PRO II 8.0 Component and Thermophysical Properties - Reference Manual PDF

PRO/II 8.
0
Component and Thermophysical
Properties
Reference Manual
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BATCH MODULE
Contents
Chapter 1 Introduction
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
What is in This Manual? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
Who Should Use This Manual? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
Finding What you Need . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-2
Chapter 2 Component Data

Defined Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1
Component Libraries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1
Fixed Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-3
Temperature-dependent Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-3
Properties From Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-5
Petroleum Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-5
Property Generation SIMSCI Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-6
Property Generation CAVETT Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-11
Property Generation Lee-Kesler Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-14
Assay Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-16
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-16
Interconversion of Distillation Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-20
Cutting TBP Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-25
Generating Pseudocomponent Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-30
Vapor Pressure Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-31
Chapter 3 Thermodynamic Methods

Basic Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-1
Phase Equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-2
Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-5
Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-8
Application Guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-10
Refinery and Gas Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-10
Natural Gas Processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-13
PRO/II Component and Thermophysical Properties Reference Manual 1

Chemical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-19
Generalized Correlation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-23
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-23
Ideal (IDEAL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-23
Chao-Seader (CS). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-25
Grayson-Streed (GS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-26
Erbar Modification to Chao-Seader (CSE) and Grayson-Streed (GSE). . . . . . . . . 3-27
Improved Grayson-Streed (IGS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-27
Curl-Pitzer (CP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-27
Johnson-Grayson (JG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-29
Lee-Kesler (LK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-30
API . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-30
Rackett . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-31
COSTALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-32
Equations of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-35
General Cubic Equation of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-35
Alpha Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-37
Mixing Rules (for Equations of State) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-41
Soave-Redlich Kwong (SRK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-42
Peng-Robinson (PR). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-42
Soave-Redlich-Kwong Kabadi-Danner (SRKKD). . . . . . . . . . . . . . . . . . . . . . . . . 3-42
Soave-Redlich-Kwong Panagiotopoulos-Reid (SRKP) and Peng-Robinson
Panagiotopoulos-Reid (PRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-44
Soave-Redlich-Kwong Modified (SRKM) and Peng-Robinson Modified (PRM) 3-45
Soave-Redlich-Kwong SimSci (SRKS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-45
Soave-Redlich-Kwong Huron-Vidal (SRKH) and Peng-Robinson Huron-Vidal
(PRH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-47
HEXAMER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-49
UNIWAALS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-52
Benedict-Webb-Rubin-Starling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-53
Lee-Kesler-Plcker (LKP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-54
Twu-Bluck-Coon( TBC). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-56
Free Water Decant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-59
Calculation Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-59
Liquid Activity Coefficient Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-62
Margules Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-65
2 Contents
van Laar Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-66
Regular Solution Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-67
Flory-Huggins Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-68
Wilson Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-69
NRTL Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-71
UNIQUAC Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-72
UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-74
Modifications to UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-78
Fill Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-81
Henry's Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-84
Heat of Mixing Calculations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-85
Vapor Phase Fugacities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-88
Equations of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-89
Truncated Virial Equation of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-89
Hayden-O'Connell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-91
Special Packages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-93
Alcohol Package (ALCOHOL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-93
Glycol Package (GLYCOL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-95
Sour Package (SOUR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-98
GPA Sour Water Package (GPSWATER) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-101
Amine Package (AMINE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-103
Electrolyte Mathematical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-107
Discussion of Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-107
Modeling Example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-109
Electrolyte Thermodynamic Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-112
Thermodynamic Framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-112
Equilibrium Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-112
Aqueous Phase Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-114
Vapor Phase Fugacities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-118
Organic Phase Activities. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-122
Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-123
Aqueous Liquid Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-124
Molar Volume and Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-125
Aqueous Liquid Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-125
Solid-Liquid Equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-128
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-128
PRO/II Component and Thermophysical Properties Reference Manual 3

van't Hoff Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-128
Solubility Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-129
Fill Options for Solubility Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-130
Transport Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-131
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-131
PURE Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-131
Liquid Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-134
TRAPP Correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-137
Special Methods for Liquid Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-139
Liquid Diffusivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-142
Index
4 Contents
Chapter 1
Introduction
General Information
The PRO/II Unit Operations Reference Help provides details on the
basic equations and calculation techniques used in the PRO/II simu-
lation program and the PROVISION Graphical User Interface. It is
intended as a reference source for the background behind the vari-
ous PRO/II calculation methods.
What is in This Manual?

This on-line manual contains the correlations and methods used to
calculate thermodynamic and physical properties, such as the
Soave-Redlich-Kwong (SRK) cubic equation of state for phase
equilibria. This volume also contains information on the definition
of pure components and petroleum fractions.
For each method described, the basic equations are presented, and
appropriate references provided for details on their derivation. Gen-
eral application guidelines are provided, and, for many of the meth-
ods, hints to aid solution are supplied.
Who Should Use This Manual?

For novice, average, and expert users of PRO/II, this on-line man-
ual provides a good overview of the calculation modules used to
simulate a single unit operation or a complete chemical process or
plant. Expert users can find additional details on the theory pre-
sented in the numerous references cited for each topic. For the nov-
ice to average user, general references are also provided on the
topics discussed, e.g., to standard textbooks.
Specific details concerning the data entry steps required for the
PROVISION Graphical User Interface may be found in the main
PRO/II Help. Detailed sample problems are provided in the PRO/II
Application Briefs Manual, in the \USER\APPLIB\ directory, and
in the PRO/II Casebooks.
PRO/II Component and Thermophysical Properties Reference Manual 1-1

Finding What you Need
A Table of Contents is provided for this on-line manual. Cross-ref-
erences and hypertext links are provided to the appropriate sections
of the main PRO/II Help to assist in preparing and entering the
required input data.
1-2 Introduction
Chapter 2
Component Data
PRO/II allows the user to specify pure-component physical prop-

erty data for a given simulation. Pure component data are usually
associated with either a predefined component in a data library, a
user-defined (non-library) component, or a petroleum pseudocom-
ponent.
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.
Defined Components
Component Libraries
Table 2-1 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 property
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 because they are usually covered by contractual
agreements which disallow their display in a simulation.

Reference
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, spon-
sored by the American Institute of Chemical Engineers.
Table 2-1: PRO/II Library Component Properties
Fixed Properties and Constants Temperature-dependent
Properties
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
2-2 Component Data

Table 2-1: PRO/II Library Component Properties
Solubility Parameter
Specific Gravity
Triple Point Temperature
Triple Point Pressure
UNIFAC Structure
van der Waals Area and Volume
Fixed Properties
Specific gravities of permanent gases are often given relative to
air, without any annotations in the output, and liquid molar vol-
umes can be extrapolated from a condition very different from
77 F (25 C), if the component doesn't 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 Key-
word Input Manual. The equations that are typically used to repre-
sent a property are listed in Table 2-2. While temperature-dependent
library properties are fitted and are usually very accurate at satu-
rated, subcritical conditions, caution must be used in the super-
heated 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 2-2,
based on the property, for extrapolation of the temperature-depen-
dent correlations
Table 2-2: PRO/II Temperature-dependent Property Equations and

Extrapolation Conventions
Temperature- Recommended Extrapolation
dependent Equations Method
Property
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

Table 2-2: PRO/II Temperature-dependent Property Equations and
Extrapolation Conventions
Enthalpy of 4, 15, 36, 43 Prop. vs. T
Vaporization
Saturated Liquid 1, 42, 35 Prop. vs. T
Enthalpy
Liquid Viscosity 13, 20, 21 ln(Prop.) vs. 1/T
Vapor Viscosity 1, 19, 26, 27 Prop. vs. T
Liquid Thermal 1, 4, 34 Prop. vs. T
Conductivity
Vapor Thermal 1, 19, 33 Prop. vs. T
Conductivity
Surface Tension 1, 15, 30 Prop. vs. T
Solid Thermal 1 Prop. vs. T
Conductivity
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 sub-
sets of the available coefficients with these equations corresponding
to the more traditional equations. Table 2-3 gives some examples of
this mapping.
Table 2-3: PRO/II Vapor Pressure Equations
Common Equation 20 / 21 Coefficients
Vapor
Pressure
Equations (#) C1 C2 C3 C4 C5 C6 C7
Clapeyron (20 x x
or 21)
Antoine (21) x x x
Riedel (20) x x x x
Frost-Kalkwarf x x x x
(21)
Reidel-Plank- x x x x
Miller (20)
2-4 Component Data

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 func-
tional groups for both an alcohol and an alcohol amine.
Petroleum Components
General Information
Petroleum components (often called pseudocomponents) are either
defined on a one-by-one basis on PETROLEUM statements or gen-
erated from one or more streams given in terms of assay data. The
processing of assays is described in Assay Processing section. Each
individual pseudocomponent 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 key-
word). 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, SIMSCI, and Lee-Kesler methods. The
Cavett methods developed in 1962 have been the default in all ver-
sions of PRO/II up to and including the 3.5 series. The SIMSCI
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
Critical Properties and Acentric Factor
The SIMSCI characterization method was developed by Twu in
1984. It expresses the critical properties (and molecular weight) of
hydrocarbon components as a function of NBP and specific gravity.
The correlation is expressed as a perturbation about a reference sys-
tem of normal alkanes. The critical temperature (in degrees Rank-
ine) is given by:
(1)
(2)
(3)
(4)
(5)
where:
SG =specific gravity
Tb = normal boiling point, degrees Rankine
= 1 - Tb / Tc
SG = specific gravity correction
f = correction factor
SG = specific gravity
subscript T refers to the temperature
subscript c refers to the critical conditions
superscript refers to the reference system
2-6 Component Data

The critical volume (in cubic feet per pound mole) and the critical
pressure (in psia) are given by similar expressions:
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
where:
V = molar volume, ft3/lbmole
P = pressure, psia
subscripts V and P refer to the volume and pressure
The acentric factor for the SIMSCI method is estimated with the use
of a generalized Frost-Kalkwarf vapor equation developed at Sim-
Sci. The equation is given by:
(14)
where:

A1 to A7 = constants given in Table 2-4
PR = reduced pressure (P/Pc)
TR = reduced temperature (T/Tc),
= a parameter evaluated at the NBP and given by:
the NBP and given by:
(15)
where:
subscripts R,b indicate reduced properties evaluated at the
normal boiling point
Functions and are given by:
(16)
(17)
The values of the seven constants in these equations are shown in

Table 2-4.
Table 2-4: Values of
Constants for Equations (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.
2-8 Component Data

(18)
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)
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.
The ideal-gas enthalpy (needed for equation-of-state calculations) is
calculated 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 variety of ideal-gas heat capacity data for
hydrocarbons from the API 44 project and other sources. The equa-
tion (which produces enthalpies in Btu/lb and uses temperatures in
degrees Rankine) is as follows:
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
(28)
(29)

(30)
The Watson characterization factor, K, is defined as:
(31)
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 liquid 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 refer-
ence 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 also is calculated from equation 14, and
then is related to the vapor pressure using the Clausius-Clapyron
equation. Saturated liquid enthalpy 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 com-
puted by applying the Rackett equation (see Section - Generalized
Correlation Methods) to saturated temperature and pressure condi-
tions as predicted from the vapor-pressure equation-14.
Property Generation CAVETT Method

Optionally, the user may choose to compute critical properties from

the methods developed in 1962 by Cavett. This option is called the
CAVETT method. The equations are:
2-10 Component Data

(32)
Tc = 768.0712 + 1.7133693(Tb ) 0.0010834(Tb ) 2 0.008921258(Tb )( API )

+ 3.8890584 x10 7 (Tb 3 ) + 5.309492 x10 6 (Tb 2 )( API ) + 3.27116 x10 8 (Tb xAPI ) 2
(33)
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 acen-
tric factor is computed by a method due to Edmister (1958):
(34)
In equation 2-34, Pc is in atmospheres. Finally, the critical volume
is estimated from the following equation:
(35)

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 follow-
ing equations:
(36)

(37)
(38)
(39)
(40)
(41)
(42)
(43)
(44)
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)
(46)
2-12 Component Data

(47)
Temperatures (including the critical temperature Tc and normal
boiling point Tb) are in degrees Rankine.
The saturated liquid density (in lb/ft3) is computed as follows:
(48)
(49)
(50)
(51)
where:
= 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
combination of the Watson equation (Watson, 1943, Thek and Stiel,
1966), for the temperature variation of the heat of vaporization, and
the expression of Kistiakowsky (1923), for the heat of vaporization
at the normal boiling point:
(52)
(53)
The critical temperature Tc, normal boiling point Tb, and tempera-
ture 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: Gener-
alized Correlation Methods. A constant is added so that the satu-
rated liquid enthalpy is zero at 0 C.

Property Generation Lee-Kesler Method
Kesler and Lee used the following equations in 1976 to correlate
critical temperatures and critical pressures of hydrocarbons:
(54)
(55)
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)
where:
subscripts R,b indicate reduced properties evaluated at the normal
boiling point
The critical volume is then estimated from the following equation:
(57)

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.
2-14 Component Data

Ideal-gas enthalpies (in Btu/lb-mole) are computed by integrating
the following equation for the ideal-gas heat capacity:
(58)
The factor CF is given by:
(59)
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 sat-
urated 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 vaporization are all calculated by the methods used for
CAVETT characterization, as described in the previous section.
Reference
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 Calcula-
tions - Vapor-Liquid Equilibria, 27th Mid-year Meeting of
the API Division of Refining, 42[III], 351-357.
3 Edmister, W.C., 1958, Applied Hydrocarbon Thermody-
namics, 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 Thermo-
dynamic Correlation Based on Three-Parameter Corre-
sponding 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.
Assay Processing
General Information
Hydrocarbon streams may be defined in terms of laboratory assay
data. Typically, such an assay would consist of distillation data
(TBP, ASTM D86, ASTM D1160, or ASTM D2887), gravity data
(an average gravity and possibly a gravity curve), and perhaps data
for molecular weight, lightends components, 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 pseudocom-
ponents which are then used to represent the composition of each
assay stream.The process by which assay data are converted to
pseudocomponents can be analyzed in terms of several distinct
steps. Before each of these is examined in detail, 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 default set of cutpoints that PRO/II provides). These cut-
points define the (atmospheric) boiling ranges that will ulti-
mately correspond to each pseudocomponent. Multiple
cutpoint sets (also known as blends) may also be defined to bet-
ter 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 program "cuts" each curve to determine what percent-
2-16 Component Data

age 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 boil-
ing 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 combined 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 (critical
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 pseudocomponents and their subsequent pro-
cessing by the simulator is outside the scope of this chapter but
will be covered in a later document.
Cutpoint Sets (Blends)

Defining Cutpoints
In any simulation, there is always a "primary" cutpoint set, which
defaults as shown in Table 2-5.
Table 2-5: Primary TBP Cutpoint Set
Number of Width percut, F
TBP Range, F Components
100-800 28 25
800-1200 8 50
1200-1600 4 100
The primary cutpoints shown in Table 2-5 may be overridden by

supplying 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 primary cut-

point set will be the default. Each cutpoint set (if it is actually used
by one or more streams) will produce its own set of pseudocompo-
nents for use in the flowsheet.
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 explic-
itly 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 defined, a new blend with
that name is created using the same cutpoints as the primary cut-
point set. The user may also specify that a stream use a certain set of
cutpoints but not contribute to the blended properties of the
pseudocomponents generated from that set (this might be appropri-
ate 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 blending. The default is
for the stream to be included in the blending for the purposes of
pseudocomponent property generation; this is called the BLEND
option. It is not allowed for the XBLEND option to be used on all
streams associated 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:
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, suppose the following streams
(where extraneous information like the initial conditions is not
shown) are given:
Table 2-6: Blending Example
Stream Blend Option Blend Name
S1 none given none given
(defaulted to BLEND) (defaulted to A1)
S2 XBLEND none given
(defaulted to A1)
S3 XBLEND A1
S4 BLEND A2
S5 BLEND B1
2-18 Component Data

Table 2-6: Blending Example
S6 XBLEND B1
S7 BLEND B2
Streams S1 and S2 will use the pseudocomponents defined by sec-

ondary cutpoint set A1, since it is the default. S3 will also use A1's
pseudocomponents since it is specified directly. The pseudocompo-
nents 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 defined 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 S5's cuts will be used to determine the
properties of the pseudocomponents in blend B1. Finally, stream S7
will use another new blend, B2, also with the cutpoints from the pri-
mary 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.
Application Considerations
The selection of cutpoints is an important consideration in the simu-
lation of hydrocarbon processing systems. Too few cuts can result
in poor representation of yields and stream properties when distilla-
tion 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 unnecessarily. It is wise to
examine the cut definition for each problem in light of simulation
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" functional-
ity is useful when different portions of a flowsheet are best repre-
sented 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 aromatic
stream (producing pseudocomponents with properties characteristic
of aromatics) and a paraffinic stream feeding into the same flow-
sheet. The extra detail and accuracy possible with this feature must

be balanced against the increase in CPU time caused by the
increased number of pseudocomponents.
Interconversion of Distillation Curves

Types of Distillation Curves
Assays of hydrocarbon streams are represented by distillation
curves. A distillation curve represents the amount of a fluid sample
that is vaporized as the temperature of the sample is raised. The
temperature where the first vaporization takes place is referred to as
the initial point (IP), and the temperature at which the last liquid
vaporizes is called the end point (EP). Each data point represents a
cumulative portion (usually represented as volume percent) 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, rigor-
ous 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.
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 specifica-
tions are given in volume 5 (Petroleum Products and Lubricants) of
the Annual Book of ASTM Standards.
Conversion 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 tempera-
2-20 Component Data

ture given the normal boiling point, but the same equations may
be solved to yield a normal boiling temperature given the boil-
ing temperature at another pressure. The equations used are as
follows:
(1)
(2)
(3)
where:
P* = vapor pressure in mm Hg at temperature T (in degrees Rank-
ine)
The parameter X is defined by:
(4)
where:
Tb = boiling point (in degrees Rankine) at a pressure of 760 mm
Hg
For conversions where neither pressure is 760 mm Hg, the conver-
sion may be made by applying the above equations twice in succes-
sion, 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)
where:
D86 and SD = the ASTM D86 and ASTM D2887 temperatures in
degrees Rankine at each volume percent (for D86) and the corre-
sponding weight percent (for SD), and a, b, and c are constants
varying with percent distilled according toTable 2-7.
Table 2-7: Values of Constants a, b, c

Percent
Distilled 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
95 1.9073 0.9007 0.0625
The parameter F in equation 2-64 is calculated by the following

equation:
(6)
where:
SD10% and SD50% = D2887 temperatures in degrees Rankine at
the 10% and 50% points, respectively
2-22 Component Data

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-Oka-
moto correlation. In addition, a correction 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)
where:
= the corrected and observed temperatures, respec-
tively, 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)
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)
where a and b are constants varying with percent of liquid sample
distilled as given in Table 2-8.
Table 2-8: Values of Constants a, b

Percent Distilled 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
95 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 corre-
lation has been converted to equation form by SimSci.
c) Conversion of D86 Curves with Edmister-Okamoto Method

Edmister and Okamoto (1969) 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 equa-
tions by SimSci) is used for conversion of D86 to TBP curves.
Cutting TBP Curves

Fitting of Distillation Curves
Before a curve is cut into pseudocomponents, the distillation data
must be fitted 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 cubic spline function is used to fit all given volume per-
cents 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 distribu-
2-24 Component Data

tion function to extrapolate to the 0.01% and 99.99% points, respec-
tively. If only two points are supplied, the entire curve is defined by
the distribution function fit. This extrapolation feature is particu-
larly valuable when extrapolating heavy ends distillations which
often terminate well below 50 volume percent. This method in gen-
eral 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 propa-
gate throughout the entire length of the curve. Should this happen,
the input data should be checked for validity.
The quadratic fit method (known as the QUADRATIC option) pro-
vides a successive 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 differences between
the curve and the input data. If desired, the curve may be con-
strained to pass through either or both of the initial point and end
point. The PDF method is recommended whenever it is suspected
that the distillation 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 section. That is because most of the conversion proce-
dures work by doing the conversion at a fixed set of volume per-
cents, which must be obtained by interpolation 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 define the percent of the stream's vol-
ume that is assigned to the pseudocomponent defined by the inter-
val between two adjacent cutpoints. For example, using the default
set of cutpoints shown in Table 2-5, the first pseudocomponent
would contain all material boiling between 100 F and 125 F, the
second would contain the material boiling between 125 F and 150 F,

and so forth. Material boiling 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 distillation 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 vol-
ume-fraction average (or, in rare cases where TBP, D86, or D1160
distillations are entered on a weight basis, as a weight-fraction aver-
age) 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 2.1 for a fictitious
assay with an IP of 90 F being cut according to the default cutpoint
set (Table 2-5); for simplicity only the first ten percent of the curve
is shown. In addition 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 integrating 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 similar man-
ner.
2-26 Component Data

Figure 2.1:Cutting TBP Curves
Gravity Data
PRO/II requires the user to enter an average gravity (either as a Spe-
cific 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 grav-
ity 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
estimate of the 100% point gravity value and letting the program
normalize the curve, particularly when gravity data are available to
80% or beyond.
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 WATSONK method. For a pure component, the
Watson K-factor is defined by the following equation:
(10)

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 boiling point computed from the
distillation curve. The gravity curve is generated by assuming a
constant value of the Watson K, applying equation (69) to each cut
to get a gravity, averaging these values, and then adjusting the
assumed 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 prima-
rily for compatibility with older versions. It is similar to the pre-
ferred 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 incorrect. Hence, for truly accu-
rate 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 pro-
gram.
The user may supply a molecular weight curve, which is quadrati-
cally interpolated and extrapolated to cover the entire range of
pseudocomponents. Optionally, the user may also supply an aver-
age 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 molecular weight curve
is normalized to match the given average.
2-28 Component Data

If no molecular-weight data are supplied, the molecular weights are
estimated; the default method is a proprietary modification (known
as the SIMSCI method) of the method developed by Twu (1984).
This method is a perturbation expansion with the normal alkanes as
a reference fluid.
Twu's 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)
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 accu-
rate 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. Typically, 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 compo-
nents 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 2.2 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 por-
tion of the cut encompassing that point) are discarded.
Figure 2.2: 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 light-
ends components can be normalized 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 pro-
duce average properties for the pseudocomponents from each cut-
point 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
2-30 Component Data

the above totals, the average molecular weight and gravity are cal-
culated 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 pseudocompo-
nent, 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
Petroleum Components section.
Vapor Pressure Calculations

While not a part of the program's 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 allows 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.
True Vapor Pressure

The TVP of a stream is defined as the bubble-point pressure at a
given reference temperature. By default, that reference temperature
is 100 F, but this may be overridden by the user. The user may spec-
ify a specific thermodynamic system to be used in performing all
TVP calculations in the flowsheet; by default, the calculation for a
stream is performed using the thermodynamic system used to gen-
erate that stream.
Reid Vapor Pressure (RVP) Calculations

The RVP laboratory procedure provides an inexpensive and repro-
ducible measurement correlating to the vapor pressure of a fluid.
The measured RVP is usually 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 pres-
sure is a rough measure of the true vapor pressure. Six different cal-
culation methods are available. 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 sys-
tem 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 converted to equation form by
Simsci. This method is the default for PRO/II's RVP calculations. It
is useful for many gasolines and other finished petroleum products,
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 func-
tion of the TVP and the slope of the D86 curve at the 10% point.
The graphical data have been converted to equation form by Sim-
Sci. It is primarily intended for crude oils.
The ASTM D323-82 method (known as the D323 method) simu-
lates a standard 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 (corresponding 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 available for compatibility with earlier versions of the program.
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 simu-
lating this method is identical to that for D323, except that no water
is added to the mixture. Air should be in the component 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 measured. In the
simulator, this is accomplished by flashing, at constant volume, a
mixture of 1 part sample (at 33 F and 1 atm) and 4 parts air (at the
2-32 Component Data

near-vacuum conditions of 0.01 psia and 100 F). The resulting total
pressure is then converted to a dry vapor pressure equivalent
(DVPE) using the following equation:
(12)
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 com-
ponent 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 com-
ponents rather than as pseudocomponents; oxygenated compounds
blended into gasolines should also be represented as defined com-
ponents rather than as part of an assay. It is also important to apply a
thermodynamic method that is appropriate for the stream in ques-
tion (see section - 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 SimSci alpha formulation
and one of the advanced mixing rules (see section - Equations of
State). It is important to have binary interaction parameters between
the oxygenates and the hydrocarbon components of the system.
PRO/II's 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 simula-
tion may not be identical to that of the experimental sample.
One of the less appreciated effects in experimental measurements is
the presence 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, lowering 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. There-
fore, a "wet" test performed with air that was not dry would be
expected to give results intermediate between PRO/II's D323 and
D4953 calculations. The results from the D5191 method (both in
terms of the experimental and calculated numbers) should in gen-
eral 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 procedure applied to that stream. Secondary consider-
ations include limitations of the individual methods. The API-
NAPHTHA and APICRUDE methods are good only for
hydrocarbon naphtha and crude streams, respectively. The D323
method (and its obsolete predecessor, P323) is intended for hydro-
carbon 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.
Reference
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, Lubri-
cants, and Fossil Fuels), ASTM, Philadelphia, PA (issued
annually).
3 Edmister, W.C., and Okamoto, K.K., 1959, Applied Hydro-
carbon Thermodynamics, Part 12: Equilibrium Flash
Vaporization Calculations for Petroleum Fractions, Petro-
leum 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.
2-34 Component Data

