-water decant - Not supported
VLLE - IDIMER only calculates vapor phase
properties, but VLLE methods may be used
with IDIMER methods.
1 Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

II-5-74 Liquid Activity Methods

 Input Description
The METHOD Statement
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, PHI=IDIMER,
ENTHALPY(V)=IDIMER, ENTROPY(V)=IDIMER,
DENSITY(V)=IDIMER, . . .
or
METHOD KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or
UFT2 or UFT3 or UNFV or WILSON or VANLAAR or
MARGULES or REGULAR or FLORY, PHI=IDIMER,
ENTHALPY(V)=IDIMER, ENTROPY(V)=IDIMER,
DENSITY(V)=IDIMER, . . .

SYSTEM A liquid activity method system must be chosen if

the IDIMER method is to be used.
KVALUE Selects the method for K-value calculations. Only
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
ENTHALPY(V) and/or densities.
and/or
ENTROPY(V)
and/or
DENSITY(V)

K-value Data (optional)

KVALUE POYNTING=ON or OFF, MOLVOL=STANDARD
or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE
or bankid, FILL=NONE or UNIFAC or UFT1 or FLORY
or REGULAR.

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).

Thermodynamic Data Input Manual II-5-75

 RACKETT Selects the Rackett liquid density
method.
RCK2 Selects the Rackett 2 liquid density
method.
LIBRARY Selects the LIBRARY liquid density
method.

Vapor Fugacity Data

PHI BANK=SIMSCI or NONE or bankid
IDIMER(tunit, punit, log or ln)i, i, Aii, Bii/ i, j, A ij, B ij/ . . .

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.
SIMSCI Selects the SIMSCI standard
databank (default).
NONE This option disables all data retrieval
from databanks for interaction
parameters.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.
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(tunit, punit, log or ln) i, i, Aii, B ii/ 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.

II-5-76 Liquid Activity Methods

 See above under Vapor Fugacity Data for format and definition of
these entries.

Examples
5.25: 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
PROP STREAM=1, TEMP=100, PRES=700, &
COMP=0.477/0.094/0.729
UNIT OPERATION
FLASH UID=FL1
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

Thermodynamic Data Input Manual II-5-77

Redlich-Kister, Gamma Heat of Mixing
Typical Usage

...
COMPONENT DATA
LIBID 1, IPA/ 2, H2O/ 3, CH
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 5-18: Attributes of the Redlich-Kister, Gamma Heat of Mixing

Properties predicted by RK1, RK2, GAMMA
Liquid enthalpy heat of mixing corrections

Required pure component properties

None
Two liquid phase behavior
Free-water decant - N/A
VLLE - N/A

Input Description
The METHOD Statement
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
or

II-5-78 Liquid Activity Methods

 METHOD KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or
UFT2 or UFT3 or UNFV or WILSON or VANLAAR or
MARGULES or REGULAR or FLORY, . . . ,
ENTHALPY(L)=IDEAL, . . .

SYSTEM A liquid activity method system must be chosen if

the Gamma method is to be used.
KVALUE Selects the method for K-value calculations. Only
liquid 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
ENTHALPY BANK=SIMSCI or NONE or bankid,
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/ . . .

BANK This option selects one or more databanks from which

to retrieve vapor phase binary interaction data.
SIMSCI Selects the SIMSCI standard
databank (default).
NONE This option disables all data retrieval
from databanks for interaction
parameters.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.
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 This option selects different
or formulations of the Redlich-Kister
RK2 correlation.

Thermodynamic Data Input Manual II-5-79

 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
or interaction parameters for the Redlich-Kister heat of
RK2 mixing correlation methods RK1 and RK2. The
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
∑ ∑ xi xj ( ai j + bij X + c i j X
H 2 3 4 5 6 7
---------- = --- + d ij X + e i jX + f i j X + g ij X + h i j X )
RT T
i j

when unit is KCAL or KJ:

EX
1
∑ ∑ xi x j ( aij + b ij X + c i j X
H 2 3 4 5 6 7
---------- = ------- + d ij X + e i j X + f i j X + g ij X + h i j X )
RT RT
i j

where
X = x i – xj (form 1 of Redlich-Kister)

xi – xj (form 2 of Redlich-Kister)
X = --------------
xi + x j

II-5-80 Liquid Activity Methods

Examples
5.26: 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
ENTHALPY(L) HMIX=RK1
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

5.27: For the same problem, use TVIRIAL for vapor fugacities
and specify API liquid densities.
THERMODYNAMIC DATA
METHOD SYSTEM=NRTL, PHI=TVIRIAL, DENSITY(L)=API
ENTHALPY(L) HMIX=RK1

Thermodynamic Data Input Manual II-5-81

II-5-82 Liquid Activity Methods
 Chapter 6
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 involv-

ing alcohols, especially for azeotropic distillation common in alco-
hol dehydration plants. Refer to the PRO/II Reference Manual for
information.

Thermodynamic Data Input Manual II-6-1

 Table 6-1: Attributes of the ALCOHOL Package
Properties predicted by the ALCOHOL method
K-values

Required pure component properties1

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 BWRS or UNIWAAL
Acentric factor
Vapor pressure When used with POYNTING=ON
Liquid molar volume
Suggested application ranges
Pressure - up to 1500 psia
Temperature - 122-230 F (H2O-Alcohol),
150-230 F (Other systems)
Components - Alcohols, water, other polar components
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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}, ...

II-6-2 Special Packages

 SYSTEM Selects a combination of consistent thermodynamic
property 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.
KVALUE Selects the method for K-value calculations. Both VLE
and LLE K-value calculations are available with the
ALCOHOL package. The VLLE option automatically
selects both. See “Vapor-liquid-liquid Equilibrium
Considerations” on page 1-34 for more details on liquid-
liquid equilibrium calculations.
PHI Selects the option used to calculate pure component and
mixture vapor phase fugacity coefficients (φi). 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, BWRS and UNIWAAL (see
Chapter 4) and HOCV (the Hayden-O'Connell method),
TVIRIAL (the Truncated Virial method) and the IDIMER
method. See “Hayden-O’Connell Vapor Fugacity” on
page 5-66; “Truncated Virial Vapor Fugacity” on page 5-
70; and “IDIMER Vapor Fugacity” on page 5-74 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 “Henry’s Law for Non-condensible
Components” on page 5-60 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 5-78 for further information on the use of this
option.

Thermodynamic Data Input Manual II-6-3

 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 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, α’ij, β’ij /...
and/or
NRTL8(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, α’ij, β’ij/...
and/or
AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ...
and/or
INFINITE(tunit) i, j, temp, γioo, γjoo / ...
and/or
MUTUAL(basis, tunit) i, j, temp, xiI, xiII / ...
and/or
IDEAL i, j/ ...

Note: The NRTL3, NRTL, NRTL6, NRTL8, 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.
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.

II-6-4 Special Packages

 BANK This option selects the alcohol databank from which to
retrieve vapor and/or liquid phase binary interaction
data.
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 6-2 for the
components available in this databank and
Table 6-3 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.
NONE This option disables all data retrieval from
databanks for interaction parameters.
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 5-54 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).

Thermodynamic Data Input Manual II-6-5

 NRTL3 This statement allows entry of the binary interaction
and/or data parameters for the NRTL K-value method used in
NRTL the ALCOHOL package. The statements can be mixed in
and/or order to enter the data in the most convenient form. The
NRTL6 binary parameters aij, bij, cij, aji, bji, cji, α’ij and β’ij are
and/or related to the liquid activity coefficients γi by the
NRTL8 following equations:

∑ τ ji Xj Gi j 
∑ xk τ kj G kj
- + ∑ ---------------------  τ ij – ---------------------------
In γ i = --------------------
j k 
 
∑ Gki Xk j ∑ Gk j Xk  ∑ G kj X k 
k k k
b C
τ ij = a ij + -----ij- + ------i-j
T T2 (when unit is K)

b ij C ij
τ ij = a ij + ------
- + -----------
-
RT R 2 T 2 (when unit is KCAL or KJ)

G j i = exp ( – φγiτj i ), φγi = a' ji + β' ji T

AZEOTROPE These statements are used to enter data for binary pairs.
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 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, AZEO-

TROPE, INFINITE, MUTUAL and IDEAL statements are used in
preference to any data retrieved from the databanks or estimated
using FILL options. See “Filling in Missing Parameters” on page 5-
54 for further details.

II-6-6 Special Packages

 Enthalpy, Entropy, and Density Data (optional)
ENTHALPY(V) BANK=SIMSCI or NONE or bankid
ALPHA=SIMSCI or ACENTRIC or bankid

ENTROPY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

DENSITY(V) BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC 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).
NONE This option disables all data retrieval from
databanks for interaction parameters.
bankid This option selects a user-created databank
named “bankid” that is created and
maintained with 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 original Soave acentric form for alpha
(default).
bankid This option selects a user-created databank
named “bankid” that is created and
maintained with the LIBMGR program.

