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and Thermophysical

Properties

Reference Manual

agreement and may be used only in accordance with the terms of that

agreement.

Information in this document is subject to change without notice.

Simulation Sciences Inc. assumes no liability for any damage to any

hardware or software component or any loss of data that may occur as

a result of the use of the information contained in this manual.

Copyright Notice

part of this publication may be copied and/or distributed without the

express written permission of Simulation Sciences Inc., 601 S. Valencia

Avenue, Brea, CA 92621, USA.

Trademarks

SIMSCI is a service mark of Simulation Sciences Inc.

Printed in the United States of America.

Credits

Contributors:

Althea Champagnie, Ph.D.

John Cunningham

Allan Harvey, Ph.D.

John Tanger, Ph.D.

C.H. Twu, Ph.D.

Layout:

Kris Oca

On-line Document Conversion:

Mark Norton

Peter Stepman

Althea Champagnie, Ph.D.

Table of Contents

1.1

List of Tables

List of Figures

TOC-5

TOC-6

Introduction

Int-1

Int-1

Int-1

Finding What you Need

Int-1

Int-1

Component Data

I-3

1.1.1

Defined Components

Component Libraries

I-4

I-4

Using DATAPREPTM

Fixed Properties

I-6

I-6

Temperature-dependent Properties

I-6

Petroleum Components

General Information

Property Generation--SIMSCI Method

I-8

I-9

I-9

I-9

I-13

Assay Processing

General Information

I-16

I-18

I-18

Interconversion of Distillation Curves

I-19

I-21

I-25

Vapor Pressure Calculations

I-30

I-30

1.1.2

1.1.3

1.2

General Information

Thermodynamic Methods

I-37

1.2.1

Basic Principles

General Information

I-38

I-38

Phase Equilibria

Enthalpy

I-38

I-41

Entropy

I-43

Density

Application Guidelines

General Information

Thermodynamic Expert System (TES)

I-44

I-45

I-45

I-45

I-46

Petrochemical Applications

I-49

I-52

Chemical Applications

I-54

1.2.2

Reference Manual

Table of Contents

TOC-1

1.2.3

1.2.4

General Information

Ideal (IDEAL)

I-58

I-58

I-58

Chao-Seader (CS)

Grayson-Streed (GS)

I-60

I-61

Grayson-Streed (GSE)

Improved Grayson-Streed (IGS)

I-61

I-62

Curl-Pitzer (CP)

I-62

Johnson-Grayson (JG)

I-63

I-64

Lee-Kesler (LK)

I-64

API

Rackett

I-65

I-65

COSTALD

I-66

Equations of State

General Information

I-69

I-69

I-69

Alpha Formulations

Mixing Rules

I-71

I-73

Peng-Robinson (PR)

I-74

I-74

I-75

Soave-Redlich-KwongPanagiotopoulos-Reid

(SRKP) and Peng-Robinson PanagiotopoulosReid (PRP)

I-76

Panagiotopoulos-Reid (PRM)

I-77

1.2.5

1.2.6

TOC-2

Table of Contents

Soave-Redlich-Kwong Huron-Vidal (SRKH) and

Peng-Robinson Huron-Vidal (PRH)

I-77

HEXAMER

UNIWAALS

I-80

I-83

Benedict-Webb-Rubin-Starling

I-84

Lee-Kesler-Plcker (LKP)

Free Water Decant

General Information

Calculation Methods

I-85

I-88

I-88

I-88

General Information

Margules Equation

I-90

I-90

I-93

I-94

Flory-Huggins Theory

I-95

I-96

Wilson Equation

I-97

NRTL Equation

UNIQUAC Equation

I-98

I-99

UNIFAC

I-101

Modifications to UNIFAC

Fill Methods

I-104

I-107

I-79

May 1994

1.2.7

1.2.8

1.2.9

1.2.10

1.2.11

1.2.12

Henrys Law

I-110

Vapor Phase Fugacities

General Information

Equations of State

I-111

I-113

I-113

I-114

I-114

Hayden-OConnell

Special Packages

General Information

I-116

I-117

I-117

Glycol Package (GLYCOL)

I-117

I-120

I-122

Amine Package (AMINE)

I-125

I-127

Discussion of Equations

I-131

I-131

Modeling Example

I-133

Thermodynamic Framework

I-135

I-135

Equilibrium Constants

I-135

Vapor Phase Fugacities

I-136

I-139

Enthalpy

I-143

I-143

I-144

Solid-Liquid Equilibria

General Information

I-144

I-147

I-147

Solubility Data

I-147

I-148

I-148

Transport Properties

General Information

I-150

I-150

PURE Methods

PETRO Methods

I-150

I-151

TRAPP Correlation

I-155

Liquid Diffusivity

I-157

I-159

Index

Reference Manual

Idx-1

Table of Contents

TOC-3

List of Tables

TOC-4

1.1.1-1

1.1.1-2

Extrapolation Conventions . . . . . . . . . . . . . . . . . . . I-7

1.1.1-3

1.1.2-1

1.1.3-1

1.1.3-2

1.1.3-3

1.1.3-4

1.2.2-1

1.2.2-2

1.2.2-3

1.2.2-4

De-asphalting Units . . . . . . . . . . . . . . . . . . . . . . . I-48

1.2.2-5

1.2.2-6

1.2.2-7

1.2.2-8

1.2.2-9

1.2.2-10

Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-54

1.2.2-11

1.2.2-12

1.2.2-13

1.2.2-14

1.2.2-15

1.2.4-1

1.2.4-2

1.2.4-3

1.2.5-1

1.2.6-1

1.2.6-2

1.2.6-3

1.2.6-4

1.2.6-5

Table of Contents

May 1994

1.2.65

1.2.6-6

1.2.6-7

1.2.6-8

UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-101

1.2.8-1

1.2.8-2

1.2.8-3

1.2.11-1

1.2.12-1

1.2.12-2

1.2.12-3

List of Figures

1.1.3-1

1.1.3-2

1.2.6-1

1.2.8-1

1.2.8-2

Reference Manual

Table of Contents

TOC-5

TOC-6

Table of Contents

May 1994

Introduction

General

Information

provides details on the basic equations and calculation techniques used in the

PRO/II simulation program. It is intended as a complement to the PRO/II

Keyword Input Manual, providing a reference source for the background behind

the various PRO/II calculation methods.

What is in

This Manual?

This manual contains the correlations and methods used to calculate thermodynamic and physical properties, such as the Soave-Redlich-Kwong (SRK)

cubic equation of state for phase equilibria. This manual 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. General application

guidelines are provided, and, for many of the methods, hints to aid solution

are supplied.

This Manual?

For novice, average, and expert users of PRO/II, this manual provides a good

overview of the property calculation methods used to simulate a single unit

operation or a complete chemical process or plant. Expert users can find

additional details on the theory presented in the numerous references cited

for each method. For the novice to average user, general references are also

provided on the topics discussed, e.g., to standard textbooks.

Specific details concerning the coding of the keywords required for the

PRO/II input file can be found in the PRO/II Keyword Input Manual.

Detailed sample problems are provided in the PRO/II Application Briefs

Manual and in the PRO/II Casebooks.

Finding What

you Need

A Table of Contents and an Index are provided for this manual. Crossreferences are provided to the appropriate section(s) of the PRO/II Keyword

Input Manual for help in writing the input files.

Reference Manual

Introduction

Int-1

Symbol

Meaning

symbol indicates the section in the PRO/II Keyword Input

Manual to refer to for more information on coding the

input file.

Indicates an important note.

Int-2

Introduction

May 1994

Section 1.1

1.1

Component Data

Component Data

PRO/II allows the user to specify pure-component physical property data for a

given simulation. Pure component data are usually associated with either a predefined component in a data library, a user-defined (non-library) component, or a

petroleum pseudocomponent.

Properties for defined components can be accessed in a variety of ways. They can be

retrieved from an on-line databank or library, estimated from structural or other

data, or input by the user as non-library components. User input can be used to

override properties retrieved from the libraries.

Properties for pseudo or petroleum components are derived from generalized

correlations based on minimal data, usually the normal boiling point, molecular

weight, and standard density. Hydrocarbon streams defined in terms of assay data

(including distillation data) can be converted to discrete pseudocomponents by a

number of assay processing methods.

Reference Manual

I-3

Component Data

1.1.1

Section 1.1

Defined Components

Component

Libraries

Table 1.1.1-1 lists the property data available in the built-in component libraries for

predefined components. These libraries include the PROCESS library (the physical

property library used as the default in PROCESS, PIPEPHASE, HEXTRAN, and

early versions of PRO/II), the SIMSCI library (a fully documented physical 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.

References

I-4

Defined Components

1.

Physical Laboratory, National Engineering Laboratory, and the Institution

of Chemical Engineers in the UK.

2.

American Institute of Chemical Engineers.

May 1994

Section 1.1

Component Data

Table 1.1.1-1: PRO/II Library Component Properties

Fixed Properties and Constants

Temperature-dependent Properties

Acentric Factor

Enthalpy of Vaporization

Carbon Number

Liquid Density

Chemical Formula

Liquid Viscosity

Critical Pressure

Critical Temperature

Solid Density

Critical Volume

Dipole Moment

Enthalpy of Combustion

Surface Tension

Enthalpy of Fusion

Vapor Pressure

Flash Point

Vapor Viscosity

Gross Heating Value

Heat of Formation

Hydrogen Deficiency Number

Liquid Molar Volume

Lower Heating Value

Molecular Weight

Normal Boiling Point

Rackett Parameter

Radius of Gyration

Solubility Parameter

Specific Gravity

Triple Point Temperature

Triple Point Pressure

UNIFAC Structure

van der Waals Area and Volume

Reference Manual

Defined Components

I-5

Component Data

Using DATAPREPTM

Section 1.1

SimSci provides an interactive program, DATAPREP, for review and manipulation of the pure component fixed and temperature-dependent properties available for defined components in libraries. DATAPREP is PC based.

Detailed descriptions for both the fixed and temperature-dependent library

properties mentioned above are contained in Appendix A of the DATAPREP

User Guide.

A comprehensive summary of the available data for each component, for any

release of the libraries, can also be generated by using DATAPREP.

DATAPREPs functionality also includes the ability to generate keyword

input file inserts containing component properties for non-library components. Private pure component libraries can also be made using DATAPREP.

In addition to the USER.LB1 and USER.LB2 files that can be used directly

by PRO/II on a PC, ASCII input files are generated for input to the library

manager program for use on other platforms. Please refer to the DATAPREP

User Guide for further information about its capabilities.

Reference

DATAPREP User Guide, 1991, Simulation Sciences Inc.

Fixed Properties

As explained in the above section, these properties are described in Appendix A of the DATAPREP User Guide. Some things to be aware of are that

the specific gravities of permanent gases are often given relative to air, without any annotations in the output, and liquid molar volumes can be

extrapolated from a condition very different from 77 F (25 C), if the

component doesnt naturally exist as a liquid at 77 F.

Temperaturedependent

Properties

in Section 17, Component Properties, of the PRO/II Keyword Input Manual.

The equations that are typically used to represent a property are listed in Table 1.1.1-2. While temperature-dependent library properties are fitted and are

usually very accurate at saturated, subcritical conditions, caution must be

used in the superheated or supercritical regions.

Because of the form of some of the allowable temperature-dependent equations,

extrapolation beyond the minimum and maximum temperatures is not done using

the actual correlation. PRO/II has adopted the rules shown in Table 1.1.1-2, based

on the property, for extrapolation of the temperature-dependent correlations.

I-6

Defined Components

May 1994

Section 1.1

Component Data

Table 1.1.1-2: PRO/II Temperature-dependent Property Equations and

Extrapolation Conventions

Temperature-dependent

Property

Recommended

Equations

Extrapolation

Method

Vapor Pressure

Liquid Density

1, 4, 16, 32

Prop. vs. T

1, 17, 41

Prop. vs. T

Enthalpy of Vaporization

4, 15, 36, 43

Prop. vs. T

1, 42, 35

Prop. vs. T

Liquid Viscosity

13, 20, 21

Vapor Viscosity

1, 19, 26, 27

Prop. vs. T

1, 4, 34

Prop. vs. T

1, 19, 33

Prop. vs. T

Surface Tension

1, 15, 30

Prop. vs. T

Prop. vs. T

Solid Density

Prop. vs. T

Solid Cp or Enthalpy

Prop. vs. T

20

component vapor pressures. These equations are actually combinations of

two or more traditionally used vapor pressure equations (e.g., Antoine). It is

intended that the user apply only subsets of the available coefficients with

these equations corresponding to the more traditional equations. Table

1.1.1-3 gives some examples of this mapping.

Equation 20 / 21 Coefficients

Common VP Equations (#)

C1

C2

Antoine (21)

Riedel (20)

Frost-Kalkwarf (21)

Reidel-Plank-Miller (20)

Reference Manual

C3

C4

C5

C6

C7

x

x

x

Defined Components

I-7

Component Data

Properties From

Structure

I-8

Defined Components

Section 1.1

estimated if the user supplies a component structure and invokes the FILL

option in the component data category of input. This procedure primarily

uses the methods of Joback and is good for components with molecular

weights below 400 and components with less than 20 unique structural

groups. More accurate results are obtained for components containing just

one type of functional group. For example, amine properties would be more

accurate than those predicted for an ethanol amine, which would contain

functional groups for both an alcohol and an alcohol amine. This feature is

available in DATAPREP and in PRO/II for all versions subsequent to v3.3.

Complete documentation of the estimation techniques used is contained in

Section 3.7, Prediction, of the DATAPREP User Guide.

May 1994

Section 1.1

1.1.2

Component Data

Petroleum Components

General

Information

on a one-by-one basis on PETROLEUM statements or generated from one or

more streams given in terms of assay data. The processing of assays is described in Section 1.1.3, Assay Processing. 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 keyword). These methods are

described in the sections below.

From those three basic properties, the program estimates all other properties

needed for the calculation of thermophysical properties. Three different sets of

characterization methods are provided. These are known as the CAVETT, SIMSCI, and Lee-Kesler methods. The Cavett methods developed in 1962 have been

the default in all versions of PRO/II up to and including the 3.5 series. The 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

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 system of normal alkanes. The

critical temperature (in degrees Rankine) is given by:

Tc = Tc 1 + 2fT 1 2fT

(1)

12

12

fT = SGT0.362456 Tb + 0.03982850.948125 Tb SGT

(2)

Reference Manual

Petroleum Components

I-9

Component Data

Section 1.1

SGT = exp5SG SG 1

(3)

3

7 2

(4)

(5)

12

where:

SG =

specific gravity

Tb =

1 - T b / T c

f=

correction factor

SG =

specific gravity

subscript c refers to the critical conditions

superscript refers to the reference system

The critical volume (in cubic feet per pound mole) and the critical pressure

(in psia) are given by similar expressions:

Vc = Vc 1 + 2fV 1 2fV

12

fV = SGV 0.466590 Tb

(6)

1 2

+ 0.182421 + 3.01721 Tb SGV

(7)

(8)

(9)

3

14

Vc = 1 0.419869 0.505839 1.56436 9481.70

Pc = Pc Tc Tc Vc Vc 1 + 2fP 1 2fP

(10)

12

1 2

+ 11.4277 + 252.140 Tb

0.00127885Tb

(11)

+ 0.00230535Tb SGP]

SGP = exp0.5SG SG 1

Pc = 3.83354 + 1.19629

where:

12

2

4

+ 34.8888 + 36.1952 + 104.193

V=

P=

pressure, psia

(12)

2

(13)

I-10

Petroleum Components

May 1994

Section 1.1

Component Data

The acentric factor for the SIMSCI method is estimated with the use of a generalized Frost-Kalkwarf vapor equation developed at SimSci. The equation is

given by:

lnPR = A1 + A4 + A2 + A5 TR + A3 + A6 lnTR + A7PRTR

(14)

where:

A1 to A7 =

PR =

TR =

lnP A P T 2 f T

R,b

7 R,b R,b

R,b

=

f TR,b

(15)

where:

subscripts R,b indicate reduced properties evaluated at the

normal boiling point

Functions f and f are given by:

f (TR) = A1 + A2 TR + A3 lnTR

(16)

f (TR) = A4 + A5 TR + A6 lnTR

(17)

The values of the seven constants in these equations are shown in Table 1.1.2-1.

Table 1.1.2-1: 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

(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:

= log10 PR,T

Reference Manual

=0.7

(18)

Petroleum Components

I-11

Component Data

Section 1.1

The heat of formation is computed from a proprietary correlation developed by

SimSci. The solubility parameter is estimated from the following equation:

HV RT 1 2

=

VL

(19)

The molar latent heat of vaporization, HV, is computed from the KistiakowskyWatson method described later on in this section, while VL is the liquid molar

volume at 25 C.

Temperature-dependent Properties

The ideal-gas enthalpy (needed for equation-of-state calculations) is 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 equation (which produces enthalpies in Btu/lb and

uses temperatures in degrees Rankine) is as follows:

(20)

A3 2 A4 3

T +

T

2

3

H = A1 + A2 T +

A2 = C1 + C7C4

(21)

A3 = C2 + C7C5

(22)

A4 = C3 + C7C6

(23)

C1 = 0.33886 + 0.02827 K

(24)

2

7

(25)

C3 = 1.665810

(26)

C4 = (0.26105 0.59332K)

(27)

C5 = 4.9210

(28)

7

(29)

C6 = (0.536 0.6828K)10

(30)

K=

1 3

NBP

SG

(31)

where:

NBP = normal boiling point in degrees Rankine

SG =

I-12

Petroleum Components

specific gravity

May 1994

Section 1.1

Component Data

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

reference point and the ideal-gas state.

The vapor pressure is calculated from the reduced vapor-pressure equation

(14) used above in the calculation of the acentric factor. The latent heat of

vaporization is also calculated from equation (14). The saturated liquid 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

computed by applying the Rackett equation (see Section 1.2.3, Generalized

Correlation Methods) to saturated temperature and pressure conditions as

predicted from the vapor-pressure equation (14).

Property

Generation-CAVETT Method

Optionally, the user may choose to compute critical properties from the methods developed in 1962 by Cavett. This option is called the CAVETT method.

The equations are:

2

6 3

(32)

2 2

3

5 2

(33)

4

8 3

7

2 2

where:

Tc =

Pc =

Tb =

API =

API gravity

When the CAVETT characterization options are chosen, the acentric factor is

computed by a method due to Edmister (1958):

=

3 log10 Pc

1

7 (Tc Tb) 1

Reference Manual

(34)

Petroleum Components

I-13

Component Data

Section 1.1

In equation (34), Pc is in atmospheres. Finally, the critical volume is estimated from the following equation:

Zc =

15

Pc Vc

RTc

(35)

= 0.291 0.08

method, see Section 15, Petroleum Component Properties, of the PRO/II

Keyword Input Manual.

Other Fixed Properties

When the CAVETT characterization option is chosen, the heat of formation

and solubility parameter are calculated exactly as in the SIMSCI method

above.

Temperature-dependent Properties

Ideal-gas enthalpies (in Btu/lb-mole) are computed with the following equations:

H = A + BT + CT + DT

(36)

A = a5MW a4 + a0

(37)

(38)

C = a2 1379.01a1

(39)

11

8

D = a1 = 9.17510 API 5.63310 MW

(40)

a2 = 3.10710

5.83210

a3 = 1.702510

API MW

1.48910

5

API API 2.85710 API

+ 4.29310 3.08410

3

(41)

(42)

K K + 0.088) K 0.819 MW

(43)

(44)

+ 3.53510

3

API 0.053API 5.95610 K + 3.544 API

where:

T=

MW = molecular weight

API =

API gravity

K=

arbitrary zero of enthalpy, which is the saturated liquid at 0 C.