Chapter 3
Thermodynamic 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-O'Connell
Method for dimerizing species,
Special methods for calculating the properties of specific sys-
tems of components such as alcohols, amines, glycols, and sour
water systems.
Basic Principles
General Information
When modeling a single chemical process, or 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 and vapor phase enthalpies.
Liquid and vapor phase entropies.
Liquid 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 equilib-
rium for a multicomponent system, the temperature, pressure, and
chemical potential of component i is the same in every phase, i.e.:
(1)
(2)
(3)
where:
T = system temperature
P = system pressure
= the chemical potential
, , ..., represent the phases
The fugacity of a substance is then defined as:
(4)
where:
= fugacity of component i
= standard state fugacity of component i at T, P
= standard state chemical potential of component i at T, P
It follows from (3) and (4) that the fugacities in each phase must
also be equal:
(5)
The fugacity of a substance can be visualized as a "corrected partial
pressure" such that the fugacity of a component in an ideal-gas mix-
ture is equal to the component partial pressure.
For vapor-liquid equilibrium calculations, the ratio of the mole frac-
tion of a component in the vapor phase to that in the liquid phase is
defined as the K-value:
3-2 Thermodynamic Methods

(6)
where:
= K-value, or equilibrium ratio
= mole fraction in the vapor phase
= mole fraction in the liquid phase
For liquid-liquid equilibria, a corresponding equilibrium ratio or
distribution coefficient is defined:
(7)
where:
= liquid-liquid distribution coefficient

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

If a liquid activity coefficient method is used in the liquid phase cal-
culation, then the activity coefficient of the liquid phase can be
related to the liquid fugacity by the following relationship:
(9)
where:
= liquid-phase activity coefficient

= standard state fugacity of pure liquid i
With this definition of liquid fugacity, iL 1 as xi 1. The stan

dard state fugacity is as follows:
(10)
where:
= saturated vapor pressure of component i at T

R = gas constant
= liquid molar volume of component i at T and P
= fugacity coefficient of pure component i at T and Pisat
Equation (10) provides two correction factors for the pure liquid
fugacity. The fugacity coefficient, , corrects for deviations of
the saturated vapor from ideal-gas behavior. The exponential cor-
rection factor, known as the Poynting correction factor, corrects for
the effect of pressure on the liquid fugacity. The Poynting correc-
tion factor is usually negligible for low and moderate pressures.
Combining equations (6), (8), and (9) yields:
(11)
Combining equations (7) and (9) yields:
(12)
If an equation of state is applied to both vapor and liquid phases, the
vapor-liquid K-values can be written as:
(13)
The liquid-liquid equilibria can be written as:
(14)
Equations (11), (12), (13), and (14) are used to calculate the distri-
bution 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 applicable over a wide range
of densities, from near-zero density for gases to high liquid densi-
ties, using constants obtained from pure-component data. Equations
of state are not very accurate for nonideal systems unless combined
with component mixing rules and alpha formulations (see Section,
Equations of State) appropriate for those components.
Equation (11) may be solved by using equation-of-state methods to
calculate vapor fugacities combined with liquid activity methods to
compute liquid activity coefficients (see Section, Liquid Activity
Methods). Liquid activity methods are most often used to describe
the behavior of strongly nonideal mixtures.
Reference
1 Prausnitz, J. M., Lichtenthaler, R. N., and Gomes de Aze-

vedo, E., 1986, Molecular Thermodynamics of Fluid-Phase
Equilibria, 2nd Ed., Prentice-Hall, N.Y.
2 Sandler, S. I., 1989, Chemical and Engineering Thermody-
namics, 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 Ther-
modynamics of Nonelectrolyte Solutions: With Applica-
tions to Phase Equilibria, McGraw-Hill, New York.
Enthalpy
The enthalpy of a system, H, is defined in terms of the energy of the
system, U as follows:
(15)
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 sys-
tem is related to the volume by:
(16)
The enthalpy of the system is then given by:
The enthalpy of the system is then given by:
(17)
where:
H* = mixture ideal gas enthalpy =
= molar enthalpy of ideal gas i at temperature T
z = compressibility factor PV/nTRT
PRO/II provides two distinct approaches to the calculation of
enthalpy. For the majority of thermodynamic systems of methods,
enthalpy is calculated as a departure 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 corresponding 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 corre-
lates saturated-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 become indistinguishable.
Note: The normal boiling point of a library component typically

occurs when Tr is approximately equal to 0.7.
In general, the use of liquid activity coefficient models is not rec-
ommended for system pressures above 1000 kPA. Below these con-
ditions, the use of LIBRARY enthalpy methods will not introduce
significant errors provided that the system temperature is below the
critical temperatures of all components present in significant quan-
tities. 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 Henry's Law constant.
However, the problem of adding the supercritical components' con-
tribution to the liquid enthalpies remains. For the liquid phase con-
tribution, PRO/II extrapolates the component's saturated liquid
enthalpy curve linearly from the critical temperature.Above the crit-
ical this extrapolation uses the slope of the library enthalpy tangent
to the liquid saturation curve at the normal boiling point. At temper-
atures 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 nor-
mal boiling point temperature.
Note: At temperatures near Tc, the enthalpy of the saturated vapor

for a pure component 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 sat-
uration 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 enthalpies 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 activity 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

nonideality, 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 equations using an alpha formulation
which correctly predicts pure component vapor 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 saturation 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 equiva-
lent results as adding the latent heat to zero-liquid enthalpy. For
components that are supercritical at 273.15 K, using an alpha for-
mulation 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)
and
(19)
where:
= fugacity coefficient of mixture
= reference pressure of 1 atmosphere
S* = mixture ideal-gas entropy
= molar entropy of ideal gas i
ni = moles of component i
xi = mole fraction of component i
The ideal molar entropy is related to the ideal molar enthalpy by:

(20)
where:
= reference temperature, 1 degree Rankine in PRO/II

= 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 calcu-
lated in PRO/II using either an equation of state method such as
SRKM, or a generalized correlation method such as Curl-Pitzer.
Density
Cubic equation-of-state methods are generally not very accurate in
predicting 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, Generalized Correlation Methods.
Vapor densities are computed in PRO/II using the following formu-
lae:
(21)
(22)
where:
= 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.

Application Guidelines
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 application. 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 most thermodynamic methods, the
PRO/II databanks contain adjustable binary parameters obtained
from fitting published experimental and/or plant data. The thermo-
dynamic method chosen should ideally be used only in the tempera-
ture and pressure ranges at which the parameters were regressed.
Ideally, for each simulation, actual experimental or plant data
should be regressed in order to obtain the best interaction parame-
ters 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 Casebooks
PRO/II Application Briefs Manual
These show how PRO/II is used to simulate many refinery, chemi-
cal, and petrochemical processing applications using the thermody-
namic methods appropriate to each system.
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 fraction-
ators, 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 %
light ends. Moreover, the petroleum fractions present in the feed
exhibit nearly ideal behavior. For these units, the characterization of
the petroleum fractions is far more important than the thermody-
namic method used. The user should try different assay and charac-
terization 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, how-
ever, provide only gross estimates for the K-values for H2, and is
not recommended for streams containing 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 pre-defined
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 temperatures of less than 0.6. This is the lower limit of
the Curl-Pitzer enthalpy method. For these units, therefore, substi-
tuting the Lee-Kesler (LK) method for Curl-Pitzer enthalpies may
improve the results.
In addition, the top of many of these low pressure units often con-
tain significant 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.
Table 3-1: 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.

Table 3-1: Methods Recommended for Low Pressure
Crude Systems
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 important than the thermodynamic method used.
The user should again try different assay and characterization meth-
ods 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 hydrogen deficient than are crude fractions. Since most char-
acterization correlations are derived from crude petroleum data, it is
expected that the results will be less accurate than for crude frac-
tions.
Table 3-2: Methods Recommended for High 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 vacuum
towers.
SRK/PR Provides better results when light ends dominate.
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 con-
tain extensive binary interaction parameter data for component
pairs involving hydrogen.
Table 3-3: Methods Recommended for Reformers and

Hydrofiners
GS/GSE/IGS Quicker but generally less accurate than SRK or PR,
especially for predicting the hydrogen content of the
liquid phase.

Table 3-3: Methods Recommended for Reformers and
Hydrofiners
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.
These methods provide results 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.
Lube Oil and Solvent De-asphalting Units

These units contain streams with nonideal components such as H2S
and mercaptans. The SimSci modified SRK or PR methods, SRKM
or PRM, are recommended, but only if user-supplied binary interac-
tion 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 methods are recom-
mended.
Table 3-4: Methods Recommended for Lube Oil and

Solvent
De-asphalting Units
SRKM/ Recommended when user-supplied binary interac-
PRM tion 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 hydrocarbon components. Natural gas streams may be
treated by a number of methods, e.g., to sweeten using amines, or to
dehydrate using glycol.
For natural gas systems containing less than 5% N2, CO2, or H2S,
but no polar components, SRK, PR, or BWRS methods provide
excellent answers. The SRK and PR binary interaction parameters
between these lower molecular weight molecules and other compo-
nents are estimated by correlations based on the molecular weight

of the hydrogen molecule. For small amounts of these components,
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 constraints, and so does not extrapolate well into
the critical region.
For natural gas systems containing more than 5% N2, CO2, or H2S,
but no polar components, equation-of-state methods such as SRK or
PR are still recommended, although the binary parameters esti-
mated by molecular weight correlations may not produce the best
results. The user should provide binary interaction parameters for
component pairs involving these lower molecular weight compo-
nents if possible.
For natural gas systems containing water at low pressures, equa-
tion-of-state methods such as SRK or PR may be used, along with
the default water decant option, to predict the behavior of these sys-
tems.
Table 3-5: Methods Recommended for Natural Gas

Systems
SRK/PR/ Recommended for most natural gas and low pres-
BWRS sure natural gas + water systems
SRKKD Recommended for high pressure natural gas +
water systems
SRKM/ Recommended for natural gas + polar components
PRM
/SRKS
For these systems at high pressures, where the solubility of hydro-
carbon in water is significant, the default water decant option,
which predicts a pure water phase, is unacceptable. In this case,
equation-of-state methods containing 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 interac-
tion 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.

For natural gas systems containing polar components such as meth-
anol, the SRKM, PRM, or SRKS methods are recommended to pre-
dict the vapor-liquid-liquid behavior of these systems.
The 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 spe-
cially created for these systems. This system uses the predefined
system SRKM but invokes the GLYCOL databank. This databank
contains binary interaction parameters for component pairs involv-
ing glycols tri-ethylene glycol (TEG) and, to a lesser extent, dieth-
ylene glycol (DEG) and ethylene glycol (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
This method is described in more detail in page 93, of this manual,
Special Packages.
SourWater Systems
The standard version of PRO/II contains two methods, SOUR and
GPSWATER, for predicting the VLE behavior of sour water sys-
tems. These methods are described in more detail in Special Pack-
ages Section. The recommended temperature, pressure and
composition ranges for each method is given in Table 3-6 below.
Table 3-6: Methods Recommended for Sour Water Systems

SOUR Recommended Ranges:
68 < T (F) < 300
P(psia) < 1500
wNH3 + wCO2 + wH2S < 0.30

Table 3-6: Methods Recommended for Sour Water Systems
GPSWAT Recommended Ranges:
ER 68 < T(F) < 600
P(psia) < 2000
wNH3 < 0.40
PCO2 + PH2S < 1200 psia
Electroly Recommended when strong electrolytes such as caustic
te are used, or when pH control or accurate prediction of HCN
Version or phenol phase distribution is important. Recommended
of PRO/II Ranges: 32 < T(F) < 400
P(psia) < 3000 xdissolved gases < 0.30
Amine Systems
Amine systems used to sweeten natural gas streams may be mod-
eled in PRO/II using the AMINE special package (see Section, Spe-
cial Packages). Data is provided for amines MEA, DEA, DGA,
DIPA, and MDEA. Results obtained for MEA and DEA are accu-
rate 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.
The recommended temperature, pressure, and loading ranges
(gmoles sour gases per gmole amine) for each amine system avail-
able in PRO/II is given in Table 3-7.
Table 3-7: Methods Recommended for Amine 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

Table 3-7: Methods Recommended for Amine Systems
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 SRKM or SRKS equation of state should be used to best predict
the water solubility in the hydrocarbon phase. The COSTALD liq-
uid density was developed expressly for light hydrocarbon mix-
tures. This method is over 99.8% accurate in predicting the liquid
densities of these mixtures, and should be requested by the user.
Table 3-8: Methods Recommended for Light Hydrocarbons

SRK/PR/ Recommended for systems of similar light
BWRS hydrocarbons at low pressures
SRKM Recommended at higher pressures
/SRKS
COSTALD Recommended for liquid density
Aromatic Systems
Mixtures of pure aromatic components such as aniline, and
nitrobenzene at low pressures less than 2 atmospheres exhibit close

to ideal behavior. Ideal methods 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 equilib-
ria. The SRK or PR equations of state should provide better results,
but with a small CPU penalty.
Table 3-9: Methods Recommended for Aromatics

IDEAL Recommended for systems at low pressures below 2
atm
GS/ SRK/ PR Recommended at pressures higher than 2 atm
IDEAL/ API/ Recommended for liquid density. The COSTALD
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 non-ideal. Liquid activity methods such as NRTL or UNI-
QUAC, 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
contain an extensive variety of interaction data for the NRTL and
UNIQUAC, and SRKM 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 missing 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 molecular weight values, and the user may supply UNIFAC
structures for components not in the PROII databanks.
When gases such as H2, N2, or O2 are present in small quantities
(up to about 5 mole %), the Henry's Law option may be used to cal-
culate the gas solubilities. Once the Henry's Law option is selected
by the user, PRO/II arbitrarily defines all components with critical
temperatures less than 400 Kelvin as solute components, though the
user may override these selections.

For large amounts of supercritical gases, an equation-of-state
method with an advanced mixing rule should be used to predict the
phase behavior.
Table 3-10: Methods Recommended for Aromatic/Non-

aromatic Systems
SRKM/ Recommended at high pressures or when > 5 mole %
PRM supercritical gases are present
NRTL/ Recommended with the FILL option when binary
UNIQUAC 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 sys-
tems containing alcohols with water. This package uses a special
databank of NRTL parameters containing interaction parameters
expressly regressed under temperature and pressure conditions
commonly found in dehydration systems. The NRTL method is
suggested if user-supplied interaction data are to be used.
Table 3-11: Methods Recommended for Alcohol Systems

ALCOHOL Recommended for all alcohol dehydration systems.
NRTL/ Recommended when user-supplied data are
UNIQUAC provided.
Chemical Applications
Non-ionic Systems
These systems, which typically contain oxygen, nitrogen, or halo-
gen derivatives of hydrocarbons such as amides, esters, or ethers,
are also similar to non-hydrocarbon systems found in petrochemical
applications. For low pressure systems, a liquid activity coefficient
method is recommended. For single liquid phase systems, the WIL-
SON, NRTL, or UNIQUAC methods are equally good, provided all
interaction parameters are provided. PRO/II databanks 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 meth-
ods should be used, provided that at least some interaction data is

available. The FILL option can be used to fill in any missing inter-
action data using the UNIFAC 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 pressure 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 automatically selected also.
It is also important to note that all the interaction parameters in the
PRO/II databanks, except for dimerizing components such as car-
boxylic acids, were regressed without including any vapor-phase
nonideality. This means that the PHI option should be used for car-
boxylic acid systems at all pressures, but should only be used for
most components at high pressures. For systems containing compo-
nents such as carboxylic acids that dimerize in the vapor phase, the
Hayden-O'Connell fugacity method may be used to calculate all
vapor-phase properties such as fugacity, enthalpy, and density. For
components such as hydrogen fluoride which forms hexamers in the
vapor phase, PRO/II contains an equation of state specially created
for such systems, HEXAMER. This method is recommended for
processes such as HF alkylation or the manufacture of refrigerants
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.
When supercritical gases are present in small quantities (generally
less than 5 mole %), the Henry's Law option should be used to
compute gas solubilities. 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 UNIWAALS equation-
of-state method uses UNIFAC structure information to predict
phase behavior. This method is useful when interaction data are not

avaialable and, unlike a liquid activity method such as UNIFAC, is
able to handle supercritical gases.
Table 3-12: Methods Recommended for Non-ionic Chemical

Systems
WILSON Recommended for single liquid phase slightly nonideal
mixtures. If all interaction data are not available use the
FILL=UNIFAC option.
NRTL/ Recommended for all nonideal mixtures. Use with the
UNIQUAC 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
nonidealities.
SRKS/ Recommended for high pressure systems or when > 5
SRKM/ PRM/ mole % supercritical gases are present.
UNIWAALS
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 electro-
lytes 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. Chem-
ical systems which may be modeled by this special version include
amine, acid, mixed salts, sour water, caustic, and Ben-field systems.
See Sections, Electrolyte Mathematical Model, and 1.2.10, Electro-
lyte Thermodynamic Equations for further details.
Table 3-13: Methods Recommended for Ionic Chemical

Systems
PRO/II Electrolyte Version
Environmental Applications
These systems typically involve stripping dilute pollutants out of
water. By themselves, 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 combination with Henry's Law

constants at the process temperature to model these dilute aqueous
systems. PRO/II contains Henry's Law constants for many compo-
nents such as HCl, SO2, and ethanediol in water. Some additional
Henry's Law constants for chlorofluorocarbons (CFCs) and hydrof-
luorocarbons (HFCs) in water are also available in the PRO/II data-
banks. Other sources for Henry's Law data include the U.S.
Environmental Protection Agency.
Table 3-14: Methods Recommended for Environmental

Applications
Liquid Activity Method + Henry's 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-sup-
plied 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 crys-
tallization systems, which are very near ideal in behavior, the vant
Hoff SLE method provides good results. The VLE behavior can
usually be adequately represented by IDEAL or any liquid activity
methods. Precipitation of solid salts and minerals from aqueous
solutions can be calculated more rigorously by using the electrolyte
version of PRO/II.
Table 3-15: Methods Recommended for Solid Applications

Ideal or Liquid Activity Recommended for most solid systems
Method(VLE) + VANT HOFF involving organics.
Method (SLE)
PRO/II Electrolyte Version Recommended for solid salt and
mineral precipitation from aqueous
solutions.

Generalized Correlation 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 pres-
sure correlations such as the K10 charts developed by Cajander et
al. Densities, enthalpies, and entropies can also be calculated using
a number of correlation methods such as Lee-Kesler, and COS-
TALD.
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 pressure, the fugacity of every component
is proportional to its mole fraction. For every component i, the fol-
lowing fundamental thermodynamic equilibrium relationship holds:
(1)
where:
superscript L refers to the liquid phase
superscript V refers to the vapor phase
= fugacity of component i
In the vapor phase, the fugacity is assumed to be equal to the partial
pressure:
(2)
where:
= vapor mole fraction

P = system pressure
In the liquid phase for an "ideal" liquid (ignoring correction factors
that are usually small):

(3)
where:
= liquid mole fraction
= pure component i liquid fugacity
= vapor pressure of component i at the system temperature
Raoult's law thus holds:
(4)
The ideal K-value is therefore given by:
K i = yi / xi = P sat i / P
(5)
Note that there is no compositional dependency of the K-values.
They are only a function of temperature (due to the dependence of
Pisat on T) and pressure.
Ideal vapor densities are obtained from the ideal gas law:
(6)
where:
= vapor 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 correlations, and the corresponding vapor enthalpies are
obtained by adding in the effect of the known latent heat of vapor-
ization of the component.
Ideal entropies are calculated from the ideal enthalpy data using the
following equation
(7)
where:
= ideal entropy
= ideal component heat capacity

= ideal enthalpy
= reference temperature (1 degree Rankine)
T = temperature of mixture
Chao-Seader (CS)
Chao and Seader calculated liquid K-values for the components of
nonideal mixtures using the relationship:
(8)
where:
= the standard-state fugacity of component i in the pure liquid
phase
i= the activity coefficient of component i in the equilibrium liq-
uid mixture
= 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, Equations of State), was used to evaluate .
Chao and Seader presented a generalized correlation for , the
fugacity coefficient of pure liquid "I" in real and hypothetical states.
In the development of their correlation for their vapor-liquid K-

value correlation, Chao and Seader used the framework of Pitzer's
modified form of the principle of corresponding states for the pure-
liquid fugacity coefficients, giving values of as a function of
reduced temperature, reduced pressure, and acentric factor for both
real and hypothetical liquids:
(9)
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 correc-
tion accounting for the departure of the properties of real fluids
from those of simple fluids.
Limitations of the Chao-Seader method are given below:
For all hydrocarbons (except methane);
Pressure: up to 2000 psia, but not exceeding 0.8 of the critical pres-
sure of the system.
Temperature: -100 oF to 500 oF, and pseuodoreduced temperature,
Tr, of the equilibrium liquid mixture less than 0.93. The pseu-
doreduced temperature is based on the molar average of the critical
temperatures of the components.
Concentration: up to 20 mole % of other dissolved gases in the liq-
uid.
This method is not suitable for other non-hydrocarbon compo-
nents 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 coefficients for hydrogen and methane
are supplied because typical application temperatures are far above
the critical points of these two components. Grayson and Streed's
modifications have extended the application range for hydrocarbon
systems up to 800 oF and 3000 psia. The lower limits imposed by
Chao and Seader still apply.
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.
A limitation of this modified method, however, is that the H2S cor-
relation 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 Sys-
tems, 6th World Congress, Frankfurt am Main, June 19-26.
Improved Grayson-Streed (IGS)

For hydrocarbon-water mixtures, the Grayson-Streed and Erbar-
modified Grayson-Streed methods accurately predict the phase
behavior of the hydrocarbon-rich phase, but does not do as well in
predicting the water-rich phase. A separate set of solubility parame-
ters was used in the water-rich phase, and a new set of liquid fugac-
ity coefficients developed for N2, H2O, H2S, CO, and O2. This
new method is known as the 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 liquid fugacity coefficient for the
"simple" fluid was therefore replaced by that for hydrogen at
reduced temperatures of 2.5 and above.
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 tem-
perature 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 satu-

rated vapor is sometimes at a reduced temperature of less than 0.6.
In this case, the CP correlation extrapolates reasonably, producing
satisfactory results.
The Curl-Pitzer method is generally useful for refinery hydrocar-
bons, and in oil absorption gas plants.
Reference
5 Stewart, Burkhart, and Voo, 1959, Prediction of Pseudo-

Critical Constants for Mixtures, Paper presented at AIChE
Meeting, Kansas City.
Petroleum Refining, 2nd Ed., Procedure 7B3.1, 7-29 - 7-
286.
Petroleum Refining, 2nd Ed., Procedure 7H2.1, 7-201 - 7-
202.
Braun K10 (BK10)

The K-value of each component is a function of the system temper-
ature, pressure, and the composition of the vapor and liquid phases.
For natural gas systems, the convergence pressure can be used as
the parameter that represents the composition of the vapor and liq-
uid phases in equilibrium. The convergence pressure is, in general,
the critical pressure of a system at a given temperature at which 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 pressure equilibrium ratio, arbitrarily taken at 10 psia sys-
tem pressure and 5000 psi convergence pressure. For many hydro-
carbon systems, no experimental data are available. For these cases,
the equilibrium K-values may be predicted from vapor pressure:
(10)
where:
= saturated vapor pressure in psia.
The relationship given in equation (10) only holds for K-values less
than 2.5. For 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 unknown, 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 = 1.27 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 pres-
sures, e.g., for mixtures of one molecule type such as mixtures of
paraffins and olefins. For mixtures of naphthalenes mixed with ole-
fins and paraffins, the accuracy of BK10 is slightly poorer. Large
errors can be expected for mixtures of aromatics with paraffins, ole-
fins, or naphthalenes, which cause nonidealities and form azeo-
tropes.
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(3), 251-259.
Johnson-Grayson (JG)
enthalpies. It is essentially an ideal-enthalpy correlation, using satu-
rated liquid at 0 C as the datum for the correlation (-200 F in ver-
sions 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 correlation should not be used if the mixture is
C4-C5 or lighter.
Reference
Johnson, and Grayson, 1961, Enthalpy of Petroleum Fractions,
Petroleum Refiner, 40(2), 123-29.

