20 (Components & Thermodynamics)

PRO/II Component
and Thermophysi cal

Properti es
Reference Manual
The software described in this manual is furnished under a license
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.
Copyri ght Noti ce Copyright 1994 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 S. Valencia
Avenue, Brea, CA 92621, USA.
Trademarks PRO/II is a registered mark of Simulation Sciences Inc.
SIMSCI is a service mark of Simulation Sciences Inc.
Printed in the United States of America.
Credi ts Contri butors:
Althea Champagnie, Ph.D.
J ohn Cunningham
Allan Harvey, Ph.D.
J ohn Tanger, Ph.D.
C.H. Twu, Ph.D.
Layout:
Kris Oca
On-l i ne Document Conversi on:
Mark Norton
Peter Stepman
Althea Champagnie, Ph.D.
Tabl e of Contents
Li st of Tabl es TOC-5
Li st of Fi gures TOC-6
Introducti on Int-1
General Information Int-1
What is in This Manual? Int-1
Who Should Use This Manual? Int-1
Finding What you Need Int-1
1. 1 Component Data I-3
1. 1. 1 Defi ned Components I-4
Component Libraries I-4
Using DATAPREPTM I-6
Fixed Properties I-6
Temperature-dependent Properties I-6
Properties From Structure I-8
1. 1. 2 Petrol eum Components I-9
General Information I-9
Property Generation--SIMSCI Method I-9
Property Generation--CAVETT Method I-13
Property Generation--Lee-Kesler Method I-16
1. 1. 3 Assay Processi ng I-18
Cutpoint Sets (Blends) I-19
Interconversion of Distillation Curves I-21
Cutting TBP Curves I-25
Generating Pseudocomponent Properties I-30
Vapor Pressure Calculations I-30
1. 2 Thermodynami c Methods I-37
1. 2. 1 Basi c Pri nci pl es I-38
Phase Equilibria I-38
Enthalpy I-41
Entropy I-43
Density I-44
1. 2. 2 Appl i cati on Gui del i nes I-45
Thermodynamic Expert System (TES) I-45
Refinery and Gas Processes I-46
Natural Gas Processing I-49
Petrochemical Applications I-52
Chemical Applications I-54
PRO/II Component and Thermophysical Properties Tabl e of Contents TOC-1
Reference Manual
1. 2. 3 General i zed Correl ati on Methods I-58
Ideal (IDEAL) I-58
Chao-Seader (CS) I-60
Grayson-Streed (GS) I-61
Erbar Modification to Chao-Seader (CSE) and
Grayson-Streed (GSE) I-61
Improved Grayson-Streed (IGS) I-62
Curl-Pitzer (CP) I-62
Braun K10 (BK10) I-63
J ohnson-Grayson (J G) I-64
Lee-Kesler (LK) I-64
API I-65
Rackett I-65
COSTALD I-66
1. 2. 4 Equati ons of State I-69
General Cubic Equation of State I-69
Alpha Formulations I-71
Mixing Rules I-73
Soave-Redlich Kwong (SRK) I-74
Peng-Robinson (PR) I-74
Soave-Redlich-Kwong Kabadi-Danner (SRKKD) I-75
Soave-Redlich-KwongPanagiotopoulos-Reid
(SRKP) and Peng-Robinson Panagiotopoulos-
Reid (PRP) I-76
Soave-Redlich-Kwong Modified Panagiotopoulos-
Reid (SRKM) and Peng-Robinson Modified
Panagiotopoulos-Reid (PRM) I-77
Soave-Redlich-Kwong SimSci (SRKS) I-77
Soave-Redlich-Kwong Huron-Vidal (SRKH) and
Peng-Robinson Huron-Vidal (PRH) I-79
HEXAMER I-80
UNIWAALS I-83
Benedict-Webb-Rubin-Starling I-84
Lee-Kesler-Plcker (LKP) I-85
1. 2. 5 Free Water Decant I-88
Calculation Methods I-88
1. 2. 6 Li qui d Acti vi ty Coeffi ci ent Methods I-90
Margules Equation I-93
van Laar Equation I-94
Regular Solution Theory I-95
Flory-Huggins Theory I-96
Wilson Equation I-97
NRTL Equation I-98
UNIQUAC Equation I-99
UNIFAC I-101
Modifications to UNIFAC I-104
Fill Methods I-107
TOC-2 Tabl e of Contents May 1994
Henrys Law I-110
Heat of Mixing Calculations I-111
1. 2. 7 Vapor Phase Fugaci ti es I-113
Equations of State I-114
Truncated Virial Equation of State I-114
Hayden-OConnell I-116
1. 2. 8 Speci al Packages I-117
Alcohol Package (ALCOHOL) I-117
Glycol Package (GLYCOL) I-120
Sour Package (SOUR) I-122
GPA Sour Water Package (GPSWATER) I-125
Amine Package (AMINE) I-127
1. 2. 9 El ectrol yte Mathemati cal Model I-131
Discussion of Equations I-131
Modeling Example I-133
1. 2. 10 El ectrol yte Thermodynami c Equati ons I-135
Thermodynamic Framework I-135
Equilibrium Constants I-135
Aqueous Phase Activities I-136
Vapor Phase Fugacities I-139
Organic Phase Activities I-143
Enthalpy I-143
Aqueous Liquid Phase I-144
Molar Volume and Density I-144
1. 2. 11 Sol i d-Li qui d Equi l i bri a I-147
vant Hoff Equation I-147
Solubility Data I-148
Fill Options for Solubility Data I-148
1. 2. 12 Transport Properti es I-150
PURE Methods I-150
PETRO Methods I-151
TRAPP Correlation I-155
Special Methods for Liquid Viscosity I-157
Liquid Diffusivity I-159
Index Idx-1
Reference Manual
Li st of Tabl es
1.1.1-1 PRO/II Library Component Properties . . . . . . . . . . . . . I-5
1.1.1-2 PRO/II Temperature-dependent Property Equations and
Extrapolation Conventions . . . . . . . . . . . . . . . . . . . I-7
1.1.1-3 PRO/II Vapor Pressure Equations . . . . . . . . . . . . . . . . I-7
1.1.2-1 Values of Constants for Equations (14)-(17) . . . . . . . . . . I-11
1.1.3-1 Primary TBP Cutpoint Set . . . . . . . . . . . . . . . . . . . . I-19
1.1.3-2 Blending Example . . . . . . . . . . . . . . . . . . . . . . . . I-20
1.1.3-3 Values of Constants a, b, c . . . . . . . . . . . . . . . . . . . I-23
1.1.3-4 Values of Constants a, b . . . . . . . . . . . . . . . . . . . . . I-25
1.2.2-1 Methods Recommended for Low Pressure Crude Systems . . I-47
1.2.2-2 Methods Recommended for High Pressure Crude Systems . . I-47
1.2.2-3 Methods Recommended for Reformers and Hydrofiners . . . . I-48
1.2.2-4 Methods Recommended for Lube Oil and Solvent
De-asphalting Units . . . . . . . . . . . . . . . . . . . . . . . I-48
1.2.2-5 Methods Recommended for Natural Gas Systems . . . . . . . I-50
1.2.2-6 Methods Recommended for Sour Water Systems . . . . . . . I-51
1.2.2-7 Recommended Ranges for Amine Systems . . . . . . . . . . . I-52
1.2.2-8 Methods Recommended for Light Hydrocarbons . . . . . . . . I-52
1.2.2-9 Methods Recommended for Aromatics . . . . . . . . . . . . . I-53
1.2.2-10 Methods Recommended for Aromatic/Non-aromatic
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-54
1.2.2-11 Methods Recommended for Alcohol Systems . . . . . . . . . I-54
1.2.2-12 Methods Recommended for Non-ionic Chemical Systems . . . I-56
1.2.2-13 Methods Recommended for Ionic Chemical Systems . . . . . I-56
1.2.2-14 Methods Recommended for Environmental Applications . . . I-57
1.2.2-15 Methods Recommended for Solid Applications . . . . . . . . I-57
1.2.4-1 Some Cubic Equations of State . . . . . . . . . . . . . . . . . I-69
1.2.4-2 Constants for Two-parameter Cubic Equations of State . . . . I-70
1.2.4-3 Alpha Formulations . . . . . . . . . . . . . . . . . . . . . . . I-72
1.2.5-1 Components Available in the SIMSCI Water Solubility Method . I-89
1.2.6-1 Margules Equation . . . . . . . . . . . . . . . . . . . . . . . I-93
1.2.6-2 van Laar Equation . . . . . . . . . . . . . . . . . . . . . . . . I-94
1.2.6-3 Regular Solution Theory . . . . . . . . . . . . . . . . . . . . I-95
1.2.6-4 Flory-Huggins Theory . . . . . . . . . . . . . . . . . . . . . . I-96
1.2.6-5 Wilson Equation . . . . . . . . . . . . . . . . . . . . . . . . . I-97
1.2.65 Wilson Equation . . . . . . . . . . . . . . . . . . . . . . . . . I-97
1.2.6-6 NRTL Equation . . . . . . . . . . . . . . . . . . . . . . . . . . I-98
1.2.6-7 UNIQUAC Equation . . . . . . . . . . . . . . . . . . . . . . . I-99
1.2.6-8 UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-101
1.2.8-1 Components Available for ALCOHOL Package . . . . . . . . . I-118
1.2.8-2 Components Available for GLYCOL Package . . . . . . . . . . I-120
1.2.8-3 Application Guidelines for Amine Systems . . . . . . . . . . . I-129
1.2.11-1 vant Hoff . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-148
1.2.12-1 Transport Properties . . . . . . . . . . . . . . . . . . . . . . . I-150
1.2.12-2 Stream Average Properties . . . . . . . . . . . . . . . . . . . I-151
1.2.12-3 TRAPP Components (3.3 versions) . . . . . . . . . . . . . . . I-156
Li st of Fi gures
1.1.3-1 Cutting TBP Curves . . . . . . . . . . . . . . . . . . . . . . . I-27
1.1.3-2 Matching Lightends to TBP Curve . . . . . . . . . . . . . . . . I-30
1.2.6-1 Flowchart for FILL Methods . . . . . . . . . . . . . . . . . . . I-109
1.2.8-1 Binary Interaction Data in the Alcohol Databank . . . . . . . . I-119
1.2.8-2 Binary Interaction Data in the Glycol Databank . . . . . . . . . I-121
Reference Manual
This page left intentionally blank.
Introducti on
General
Information
The PRO/II Component and Thermophysical Properties Reference Manual
provides details on the basic equations and calculation techniques used in the
PRO/II simulation program. It is intended as a complement to the PRO/II
Keyword Input Manual, providing a reference source for the background behind
the various PRO/II calculation methods.
What is in
This Manual?
This manual contains the correlations and methods used to calculate thermo-
dynamic and physical properties, such as the Soave-Redlich-Kwong (SRK)
cubic equation of state for phase equilibria. This manual also contains infor-
mation on the definition of pure components and petroleum fractions.
For each method described, the basic equations are presented, and appropri-
ate references provided for details on their derivation. General application
guidelines are provided, and, for many of the methods, hints to aid solution
are supplied.
Who Should Use
This Manual?
For novice, average, and expert users of PRO/II, this manual provides a good
overview of the property calculation methods used to simulate a single unit
operation or a complete chemical process or plant. Expert users can find
additional details on the theory presented in the numerous references cited
for each method. For the novice to average user, general references are also
provided on the topics discussed, e.g., to standard textbooks.
Specific details concerning the coding of the keywords required for the
PRO/II input file can be found in the PRO/II Keyword Input Manual.
Detailed sample problems are provided in the PRO/II Application Briefs
Manual and in the PRO/II Casebooks.
Finding What
you Need
A Table of Contents and an Index are provided for this manual. Cross-
references are provided to the appropriate section(s) of the PRO/II Keyword
Input Manual for help in writing the input files.
PRO/II Component and Thermophysical Properties Introducti on Int-1
Reference Manual
Symbol s Used i n Thi s Manual
Symbol Meani ng
Indicates a PRO/II input coding note. The number beside the
symbol indicates the section in the PRO/II Keyword Input
Manual to refer to for more information on coding the
input file.
Indicates an important note.
Indicates a list of references.

Int-2 Introducti on May 1994
Component Data
PRO/II allows the user to specify pure-component physical property data for a
given simulation. Pure component data are usually associated with either a prede-
fined component in a data library, a user-defined (non-library) component, or a
petroleum pseudocomponent.
Properties for defined components can be accessed in a variety of ways. They can be
retrieved from an on-line databank or library, estimated from structural or other
data, or input by the user as non-library components. User input can be used to
override properties retrieved from the libraries.
Properties for pseudo or petroleum components are derived from generalized
correlations based on minimal data, usually the normal boiling point, molecular
weight, and standard density. Hydrocarbon streams defined in terms of assay data
(including distillation data) can be converted to discrete pseudocomponents by a
number of assay processing methods.
1. 1
Section 1.1 Component Data
PRO/II Component and Thermophysical Properties I-3
Reference Manual
Defi ned Components
Component
Libraries
Table 1.1.1-1 lists the property data available in the built-in component libraries for
predefined components. These libraries include the PROCESS library (the physical
property library used as the default in PROCESS, PIPEPHASE, HEXTRAN, and
early versions of PRO/II), the SIMSCI library (a fully documented physical prop-
erty bank), the DIPPR (Design Institute for Physical Property Research) library
from the American Institute of Chemical Engineers, and the OLILIB library of
electrolyte species, which contains a subset of the library component properties
listed in the following sections.
Most of the fixed properties used in a simulation can be found in the input
reprint of the simulation. The coefficients of the correlations used for the
temperature-dependent properties stored in the libraries are not shown be-
cause they are usually covered by contractual agreements which disallow
their display in a simulation.
References
1. PPDS, Physical Property Data Service, jointly sponsored by the National
Physical Laboratory, National Engineering Laboratory, and the Institution
of Chemical Engineers in the UK.
2. DIPPR, Design Institute for Physical Property Data, sponsored by the
American Institute of Chemical Engineers.
1. 1. 1
Component Data Section 1.1
I-4 Defi ned Components May 1994
Tabl e 1. 1. 1-1: PRO/II Li brary Component Properti es
Fi xed Properti es and Constants Temperature-dependent Properti es
Acentric Factor Enthalpy of Vaporization
Carbon Number Ideal Vapor Enthalpy
Chemical Abstract Number Liquid Density
Chemical Formula Liquid Thermal Conductivity
Critical Compressibility Factor Liquid Viscosity
Critical Pressure Saturated Liquid Enthalpy
Critical Temperature Solid Density
Critical Volume Solid Heat Capacity
Dipole Moment Solid Vapor Pressure
Enthalpy of Combustion Surface Tension
Enthalpy of Fusion Vapor Pressure
Flash Point Vapor Thermal Conductivity
Free Energy of Formation Vapor Viscosity
Freezing Point (normal melting point)
Gross Heating Value
Heat of Formation
Hydrogen Deficiency Number
Liquid Molar Volume
Lower Heating Value
Molecular Weight
Normal Boiling Point
Rackett Parameter
Radius of Gyration
Solubility Parameter
Specific Gravity
Triple Point Temperature
Triple Point Pressure
UNIFAC Structure
van der Waals Area and Volume
PRO/II Component and Thermophysical Properties Defi ned Components I-5
Reference Manual
Using DATAPREP
TM
SimSci provides an interactive program, DATAPREP, for review and ma-
nipulation of the pure component fixed and temperature-dependent proper-
ties available for defined components in libraries. DATAPREP is PC based.
Detailed descriptions for both the fixed and temperature-dependent library
properties mentioned above are contained in Appendix A of the DATAPREP
User Guide.
A comprehensive summary of the available data for each component, for any
release of the libraries, can also be generated by using DATAPREP.
DATAPREPs functionality also includes the ability to generate keyword
input file inserts containing component properties for non-library compo-
nents. Private pure component libraries can also be made using DATAPREP.
In addition to the USER.LB1 and USER.LB2 files that can be used directly
by PRO/II on a PC, ASCII input files are generated for input to the library
manager program for use on other platforms. Please refer to the DATAPREP
User Guide for further information about its capabilities.
Reference
DATAPREP User Guide, 1991, Simulation Sciences Inc.
Fixed Properties As explained in the above section, these properties are described in Appen-
dix A of the DATAPREP User Guide. Some things to be aware of are that
the specific gravities of permanent gases are often given relative to air, with-
out any annotations in the output, and liquid molar volumes can be
extrapolated from a condition very different from 77 F (25 C), if the
component doesnt naturally exist as a liquid at 77 F.
Temperature-
dependent
Properties
The temperature-dependent correlations available for use in PRO/II are listed
in Section 17, Component Properties, of the PRO/II Keyword Input Manual.
The equations that are typically used to represent a property are listed in Ta-
ble 1.1.1-2. While temperature-dependent library properties are fitted and are
usually very accurate at saturated, subcritical conditions, caution must be
used in the superheated or supercritical regions.
Because of the form of some of the allowable temperature-dependent equations,
extrapolation beyond the minimum and maximum temperatures is not done using
the actual correlation. PRO/II has adopted the rules shown in Table 1.1.1-2, based
on the property, for extrapolation of the temperature-dependent correlations.
Tabl e 1. 1. 1-2: PRO/II Temperature-dependent Property Equati ons and
Extrapol ati on Conventi ons
Temperature-dependent
Property
Recommended
Equati ons
Extrapol ati on
Method
Vapor Pressure 14, 20, 21, 22 ln(Prop.) vs. 1/T
Liquid Density 1, 4, 16, 32 Prop. vs. T
Ideal Vapor Enthalpy 1, 17, 41 Prop. vs. T
Enthalpy of Vaporization 4, 15, 36, 43 Prop. vs. T
Saturated Liquid Enthalpy 1, 42, 35 Prop. vs. T
Liquid Viscosity 13, 20, 21 ln(Prop.) vs. 1/T
Vapor Viscosity 1, 19, 26, 27 Prop. vs. T
Liquid Thermal Conductivity 1, 4, 34 Prop. vs. T
Vapor Thermal Conductivity 1, 19, 33 Prop. vs. T
Surface Tension 1, 15, 30 Prop. vs. T
Solid Thermal Conductivity 1 Prop. vs. T
Solid Density 1 Prop. vs. T
Solid Cp or Enthalpy 1 Prop. vs. T
Solid Vapor Pressure 20 ln(Prop.) vs. 1/T
Another note of caution concerns the use of equations 20 and 21 in modeling
component vapor pressures. These equations are actually combinations of
two or more traditionally used vapor pressure equations (e.g., Antoine). It is
intended that the user apply only subsets of the available coefficients with
these equations corresponding to the more traditional equations. Table
1.1.1-3 gives some examples of this mapping.
Tabl e 1. 1. 1-3: PRO/II Vapor Pressure Equati ons
Equati on 20 / 21 Coeffi ci ents
Common VP Equati ons (#) C1 C2 C3 C4 C5 C6 C7
Clapeyron (20 or 21) x x
Antoine (21) x x x
Riedel (20) x x x x
Frost-Kalkwarf (21) x x x x
Reidel-Plank-Miller (20) x x x x
PRO/II Component and Thermophysical Properties Defi ned Components I-7
Reference Manual
Properties From
Structure
Properties for defined components, either library or non-library, may be
estimated if the user supplies a component structure and invokes the FILL
option in the component data category of input. This procedure primarily
uses the methods of Joback and is good for components with molecular
weights below 400 and components with less than 20 unique structural
groups. More accurate results are obtained for components containing just
one type of functional group. For example, amine properties would be more
accurate than those predicted for an ethanol amine, which would contain
functional groups for both an alcohol and an alcohol amine. This feature is
available in DATAPREP and in PRO/II for all versions subsequent to v3.3.
Complete documentation of the estimation techniques used is contained in
Section 3.7, Prediction, of the DATAPREP User Guide.
Petrol eum Components
General
Information
Petroleum components (often called pseudocomponents) are either defined
on a one-by-one basis on PETROLEUM statements or generated from one or
more streams given in terms of assay data. The processing of assays is de-
scribed in Section 1.1.3, Assay Processing. Each individual pseudocompo-
nent is typically a narrow-boiling cut or fraction. Component properties are
generated based on two of the following three properties:
Molecular weight.
Normal boiling point (NBP).
Standard liquid density.
If only two are supplied, the third is computed with the SIMSCI method (or
with another method if requested with the MW keyword). These methods are
described in the sections below.
From those three basic properties, the program estimates all other properties
needed for the calculation of thermophysical properties. Three different sets of
characterization methods are provided. These are known as the CAVETT, SIM-
SCI, and Lee-Kesler methods. The Cavett methods developed in 1962 have been
the default in all versions of PRO/II up to and including the 3.5 series. The SIM-
SCI methods use a combination of published (Black and Twu, 1983; Twu, 1984)
and proprietary methods developed by SimSci. These are the default for all
PRO/II versions subsequent to the 3.5 series. The LK option accesses methods
developed by Lee and Kesler in 1975 and 1976.
Property
Generation--
SIMSCI Method
Cri ti cal Properti es and Acentri c Factor
The SIMSCI characterization method was developed by Twu in 1984. It
expresses the critical properties (and molecular weight) of hydrocarbon com-
ponents as a function of NBP and specific gravity. The correlation is ex-
pressed as a perturbation about a reference system of normal alkanes. The
critical temperature (in degrees Rankine) is given by:
(1)
T
c
T
c
1 + 2f
T
_
,

1 2f
T
_
,
1
]
2
(2)
f
T
SG
T
0.362456

T
b
1

2
+
0.03982850.948125

T
b
1

2
_
,
SG
T
1
]
1. 1. 2
PRO/II Component and Thermophysical Properties Petrol eum Components I-9
Reference Manual
(3)
SG
T
exp
SG
SG
_
,
1
]
1
(4)
T
c
T
b
(0.533272 + 0.19101710
3
T
b
+ 0.77968110
7
T
b
2
0.28437610
10
T
b
3
+ 0.95946810
28
T
b

13
)
1
(5)
SG
0.843593 0.128624 3.36159

3
13749.5
12
where:
SG = specific gravity
Tb = normal boiling point, degrees Rankine
= 1 - Tb / Tc
SG = specific gravity correction

f = correction factor
subscript T refers to the temperature
subscript c refers to the critical conditions
superscript refers to the reference system
The critical volume (in cubic feet per pound mole) and the critical pressure
(in psia) are given by similar expressions:
(6)
V
c
V
c
1 + 2f
V
_
,

1 2f
V
_
,
1
]
2
(7)
f
V
SG
V

0.466590

T
b
1

2
+
0.182421+ 3.01721

T
b
1

2
_
,
SG
V
1
]
(8)
SG
V
exp
SG
2
SG
2
_
,
1
]
1
(9)
V
c
0.419869 0.505839 1.56436

3
9481.70
14
_
,
1
]
8
(10)
P
c
P
c
T
c

T
c
_
,

V
c

V
c
_
,

1 + 2f
P
_
,

1 2f
P
_
,
1
]
2
(11)
f
P
SG
P
[
2.53262 46.1955

T
b
1

2
0.00127885T
b
_
,
+
11.4277 + 252.140

T
b
1

2
+ 0.00230535T
b
_
,
SG
P
]
(12)
SG
P
exp
0.5
SG
SG
_
,
1
]
1
(13)
P
c
3.83354+ 1.19629
1

2
+ 34.8888 + 36.1952
2
+ 104.193
4
_
,
2
where:
V = molar volume, ft
3
/lbmole
P = pressure, psia
subscripts V and P refer to the volume and pressure
I-10 Petrol eum Components May 1994
The acentric factor for the SIMSCI method is estimated with the use of a gen-
eralized Frost-Kalkwarf vapor equation developed at SimSci. The equation is
given by:
(14)
lnP
R

A
1
+ A
4
_
,
+
A
2
+ A
5
_
,

T
R
+
A
3
+ A
6
_
,
lnT
R
+ A
7
P
R
T
R
2
where:
A1 to A7 = constants given in Table 1.1.2-1
PR = reduced pressure (P/Pc)
TR = reduced temperature (T/Tc),
= a parameter evaluated at the NBP and given by:
(15)

lnP
R,b
A
7
P
R,b

T
R,b
2
_
,
f
T
R,b
_
,
f
T
R,b
_
,
where:
subscripts R,b indicate reduced properties evaluated at the
normal boiling point
Functions f and f are given by:
(16) f (T
R
) A
1
+ A
2

T
R
+ A
3
lnT
R
(17) f (T
R
) A
4
+ A
5

T
R
+ A
6
lnT
R
The values of the seven constants in these equations are shown in Table 1.1.2-1.
Tabl e 1. 1. 2-1: Val ues of
Constants for Equati ons (14)-(17)
A1 10.2005
A2 -10.6317
A3 -5.58058
A4 2.09167
A5 -2.09167
A6 1.70214
A7 0.4312
To compute the acentric factor, the parameter is determined using equation
(15) and the known (or already estimated) values for the critical temperature
and pressure and the normal boiling point (NBP). This is then used in equation
(14) to compute the reduced vapor pressure at a reduced temperature of 0.7,
which is then used in the definition of the acentric factor:
(18) log
10

P
R,T
R
0.7
_
,
1
Reference Manual
Other Fixed Properties
The heat of formation is computed from a proprietary correlation developed by
SimSci. The solubility parameter is estimated from the following equation:
(19)

H
V
RT
V
L
_
,

1 2
The molar latent heat of vaporization, HV, is computed from the Kistiakowsky-
Watson method described later on in this section, while VL is the liquid molar
volume at 25 C.
Temperature-dependent Properties
The ideal-gas enthalpy (needed for equation-of-state calculations) is calcu-
lated from the method of Black and Twu developed in 1983. The method was
an extension of work done by Lee and Kesler and involved fitting a wide vari-
ety of ideal-gas heat capacity data for hydrocarbons from the API 44 project
and other sources. The equation (which produces enthalpies in Btu/lb and
uses temperatures in degrees Rankine) is as follows:
(20)
H
A
1
+ A
2
T +
A
3
2
T
2
+
A
4
3
T
3
(21) A
2
C
1
+ C
7
C
4
(22) A
3
C
2
+ C
7
C
5
(23) A
4
C
3
+ C
7
C
6
(24) C
1
0.33886 + 0.02827 K
(25)
C
2
(0.9291 1.1543K + 0.0368K
2
)10
4
(26)
C
3
1.665810
7
(27) C
4
(0.26105 0.59332K)
(28)
C
5
4.9210
4
(29)
C
6
(0.536 0.6828K)10
7
(30)
C
7
[(12.8 K) (10 K)

10K]
2
The Watson characterization factor, K, is defined as:
(31)
K
NBP
1 3
SG
where:
NBP = normal boiling point in degrees Rankine
The constant A1 in equation (20) is determined so as to give an enthalpy of zero
at the arbitrarily chosen zero for enthalpy, which is the saturated liquid at 0 C.
The latent heat of vaporization as described below (to get from saturated liq-
uid to saturated vapor) and the SRK equation of state (to get from saturated
vapor to ideal gas) are used to compute the enthalpy departure between this
reference point and the ideal-gas state.
The vapor pressure is calculated from the reduced vapor-pressure equation
(14) used above in the calculation of the acentric factor. The latent heat of
vaporization is also calculated from equation (14). The saturated liquid en-
thalpy is calculated by computing the departure from the ideal-gas enthalpy,
as a sum of the latent heat and the enthalpy departure (computed with the
SRK equation of state) for the saturated vapor. The saturated liquid density is
computed by applying the Rackett equation (see Section 1.2.3, Generalized
Correlation Methods) to saturated temperature and pressure conditions as
predicted from the vapor-pressure equation (14).
Property
Generation--
CAVETT Method
Optionally, the user may choose to compute critical properties from the meth-
ods developed in 1962 by Cavett. This option is called the CAVETT method.
The equations are:
(32)
T
c
768.07121 + 1.7133693T
b
0.0010834003T
b
2
0.0089212579(API)T
b
+ 0.3889058410
6
T
b
3
+ 0.5309492(API)T
b
2
+ 0.32711610
7
(API)
2
T
b
2
(33)
log
10
P
c
2.8290406 + 0.9412010910
3
T
b
0.3047474910
5
T
b
2
0.208761110
4
(API)T
b
+ 0.1518410310
8
T
b
3
+ 0.1104789910
7
(API)T
b
2
0.4827159910
7
(API)
2
T
b
+ 0.1394961910
9
(API)
2
T
b
2
where:
Tc = critical temperature in degrees Rankine
Pc = critical pressure in psia
Tb = normal boiling point in degrees Fahrenheit
API = API gravity
When the CAVETT characterization options are chosen, the acentric factor is
computed by a method due to Edmister (1958):
(34)

3
7

log
10
P
c
(T
c

T
b
) 1
_
,
1
Reference Manual
In equation (34), Pc is in atmospheres. Finally, the critical volume is esti-
mated from the following equation:
(35)
Z
c

P
c
V
c
RT
c
0.291 0.08
15 PRO/II Note: For more information on using the CAVETT characterization
method, see Section 15, Petroleum Component Properties, of the PRO/II
Keyword Input Manual.
When the CAVETT characterization option is chosen, the heat of formation
and solubility parameter are calculated exactly as in the SIMSCI method
above.
Ideal-gas enthalpies (in Btu/lb-mole) are computed with the following equations:
(36)
H
A + BT + CT
2
+ DT
3
(37) A a
5
MW a
4
+ a
0
(38) B 459.67 (1379.01a
1
2a
2
) + a
3
(39) C a
2
1379.01a
1
(40)
D a
1

9.17510
11
API 5.63310
8
_
,
MW
(41)
a
2

3.10710
4
5.83210
8
API
_
,
MW
(42)
a
3

'
1.702510
6
1.48910
6
API
_
,
API 2.85710
5
_
,
API
+
'
4.29310
3
3.08410
4
K
_
,
K + 0.088) K 0.819
;
)
MW
(43) a
4
459.67
'
459.67
459.67a
1
a
2
_
,
+ a
3
;
)
(44) a
5

'
(0.351K 8.953) K + 43.402
;
)
K + 188.25
+
'
3.53510
4
API 0.053
_
,
API 5.95610
3
K + 3.544
;
)
API
where:
T = temperature in degrees Rankine
MW = molecular weight
API = API gravity
K = Watson K-factor defined by equation (31)
The constant a0 in equation (37) is determined so as to be consistent with the
arbitrary zero of enthalpy, which is the saturated liquid at 0 C.
Vapor pressures (in psia) are computed from a generalized Antoine equation:
(45)
ln P A +
B
T 80.0
(46)
A ln(14.696)
B
T
b
80.0
(47)
B
ln P
c
ln(14.696)
1
T
c
80.0

1
T
b
80.0
Temperatures (including the critical temperature Tc and normal boiling point
Tb) are in degrees Rankine.
The saturated liquid density (in lb/ft
3
) is computed as follows:
(48)
L
A + BT + CT
2
(49)
A 1.328
L,60
(50)
B
0.3076
L,60
T
c
(51)
C
0.3989
L,60
T
c
2
where:
L,60
=
liquid density at 60 F, calculated from the specific gravity
and the density of water
Temperatures are in degrees Rankine
The latent heat of vaporization (in Btu/lb-mole) is calculated from a combina-
tion of the Watson equation (Watson, 1943, Thek and Stiel, 1966), for the tem-
perature variation of the heat of vaporization, and the expression of
Kistiakowsky (1923), for the heat of vaporization at the normal boiling point:
(52)
H
vap
H
0

T
c
T
T
c
T
b
_
,
0.38
(53)
H
0
T
b

7.58 + 4.571 lnT

b
_
,
The critical temperature Tc, normal boiling point Tb, and temperature T are
all in degrees Rankine.
The saturated liquid enthalpy is estimated with the correlation of Johnson
and Grayson. This method is discussed in Section 1.2.3, Generalized Correla-
tion Methods. A constant is added so that the saturated liquid enthalpy is
zero at 0 C.
Reference Manual
Property
Generation--Lee-
Kesler Method
Kesler and Lee used the following equations in 1976 to correlate critical tem-
peratures and critical pressures of hydrocarbons:
(54)
T
c
341.7 + 811SG + (0.4244 + 0.1174 SG)T
b
+ (0.4669 3.2623 SG)10
5

T
b
(55)
lnP
c
8.3634 0.0566

SG
0.24244 + 2.2898

SG + 0.11857

SG
2
_
,
10
3
T
b
+
1.4685 + 3.648

SG + 0.47227

SG
2
_
,
10
7
T
b
2

0.42019 + 1.6977

SG
2
_
,
10
10
T
b
3
where:
Tc, Tb = critical and normal boiling temperatures (both in degrees
Rankine)
Pc = critical pressure in psia
The acentric factor is estimated from an equation in an earlier work by Lee
and Kesler (1975):
(56)

lnP
R,b
5.92714 + 6.09648

T
R,b
+ 1.28862lnT
R,b
0.169347T
R,b
6
15.2518 15.6875

T
R,b
13.4721 lnT
R,b
+ 0.43577 T
R,b
6
where:
subscripts R,b indicate reduced properties evaluated at the normal
boiling point
The critical volume is then estimated from the following equation:
(57)
Z
c

P
c
V
c
RT
c
0.2905 0.085
When the Lee-Kesler characterization option is chosen, the heat of formation
and the solubility parameter are calculated exactly as in the SIMSCI method
described previously.
Ideal-gas enthalpies (in Btu/lb-mole) are computed by integrating the follow-
ing equation for the ideal-gas heat capacity:
(58)
C
p
0.33886 + 0.02827K
0.9291 1.1543K + 0.0368K