I-14

Petroleum Components

May 1994

Section 1.1

Component Data

Vapor pressures (in psia) are computed from a generalized Antoine equation:

ln P = A +

A = ln(14.696)

B=

(45)

B

T 80.0

(46)

B

Tb 80.0

ln Pc ln(14.696)

1

1

Tc 80.0 Tb 80.0

(47)

Tb) are in degrees Rankine.

The saturated liquid density (in lb/ft3) is computed as follows:

= A + BT + CT

(48)

A = 1.328 L,60

(49)

B=

C=

0.3076 L,60

Tc

(50)

0.3989 L,60

(51)

2

Tc

where:

L,60 = liquid density at 60 F, calculated from the specific gravity

and the density of water

Temperatures are in degrees Rankine

The latent heat of vaporization (in Btu/lb-mole) is calculated from a 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:

Tc T

Hvap = H0

Tc Tb

(52)

(53)

0.38

The critical temperature Tc, normal boiling point Tb, and temperature T are

all in degrees Rankine.

The saturated liquid enthalpy is estimated with the correlation of Johnson

and Grayson. This method is discussed in Section 1.2.3, Generalized Correlation Methods. A constant is added so that the saturated liquid enthalpy is

zero at 0 C.

Reference Manual

Petroleum Components

I-15

Component Data

Property

Generation--LeeKesler Method

Section 1.1

Kesler and Lee used the following equations in 1976 to correlate critical temperatures and critical pressures of hydrocarbons:

(54)

5

(55)

2

3

lnPc = 8.3634 0.0566 SG 0.24244 + 2.2898 SG + 0.11857 SG 10 Tb +

where:

Tc, Tb = critical and normal boiling temperatures (both in degrees

Rankine)

Pc =

SG =

specific gravity

and Kesler (1975):

6

(56)

6

where:

subscripts R,b indicate reduced properties evaluated at the normal

boiling point

The critical volume is then estimated from the following equation:

Zc =

Pc Vc

= 0.2905 0.085

RTc

(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.

Temperature-dependent Properties

Ideal-gas enthalpies (in Btu/lb-mole) are computed by integrating the following equation for the ideal-gas heat capacity:

(58)

2

4

7 2

Cp = 0.33886 + 0.02827K 0.9291 1.1543K + 0.0368K 10 T 1.665810 T

4

7 2

(CF)0.26105 0.59332 (4.56 9.48)10 T (0.536 0.6828)10 T

I-16

Petroleum Components

May 1994

Section 1.1

Component Data

CF = [(12.8 K)(10 K) (10)]

(59)

where:

K=

T=

arbitrarily chosen basis for enthalpy, which is the saturated liquid at 0 C.

When the Lee-Kesler characterization option is chosen, the vapor pressure,

saturated liquid density, saturated liquid enthalpy, and latent heat of vaporization are all calculated by the methods used for CAVETT characterization, as

described in the previous section.

References

1.

Thermodynamic Properties for Heavy Petroleum, Shale Oils, Tar Sands

and Coal Liquids, paper presented at AIChE Spring Meeting, Houston,

March 1983.

2.

Cavett, R.H., 1962, Physical Data for Distillation Calculations Vapor-Liquid Equilibria, 27th Mid-year Meeting of the API Division of

Refining, 42[III], 351-357.

3.

Compressibility Factors and Equations of State, Petroleum Refiner,

37(4), 173.

4.

fractions, Hydrocarbon Proc., 53(3), 153-158.

5.

6.

Correlation Based on Three-Parameter Corresponding States, AIChE J.,

21, 510-527.

7.

Thek, R.E., and Stiel, L.I., 1966, A New Reduced Vapor Pressure Equation,

AIChE J., 12, 599-602.

8.

Critical Properties and Molecular Weights of Petroleum and Coal-tar

Liquids, Fluid Phase Equil., 16, 137-150.

9.

Reference Manual

Petroleum Components

I-17

Component Data

1.1.3

Section 1.1

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

pseudocomponents which are then used to represent the composition of each

assay stream.

The process by which assay data are converted to pseudocomponents can be 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 cutpoints define the

(atmospheric) boiling ranges that will ultimately correspond to each

pseudocomponent. Multiple cutpoint sets (also known as blends) may

also be defined to better model different sections of a process.

Each set of user-supplied distillation data is converted to a TBP (True

Boiling Point) basis at one atmosphere (760 mm Hg) pressure.

The resulting TBP data are fitted to a continuous curve and then the program cuts each curve to determine what percentage of each assay

goes into each pseudocomponent as defined by the appropriate cutpoint

set. Gravity and molecular weight data are similarly processed so that

each cut has a normal boiling point, specific gravity, and molecular

weight. During this step, the lowest-boiling cuts may be eliminated or

modified to account for any lightends components input by the user.

Within each cutpoint set, all assay streams using that set (unless they are

explicitly excluded from the blending - this is described later) are 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 processing by the simulator is outside the

scope of this chapter but will be covered in a later document.

I-18

Assay Processing

May 1994

Section 1.1

Cutpoint Sets

(Blends)

Component Data

Defining Cutpoints

In any simulation, there is always a primary cutpoint set, which defaults

as shown in Table 1.1.3-1.

Table 1.1.3-1: Primary TBP Cutpoint Set

TBP Range, oF

Number of

Components

Width, oF

100-800

28

25

800-1200

50

1200-1600

100

The primary cutpoints shown in Table 1.1.3-1 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 cutpoint set will be the default. Each cutpoint set (if it is actually used

by one or more streams) will produce its own set of pseudocomponents for

use in the flowsheet.

15

PRO/II Note: For more information on specifying TBP cutpoint sets, see Section

15, Petroleum Component Properties, of the PRO/II Keyword Input Manual.

Association of Streams With Blends

Each assay stream is associated with a particular blend. By default, an assay

stream is assigned to the default cutpoint set. A stream may be associated

with a specific secondary cutpoint set by explicitly specifying the name of

that cutpoint set (blend) in association with the stream. If the assay stream is

associated with a blend name not given for any cutpoint set previously defined, a new blend with that name is created using the same cutpoints as the

primary cutpoint set. The user may also specify that a stream use a certain set

of cutpoints but not contribute to the blended properties of the pseudocomponents generated from that set (this might be appropriate if an estimate were

being supplied for a recycle stream, for example). This is done by selecting

the XBLEND option, which excludes the stream in question from the 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:

Reference Manual

Assay Processing

I-19

Component Data

Section 1.1

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 1.1.3-2: Blending Example

Stream

Blend Option

Blend Name

S1

none given

(defaulted to

BLEND)

none given

(defaulted to A1)

S2

XBLEND

none given

(defaulted to A1)

S3

XBLEND

A1

S4

BLEND

A2

S5

BLEND

B1

S6

XBLEND

B1

S7

BLEND

B2

Streams S1 and S2 will use the pseudocomponents defined by secondary cutpoint set A1, since it is the default. S3 will also use A1s pseudocomponents

since it is specified directly. The pseudocomponents in blend A1 will have

properties determined only by the cuts from stream S1, since the XBLEND

option was used for S2 and S3. Stream S4 will use the pseudocomponents 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 S5s 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 primary cutpoint set.

Since it is a different blend, however, the pseudocomponents from blend B2

will be completely distinct (even though they will use the same cutpoint

ranges) from those of blend B1.

15

I-20

Assay Processing

PRO/II Note: For more information on blending options for assay streams, see

Section 15, Petroleum Component Properties, of the PRO/II Keyword Input

Manual.

May 1994

Section 1.1

Component Data

Application Considerations

The selection of cutpoints is an important consideration in the simulation of

hydrocarbon processing systems. Too few cuts can result in poor representation of yields and stream properties when distillation operations are

simulated; moreover, desired separations may not be possible because of

component distributions. On the other hand, the indiscriminate use of cuts

not needed for a simulation serves only to increase the CPU time 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 functionality is useful when different portions of a flowsheet are best represented by different TBP cuts; for

example, one part of the process may have streams that are much heavier

than another and for which more cutpoints at higher temperatures would be

desirable. It is also useful when hydrocarbon feeds to a flowsheet differ in

character; for example, different blends might be used to represent an aromatic stream (producing pseudocomponents with properties characteristic of

aromatics) and a paraffinic stream feeding into the same flowsheet. The extra

detail and accuracy possible with this feature must be balanced against the increase in CPU time caused by the increased number of pseudocomponents.

Interconversion 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, rigorous TBP distillations are

difficult and not well standardized so it is common to perform some other

well-defined distillation procedure; standard methods are defined by the

American Society for Testing and Materials (ASTM). The ASTM procedures

most commonly used for hydrocarbons are D86, D1160, and D2887.

Reference Manual

Assay Processing

I-21

Component Data

Section 1.1

ASTM D86 distillation is typically used for light and medium petroleum

products and is carried out at atmospheric pressure. D1160 distillation is

used for heavier petroleum products and is often carried out under vacuum,

sometimes at absolute pressures as low as 1 mm Hg. The D2887 method uses

gas chromatography to produce a simulated distillation curve; it is applicable

to a wide range of petroleum systems. D2887 results are always reported by

weight percent; other distillations are almost always reported on a volume

percent basis. More details on these distillation procedures may be found in

the API Technical Data Book; complete specifications are given in volume 5

(Petroleum Products and Lubricants) of the Annual Book of ASTM Standards.

Conversion of D1160 Curves

PRO/II converts D1160 curves to TBP curves at 760 mm Hg using the threestep procedure recommended in the API Technical Data Book:

Convert to D1160 at 10 mm Hg using API procedure 3A4.1 (which in

turn references procedure 5A1.13). This procedure is expressed as a way

to estimate a vapor pressure at any temperature given the normal boiling

point, but the same equations may be solved to yield a normal boiling

temperature given the boiling temperature at another pressure. The equations used are as follows:

log10P =

3000.538X 6.76156

for X > 0.0022 (P < 2 mm Hg)

43X 0.987672

log 10P =

2663.129 X 5.994296

0.0013 X 0.0022

95.76X 0.972546

(1)

(2)

(2 P 760 mm Hg)

log10P =

2770.085X 6.412631

for X < 0.0013 (P > 760 mm Hg)

36X 0.989679

(3)

where:

P* =

Rankine)

Tb

X=

0.0002867Tb

(4)

T

748.1 0.2145Tb

where:

Tb =

I-22

Assay Processing

Hg

May 1994

Section 1.1

Component Data

For conversions where neither pressure is 760 mm Hg, the conversion may

be made by applying the above equations twice in succession, using 760 mm

Hg as an intermediate point:

Convert to TBP at 10 mm Hg using API Figure 3A2.1 (which has been

converted to equation form by SimSci).

Convert to TBP at 760 mm Hg using API procedure 3A4.1.

Conversion of D2887 Curves

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:

b c

(5)

D86 = a(SD) F

where:

D86 and SD = the ASTM D86 and ASTM D2887 temperatures in degrees Rankine at each volume percent (for D86) and the

corresponding weight percent (for SD), and a, b, and c

are constants varying with percent distilled according

to Table 1.1.3-3.

Table 1.1.3-3: Values of Constants a, b, c

Percent

Distilled

6.0154

0.7445

0.2879

10

4.2262

0.7944

0.2671

30

4.8882

0.7719

0.3450

50

24.1357

0.5425

0.7132

70

1.0835

0.9867

0.0486

90

1.0956

0.9834

0.0354

100

1.9073

0.9007

0.0625

0.05434

F = 0.009524(SD 10%)

(6)

0.6147

(SD 50%)

where:

SD10% and SD50% = D2887 temperatures in degrees Rankine at the 10% and

50% points, respectively

Reference Manual

Assay Processing

I-23

Component Data

Section 1.1

described in the section Conversion of D86 Curves with New (1987) API

Method below.

Conversion of D86 Curves

PRO/II has three options for the conversion of D86 curves to TBP curves at 760

mm Hg. These are the currently recommended (1987) API method, the older

(1963) API method, and the Edmister-Okamoto correlation. In addition, a 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 recommended 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:

Tcorr = Tobs + D ; log10D = 1.587 + 0.00473Tobs

(7)

where:

Tcorr, Tobs = the corrected and observed temperatures, respectively,

in degrees Fahrenheit.

If necessary, convert the D86 curve at pressure P to D86 at 760 mm Hg

with the standard ASTM correction factor:

T760 = TP + 0.00012(760 P)(460 + TP)

(8)

where:

TP =

Convert from D86 at 760 mm Hg to TBP at 760 mm Hg using one of the

three procedures below.

a)

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:

TBP = a(D86)

(9)

where a and b are constants varying with percent of liquid sample distilled

as given in Table 1.1.3-4:

I-24

Assay Processing

May 1994

Section 1.1

Component Data

Table 1.1.3-4: Values of Constants a, b

Percent Distilled

0.9167

1.0019

10

0.5277

1.0900

30

0.7429

1.0425

50

0.8920

1.0176

70

0.8705

1.0226

90

0.9490

1.0110

100

0.8008

1.0355

This method, while no longer the default, is still available for users whose

flowsheets may be tuned to the results using the old method. This method

was recommended (and shown in graphical form) in older editions of the

API Technical Data Book. The graphical correlation has been converted to

equation form by SimSci.

c)

Edmister and Okamoto (1959) developed a method which is still widely

used for converting ASTM D86 curves to TBP curves. If the EdmisterOkamoto method is specified as the conversion method, their procedure

(converted from the original graphical form to equations by SimSci) is

used for conversion of D86 to TBP curves.

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 percents between the first

and last points. Beyond those bounds, points 1 and 2 and points N and N-1

are used to define a normal distribution function to extrapolate to the 0.01%

and 99.99% points, respectively. If only two points are supplied, the entire

curve is defined by the distribution function fit. This extrapolation feature is

particularly valuable when extrapolating heavy ends distillations which often

terminate well below 50 volume percent. This method in general results in an

excellent curve fit. The only exception is when the distillation data contain a

significant step function (such a step is often the unphysical result of an error

in obtaining or reporting the data); in that case, the step creates an instability

that tends to propagate throughout the entire length of the curve. Should this

happen, the input data should be checked for validity.

Reference Manual

Assay Processing

I-25

Component Data

Section 1.1

The quadratic fit method (known as the QUADRATIC option) provides 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

constrained to pass through either or both of the initial point and end point.

The PDF method is recommended whenever it is suspected that the 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 procedures work by doing the

conversion at a fixed set of volume percents, 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 streams volume that is assigned to the pseudocomponent

defined by the interval between two adjacent cutpoints. For example, using the

default set of cutpoints shown in Table 1.1.3-1, the first pseudocomponent would

contain all material boiling between 100 F and 125 F, the second would 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 volume-fraction average (or, in rare cases where TBP, D86, or D1160 distillations are

entered on a weight basis, as a weight-fraction average) by integrating across

the cut range. For small cut ranges, this will closely approach other types of

average boiling points. These average boiling points are used (possibly after

blending with cuts from other assay streams in the flowsheet) as correlating

parameters when calculating other thermophysical properties for each

pseudocomponent.

I-26

Assay Processing

May 1994

Section 1.1

Component Data

with an IP of 90 F being cut according to the default cutpoint set (Table

1.1.3-1); for simplicity only the first ten percent of the curve is shown. In 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 manner.

Figure 1.1.3-1:

Cutting TBP Curves

Gravity Data

PRO/II requires the user to enter an average gravity (either as a Specific

Gravity, API Gravity, or Watson K-factor) for each assay. If a Watson K is

given, it is converted to a gravity using the TBP data for the curve. Entry of a

gravity curve is recommended but not required.

If a user-supplied gravity curve does not extend to the 95% point, quadratic

extrapolation is used to generate an estimate for the gravity at the 100%

point. A gravity for each cut is determined at its mid-point, and an average

gravity for the stream is computed. If this average does not agree with the

specified average, the program will either normalize the gravity curve (if

data are given up to 95%) or adjust the estimated 100% point gravity value to

force agreement. Since the latter could in some cases result in unreasonable

gravity values for the last few cuts, the user should consider providing an estimate of the 100% point gravity value and letting the program normalize the

curve, particularly when gravity data are available to 80% or beyond.

Reference Manual

Assay Processing

I-27

Component Data

Section 1.1

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:

K=

13

NBP

SG

(10)

where:

NBP = normal boiling point in degrees Rankine

SG =

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 (10)

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 primarily for compatibility with older versions. It is similar to the preferred method described

above, except that the average Watson K is estimated from the 10, 30, 50, 70,

and 90 percent points on a D86 curve (which can be obtained from the TBP

curve by reversing one of the procedures in the previous section) and then

applied to the NBP of each TBP cut to generate a gravity curve. This curve is

then normalized to produce the specified average gravity.

The preferred method (constant Watson K applied to TBP curve) is justified

by the observation that, for many petroleum crude streams, the Watson K of

various petroleum cuts above light naphtha tends to remain fairly constant.

For other types of petroleum streams, however, this assumption is often incorrect. Hence, for truly accurate simulation work, the user is advised to supply

gravity curves whenever possible.

Molecular Weight Data

In addition to the NBP and specific gravity, simulation with assays requires

the molecular weight of each cut. These may be omitted completely by the

user, in which case they are estimated by the program.

The user may supply a molecular weight curve, which is quadratically interpolated and extrapolated to cover the entire range of pseudocomponents. Optionally, the user may also supply an average molecular weight. In that case,

the molecular weight value for the last cut is adjusted so that the curve

matches the given average, or if the 100% value is provided, the entire molecular weight curve is normalized to match the given average.

I-28

Assay Processing

May 1994

Section 1.1

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. Twus

method was originally developed to be an improvement over Figure 2B2.1 in

older editions of the API Technical Data Book. That figure relates molecular

weight to NBP and API gravity for NBPs greater than 300 F. The SIMSCI

method matches that data between normal boiling points of 300 F and 800

F, and better extrapolates outside that temperature range.

The unaltered old API method is (API63) is also available.

A newer API method, called the extended API method (known as the EXTAPI

option), is also available. This is API procedure 2B2.1, and it is an extension of

the earlier API method which better matches known pure-component data below

300 F. The equation is as follows:

(11)

4

3

1.26007

4.98308

MW = 20.486 exp (1.165 10 Tb 7.78712 SG + 1.1582 10 Tb SG) Tb

SG

where:

SG =

Tb =

Lightends Data

Hydrocarbon streams often contain significant amounts of light hydrocarbons

(while there is no universal definition of light, C6 is a common upper limit).

Simulation of such systems is more accurate if these components are considered

explicitly rather than being lumped into pseudocomponents. If the distillation

curve is reported on a lightends-free basis, the light components can be fed to

the flowsheet in a separate stream and handled in a straightforward manner. 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 components are adjusted up or down, all

in the same proportion, until the NBP of the highest-boiling lightends component

exactly intersects the TBP curve. All of the cuts from the TBP curve falling into the

region covered by the lightends are then discarded and the lightends components

are used in subsequent calculations. This procedure is illustrated in Figure 1.1.3-2,

where lightend component flows are adjusted until the highest-boiling lightend

(nC5 in this example) has a mid-volume percent (point a) that exactly coincides

with the point on the TBP curve where the temperature is equal to the NBP of nC5.

The cumulative volume percent of lightends is represented by point b, and the

cuts below point b (and the low-boiling portion of the cut encompassing that point)

are discarded.