Lee-Kesler (LK)
enthalpies, entropies, and densities. This correlation uses the three-
parameter corresponding-states theory, which essentially states that
all fluids having the same acentric factor must have the same prop-
erties at the same reduced temperature and pressure. Special mixing
rules have been used to calculate the mixture reduced properties.
For most fluids, the Lee-Kesler method is 98% accurate in predict-
ing the gas phase compressibility factors. The method also gives
reasonable results for slightly polar mixtures. This method is not
recommended for highly polar mixtures, or those which form
strongly associative hydrogen bonds. However, the Lee-Kesler
method provides accurate results for polar fluids at low tempera-
tures near the saturated vapor region. The Lee-Kesler method is not
recommended for calculating liquid densities of hydrocarbons
heavier than C8.
Reference
8 American Petroleum Institute, 1975, Technical Data Book,

Petroleum Refining, 3rd Ed., 2-1 - 7-4.
9 Lee, B. I., and Kesler, M. G., 1975, A Generalized Thermo-
dynamic Correlation Based on Three-Parameter Corre-
sponding States, AIChE J., 21, 510-527.
10 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 compo-
nents. The reduced temperature and pressure of the stream at 60 F
and 14.7 psia are computed using Kay's rule, i.e., the reduced tem-
perature and pressure are assumed to be a linear function of the liq-
uid mole fraction. A density factor C, is then read from Figure
6A2.21 in the API Technical Data Book. A second correction factor
is then determined corresponding to the reduced temperature and
pressure at the actual fluid conditions. The actual liquid density is
then calculated according to:
(11)
where:

= actual liquid density
= liquid density at 60 F
= actual correction factor
= correction factor at 60 F
The API method works well for most hydrocarbon systems, pro-
vided that the reduced temperature is less than 1.0.
Reference
American Petroleum Institute, 1978, Technical Data Book - Petro-
leum Refining, 5th Ed., 6-45 - 6-46.
Rackett
This correlation may be used to predict liquid densities. The satu-
rated liquid density is obtained from:
(12)
where:
= saturated liquid volume
= Rackett parameter for component i
= critical temperature and pressure for component i
= reduced temperature for component i
The PRO/II databanks contain Rackett parameters for many compo-
nents. However, if Rackett parameters are not available, PRO/II
will use the critical compressibility factor, zc. When the Rackett
parameter is missing for a petroleum or assay component, PRO/II
back-calculates the missing parameter to ensure the specific gravity
of the pseudocomponent is correct.
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 equation (12) for the molar volume of each pure compo-

nent 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 determine effective critical
parameters for the mixture and then equation (12) is used to deter-
mine the mixture density. For most mixtures, the difference
between these two methods will not be significant.
Reference
11 Rackett, H. G., 1970, Equation of State for Saturated Liq-

uids, J. Chem. Eng. Data, 15, 514.
12 Spencer, C. F., and Danner, R. P., 1972, Improved Equation
for Prediction of Saturated Liquid Density, J. Chem. Eng.
Data, 17, 236-241.
13 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 for predicts the liq-
uid 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 characteristic parame-
ters for each pure component in the mixture - a characteristic vol-
ume, V*, and a "tuned" acentric factor, . The acentric factor is
chosen such that the SRK equation of state best matches the vapor
pressure data. Typically, this "tuned" acentric factor varies little in
value from the standard acentric factor. The saturated volume is
given by:
(13)
(14)
(15)
where:

= saturated molar volume
V* = characteristic volume
= reduced volume
= COSTALD parameters
= SRK "tuned" acentric factor
For mixtures, the following mixing rules are used:
(16)
(17)
(18)
(19)
where:
subscript m refers to mixture properties.
For compressed pure liquids and liquid mixtures, the original work
was extended by Thomson et al. in 1982, adding a pressure correc-
tion of the form:
(20)
where:
B, C are constants, dependent on composition
= saturated vapor pressure, obtained from a generalized
vapor pressure relationship.
V = molar volume
The COSTALD method is valid for aromatics and light hydrocar-
bons up to reduced temperatures of 0.95. PRO/II databanks contain
COSTALD characteristic volume, V* for many components. How-
ever, if the characteristic volume 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 character-
istic volume, if missing, in order to provide a correct specific grav-
ity for the pseudocomponent.
Reference
14 Hankinson, R. W., and G. H. Thomson, 1979, A New Cor-

relation for Saturated Densities of Liquids and Their Mix-
tures, AIChE J., 25(4), 653.
15 Thomson, G. H., Brobst, K. R., and Hankinson, R. W.,
1982, An Improved Correlation for Densities of Com-
pressed Liquids and Liquid Mixtures, AIChE J., 28(4), 671.

Equations 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 calculate 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 deviations from the ideal-gas
state are determined by calculating fugacity coefficients for both
phases. For cubic equations of state in particular, critical and super-
critical conditions can be predicted quite accurately. By using an
appropriate temperature-dependent function to describe the attrac-
tive 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)
where:
P = the pressure
T = the absolute temperature
v = the molar volume
u,w = constants, typically integers
The values of u and w determine the type of cubic equation of state.
Table 3-16 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 developed their equation of state in
1976 by setting u=2 and w=-1.
Table 3-16: Some Cubic Equations of State

u w Equation of state
0 0 van der Waals (vdW)
1 0 Redlich-Kwong (RK)

Table 3-16: Some Cubic Equations of State
2 -1 Peng-Robinson (PR)
The parameters a and b at the critical temperature, ( and ) 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 critical point to equation (1) yields:
(2)
(3)
(4)
where:
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 appear-
ing in these equations, because Pc, Tc, and Vc (and hence Zc) are
properties of a substance, having numerical values independent of
any equation of state. In solving these three equations, Vc is in fact
treated as a third unknown. Table 3-17 lists these constants for the
van der Waals, Redlich-Kwong, and Peng-Robinson equations of
state.
Table 3-17: Constants for Two-Parameter Cubic Equations

of State
Ac Bc Zc Equation 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)

Reference
16 Abbott, M. M., 1973, Cubic Equations of State, AIChE J.,

19(3), 596-601.
17 van der Waals, J. D., 1873, Over de Constinuiteit van den
gas-en Vloeistoftoestand, Doctoral Dissertation, Leiden,
Holland.
18 Redlich, O., and Kwong, N. S., 1949, On the Thermody-
namics of Solutions. v: An Equation of State. Fugacities of
Gaseous Solutions, Chem. Rev., 44, 233.
19 Peng, D. Y., and Robinson, D. B., 1976, A New Two-con-
stant Equation of State for Fluids and Fluid Mixtures, Ind.
Eng. Chem. Fundam., 15, 58-64.
Alpha Formulations
The temperature dependent parameter a(T) can be rewritten as:
(5)
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 pres-
sures (and therefore to a large extent for mixture 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
temperatures, and this requires that goes to a finite number as the
temperature becomes infinite. Three basic requirements for the tem-
perature-dependent alpha function must therefore all be satisfied:
The function must be finite and positive for all temperatures,
The function must equal unity at the critical point, and
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)

PRO/II allows the user to utilize a choice of 11 different alpha for-
mulations for cubic equations of state (SRK, PR, modified SRK or
PR, or UNIWAALS). Table 3-18 shows the 11 available alpha for-
mulations for (T).
Table 3-18: a) Alpha Formulations

Form Equation Reference
01 Soave (1972)
02 Peng-Robinson
(1980)
03 Soave (1979)
04 Boston-Math-
ias (1980)
05 Twu (1988)
06 Twu-Bluck-
Cunningham-
Coon (1991)
(Recom-
mended by
SimSci)
07 Alternative for
form (04)
08 Alternative for
form (06)
09 Mathias-Cope-
man (1983)
10 Mathias (1983)

Table 3-18: a) Alpha Formulations
11 Melhem-Saini-
Goodwin
(1989)
Some newer formulations(9) have been added for the temperature
dependent alpha term. These forms do not require the user to sup-
ply values for constants (C1, C2, etc.) Instead, they perform trans-
forms on the acentric factors of the components of interest.
Note: These forms automatically are applied to PETRO compo-

nents whenever the SIMSCI alpha formulation method (equation
6 above) is in effect.
Table 3-19: b Alpha Formulations

Form Equation Reference
15 Twu-Coon-Cunning-
ham (1995)
where:
and

Table 3-19: b Alpha Formulations
16 Twu-Coon-Cunning-
ham (1995)
where:
and
where:
= constants
= reduced temperature
= acentric factor
Reference
20 Soave, G., 1972, Equilibrium Constants from a Modified

Redlich-Kwong Equation of State, Chem. Eng. Sci., 35,
1197.
21 Soave, G, 1979, Application of a Cubic Equation of State to
Vapor-Liquid Equilibria of Systems Containing Polar Com-
ponents, Inst. Chem. Eng. Symp. Ser., No. 56, 1
22 Boston, J. F., and Mathias, P. M., 1980, Phase Equilibria in
a Third Generation Process Simulation, Proc. of the 2nd
Inter. Conf. on Phase Equil. & Fluid Properties in the
Chemical Process Industries, Berlin (West), March 17-21.
23 Twu, C. H, 1988, A Modified Redlich-Kwong Equation of
State for Highly Polar, Supercritical Systems, Inter. Symp.
on Thermodynamics in Chemical Engineering and Indus-
try, May 30-June 2.
24 Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E.,
1991, A Cubic Equation of State with a New Alpha Func-
tion and New Mixing Rule, Fluid Phase Equil., 69, 33-50.

25 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.
26 Mathias, P. M., 1983, A Versatile Phase Equilibrium Equa-
tion of State, Ind. Eng. Chem. Proc. Des. Dev., 22, 358-391.
27 Melhem, G. A., Saini, R., and Goodwin, B. M., 1989, A
Modified Peng-Robinson Equation of State, Fluid Phase
Equil., 47, 189-237.
28 Twu, C.H., Coon, J.E., Cunningham, J.R., 1995, A New
Generalized Alpha Function for a Cubic Equation of State;
part 1: Peng-Robinson equation; part 2: Redlich-Kwong
equation, Fluid Phase Equil., 105, 49-69.
Mixing Rules (for Equations of State)

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 calculating a and b in equation (1) for
mixtures. The original mixing rule was derived from the van der
Waals one-fluid approximation:
(7)
(8)
where:
= mole fraction of component i.
The binary interaction parameter, kij, is introduced into the mixing
rule to correct the geometric mean rule of parameter a in the general
cubic equation of state (1):
(9)
where:
= 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 temperature-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 following form of a(T):
(10)
(11)
where:
= 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 non-polar compo-
nents. This equation of state does not accurately predict the behav-
ior of polar components or light gases such as hydrogen. However,
the simplicity of equations (10) and (11), and its accuracy for calcu-
lating vapor pressures at temperatures higher than the normal boil-
ing point for hydrocarbons allowed it to gain widespread popularity
in industry. PRO/II contains correlations for the kijs of hydrocar-
bons 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 because a somewhat different set of data
was used.
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 sys-

tems, 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 expressly for water and
well-defined hydrocarbon systems:
(12)
(13)
(14)
where:
= interaction parameter between hydrocarbons and water in

the hydrocarbon-rich phase
= hydrocarbon group contribution from group j
= 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 available, Kabadi and Danner developed a procedure for esti-
mating the binary interaction parameters kij and Gi. Within a
homologous series of hydrocarbons, kij was found to be approxi-
mately constant and recommended values were given for seven
hydrocarbon classes. A group contribution method was proposed
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.
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(3), 537-541.

Soave-Redlich-Kwong Panagiotopoulos-Reid (SRKP) and
Peng-Robinson Panagiotopoulos-Reid (PRP)
In 1986 Panagiotopoulos and Reid proposed an asymmetric mixing
rule containing 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:
(15)
The two adjustable interaction parameters are kij and kji. This
asymmetric definition of the binary interaction parameters signifi-
cantly improves the accuracy in correlating binary data for polar
and non-polar systems. This mixing rule has been used to test sev-
eral systems, including low pressure non-ideal systems, high pres-
sure systems, three-phase systems, and systems with supercritical
fluids. The results in all cases reported are in good agreement with
experimental data.
Reference
1 Panagiotopoulos, A. Z., and Reid, R. C., 1986, A New Mix-

ing Rule for Cubic Equations of State for Highly Polar
Asymmetric Systems, ACS Symp. Ser. 300, American
Chemical Society, Washington, DC, 71-82.
2 The Panagiotopoulos-Reid mixing rule, however, is funda-
mentally inconsistent for multicomponent systems. This
inconsistency is exhibited in two (related) flaws:
3 The dilution of the mixture with additional components
(reducing all the mole fractions xi) nullifies the effect of the
second binary parameter kij. In the limit of an infinite num-
ber of components so that all the xi approach zero, the mix-
ing rule reduces to the original van der Waals mixing rule,
equation (9).
4 The mixing rule is not invariant to dividing a component
into a number of identical pseudocomponents. For exam-
ple, if methane in a mixture is divided arbitrarily into
"alpha" and "beta" methane, the calculated properties of the
mixture will be slightly different.

Soave-Redlich-Kwong Modified (SRKM) and Peng-Robinson
Modified (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:
(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 interchanging 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, equation
(16) becomes identical to the mixing rule proposed (also for the
purpose of overcoming the first flaw noted 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 par-
ticular, 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 following form for a12:
. (17)
(18)
(19)

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 binary polar-nonpolar systems, which have the
greatest deviation from ideality, 12 is not set equal to 21. For
binary polar systems however, 12 can generally 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 deter-
mined 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 compo-
nents 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 conven-
tional mixing rule obtained by setting k12 = k21 and 12 = 21 = 0
for a binary system either results in a compromise of the phase equi-
librium representation, or fails to correlate highly asymmetric sys-
tems.
For a multicomponent system, equation (17) can be generalized as:
(20)
(21)
(22)
where:
subscript m refers to the multicomponent system 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 Mix-
ing Rule, Fluid Phase Equil., 69, 33-50.
Soave-Redlich-Kwong Huron-Vidal (SRKH) and Peng-Robin-

son Huron-Vidal (PRH)
The previous SRK and PR mixing rule modifications include com-
position-dependence for applying these equations of state to com-
plex 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, Liquid Activity Methods). This approach
was proposed by Huron and Vidal in 1979. The general equation
relating excess Gibbs free energy to fugacity coefficients is given
by:
(23)
where:
= 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)
where:
= 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)
The excess Gibbs free energy can be calculated by any liquid activ-
ity method. Huron and Vidal chose to use the NRTL liquid activity
method to calculate
(26)
(27)
(28)
The only difference between the classical NRTL equation and equa-
tions (26-28) given above are the definition of the local composition
as corrected volume fractions, which leads to the introduction of the
volume parameter bj in the calculation of Gji. Substituting for the
excess Gibbs free energy in equation (25) yields:
(29)
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 mix-
ing rules are highly empirical in nature. However, the prediction of
equilibria at low densities is reasonable, 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 activity coefficient excess Gibbs energy model at
low pressure.
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 Mixtures, Fluid Phase Equil., 3, 255-271.

HEXAMER
Hydrogen fluoride is an important chemical used in many vital pro-
cesses, including HF alkylation, and in the manufacture of refriger-
ants and other halogenated compounds. Unlike hydrocarbons,
however, hydrogen fluoride is polar and hydrogen bonded, and
therefore self-associates not only in the liquid phase, but also in the
vapor phase. Experimental evidence strongly suggests that the HF
vapor exists primarily as a monomer and a hexamer mixture. 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 coeffi-
cients, vapor compressibility factors, heat of vaporization, and
enthalpies.
Twu et al. (1993), developed a cubic equation of state with a built-in
chemical equilibrium model to account for HF association. The
cubic equation of state incorporating association is given by:
(30)
(31)
(32)
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
= extent of association
= total number of moles of monomer and hexamers
= the number of moles that would exist in the absence of asso-
ciation

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 con-
stants for the Redlich-Kwong equation of state (see Table 3-17),
and the critical temperature and pressure for HF. The alpha func-
tion, (T), is obtained by matching the equation 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 association. The value of nr is 1.0 when there is no
association, and approaches 1/6 when there is complete hexamer-
ization. As the temperature increases, the extent of hexamerization
should decrease, i.e., the value of should increase.
The total number of moles of monomer and hexamer, , and the
total number of moles that would exist in the absence of associa-
tion, , are related by:
(33)
where:
= the true mole fraction of species i
= number of moles of species i
The hexamerization equilibrium reaction is written as:
(34)
The corresponding chemical equilibrium constant for this reaction,
which is a function of temperature only, is defined as:
(35)
where:
K = equilibrium constant
= fugacity coefficient of the true monomer species
= fugacity coefficient of the true hexamer species
= true mole fraction of the monomer species

= 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 substi-
tuting equation (33) into equation (35), and using the overall mate-
rial balance, this reduces to:
(36)
where:
= the reduced equilibrium constant

Once the equilibrium constant K is known, equation (36) can be
solved to obtain a value for z1 and a corresponding value for z6.
The equilibrium constant for HF hexamerization can be calculated
from the following relationship:
(37)
where:
K = equilibrium constant,
T = temperature, K
Twu et al. have shown that, at the critical point, the values of z1, the
true mole fraction of monomer, and nr, are given by:
(38)
(39)
So, even at the critical point, there is still a considerable amount of
the hexamer species present.
Mixture properties may be computed by using the SRKS mixing
rule, equation (20), discussed previously.
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, the
cubic equation of state is combined with the excess Gibbs free
energy model. By using this approach, 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 Sec-
tion, Liquid Activity Methods) are readily available for numerous
groups. The equations for the UNIWAALS method are developed
by equating the gE derived from the van der Waals equation of state
to the gE derived from UNIFAC at the system temperature and
pressure. This equality produces the following mixing rule:
(40)
(41)
(42)
where:
= 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 liquid 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 . Subse-
quently, the van der Waals equation of state and equation (42) are
solved simultaneously to obtain the mixture volume, v, and a/RTb.
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 volume 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 satisfied 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 UNIFAC model at low temperatures, and the
accuracy deteriorates with increasing 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 predict liquid and vapor properties at high temperatures,
and to correlate vapor-liquid equilibria for light hydrocarbon mix-
tures. 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 regions, and at high temperatures, the BWR equation
was modified by Starling in 1973 to give the following form:
(43)
The eleven parameters for pure components (B0, A0, etc.) are gen-
eralized as functions of component acentric factor, critical tempera-
ture, and critical density. The mixing rules for the eleven mixture
parameters are analogous to the mixing rules used for the BWR
equation. The single binary interaction parameter for the BWRS
equation of state is built into the mixing rules. The BWRS equation
of state can predict pure-component properties for light hydrocar-

bons very accurately when experimental data covering entire ranges
are available.
Limitations to the BWRS equation of state are given below:
1 Because the equation is generalized in terms of critical tem-
peratures, critical density, and acentric factor, it has diffi-
culty predicting properties for heavy hydrocarbons and
polar systems.
2 The BWRS equation does not satisfy the critical con-
straints, and therefore the equation is inferior to cubic
equations of state when applied to the critical and supercrit-
ical regions.
3 The BWRS equation if less predictive that cubic equations
of state for mixture calculations.
4 Unlike cubic equations of state, BWRS cannot be solved
analytically, and normally requires more CPU time.
Reference
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, Pro-
pane, 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 Pitzer's extended
theory of corresponding states. Thermodynamic data are correlated
as a function of critical temperature and pressure and the acentric
factor as follows:
(44)
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 accomplished by the introduction of an exponent,
into the mixing rules.
The mixing rules proposed here are:
(45)
(46)
(47)
where:
Vc = the molar critical volume
Tc = the critical temperature
z = mole fraction in vapor or liquid phase
= the acentric factor
The cross coefficients are given by:
(48)
(49)
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)
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 mix-
tures, is zero; for strongly asymmetric 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 determina-
tion is not available. PRO/II uses a default value of 0.25.
Adjustable binary parameters, Kij's 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
Starling's BWRS equation for highly asymmetric systems. The
method is not accurate around the critical point because the mixture
critical constants are empirical, and do not represent the true critical
point. Therefore, the authors recommend that the method not be
used above a reduced temperature of 0.96.
Reference
1 Lee, B.I., and Kesler, M.G., 1975, A Generalized Thermody-
namic 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 Solu-
tions, J. Am. Chem. Soc., 80, 4793-96.
4. Plcker, U., Knapp, H., and Prausnitz, J.M., 1978, Calculation
of High-Pressure Vapor-Liquid Equilibria from a Correspond-
ing 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 Con-
stants from Volumetric Data for Gas Mixtures, AIChE J., 4,
494.
Twu-Bluck-Coon( TBC)
The previous SRK and PR mixing rule modifications included com-
position-dependence for applying these equations of state to com-
plex mixtures. A more rigorous way to represent the phase behavior
of strongly nonideal systems is to develop the relationship between
the mixing rule and excess free energy model such that the zero-
pressure Gibbs free energy could be expressed by a NRTL-like
method (see Section , Liquid Activity Methods). Such approach had

been extended by Twu, Bluck and Coon in 1998 with a newly
developed zero-pressure-based mixing rule which would accurately
reproduce the excess Gibbs model and allow the available activity
coefficient models at low pressures be used directly.
The general Helmholtz free-energy departure function is given by:
(51)
At zero pressure, equation 3-93 can be derived as:
(52)
where:
A0E = excess Helmholtz free energy at zero-pressure;

A0Evdw = excess Helmholtz free energy at zero-pressure
calculated by a CEOS, such as SRK;
C v0 = density function calculated from SRK;
Equation 3-94 can be written to obtain the new mixing rule:
(53)
and
(54)
At zero pressure, the value of the excess Helmholtz energy is identi-
cal to the excess Gibbs energy model. Therefore, any activity model
such as the NRTL equation can be used directly for . For a solution
of n components, NRTL equation is given as,

(55)
where:
A ji
ji = and G ji = exp( ji ji )
T
By regressing experimental data to obtain the parameters in the
NRTL expression, excellent representation of vapor-liquid equilib-
ria can be made. The prediction of equilibria at low densities is rea-
sonable, and the equation of state can be expected to yield better
results at higher pressures, because the mixing rules have been
derived at the zero pressure limit of the excess Gibbs free energy.
TBC equation of state overcomes the limitation of infinite-pressure
based models, such as Huron-Vidal (SRKH, PRH,) that it can
directly utilize parameters for the NRTL method correlated from
low temperature data.
Reference
1. Twu, C. H.; Coon, J. E.; Bluck, D. "Comparison of the Peng-
Robinson and Soave-Redlich-Kwong Equations of State Using
a New Zero-Pressure-Based Mixing Rule for the Prediction of
High-Pressure and High-Temperature Phase Equilibria". Ind.
Eng. Chem. Res. 1998, 37, 1580-1585.