2
_
,
10
4
T 1.665810
7
T
2
(CF)
0.26105 0.59332 (4.56 9.48)10

4
T (0.536 0.6828)10
7
T
2
1
]
The factor CF is given by:
(59)
CF [(12.8 K)(10 K)

(10)]
2
where:
K = Watson K-factor defined by equation (31)
T = temperature in degrees Rankine
= acentric factor as calculated by equation (56)
The constant of integration is determined so as to give an enthalpy of zero at the
arbitrarily chosen basis for enthalpy, which is the saturated liquid at 0 C.
When the Lee-Kesler characterization option is chosen, the vapor pressure,
saturated liquid density, saturated liquid enthalpy, and latent heat of vaporiza-
tion are all calculated by the methods used for CAVETT characterization, as
described in the previous section.
References
1. Black, C., and Twu, C.H., 1983, Correlation and Prediction of
Thermodynamic Properties for Heavy Petroleum, Shale Oils, Tar Sands
and Coal Liquids, paper presented at AIChE Spring Meeting, Houston,
March 1983.
2. Cavett, R.H., 1962, Physical Data for Distillation Calculations -
Vapor-Liquid Equilibria, 27th Mid-year Meeting of the API Division of
Refining, 42[III], 351-357.
3. Edmister, W.C., 1958, Applied Hydrocarbon Thermodynamics, Part 4:
Compressibility Factors and Equations of State, Petroleum Refiner,
37(4), 173.
4. Kesler, M.G., and Lee, B.I., 1976, Improve prediction of enthalpy of
fractions, Hydrocarbon Proc., 53(3), 153-158.
5. Kistiakowsky, W., 1923, Z. Phys. Chem., 107, 65.
6. Lee, B.I., and Kesler, M.G., 1975, A Generalized Thermodynamic
Correlation Based on Three-Parameter Corresponding States, AIChE J.,
21, 510-527.
7. Thek, R.E., and Stiel, L.I., 1966, A New Reduced Vapor Pressure Equation,
AIChE J., 12, 599-602.
8. Twu, C.H., 1984, An Internally Consistent Correlation for Predicting the
Critical Properties and Molecular Weights of Petroleum and Coal-tar
Liquids, Fluid Phase Equil., 16, 137-150.
9. Watson, K.M., 1943, Ind. Eng. Chem., 35, 398.
Reference Manual
Assay Processi ng
General
Information
Hydrocarbon streams may be defined in terms of laboratory assay data. Typi-
cally, such an assay would consist of distillation data (TBP, ASTM D86,
ASTM D1160, or ASTM D2887), gravity data (an average gravity and possi-
bly a gravity curve), and perhaps data for molecular weight, lightends compo-
nents, and special refining properties such as pour point and sulfur content.
This information is used by PRO/II to produce one or more sets of discrete
pseudocomponents which are then used to represent the composition of each
assay stream.
The process by which assay data are converted to pseudocomponents can be ana-
lyzed in terms of several distinct steps. Before each of these is examined in de-
tail, it will be useful to list briefly each step of the process in order:
The user defines one or more sets of TBP cutpoints (or accepts the de-
fault set of cutpoints that PRO/II provides). These cutpoints define the
(atmospheric) boiling ranges that will ultimately correspond to each
pseudocomponent. Multiple cutpoint sets (also known as blends) may
also be defined to better model different sections of a process.
Each set of user-supplied distillation data is converted to a TBP (True
Boiling Point) basis at one atmosphere (760 mm Hg) pressure.
The resulting TBP data are fitted to a continuous curve and then the pro-
gram cuts each curve to determine what percentage of each assay
goes into each pseudocomponent as defined by the appropriate cutpoint
set. Gravity and molecular weight data are similarly processed so that
each cut has a normal boiling point, specific gravity, and molecular
weight. During this step, the lowest-boiling cuts may be eliminated or
modified to account for any lightends components input by the user.
Within each cutpoint set, all assay streams using that set (unless they are
explicitly excluded from the blending - this is described later) are com-
bined to get an average normal boiling point, gravity, and molecular
weight for each of the pseudocomponents generated from that cutpoint
set. These properties are then used to generate all other properties (criti-
cal properties, enthalpy data, etc.) for that pseudocomponent.
Note: Special refinery properties such as cloud point and sulfur content may
also be defined within assays. The distribution of these properties into pseudo-
components and their subsequent processing by the simulator is outside the
scope of this chapter but will be covered in a later document.
1. 1. 3
I-18 Assay Processi ng May 1994
Cutpoint Sets
(Blends)
Defi ni ng Cutpoi nts
In any simulation, there is always a primary cutpoint set, which defaults
as shown in Table 1.1.3-1.
Tabl e 1. 1. 3-1: Pri mary TBP Cutpoi nt Set
TBP Range,
o
F
Number of
Components Wi dth,
o
F
100-800
28 25
800-1200
8 50
1200-1600
4 100
The primary cutpoints shown in Table 1.1.3-1 may be overridden by supply-
ing a new set for which no name is assigned. In addition, secondary sets
of cutpoints may be supplied by supplying a set and giving it a name. The
blend with no name (primary cutpoint set) always exists (even if only named
blends are specifically given); there is no limit to the number of named
blends (secondary cutpoint sets) that may be defined. The user may designate
one cutpoint set as the default; if no default is explicitly specified, the pri-
mary cutpoint set will be the default. Each cutpoint set (if it is actually used
by one or more streams) will produce its own set of pseudocomponents for
use in the flowsheet.
15 PRO/II Note: For more information on specifying TBP cutpoint sets, see Section
15, Petroleum Component Properties, of the PRO/II Keyword Input Manual.
Association of Streams With Blends
Each assay stream is associated with a particular blend. By default, an assay
stream is assigned to the default cutpoint set. A stream may be associated
with a specific secondary cutpoint set by explicitly specifying the name of
that cutpoint set (blend) in association with the stream. If the assay stream is
associated with a blend name not given for any cutpoint set previously de-
fined, a new blend with that name is created using the same cutpoints as the
primary cutpoint set. The user may also specify that a stream use a certain set
of cutpoints but not contribute to the blended properties of the pseudocompo-
nents generated from that set (this might be appropriate if an estimate were
being supplied for a recycle stream, for example). This is done by selecting
the XBLEND option, which excludes the stream in question from the blend-
ing. The default is for the stream to be included in the blending for the pur-
poses of pseudocomponent property generation; this is called the BLEND
option. It is not allowed for the XBLEND option to be used on all streams as-
sociated with a blend, since at least one stream must be blended in to define
the pseudocomponent properties. The blending logic is best illustrated by an
example:
PRO/II Component and Thermophysical Properties Assay Processi ng I-19
Reference Manual
Suppose that two secondary cutpoint sets A1 and A2 were defined, and that
A1 was designated as the default. This means that three sets actually exist,
since the primary cutpoint set supplied by PRO/II still exists (though it is no
longer the set with which streams will be associated by default). Now, sup-
pose the following streams (where extraneous information like the initial con-
ditions is not shown) are given:
Tabl e 1. 1. 3-2: Bl endi ng Exampl e
Stream Bl end Opti on Bl end Name
S1 none given
(defaulted to
BLEND)
none given
(defaulted to A1)
S2 XBLEND none given
(defaulted to A1)
S3 XBLEND A1
S4 BLEND A2
S5 BLEND B1
S6 XBLEND B1
S7 BLEND B2
Streams S1 and S2 will use the pseudocomponents defined by secondary cut-
point set A1, since it is the default. S3 will also use A1s pseudocomponents
since it is specified directly. The pseudocomponents in blend A1 will have
properties determined only by the cuts from stream S1, since the XBLEND
option was used for S2 and S3. Stream S4 will use the pseudocomponents de-
fined by cutpoint set A2. Streams S5 and S6 will go into a new blend B1
which will use the cutpoints of the primary cutpoint set. Since XBLEND is
used for stream S6, only stream S5s cuts will be used to determine the prop-
erties of the pseudocomponents in blend B1. Finally, stream S7 will use an-
other new blend, B2, also with the cutpoints from the primary cutpoint set.
Since it is a different blend, however, the pseudocomponents from blend B2
will be completely distinct (even though they will use the same cutpoint
ranges) from those of blend B1.
15 PRO/II Note: For more information on blending options for assay streams, see
Section 15, Petroleum Component Properties, of the PRO/II Keyword Input
Manual.
Application Considerations
The selection of cutpoints is an important consideration in the simulation of
hydrocarbon processing systems. Too few cuts can result in poor repre-
sentation of yields and stream properties when distillation operations are
simulated; moreover, desired separations may not be possible because of
component distributions. On the other hand, the indiscriminate use of cuts
not needed for a simulation serves only to increase the CPU time unnecessar-
ily. It is wise to examine the cut definition for each problem in light of simu-
lation goals and requirements. The default primary cutpoint set in PRO/II
represents, in our experience, a good selection for a wide range of refinery
applications.
In some circumstances, it may be desirable to use more than one cutpoint set
in a given problem. This multiple blends functionality is useful when dif-
ferent portions of a flowsheet are best represented by different TBP cuts; for
example, one part of the process may have streams that are much heavier
than another and for which more cutpoints at higher temperatures would be
desirable. It is also useful when hydrocarbon feeds to a flowsheet differ in
character; for example, different blends might be used to represent an aro-
matic stream (producing pseudocomponents with properties characteristic of
aromatics) and a paraffinic stream feeding into the same flowsheet. The extra
detail and accuracy possible with this feature must be balanced against the in-
crease in CPU time caused by the increased number of pseudocomponents.
Interconversion of
Distillation Curves
Types of Di sti l l ati on Curves
Assays of hydrocarbon streams are represented by distillation curves. A dis-
tillation curve represents the amount of a fluid sample that is vaporized as
the temperature of the sample is raised. The temperature where the first va-
porization takes place is referred to as the initial point (IP), and the tempera-
ture at which the last liquid vaporizes is called the end point (EP). Each data
point represents a cumulative portion (usually represented as volume per-
cent) of the sample vaporized when a certain temperature is reached.
Estimation of thermophysical properties for the pseudocomponents requires
(among other things) a distillation curve that represents the true boiling point
(TBP) of each cut in the distillation. However, rigorous TBP distillations are
difficult and not well standardized so it is common to perform some other
well-defined distillation procedure; standard methods are defined by the
American Society for Testing and Materials (ASTM). The ASTM procedures
most commonly used for hydrocarbons are D86, D1160, and D2887.
Reference Manual
ASTM D86 distillation is typically used for light and medium petroleum
products and is carried out at atmospheric pressure. D1160 distillation is
used for heavier petroleum products and is often carried out under vacuum,
sometimes at absolute pressures as low as 1 mm Hg. The D2887 method uses
gas chromatography to produce a simulated distillation curve; it is applicable
to a wide range of petroleum systems. D2887 results are always reported by
weight percent; other distillations are almost always reported on a volume
percent basis. More details on these distillation procedures may be found in
the API Technical Data Book; complete specifications are given in volume 5
(Petroleum Products and Lubricants) of the Annual Book of ASTM Standards.
Conversi on of D1160 Curves
PRO/II converts D1160 curves to TBP curves at 760 mm Hg using the three-
step procedure recommended in the API Technical Data Book:
Convert to D1160 at 10 mm Hg using API procedure 3A4.1 (which in
turn references procedure 5A1.13). This procedure is expressed as a way
to estimate a vapor pressure at any temperature given the normal boiling
point, but the same equations may be solved to yield a normal boiling
temperature given the boiling temperature at another pressure. The equa-
tions used are as follows:
(1)
(2)
log
10
P =
2663.129X 5.994296
95.76X 0.972546
0.0013 X 0.0022
(2 P 760 mm Hg)
(3)
where:
P* = vapor pressure in mm Hg at temperature T (in degrees
Rankine)
The parameter X is defined by:
(4)
X =
T
b
T
0.0002867T
b
748.1 0.2145T
b
where:
Tb = boiling point (in degrees Rankine) at a pressure of 760 mm
Hg
log10P =
3000.538X 6.76156
43X 0.987672
for X > 0.0022 (P < 2 mm Hg)
log10P =
2770.085X 6.412631
36X 0.989679
for X < 0.0013 (P > 760 mm Hg)
For conversions where neither pressure is 760 mm Hg, the conversion may
be made by applying the above equations twice in succession, using 760 mm
Hg as an intermediate point:
Convert to TBP at 10 mm Hg using API Figure 3A2.1 (which has been
converted to equation form by SimSci).
Convert to TBP at 760 mm Hg using API procedure 3A4.1.
PRO/II converts D2887 simulated distillation data to TBP curves at 760 mm Hg
using the two-step procedure recommended in the API Technical Data Book:
Convert to D86 at 760 mm Hg using API procedure 3A3.1. This procedure
converts D2887 Simulated Distillation (SD) points (in weight percent) to
D86 points (in volume percent) using the following equation:
(5)
D86 = a(SD)
b
F
c
where:
D86 and SD = the ASTM D86 and ASTM D2887 temperatures in de-
grees Rankine at each volume percent (for D86) and the
corresponding weight percent (for SD), and a, b, and c
are constants varying with percent distilled according
to Table 1.1.3-3.
Tabl e 1. 1. 3-3: Val ues of Constants a, b, c
Percent
Di sti l l ed a b c
0 6.0154 0.7445 0.2879
10 4.2262 0.7944 0.2671
30 4.8882 0.7719 0.3450
50 24.1357 0.5425 0.7132
70 1.0835 0.9867 0.0486
90 1.0956 0.9834 0.0354
100 1.9073 0.9007 0.0625
The parameter F in equation (5) is calculated by the following equation:
(6)
F = 0.009524(SD 10%)
0.05434
(SD 50%)
0.6147
where:
SD10% and SD50% = D2887 temperatures in degrees Rankine at the 10% and
50% points, respectively
Reference Manual
Convert to TBP at 760 mm Hg using API procedure 3A1.1, which is
described in the section Conversion of D86 Curves with New (1987) API
Method below.
PRO/II has three options for the conversion of D86 curves to TBP curves at 760
mm Hg. These are the currently recommended (1987) API method, the older
(1963) API method, and the Edmister-Okamoto correlation. In addition, a correc-
tion for cracking may be applied to D86 data; this correction was recommended
by the API for use with their older conversion procedure, but is not recom-
mended for use with the current (1987) method. The conversion of D86
curves takes place in the following steps:
If a cracking correction is desired, correct the temperatures above 475 F as
follows:
(7)
T
corr
= T
obs
+ D ; log
10
D = 1.587 + 0.00473T
obs
where:
Tcorr, Tobs = the corrected and observed temperatures, respectively,
in degrees Fahrenheit.
If necessary, convert the D86 curve at pressure P to D86 at 760 mm Hg
with the standard ASTM correction factor:
(8) T
760
= T
P
+ 0.00012(760 P)(460 + T
P
)
where:
TP = D86 temperature in Fahrenheit at pressure P
T760 = D86 temperature in Fahrenheit at 760 mm Hg
Convert from D86 at 760 mm Hg to TBP at 760 mm Hg using one of the
three procedures below.
a) Conversion of D86 Curves with New (1987) API Method
By default, PRO/II converts ASTM D86 distillation curves to TBP curves
at 760 mm Hg using procedure 3A1.1 (developed by Riazi and Daubert in
1986) recommended in the 5th edition of the API Technical Data Book.
The equation for this procedure is as follows:
(9)
TBP = a(D86)
b
where a and b are constants varying with percent of liquid sample distilled
as given in Table 1.1.3-4:
Tabl e 1. 1. 3-4: Val ues of Constants a, b
Percent Di sti l l ed a b
0 0.9167 1.0019
10 0.5277 1.0900
30 0.7429 1.0425
50 0.8920 1.0176
70 0.8705 1.0226
90 0.9490 1.0110
100 0.8008 1.0355
b) Conversion of D86 Curves with Old (1963) API Method
This method, while no longer the default, is still available for users whose
flowsheets may be tuned to the results using the old method. This method
was recommended (and shown in graphical form) in older editions of the
API Technical Data Book. The graphical correlation has been converted to
equation form by SimSci.
c) Conversion of D86 Curves with Edmister-Okamoto Method
Edmister and Okamoto (1959) developed a method which is still widely
used for converting ASTM D86 curves to TBP curves. If the Edmister-
Okamoto method is specified as the conversion method, their procedure
(converted from the original graphical form to equations by SimSci) is
used for conversion of D86 to TBP curves.
Cutting TBP Curves Fi tti ng of Di sti l l ati on Curves
Before a curve is cut into pseudocomponents, the distillation data must be fit-
ted to a continuous curve. This is necessary because the supplied data points
will not in general correspond to the desired cutpoints. PRO/II offers three
methods for fitting distillation curves.
The default is the cubic spline method (known as the SPLINE option). A cu-
bic spline function is used to fit all given volume percents between the first
and last points. Beyond those bounds, points 1 and 2 and points N and N-1
are used to define a normal distribution function to extrapolate to the 0.01%
and 99.99% points, respectively. If only two points are supplied, the entire
curve is defined by the distribution function fit. This extrapolation feature is
particularly valuable when extrapolating heavy ends distillations which often
terminate well below 50 volume percent. This method in general results in an
excellent curve fit. The only exception is when the distillation data contain a
significant step function (such a step is often the unphysical result of an error
in obtaining or reporting the data); in that case, the step creates an instability
that tends to propagate throughout the entire length of the curve. Should this
happen, the input data should be checked for validity.
Reference Manual
The quadratic fit method (known as the QUADRATIC option) provides a suc-
cessive quadratic approximation to the shape of the input assay curve. This
method is recommended in the rare case (see above) where a cubic spline fit
is unstable.
The Probability Density Function (PDF) method (known as the PDF option)
is different in that it does not necessarily pass through all the points input by
the user. Instead, it fits a probability density function to all points supplied.
The resulting curve will maintain the probability-curve shape characteristic
of petroleum distillations, while minimizing the sum of the squares of the dif-
ferences between the curve and the input data. If desired, the curve may be
constrained to pass through either or both of the initial point and end point.
The PDF method is recommended whenever it is suspected that the distilla-
tion data are noisy, containing significant random errors.
It is worth noting that the choice of curve-fitting procedure will also have a
slight impact on the distillation interconversions described in the previous sec-
tion. That is because most of the conversion procedures work by doing the
conversion at a fixed set of volume percents, which must be obtained by interpo-
lation and sometimes extrapolation, using some curve-fitting procedure.
Division into Pseudocomponents
Once a smooth distillation curve is obtained, the volume percent distilled at each
cutpoint is determined. The differences between values at adjacent cutpoints de-
fine the percent of the streams volume that is assigned to the pseudocomponent
defined by the interval between two adjacent cutpoints. For example, using the
default set of cutpoints shown in Table 1.1.3-1, the first pseudocomponent would
contain all material boiling between 100 F and 125 F, the second would con-
tain the material boiling between 125 F and 150 F, and so forth. Material boil-
ing above the last cutpoint (1600 F) would be combined with the last
(1500-1600) cut, while (with the exception of lightends as discussed below)
material boiling below 100 F would be combined with the first cut. If the distil-
lation data do not extend into all of the cut ranges (in this example, if the initial
point were higher than 125 F or if the end point were lower than 1500 F), the
unused cuts are omitted from the simulation.
The normal boiling point (NBP) of each cut is determined as a volume-frac-
tion average (or, in rare cases where TBP, D86, or D1160 distillations are
entered on a weight basis, as a weight-fraction average) by integrating across
the cut range. For small cut ranges, this will closely approach other types of
average boiling points. These average boiling points are used (possibly after
blending with cuts from other assay streams in the flowsheet) as correlating
parameters when calculating other thermophysical properties for each
pseudocomponent.
These procedures are demonstrated in Figure 1.1.3-1 for a fictitious assay
with an IP of 90 F being cut according to the default cutpoint set (Table
1.1.3-1); for simplicity only the first ten percent of the curve is shown. In ad-
dition to its range, the first cut picks up the portion boiling below 100 F, and
its average boiling point (about 110 F in this case) is determined by integrat-
ing the curve from the IP to the 125 F point. The second cut is assigned the
material boiling from 125 F to 150 F, which is integrated to get a NBP of
approximately 138 F. The third and subsequent cuts are generated in a simi-
lar manner.
Figure 1.1.3-1:
Cutting TBP Curves
Gravity Data
PRO/II requires the user to enter an average gravity (either as a Specific
Gravity, API Gravity, or Watson K-factor) for each assay. If a Watson K is
given, it is converted to a gravity using the TBP data for the curve. Entry of a
gravity curve is recommended but not required.
If a user-supplied gravity curve does not extend to the 95% point, quadratic
extrapolation is used to generate an estimate for the gravity at the 100%
point. A gravity for each cut is determined at its mid-point, and an average
gravity for the stream is computed. If this average does not agree with the
specified average, the program will either normalize the gravity curve (if
data are given up to 95%) or adjust the estimated 100% point gravity value to
force agreement. Since the latter could in some cases result in unreasonable
gravity values for the last few cuts, the user should consider providing an es-
timate of the 100% point gravity value and letting the program normalize the
curve, particularly when gravity data are available to 80% or beyond.
Reference Manual
If no gravity curve is given, the program will generate one from the specified
average gravity. The default method for doing this is referred to as the WAT-
SONK method. For a pure component, the Watson K-factor is defined by the
following equation:
(10)
K =
NBP
1

3
SG
where:
NBP = normal boiling point in degrees Rankine
SG = specific gravity at 60 F relative to H2O at 60 F
For a mixture (such as a petroleum cut), the NBP is traditionally replaced by a
more complicated quantity called the mean average boiling point (MeABP). For
this purpose, however, it is sufficient to simply use the volume-averaged boil-
ing point computed from the distillation curve. The gravity curve is gener-
ated by assuming a constant value of the Watson K, applying equation (10)
to each cut to get a gravity, averaging these values, and then adjusting the as-
sumed value of the Watson K until the resulting average gravity agrees with
the average gravity input by the user.
Another method (known as the PRE301 option) is available primarily for com-
patibility with older versions. It is similar to the preferred method described
above, except that the average Watson K is estimated from the 10, 30, 50, 70,
and 90 percent points on a D86 curve (which can be obtained from the TBP
curve by reversing one of the procedures in the previous section) and then
applied to the NBP of each TBP cut to generate a gravity curve. This curve is
then normalized to produce the specified average gravity.
The preferred method (constant Watson K applied to TBP curve) is justified
by the observation that, for many petroleum crude streams, the Watson K of
various petroleum cuts above light naphtha tends to remain fairly constant.
For other types of petroleum streams, however, this assumption is often incor-
rect. Hence, for truly accurate simulation work, the user is advised to supply
gravity curves whenever possible.
Molecular Weight Data
In addition to the NBP and specific gravity, simulation with assays requires
the molecular weight of each cut. These may be omitted completely by the
user, in which case they are estimated by the program.
The user may supply a molecular weight curve, which is quadratically inter-
polated and extrapolated to cover the entire range of pseudocomponents. Op-
tionally, the user may also supply an average molecular weight. In that case,
the molecular weight value for the last cut is adjusted so that the curve
matches the given average, or if the 100% value is provided, the entire mo-
lecular weight curve is normalized to match the given average.
If no molecular-weight data are supplied, the molecular weights are esti-
mated; the default method is a proprietary modification (known as the SIM-
SCI method) of the method developed by Twu (1984). This method is a
perturbation expansion with the normal alkanes as a reference fluid. Twus
method was originally developed to be an improvement over Figure 2B2.1 in
older editions of the API Technical Data Book. That figure relates molecular
weight to NBP and API gravity for NBPs greater than 300 F. The SIMSCI
method matches that data between normal boiling points of 300 F and 800
F, and better extrapolates outside that temperature range.
The unaltered old API method is (API63) is also available.
A newer API method, called the extended API method (known as the EXTAPI
option), is also available. This is API procedure 2B2.1, and it is an extension of
the earlier API method which better matches known pure-component data below
300 F. The equation is as follows:
(11)
MW = 20.486
exp(1.16510
4
T
b
7.78712 SG + 1.1582 10
3
T
b
SG)
T
b
1.26007
SG
4.98308
where:
SG = specific gravity of the pseudocomponent
Tb = normal boiling point in degrees Rankine
Lightends Data
Hydrocarbon streams often contain significant amounts of light hydrocarbons
(while there is no universal definition of light, C6 is a common upper limit).
Simulation of such systems is more accurate if these components are considered
explicitly rather than being lumped into pseudocomponents. If the distillation
curve is reported on a lightends-free basis, the light components can be fed to
the flowsheet in a separate stream and handled in a straightforward manner. Typi-
cally, however, the lightends make up the initial part of the reported distillation
curve, and adjustment of the cut-up curves is required to avoid double-counting
the lightends components.
By default, the program matches user-supplied lightends data to the TBP curve.
The user-specified rates for all lightends components are adjusted up or down, all
in the same proportion, until the NBP of the highest-boiling lightends component
exactly intersects the TBP curve. All of the cuts from the TBP curve falling into the
region covered by the lightends are then discarded and the lightends components
are used in subsequent calculations. This procedure is illustrated in Figure 1.1.3-2,
where lightend component flows are adjusted until the highest-boiling lightend
(nC5 in this example) has a mid-volume percent (point a) that exactly coincides
with the point on the TBP curve where the temperature is equal to the NBP of nC5.
The cumulative volume percent of lightends is represented by point b, and the
cuts below point b (and the low-boiling portion of the cut encompassing that point)
are discarded.
Reference Manual
Figure 1.1.3-2:
Matching Lightends
to TBP Curve
Alternatively, the lightends may be specified as a fraction or percent (on a
weight or liquid-volume basis) of the total assay or as a fixed lightends flowrate.
In these cases, the input numbers for the lightends components can be normal-
ized to determine the individual component flowrates. A final alternative is to
specify the flowrate of each lightends component individually.
Generating
Pseudocomponent
Properties
Once each curve is cut, the program processes each blend to produce average
properties for the pseudocomponents from each cutpoint interval in that
blend. All the streams in a given blend (except for those for which the
XBLEND option was used) are totaled to get the weights, volumes, and
moles for each cutpoint interval. Using the above totals, the average molecu-
lar weight and gravity are calculated for each cut range. Finally, the normal
boiling point for each pseudocomponent is calculated by weight averaging
the individual values from the contributing streams.
Once the normal boiling point, gravity, and molecular weight are known for
each pseudocomponent, all other properties (critical properties, enthalpies,
etc.) are determined according to the characterization method selected by the
user (or defaulted by the program). These methods are described in Section
1.1.2, Petroleum Components.
Vapor Pressure
Calculations
While not a part of the programs actual processing of assay streams, many
problems involving hydrocarbon systems will involve a specification on
some vapor pressure measurement. The two most common of these are the
True Vapor Pressure (TVP) and the Reid Vapor Pressure (RVP). PRO/II al-
lows specification of these quantities from several unit operations, and they
may be reported in output in the Heating/Cooling Curve (HCURVE) utility
or as part of a user-defined stream report.
True Vapor Pressure (TVP) Calculations
The TVP of a stream is defined as the bubble-point pressure at a given refer-
ence temperature. By default, that reference temperature is 100 F, but this
may be overridden by the user. The user may specify a specific thermody-
namic system to be used in performing all TVP calculations in the flowsheet;
by default, the calculation for a stream is performed using the thermody-
namic system used to generate that stream.
Rei d Vapor Pressure (RVP) Cal cul ati ons
The RVP laboratory procedure provides an inexpensive and reproducible meas-
urement correlating to the vapor pressure of a fluid. The measured RVP is usu-
ally within 1 psi of the TVP of a stream. It is always reported as psi, although
the ASTM test procedures (except for D5191 which, as mentioned below, uses
an evacuated sample bomb) actually read gauge pressure. Since the air in the
bomb accounts for approximately 1 atm, the measured gauge pressure is a rough
measure of the true vapor pressure. Six different calculation methods are avail-
able. Within each calculation method, the answer will depend somewhat on the
thermodynamic system used. As with the TVP, the thermodynamic system for
RVP calculations may be specified explicitly or, by default, the thermodynamic
system used to generate the stream will be used.
The APINAPHTHA method calculates the RVP from Figure 5B1.1 in the API
Technical Data Book, which represents the RVP as a function of the TVP and
the slope of the D86 curve at the 10% point. The graphical data have been con-
verted to equation form by Simsci. This method is the default for PRO/IIs RVP
calculations. It is useful for many gasolines and other finished petroleum prod-
ucts, but it should not be used for oxygenated gasoline blends.
The APICRUDE method calculates the RVP from Figure 5B1.2 in the API
Technical Data Book, which represents the RVP as a function of the TVP and
the slope of the D86 curve at the 10% point. The graphical data have been
converted to equation form by SimSci. It is primarily intended for crude oils.
The ASTM D323-82 method (known as the D323 method) simulates a stand-
ard ASTM procedure for RVP measurement. The liquid hydrocarbon portion
of the sample is saturated with air at 33 F and 1 atm pressure. This liquid is
then mixed at 100 F with air in a 4:1 volume ratio. Since the test chamber is
not dried in this procedure, a small amount of water is also added to simulate
this mixture. The mixture is flashed at 100 F at a constant volume (corre-
sponding to the experiment in a sealed bomb), and the gauge pressure of the
resulting vapor-liquid mixture is reported as the RVP. Both air and water
should be in the component list for proper use of this method.
The obsolete ASTM D323-73 method (known as the P323 method) is avail-
able for compatibility with earlier versions of the program.
Reference Manual
The ASTM D4953-91 method (known as the D4953 method) was developed
by the ASTM primarily for oxygenated gasolines. The experimental method
is identical to the D323 method, except that the system is kept completely
free of water. The algorithm for simulating this method is identical to that for
D323, except that no water is added to the mixture. Air should be in the com-
ponent list for proper use of this method.
The ASTM D5191-91 method (known as the D5191 method) was developed as an
alternative to the D4953 method for gasolines and gasoline-oxygenate blends. In
this method, the air-saturated sample is placed in an evacuated bomb with five
times the volume of the sample, and then the total pressure of the sample is meas-
ured. In the simulator, this is accomplished by flashing, at constant volume, a mix-
ture of 1 part sample (at 33 F and 1 atm) and 4 parts air (at the near-vacuum
conditions of 0.01 psia and 100 F). The resulting total pressure is then con-
verted to a dry vapor pressure equivalent (DVPE) using the following equation:
(12) DVPE = 0.965X A
where:
X = the measured total pressure
A = 0.548 psi (3.78 kPa)
This number is then reported as the RVP. Air should be in the component list
for proper use of this method.
Comments on RVP and TVP Methods
Because of the sensitivity of the RVP (and the TVP) to the light components
of the mixture, these components should be modeled as exactly as possible if
precise values of RVP or TVP are important. This might mean treating more
light hydrocarbons as defined components rather than as pseudocomponents;
oxygenated compounds blended into gasolines should also be represented as
defined components rather than as part of an assay. It is also important to ap-
ply a thermodynamic method that is appropriate for the stream in question
(see Section 1.2.2, Application Guidelines). The thermodynamics becomes
particularly important for oxygenated systems, which are not well-modeled
by traditional hydrocarbon methods such as Grayson-Streed. These systems
are probably best modeled by an equation of state such as SRK with the Sim-
Sci alpha formulation and one of the advanced mixing rules (see Section
1.2.4, Equations of State). It is important to have binary interaction parame-
ters between the oxygenates and the hydrocarbon components of the system.
PRO/IIs databanks contain many such parameters, but others may have to be
regressed to experimental data or estimated.
One should not be too surprised if calculated values for RVP differ from an
experimental measurement by as much as one psi. Part of this is due to the
uncertainty in the experimental procedure, and part is due to the fact that the
lightends composition inside the simulation may not be identical to that of
the experimental sample.
One of the less appreciated effects in experimental measurements is the pres-
ence of water, not only in the sample vessel, but also in the air in the form of
humidity. The difference between the D323 (a wet method) RVP and the
D4953 (a dry method) RVP will be approximately the vapor pressure of
water at 100 F (about 0.9 psi), with the D323 RVP being higher. Both of
these calculations assume that dry air is used in the procedure. The presence
of humidity in the air mixed with the sample can alter the D323 results, low-
ering the measured RVP because of the decreased driving force for vaporiza-
tion of the liquid water. In the extreme case of 100% humidity, the D323
results will be nearly identical with the D4953 results. Therefore, a wet
test performed with air that was not dry would be expected to give results in-
termediate between PRO/IIs D323 and D4953 calculations. The results from
the D5191 method (both in terms of the experimental and calculated num-
bers) should in general be very close to D4953 results.
The primary application guideline for which RVP calculational model to use
is, of course, to choose the one that corresponds to the experimental proce-
dure applied to that stream. Secondary considerations include limitations of
the individual methods. The APINAPHTHA and APICRUDE methods are
good only for hydrocarbon naphtha and crude streams, respectively. The
D323 method (and its obsolete predecessor, P323) is intended for hydrocar-
bon streams; the presence of water makes it less well-suited for use with
streams containing oxygenated compounds. The D4953 and D5191 methods
are both better suited for oxygenated systems, and calculations with these
methods should give similar results.
References
1. American Petroleum Institute, 1988, Technical Data Book - Petroleum
Refining, 5th edition (also previous editions), American Petroleum
Institute, Washington, DC.
2. American Society for Testing of Materials, Annual Book of ASTM
Standards, section 5 (Petroleum Products, Lubricants, and Fossil Fuels),
ASTM, Philadelphia, PA (issued annually).
3. Edmister, W.C., and Okamoto, K.K., 1959, Applied Hydrocarbon
Thermodynamics, Part 12: Equilibrium Flash Vaporization Calculations
for Petroleum Fractions, Petroleum Refiner, 38(8), 117.
4. Twu, C.H., 1984, An Internally Consistent Correlation for Predicting the
Critical Properties and Molecular Weights of Petroleum and Coal-tar
Liquids, Fluid Phase Equil., 16, 137-150.
Reference Manual
Thermodynami c Methods
PRO/II offers numerous methods for calculating thermodynamic properties such
as K-values, enthalpies, entropies, densities, gas and solid solubilities in liquids,
and vapor fugacities. These methods include:
Generalized correlations, such as the Chao-Seader K-value method and the API
liquid density method.
Equations of state, such as the Soave-Redlich-Kwong method for calculating
K-values, enthalpies, entropies, and densities.
Liquid activity coefficient methods, such as the Non-Random Two-Liquid
(NRTL) method for calculating K-values.
Vapor fugacity methods, such as the Hayden-OConnell method for dimerizing
species.
Special methods for calculating the properties of specific systems of compo-
nents such as alcohols, glycols, and sour water systems.
Solid-liquid equilibria methods such as the vant Hoff method for calculating
the solubility of a solid in a liquid.
In addition, the electrolyte version of PRO/II contains a number of thermody-
namic methods to handle systems containing aqueous ionic species.
1. 2
Section 1.2 Thermodynami c Methods
PRO/II Component and Thermophysical Properties I-37
Reference Manual
Basi c Pri nci pl es
General
Information
When modeling a single chemical process or an entire chemical plant, the use of
appropriate thermodynamic methods and precise data is essential in obtaining a
good design. PRO/II contains numerous proven thermodynamic methods for the
calculation of the following thermophysical properties:
Distribution of components between phases in equilibrium (K-values).
Liquid-phase and vapor-phase enthalpies.
Liquid-phase and vapor-phase entropies.
Liquid-phase and vapor-phase densities.
Phase
Equilibria
When two or more phases are brought into contact, material is transferred
from one to another until the phases reach equilibrium, and the compositions
in each phase become constant. At equilibrium for a multicomponent system,
the temperature, pressure, and chemical potential of component i is the same
in every phase, i.e.:
(1)
T
(2)
P
(3)
where:
T = system temperature
P = system pressure
= the chemical potential
, , ..., represent the phases
The fugacity of a substance is then defined as:
(4)

i

i
0
RT ln
f
i

/
f
i
0
_
,
where:
fi = fugacity of component i
fi
0
= standard-state fugacity of component i at T, P
i
0
= standard-state chemical potential of component i at T, P
1. 2. 1
Thermodynami c Methods Section 1.2
I-38 Basi c Pri nci pl es May 1994
It follows from (3) and (4) that the fugacities in each phase must also be equal:
(5)
f
i
f
i
f
i
, i 1,2, n
The fugacity of a substance can be visualized as a corrected partial pres-
sure such that the fugacity of a component in an ideal-gas mixture is equal
to the component partial pressure.
For vapor-liquid equilibrium calculations, the ratio of the mole fraction of a com-
ponent in the vapor phase to that in the liquid phase is defined as the K-value:
(6) K
i
y
i

/
x
i
where:
Ki = K-value, or equilibrium ratio
yi = mole fraction in the vapor phase
xi = mole fraction in the liquid phase
For liquid-liquid equilibria, a corresponding equilibrium ratio or distribution
coefficient is defined:
(7)
K
Di
x
i
I