Note: The SRKM and SAxx statements may follow each

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

Thermodynamic Data Input Manual II-6-7

 Table 6-2: ALCOHOL Databank Components
Component Formula LIBID
Water H2O H2O
Alcohols
Methanol CH4O MEOH
Ethanol C2H6O ETOH
N-propanol C3H8O NPRA
Isopropanol C3H8O IPA
N-butanol C4H10O IBA
Isobutanol C4H10O SBA
Sec-butanol C5H12O TBA
Tert-butanol C5H12O 3M1BA
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 Ketone C4H8O MEK
Acetone C3H6O DMK
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

II-6-8 Special Packages

 Table 6-2: ALCOHOL Databank Components
Component Formula LIBID
Hydrocarbons
Isopentane C5H12 IC5
N-Pentane C5H12 NC5
Cyclopentane C5H10 CP
2 Methylpentane C6H14 2MP
1-Hexene C6H12 1HEXENE
N-Hexane C6H14 NC6
Methylcyclopentane C6H12 MCP
Benzene C6H6 C6H6
Cyclohexane C6H12 CH
2-4 Dimethylpentane C7H16 24DMP
3-Methylhexane CYH16 3MHX
1-Trans-2-Dimethyl-
cyclopentane C7H14 1T2MCP
N-Heptane C7H16 NC7
Methylcyclohexane C7H14 MCH
Toluene C7H8 TOLU
2-4 Dimethylhexane C8H18 24DMHX
1-Trans-2-Cis-4-Tri-
Methylcyclopentane C8H16 1T2C4MCP

Thermodynamic Data Input Manual II-6-9

 Table 6-3: Binary Interaction Data
Nitrogen X
Nitrogen
Oxygen XX X
Dioxide XX
CarbonOxygen XX X
Carbon Dioxide XX
Isopentane XX X
X X
Isopentane
n-Pentane XX XX X
X X
X X
n-Pentane XX
2-Methylpentane XX X
X X
X XX X
n-Hexane XX
2-Methylpentane XX X
X X
X XX XX X
n-Hexane XX
2,4,-Dimethylpentane XX X
X X
X XX XX X
X X
2,4,-Dimethylpentane
3-Methylhexane XX XX X
X X
X XX XX X
X X
X X
3-Methylhexane
n-Heptane XX XX X
X X
X XX XX X
X X
X XX X
n-Heptane XX
2,4-Dimethylhexane XX X
X X
X XX XX X
X X
X XX XX X
2,4-Dimethylhexane
Cyclopentane XX XX X
X X
X XX XX X
X X
X XX XX X
X X
Cyclopentane XX
Methylcyclopentane XX X
X X
X XX XX X
X X
X XX XX X
X X
X X
Cyclohexane XX
Methylcyclopentane XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX X
Cyclohexane XX
1-T-2DM-Cyclopentane XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX XX X
1-T-2DM-Cyclopentane
Methylcyclohexane XX XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX XX XX X
Methylcyclohexane
1-T,2-C-4 TMCP XX XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX XX XX XX X
1-T,2-C-4 TMCP XX
1-Hexene XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX XX XX XX XX X
1-Hexene
Benzene XX XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX XX XX XX XX XX X
Benzene
Toluene XX XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX XX XX XX XX XX XX X
Toluene
DIPE XX XX X
X X
X X X X X X X X X X X X X X X X X
DEE XX
DIPE XX X
X X
X
DEE
DME XX XX X
X X
X X
AceticDMEAcid XX XX X
X X
X X XX
Acetic Acid
Formic Acid XX XX X
X X
X XX X X
Formic MEK Acid XX XX X
X X
X XX X XX
Acetone XX
MEK XX X
X X
X XX XX XX X
EthylAcetone
Acetate XX XX X
X X
X XX XX XX XX X
Ethyl Formate
Mrthyl Acetate XX XX X
X X
X X X X XX XX
Methyl Formate XX
Acetaldehyde XX X
X X
X X X XX XX X
Acetaldehyde
Sulfolane XX XX X
X X
X X X X X X X X X X X X X X X X X X X X X X X
Sulfolane XX
n-Pentanol XX X
X X
X X X X X X X X X X X X X X X X X X
n-Pentanol XX
3-M-1-Butanol XX X
X X
X X
n-Butanol XX
3-M-1-Butanol XX X
X X
X XX X
n-Butanol X
Isobutanol X X X X X X X X X XX XX X
secIsobutanol
-Butanol X X X X X X X X X X XX XX XX X
sec
tert-Butanol
-Butanol XX XX X
X X
X X X X XX XX XX XX X
tert -Butanol XX
n-Propanol XX X
X X
X X X X XX XX XX XX XX X
n-Propanol XX
Isopropanol XX X
X X
X X X X X X X X X X XX XX XX XX XX XX X
Isopropanol
Ethanol XX XX X
X X
X X X X X X X X X X X XX X X X X XX X XX XX XX XX XX XX X XX XX XX XX XX XX XX XX X
Methaol XX
Ethanol XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX XX XX XX XX XX XX XX XX XX XX X XX XX XX XX XX XX XX XX XX XX XX XX XX XX X
Water XX
Methanol XX X
X X
X XX XX X
X X
X XX XX X
X X
X XX XX XX XX XX XX XX XX XX XX XX XX XX X XX XX XX X XX X XX XX XX XX XX XX XX XX XX X
Water X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
MOLVOL(unit) i, value / ...
VP
...
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”. 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

II-6-10 Special Packages

 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
6.1: 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
PROP STREAM=1,TEMP=100,PRES=100, &
COMP=50/25/20/5
UNIT OPERATION
FLASH UID=FL2B
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.2
END

6.2: 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

Thermodynamic Data Input Manual II-6-11

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 6-4: Attributes of the GLYCOL Package

Properties predicted by GLYCOL method
K-values

Required pure component properties1

Critical temperature Acentric factor
Critical pressure
Suggested application ranges
Pressure - up to 2000 psia
Temperature - 80-400 F
Components - A glycol or water must be present
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

II-6-12 Special Packages

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

SYSTEM Selects a combination of consistent

thermodynamic property 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 1-34 for more details on
liquid-liquid equilibrium calculations.

K-value Data (optional)

KVALUE(VLE or LLE or VLLE)
BANK=GLYCOL and SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC 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.

Thermodynamic Data Input Manual II-6-13

 BANK This option selects the GLYCOL databank from which
to retrieve vapor and/or liquid phase binary interaction
data.
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 6-5 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.
NONE This option disables all data retrieval
from databanks for interaction
parameters.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained 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).
ACENTRIC Uses original Soave acentric form
for alpha (default).
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.

II-6-14 Special Packages

 SRKM This statement inputs binary interaction parameters
and/or and alpha formulation data for the SRKM method used
SA01 to SA11 to calculate K-values for the GLYCOL package. See
“Modified Soave-Redlich-Kwong and Peng-Robinson”
on page 4-13 for further details.

Enthalpy, Entropy, and Density Data (optional)

ENTHALPY BANK=SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC or bankid

ENTROPY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

DENSITY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

SRKM(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...

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

All these interaction parameters and alpha formulations may be
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.

See above under K-value Data for format and definition of these
entries.
Table 6-5: Components Available for GLYCOL Package
Gas Component Formula LIBID
Hydrogen H2 H2
Nitrogen N2 N2
Oxygen O2 O2
Carbon Dioxide CO2 CO2
Hydrogen Sulfide H2S H2S
Methane CH4 C1
Ethane C2H6 C2
Propane C3H8 C3
Isobutane C4H10 IC4
N-butane C4H10 NC4

Thermodynamic Data Input Manual II-6-15

 Table 6-5: Components Available for GLYCOL Package
Liquid Components Formula LIBID
Isopentane C5H12 IC5
Pentane C5H12 NC5
Hexane C6H14 NC6
Heptane C7H16 NC7
Cyclohexane C6H12 CH
Methylcyclohexane C7H14 MCH
Ethylcyclohexane C8H16 ECH
Benzene C6H6 BNZN
Toluene C7H8 TOLU
O-xylene C8H10 OXYL
M-xylene C8H10 MXYL
P-xylene C8H10 PXYL
Ethylbenzene C8H10 EBZN
Ethylene Glycol C2H6O2 EG
Diethylene Glycol C4H10O3 DEG
Triethylene Glycol C6H14O4 TEG
Water H2O H2O

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
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
6.3: 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
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/25/20/5

II-6-16 Special Packages

 UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC TEMP=100
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.2
END

6.4: 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
behavior. This method does not support free water decant. This sys-
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.

Thermodynamic Data Input Manual II-6-17

 Table 6-6: Attributes of the SOUR Package
Properties predicted by SOUR method
K-values

Required pure component properties1

Critical temperature
Critical pressure
Acentric factor
Suggested application ranges
Pressure - up to 1500 psia
Temperature - 68-300 F
Components - xwt wt wt
NH3 + x CO2+ x H2S< 0.30
(H2O, NH3, and one acid gas required)
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1 Automatically
supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
METHOD SYSTEM(VLE or VLLE)=SOUR,...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=SOUR,
ENTHALPY(V)=SRKM, ENTHALPY(L)=IDEAL,
ENTROPY=SRKM, DENSITY(V)=SRKM,
DENSITY(L)=IDEAL, ...

SYSTEM Selects a combination of consistent thermodynamic

property 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.
KVALUE Selects the method for K-value calculations. Both VLE
and VLLE K-value calculations are available with the
SOUR package.

II-6-18 Special Packages

 Enthalpy, Entropy, and Density Data (optional)
ENTHALPY BANK=SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC or bankid

ENTROPY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

DENSITY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

SRKM(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...

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

All these interaction parameters and alpha formulations may be
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.
SIMSCI Selects the SimSci standard databank
(default).
NONE This option disables all data retrieval
from databanks for interaction
parameters.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained 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).
ACENTRIC Uses original Soave acentric form for
alpha (default).
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.