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 implemented 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 meth-
ods.
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 Gray-
son-Steeed and Chao-Seader, Braun K10, or Benedict-Webb-
Rubin-Starling methods. Water decant is automatically activated
when either 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, , are known. These
are calculated using the following relationship:
(1)
where:
= water partial pressure at temperature T

= 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 recommended for natural gas mixtures above
2000 psia. Three sets of steam tables can be used:
Water properties can be calculated assuming saturated vapor
and liquid conditions.
Steam tables for superheated water vapor based on the Keenan
and Keyes equation of state.
IF 97 Steam Tables - International Association for the Proper-
ties of Water and Steam - Industrial Formulation 1997 steam
tables are used for the property calculations.
The water solubility, , can be computed by one of three

methods in PRO/II:
1. The default method developed by SimSci. In this method,
water solubility is calculated for individual hydrocarbons and
light gases given in Table 3-20. The SimSci method uses a cor-
relation based on the number of carbon and hydrogen atoms
present in the component. For pseudo-components, the water
solubility is calculated as a function of the Watson (UOP) K-
factor.
2. 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 decant option is
chosen, and a component not included in Table 3-20 is present
in the system.
3. The third method employs the equation-of-state method that is
being used for calculating the K-values of the other compo-
nents present in the system to compute the water K-value.
Missing binary interaction parameters for the water-hydrocar-
bon components 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.
Table 3-20: Components Available in the SIMSCI Water
Solubility Method
Paraffins Naphthenes
Unsaturated Hydrocarbons Aromatics

Table 3-20: Components Available in the SIMSCI Water
Solubility Method
Methyl Mercaptan CS2
NH3 Argon
CO2 Helium
HCl H2S
N2 NO
O2 SO2

Liquid Activity Coefficient Methods
General Information
Liquid activity coefficient methods for phase equilibrium calcula-
tions differ at a fundamental level from equation of state (EOS)
methods. In EOS methods, 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 temperature 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 equation of state.
The thermodynamics of liquid mixtures within an activity coeffi-
cient framework is 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)
where:
= fugacity of component i in liquid phase
= 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 is defined as that of the pure liquid
i at the temperature and pressure of the mixture. With this defini-
tion, gi approaches one in the limit xi 1. The standard-state
fugacity may be related to the vapor pressure of component i as fol-
lows:
(2)
where:

P = system pressure
= vapor pressure of component i at the system temperature

R = gas constant
= liquid molar volume of component i at T and P
= fugacity coefficient of pure component i at temperature T
and pressure .
The exponential term in Equation (2) is the Poynting factor which
accounts for the effect of pressure on the liquid fugacity. If the pres-
sure does not exceed a few atmospheres, this correction can gener-
ally be neglected. Since liquid volumes do not depend greatly on
pressure, Equation (2) can be simplified to:
(3)
When liquid activity coefficients are used, any method may be used
to compute the vapor-phase fugacity. An ideal gas is often assumed,
but in general vapor fugacities may be written as:
(4)
where:
= fugacity of component i in vapor phase

yi = mole fraction of component i in vapor
= fugacity coefficient of component i in vapor
For an ideal gas, the fugacity coefficient is 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 equa-
tions do not in general "match" at the vapor-liquid critical point,

where vapor and liquid phases become indistinguishable. Phase
equilibrium calculations near a vapor-liquid critical point must be
carried out with some other method such as an equation 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)
At low and moderate pressures, the Poynting correction is often
ignored and Equation (5) becomes
(6)
Unless there is vapor-phase association (as is the case with carboxy-
lic acids, for example), the fugacity coefficients may also be
ignored at low and moderate pressures. Equation (5) then simplifies
to
(7)
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 equa-
tion (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 calculations using
the regressed parameters employ differing sets of simplying
assumptions. In general, calculations should be performed using
the same assumptions about vapor fugacities and the Poynting fac-
tor 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 substantially 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

(8)
where:
= excess Gibbs energy of liquid mixture
ni = moles of component i in liquid
The following sections describe the expressions available for
describing liquid-phase activity coefficients.
Reference
1 Prausnitz, J.M., Lichtenthaler, R.N. and Gomes de Aze-

vedo, E., 1986, Molecular Thermodynamics of FluidPhase
Equilibria, 2nd ed., PrenticeHall, Englewood Cliffs, NJ.
2 Sandler, S.I., 1989, Chemical and Engineering Thermody-
namics, 2nd ed., John Wiley & Sons, New York.
3 Smith, J.M. and Van Ness, H.C., 1987, Introduction to
Chemical Engineering Thermodynamics, 4th ed.,
McGrawHill, New York.
4 Van Ness, H.C. and Abbott, M.M., 1982, Classical Thermo-
dynamics of Nonelectrolyte Solutions: With Applications
to Phase Equilibria, McGrawHill, New York.
5 Walas, S.M., 1985, Phase Equilibria in Chemical Engineer-
ing, Butterworth, Boston.
Margules Equation
Table 3-21: Margules Equation
Required Pure Component Application Guidelines
Properties
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 Margules equa-
tion. The resulting expression for the activity coefficient is:
(9)
where:
Thus, for each ij binary pair in a multicomponent system, the

parameters are aij, aji, and dij. No temperature dependence is
included in this implementation; one should therefore be cautious
about using this equation at temperatures differing substantially
from the range in which the parameters were fitted.
Reference
1 Margules, 1895, Sitzber., Akad. Wiss. Wien, Math.

Naturw., (2A), 104, 1234.
2 Redlich, O. and Kister, A. T., 1948, Algebraic Representa-
tion of Thermodynamic Properties and the Classification
of Solutions, Ind. Eng. Chem. 40, 345348.
van Laar Equation

Table 3-22: van Laar Equation
Properties
Vapor Component Use for chemically
pressure s similar
components

Another old correlation which is still frequently used is the van Laar
equation. It may be obtained by discarding ternary and higherorder
terms in an alternative expansion of the excess Gibbs energy
(known as Wohl's equation), though that is not how van Laar
derived it originally. The resulting expression for the activity coeffi-
cient is:
(10)
where:
Two parameters, aij and aji, are required for each binary. As with
the Margules equation, no method is included for making the
parameters temperature 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 relationship between activity
coefficient and mole fraction. In practice, however, such maxima
and minima are relatively rare.
Reference
1 van Laar, J. J., 1910, The Vapor Pressure of Binary Mix-

tures, 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

Table 3-23: Regular Solution Theory
Properties
Vapor pressure Components Not valid for polar
components and
Liquid molar volume solutions
Solubility parameter containing
fluorocarbons

Hildebrand defined a regular solution as one in which the excess
entropy vanishes when the solution is mixed at constant tempera-
ture and constant volume. This is nearly the case for most solutions
of nonpolar compounds, provided the molecules do not differ
greatly in size. The excess Gibbs energy is then primarily deter-
mined by the attractive intermolecular forces. Scatchard and Hilde-
brand made a simple assumption relating mixture interactions to
those in pure fluids; the result is a simple theory in which the activ-
ity coefficients are a function of pure-component properties only.
The important property is the solubility parameter, which is related
to the energy required to vaporize a liquid component to an ideal
gas state. The activity coefficient expression is
(11)
where:
= 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 parameters have been tabulated for numer-
ous compounds, and these parameters are included for most compo-
nents in PRO/II's library.
Reference
Hildebrand, J.H., Prausnitz, J. M. and Scott, R. L., 1970, Regular
and Related Solutions, Van Nostrand Reinhold Co., New York.
Flory-Huggins Theory
Table 3-24: FloryHuggins Theory
Properties
Vapor pressure Components Best for components
which are chemically
Liquid molar volume similar and which
Solubility parameter differ only in size (e.g.
polymer solutions)

The Flory-Huggins model may be considered a correction to the
Regular Solution Theory for the entropic effects of mixing mole-
cules which differ greatly in size. It is therefore suitable for poly-
mer/solvent systems, especially if the molecules involved are
nonpolar. In this simplest implementation of the theory, there are no
binary parameters. The activity coefficient expression is:
(12)
where:
= activity coefficient from regular solution theory

= liquid molar volume of component i
= liquid molar volume of solution
Reference
1 Flory, P. J., 1942, Thermodynamics of Higher Polymer

Solutions, J.Chem.Phys., 10, 51.
2 Huggins, M. L., 1942, Thermodynamic Properties of Solu-
tions of LongChain 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
Table 3-25: Wilson Equation
Properties
Vapor Components Useful for polar or
pressure associating
components in
Liquid molar nonpolar solvents
volume and for completely
miscible liquids

The Wilson equation was the first to incorporate the concept of
"local composition." 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, associated
with the degree to which each molecule can produce a change in the
composition of its local environment. The expression for the activ-
ity coefficient is:
where:
(when unit of aij is K)
(when unit of aij is KCAL or KJ)
(when unit of aij is NODIME)

and is 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 equation's parameters, the derivation is such that the equa-
tion may be used with some confidence over a wider range of tem-
peratures than either the Margules or van Laar equations. It is also
much more successful in correlating mixtures containing polar
components. The Wilson equation cannot describe local maxima or
minima in the activity coefficient. Its single significant shortcom-
ing, however, is that it is mathematically unable to predict the split-
ting of a liquid into two partially miscible phases. It is therefore
completely unsuitable for problems involving liquid-liquid equilib-
ria.

Reference
1 Holmes, M. H. and van Winkle, M., 1970, Wilson Equa-

tion Used to Predict Vapor Compositions, Ind. Eng. Chem.,
62(1), 2231.
2 Orye, R. V. and Prausnitz, J. M., 1965, Multicomponent
Equilibria with the Wilson Equation, Ind. Eng.Chem.,
57(5), 1826.
3 Wilson, G. M., 1964, VaporLiquid Equilibrium XI. A New
Expression for the Excess Free Energy of Mixing, J. Amer.
Chem. Soc., 86, 127.
NRTL Equation
Table 3-26: NRTL Equation
Properties
Vapor pressure Components Useful for strongly
nonideal mixtures
and for partially
immiscible 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 equation's inability to predict liquid-liq-
uid phase separation. The resulting equation has been quite success-
ful in correlating a wide variety of systems. The expression for the
activity coefficient is:
(13)
where:
(when unit is K)
(when unit is KCAL or KJ)

Three parameters, ij, ji, and ij = ji are required for each
binary. These parameters may be made temperaturedependent as
described above. If tij is to be represented with only one constant, it
has been found empirically that better results over a range of tem-
peratures 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.
Reference
1 Renon, H. and Prausnitz, J. M., 1968, Local Composition

in Thermodynamic Excess Functions for Liquid Mixtures,
AIChE J., 14, 135144.
2 Harris, R. E., 1972, Chem. Eng. Prog., 68(10), 57.
UNIQUAC Equation
Table 3-27: UNIQUAC Equation
Required Pure Application
Component Guidelines
Properties
Vapor pressure Components Useful for

nonelectrolyte
van der Waals mixtures containing
area and volume 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 consider-
ations and the lattice-based quasichemical model of Guggenheim.
As in the Wilson and NRTL equations, local compositions are used.
However, local surface-area fractions are used as the primary com-
position variable instead of volume fractions. Each molecule i is
characterized by a volume parameter ri and a surface-area parame-
ter qi.
The excess Gibbs energy (and therefore the logarithm of the activity
coefficient) is divided into a combinatorial and a residual part. The
combinatorial part depends only on the sizes and shapes of the indi-

vidual molecules; it contains no binary parameters. The residual
part, which accounts for the energetic interactions, has two adjust-
able 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:
(14)
(15)
(16)
where:
(when unit is K)
(when unit is KCAL or KJ)

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 tempera-
ture dependence is used for Uij, better results over a range of tem-
peratures are normally obtained by using aij and setting bij = 0.
Reference
1 Abrams, D. S. and Prausnitz, J. M., 1975, Statistical Thermody-
namics 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. VaporLiquid 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. LiquidLiquid Equilibria, Ind. Eng. Chem. Proc.
Des. Dev., 17, 561-567.
4. Maurer, G. and Prausnitz, J. M., 1978, On the Derivation and
Extension of the UNIQUAC Equation, Fluid Phase Equilibria,
2, 91-99.
UNIFAC
Required Pure Application Guidelines
Component Properties
Vapor Pressure Pressure up to 100 atmospheres
van der Waals area and Temperature 32 300F
volume

Components All Comonents well
below their critical
points
The UNIFAC (universal functional activity coefficient) method was

developed in 1975 by Fredenslund, Jones, and Prausnitz. This
method estimates activity coefficients based on the group contribu-
tion concept following the Analytical Solution of Groups (ASOG)
model proposed by Derr and Deal in 1969. Interactions between
two molecules are assumed to be a function of group-group interac-
tions. Whereas there are thousands of chemical compounds of
interest in chemical processing, the number of functional groups is
much smaller. Group-group interaction data are obtained from
reduction of experimental data for binary component pairs.
The UNIFAC method is based on the UNIQUAC model which rep-
resents the excess Gibbs energy (and logarithm of the activity coef-
ficient) as a combination of two effects. Equation (13) is therefore
used:
The combinational term, , is computed directly from the

UNIQUAC equation (14) using the van der Waals area and volume
parameter calculated from the individual structural groups:
where:

where:
NOC = number of components
NOG = number of different groups in the mixture
z = lattice coordination number = 10
= 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 molecular structure.
(17)
(18)
where:
Vwk = van der Waals volume of group k
Awk = van der Waals area of group k
The residual term, , is given by:

(19)
where:
= residual activity coefficient of group k in the mixture

= residual activity coefficient of group k in a reference solution
containing only molecules of group type i. This quantity is
required so that as xi 1
The residual activity coefficient is given by:
(20)
where:
m, n = 1, 2, ... NOG
The parameter tmk is given by
(21)
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 inter-
action parameters between structural groups, as well as group size
and shape parameters have been incorporated into PRO/II.
Reference
1 Derr, 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 Rasmus-
sen, P., 1979, VaporLiquid Equilibria by UNIFAC Group

Contribution. Revision and Extension, Ind. Eng. Chem.
Proc. Des. Dev., 18(4), 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(10), 676-678.
5 Hansen, H.K., Rasmussen, P., Fredenslund, Aa., Schiller,
M., and Gmehling, J., 1991, VaporLiquid Equilibria by
UNIFAC Group Contribution. 5. Revision and Extension,
Ind. Eng. Chem. Res., 30(10), 2352-2355.
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 modified UNIFAC

Researchers at Lyngby developed a three-parameter temperature
dependent form for the binary interaction parameter. The parameter
mk is now given by:
(22)
(23)
where:
amk, bmk, cmk = binary interaction parameters
To = 298.15 K
The combinatorial part of the logarithm of the activity coefficient is
given by:
(24)

(25)
Reference
Larsen, B.L., Rasmussen, P., and Fredenslund, Aa., 1987, A Modi-
fied UNIFAC Group Contribution Model for Prediction of Phase
Equilibria and Heats of Mixing, Ind. Eng. Chem. Res., 26(11),
2274-2286.
UFT2 Dortmund modified UNIFAC

For this modified method, the temperature-dependent form of Amk
is given by:
(26)
The combinational part of the logarithm of the activity coefficient is
given by:
(27)
(28)
where:
z = lattice coordination number = 10

Reference
1 Weidlich, V., and Gmehling, J., 1987, A Modified UNIFAC

Model. 1. Prediction of VLE, hE, and , Ind. Eng. Chem.
Res., 26, 1372-1381.
2 Gmehling, J., Li, J., and Schiller, M., 1993, "A Modified
UNIFAC Model. 2. Present Parameter Matrix and Results
for Different Thermodynamic Properties," Ind. Eng. Chem
Res., 32(1) 178.
3 Gmehling, J., Lohmann, J., Jakob, A., Li, J., Joh, R., 1998,
"A Modified UNIFAC Model. 3. Revision and Extension,"
Ind. Eng. Chem Res., 37,4876.
UFT3
For this modified UNIFAC method, the temperature-dependent
form of Amk is given by:
(29)
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 Applica-
tions of UNIFAC, Fluid Phase Equil., 29, 69-76.
UNFV - Free volume modification to UNIFAC

This method was developed for modeling polymer systems. The
liquid activity coefficient is given by a combination of the same
combinatorial and residual terms as UNIFAC, plus a free volume
effect term:
(30)
(31)
where:

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 sol-
vent i = 3.3
Reference
Oishi, T., and Prausnitz, J.M., 1978, Estimation of Solvent Activi-
ties in Polymer Solutions Using a GroupContribution Method, Ind.
Eng. Chem. Proc. Des. Dev., 17(3), 333-339.
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 binary
interaction data the model needs:
1 Any user-supplied binary interaction parameters, or mutual
solubility, infinite dilution, or azeotropic data are used in
preference to any other data.
2 The VLE and LLE databanks which contain binary interac-
tion 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 parameters, then the group contribution methods
UNIFAC or its modification UFT1, or the regular solution
method, or the Flory-Huggins method may be used to pro-
vide estimates for the interaction parameters. For LLE cal-
culations, UNIFAC or the modified UNIFAC method UFT1
is used to supply the parameter estimates.
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 binary 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 following order in searching for binary parameters for both
VLE and LLE calculations:
1.The user-supplied values given on the KVALUE(VLE) state-
ment
2. The LLE databank
3. The VLE databank
If the user supplies LLE interaction data only, or both VLE and
LLE interaction data, for LLE calculations, the databanks are
searched in the order:
1.The user-supplied data given on the KVALUE(LLE) state-
ment

2 The LLE databank
3 The VLE databank
If the user supplies LLE interaction data only, or both VLE and
LLE interaction data, for VLE calculations, the databanks are
searched in the order:
1.The user-supplied data given on the KVALUE(VLE) state-
ment
2 The VLE databank
Figure 3-32: Flowchart for FILL Methods

Henry's Law
When liquid activity methods are used, the standard-state fugacity
for a component is the fugacity of the pure liquid. This standard
state is not convenient, 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
Henry's constant.
Thermodynamically, the Henry's 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:
(33)
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:
(34)
This relationship is strictly true only in the infinite-dilution limit,
but K-values from Henry's law generally remain accurate at solute
mole fractions up to approximately five percent.
PRO/II correlates Henry's constants to the following functional
form:
(35)
The temperature dependence in equation (33) is that expected from
a thermodynamic analysis provided the solvent's critical point is not
approached too closely. Thermodynamics also predicts that the
effect of pressure on the effective Henry's constant at conditions
beyond infinite dilution is linear in pressure (with C4 proportional
to the solute's partial molar volume). The pressure correction is neg-
ligible 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 below 400 K are automatically designated as solute
components by PRO/II. The user may, however, override these des-
ignations as desired. PRO/II has an extensive databank of Henry's
constants for supercritical gases in various solvents and also for
many organic compounds in water. Henry's constants may also be
input by the user. If no Henry's constant is given for a solute, PRO/
II substitutes the solute's vapor pressure (extrapolated if necessary).
This substitution is good only for nearly ideal solutions. In particu-
lar if no Henry's 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 Henry's constants is very

important. Especially for organic solutes in water, often only a
single value at 25 C is reported. Calculations 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 solute's Henry's
constant is the same as for its vapor pressure. The slope of ln Psat
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 Henry's constant of a solute in a mixture of solvents is com-
puted from the following mixing rule:
(36)
where the sum is taken over all solute species j, and the mole frac-
tions 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 FluidPhase Equilibria, 2nd
edition, PrenticeHall, Englewood Cliffs, NJ, Chapter 8.
Heat of Mixing Calculations

For many liquid mixtures, the enthalpy may be accurately approxi-
mately as a mole fraction sum of pure-component enthalpies (see

Ideal in Section, Generalized Correlations). 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 important. It should be noted that SimSci's equations of
state and generalized correlations produce a heat of mixing as a nat-
ural 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 temper-
ature dependence. This is known as the GAMMA option, and the
equation is:
(37)
where:
= excess heat of mixing

Despite the attractiveness of this direct thermodynamic computa-
tion, experience has shown that the activity-coefficient parameters
which correlate phase equilibria do not in general produce very
accurate values for excess enthalpies. 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.
Redlich-KisterExpansion
Experimental data for heats of mixing for binary systems are most
often represented by an expansion about an equimolar mixture:
(38)
where:
In equation (36), known as the Redlich-Kister expansion, a12 repre-

sents the excess enthalpy of a 50-50 binary mixture. Higher-order
terms correlate asymmetry in the curve of excess enthalpy versus
composition.

SimSci's 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 Sim-
Sci's REGRESS program and then entered through input by the
user.
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:
(39)
where:
(form RK1)
(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 pref-
erable from the standpoint of theoretical consistency.

Vapor Phase Fugacities
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 usually requires different
techniques. 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 equation of state. The fugacity coefficients are obtained
from classical thermodynamics as follows:
(1)
(2)
where:
i = fugacity coefficient of component i
fi = fugacity 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 mix-
ture is equivalent to the problem of establishing 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).

Equations of State
Equations of state are powerful methods for calculating vapor-
phase fugacities at low and high densities. The analytical expres-
sion of the fugacity coefficient can be derived from a cubic equa-
tion 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 systems comprising mixtures of nonpolar or
weakly polar components. The usefulness 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 (see
Section, 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 Equation of State and the
Hayden O'Connell method, discussed in a later section.
The equation-of-state methods are generally more reliable for cal-
culating vapor phase fugacity coefficients than any other method,
except for dimerizing components where the Hayden-O'Connell
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 assump-
tions. The virial equation gives the compressibility factor as a
power series in the reciprocal molar volume:
(3)
where:
v = molar volume
B, C, D, .. = second, third, fourth etc. virial coefficients
The virial coefficients are a function of temperature and composi-
tion 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)
The compositiona dependence of B for a mixture containing N
components is given by:
(5)
where:
Bii = second virial coefficient for pure component i
Bij = second virial cross coefficient
The cross coefficients characterize on interaction using 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.
O'Connell and Prausnitz developed a correlation for the reduced
second virial coefficient (both pure component and cross coeffi-
cients) which consists of three generalized functions:
1. One for nonpolar contributions to the second virial coefficient,
2. One for polar interactions based on the dipole moment, and,
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 asso-
ciation 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.
Reference
O'Connell, J. P., and Prausnitz, J. M., 1967, Empirical Correlation
of Second Virial Coefficients for Vapor-Liquid Equilibrium Calcu-
lations, Ind. Eng. Chem. Proc. Des. Dev., 6(2), 245-250.

Hayden-O'Connell
The truncated virial equation of state described above is useful for
predicting deviations from ideality in those systems where moder-
ate 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 negative
deviations from vapor ideality even at very low pressures.
To account for dimerization, Hayden and O'Connell in 1975, devel-
oped an expression of 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 O'Connell related second virial coefficients to the
dimerization equilibrium constants, KA2, KB2, 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.
Association and solution parameters for common associating com-
ponents are available in PRO/II's databanks.
This method is a reliable generalized method for calculating vapor
phase fugacities up to moderate pressures, especially for systems
where no data are available.

Reference
Hayden, J. G., and, O'Connell, J. P., 1975, A Generalized Method
for Predicting Second Virial Coefficients, Ind. Eng. Chem. Proc.
Des. Dev., 14(3), 209-216.