/
x
i
II
where:
KDi = liquid-liquid distribution coefficient
I, II represent the two liquid phases
The vapor-phase fugacity coefficient of a component,
i
V
, is defined as the
ratio of its fugacity to its partial pressure, i.e.:
(8)

i
V
f
i
V

/
y
i
P
where:
i
V
= vapor-phase fugacity coefficient of component i
If a liquid activity coefficient method is used in the liquid phase calculation,
then the activity coefficient of the liquid phase can be related to the liquid
fugacity by the following relationship:
(9)
f
i
L

i
L
x
i
f
i
OL
where:
i
L
=
liquid-phase activity coefficient
fi
0L
= standard-state fugacity of pure liquid i
PRO/II Component and Thermophysical Properties Basi c Pri nci pl es I-39
Reference Manual
With this definition of liquid fugacity, i
L
1 as xi 1. The standard-state
fugacity is as follows:
(10)
f
i
0L
P
i
sat

i
sat
exp

P
i
sat
P
v
i
L

/
RT dP
1
1
]
where:
P
i
sat
= saturated vapor pressure of component i at T
R = gas constant
vi
L
= liquid molar volume of component i at T and P

i
sat
=
fugacity coefficient of pure component i at T and Pi
sat
Equation (10) provides two correction factors for the pure liquid fugacity. The
fugacity coefficient, i
sat
, corrects for deviations of the saturated vapor from
ideal-gas behavior. The exponential correction factor, known as the Poynting cor-
rection factor, corrects for the effect of pressure on the liquid fugacity. The
Poynting correction factor is usually negligible for low and moderate pressures.
Combining equations (6), (8), and (9) yields:
(11)
K
i

i
L
f
i
OL

/
P
i
V
Combining equations (7) and (9) yields:
(12)
K
Di

i
L
II

/

i
L
I
If an equation of state is applied to both vapor and liquid phases, the vapor-
liquid K-values can be written as:
(13)
K
i

i
L

/

i
V
The liquid-liquid equilibria can be written as:
(14)
K
Di

i
L
II

i
L
I
Equations (11), (12), (13), and (14) are used to calculate the distribution of
components between phases.
For vapor-liquid equilibria, equation-of-state methods may be used to calculate
the fugacity coefficients for both liquid and vapor phases using equation (13).
One important limitation of equation-of-state methods is that they have to be ap-
plicable over a wide range of densities, from near-zero density for gases to high
liquid densities, using constants obtained from pure-component data. Equations
of state are not very accurate for nonideal systems unless combined with compo-
nent mixing rules and alpha formulations (see Section 1.2.4, Equations of State)
appropriate for those components.
Equation (11) may be solved by using equation-of-state methods to calculate va-
por fugacities combined with liquid activity methods to compute liquid activity
coefficients (see Section 1.2.6, Liquid Activity Methods). Liquid activity meth-
ods are most often used to describe the behavior of strongly nonideal mixtures.
References
1. Prausnitz, J. M., Lichtenthaler, R. N., and Gomes de Azevedo, E., 1986, Molecular
Thermodynamics of Fluid-Phase Equilibria, 2nd Ed., Prentice-Hall, N.Y.
2. Sandler, S.I., 1989, Chemical and Engineering Thermodynamics, 2nd ed.,
John Wiley & Sons, New York.
3. Smith, J.M. and Van Ness, H.C., 1987, Introduction to Chemical Engineering
Thermodynamics, 4th ed., McGraw-Hill, New York.
4. Van Ness, H.C. and Abbott, M.M., 1982, Classical Thermodynamics of
Nonelectrolyte Solutions: With Applications to Phase Equilibria, McGraw-
Hill, New York.
Enthalpy The enthalpy of a system, H, is defined in terms of the internal energy of the
system, U as follows:
(15) H = U + PV
where:
H = enthalpy of the system of nT moles
U = internal energy of the system of nT moles
V = total volume of the system
At constant temperature and pressure, the internal energy of the system is re-
lated to the volume by:
(16) dU
T(P
/
T)
V,n
T
P1
]
dV
The enthalpy of the system is then given by:
(17)
H
P T(P
/
T)
V,n
T
1
]
dV + RT(z 1) + H
where:
H
*
= mixture ideal gas enthalpy =

i
n
i
h
i
0

hi
0
= molar enthalpy of ideal gas i at temperature T
z =
compressibility factor PV

nTRT
Reference Manual
PRO/II provides two distinct approaches to the calculation of enthalpy. For the
majority of thermodynamic systems of methods, enthalpy is calculated as a de-
parture from the ideal-gas enthalpy of the mixture. Enthalpy departure functions
for both vapor and liquid phases are calculated by an equation of state or corre-
sponding states model.
For liquid activity coefficient thermodynamic systems, however, PRO/II by
default invokes the LIBRARY thermodynamic method for vapor and liquid
enthalpy calculations.
The LIBRARY method consists of two correlations. The first correlates satu-
rated-liquid enthalpy as a function of temperature, and the second correlates
latent heat of vaporization, also as a function of temperature. At temperatures
below the critical, vapor enthalpy is calculated by adding the latent heat to the
saturated liquid enthalpy at the system temperature. In other words, the vapor
enthalpy is the saturated vapor enthalpy at the system temperature. For both
phases, the pressure is implicitly the saturated vapor pressure at the system
temperature. No other pressure correction term is applied.
For almost all library components, the correlations in use for liquid enthalpy
can be used safely up to a reduced temperature, T/Tc, of approximately 0.9.
Tc is the temperature at the critical point, beyond which vapor and liquid be-
come indistinguishable.
Note: The normal boiling point of a library component typically occurs when
the reduced temperature, Tr, is approximately equal to 0.7.
In general, the use of liquid activity coefficient models is not recommended
for system pressures above 1000 kPA. Below these conditions, the use of LI-
BRARY enthalpy methods will not introduce significant errors, provided that
the system temperature is below the critical temperatures of all components
present in significant quantities.
Quite often, however, we would like to use a liquid activity coefficient model
when permanent gases are present in the mixture. As the system temperature is
usually above the critical temperature of these gases, there is no standard-state
liquid fugacity at system conditions, so we replace that term by the Henrys Law
constant. However, the problem of adding the supercritical components contri-
bution to the liquid enthalpies remains.
For the liquid-phase contribution, PRO/II extrapolates the components satu-
rated liquid enthalpy curve linearly from the critical temperature. Above the
critical this extrapolation uses the slope of the library enthalpy tangent to the
liquid saturation curve at the normal boiling point. At temperatures above the
critical, there is no distinction between vapor and liquid phases and the vapor
enthalpy is set equal to the extrapolated liquid enthalpy. The point at which
the slope for linear extrapolation is obtained is chosen quite arbitrarily; as
mentioned, we use the normal boiling point temperature.
Note: At temperatures near Tc, the enthalpy of the saturated vapor for a pure com-
ponent exhibits a decrease with temperature. This can lead to the computation of a
negative value of the constant-pressure heat capacity cp when using the LIBRARY
method for vapor enthalpies. This is entirely an artifact of the fact that the satura-
tion curve is not a constant-pressure path. The printout of a negative heat capacity
is therefore a sign that the temperature is too high to be using LIBRARY vapor
enthalpies, and the user should switch to another method.
For low pressure and temperatures well below the lowest critical, LIBRARY en-
thalpies are often satisfactory. For high pressures or temperatures above the
critical of a component, it will usually be better to use an equation of state
for vapor and, possibly, liquid enthalpies. Beware, however, if a liquid activ-
ity coefficient method was selected for K-value; in such systems the traditional
cubic equation of state may not be capable of describing the liquid phase nonide-
ality, and it is therefore unlikely that the equation of state will predict the correct
liquid-phase enthalpy. In this situation, one of the more advanced cubic equa-
tions using an alpha formulation, which correctly predicts pure-component va-
por pressures is a better choice. As the contribution to the liquid enthalpy of
dissolved supercritical components is usually small, the LIBRARY method can
usually safely be used for liquid enthalpies. Ideal-gas based enthalpies and satu-
ration enthalpies can be used in combination for vapor and liquid, respectively,
for defined components, because the ideal-gas enthalpy datum has been fixed
relative to the saturated-liquid enthalpy datum (HL = 0 at T = 273.15 K). For
components that are sub-critical at 273.15 K, the SRK vapor enthalpy departure
function, which applied to the ideal-gas enthalpy, gives the equivalent results as
adding the latent heat to zero-liquid enthalpy. For components that are supercriti-
cal at 273.15 K, using an alpha formulation will give consistent results between
departure-based and library enthalpies.
Entropy The entropy of a system, S, is defined in terms of the enthalpy, as follows:
(18)
S S
R ln R ln
P
/
P
ref
_
,

H H
_
,

/
T
and,
(19)
S

i
n
i
s
i
0
R

i
n
i
ln x
i
where:
= fugacity coefficient of mixture
Pref = reference pressure of 1 atmosphere
S
*
= mixture ideal gas entropy
si
0
= molar entropy of ideal gas i
ni = moles of component i
xi = mole fraction of component i
Reference Manual
The ideal molar entropy is related to the ideal molar enthalpy by:
(20)
s
i
0

T
ref
T
c
pi
dT
/
T
1
]

T
ref
T
h
i
0

/
T
_
,
P dT
/
T
where:
Tref = reference temperature, 1 degree Rankine in PRO/II
cpi
*
= ideal gas heat capacity of component i
Ideal gas entropy at the reference temperature is set equal to zero.
As for enthalpy computations, liquid and vapor entropies are calculated in
PRO/II using either an equation-of-state method such as SRKM or a general-
ized correlation method such as Curl-Pitzer.
Density Cubic equation-of-state methods are generally not very accurate in predict-
ing liquid densities. More accurate predictive methods have been developed
especially for liquid mixtures. Such methods include the API and Rackett
correlation methods. These methods are described in detail in Section 1.2.3,
Generalized Correlation Methods.
Vapor densities are computed in PRO/II using the following formulae:
(21) v zRT
/
P
(22)

v
MW
/
v
where:
v
=
vapor density
v = molar vapor volume
z = compressibility factor
Vapor densities can be predicted quite accurately using equation-of-state
methods, in addition to generalized correlation methods. The IDEAL
vapor-density method corresponds to z=1.
Appl i cati on Gui del i nes
General
Information
Choosing an appropriate thermodynamic method for a specific application is
an important step in obtaining an accurate process simulation. Normally,
there may be any number of thermodynamic methods suitable for a given ap-
plication. The user is left to use his or her best judgement, experience, and
knowledge of the available thermodynamic methods to choose the best
method.
It is important to note that, for many thermodynamic methods, the PRO/II
databanks contain adjustable binary parameters obtained from fitting publish-
ed experimental and/or plant data. The thermodynamic method chosen
should ideally be used only in the temperature and pressure ranges at which
the parameters were regressed. Ideally, for each simulation, actual experimen-
tal or plant data should be regressed in order to obtain the best interaction pa-
rameters for the application.
There are several places where the user can find information and guidelines
on using the thermodynamic methods available in PRO/II. These are:
PRO/II Keyword Input Manual.
PRO/II Application Briefs Manual.
PRO/II Thermodynamic Expert System.
The first source outlines the PRO/II keywords needed to code the thermody-
namic category in a PRO/II input file and provides some information on the
limitations and strengths of each thermodynamic method. The second source
shows how PRO/II is used to simulate many refinery, chemical, petrochemi-
cal, and solid processing applications using the thermodynamic methods ap-
propriate to each system. The third source, available only in the PC (DOS)
version of PRO/II, is described below.
Thermodynamic
Expert System (TES)
The Thermodynamic Expert System (TES) is available only to PRO/II PC
(DOS) users who access PRO/II through the Graphics User Interface (GUI).
This system utilizes nearly 300 proven heuristics to determine the best ther-
modynamic method for a particular simulation. The following information is
used by the TES:
1. 2. 2
PRO/II Component and Thermophysical Properties Appl i cati on Gui del i nes I-45
Reference Manual
The list of components in the simulation.
The presence of any assay streams.
The expected temperature and pressure ranges.
The number of expected liquid phases.
The presence or absence of a vapor phase.
The water handling option chosen (i.e., whether water should be de-
canted or handled rigorously).
This option should be used if available.
Refinery and Gas
Processes
These processes may be subdivided into the following:
Low pressure crude systems (vacuum towers and atmospheric stills).
High pressure crude systems (including FCCU main fractionators and
coker fractionators).
Reformers and hydrofiners.
Lube oil and solvent de-asphalting units.
Low Pressure Crude Units
Low pressure crude units generally contain less than 3 volume percent light
ends. Moreover, the petroleum fractions present in the feed exhibit nearly
ideal behavior. For these units, the characterization of the petroleum frac-
tions is far more important than the thermodynamic method used. The user
should try different assay and characterization methods first if the simulation
results do not match the plant data.
Since these units contain a small amount of light ends, the Braun K10
(BK10) method should be used quickly as a first attempt and will likely give
acceptable answers. The BK10 method does, however, provide only gross es-
timates for the K-values for H2 and is not recommended for streams contain-
ing a significant amount of H2. For such systems, and for other systems
where the BK10 results are not satisfactory, the Grayson-Streed (GS),
Grayson-Streed Erbar (GSE), or Improved Grayson-Streed (IGS) methods
should be chosen. These methods contain special coefficients for hydrogen
and methane and, as such, provide better predictions for streams containing
small amounts of H2 at low pressures. It is important to note that the prede-
fined thermodynamic systems GS, GSE, and IGS use the Curl-Pitzer (CP)
method for calculating enthalpies. For systems containing heavy ends such
as vacuum towers, however, the saturated vapor is often at reduced tempera-
tures of less than 0.6. This is the lower limit of the Curl-Pitzer enthalpy
method. For these units, therefore, substituting the Lee-Kesler (LK) method
for Curl-Pitzer enthalpies may improve the results.
I-46 Appl i cati on Gui del i nes May 1994
20. 4 PRO/II Note: For more information on using predefined systems of thermody-
namic methods, see Section 20.4, Predefined Systems, of the PRO/II Keyword
Input Manual.
In addition, the top of many of these low pressure units often contain signifi-
cant amounts of light components such as methane. Under these conditions,
an equation-of-state method such as Soave-Redlich-Kwong (SRK) or Peng-
Robinson (PR) will provide better answers than the BK10 or Grayson-Streed
methods.
Tabl e 1. 2. 2-1:
Methods Recommended for Low Pressure Crude Systems
BK10 Gives fast and acceptable answers.
GS/GSE/IGS Generally more accurate than BK10, especially for streams
containing H2. Use LK enthalpies instead of CP enthalpies
for vacuum towers.
SRK/PR Provides better results when light ends dominate.
High Pressure Crude Units
High pressure crude units generally contain greater amounts of light ends
than low pressure units. Still, for these units, as for the low pressure crude
units, the characterization of the petroleum fractions remains far more impor-
tant than the thermodynamic method used. The user should again try differ-
ent assay and characterization methods first if the simulation results do not
match the plant data. Since these units contain larger amounts of light ends,
the GS, GSE, IGS, SRK, or PR methods should be used and will likely give
acceptable answers.
For FCCU main fractionators, the petroleum fractions are much more hydro-
gen deficient than are crude fractions. Since most characterization correla-
tions are derived from crude petroleum data, it is expected that the results
will be less accurate than for crude fractions.
See Section 1.1.3 of this manual, Assay Processing, for more information on
characterizing petroleum fractions.
Tabl e 1. 2. 2-2:
Methods Recommended for Hi gh Pressure Crude Systems
GS/GSE/IGS Quicker but generally less accurate than SRK or PR,
especially for streams containing light ends. Use LK
enthalpies instead of CP enthalpies for better results.
SRK/PR Provides better results when light ends dominate.
Reference Manual
Reformers and Hydrofiners
These units contain streams with a high hydrogen content. The Grayson-
Streed method, which contains special liquid activity curves for methane and
hydrogen, may be used to provide adequate answers. For the SRK and PR
methods, the PRO/II databanks contain extensive binary interaction parame-
ter data for component pairs involving hydrogen. These methods provide re-
sults comparable or better than the GS methods. Moreover, these methods
are more accurate than GS methods in predicting the hydrogen solubility in
the liquid phase. If the user wishes to obtain the most accurate prediction of
hydrogen solubility in the hydrocarbon liquid phase, he/she should use the
SimSci modified SRK or PR methods, SRKM or PRM.
Tabl e 1. 2. 2-3:
Methods Recommended for Reformers and Hydrofi ners
GS/GSE/IGS Quicker but generally less accurate than SRK or PR,
especially for predicting the hydrogen content of the liquid
phase.
SRK/PR Provides better results than GS methods.
SRKM/PRM Provides better results than SRK/PR when predicting the
hydrogen content of the liquid phase.
Lube Oil and Solvent De-asphalting Units
These units contain streams with nonideal components such as H2S and mer-
captans. The SimSci modified SRK or PR methods, SRKM or PRM, are rec-
ommended, but only if user-supplied binary interaction data are available. If
no binary interaction data specifically regressed for the system are available,
then the data in the PRO/II databanks can be used, and the SRK or PR meth-
ods are recommended.
Tabl e 1. 2. 2-4:
Methods Recommended for Lube Oi l and Sol vent De-asphal ti ng Uni ts
SRKM/PRM Recommended when user-supplied binary interaction data
are available.
SRK/PR Recommended when no user-supplied binary interaction
data are available.
Natural Gas
Processing
Natural gas systems often contain inerts such as N2, acid or sour gases such
as CO2, H2S, or mercaptans, and water, along with the usual light hydrocar-
bon components. Natural gas streams may be treated by a number of meth-
ods, e.g., sweetening using amines or dehydration using glycol.
For natural gas systems containing less than 5% N2, CO2, or H2S, and no
other polar components, SRK, PR, or Benedict-Webb-Rubin-Starling
(BWRS) methods provide excellent answers. The SRK and PR binary inter-
action parameters between these lower molecular weight molecules and
other components are estimated by correlations based on the molecular
weight of the hydrocarbon molecule. For small amounts of these compo-
nents, this is satisfactory. The BWRS equation of state also contains many
binary interaction parameters for component pairs involving lower weight
components supplied in Dechema. Unlike cubic equations of state such as
SRK or PR, the BWRS equation of state does not satisfy the critical con-
straints, and so does not extrapolate well into the critical region.
For natural gas systems containing more than 5% N2, CO2, or H2S, but no other
polar components, equation-of-state methods such as SRK or PR are still recom-
mended, although the binary parameters estimated by molecular weight correla-
tions may not produce the best results. The user should provide binary
interaction parameters for component pairs involving these lower molecular
weight components if possible.
For natural gas systems containing water at low pressures, equation-of-state
methods such as SRK or PR may be used, along with the default water de-
cant option, to predict the behavior of these systems.
For these systems at high pressures, where the solubility of hydrocarbon in
water is significant, the default water decant option, which predicts a pure
water phase, is unacceptable. In this case, equation-of-state methods contain-
ing advanced mixing rules such as SRKM, PRM, or SRKS, or the Kabadi-
Danner modification to SRK (SRKKD) should be used to predict the
vapor-liquid-liquid behavior of these systems. These methods provide the
best answers if all the relevant binary interaction parameters are available.
For the SRKKD method in particular, PRO/II contains binary interaction
parameters for component pairs involving N2, H2, CO2, CO, and H2S. For
SRKM, PRM, or SRKS methods, the user should make sure that all relevant
binary interaction data are entered.
Reference Manual
For natural gas systems containing polar components such as methanol, the
SRKM, PRM, or SRKS methods are recommended to predict the vapor-liq-
uid-liquid behavior of these systems. Interaction parameters for the impor-
tant binaries are required if accurate answers are to be obtained.
Tabl e 1. 2. 2-5:
Methods Recommended for Natural Gas Systems
SRK/PR/
BWRS
Recommended for most natural gas and low pressure natural gas +
water systems.
SRKKD Recommended for high pressure natural gas +water systems.
SRKM/PRM/
SRKS
Recommended for natural gas +polar components.
The common processes used to treat natural gas streams may be sub-divided
into the following:
Glycol dehydration systems.
Sour water systems.
Amine systems.
Glycol Dehydration Systems
The predefined thermodynamic system GLYCOL has been specially created
for these systems. This system uses the predefined system SRKM but in-
vokes the GLYCOL databank. This databank contains binary interaction pa-
rameters for component pairs involving TEG and, to a lesser extent, DEG
and EG. These data have been regressed in the temperature and pressure
range normally seen in glycol dehydrators:
Temperature: 80-400 F.
Pressure: up to 2000 psia.
See Section 1.2.8, of this manual, Special Packages, for more information on
this method.
Sour Water Systems
The standard version of PRO/II contains two methods, SOUR and GPSWATER,
for predicting the VLE behavior of sour water systems. These methods are de-
scribed in more detail in Section 1.2.8, of this manual, Special Packages. The
electrolyte version of PRO/II also contains a rigorous sour water method which
is described in Section 1.2.10 of this manual, Electrolyte Thermodynamic Equa-
tions. The recommended temperature, pressure and composition ranges for each
method are given in Table 1.2.2-6 below.
Tabl e 1. 2. 2-6:
Methods Recommended for Sour Water Systems
SOUR Recommended Ranges:
68 <T (F) <300
P(psia) <1500
wNH3 +wCO2 +wH2S < 0.30
GPSWATER Recommended Ranges:
68 <T(F) <600
P(psia) <2000
wNH3 <0.40
PCO2 +PH2S <1200 psia
Electrolyte
Version of
PRO/II
Recommended when strong electrolytes such as caustic
are used, or when pH control or accurate prediction of HCN
or phenol phase distribution is important. Recommended
Ranges:
32 <T(F) <400
P(psia) <3000
xdissolved gases <0.30
Amine Systems
Amine systems used to sweeten natural gas streams may be modeled in
PRO/II using the AMINE special package (see Section 1.2.8, Special Pack-
ages). Data is provided for amines MEA, DEA, DGA, DIPA, and MDEA. Re-
sults obtained for MEA and DEA are accurate enough for use in final design
work. However, results for DIPA systems are not suitable for final design
work. For MDEA or DGA systems, the results may be made to more closely
fit plant data by the use of a dimensionless residence time correction.
25. 5 PRO/II Note: For more information on using the dimensionless residence time
correction factor for MDEA or DGA systems, see Section 25.5, Amine, of the
PRO/II Keyword Input Manual.
The recommended temperature, pressure, and loading ranges (gmoles sour
gases per gmole amine) for each amine system available in PRO/II are given
in Table 1.2.2-7.
Reference Manual
Tabl e 1. 2. 2-7:
Recommended Ranges for Ami ne Systems
MEA Recommended Ranges:
25 <P(psig) <500
T(F) <275
wamine ~0.15 - 0.25
0.5-0.6 gmole gas/gmole amine
DEA Recommended Ranges:
100 <P(psig) <1000
T(F) <275
wamine ~0.25 - 0.35
0.45 gmole gas/gmole amine
DGA Recommended Ranges:
100 <P(psig) <1000
T(F) <275
wamine ~0.55 - 0.65
MDEA Recommended Ranges:
100 <P(psig) <1000
T(F) <275
wamine ~0.50
DIPA Recommended Ranges:
100 <P(psig) <1000
T(F) <275
wamine ~0.30
Petrochemical
Applications
Common examples of these processes are the following:
Light hydrocarbon applications.
Aromatic systems.
Aromatic/non-aromatic systems.
Alcohol dehydration systems.
Light Hydrocarbon Applications
Most light hydrocarbon mixtures at low pressures may be modeled well by
the SRK or PR equations of state. The BWRS equation of state, which was
developed for light hydrocarbon mixtures, is also recommended, but not near
the critical region. At high pressures, the SRKKD equation of state should be
used to best predict the water solubility in the hydrocarbon phase. The
COSTALD liquid density method was developed expressly for light
hydrocarbon mixtures. This method is over 99.8% accurate in predicting the
liquid densities of these mixtures and should be requested by the user.
Tabl e 1. 2. 2-8:
Methods Recommended for Li ght Hydrocarbons
SRK/PR/
BWRS
Recommended for systems of similar light hydrocarbons at
low pressures.
SRKKD Recommended at higher pressures.
COSTALD Recommended for liquid density.
Aromatic Systems
Mixtures of aromatic components, such as aniline and nitrobenzene at low
pressures less than 2 atmospheres, exhibit close to ideal behavior. Ideal meth-
ods can therefore be used to predict phase behavior and compute enthalpies,
entropies, and densities. At pressures above 2 atmospheres, the Grayson-
Streed or SRK or PR methods provide good results in the prediction of phase
equilibria. The SRK or PR equations of state should provide better results,
but with a small CPU penalty.
Tabl e 1. 2. 2-9:
Methods Recommended for Aromati cs
IDEAL Recommended for systems at low pressures below 2 atm.
GS/SRK/PR Recommended at pressures higher than 2 atm.
IDEAL/API/
COSTALD
Recommended for liquid density. The COSTALD method is
best at high temperatures and if light components such as
CH4 are present.
Aromatic/Non-aromatic Systems
Systems of mixtures of aromatic and non-aromatic components are highly
nonideal. Liquid activity methods such as NRTL or UNIQUAC, or equation-of-
state methods with advanced mixing rules such as SRKM or SRKS can be used
to model these systems. Both types of methods can be used to successfully
model aromatic/non-aromatic mixtures, provided that all the binary interaction
data for the components in the system are provided. The PRO/II databanks con-
tain an extensive variety of interaction data for the NRTL, UNIQUAC, SRKM,
and SRKS methods. One advantage to using the liquid activity methods NRTL
or UNIQUAC, however, is that the FILL option may be used to fill in any miss-
ing interaction parameters using UNIFAC. All library components in the PRO/II
databanks have UNIFAC structures already defined. PRO/II also will estimate
UNIFAC structures for petro components based on their Watson K and molecu-
lar weight values, and the user may supply UNIFAC structures for components
not in the PROII databanks.
24. 10 PRO/II Note: For more information on using the FILL option to fill in missing
interaction parameters for liquid activity methods, see Section 24.10, Filling in
Missing Parameters, of the PRO/II Keyword Input Manual.
When gases such as H2, N2, or O2 are present in small quantities (up to about 5
mole %), the Henrys Law option may be used to calculate the gas solubilities.
Once the Henrys Law option is selected by the user, PRO/II arbitrarily defines
all components with critical temperatures less than 400 Kelvin as solute compo-
nents, though the user may override these selections.
24. 11 PRO/II Note: For information on using the SOLUTE option to define Henrys
components, see Section 24.11, Henrys Law for Non-condensible Compo-
nents, of the PRO/II Keyword Input Manual.
Reference Manual
For large amounts of supercritical gases, an equation-of-state method with an
advanced mixing rule should be used to predict the phase behavior.
Tabl e 1. 2. 2-10:
Methods Recommended for Aromati c/Non-aromati c Systems
SRKM/PRM Recommended at high pressures or when >5 mole %
supercritical gases are present.
NRTL/
UNIQUAC
Recommended with the FILL option when binary
interaction parameters are not available or with the HENRY
option when <5 mole % supercritical gases are present.
Alcohol Dehydration Systems
The PRO/II special package ALCOHOL is recommended for systems con-
taining alcohols with water. This package uses a special databank of NRTL
parameters containing interaction parameters expressly regressed under tem-
perature and pressure conditions commonly found in dehydration systems.
The NRTL method is suggested if user-supplied interaction data are to be
used.
25. 1 PRO/II Note: For information on using the ALCOHOL method, see Section
25.1, Alcohol, of the PRO/II Keyword Input Manual.
Tabl e 1. 2. 2-11:
Methods Recommended for Al cohol Systems
ALCOHOL Recommended for all alcohol dehydration systems.
NRTL/
UNIQUAC
Recommended when user-supplied data are provided.
Chemical
Applications
Non-i oni c Systems
These systems, which typically contain oxygen, nitrogen, or halogen deriva-
tives of hydrocarbons, such as amides, esters, or ethers, are also similar to
non-hydrocarbon systems found in petrochemical applications. For low pres-
sure systems, a liquid activity coefficient method is recommended. For single
liquid phase systems, the WILSON, NRTL, or UNIQUAC methods are
equally good, provided all interaction parameters are provided. PRO/II dat-
abanks contain extensive parameters for NRTL and UNIQUAC, but the user
must supply interaction data for the WILSON method. The WILSON method
is the simplest and requires the least CPU time.
For systems with two liquid phases, the NRTL or UNIQUAC methods
should be used, provided that at least some interaction data are available. The
FILL option can be used to fill in any missing interaction data using the UNI-
FAC method. If no interaction data are available, the UNIFAC method
should be used since the PRO/II databanks contain a large amount of group
interaction data for both VLE and LLE applications. For moderate pressure
systems up to 10 atmospheres, a liquid activity method can still be used,
provided that the interaction parameters used are still valid in that pressure
range. For example, if the system pressure were much higher than the pres-
sure at which the interaction parameters were regressed, the vapor-phase
fugacity may be taken into account in modeling the phase behavior. If the
PHI option is selected, the liquid-phase Poynting correction factor is automat-
ically selected also.
It is also important to note that all the interaction parameters in the PRO/II
databanks, except for dimerizing components such as carboxylic acids, were
regressed without including any vapor-phase non-ideality. This means that
the PHI option should be used for carboxylic acid systems at all pressures,
but should only be used for most components at high pressures. For systems con-
taining components such as carboxylic acids that dimerize in the vapor phase,
the Hayden-OConnell fugacity method may be used to calculate all vapor-phase
properties such as fugacity, enthalpy, and density. For components such as hydro-
gen fluoride which forms hexamers in the vapor phase, PRO/II contains an equa-
tion of state specially created for such systems, HEXAMER. This method is
recommended for processes such as HF alkylation or the manufacture of refriger-
ants such as HFC-134a. For all other components, an equation-of-state method
such as SRK or PR may be used to calculate vapor-phase fugacities.
24 PRO/II Note: For information on using the PHI option to calculate the
vapor-phase fugacity when using a liquid activity method, see Section 24,
Liquid Activity Methods, of the PRO/II Keyword Input Manual.
When supercritical gases are present in small quantities (generally less than
5 mole %), the Henrys Law option should be used to compute gas solubili-
ties. For high pressure systems, greater than 10 atmospheres, or for systems
with large quantities of supercritical gas, an equation-of-state method using
an advanced mixing rule, such as SRKM or PRM, should be used. The UNI-
WAALS equation-of-state method uses UNIFAC structure information to
predict phase behavior. This method is useful when interaction data are not
available and, unlike a liquid activity method such as UNIFAC, is able to
handle supercritical gases.
Reference Manual
Tabl e 1. 2. 2-12:
Methods Recommended for Non-i oni c Chemi cal Systems
WILSON Recommended for single liquid phase slightly nonideal
mixtures. If all interaction data are not available, use the
FILL=UNIFAC option.
NRTL/
UNIQUAC
Recommended for all nonideal mixtures. Use with the FILL
option when binary interaction parameters are not available
or with the HENRY option when <5 mole % supercritical
gases are present. For moderate pressures, use the PHI
option for vapor phase non-idealities.
SRKS/
SRKM/PRM/
UNIWAALS
Recommended for high pressure systems or when >5
mole % supercritical gases are present.
HOCV Recommended for vapor fugacity and enthalpy and density
calculations in systems containing dimerizing components
such as carboxylic acids. Use with a liquid activity method .
HEXAMER Recommended for systems containing hexamerizing
components such as HF.
Ionic Systems
A special version of PRO/II expressly made for aqueous electrolytes is rec-
ommended when modeling these systems. This version combines the PRO/II
flowsheet simulator with rigorous electrolyte thermodynamic algorithms devel-
oped by OLI Systems, Inc. Chemical systems which may be modeled by this
special version include amine, acid, mixed salts, sour water, caustic, and Ben-
field systems. See Sections 1.2.9, Electrolyte Mathematical Model, and 1.2.10,
Electrolyte Thermodynamic Equations for further details.
Tabl e 1. 2. 2-13:
Methods Recommended for Ioni c Chemi cal Systems
PRO/II Electrolyte Version
Envi ronmental Appl i cati ons
These systems typically involve stripping dilute pollutants out of water. By them-
selves, liquid activity methods such as NRTL do not model these dilute systems
with much accuracy. A better approach is to use a liquid activity method in com-
bination with Henrys constants at the process temperature to model these dilute
aqueous systems. PRO/II contains Henrys Law constants for many components
such as HCl, SO2, and ethanediol in water. Some additional Henrys constants
for chlorofluorocarbons (CFCs) and hydrofluorocarbons (HFCs) in water are
also available in the PRO/II databanks. Other sources for Henrys Law data
include the U.S. Environmental Protection Agency.
Tabl e 1. 2. 2-14:
Methods Recommended for Envi ronmental Appl i cati ons
Liquid Activity Method +Henrys Law Option
Solid Applications
Solid-liquid equilibria for most systems can be represented in PRO/II by the
vant Hoff (ideal) solubility method or by using user-supplied solubility data.
In general, for those systems where the solute and solvent components are
chemically similar and form a near-ideal solution, the vant Hoff method is
appropriate. For nonideal systems, solubility data should be supplied. For
many organic crystallization systems, which are very near ideal in behavior,
the vant Hoff SLE method provides good results. The VLE behavior can usu-
ally be adequately represented by IDEAL or any liquid activity methods.
Precipitation of solid salts and minerals from aqueous solutions can be calcu-
lated more rigorously by using the electrolyte version of PRO/II.
26. 1 PRO/II Note: For information on using the ideal solid-liquid equilibria method
VANTHOFF, see Section 26.1, Vant Hoff Solubility, of the PRO/II Keyword
Input Manual.
Tabl e 1. 2. 2-15:
Methods Recommended for Sol i d Appl i cati ons
Ideal or Liquid
Activity
Method(VLE)
+VANT HOFF
Method (SLE)
Recommended for most solid systems involving organics.
PRO/II
Electrolyte
Version
Recommended for solid salt and mineral precipitation
from aqueous solutions.
Reference Manual
General i zed Correl ati on Methods
General
Information
Vapor-liquid equilibria can be predicted for hydrocarbon mixtures using
various general correlation methods. Examples of these are those developed
by Chao and Seader or Grayson and Streed. Vapor-liquid equilibria can also
be predicted by convergence pressure correlations such as the K10 charts de-
veloped by Cajander et al. Densities, enthalpies, and entropies can also be
calculated using a number of correlation methods such as Lee-Kesler and
COSTALD.
Ideal
(IDEAL)
Ideal K-values are generally applicable to systems which exhibit behavior
close to ideality in the liquid phase. Mixtures of similar fluids often exhibit
nearly ideal behavior. In an ideal solution at constant temperature and pres-
sure, the fugacity of every component is proportional to its mole fraction.
For every component i, the following fundamental thermodynamic equilib-
rium relationship holds:
(1)
f
i
L
f
i
V
where:
superscript L refers to the liquid phase
superscript V refers to the vapor phase
In the vapor phase, the fugacity is assumed to be equal to the partial pressure:
(2)
f
i
V
y
i
P
where:
yi = vapor mole fraction
P = system pressure
In the liquid phase for an ideal liquid (ignoring correction factors that are
usually small):
(3)
f
i
L
x
i
f
pure i
L
x
i
P
i
sat
where:
xi = liquid mole fraction
f
L
pure i = pure-component i liquid fugacity
Pi
sat
= vapor pressure of component i at the system temperature
1. 2. 3
I-58 General i zed Correl ati on Methods May 1994
Raoults law thus holds:
(4)
y
i
P x
i
P
i
sat
The ideal K-value is therefore given by:
(5)
K
i
y
i

/
x
i
P
i
sat

/
P
Note that there is no compositional dependency of the K-values. They are only a
function of temperature (due to the dependence of Pi
sat
on T) and pressure.
Ideal vapor densities are obtained from the ideal gas law:
(6) P
/
RT
where:
= vapor molar density of mixture
Ideal liquid densities are obtained from pure-component saturated-liquid density
correlations.
Ideal liquid enthalpies are obtained from pure-component liquid enthalpy cor-
relations, and the corresponding vapor enthalpies are obtained by adding in
the effect of the known latent heat of vaporization of the component.
Ideal entropies are calculated from the ideal enthalpy data using the follow-
ing equation:
(7)
S
i

c
pi
dT
/
T
H
i

/
T_
,P
dT
/
T
where:
Si = ideal entropy
cpi = ideal heat capacity of component i
Hi = ideal enthalpy
Tref = reference temperature (1 degree Rankine)
T = temperature of mixture
22. 1 PRO/II Note: For more information on using the IDEAL and LIBRARY methods,
see Section 22.1, IDEAL and LIBRARY, of the PRO/II Keyword Input Manual.
PRO/II Component and Thermophysical Properties General i zed Correl ati on Methods I-59
Reference Manual
Chao-Seader
(CS)
Chao and Seader calculated liquid K-values for the components of nonideal
mixtures using the relationship:
(8)
K
i
y
i