Thermodynamic Data Input Manual II-6-19

 SRKM This statement inputs binary interaction parameters
and/or and alpha formulation data for the SRKM method used
SA01 to SA11 to 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.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
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
6.5: 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
PROP STREAM=1, TEMP=100, PRES=100, &
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

6.6: 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

II-6-20 Special Packages

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 6-17).
Table 6-7: Attributes of GPSWATER Package
Properties predicted by GPSWATER method
K-values

Required pure component properties1

Critical temperature Acentric factor
Critical pressure
Suggested application ranges
Pressure - up to 2000 psia
Temperature - 68-600 F
Components - xwt
NH3 < 0.40, PCO2+ PH2S < 1200 psia
(H2O, NH3, H2S, and CO2 required)
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Thermodynamic Data Input Manual II-6-21

 Input Description
The METHOD Statement
METHOD SYSTEM(VLE or VLLE)=GPSWATER,...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=GPSWATER,
ENTHALPY(V)=SRKM, ENTHALPY(L)=IDEAL,
ENTROPY=SRKM, DENSITY(V)=SRKM,
DENSITY(L)=IDEAL, ...

SYSTEM Selects a combination of consistent thermodynamic

property 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.
KVALUE Selects the method for K-value calculations. Both VLE
and VLLE K-value calculations are available with the
GPSWATER package.

Enthalpy, Entropy, and Density Data (optional)

ENTHALPY BANK=SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC or bankid

ENTROPY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

DENSITY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

SRKM(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...

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

All these interaction parameters and alpha formulations may be
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.

II-6-22 Special Packages

 BANK This option selects the databank from which to retrieve
vapor and/or liquid phase binary interaction data.
SIMSCI Selects the SimSci standard databank
(default).
NONE This option disables all data retrieval
from databanks for interaction
parameters.
bankid This option selects a user-created
databank named “bankid” that is
created and maintained 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).
ACENTRIC Uses original Soave acentric form for
alpha (default).
bankid This option selects a user-created
databank named “bankid” that is
created and maintained with the
LIBMGR program.
SRKM This statement inputs binary interaction parameters
and/or and alpha formulation data for the SRKM method used
SA01 to SA11 to 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.

Method-specific Pure Component Properties (optional)

TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
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”.

Thermodynamic Data Input Manual II-6-23

Examples
6.7: 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
METHOD SYSTEM=GPSWATER
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
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.2
END

6.8: For the same problem, supply SRKM enthalpy interaction

data for component pairs 1-2 and 1-4.
THERMO DATA
METHOD SYSTEM=GPSWATER
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,H2O/ 2, H2S/ 3, MEA/ 4, C1
THERMO DATA
METHOD SYSTEM=AMINE
STREAM DATA
. . .

II-6-24 Special Packages

 General Information
The AMINE package is used to predict VLE and/or LLE phase
behavior. This method does not support free water decant. This sys-
tem uses the Kent-Eisenberg model for reaction equilibria with
MEA, DEA, and DIPA and an additional residence time correction
for MDEA and 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.

Table 6-8: Attributes of the AMINE Package

Properties predicted by the AMINE method
K-values

Required pure component properties1

Critical temperature Acentric factor
Critical pressure
Suggested application ranges
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)
Two liquid phase behavior
Free-water decant - Not supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Thermodynamic Data Input Manual II-6-25

 Input Description
The METHOD Statement
METHOD SYSTEM(VLE or VLLE)=AMINE,...
or
METHOD KVALUE(VLE and/or LLE or VLLE)=AMINE,
ENTHALPY(V)=SRKM, ENTHALPY(L)=AMINE,
ENTROPY=SRKM, DENSITY(V)=SRKM,
DENSITY(L)=IDEAL, ...

SYSTEM Selects a combination of consistent thermodynamic

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.
KVALUE Selects the method for K-value calculations. Both VLE
and VLLE K-value calculations are available with the
AMINE package.

K-value Data (optional)

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.

II-6-26 Special Packages

 Enthalpy, Entropy, and Density Data (optional)
ENTHALPY BANK=SIMSCI or NONE or bankid,
ALPHA=SIMSCI or ACENTRIC or bankid

ENTROPY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

DENSITY BANK=SIMSCI or NONE or bankid,

ALPHA=SIMSCI or ACENTRIC or bankid

SRKM(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...

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

All these interaction parameters and alpha formulations may be
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 and/or liquid phase binary interaction data.
SIMSCI Selects the SimSci standard databank
(default).
NONE This option disables all data retrieval from
databanks for interaction parameters.
bankid This option selects a user-created databank
named “bankid” that is created and
maintained 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).
ACENTRIC Uses original Soave acentric form for alpha
(default).
bankid This option selects a user-created databank
named “bankid” that is created and
maintained with the LIBMGR program.
SRKM This statement inputs binary interaction parameters and
and/or alpha formulation data for the SRKM method used to
SA01 to calculate vapor enthalpies, vapor densities and liquid and
SA11 vapor entropies for the AMINE package. See “Modified
Soave-Redlich-Kwong and Peng-Robinson” on page 4-13
for further details.

Thermodynamic Data Input Manual II-6-27

 Method-specific Pure Component Properties (optional)
TC(unit) i, value / ...
PC(unit) i, value / ...
ACENTRIC i, value / ...
...
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
6.9: 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
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=30/5/10/5/50
UNIT OPERATION
FLASH UID=FL3
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.2
END

6.10: 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

II-6-28 Special Packages

User-added Subroutines
Typical Usage

...
COMPONENT DATA
LIBID 1,IC4/ 2, NC4/ 3, H2O
THERMO DATA
METHOD KVALUE=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 6-9: Attributes of User-Added Subroutines

Properties predicted by User-Added Subroutines
K-values Liquid/vapor entropies
Liquid/vapor densities Liquid/vapor enthalpies

Required pure component properties1

As required by the subroutine
Two liquid phase behavior
Free-water decant - Supported
VLLE - Supported
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Thermodynamic Data Input Manual II-6-29

 Input Description
The METHOD Statement
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 the user-added method for K-value, liquid/

and/or vapor enthalpy, liquid/vapor entropy, and liquid/vapor
ENTHALPY density calculations. Both VLE and LLE K-value
and/or calculations are available when supplying user-added
ENTROPY subroutines. The VLLE option automatically selects
and/or both. See the PRO/II Data Transfer System and User-
DENSITY Added Subroutines User’s Guide for more details on
specifying these subroutines.

K-value Data (optional)

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 will

be used by the user-added subroutine for the
calculation of equilibrium K-values. See the PRO/II
Data Transfer System and User-added Subroutines
User's Guide for more information.

Enthalpy, Entropy, and Density Data (optional)

ENTHALPY

ENTROPY

DENSITY

UDATA i, value /...

See above under K-value Data for format and definition of these
entries.

II-6-30 Special Packages

Examples
6.11: 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
PROP STREAM=1,TEMP=100,PRES=100, &
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

Thermodynamic Data Input Manual II-6-31

II-6-32 Special Packages
 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.

Thermodynamic Data Input Manual II-7-1

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

Required pure component properties1

Triple point temperature
Two liquid phase behavior
Free-water decant - N/A
VLLE - N/A
1
Automatically supplied for library and petroleum components. Must be supplied by the user
for non-library components.

Input Description
The METHOD Statement
METHOD KVALUE(SLE)=VANTHOFF, ...

KVALUE Selects the method for K-value calculations. Only

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 ∆C p T
ln x i = ----------- ---- – 1 + ---------- ----t – 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.

II-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.

Thermodynamic Data Input Manual II-7-3

 Table 7-2: Attributes of the SOLDATA Method
Properties predicted by the SOLDATA method
K-values

Required pure component properties1

None
Two liquid phase behavior
Free-water decant - N/A
VLLE - N/A
1
Automatically supplied for library and petroleum components. Must be supplied by the user for non-
library components.

Input Description
The METHOD Statement
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(tunit) i, l, c1, c2, c3...

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.

II-7-4 Solid Solubility Methods

 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:
c
ln x il = c 1 + ----2- + 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
l≠i

The temperature units (tunit) 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.

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

Thermodynamic Data Input Manual II-7-5

 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

II-7-6 Solid Solubility Methods

 Chapter 8
Transport and Special Properties

The program provides a number of methods for calculating trans-

port properties, and various stream properties such as kinematic vis-
cosities, cloud and flash point temperatures and sulfur content.

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.

Thermodynamic Data Input Manual II-8-1

 Table 8-1: Attributes of the TRANSPORT Method
Properties predicted by the 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

Required pure component properties1

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
The METHOD Statement

METHOD . . .,

TRANSPORT=NONE or TRANSPORT=PURE or PETRO or TRAPP or

TACITE or U1 or U2 ... or U5, 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, CON-
DUCTIVITY(VL)=NONE or CONDUCTIVITY(VL)= PURE or PETRO or
TRAPP or U1 or U2 or ... U5, SURFACE(L)=NONE or SURFACE(L)=PURE
or PETRO or PARACHOR or U1 or U2 ... or U5}

or

VISCOSITY(VL)=NONE or VISCOSITY(VL)=SHELL or PURE or PETRO or

TRAPP or U1 or U2 ... or U5 or VISCOSITY(V)=PURE or PETRO or TRAPP
or U1 or U2 ... or U5 or API

and/or

VISCOSITY(L)=PURE or PETRO or TRAPP or KVIS or LBC or U1 or U2 ...

or U5 or SIMSCI or API

and/or
CONDUCTIVITY(VL)=NONE or

II-8-2 Transport and Special Properties

 CONDUCTIVITY(VL or V and/or L)= PURE or
PETRO or TRAPP or U1 or U2 ... or U5,

and/or

SURFACE(L)=NONE or SURFACE(L)= PURE or

PETRO or PARACHOR or U1 or U2 ... or U5,

and/or

DIFFUSIVITY(L)=NONE or
DIFFUSIVITY(L)=WILKE or DIFDATA

TRANSPORT This keyword selects the method used for calculation

of transport properties including liquid and vapor
viscosities, liquid and vapor thermal conductivities
and liquid surface tension values. If the TRANSPORT
keyword is absent, the default is that no transport
method is selected. If the TRANSPORT keyword is
present, the available options are:

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
TRAPP conductivity methods, and the
PARACHOR surface tension method.
U1-U5 This option selects one of the up to 5
user-defined subroutines that are
available to compute transport
properties.