Special Packages
General Information
PRO/II contains a number of thermodynamic methods specifically
developed for special industrial applications. Data packages are
available for the following applications:
Alcohol 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 systems, a special alcohol databank, in combi-
nation 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 equilib-
rium calculations.
Alcohol Package (ALCOHOL)

The alcohol data package uses the NRTL liquid activity method to
calculate phase equilibria (see Section, Liquid Activity Methods).
This system uses a special set of NRTL binary interaction data for
systems containing alcohols, water, and other polar components.
The binary parameters have been obtained by the regression of
experimental data for alcohol systems. The recommended tempera-
ture and pressure ranges for the ALCOHOL data package are as fol-
lows:
Temperature:
122-230 oF for H2O-alcohol systems
150-230 oF 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,
Equations of State), while the liquid enthalpy and density are calcu-

lated using ideal methods (see Section, Generalized Correlation
Methods).
Table 3-29 shows the components present in the ALCOHOL data-
bank for which there are binary interaction parameters available.
Table 3-29: Components Available for ALCOHOL Package

Components Formula LIBID
Miscellaneous
Acetaldehyde C2H4O ACH
Sulfolane C4H8O2SH2S SULFLN
Light Gases
Hydrogen H2 H2
Nitrogen N2 N2
Oxygen O2 O2
Carbon Dioxide CO2 CO2
Hydrocarbons
Isopentane C5H12 IC5
N-pentane C5H12 NC5
Cyclopentane C5H10 CP
2 Methylpentane C6H14 2MP
1-Hexene C6H12 1HEXENE
N-Hexane C6H14 NC6
Methylcyclopentane C6H12 MCP
Benzene C6H6 C6H6
Cyclohexane C6H12 CH
2-4 Dimethylpentane C7H16 24DMP
3-Methylhexane C7H16 3MHX
1-Trans-2- C7H14 1T2MCP
Dimethylcyclopentane
n-heptane C7H16 NC7
Methylcyclohexane C7H14 MCH
Toluene C7H8 TOLU
2-4 Dimethylhexane C8H10 24DMHX
1-Trans-2-Cis-4-Tri-
methylcyclopentane C8H10 1T2C4MCP

Figure 3-9: Binary Interaction Data in the Alcohol Databank
Glycol Package (GLYCOL)

The glycol data package uses the SRKM equation of state to calcu-
late phase equilibria for glycol dehydration applications (see Sec-
tion, Equations of State). This system uses a special set of SRKM
binary interaction data and alpha parameters for systems containing
glycols, water, and other components. The binary parameters and
alpha parameters have been obtained by the regression of experi-
mental 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, entropy, and vapor density are calculated using the SRKM
equation of state, while the liquid density is calculated using the
API method (see Section, Generalized Correlation Methods).
Table 3-30 shows the components present in the GLYCOL databank
for which there are binary interaction parameters available.
Table 3-30: Components Available for GLYCOL Package

Components Formula LIBID
Hydrogen H2 H2
Nitrogen N2 N2
Oxygen O2 O2
Carbon Dioxide CO2 CO2
Hydrogen Sulfide H2S H2S
Methane CH4 C1
Ethane C2H6 C2
Propane C3H8 C3
Isobutane C4H10 IC4
N-butane C4H10 NC4
Isopentane C5H12 IC5
Pentane C5H12 NC5
Hexane C6H14 NC6
Heptane C7H16 NC7
Cyclohexane C6H12 CH
Methylcyclohexane C7H14 MCH
Ethylcyclohexane C8H16 ECH
Benzene C6H6 BNZN
Toluene C7H8 TOLU
O-xylene C8H10 OXYL
M-xylene C8H10 MXYL
P-xylene C8H10 PXYL
Ethylbenzene C8H10 EBZN
Ethylene Glycol C2H6O2 EG
Diethylene Glycol C4H10O3 DEG
Triethylene Glycol C6H14O4 TEG
Water H2O H2O
Figure 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 denoted by "x" or "o", the missing binary interaction

parameters are estimated using a molecular weight correlation, or
are set equal to 0.0.
Figure 3-1: Binary Interaction Data in the Glycol Databank

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 Krev-
elen model assumes that H2S and CO2 only exist in solution as ion-
ized species. This is only true for solutions containing an excess of
NH3 or other basic gas. This limitation has been removed 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)
(2)
where:
= partial pressure of component i
= Henry's Law constant for component i in water
= concentration of component i in the liquid phase, gmoles/kg
solution
The SWEQ model uses Henry's Law constants for each component
in solution as a function of temperature and composition of the
undissociated molecular species in the liquid phase. The Henry's
constants for H2S and CO2 were obtained from data published by
Kent and Eisenberg who developed a model for predicting H2S-
CO2-MEA-H2O and H2S-CO2-DEA-H2O systems. The Henry's
Law constants used in the SWEQ model for equations (1) and (2)
are:
(3)
(4)

where:
T = system temperature, degrees Rankine
The Henry's 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)
The Henry's Law constant for NH3 was taken from data published
by Edwards et al.:
(6)
The chemical equilibria of all the main reactions in the liquid phase
due to the dissociation of the sour gas molecules are considered in
the model. The reaction equilibrium constants, Ki, are correlated as
functions of temperature, composition of undissociated sour gas
molecules in the liquid phase, and ionic strength.
(7)
where:
= equilibrium constant of reaction i
= equilibrium constant at infinite dilution for all species
a,b,c = constants
I = ionic strength =
= ionic charge of species j
The reaction equilibrium constants at infinite dilution, , are
given in the form first proposed by Kent and Eisenberg:
(8)
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 PRO/II , thus extending the applica-
ble 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, Equations
of State). The following limits apply to the SOUR method as imple-
mented in PRO/II:
Composition:
where:
= weight fraction of component i
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, Generalized Correla-
tion Methods).
Reference
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-Liq-
uid Equilibria, Ind. Eng. Chem., 50(3), 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., 1975,
Thermodynamics of Aqueous Solutions Containing Vola-
tile Weak Electrolytes, AIChE J., 21, 248-259.
GPA Sour Water Package (GPSWATER)

This sour water package uses the method developed by the Gas Pro-
cessors Association in 1990 for sour water systems containing com-
ponents 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 nonide-
alities, 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
involving the NH3, H2S, CO2, CO, methyl mercaptan (MeSH), and
ethyl mercaptan (EtSH) in water are considered. The components
CO, methyl mercaptan (MeSH), and ethyl mercaptan (EtSH) are
treated as Henry's Law components (see Section, Liquid Activity
Methods) Reactions considered include:
Water:
(9)
Ammonia:
) (10)
Hydrogen Sulfide:
(11)
Bisulfide:
(12)
Carbon Dioxide:
(13)
Bicarbonate:

(14)
Carbon Dioxide and Ammonia:
(15)
(16)
(17)
The chemical equilibrium constants, Ki, are correlated as functions
of temperature 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 accounted 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)
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, Equations
of State).
The following limits apply to the GPSWATER method:
Composition: wNH3 < 0.40
where:

= weight fraction of component i
= partial pressure of component i in the vapor phase
Note: NH3, CO2, H2S, and water must be present when using the
GPSWATER 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, Generalized Correla-
tion Methods).
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 alkanola-
mines. Alkanolamines are formed by ammonia reacting with an
alcohol. Amines are considered to be either primary, 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 amines monoethanolamine (MEA), secondary
amines diethanolamine (DEA), diglycolamine (DGA), and diiso-
propanolamine (DIPA), and the tertiary amine methyldiethanola-
mine (MDEA). MEA and DEA are the most frequently used amines
in industry.
In aqueous solutions, H2S and CO2 react in an acid-base buffer
mechanism with alkanolamines. The acid-base equilibrium reac-
tions are written as chemical dissociations following the approach
taken by Kent and Eisenberg:
Water:
(19)
Hydrogen Sulfide:
(20)

Bisulfide:
(21)
Carbon Dioxide:
(22)
Bicarbonate:
(23)
Alkanolamine:
(24)
where:
= equilibrium constant for reaction i
= 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)
Tertiary amines such as MDEA are not known to form stable car-
bamates. In an aqueous solution with MDEA, CO2 forms bicarbon-
ate ions by reaction (22) only.
Note: CO2, H2O, and H2S must be present when using the
AMINE method.
The chemical equilibrium constants, Ki, are represented by the fol-
lowing equation:

(26)
The equlibrium constant for the protonated amine dissociation reac-
tion 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 experi-
mental data for the system amine-water.
The liquid enthalpy is calculated using ideal methods and adding a
correction for the heat of reaction as follows using either a modified
Clausius-Clapeyron equation or fits of data from the Gas Processors
Association:
(27)
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 Sec-
tion, Equations of State). Ideal methods are used to calculate the liq-
uid-phase density (see Section, 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 was available, and so the DIPA results are not
recommended for final design purposes. For MDEA and DGA sys-
tems, the user is allowed to input a residence time correction to
allow the simulation results to more closely match plant data. The
following application ranges are suggested for amine systems:
Table 3-31: Application Guidelines for Amine Systems

MEA DEA DGA MDEA DIPA
Pressure, 25-500 100-1000 100-1000 100- 100-
psig 1000 1000
Temperatu <275 <275 <275 <275 <275
re, F

Table 3-31: Application Guidelines for Amine Systems
Concentra ~15-25 ~25-35 ~55-65 ~50 ~30
tion, wt %
amine
Acid gas 0.5-0.6 0.45 0.50 0.4 0.4
loading,
gmole
gas/gmole
amine
Reference
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, Ethano-
lamine Process Simulated by Rigorous Calculation, Hydro-
carbon Processing, 60, 139-142.

Electrolyte Mathematical 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 Exressions
For each vapor-liquid, liquid-liquid, solid-liquid, and liquid
intraphase equilibrium, there is an equation of the form:
(1)
where:
K = thermodynamic equilibrium constant: a function of tempera-
ture and pressure
= activity coefficient or, for vapors, fugacity coeffi-
cient of the ith product and reactant, respectively; a function
of temperature, pressure, and composition
= stoichiometric coefficient of the ith product and
reactant, respectively
= molality or, for vapors, partial pressure of the ith
product and reactant, respectively.
Note: When H2O (the solvent) appears in the equilibrium expres-

sion, 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 defined 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 approaches one as the molality of all solutes approaches
zero.

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 pressure dependence of the water properties. This effect
is negligible except at conditions approaching water's 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)
where:
Zi = species charge
NC, NA = number of cations and anions, respectively
Equations For Solutions Involving a Second Liquid Phase,
(liquid-liquid equilibrium)
(3)
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, com-

pletes 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 compo-
nent 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 molecular 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.
As noted above, the number of NB equations required is that num-
ber 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 represented by H2O-CO2-NACL. The reactions considered
will be:
(4)
(5)
(6)
(7)
(8)
(9)
Based upon the general model described earlier, this leads to:
Equilibrium Expressions
(10)
(11)
(12)

(13)
(14)
(15)
Electroneutrality Equation
(16)
Liquid-liquid Equilibrium Equations
There are none in this example.
Material Balance Equations
Overall material balance:
(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.
3 Vapor balance
(18)
where:
y = mole fraction for vapor species
Sodium balance
(19)

Chlorine balance
(20)
Carbon balance
(21)
Equations (10) (21) are the required 12 equations. Assuming that
the temperature and pressure are known, and further assuming that
deterministic formulations are available for the equilibrium con-
stants, activity coefficients, fugacity coefficients, and the activity of
water, then the corresponding 12 unknowns (calculated variables)
are:
and moles of water.

Electrolyte Thermodynamic Equations
Thermodynamic Framework
The mathematical model described in the previous section utilizes
several thermodynamic quantities. Specifically these are:
Equilibrium constants - normally strong functions of tempera-
ture and weaker functions of pressure.
Aqueous-phase activity coefficients - normally strong functions
of temperature and composition and weaker functions of pres-
sure.
Vapor-phase fugacity coefficients - normally significant func-
tions of temperature, pressure and composition, particularly at
elevated pressures.
Organic liquid-phase activities - normally strong functions of
temperature 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 calculation of enthalpies
and densities for aqueous liquid, organic liquid, vapor, and solid
phases. These latter formulations are also presented below.
Equilibrium Constants
By considering basic thermodynamic relationships and assuming a
constant heat capacity of reaction, the following general equation
can be derived:
(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, sum-
ming the product of the reaction coefficient times Gf over all

reactants and then, over all products. Next, the sum for the reactants
is subtracted from the sum for the products to obtain G.
H = corresponding standard state heat of reaction at the refer-
ence conditions. Obtained from the standard-state enthalpy of for-
mation, Hf , 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
capacity, 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 Thermodynam-
ics(Ref. 1). Values of Gf, f, and Cp for reaction species
are usually available in the critically evaluated data compilations of
the National Bureau of Standards(Ref. 2) or
the Russian Academy of Sciences(Ref. 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 stan-
dard states as used by the NBS2.
The original implementation now is referred to as the "Old Frame-
work". For some reactions, where sufficient measurements are
available, it uses empirically fitted functions for K values as a func-
tion of temperature instead of equation (1). The "Old Framework"
is used for all models supplied by SIMSCI and by the PUBLIC
library.
A new framework was introduced in the PUBNEW library starting
with PRO/II 5.11. This new form uses an equation of state to pre-
dict K values as a function of both temperature and pressure. Con-
currently, a new version of the Electrolyte Utility package (EUP
version 6) has been adopted. It is fully compatible with version 6 of
software from OLI Systems, Inc., a partner with SIMSCI in the
development of electrolyte models. The EUP version 6 uses the
new framework exclusively. The older EUP allowed the user the
choice of building a model using either framework. The new (cur-
rent) EUP only supports the new framework.

Aqueous Phase Activities
The key to successful simulation of aqueous systems is to accu-
rately predict the reaction equilibria described in the previous sec-
tion. 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 number of alternative as well as complementary formulations.
The common element 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.
Ions
For ions the formulation used is:
(2)
DHi = Debye-Hckel term for long-range, ion-ion interactions,
defined as:
(3)
where:
A = Debye-Hckel constant, a known function of temperature and
solvent density(Ref. 1)
I = ionic strength =

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(Refs. 4,5) term for short-range, ion-ion
interactions, defined as:
(4)
where:
(5)
NO = number of ions with charge opposite to that of the ion being
represented.
Bij,Cij,Dij = three interaction coefficients for each cation-anion
interaction. These are each made 3-parameter functions of temper-
ature. Thus, for each cation-anion interaction, there are 9 coeffi-
cients that must be established.
Pi = Pitzer(Refs. 6,7) term for short-range, ion-molecular interac-
tions, defined as:
(6)
where:
(7)
and

(8)
and
(9)
where:
NM = number of molecular species in solution
NS = number of species in solution
= two interaction coefficients for each ion-molecule or

molecule-molecule interaction.
Note: Each of the ij interaction coefficients is a 3-parameter func-
tion of temperature. Thus, for each interaction, there are 6 coeffi-
cients 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 formu-
lation is from Pitzer(Refs 6,7). The Setschenow and Pitzer relations
are:
(10)
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)
BPij is defined by equation (7) above.
Water Activity
The water activity for multicomponent systems is obtained from an
integrated form of the Gibbs-Duhem equation, together with a mix-
ing rule suggested by Meissner and Kusik(Ref. 8). The formulation
can be represented as:
(12)
where:
(13)
(14)
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 interac-
tion coefficients have been fit to cover the conditions being simu-
lated, quite adequate for predicting 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.(Ref. 9) developed a method for calculating fugac-
ity coefficients in mixtures at moderate pressures. The main feature
of the method is the inclusion of dimerization effects on the second
virial coefficient.
The equation of state is written as:
(15)
where:
bm = size parameter for mixture, cm3 / mole
nT = number of moles of true species
P = pressure, atmospheres
R = gas constant, 82.056 cm3 atm / mole K
T = temperature, Kelvins
V = total volume, cm3
nT is obtained from the solution of the dimerization equilibria
described below. bm is given by a sum over all true species:
(16)
where:
bi = size parameter for true species i, cm3 / 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)
Values of b for monomers are tabulated in the original reference.
For component j, the fugacity coefficient is given by:
(18)
where:
bj = size parameter for monomer j, cm3 / 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 equi-
libria. Each dimerization is described by an equilibrium constant
Kij:
(19)
(20)
The dimerization equilibrium constants are related to the enthalpy
and entropy of dimerization:
(21)
where:
Hij = enthalpy of dimerization, cal/mole
Sij = entropy of dimerization, cal/mole
R = gas constant, 82.056 cm3 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 param-
eters for 178 components, may be found in the original paper(Ref.
9).
Nakamura Method
Nakamura et al.(Ref. 10) proposed the following perturbed-hard-
sphere equation of state for gas mixtures:
(22)
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, liter /
mole
a = parameter signifying the attractive force strength, atm/mole
In addition to equations for the reduced enthalpy difference and
entropy difference, the following equation was presented for calcu-
lating the fugacity coefficient of a species k in the gas mixture:
(23)
With the P, R, T, v, and terms defined earlier, the following defini-
tions and calculations apply:
n = number of species

(24)
where:
g = pure-component parameter
=pure-component parameter
(25)
where:
yi = vapor mole fraction of i
ck = pure-component parameter
(26)
z= compressibility factor = (27)
(28)
(29)
where:
= pure-component parameter
ij = interaction parameter
(30)

(31)
(32)
(33)
(34)
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 Naka-
mura 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, Equations of State, of this
manual.
Note: For both the Nothnagel and Nakamura options, if an elec-

trolyte model contains a volatile species not covered in the origi-
nal 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 limi-
tation.
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, 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 introduce significant uncertainties in enthalpy calcula-
tions 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 users 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 composition of interest is evaluated using:
(35)
where:
Hio, yi = the standard state molar enthalpy and the mole fraction,
respectively, 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, Hio is evaluated using:
(36)
where:
, = 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 for vapor and solid species are obtained from empir-
ical functions of temperature, which are given by:
(37)
(for vapor)

(38)
(for solid)
where:
Ai, Bi, Ci = temperature-independent, but phase-dependent con-
stants 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)
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(Ref. 11). At the tempera-
ture and solution composition of interest, Hi is evaluated using:
(40)
where:
i = the activity coefficient of the ith solute species
R = the gas constant
Values of i and 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 and for aqueous species and using the

following relations to represent for ionic and molecular sol-
utes:
(for ionic solutes) (41)
(for molecular solutes) (42)

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)
where:
vw = the molar volume of pure water at the temperature and pres-
sure of interest, as given by the HGK(Ref. 11) equation of state
= 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 Rack-
ett method for liquid density. This method is described in Section ,
Generalized Correlations, of this manual.
Solid Phase

The molar volume of the solid phase, vsol, at the temperature of
interest is evaluated using:
(44)
where:
= the standard state molar volume of the ith pure solid

component at the reference temperature
References
1 Zemaitis, J.F. Jr., Clark, D.M., Rafal, M., and Scrivner,
N.C., 1986, Handbook of Aqueous Electrolyte Thermody-
namics, AIChE.
2 Wagman, D.D., et al., 1968-1973, Selected Values of
Chemical Thermodynamic Properties, NBS Tech Note,
270-3 to 8.
3 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.
4 Wagman. D. D., et al., 1982, The NBS Tables of Chemical
Thermodynamic Properties, J. Phys. Chem. Ref. Data, 11,
Supplement no. 2, 392 pp.
5 Glushko, V.P., editor, 1965-1981, Thermal Constants of
Compounds, Russian Academy of Sciences, Vols. I-X.
6 Zemaitis, J.F., Jr., 1980, Predicting Vapor-Liquid-Solid
Equilibria in Multicomponent Aqueous Solutions of Elec-
trolytes, Thermodynamics of Aqueous Systems with Indus-
trial Applications, S.A. Newman, ed., ACS Symposium
Series, 133, 227-246.
7 Bromley, L.A., 1973, Thermodynamic Properties of Strong
Electrolytes in Aqueous Solutions, AIChE J., 19, 313-320.
8 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.

9 Pitzer, K.S., 1980, Thermodynamics of Aqueous Electro-
lytes at Various Temperatures, Pressures and Compositions,
Thermodynamics of Aqueous Systems with Industrial
Applications, S.A. Newman, ed., ACS Symposium Series,
133, 451-466.
10 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.
11 Nothnagel, K.H., Abrams, D.S., and Prausnitz, J.M., 1973,
Generalized Correlation of Fugacity Coefficients in Mix-
tures at Moderate Pressures, Ind. Eng. Chem. Proc. Des.
Dev., 12, 25-35.
12 Nakamura, R., Breedveld, G.J.F., and Prausnitz, J.M.,
1976, Thermodynamic Properties of Gas Mixtures Contain-
ing Polar and Nonpolar Components, Ind. Eng. Chem.
Proc. Des. Dev., 15, 557-564.
13 Haar, L., Gallagher, J.S., and Kell, G.S., 1984, NBS/NRC Steam
Tables, Hemisphere Press, Washington D.C., 320 pp.

Solid-Liquid Equilibria
General Information
The solubility of solids in liquids can be described by the van't Hoff
(ideal-solubility) equation. This is sufficient for many systems
where non-idealities are small. Alternatively, solubility data, corre-
lated as a function of temperature, may be entered directly. Precipi-
tation of solid salts and minerals from aqueous solutions may be
calculated rigorously using PRO/II Electrolytes. This capability is
described separately in Sections, Electrolyte Mathematical Model,
and 1.2.10, Electrolyte Thermodynamic Equations, of this manual.
van't 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 solid's fugacity to its standard-state fugacity
in the liquid phase, which is that of a pure subcooled liquid. This
ratio is one at the solute's 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 van't Hoff, after the Dutch chemist who
first proposed it) equation is given by Prausnitz et al. The result is:
(1)
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 usu-
ally used instead of the triple-point temperature. The difference is
almost always negligible. 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 sol-
vent are of a similar chemical nature and form a nearly ideal solu-

tion. For example, the solubility of aromatic hydrocarbons in
benzene is well described by equation (1).
Table 3-32: van't Hoff

Required pure component Application Guidelines
properties
Triple-point (or melting Compo- Solute and sol-
temperature tempera- nents vent should be of
(Tt) ture if Tt is a similar chemi-
not avail- cal nature (i.e.
able) 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
van't Hoff equation:
(2)
where:
xij = the equilibrium solubility of solute i in solvent j at tempera-
ture
For solubility of a solid solute i in a mixed solvent, theory dictates
that the mixing rule should have the following form:
(3)
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" liquid mole fractions are denoted by z, this is
written as:
(4)

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
van't Hoff equation.
Note: When the van't 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 solute's 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:
(5)
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 van't Hoff equa-
tion.
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.

Transport Properties
General Information
The following transport properties are calculated and/or used by
PRO/II:
Table 3-33: Transport Properties

Liquids 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 ten-
sion as part of the stored physical property data. Several correla-
tions 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 fol-
low.With the exception of the PURE and TRAPP methods, there are
no special provisions to characterize the hydrocarbon type (paraf-
finic, 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 paraffins, with a degradation in accu-
racy for olefins or aromatics. Non-hydrocarbon transport properties
are best represented by the properties from structure methods dis-
cussed in Section, Component Data.
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 component 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 temperature
of interest are combined to calculate stream average properties
according to the following mixing rules:

Table 3-34: Stream Average Properties
Stream Property Additive Basis
Liquid Thermal Conductivity
wi = Weight fraction (1)
Vapor Thermal Conductivity

yi = Mole fraction (2)
Liquid Viscosity
xi = Mole fraction (3)
Vapor Viscosity
yi = Mole fraction (4)
Surface Tension
xi = Mole fraction (5)
The user may also provide individual component values as a func-

tion of temperature either in tabular or equation forms.
PETRO Methods
Liquid Viscosity
The method selected for liquid viscosity is dependent on the
reduced temperature, which is in turn calculated by Kay's 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 sec-

tion 9-12 in Reid, Prausnitz and Poling) are used. These methods
were developed 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.
For intermediate ranges (Tb<T<0.76<Tc), the Andrade equation is
used to determine the viscosity, based on reference values at the
normal boiling point and a reduced temperature of 0.76. The refer-
ence 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 vis-
cosities are taken from the component data library. A "wet" viscos-
ity is then calculated for water/hydrocarbon streams by combining
the hydrocarbon and water viscosities with the following mixing
rule:
(6)
where:
= viscosity
x = mole fraction
subscripts aq and hc refer to the aqueous and hydrocarbon portions
of the stream
Reference
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 Liq-
uids, II, The Viscosity - Composition Curve for Ideal Liq-
uid 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
conductivities. 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 ther-
mal conductivities are taken from the component data library. A
"wet" thermal conductivity is then calculated for water/hydrocarbon
streams by combining the hydrocarbon and water viscosities with
the following mixing rule:
(7)
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
Reference
10 American Petroleum Institute, 1978, Data Book, 5th edi-

tion.
11 Reidel, L., 1950, The Determination of the Thermal Con-
ductivity and the Specific Heat of Various Mineral Oils,
Chem. Ing. Tech., 21, 349.
Surface Tension
The surface tension for hydrocarbon liquids is estimated with pro-
cedure 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 values for decant hydrocarbon
systems are computed with the formula:
(8)
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)
where:
= mole fraction in the vapor phase

of the stream
Reference
1 Thodos, G., and Yoon, 1970, Viscosity of Nonpolar Gas-

eous Mixtures at Normal Pressures, AIChE J., 16, 300-304.
2 Dean, D.G., and Stiel, L.S., 1965, The Viscosity of Nonpo-
lar Gas Mixtures at Moderate and High Pressures, AIChE
J., 11, 526-532.
3 Herning, F., and Zipperer, L., 1936, Calculation of the Vis-
cosity of Technical Gas Mixtures from the Viscosities of
the Individual Gases, Gas-U. Wasserfach., 79, 69.
Vapor Thermal Conductivity

The Roy-Thodos method is used to determine vapor thermal con-
ductivities. The function of temperature used is the one that is pre-
sented by the authors for saturated hydrocarbons. This method is
corrected for pressure effects using the equations of Stiel and Tho-
dos.
Data for water are retrieved from the component data library. "Wet"
conductivities are predicted for water/hydrocarbon systems as fol-
lows:
(10)
where:
y = mole fraction in the vapor phase
of the stream.
Reference
1 Perry, R.H., and Green, D., 1984, Perry's Chemical Engi-

neers 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 Substances 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 computed from the PETRO correlation described ear-
lier 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-workers. Mathematically, the viscosity of a fluid mix-
ture or component is given by:
(11)
and the thermal conductivity is represented by:
(12)
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 tempera-
tures, from the dilute gas to the dense liquid. The required con-

stants for each component are the critical constants (Tc, Pc and Vc)
and the acentric factor.
Note: The method originally was developed for, and was

restricted to, the list of components given in Table 3-35. Com-
plete parameters are available in the component libraries for these
components. However, in the current versions of PRO/II, correla-
tions have been added to generate any required parameters that
are not supplied by the user. Currently, the TRAPP method
applies to all library, petro, and non-library components. It may
not be suitable for use with electrolyte or polymer components.
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.
Table 3-35: TRAPP Components (3.3 versions)

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- 2BT1
BUTENE
3-METHYLPENTANE 3MP 3-METHYL-1- 3BT1
BUTENE
2,2- 22MB 2-METHYL-2- 2BT2
DIMETHYLBUTANE BUTENE
2,3- 23MB 1-HEXENE HXE1
DIMETHYLBUTANE
n-HEPTANE HEPTANE 1-HEPTENE HPT1
n-OCTANE OCTANE PROPADIENE ALEN

Table 3-35: TRAPP Components (3.3 versions)
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 CO
MONOXIDE
CYCLOPENTANE CP HYDROGEN H2
METHYLCYCLOPENT MCP HYDROGEN H2S
ANE SULFIDE
CYCLOHEXANE CH OXYGEN O2
METHYLCYCLOHEX MCH NITROGEN N2
ANE
ETHYLCYCLOPENTA ECP SULFUR DIOXIDE SO2
NE
ETHYLCYCLOHEXAN ECH WATER H2O
E
ETHYLENE ETLN
1 Leland, T. W., Robinson, J. S., and Suther G.A., 1968, Sta-

tistical Thermodynamics of Mixtures of Molecules of Dif-
ferent Sizes, Trans. Farad. Soc., 64, 1447-1460.
2 Ely, J. F., and Hanley, H. J. M., 1981, Prediction of Viscos-
ity and Thermal Conductivity in Hydrocarbon Mixtures-
Computer Program TRAPP, Proceedings of 60th Annual
Convention, Gas Processors Association.
Special Methods for Liquid Viscosity