/
x
i

f
i
0L
P
_
,
where:
fi
0L
= the standard-state fugacity of component i in the pure
liquid phase
i = the activity coefficient of component i in the equilibrium
liquid mixture
i = the fugacity coefficient of component i in the equilibrium
vapor mixture
It was shown that i could be calculated from molar liquid volumes and solubility
parameters, using the Scatchard-Hildebrand equation, with regular liquid solution
assumed. The Redlich-Kwong equation of state (see Section 1.2.4, Equations of
State) was used to evaluate . Chao and Seader presented a generalized correlation
for fi
0L
/P, the fugacity coefficient of pure liquid i in real and hypothetical states.
In the development of their correlation for vapor-liquid K-values, Chao and
Seader used the framework of Pitzers modified form of the principle of cor-
responding states for the pure-liquid fugacity coefficients, giving values of
fi
0L
/P as a function of reduced temperature, reduced pressure, and acentric
factor for both real and hypothetical liquids:
(9)
ln
f
i
OL

/
P
_
,
ln
f
i
OL

/
P
_
,
0
+ ln
f
i
OL

/
P
_
,
1
where:
= acentric factor
The first term on the right hand side of equation (9) represents the fugacity
coefficient of simple fluids. The second term is a correction accounting for the
departure of the properties of real fluids from those of simple fluids.
22. 3 PRO/II Note: For more information on using the Chao-Seader method, see Sec-
tion 22.3, Chao-Seader, of the PRO/II Keyword Input Manual.
Limitations of the Chao-Seader method are given below:
For all hydrocarbons;
Pressure: up to 2000 psia, but not exceeding 0.8 of the critical pressure
of the system.
Temperature: -100 F to 500 F and pseudoreduced temperature, Tr,
of the equilibrium liquid mixture less than 0.93. The pseudoreduced
temperature is based on the molar average of the critical temper-
atures of the components.
Concentration: up to 20 mole % of other dissolved gases in the
liquid.
The method is not suitable for other non-hydrocarbon components such
as N2, H2S, CO2, etc.
Reference
Chao, K. C., and Seader, J. D., 1961, A Generalized Correlation of
Vapor-Liquid Equilibria in Hydrocarbon Mixtures, AIChE J., 7(4),
598-605.
Grayson-Streed
(GS)
Grayson and Streed modified the Chao-Seader correlation in 1963 by fitting
data over a wider range of conditions and, hence, deriving different constants for
the equations giving the fugacity coefficients of the pure liquids. Special coeffi-
cients for hydrogen and methane are supplied because typical application tem-
peratures are far above the critical points of these two components. Grayson and
Streeds modifications have extended the application range for hydrocarbon sys-
tems up to 800 F and 3000 psia. The lower limits imposed by Chao and
Seader still apply.
22. 2 PRO/II Note: For more information on using the Grayson-Streed method, see
Section 22.2, Grayson-Streed, of the PRO/II Keyword Input Manual.
Reference
Grayson, H. G., and Streed, C. W., 1963, Vapor-Liquid Equilibria for
High Temperature, High Pressure Hydrocarbon-Hydrocarbon Systems, 6th
World Congress, Frankfurt am Main, June 19-26.
Erbar Modification
to Chao-Seader
(CSE) and Grayson-
Streed (GSE)
In 1963, Erbar and Edmister developed a new set of constants for the Chao-
Seader liquid fugacity coefficient, specifically for N2, H2S, and CO2, in
order to improve the prediction of the K-values of these gases. At the same
time, new solubility parameter and molar volume values were found for
these components.
22. 4 PRO/II Note: For more information on using the Erbar-modified Chao-Seader
and Grayson-Streed methods, see Section 22.4, Modifications to Grayson-
Streed and Chao-Seader, of the PRO/II Keyword Input Manual.
A limitation of this modified method, however, is that the H2S correlation
cannot be used in any cases where an azeotrope may exist (e.g., H2S/C3H8
mixtures), as the azeotrope will not be predicted.
Reference
Erbar, J. H., and Edmister, W. C., 1963, Vapor-Liquid Equilibria for
High Temperature, High Pressure Hydrocarbon-Hydrocarbon Systems, 6th
World Congress, Frankfurt am Main, June 19-26.
Reference Manual
Improved Grayson-
Streed (IGS)
For hydrocarbon-water mixtures, the Grayson-Streed and Erbar-modified
Grayson-Streed methods accurately predict the phase behavior of the hydro-
carbon-rich phase, but are incapable of predicting the composition of the
water-rich phase. A new method has been developed in which a separate set
of solubility parameters was used in the water-rich phase, and a new set of
liquid fugacity coefficients developed for N2, H2O, H2S, CO, and O2. This
new method is known as Improved Grayson-Streed. It was found that the
Grayson-Streed liquid fugacity coefficient for the simple fluid decreases
rapidly as Tr increases above 2.5, and can in fact become negative. The liq-
uid fugacity coefficient for the simple fluid was therefore replaced by that
for hydrogen at reduced temperatures of 2.5 and above.
22. 4 PRO/II Note: For more information on using the Improved Grayson-Streed
method, see Section 22.4, Modifications to Grayson-Streed and Chao-Seader,
of the PRO/II Keyword Input Manual.
Curl-Pitzer (CP) This correlation may be used to predict both liquid and vapor enthalpies and
entropies. It computes the enthalpy deviation using the principle of
corresponding states, i.e., in terms of the reduced temperature, reduced
pressure, and acentric factor. The critical temperature and pressure for the
mixture is computed using the mixture rules of Stewart, Burkhart, and Voo.
The mixture acentric factor used is the molar average value.
The Curl-Pitzer method is limited to nonpolar mixtures and may be used for
Pr up to 10, and Tr from 0.35 to 4.0 for liquids, and Tr from 0.6 to 4.0 for
vapors. For systems containing heavy ends, the saturated vapor is sometimes
at a reduced temperature of less than 0.6. In this case, the CP correlation ex-
trapolates reasonably, producing satisfactory results.
22. 5 PRO/II Note: For more information on using the Curl-Pitzer method, see Sec-
tion 22.5, Curl-Pitzer, of the PRO/II Keyword Input Manual.
The Curl-Pitzer method is generally useful for refinery hydrocarbons and in
oil absorption gas plants.
References
1. Stewart, Burkhart, and Voo, 1959, Prediction of Pseudo-Critical Constants
for Mixtures, Paper presented at AIChE Meeting, Kansas City.
Refining, 2nd Ed., Procedure 7B3.1.
Refining, 2nd Ed., Procedure 7H2.1, 7-201 - 7-202.
Braun K
10
(BK10) The K-value of each component is a function of the system temperature,
pressure, and the composition of the vapor and liquid phases. For natural gas
systems, the convergence pressure can be used as the parameter that repre-
sents the composition of the vapor and liquid phases in equilibrium. The
convergence pressure is, in general, the critical pressure of a system at a
given pressure. At a given temperature, and as the system pressure increases,
the K-values of all components converge to unity when the system pressure
reaches the convergence pressure.
The Braun K10 charts developed by Cajander et al. in 1960 show the low pres-
sure equilibrium ratio, arbitrarily taken at 10 psia system pressure and 5000 psi
convergence pressure. For many hydrocarbon systems, no experimental data are
available. For these cases, the equilibrium K-values may be predicted from
vapor pressure:
(10)
K
10
P
sat

/
10
where:
P
sat
= saturated vapor pressure in psia.
The relationship given in equation (10) only holds for K-values less than 2.5.
For nonhydrocarbons like H2, the K-value is assumed to be 10 times as large
as the methane value. For N2, O2, and CO, the K-values are assumed to be
identical to that of methane. The K-values for CO2 and H2S are assumed to
be identical to that of propylene.
For petroleum fractions in which the form of the vapor pressure curve is un-
known, a rough K10 chart is developed from the normal boiling point of the
fraction. The following method is used:
On the appropriate K10 chart, the point K10 = 14.7/10 = 1.47 is plotted at
the atmospheric boiling point.
The whole K10 curve can then be sketched in by similitude to the known
K10 curves for homologous hydrocarbons.
The K10 charts apply to mixtures that behave ideally at low pressures, e.g.,
for mixtures of one molecule type such as mixtures of paraffins and olefins.
For mixtures of naphthalenes mixed with olefins and paraffins, the accuracy
of BK10 is slightly poorer. Large errors can be expected for mixtures of aro-
matics with paraffins, olefins, or naphthalenes, which cause nonidealities and
form azeotropes.
22. 6 PRO/II Note: For more information on using the Braun K10 method, see Sec-
tion 22.6, Braun K10, of the PRO/II Keyword Input Manual.
Reference
Cajander, B. C., Hipkin, H. G., and Lenior, J. M., 1960, Prediction of
Equilibrium Ratios from Nomographs of Improved Accuracy, J. Chem.
Eng. Data, 5, 251-259.
Reference Manual
Johnson-Grayson
(JG)
This correlation may be used to predict both liquid and vapor enthalpies. It is
essentially an ideal-enthalpy correlation, using saturated liquid at 0 C as
the datum for the correlation (-200 F in versions 3.5 and earlier).
Vapor-phase corrections are calculated using the Curl-Pitzer correlation.
Pressure effects are not considered for the liquid phase.
Johnson-Grayson is useful for systems containing heavy ends between 0 F
and 1200 F. However, it can be extrapolated to higher temperatures. The cor-
relation should not be used if the mixture is C4-C5 or lighter.
22. 7 PRO/II Note: For more information on using the Johnson-Grayson method, see
Section 22.7, Johnson-Grayson, of the PRO/II Keyword Input Manual.
Reference
Johnson, and Grayson, 1961, Enthalpy of Petroleum Fractions,
Petroleum Refiner, 40(2), 123-29.
Lee-Kesler (LK) This correlation may be used to predict both liquid and vapor enthalpies, en-
tropies, and densities. This correlation uses the three-parameter correspond-
ing-states theory, which essentially states that all fluids having the same
acentric factor must have the same properties at the same reduced tempera-
ture and pressure. Special mixing rules have been used to calculate the mix-
ture reduced properties. For most fluids, the Lee-Kesler method is 98%
accurate in predicting the gas-phase compressibility factors. The method also
gives reasonable results for slightly polar mixtures. This method is not rec-
ommended for highly polar mixtures, or those which form strongly associa-
tive hydrogen bonds. However, the Lee-Kesler method provides accurate
results for polar fluids at low temperatures near the saturated-vapor region.
The Lee-Kesler method is not recommended for calculating liquid densities
of hydrocarbons heavier than C8.
22. 8 PRO/II Note: For more information on using the Lee-Kesler method, see Sec-
tion 22.8, Lee-Kesler, of the PRO/II Keyword Input Manual.
References
1. American Petroleum Institute, 1975, Technical Data Book-Petroleum
Refining, 3rd Ed., 2-1 - 7-4.
2. Lee, B. I., and Kesler, M. G., 1975, A Generalized Thermodynamic
Correlation Based on Three-Parameter Corresponding States, AIChE J., 21,
510-27.
3. Kesler, M. G., and Lee, B. I., 1976, Improved Prediction of Enthalpy of
Fractions, Hydrocarbon Proc., 53, 153-158.
API This correlation may be used to predict liquid densities. An initial density is
calculated at 60 F using the weight average of the components. The reduced
temperature and pressure of the stream at 60 F and 14.7 psia are computed
using Kays rule, i.e., the reduced temperature and pressure are assumed to
be a linear function of the liquid mole fraction. A density factor C is then
read from Figure 6A2.21 in the API Technical Data Book. A second correc-
tion factor is then determined, corresponding to the reduced temperature and
pressure, at the actual fluid conditions. Finally, the actual liquid density is
calculated according to:
(11)
act
L

60
L

C
act

/
C
60
_
,
where:
act
L
= actual liquid density
60
L
=
liquid density at 60 F
Cact = actual correction factor
C60 =
correction factor at 60 F
22. 9 PRO/II Note: For more information on using the API method, see Section
22.9, API Liquid Density, of the PRO/II Keyword Input Manual.
The API method works well for most hydrocarbon systems, provided that the
reduced temperature is less than 1.0.
Reference
American Petroleum Institute, 1978, Technical Data Book - Petroleum
Refining, 5th Ed., 6-45 - 6-46.
Rackett This correlation may be used to predict liquid densities. The saturated-liquid
density is obtained from:
(12)
V
si

RT
ci

/
P
ci
_
,
Z
rai
i
1 + (1T
ri
)
2
/
7
for T
ri
0.75
i
1.6 +
6.9302610
3
T
ri
0.655
for T
ri
> ~ 0.75
where:
Vsi = saturated liquid volume
Zrai = Rackett parameter for component i
Tci, Pci = critical temperature and pressure for component i
Tri = reduced temperature for component i
Reference Manual
22. 10 PRO/II Note: For more information on using the Rackett liquid density method,
see Section 22.10, Rackett Liquid Density, of the PRO/II Keyword Input
Manual.
The PRO/II databanks contain Rackett parameters for many components.
However, if Rackett parameters are not available, PRO/II will use the critical
compressibility factor, zc.
For mixtures, there are two ways to use the Rackett equation. The most
straightforward, known as the RACKETT method in PRO/II, is to use equa-
tion (12) for the molar volume of each pure component and then mix the
volumes together linearly. A second approach is the One-Fluid" Rackett
method (known as the RCK2 method), in which mixing rules are used to de-
termine effective critical parameters for the mixture and then equation (12) is
used to determine the mixture density. For most mixtures, the difference be-
tween these two methods will not be significant.
References
1. Rackett, H. G., 1970, Equation of State for Saturated Liquids, J. Chem. Eng.
Data, 15, 514.
2. Spencer, C. F., and Danner, R. P., 1972, Improved Equation for Prediction
of Saturated Liquid Density, J. Chem. Eng. Data, 17, 236-241.
3. Spencer, C. F., and Adler, S. B., 1978, A Critical Review of Equations for
Predicting Saturated Liquid Density, J. Chem. Eng. Data, 23, 82-89.
COSTALD The corresponding-states liquid density model predicts the liquid densities of
LNG-like fluids. This accurate and reliable method is over 99.8% accurate in
predicting the densities of light hydrocarbon mixtures. This model uses two char-
acteristic parameters for each pure component in the mixture - a characteristic
volume, V
*
, and a tuned acentric factor, SRK. The acentric factor is chosen
such that the SRK equation of state best matches the vapor-pressure data. Typi-
cally, this tuned acentric factor varies little in value from the standard acentric
factor. The saturated volume is given by:
(13)
V
s

/
V
V
r
(0)

1
SRK
V
r
()
1
]
(14)
V
r
(0)
1 +

1
4
A
k
(1 T
r
)
k
/
3
, 0.25 < T
r
< 0.95
(15)
V
r
()

0
3
B
k
T
r
k
1
1
]
1
1

/

T
r
1.00001_
,
, 0.25 < T
r
< 1.0
where:
Vs = saturated molar volume
V
*
= characteristic volume
Vr = reduced volume
Ak, Bk = COSTALD parameters
SRK = SRK tuned acentric factor
For mixtures, the following mixing rules are used:
(16)
T
cm

j
x
i
x
j
V
ij

T
cij
_
,

/
V
m
(17)
V
m
1
/
4
x
i
i
V
i
+ 3
x
i
i
V
i
2
/
3_
x
i
i
V
i
1
/
3_
,
1
1
]
(18)
V
ij
T
cij

V
i
T
ci
V
j
T
cj
_
,
1
/
2
(19)
SRK

x
i
i
SRKi
where:
subscript m refers to mixture properties.
For compressed pure liquids and liquid mixtures, the original work was ex-
tended by Thomson et al. in 1982, adding a pressure correction of the form:
(20)
V V
s

1 Cln
'
(B + P)
/
(B + P
sat
)
_
,
where:
B, C are constants, dependent on composition
P
sat
= saturated vapor pressure, obtained from a generalized vapor
pressure relationship.
V = molar volume
22. 11 PRO/II Note: For more information on using the COSTALD liquid density
method, see Section 22.11, Costald Liquid Density, of the PRO/II Keyword
Input Manual.
The COSTALD method is valid for aromatics and light hydrocarbons up to
reduced temperatures of 0.95. PRO/II databanks contain COSTALD charac-
teristic volume, V
*
, for many components. However, if the characteristic vol-
ume is not available, PRO/II will use the critical volume of the pure
component, Vc. For petroleum and assay components, however, PRO/II will
back calculate a characteristic volume, if missing, in order to provide a cor-
rect specific gravity for the pseudocomponent.
Reference Manual
References
1. Hankinson, R. W., and Thomson, G. H., 1979, A New Correlation for Saturated
Densities of Liquids and Their Mixtures, AIChE J., 25o, 653-663.
2. Thomson, G. H., Brobst, K. R., and Hankinson, R. W., 1982, An Improved
Correlation for Densities of Compressed Liquids and Liquid Mixtures,
AIChE J., 28, 671-676.
Equati ons of State
General
Information
Equations of state for phase-equilibrium calculations are applicable to wide
ranges of temperature and pressure conditions. They can also be used to calcu-
late all the related thermodynamic properties such as enthalpy and entropy. The
reference state for both the vapor and liquid phase is the ideal gas, and devia-
tions from the ideal-gas state are determined by calculating fugacity coefficients
for both phases. For cubic equations of state in particular, critical and supercriti-
cal conditions can be predicted quite accurately. By using an appropriate tem-
perature-dependent function to describe the attractive forces between molecules,
volume function, and mixing rule, cubic equations of state have been shown to
be quite successful in predicting vapor-liquid equilibria for highly nonideal
systems.
General Cubic
Equation of State
A general two-parameter cubic equation of state can be expressed by the
equation:
(1)
P RT
/
(vb) a(T)
/

v
2
+ ubv + wb
2
_
,
where:
P = pressure
T = absolute temperature
v = molar volume
u,w = constants, typically integers
The values of u and w determine the type of cubic equation of state. Table
1.2.4-1 shows three of the best known of these. The van der Waals equation
developed in 1873 is obtained by setting u=w=0. By setting u=1 and w=0,
the Redlich-Kwong equation (1949) is obtained. Peng and Robinson devel-
oped their equation of state in 1976 by setting u=2 and w=-1.
Tabl e 1. 2. 4-1: Some Cubi c Equati ons of State
u w Equati on of state
0 0 van der Waals (vdW)
1 0 Redlich-Kwong (RK)
2 -1 Peng-Robinson (PR)
The parameters a and b at the critical temperature (ac and bc) are found by
setting the first and second derivatives of pressure with respect to volume
equal to zero at the critical point. Application of these constraints at the criti-
cal point to equation (1) yields:
1. 2. 4
PRO/II Component and Thermophysical Properties Equati ons of State I-69
Reference Manual
'
u + (u1)
2

/
3 + (u1)
3

/
27
B
c
3
+
'
u + w 2
/
3(u1) 1
/
9(u1)
2
B
c
2
+
'
1
/
3 + 1
/
9(u1)
B
c
1
/
27 0
(2)
(3)
A
c
3Z
c
2
+ uB
c
+ (uw) B
c
2
(4) Z
c
1
/
3 (u1) B
c

/
3
where:
Ac = Pcac/R
2
Tc
2
Bc = Pcbc/RTc
subscript c refers to the critical point
The critical constraints result in three expressions for three unknowns, Ac, Bc,
and Zc. These unknowns depend on the values of u and w. Actually, Ac and Bc
are the only true unknowns appearing in these equations, because Pc, Tc, and Vc
(and hence Zc) are properties of a substance, having numerical values inde-
pendent of any equation of state. In solving these three equations, Vc is in fact
treated as a third unknown. Table 1.2.4-2 lists these constants for the van der
Waals, Redlich-Kwong, and Peng-Robinson equations of state.
Tabl e 1. 2. 4-2: Constants for Two-parameter Cubi c Equati ons of State
Ac Bc Zc Equati on of state
0.42188 0.1250 0.3750 van der Waals (vdW)
0.42747 0.0866403 0.3333 Redlich-Kwong (RK)
0.45724 0.0778 0.3074 Peng-Robinson (PR)
References
1. Abbott, M. M., 1973, Cubic Equations of State, AIChE J., 19, 596-601.
2. van der Waals, J. D., 1873, Over de Constinuiteit van den gas-en Vloeis-
toftoestand, Doctoral Dissertation, Leiden, Holland.
3. Redlich, O., and Kwong, N. S., 1949, On the Thermodynamics of Solutions.
v: An Equation of State. Fugacities of Gaseous Solutions, Chem. Rev., 44,
233.
4. Peng, D. Y., and Robinson, D. B., 1976, A New Two-constant Equation of
State for Fluids and Fluid Mixtures, Ind. Eng. Chem. Fundam., 15, 58-64.
I-70 Equati ons of State May 1994
Alpha
Formulations
The temperature-dependent parameter a(T) can be rewritten as:
(5) a(T) (T) a(T
c
)
In equation (5), (T) is a temperature-dependent function which takes into
account the attractive forces between molecules. The accuracy of the equation of
state for pure-component vapor pressures (and therefore to a large extent for mix-
ture phase equilibria) depends on the form of the alpha formulation, (T), from
equation (5). The real-gas behavior approaches that of the ideal gas at high tem-
peratures, and this requires that goes to a finite number as the temperature
becomes infinite. Three basic requirements for the temperature-dependent alpha
function must therefore all be satisfied:
1. The function must be finite and positive for all temperatures.
2. The function must equal unity at the critical point.
3. The function must approach a finite value as the temperature approaches
infinity.
For the Redlich-Kwong equation of state, which works well for the vapor
phase at high temperatures, (T) is given by:
(6)
(T) T
r

1
/
2
PRO/II allows the user to utilize a choice of 11 different alpha formulations
for cubic equations of state (SRK, PR, modified SRK or PR, or UNI-
WAALS). Table 1.2.4-3 shows the 11 available formulations for (T).
Reference Manual
Tabl e 1. 2. 4-3: Al pha Formul ati ons
Form Equati on Reference
01
1 + C1
1 T r
0.5
_
,
1
]

2 Soave (1972)
02
C
1
+ C
2
1 T
r
C3
_
,
1
]

2 Peng-Robinson (1980)
03 1 + (1 T
r
)
C
1
+
C
2
T
r
_
,
Soave (1979)
04 exp
C1
1 T r
C
2
_
,
1
]
Boston-Mathias (1980)
05
T r
2(C
2
1)
exp
C1
1 T r
2C
2
_
,
1
]
Twu (1988)
06
T r
C
3
(C
2
1)
exp
C1
1 T r
C
2
C
3
_
,
1
]
Twu-Bluck-Cunningham-
Coon (1991)
(Recommended by SimSci)
07 exp
2C1
1 + C1

1 T
r
(C1 + 1)

2
)
_
,
Alternative for form (04)
08 T r
C
3
exp
C1
1 T r
C
2
_
,
1
]
Alternative for form (06)
09

1 + C
1
1 T
r
0.5
_
,
+ C
2
1 T
r
0.5
_
,
2
+ C
3
1 T
r
0.5
_
,
3
1
]
2 Mathias-Copeman (1983)
10

1 + C
1
1 T
r
0.5
_
,
+ C
2
1 T
r
_
,

0.7 T
r
_
,
1
]

2 Mathias (1983)
11
exp
C1
1 Tr
_
,
+ C2
1 T r
0.5
_
,
2
1
]
Melhem-Saini-Goodwin
(1989)
where:
C1, C2, C3 = constants
Tr =T/Tc =reduced temperature
23. 5 PRO/II Note: For more information on using alpha functions, see Section 23.5,
Cubic Equation of State Alpha Formulations, of the PRO/II Keyword Input
Manual.
References
1. Soave, G., 1972, Equilibrium Constants from a Modified Redlich-Kwong
Equation of State, Chem. Eng. Sci., 35, 1197.
2. Soave, G, 1979, Application of a Cubic Equation of State to Vapor-
Liquid Equilibria of Systems Containing Polar Components, Inst. Chem.
Eng. Symp. Ser., No. 56, 1.
3. Boston, J. F., and Mathias, P. M., 1980, Phase Equilibria in a Third
Generation Process Simulator, Proc. of the 2nd Inter. Conf. on Phase
Equil. & Fluid Properties in the Chemical Process Industries, Berlin
(West), March 17-21.
4. Twu, C. H., 1988, A Modified Redlich-Kwong Equation of State for Highly
Polar, Supercritical Systems, Inter. Symp. on Thermodynamics in Chemi-
cal Engineering and Industry, May 30-June 2.
5. Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E., 1991, A Cubic
Equation of State with a New Alpha Function and New Mixing Rule,
Fluid Phase Equil., 69, 33-50.
6. Mathias, P. M., and Copeman, T. W., 1983, Extension of the Peng-
Robinson Equation of State to Complex Mixtures, Fluid Phase Equil., 13,
91-108.
7. Mathias, P. M., 1983, A Versatile Phase Equilibrium Equation of State, Ind.
Eng. Chem. Proc. Des. Dev., 22, 358-391.
8. Melhem, G. A., Saini, R., and Goodwin, B. M., 1989, A Modified Peng-Ro-
binson Equation of State, Fluid Phase Equil., 47, 189-237.
Mixing Rules The accuracy of correlating vapor-liquid equilibrium data using a cubic equation
of state can be improved further by choosing an appropriate mixing rule for cal-
culating a and b in equation (1) for mixtures. The original mixing rule was de-
rived from the van der Waals one-fluid approximation:
(7)
a

j
x
i
x
j
a
ij
(8)
b

i
x
i
b
i
where:
xi = mole fraction of component i.
The binary interaction parameter, kij, is introduced into the mixing rule to cor-
rect the geometric mean rule of parameter a in the general cubic equation of
state (1):
Reference Manual
(9)
a
ij
(a
i
a
j
)
1
/
2
(1k
ij
)
where:
kij = kji = binary interaction parameter.
The original mixing rule is capable of representing vapor-liquid equilibria
for nonpolar and/or slightly polar systems using only one (possibly tempera-
ture-dependent) binary interaction parameter.
Soave-Redlich
Kwong (SRK)
In 1972, to improve the prediction of the vapor pressure of pure components,
and thus multicomponent vapor-liquid equilibria, Soave proposed the follow-
ing form of (T):
(10)
(T)
1 + M
1T
r
1
/
2_
,
1
1
]
2
(11)
M 0.480 + 1.574 0.176
2
where:
Tr = reduced temperature, T/Tc
= acentric factor
The constants in (11) were obtained from the reduction of vapor-pressure data
for a limited number of common hydrocarbons. This limits the use of the SRK
equation of state to nonpolar components. This equation of state does not
accurately predict the behavior of polar components or light gases such as hy-
drogen. However, the simplicity of equations (10) and (11), and its accuracy
for calculating vapor pressures at temperatures higher than the normal boil-
ing point for hydrocarbons allowed it to gain widespread popularity in indus-
try. PRO/II contains correlations for the kijs of hydrocarbons with N2, O2, H2,
H2S, CO2, mercaptans and other sulfur compounds.
Peng-Robinson
(PR)
The form of (T) proposed by Peng and Robinson in 1976 is the same as
that proposed in 1972 by Soave. The numerical values for the constants in
equation (11) are different because the volume function is different and be-
cause a somewhat different set of data was used.
23. 2 PRO/II Note: For more information on using SRK and PR equations of state in
PRO/II, see Section 23.1, Soave-Redlich-Kwong, and Section 23.2, Peng-
Robinson, of the PRO/II Keyword Input Manual.
Soave-Redlich-
Kwong Kabadi-
Danner (SRKKD)
While the K-values between the hydrocarbon-rich liquid phase and vapor
phase can be accurately predicted by most cubic equations of state, the
K-values involving the water-rich liquid phase are not. In order to apply
cubic equations of state to water-hydrocarbon systems, Kabadi and Danner
in 1985 proposed a two-parameter mixing rule for the SRK equation of state.
This proposed mixing rule is composition-dependent and is designed ex-
pressly for water and well-defined hydrocarbon systems:
(12)
a

j
x
i
x
j
(a
i
a
j
)
1
/
2
(1k
ij
) +

iw
a
wi
x
w
2
x
i
(13)
a
wi
G
i
1T
rw
0.8
_
,
(14)
G
i

j
g
j
where:
Trw = T/Tcw
awi = interaction parameter between hydrocarbons and water in
the hydrocarbon-rich phase
gj = hydrocarbon group contribution from group j
Gi = sum of group contributions from the different structural
groups forming a hydrocarbon molecule i
To provide estimates for water/hydrocarbon equilibria when no data are avail-
able, Kabadi and Danner developed a procedure for estimating the binary in-
teraction parameters kij and Gi. Within a homologous series of hydrocarbons,
kij was found to be approximately constant, and recommended values were
given for seven hydrocarbon classes. A group contribution method was pro-
posed for estimating Gi.
One limitation of this method, however, is that the solubility of hydrocarbon in
the aqueous phase is predicted only within an order of magnitude.
20. 6 PRO/II Note: See Section 21, Application Guidelines, and Section 20.6, Free-
Water Decant Considerations, of the PRO/II Keyword Input Manual for infor-
mation on how to handle hydrocarbon-water systems in PRO/II.
Reference
Kabadi, V. N., and Danner, R. P., 1985, A Modified Soave-Redlich-Kwong
Equation of State for Water-Hydrocarbon Phase Equilibria, Ind. Eng.
Chem. Proc. Des. Dev., 24, 537-541.
Reference Manual
Soave-Redlich-
Kwong
Panagiotopoulos-
Reid (SRKP) and
Peng-Robinson
Panagiotopoulos-
Reid (PRP)
In 1986 Panagiotopoulos and Reid proposed an asymmetric mixing rule con-
taining two parameters for the SRK and PR equations of state (denoted as
SRKP and PRP). The interaction parameter they proposed to be used in
equation (7) is given by:
a
ij
(a
i
a
j
)
1
/
2
'
(1k
ij
) + (k
ij
k
ji
)x
i
(15)
The two adjustable interaction parameters are kij and kji. This asymmetric
definition of the binary interaction parameters significantly improves the
accuracy in correlating binary data for polar and nonpolar systems. This
mixing rule has been used to test several systems, including low pressure
nonideal systems, high pressure systems, three-phase systems, and systems
with supercritical fluids. The results in all cases reported are in good agree-
ment with experimental data.
Reference
Panagiotopoulos, A. Z., and Reid, R. C., 1986, A New Mixing Rule for Cubic
Equations of State for Highly Polar Asymmetric Systems, ACS Symp. Ser.
300, American Chemical Society, Washington, DC, 71-82.
The Panagiotopoulos-Reid mixing rule, however, is fundamentally inconsis-
tent for multicomponent systems. This inconsistency is exhibited in two
(related) flaws:
1. The dilution of the mixture with additional components (reducing all the mole
fractions, xi) nullifies the effect of the second binary parameter kji. In the
limit of an infinite number of components so that all the xi approach zero,
the mixing rule reduces to the original van der Waals mixing rule,
equation (9).
2. The mixing rule is not invariant to dividing a component into a number of
identical pseudocomponents. For example, if methane in a mixture is di-
vided arbitrarily into alpha and beta methane, the calculated proper-
ties of the mixture will be slightly different.
Soave-Redlich-
Kwong Modified
Panagiotopoulos-
Reid (SRKM) and
Peng-Robinson
Modified
Panagiotopoulos-
Reid (PRM)
SimSci has modified equation (15) in a way that eliminates the first of the
two flaws noted above. This improvement provides better predictions of
properties for multicomponent systems:
aij (aiaj)
1
/
2

'
(1kij) + (kij kji) (xi

/
xi + xj)
c
ij
(16)
Equation (16) is identical to equation (15) for binary systems if c12 = 1. The
expression for aji, which is similar to equation (16), can be obtained by inter-
changing subscripts i and j. The four adjustable interaction parameters are kij
and kji, and cij and cji. For binary nonpolar systems, where deviations from
ideality are not large, or are only weakly asymmetric, only two parameters,
k12 and k21, are sufficient to fit the data (i.e., c12 = c21 = 1). In this case, equa-
tion (16) becomes identical to the mixing rule proposed (also for the purpose
of overcoming the first flaw mentioned above) by Harvey and Prausnitz in
1989. For binary polar or polar-nonpolar systems, where the nonideality is
large or strongly asymmetric, it may be necessary to include the additional
parameters c12 and c21. In particular, for binary polar-nonpolar systems,
which have the greatest deviation from ideality, c12 is not set equal to c21.
For binary polar systems however, c12 can generally be set equal to c21.
Reference
Harvey, A.H., and Prausnitz, J.M., 1989, Thermodynamics of High-Pressure
Aqueous Systems Containing Gases and Salts, AIChE J., 35, 635-644.
Soave-Redlich-
Kwong SimSci
(SRKS)
In 1991, Twu et al. proposed another modified mixing rule that eliminated
both of the inconsistencies of the Panagiotopoulos-Reid mixing rule noted
above. For a binary system, the mixing rule can be expressed in the follow-
ing form for a12:
(17)
a
12
(a
1
a
2
)
1
/
2

'
(1k
12
+ (H
12
G
12
x
2
2

/
x
1
+G
12
x
2
)
(18)
H
12
(k
21
k
12
)
(19)
G
12
exp(
12
H
12
)
Reference Manual
The four adjustable parameters are: k12, k21, 12, and 21. Again, as for the
SRKM equation of state, for binary nonpolar systems, where deviations from
ideality are not large or are only weakly asymmetric, only two parameters, k12
and k21, are sufficient to fit the data (i.e., 12 = 21 = 1). For binary polar or polar-
nonpolar systems, where the nonideality is large or strongly asymmetric, it may be
necessary to include the additional parameters 12 and 21. In particular, for bi-
nary polar-nonpolar systems, which have the greatest deviation from ideality,
12 is not set equal to 21. For binary polar systems however, 12 can gener-
ally be set equal to 21. Twu et al. have derived the activity coefficients from
the SRKS equation of state and have found that, for a binary system, k12 or
k21 are directly related to the infinite-dilution activity coefficients 1 or 2,
respectively. The values of k12 and k21 are therefore determined when both
values of the infinite-dilution activity coefficients are known for a binary
system. The physical meaning of the binary parameters k12 and k21 is that
they are used to locate the infinite-dilution activity coefficients in a binary
system containing components 1 and 2. After both end points of the liquid
activity coefficients are found, the parameters 12 and 21 are then required
to describe the shapes of the liquid activity coefficient curves for
components 1 and 2 in the finite range of concentration. In general, for real
systems, kij is not equal to kji, and ij and ji are not equal to zero. The con-
ventional mixing rule, obtained by setting k12 = k21 and 12 = 21 = 0 for a
binary system, either results in a compromise of the phase-equilibrium
representation, or fails to correlate highly asymmetric systems.
For a multicomponent system, equation (17) can be generalized as:
(20)
am

j
xixj (aiaj)
1
/
2
(1kij) +
xi
i

'
Hij
j

1
/
3
Gij
1
/
3
(aiaj)
1
/
6
xj

3

/

Gij
j
xj
(21) H
ij
(k
ji
k
ij
)
(22) G
ij
exp (
ij
H
ij
)
where:
subscript m refers to the multicomponent mixture.
Reference
Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E., 1991, A Cubic
Equation of State with a New Alpha Function and New Mixing Rule,
Fluid Phase Equil., 69, 33-50.
Soave-Redlich-
Kwong Huron-
Vidal (SRKH) and
Peng-Robinson
Huron-Vidal
(PRH)
The previous SRK and PR mixing rule modifications include composition-
dependence for applying these equations of state to complex mixtures. A
more complicated way to represent the phase behavior of strongly nonideal
systems is to develop the relationship between the mixing rule and excess
Gibbs free energy, such that the infinite-pressure Gibbs free energy could be
expressed by a NRTL-like method (see Section 1.2.6, Liquid Activity Coeffi-
cient Methods). This approach was proposed by Huron and Vidal in 1979.
The general equation relating excess Gibbs free energy to fugacity coeffi-
cients is given by:
(23)
g
E
RT
ln
x
i
i
ln
i
1
1
]
where:
g
E
= excess Gibbs free energy per mole
= fugacity coefficient of the mixture
i = fugacity coefficient of pure component i
At infinite pressure, the excess Gibbs free energy is calculated using the
Redlich-Kwong equation of state and linear mixing rules for the parameter b
from the general cubic equation of state. At infinite pressure, equation (23)
then becomes:
(24)
g
a
/
b
(a
i
i
x
i