Thermodynamic Data Input Manual II-8-3

 VISCOSITY This keyword requests the calculation of vapor and
(VL or liquid viscosities. The options available with this
V and/or L) keyword are:
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 option is available for both
vapor and liquid viscosity calculations.
PETRO This option uses predictive correlations
that apply to bulk 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 up to 5
user-defined subroutines that are
available to compute transport
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.

II-8-4 Transport and Special Properties

 API This option uses liquid viscosities from
the API Technical Data Book. This option
is available only with the VISCOSITY(L)
keyword.
CONDUCTIVITY This keyword requests the calculation of vapor and
(VL or V and/or L) liquid thermal conductivities. The options available
with this keyword are:
PURE This option applies simple mixing rules
to the temperature-dependent pure
component values available in the
selected 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.
PETRO This option uses predictive correlations
that apply to bulk 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.
U1-U5 This option selects one of the up to 5
user-defined subroutines that are
available to compute transport
properties. This option is available for
both vapor and liquid thermal
conductivity calculations.
SURFACE(L) This keyword selects the calculation method for liquid
surface tensions. Options available are:
PURE This option applies simple mixing rules
to the temperature-dependent pure
component values available in the
selected databanks to calculate mixture
viscosity properties. Saturation values
are used and no pressure corrections
apply.
PETRO This option uses predictive correlations
that apply to bulk hydrocarbon mixtures.
Pressure corrections apply.
PARACHOR This option uses the PARACHOR
prediction method.

Thermodynamic Data Input Manual II-8-5

 U1-U5 This option selects one of the up to 5
user-defined subroutines that are
available to compute transport
properties.
DIFFUSIVITY(L) This keyword selects the diffusivity calculation method
and/or provides diffusivity data. If the DIFFUSIVITY(L)
keyword is absent, the default is that no diffusivity
method is selected. If the DIFFUSIVITY(L) keyword is
present, the Wilke-Chang correlation (WILKE) is the
default. The other option is DIFDATA, which is selected
when user-supplied data only are to be used.

Note: The TRANSPORT, VISCOSITY, CONDUCTIVITY, SUR-

FACE and DIFFUSIVITY statements are usually optional but are
required when certain features or unit operations are used. Table
8-2 gives the PRO/II features that require transport properties.

Table 8-2: Features that Require Transport Properties

Feature Property
Stream Output TRANSPORT
Transport properties option
HCURVE TRANSPORT
Transport properties tables
COLUMN
Tray vapor/liquid transport TRANSPORT
properties 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.

II-8-6 Transport and Special Properties

 Diffusivity Data
DIFFUSIVITY(L)
DIFDATA(tunit) i, j, c1, c2, c3/ ...

DIFFUSIVITY(L) The DIFFUSIVITY statement signifies that diffusivity

data is being supplied by the user.
DIFDATA This statement supplies the diffusivity of a solute i in a
mixture of 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: The program currently allows for the calculation of liquid

diffusivities only when using a KVALUE(SLE) method. The
DIFDATA statements may follow the DIFFUSIVITY(L) state-
ment.

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 Data Transfer System
and User-added Subroutines User’s Guide for more
information.

Thermodynamic Data Input Manual II-8-7

 Method-specific Pure Component Properties (optional)
VISCOSITY
CONDUCTIVITY
SURFACE
...

Note: These required pure component properties are all tempera-

ture dependent and may not be supplied in the Thermodynamic
Data Category. They may only be supplied globally in the Com-
ponent Data Category. 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
8.1: In this example, 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

II-8-8 Transport and Special Properties

 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 method 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

Thermodynamic Data Input Manual II-8-9

Special Properties
Typical Usage

...
COMPONENT DATA
LIBID 1,IC4/ 2,NC4/ 3,NC5
THERMO DATA
METHOD SYSTEM=LKP, CLOUD=INDEX
STREAM DATA
. . .

General Information
The program provides numerous methods to compute special
stream refinery properties. These properties include KVIS which
calculates liquid kinematic viscosities, CLOUD and FLPT (cloud
and flash point temperatures respectively), and SULF (sulfur con-
tent). Descriptions of all the stream refinery special properties avail-
able are given in Table 8-3.

II-8-10 Transport and Special Properties

 Table 8-3: 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
FLPT Flash point temperature
RON Research octane number
MON Motor octane number
IBP Initial boiling point
FBP Final boiling point
RCR Ramsbottom carbon
TAN Total acid number
OLEF Olefinic content
CETA Cetane index
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

Thermodynamic Data Input Manual II-8-11

 Table 8-3: Keywords for Special Stream Refinery Properties
Keyword Property
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
CABP Cubic average boiling point
MOAB Molal average boiling point
NHV Net heating value
WAX Wax content
ASH Ash content
NOAC Noack volatility
SOFT Softening point
PEN Penetration index
SPROP User-defined special property

Input Description
The METHOD Statement
For all stream refinery properties, the general METHOD statement
is:
METHOD ..., property(qualifier, basis)=method, {REFPROP=SIMSCI}
The appropriate qualifier, basis, and method for each property are
given in Table 8-4.

II-8-12 Transport and Special Properties

 Table 8-4: Special Refinery Property Entries for the METHOD Statement
Property Qualifier Basis Method
KVIS — M or WT or LV INDEX or SIMSCI
POUR — M or WT or LV INDEX
CLOU — M or WT or LV INDEX or SIMSCI
FRZP — M or WT or LV INDEX
CFPP — M or WT or LV INDEX
FLPT — M or WT or LV INDEX or NELSON or
API
RON C or L M or WT or LV INDEX or SUM
MON C or L M or WT or LV INDEX or SUM
IBP — — SIMSCI
FBP — — SIMSCI
RCR — M or WT or LV INDEX or SIMSCI or
SHELL
TAN — M or WT or LV INDEX or SUM
OLEF MONO M or WT or LV INDEX or SUM
CETA — M or WT or LV API
CETN — M or WT or LV INDEX or SUM
REFR C20 or C70 M or WT or LV INDEX or SUM
ANIL — M or WT or LV SUM
AROM TOTA or RING M or WT or LV INDEX or SUM
WTAR — — SUM
NAPH — M or WT or LV INDEX or SUM
WTNA — — SUM
PARA — M or WT or LV INDEX or SUM
WTPA — — SUM
NPHL — WT or LV SUM
H2 — WT INDEX or SUM
CARB — WT INDEX or SUM
CHRA — WT INDEX or SUM
SMOK — M or WT or LV INDEX or SUM

Thermodynamic Data Input Manual II-8-13

 Table 8-4: Special Refinery Property Entries for the METHOD Statement
Property Qualifier Basis Method
LUMI — WT INDEX or SUM or
D1740
SULF — M or WT or LV INDEX or SUM
MERC — WT SUM
ASUL — WT SUM
NITR TOTA or BASI WT INDEX or SUM
or NONB
OXYG — WT INDEX or SUM
CCR — M or WT or LV INDEX or SUM
NICK — WT INDEX or SUM
VANA — WT INDEX or SUM
IRON — WT SUM
ASPH C5 or C7 WT INDEX or SUM
PHEN — WT SUM
ANEU — WT or LV SUM
BROM — WT or LV SUM
MEAB — — API
CABP — — API
MOAB — — API
NHV — — API
WAX — WT INDEX or SUM
ASH — WT INDEX or SUM
NOAC — WT INDEX or SUM
SOFT — WT or LV SUM
PEN — M or WT or LV INDEX or SUM
SPROP i M or WT or LV INDEX or SUM

Note: 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.

II-8-14 Transport and Special Properties

 .For example, when specifying the SIMSCI mixing method for
KVIS using the default liquid volume basis, the METHOD state-
ment becomes:
METHOD ..., KVIS=SIMSCI, ...
When specifying the INDEX mixing method for research octane
number (RON) and using the default weight basis, the METHOD
statement becomes:
METHOD ..., RON(L, WT)=INDEX, ...

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 v3.3 calculation methods
and PRO/II v3.3 properties. These properties are KVIS,
CLOU, POUR, FLPT, SULF, and CETA.

The available mixing methods for special refinery properties are

described below:

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:

log ( INDEX ) =  -----------------------  log ( VALUE ) + CONSTANT

1.0
(1)
 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 This mixing rule is available for the cloud
point (CLOU) and kinematic viscosity
(KVIS) methods only. This mixing method
sums the component property index
values. However, a different formula than
the one shown in equation (1) is used to
convert to data values to indices. For
CLOU, the conversion equation is:

Thermodynamic Data Input Manual II-8-15

 GAMMA CPF + 460.0
( INDEX ) = ---------------------------------------------------------------------------------------- (2)
exp ( 6.39693 – 9.21034 × GAMMA )

For CLOU, GAMMA defaults to a value of

0.05.
For KVIS, the conversion equation is:
2
INDEX = 72.0509 – 22.1322 ln ( KVIS ) + 4.35618 { ln ( KVIS ) }
(3)

NELSON The Nelson method is an alternate method

used to calculate the flash point
temperature.
API The FLPT, CETA, MEAB, CABP, MOAB, and
NHV properties may all be calculated using
methods based on the API Technical Data
Book.
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.