Reference Manual

Assay Processing

I-29

Component Data

Section 1.1

Figure 1.1.3-2:

Matching Lightends

to TBP Curve

weight or liquid-volume basis) of the total assay or as a fixed lightends flowrate.

In these cases, the input numbers for the lightends components can be 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 produce average

properties for the pseudocomponents from each cutpoint interval in that

blend. All the streams in a given blend (except for those for which the

XBLEND option was used) are totaled to get the weights, volumes, and

moles for each cutpoint interval. Using the above totals, the average molecular weight and gravity are calculated for each cut range. Finally, the normal

boiling point for each pseudocomponent is calculated by weight averaging

the individual values from the contributing streams.

Once the normal boiling point, gravity, and molecular weight are known for

each pseudocomponent, all other properties (critical properties, enthalpies,

etc.) are determined according to the characterization method selected by the

user (or defaulted by the program). These methods are described in Section

1.1.2, Petroleum Components.

Vapor Pressure

Calculations

I-30

Assay Processing

While not a part of the programs actual processing of assay streams, many

problems involving hydrocarbon systems will involve a specification on

some vapor pressure measurement. The two most common of these are the

True Vapor Pressure (TVP) and the Reid Vapor Pressure (RVP). PRO/II 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.

May 1994

Section 1.1

Component Data

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 specify 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 generate that stream.

Reid Vapor Pressure (RVP) Calculations

The RVP laboratory procedure provides an inexpensive and reproducible 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 pressure is a rough

measure of the true vapor pressure. Six different calculation 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

system used to generate the stream will be used.

The APINAPHTHA method calculates the RVP from Figure 5B1.1 in the API

Technical Data Book, which represents the RVP as a function of the TVP and

the slope of the D86 curve at the 10% point. The graphical data have been converted to equation form by Simsci. This method is the default for PRO/IIs RVP

calculations. It is useful for many gasolines and other finished petroleum 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 function of the TVP and

the slope of the D86 curve at the 10% point. The graphical data have been

converted to equation form by SimSci. It is primarily intended for crude oils.

The ASTM D323-82 method (known as the D323 method) simulates a 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.

Reference Manual

Assay Processing

I-31

Component Data

Section 1.1

The ASTM D4953-91 method (known as the D4953 method) was developed

by the ASTM primarily for oxygenated gasolines. The experimental method

is identical to the D323 method, except that the system is kept completely

free of water. The algorithm for simulating this method is identical to that for

D323, except that no water is added to the mixture. Air should be in the 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 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:

DVPE = 0.965X A

(12)

where:

X=

A=

This number is then reported as the RVP. Air should be in the component list

for proper use of this method.

Comments on RVP and TVP Methods

Because of the sensitivity of the RVP (and the TVP) to the light components

of the mixture, these components should be modeled as exactly as possible if

precise values of RVP or TVP are important. This might mean treating more

light hydrocarbons as defined components rather than as pseudocomponents;

oxygenated compounds blended into gasolines should also be represented as

defined components rather than as part of an assay. It is also important to apply a thermodynamic method that is appropriate for the stream in question

(see Section 1.2.2, Application Guidelines). The thermodynamics becomes

particularly important for oxygenated systems, which are not well-modeled

by traditional hydrocarbon methods such as Grayson-Streed. These systems

are probably best modeled by an equation of state such as SRK with the SimSci alpha formulation and one of the advanced mixing rules (see Section

1.2.4, Equations of State). It is important to have binary interaction parameters between the oxygenates and the hydrocarbon components of the system.

PRO/IIs databanks contain many such parameters, but others may have to be

regressed to experimental data or estimated.

One should not be too surprised if calculated values for RVP differ from an

experimental measurement by as much as one psi. Part of this is due to the

uncertainty in the experimental procedure, and part is due to the fact that the

lightends composition inside the simulation may not be identical to that of

the experimental sample.

I-32

Assay Processing

May 1994

Section 1.1

Component Data

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 vaporization of the liquid water. In the extreme case of 100% humidity, the D323

results will be nearly identical with the D4953 results. Therefore, a wet

test performed with air that was not dry would be expected to give results intermediate between PRO/IIs D323 and D4953 calculations. The results from

the D5191 method (both in terms of the experimental and calculated numbers) should in general be very close to D4953 results.

The primary application guideline for which RVP calculational model to use

is, of course, to choose the one that corresponds to the experimental procedure applied to that stream. Secondary considerations include limitations of

the individual methods. The APINAPHTHA and APICRUDE methods are

good only for hydrocarbon naphtha and crude streams, respectively. The

D323 method (and its obsolete predecessor, P323) is intended for hydrocarbon streams; the presence of water makes it less well-suited for use with

streams containing oxygenated compounds. The D4953 and D5191 methods

are both better suited for oxygenated systems, and calculations with these

methods should give similar results.

References

1.

Refining, 5th edition (also previous editions), American Petroleum

Institute, Washington, DC.

2.

Standards, section 5 (Petroleum Products, Lubricants, and Fossil Fuels),

ASTM, Philadelphia, PA (issued annually).

3.

Thermodynamics, Part 12: Equilibrium Flash Vaporization Calculations

for Petroleum Fractions, Petroleum Refiner, 38(8), 117.

4.

Critical Properties and Molecular Weights of Petroleum and Coal-tar

Liquids, Fluid Phase Equil., 16, 137-150.

Reference Manual

Assay Processing

I-33

I-34

Assay Processing

May 1994

Section 1.2

1.2

Thermodynamic Methods

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-OConnell method for dimerizing

species.

Special methods for calculating the properties of specific systems of components such as alcohols, glycols, and sour water systems.

Solid-liquid equilibria methods such as the vant Hoff method for calculating

the solubility of a solid in a liquid.

In addition, the electrolyte version of PRO/II contains a number of thermodynamic methods to handle systems containing aqueous ionic species.

Reference Manual

I-37

Thermodynamic Methods

1.2.1

Section 1.2

Basic Principles

General

Information

When modeling a single chemical process or an entire chemical plant, the use of

appropriate thermodynamic methods and precise data is essential in obtaining a

good design. PRO/II contains numerous proven thermodynamic methods for the

calculation of the following thermophysical properties:

Distribution of components between phases in equilibrium (K-values).

Liquid-phase and vapor-phase enthalpies.

Liquid-phase and vapor-phase entropies.

Liquid-phase and vapor-phase densities.

Phase

Equilibria

When two or more phases are brought into contact, material is transferred

from one to another until the phases reach equilibrium, and the compositions

in each phase become constant. At equilibrium for a multicomponent system,

the temperature, pressure, and chemical potential of component i is the same

in every phase, i.e.:

(1)

(2)

(3)

T =T ==T

P =P ==P

i = i = = i

where:

T=

system temperature

P=

system pressure

The fugacity of a substance is then defined as:

0

0

i i = RT lnfi / f i

(4)

where:

fi =

0

I-38

Basic Principles

fugacity of component i

fi =

0i =

May 1994

Section 1.2

Thermodynamic Methods

It follows from (3) and (4) that the fugacities in each phase must also be equal:

(5)

fi = fi = = fi , i = 1,2, n

The fugacity of a substance can be visualized as a corrected partial pressure such that the fugacity of a component in an ideal-gas mixture is equal

to the component partial pressure.

For vapor-liquid equilibrium calculations, the ratio of the mole fraction of a component in the vapor phase to that in the liquid phase is defined as the K-value:

Ki yi / xi

(6)

where:

Ki =

yi =

xi =

coefficient is defined:

I

(7)

II

KDi x i / x i

where:

KDi =

The vapor-phase fugacity coefficient of a component, Vi , is defined as the

ratio of its fugacity to its partial pressure, i.e.:

V

(8)

i fi / yiP

where:

Vi =

then the activity coefficient of the liquid phase can be related to the liquid

fugacity by the following relationship:

L

OL

f i = i xi f i

(9)

where:

Li =

0L

fi =

Reference Manual

standard-state fugacity of pure liquid i

Thermodynamic Methods

Section 1.2

fugacity is as follows:

P L

0L

sat sat

f i = Pi i exp sat vi / RT dP

Pi

(10)

where:

Psat

i = saturated vapor pressure of component i at T

R=

gas constant

vLi

sat

i

Equation (10) provides two correction factors for the pure liquid fugacity. The

fugacity coefficient, isat, corrects for deviations of the saturated vapor from

ideal-gas behavior. The exponential correction factor, known as the Poynting correction factor, corrects for the effect of pressure on the liquid fugacity. The

Poynting correction factor is usually negligible for low and moderate pressures.

Combining equations (6), (8), and (9) yields:

L OL

Ki = i f i / P i

(11)

L

KDi = i II / i I

(12)

If an equation of state is applied to both vapor and liquid phases, the vaporliquid K-values can be written as:

V

Ki = i / i

(13)

L

KDi =

i II

(14)

iI

Equations (11), (12), (13), and (14) are used to calculate the distribution of

components between phases.

For vapor-liquid equilibria, equation-of-state methods may be used to calculate

the fugacity coefficients for both liquid and vapor phases using equation (13).

One important limitation of equation-of-state methods is that they have to be applicable over a wide range of densities, from near-zero density for gases to high

liquid densities, using constants obtained from pure-component data. Equations

of state are not very accurate for nonideal systems unless combined with component mixing rules and alpha formulations (see Section 1.2.4, Equations of State)

appropriate for those components.

I-40

Basic Principles

May 1994

Section 1.2

Thermodynamic Methods

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 1.2.6, Liquid Activity Methods). Liquid activity methods are most often used to describe the behavior of strongly nonideal mixtures.

References

Enthalpy

1.

Prausnitz, J. M., Lichtenthaler, R. N., and Gomes de Azevedo, E., 1986, Molecular

Thermodynamics of Fluid-Phase Equilibria, 2nd Ed., Prentice-Hall, N.Y.

2.

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.

Nonelectrolyte Solutions: With Applications to Phase Equilibria, McGrawHill, New York.

system, U as follows:

(15)

H = U + PV

where:

H=

U=

V=

At constant temperature and pressure, the internal energy of the system is related to the volume by:

dU = T(P / T)V,n P dV

T

(16)

H=

(17)

T

where:

H* =

hi0 =

z=

Reference Manual

Thermodynamic Methods

Section 1.2

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 correlates 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

the reduced temperature, Tr, is approximately equal to 0.7.

In general, the use of liquid activity coefficient models is not recommended

for system pressures above 1000 kPA. Below these conditions, the use of LIBRARY enthalpy methods will not introduce significant errors, provided that

the system temperature is below the critical temperatures of all components

present in significant quantities.

Quite often, however, we would like to use a liquid activity coefficient model

when permanent gases are present in the mixture. As the system temperature is

usually above the critical temperature of these gases, there is no standard-state

liquid fugacity at system conditions, so we replace that term by the Henrys Law

constant. However, the problem of adding the supercritical components contribution to the liquid enthalpies remains.

For the liquid-phase contribution, PRO/II extrapolates the components saturated liquid enthalpy curve linearly from the critical temperature. Above the

critical this extrapolation uses the slope of the library enthalpy tangent to the

liquid saturation curve at the normal boiling point. At temperatures above the

critical, there is no distinction between vapor and liquid phases and the vapor

enthalpy is set equal to the extrapolated liquid enthalpy. The point at which

the slope for linear extrapolation is obtained is chosen quite arbitrarily; as

mentioned, we use the normal boiling point temperature.

I-42

Basic Principles

May 1994

Section 1.2

Thermodynamic Methods

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 saturation 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 equivalent results as

adding the latent heat to zero-liquid enthalpy. For components that are supercritical at 273.15 K, using an alpha formulation will give consistent results between

departure-based and library enthalpies.

Entropy

S = S R ln R ln P / Pref H H / T

(18)

and,

S = nisi R ni ln xi

0

(19)

where:

=

Pref =

si =

ni =

moles of component i

xi =

S =

Reference Manual

Thermodynamic Methods

Section 1.2

The ideal molar entropy is related to the ideal molar enthalpy by:

si =

0

T

Tref

(20)

0

c dT T =

/ hi / TP dT / T

pi

T

ref

where:

Tref =

cpi* =

As for enthalpy computations, liquid and vapor entropies are calculated in

PRO/II using either an equation-of-state method such as SRKM or a 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 1.2.3,

Generalized Correlation Methods.

Vapor densities are computed in PRO/II using the following formulae:

v = zRT / P

(21)

v = MW / v

(22)

where:

v =

vapor density

MW = molecular weight

v=

z=

compressibility factor

methods, in addition to generalized correlation methods. The IDEAL

vapor-density method corresponds to z=1.

I-44

Basic Principles

May 1994

Section 1.2

1.2.2

Thermodynamic Methods

Application Guidelines

General

Information

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 many thermodynamic methods, the PRO/II

databanks contain adjustable binary parameters obtained from fitting published experimental and/or plant data. The thermodynamic method chosen

should ideally be used only in the temperature and pressure ranges at which

the parameters were regressed. Ideally, for each simulation, actual experimental or plant data should be regressed in order to obtain the best interaction parameters for the application.

There are several places where the user can find information and guidelines

on using the thermodynamic methods available in PRO/II. These are:

PRO/II Keyword Input Manual.

PRO/II Application Briefs Manual.

PRO/II Thermodynamic Expert System.

The first source outlines the PRO/II keywords needed to code the thermodynamic category in a PRO/II input file and provides some information on the

limitations and strengths of each thermodynamic method. The second source

shows how PRO/II is used to simulate many refinery, chemical, petrochemical, and solid processing applications using the thermodynamic methods appropriate to each system. The third source, available only in the PC (DOS)

version of PRO/II, is described below.

Thermodynamic

Expert System (TES)

(DOS) users who access PRO/II through the Graphics User Interface (GUI).

This system utilizes nearly 300 proven heuristics to determine the best thermodynamic method for a particular simulation. The following information is

used by the TES:

Reference Manual

Thermodynamic Methods

Section 1.2

The presence of any assay streams.

The expected temperature and pressure ranges.

The number of expected liquid phases.

The presence or absence of a vapor phase.

The water handling option chosen (i.e., whether water should be decanted or handled rigorously).

This option should be used if available.

Processes

Low pressure crude systems (vacuum towers and atmospheric stills).

High pressure crude systems (including FCCU main fractionators and

coker fractionators).

Reformers and hydrofiners.

Lube oil and solvent de-asphalting units.

Low Pressure Crude Units

Low pressure crude units generally contain less than 3 volume percent light

ends. Moreover, the petroleum fractions present in the feed exhibit nearly

ideal behavior. For these units, the characterization of the petroleum fractions is far more important than the thermodynamic method used. The user

should try different assay and characterization methods first if the simulation

results do not match the plant data.

Since these units contain a small amount of light ends, the Braun K10

(BK10) method should be used quickly as a first attempt and will likely give

acceptable answers. The BK10 method does, however, provide only gross estimates for the K-values for H2 and is not recommended for streams containing a significant amount of H2. For such systems, and for other systems

where the BK10 results are not satisfactory, the Grayson-Streed (GS),

Grayson-Streed Erbar (GSE), or Improved Grayson-Streed (IGS) methods

should be chosen. These methods contain special coefficients for hydrogen

and methane and, as such, provide better predictions for streams containing

small amounts of H2 at low pressures. It is important to note that the predefined 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, substituting the Lee-Kesler (LK) method

for Curl-Pitzer enthalpies may improve the results.

I-46

Application Guidelines

May 1994

Section 1.2

20.4

Thermodynamic Methods

PRO/II Note: For more information on using predefined systems of thermodynamic methods, see Section 20.4, Predefined Systems, of the PRO/II Keyword

Input Manual.

In addition, the top of many of these low pressure units often contain significant amounts of light components such as methane. Under these conditions,

an equation-of-state method such as Soave-Redlich-Kwong (SRK) or PengRobinson (PR) will provide better answers than the BK10 or Grayson-Streed

methods.

Table 1.2.2-1:

Methods Recommended for Low Pressure Crude Systems

BK10

GS/GSE/IGS

containing H2. Use LK enthalpies instead of CP enthalpies

for vacuum towers.

SRK/PR

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 methods first if the simulation results do not

match the plant data. Since these units contain larger amounts of light ends,

the GS, GSE, IGS, SRK, or PR methods should be used and will likely give

acceptable answers.

For FCCU main fractionators, the petroleum fractions are much more hydrogen deficient than are crude fractions. Since most characterization correlations are derived from crude petroleum data, it is expected that the results

will be less accurate than for crude fractions.

See Section 1.1.3 of this manual, Assay Processing, for more information on

characterizing petroleum fractions.

Table 1.2.2-2:

Methods Recommended for High Pressure Crude Systems

GS/GSE/IGS

especially for streams containing light ends. Use LK

enthalpies instead of CP enthalpies for better results.

SRK/PR

Reference Manual

Thermodynamic Methods

Section 1.2

These units contain streams with a high hydrogen content. The GraysonStreed method, which contains special liquid activity curves for methane and

hydrogen, may be used to provide adequate answers. For the SRK and PR

methods, the PRO/II databanks contain extensive binary interaction parameter data for component pairs involving hydrogen. 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.

Table 1.2.2-3:

Methods Recommended for Reformers and Hydrofiners

GS/GSE/IGS

especially for predicting the hydrogen content of the liquid

phase.

SRK/PR

SRKM/PRM

hydrogen content of the liquid phase.

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 interaction data are available. If

no binary interaction data specifically regressed for the system are available,

then the data in the PRO/II databanks can be used, and the SRK or PR methods are recommended.

Table 1.2.2-4:

Methods Recommended for Lube Oil and Solvent De-asphalting Units

I-48

Application Guidelines

SRKM/PRM

are available.

SRK/PR

data are available.

May 1994

Section 1.2

Natural Gas

Processing

Thermodynamic Methods

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., sweetening using amines or dehydration using glycol.

For natural gas systems containing less than 5% N2, CO2, or H2S, and no

other polar components, SRK, PR, or Benedict-Webb-Rubin-Starling

(BWRS) methods provide excellent answers. The SRK and PR binary interaction parameters between these lower molecular weight molecules and

other components are estimated by correlations based on the molecular

weight of the hydrocarbon molecule. For small amounts of these 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 other

polar components, equation-of-state methods such as SRK or PR are still recommended, although the binary parameters estimated 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 components if possible.

For natural gas systems containing water at low pressures, equation-of-state

methods such as SRK or PR may be used, along with the default water decant option, to predict the behavior of these systems.

For these systems at high pressures, where the solubility of hydrocarbon in

water is significant, the default water decant option, which predicts a pure

water phase, is unacceptable. In this case, equation-of-state methods containing advanced mixing rules such as SRKM, PRM, or SRKS, or the KabadiDanner modification to SRK (SRKKD) should be used to predict the

vapor-liquid-liquid behavior of these systems. These methods provide the

best answers if all the relevant binary interaction parameters are available.

For the SRKKD method in particular, PRO/II contains binary interaction

parameters for component pairs involving N2, H2, CO2, CO, and H2S. For

SRKM, PRM, or SRKS methods, the user should make sure that all relevant

binary interaction data are entered.

Reference Manual

Thermodynamic Methods

Section 1.2

For natural gas systems containing polar components such as methanol, the

SRKM, PRM, or SRKS methods are recommended to predict the vapor-liquid-liquid behavior of these systems. Interaction parameters for the important binaries are required if accurate answers are to be obtained.