/
b
i
)
_
,
ln(2)
where:
g
E
=
the excess Gibbs free energy at infinite pressure
Equation (24) can be rewritten to produce a new mixing rule for the cubic
equation of state parameter a:
(25)
a b
'
(a
i
i
x
i

/
b
i
) g
E

/
ln (2)
ln(2)
The excess Gibbs free energy can be calculated by any liquid activity
method. Huron and Vidal chose to use the NRTL liquid activity method to
calculate g
E
:
(26)
g
x
i
i

x
j
j
G
ji
c
ji
_
,

/

k
x
k
G
ki
(27) c
ij
g
ji
g
ii
(28)
G
ji
b
j
exp
a
ji
c
ji

/
RT_
,
Reference Manual
The only difference between the classical NRTL equation and equations (26-
28) given above are the definition of the local composition as corrected vol-
ume fractions, which leads to the introduction of the volume parameter bj in
the calculation of Gji. Substituting for g
E
in equation (25) yields:
(29)
a b
x
i
i

'
(a
i

/
b
i
) 1
/
ln(2) (
x
j
j
G
ji
c
ji
)
/

x
k
k
G
ki
By regressing experimental data to obtain the parameters in the modified

NRTL expression, excellent representation of vapor-liquid equilibria can be
made for several systems. The Huron-Vidal mixing rules are highly empirical
in nature. However, the prediction of equilibria at low densities is reason-
able, and the equation of state can be expected to yield better results at
higher pressures, because the mixing rules have been derived at the infinite-
pressure limit of the excess Gibbs free energy. One limitation of this model
is that it cannot directly utilize parameters for the NRTL method correlated
from low temperature data. This is because an excess Gibbs energy model
from an equation of state at infinite pressure cannot be equated with an activ-
ity coefficient excess Gibbs energy model at low pressure.
23. 3 PRO/II Note: See Section 23.3, Modified Soave-Redlich-Kwong and Peng-Ro-
binson, of the PRO/II Keyword Input Manual for more information on using
the modified SRK and PR methods in PRO/II.
Reference
Huron, M. J., and Vidal, J., 1979, New Mixing Rules in Simple Equations of
State for Representing Vapor-Liquid Equilibria of Strongly Non-ideal Mix-
tures, Fluid Phase Equil., 3, 255-271.
HEXAMER Hydrogen fluoride is an important chemical used in many vital processes, in-
cluding HF alkylation, and in the manufacture of refrigerants and other halo-
genated compounds. Unlike hydrocarbons, however, hydrogen fluoride is
polar and hydrogen bonded, and therefore self-associates not only in the liq-
uid phase, but also in the vapor phase. Experimental evidence strongly sug-
gests that the HF vapor exists primarily as a mixture of monomer and
hexamer. In addition, evidence points to the hexamer existing in the form of
a cyclic benzene-like species. This behavior results in significant departures
from ideality, especially in calculating fugacity coefficients, vapor com-
pressibility factors, heat of vaporization, and enthalpies.
Twu et al. (1993), developed a cubic equation of state with a built-in chemi-
cal equilibrium model to account for HF association. The cubic equation of
state incorporating association is given by:
(30)
P n
r

RT
(v b)

a(T)
v
2
+ ubv + wb
2

(31)
n
r

n
T
n
0
(32)
v
V
n
0
where:
a(T) = (T)a(Tc) = Redlich-Kwong equation-of-state
parameter which refers to the monomer
b = Redlich-Kwong equation-of-state parameter which refers to
the monomer
v = molar volume
V = total volume
n
r
= extent of association
n
T
= total number of moles of monomer and hexamers
n0 = the number of moles that would exist in the absence of
association
Note: Only 1 hexamerizing component (HF) may be present when using the
HEXAMER method.
The values of a(Tc) and b can be obtained from the critical constants for the
Redlich-Kwong equation of state (see Table 1.2.4-2) and the critical temperature
and pressure for HF. The alpha function, (T), is obtained by matching the equa-
tion of state to HF vapor pressure data. Comparing equation (30) above to the
general two-parameter equation of state given by equation (1), it can be seen that
the only difference is the term nr, which accounts for the contribution of associa-
tion. The value of nr is 1.0 when there is no association, and approaches 1/6
when there is complete hexamerization. As the temperature increases, the extent
of hexamerization should decrease, i.e., the value of nr should increase.
The total number of moles of monomer and hexamer, nT, and the total num-
ber of moles that would exist in the absence of association, n0, are related by:
(33) n
0
n
T

i
iz
i
, i 1,6
where:
zi = the true mole fraction of species i
ni = number of moles of species i
Reference Manual
The hexamerization equilibrium reaction is written as:
(34) 6(HF) (HF)
6
The corresponding chemical equilibrium constant for this reaction, which is
a function of temperature only, is defined as:
(35)
K(T)
1
6

z
6
z
1
6

1
P
5
where:
K = equilibrium constant
1
= fugacity coefficient of the true monomer species
6
= fugacity coefficient of the true hexamer species
z
1
= true mole fraction of the monomer species
z
6
= true mole fraction of the hexamer species
P = total pressure
The fugacity coefficients in equation (35) are found from the cubic equation of
state using classical thermodynamics. Then, by substituting equation (33) into
equation (35) and using the overall material balance, this reduces to:
(36)
K
z
1
6
(6 5 z
1
)
5
(1 z
1
)
where:
K
RT
vb
1
1
]
5
= the reduced equilibrium constant
Once the equilibrium constant K is known, equation (36) can be solved to ob-
tain a value for z
1
and a corresponding value for z
6
.
The equilibrium constant for HF hexamerization can be calculated from the
following relationship:
(37)
log
10
K 43.65 +
8910
T
where:
K = equilibrium constant, 1/mmHg
5
T = temperature, K
Twu et al. have shown that, at the critical point, the values of z
1
, the true
mole fraction of monomer, and nr are given by:
(38-39)
z
1
(T
c
) 0.7006
n
r
(T
c
) 0.4005
So, even at the critical point, there is still a considerable amount of the hex-
amer species present.
Mixture properties are computed by using the SRKS mixing rule, equation
(20), discussed previously.
23. 7 PRO/II Note: See Section 23.7, Associating Equation of State, of the PRO/II
Keyword Input Manual for more information on using the HEXAMER method
in PRO/II.
Reference
Twu, C. H., Coon, J. E., and Cunningham, J. R., 1993, An Equation of State
for Hydrogen Fluoride, Fluid Phase Equil., 86, 47-62.
UNIWAALS In the UNIWAALS model proposed by Gupte et al. in 1986, a cubic equation of
state is combined with an excess Gibbs free energy model. By using this ap-
proach, the same parameters of the excess Gibbs free energy model based on
low pressure VLE data can be extended to apply to high pressures by using the
equation of state. This is a valuable method because group interaction parame-
ters from group contribution methods such as UNIFAC (see Section 1.2.6, UNI-
FAC) are readily available for numerous groups. The equations for the
UNIWAALS method are developed by equating the g
E
derived from the van der
Waals equation of state to the g
E
derived from UNIFAC at the system tempera-
ture and pressure. This equality produces the following mixing rule:
(40)
a
/
RTb f
'
P
v
E

/
RT
lnP(vb)
/
RT
x
i
i
ln(P(v
i
b
i
)
/
RT
1
1
]
+
f
x
i
i
a
i

/
(f
i
RTB
i
) f
g
E

/
RT
(41) f b
/
v
(42)
f
i
b
i

/
v
i
where:
v
E
= excess volume
The mixing rule for the a/b parameter contains the mixture (v) and pure (vi)
fluid volumes. The volumes of the pure components are obtained for the liq-
uid phase at the given temperature and pressure conditions. The parameter b
for the mixture is calculated using the original mixing rule developed for the
RK equation of state given in equation (8), and UNIFAC is used to calculate
g
E
/RT. Subsequently, the van der Waals equation of state and equation (40)
are solved simultaneously to obtain the mixture volume, v, and a/RTb.
Reference Manual
23. 4 PRO/II Note: See Section 23.4, UNIWAALS, of the PRO/II Keyword Input
Manual, for more information on using the UNIWAALS method in PRO/II.
Several limitations to this method should be noted:
1. For the calculation of the parameter a, the mixture and pure-component
liquid volumes (v and vi) are required, even if the liquid phase does not
actually exist at the given temperature and pressure.
2. The mixture parameter v is volume dependent, and thus pressure and vol-
ume become related through a differential equation, rather than through a
conventional algebraic equation.
3. The critical constraints of the UNIWAALS equation of state are no longer sat-
isfied by the values of the parameters a and b at the critical temperature. The
resulting equation of state is no longer a cubic equation of state, and analytical
solution of the equation of state is impossible.
4. The fugacity coefficients are cumbersome to evaluate.
5. The accuracy of the UNIWAALS model is not better than that of the UNI-
FAC model at low temperatures, and the accuracy deteriorates with in-
creasing temperatures.
Reference
Gupte, P. A., Rasmussen, P., and Fredenslund, A., 1986, A New
Group-Contribution Equation of State for Vapor-Liquid Equilibria, Ind.
Eng. Chem. Fundam., 25, 636-645.
Benedict-Webb-
Rubin-Starling
The Benedict-Webb-Rubin equation of state was first proposed in 1940 to pre-
dict liquid and vapor properties at high temperatures, and to correlate vapor-liq-
uid equilibria for light hydrocarbon mixtures. This original (BWR) equation of
state however provided poor results at low temperatures and around the critical
point. To improve the accuracy of this equation in predicting thermodynamic
properties for light hydrocarbons in the cryogenic liquid, gas, and dense fluid re-
gions, and at high temperatures, the BWR equation was modified by Starling in
1973 to give the following form:
(43)
P RT +
B
0
RT A
0
C
0

/
T
2
+ D
0

/
T
3
E
0

/
T
4
_
,

2
+
(bRT a d
/
T)
3
+ (a+d
/
T)
6
+ c
3

/
T
2
(1+
2
)exp(
2
)
The eleven parameters for pure components (B0, A0, etc.) are generalized as
functions of component acentric factor, critical temperature, and critical den-
sity. The mixing rules for the eleven mixture parameters are analogous to the
mixing rules used for the BWR equation. The single binary interaction pa-
rameter for the BWRS equation of state is built into the mixing rules. The
BWRS equation of state can correlate pure-component properties for light
hydrocarbons very accurately when experimental data covering entire ranges
are available.
23. 6 PRO/II Note: See Section 23.6, Benedict-Webb-Rubin-Starling, of the PRO/II
Keyword Input Manual for information on using the BWRS method in PRO/II.
Limitations to the BWRS equation of state are given below:
1. Because the equation is generalized in terms of critical temperatures, criti-
cal density, and acentric factor, it has difficulty predicting properties for
heavy hydrocarbons and polar systems.
2. The BWRS equation does not satisfy the critical constraints, and therefore
the equation is inferior to cubic equations of state when applied to the criti-
cal and supercritical regions.
3. The BWRS equation is less predictive than cubic equations of state for
mixture calculations.
4. Unlike cubic equations of state, BWRS cannot be solved analytically and
normally requires more CPU time.
References
1. Benedict, M., Webb, G. R., and Rubin, L. C., 1940, An Empirical Equation
for Thermodynamic Properties of Light Hydrocarbons and Their Mixtures.
I. Methane, Ethane, Propane, and Butane, J. Chem. Phys., 8, 334-345.
2. Starling, K. E., 1973, Fluid Thermodynamic Properties for Light Petroleum
Systems, Gulf Publishing Company, Houston, TX.
Lee-Kesler-Plcker
(LKP)
The LKP equation (available in versions 3.5 and later) is based on the
Benedict-Webb-Rubin equation of state and on Pitzers extended theory of
corresponding states. Thermodynamic data are correlated as a function of
critical temperature and pressure and the acentric factor as follows:
(44)
Z Z
o
+

r
_
Z
r
Z
o
_
,
where:
Z = compressibility factor
= acentric factor
subscripts o, r denote Simple and Reference fluids, respectively.
The work of Plcker et al., introduces new mixing rules which are purported by
the authors to better handle mixtures of asymmetric molecules. This is accom-
plished by the introduction of an exponent, , into the mixing rules.
Reference Manual
The mixing rules proposed here are:
(45)
T
c, mix

1
V
c, mix

k
z
j
z
k
V
cjk
T
cjk
(46)
V
c, mix

k
z
j
z
k
V
cjk
(47)

mix

j
z
j

j
where:
Vc = the molar critical volume
Tc = the critical temperature
z = mole fraction in liquid or vapor phase
= the acentric factor
The cross coefficients are given by:
(48)
T
cjk

T
cj
T
ck
_
,
1

2
K
jk
(49)
V
cjk

1
8

V
cj
13
+ V
ck
1

3
_
,
3
where:
Kjk is an adjustable binary parameter, characteristic of the j-k binary,
independent of temperature, density, and composition.
The pseudo-critical pressure is found by:
(50)
P
c, mix

0.2905 0.085
mix
_
,
R
T
c, mix
v
c, mix
When is zero, the mixing rules are similar to those of Prausnitz and Gunn;
when is 1.0, the mixing rules become the van der Waals mixing rules, as
used by Leland et al. For symmetric mixtures, is zero; for strongly asym-
metric mixtures, is a positive value less than unity. Based on an analysis of
experimental data, the authors suggest using a value of 0.25 when a specific
determination is not available. PRO/II uses a default value of 0.25.
Adjustable binary parameters, Kijs are also used in the mixing rules. Values
reported by Plcker et al. have been incorporated into PRO/II. The LKP
method is claimed by the authors to be superior to Starlings BWRS equation
for highly asymmetric systems. The method is not accurate around the criti-
cal point because the mixture critical constants are empirical, and do not rep-
resent the true critical point. Therefore, the authors recommend that the
method not be used above a reduced temperature of 0.96.
References
1. Lee, B.I., and Kesler, M.G., 1975, A Generalized Thermodynamic
Correlation Based on Three-Parameter Corresponding States, AIChE J., 21,
510-527.
2. Leland, T.W., and Mueller, W.H., 1959, Applying the Theory of
Corresponding States to Multicomponent Mixtures, Ind. Eng. Chem., 51,
597-600.
3. Pitzer, K.S., and Hultgren G.O., 1958, The Volumetric and Thermodynamic
Properties of Fluids, V. Two Component Solutions, J. Am. Chem. Soc., 80,
4793-96.
4. Plcker, U., Knapp, H., and Prausnitz, J.M., 1978, Calculation of High-Pres-
sure Vapor-Liquid Equilibria from a Corresponding States Correlation
with Emphasis on Asymmetric Mixtures, Ind. Eng. Chem. Proc. Des. Dev.,
17, 324-332.
5. Prausnitz, J.M., and Gunn, R.D., 1958, Volumetric Properties of Nonpolar
Gaseous Mixtures, AIChE J., 4, 430-35.
6. Prausnitz, J.M., and Gunn, R.D., 1958, Pseudocritical Constants from
Volumetric Data for Gas Mixtures, AIChE J., 4, 494.
Reference Manual
Free Water Decant
General
Information
In many hydrocarbon-water mixtures, including those found in refinery and
gas processing plants, the water phase formed is nearly immiscible with the
liquid hydrocarbon phase. For such systems, the water phase can be assumed
to decant as a pure aqueous phase. This reduces the number of computations
involved with rigorous VLLE methods. The water-decant method as imple-
mented in PRO/II follows these steps:
Water vapor is assumed to form an ideal mixture with the hydrocarbon
vapor phase.
The water partial pressure is calculated using one of two methods.
The pressure of the system, P, is calculated on a water-free basis by
subtracting the water partial pressure.
A pure water liquid phase is formed when the partial pressure of water
reaches its saturation pressure at that temperature.
The amount of water dissolved in the hydrocarbon-rich liquid phase is
computed using one of a number of water solubility correlations.
Note: The free water decant option may only be used with the Soave-Redlich-
Kwong, Peng-Robinson, Grayson-Streed, Chao-Seader, Improved Grayson-
Streed, Erbar modifications to Grayson-Streed and Chao-Seader, Braun K10,
or Benedict-Webb-Rubin-Starling methods. Water decant is automatically acti-
vated when one of these methods is selected.
Calculation
Methods
The amount of water dissolved in the hydrocarbon-rich liquid phase can be
computed once the water K-values, Kw, are known. These are calculated us-
ing the following relationship:
(1) K
w
P
w

/

P x
w
_
,
where:
Pw = water partial pressure at temperature T
xw = solubility of water in the hydrocarbon-rich liquid phase
P = system pressure
The water partial pressure is calculated using either the ASME steam tables
or Chart 15-14 in the GPSA Data Book. The GPSA Data Book option is rec-
ommended for natural gas mixtures above 2000 psia. Two methods are avail-
able for calculating water properties:
1. 2. 5
I-88 Free Water Decant May 1994
Water properties can be calculated assuming saturated vapor and liquid
conditions.
Water properties can be calculated using steam tables based on the
Keenan and Keyes equation of state.
The water solubility, xw, can be computed by one of three methods in PRO/II:
The default method developed by SimSci. In this method, water solubil-
ity is calculated for individual hydrocarbons and light gases given in
Table 1.2.5-1. The SimSci method uses a correlation based on the
number of carbon and hydrogen atoms present in the component. For
pseudocomponents, the water solubility is calculated as a function of the
Watson (UOP) K-factor.
The second method uses Figure 9A1.2 in the API Technical Data Book
to compute water solubility in kerosene. PRO/II will automatically
invoke this option if the SIMSCI solubility option is chosen, and a
component not included in Table 1.2.5-1 is present in the system.
The third method employs the equation-of-state method that is being
used for calculating the K-values of the other components present in the
system to compute the water K-value. Missing binary interaction pa-
rameters for the water-hydrocarbon component pairs are estimated using
the Soave-Redlich-Kwong Kabadi-Danner equation of state. This
method is only valid for SRK or PR equations of state.
Tabl e 1. 2. 5-1:
Components Avai l abl e i n the SIMSCI Water Sol ubi l i ty Method
Paraffins Naphthenes
Unsaturated Hydrocarbons Aromatics
Methyl Mercaptan CS2
NH3
CO2 Helium
HCl H2S
N2 NO
O2 SO2
20. 6 PRO/II Note: For more information on using the free-water decant option, see
Section 20.6, Free Water Decant Considerations, of the PRO/II Keyword Input
Manual.
Argon
PRO/II Component and Thermophysical Properties Free Water Decant I-89
Reference Manual
Li qui d Acti vi ty Coeffi ci ent Methods
General
Information
Liquid activity coefficient methods for phase-equilibrium calculations differ
at a fundamental level from equation-of-state (EOS) methods. In EOS meth-
ods, fugacity coefficients (referring to an ideal-gas state) are computed for
both vapor and liquid phases. In activity coefficient methods, the reference
state for each component in the liquid phase is the pure liquid at the tempera-
ture and pressure of the mixture. It is often more convenient and accurate to
use this approach when the liquid phase is a mixture of components which
do not differ greatly in volatility; it is also often easier to describe strongly
nonideal systems with a liquid activity coefficient model than with an equa-
tion of state.
The thermodynamic methods of liquid mixtures within an activity coefficient
framework are covered in standard textbooks, a few of which are referenced
at the end of this section. The activity coefficient is introduced in the way
the fugacity of component i in the liquid phase is written:
(1)
f
i
L

i
x
i
f
i
oL
where:
f
i
L
= fugacity of component i in liquid phase
f
i
oL
= standard-state liquid fugacity of component i
xi = mole fraction of component i in liquid
i = liquid-phase activity coefficient of component i
The standard-state fugacity f
i
oL
is defined as that of the pure liquid i at the
temperature and pressure of the mixture. With this definition, i approaches
one in the limit xi 1. The standard-state fugacity may be related to the va-
por pressure of component i as follows:
(2)
f
i
0L
P
i
sat

i
sat
exp

P
i
sat
P
v
i
L

/
RT dP
1
1
]
where:
P = system pressure
Pi
sat
= vapor pressure of component i at the system temperature
R = gas constant
v
i
L
= liquid molar volume of component i at T and P
i
sat
= fugacity coefficient of pure component i at temperature T
and pressure Pi
sat
1. 2. 6
I-90 Li qui d Acti vi ty Coeffi ci ent Methods May 1994
The exponential term in equation (2) is the Poynting factor which accounts for
the effect of pressure on the liquid fugacity. If the pressure does not exceed a few
atmospheres, this correction can generally be neglected. Since liquid volumes
do not depend greatly on pressure, equation (2) can be simplified to:
(3)
f
i
L
P
i
sat

i
sat
exp
(P P
i
sat
) v
i
L

RT
1
]
When liquid activity coefficients are used, any method may be used to com-
pute the vapor-phase fugacity. An ideal gas is often assumed, but in general
vapor fugacities may be written as:
(4)
f
i
V

i
V
y
i
P
where:
fi
V
= fugacity of component i in vapor phase
yi = mole fraction of component i in vapor

i
V
= fugacity coefficient of component i in vapor
For an ideal gas, the fugacity coefficient
i
V
equals one, but it may also be
computed from an equation of state or other correlation.
Equations (1) and (4) are fundamentally different in the way they describe
liquid and vapor fugacities, respectively. The two equations do not in general
match at the vapor-liquid critical point, where vapor and liquid phases be-
come indistinguishable. Phase-equilibrium calculations near a vapor-liquid
critical point must be carried out with some other method such as an equa-
tion of state.
The familiar vapor-liquid K-value is defined as the ratio of yi to xi and can be
obtained by combining equations (1) and (4):
(5)
K
i

y
i
x
i

i
f
i
oL

i
V
P
At low and moderate pressures, the Poynting correction is often ignored and
equation (5) becomes:
(5a)
K
i

i

i
sat
P
i
sat

i
V
P
Unless there is vapor-phase association (as is the case with carboxylic acids,
for example), the fugacity coefficients may also be ignored at low and moder-
ate pressures. Equation (5) then simplifies to:
(5b)
K
i

i
P
i
sat
P
PRO/II Component and Thermophysical Properties Li qui d Acti vi ty Coeffi ci ent Methods I-91
Reference Manual
For most low-pressure systems, the regression of experimental vapor-liquid
equilibrium data will produce essentially the same parameters if equation
(5a) or (5b) is used in place of the full equation (5). This is not necessarily
the case at higher pressures and for systems where vapor-phase nonideality is
important. Significant errors can be introduced when the regression and cal-
culations using the regressed parameters employ differing sets of simplying
assumptions. In general, calculations should be performed using the same as-
sumptions about vapor fugacities and the Poynting factor as those employed
in fitting the parameters. An important exception to this rule is the case
where parameters were fitted at low pressure, but the calculations are at a sub-
stantially higher pressure. In such a case, it is best to employ nonideal vapor-
phase fugacities and the Poynting correction in the calculation even if they were
not used in the original fit.
Liquid activity coefficients are derived from expressions for the excess Gibbs
energy of a liquid mixture. The defining equation is:
(6)
ln
i

1
RT

G
E
n
i
_
,
T,P,n
ji
where:
G
E
= excess Gibbs energy of liquid mixture
ni = moles of component i in liquid
The following sections describe the expressions available for describing liq-
uid-phase activity coefficients.
References
1. Prausnitz, J.M., Lichtenthaler, R.N. and Gomes de Azevedo, E., 1986,
Molecular Thermodynamics of Fluid-Phase Equilibria, 2nd ed., Prentice-
Hall, Englewood Cliffs, NJ.
2. Sandler, S.I., 1989, Chemical and Engineering Thermodynamics, 2nd ed.,
John Wiley & Sons, New York.
3. Smith, J.M. and Van Ness, H.C., 1987, Introduction to Chemical
Engineering Thermodynamics, 4th ed., McGraw-Hill, New York.
4. Van Ness, H.C. and Abbott, M.M., 1982, Classical Thermodynamics of
Nonelectrolyte Solutions: With Applications to Phase Equilibria,
McGraw-Hill, New York.
5. Walas, S.M., 1985, Phase Equilibria in Chemical Engineering, Butter-
worth, Boston.
Margules
Equation
Tabl e 1. 2. 6-1: Margul es Equati on
Requi red Pure-component Properti es Appl i cati on Gui del i nes
Vapor pressure Temperature Use at or near
temperatures where
parameters were
fitted.
The oldest empirical correlations for liquid activity coefficients, such as the
Margules equation (1895), are derived from simple polynomial expansions.
The most popular form of the Margules equation was proposed by Redlich
and Kister (1948). When that expansion is truncated after the quadratic term,
the resulting three-parameter correlation is known as the four-suffix Mar-
gules equation. The resulting expression for the activity coefficient is:
(7)
ln
i
(1 x
i
)
2

A
i
+ 2
B
i
A
i
D
i
_
,
x
i
+ 3D
i
x
i
2
1
]
where:
A
i

j1
N
x
j
a
ij
B
i

j1
N
x
j
a
ji
D
i

j1
N
x
j
d
ij
d
ij
d
ji
Thus, for each ij binary pair in a multicomponent system, the parameters are
aij, aji, and dij. No temperature dependence is included in this implementa-
tion; one should therefore be cautious about using this equation at tempera-
tures differing substantially from the range in which the parameters were
fitted.
References
1. Margules, 1895, Sitzber., Akad. Wiss. Wien, Math. Naturw., (2A),
104, 1234.
2. Redlich, O. and Kister, A. T., 1948, Algebraic Representation of
Thermodynamic Properties and the Classification of Solutions, Ind. Eng.
Chem. 40, 345-348.
Reference Manual
van Laar Equation
Tabl e 1. 2. 6-2: van Laar Equati on
Vapor pressure Components Use for chemically similar
components.
Tabl e 1. 2. 6-2 van Laar Equati on
Another old correlation which is still frequently used is the van Laar equation. It
may be obtained by discarding ternary and higher-order terms in an alternative
expansion of the excess Gibbs energy (known as Wohls equation), though that is
not how van Laar derived it originally. The resulting expression for the activity co-
efficient is:
(8)
ln
i

l1
N
a
il
Z
l

j1
N
a
ij
Z
i
Z
j

1
2

j1
N

k1
N
j,kl
a
jk

a
ij
a
ji
Z
j
Z
k
where:
Z
l

x
l

j
x
j

a
il
a
li
_
,
Two parameters, aij and aji, are required for each binary. As with the Mar-
gules equation, no method is included for making the parameters tempera-
ture dependent. It should also be noted that the van Laar equation, because of
its functional form, is incapable of representing maxima or minima in the re-
lationship between activity coefficient and mole fraction. In practice, how-
ever, such maxima and minima are relatively rare.
References
1. van Laar, J. J., 1910, The Vapor Pressure of Binary Mixtures, Z. Phys.
Chem., 72, 723-751.
2. Wohl, K., 1946, Thermodynamic Evaluation of Binary and Ternary Liquid
Systems, Trans. AIChE, 42, 215-249.
Regular Solution
Theory
Tabl e 1. 2. 6-3: Regul ar Sol uti on Theory
Vapor pressure
Liquid molar volume,
Solubility parameter
Components Not recommended for polar
components and solutions
containing fluorocarbons.
Hildebrand defined a regular solution as one in which the excess entropy
vanishes when the solution is mixed at constant temperature and constant vol-
ume. This is nearly the case for most solutions of nonpolar compounds, pro-
vided the molecules do not differ greatly in size. The excess Gibbs energy is
then primarily determined by the attractive intermolecular forces. Scatchard
and Hildebrand made a simple assumption relating mixture interactions to
those in pure fluids; the result is a simple theory in which the activity coeffi-
cients are a function of pure-component properties only. The important prop-
erty is the solubility parameter, which is related to the energy required to
vaporize a liquid component to an ideal-gas state. The activity coefficient ex-
pression is:
(9)
RT ln
i
v
i
L

j

j

i
1
1
]

2

j

x
j
v
j
L

k
x
k
v
k
L
where:
v
i
L
= liquid molar volume of component i
i = solubility parameter of component i
There are no adjustable parameters in regular solution theory. It is useful for
mixtures of nonpolar components, but it should not be used for highly
nonideal mixtures, especially if they contain polar components. Solubility pa-
rameters have been tabulated for numerous compounds, and these parameters
are included for most components in PRO/IIs library.
Reference
Hildebrand, J.H., Prausnitz, J. M., and Scott, R. L., 1970, Regular and
Related Solutions, Van Nostrand Reinhold Co., New York.
Reference Manual
Flory-Huggins
Theory
Tabl e 1. 2. 6-4: Fl ory-Huggi ns Theory
Vapor pressure
Liquid molar volume,
Components Best for components which
are chemically similar and
which differ only in size
(e.g., polymer solutions).
Tabl e 1. 2. 64 Fl ory-Huggi ns Theory
The Flory-Huggins model may be considered a correction to the Regular Solu-
tion Theory for the entropic effects of mixing molecules which differ greatly in
size. It is therefore suitable for polymer/solvent systems, especially if the mole-
cules involved are nonpolar. In this simplest implementation of the theory, there
are no binary parameters. The activity coefficient expression is:
(10)
ln
i
ln
i
reg
+ ln
v
i
L
v
L
_
,
+ 1
v
i
L
v
L
where:
i
reg
= activity coefficient from regular solution theory
vi
L
= liquid molar volume of component i
v
L
= liquid molar volume of solution
References
1. Flory, P. J., 1942, Thermodynamics of Higher Polymer Solutions,
J.Chem.Phys., 10, 51.
2. Huggins, M. L., 1942, Thermodynamic Properties of Solutions of Long-
Chain Compounds, Ann. N.Y. Acad. Sci., 43, 9.
3. Misovich, M. J., Grulka, E. A., and Banks, R. F., 1985, Generalized
Correlation for Solvent Activities in Polymer Solutions, Ind. Eng. Chem.
Proc. Des. Dev., 24, 1036.
Wilson Equation
Tabl e 1. 2. 6-5: Wi l son Equati on
Vapor pressure
Liquid molar volume
Components Useful for polar or
associating components in
nonpolar solvents. Cannot
be used if liquid-liquid
immiscibility exists.
Tabl e 1. 2. 65 Wi l son Equati on
The Wilson equation was the first to incorporate the concept of local composi-
tion. The basic idea is that, because of differences in intermolecular forces, the
composition in the neighborhood of a specific molecule in solution will differ from
that of the bulk liquid. The two parameters per binary are, at least in principle, asso-
ciated with the degree to which each molecule can produce a change in the compo-
sition of its local environment. The expression for the activity coefficient is:
(11)
ln
i
1 ln

j1
N
x
j
A
ij

k1
N

x
k
A
ki

j1
N
x
j
A
kj
where:
A
ij

v
i
L
v
j
L
exp

a
ij
T
1
]
(when unit of a
ij
is K)
A
ij

v
i
L
v
j
L
exp

a
ij
RT
1
]
(when unit of a
ij
is KCAL or KJ)
A
ij
a
ij
(when unit of a
ij
is NODIME)
v
i
L
= the liquid molar volume of component i
aij represents a characteristic energy of interaction between species i and j.
While there is no explicit temperature dependence in the Wilson equations
parameters, the derivation is such that the equation may be used with some confi-
dence over a wider range of temperatures than either the Margules or van Laar
equations. It is also much more successful in correlating mixtures containing po-
lar components. The Wilson equation cannot describe local maxima or minima
in the activity coefficient. Its single significant shortcoming, however, is that it is
mathematically unable to predict the splitting of a liquid into two partially misci-
ble phases. It is therefore completely unsuitable for problems involving liquid-
liquid equilibria.
Reference Manual
References
1. Holmes, M. H. and van Winkle, M., 1970, Wilson Equation Used to
Predict Vapor Compositions, Ind. Eng. Chem., 62(1), 22-31.
2. Orye, R. V. and Prausnitz, J. M., 1965, Multicomponent Equilibria with
the Wilson Equation, Ind. Eng.Chem., 57(5), 18-26.
3. Wilson, G. M., 1964, Vapor-Liquid Equilibrium XI. A New Expression for
the Excess Free Energy of Mixing, J. Amer. Chem. Soc., 86, 127.
NRTL Equation
Tabl e 1. 2. 6-6: NRTL Equati on
Vapor pressure Components Useful for strongly nonideal
mixtures and for partially
miscible systems.
The NRTL (non-random two-liquid) equation was developed by Renon and
Prausnitz to make use of the local composition concept, while avoiding the
Wilson equations inability to predict liquid-liquid phase separation. The re-
sulting equation has been quite successful in correlating a wide variety of
systems. The expression for the activity coefficient is:
(12)
ln
i

j
ji
G
ji
x
j

k
G
ki
x
k
+

j

x
j
G
ij

k
G
kj
x
k

ij

k
x
k

kj
G
kj

k
G
kj
x
k

_
,
where:
ij
a
ij
+
b
ij
T
+
c
ij
T
2
(when unit is K)
ij
a
ij
+
b
ij
RT
+
c
ij
R
2
T
2
(when unit is KCAL or KJ)
G
ji
exp(
ji

ji
) ,
ji

ji
+
ji
T
Three parameters, ij, ji, and ij = ji, are required for each binary. These
parameters may be made temperature-dependent as described above. If ij is
to be represented with only one constant, it has been found empirically that
better results over a range of temperatures are obtained if only bij is used and
aij = cij = 0. The parameter does not vary greatly from binary to binary,
and it is often satisfactory to fix it at 0.3 for vapor-liquid systems and 0.2 for
liquid-liquid systems.
References
1. Renon, H. and Prausnitz, J. M., 1968, Local Composition in Thermody-
namic Excess Functions for Liquid Mixtures, AIChE J., 14, 135-144.
2. Harris, R. E., 1972, Chem. Eng. Prog., 68(10), 57.
UNIQUAC
Equation
Tabl e 1. 2. 6-7: UNIQUAC Equati on
Vapor pressure
van der Waals
area and volume
Components Useful for nonelectrolyte
mixtures containing polar
or nonpolar components
and for partially miscible
systems.
The UNIQUAC (universal quasi-chemical) equation was developed by Abrams
and Prausnitz based on statistical-mechanical considerations and the lattice-
based quasi-chemical model of Guggenheim. As in the Wilson and NRTL equa-
tions, local compositions are used. However, local surface-area fractions are
used as the primary composition variable instead of volume fractions. Each
molecule i is characterized by a volume parameter ri and a surface-area pa-
rameter qi.
The excess Gibbs energy (and therefore the logarithm of the activity coeffi-
cient) is divided into a combinatorial and a residual part. The combinatorial
part depends only on the sizes and shapes of the individual molecules; it con-
tains no binary parameters. The residual part, which accounts for the ener-
getic interactions, has two adjustable binary parameters. The UNIQUAC
equation has, like the NRTL equation, been quite successful in correlating a
wide variety of systems. The expression for the activity coefficient is:
(13)
ln
i
ln
i
C
+ ln
i
R
(14)
ln
i
C
ln
i
x
i
_
,
+
z
2
q
i
ln
i
_
,
+ l
i

i
x
i

j1
M
x
j
l
j
Reference Manual
(15)
ln
i
R
q
i

1 ln

j1
M

j

ji
_

j1
M

j

ij

k1
M
k

kj
_
where:
ij
exp

U
ij
T

1
]
(when unit is K)
ij
exp

U
ij
RT

1
]
(when unit is KCAL or KJ)
U
ij
a
ij
+ b
ij
T
i

x
i
q
i

i1
M
x
i
q
i

l
j

z
2
(r
j
q
j
) (r
j
1)
i

x
i
r
i

j1
M
x
j
r
j
q
i

A
wi
2.5 x 10
9
r
i

V
wi
15.17
z
10
Awi = van der Waals area of molecule i
Vwi = van der Waals volume of molecule i
Two parameters, Uij and Uji, are required for each binary; they may be made
temperature-dependent as described above. If no temperature-dependence is
used for Uij, better results over a range of temperatures are normally ob-
tained by using aij and setting bij = 0.
References
1. Abrams, D. S. and Prausnitz, J. M., 1975, Statistical Thermodynamics
of Mixtures: A New Expression for the Excess Gibbs Free Energy of
Partly or Completely Miscible Systems, AIChE J., 21, 116-128.
2. Anderson, T. F. and Prausnitz, J. M., 1978, Application of the UNIQUAC
Equation to Calculation of Multicomponent Phase Equilibria. 1. Vapor-Liq-
uid Equilibria, Ind. Eng. Chem. Proc. Des. Dev., 17, 552-561.
3. Anderson, T. F. and Prausnitz, J. M., 1978, Application of the UNIQUAC
Equation to Calculation of Multicomponent Phase Equilibria. 2. Liquid-Liq-
uid Equilibria, Ind. Eng. Chem. Proc. Des. Dev., 17, 561-567.
4. Maurer, G. and Prausnitz, J. M., 1978, On the Derivation and Extension of
the UNIQUAC Equation, Fluid Phase Equilibria, 2, 91-99.
UNIFAC
Tabl e 1. 2. 6-8: UNIFAC
Vapor pressure Pressure Up to 10 atmospheres
van der Waals
area and volume
Temperature 32 - 300 F
Components All components well below
their critical points
The UNIFAC (universal functional activity coefficient) method was devel-
oped in 1975 by Fredenslund, Jones, and Prausnitz. This method estimates
activity coefficients based on the group contribution concept following the
Analytical Solution of Groups (ASOG) model proposed by Deer and Deal in
1969. Interactions between two molecules are assumed to be a function of
group-group interactions. Whereas there are thousands of chemical com-
pounds of interest in chemical processing, the number of functional groups is
much smaller. Group-group interaction data are obtained from reduction of
experimental data for binary component pairs.
The UNIFAC method is based on the UNIQUAC model, which represents
the excess Gibbs energy (and logarithm of the activity coefficient) as a com-
bination of two effects. Equation (13) is therefore used:
ln
i
ln
i
C
+ ln
i
R
The combinational term, ln i
C
, is computed directly from the UNIQUAC
equation (14) using the van der Waals area and volume parameter calculated
from the individual structural groups:
Reference Manual
ln
i
c
ln

i
x
i
_
,
+
z
2
q
i
ln
i

i
_
,
+ l
i

i
x
i

j1
NOC
x
j
l
j
where:
i

x
i
r
i

j1
NOC
x
j
r
j
i

x
i
q
i

j1
NOC
x
j
q
j

l
i

z
2
(r
i
q
i
) (r
i
1)
r
i

k1
NOG

k
i
R
k
q
i

k1
NOG

k
i
Q
k
where:
NOC = number of components
NOG = number of different groups in the mixture
z
= lattice coordination number = 10

v
k
i
=
number of functional groups of type k in molecule i
Rk = volume parameter of functional group k
Qk = area parameter of functional group k
xi = mole fraction of component i in the liquid phase
The group volume and area parameters are obtained from the atomic and mo-
lecular structure.
(16)
R
k