Special Property Methods Data

property(qualifier, basis) {GAMMA=value, REFINDEX=value,
REFVALUE(unit)=value},{NCFILL=ncfill},
{NCBLEND=ncblend}

DATA(unit) i, datvalue/ ...

INDEX i, ndvalue/ ...

II-8-16 Transport and Special Properties

 For KVIS only:
KVIS(M or WT or LV) {GAMMA=value, REFINDEX=value,
REFVALUE(kvisunit)=value,}
{NCFILL=ncfill}, {NCBLEND=ncblend}

DATA(tunit, kvisunit) t1, t2, /i, p1, p2, /...

INDEX(tunit) t1, t2, /i, p1, p2, /...
The entries and qualifiers for each special refinery property are
given in Table 8-5.
Table 8-5: Special Refinery Property Data Entries

Property Qualifier1 Basis1 Unit NCFILL NCBLEND

KVIS — M or WT or kvis-unit SIMSCI or ZERO MISS or ZERO
LV or NOFILL or API or EXCL
POUR — M or WT or temp API or ZERO or MISS or ZERO
LV NOFILL or EXCL
CLOU — M or WT or temp ZERO or NOFILL MISS or ZERO
LV or EXCL
FZPT — M or WT or temp ZERO or NOFILL MISS or ZERO
LV or EXCL
CFPP — M or WT or temp ZERO or NOFILL MISS or ZERO
LV or EXCL
FLPT — M or WT or temp ZERO or NOFILL MISS or ZERO
LV or EXCL
RON C or L M or WT or — ZERO or NOFILL MISS or ZERO
LV or EXCL
MON C or L M or WT or — ZERO or NOFILL MISS or ZERO
LV or EXCL
CETA — — No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
CETN — M or WT or — ZERO or NOFILL MISS or ZERO
LV or EXCL
REFR C20 or C70 M or WT or — ZERO or NOFILL MISS or ZERO
LV or API or EXCL
1
For those properties with bases “frac,” “ppm,” or “pct,” any one of these three bases may be specified. The basis “frac” or
“ppm” or pct” indicated is the default for that property.

Thermodynamic Data Input Manual II-8-17

 Table 8-5: Special Refinery Property Data Entries

Property Qualifier1 Basis1 Unit NCFILL NCBLEND

ANIL — M or WT or No ZERO or NOFILL MISS or ZERO
LV GAMMA, or EXCL
REFI, or
REFV
entries
allowed
AROM TOTA or M or WT or — ZERO or NOFILL MISS or ZERO
RING LV, frac or SIMSCI or EXCL

OLEF MONO M or WT or — ZERO or NOFILL

LV, frac or SIMSCI
WTAR — — No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
NAPH — M or WT or — ZERO or NOFILL MISS or ZERO
LV, frac or SIMSCI or EXCL

PARA TOTA or ISO M or WT or — ZERO or NOFILL MISS or ZERO

LV, frac or SIMSCI or EXCL
WTNA — — No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
WTPA — — No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
NPHL M or WT or M or WT or No ZERO or NOFILL MISS or ZERO
LV LV GAMMA, or EXCL
REFI, or
REFV
entries
allowed
1 For those properties with bases “frac,” “ppm,” or “pct,” any one of these three bases may be specified. The basis “frac” or
“ppm” or pct” indicated is the default for that property.

II-8-18 Transport and Special Properties

 Table 8-5: Special Refinery Property Data Entries

Property Qualifier1 Basis1 Unit NCFILL NCBLEND

H2 — WT, frac — SIMSCI ZERO MISS or ZERO
or NOFILL or EXCL
CARB — WT, frac — SIMSCI ZERO MISS or ZERO
or NOFILL or EXCL
CHRA — WT — SIMSCI ZERO MISS or ZERO
or NOFILL or EXCL
SMOK — M or WT or — NELSON or MISS or ZERO
LV ZERO or SIMSCI or EXCL
or NOFILL
LUMI — M or WT or No ZERO or NOFILL MISS or ZERO
LV GAMMA, or EXCL
REFI, or
REFV
entries
allowed
SULF — M or WT or — ZERO or NOFILL MISS or ZERO
LV, frac or EXCL
MERC — WT, frac No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
ASUL — WT No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
NITR TOTA or TOTA or ZERO or NOFILL MISS or ZERO
BASI or BASI or — or EXCL
NONB NONB
OXYG — WT, frac — ZERO or NOFILL MISS or ZERO
or EXCL
CCR — M or WT or — ZERO or NOFILL MISS or ZERO
LV, frac or EXCL
NICK — WT, frac — ZERO or NOFILL MISS or ZERO
or EXCL
1 For those properties with bases “frac,” “ppm,” or “pct,” any one of these three bases may be specified. The basis “frac” or
“ppm” or pct” indicated is the default for that property.

Thermodynamic Data Input Manual II-8-19

 Table 8-5: Special Refinery Property Data Entries

Property Qualifier1 Basis1 Unit NCFILL NCBLEND

VANA — WT, frac — ZERO or NOFILL MISS or ZERO
or EXCL
IRON — WT No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
ASPH C5 or C7 WT, frac — ZERO or NOFILL MISS or ZERO
or EXCL
PHEN — WT No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
ANEU — WT or LV No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
BROM — WT or LV No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
WAX — WT, frac — ZERO or NOFILL MISS or ZERO
or EXCL
ASH — WT, frac — ZERO or NOFILL MISS or ZERO
or EXCL
SOFT WT or LV WT or LV No ZERO or NOFILL MISS or ZERO
GAMMA, or EXCL
REFI, or
REFV
entries
allowed
IBP — — temp SIMSCI —
1
For those properties with bases “frac,” “ppm,” or “pct,” any one of these three bases may be specified. The basis “frac” or
“ppm” or pct” indicated is the default for that property.

II-8-20 Transport and Special Properties

 Table 8-5: Special Refinery Property Data Entries

Property Qualifier1 Basis1 Unit NCFILL NCBLEND

FBP — — temp SIMSCI —
PEN M or WT or M or WT or — ZERO or NOFILL MISS or ZERO
LV LV or EXCL
1
For those properties with bases “frac,” “ppm,” or “pct,” any one of these three bases may be specified. The basis “frac” or
“ppm” or pct” indicated is the default for that property.

Note: For the properties NOAC, MEAB, CABP, MOAB, and

NHV no individual component data entries are possible. There-
fore these properties do not require a special methods data state-
ment.

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 8-6.

Table 8-6: 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)

For user-defined special refinery properties, the data statement is:

SPROP(M or WT or LV, frac, i) {GAMMA=value, REFINDEX=value,
REFVALUE=value, NAME=text}

DATA i, datvalue/...
INDEX i, indvalue/ ...

SPROP The user-defined special refinery property may be supplied

on a molar, weight, or liquid volume basis.

Thermodynamic Data Input Manual II-8-21

 i This integer value must be supplied and may
be any number between 1 and 9999. The total
number of SPROPs defined in any given
problem must be less than or equal to 60.
NAME This entry is valid only for the SPROP statement and is
used to supply a descriptive name for the user-defined
special stream property. It may contain up to 24
alphanumeric characters including embedded blanks, but
excluding delimiters. It serves only to identify the user-
defined stream property in the stream summary, and does
not have to be unique.

The following keyword descriptions apply to all the property data

statements outlined in Table 8-5:

GAMMA, These entries must be supplied if the INDEX or SIMSCI

REFINDEX, 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 8-15.
NCFILL Estimates refinery properties for narrow cuts generated
from assay streams or PETRO components. For all special
refinery properties except NOAC, MEAB, CABP, MOAB, 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 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.

II-8-22 Transport and Special Properties

 SHELL This fill option uses Shell-specific methods
from FEEDPREP or SMBP to supply missing
values.
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, 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
INDEX stream 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, t2 These are the temperatures at which kinetic
viscosity data and/or index values will be
supplied. The tunit 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.

Thermodynamic Data Input Manual II-8-23

 p1, p2 These entries provide the kinematic viscosity
data or index values at 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 8-5 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 Ä 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 20°C.

C70 Measurements taken at 70°C.

Examples
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

II-8-24 Transport and Special Properties

 methods for KVIS, CHRA, H2, and CARB. Use the
NELSON fill method for SMOK, and the API fill method
for POUT 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
REFR NCFILL=API
SMOK NCFILL=NELSON
CARB NCFILL=SIMSCI
H2 NCFILL=SIMSCI
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

Thermodynamic Data Input Manual II-8-25

II-8-26 Transport and Special Properties
 Chapter 9
Method-specific Pure Component Data

The calculation of thermodynamic properties requires various pure

component data, e.g., critical temperature and pressure and liquid
molar volume. The component data statements required for each
thermodynamic generator are outlined in this section. Data are nor-
mally found in the libraries or supplied in the Component Data Cat-
egory. Supplying data in the Thermodynamic Data Category allows
for the user to override pure component data within each individual
method set.

Method-specific Pure Component Data

Typical Usage

...
COMPONENT DATA
LIBID 1, IC4/ 2, NC4/ 3, NC5
THERMO DATA
METHOD SYSTEM=SRK
KVALUE
TC 1, 373
STREAM DATA
. . .