Table 1.2.2-5:

Methods Recommended for Natural Gas Systems

SRK/PR/

BWRS

Recommended for most natural gas and low pressure natural gas +

water systems.

SRKKD

SRKM/PRM/

SRKS

The common processes used to treat natural gas streams may be sub-divided

into the following:

Glycol dehydration systems.

Sour water systems.

Amine systems.

Glycol Dehydration Systems

The predefined thermodynamic system GLYCOL has been specially created

for these systems. This system uses the predefined system SRKM but invokes the GLYCOL databank. This databank contains binary interaction parameters for component pairs involving TEG and, to a lesser extent, DEG

and EG. These data have been regressed in the temperature and pressure

range normally seen in glycol dehydrators:

Temperature: 80-400 F.

Pressure: up to 2000 psia.

See Section 1.2.8, of this manual, Special Packages, for more information on

this method.

Sour Water Systems

The standard version of PRO/II contains two methods, SOUR and GPSWATER,

for predicting the VLE behavior of sour water systems. These methods are described in more detail in Section 1.2.8, of this manual, Special Packages. The

electrolyte version of PRO/II also contains a rigorous sour water method which

is described in Section 1.2.10 of this manual, Electrolyte Thermodynamic Equations. The recommended temperature, pressure and composition ranges for each

method are given in Table 1.2.2-6 below.

I-50

Application Guidelines

May 1994

Section 1.2

Thermodynamic Methods

Table 1.2.2-6:

Methods Recommended for Sour Water Systems

SOUR

Recommended Ranges:

68 < T (F) < 300

P(psia) < 1500

wNH3 + wCO2 + wH2S < 0.30

GPSWATER

Recommended Ranges:

68 < T(F) < 600

P(psia) < 2000

wNH3 < 0.40

PCO2 + PH2S < 1200 psia

Electrolyte

Version of

PRO/II

are used, or when pH control or accurate prediction of HCN

or phenol phase distribution is important. Recommended

Ranges:

32 < T(F) < 400

P(psia) < 3000

xdissolved gases < 0.30

Amine Systems

Amine systems used to sweeten natural gas streams may be modeled in

PRO/II using the AMINE special package (see Section 1.2.8, Special Packages). Data is provided for amines MEA, DEA, DGA, DIPA, and MDEA. Results obtained for MEA and DEA are accurate enough for use in final design

work. However, results for DIPA systems are not suitable for final design

work. For MDEA or DGA systems, the results may be made to more closely

fit plant data by the use of a dimensionless residence time correction.

25.5

PRO/II Note: For more information on using the dimensionless residence time

correction factor for MDEA or DGA systems, see Section 25.5, Amine, of the

PRO/II Keyword Input Manual.

The recommended temperature, pressure, and loading ranges (gmoles sour

gases per gmole amine) for each amine system available in PRO/II are given

in Table 1.2.2-7.

Reference Manual

Thermodynamic Methods

Section 1.2

Table 1.2.2-7:

Recommended Ranges for Amine Systems

Petrochemical

Applications

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

0.50 gmole gas/gmole amine

MDEA

Recommended Ranges:

100 < P(psig) < 1000

T(F) < 275

wamine ~ 0.50

0.40 gmole gas/gmole amine

DIPA

Recommended Ranges:

100 < P(psig) < 1000

T(F) < 275

wamine ~ 0.30

0.40 gmole gas/gmole amine

Light hydrocarbon applications.

Aromatic systems.

Aromatic/non-aromatic systems.

Alcohol dehydration systems.

Light Hydrocarbon Applications

Most light hydrocarbon mixtures at low pressures may be modeled well by

the SRK or PR equations of state. The BWRS equation of state, which was

developed for light hydrocarbon mixtures, is also recommended, but not near

the critical region. At high pressures, the SRKKD equation of state should be

used to best predict the water solubility in the hydrocarbon phase. The

COSTALD liquid density method was developed expressly for light

hydrocarbon mixtures. This method is over 99.8% accurate in predicting the

liquid densities of these mixtures and should be requested by the user.

Table 1.2.2-8:

Methods Recommended for Light Hydrocarbons

I-52

Application Guidelines

SRK/PR/

BWRS

low pressures.

SRKKD

COSTALD

May 1994

Section 1.2

Thermodynamic Methods

Aromatic Systems

Mixtures of 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 GraysonStreed or SRK or PR methods provide good results in the prediction of phase

equilibria. The SRK or PR equations of state should provide better results,

but with a small CPU penalty.

Table 1.2.2-9:

Methods Recommended for Aromatics

IDEAL

GS/SRK/PR

IDEAL/API/

COSTALD

best at high temperatures and if light components such as

CH4 are present.

Aromatic/Non-aromatic Systems

Systems of mixtures of aromatic and non-aromatic components are highly

nonideal. Liquid activity methods such as NRTL or UNIQUAC, or equation-ofstate 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, UNIQUAC, SRKM,

and SRKS methods. One advantage to using the liquid activity methods NRTL

or UNIQUAC, however, is that the FILL option may be used to fill in any 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.

24.10

PRO/II Note: For more information on using the FILL option to fill in missing

interaction parameters for liquid activity methods, see Section 24.10, Filling in

Missing Parameters, of the PRO/II Keyword Input Manual.

When gases such as H2, N2, or O2 are present in small quantities (up to about 5

mole %), the Henrys Law option may be used to calculate the gas solubilities.

Once the Henrys Law option is selected by the user, PRO/II arbitrarily defines

all components with critical temperatures less than 400 Kelvin as solute components, though the user may override these selections.

24.11

PRO/II Note: For information on using the SOLUTE option to define Henrys

components, see Section 24.11, Henrys Law for Non-condensible Components, of the PRO/II Keyword Input Manual.

Reference Manual

Thermodynamic Methods

Section 1.2

advanced mixing rule should be used to predict the phase behavior.

Table 1.2.2-10:

Methods Recommended for Aromatic/Non-aromatic Systems

SRKM/PRM

supercritical gases are present.

NRTL/

UNIQUAC

interaction parameters are not available or with the HENRY

option when < 5 mole % supercritical gases are present.

The PRO/II special package ALCOHOL is recommended for systems 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.

25.1

PRO/II Note: For information on using the ALCOHOL method, see Section

25.1, Alcohol, of the PRO/II Keyword Input Manual.

Table 1.2.2-11:

Methods Recommended for Alcohol Systems

Chemical

Applications

ALCOHOL

NRTL/

UNIQUAC

Non-ionic Systems

These systems, which typically contain oxygen, nitrogen, or halogen 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 WILSON, 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.

I-54

Application Guidelines

May 1994

Section 1.2

Thermodynamic Methods

For systems with two liquid phases, the NRTL or UNIQUAC methods

should be used, provided that at least some interaction data are available. The

FILL option can be used to fill in any missing interaction data using the 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 carboxylic acids, were

regressed without including any vapor-phase non-ideality. This means that

the PHI option should be used for carboxylic acid systems at all pressures,

but should only be used for most components at high pressures. For systems containing components such as carboxylic acids that dimerize in the vapor phase,

the Hayden-OConnell fugacity method may be used to calculate all vapor-phase

properties such as fugacity, enthalpy, and density. For components such as 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.

24

PRO/II Note: For information on using the PHI option to calculate the

vapor-phase fugacity when using a liquid activity method, see Section 24,

Liquid Activity Methods, of the PRO/II Keyword Input Manual.

When supercritical gases are present in small quantities (generally less than

5 mole %), the Henrys Law option should be used to compute gas 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

available and, unlike a liquid activity method such as UNIFAC, is able to

handle supercritical gases.

Reference Manual

Thermodynamic Methods

Section 1.2

Table 1.2.2-12:

Methods Recommended for Non-ionic Chemical Systems

WILSON

mixtures. If all interaction data are not available, use the

FILL=UNIFAC option.

NRTL/

UNIQUAC

option when binary interaction parameters are not available

or with the HENRY option when < 5 mole % supercritical

gases are present. For moderate pressures, use the PHI

option for vapor phase non-idealities.

SRKS/

SRKM/PRM/

UNIWAALS

mole % supercritical gases are present.

HOCV

calculations in systems containing dimerizing components

such as carboxylic acids. Use with a liquid activity method .

HEXAMER

components such as HF.

Ionic Systems

A special version of PRO/II expressly made for aqueous electrolytes is recommended when modeling these systems. This version combines the PRO/II

flowsheet simulator with rigorous electrolyte thermodynamic algorithms developed by OLI Systems, Inc. Chemical systems which may be modeled by this

special version include amine, acid, mixed salts, sour water, caustic, and Benfield systems. See Sections 1.2.9, Electrolyte Mathematical Model, and 1.2.10,

Electrolyte Thermodynamic Equations for further details.

Table 1.2.2-13:

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 Henrys constants at the process temperature to model these dilute

aqueous systems. PRO/II contains Henrys Law constants for many components

such as HCl, SO2, and ethanediol in water. Some additional Henrys constants

for chlorofluorocarbons (CFCs) and hydrofluorocarbons (HFCs) in water are

also available in the PRO/II databanks. Other sources for Henrys Law data

include the U.S. Environmental Protection Agency.

I-56

Application Guidelines

May 1994

Section 1.2

Thermodynamic Methods

Table 1.2.2-14:

Methods Recommended for Environmental Applications

Liquid Activity Method + Henrys Law Option

Solid Applications

Solid-liquid equilibria for most systems can be represented in PRO/II by the

vant Hoff (ideal) solubility method or by using user-supplied solubility data.

In general, for those systems where the solute and solvent components are

chemically similar and form a near-ideal solution, the vant Hoff method is

appropriate. For nonideal systems, solubility data should be supplied. For

many organic crystallization systems, which are very near ideal in behavior,

the vant Hoff SLE method provides good results. The VLE behavior can 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.

26.1

PRO/II Note: For information on using the ideal solid-liquid equilibria method

VANTHOFF, see Section 26.1, Vant Hoff Solubility, of the PRO/II Keyword

Input Manual.

Table 1.2.2-15:

Methods Recommended for Solid Applications

Ideal or Liquid

Activity

Method(VLE)

+ VANT HOFF

Method (SLE)

PRO/II

Electrolyte

Version

from aqueous solutions.

Reference Manual

Thermodynamic Methods

1.2.3

Section 1.2

General

Information

Ideal

(IDEAL)

various general correlation methods. Examples of these are those developed

by Chao and Seader or Grayson and Streed. Vapor-liquid equilibria can also

be predicted by convergence pressure correlations such as the K10 charts developed by Cajander et al. Densities, enthalpies, and entropies can also be

calculated using a number of correlation methods such as Lee-Kesler and

COSTALD.

Ideal 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 following fundamental thermodynamic equilibrium relationship holds:

L

(1)

fi = fi

where:

superscript L refers to the liquid phase

superscript V refers to the vapor phase

fi =

fugacity of component i

In the vapor phase, the fugacity is assumed to be equal to the partial pressure:

(2)

fi = yi P

where:

yi =

P=

system pressure

In the liquid phase for an ideal liquid (ignoring correction factors that are

usually small):

L

sat

(3)

fi = xi fpure i = xi Pi

where:

xi =

f

Pisat = vapor pressure of component i at the

I-58

system temperature

May 1994

Section 1.2

Thermodynamic Methods

(4)

sat

yi P = xi Pi

sat

(5)

Ki = yi / xi = Pi / P

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:

= P / RT

(6)

where:

= vapor molar density of mixture

Ideal liquid densities are obtained from pure-component saturated-liquid density

correlations.

Ideal liquid enthalpies are obtained from pure-component liquid enthalpy correlations, and the corresponding vapor enthalpies are obtained by adding in

the effect of the known latent heat of vaporization of the component.

Ideal entropies are calculated from the ideal enthalpy data using the following equation:

Si = cpi dT / T = Hi / T dT / T

P

(7)

where:

22.1

Si =

ideal entropy

cpi =

Hi =

ideal enthalpy

Tref =

T=

temperature of mixture

PRO/II Note: For more information on using the IDEAL and LIBRARY methods,

see Section 22.1, IDEAL and LIBRARY, of the PRO/II Keyword Input Manual.

Reference Manual

Thermodynamic Methods

Chao-Seader

(CS)

Section 1.2

Chao and Seader calculated liquid K-values for the components of nonideal

mixtures using the relationship:

Ki = yi / xi =

0L

i fi

(8)

i P

where:

fi0L =

liquid phase

i =

liquid mixture

i =

vapor mixture

It was shown that i could be calculated from molar liquid volumes and solubility

parameters, using the Scatchard-Hildebrand equation, with regular liquid solution

assumed. The Redlich-Kwong equation of state (see Section 1.2.4, Equations of

State) was used to evaluate . Chao and Seader presented a generalized correlation

for fi0L/P, the fugacity coefficient of pure liquid i in real and hypothetical states.

In the development of their correlation for vapor-liquid K-values, Chao and

Seader used the framework of Pitzers modified form of the principle of corresponding states for the pure-liquid fugacity coefficients, giving values of

fi0L/P as a function of reduced temperature, reduced pressure, and acentric

factor for both real and hypothetical liquids:

OL

OL

OL

ln fi / P = ln fi / P + ln fi / P

0

1

(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 correction accounting for the

departure of the properties of real fluids from those of simple fluids.

22.3

PRO/II Note: For more information on using the Chao-Seader method, see Section 22.3, Chao-Seader, of the PRO/II Keyword Input Manual.

Limitations of the Chao-Seader method are given below:

For all hydrocarbons;

Pressure: up to 2000 psia, but not exceeding 0.8 of the critical pressure

of the system.

Temperature: -100 F to 500 F and pseudoreduced temperature, Tr,

of the equilibrium liquid mixture less than 0.93. The pseudoreduced

temperature is based on the molar average of the critical temperatures of the components.

Concentration: up to 20 mole % of other dissolved gases in the

liquid.

I-60

May 1994

Section 1.2

Thermodynamic Methods

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)

22.2

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

Streeds modifications have extended the application range for hydrocarbon systems up to 800 F and 3000 psia. The lower limits imposed by Chao and

Seader still apply.

PRO/II Note: For more information on using the Grayson-Streed method, see

Section 22.2, Grayson-Streed, of the PRO/II Keyword Input Manual.

Reference

Grayson, H. G., and Streed, C. W., 1963, Vapor-Liquid Equilibria for

High Temperature, High Pressure Hydrocarbon-Hydrocarbon Systems, 6th

World Congress, Frankfurt am Main, June 19-26.

Erbar Modification

to Chao-Seader

(CSE) and GraysonStreed (GSE)

22.4

In 1963, Erbar and Edmister developed a new set of constants for the ChaoSeader 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.

PRO/II Note: For more information on using the Erbar-modified Chao-Seader

and Grayson-Streed methods, see Section 22.4, Modifications to GraysonStreed and Chao-Seader, of the PRO/II Keyword Input Manual.

A limitation of this modified method, however, is that the H2S correlation

cannot be used in any cases where an azeotrope may exist (e.g., H2S/C3H8

mixtures), as the azeotrope will not be predicted.

Reference

Erbar, J. H., and Edmister, W. C., 1963, Vapor-Liquid Equilibria for

High Temperature, High Pressure Hydrocarbon-Hydrocarbon Systems, 6th

World Congress, Frankfurt am Main, June 19-26.

Reference Manual

Thermodynamic Methods

Section 1.2

Grayson-Streed methods accurately predict the phase behavior of the hydrocarbon-rich phase, but are incapable of predicting the composition of the

water-rich phase. A new method has been developed in which a separate set

of solubility parameters was used in the water-rich phase, and a new set of

liquid fugacity coefficients developed for N2, H2O, H2S, CO, and O2. This

new method is known as Improved Grayson-Streed. It was found that the

Grayson-Streed liquid fugacity coefficient for the simple fluid decreases

rapidly as Tr increases above 2.5, and can in fact become negative. The liquid fugacity coefficient for the simple fluid was therefore replaced by that

for hydrogen at reduced temperatures of 2.5 and above.

22.4

method, see Section 22.4, Modifications to Grayson-Streed and Chao-Seader,

of the PRO/II Keyword Input Manual.

Curl-Pitzer (CP)

This correlation may be used to predict both liquid and vapor enthalpies and

entropies. It computes the enthalpy deviation using the principle of

corresponding states, i.e., in terms of the reduced temperature, reduced

pressure, and acentric factor. The critical temperature and pressure for the

mixture is computed using the mixture rules of Stewart, Burkhart, and Voo.

The mixture acentric factor used is the molar average value.

The Curl-Pitzer method is limited to nonpolar mixtures and may be used for

Pr up to 10, and Tr from 0.35 to 4.0 for liquids, and Tr from 0.6 to 4.0 for

vapors. For systems containing heavy ends, the saturated vapor is sometimes

at a reduced temperature of less than 0.6. In this case, the CP correlation extrapolates reasonably, producing satisfactory results.

22.5

PRO/II Note: For more information on using the Curl-Pitzer method, see Section 22.5, Curl-Pitzer, of the PRO/II Keyword Input Manual.

The Curl-Pitzer method is generally useful for refinery hydrocarbons and in

oil absorption gas plants.

References

I-62

1.

for Mixtures, Paper presented at AIChE Meeting, Kansas City.

2.

Refining, 2nd Ed., Procedure 7B3.1.

3.

Refining, 2nd Ed., Procedure 7H2.1, 7-201 - 7-202.

May 1994

Section 1.2

Thermodynamic Methods

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 liquid phases in equilibrium. The

convergence pressure is, in general, the critical pressure of a system at a

given pressure. At a given temperature, and as the system pressure increases,

the K-values of all components converge to unity when the system pressure

reaches the convergence pressure.

The Braun K10 charts developed by Cajander et al. in 1960 show the low pressure equilibrium ratio, arbitrarily taken at 10 psia system pressure and 5000 psi

convergence pressure. For many hydrocarbon systems, no experimental data are

available. For these cases, the equilibrium K-values may be predicted from

vapor pressure:

sat

(10)

K10 = P

/ 10

Psat =

where:

The relationship given in equation (10) only holds for K-values less than 2.5.

For nonhydrocarbons like H2, the K-value is assumed to be 10 times as large

as the methane value. For N2, O2, and CO, the K-values are assumed to be

identical to that of methane. The K-values for CO2 and H2S are assumed to

be identical to that of propylene.

For petroleum fractions in which the form of the vapor pressure curve is 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 = 1.47 is plotted at

the atmospheric boiling point.

The whole K10 curve can then be sketched in by similitude to the known

K10 curves for homologous hydrocarbons.

The K10 charts apply to mixtures that behave ideally at low pressures, e.g.,

for mixtures of one molecule type such as mixtures of paraffins and olefins.

For mixtures of naphthalenes mixed with olefins and paraffins, the accuracy

of BK10 is slightly poorer. Large errors can be expected for mixtures of aromatics with paraffins, olefins, or naphthalenes, which cause nonidealities and

form azeotropes.

22.6

PRO/II Note: For more information on using the Braun K10 method, see Section 22.6, Braun K10, of the PRO/II Keyword Input Manual.

Reference

Cajander, B. C., Hipkin, H. G., and Lenior, J. M., 1960, Prediction of

Equilibrium Ratios from Nomographs of Improved Accuracy, J. Chem.

Eng. Data, 5, 251-259.

Reference Manual

Thermodynamic Methods

Johnson-Grayson

(JG)

Section 1.2

This correlation may be used to predict both liquid and vapor enthalpies. It is

essentially an ideal-enthalpy correlation, using saturated liquid at 0 C as

the datum for the correlation (-200 F in versions 3.5 and earlier).