V
wk
15.17
(17)
Q
k

A
wk
2.5x10
9
where:
Vwk = van der Waals volume of group k
Awk = van der Waals area of group k
The residual term, ln i
R
, is given by:
(18)
ln
i
R

k1
NOG

ln
k
ln
k
i
_
,
where:
k = residual activity coefficient of group k in the mixture

k
i
= residual activity coefficient of group k in a reference solution
containing only molecules of group type i. This quantity is re-
quired so that
i
R
1 as xi 1
The residual activity coefficient is given by:
(19)
ln
k
Q
k

'
1 ln

m

m

mk
_
m

km
n

nm
where:
m, n = 1, 2, ... NOG
The parameter mk is given by:
(20)
mk
exp
'

a
mk
RT
where:
amk = binary interaction parameter for groups m and k
The binary energy interaction parameter amk is assumed to be a constant and
not a function of temperature. A large number of interaction parameters be-
tween structural groups, as well as group size and shape parameters have
been incorporated into PRO/II.
References
1. Deer, E.L., and Deal, C.H., 1969, Inst. Chem. Eng. Symp. Ser., 32(3), 40.
2. Fredenslund, Aa., Jones, R.L., and Prausnitz, J.M., 1975, Group
Contribution Estimation of Activity Coefficients in Nonideal Liquid
Mixtures, AIChE J., 27, 1086-1099.
3. Skjold-Jrgensen, S., Kolbe, B., Groehling, J., and Rasmussen, P., 1979,
Vapor-Liquid Equilibria by UNIFAC Group Contribution. Revision and
Extension, Ind. Eng. Chem. Proc. Des. Dev., 18, 714-722.
4. Gmehling, J., Rasmussen, P., and Fredenslund, Aa., 1983, Vapor-Liquid
Equilibria by UNIFAC Group Contribution. Revision and Extension,
Ind. Eng. Chem. Proc. Des. Dev., 22, 676-678.
5. Hansen, H.K., Rasmussen, P., Fredenslund, Aa., Schiller, M., and
Gmehling, J., 1991, Vapor-Liquid Equilibria by UNIFAC Group
Contribution. 5. Revision and Extension, Ind. Eng. Chem. Res., 30,
2352-2355.
Reference Manual
Modifications
to UNIFAC
The UNIFAC method provides good order-of-magnitude estimates. The
accuracy of the method can be improved by incorporating a temperature-
dependent form for the binary group energy interaction parameter.
UFT1 - Lyngby modi fi ed UNIFAC
Researchers at Lyngby developed a three-parameter temperature-dependent
form for the binary interaction parameter. The parameter mk is given by:
(21)
mk
exp
'

A
mk
RT
(22)
A
mk
a
mk
+ b
mk
(T T
o
) + C
mk

Tln
T
o
T
+ T T
o
_
,
where:
amk, bmk, cmk = binary interaction parameters
To = 298.15 K
The combinatorial part of the logarithm of the activity coefficient is given by:
(23)
ln
i
c
ln
w
i
x
i
+ 1
w
i
x
i
(24)
w
i

r
i
2
3
x
i

i1
NOC
r
i
2
3
x
i
Reference
Larsen, B.L., Rasmussen, P., and Fredenslund, Aa., 1987, A Modified UNI-
FAC Group Contribution Model for Prediction of Phase Equilibria and
Heats of Mixing, Ind. Eng. Chem. Res., 26, 2274-2286.
UFT2 - Dortmund modi fi ed UNIFAC
For this modified method, the temperature-dependent form of Amk is given
by:
(25)
A
mk
a
mk
+ b
mk
T + c
mk
T
2
The combinational part of the logarithm of the activity coefficient is given
by:
(26)
ln
i
c
ln
w
i
x
i
+ 1
w
i
x
i

z
q
i
2

ln
i
i
+ 1
i
Q
i
_
,
(27)
w
i

r
i
3
4
x
i

j1
NOC
r
j
3
4
x
j
where:
z = lattice coordination number = 10
i

x
i
r
i

j1
NOC
x
j
r
j
i

x
i
q
i

j1
NOC
x
j
q
j

Reference
Weidlich, V., and Gmehling, J., 1987, A Modified UNIFAC Model:
1. Prediction of VLE, h
E
, and
, Ind. Eng. Chem. Res., 26, 1372-1381.

UFT3
For this modified UNIFAC method, the temperature-dependent form of Amk
is given by:
(28)
A
mk
a
mk
+ b
mk
T + c
mk
T
3
The combinatorial and residual parts of the activity coefficient are identical
to those described previously for the UNIFAC method.
Reference
Torres-Marchal, C., and Cantalino, A.L., 1986, Industrial Applications
of UNIFAC, Fluid Phase Equil., 29, 69-76.
Reference Manual
UNFV - Free vol ume modi fi cati on to UNIFAC
This method was developed for modeling polymer systems. The liquid activ-
ity coefficient is given by a combination of the same combinatorial and resid-
ual terms as UNIFAC, plus a free volume effect term:
(29)
l
n

i
l
n

i
c
+ l
n

i
R
+ l
n

i
FV
(30)
l
n

i
FV
3 C
i
l
n

i
1
3
1
V

m
1
3
1
_
C
i

'

i
V

m
1
_
1
1
V

i
1
3
_
where:
V

i

V
wi
15.17 br
i
r
i

1
M
i

k1
NOG
k
i
R
k
V

m

V
i
w
i
+ V
j
w
j
15.17b (r
i
w
i
+ r
j
w
j
)
b = 1.28
where:
Vi = volume per gram of solvent i
Mi = molecular weight of solvent i
wi = weight fraction of component i
Ci = number of effective degrees of freedom per molecule of
solvent i = 3.3
Reference
Oishi, T., and Prausnitz, J.M., 1978, Estimation of Solvent Activities
in Polymer Solutions Using a Group-Contribution Method, Ind. Eng.
Fill Methods The ability of a liquid activity method to accurately predict vapor-liquid
equilibria and/or vapor-liquid-liquid equilibria depends to a great degree on
whether or not binary interaction parameters are available for that method.
PRO/II contains a proven mechanism for filling in missing binary interaction
parameters for liquid activity methods. When a liquid activity method such
as NRTL is selected for phase-equilibrium calculations, and the FILL option
is selected, PRO/II uses the following mechanism in order to obtain the bi-
nary interaction data the model needs:
1. Any user-supplied binary interaction parameters or mutual solubility, infi-
nite dilution, or azeotropic data are used in preference to any other data.
2. The VLE and LLE databanks which contain binary interaction parameters
are then searched for data.
3. The SimSci azeotropic databank is searched for appropriate azeotropic
data, which are then regressed to provide binary interaction data.
4. For VLE calculations, if steps 1 through 3 do not supply the required pa-
rameters, then the group contribution methods, UNIFAC or its modifica-
tion UFT1 or the regular solution method or the Flory-Huggins method,
may be used to provide estimates for the interaction parameters. For LLE
calculations, UNIFAC or the modified UNIFAC method UFT1 is used to
supply the parameter estimates.
24. 10 PRO/II Note: For more information on using the FILL option, see Section 24.10,
Filling In Missing Parameters, of the PRO/II Keyword Input Manual.
5. Finally, if binary interaction parameters are still missing after steps 1-4 are
followed, then all missing parameters are set equal to zero.
Figure 1.2.6-1 shows the mechanism used by PRO/II to backfill missing
binary parameters for VLE or VLLE calculations.
For VLLE calculations, in order to avoid conflicts between VLE and LLE bi-
nary interaction data, PRO/II follows a number of strict rules when filling in
these binary interaction data.
If no VLE or LLE interaction data are supplied by the user, PRO/II uses
the following order in searching for interaction data for both VLE and
LLE calculations:
1. The LLE databank.
2. The VLE databank.
If the user supplies VLE interaction data only, then PRO/II uses the fol-
lowing order in searching for binary parameters for both VLE and LLE
calculations:
1. The user-supplied values given on the KVALUE(VLE) statement.
Reference Manual
If the user supplies LLE interaction data only, or both VLE and LLE interac-
tion data, for LLE calculations, the databanks are searched in the order:
1. The user-supplied data given on the KVALUE(LLE) statement.
If the user supplies LLE interaction data only, or both VLE and LLE interac-
tion data, for VLE calculations, the databanks are searched in the order:
1. The user-supplied data given on the KVALUE(VLE) statement.
20. 7 PRO/II Note: For more information on specifying VLLE methods, see Section
20.7, Vapor-Liquid-Liquid Equilibrium Considerations, of the PRO/II Key-
word Input Manual.
Figure 1.2.6-1:
Fl owchart for FILL
Methods
Reference Manual
Henrys Law When liquid activity methods are used, the standard-state fugacity for a com-
ponent is the fugacity of the pure liquid. This standard state is not conven-
ient, however, for dissolved gases, especially if the temperature is above the
critical temperature of the solute in question. For supercritical gases and also
for trace solutes such as organic pollutants in water, it is more convenient to
use a standard state defined at infinite dilution. This standard-state fugacity
is the Henrys constant.
24. 11 PRO/II Note: For more information on using Henrys Law, see Section 24.11,
Henrys Law for Non-condensible Components, of the PRO/II Keyword Input
Manual.
Thermodynamically, the Henrys constant of a solute i in a solvent j is defined as
the infinite-dilution limit of the ratio of the fugacity to the mole fraction:
(31)
H
i,j
lim
x
j
1
x
i
0

f
i
x
i
Unless the pressure is high or there is vapor-phase association, the fugacity fi can
be replaced by the partial pressure yiP. The K-value can then be expressed as:
(32)
K
i

H
i,j
P
This relationship is strictly true only in the infinite-dilution limit, but K-val-
ues from Henrys law generally remain accurate at solute mole fractions up
to approximately five percent.
PRO/II correlates Henrys constants to the following functional form:
(33)
ln H
i,j
C
1
+
C
2
T
+ C
3
ln T + C
4
P
The temperature dependence in equation (33) is that expected from a thermody-
namic analysis, provided the solvents critical point is not approached too
closely. Thermodynamics also predicts that the effect of pressure on the effective
Henrys constant at conditions beyond infinite dilution is linear in pressure (with
C4 proportional to the solutes partial molar volume). The pressure correction is
negligible at low and moderate pressures; if the pressure is sufficiently high for
that term to become important, it is likely that better results could be obtained by
an equation of state with an advanced mixing rule.
When the HENRY option is specified, components with critical temperatures be-
low 400 K are automatically designated as solute components by PRO/II. The user
may, however, override these designations as desired. PRO/II has an extensive dat-
abank of Henrys constants for supercritical gases in various solvents and also for
many organic compounds in water. Henrys constants may also be input by the
user. If no Henrys constant is given for a solute, PRO/II substitutes the sol-
utes vapor pressure (extrapolated if necessary). This substitution is good only
for nearly ideal solutions. In particular, if no Henrys constant is available for an
organic solute in water, it is better to remove the organic from the list of solutes
and allow the liquid activity method (with interaction parameters filled in via
UNIFAC, if necessary) to compute the K-value.
Note: The temperature dependence of Henrys constants is very important. Espe-
cially for organic solutes in water, often only a single value at 25 C is reported. Cal-
culations using this input value at significantly different temperatures (for example,
steam stripping near 100 C) are likely to produce unrealistic answers (for example,
drastically overestimating the amount of steam required). In such cases, the user can
obtain a better answer by assuming that the temperature dependence of the solutes
Henrys constant is the same as for its vapor pressure. The slope of ln P
sat
versus 1/T
becomes C2 in equation (33), and (with C3=C4=0) the 25 C point can then be used
to solve for C1.
The Henrys constant of a solute in a mixture of solvents is estimated from
the following mixing rule:
(34)
ln H
i,mix

j1
n
x
j
ln H
i,j
where the sum is taken over all solute species j, and the mole fractions xj
used in the sum are computed on a solute-free basis.
Reference
Prausnitz, J.M., Lichtenthaler, R.N., and Gomes de Azevedo, E., 1986,
Molecular Thermodynamics of Fluid-Phase Equilibria, 2nd edition, Pren-
tice-Hall, Englewood Cliffs, NJ, Chapter 8.
Heat of Mixing
Calculations
For many liquid mixtures, the enthalpy may be accurately approximated as a
mole fraction sum of pure-component enthalpies (see Section 1.2.3, Ideal). For
some systems, however, the excess enthalpy, or heat of mixing, is not negligible
and should be accounted for if accurate prediction of the liquid enthalpy is im-
portant. It should be noted that SimScis equations of state and generalized corre-
lations produce a heat of mixing as a natural part of their calculations. Therefore,
explicit calculation of the heat of mixing is only used in conjunction with the
IDEAL method for liquid enthalpy, which is normally used with liquid activity
coefficient K-value methods.
Gamma Method
Thermodynamics allows the excess enthalpy to be computed directly from
the activity coefficients in a mixture and their temperature dependence. This
is known as the GAMMA option, and the equation is:
(35)
H
ex

i

x
i

RT
2

ln
i
T
_
,
where:
H
ex
excess heat of mixing
Reference Manual
Despite the attractiveness of this direct thermodynamic computation, experi-
ence has shown that the activity-coefficient parameters which correlate phase
equilibria do not in general produce very accurate values for excess enthal-
pies. GAMMA is a viable option when no other method is available, but the
resulting heats of mixing may only be accurate to within a factor of two.
Redl i ch-Ki ster Expansi on
Experimental data for heats of mixing for binary systems are most often rep-
resented by an expansion about an equimolar mixture:
(36)
H
ex
a
12
+ b
12
X + c
12
X
2
+ d
12
X
3
+ e
12
X
4
+ f
12
X
5
+ g
12
X
6
+ h
12
X
7
where:
X x
1
x
2
In equation (36), known as the Redlich-Kister expansion, a12 represents the
excess enthalpy of a 50-50 binary mixture. Higher-order terms correlate
asymmetry in the curve of excess enthalpy versus composition.
SimScis databanks contain regressed values of the coefficients in equation
(36) for approximately 2200 binary mixtures. In addition, these parameters
may be regressed to heat-of-mixing data with SimScis REGRESS program
and then entered through input by the user.
24. 14 PRO/II Note: For more information on using the heat-of-mixing corrections to
liquid-enthalpy calculations, see Section 24.14, Redlich-Kister, Gamma Heat
of Mixing, of the PRO/II Keyword Input Manual.
The empirical nature of the Redlich-Kister expansion means that there is some
degree of arbitrariness in the way it is extended to mixtures. SimSci offers two
options, known as RK1 and RK2. Both have the same basic form:
(37)
H
ex

j

x
i
x
j
(a
ij
+ b
ij
X + c
ij
X
2
+ d
ij
X
3
+ e
ij
X
4
+ f
ij
X
5
+ g
ij
X
6
+ h
ij
X
7
)
where:
X xi xj (form RK1)
X
x
i
x
j
x
i
+ x
j
(form RK2)
Note: Which mixture rule is better for a multicomponent system (they are
equivalent for binaries) depends upon the system, and there are no general
guidelines. RK2 is, however, somewhat preferable from the standpoint of
theoretical consistency.
Vapor Phase Fugaci ti es
General
Information
In vapor-liquid equilibrium calculations, it becomes necessary to calculate
separately the fugacity of each component in the vapor and liquid phases. Each
of the two phases may require a different technique. For example, liquid-phase
nonidealities may be described by activity coefficients, while deviations from
ideal-gas behavior in the vapor phase are described by fugacity coefficients. The
vapor-phase fugacity coefficients may be obtained through the use of an equa-
tion of state. The fugacity coefficients are obtained from classical thermodynam-
ics as follows:
(1)
ln
i
1
/
RT
P
n
i
_
,
T,V,n
j
RT
/
V
1
1
]
1
1
dV lnz
(2)
i
f
i

/
y
i
P
where:
i = fugacity coefficient of component i
R = gas constant
P = system pressure
ni = number of moles of i
yi = mole fraction of i in the vapor phase
V = volume of system
z = compressibility factor of the mixture
In equation (1), the partial derivatives of P with respect to ni must be evaluated
using an appropriate equation of state. Therefore the problem of calculating
fugacities of components in a gaseous mixture is equivalent to the problem of es-
tablishing a reliable equation of state for such a mixture. Once such an equation
of state is found, the fugacities can be derived from equations (1) and (2).
1. 2. 7
PRO/II Reference Manual Vapor Phase Fugaci ti es I-113
Volume I: Component and Thermophysical Properties
Equations of State Equations of state are powerful methods for calculating vapor-phase fugacities at
low and high densities. The analytical expression of the fugacity coefficient can be
derived from a cubic equation of state. The derivation of the fugacity coefficient
from a cubic equation of state is straightforward because the cubic equation of state
in pressure is volume-explicit. Cubic equations of state are usually applied to sys-
tems comprising mixtures of nonpolar or weakly polar components. The useful-
ness of a cubic equation of state can be greatly enhanced by using an advanced
alpha function and an advanced mixing rule. These modified cubic equations of
state can be suitable for systems containing polar components.
Note: See Section 1.2.4 of this manual, Equations of State, for more informa-
tion on using equations of state.
In addition, a cubic equation of state, when incorporated with a chemical
theory of association, is suitable for systems containing polar and hydrogen-
bonding molecules. These include carboxylic acids which form monomer-
dimer pairs and hydrogen fluoride. Such methods include the Associating
Hexamer Equation of State and the Hayden OConnell method, discussed in
a later section.
23. 7 PRO/II Note: For more information on using the SimSci-developed Associating
Hexamer Equation of State method for vapor fugacities, see Section 23.7, Associat-
ing Hexamer Equation of State, of the PRO/II Keyword Input Manual.
The equation-of-state methods are generally more reliable for calculating va-
por-phase fugacity coefficients than any other method, except for dimerizing
components, where the Hayden-OConnell method should be used.
Truncated Virial
Equation of State
Many equations of state have been proposed for calculating vapor fugacities, as
mentioned in the previous section, but almost all of them are empirical in nature.
The virial equation of state for gases has a sound theoretical foundation and is
free of arbitrary assumptions. The virial equation gives the compressibility fac-
tor as a power series in the reciprocal molar volume:
(3)
z Pv
/
RT 1 + B
/
v + C
/
v
2
+ D
/
v
3
+
where:
v = molar volume
B, C, D, .. = second, third, fourth, etc. virial coefficients
The virial coefficients are a function of temperature and composition only.
For low or moderate vapor densities, the virial equation can be truncated
after the second virial coefficient and converted to a pressure-explicit form:
(4) z 1 + BP
/
RT
I-114 Vapor Phase Fugaci ti es May 1994
The compositional dependence of B for a mixture containing N components
is given by:
(5)
B

i
N

j
N
y
i
y
j
B
ij
where:
Bii = second virial coefficient for pure component i
Bij = second virial cross coefficient
The cross coefficients characterize the interaction between one molecule of
component i and one of component j. They may be obtained from mixture data,
though often they are estimated from the pure component coefficients.
OConnell and Prausnitz developed a correlation for the reduced second
virial coefficient (both pure component and cross coefficients) which con-
sists of three generalized functions:
1. One for nonpolar contributions to the second virial coefficient.
2. One for polar interactions based on the dipole moment.
3. An association function for substances which exhibit specific forces such
as hydrogen bonds.
Use of this correlation requires the critical temperature, critical pressure,
critical volume, acentric factor, dipole moment, and association constant for
each component present. Missing dipole moments and association constants
are assumed to be zero. One limitation of this method is that, as the virial
equation of state is an expansion about the compressibility factor of an ideal
gas, higher-order terms cannot be neglected in high density regions. The
virial equation of state can provide reliable estimates of vapor-phase fugacity
coefficients at low pressures or high temperatures only.
24. 13 PRO/II Note: For more information on using the Truncated Virial fugacity
method, see Section 24.13, Truncated Virial Vapor Fugacity, of the PRO/II
Reference
OConnell, J. P., and Prausnitz, J. M., 1967, Empirical Correlation of Second
Virial Coefficients for Vapor-Liquid Equilibrium Calculations, Ind. Eng.
PRO/II Reference Manual Vapor Phase Fugaci ti es I-115
Hayden-
OConnell
The truncated virial equation of state described above is useful for predicting
deviations from ideality in those systems where moderate attractive forces yield
fugacity coefficients not far removed from unity. However, in systems containing
carboxylic acids, two acid molecules tend to form a dimer, resulting in large nega-
tive deviations from vapor ideality even at very low pressures.
To account for dimerization, Hayden and OConnell, in 1975, developed an
expression for the fugacity coefficient based on the chemical theory of vapor
imperfection. The chemical theory assumes that there are dimerization
equilibria for a binary mixture of components A and B:
(6)
(7)
(8)
where:
A1, B1 = monomers
A2, B2 = dimers
AB = cross dimer
Hayden and OConnell related second virial coefficients to the dimerization
equilibrium constants, KA
2
, KB
2
, and KAB, and developed generalized second
virial coefficients for simple and complex systems. Properties required to use
this correlation are: the critical temperature, critical pressure, mean radius of
gyration, dipole moment, association parameter, and solvation parameter. As-
sociation and solution parameters for common associating components are
available in PRO/IIs databanks.
24. 12 PRO/II Note: For more information on using the Hayden-OConnell fugacity
method, see Section 24.12, Hayden-OConnell Vapor Fugacity, of the PRO/II
This method is a reliable generalized method for calculating vapor fugacities
up to moderate pressures, especially for systems where no data are available.
Reference
Hayden, J. G., and OConnell, J. P., 1975, A Generalized Method for
Predicting Second Virial Coefficients, Ind. Eng. Chem. Proc. Des. Dev.,
14, 209-216.
A1 + A1
K
A2
A2
B1 + B1
KB
2
B2
A
1
+ B
1

K
AB
AB
I-116 Vapor Phase Fugaci ti es May 1994
Speci al Packages
General
Information
PRO/II contains a number of thermodynamic methods specifically developed
for special industrial applications. Data packages are available for the follow-
ing applications:
Alcohol dehydration systems.
Glycol systems.
Sour water systems.
Amine systems.
For many applications, databanks containing binary interactions specifically
regressed for components commonly found in the application have been developed
and incorporated into PRO/II. For example, for alcohol dehydration systems, a
special alcohol databank, in combination with the NRTL K-value method, is used
to calculate the K-values. For other applications, such as the SOUR or GPSWAT
method for sour systems containing NH3, H2S, CO2, and H2O, a K-value method
has been specifically developed for phase equilibrium calculations.
Alcohol
Package
(ALCOHOL)
The alcohol data package uses the NRTL liquid activity method to calculate
phase equilibria (see Section 1.2.6 of this manual, Liquid Activity Methods).
This system uses a special set of NRTL binary interaction parameters for
systems containing alcohols, water, and other polar components. The binary
parameters have been obtained by the regression of experimental data for al-
cohol systems. The recommended temperature and pressure ranges for the
ALCOHOL data package are as follows:
Temperature:
122-230 F for H2O-alcohol systems.
150-230 F for all other systems.
The vapor enthalpy and density and the vapor and liquid entropies are
calculated using the SRKM equation of state (see Section 1.2.4 of this man-
ual, Equations of State), while the liquid enthalpy and density are calculated
using ideal methods (see Section 1.2.3, Generalized Correlation Methods).
Table 1.2.8-1 shows the components present in the ALCOHOL databank for
which there are binary interaction parameters available.
1. 2. 8
PRO/II Reference Manual Speci al Packages I-117
Tabl e 1. 2. 8-1: Components Avai l abl e for ALCOHOL Package
Component Formul a LIBID
Mi scel l aneous
Acetaldehyde
Sulfolane
C2H4O
C4H8O2S
ACH
SULFLN
Li ght Gases
Hydrogen
Nitrogen
Oxygen
Carbon Dioxide
H2
N2
O2
CO2
H2
N2
O2
CO2
Hydrocarbons
Isopentane
n-Pentane
Cyclopentane
2-Methylpentane
1-Hexene
n-Hexane
Methylcyclopentane
Benzene
Cyclohexane
2,4-Dimethylpentane
3-Methylhexane
1-Trans-2-Dimethyl
cyclopentane
n-Heptane
Methylcyclohexane
Toluene
2,4-Dimethylhexane
1-Trans-2-Cis-4-Tri-
methylcyclopentane
C5H12
C5H12
C5H10
C6H14
C6H12
C6H14
C6H12
C6H6
C6H12
C7H16
C7H16
C7H14
C7H16
C7H14
C7H8
C8H18
C8H16
IC5
NC5
CP
2MP
1HEXENE
NC6
MCP
C6H6
CH
24DMP
3MHX
1T2MCP
NC7
MCH
TOLU
24DMHX
1T2C4MCP
Figure 1.2.8-1 shows the binary interaction parameters present in the ALCO-
HOL databank. It should be noted that for all pairs not denoted by x, the
missing binary interaction parameter can be filled in, based on the hierachy
discussed in Section 1.2.7, Liquid Activity Methods.
25. 1 PRO/II Note: For more information on using the ALCOHOL method, see Sec-
tion 25.1, Alcohol, of the PRO/II Keyword Input Manual.
I-118 Speci al Packages May 1994
Figure 1.2.8-1:
Binary Interaction Data
in the Alcohol Databank
Nitrogen X
Oxygen X X
Carbon Dioxide X X X
Isopentane X X X X
n-Pentane X X X X X
2-Methylpentane X X X X X X
n-Hexane X X X X X X X
2, 4-Dimethylpentane X X X X X X X X
3-Methylhexane X X X X X X X X X
n-Heptane X X X X X X X X X X
2, 4-Dimethylhexane X X X X X X X X X X X
Cyclopentane X X X X X X X X X X X X
Methylcyclopentane X X X X X X X X X X X X X
Cyclohexane X X X X X X X X X X X X X X
1-T-2DM-Cyclopentane X X X X X X X X X X X X X X X
Methylcyclohexane X X X X X X X X X X X X X X X X
1-T,2-C-4 TMCP X X X X X X X X X X X X X X X X X
1-Hexene X X X X X X X X X X X X X X X X X X
Benzene X X X X X X X X X X X X X X X X X X X
Toluene X X X X X X X X X X X X X X X X X X X X
DIPE X X X X
DEE X X X X
DME X X X X X
Acetic Acid X X X X X X
Formic Acid X X X X X X
MEK X X X X X X X
Acetone X X X X X X X X
Ethyl Acetate X X X X X X X X X
Methyl Formate X X X X X X
Acetaldehyde X X X X X X X X X
Sulfolane X X X X X X X X X X X X X X X X X X X X X
n-Pentanol X X X X
3-M-1-Butanol X X X X X
n-Butanol X X X X X X X X X X X X
Isobutanol X X X
Sec-Butanol X X X X X X X X
Tert-Butanol X X X X X X X X X X X X
n-Propanol X X X X X X X X X X
Isopropanol X X X X X X X X X X X X X X X X X X X X
Ethanol 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
Methanol 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
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
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Glycol
Package
(GLYCOL)
The glycol data package uses the SRKM equation of state to calculate phase
equilibria for glycol dehydration applications (see Section 1.2.4 of this man-
ual, Equations of State). This system uses a special set of SRKM binary
interaction data and alpha parameters for systems containing glycols (particu-
larly TEG), water, and other components. The binary parameters and alpha
parameters have been obtained by the regression of experimental data for
glycol systems. The recommended temperature and pressure ranges for the
GLYCOL package are:
Other thermodynamic properties such as the vapor and liquid enthalpy, en-
tropy, and vapor density are calculated using the SRKM equation of state,
while the liquid density is calculated using the API method (see Section
1.2.3, Generalized Correlation Methods).
Table 1.2.8-2 shows the components present in the GLYCOL databank for
which there are binary interaction parameters available.
Tabl e 1. 2. 8-2: Components Avai l abl e for GLYCOL Package
Components Formul a LIBID
Hydrogen
Nitrogen
Oxygen
Carbon Dioxide
Hydrogen Sulfide
Methane
Ethane
Propane
Isobutane
n-Butane
Isopentane
Pentane
Hexane
Heptane
Cyclohexane
Methylcyclohexane
Ethylcyclohexane
Benzene
Toluene
o-Xylene
m-Xylene
p-Xylene
Ethylbenzene
Ethylene Glycol
Diethylene Glycol
Triethylene Glycol
Water
H2
N2
O2
CO2
H2S
CH4
C2H6
C3H8
C4H10
C4H10
C5H12
C5H12
C6H14
C7H16
C6H12
C7H14
C8H16
C6H6
C7H8
C8H10
C8H10
C8H10
C8H10
C2H6O2
C4H10O3
C6H14O4
H2O
H2
N2
O2
CO2
H2S
C1
C2
C3
IC4
NC4
IC5
NC5
NC6
NC7
CH
MCH
ECH
BNZN
TOLU
OXYL
MXYL
PXYL
EBZN
EG
DEG
TEG
H2O
Figure 1.2.8-2 shows the binary interaction parameters, denoted by x,
present in the glycol databank. Interaction parameters denoted by o are
supplied from the SRK databank. It should be noted that for all pairs not de-
noted by x or o, the missing binary interaction parameters are estimated
using a molecular weight correlation or are set equal to 0.0.
Figure 1.2.8-2:
Bi nary Interacti on Data
in the Glycol Databank
25. 2 PRO/II Note: For more information on using the GLYCOL method, see Sec-
tion 25.2, Glycol, of the PRO/II Keyword Input Manual.
Nitrogen X
Oxygen X O
Carbon Dioxide X O
Hydrogen Sulfide X O O
Methane X O O O
Ethane X O O O X
Propane X O O O X X
Isobutane X O O O O O O
N-butane X O O O O O O O
Isopentane X O O O O O
Pentane X O O O X X O O O
Hexane X O X O O X X O O
Heptane X O X O O O O O O O
Cyclohexane O O O O O O O O
Methylcyclohexane
Ethylcyclohexane
Benzene X O O X X X O O O
Toluene X O X O O
o-xylene X X
m-xylene X X X
p-xylene X X
Ethylbenzene X X X
Ethylene Glycol
Diethylene Glycol X X X
Triethylene Glycol X X X X X X X X X X X X X X X X X X X X X 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
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Sour Package
(SOUR)
This sour water package uses the SWEQ (Sour Water EQuilibrium) method
developed by Wilson for a joint API/EPA project. Phase equilibria for sour
water components NH3, H2S, CO2, and H2O are modeled using a modified
van Krevelen approach. The van Krevelen model assumes that H2S and CO2
exist in solution only as ionized species. This is true only for solutions con-
taining an excess of NH3 or other basic gas. This limitation has been re-
moved in the SWEQ method by considering the chemical equilibrium
between ionic species of H2S or CO2 and their undissociated molecules in
the liquid phase.
In the SWEQ model, the partial pressure in the vapor phase for H2S or CO2 is
given by:
(1) p
H2S
= H
H2S
C
H2S
(2)
p
CO2
= H
CO2
C
CO2
where:
pi = partial pressure of component i
Hi = Henrys Law constant for component i in water
Ci = concentration of component i in the liquid phase, gmoles/
kg solution
The SWEQ model uses Henrys Law constants for each component in solution
as a function of temperature and composition of the undissociated molecular spe-
cies in the liquid phase. The Henrys constants for H2S and CO2 were obtained
from data published by Kent and Eisenberg, who developed a model for predict-
ing H2S-CO2-MEA-H2O and H2S-CO2-DEA-H2O systems. The Henrys Law
constants used in the SWEQ model for equations (1) and (2) are:
(3)
ln(H
CO2
) = 18.33 2.48951 x 10
4

/
T + 2.23996 x 10
7

/
T
2

9.0918 x 10
9

/
T
3
+ 1.2601 x 10
12

/
T
4
(4)
ln(H
H2S) = 100.684 2.46254 x 10
5

/
T + 2.39029 x 10
8

/
T
2
1.01898 x 10
11

/
T
3
+
1.5973 x 10
13

/
T
4
5.0 x 10
2
C
NH3
+ (0.965 486
/
T)C
CO2
where:
T = system temperature, degrees Rankine
The Henrys Law constant for water was obtained by correlating H2O vapor
pressure data from the A.S.M.E. steam tables over the range 25 C to 150 C:
(5)
ln
H
H2O
= 14.466 6.9966 x 10
3

/

T 77.67
The Henrys Law constant for NH3 was taken from data published by
Edwards et al.:
(6)
ln(H
NH3) = 178.339 1.55179 x 10
4