General Information
The calculation of thermodynamic properties requires various pure
component property data. The exact property data required depend
on the thermodynamic methods that are selected. For example, the
Soave modified Redlich-Kwong equation of state requires pure

Thermodynamic Data Input Manual II-9-1

 component 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
the component data required. Non-library components must be
given all the user-supplied pure component property data required
for the thermodynamic method(s) selected.
Data are normally found in the libraries or supplied in the Compo-
nent Data Category. Supplying data in the Thermodynamic Data
Category allows for the user to override pure component data within
each individual method set.

Input Description
The METHOD Statement
METHOD ..., property=method, ...
property
data(unit) i, value/j,value/...

property This selects the thermodynamic property for which

data are to be supplied. For example, this property
could be the vapor density (DENSITY(V)). The
calculation method could be the Soave modified
Redlich-Kwong equation of state (SRK).
data This statement is used for inputting the data for the
property method selected. Any data supplied here are
used in preference to data supplied elsewhere or
retrieved from data-banks. The hierarchy of data
selection is discussed later on in this section. The
keywords allowed for this entry appear on the
following page.

Note: Data statements must appear immediately after a property

statement. The 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 the data statement
apply only to that property method calculation. They do not act as
default values for any other property calculations. However, if val-
ues are supplied on the data statement only for the K-value prop-
erty, these values act as defaults for other property calculations
using the same method.

II-9-2 Method-specific Pure Component Data

 The pure component data required for each generator are given in
Table 9-1. Only temperature independent data may be given in the
Thermodynamic Data Category. See “Solid Component Properties”
and “Component Properties” in Volume I, for further details on for-
mat 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.
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 statement.
4. Data stored in the component libraries as selected using the
BANK option.
If data are still missing after steps 1-4 are completed, an error mes-
sage is printed and the program is terminated after input processing
is completed.
Table 9-1: Required Pure Component Data For Property Generators
Generalized Correlation Methods
SPGR
Method Tc Pc ω MV Vc Zc Zra vdW DM Rad NBP SP η µ κ α Data or VP H0 Hvap Hliq ρ
API

IDEAL C C C C

GS X X X X X C C

CS X X X X X C C

IGS X X X X X C C

GSE X X X X X C C

CSE X X X X X C C

CP X X X C C C C

BK10 X X X X C

JG X X X C

LK X X X C C

API C C C C

RACKETT X X X X C

COSTALD X X C

LIBRARY C

Thermodynamic Data Input Manual II-9-3

Table 9-1: Required Pure Component Data For Property Generators
Equation of State Methods
SPGR
Method Tc Pc ω MV Vc Zc Zra vdW DM Rad NBP SP η µ κ α Data or VP H0 Hvap Hliq ρ
API

SRK,SRKKD,SRKH X X X C C

SRKP,SRKM,SRKS X X X C C

PR,PRH,PRP,PRM X X X C C

UNIWAALS X X X C C

BWRS X X X C C

HEXAMER X X X C C

Liquid Activity Methods

SPGR
Method Tc Pc ω MV Vc Zc Zra vdW DM Rad NBP SP η µ κ α Data or VP H0 Hvap Hliq ρ
API

NRTL C C C C C

UNIQUAC, UNQ4 C C C C C C

UNIFAC C C C C C C

UFT 1/2/3 C C C C C C

UNFV C C C C C

WILSON X C C C C C

VANLAAR C C C C C

MARGULES C C C C C

REGULAR C C C C C C C

FLORY C X C C C C C

HOCV X X X X C

TVIRIAL X X C

Special Packages
SPGR
Method Tc Pc ω MV Vc Zc Zra vdW DM Rad NBP SP η µ κ α Data or VP H0 Hvap Hliq ρ
API

ALCOHOL C C C C C C

GLYCOL C C

SOUR C C

GPSWATER C C

AMINE C C

U1-U15 C

II-9-4 Method-specific Pure Component Data

Table 9-1: Required Pure Component Data For Property Generators
Additional Thermodynamic Generators
SPGR
Method Tc Pc ω MV Vc Zc Zra vdW DM Rad NBP SP η µ κ α Data or VP H0 Hvap Hliq ρ
API

VANTHOFF C

SOLDATA C

VISCOSITY X C

CONDUCT X C

SURFACE X C

Table 9-2: Legend

Legend Keyword Description Legend Keyword Description

Tc TC Critical temperature κ CONDUCTIVITY Thermal conductivity

Pc PC Critical pressure σ SURFACE Surface tension

w ACENTRIC Acentric factor ρ DENSITY (L) Liquid density

MV MOLVOL Liquid molar volume Data DATA or Special property data/index values

Vc VC Critical volume INDEX

Zc ZC Critical compressibility factor X The user may supply these data

either globally in the Component
Zra RACKETT Rackett parameter
Data Category or locally for a
vdW VANDERWAALS van der Waals area and volume given method set in the Thermo-
DM DIPOLE Dipole moment dynamic Data Category.

Rad RADIUS Radius of gyration

NBP NBP Normal boiling point (temperature) C The user may supply these data only
in the Component Data Category.
SP SOLUPARA Hildebrand solubility parameter

H 0 ENTHALPY (V) Ideal vapor enthalpy

Hvap LATENT Latent heat of vaporization A The user may supply these data or
index values either globally in the
Hliq ENTHALPY (L) Saturated liquid enthalpies
Component Data or Stream Data
VP VP Vapor pressure Categories or locally in the Thermo-
dynamic Data Category for a given
SpGr SPGR Specific gravity
method sets.
API API API gravity

η ETA Truncated virial equation

coefficients

µ VISCOSITY Viscosity

Thermodynamic Data Input Manual II-9-5

 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
PROP STREAM=1, TEMP=100, PRES=100, &
COMP=50/50
UNIT OPERATION
FLASH UID=FLSH
FEED 1
PROD V=2, L=3
TPSPEC PRES=50
SPEC STREAM=2, RATE, RATIO, STREAM=1, &
RATE, VALUE=0.5
END

II-9-6 Method-specific Pure Component Data

 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

Thermodynamic Data Input Manual II-9-7

II-9-8 Method-specific Pure Component Data
 Index

A Natural Gas Systems , II-2-5

Petrochemical Applications , II-2-8
Refinery and Gas Processing, II-2-2
Alcohol Dehydration Systems , II-2-12
Aromatic Systems , II-2-9
Alcohols
Aromatic/Non-aromatic Systems , II-2-9
ALCOHOL Databank Components , II-6-8
Attributes of the ALCOHOL Package , II-6-2 Associating Hexamer Equation Of State
Enthalpy, Entropy, and Density Data , II-4-39
Enthalpy, Entropy, and Density Data , II-6-7
Examples , II-4-40
Examples , II-6-11
K-value Data , II-4-39
K-value Data , II-6-4
METHOD Statement, II-4-38
METHOD Statement , II-6-2
Method-specific Pure Component
Method-specific Pure Component
Properties, II-4-40
Properties , II-6-10
Typical Usage , II-4-37
Typical Usage , II-6-1
Alpha Formulations
Enthalpy, Entropy, and Density Data , II-4-32
Examples , II-4-33
B
General Information , II-4-29
K-value Data , II-4-30 Benedict-Webb-Rubin-Starling
Typical Usage , II-4-29 Attributes of, II-4-34
Vapor Phase Fugacity Data , II-4-32 Enthalpy, Entropy, and Density Data , II-4-35
Amine Systems , II-2-7 Examples , II-4-36
K-value Data , II-4-35
Amines
METHOD Statement, II-4-34
Attributes of the AMINE Package , II-6-25
Method-specific Pure Component
Enthalpy, Entropy, and Density Data , II-6-27
Properties, II-4-36
Examples , II-6-28
Typical Usage , II-4-33
K-value Data , II-6-26
Water Handling Options, II-4-36
METHOD Statement , II-6-26
Binary Interaction Data
Method-specific Pure Component
Properties , II-6-28 BWRS Equation of State Data, II-1-6
Typical Usage , II-6-24 Hayden-O’Connell Data , II-1-7
HEXAMER Equation of State Data, II-1-6
API Liquid Density
IDIMER Data, II-1-7
Attributes of , II-3-26
LKP Equation of State Data, II-1-6
Examples , II-3-27
Redlich-Kister Excess Properties Data , II-1-7
METHOD Statement , II-3-26
Typical Usage , II-3-26 Truncated Virial Data , II-1-7
Braun K10
Application Guidelines , II-2-1
Attributes of, II-3-18
Chemical and Environmental Applications , II-2-13
Examples , II-3-19
Examples , II-2-15
METHOD Statement, II-3-19