Vapor-phase corrections are calculated using the Curl-Pitzer correlation.

Pressure effects are not considered for the liquid phase.

Johnson-Grayson is useful for systems containing heavy ends between 0 F

and 1200 F. However, it can be extrapolated to higher temperatures. The correlation should not be used if the mixture is C4-C5 or lighter.

22.7

PRO/II Note: For more information on using the Johnson-Grayson method, see

Section 22.7, Johnson-Grayson, of the PRO/II Keyword Input Manual.

Reference

Johnson, and Grayson, 1961, Enthalpy of Petroleum Fractions,

Petroleum Refiner, 40(2), 123-29.

Lee-Kesler (LK)

22.8

This correlation may be used to predict both liquid and vapor 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 properties 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 predicting 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 temperatures near the saturated-vapor region.

The Lee-Kesler method is not recommended for calculating liquid densities

of hydrocarbons heavier than C8.

PRO/II Note: For more information on using the Lee-Kesler method, see Section 22.8, Lee-Kesler, of the PRO/II Keyword Input Manual.

References

I-64

1.

Refining, 3rd Ed., 2-1 - 7-4.

2.

Correlation Based on Three-Parameter Corresponding States, AIChE J., 21,

510-27.

3.

Fractions, Hydrocarbon Proc., 53, 153-158.

May 1994

Section 1.2

Thermodynamic Methods

API

calculated at 60 F using the weight average of the components. The reduced

temperature and pressure of the stream at 60 F and 14.7 psia are computed

using Kays rule, i.e., the reduced temperature and pressure are assumed to

be a linear function of the liquid mole fraction. A density factor C is then

read from Figure 6A2.21 in the API Technical Data Book. A second correction factor is then determined, corresponding to the reduced temperature and

pressure, at the actual fluid conditions. Finally, the actual liquid density is

calculated according to:

L

(11)

where:

L60 =

liquid density at 60 F

C60 =

22.9

correction factor at 60 F

PRO/II Note: For more information on using the API method, see Section

22.9, API Liquid Density, of the PRO/II Keyword Input Manual.

The API method works well for most hydrocarbon systems, provided that the

reduced temperature is less than 1.0.

Reference

American Petroleum Institute, 1978, Technical Data Book - Petroleum

Refining, 5th Ed., 6-45 - 6-46.

Rackett

density is obtained from:

(12)

i

Vsi = RTci / Pci Zrai

2 7

i = 1 + (1Tri) / for Tri 0.75

3

i = 1.6 +

6.9302610

for Tri > ~ 0.75

Tri 0.655

Vsi =

Zrai =

where:

Tci, Pci =

Tri =

Reference Manual

Thermodynamic Methods

22.10

Section 1.2

PRO/II Note: For more information on using the Rackett liquid density method,

see Section 22.10, Rackett Liquid Density, of the PRO/II Keyword Input

Manual.

The PRO/II databanks contain Rackett parameters for many components.

However, if Rackett parameters are not available, PRO/II will use the critical

compressibility factor, zc.

For mixtures, there are two ways to use the Rackett equation. The most

straightforward, known as the RACKETT method in PRO/II, is to use equation (12) for the molar volume of each pure component and then mix the

volumes together linearly. A second approach is the One-Fluid" Rackett

method (known as the RCK2 method), in which mixing rules are used to determine effective critical parameters for the mixture and then equation (12) is

used to determine the mixture density. For most mixtures, the difference between these two methods will not be significant.

References

COSTALD

1.

Rackett, H. G., 1970, Equation of State for Saturated Liquids, J. Chem. Eng.

Data, 15, 514.

2.

Spencer, C. F., and Danner, R. P., 1972, Improved Equation for Prediction

of Saturated Liquid Density, J. Chem. Eng. Data, 17, 236-241.

3.

Spencer, C. F., and Adler, S. B., 1978, A Critical Review of Equations for

Predicting Saturated Liquid Density, J. Chem. Eng. Data, 23, 82-89.

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 parameters for each pure component in the mixture - a characteristic

volume, V*, and a tuned acentric factor, SRK. The acentric factor is chosen

such that the SRK equation of state best matches the vapor-pressure data. Typically, this tuned acentric factor varies little in value from the standard acentric

factor. The saturated volume is given by:

(0)

()

Vs / V = Vr 1 SRK Vr

(0)

Vr

k 3

= 1 + Ak (1 Tr) / , 0.25 < Tr < 0.95

(13)

(14)

I-66

May 1994

Section 1.2

Thermodynamic Methods

()

(15)

where:

Vs =

V* =

characteristic volume

Vr =

reduced volume

SRK = SRK tuned acentric factor

For mixtures, the following mixing rules are used:

i j

Vm = 1 / 4

(16)

2 3

1 3

x V + 3xiVi / xiVi /

i i

i

i

i

(17)

(18)

1/2

SRK = xiSRKi

(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 correction of the form:

sat

V = Vs 1 Cln (B + P) / (B + P )

(20)

where:

B, C are constants, dependent on composition

22.11

Psat =

pressure relationship.

V=

molar volume

PRO/II Note: For more information on using the COSTALD liquid density

method, see Section 22.11, Costald Liquid Density, of the PRO/II Keyword

Input Manual.

The COSTALD method is valid for aromatics and light hydrocarbons up to

reduced temperatures of 0.95. PRO/II databanks contain COSTALD characteristic volume, V*, for many components. However, 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 characteristic volume, if missing, in order to provide a correct specific gravity for the pseudocomponent.

Reference Manual

Thermodynamic Methods

Section 1.2

References

I-68

1.

Hankinson, R. W., and Thomson, G. H., 1979, A New Correlation for Saturated

Densities of Liquids and Their Mixtures, AIChE J., 25o, 653-663.

2.

Correlation for Densities of Compressed Liquids and Liquid Mixtures,

AIChE J., 28, 671-676.

May 1994

Section 1.2

1.2.4

Thermodynamic Methods

Equations of State

General

Information

General Cubic

Equation of State

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 supercritical conditions can be predicted quite accurately. By using an appropriate temperature-dependent function to describe the attractive forces between molecules,

volume function, and mixing rule, cubic equations of state have been shown to

be quite successful in predicting vapor-liquid equilibria for highly nonideal

systems.

A general two-parameter cubic equation of state can be expressed by the

equation:

2

2

P = RT / (vb) a(T) / v + ubv + wb

(1)

where:

P=

pressure

T=

absolute temperature

v=

molar volume

u,w =

The values of u and w determine the type of cubic equation of state. Table

1.2.4-1 shows three of the best known of these. The van der Waals equation

developed in 1873 is obtained by setting u=w=0. By setting u=1 and w=0,

the Redlich-Kwong equation (1949) is obtained. Peng and Robinson developed their equation of state in 1976 by setting u=2 and w=-1.

Table 1.2.4-1: Some Cubic Equations of State

Equation of state

Redlich-Kwong (RK)

-1

Peng-Robinson (PR)

The parameters a and b at the critical temperature (ac and bc) are found by

setting the first and second derivatives of pressure with respect to volume

equal to zero at the critical point. Application of these constraints at the critical point to equation (1) yields:

Reference Manual

Equations of State

I-69

Thermodynamic Methods

Section 1.2

1 / 3 + 1 / 9(u1) Bc 1 / 27 = 0

(2)

(3)

Zc = 1 / 3 (u1) Bc / 3

(4)

where:

Ac = Pcac/R2Tc2

Bc = Pcbc/RTc

subscript c refers to the critical point

The critical constraints result in three expressions for three unknowns, Ac, Bc,

and Zc. These unknowns depend on the values of u and w. Actually, Ac and Bc

are the only true unknowns appearing in these equations, because Pc, Tc, and Vc

(and hence Zc) are properties of a substance, having numerical values independent of any equation of state. In solving these three equations, Vc is in fact

treated as a third unknown. Table 1.2.4-2 lists these constants for the van der

Waals, Redlich-Kwong, and Peng-Robinson equations of state.

Table 1.2.4-2: Constants for Two-parameter Cubic Equations of State

Ac

Bc

Zc

Equation of state

0.42188

0.1250

0.3750

0.42747

0.0866403

0.3333

Redlich-Kwong (RK)

0.45724

0.0778

0.3074

Peng-Robinson (PR)

References

I-70

Equations of State

1.

Abbott, M. M., 1973, Cubic Equations of State, AIChE J., 19, 596-601.

2.

van der Waals, J. D., 1873, Over de Constinuiteit van den gas-en Vloeistoftoestand, Doctoral Dissertation, Leiden, Holland.

3.

v: An Equation of State. Fugacities of Gaseous Solutions, Chem. Rev., 44,

233.

4.

State for Fluids and Fluid Mixtures, Ind. Eng. Chem. Fundam., 15, 58-64.

May 1994

Section 1.2

Alpha

Formulations

Thermodynamic Methods

a(T) = (T) a(Tc)

(5)

account the attractive forces between molecules. The accuracy of the equation of

state for pure-component vapor pressures (and therefore to a large extent for 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 temperature-dependent alpha

function must therefore all be satisfied:

1.

2.

3.

infinity.

For the Redlich-Kwong equation of state, which works well for the vapor

phase at high temperatures, (T) is given by:

(T) = Tr

(6)

1 / 2

for cubic equations of state (SRK, PR, modified SRK or PR, or UNIWAALS). Table 1.2.4-3 shows the 11 available formulations for (T).

Reference Manual

Equations of State

I-71

Thermodynamic Methods

Section 1.2

Form

Equation

Reference

Soave (1972)

01

= 1 + C11 T 0.5

r

02

3

= C1 + C21 T C

r

C2

= 1 + (1 Tr) C1 +

Tr

Soave (1979)

03

04

2

= exp C1 1 T C

r

Boston-Mathias (1980)

05

2 1)

2

= T 2(C

exp C1 1 T 2C

r

r

Twu (1988)

06

3(C2 1)

2C3

=TC

exp C1 1 T C

r

r

Twu-Bluck-CunninghamCoon (1991)

(Recommended by SimSci)

2C1

= exp

1 Tr( C1 + 1) 2

1

+

C

1

07

08

C2

3

=TC

r exp C11 T r

09

0.5

0.5

= 1 + C11 T 0.5

r + C21 T r + C31 T r

10

11

r

Peng-Robinson (1980)

3 2

Mathias-Copeman (1983)

Mathias (1983)

Melhem-Saini-Goodwin

(1989)

where:

C1, C2, C3 = constants

Tr = T/Tc = reduced temperature

23.5

I-72

Equations of State

PRO/II Note: For more information on using alpha functions, see Section 23.5,

Cubic Equation of State Alpha Formulations, of the PRO/II Keyword Input

Manual.

May 1994

Section 1.2

Thermodynamic Methods

References

Mixing Rules

1.

Equation of State, Chem. Eng. Sci., 35, 1197.

2.

Soave, G, 1979, Application of a Cubic Equation of State to VaporLiquid Equilibria of Systems Containing Polar Components, Inst. Chem.

Eng. Symp. Ser., No. 56, 1.

3.

Generation Process Simulator, Proc. of the 2nd Inter. Conf. on Phase

Equil. & Fluid Properties in the Chemical Process Industries, Berlin

(West), March 17-21.

4.

Polar, Supercritical Systems, Inter. Symp. on Thermodynamics in Chemical Engineering and Industry, May 30-June 2.

5.

Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E., 1991, A Cubic

Equation of State with a New Alpha Function and New Mixing Rule,

Fluid Phase Equil., 69, 33-50.

6.

Mathias, P. M., and Copeman, T. W., 1983, Extension of the PengRobinson Equation of State to Complex Mixtures, Fluid Phase Equil., 13,

91-108.

7.

Eng. Chem. Proc. Des. Dev., 22, 358-391.

8.

Melhem, G. A., Saini, R., and Goodwin, B. M., 1989, A Modified Peng-Robinson Equation of State, Fluid Phase Equil., 47, 189-237.

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:

a = xi xj aij

i

(7)

b = xi bi

(8)

where:

xi =

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):

Reference Manual

Equations of State

I-73

Thermodynamic Methods

Section 1.2

(9)

1 2

aij = (aiaj) / (1kij)

where:

kij = kji =

for nonpolar and/or slightly polar systems using only one (possibly temperature-dependent) binary interaction parameter.

Soave-Redlich

Kwong (SRK)

and thus multicomponent vapor-liquid equilibria, Soave proposed the following form of (T):

(10)

1 2

(T) = 1 + M1Tr /

(11)

where:

Tr =

acentric factor

The constants in (11) were obtained from the reduction of vapor-pressure data

for a limited number of common hydrocarbons. This limits the use of the SRK

equation of state to nonpolar components. This equation of state does not

accurately predict the behavior of polar components or light gases such as hydrogen. However, the simplicity of equations (10) and (11), and its accuracy

for calculating vapor pressures at temperatures higher than the normal boiling point for hydrocarbons allowed it to gain widespread popularity in industry. PRO/II contains correlations for the kijs of hydrocarbons with N2, O2, H2,

H2S, CO2, mercaptans and other sulfur compounds.

Peng-Robinson

(PR)

23.2

I-74

Equations of State

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.

PRO/II Note: For more information on using SRK and PR equations of state in

PRO/II, see Section 23.1, Soave-Redlich-Kwong, and Section 23.2, PengRobinson, of the PRO/II Keyword Input Manual.

May 1994

Section 1.2

Thermodynamic Methods

While the K-values between the hydrocarbon-rich liquid phase and vapor

phase can be accurately predicted by most cubic equations of state, the

K-values involving the water-rich liquid phase are not. In order to apply

cubic equations of state to water-hydrocarbon systems, Kabadi and Danner

in 1985 proposed a two-parameter mixing rule for the SRK equation of state.

This proposed mixing rule is composition-dependent and is designed expressly for water and well-defined hydrocarbon systems:

(12)

1 2

2

a = xixj(aiaj) / (1kij) + awi xw xi

i

iw

0.8

awi = Gi1Trw

(13)

Gi = gj

(14)

where:

Trw = T/Tcw

awi =

the hydrocarbon-rich phase

gj =

Gi =

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 estimating the binary interaction parameters kij and Gi. Within a homologous series of hydrocarbons,

kij was found to be approximately constant, and recommended values were

given for seven hydrocarbon classes. A group contribution method was 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.

20.6

PRO/II Note: See Section 21, Application Guidelines, and Section 20.6, FreeWater Decant Considerations, of the PRO/II Keyword Input Manual for information on how to handle hydrocarbon-water systems in PRO/II.

Reference

Kabadi, V. N., and Danner, R. P., 1985, A Modified Soave-Redlich-Kwong

Equation of State for Water-Hydrocarbon Phase Equilibria, Ind. Eng.

Chem. Proc. Des. Dev., 24, 537-541.

Reference Manual

Equations of State

I-75

Thermodynamic Methods

Soave-RedlichKwong

PanagiotopoulosReid (SRKP) and

Peng-Robinson

PanagiotopoulosReid (PRP)

Section 1.2

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:

aij = (ai aj) 1 / 2( 1kij) + (kijkji) xi

(15)

The two adjustable interaction parameters are kij and kji. This asymmetric

definition of the binary interaction parameters significantly improves the

accuracy in correlating binary data for polar and nonpolar systems. This

mixing rule has been used to test several systems, including low pressure

nonideal systems, high pressure systems, three-phase systems, and systems

with supercritical fluids. The results in all cases reported are in good agreement with experimental data.

Reference

Panagiotopoulos, A. Z., and Reid, R. C., 1986, A New Mixing Rule for Cubic

Equations of State for Highly Polar Asymmetric Systems, ACS Symp. Ser.

300, American Chemical Society, Washington, DC, 71-82.

The Panagiotopoulos-Reid mixing rule, however, is fundamentally inconsistent for multicomponent systems. This inconsistency is exhibited in two

(related) flaws:

I-76

Equations of State

1.

The dilution of the mixture with additional components (reducing all the mole

fractions, xi) nullifies the effect of the second binary parameter kji. In the

limit of an infinite number of components so that all the xi approach zero,

the mixing rule reduces to the original van der Waals mixing rule,

equation (9).

2.

identical pseudocomponents. For example, if methane in a mixture is divided arbitrarily into alpha and beta methane, the calculated properties of the mixture will be slightly different.

May 1994

Section 1.2

Soave-RedlichKwong Modified

PanagiotopoulosReid (SRKM) and

Peng-Robinson

Modified

PanagiotopoulosReid (PRM)

Thermodynamic Methods

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 mentioned above) by Harvey and Prausnitz in

1989. For binary polar or polar-nonpolar systems, where the nonideality is

large or strongly asymmetric, it may be necessary to include the additional

parameters c12 and c21. In particular, for binary polar-nonpolar systems,

which have the greatest deviation from ideality, c12 is not set equal to c21.

For binary polar systems however, c12 can generally be set equal to c21.

Reference

Harvey, A.H., and Prausnitz, J.M., 1989, Thermodynamics of High-Pressure

Aqueous Systems Containing Gases and Salts, AIChE J., 35, 635-644.

Soave-RedlichKwong 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:

2

1 2

a12 = (a1a2) / (1k12 + (H12G12x2 / x1+G12x2)

(17)

(18)

G12 = exp(12H12)

(19)

Reference Manual

Equations of State

I-77

Thermodynamic Methods

Section 1.2

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 polarnonpolar 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 determined when both

values of the infinite-dilution activity coefficients are known for a binary

system. The physical meaning of the binary parameters k12 and k21 is that

they are used to locate the infinite-dilution activity coefficients in a binary

system containing components 1 and 2. After both end points of the liquid

activity coefficients are found, the parameters 12 and 21 are then required

to describe the shapes of the liquid activity coefficient curves for

components 1 and 2 in the finite range of concentration. In general, for real

systems, kij is not equal to kji, and ij and ji are not equal to zero. The conventional mixing rule, obtained by setting k12 = k21 and 12 = 21 = 0 for a

binary system, either results in a compromise of the phase-equilibrium

representation, or fails to correlate highly asymmetric systems.

For a multicomponent system, equation (17) can be generalized as:

(20)

1 2

1 3 1 3

1 6 3

i j

i

j

j

(21)

(22)

where:

subscript m refers to the multicomponent mixture.

Reference

Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E., 1991, A Cubic

Equation of State with a New Alpha Function and New Mixing Rule,

Fluid Phase Equil., 69, 33-50.

I-78

Equations of State

May 1994

Section 1.2

Peng-Robinson

Huron-Vidal

(PRH)

Thermodynamic Methods

The previous SRK and PR mixing rule modifications include compositiondependence for applying these equations of state to complex mixtures. A

more complicated way to represent the phase behavior of strongly nonideal

systems is to develop the relationship between the mixing rule and excess

Gibbs free energy, such that the infinite-pressure Gibbs free energy could be

expressed by a NRTL-like method (see Section 1.2.6, Liquid Activity Coefficient 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:

E

g = RT ln xi ln i

(23)

where:

gE =

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:

g = a / b (aixi / bi) ln(2)

(24)

where:

gE =

Equation (24) can be rewritten to produce a new mixing rule for the cubic

equation of state parameter a:

a = b (aixi / bi) g / ln (2) ln(2)

(25)

The excess Gibbs free energy can be calculated by any liquid activity

method. Huron and Vidal chose to use the NRTL liquid activity method to

calculate gE:

E

g = xi xj Gji cji / xkGki

i

k

j

(26)

(27)

Gji = bjexpajicji / RT

(28)

Reference Manual

Equations of State

I-79

Thermodynamic Methods

Section 1.2

The only difference between the classical NRTL equation and equations (2628) 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 gE in equation (25) yields:

a = bxi (ai / bi) 1 / ln(2) (xj Gji cji) / xkGki

i

j

k

(29)

NRTL expression, excellent representation of vapor-liquid equilibria can be

made for several systems. The Huron-Vidal mixing rules are highly empirical

in nature. However, the prediction of equilibria at low densities is 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 infinitepressure 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.