SIMSCI (Twu) Correlation
For petroleum fractions, viscosity prediction methods are usually
based on boiling point and specific gravity. The API Technical
Data Book (1978) expresses the Watson correlation in a nomograph
form. However, the graphical form is unsuitable for simulation pur-

poses 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 sys-
tem (petroleum fractions, in this case) are expanded about the val-
ues of a reference system (chosen to be n-alkanes). The kinematic
viscosity of a petroleum fraction at 210 F is expressed in the follow-
ing manner:
(13)
(14)
(15)
(16)
Similar equations for kinematic viscosity at 100 F are given below:
(17)
(18)
You can then determine the relationship between viscosities at any
two temperatures, given the kinematic viscosity at the 2 tempera-
tures from equations (13-18) above and using the generalized rela-
tionship developed by Wright (and modified by Twu), given in
equations (19-22) below.
(19)
(20)

(21)
(22)
where:
= kinematic viscosity
Reference
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 Pre-
dicting Liquid Viscosities 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 cor-
relation discussed 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 lin-
ear function of API gravity. Hence, this relationship is extended as
follows:
(23)
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, equa-
tion (23) can be simplified based on the definition of Watson char-
acterization factor and of API gravity as:

(24)
where:
K = the Watson Characterization factor.
The viscosity of the reference fluid (either fluid 1 or fluid 2) can be
expressed as:
(25)
where:
C1, C2, C3, C4, C5, C6 = empirical constants.
Reference
Twu, C. H., 1986, A Generalized Method for Predicting Viscosities
of Petroleum Fractions, AIChE J., 32, 2091-2094.
Liquid Diffusivity
PRO/II's 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 esti-
mate them from the Wilke-Chang correlation.
User-supplied Diffusivity Data
When the user supplies diffusivity data, the user must specify which
component (or components) is to be considered the solute. Diffusiv-
ity data can then be supplied for each solute in each solvent in the
following form:
(26)
where:
Dij = diffusivity (in m2/sec) of solute i in solvent j
c1, c2, c3 = constants

For the diffusivity of a solute in a mixture of solvents, the following
mixing rule is used:
(27)
where:
Di,m = diffusivity (in m2/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 dif-
fusivity 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 correlation is of limited accuracy, but it will gen-
erally provide a diffusivity that is good to within 50%. The correla-
tion should not be used in cases where the solute is water or where
the solute is electrolytic. The equation is as follows:
(28)
where:
Di,m = diffusivity (in m2/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

Index
Nume Additive Basis , 3-132

rics Adler , 3-32
Advanced Treatise , 3-134
1-BUTENE , 3-138 AH2O , 3-107
1-HEPTENE , 3-138 Ai , 3-107, 3-108, 3-124, 3-125
1-HEXENE , 3-94, 3-138 AIChE , 3-67, 3-126
1HEXENE , 3-94 AIChE J , 3-26, 3-30, 3-34, 3-37, 3-45, 3-56, 3-72, 3-74,
1-PENTENE , 3-138 3-77, 3-101, 3-142
1T2C4MCP , 3-94 AIChE Meeting , 3-28
1T2MCP , 3-94 Aij , 3-66, 3-67, 3-70, 3-72, 3-74, 3-120
1-Trans-2 , 3-93 Aji , 3-45, 3-66, 3-67, 3-71
1-Trans-2-Cis-4-Tri , 3-93 Akad , 3-66
2-DIMETHYLBUTANE , 3-138 Al.Ref , 3-118, 3-120
2-METHYL-2-BUTENE , 3-138 ALCOHOL , 3-17, 3-19, 3-93, 3-94
2-METHYLPENTANE , 3-138 Alcohol data package , 3-93
3-BUTADIENE , 3-138 Alcohol data package uses , 3-93
3-DIMETHYLBUTANE , 3-138 ALCOHOL databank , 3-94
3-METHYL-1-BUTENE , 3-138 Alcohol Dehydration Systems , 3-17, 3-19
3-Methylhexane , 3-94 Alcohol Package

Table 1.2.8-1 Components Available , 3-94
3-METHYLPENTANE , 3-138
ALEN , 3-138
6th World Congress , 3-26, 3-27
Algebraic Representation , 3-65
Thermodynamic Properties , 3-66
A Alkanes , 2-6, 2-29
Alkanol , 3-104
A.S.M.E. , 3-99 Alkanolamine , 3-104
Acad , 3-69 Alkanolamines , 3-103, 3-104
According , 2-22, 2-30 Alpha formulation , 3-8, 3-37, 3-39

characterization , 2-30 Alter , 2-34
Account , 3-91 Amer , 3-71, 3-134
dimerization , 3-91 American Chemical Society , 3-44
Acentric , 3-39, 3-40, 3-132 American Petroleum Institute , 3-28, 3-30, 3-31
Acentric factor , 2-2, 2-7, 2-9, 2-10, 2-11, 2-14, 2-15, American Society , 2-20, 2-34
3-25, 3-27, 3-30, 3-32, 3-33, 3-40, 3-42, 3-53, 3-54, Testing , 2-20
3-55, 3-90, 3-138
AMINE , 3-15, 3-16, 3-17, 3-104, 3-105, 3-106
ACH , 3-94
Amine data package , 3-103
ACS Symp , 3-44
Amine Package , 3-103
ACS Symposium Series , 3-126, 3-127
Amine Systems , 3-13
Activity Coefficients , 3-74, 3-126 Methods Recommended , 3-13
Group Contribution Estimation , 3-74
Amine Treating , 3-100, 3-106
Activity-coefficient , 3-86
IX-1 Index
Better Data , 3-100, 3-106 ASME , 3-60
Amines , 3-1, 3-13, 3-16, 3-103, 3-104 ASOG , 3-74
Amines diethanolamine , 3-103 Assay Processing , 2-16, 2-18, 2-20, 2-25, 2-30, 2-31
Amines MEA , 3-13 Assay streams , 2-18
Amines monoethanolamine , 3-103 Associating equation of state , 3-49
Amk , 3-77, 3-78, 3-79, 3-80 Association , 3-49, 3-50
Ammonia , 3-101 extent , 3-49, 3-50
Analytical Solution , 3-75 ASTM , 2-20, 2-21, 2-22, 2-23, 2-24
following , 3-75 ASTM D1160 , 2-16
And/or , 3-41, 3-131 ASTM D2887 , 2-16
And/or vapor-liquid-liquid , 3-81 ASTM D323-73 , 2-32
Anderson , 3-74 ASTM D49 , 2-31
Andrade , 3-133 ASTM D5191-91 , 2-32
Ann , 3-69 ASTM D86 , 2-16, 2-20
Annual Book , 2-21 converting , 2-24
ASTM Standards , 2-20, 2-34 ASTM Standards , 2-21
Antoine , 2-4, 2-13 Annual Book , 2-20
API , 2-9, 2-11, 2-12, 2-14, 2-16, 2-21, 2-22, 2-23, 2-24, Azeotrope , 3-27
2-27, 2-29, 3-1, 3-9, 3-30, 3-31, 3-60, 3-96, 3-133, Azeotropes , 3-29
3-134, 3-135, 3-139, 3-140, 3-141
azeotropic data , 3-81
API gravity , 2-11, 2-12, 2-27, 2-29, 3-141 Azevedo , 3-5, 3-65, 3-85, 3-130
API liquid density , 3-1, 3-2, 3-30
API Method , 2-23, 3-141
API Technical Data Book , 2-21, 2-24, 2-29, 2-32, 3-30, B
3-59, 3-133, 3-134, 3-135, 3-139
API/EPA , 3-98 Backfill , 3-82
API63 , 2-25 PRO/II , 3-81, 3-82
APINAPHTHA , 2-32, 2-34 Banks , 3-69
Application Guidelines , 2-31, 3-25, 3-26, 3-27, 3-29, Benedict-Webb-Rubin , 3-53, 3-54
3-30, 3-31, 3-32 Benedict-Webb-Rubin-Starling , 3-53, 3-59
application ranges , 3-26, 3-84 BENZENE , 3-139
Applications , 3-2 Bicarbonate , 3-103
Phase Equilibria , 3-5, 3-65 Carbamate Reversion , 3-104
Applied Hydrocarbon Thermodynamics , 2-16, 2-34 Bii , 3-90
Applying , 2-6 Bij , 3-45, 3-72, 3-74, 3-90, 3-114, 3-120
Rackett , 2-10 setting , 3-74
Aqueous Electrolyte Thermodynamics , 3-112 Binary , 3-66
Handbook , 3-113 Thermodynamic Evaluation , 3-67
Aqueous Liquid Phase , 3-108, 3-124, 3-125 binary interaction databank , 3-93, 3-95
Aqueous Phase Activities , 3-114, 3-116, 3-117 Binary Mixtures , 3-67
Aqueous Solutions , 3-126 Bisulfide , 3-101, 3-103
Two , 3-127
BK10 , 3-11, 3-29
Aqueous Solutions Containing Volatile Weak
Electrolytes , 3-101 Black , 2-9
Aqueous Sour Water Systems , 3-100 Blending , 2-18, 2-19

Example , 2-19, 2-20
Aromatic Systems , 3-17
Bluck , 3-47
PRO/II Component and Thermophysical PropertiesReferene Manual IX-2

Boston , 3-40, 3-65 fugacity , 3-2, 3-3, 3-4, 3-5, 3-35, 3-49, 3-50, 3-51,
Boston-Mathias , 3-38 3-118, 3-119, 3-120
Braun K10 , 3-11, 3-28, 3-59 Calculation , 3-72

Multicomponent Phase Equilibria , 3-74
Brobst , 3-34
Calculation Methods , 3-59
Bromley-Zemaitis , 3-114
Cantalino , 3-80
Burkhart , 3-27, 3-28
Carbamate , 3-104
Butane , 3-54
Carbamate Reversion , 3-103
Butterworth , 3-65
Bicarbonate , 3-104
BWR , 3-53
Carbamates , 3-104
BWRS , 3-13, 3-14, 3-17, 3-53, 3-54, 3-56
CARBON DIOXIDE , 3-94, 3-96, 3-102, 3-103, 3-139
Carbon Number , 2-2
C CAVETT , 2-5, 2-11
CFCs , 3-19
C.A. Downey , 3-126 CH , 3-94, 3-96, 3-139
C2H4 , 3-122 CH4 , 3-18, 3-96, 3-122
C2H4O , 3-94 Chang , 3-143
C2H6 , 3-96, 3-122 Chao-Seader , 3-1, 3-25, 3-26, 3-27, 3-59
Erbar Modification , 3-27
C2H6O2 , 3-96
Chao-Seader K-value , 3-1
C3 , 2-4, 3-84, 3-96, 3-142
characteristic volume , 3-32, 3-33, 3-34
C3H6 , 3-122
Characterization , 2-5, 2-31, 3-11, 3-12
C3H8 , 3-96, 3-122
according , 2-31
C4 , 2-4, 3-84, 3-142
sets , 2-5
C4-C5 , 3-29
Characterization-Lee-Kesler , 2-14
C4H10 , 3-96
Chemical Abstract Number , 2-2
C4H10O3 , 3-96
Chemical Applications , 3-19
C4H8O2SH2S , 3-94
Chemical Engineering Thermodynamics , 3-2, 3-65
C5 , 2-4, 3-142
Chemical Engineers , 3-37
C5H10 , 3-94
Chemical Thermodynamic Properties
C5H12 , 3-94, 3-96 NBS Tables , 3-126
C6 , 2-4, 2-29, 3-142 Chim , 3-100
C6H12 , 3-94, 3-96 Chlorofluorocarbons , 3-22
C6H14 , 3-94, 3-96 choice , 3-38
C6H14O4 , 3-96 Cis-2-PENTENE , 3-138
C6H6 , 3-94, 3-96 Clapeyron , 2-4
C7 , 2-4 Classical Thermodynamics , 3-5, 3-65
C7H14 , 3-94, 3-96 Nonelectrolyte Solutions , 3-2
C7H16 , 3-94, 3-96 Clausius-Clapeyron , 3-105
C7H8 , 3-94, 3-96 Clausius-Clapyron , 2-10
C8 , 3-30 CO , 3-13, 3-27, 3-28, 3-101, 3-120
C8H10 , 3-94, 3-96 CO2 , 3-13, 3-14, 3-26, 3-27, 3-29, 3-42, 3-61, 3-93, 3-94,
C8H16 , 3-96 3-96, 3-98, 3-100, 3-101, 3-103, 3-104, 3-122, 3-139
Calculate , 2-31, 3-2, 3-35, 3-49, 3-88, 3-118, 3-120 Coal-tar Liquids , 2-16, 2-34
fugacities , 3-88 Coker fractionators , 3-10
Complex Mixtures , 3-41
IX-3 Index
Component Data , 2-1, 2-5, 3-133, 3-134, 3-135, 3-136 cubic equation forms , 3-35
Component Libraries , 2-1, 3-131, 3-132 Cubic equation-of-state , 3-9
Component Name , 3-138 Cunningham , 3-40, 3-41, 3-47, 3-51
Component Properties , 2-3 Curl-Pitzer , 3-9, 3-10, 3-27, 3-28, 3-29
Component properties-extrapolation conventions , 2-3 Curves , 2-20
Component properties-temperature correlation TBP , 2-20
equations , 2-3 Cutpoint , 2-17, 2-18, 2-19, 2-20, 2-30
Component Solutions , 3-56 Cutpoint Sets , 2-19
Components Available , 3-60 Cutpoints , 2-17, 2-18, 2-25, 2-26
components in databank , 3-93, 3-95 Defining , 2-18
Composition Curve set , 2-17, 2-18, 2-19, 2-20, 2-26
Ideal Liquid Mixtures , 3-134 use , 2-19, 2-20
Composition-dependence , 3-47 Cutpoints-application guidelines , 2-18
Compressed Liquids , 3-34 Cutpoints-multiple sets , 2-18
Compressibility , 3-5, 3-9, 3-30, 3-49, 3-54, 3-88, 3-89, Cutpoints-secondary set , 2-18
3-101, 3-120 Cutting TBP Curves , 2-25
Compressibility Factors , 2-16 CYCLOHEXANE , 3-94, 3-96, 3-139
Contents , 1-2, 2-16, 3-10 CYCLOPENTANE , 3-94, 3-139
Table , 1-2
Convert
ASTM D86 , 2-20 D
D86 , 2-20
TBP , 2-20
D.M. Rafal , 3-126
Coon , 3-40, 3-41, 3-47, 3-51
D1160 Curves , 2-20
Copeman , 3-41
D2887 , 2-20, 2-21, 2-22, 2-23
Correlations , 3-139
D2887 Curves , 2-20
Predicting Liquid Viscosities , 3-139
D2887 Simulated Distillation , 2-22
Corresponding States , 3-54
Multicomponent Mixtures , 3-54 D323 , 2-31
Corresponding States Correlation , 3-56 D323 RVP , 2-34
Saturated Liquid Volume , 3-133 D4953 , 2-32, 2-33, 2-34
Corresponding-states , 3-32 D5191 , 2-31, 2-34
COSTALD , 3-17, 3-18, 3-23, 3-33 D86 Curves , 2-20
COSTALD liquid density , 3-17, 3-32 Danner , 3-32, 3-43
Critical compressibility factor , 2-2, 3-31 data estimation
Critical pressure , 2-2, 2-7, 2-11, 2-14, 3-26, 3-28, 3-90, FILL , 3-83
3-91 Databank , 2-1, 3-13, 3-84, 3-93, 3-95
Critical Properties , 2-6, 2-11 Henry s , 3-84
Critical Review , 3-32 NRTL , 3-18, 3-19
Equations , 3-32 databank components , 3-93, 3-95, 3-98, 3-101, 3-103
Critical temperature , 2-2, 2-6, 2-9, 2-11, 2-13, 2-14, Databanks , 3-81, 3-82, 3-83, 3-93
3-7, 3-27, 3-31, 3-36, 3-50, 3-53, 3-54, 3-55, 3-84, Daubert , 2-24
3-90, 3-91, 3-133
DEA , 3-16, 3-103, 3-105
Critical volume , 2-2, 2-7, 2-11, 2-15, 3-34, 3-55, 3-90
Deal , 3-75, 3-77
Cross-references , 1-2
De-asphalting , 3-10, 3-13
Cubic , 3-37, 3-44, 3-45
Debye-Hckel , 3-114, 3-115
New Generalized Alpha Function , 3-37
Debye-Hckel , 3-114

Dechema , 3-14 Fitting , 2-25
Defined Components , 2-3, 2-5 Interconversion , 2-20
Types , 2-20
Defining , 2-18
Cutpoints , 2-18 Distillation data-API 1963 method , 2-20
pseudocomponent , 2-18 Distillation data-API 1987 method , 2-20
Density , 2-1, 2-3, 2-5, 2-6, 2-11, 2-14, 2-25, 3-1, 3-2, Distillation data-ASTM D1160 , 2-20
3-9, 3-19, 3-23, 3-30, 3-31, 3-32, 3-47, 3-53, 3-54, Distillation data-ASTM D2887 , 2-20
3-89, 3-93, 3-95, 3-98, 3-101, 3-103, 3-112, 3-114,
Distillation data-ASTM D86 , 2-20
3-120, 3-125, 3-132, 3-137
Improved Correlation , 3-32 Distillation data-Edmister-Okamoto method , 2-20
Density model , 3-32 Domash , 3-141
Departure-based , 3-8 Dortmund modified UNIFAC
UFT2 , 3-79
Derr , 3-75, 3-77
DSG , 2-6
Des , 3-41, 3-43, 3-56, 3-69, 3-74, 3-78, 3-90, 3-92, 3-141
Design Institute
Physical Property Data , 2-2
E
deviations , 3-45
equation , 3-45
parameters , 3-45 EBZN , 3-96, 3-139
DGA , 3-16, 3-105 ECH , 3-96, 3-139
Diethylene , 3-15 Edmister , 2-11, 2-16, 2-24, 2-34, 3-27
Diethylene Glycol , 3-96 Edmister-Okamoto , 2-23, 2-24, 2-25
Diffusivities , 3-142 Edwards , 3-99, 3-101
Diffusivity , 3-131, 3-142 Eisenberg , 3-98, 3-100, 3-106
estimating , 3-143 El , 3-126
provide , 3-143 Electrolyte Mathematical Model , 3-107, 3-109
requires , 3-142 Electrolyte Solutions , 3-126
Diglycolamine , 3-103 Electrolyte Thermodynamic Equations , 3-112, 3-114,
Diisopropanolamine , 3-103 3-116, 3-117, 3-118, 3-120, 3-122, 3-123, 3-124,
Dimer , 3-91, 3-119 3-125, 3-126
Dimerization , 3-91, 3-118 Electrolyte Utility , 3-113
Dimerize , 3-20 Electrolytes , 3-126, 3-127
Dimerizing , 3-1, 3-89 Electroneutrality Equation , 3-108, 3-110
except , 3-20, 3-89 Empirical Correlation , 3-89
Hayden-O Connell Method , 3-1 Second Virial Coefficients , 3-90
Dimethylcyclopentane , 3-94 Empirical Equation , 3-54
Dimethylhexane , 3-94 Thermodynamic Properties , 3-53
Dimethylpentane , 3-94 Englewood Cliffs , 3-65, 3-85, 3-130
DIPA , 3-16, 3-17, 3-105 Enthalpy , 2-3, 2-6, 2-11, 2-16, 2-30, 3-1, 3-2, 3-5, 3-8,
containing , 3-105 3-10, 3-23, 3-27, 3-29, 3-30, 3-35, 3-49, 3-85, 3-93,
3-95, 3-98, 3-101, 3-103, 3-112, 3-118, 3-120, 3-123,
results , 3-14, 3-16
3-124, 3-128
Dipole moment , 2-2, 3-90, 3-91 Improved Prediction , 3-30
Dissociations , 3-103 Enthalpy-ideal-gas , 2-14
Dissolver , 3-142 Entropic , 3-69
Distillation Calculations , 2-16 Entropy , 3-1, 3-2, 3-8, 3-23, 3-27, 3-30, 3-35, 3-67, 3-93,
Physical Data , 2-16 3-95, 3-98, 3-101, 3-103, 3-118, 3-120
Distillation Curves Environmental Applications , 3-19
IX-5 Index
Equation of state incorporating , 3-49 association , 3-49
equation of state water solubility method , 3-59 extent of association , 3-49
Equation-of-state , 2-9, 3-5, 3-14, 3-18, 3-19, 3-20, 3-60, Extrapolation Conventions , 2-3
3-89
Equations For Solutions Involving , 3-108
Second Liquid Phase , 3-107 F
Equations of State , 1-1, 2-6, 2-16, 3-1, 3-2, 3-5, 3-8,
3-9, 3-10, 3-13, 3-19, 3-25, 3-31, 3-32, 3-35, 3-37,
FCCU , 3-10, 3-12
3-41, 3-42, 3-44, 3-45, 3-47, 3-49, 3-52, 3-53, 3-54,
including , 3-10
3-59, 3-84, 3-85, 3-88, 3-89, 3-91, 3-93, 3-95, 3-98,
3-101, 3-103, 3-112, 3-118, 3-120, 3-122, 3-124, Feeds , 2-18
3-125 flowsheet , 2-18, 2-20
Equilibrium constant K , 3-51 FILL , 2-5, 3-19, 3-130
Equilibrium constant Kij , 3-118 Fill Options for _Solubility Data , 3-130
Equilibrium Constants , 3-40, 3-49, 3-99, 3-104, 3-108, Fitting , 2-25
3-112, 3-119 Distillation Curves , 2-25
Equilibrium Expressions , 3-107, 3-109 Fixed Properties , 2-3
Equilibrium Flash Vaporization Calculations , 2-31 Flash point , 2-2
Equilibrium Ratios , 3-29 FloryHuggins Theory , 3-68
equilibrium reactions , 3-91, 3-103 Flowrate , 2-30
Equimolar , 3-86 Flowsheet , 2-18, 2-25, 2-31
Equlibrium , 3-105 feeds , 2-20
Erbar , 3-27, 3-59 Flowsheets , 2-24
Erbar Modification , 3-27 Fluid Mixtures , 3-37
Chao-Seader , 3-27 Fluid Phase Equil , 3-40, 3-41, 3-47, 3-48, 3-51, 3-80
Erbar modification to Chao-Seader , 3-27 Fluid Phase Equilibria , 3-74
Erbar modification to Grayson-Streed , 3-27 Fluid Properties , 3-40
Erbar-modified Grayson-Streed , 3-27 Fluid Thermodynamic Properties , 3-53
Estimates , 3-43, 3-142 Light Petroleum Systems , 3-53
diffusivity , 3-142, 3-143 Fluid-Phase Equilibria , 3-2, 3-130
Gi , 3-43 FluidPhase Equilibria , 3-84
water/hydrocarbon , 3-43 Molecular Thermodynamics , 3-65, 3-85
Ethanediol , 3-22 Fluids , 3-37, 3-55, 3-56
Ethanolamine Process Simulated , 3-106 Thermodynamic Properties , 3-54
Ethylbenzene , 3-96 Formation , 2-9, 2-12
ETHYLCYCLOHEXANE , 3-96 Heat , 2-9, 2-10, 2-12, 2-13
ETHYLCYCLOPENTANE , 3-139 Fractionators , 3-10, 3-12
ETHYLENE , 3-139 Fredenslund , 3-53, 3-75, 3-77, 3-78, 3-79
Ethylene Glycol , 3-96 FREE , 3-130
ETLN , 3-139 Free volume modification , 3-78
EtSH , 3-101 UNIFAC , 3-78
EUP , 3-113 Free volume modification to UNIFAC
UNFV , 3-78
Excess Free Energy , 3-71
free volume modified UNIFAC
New Expression , 3-69
UNFV , 3-78
Excess Gibbs Free Energy , 3-74
Free Water Decant , 3-59
New Expression , 3-74
Frost-Kalkwarf , 2-4, 2-7
Extent , 3-49

Fugacities , 3-1, 3-2, 3-5, 3-20, 3-35, 3-63, 3-64, 3-88, Generalized Method , 3-91, 3-139
3-89, 3-107 Predicting Second Virial Coefficients , 3-91
calculating , 3-88 Predicting Viscosities , 3-139
Gaseous Solutions , 3-35 Generalized Thermodynamic Correlation Based on
intead , 3-108 Three-Parameter Corresponding States , 2-16,
terms , 3-108 3-30, 3-54
Fugacity , 3-2, 3-5, 3-8, 3-19, 3-23, 3-25, 3-26, 3-27, Generating , 2-30
3-35, 3-47, 3-49, 3-52, 3-84, 3-88, 3-89, 3-91, 3-107, Pseudocomponent Properties , 2-30
3-109, 3-118, 3-120, 3-122, 3-125, 3-128
Generating Pseudocomponent Properties , 2-30
calculate , 3-4, 3-5, 3-35, 3-49, 3-118, 3-120
Gibbs , 3-47, 3-52, 3-66, 3-67, 3-72, 3-74, 3-112
giving , 3-26
represents , 3-26 Gibbs-Duhem , 3-117
form , 3-117
Fugacity Coefficients , 3-127
Generalized Correlation , 3-127 Gimi , 3-107
Fugacity fi , 3-84 Glushko , 3-126
Fundam , 3-37, 3-53 GLYCOL , 3-13, 3-15, 3-95, 3-96
Fusion , 2-2 Glycol data package , 3-95