Thermodynamic Data Input Manual II-IX-1

 Method-specific Pure Component Lee-Kesler-Plocker , II-4-41
Properties , II-3-19 Modified SRK and PR , II-4-13
Typical Usage , II-3-18 Peng-Robinson , II-4-7
Water Handling Options , II-3-19 Soave Modified Redlich-Kwong , II-4-1
UNIWAALS , II-4-23
Examples
C Alcohol , II-6-11
Alpha Formulations , II-4-33
Carboxylic Acid Systems , II-2-14 API Liquid Density , II-3-27
CHAO-SEADER Associating Hexamer Equation Of State , II-4-40
Examples , II-3-10 Benedict-Webb-Rubin-Starling , II-4-36
Method-specific Pure Component Braun K10 , II-3-19
Properties , II-3-9 CHAO-SEADER , II-3-10
Chao-Seader Chemical and Environmental Application , II-2-18
Attributes of , II-3-8 Costald Liquid Density , II-3-31
METHOD Statement , II-3-9 Cubic Equation Of State Alpha
Formulations , II-4-33
Typical Usage , II-3-8
Curl-Pitzer , II-3-16
Water Handling Options , II-3-9
Filling in Missing Parameters for Liquid Activity
Chemical and Environmental Applications Methods , II-5-58
Carboxylic Acid Systems , II-2-14 Flory-Huggins , II-5-54
Environmental Applications , II-2-14 Free-water Decant , II-1-34
Non-Ionic Systems , II-2-13 Glycol , II-6-16
Solid Applications , II-2-15 GPA Sour Water , II-6-24
Costald Liquid Density Grayson-Streed Method , II-3-6
Attributes of , II-3-30 Hayden-O’Connell Vapor Fugacity , II-5-70
Examples , II-3-31 Henry’s Law , II-5-66
Input Description , II-3-30 Ideal Methods , II-3-3
METHOD Statement , II-3-30 IDIMER Vapor Fugacity , II-5-77
Method-specific Pure Component Johnson-Grayson , II-3-22
Properties , II-3-30
Lee-Kesler , II-3-25
Typical Usage , II-3-30
Lee-Kesler-Plocker , II-4-44
Curl-Pitzer Margules , II-5-44
Attributes of , II-3-15 Method-specific Pure Component Data , II-9-6
Examples , II-3-16 Minimum Required User Input , II-1-13
METHOD Statement , II-3-15 Modifications to GS and CS , II-3-13
Method-specific Pure Component
Modifications to UNIFAC , II-5-34
Properties , II-3-16
Modified Soave-Redlich-Kwong and
Typical Usage , II-3-15 Peng-Robinson , II-4-20
Multiple Thermodynamic Sets , II-1-30
Natural Gas Application , II-2-17
E NRTL , II-5-6
Peng-Robinson , II-4-11
Entropy Petrochemical Application , II-2-18
Features that Require Entropy , II-1-20 Rackett Liquid Density , II-3-29
Environmental Applications , II-2-14 Redlich-Kister, Gamma Heat of Mixing , II-5-81
Refinery Application , II-2-16
Equations of State , II-4-1
Regular Solution , II-5-48
Associating Hexamer Equation Of State , II-4-37
Soave Modified Redlich-Kwong , II-4-5
Benedict-Webb-Rubin-Starling , II-4-33
Cubic Equation Of State Alpha Soave Redlich-Kwong , II-4-5
Formulations , II-4-29 Solid Application , II-2-19
Filling in Missing Parameters , II-4-27 Sour Water , II-6-20
Sour Water Application , II-2-16

Thermodynamic Data Input Manual II-IX-2

 Special Properties , II-8-24 Braun K10, II-3-18
Transport Properties , II-8-8 Chao-Seader, II-3-8
Truncated Virial Vapor Fugacity , II-5-73 Costald Liquid Density, II-3-30
UNIFAC , II-5-20 Curl-Pitzer , II-3-15
UNIQUAC , II-5-13 Grayson-Streed, II-3-4
UNIWAALS , II-4-26 Ideal and Library Methods , II-3-1
User-added Subroutines , II-6-31 Ideal Methods , II-3-1
User-supplied K-value Data , II-3-34 Johnson-Grayson , II-3-21
User-supplied Solubility , II-7-5 Lee-Kesler, II-3-23
Van Laar , II-5-39 Library Methods , II-3-1
Van’t Hoff Solubility , II-7-3 Modifications to GS and CS , II-3-11
Vapor-liquid-liquid Equilibrium Rackett Liquid Density, II-3-28
Considerations , II-1-41 Typical Usage , II-3-1
User-supplied K-value Data , II-3-32
Glycol Dehydration Systems , II-2-6
F Glycols
Attributes of the GLYCOL Package , II-6-12
FCCU , II-2-3 Components Available for GLYCOL
Filling in Missing Parameters Package, II-6-15
Attributes of the FILL Option for Liquid Activity Enthalpy, Entropy, and Density Data , II-6-15
Methods , II-5-55 Examples , II-6-16
Cubic Equations of State FILL options , II-4-28 K-value Data , II-6-13
Data Estimation Options for Liquid Activity METHOD Statement, II-6-13
Methods , II-5-58 Method-specific Pure Component
Examples for Liquid Activity Methods , II-5-58 Properties, II-6-16
General Information for Liquid Activity Typical Usage , II-6-12
Methods , II-5-55 GPA Sour Water
K-value Data for Cubic EOS , II-4-28 Attributes of GPSWATER Package, II-6-21
K-value Data for Liquid Activity Methods , II-5-56 Enthalpy, Entropy, and Density Data , II-6-22
METHOD Statement for Cubic EOS , II-4-28 Examples , II-6-24
METHOD Statement for Liquid Activity METHOD Statement, II-6-22
Methods , II-5-55 Method-specific Pure Component
Typical Usage for Cubic EOS , II-4-27 Properties, II-6-23
Typical Usage for Liquid Activity Methods , II-5-54 Typical Usage , II-6-21
Flory-Huggins Grayson-Streed
Attributes of FLORY Methods , II-5-50 Attributes of, II-3-5
Examples , II-5-54 METHOD Statement, II-3-5
K-value Data , II-5-51 Typical Usage , II-3-4
METHOD Statement , II-5-50 Water Handling Options, II-3-6
Method-specific Pure Component Grayson-Streed Method
Properties , II-5-53
Examples , II-3-6
Typical Usage , II-5-49
Method-specific Pure Component
Free-water Decant Considerations , II-1-31 Properties, II-3-6
Examples , II-1-34
General Information , II-1-31
Water Handling Statement , II-1-32 H
Hayden-O’Connell Vapor Fugacity
G Attributes of the HOCV Vapor Fugacity
Method, II-5-67
Generalized Correlations Enthalpy, Entropy and Density Data , II-5-69
API Liquid Density , II-3-26 Examples , II-5-70

II-IX-3 Index
 K-value Data , II-5-68 L
METHOD Statement , II-5-67
Method-specific Pure Component
Properties , II-5-69 Lee-Kesler
Typical Usage , II-5-66 Attributes of , II-3-23
Vapor Fugacity Data , II-5-68 Examples , II-3-25
Henry’s Law METHOD Statement , II-3-24
Attributes of the Henry’s Law Option , II-5-60 Method-specific Pure Component
Properties, II-3-24
Examples , II-5-66
Typical Usage , II-3-23
Henry’s Law Data , II-5-64
Henry’s Law Package Available Pairs , II-5-62 Lee-Kesler-Plocker
METHOD Statement , II-5-61 Attributes of , II-4-42
Method-specific Pure Component Enthalpy, Entropy, and Density Data , II-4-44
Properties , II-5-65 Examples , II-4-44
Typical Usage , II-5-60 K-value Data , II-4-43
Hierarchy of Pure Component Data , II-9-3 METHOD Statement , II-4-42
Method-specific Pure Component
High Pressure Crude Systems , II-2-3 Properties, II-4-44
Hydrofiners , II-2-4 Typical Usage , II-4-41
Library Method
Attributes of , II-3-2
I METHOD Statement , II-3-2
Light Hydrocarbon Systems , II-2-8
Ideal Method Liquid Activity Methods
Attributes of , II-3-2 Filling in Missing Parameters , II-5-54
METHOD Statement , II-3-2 Flory-Huggins , II-5-49
Ideal Methods Hayden-O’Connell Vapor Fugacity , II-5-66
Examples , II-3-3 Henry’s Law , II-5-60
IDIMER Vapor Fugacity IDIMER Vapor Fugacity , II-5-74
Attributes of , II-5-74 Margules , II-5-40
Enthalpy, Entropy and Density Data , II-5-76 Modifications to UNIFAC , II-5-21
Examples , II-5-77 NRTL , II-5-1
K-value Data , II-5-75 Redlich-Kister, Gamma Heat of Mixing , II-5-78
METHOD Statement , II-5-75 Regular Solution , II-5-45
Typical Usage , II-5-74 Truncated Virial Vapor Fugacity , II-5-70
Vapor Fugacity Data , II-5-76 UNIFAC , II-5-13
Input Description , II-1-21 UNIQUAC , II-5-7
Van Laar , II-5-34
Wilson , II-5-29
J Liquid Phase Activity Binary Interaction Data
Flory-Huggins Data , II-1-8
Henry’s Law Data , II-1-9
Johnson-Grayson
Margules Data, , II-1-8
Attributes of , II-3-21
NRTL Data , II-1-8
Examples , II-3-22
Other Binary Data for Liquid Activity
METHOD Statement , II-3-21 Methods , II-1-8
Method-specific Pure Component UNIFAC Group Contribution Data , II-1-9
Properties , II-3-22
UNIQUAC Data , II-1-8
Typical Usage , II-3-21
UNIWAALS Modified Group Contribution
Interaction Data, II-1-9
Van Laar Data , II-1-8
Wilson Data , II-1-8