23.3

PRO/II Note: See Section 23.3, Modified Soave-Redlich-Kwong and Peng-Robinson, of the PRO/II Keyword Input Manual for more information on using

the modified SRK and PR methods in PRO/II.

Reference

Huron, M. J., and Vidal, J., 1979, New Mixing Rules in Simple Equations of

State for Representing Vapor-Liquid Equilibria of Strongly Non-ideal Mixtures, Fluid Phase Equil., 3, 255-271.

HEXAMER

I-80

Equations of State

Hydrogen fluoride is an important chemical used in many vital processes, including HF alkylation, and in the manufacture of refrigerants 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 mixture of monomer and

hexamer. In addition, evidence points to the hexamer existing in the form of

a cyclic benzene-like species. This behavior results in significant departures

from ideality, especially in calculating fugacity coefficients, vapor compressibility factors, heat of vaporization, and enthalpies.

May 1994

Section 1.2

Thermodynamic Methods

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:

P = nr

nr =

v=

(30)

a(T)

RT

(v b) v2 + ubv + wb2

(31)

nT

n0

(32)

V

n0

where:

a(T) = (T)a(Tc ) =

Redlich-Kwong equation-of-state

parameter which refers to the monomer

b=

the monomer

v=

molar volume

V=

total volume

nr =

extent of association

nT =

n0 =

association

Note: Only 1 hexamerizing component (HF) may be present when using the

HEXAMER method.

The values of a(Tc) and b can be obtained from the critical constants for the

Redlich-Kwong equation of state (see Table 1.2.4-2) and the critical temperature

and pressure for HF. The alpha function, (T), is obtained by matching the 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 hexamerization. As the temperature increases, the extent

of hexamerization should decrease, i.e., the value of nr should increase.

The total number of moles of monomer and hexamer, nT, and the total number of moles that would exist in the absence of association, n0, are related by:

(33)

n0

=

iz , i = 1,6

nT i

i

where:

zi =

ni =

Reference Manual

Equations of State

I-81

Thermodynamic Methods

Section 1.2

6(HF) (HF)6

(34)

a function of temperature only, is defined as:

K(T) =

6 z6 1

6 6 5

1 z1 P

(35)

where:

K=

equilibrium constant

1 =

6 =

z1 =

z6 =

P=

total pressure

The fugacity coefficients in equation (35) are found from the cubic equation of

state using classical thermodynamics. Then, by substituting equation (33) into

equation (35) and using the overall material balance, this reduces to:

6

(36)

K z1 = (6 5 z1) (1 z1)

where:

5

RT

K = K

= the reduced equilibrium constant

v

b

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:

log10 K = 43.65 +

(37)

8910

where:

K=

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:

z1(Tc) = 0.7006

(38-39)

nr (Tc) = 0.4005

I-82

Equations of State

May 1994

Section 1.2

Thermodynamic Methods

So, even at the critical point, there is still a considerable amount of the hexamer species present.

Mixture properties are computed by using the SRKS mixing rule, equation

(20), discussed previously.

23.7

PRO/II Note: See Section 23.7, Associating Equation of State, of the PRO/II

Keyword Input Manual for more information on using the HEXAMER method

in PRO/II.

Reference

Twu, C. H., Coon, J. E., and Cunningham, J. R., 1993, An Equation of State

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

UNIWAALS

state is combined with an 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 parameters from group contribution methods such as UNIFAC (see Section 1.2.6, UNIFAC) 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:

a / RTb = fPv / RT lnP(vb) / RT xiln(P(vibi) / RT +

(40)

f xiai / (fiRTBi) fg / RT

E

f=b/v

(41)

fi = bi / vi

(42)

where:

vE =

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

gE/RT. Subsequently, the van der Waals equation of state and equation (40)

are solved simultaneously to obtain the mixture volume, v, and a/RTb.

Reference Manual

Equations of State

I-83

Thermodynamic Methods

23.4

Section 1.2

PRO/II Note: See Section 23.4, UNIWAALS, of the PRO/II Keyword Input

Manual, for more information on using the UNIWAALS method in PRO/II.

Several limitations to this method should be noted:

1.

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.

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-WebbRubin-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 mixtures. This original (BWR) equation of

state however provided poor results at low temperatures and around the critical

point. To improve the accuracy of this equation in predicting thermodynamic

properties for light hydrocarbons in the cryogenic liquid, gas, and dense fluid regions, and at high temperatures, the BWR equation was modified by Starling in

1973 to give the following form:

2

3

4

2

P = RT + B0RT A0C0 / T + D0 / T E0 / T +

(43)

3

The eleven parameters for pure components (B0, A0, etc.) are generalized as

functions of component acentric factor, critical temperature, 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 correlate pure-component properties for light

hydrocarbons very accurately when experimental data covering entire ranges

are available.

I-84

Equations of State

May 1994

Section 1.2

23.6

Thermodynamic Methods

Keyword Input Manual for information on using the BWRS method in PRO/II.

Limitations to the BWRS equation of state are given below:

1.

Because the equation is generalized in terms of critical temperatures, critical density, and acentric factor, it has difficulty predicting properties for

heavy hydrocarbons and polar systems.

2.

The BWRS equation does not satisfy the critical constraints, and therefore

the equation is inferior to cubic equations of state when applied to the critical and supercritical regions.

3.

The BWRS equation is less predictive than cubic equations of state for

mixture calculations.

4.

normally requires more CPU time.

References

Lee-Kesler-Plcker

(LKP)

1.

Benedict, M., Webb, G. R., and Rubin, L. C., 1940, An Empirical Equation

for Thermodynamic Properties of Light Hydrocarbons and Their Mixtures.

I. Methane, Ethane, Propane, and Butane, J. Chem. Phys., 8, 334-345.

2.

Systems, Gulf Publishing Company, Houston, TX.

The LKP equation (available in versions 3.5 and later) is based on the

Benedict-Webb-Rubin equation of state and on Pitzers extended theory of

corresponding states. Thermodynamic data are correlated as a function of

critical temperature and pressure and the acentric factor as follows:

Z = Zo + Zr Zo

(44)

where:

Z=

compressibility factor

acentric factor

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.

Reference Manual

Equations of State

I-85

Thermodynamic Methods

Section 1.2

Tc, mix =

(45)

zj zk Vcjk Tcjk

Vc, mix j

j

mix

(46)

= zj j

(47)

where:

Vc =

Tc =

z=

12

Vcjk =

(48)

Kjk

(49)

3

1 1 3

1 3

Vcj + Vck

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:

Tc, mix

Pc, mix = 0.2905 0.085 mix R

vc, mix

(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 mixtures, 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

determination is not available. PRO/II uses a default value of 0.25.

Adjustable binary parameters, Kijs are also used in the mixing rules. Values

reported by Plcker et al. have been incorporated into PRO/II. The LKP

method is claimed by the authors to be superior to Starlings BWRS equation

for highly asymmetric systems. The method is not accurate around the 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.

I-86

Equations of State

May 1994

Section 1.2

Thermodynamic Methods

References

1.

Correlation Based on Three-Parameter Corresponding States, AIChE J., 21,

510-527.

2.

Corresponding States to Multicomponent Mixtures, Ind. Eng. Chem., 51,

597-600.

3.

Pitzer, K.S., and Hultgren G.O., 1958, The Volumetric and Thermodynamic

Properties of Fluids, V. Two Component Solutions, J. Am. Chem. Soc., 80,

4793-96.

4.

Plcker, U., Knapp, H., and Prausnitz, J.M., 1978, Calculation of High-Pressure Vapor-Liquid Equilibria from a Corresponding States Correlation

with Emphasis on Asymmetric Mixtures, Ind. Eng. Chem. Proc. Des. Dev.,

17, 324-332.

5.

Gaseous Mixtures, AIChE J., 4, 430-35.

6.

Volumetric Data for Gas Mixtures, AIChE J., 4, 494.

Reference Manual

Equations of State

I-87

Thermodynamic Methods

1.2.5

Section 1.2

General

Information

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 methods.

The pressure of the system, P, is calculated on a water-free basis by

subtracting the water partial pressure.

A pure water liquid phase is formed when the partial pressure of water

reaches its saturation pressure at that temperature.

The amount of water dissolved in the hydrocarbon-rich liquid phase is

computed using one of a number of water solubility correlations.

Note: The free water decant option may only be used with the Soave-RedlichKwong, Peng-Robinson, Grayson-Streed, Chao-Seader, Improved GraysonStreed, Erbar modifications to Grayson-Streed and Chao-Seader, Braun K10,

or Benedict-Webb-Rubin-Starling methods. Water decant is automatically activated when one of these methods is selected.

Calculation

Methods

computed once the water K-values, Kw, are known. These are calculated using the following relationship:

Kw = P w / P xw

(1)

where:

Pw =

xw =

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. Two methods are available for calculating water properties:

I-88

May 1994

Section 1.2

Thermodynamic Methods

conditions.

Water properties can be calculated using steam tables based on the

Keenan and Keyes equation of state.

The water solubility, xw, can be computed by one of three methods in PRO/II:

The default method developed by SimSci. In this method, water solubility is calculated for individual hydrocarbons and light gases given in

Table 1.2.5-1. The SimSci method uses a correlation based on the

number of carbon and hydrogen atoms present in the component. For

pseudocomponents, the water solubility is calculated as a function of the

Watson (UOP) K-factor.

The second method uses Figure 9A1.2 in the API Technical Data Book

to compute water solubility in kerosene. PRO/II will automatically

invoke this option if the SIMSCI solubility option is chosen, and a

component not included in Table 1.2.5-1 is present in the system.

The third method employs the equation-of-state method that is being

used for calculating the K-values of the other components present in the

system to compute the water K-value. Missing binary interaction parameters for the water-hydrocarbon component pairs are estimated using

the Soave-Redlich-Kwong Kabadi-Danner equation of state. This

method is only valid for SRK or PR equations of state.

Table 1.2.5-1:

Components Available in the SIMSCI Water Solubility Method

20.6

Paraffins

Naphthenes

Unsaturated Hydrocarbons

Aromatics

Methyl Mercaptan

CS2

NH3

Argon

CO2

Helium

HCl

H2S

N2

NO

O2

SO2

PRO/II Note: For more information on using the free-water decant option, see

Section 20.6, Free Water Decant Considerations, of the PRO/II Keyword Input

Manual.

Reference Manual

I-89

Thermodynamic Methods

1.2.6

Section 1.2

General

Information

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 thermodynamic methods of liquid mixtures within an activity coefficient

framework are covered in standard textbooks, a few of which are referenced

at the end of this section. The activity coefficient is introduced in the way

the fugacity of component i in the liquid phase is written:

L

(1)

oL

f i = i xi f i

where:

fLi =

foL

i

xi =

i =

i is defined as that of the pure liquid i at the

temperature and pressure of the mixture. With this definition, i approaches

one in the limit xi 1. The standard-state fugacity may be related to the vapor pressure of component i as follows:

f i = Pi i exp

0L

sat

sat

P

sat

Pi

L

vi / RT dP

(2)

where:

P=

system pressure

Psat

i =

R=

gas constant

T=

system temperature

vLi =

sat

i = fugacity coefficient of pure component i at temperature T

and pressure Psat

i

I-90

May 1994

Section 1.2

Thermodynamic Methods

The exponential term in equation (2) is the Poynting factor which accounts for

the effect of pressure on the liquid fugacity. If the pressure does not exceed a few

atmospheres, this correction can generally be neglected. Since liquid volumes

do not depend greatly on pressure, equation (2) can be simplified to:

f i = Pi i exp (P Pi ) vi RT

sat

sat

sat

(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:

V

(4)

fi = i yiP

where:

fVi =

yi =

V

i

For an ideal gas, the fugacity coefficient Vi equals one, but it may also be

computed from an equation of state or other correlation.

Equations (1) and (4) are fundamentally different in the way they describe

liquid and vapor fugacities, respectively. The two equations do not in general

match at the vapor-liquid critical point, where vapor and liquid phases 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)

oL

yi i f i

Ki = = V

xi P

i

At low and moderate pressures, the Poynting correction is often ignored and

equation (5) becomes:

sat

Ki =

(5a)

sat

i i Pi

V

iP

Unless there is vapor-phase association (as is the case with carboxylic acids,

for example), the fugacity coefficients may also be ignored at low and moderate pressures. Equation (5) then simplifies to:

(5b)

sat

i Pi

Ki =

P

Reference Manual

I-91

Thermodynamic Methods

Section 1.2

equilibrium data will produce essentially the same parameters if equation

(5a) or (5b) is used in place of the full equation (5). This is not necessarily

the case at higher pressures and for systems where vapor-phase nonideality is

important. Significant errors can be introduced when the regression and 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 factor as those employed

in fitting the parameters. An important exception to this rule is the case

where parameters were fitted at low pressure, but the calculations are at a substantially higher pressure. In such a case, it is best to employ nonideal vaporphase 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:

1 G

RT ni

T,P,n

(6)

ln i =

ji

where:

GE =

ni =

The following sections describe the expressions available for describing liquid-phase activity coefficients.

References

I-92

1.

Molecular Thermodynamics of Fluid-Phase Equilibria, 2nd ed., PrenticeHall, Englewood Cliffs, NJ.

2.

John Wiley & Sons, New York.

3.

Engineering Thermodynamics, 4th ed., McGraw-Hill, New York.

4.

Nonelectrolyte Solutions: With Applications to Phase Equilibria,

McGraw-Hill, New York.

5.

May 1994

Section 1.2

Thermodynamic Methods

Margules

Equation

Table 1.2.6-1: Margules Equation

Required Pure-component Properties

Vapor pressure

Application Guidelines

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 equation. The resulting expression for the activity coefficient is:

2

ln i = ( 1 xi ) Ai + 2Bi Ai Di xi + 3Di xi

where:

(7)

Ai = xj aij

j=1

N

Bi = xj aji

j=1

N

Di = xj dij

j=1

dij = dji

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.

References

1.

104, 1234.

2.

Thermodynamic Properties and the Classification of Solutions, Ind. Eng.

Chem. 40, 345-348.

Reference Manual

I-93

Thermodynamic Methods

Section 1.2

Table 1.2.6-2: van Laar Equation

Required Pure-component Properties

Application Guidelines

Vapor pressure

Components

components.

Another old correlation which is still frequently used is the van Laar equation. It

may be obtained by discarding ternary and higher-order terms in an alternative

expansion of the excess Gibbs energy (known as Wohls equation), though that is

not how van Laar derived it originally. The resulting expression for the activity coefficient is:

N

ln i =

1

ail Zl aij Zi Zj

2

l=1

j=1

j=1 k=1

j,kl

(8)

ajk

aij

aji

Zj Zk

where:

Zl =

xl

xj ail

j

li

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.

References

I-94

1.

van Laar, J. J., 1910, The Vapor Pressure of Binary Mixtures, Z. Phys.

Chem., 72, 723-751.

2.

Systems, Trans. AIChE, 42, 215-249.

May 1994

Section 1.2

Thermodynamic Methods

Regular Solution

Theory

Table 1.2.6-3: Regular Solution Theory

Required Pure-component Properties

Vapor pressure

Application Guidelines

Components

Solubility parameter

components and solutions

containing fluorocarbons.

vanishes when the solution is mixed at constant temperature 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 determined by the attractive intermolecular forces. Scatchard

and Hildebrand made a simple assumption relating mixture interactions to

those in pure fluids; the result is a simple theory in which the activity 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:

L

2

RT ln i = v i i j i

(9)

j=

xj vj

xk vk

where:

vLi =

i =

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 numerous compounds, and these parameters

are included for most components in PRO/IIs library.

Reference

Hildebrand, J.H., Prausnitz, J. M., and Scott, R. L., 1970, Regular and

Related Solutions, Van Nostrand Reinhold Co., New York.

Reference Manual

I-95

Thermodynamic Methods

Section 1.2

Flory-Huggins

Theory

Table 1.2.6-4: Flory-Huggins Theory

Required Pure-component Properties

Vapor pressure

Application Guidelines

Components

Solubility parameter

are chemically similar and

which 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 molecules which differ greatly in

size. It is therefore suitable for polymer/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:

reg

ln i = lni

L

vL

vi

i

+ ln L + 1 L

v

v

(10)

where:

reg

i =

L

vi =

L

v =

liquid molar volume of component i

liquid molar volume of solution

References

I-96

1.

J.Chem.Phys., 10, 51.

2.

Huggins, M. L., 1942, Thermodynamic Properties of Solutions of LongChain Compounds, Ann. N.Y. Acad. Sci., 43, 9.

3.

Correlation for Solvent Activities in Polymer Solutions, Ind. Eng. Chem.

Proc. Des. Dev., 24, 1036.

May 1994

Section 1.2

Thermodynamic Methods

Wilson Equation

Table 1.2.6-5: Wilson Equation

Required Pure-component Properties

Application Guidelines

Vapor pressure

Components

associating components in

nonpolar solvents. Cannot

be used if liquid-liquid

immiscibility exists.

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 activity coefficient is:

N

j=1

k=1

ln i = 1 ln xj Aij

(11)

xk Aki

N

xj Akj

j=1

where:

L

Aij =

vi

L

vj

L

Aij =

vi

L

vj

exp

aij

exp

aij

Aij = aij

RT

(when unit of aij is NODIME)

aij represents a characteristic energy of interaction between species i and j.

While there is no explicit temperature dependence in the Wilson equations

parameters, the derivation is such that the equation may be used with some confidence over a wider range of temperatures 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 shortcoming, however, is that it is

mathematically unable to predict the splitting of a liquid into two partially miscible phases. It is therefore completely unsuitable for problems involving liquidliquid equilibria.

Reference Manual

I-97

Thermodynamic Methods

Section 1.2

References

1.

Predict Vapor Compositions, Ind. Eng. Chem., 62(1), 22-31.

2.

the Wilson Equation, Ind. Eng.Chem., 57(5), 18-26.

3.

the Excess Free Energy of Mixing, J. Amer. Chem. Soc., 86, 127.

NRTL Equation

Table 1.2.6-6: NRTL Equation

Required Pure-component Properties

Application Guidelines

Vapor pressure

Components

mixtures and for partially

miscible systems.

Prausnitz to make use of the local composition concept, while avoiding the

Wilson equations inability to predict liquid-liquid phase separation. The resulting equation has been quite successful in correlating a wide variety of

systems. The expression for the activity coefficient is:

ji Gji xj

ln i =

Gki xk

xj Gij

Gkj xk

ij

xk kj Gkj

k

Gkj xk

(12)

where:

ij = aij +

bij

ij = aij +

bij

RT

+

+

cij

T

cij

2 2

(when unit is K)

R T

I-98

May 1994

Section 1.2

Thermodynamic Methods

Three parameters, ij, ji, and ij = ji, are required for each binary. These

parameters may be made temperature-dependent as described above. If ij is

to be represented with only one constant, it has been found empirically that

better results over a range of temperatures are obtained if only bij is used and

aij = cij = 0. The parameter does not vary greatly from binary to binary,

and it is often satisfactory to fix it at 0.3 for vapor-liquid systems and 0.2 for

liquid-liquid systems.