Glycol data package uses , 3-95
GLYCOL databank , 3-15, 3-96
G Glycol Dehydration Systems , 3-15
Glycol Package , 3-95
Gallagher , 3-124 Glycols , 3-1, 3-95
GAMMA , 3-86 Glycols tri-ethylene , 3-15
Gamma Method , 3-86 involving , 3-14, 3-15
Gas Mixtures , 3-54 Gmehling , 3-78, 3-80
Volumetric Data , 3-56 Gomes , 3-5, 3-65, 3-85, 3-130
Gas Mixtures Containing Polar , 3-127 Goodwin , 3-41
Thermodynamic Properties , 3-126, 3-127 GPA Research Report RR-118 , 3-103
Gas Processes , 3-10 GPA Sour Water Equilibria Correlation , 3-103
Gas Processors Association , 3-101, 3-103 GPA Sour Water Package , 3-101
Gaseous , 3-113 GPSA Data Book , 3-59
Gaseous Solutions , 3-35 GPSWAT , 3-93, 3-101
Fugacities , 3-37
GPSWATER , 3-15, 3-16, 3-102, 3-103
Gases , 3-134, 3-136
GPSWATER data package , 3-101
Properties , 3-134
Thermal Conductivity , 3-132 Gravity data , 2-16, 2-27
Gasoline-oxygenate , 2-32 Grayson , 2-14, 3-23, 3-26, 3-29
General Cubic Equation , 3-35, 3-41, 3-47 Grayson-Steeed , 3-59

State , 3-35, 3-41, 3-47 Grayson-Streed , 3-11, 3-12, 3-18, 3-26, 3-27, 3-59
general cubic equation of state , 3-35, 3-41, 3-47 Grayson-Streed Erbar , 3-11
GeneralInformation , 1-1, 3-1, 3-23, 3-35, 3-59, 3-88, Groehling , 3-77
3-93, 3-128, 3-131 Gross heating value , 2-2
Generalized Correlation , 3-25, 3-69 Group Contribution Estimation , 3-77
Solvent Activities , 3-69 Activity Coefficients , 3-75, 3-77
Vapor-Liquid Equilibria , 3-26 Group interaction data , 3-20, 3-74, 3-78
Generalized Correlation Methods , 3-8, 3-23, 3-25, GroupContribution Method
3-26, 3-27, 3-28, 3-29, 3-30, 3-31, 3-32 Polymer Solutions Using , 3-78
Generalized Information , 3-23 Groups , 3-75, 3-76, 3-77
IX-7 Index
Grulka , 3-69 Formation , 2-6, 2-11
GS , 3-11, 3-12, 3-13, 3-26 Mixing , 3-79
Mixing Calculations , 3-85
GS/GSE/IGS , 3-11, 3-12
reaction , 3-104, 3-105, 3-112, 3-113
GSE , 3-11, 3-12, 3-27
Heat of formation , 2-6, 2-11, 2-15
Guggenheim , 3-72
Heat of Mixing Calculations , 3-85
Guidelines , 3-65, 3-66, 3-67, 3-68, 3-69, 3-71, 3-72,
3-74, 3-129 Heat of Reaction , 3-105, 3-113
Gunn , 3-55, 3-56 heat of reaction correction , 3-103
Gupte , 3-52, 3-53 Heavy Petroleum , 2-16
Gyration , 3-91 HENRY , 3-19, 3-21, 3-85

Radius , 3-91 Henry s , 3-84, 3-98
databank , 3-85
Henry s Law Option , 3-19
H Henry's constants , 3-84, 3-85
Henry's Law , 3-7, 3-18, 3-20, 3-21, 3-22, 3-84, 3-98,
H.K. Rasmussen , 3-74 3-99, 3-101
H.P. , 3-127 Henry's Law constants , 3-5, 3-98
H2O , 3-27, 3-93, 3-96, 3-98, 3-99, 3-101, 3-104, 3-107, Henry's law gas solubility , 3-84
3-108, 3-110, 3-122, 3-124 HEPTANE , 3-96
correlating , 3-99 Herning , 3-136
pressure , 3-124
HEXAMER , 3-21, 3-49, 3-50, 3-51
H2O-alcohol , 3-93
Hexamers , 3-20, 3-49
oF , 3-93
HF , 3-49
H2O-CO2-NACL , 3-109
HF alkylation , 3-49
H2S , 3-13, 3-14, 3-26, 3-27, 3-29, 3-42, 3-61, 3-93, 3-96,
3-98, 3-100, 3-101, 3-103, 3-104, 3-122, 3-139 HF hexamerization , 3-51
H2S Volatility Data , 3-100 High Pressure Crude Systems , 3-10
Methods Recommended , 3-10
H2S/C3H8 , 3-27
High Pressure Crude Units , 3-12
H2S-CO2-DEA-H2O , 3-98
High Pressure Hydrocarbon-Hydrocarbon
H2S-CO2-MEA-H2O , 3-98
Systems , 3-26, 3-27
Haar , 3-124, 3-127
High Pressures , 3-136
Halogenated , 3-49
High Temperature , 3-26, 3-27
Handbook , 3-112 Vapor-Liquid Equilibria , 3-26
Aqueous Electrolyte Thermodynamics , 3-112
Higher Polymer Solutions , 3-69
Hankinson , 3-34
Highest-boiling
Hanley , 3-137, 3-139 lightend , 2-25
Hansen , 3-78 Highly Polar , 3-40
Harris , 3-72 Highly Polar Asymmetric Systems , 3-44
Harvey , 3-45 High-Pressure Aqueous Systems Containing
Hayden-O'Connell , 3-1, 3-20, 3-89, 3-91 Gases , 3-45
Hayden-O'Connell fu , 3-19 High-Pressure Vapor-Liquid Equilibria , 3-56
Hayden-O'Connell fugacity , 3-91 Hildebrand , 3-68
HCl , 3-22, 3-61 Hipkin , 3-29
HClO , 3-122 HOCV , 3-21
HCN , 3-16 Hoftijzer , 3-100
Heat , 2-6, 2-11, 3-78, 3-85, 3-103, 3-112 Holland , 3-37

Holmes , 3-71 Prediction , 3-32
HPDC , 3-139 Improved Grayson-Streed , 3-10, 3-27, 3-59
HPT1 , 3-138 Improved Prediction , 3-30
Huggins , 3-69 Enthalpy , 3-30
Hultgren G.O. 1958 , 3-54 Improved Viscosity-temperature Chart , 3-141
Huntjens , 3-100 Hydrocarbons , 3-141
Industrial Applications , 3-80, 3-126, 3-127
Huron , 3-47, 3-48
Industry , 3-40
Huron-Vidal , 3-48
Huron-Vidal SRK and PR , 3-47 Infinite-dilution , 3-84, 3-105
Infinite-pressure Gibbs , 3-47
Hydrocarbon Mixtures , 3-26
Hydrocarbon Mixtures-Computer Program Intead , 3-107
TRAPP , 3-139 fugacities , 3-108
Hydrocarbon Proc , 3-30 Interconversion , 2-20, 2-25
Hydrocarbon Processing , 3-100, 3-106 Interconversion of Distillation Curves , 2-20
Hydrocarbon-rich , 3-27, 3-42, 3-43, 3-59, 3-60 Internally Consistent Correlation , 3-141
Hydrocarbons , 3-139 Predicting , 2-16, 2-34
Predicting Liquid Viscosities , 3-141
Improved Viscosity-temperature Chart , 3-139
Hydrocarbon-water , 3-27, 3-59 Intraphase , 3-107
Introduction , 1-1, 3-5, 3-48, 3-55, 3-65
Hydrofiners , 3-10, 3-12
Ion Interaction Approach , 3-126
Hydrofluorocarbons , 3-22
HYDROGEN , 3-139 Ionic Chemical Systems , 3-19
Methods Recommended , 3-21, 3-22
Hydrogen deficiency number , 2-2
Ions , 3-104, 3-114, 3-115, 3-116, 3-126
Hydrogen Fluoride , 3-49, 3-51
Isobutane , 3-96
HYDROGEN SULFIDE , 3-96, 3-101, 3-103, 3-139
ISOPENTANE , 3-94, 3-96
I
J
IC4 , 3-96, 3-138
J.Chem.Phys , 3-69
IC5 , 3-94, 3-96
J.E. Cunningham , 3-37
ID Name , 3-138
J.H. Prausnitz , 3-67
IDEAL , 3-9, 3-18, 3-22, 3-23, 3-24, 3-25, 3-86
J.M. Lichtenthaler , 3-84, 3-130
IDEAL and LIBRARY , 3-2, 3-23
JANAF Thermochemical Tables , 3-126
Ideal Liquid Mixtures
Composition Curve , 3-134 Joback , 2-5
Ideal Vapor Enthalpy , 2-3 John Wiley , 3-5, 3-65
Ideal-solubility , 3-128 Johnson , 2-14, 3-29
IGS , 3-11, 3-12, 3-27 Johnson-Grayson , 3-29
IGS use , 3-11 Jones , 3-75, 3-77

Curl-Pitzer , 3-11
Immiscible , 3-59, 3-71
Improved Accuracy , 3-29
K
Nomographs , 3-29
Improved Correlation , 3-34 K.H. Abrams , 3-126
Densities , 3-32, 3-34 Kabadi , 3-43
Improved Equation , 3-32 Kabadi-Danner , 3-14, 3-122
IX-9 Index
Kabadi-Danner SRK , 3-42 Lichtenthaler , 3-5
Kansas City , 3-28 Light Gases , 3-93
Kay s , 3-30 Light Hydrocarbon Applications , 3-17
Keenan , 3-60 Light Hydrocarbons , 3-17, 3-53, 3-54
Kell , 3-124, 3-127 Light Petroleum Systems , 3-54
Kelvin , 3-18 Fluid Thermodynamic Properties , 3-54
Kelvins , 3-112, 3-118, 3-120, 3-142, 3-143 Lightend , 2-25
Kendall , 3-134 Lightends , 2-16, 2-25, 2-31
kerosene water solubility method , 3-59 Matching , 2-30
number , 2-25
Kesler , 2-6, 2-9, 3-30, 3-56
Lightends data , 2-29
Keyes , 3-60
Lightends data-matching , 2-25
K-factor , 3-60
Lightends-free , 2-29
K-free , 3-130
Liquid
Kinematic , 3-140, 3-141 vapor , 3-1
Kister , 3-65, 3-66
Liquid Activity Coefficient Methods , 3-2, 3-5, 3-19,
Kistiakowsky , 2-13 3-62, 3-65, 3-66, 3-67, 3-68, 3-69, 3-71, 3-72, 3-74,
Kistiakowsky-Watson , 2-9 3-78, 3-84, 3-85
Knapp , 3-56 Liquid activity methods , 3-21, 3-22, 3-47, 3-78, 3-81,
3-84, 3-93
Kolbe , 3-77
Liquid Diffusivity , 3-131, 3-142
Krevelen , 3-98, 3-100
Liquid Mixtures , 3-33, 3-34, 3-71
Kusik , 3-117, 3-127
Thermodynamic Excess Functions , 3-71
K-value , 3-2, 3-5, 3-23, 3-25, 3-28, 3-59, 3-84, 3-85,
3-93 Liquid molar volume , 2-2, 2-9, 3-4, 3-63, 3-67, 3-68,
compute , 3-85 3-69, 3-70
selected , 3-7 Liquid Regions , 3-137
K-values , 3-1, 3-4, 3-11, 3-23, 3-24, 3-25, 3-27, 3-28, Liquid Thermal Conductivity , 2-4, 3-132
3-29, 3-42, 3-59, 3-60, 3-84, 3-93, 3-105 Liquid Viscosity , 2-4, 3-132, 3-139
Kwong , 3-37 Special Methods , 3-139
LiquidLiquid Equilibria , 3-74
Liquid-Liquid Equilibrium Equations , 3-110
L Liquids , 3-32
Liquids on Reduced Temperature , 3-134
Larsen , 3-79 LK , 2-6, 3-11, 3-12, 3-30
Latent heat of vaporization , 2-6, 2-11, 2-15, 3-5, 3-23 LKP , 3-54, 3-56
Lee , 2-5, 2-9, 2-14, 2-16, 3-30 LLE , 3-19
Lee-Kesler , 2-5, 3-11, 3-23, 3-30 LLE databank , 3-82, 3-83
Lee-Kesler characterization , 2-15 Local Composition , 3-71, 3-72
Lee-Kesler-Plcker , 3-54 LongChain Compounds , 3-69
Leiden , 3-37 Low Pressure Crude Systems , 3-10
Leland , 3-55, 3-56, 3-137, 3-139 Methods Recommended , 3-10
Lenior , 3-29 Low Pressure Crude Units , 3-11, 3-12
LIBID , 3-94, 3-96 Lube Oil , 3-10
LIBRARY , 3-5, 3-131 Methods Recommended , 3-10
use , 3-6, 3-7 Lubricants , 2-20
LIBRARY enthalpies , 3-7, 3-8 Lyngby , 3-78

Lyngby modified UNIFAC Methylpentane , 3-94
UFT1 , 3-78 Misovich , 3-69
Mixing , 3-41, 3-69, 3-78
Heats , 3-79
M Rules , 3-41
Mixing Calculations , 3-85
Maddox , 3-106 Heat , 3-86
Main , 3-26, 3-27, 3-103 mixing rules , 3-18, 3-19, 3-35, 3-37, 3-41, 3-42, 3-44,
Margules , 3-65, 3-66, 3-70 3-45, 3-47, 3-48, 3-49, 3-52, 3-84, 3-117, 3-129,
3-132, 3-142
Margules Equation , 3-65, 3-66, 3-67
Mixtures , 3-27, 3-28, 3-72, 3-127, 3-137
Material Balance Equations , 3-110
Pseudo-Critical Constants , 3-27
Materials , 2-20, 3-141
Statistical Thermodynamics , 3-137
Mathematical Models , 3-107, 3-112
Model , 3-109
Mathias , 3-38, 3-40, 3-41 Example , 3-110
Mathias-Copeman , 3-38 modeling , 3-1
Maurer , 3-74 Modifications , 3-78
MCH , 3-94, 3-96 UNIFAC , 3-78, 3-79, 3-80
MCP , 3-94, 3-139 Modifications to UNIFAC , 3-78
MDEA , 3-16, 3-17, 3-104, 3-105 Modified , 3-38, 3-40, 3-41, 3-43
MEA , 3-16, 3-103, 3-105, 3-122 modified UNIFAC , 3-78
MeABP , 2-25 UFT3 , 3-78
Meissner , 3-117 Modified UNIFAC Group Contribution Model , 3-79
Melhem , 3-41 Prediction , 3-79, 3-80
Melhem-Saini-Goodwin , 3-39 Modified UNIFAC Model , 3-80
Melting temperature , 3-128, 3-129 Molalities , 3-108
Mercaptan , 3-101 Molality , 3-107, 3-113, 3-115
Mercaptans , 3-13, 3-42 Molar Volume and Density , 3-125, 3-126
MESH , 3-101 Molecular Thermodynamics , 3-5, 3-84, 3-130

Fluid-Phase Equilibria , 3-5, 3-130
METHANE , 3-138
FluidPhase Equilibria , 3-65, 3-85
Methods Recommended , 3-11, 3-12, 3-13, 3-17, 3-18,
3-19 Molecular weight , 2-1, 2-5, 2-6, 2-11, 2-16, 2-30, 3-9,
3-13, 3-78, 3-95, 3-142
Amine Systems , 3-15, 3-16
Aromatic/Non-aromatic Systems , 3-17, 3-18 Molecular weight data , 2-17, 2-28
Environmental Applications , 3-21, 3-22 Molecular weight data-API method , 2-25
High Pressure Crude Systems , 3-10 Molecular weight data-extended API (EXTAPI) , 2-25
Ionic Chemical Systems , 3-19 Molecular weight data-SimSci method , 2-25
Low Pressure Crude Systems , 3-10
Molecular weight value , 2-28
Lube Oil , 3-10, 3-13
Natural Gas Systems , 3-13, 3-14, 3-15 Molecular-weight , 2-29
Reformers , 3-10 Molecule-molecule , 3-116
Solid Applications , 3-22 Molecules , 3-137
Sour Water Systems , 3-13 Different Sizes , 3-139
METHY , 3-137 Monomer-dimer , 3-89
Methyl Mercaptan , 3-61 Mueller , 3-56
METHYLCYCLOHEXANE , 3-94, 3-96 Multicomponent , 3-2, 3-42, 3-44, 3-45, 3-65, 3-85,
METHYLCYCLOPENTANE , 3-94, 3-139 3-117, 3-130, 3-142
Methyldiethanolamine , 3-103 Multicomponent Aqueous Solutions , 3-126
IX-11 Index
Multicomponent Equilibria , 3-71 New Two-constant , 3-37
Multicomponent Mixtures , 3-56 Newman , 3-101, 3-126, 3-127
Corresponding States , 3-54, 3-56 NH3 , 3-61, 3-93, 3-98, 3-101, 3-103, 3-122
Multicomponent Phase Equilibria , 3-72 containing , 3-93
Calculation , 3-74 involving , 3-101
Multiple cutpoint , 2-17 New Correlation , 3-98
M-XYLENE , 3-96, 3-139 N-HEPTADECANE , 3-139
N-HEPTANE , 3-94, 3-138
N-HEXADECANE , 3-139
N N-HEXANE , 3-94, 3-138
Ni , 3-8, 3-65, 3-88, 3-116, 3-118, 3-124
NACLppt , 3-110 N-NONANE , 3-139
Nakamura , 3-120, 3-122 NOC , 3-76
Nakamura Method , 3-118, 3-120 N-OCTANE , 3-138
N-alkanes , 3-139 NODIME , 3-69
Naphthalenes , 3-29 NOG , 3-76, 3-77
Naphthenes , 3-60 Nomograph , 3-139
Natural Gas Processing , 3-13 Nomographs , 3-28
Natural Gas Systems , 3-13 Improved Accuracy , 3-28
Methods Recommended , 3-13 Nonelectrolyte Solutions , 3-2
NBP , 2-5, 2-6, 2-8, 2-10, 2-26, 2-28, 2-29, 2-30 Classical Thermodynamics , 3-2
equal , 2-30 Non-hydrocarbon , 3-19, 3-26, 3-131
function , 2-6
Nonideal Liquid Mixtures , 3-77
NBS Tables , 3-126
Nonidealities , 3-21, 3-29, 3-88, 3-100, 3-101
Chemical Thermodynamic Properties , 3-126
Nonideality , 3-8, 3-20, 3-45, 3-46, 3-64
NBS Tech Note , 3-126
Non-ionic Chemical Systems , 3-19
NBS2 , 3-113
Nonpolar Gas Mixtures , 3-136
N-butane , 3-96
Nonpolar Gaseous Mixtures , 3-56, 3-136
NC4 , 3-96
Nonpolar Substances , 3-137
NC5 , 3-94, 3-96
Thermal Conductivity , 3-132
NC6 , 3-94, 3-96
Non-Random Two-Liquid , 3-1
NC7 , 3-94, 3-96
Normal boiling point , 2-2
N-DECANE , 3-139
Normal Pressures , 3-136
N-DODECANE , 3-139
Nothnagel , 3-118, 3-122
NEOPENTANE , 3-138
Nothnagel Method , 3-118
New Alpha Function , 3-40, 3-47
N-PENTADECANE , 3-139
New Correlation , 3-34, 3-100
N-PENTANE , 3-94, 3-138
NH3 , 3-98, 3-99, 3-100
NRTL , 3-1, 3-19, 3-47, 3-71, 3-72, 3-93
Saturated Densities , 3-34
databank , 3-19
New Expression , 3-71, 3-72
NRTL K-value , 3-93
Excess Free Energy , 3-69
Excess Gibbs Free Energy , 3-72 N-TETRADECANE , 3-139
New Generalized Alpha Function , 3-41 N-TRIDECANE , 3-139
Cubic , 3-38, 3-40, 3-41 Number , 2-25, 3-108, 3-109
New Group-Contribution , 3-53 NB , 3-108, 3-109
New Mixing Rules , 3-47 N-UNDECANE , 3-139

O Petroleum Refining , 3-28, 3-30, 3-31
Phase Equil , 3-37
Phase Equilibria , 3-2, 3-40, 3-79
O2 , 3-18, 3-27, 3-28, 3-42, 3-61, 3-94, 3-96, 3-139
Applications , 3-5, 3-65
OCTANE , 3-138
Phase-dependent , 3-124
Oishi , 3-81
Phase-equilibrium , 3-35
Okamoto , 2-24
Phase-independent , 3-125
Old Framework , 3-112
Physical Property Data Service , 2-2
Olefinic , 3-131
Physics , 3-100
OLI Systems , 3-113
Pi , 3-107
Order-of-magnitude , 3-78
Pitzer , 3-56, 3-114, 3-116, 3-126, 3-127
Organic Liquid Phase , 3-107, 3-122, 3-125
Pitzer term , 3-114
Organic Phase Activities , 3-122
Plcker , 3-55, 3-56
Orye , 3-71
work , 3-55
OXYGEN , 3-139
Poling , 3-134
OXYL , 3-96
Polymer Solutions , 3-68
O-XYLENE , 3-96, 3-139
Polymer Solutions Using , 3-81
Polymer/solvent , 3-69
P Poynting , 3-63, 3-64
Poynting correction , 3-4, 3-20, 3-64, 3-101, 3-102
Panagiotopoulos-Reid , 3-44, 3-45 PR , 2-8, 3-12, 3-13, 3-14, 3-18, 3-19, 3-27, 3-35, 3-37,
3-42, 3-44, 3-47, 3-59
Panagiotopoulos-Reid SRK and PR , 3-44
Prausnitz , 3-5, 3-45, 3-55, 3-56, 3-65, 3-71, 3-72, 3-74,
Partington , 3-134 3-75, 3-77, 3-81, 3-85, 3-90, 3-101, 3-127, 3-128,
Peng , 3-35, 3-37, 3-42 3-130, 3-133, 3-134
Peng-Robinson , 3-11, 3-36, 3-38, 3-41, 3-42, 3-44, Predicting , 2-14, 2-31, 3-13, 3-126, 3-132
3-45, 3-47, 3-59 Internally Consistent Correlation , 2-16, 2-34
Peng-Robinson Huron-Vidal , 3-47 vapor-liquid-liquid , 3-14, 3-15
Peng-Robinson modified , 3-45 Vapor-Liquid-Solid Equilibria , 3-126
Peng-Robinson Panagiotopoulos-Reid , 3-44 Predicting Liquid Viscosities , 3-139
Correlation , 3-139, 3-140, 3-141
PENTANE , 3-138
Internally Consistent Correlation , 3-139
Percent Distilled , 2-22, 2-24
Predicting Saturated Liquid Density , 3-31
Perturbed-hard-sphere , 3-120
Predicting Second Virial Coefficients , 3-92
following , 3-120, 3-122
Generalized Method , 3-91, 3-92
Petro , 3-37
Predicting Viscosities , 3-142
UNIFAC structures , 3-18
Generalized Method , 3-142
PETRO Methods , 3-131, 3-132
Prediction , 2-16, 3-31, 3-78
PETROLEUM , 2-5
Improved Equation , 3-31
Petroleum Components , 2-5, 2-6, 2-11, 2-14 Modified UNIFAC Group Contribution Model , 3-78
Petroleum components-acentric factor , 2-6, 2-11, 2-14 Thermodynamic Properties , 2-16
Petroleum components-critical properties , 2-6, 2-11, Pressure , 2-20, 3-49, 3-107, 3-124
2-14 760 , 2-21, 2-22, 2-23, 2-24
Petroleum Fractions , 3-29, 3-139, 3-141, 3-142 H2O , 3-124
Equilibrium Flash Vaporization Calculations , 2-34 HF , 3-49, 3-50, 3-51
Petroleum Products , 2-21, 2-32 Pressure-explicit , 3-90
Petroleum Refiner , 2-16, 2-34, 3-29 Pressure-independent , 3-123
IX-13 Index
PRH , 3-47 Q
Primary TBP Cutpoint Set , 2-18
PRLN , 3-138
QUADRATIC , 2-25, 2-27
PRM , 3-13, 3-14, 3-15, 3-19, 3-20, 3-45
Quasichemical , 3-72
PRO/II Application Briefs Manual , 1-1
PRO/II back-calculates , 3-31
PRO/II Casebooks , 1-1 R
PRO/II databanks , 3-12, 3-13, 3-18, 3-31, 3-33
PRO/II Electrolytes , 3-107, 3-112, 3-114, 3-123, 3-128 RACKETT , 2-6, 3-9, 3-31, 3-125
PRO/II flowsheet , 3-21 applying , 2-10
use , 3-31
PRO/II Help , 1-2
Rackett liquid density , 3-31
PRO/II Keyword Input Manual , 2-3
Rackett parameter , 2-2, 3-31
PRO/II s databanks , 2-31, 3-91
PRO/II Temperature-dependent Property Radius , 3-91
Equations , 2-3 Gyration , 3-91
PRO/II Unit Operations Reference Help , 1-1 Radius of gyration , 2-2, 3-91
Probability-curve , 2-25 Rankine , 2-6, 2-10, 2-11, 2-12, 2-13, 2-14, 2-15, 2-22,
maintain , 2-25 2-23, 2-28, 2-29, 3-9, 3-23, 3-99
PROII databanks , 3-18 Raoult s , 3-23
PROPADIENE , 3-138 Rasmussen , 3-53, 3-77, 3-78
PROPANE , 3-138 Reached.Estimation , 2-20

thermophysical , 2-20
Properties , 3-132
Reaction , 3-103, 3-112
Properties From Structure , 2-5, 3-131
heat , 3-105, 3-112, 3-113
Property Generation CAVETT Method , 2-11
recommended ranges , 3-13, 3-25, 3-27, 3-29, 3-30,
Property Generation SIMSCI Method , 2-6 3-31, 3-32, 3-93, 3-95, 3-98, 3-101, 3-103
Property GenerationLee-Kesler Method , 2-14 Redlich , 3-37, 3-65, 3-66
PROVISION Graphical User Interface , 1-1 Redlich-Kister , 3-86, 3-87
PRP , 3-44 Redlich-Kister Expansion , 3-86, 3-87
Pseudocomponent , 2-1, 2-5, 2-16, 2-18, 2-25, 2-30, Redlich-Kwong , 3-25, 3-35, 3-36, 3-37, 3-40, 3-41, 3-47,
3-31, 3-32, 3-131 3-49, 3-50
define , 2-18
Reference , 3-55
Pseudocomponent Properties , 2-30
Refinery , 3-10
Generating , 2-30
Reformers , 3-10, 3-12
Pseudo-components , 3-60
Methods Recommended , 3-10
Pseudocomponents , 2-1, 2-5, 2-16, 2-17, 2-18, 2-19,
Regular Solution Theory , 3-67, 3-69
2-20, 2-25, 2-26, 2-28, 2-29, 2-30, 3-44, 3-131
Reid , 3-44
Pseudo-critical , 3-55
Reid vapor pressure (RVP) , 2-31
Pseudo-Critical Constants , 3-28
Mixtures , 3-27 Reid vapor pressure (RVP)-APICRIDE method , 2-31
Reid vapor pressure (RVP)-APINAPHTHA
Pseudocritical Constants , 3-56
method , 2-31
Pseudoreduced , 3-26
Reid vapor pressure (RVP)-ASTM D323-73
Pseuodoreduced , 3-26 method , 2-31
Pure , 3-131 Reid vapor pressure (RVP)-ASTM D323-82
PURE Methods , 3-131 method , 2-31
P-XYLENE , 3-96, 3-139 Reid vapor pressure (RVP)-ASTM D4953-91
method , 2-31
Pytkowicz , 3-126