Thermodynamic Data Input Manual II-IX-4

Low Pressure Crude Systems , II-2-3 Enthalpy, Entropy, and Density Data , II-4-19
Lube Oil Units , II-2-4 Examples , II-4-20
Huron-Vidal modifications to PR, II-4-15
Huron-Vidal modifications to SRK, II-4-14
M Kabadi-Danner modifications to SRK, II-4-15
K-value Data , II-4-16
METHOD Statement, II-4-14
Main Coker Fractionators , II-2-3 Method-specific Pure Component
Margules Properties, II-4-19
Attributes of MARGULES Methods , II-5-40 Modified Panagiotopoulos-Reid modifications to
Examples , II-5-44 PR , II-4-15
K-value Data , II-5-42 Modified Panagiotopoulos-Reid modifications to
METHOD Statement , II-5-41 SRK, II-4-14
Method-specific Pure Component Panagiotopoulos-Reid modifications to
Properties , II-5-44 PR , II-4-16
Typical Usage , II-5-40 SimSci modifications to SRK, II-4-15
Typical Usage , II-4-13
METHOD Statement , II-1-3
Multiple Thermodynamic Sets , II-1-28
Method-specific Pure Component Data , II-1-11, II-9-1
Avoiding Inconsistent Methods, II-1-29
Examples , II-9-6
Default Method Set, II-1-28
General Information , II-9-1
Examples , II-1-30
Hierarchy , II-9-3
General Information , II-1-28
METHOD Statement , II-9-2
Method Set Requirements, II-1-29
Typical Usage , II-9-1
Multiple Method Sets in Distillation
Method-specific Water Handling Options , II-1-4 Columns , II-1-29
Minimum Required User Input , II-1-12
Modifications to GS and CS
Attributes of the Modified GS and CS N
Methods , II-3-12
Erbar modifications to Grayson-Streed and
Chao-Seader , II-3-12 Natural Gas Systems , II-2-5
Examples , II-3-13 Amine Systems , II-2-7
Improved Grayson-Streed , II-3-12 Glycol Dehydration Systems , II-2-6
METHOD Statement , II-3-12 Sour Water Systems , II-2-7
Method-specific Pure Component Non-hydrocarbon Systems , II-2-10
Properties , II-3-13 Non-Ionic Systems , II-2-13
Typical Usage , II-3-11
Notes Statement , II-1-3, II-1-12
Water Handling Options , II-3-13
NRTL
Modifications to UNIFAC
Attributes of NRTL methods , II-5-2
Attributes of Modified UNIFAC Methods , II-5-22
Examples , II-5-6
Examples , II-5-34
K-value Data , II-5-3
K-value Data , II-5-24
METHOD Statement, II-5-2
METHOD Statement , II-5-22
Method-specific Pure Component
Method-specific Pure Component Properties, II-5-6
Properties , II-5-28, II-5-33
Typical Usage , II-5-1
Typical Usage , II-5-21
UFT1-Lyngby modified UNIFAC , II-5-24
UFT2-Dortmund modified UNIFAC , II-5-24
UFT3-Modified UNIFAC , II-5-24
O
UNFV-Free Volume modification , II-5-24
Modified SRK and PR Order of Input , II-1-15

II-IX-5 Index
 P High Pressure Crude Systems , II-2-3
Low Pressure Crude Systems , II-2-3
Lube Oil and Solvent De-asphalting Units , II-2-4
Peng-Robinson , II-4-7 Main Coker Fractionators , II-2-3
Enthalpy, Entropy, and Density Data , II-4-10 Reformers and Hydrofiners , II-2-4
Examples , II-4-11 Water Handling , II-2-2
K-value Data , II-4-9
Reformers , II-2-4
METHOD Statement , II-4-8
Regular Solution
Method-specific Pure Component
Properties , II-4-11 Attributes of REGULAR Methods , II-5-45
Typical Usage , II-4-7 Examples , II-5-48
Water Handling Options , II-4-11 K-value Data , II-5-47
METHOD Statement , II-5-46
Petrochemical Applications
Method-specific Pure Component
Alcohol Dehydration Systems , II-2-12
Properties, II-5-48
Aromatic Systems , II-2-9
Typical Usage , II-5-45
Aromatic/Non-aromatic Systems , II-2-9
HF Systems , II-2-12
Light Hydrocarbon Systems , II-2-8
Non-hydrocarbon Systems , II-2-10
S
Predefined Systems , II-1-25
Selecting Individual Methods , II-1-3
Property Statements
Density Options , II-1-5 Soave Redlich-Kwong , II-4-1
Diffusivity Options , II-1-5 Attributes of , II-4-2
Enthalpy Options , II-1-6 Enthalpy, Entropy, and Density Data , II-4-4
Entropy Options , II-1-6 Examples , II-4-5
Henry’s Law Options , II-1-5 K-value Data , II-4-3
Liquid-Liquid Equilibrium Options , II-1-5 METHOD Statement , II-4-2
Solid-Liquid Equilibrium Options , II-1-5 Method-specific Pure Component
Vapor Fugacity Options , II-1-5 Properties, II-4-5
Typical Usage , II-4-1
Vapor-Liquid Equilibrium Options , II-1-4
Water Handling Options , II-4-5
Pure Component Alpha Formulations , II-1-10
Solid Applications , II-2-15
Solid Solubility Methods , II-7-1
R User-supplied Solubility , II-7-3
Van’t Hoff Solubility , II-7-1
Solvent De-asphalting Units , II-2-4
Rackett Liquid Density
Examples , II-3-29 Sour Water , II-6-17
Input Description , II-3-28 Attributes of SOUR Package , II-6-18
METHOD Statement , II-3-28 Enthalpy, Entropy, and Density Data , II-6-19
Method-specific Pure Component Examples , II-6-20
Properties , II-3-28 METHOD Statement , II-6-18
Typical Usage , II-3-28 Method-specific Pure Component
Redlich-Kister, Gamma Heat of Mixing Properties, II-6-20
Attributes of , II-5-78 Typical Usage , II-6-17
Enthalpy Data , II-5-79 Sour Water Systems , II-2-7
Examples , II-5-81 Special Packages
METHOD Statement , II-5-78 Alcohols , II-6-1
Typical Usage , II-5-78 Amines , II-6-24
Refinery and Gas Processing , II-2-2 Glycols , II-6-12
Refinery and Gas Processing Applications GPA Sour Water , II-6-21
FCCU , II-2-3 Sour Water , II-6-17
User-added Subroutines , II-6-29

Thermodynamic Data Input Manual II-IX-6

Special Properties , II-8-10 METHOD Statement, II-5-15
Examples , II-8-24 Method-specific Pure Component
General Information , II-8-10 Properties, II-5-19
Keywords for Special Stream Refinery Typical Usage , II-5-13
Properties , II-8-11 UNIQUAC
METHOD Statement , II-8-12 Attributes of UNIQUAC Methods, II-5-8
Special Property Methods Data , II-8-16 Examples , II-5-13
Special Refinery Property Entries , II-8-13 K-value Data , II-5-9
Typical Usage , II-8-10 METHOD Statement, II-5-8
Special Property Methods Data , II-1-10 Method-specific Pure Component
Properties, II-5-12
SRK or PR Equation of State Interaction
Parameters , II-1-7 Typical Usage , II-5-7

Systems of Thermodynamic Methods , II-1-26 UNIWAALS , II-4-23

Attributes of, II-4-23
Enthalpy, Entropy, and Density Data , II-4-25
T Examples , II-4-26
K-value Data , II-4-24
METHOD Statement, II-4-24
Thermodynamic Data Method-specific Pure Component
General Information , II-1-1 Properties, II-4-26
Thermodynamic Generators , II-1-18 Typical Usage , II-4-23
Thermodynamic Sets , II-1-16 User-added Subroutine Data , II-1-11
Transport Properties , II-8-1 User-added Subroutines
Diffusivity Data , II-8-7 Attributes of, II-6-29
Examples , II-8-8 Enthalpy, Entropy, and Density Data , II-6-30
General Information , II-8-1 Examples , II-6-31
METHOD Statement , II-8-2 K-value Data , II-6-30
Method-specific Pure Component METHOD Statement, II-6-30
Properties , II-8-8 Typical Usage , II-6-29
Typical Usage , II-8-1 User-supplied K-value Data , II-1-6
User-supplied Conductivity Data , II-8-7 Attributes of, II-3-32
User-supplied Surface Tension Data , II-8-7 Examples , II-3-34
User-supplied Viscosity Data , II-8-7 Input Description , II-3-33
Truncated Virial Vapor Fugacity K-value Data (required), II-3-33
Attributes of the TVIRIAL Vapor Fugacity METHOD Statement, II-3-33
Method , II-5-71 Typical Usage , II-3-32
Examples , II-5-73
User-supplied Solubility
K-value Data , II-5-72
Examples , II-7-5
METHOD Statement , II-5-71
General Information , II-7-3
Method-specific Pure Component
K-value Data , II-7-4
Properties , II-5-73
METHOD Statement, II-7-4
Typical Usage , II-5-70
Typical Usage , II-7-3
Vapor Fugacity Data , II-5-72

U V
Van Laar
UNIFAC
Attributes of VANLAAR Methods, II-5-35
Attributes of UNIfAC Methods , II-5-14
Examples , II-5-39
Available UNIFAC Interaction Parameters , II-5-20
K-value Data , II-5-36
Examples , II-5-20
METHOD Statement, II-5-35
K-value Data , II-5-16

II-IX-7 Index
 Method-specific Pure Component Examples , II-1-41
Properties , II-5-38 K-value Data , II-1-40
Typical Usage , II-5-34 METHOD Statement , II-1-40
Van’t Hoff Solubility Specifying Key Components , II-1-38
Examples , II-7-3 Specifying Separate VLE and LLE Models, II-1-38
General Information , II-7-1 VLLE Predefined Systems and K-value
METHOD Statement , II-7-2 Generators, II-1-35
Typical Usage , II-7-1
Vapor-liquid-liquid Equilibrium
Considerations , II-1-34 W
Available Databanks , II-1-36
Declaring a VLLE set , II-1-34
Water Handling , II-2-2

Thermodynamic Data Input Manual II-IX-8