References

1.

Renon, H. and Prausnitz, J. M., 1968, Local Composition in Thermodynamic Excess Functions for Liquid Mixtures, AIChE J., 14, 135-144.

2.

UNIQUAC

Equation

Table 1.2.6-7: UNIQUAC Equation

Required Pure-component Properties

Vapor pressure

Application Guidelines

Components

area and volume

mixtures containing polar

or nonpolar components

and for partially miscible

systems.

and Prausnitz based on statistical-mechanical considerations and the latticebased quasi-chemical model of Guggenheim. As in the Wilson and NRTL equations, local compositions are used. However, local surface-area fractions are

used as the primary composition variable instead of volume fractions. Each

molecule i is characterized by a volume parameter ri and a surface-area parameter 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 individual molecules; it contains no binary parameters. The residual part, which accounts for the energetic interactions, has two adjustable binary parameters. The UNIQUAC

equation has, like the NRTL equation, been quite successful in correlating a

wide variety of systems. The expression for the activity coefficient is:

C

(13)

ln i = ln i + ln i

_

M

i z

i

i

C

x l

ln i = ln + qi ln + li

xi j j

xi 2

i

j=1

Reference Manual

(14)

I-99

Thermodynamic Methods

Section 1.2

M

M

R

ln i = qi 1 ln j ji

j=1

j=1

j ij

M

(15)

k kj

k=1

where:

ij = exp

Uij

(when unit is K)

ij = exp

Uij

RT

x i qi

i =

xi qi

i=1

lj =

i =

_

z

(r qj) (rj 1)

2 j

xi ri

M

xj rj

j=1

qi =

ri =

Awi

9

2.5 x 10

Vwi

15.17

_

z = 10

Awi =

Vwi =

Two parameters, Uij and Uji, are required for each binary; they may be made

temperature-dependent as described above. If no temperature-dependence is

used for Uij, better results over a range of temperatures are normally obtained by using aij and setting bij = 0.

I-100

May 1994

Section 1.2

Thermodynamic Methods

References

1.

of Mixtures: A New Expression for the Excess Gibbs Free Energy of

Partly or Completely Miscible Systems, AIChE J., 21, 116-128.

2.

Equation to Calculation of Multicomponent Phase Equilibria. 1. Vapor-Liquid Equilibria, Ind. Eng. Chem. Proc. Des. Dev., 17, 552-561.

3.

Equation to Calculation of Multicomponent Phase Equilibria. 2. Liquid-Liquid Equilibria, Ind. Eng. Chem. Proc. Des. Dev., 17, 561-567.

4.

the UNIQUAC Equation, Fluid Phase Equilibria, 2, 91-99.

UNIFAC

Table 1.2.6-8: UNIFAC

Required Pure-component Properties

Application Guidelines

Vapor pressure

Pressure

Up to 10 atmospheres

area and volume

Temperature

32 - 300 F

Components

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 contribution concept following the

Analytical Solution of Groups (ASOG) model proposed by Deer and Deal in

1969. Interactions between two molecules are assumed to be a function of

group-group interactions. Whereas there are thousands of chemical 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 represents

the excess Gibbs energy (and logarithm of the activity coefficient) as a combination of two effects. Equation (13) is therefore used:

C

ln i = ln i + ln i

i , is computed directly from the UNIQUAC

equation (14) using the van der Waals area and volume parameter calculated

from the individual structural groups:

Reference Manual

I-101

Thermodynamic Methods

Section 1.2

_

i

i z

i

c

ln i = ln + qi ln + li

xi

xi 2

i

NOC

xj lj

j=1

where:

xi ri

i =NOC

xj rj

j=1

x i qi

i =NOC

xj qj

j=1

_

z

li = (ri qi) (ri 1)

2

NOG

ri = k Rk

i

k=1

NOG

qi = k Qk

i

k=1

where:

NOC = number of components

NOG = number of different groups in the mixture

_

z=

lattice coordination number = 10

i

vk =

Rk =

Qk =

xi =

The group volume and area parameters are obtained from the atomic and molecular structure.

Rk =

Qk =

(16)

Vwk

15.17

(17)

Awk

2.5x10

where:

I-102

Vwk =

Awk =

May 1994

Section 1.2

Thermodynamic Methods

(18)

NOG

R

i

ln i = ln k ln k

k=1

where:

k =

i

k =

residual activity coefficient of group k in a reference solution

containing only molecules of group type i. This quantity is required so that Ri 1 as xi 1

ln k = Qk 1 ln m mk

m

m

m km

n nm

n

(19)

where:

m, n = 1, 2, ... NOG

The parameter mk is given by:

amk

mk = exp

RT

(20)

where:

amk =

not a function of temperature. A large number of interaction parameters between structural groups, as well as group size and shape parameters have

been incorporated into PRO/II.

References

1.

Deer, E.L., and Deal, C.H., 1969, Inst. Chem. Eng. Symp. Ser., 32(3), 40.

2.

Contribution Estimation of Activity Coefficients in Nonideal Liquid

Mixtures, AIChE J., 27, 1086-1099.

3.

Skjold-Jrgensen, S., Kolbe, B., Groehling, J., and Rasmussen, P., 1979,

Vapor-Liquid Equilibria by UNIFAC Group Contribution. Revision and

Extension, Ind. Eng. Chem. Proc. Des. Dev., 18, 714-722.

4.

Equilibria by UNIFAC Group Contribution. Revision and Extension,

Ind. Eng. Chem. Proc. Des. Dev., 22, 676-678.

5.

Gmehling, J., 1991, Vapor-Liquid Equilibria by UNIFAC Group

Contribution. 5. Revision and Extension, Ind. Eng. Chem. Res., 30,

2352-2355.

Reference Manual

I-103

Thermodynamic Methods

Modifications

to UNIFAC

Section 1.2

accuracy of the method can be improved by incorporating a temperaturedependent 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 given by:

Amk

mk = exp

RT

(21)

+ T To

T

(22)

To

where:

amk, bmk, cmk =

To =

298.15 K

The combinatorial part of the logarithm of the activity coefficient is given by:

c

ln i = ln

(23)

wi

wi

+1

xi

xi

(24)

ri 3 xi

wi = NOC

2

3

ri

xi

i=1

Reference

Larsen, B.L., Rasmussen, P., and Fredenslund, Aa., 1987, A Modified UNIFAC Group Contribution Model for Prediction of Phase Equilibria and

Heats of Mixing, Ind. Eng. Chem. Res., 26, 2274-2286.

For this modified method, the temperature-dependent form of Amk is given

by:

2

I-104

(25)

May 1994

Section 1.2

Thermodynamic Methods

by:

ln

c

i

_

wi zqi ln i

i

wi

= ln + 1

+1

xi

xi 2 i

Qi

(27)

ri 4 xi

wi = NOC

3

4

rj

(26)

xj

j=1

where:

z = lattice coordination number = 10

xi ri

i = NOC

xj rj

j=1

xi qi

i = NOC

xj qj

j=1

Reference

Weidlich, V., and Gmehling, J., 1987, A Modified UNIFAC Model:

1. Prediction of VLE, hE, and , Ind. Eng. Chem. Res., 26, 1372-1381.

UFT3

For this modified UNIFAC method, the temperature-dependent form of Amk

is given by:

(28)

The combinatorial and residual parts of the activity coefficient are identical

to those described previously for the UNIFAC method.

Reference

Torres-Marchal, C., and Cantalino, A.L., 1986, Industrial Applications

of UNIFAC, Fluid Phase Equil., 29, 69-76.

Reference Manual

I-105

Thermodynamic Methods

Section 1.2

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:

c

(29)

FV

ln i = ln i + ln i + ln i

13

V i

FV

i

ln i = 3 Ci ln

Ci 1

1

V 3 1

V

m

m

1 1

V i 3

(30)

where:

Vi=

Vwi

15.17 bri

NOG

1

ri =

Mi

k Rk

i

k=1

Vi wi + Vj wj

Vm=

b = 1.28

where:

Vi =

Mi =

wi =

Ci =

solvent i = 3.3

Reference

Oishi, T., and Prausnitz, J.M., 1978, Estimation of Solvent Activities

in Polymer Solutions Using a Group-Contribution Method, Ind. Eng.

Chem. Proc. Des. Dev., 17, 333-339.

I-106

May 1994

Section 1.2

Fill Methods

24.10

Thermodynamic Methods

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 interaction parameters

are then searched for data.

3.

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 provide estimates for the interaction parameters. For LLE

calculations, UNIFAC or the modified UNIFAC method UFT1 is used to

supply the parameter estimates.

PRO/II Note: For more information on using the FILL option, see Section 24.10,

Filling In Missing Parameters, of the PRO/II Keyword Input Manual.

5.

Finally, if binary interaction parameters are still missing after steps 1-4 are

followed, then all missing parameters are set equal to zero.

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.

2.

3.

The LLE databank.

The VLE databank.

Reference Manual

I-107

Thermodynamic Methods

Section 1.2

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) statement.

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.

2.

20.7

I-108

The VLE databank.

PRO/II Note: For more information on specifying VLLE methods, see Section

20.7, Vapor-Liquid-Liquid Equilibrium Considerations, of the PRO/II Keyword Input Manual.

May 1994

Section 1.2

Thermodynamic Methods

Figure 1.2.6-1:

Flowchart for FILL

Methods

Reference Manual

I-109

Thermodynamic Methods

Henrys Law

24.11

Section 1.2

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 Henrys constant.

PRO/II Note: For more information on using Henrys Law, see Section 24.11,

Henrys Law for Non-condensible Components, of the PRO/II Keyword Input

Manual.

Thermodynamically, the Henrys constant of a solute i in a solvent j is defined as

the infinite-dilution limit of the ratio of the fugacity to the mole fraction:

(31)

fi

x

1 i

Hi,j = lim

xj

xi 0

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:

Ki =

(32)

Hi,j

P

This relationship is strictly true only in the infinite-dilution limit, but K-values from Henrys law generally remain accurate at solute mole fractions up

to approximately five percent.

PRO/II correlates Henrys constants to the following functional form:

ln Hi,j = C1 +

C2

T

+ C3ln T + C4P

(33)

The temperature dependence in equation (33) is that expected from a thermodynamic analysis, provided the solvents critical point is not approached too

closely. Thermodynamics also predicts that the effect of pressure on the effective

Henrys constant at conditions beyond infinite dilution is linear in pressure (with

C4 proportional to the solutes partial molar volume). The pressure correction is

negligible at low and moderate pressures; if the pressure is sufficiently high for

that term to become important, it is likely that better results could be obtained by

an equation of state with an advanced mixing rule.

When the HENRY option is specified, components with critical temperatures below 400 K are automatically designated as solute components by PRO/II. The user

may, however, override these designations as desired. PRO/II has an extensive databank of Henrys constants for supercritical gases in various solvents and also for

many organic compounds in water. Henrys constants may also be input by the

user. If no Henrys constant is given for a solute, PRO/II substitutes the solutes vapor pressure (extrapolated if necessary). This substitution is good only

for nearly ideal solutions. In particular, if no Henrys constant is available for an

organic solute in water, it is better to remove the organic from the list of solutes

and allow the liquid activity method (with interaction parameters filled in via

UNIFAC, if necessary) to compute the K-value.

I-110

May 1994

Section 1.2

Thermodynamic Methods

Note: The temperature dependence of Henrys 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 solutes

Henrys 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 Henrys constant of a solute in a mixture of solvents is estimated from

the following mixing rule:

(34)

j=1

where the sum is taken over all solute species j, and the mole fractions xj

used in the sum are computed on a solute-free basis.

Reference

Prausnitz, J.M., Lichtenthaler, R.N., and Gomes de Azevedo, E., 1986,

Molecular Thermodynamics of Fluid-Phase Equilibria, 2nd edition, Prentice-Hall, Englewood Cliffs, NJ, Chapter 8.

Heat of Mixing

Calculations

mole fraction sum of pure-component enthalpies (see Section 1.2.3, Ideal). For

some systems, however, the excess enthalpy, or heat of mixing, is not negligible

and should be accounted for if accurate prediction of the liquid enthalpy is important. It should be noted that SimScis equations of state and generalized correlations produce a heat of mixing as a natural part of their calculations. Therefore,

explicit calculation of the heat of mixing is only used in conjunction with the

IDEAL method for liquid enthalpy, which is normally used with liquid activity

coefficient K-value methods.

Gamma Method

Thermodynamics allows the excess enthalpy to be computed directly from

the activity coefficients in a mixture and their temperature dependence. This

is known as the GAMMA option, and the equation is:

(35)

ex

2 lni

H = xi RT

where:

Hex = excess heat of mixing

Reference Manual

I-111

Thermodynamic Methods

Section 1.2

Despite the attractiveness of this direct thermodynamic computation, 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-Kister Expansion

Experimental data for heats of mixing for binary systems are most often represented by an expansion about an equimolar mixture:

ex

(36)

where:

X = x1 x2

In equation (36), known as the Redlich-Kister expansion, a12 represents the

excess enthalpy of a 50-50 binary mixture. Higher-order terms correlate

asymmetry in the curve of excess enthalpy versus composition.

SimScis databanks contain regressed values of the coefficients in equation

(36) for approximately 2200 binary mixtures. In addition, these parameters

may be regressed to heat-of-mixing data with SimScis REGRESS program

and then entered through input by the user.

24.14

liquid-enthalpy calculations, see Section 24.14, Redlich-Kister, Gamma Heat

of Mixing, of the PRO/II Keyword Input Manual.

The empirical nature of the Redlich-Kister expansion means that there is some

degree of arbitrariness in the way it is extended to mixtures. SimSci offers two

options, known as RK1 and RK2. Both have the same basic form:

(37)

ex

where:

X = xi xj

xi xj

X =

xi + xj

(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 preferable from the standpoint of

theoretical consistency.

I-112

May 1994

Section 1.2

1.2.7

Thermodynamic Methods

General

Information

separately the fugacity of each component in the vapor and liquid phases. Each

of the two phases may require a different technique. For example, liquid-phase

nonidealities may be described by activity coefficients, while deviations from

ideal-gas behavior in the vapor phase are described by fugacity coefficients. The

vapor-phase fugacity coefficients may be obtained through the use of an equation of state. The fugacity coefficients are obtained from classical thermodynamics as follows:

P

ln i = 1 / RT

V ni

T,V,nj

RT / V dV lnz

i = fi / yiP

(1)

(2)

where:

i =

fi =

fugacity of component i

R=

gas constant

T=

system temperature

P=

system pressure

ni =

number of moles of i

yi =

V=

volume of system

z=

using an appropriate equation of state. Therefore the problem of calculating

fugacities of components in a gaseous mixture 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).

Volume I: Component and Thermophysical Properties

Thermodynamic Methods

Equations of State

Section 1.2

low and high densities. The analytical expression of the fugacity coefficient can be

derived from a cubic equation of state. The derivation of the fugacity coefficient

from a cubic equation of state is straightforward because the cubic equation of state

in pressure is volume-explicit. Cubic equations of state are usually applied to 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.

Note: See Section 1.2.4 of this manual, Equations of State, for more information on using equations of state.

theory of association, is suitable for systems containing polar and hydrogenbonding molecules. These include carboxylic acids which form monomerdimer pairs and hydrogen fluoride. Such methods include the Associating

Hexamer Equation of State and the Hayden OConnell method, discussed in

a later section.

23.7

Hexamer Equation of State method for vapor fugacities, see Section 23.7, Associating Hexamer Equation of State, of the PRO/II Keyword Input Manual.

The equation-of-state methods are generally more reliable for calculating vapor-phase fugacity coefficients than any other method, except for dimerizing

components, where the Hayden-OConnell method should be used.

Truncated Virial

Equation of State

Many equations of state have been proposed for calculating vapor fugacities, as

mentioned in the previous section, but almost all of them are empirical in nature.

The virial equation of state for gases has a sound theoretical foundation and is

free of arbitrary assumptions. The virial equation gives the compressibility factor as a power series in the reciprocal molar volume:

2

(3)

z = Pv / RT = 1 + B / v + C / v + D / v +

where:

v=

molar volume

B, C, D, .. =

For low or moderate vapor densities, the virial equation can be truncated

after the second virial coefficient and converted to a pressure-explicit form:

z = 1 + BP / RT

I-114

(4)

May 1994

Section 1.2

Thermodynamic Methods

is given by:

N

B=

i

(5)

yiyjBij

j

where:

Bii =

Bij =

component i and one of component j. They may be obtained from mixture data,

though often they are estimated from the pure component coefficients.

OConnell and Prausnitz developed a correlation for the reduced second

virial coefficient (both pure component and cross coefficients) which consists of three generalized functions:

1.

2.

3.

as hydrogen bonds.

critical volume, acentric factor, dipole moment, and association constant for

each component present. Missing dipole moments and association constants

are assumed to be zero. One limitation of this method is that, as the virial

equation of state is an expansion about the compressibility factor of an ideal

gas, higher-order terms cannot be neglected in high density regions. The

virial equation of state can provide reliable estimates of vapor-phase fugacity

coefficients at low pressures or high temperatures only.

24.13

PRO/II Note: For more information on using the Truncated Virial fugacity

method, see Section 24.13, Truncated Virial Vapor Fugacity, of the PRO/II

Keyword Input Manual.

Reference

OConnell, J. P., and Prausnitz, J. M., 1967, Empirical Correlation of Second

Virial Coefficients for Vapor-Liquid Equilibrium Calculations, Ind. Eng.

Chem. Proc. Des. Dev., 6, 245-250.

Volume I: Component and Thermophysical Properties

Thermodynamic Methods

HaydenOConnell

Section 1.2

The truncated virial equation of state described above is useful for predicting

deviations from ideality in those systems where moderate attractive forces yield

fugacity coefficients not far removed from unity. However, in systems containing

carboxylic acids, two acid molecules tend to form a dimer, resulting in large negative deviations from vapor ideality even at very low pressures.

To account for dimerization, Hayden and OConnell, in 1975, developed an

expression for the fugacity coefficient based on the chemical theory of vapor

imperfection. The chemical theory assumes that there are dimerization

equilibria for a binary mixture of components A and B:

KA2

A1 + A1 A2

KB2

B1 + B1 B2

KA B

A1 + B1 AB

(6)

(7)

(8)

where:

A1, B1 = monomers

A2, B2 = dimers

AB =

cross dimer

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 components are

available in PRO/IIs databanks.

24.12

method, see Section 24.12, Hayden-OConnell Vapor Fugacity, of the PRO/II

Keyword Input Manual.

This method is a reliable generalized method for calculating vapor fugacities

up to moderate pressures, especially for systems where no data are available.

Reference

Hayden, J. G., and OConnell, J. P., 1975, A Generalized Method for

Predicting Second Virial Coefficients, Ind. Eng. Chem. Proc. Des. Dev.,

14, 209-216.

I-116

May 1994

Section 1.2

1.2.8

Thermodynamic Methods

Special Packages

General

Information

for special industrial applications. Data packages are available for the following applications:

Alcohol dehydration systems.

Glycol systems.

Sour water systems.

Amine systems.

For many applications, databanks containing binary interactions specifically

regressed for components commonly found in the application have been developed

and incorporated into PRO/II. For example, for alcohol dehydration systems, a

special alcohol databank, in combination with the NRTL K-value method, is used

to calculate the K-values. For other applications, such as the SOUR or GPSWAT

method for sour systems containing NH3, H2S, CO2, and H2O, a K-value method

has been specifically developed for phase equilibrium calculations.