/
T 25.6767ln(T) + 1.966 x 10
2
T +
(131.4
/
T 0.1682)C
NH3
+ 6.0 x 10
2

2C
CO2
+ C
H2S
The chemical equilibria of all the main reactions in the liquid phase due to the dis-
sociation of the sour gas molecules are considered in the model. The reaction equi-
librium constants, Ki, are correlated as functions of temperature, composition of
undissociated sour gas molecules in the liquid phase, and ionic strength.
(7)
ln K
i
= ln K
i
0
+ aC
H2S
+ bC
CO2
+ cI
0.4
where:
Ki = equilibrium constant of reaction i
Ki
0
= equilibrium constant at infinite dilution for all species
a,b,c = constants
I = ionic strength = 1
/
2

j
CjZj
2
Zj = ionic charge of species j
The reaction equilibrium constants at infinite dilution, Ki
0
, are given in the
form first proposed by Kent and Eisenberg:
(8)
ln K
i
0
= A + B
/
T + C
/
T
2
+ D
/
T
3
+ E
/
T
4
where:
A,B,C,D,E = constants
The constants used in the SWEQ model for equations (7) and (8), obtained by
the regression of experimental data, are given in the original EPA report. The
original SWEQ method was developed for pressures less than 50 psia where
nonidealities in the vapor phase are not important. Corrections for vapor-phase
nonidealities using SRKM have been incorporated into PRO/II, thus extending
the applicable pressure range to 1500 psia.
The phase behavior of all other components present in the system is modeled
using the SRKM equation of state (see Section 1.2.4 of this manual, Equa-
tions of State). The following limits apply to the SOUR method as
implemented in PRO/II:
Composition: wNH3 + wCO2 + wH2S <0.30.
where:
Note: NH3 and water must be present when using the SOUR method.
Other thermodynamic properties such as the vapor enthalpy, vapor and liquid
entropy, and vapor density are calculated using the SRKM equation of state,
while the liquid enthalpy and density are calculated using ideal methods (see
Section 1.2.3, Generalized Correlation Methods).
25. 3 PRO/II Note: For more information on using the SOUR method, see Section
25.3, Sour, of the PRO/II Keyword Input Manual.
References
1. Wilson, G. M., 1980, A New Correlation for NH3, CO2, H2S Volatility Data
from Aqueous Sour Water Systems, EPA Report EPA-600/2-80-067.
2. van Krevelen, D. W., Hoftijzer, P. J., and Huntjens, F. J., 1949, Rec. Trav.
Chim., 68, 191-216.
3. Black, C., 1958, Vapor Phase Imperfections in Vapor-Liquid Equilibria, Ind.
Eng. Chem., 50, 391-402.
4. Kent, R. L., and Eisenberg, B., 1976, Better Data for Amine Treating,
Hydrocarbon Processing, Feb., 87-90.
5. Handbook of Chemistry and Physics, 1971, 51st Edition, The Chemical
Rubber Co.
6. Edwards, T. J., Newman, J., and Prausnitz, J. M., Thermodynamics of Aqueous
Solutions Containing Volatile Weak Electrolytes, 1975, AIChE J., 21, 248-259.
GPA Sour Water
Package
(GPSWATER)
This sour water package uses the method developed for the Gas Processors
Association in 1990 for sour water systems containing components NH3, H2S,
CO2, CO, CS2, MeSH, EtSH, and H2O. This model uses the SWEQ model (see
above) as a precursor, extending the temperature range of applicability to 600
F. The total pressure limit is increased to 2000 psia by allowing for vapor
phase non-idealities and accounting for pressure effects in the liquid phase,
using a Poynting correction factor.
As in the SWEQ model, the chemical equilibria for all the reactions involv-
ing the NH3, H2S, and CO2 in water are considered. The components CO,
methyl mercaptan (MeSH), and ethyl mercaptan (EtSH) are treated as
Henrys Law components (see Section 1.2.6, Liquid Activity Coefficient
Methods). Reactions considered include:
Water:
(9)
H
2
O
1
H
+
+ OH
Ammonia:
(10)
NH
3
+ H
+

2
NH
4

+
Hydrogen Sulfide:
(11)
H
2
S + OH
3
H
2
O + HS
Bisulfide:
(12)
HS
+ OH
4
H
2
O + S
2
Carbon Dioxide:
(13)
CO
2
+ OH
5
HCO
3
Bicarbonate:
(14)
HCO
3
+ OH
6
H
2
O + CO
3
2
Carbon Dioxide and Ammonia:
(15)
NH
3
+ CO
2

7
H
2
NCOOH
(16)
H
2
NCOOH + OH
8
H
2
NCOO
+ H
2
O
(17)
H
2
NCOOH + NH
3

9
H
2
NCONH
2
+ H
2
O
The chemical equilibrium constants, Ki, are correlated as functions of tempera-
ture and composition. In addition, the effect of inert gases such as N2 and H2 on
phase equilibria is also considered. In the liquid phase, pressure effects are ac-
counted for by the use of a Poynting correction factor, and electrostatic effects
are incorporated into the calculated liquid activity coefficients.
Vapor-phase nonidealities are computed using a truncated virial equation of
state. The virial equation used is truncated after the third virial coefficient as
follows:
(18)
z = 1 + B
/
v + C
/
v
2
where:
B, C are the second and third virial coefficients
v = molar volume
z = compressibility factor
Phase equilibria for all other components present in the system are modeled
using the SRKM equation of state (see Section 1.2.4 of this manual, Equa-
tions of State).
The following limits apply to the GPSWATER method:
Composition:
wNH3 < 0.40.
pCO2 + pH2S < 1200 psia
where:
pi = partial pressure of component i in the vapor phase
Note: NH3, CO2, H2S, and water must be included in the component list
when using the GPSWATER method.
Other thermodynamic properties such as the vapor enthalpy, vapor and liquid en-
tropy, and vapor density are calculated using the SRKM equation of state, while
the liquid enthalpy and density are calculated using ideal methods (see Section
1.2.3, Generalized Correlation Methods).
25. 4 PRO/II Note: For more information on using the GPSWATER method, see
Section 25.4, GPA Sour Water, of the PRO/II Keyword Input Manual.
Reference
Wilson, G. M., and Eng, W. W. Y., 1990, GPSWAT: GPA Sour Water
Equilibria Correlation and Computer Program, GPA Research Report RR-
118, Gas Processors Association.
Amine Package
(AMINE)
The PRO/II simulation program contains a method to model the removal of H2S
and CO2 from natural gas feeds using alkanolamines. Alkanolamines are formed
by ammonia reacting with an alcohol. Amines are considered to be either pri-
mary, secondary, or tertiary, depending on whether 1 or 2 or 3 of the hydrogen
atoms have been replaced on the ammonia molecule. PRO/II provides data for
the primary amine monoethanolamine (MEA), secondary amines diethano-
lamine (DEA), diglycolamine (DGA), and diisopropanolamine (DIPA), and the
tertiary amine methyldiethanolamine (MDEA). MEA and DEA are frequently
used amines in industry.
In aqueous solutions, H2S and CO2 react in an acid-base buffer mechanism with
alkanolamines. The acid-base equilibrium reactions are written as chemical dis-
sociations following the approach taken by Kent and Eisenberg:
Water:
(19)
H
2
O
1
H
+
+ OH
Hydrogen Sulfide:
(20)
H
2
S
2
H
+
+HS
Bisulfide:
(21)
HS
3
H
+
+ S
2
Carbon Dioxide:
(22)
H
2
O + CO
2

4
H
+
+ HCO
3
Bicarbonate:
(23)
HCO
3
5
H
+
+CO
3
2
Alkanolamine:
(24)
RR NH
2
+
+
6
H
+
+ RRNH
where:
Ki = equilibrium constant for reaction i
RRNR = alkanolamine
R represents an alkyl group, alkanol, or hydrogen
In addition to the acid-base reactions above, CO2 also reacts directly with
primary and secondary alkanolamines to form a stable carbamate, which can
revert to form bicarbonate ions.
Carbamate Reversion to Bicarbonate:
(25)
RR NCOO
+ H
2
O
7
RR NH + HCO
3
Tertiary amines such as MDEA are not known to form stable carbamates. In
an aqueous solution with MDEA, CO2 forms bicarbonate ions by reaction
(22) only.
Note: CO2, H2O, and H2S must be included in the component list when using
the AMINE method.
The chemical equilibrium constants, Ki, are represented by the following
equation:
(26)
ln K
i
= A + B

T + C

T
2
+ D

T
3
The equlibrium constant for the protonated amine dissociation reaction given
in reaction (24) is corrected to the pure amine reference state. This is done
by relating the constant to the infinite-dilution activity coefficient of the
amine in water estimated from experimental data for the system amine-water.
The liquid enthalpy is calculated using ideal methods and adding a correc-
tion for the heat of reaction as follows, using either a modified Clausius-
Clapeyron equation or fits of data from the Gas Processors Association:
(27) H
r
= ln
K
T1

/
K
T2
R
/

1
/
T
1
1
/
T
2
where:
Hr = heat of reaction
R = gas constant
KT1, KT2 = K-values at temperatures T1 and T2
The vapor-phase enthalpy and density, and liquid- and vapor-phase entropy
are calculated using the SRKM equation of state (see Section 1.2.4 of this
manual, Equations of State). Ideal methods are used to calculate the liquid-
phase density (see Section 1.2.3, Generalized Correlation Methods).
For MEA and DEA systems, data have been regressed from a large number of
sources, resulting in good prediction of phase equilibria for these systems. For
systems containing DIPA, a limited amount of experimental data were available,
and so the DIPA results are not recommended for final design purposes. For
MDEA and DGA systems, the user is allowed to input a residence time correc-
tion to allow the simulation results to more closely match plant data. The applica-
tion ranges suggested for amine systems are shown in Table 1.2.8-3.
Tabl e 1. 2. 8-3: Appl i cati on Gui del i nes for Ami ne Systems
Ami ne
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 %
amine
~15-25 ~25-35 ~55-65 ~50 ~30
Acid gas loading,
gmole gas/gmole
amine
0.5-0.6 0.45 0.50 0.4 0.4
25. 5 PRO/II Note: For more information on using the AMINE method, see Section
25.5, Amine, of the PRO/II Keyword Input Manual.
References
1. Kent, R. L., and Eisenberg, B., 1976, Better Data for Amine Treating,
Hydrocarbon Processing, Feb., 87-90.
2. Maddox, R. N., Vaz, R. N., and Mains, G. J., 1981, Ethanolamine Process
Simulated by Rigorous Calculation, Hydrocarbon Processing, 60, 139-142.
El ectrol yte Mathemati cal Model
Discussion of
Equations
The mathematical model employed in PRO/II Electrolytes is a deterministic
set of nonlinear algebraic equations. The equation set is composed of:
Equilibrium Expressions
For each vapor-liquid, liquid-liquid, solid-liquid, and liquid intraphase equi-
librium, there is an equation of the form:
(1)
K =

iP

(
iP
)
n
iP
(m
iP
)
n
iP

iR

(
iR
)
n
iR
(m
iR
)
n
iR
where:
K = thermodynamic equilibrium constant: a function of tem-
perature and pressure
iP
,
iR
= activity coefficient or, for vapors, fugacity coefficient
of the ith product and reactant, respectively; a function
of temperature, pressure, and composition
n
iP
, n
iR
= stoichiometric coefficient of the ith product and reac-
tant, respectively
miP, miR = molality or, for vapors, partial pressure of the ith prod-
uct and reactant, respectively
Note: When H2O (the solvent) appears in the equilibrium expression, its
contribution is expressed as aH2O, the activity of water. All pure solid
component activities are assumed to be one. The fugacity coefficient, i is de-
fined as fi/yiP or fi/Pi, where f denotes fugacity, P represents total pressure, and
Pi stands for partial pressure. The adopted convention is that i approaches one
as total pressure approaches zero. The activity ai is given by imi, where i ap-
proaches one as the molality of all solutes approaches zero.
1. 2. 9
PRO/II Reference Manual El ectrol yte Mathemati cal Model I-131
Note: Equilibrium constants often are written entirely in terms of fugacities, in
which case thermodynamics requires that K is a function of temperature only.
When activities are used intead of fugacities, as in the present treatment, then
K is affected by the choice of standard state. Since the standard state for solutes
is infinite dilution in H2O, a pressure dependence is introduced from the pres-
sure dependence of the water properties. This effect is negligible except at con-
ditions approaching waters critical point. Consequently, over the temperature
and pressure validity range for the electrolyte thermodynamic methods (0-200
C; 0-200 atm), K is treated only as a function of temperature.
An Electroneutrality Equation
(2)

i=1
NC
| Z
i
| m
i
=

i=1
NA
| Z
i
| m
i
where:
Zi = species charge
NC, NA = number of cations and anions, respectively
Equations For Solutions Involving a Second Liquid Phase,
(liquid-liquid equilibrium)
(3)
a
i
A
= a
i
O
i = 1,NM
where:
ai = activity of ith species
A, O = represent aqueous and organic phases, respectively
NM = number of molecular species distributing between phases
Note: The required number of material balances, i.e. NB, completes the model
and assures that the number of equations and the number of unknowns are
equal. Normally these balances include an overall, a vapor phase, an organic
phase, and several component balances.
Thus, assuming NK equilibrium equations, the model has NK + NB + NM + 1
equations. The customary unknowns are:
The moles of H2O in the aqueous liquid phase plus all ionic and molecu-
lar species molalities.
The vapor phase: species mole fractions plus overall vapor fraction.
The organic liquid phase: species mole fractions plus overall organic
phase fraction (if second liquid phase is present).
The solid phase composition: moles precipitated for all solid species.
I-132 El ectrol yte Mathemati cal Model May 1994
As noted above, the number of NB equations required is that number which
assures that the number of equations equals the overall number of unknowns.
This is a natural consequence of the phase rule.
Modeling
Example
To better understand this modeling concept, consider the aqueous system rep-
resented by H2O-CO2-NACL. The reactions considered will be:
(4) H2Ovap H2O
(5) CO2vap CO2aq
(6)
H2Oaq H
+1
+ OH
1
(7)
CO2aq + H2Oaq H
+1
+ HCO3
1
(8)
HCO3
1
H
+1
+ CO3
2
(9)
NACLppt NA
+1
+ CL
1
Based upon the general model described earlier, this leads to:
Equilibrium Expressions
(10)
KH2Ovap =
a
H2O

H2Ovap
y
H2Ovap
P
(11)
KCO2vap =
CO2aq
m
CO2aq

CO2vap
y
CO2vap
P
(12)
KH2Oaq =
H+1
m
H+1

OH1
m
OH1
a
H2O
(13)
KCO2aq =
H+1
m
H+1

HCO31
m
HCO31
CO2aq
m
CO2aq
a
H2O
(14)
KHCO3ion =
H+1
m
H+1

CO32
m
CO32
HCO31
m
HCO31
(15)
KNACLppt=
NA+1
m
NA+1

CL1
m
CL2
a
NACLppt
Electroneutrality Equation
(16) m
H+1
+ m
NA+1
= m
HCO31
+ 2m
CO32
+ m
OH1
+ m
CL1
Liquid-liquid Equilibrium Equations
There are none in this example.
PRO/II Reference Manual El ectrol yte Mathemati cal Model I-133
Material Balance Equations
Overall material balance:
3H2Oin + 3CO2in + 2NACLin = 2NACLppt + 3H2O + (H2O
/
55.51)
(3m
CO2aq
+ 5m
HCO31
+ 4m
CO32
+ m
H+1
+ 2m
OH1
+
m
CL1
+ m
NA+1
) + V(3y
H2Ovap
+ 3y
CO2vap
) (17)
where:
in = inflow or feed component in units of moles
V = overall vapor fraction on a mole basis
In equation (17), the products H2O and NACLppt are in units of moles.
Vapor balance
(18)
y
H2Ovap
+ y
CO2vap
= 1
where:
y = mole fraction for vapor species
Sodium balance
(19) NACLin = (H2O
/
55.51)(m
NA+1
) + NACLppt
Chlorine balance
(20) NACLin = (H2O
/
55.51)(m
CL1
) + NACLppt
Carbon balance
(21) CO2in = (H2O
/
55.51)(m
CO32
+ m
HCO31
+ m
CO2aq
) + V (y
CO2vap
)
Equations (10) -- (21) are the required 12 equations. Assuming that the tem-
perature and pressure are known, and further assuming that deterministic for-
mulations are available for the equilibrium constants, activity coefficients,
fugacity coefficients, and the activity of water, then the corresponding 12 un-
knowns (calculated variables) are:
V, y
H2Ovap
, y
CO2vap
, m
H+1
m
OH1
, m
CO32
,
m
HCO31
, m
NA+1
, m
CL1
, m
CO2aq
, moles NACLppt,
and moles water.
164 PRO/II Note: A summary of the pregenerated electrolyte models available in
PRO/II is given in Section 164, Electrolyte Models, of the PRO/II Keyword In-
put Manual. Additional models may be generated by the user with the PRO/II
Electrolyte Utility Package (EUP).
I-134 El ectrol yte Mathemati cal Model May 1994
El ectrol yte Thermodynami c Equati ons
Thermo-
dynamic
Framework
The mathematical model described in the previous section utilizes several
thermodynamic quantities. Specifically these are:
Equilibrium constants -- normally strong functions of temperature and
weaker functions of pressure.
Aqueous-phase activity coefficients -- normally strong functions of tem-
perature and composition and weaker functions of pressure.
Vapor-phase fugacity coefficients -- normally significant functions of tem-
perature, pressure and composition, particularly at elevated pressures.
Organic liquid-phase activities -- normally strong functions of tempera-
ture and composition and weaker functions of pressure.
The formulations used by PRO/II Electrolytes for each of these quantities are
described below.
In addition, the thermodynamic framework includes formulations for the cal-
culation of enthalpies and densities for aqueous liquid, organic liquid, vapor,
and solid phases. These latter formulations are also presented below.
163 PRO/II Note: For information on using the electrolyte thermodynamic methods
in PRO/II, see Section 163, Electrolyte Thermodynamic Data, of the PRO/II
Equilibrium
Constants
By considering basic thermodynamic relationships and assuming a constant heat
capacity of reaction, the following general equation can be derived:
(1)
ln K (T)
G
RT
r

H
R

1
T

1
T
r
1
1
]

Cp
R

ln
T
r
T

T
r
T
+ 1
1
1
]
where:
T = temperature in Kelvins
Tr = reference temperature, 298.15 K
G = free energy of the reaction in the standard state at the refer-
ence temperature (and pressure, 1 bar). This is derived
from the standard-state Gibbs free energies of formation,
Gf
, by first, summing the product of the reaction coeffi-

cient times Gf
over all reactants and then, over all prod-

ucts. Next, the sum for the reactants is subtracted from the
sum for the products to obtain G
.
1. 2. 10
PRO/II Reference Manual El ectrol yte Thermodynami c Equati ons I-135
H = corresponding standard state heat of reaction at the reference
conditions. Obtained from the standard-state enthalpy of for-
mation, H
f
, using the same general procedure as used for

G
.
Cp= corresponding standard state heat capacity of reaction at the
reference conditions. Obtained from the standard state heat ca-
pacity, Cp, using the same general procedure as used in G.
R = gas constant
The derivation of the relationship given in equation (1) can be found in the
Handbook of Aqueous Electrolyte Thermodynamics
1
. Values of Gf
, Hf
,
and Cp for reaction species are usually available in the critically evaluated
data compilations of the National Bureau of Standards
2
or the Russian Acad-
emy of Sciences
3
.
The chosen standard states for the thermodynamic framework are as follows:
Aqueous solutes - hypothetical, infinitely dilute solution at unit molality;
Solvent - pure fluid; Gaseous species - hypothetical 1 bar ideal gas; Solid
species - pure solid. These are the same standard states as used by the NBS
2
.
For some reactions, where sufficient measurements are available for K as a
function of temperature, fitted functions of temperature are used instead of
equation (1).
Aqueous Phase
Activities
The key to successful simulation of aqueous systems is to accurately predict the
reaction equilibria described in the previous section. Greater precision is added
by a good description of the following correction factors:
Activity coefficients of ions in solution.
Activity coefficients of molecules in solution.
Activity of water.
In PRO/II Electrolytes, these quantities can be represented in terms of a num-
ber of alternative as well as complementary formulations. The common ele-
ment of all of these formulations is that they involve the interaction of pairs
of species in solution. Two general assumptions are made:
Interactions between like-charged ions are not significant.
Higher-level interactions (involving more than two species) are not
significant.
I-136 El ectrol yte Thermodynami c Equati ons May1994
Ions
For ions the formulation used is:
(2) ln
i
DH
i
+ BZ
i
+ P
i

DHi = Debye-Hckel term for long-range, ion-ion interactions,
defined as:
(3)
DH
i

A | Z
i
|
2
I
1
/
2
1 + I
1
/
2
where:
A = Debye-Hckel constant, a known function of temperature
and solvent density.
1
I = ionic strength = 1
/
2

i1
NI
Z
i
2
m
i
; where m = molality
Zi = charge on ion i
The Debye-Hckel term predicts the long-range or electrostatic effects. For
dilute solutions of ionic strength less than 0.1, this is the only term needed.
BZi = Bromley-Zemaitis
4,5
term for short-range, ion-ion
interactions, defined as:
(4)
BZ
i

j1
NO

| Z
i
| + | Z
j
|
2
1
1
]

2

ij
m
j
where:
(5)
ij

(0.06 + 0.6 B
ij
) | Z
i
Z
j
|
(1 + 1.5
/
| Z
i
Z
j
| I)
2
+ B
ij
+ C
ij
I + D
ij
I
2
NO = number of ions with charge opposite to that of the ion be-
ing represented.
Bij,Cij,Dij = three interaction coefficients for each cation-anion interac-
tion. These are each made 3-parameter functions of tem-
perature. Thus, for each cation-anion interaction, there
are 9 coefficients that must be established.
Pi = Pitzer
6,7
term for short-range, ion-molecular interactions,
defined as:
(6)
P
i

j1
NM

BP
ij
+
Z
1
2
4I
2
BPS
j
1
1
]
m
j
where:
(7)
BP
ij

ij
(0)
+
ij
(1)

1 + 2I
1
/
2_
,

1 exp
2I
1
/
2_
,
_
,

/
2I
and
(8)
BPS
j
0.86859

k1
NS
BPP
jk
m
k
and
(9)
BPP
jk

jk
(1)

1 + 2I
1
/
2
+ 2I
_
,
exp
2I
1
/
2_
,
1
]
where:
NM = number of molecular species in solution
NS = number of species in solution
ij
(0)
,
ij
(1)
= two interaction coefficients for each ion-molecule or
molecule-molecule interaction.
Note: Each of the ij interaction coefficients is a 3-parameter function of
temperature. Thus, for each interaction, there are 6 coefficients that must be
established.
Molecules Other Than Water
For molecules other than water, the Setschenow equation is used. Where
ij
(0)
and ij
(1)
parameters are available, the preferred formulation is from
Pitzer
6,7
. The Setschenow and Pitzer relations are:
(10)
ln
i
b
i
I +

j1
NI
b
j
m
j
where:
bi = Setschenow coefficient for the neutral species
bj = Salting-out coefficient particular to each ion
NI = the number of ionic species in solution
and
(11)
ln
i
2

j1
NS
BP
ij
m
i
BPij is defined by equation (7) above.
Water Activity
The water activity for multicomponent systems is obtained from an inte-
grated form of the Gibbs-Duhem equation, together with a mixing rule sug-
gested by Meissner and Kusik
8
. The formulation can be represented as:
(12)
ln a
H
2
O

1
AZ

i1
NC

j1
NA
| Z
i
Z
j
|
ij
m
i
m
j
0.01801

i1
NM

m
i
+ 2

j1
NS
BPW
ij
m
i
m
j
1
1
]
1
1
where:
(13)
AZ

i1
NC
Z
i
2
m
i
1
1
]
1
1

i1
NA
Z
i
2
m
i
1
1
]
1
1
(14)
BPW
ij

ij
(0)
+
ij
(1)
exp
2I
1
/
2_
,
NC = the number of cation species in solution
NA = the number of anion species in solution
The above formulations are, in cases where the necessary interaction coefficients
have been fit to cover the conditions being simulated, quite adequate for predict-
ing systems in which water is the principal solvent.
Vapor Phase
Fugacities
Four alternative methods are provided:
Ideal, all fugacity coefficients are assumed to be 1.0.
Nothnagel method, generally valid up to 20 atmospheres.
Nakamura method, generally valid up to 200 atmospheres.
Soave-Redlich-Kwong (SRK) method, valid over a wide range of conditions
and generally recommended when vapor-phase non-ideality is important.
Nothnagel Method
Nothnagel et al.
9
developed a method for calculating fugacity coefficients in
mixtures at moderate pressures. The main feature of the method is the inclu-
sion of dimerization effects on the second virial coefficient.
The equation of state is written as:
(15)
P
n
T
R T
V n
T
b
m
where:
bm = size parameter for mixture, cm
3
/ mole
n
T
= number of moles of true species
P = pressure, atmospheres
R = gas constant, 82.056 cm
3
atm / mole K
T = temperature, Kelvins
V = total volume, cm
3

n
T
is obtained from the solution of the dimerization equilibria described be-
low. bm is given by a sum over all true species:
(16)
n
T
b
m

i
n
i
b
i
where:
bi = size parameter for true species i, cm
3
/ mole
ni = number of moles of true species i
If i is a dimer formed by monomers A and B, bi is given by:
(17)
b
i

1
8

b
A
1
/
3
+ b
B
1
/
31
1
]
3
Values of b for monomers are tabulated in the original reference.
For component j, the fugacity coefficient is given by:
(18)

j

z
j
y
j
1
1
]
exp
b
j
P
/
RT_
,
where:
bj = size parameter for monomer j, cm
3
/ mole
yj = apparent mole fraction of component j
zj = true mole fraction of component j monomer
The true mole fractions zj are computed from the dimerization equilibria.
Each dimerization is described by an equilibrium constant Kij:
(19)
K
ij

z
ij
z
i
z
j

ij
i

j
P
(20)
ij
exp
b
i
1
/
3
+ b
j
1
/
3_
,
3
P
/
8RT
1
1
]
The dimerization equilibrium constants are related to the enthalpy and en-
tropy of dimerization:
(21)
ln
RTK
ij
_
,
H
ij

/
RT S
ij

/
R
where:
Hij = enthalpy of dimerization, cal/mole
Sij = entropy of dimerization, cal/mole
R = gas constant, 82.056 cm
3
atm/mole K (left side of equation
(21)), 1.987 cal/mole K (right side of equation (21))
The correlations for Hij and Sij, along with the necessary parameters for
178 components, may be found in the original paper
9
.
Nakamura Method
Nakamura et al.
10
proposed the following perturbed-hard-sphere equation of
state for gas mixtures:
(22)
P
RT
v

1 + +
2

3
(1 )
3
1
1
]

a
v (v + c)
where:
P = pressure, atmospheres
R = gas constant, .082056 liter atm/mole K
T = temperature, Kelvins
v = molar volume, liter / mole
= reduced density, b/4v
b = parameter signifying the hard-core size of the molecule, li-
ter / mole
a = parameter signifying the attractive force strength, atm/mole
c = constant, liter / mole
In addition to equations for the reduced enthalpy difference and entropy dif-
ference, the following equation was presented for calculating the fugacity co-
efficient of a species k in the gas mixture:
ln
k

4 3
2
(1 )
2
1
1
]
+
b
k
b
M

4 2
2
(1 )
3
1
1
]

2
RTv

j1
n
y
j
a
kj
1
1
]
1
1

m1
5
(1)
m
(m + 1)

c
M
v
_
,
m
+ 1
1
1
]
1
1
+
a
M
c
k
RTv

m1
4
(1)
m
(m + 1)
(m + 2)

c
M
v
_
,
m
+
1
2
1
1
]
1
1
ln z (23)
With the P, R, T, v, and terms defined earlier, the following definitions and
calculations apply:
n = number of species
(24)
b
k
exp [2.30259 ( T)]
where:
= pure-component parameter
(25)
b
M

i1
n
y
i
b
i
where:
yi = vapor mole fraction of i
ck = pure-component parameter
(26)
c
M

i1
n
y
i
c
i
(27)
z = compressibility factor =
Pv
RT

(28)
a
M

i1
n

j1
n
y
i
y
j
a
ij
(29)
a
ij

ij
+
ij
T
where:
ij = interaction parameter
(30)
ij

ij
0
+
ij
1
(31)
ij

ij
0
+
ij
1
(32)
ij
1

i
1

j
1
(33)
ij
1

i
1

j
1
(34)
ij
0

1
2

i
0
+
j
0
_
,
i
1

i
1
0.0 for non polar gas
where:
i = pure component parameter
ij = interaction parameter
Values for the pure-component and interaction parameters used in equations
(21) through (34) are given in the original paper by Nakamura et al. for the
following components: Ar, CH4, C2H4, C2H6, C3H6, C3H8, CO, CO2, H2,
H2O, H2S, N2, NH3, and SO2.
SRK Method
Calculation of fugacity coefficients from the Soave-Redlich-Kwong equation of
state is described in Section 1.2.4, Equations of State, of this manual.
Note: For both the Nothnagel and Nakamura options, if an electrolyte model
contains a volatile species not covered in the original paper by Nakamura et
al. for the method (MEA and HClO are examples of such species) the fugacity
coefficients all default to 1.0 (ideal gas). The SRK option does not suffer from
this limitation.
Organic Phase
Activities
Activities of components in an organic liquid phase (if one exists) are obtained
from the Kabadi-Danner modification to the SRK equation of state. This method
is described in Section 1.2.4, Equations of State, of this manual.
Enthalpy The pressure dependence of the enthalpy for vapor, liquid, and solid phases
is neglected in this thermodynamic framework. However, this does not intro-
duce significant uncertainties in enthalpy calculations over the stated model
validity ranges for temperature (0 to 200 C) and pressure (up to 200 bars).
Because enthalpy is treated as pressure-independent, PRO/II Electrolytes us-
ers will receive a warning about potential failure of the flash when pressure
is varied to meet a duty specification.
Vapor and Solid Phases
The enthalpy of the vapor or solid phase at the temperature and solution com-
position of interest is evaluated using:
(35)
H
vap
or H
sol

i1
NC
y
i
H
i
where:
Hi
, yi = the standard state molar enthalpy and the mole fraction, re-
spectively, of the ith vapor or solid component
NC = the total number of components present in the vapor or
solid phase.
At the temperature of interest, Hi
is evaluated using:
(36)
H
i
H
fi,T
r

T
r
T
C
p
i
dT
where:
Cp
i
, H fi,T
r
=
the standard state, isobaric, molar heat capacity, and the
standard state molar enthalpy of formation for the ith
vapor or solid component
Tr = the reference temperature of 298K.
Values of C
pi
for vapor and solid species are obtained from empirical func-
tions of temperature, which are given by:
(37)
C
p
i
A
i
+ B
i
T + C
i
T
2
(for vapor)
(38)
C
p
i
A
i
+ B
i
T + C
i

/
T
2
(for solid)
where:
Ai, Bi, Ci = temperature-independent, but phase-dependent
constants characteristic of the ith vapor or solid
components.
Aqueous Liquid
Phase
The enthalpy of the aqueous solution, Haq, at the temperature and solution
composition of interest is evaluated using:
(39)
H
aq
X
w
H
w
+

i1
NM
x
i
H
i
+

i1
NI
x
i
H
i
where:
Hw = the molar enthalpy of pure water at the temperature of inter-
est and at the vapor/liquid saturation pressure of H2O
xi = the mole fraction of the ith solute species
NM, NI = the total number of molecular and ionic solute species,
respectively
The enthalpy of pure water is obtained from the equation of state for H2O
given by Haar, Gallagher, and Kell
11
. At the temperature and solution com-
position of interest, Hi is evaluated using:
(40)
H
i
H
i
RT
2

ln
i
T
_
,
where:
i = the activity coefficient of the ith solute species
R = the gas constant
Values of i and (lni
/
T) are obtained from equations (2) through (9) for
ionic species and from equations (10) and (11) for molecular solutes. Values
of Hi
are obtained from equation (36), using values of Cp

i
and H fi,T
r
for
aqueous species and using the following relations to represent C
pi
for ionic
and molecular solutes:
(41)
C
p
i
C
p
i
,T
r
(for ionic solutes)

(42)
C
p
i
A
i
+ B
i
T + C
i
T
2
(for molecular solutes)
where:
Ai, Bi, and Ci = temperature-independent, but phase-independent constants
characteristic of the ith molecular solute
Molar Volume and
Density
Vapor Phase
The density of the vapor phase is evaluated using the equation of state which
corresponds to the chosen vapor fugacity method.
Aqueous Liquid Phase
The molar volume of the aqueous solution, vaq, at the temperature, pressure,
and solution composition of interest is evaluated using:
(43)
v
aq
x
w
v
w
+

i1
NM
x
i
v
i,T
r

i1
NI
x
i
v
i,T
r
where:
vw = the molar volume of pure water at the temperature and pres-
sure of interest, as given by the HGK
11
equation of state
vi,
T
r
=
the standard-state molar volume of the ith molecular or
ionic aqueous solute species, at the reference temperature
Organic Liquid Phase
The density of an organic liquid phase is calculated using the Rackett
method for liquid density. This method is described in Section 1.2.3, Gener-
alized Correlations, of this manual.
Solid Phase
The molar volume of the solid phase, vsol, at the temperature of interest is
evaluated using:
(44)
v
sol

i1
NC
x
i
v
i,T
r
where:
vi,
Tr
=
the standard state molar volume of the ith pure solid com-
ponent at the reference temperature
References
1. Zemaitis, J.F. Jr., Clark, D.M., Rafal, M., and Scrivner, N.C., 1986, Hand-
book of Aqueous Electrolyte Thermodynamics, AIChE.
2a. Wagman, D.D., et al., 1968-1973, Selected Values of Chemical
Thermodynamic Properties, NBS Tech Note, 270-3 to 8.
2b. Chase, M.W. Jr., Davies, C.A., Downey, J.R. Jr., Frurip, D.J., McDonald,
R.A., and Syverud, A.N., 1985, JANAF Thermochemical Tables, 3rd edn.,
J. Phys. Chem. Ref. Data, 14, Supplement no. 1, 1856 pp.
2c. Wagman. D. D., et al., 1982, The NBS Tables of Chemical Thermodynamic
Properties, J. Phys. Chem. Ref. Data, 11, Supplement no. 2, 392 pp.
3. Glushko, V.P., editor, 1965-1981, Thermal Constants of Compounds, Rus-
sian Academy of Sciences, Vols. I-X.
4. Zemaitis, J.F., Jr., 1980, Predicting Vapor-Liquid-Solid Equilibria in Multi-
component Aqueous Solutions of Electrolytes, Thermodynamics of Aque-
ous Systems with Industrial Applications, S.A. Newman, ed., ACS
Symposium Series, 133, 227-246.
5. Bromley, L.A., 1973, Thermodynamic Properties of Strong Electrolytes in
Aqueous Solutions, AIChE J., 19, 313-320.
6. Pitzer, K.S., 1979, Theory: Ion Interaction Approach, Activity Coefficients
in Electrolyte Solutions, 1, 157-208, R.M. Pytkowicz, ed., CRC Press,
Boca Raton, FL.
7. Pitzer, K.S., 1980, Thermodynamics of Aqueous Electrolytes at Various
Temperatures, Pressures and Compositions, Thermodynamics of Aqueous
Systems with Industrial Applications, S.A. Newman, ed., ACS Symposium
Series, 133, 451-466.
8. Meissner, H.P., and Kusik, C.L., 1973, Aqueous Solutions of Two or More
Strong Electrolytes - Vapor Pressures and Solubilities, Ind. Eng. Chem.
Proc. Des. Dev., 12, 205-208.
9. Nothnagel, K.H., Abrams, D.S., and Prausnitz, J.M., 1973, Generalized Corre-
lation of Fugacity Coefficients in Mixtures at Moderate Pressures, Ind.
Eng. Chem. Proc. Des. Dev., 12, 25-35.
10. Nakamura, R., Breedveld, G.J.F., and Prausnitz, J.M., 1976, Thermody-
namic Properties of Gas Mixtures Containing Polar and Nonpolar Compo-
nents, Ind. Eng. Chem. Proc. Des. Dev., 15, 557-564.
11. Haar, L., Gallagher, J.S., and Kell, G.S., 1984, NBS/NRC Steam Tables,
Hemisphere Press, Washington D.C., 320 pp.