Reid vapor pressure (RVP)-ASTM D5191-91 Equations For Solutions Involving , 3-107
method , 2-31 Second Virial Coefficients , 3-89
Reidel , 3-133, 3-134, 3-135 Empirical Correlation , 3-90
Reidel-Plank-Miller , 2-4 Setschenow , 3-116
Renon , 3-71, 3-72 Shale Oils , 2-16
Renormalized , 3-130 Should Use This Manual , 1-1
k-free , 3-130
SimSci azeotropic databank , 3-82
required components , 3-91, 3-103 SIMSCI characterization , 2-6
Required Pure Component Properties , 3-65, 3-66,
SIMSCI library , 2-1
3-67, 3-68, 3-69, 3-71, 3-72, 3-74
Sitzber , 3-66
Riazi , 2-24
Skjold-Jrgensen , 3-77
Riedel , 2-4
SLE , 3-22
Rigorous Calculation , 3-106
SO2 , 3-22, 3-61, 3-122, 3-139
Robinson , 3-35, 3-37, 3-42, 3-139
Soave , 3-38, 3-40, 3-42
Roy , 3-136
Soave-Redlich Kwong , 3-42
Roy-Thodos , 3-136
Soave-Redlich-Kwong , 1-1, 3-1, 3-11, 3-42, 3-43, 3-44,
Rubin , 3-54 3-45, 3-47, 3-59, 3-60, 3-118, 3-122
Rules , 3-27, 3-41
Soave-Redlich-Kwong Huron-Vidal , 3-47
Mixing , 3-41, 3-42
Soave-Redlich-Kwong Kabadi-Danner , 3-42, 3-60
Stewart , 3-27, 3-28
Soave-Redlich-Kwong modified , 3-45
RVP
represents , 2-32 Soave-Redlich-Kwong Panagiotopoulos-Reid , 3-44
Soave-Redlich-Kwong Panagiotoupolos-Reid , 3-44
Soave-Redlich-Kwong SimSci , 3-45
S Solid , 3-113
Solid Applications
Saini , 3-41 Methods Recommended , 3-19
Salts , 3-45 Solid Cp , 2-4
Sandler , 3-5, 3-65 Solid Phase , 3-109, 3-123, 3-126
Sato , 3-134 Solid Thermal Conductivity , 2-4
Satu , 3-132 Solid-Liquid Equilibria , 3-128, 3-129, 3-130
Saturated Densities , 3-32 Solubility Data , 3-128, 3-129, 3-130
New Correlation , 3-32 Solubility Parameter , 2-3
Saturated Liquid Density , 3-32 Solubility parameter (Hildebrand) , 2-6, 2-14, 3-68
Saturated Liquid Enthalpy , 2-4 solute components , 3-85
Saturated Liquids , 3-32 Solutions , 3-35, 3-66, 3-69
Saturated Nonpolar Liquids , 3-134 Classification , 3-66
Saturated-liquid density , 3-24 Thermodynamic Properties , 3-69
Thermodynamics , 3-37
Saturated-liquid enthalpy , 3-6, 3-8
Solvation , 3-91
Scatchard , 3-68
Solve , 3-85
Scatchard-Hildebrand , 3-25
C1 , 3-85
Schiller , 3-78
Solvent , 3-10, 3-13, 3-113
Scott , 3-68
Solvent Activities , 3-68, 3-81
Scrivner , 3-126
Generalized Correlation , 3-68
Seader , 3-23, 3-25, 3-26
Solvent De-asphalting Units , 3-10, 3-13
Second Liquid Phase , 3-109
SOUR , 3-13, 3-15, 3-16, 3-93, 3-98, 3-99, 3-100
IX-15 Index
Sour Package , 3-98 General Cubic Equation , 3-35, 3-41, 3-47
Sour water data package , 3-98 Statistical Thermodynamics , 3-74, 3-139
Sour Water EQuilibrium , 3-98 Mixtures , 3-137, 3-139
Sour Water Systems , 3-15 Statistical-mechanical , 3-72
Methods Recommended , 3-14, 3-15, 3-16 Steil , 3-132
Special Methods , 3-139 Stewart , 3-27
Liquid Viscosity , 3-139 Stiel , 2-13
Special Methods for LiquidViscosity , 3-139 Stoichiometric , 3-107
Special Packages , 3-13, 3-93, 3-95, 3-98, 3-101, 3-103 Straightforward , 2-29, 3-31, 3-89
Specific gravity , 2-3, 2-6, 2-10, 2-13, 2-17, 2-27, 2-28, Stream Average Properties , 3-131
2-29, 3-31, 3-34, 3-139
Stream Property , 3-132
Specific Heat , 3-132
Streed , 3-23, 3-26
Specific heat capacity , 2-14
Streed s , 3-26
Spencer , 3-32
Strong Electrolytes
Spline , 2-25 Thermodynamic Properties , 3-126
SRK , 1-1, 2-10, 3-8, 3-12, 3-13, 3-14, 3-17, 3-18, 3-20, Strongly Non-ideal Mixtures , 3-48
3-32, 3-33, 3-38, 3-42, 3-43, 3-44, 3-47, 3-60, 3-96, Representing Vapor-Liquid Equilibria , 3-48
3-122
Subcooled , 3-128
SRK databank , 3-96
Subcritical , 2-3
SRK HEXAMER , 3-49
SULFLN , 3-94
SRK Method , 3-122
Sulfolane , 3-94
SRK/PR , 3-12, 3-13
SULFUR DIOXIDE , 3-139
SRKH , 3-47
Supercritical Systems , 3-40
SRKKD , 3-14, 3-42
Surface Tension , 2-4, 3-132
SRKM , 3-9, 3-13, 3-14, 3-15, 3-17, 3-18, 3-20, 3-45,
3-46, 3-93, 3-95, 3-96, 3-100, 3-102, 3-103, 3-105 Suther G.A. 1968 , 3-137
SRKM/PRM , 3-13, 3-14 SWEQ , 3-98, 3-99, 3-100, 3-101

uses , 3-98, 3-101
SRKP , 3-44
Systems Containing Polar Components , 3-37
SRKS , 3-14, 3-15, 3-17, 3-18, 3-19, 3-46, 3-51
Vapor-Liquid Equilibria , 3-40
SRKS/SRKM , 3-19
Starling , 3-53, 3-54
Starling s BWRS , 3-54 T
State , 1-1, 2-10, 3-1, 3-2, 3-3, 3-4, 3-5, 3-6, 3-7, 3-8,
3-9, 3-11, 3-14, 3-17, 3-18, 3-25, 3-32, 3-35, 3-36,
TBP , 2-16, 2-18, 2-20, 2-21, 2-22, 2-23, 2-24, 2-25
3-37, 3-38, 3-40, 3-41, 3-42, 3-43, 3-44, 3-46, 3-47,
Convert , 2-21, 2-22, 2-23, 2-24
3-48, 3-49, 3-50, 3-51, 3-52, 3-53, 3-54, 3-60, 3-62,
3-63, 3-64, 3-84, 3-86, 3-88, 3-89, 3-90, 3-91, 3-93, curves , 2-21, 2-22, 2-23, 2-24, 2-25
3-95, 3-96, 3-100, 3-102, 3-103, 3-105, 3-112, 3-113, D86 , 2-20, 2-21, 2-22, 2-23, 2-24, 2-25
3-118, 3-120, 3-122, 3-124, 3-125 Hg , 2-21, 2-22, 2-23, 2-24
Associating Equation , 3-89 resulting , 2-17
equation , 1-1, 2-7, 2-9, 2-10, 2-14, 2-15, 2-16, 2-32, TBP Curves , 2-27
2-33, 3-1, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-11, 3-14, TBP cutpoints , 2-17
3-20, 3-25, 3-26, 3-31, 3-32, 3-35, 3-36, 3-37,
sets , 2-16, 2-17
3-38, 3-39, 3-40, 3-41, 3-42, 3-43, 3-44, 3-46,
3-47, 3-48, 3-49, 3-50, 3-51, 3-52, 3-53, 3-54, TBP Range , 2-18
3-56, 3-60, 3-62, 3-63, 3-64, 3-84, 3-85, 3-86, Tc , 2-6, 2-11, 2-13, 2-14, 3-7, 3-36, 3-49, 3-55
3-87, 3-88, 3-89, 3-90, 3-91, 3-93, 3-95, 3-96, TDCN , 3-139
3-100, 3-102, 3-103, 3-105, 3-112, 3-113, 3-118,
3-119, 3-120, 3-122, 3-124, 3-125 Technical Data Book , 3-28, 3-30, 3-31

Technical Gas Mixtures , 3-132 Thermophysical , 2-5, 2-20, 3-1
TEG , 3-13, 3-96 reached.Estimation , 2-20
Temperature- dependent Properties , 2-3 Third Generation Process Simulation , 3-40
Temperature-dependent , 2-3, 3-35, 3-37, 3-41, 3-78 Thomas , 3-133, 3-134
incorporating , 3-78 Thomson , 3-33, 3-34
Temperaturedependent , 3-72 Three-parameter , 3-65, 3-78
Temperature-dependent Properties , 2-3, 2-9, 2-12 Three-parameter corresponding-states , 3-30
Temperature-independent , 3-124, 3-125 TOLU , 3-94, 3-96, 3-139
Terms , 3-107 Torres-Marchal , 3-80
fugacities , 3-107 TR , 2-8, 3-7, 3-26, 3-27, 3-112, 3-123
Ternary Liquid Systems , 3-67 Trans-2-BUTENE , 3-138
Tertiary amines , 3-103 Trans-2-PENTENE , 3-138
Theory , 1-1, 3-30, 3-54, 3-56, 3-68, 3-69, 3-89, 3-91, Transport Properties , 3-131, 3-132, 3-137, 3-139, 3-142
3-126, 3-129
Transport properties-API method , 3-139
Thermal Conductivity , 3-131, 3-134, 3-135, 3-136,
Transport properties-thermal conductivity , 3-137
3-137, 3-139
Determination , 3-135 Transport properties-TWU method , 3-139
Thermal Constants , 3-126 Transport properties-viscosity , 3-132
Thermodynamic , 3-35, 3-37 Transport properties-Wilke-Chang method , 3-142

Solutions , 3-37 TRAPP , 3-131
Thermodynamic Evaluation , 3-66 Triethylene Glycol , 3-96
Binary , 3-67 Triple Point Pressure , 2-3
Thermodynamic Excess Functions , 3-72 Triple-point temperature , 3-128, 3-129
Liquid Mixtures , 3-72 True Boiling Point , 2-16
Thermodynamic Framework , 3-112, 3-123 True boiling point (TBP) data-cubic spline , 2-25
Thermodynamic Methods , 3-5, 3-10 True boiling point (TBP) data-cutting into
Thermodynamic Methods-Chemical pseudocomponents , 2-25
Applications , 3-19 True boiling point (TBP) data-probability density
Thermodynamic Methods-Density , 3-9 function (PDF) , 2-25
Thermodynamic Methods-Enthalpy , 3-5 True boiling point (TBP) data-quadratic fit , 2-25
Thermodynamic Methods-Entropy , 3-8 True vapor pressure (TVP) , 2-31
Thermodynamic Methods-General Information , 3-1 True vapor pressure (TVP)-application
guidelines , 2-31
Thermodynamic Methods-Natural Gas
Processes , 3-13 Truncated Virial , 3-89, 3-91, 3-101
Thermodynamic Methods-Phase Equilibria , 3-2 TVIRIAL , 3-89
Thermodynamic Methods-Refinery & Gas TVP
Processes , 3-10 function , 2-32
Thermodynamic Properties , 2-14, 3-53, 3-54, 3-56, TVP Methods , 2-33
3-65, 3-68, 3-126 Two-Parameter Cubic , 3-35, 3-36
Algebraic Representation , 3-66
Twu , 2-5, 2-6, 2-9, 3-38, 3-40, 3-41, 3-45, 3-46, 3-47,
Empirical Equation , 3-53
3-49, 3-51, 3-140, 3-141, 3-142
Fluids , 3-54
Twu-Bluck-Coon , 3-56
Gas Mixtures Containing Polar , 3-126
Prediction , 2-14 Twu-Bluck-Cunningham-Coon , 3-38
Solutions , 3-68 Twu-Coon-Cunningham , 3-39, 3-40
Strong Electrolytes , 3-126 Type , 2-20
Distillation Curves , 2-20, 2-24
IX-17 Index
U VAPOR , 3-123, 3-124
Vapor and Solid Phases , 3-123
Vapor fugacity , 3-1
UFT1 , 3-82
Vapor Phase , 3-125
UFT1 Lyngby , 3-78
Vapor Phase Fugacities , 3-89, 3-91, 3-118, 3-120, 3-122
UFT2 Dortmund , 3-79
Vapor Phase Imperfections , 3-100
UFT3 , 3-80
Vapor pressure , 2-2, 2-3, 2-4, 2-9, 2-10, 2-21, 3-4, 3-6,
UNDC , 3-139
3-24, 3-28, 3-29, 3-32, 3-33, 3-42, 3-50, 3-62, 3-63,
UNFV , 3-80 3-65, 3-66, 3-67, 3-68, 3-69, 3-71, 3-72, 3-85, 3-99
UNIFAC , 3-19, 3-52, 3-74, 3-78, 3-84 Vapor Pressure Calculations , 2-31
Free volume modification , 3-80
Vapor Pressure Equations , 2-4, 2-14
UNIFAC Group Contribution , 3-78
Vapor pressure-Antoine equation , 2-11
UNIFAC Structure
Vapor Thermal Conductivity , 2-4, 3-132, 3-136
petro , 3-18
Vapor Viscosity , 2-2, 2-4, 3-132
UNIQUAC , 3-18, 3-19, 3-21, 3-72, 3-73, 3-74, 3-75
Vapor/liquid , 3-124
UNIQUAC Equation , 3-73, 3-74, 3-75
Vaporization , 2-4, 2-9, 2-10, 2-13, 3-6, 3-24
UNIWAALS , 3-20, 3-21, 3-37, 3-52, 3-53
latent heat , 2-6, 2-11, 2-15, 3-6, 3-8, 3-24
UNIWAALS equation-of-state , 3-20
Vapor-Liquid Equilibria , 2-16, 3-25, 3-26, 3-27, 3-37,
Unsaturated Hydrocarbons , 3-60 3-53, 3-74, 3-100
Use , 2-18, 2-28, 3-5, 3-11, 3-12, 3-21, 3-30, 3-31, 3-98, Generalized Correlation , 3-25, 3-26
3-102 High Temperature , 3-26
cutpoints , 2-18, 2-19, 2-20 Systems Containing Polar Components , 3-40
LIBRARY , 3-6, 3-7, 3-8
VaporLiquid Equilibria , 3-74, 3-77, 3-78
PHI , 3-20, 3-21
Vapor-Liquid Equilibrium Calculations , 3-90
Rackett , 3-31, 3-32
SimSci , 3-13 VaporLiquid Equilibrium XI , 3-71
SWEQ , 3-98, 3-101 Vapor-liquid-liquid , 3-13
three-parameter corresponding-states , 3-30 predict , 3-14, 3-15
USER , 1-1 Vapor-Liquid-Solid Equilibria , 3-126
User-supplied Diffusivity Data , 3-142 Predicting , 3-126
Utilities , 3-112 Vapor-phase fugacity , 3-112
Vapor-phase nonidealities , 3-102
Various Mineral Oils
V Specific Heat , 3-135
Versatile Phase Equilibrium , 3-41
van der Waals , 3-35, 3-36, 3-37, 3-41, 3-44, 3-52, 3-55, Vidal , 3-47, 3-48
3-72, 3-74, 3-75, 3-76 Virial , 3-89, 3-90, 3-91, 3-92, 3-102, 3-118
van der Waals area and volume , 2-3, 3-72, 3-75 Viscosity , 3-132, 3-133, 3-134, 3-135, 3-136, 3-137,
Van der Waals mixing , 3-55 3-139
van Laar , 3-66, 3-67, 3-70 Nonpolar Gas Mixtures , 3-132
Technical Gas Mixtures , 3-136
Van Laar Equation , 3-67
VL , 2-9
Van Ness , 3-5, 3-65
VLE , 3-13, 3-19, 3-52, 3-78
Van Nostrand Reinhold Co , 3-68
VLE databank , 3-82, 3-83
Van t Hoff , 3-19, 3-128
VLLE , 3-59
Van t Hoff SLE , 3-19
Vloeistoftoestand , 3-37
van't HoffEquation , 3-128, 3-129, 3-130
Volume-averaged , 2-28
VANT HOFF Method , 3-22
Volume-explicit , 3-89

Volume-fraction , 2-26 Weight-fraction , 2-26
Volumetric , 3-56 WH2S , 3-15
Volumetric Data , 3-54 Wien , 3-66
Gas Mixtures , 3-56 Wilke , 3-143
Volumetric Properties , 3-56 Wilke-Chang , 3-142, 3-143
Wilke-Chang Correlation , 3-142, 3-143
Wilke-Chang method , 3-142
W
WILSON , 3-19, 3-69, 3-71, 3-72, 3-98, 3-101
Wilson Equation , 3-70, 3-71
Walas , 3-65
Wilson Equation Used , 3-71
Wamine , 3-16, 3-17
Predict Vapor Compositions , 3-71
Wasserfach , 3-136
Winkle , 3-71
WATER , 3-138, 3-139
Wiss , 3-66
Water Activity , 3-117
WNH3 , 3-15, 3-16, 3-102
Water decant , 3-14, 3-59
Wohl , 3-67
water partial pressure , 3-59, 3-60
Wohl s , 3-66
Water/hydrocarbon , 3-42
Work , 3-54
estimates , 3-42
Plcker , 3-54
Water-hydrocarbon , 3-42, 3-43, 3-60
Wright , 3-140, 3-141
Water-Hydrocarbon Phase Equilibria , 3-43
Watson , 2-11, 2-14, 3-59, 3-139
expresses , 3-139 Y
function , 3-60
Watson characterization , 2-10, 3-141, 3-142
Yamada , 3-133
Watson K , 2-28, 3-18 Yoon , 3-136
Watson K-factor , 2-12, 2-27
WATSONK , 2-27
WCO2 , 3-15 Z
Webb , 3-54
Weidlich , 3-80 Zipperer , 3-136
IX-19 Index

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PRO/II 8.

Printed in the United States of America, June 2006.

Chapter 2 Component Data

Chapter 3 Thermodynamic Methods

PRO/II Component and Thermophysical Properties Reference Manual 1

PRO/II Component and Thermophysical Properties Reference Manual 3

What is in This Manual?

Who Should Use This Manual?

PRO/II Component and Thermophysical Properties Reference Manual 1-1

PRO/II allows the user to specify pure-component physical prop-

PRO/II Component and Thermophysical Properties Reference Manual 2-1

1 PPDS, Physical Property Data Service, jointly sponsored

2-2 Component Data

Table 2-2: PRO/II Temperature-dependent Property Equations and

PRO/II Component and Thermophysical Properties Reference Manual 2-3

Another note of caution concerns the use of equations 20 and 21 in

2-4 Component Data

PRO/II Component and Thermophysical Properties Reference Manual 2-5

2-6 Component Data

PRO/II Component and Thermophysical Properties Reference Manual 2-7

The values of the seven constants in these equations are shown in

To compute the acentric factor, the parameter is determined using

2-8 Component Data

Other Fixed Properties

PRO/II Component and Thermophysical Properties Reference Manual 2-9

Property Generation CAVETT Method

Optionally, the user may choose to compute critical properties from

2-10 Component Data

Tc = 768.0712 + 1.7133693(Tb ) 0.0010834(Tb ) 2 0.008921258(Tb )( API )

Other Fixed Properties

PRO/II Component and Thermophysical Properties Reference Manual 2-11

2-12 Component Data

PRO/II Component and Thermophysical Properties Reference Manual 2-13

Other Fixed Properties

2-14 Component Data

1 Black, C., and Twu, C.H., 1983, Correlation and Prediction

PRO/II Component and Thermophysical Properties Reference Manual 2-15

2-16 Component Data

Note: Special refinery properties such as cloud point and sulfur

Cutpoint Sets (Blends)

The primary cutpoints shown in Table 2-5 may be overridden by

PRO/II Component and Thermophysical Properties Reference Manual 2-17

Association of Streams With Blends

2-18 Component Data

Streams S1 and S2 will use the pseudocomponents defined by sec-

PRO/II Component and Thermophysical Properties Reference Manual 2-19

Interconversion of Distillation Curves

Conversion of D1160 Curves

2-20 Component Data

PRO/II Component and Thermophysical Properties Reference Manual 2-21

Table 2-7: Values of Constants a, b, c

The parameter F in equation 2-64 is calculated by the following

2-22 Component Data

Conversion of D86 Curves

a) Conversion of D86 Curves with New (1987) API Method

PRO/II Component and Thermophysical Properties Reference Manual 2-23

Table 2-8: Values of Constants a, b

b) Conversion of D86 Curves with Old (1963) API Method

c) Conversion of D86 Curves with Edmister-Okamoto Method

Cutting TBP Curves

2-24 Component Data

Division into Pseudocomponents

PRO/II Component and Thermophysical Properties Reference Manual 2-25