Sol i d-Li qui d Equi l i bri a
General
Information
The solubility of solids in liquids can be described by the vant Hoff (ideal-
solubility) equation. This is sufficient for many systems where non-idealities
are small. Alternatively, solubility data, correlated as a function of tempera-
ture, may be entered directly. Precipitation of solid salts and minerals from
aqueous solutions may be calculated rigorously using PRO/II Electrolytes.
This capability is described separately in Sections 1.2.9, Electrolyte Mathemati-
cal Model, and 1.2.10, Electrolyte Thermodynamic Equations, of this manual.
vant Hoff
Equation
The simplest description of the solubility of a solid in a liquid phase is obtained
by assuming that the activity coefficient of the solute in the liquid phase is one.
The solubility is then entirely determined by the ratio of the pure solids fugacity
to its standard-state fugacity in the liquid phase, which is that of a pure sub-
cooled liquid. This ratio is one at the solutes triple point where the solubility
also becomes one. At lower temperatures, it can be calculated with fair accuracy
using the heat of melting; a more accurate estimate results if the heat capacity
change of melting is known. A full derivation of the ideal solubility (or vant
Hoff, after the Dutch chemist who first proposed it) equation is given by Praus-
nitz et al. The result is:
(1)
ln x
i

H
m
RT

T
T
t
1
1
1
]
+
C
p
R

T
t
T
1
1
1
]

C
p
R
ln
T
t
T
where:
Hm = enthalpy change of melting
Cp = heat capacity change of melting
Tt =
triple-point temperature
In practice, the more easily accessible melting temperature is usually used in-
stead of the triple-point temperature. The difference is almost always negli-
gible. The ideal-solubility equation predicts the same solubility for a given
solute regardless of solvent composition. It is therefore primarily useful for
systems where the solute and solvent are of a similar chemical nature and form
a nearly ideal solution. For example, the solubility of aromatic hydrocarbons
in benzene is well described by equation (1).
1. 2. 11
PRO/II Reference Manual Sol i d-Li qui d Equi l i bri a I-147
Tabl e 1. 2. 11-1 van t Hoff
Requi red pure component properti es Appl i cati on Gui del i nes
Triple-point
temperature (Tt)
(or melting
temperature if Tt
is not available)
Components Solute and solvent should
be of a similar chemical
nature (i.e. form a near-
ideal solution).
Enthalpy of melting
Solubility Data For systems where sufficient data exist, solid solubilities may be entered by
the user in the form of a correlation of solubility versus temperature. This
correlation has the same functional form as the vant Hoff equation:
(2)
ln x
ij
A
ij
+ B
ij

T + C
ij
ln(T)
where:
xij = the equilibrium solubility of solute i in solvent j at
temperature
For solubility of a solid solute i in a mixed solvent, theory dictates that the
mixing rule should have the following form:
(3)
ln x
i

j
Z
j
ln x
ij
In equation (3) the sum is over all solvent species, and Zj is the mole fraction
of solvent component j normalized to a solute-free basis. If the normal liq-
uid mole fractions are denoted by z, this is written as:
(4)
Z
j

z
j
1 z
i
Fill Options for
Solubility Data
In a multicomponent mixture, data may be missing for one or more of the i,j
pairs appearing in the sum in equation (3). Three options are provided for
filling in missing values of xij. The default option is to fill in missing values
with xij as calculated by equation (1), the vant Hoff equation.
Note:
When the vant Hoff equation is used as a FILL option, the Cp terms
are ignored.
The FILL = ONE option uses values of one (complete miscibility) for the sol-
utes solubility in the missing solvents. The FILL = FREE option causes the
missing solvent or solvents to be ignored in the solubility calculation. In other
words, if a solvent k is missing solubility data for the solute, the sum in equation
(3) is only taken over those solvents for which data exist, and the mole fractions
in that sum are renormalized to a k-free (as well as solute-free) basis:
I-148 Sol i d-Li qui d Equi l i bri a May 1994
(5)
Z
j

z
j
1 z
i

k
z
k
In equation (5) the sum is over all solvents k for which there are no solubility
data. Note that equation (5) is meaningless if no solvent in the mixture has
solubility data. If FILL = FREE is specified in such a case, the calculations
are defaulted to the vant Hoff equation.
Reference
Prausnitz, J.M., Lichtenthaler, R.N., and Gomes de Azevedo, E., 1986,
Molecular Thermodynamics of Fluid-Phase Equilibria, 2nd edition, Prentice-
Hall, Englewood Cliffs, NJ, Chapter 9.
PRO/II Reference Manual Sol i d-Li qui d Equi l i bri a I-149
Transport Properti es
General
Information
The following transport properties are calculated and/or used by PRO/II:
Tabl e 1. 2. 12-1: Transport Properti es
Li qui ds Vapors
Viscosity Viscosity
Thermal Conductivity Thermal Conductivity
Diffusivity
In addition, PRO/II will calculate the vapor-liquid surface tension for a
stream. Most library components include saturated vapor and liquid values
for viscosity, thermal conductivity, and surface tension as part of the stored
physical property data. Several correlations have also been included in
PRO/II which predict the above properties for hydrocarbon mixtures. Liquid
diffusivity is used by some of the unit operations but is not stored in the
component library. The transport methods are described in the sections that
follow.
With the exception of the PURE and TRAPP methods, there are no special
provisions to characterize the hydrocarbon type (paraffinic, olefinic, etc.).
While these non-characterizing methods may be used for all hydrocarbon
types, or petroleum fractions, the best accuracy is to be expected for paraf-
fins, with a degradation in accuracy for olefins or aromatics. Non-hydrocar-
bon transport properties are best represented by the properties from structure
methods discussed in Section 1.1, Component Data.
27 PRO/II Note: For more information on specifying PURE methods, see Section
27, Transport and Special Properties, of the PRO/II Keyword Input Manual.
PURE Methods The user may choose to compute transport properties as a weighted average
of pure-component values. These PURE methods (also known as LIBRARY
methods) require that the property in question be available for each compo-
nent in the mixture with the exception of petroleum pseudocomponents. For
a pseudocomponent, the property (if not supplied by the user) is calculated
using the PETRO method below. The pure-component properties at the tem-
perature of interest are combined to calculate stream average properties ac-
cording to the following mixing rules:
1. 2. 12
I-150 Transport Properti es May 1994
Tabl e 1. 2. 12-2: Stream Average Properti es
Stream Property Addi ti ve Basi s
Liquid Thermal Conductivity
m
2

i
wi 1
2
wi =Weight fraction (1)
Vapor Thermal Conductivity
m

i
yi i (MWi)
1

3

i
yi (MWi)
1

3
yi =Mole fraction (2)
Liquid Viscosity
m
i
xi i
1 3
_
,
3
xi =Mole fraction (3)
Vapor Viscosity
m

i
yi i (MWi )
1 2

i
yi (MWi)
1

2
yi =Mole fraction (4)
Surface Tension
m
i
xi i xi =Mole fraction (5)
The user may also provide individual component values as a function of tem-
perature either in tabular or equation forms.
PETRO Methods
27 PRO/II Note: For more information on specifying the PETRO methods, see Sec-
tion 27 of the PRO/II Keyword Input Manual, Transport and Special Properties.
Liquid Viscosity
The method selected for liquid viscosity is dependent on the reduced tem-
perature, which is in turn calculated by Kays rule. When the system is near
the critical point (0.98<Tr<1.0), the method developed by Letsou and Steil is
used. For the range 0.76<Tr<0.98, equations relating viscosity to reduced
temperature and acentric factors developed by Letsou and Steil (as cited in
section 9-12 in Reid, Prausnitz and Poling) are used. These methods were de-
veloped from data on simple liquid hydrocarbons.
For low temperatures in which the temperature is below the normal boiling
point, a method based on the Arrhenius relation and the Thomas equation
was developed by SimSci. This method relates liquid density at the normal
boiling point, the critical temperature, and the system temperature. The density at
the normal boiling point is estimated using the equation of Gunn and Yamada.
PRO/II Reference Manual Transport Properti es I-151
For intermediate ranges (Tb<T<0.76Tc), the Andrade equation is used to deter-
mine the viscosity, based on reference values at the normal boiling point and
a reduced temperature of 0.76. The reference values are computed by the
methods described above.
After the mixture viscosity has been estimated using one of the above methods,
it is corrected for the effects of pressure using the method of Kouzel (also given
in the API Technical Data Book, pp. 11-47, 2nd edition). The vapor pressure,
needed for this method, is estimated with the Reidel equation.
If water decant is active for the thermodynamic method, water viscosities are
taken from the component data library. A wet viscosity is then calculated
for water/hydrocarbon streams by combining the hydrocarbon and water vis-
cosities with the following mixing rule:
(6)
wet

x
aq

aq
1

3
+ x
hc

hc
1

3
_
,
3
where:
= viscosity
x = mole fraction
subscripts aq and hc refer to the aqueous and hydrocarbon portions
of the stream
References
1. Andrade, E. N., 1930, The Viscosity of Liquids, Nature, 125, 309-310.
2. Gunn, R. D., and Yamada, T., 1971, A Corresponding States Correlation of
Saturated Liquid Volume, AIChE J., 17, 1341-1345.
3. Kendall, J., and Monroe, K. P., 1917, The Viscosity of Liquids, II, The
Viscosity - Composition Curve for Ideal Liquid Mixtures, J. Amer. Chem.
Soc., 39, 1787-1802.
4. Kouzel, 1965, Hydrocarbon Proc., 44, 120.
5. Letsou, A. and Stiel, L. I., 1973, Viscosity of Saturated Nonpolar Liquids at
Elevated Pressures, AIChE J., 19, 409-411.
6. Partington, J. R., 1949, An Advanced Treatise in Physical Chemistry, 2,
Longmans, London.
7. Reid, R. C., Prausnitz, J. M., and Poling, B. E., 1987, The Properties of
Gases and Liquids, 4th edition, McGraw-Hill, New York.
8. Reidel, L., 1954, Eine Neue Universelle Dampfdrukformel, Chem. Ing. Tech.,
26, 83.
9. Thomas, L. H., 1946, The Dependence of Viscosities of Liquids on Reduced
Temperature and a Relation Between Viscosity, Density, and Chemical
Constitution, J. Chem. Soc., Part II, 573-579.
Liquid Thermal Conductivity
The method of Sato and Reidel is used to calculate liquid thermal conductivi-
ties. Figure 12A4.1 (Page 12-11) in the API Technical Data Book is used to
correct thermal conductivities for pressure effects.
If water decant is active for the thermodynamic method, water thermal conduc-
tivities are taken from the component data library. A wet thermal conductiv-
ity is then calculated for water/hydrocarbon streams by combining the
hydrocarbon and water viscosities with the following mixing rule:
(7)
wet

1
w
aq

aq
2
+ w
hc

hc
2
_
,
1

2
where:
= thermal conductivity
w = weight fraction in the liquid phase
subscripts aq and hc refer to the aqueous (water) and hydrocarbon
portions of the stream
References
1. American Petroleum Institute, 1978, Data Book, 5th edition.
2. Reidel, L., 1950, The Determination of the Thermal Conductivity and the
Specific Heat of Various Mineral Oils, Chem. Ing. Tech., 21, 349.
Surface Tension
The surface tension for hydrocarbon liquids is estimated with procedure 10A3.1
(Page 10-17) in the API Technical Data Book (3rd edition). Surface tension for
water is extracted from the component data library. Wet surface tension val-
ues for decant hydrocarbon systems are computed with the formula:
(8)
wet
x
aq

aq
+ x
hc

hc
where:
= surface tension
x = mole fraction in the liquid phase
of the stream
Vapor Viscosity
Vapor viscosities at low pressures are computed by the method of Thodos et
al. They are then corrected for pressure effects using the equation of Dean
and Stiel. Water vapor viscosities are taken from the component library.
Wet vapor viscosities for decant systems are calculated by the following
combinatorial formula:
(9)
wet

y
aq

aq
MW
aq
1

2
+ y
hc

hc
MW
hc
1

2
y
aq
MW
aq
1

2
+ y
hc
MW
hc
1

2
where:
= mole fraction in the vapor phase
of the stream
References
1. Thodos, G., and Yoon, 1970, Viscosity of Nonpolar Gaseous Mixtures
at Normal Pressures, AIChE J., 16, 300-304.
2. Dean, D.G., and Stiel, L.S., 1965, The Viscosity of Nonpolar Gas Mixtures at
Moderate and High Pressures, AIChE J., 11, 526-532.
3. Herning, F., and Zipperer, L., 1936, Calculation of the Viscosity of Technical
Gas Mixtures from the Viscosities of the Individual Gases, Gas-U. Wasser-
fach., 79, 69.
Vapor Thermal Conductivity
The Roy-Thodos method is used to determine vapor thermal conductivities.
The function of temperature used is the one that is presented by the authors
for saturated hydrocarbons. This method is corrected for pressure effects us-
ing the equations of Stiel and Thodos.
Data for water are retrieved from the component data library. Wet conduc-
tivities are predicted for water/hydrocarbon systems as follows:
(10)
wet

y
aq

aq
MW
aq
1

3
+ y
hc

hc
MW
hc
1

3
y
aq
MW
aq
1

3
+ y
hc
MW
hc
1

3
where:
y = mole fraction in the vapor phase
subscripts aq and hc refer to the aqueous and hydrocarbon
portions of the stream.
References
1. Perry, R.H., and Green, D., 1984, Perrys Chemical Engineers Handbook,
6th edition, McGraw-Hill, New York.
2. Roy, D., and Thodos, G., 1979, Thermal Conductivity of Gases, Ind.
Eng.Chem.Fundam., 9, 71-79.
3. Stiel, L.I., and Thodos, G., 1964, The Thermal Conductivity of Nonpolar Sub-
stances in the Dense Gaseous and Liquid Regions., AIChE J., 10, 26.
TRAPP
Correlation
The TRAPP method predicts viscosities and thermal conductivities for pure
hydrocarbon components and mixtures of hydrocarbons and light inorganics
for both vapor and liquid phases.
Note: Since this method does not predict surface tension, this property is com-
puted from the PETRO correlation described earlier in this section.
A brief description of the method is presented here. For additional details,
see the Ely and Hanley reference paper.
The TRAPP method uses a one-fluid conformal model coupled with the
extended corresponding-states approach developed by Leland and his co-work-
ers. Mathematically, the viscosity of a fluid mixture or component is given by:
(11)
x
(, T)
o
(
o
, T
o
)F
and the thermal conductivity is represented by:

(12) (, T)
o
(
o
, T
o
)F
(
i
, T)
where:
= viscosity
= thermal conductivity
F = a dimensional factor
=
the fluid density
subscripts x and o denote unknown and reference fluids
superscript refers to the potential or translational contribution
superscript refers to the contribution due to internal degrees
of freedom
This method is applicable to the full range of densities and temperatures, from
the dilute gas to the dense liquid. The required constants for each component
are the critical constants (Tc, Pc and Vc) and the acentric factor. The method is
currently restricted to the list of components given in Table 1.2.12-3.
Note: The authors of the TRAPP method recommend it not be used when water
is present. It should also be used with care at reduced temperatures above 0.925.
Tabl e 1. 2. 12-3: TRAPP Components (3. 3 versi ons)
Component Name ID Name Component Name ID Name
METHANE METHANE PROPYLENE PRLN
ETHANE ETHANE 1-BUTENE BUT1
PROPANE PROPANE cis-2-BUTENE BTC2
ISOBUTANE IC4 trans-2-BUTENE BTT2
n-BUTANE BUTANE ISOBUTENE IBTE
ISOPENTANE 2MB 1,3-BUTADIENE 13BD
n-PENTANE PENTANE 1-PENTENE PNT1
NEOPENTANE 22PR cis-2-PENTENE PTC2
n-HEXANE HEXANE trans-2-PENTENE PTT2
2-METHYLPENTANE 2MP 2-METHYL-1-BUTENE 2BT1
3-METHYLPENTANE 3MP 3-METHYL-1-BUTENE 3BT1
2,2-DIMETHYLBUTANE 22MB 2-METHYL-2-BUTENE 2BT2
2,3-DIMETHYLBUTANE 23MB 1-HEXENE HXE1
n-HEPTANE HEPTANE 1-HEPTENE HPT1
n-OCTANE OCTANE PROPADIENE ALEN
n-NONANE NONANE 1,2-BUTADIENE 12BD
n-DECANE DECA BENZENE BNZN
n-UNDECANE UNDC TOLUENE TOLU
n-DODECANE DDEC m-XYLENE MXYL
n-TRIDECANE TRDC o-XYLENE OXYL
n-TETRADECANE TDCN p-XYLENE PXYL
n-PENTADECANE PNDC ETHYLBENZENE EBZN
n-HEXADECANE HXDC CARBON DIOXIDE CO2
n-HEPTADECANE HPDC CARBON MONOXIDE CO
CYCLOPENTANE CP HYDROGEN H2
METHYLCYCLOPENTANE MCP HYDROGEN SULFIDE H2S
CYCLOHEXANE CH OXYGEN O2
METHYLCYCLOHEXANE MCH NITROGEN N2
ETHYLCYCLOPENTANE ECP SULFUR DIOXIDE SO2
ETHYLCYCLOHEXANE ECH WATER H2O
ETHYLENE ETLN
References
1. Leland, T. W., Robinson, J. S., and Suther G.A., 1968, Statistical
Thermodynamics of Mixtures of Molecules of Different Sizes, Trans.
Farad. Soc., 64, 1447-1460.
2. Ely, J. F., and Hanley, H. J. M., 1981, Prediction of Viscosity and Thermal
Conductivity in Hydrocarbon Mixtures-Computer Program TRAPP, Pro-
ceedings of 60th Annual Convention, Gas Processors Association.
Special Methods
for Liquid
Viscosity
SIMSCI (Twu) Correl ati on
For petroleum fractions, viscosity prediction methods are usually based on
boiling point and specific gravity. The API Technical Data Book (1978) ex-
presses the Watson correlation in a nomograph form. However, the graphi-
cal form is unsuitable for simulation purposes and cannot be extrapolated.
Abbott et. al., (1970, 1971) give a correlation which agrees with the API
data quite well but breaks down when extrapolated.
The SimSci or Twu correlation is based on a perturbation expansion method.
Here, the properties of a real system (petroleum fractions, in this case) are ex-
panded about the values of a reference system (chosen to be n-alkanes). The
kinematic viscosity of a petroleum fraction at 210 F is expressed in the fol-
lowing manner:
(13)
ln
2
+
450
T
b
_
,
ln
2
o
+
450
T
b
_
1 + 2f
2
1 2f
2
_
,
2
(14)
f
2
|x|SG 21.1141
(SG)
2
T
b
1

2
(15)
|x| |1.99873
56.7394
T
b
1

2
|
(16) SG SG SG
Similar equations for kinematic viscosity at 100 F are given below:
(17)
ln
1
+
450
T
b
_
,
ln
1
o
+
450
T
b
_
1 + 2f
1
1 2f
1
_
,
2
(18)
f
1
1.33932 |x|SG 21.1141
(SG)
2
T
b
1

2
You can then determine the relationship between viscosities at any two tem-
peratures, given the kinematic viscosity at the 2 temperatures from equations
(13-18) above and using the generalized relationship developed by Wright
(and modified by Twu), given in equations (19-22) below.
(19) lnln(Z) A + Bln (T)
(20)
Z + 0.7 + e
(1.47 1.84 0.51
2
)
(21)
B
(lnlnZ
1
lnlnZ
2
)
(lnT
1
lnT
2
)
(22) lnlnZ lnlnZ
1
+ B(lnT ln T
1
)
where:
= kinematic viscosity
References
1. Abbott, M.M., Kaufman, T.G., and Domash, L., 1971, A Correlation for
Predicting Liquid Viscosities of Petroleum Fractions, Can. J. Chem. Eng.,
49, 379.
2. Twu, C.H., 1985, Internally Consistent Correlation for Predicting Liquid Vis-
cosities of Petroleum Fractions, Ind. Eng. Chem. Proc. Des. Dev., 24, 1287.
3. Wright, W.A., 1969, An Improved Viscosity-temperature Chart for
Hydrocarbons, J. of Materials, 4, 19.
API Method
The API method used in PRO/II is very similar to the SIMSCI correlation dis-
cussed above. Instead of using one reference fluid, two reference fluids are
used. Watson plots show that the logarithmic function of viscosity at the
same boiling point temperature is a linear function of API gravity. Hence,
this relationship is extended as follows:
(23)
ln() ln(
r1
) +
API API
r1
API
r2
API
r1

ln(
r1
) ln(
r2
)
_
,
where:
= kinematic viscosity of the petroleum fraction
API = API gravity
superscripts r1,r2 refer to reference fluids 1 and 2
Since all the calculations are made at the same boiling point, equation (23)
can be simplified based on the definition of Watson characterization factor
and of API gravity as:
(24)

r1

'
r2
r1
(1

2)(K10)
where:
K = the Watson Characterization factor.
The viscosity of the reference fluid (either fluid 1 or fluid 2) can be ex-
pressed as:
(25)
ln(
r
) C
1
+
C
2
T
6
+ C
3
ln(T
b
) + C
4
T
b
+ C
5
T
6
3
+ C
6
T
b
6
where:
C1, C2, C3, C4, C5, C6 = empirical constants.
27 PRO/II Note: For more information on specifying the SIMSCI (TWU) or API
liquid viscosity methods, see Section 27, Transport and Special Properties, of
the PRO/II Keyword Input Manual.
Reference
Twu, C. H., 1986, A Generalized Method for Predicting Viscosities of
Petroleum Fractions, AIChE J., 32, 2091-2094.
Liquid Diffusivity PRO/IIs Dissolver unit requires the diffusivity of the solute in the solvent
liquid if the user does not supply mass transfer data. PRO/II can calculate
these diffusivities based on user-input data or can estimate them from the
Wilke-Chang correlation.
User-supplied Diffusivity Data
When the user supplies diffusivity data, the user must specify which compo-
nent (or components) is to be considered the solute. Diffusivity data can then
be supplied for each solute in each solvent in the following form:
(26) lnD
ij
c
1
+ c
2

T + c
3
lnT
where:
Dij = diffusivity (in m
2
/sec) of solute i in solvent j
c
1
, c
2
, c
3
= constants
For the diffusivity of a solute in a mixture of solvents, the following mixing
rule is used:
(27)
lnD
i,m

j
X
j
ln D
ij
where:
Di,m = diffusivity (in m
2
/sec) of solute i in solvent mixture
Xj = mole fraction of solvent component j on a solute-free basis
In equation (27) the sum is over all solvent components j.
Wilke-Chang Correlation
Wilke and Chang (1955) developed a method for estimating the diffusivity of
a solute at infinite dilution in a binary mixture. SimSci has adapted this
method slightly and put it in multicomponent form. The Wilke-Chang corre-
lation is of limited accuracy, but it will generally provide a diffusivity that is
good to within 50%. The correlation should not be used in cases where the
solute is water or where the solute is electrolytic. The equation is as follows:
(28)
D
i,m

7.4x10
12

j
X
j
(
j
M
j
)1
]
1

2
T
m
V
i
0.6
where:
Di,m = diffusivity (in m
2
/sec) of solute i in solvent mixture
Xj = mole fraction of solvent component j on a solute-free basis
Mj = molecular weight of solvent component j
m = viscosity of solvent mixture in centipoise
Vi = molar volume of solute i at its normal boiling point in
cm
3
/mole
The sum in equation (28) is taken over all solvents j. The factor accounts
for association of the solvent. It is taken as 2.6 for water, 1.9 for methanol,
1.5 for ethanol, 1.20 for propyl alcohols and n-butanol, and 1.0 for all other
solvents.
Reference
Wilke, C.R., and Chang, P., 1955, Correlation of Diffusion Coefficients
in Dilute Solutions, AIChE J., 1, 264-270.
Index
A
Acentric factor I-5, I-11, I-16
Activity coefficient I-39
Alcohol data package I-117
application guidelines I-54
binary interaction databank table I-119
See also NRTL
recommended ranges I-117
Alpha formulation I-71
equation forms I-72
function requirements I-71
Amine data package I-127
equilibrium reactions I-127
heat of reaction correction I-129
required components I-128
API Data Book I-62, I-64 - I-65
API gravity I-27
API liquid density I-41, I-87
Application guidelines I-45
high pressure crude units I-47
hydrofiners I-48
low pressure crude units I-46
lube oil units I-48
reformers I-48
solids I-57
solvent de-asphalting units I-48
Assay streams I-19, I-136
Associating equation of state I-80
equilibrium constant for HF association I-82
extent of association I-81
hexamerization equilibrium reaction I-82
mixture properties I-83
Redlich-Kwong cubic equations of state I-81
ASTM distillation data
See Distillation data, ASTM D1160
B
application guidelines I-50, I-52
Binary interaction parameters I-73, I-86
Blends
See Cutpoints, multiple sets
Braun K10 I-47, I-63
Bromley-Zemaitis term I-137
C
Carbon Number I-5
Chao-Seader I-60
Characterization
CAVETT I-13
Lee-Kesler I-16
SIMSCI I-9
Chemical potential I-38
Component data
library components I-4
non-library components I-3
petroleum components I-9
Component properties
extrapolation conventions I-7
fixed properties I-6
properties from structure I-8
temperature correlation equations I-7
temperature-dependent properties I-6
COSTALD liquid density I-66
application guidelines I-52 - I-53
characteristic volume I-66
Critical compressibility factor I-5
Critical pressure I-5, I-16
Critical temperature I-5, I-9 - I-10, I-16
Critical volume I-5, I-10, I-16
Cubic equations of state
See Equation-of-state methods
Curl-Pitzer I-62
Cutpoints
multiple sets I-19, I-21
secondary set I-19
D
DATAPREP I-6
Debye-Hckel constant I-137
Decanting free water
See Free water decanting
Density I-5
definition I-44
ideal I-44
PRO/II Component and Thermophysical Properties Index Idx-1
Reference Manual
Diffusivity
See Transport properties
Dimerization I-56, I-116
Dimers
See Dimerization
Dipole moment I-5
DIPPR library I-4
Distillation data
API 1963 method I-25
API 1987 method I-24
ASTM D1160 I-22
ASTM D2887 I-23
ASTM D86 I-24
Edmister-Okamoto method I-25
Dortmund modified UNIFAC, UFT2 I-104
E
Edmister-Okamoto
See Distillation data
Electrolyte mathematical model I-131
Electrolyte thermodynamics I-135
aqueous phase activities I-136
density I-144
enthalpy I-143
equilibrium constants I-135
molar volume I-144
Nakamura method I-141
Nothnagel method I-139
organic phase activities I-143
SRK method I-142
vapor-phase fugacities I-139
Electrolytes
mathematical model I-131
thermodynamics I-135
Enthalpy I-5
basis I-43
definition I-41
heat of mixing I-111
ideal I-41
ideal-gas I-16, I-143
liquid vapor I-144
solid I-143
Entropy I-41
definition I-43
ideal I-44
Equation-of-state methods I-69
alpha formulations I-71
general cubic equation of state I-69
Lee-Kesler-Plcker I-85
mixing rules I-73, I-78
Peng-Robinson I-74
Peng-Robinson Huron-Vidal I-79
Peng-Robinson Panagiotopoulos-
Reid I-76 - I-77
Redlich-Kwong I-69
Soave-Redlich-Kwong I-74
Soave-Redlich-Kwong Huron-Vidal I-79
Soave-Redlich-Kwong Kabadi-Danner I-75
Soave-Redlich-Kwong modified I-77
Soave-Redlich-Kwong Panagiotoupolos-
Reid I-76
Soave-Redlich-Kwong SimSci I-77
UNIWAALS I-83
van der Waals I-69
Equilibrium
liquid-liquid I-39 - I-40
solid-liquid I-147
vapor-liquid I-40
vapor-liquid electrolyte I-39
Erbar-modified Chao-Seader I-61
Erbar-modified Grayson-Streed I-61
Estimating binary interaction parameters I-107
azeotropic data I-107
ideal data I-107
infinite dilution data I-107
mutual solubility data I-107
F
FILL methods
See Filling in missing interaction data
See also Filling in missing solubility data
Filling in missing interaction data I-107, I-109
databank search order I-107
Filling in missing solubility data I-148
Flash point I-5
Flory-Huggins I-96
See also Liquid activity methods
Free volume modification to UNIFAC,
UNFV I-106 - I-107
Free water decanting I-88
calculation methods I-88
equation of state water solubility method I-89
kerosene water solubility method I-89
SimSci water solubility method I-89
Fugacity I-38
coefficient I-39
G
Gamma method I-111
See Enthalpy, heat of mixing
Generalized correlation methods I-58
API liquid density I-87
Braun K10 I-63
Chao-Seader I-60
COSTALD liquid density I-66
Curl-Pitzer I-62
Erbar modification to Chao-Seader I-61
Idx-2 Index May 1994
Erbar modification to Grayson-Streed I-61
Grayson-Streed I-61
IDEAL I-58
Improved Grayson-Streed I-62
J ohnson-Grayson I-64
Lee-Kesler I-64
Rackett liquid density I-65
Glycol data package I-120
binary interaction databank I-121
GPA sour water data package
See GPSWATER data package
GPSWATER data package I-125
equilibrium reactions I-125
required components I-126
Gravity data I-27
Grayson-Streed
application guidelines I-47 - I-48, I-53, I-61
Gross heating value I-5
Group interaction data I-101
free volume modified UNIFAC,
UNFV I-105 - I-107
Lyngby modified UNIFAC, UFT1 I-104
H
Hayden-OConnell fugacity I-116
dimerization equilibrium reactions I-116
Heat capacity
See Specific heat capacity
Heat of combustion I-5
Heat of formation I-16
Heat of fusion I-5
Heat of mixing I-111
See also Gamma method
See Redlich-Kister expansion
Heat of vaporization
See Latent heat of vaporization
Henrys law gas solubility I-110
application ranges I-110
Henrys constants I-110
solute components I-110
HEXAMER
See Associating equation of state
Hexamer equation of state I-80
Hexamerization I-56, I-80
See also Hexamer equation of state
Huron-Vidal SRK and PR I-79
Hydrogen deficiency number I-5
I
IDEAL and LIBRARY I-58
densities I-59
enthalpies I-59
entropies I-59
K-values I-59
Improved Grayson-Streed I-62
Ionic solutions I-56, I-137
Ionic systems
See Ionic solutions
J
J ohnson-Grayson I-64
K
K-values I-39
Kabadi-Danner SRK I-75
mixing rule I-75
L
Latent heat of vaporization I-5, I-15
Lee-Kesler
Lightends data I-29
matching I-29, I-86
Liquid activity methods I-90
Flory-Huggins I-96
UNFV I-106 - I-107
Margules I-93
modified UNIFAC, UFT3 I-105
NRTL I-98
regular solution I-95
UNIFAC I-101
UNIQUAC I-99
van Laar I-94
Wilson I-97
Liquid molar volume I-5, I-145
Liquid-liquid equilibria
See Equilibrium, liquid-liquid
LLE
See Equilibrium, liquid-liquid
Local composition I-97
Lower heating value I-5
Reference Manual
M
Margules I-93
See also Liquid activity methods
Melting temperature I-148
Molar volume of liquid
See Liquid molar volume
Molecular weight I-5
Molecular weight data I-28
API method I-29
extended API (EXTAPI) I-29
SimSci method I-29
N
Normal boiling point I-5
Normal melting point I-5
NRTLI-98
application guidelines I-54, I-56, I-98
P
Panagiotopoulos-Reid SRK and PR I-76
mixing rule I-76
Peng-Robinson I-74
application guidelines I-47 - I-48, I-50
Petroleum components
acentric factor I-9, I-13, I-16
CAVETT method I-13
critical properties I-9, I-13, I-16
Lee-Kesler method I-16
SIMSCI method I-9
Pitzer term I-137
Pollutants I-56
Poynting correction I-40, I-91
PROCESS library I-4
Pseudocomponents I-26
R
Rackett liquid density I-65
one-fluid version I-66
Rackett parameter I-5
Radius of gyration I-5
Raoults law I-59
Redlich-Kister expansion I-112
Redlich-Kwong equation I-71
Regular solution I-95
Reid vapor pressure (RVP) I-31
APICRIDE method I-31
APINAPHTHA method I-31 - I-32
ASTM D323-73 method I-31
RK1
RK2
S
SIMSCI library I-4
SimSci modified SRK and PR I-77
application guidelines I-48, I-50, I-54, I-56
mixing rule I-76
Soave-Redlich-Kwong I-74
alpha formulation I-72, I-74
Huron-Vidal modification I-79
Kabadi-Danner modifications I-75
Panagiotopoulos-Reid modification I-76
SimSci modification I-77
Soave-Redlich-Kwong SimSci I-77
Solid molar volume I-145
Solid-liquid equilibrium (SLE) I-147 - I-148
FILL options I-148
vant Hoff solubility I-147
(Hildebrand) I-5, I-12, I-16, I-95 - I-96
Sour water data package I-122
Henrys Law constants I-122
Specific gravity I-5, I-27
Specific heat capacity I-5, I-16
Surface tension
SWEQ
See Sour water data package
T
Thermal conductivity
Thermodynamic Expert System (TES) I-45
Transport properties I-150
API method I-158
diffusivity I-159
PETRO methods I-151
PURE methods I-150
surface tension I-5
thermal conductivity I-5, I-153 - I-155
TRAPP methods I-155
TWU method I-157
viscosity I-5, I-151, I-154, I-157
Wilke-Chang method I-160
Triple-point pressure I-5
Triple-point temperature I-5, I-148
True boiling point (TBP) data
cubic spline I-25
cutting into pseudocomponents I-26
probability density function (PDF) I-26
quadratic fit I-26
True vapor pressure (TVP) I-31
Truncated virial fugacity I-114
virial coefficients I-114
U
UNIFAC I-101
data estimation, FILL I-107
UNFV I-106 - I-107
modified UNIFAC, UFT3 I-105
UNIQUAC I-99
UNIWAALS
application guidelines I-55 - I-56, I-83
User-supplied solid solubility I-148
V
van der Waals area and volume I-5
van der Waals equation I-69
van Laar I-94
vant Hoff solid solubility I-147
Vapor phase fugacity I-113
equations of state I-114, I-142
Hayden-OConnell I-116
Nakamura I-141
Nothnagel I-139
truncated virial I-114
Vapor pressure I-5
Antoine equation I-15
Vapor-liquid equilibria
See Equilibrium, vapor-liquid
Viscosity
VLE
See Equilibrium, vapor-liquid
W
Water decant
Water handling methods
Watson K-factor I-27
Wilke-Chang method I-160
Wilson
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PRO/II Component

and Thermophysi cal

0.843593 0.128624 3.36159

SG = specific gravity correction

0.419869 0.505839 1.56436

(0.351K 8.953) K + 43.402

7.58 + 4.571 lnT

0.9291 1.1543K + 0.0368K

0.26105 0.59332 (4.56 9.48)10

(1kij) + (kij kji) (xi

By regressing experimental data to obtain the parameters in the modified

= lattice coordination number = 10

, Ind. Eng. Chem. Res., 26, 1372-1381.

, by first, summing the product of the reaction coeffi-

over all reactants and then, over all prod-

, using the same general procedure as used for

are obtained from equation (36), using values of Cp

(for ionic solutes)

and the thermal conductivity is represented by:

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