Alcohol

Package

(ALCOHOL)

The alcohol data package uses the NRTL liquid activity method to calculate

phase equilibria (see Section 1.2.6 of this manual, Liquid Activity Methods).

This system uses a special set of NRTL binary interaction parameters for

systems containing alcohols, water, and other polar components. The binary

parameters have been obtained by the regression of experimental data for alcohol systems. The recommended temperature and pressure ranges for the

ALCOHOL data package are as follows:

Temperature:

122-230 F for H2O-alcohol systems.

150-230 F for all other systems.

Pressure: up to 1500 psia.

The vapor enthalpy and density and the vapor and liquid entropies are

calculated using the SRKM equation of state (see Section 1.2.4 of this manual, Equations of State), while the liquid enthalpy and density are calculated

using ideal methods (see Section 1.2.3, Generalized Correlation Methods).

Table 1.2.8-1 shows the components present in the ALCOHOL databank for

which there are binary interaction parameters available.

Volume I: Component and Thermophysical Properties

Thermodynamic Methods

Section 1.2

Table 1.2.8-1: Components Available for ALCOHOL Package

Component

Formula

LIBID

Miscellaneous

Acetaldehyde

Sulfolane

C2H4O

C4H8O2S

ACH

SULFLN

H2

N2

O2

CO2

H2

N2

O2

CO2

C5H12

C5H12

C5H10

C6H14

C6H12

C6H14

C6H12

C6H6

C6H12

C7H16

C7H16

IC5

NC5

CP

2MP

1HEXENE

NC6

MCP

C6H6

CH

24DMP

3MHX

C7H14

C7H16

C7H14

C7H8

C8H18

1T2MCP

NC7

MCH

TOLU

24DMHX

C8H16

1T2C4MCP

Light Gases

Hydrogen

Nitrogen

Oxygen

Carbon Dioxide

Hydrocarbons

Isopentane

n-Pentane

Cyclopentane

2-Methylpentane

1-Hexene

n-Hexane

Methylcyclopentane

Benzene

Cyclohexane

2,4-Dimethylpentane

3-Methylhexane

1-Trans-2-Dimethyl

cyclopentane

n-Heptane

Methylcyclohexane

Toluene

2,4-Dimethylhexane

1-Trans-2-Cis-4-Trimethylcyclopentane

Figure 1.2.8-1 shows the binary interaction parameters present in the ALCOHOL databank. It should be noted that for all pairs not denoted by x, the

missing binary interaction parameter can be filled in, based on the hierachy

discussed in Section 1.2.7, Liquid Activity Methods.

25.1

I-118

Special Packages

PRO/II Note: For more information on using the ALCOHOL method, see Section 25.1, Alcohol, of the PRO/II Keyword Input Manual.

May 1994

Section 1.2

Thermodynamic Methods

Figure 1.2.8-1:

Binary Interaction Data

in the Alcohol Databank

X

X X

X X X

X X X X

X X X X X

X X X X X X

X X X X X X X

X X X X X X X X

X X X X X X X X X

X X X X X X X X X X

X X X X X X X X X X X

X X X X X X X X X X X X

X X X X X X X X X X X X X

X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X X X X

X X X X X X X X X X X X X X X X X X X X

X X X X

X X X X

X X X X

X X X X

X

X

X X X X

X X X X

X

X

X

X

X X X X

X X X X

X

X

X

X

X

X

X

X X

X X

X X

X X X X

X X X X

X X X X X X X X X X X X X X X X X X X X X

X X X X

X X X X

X X X X

X X X X

X X X X

X X X X

X X X X

X

X X

X X X

X X X X X

X X X X

X X X X X

X X

X X

X X X X X X X X X X X X X X X X X X X X X X X

X

X X X X X X X X X X X X

X

X

X X X X X X

X X X

X X X X X

X X X X X

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

X X X X X X

X X X X X X X

X X X X X X X X

X X X X X X X X X

X X X X X X X X X X X X

Hydrogen

Nitrogen

Oxygen

Carbon Dioxide

Isopentane

n-Pentane

2-Methylpentane

n-Hexane

2,4-Dimethylpentane

3-Methylhexane

n-Heptane

2,4-Dimethylhexane

Cyclopentane

Methylcyclopentane

Cyclohexane

1-T-2DM-Cyclopentane

Methylcyclohexane

1-T,2-C-4 TMCP

1-Hexene

Benzene

Toluene

DIPE

DEE

DME

Acetic Acid

Formic Acid

MEK

Acetone

Ethyl Acetate

Methyl Formate

Acetaldehyde

Sulfolane

n-Pentanol

3-M-1-Butanol

n-Butanol

Isobutanol

Sec. Butanol

Tert-Butanol

n-Propanol

Isopropanol

Ethanol

Methanol

Nitrogen

Oxygen

Carbon Dioxide

Isopentane

n-Pentane

2-Methylpentane

n-Hexane

2, 4-Dimethylpentane

3-Methylhexane

n-Heptane

2, 4-Dimethylhexane

Cyclopentane

Methylcyclopentane

Cyclohexane

1-T-2DM-Cyclopentane

Methylcyclohexane

1-T,2-C-4 TMCP

1-Hexene

Benzene

Toluene

DIPE

DEE

DME

Acetic Acid

Formic Acid

MEK

Acetone

Ethyl Acetate

Methyl Formate

Acetaldehyde

Sulfolane

n-Pentanol

3-M-1-Butanol

n-Butanol

Isobutanol

Sec-Butanol

Tert-Butanol

n-Propanol

Isopropanol

Ethanol

Methanol

Water

Volume I: Component and Thermophysical Properties

Thermodynamic Methods

Glycol

Package

(GLYCOL)

Section 1.2

The glycol data package uses the SRKM equation of state to calculate phase

equilibria for glycol dehydration applications (see Section 1.2.4 of this manual, Equations of State). This system uses a special set of SRKM binary

interaction data and alpha parameters for systems containing glycols (particularly TEG), water, and other components. The binary parameters and alpha

parameters have been obtained by the regression of experimental data for

glycol systems. The recommended temperature and pressure ranges for the

GLYCOL package are:

Temperature: 80-400 F.

Pressure: up to 2000 psia.

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

1.2.3, Generalized Correlation Methods).

Table 1.2.8-2 shows the components present in the GLYCOL databank for

which there are binary interaction parameters available.

Components

Hydrogen

Nitrogen

Oxygen

Carbon Dioxide

Hydrogen Sulfide

Methane

Ethane

Propane

Isobutane

n-Butane

Isopentane

Pentane

Hexane

Heptane

Cyclohexane

Methylcyclohexane

Ethylcyclohexane

Benzene

Toluene

o-Xylene

m-Xylene

p-Xylene

Ethylbenzene

Ethylene Glycol

Diethylene Glycol

Triethylene Glycol

Water

I-120

Special Packages

Formula

H2

N2

O2

CO2

H2S

CH4

C2H6

C3H8

C4H10

C4H10

C5H12

C5H12

C6H14

C7H16

C6H12

C7H14

C8H16

C6H6

C7H8

C8H10

C8H10

C8H10

C8H10

C2H6O2

C4H10O3

C6H14O4

H2O

LIBID

H2

N2

O2

CO2

H2S

C1

C2

C3

IC4

NC4

IC5

NC5

NC6

NC7

CH

MCH

ECH

BNZN

TOLU

OXYL

MXYL

PXYL

EBZN

EG

DEG

TEG

H2O

May 1994

Section 1.2

Thermodynamic Methods

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.

Nitrogen

Oxygen

Carbon Dioxide

Hydrogen Sulfide

Methane

Ethane

Propane

Isobutane

N-butane

Isopentane

Pentane

Hexane

Heptane

Cyclohexane

Methylcyclohexane

Ethylcyclohexane

Benzene

Toluene

o-xylene

m-xylene

p-xylene

Ethylbenzene

Ethylene Glycol

Diethylene Glycol

Triethylene Glycol

Water

X

X O

X O

X O

X O

O

O O

X O

X O

O O X

O O X X

X O

X O

O O O O O

O O O O O O

X O

O O O

O

X O

O O X X O

X O X O O X X O

X O

O O

X O O O O

O

O O O

X O

X

O

O

X X X

X O O

X

X

O O

O

O

O O

O O

O O O

X

X

X

X

X X X

X X

X

X X X X X X X X X X X X X X X X X X X X

X

X X X X X X X X X X X X X X X X X X X X X X X X X X

Hydrogen

Nitrogen

Oxygen

Carbon Dioxide

Hydrogen Sulfide

Methane

Ethane

Propane

Isobutane

N-butane

Isopentane

Pentane

Hexane

Heptane

Cyclohexane

Methylcyclohexane

Ethylcyclohexane

Benzene

Toluene

o-xylene

m-xylene

p-xylene

Ethylbenzene

Ethylene Glycol

Diethylene Glycol

Triethylene Glycol

Figure 1.2.8-2:

Binary Interaction Data

in the Glycol Databank

25.2

PRO/II Note: For more information on using the GLYCOL method, see Section 25.2, Glycol, of the PRO/II Keyword Input Manual.

Volume I: Component and Thermophysical Properties

Thermodynamic Methods

Sour Package

(SOUR)

Section 1.2

This sour water package uses the SWEQ (Sour Water EQuilibrium) method

developed by Wilson for a joint API/EPA project. Phase equilibria for sour

water components NH3, H2S, CO2, and H2O are modeled using a modified

van Krevelen approach. The van Krevelen model assumes that H2S and CO2

exist in solution only as ionized species. This is true only for solutions 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:

pH2S = HH2S CH2S

(1)

(2)

where:

pi =

Hi =

Ci =

kg solution

The SWEQ model uses Henrys Law constants for each component in solution

as a function of temperature and composition of the undissociated molecular species in the liquid phase. The Henrys constants for H2S and CO2 were obtained

from data published by Kent and Eisenberg, who developed a model for predicting H2S-CO2-MEA-H2O and H2S-CO2-DEA-H2O systems. The Henrys Law

constants used in the SWEQ model for equations (1) and (2) are:

4

(3)

9

12

9.0918 x 10 / T + 1.2601 x 10 / T

(4)

5

11

13

where:

T=

I-122

Special Packages

May 1994

Section 1.2

Thermodynamic Methods

The Henrys Law constant for water was obtained by correlating H2O vapor

pressure data from the A.S.M.E. steam tables over the range 25 C to 150 C:

(5)

The Henrys Law constant for NH3 was taken from data published by

Edwards et al.:

4

(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.

0

(7)

0.4

ln Ki = ln Ki + aCH2S + bCCO2 + cI

where:

Ki =

Ki0 =

a,b,c =

constants

I=

Zj =

The reaction equilibrium constants at infinite dilution, Ki0, are given in the

form first proposed by Kent and Eisenberg:

0

ln Ki = A + B / T + C / T + D / T + E / T

(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 into PRO/II, thus extending

the applicable pressure range to 1500 psia.

Volume I: Component and Thermophysical Properties

Thermodynamic Methods

Section 1.2

The phase behavior of all other components present in the system is modeled

using the SRKM equation of state (see Section 1.2.4 of this manual, Equations of State). The following limits apply to the SOUR method as

implemented in PRO/II:

Temperature: 67-300 F.

Pressure: up to 1500 psia.

Composition: wNH3 + wCO2 + wH2S <0.30.

where:

wi =

Note: NH3 and water must be present when using the SOUR method.

Other thermodynamic properties such as the vapor enthalpy, vapor and liquid

entropy, and vapor density are calculated using the SRKM equation of state,

while the liquid enthalpy and density are calculated using ideal methods (see

Section 1.2.3, Generalized Correlation Methods).

25.3

PRO/II Note: For more information on using the SOUR method, see Section

25.3, Sour, of the PRO/II Keyword Input Manual.

References

I-124

Special Packages

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.

Eng. Chem., 50, 391-402.

4.

Kent, R. L., and Eisenberg, B., 1976, Better Data for Amine Treating,

Hydrocarbon Processing, Feb., 87-90.

5.

Rubber Co.

6.

Solutions Containing Volatile Weak Electrolytes, 1975, AIChE J., 21, 248-259.

May 1994

Section 1.2

Package

(GPSWATER)

Thermodynamic Methods

This sour water package uses the method developed for the Gas Processors

Association in 1990 for sour water systems containing components NH3, H2S,

CO2, CO, CS2, MeSH, EtSH, and H2O. This model uses the SWEQ model (see

above) as a precursor, extending the temperature range of applicability to 600

F. The total pressure limit is increased to 2000 psia by allowing for vapor

phase non-idealities and accounting for pressure effects in the liquid phase,

using a Poynting correction factor.

As in the SWEQ model, the chemical equilibria for all the reactions involving the NH3, H2S, and CO2 in water are considered. The components CO,

methyl mercaptan (MeSH), and ethyl mercaptan (EtSH) are treated as

Henrys Law components (see Section 1.2.6, Liquid Activity Coefficient

Methods). Reactions considered include:

Water:

1

(9)

H2O H + OH

Ammonia:

2

NH3 + H NH4

(10)

Hydrogen Sulfide:

3

(11)

H2S + OH H2O + HS

Bisulfide:

4

(12)

HS + OH H2O + S

Carbon Dioxide:

5

(13)

CO2 + OH HCO3

Bicarbonate:

(14)

2

Volume I: Component and Thermophysical Properties

Thermodynamic Methods

Section 1.2

7

(15)

8

(16)

9

(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:

2

(18)

z=1+B/v+C/v

where:

B, C are the second and third virial coefficients

v=

molar volume

z=

compressibility factor

Phase equilibria for all other components present in the system are modeled

using the SRKM equation of state (see Section 1.2.4 of this manual, Equations of State).

The following limits apply to the GPSWATER method:

Temperature: 68-600 F.

Pressure: up to 2000 psia.

Composition:

wNH3 < 0.40.

pCO2 + pH2S < 1200 psia

where:

wi =

pi =

Note: NH3, CO2, H2S, and water must be included in the component list

when using the GPSWATER method.

I-126

Special Packages

May 1994

Section 1.2

Thermodynamic Methods

Other thermodynamic properties such as the vapor enthalpy, vapor and liquid entropy, and vapor density are calculated using the SRKM equation of state, while

the liquid enthalpy and density are calculated using ideal methods (see Section

1.2.3, Generalized Correlation Methods).

25.4

PRO/II Note: For more information on using the GPSWATER method, see

Section 25.4, GPA Sour Water, of the PRO/II Keyword Input Manual.

Reference

Wilson, G. M., and Eng, W. W. Y., 1990, GPSWAT: GPA Sour Water

Equilibria Correlation and Computer Program, GPA Research Report RR118, Gas Processors Association.

Amine Package

(AMINE)

The PRO/II simulation program contains a method to model the removal of H2S

and CO2 from natural gas feeds using alkanolamines. Alkanolamines are formed

by ammonia reacting with an alcohol. Amines are considered to be either 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 amine monoethanolamine (MEA), secondary amines diethanolamine (DEA), diglycolamine (DGA), and diisopropanolamine (DIPA), and the

tertiary amine methyldiethanolamine (MDEA). MEA and DEA are frequently

used amines in industry.

In aqueous solutions, H2S and CO2 react in an acid-base buffer mechanism with

alkanolamines. The acid-base equilibrium reactions are written as chemical dissociations following the approach taken by Kent and Eisenberg:

Water:

1

(19)

H2O H + OH

Hydrogen Sulfide:

2

(20)

H2S H +HS

Bisulfide:

HS H + S

Volume I: Component and Thermophysical Properties

(21)

Thermodynamic Methods

Section 1.2

Carbon Dioxide:

4

(22)

Bicarbonate:

(23)

HCO3 H +CO3

Alkanolamine:

6

(24)

RR NH2 + H + RR NH

where:

Ki =

RRNR =

alkanolamine

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 carbamates. In

an aqueous solution with MDEA, CO2 forms bicarbonate ions by reaction

(22) only.

Note: CO2, H2O, and H2S must be included in the component list when using

the AMINE method.

The chemical equilibrium constants, Ki, are represented by the following

equation:

ln Ki = A + B T + C T + D T

2

I-128

Special Packages

(26)

May 1994

Section 1.2

Thermodynamic Methods

The equlibrium constant for the protonated amine dissociation reaction given

in reaction (24) is corrected to the pure amine reference state. This is done

by relating the constant to the infinite-dilution activity coefficient of the

amine in water estimated from experimental data for the system amine-water.

The liquid enthalpy is calculated using ideal methods and adding a correction for the heat of reaction as follows, using either a modified ClausiusClapeyron equation or fits of data from the Gas Processors Association:

Hr = lnKT1 / KT2 R / 1 / T1 1 / T2

(27)

where:

Hr = heat of reaction

R=

gas constant

KT1, KT2 =

The vapor-phase enthalpy and density, and liquid- and vapor-phase entropy

are calculated using the SRKM equation of state (see Section 1.2.4 of this

manual, Equations of State). Ideal methods are used to calculate the liquidphase density (see Section 1.2.3, Generalized Correlation Methods).

For MEA and DEA systems, data have been regressed from a large number of

sources, resulting in good prediction of phase equilibria for these systems. For

systems containing DIPA, a limited amount of experimental data were available,

and so the DIPA results are not recommended for final design purposes. For

MDEA and DGA systems, the user is allowed to input a residence time correction to allow the simulation results to more closely match plant data. The application ranges suggested for amine systems are shown in Table 1.2.8-3.

Amine

25.5

MEA

DEA

DGA

MDEA

DIPA

Pressure, psig

25-500

1001000

1001000

1001000

1001000

Temperature, F

<275

<275

<275

<275

<275

Concentration, wt %

amine

~15-25

~25-35

~55-65

~50

~30

gmole gas/gmole

amine

0.5-0.6

0.45

0.50

0.4

0.4

PRO/II Note: For more information on using the AMINE method, see Section

25.5, Amine, of the PRO/II Keyword Input Manual.

Volume I: Component and Thermophysical Properties

Thermodynamic Methods

Section 1.2

References

I-130

Special Packages

1.

Kent, R. L., and Eisenberg, B., 1976, Better Data for Amine Treating,

Hydrocarbon Processing, Feb., 87-90.

2.

Maddox, R. N., Vaz, R. N., and Mains, G. J., 1981, Ethanolamine Process

Simulated by Rigorous Calculation, Hydrocarbon Processing, 60, 139-142.

May 1994

Section 1.2

1.2.9

Thermodynamic Methods

Discussion of

Equations

set of nonlinear algebraic equations. The equation set is composed of:

Equilibrium Expressions

For each vapor-liquid, liquid-liquid, solid-liquid, and liquid intraphase equilibrium, there is an equation of the form:

K=

iP

iR

( )niP (m )niP

iP

iP

(1)

( )niR (m )niR

iR

iR

where:

K=

iP, iR =

of the ith product and reactant, respectively; a function

of temperature, pressure, and composition

niP, niR =

miP, miR =

molality or, for vapors, partial pressure of the ith product and reactant, respectively

Note: When H2O (the solvent) appears in the equilibrium expression, its

contribution is expressed as aH2O, the activity of water. All pure solid

component activities are assumed to be one. The fugacity coefficient, i is 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.

Volume I: Component and Thermophysical Properties

I-131

Thermodynamic Methods

Section 1.2

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 waters critical point. Consequently, over the temperature

and pressure validity range for the electrolyte thermodynamic methods (0-200

C; 0-200 atm), K is treated only as a function of temperature.

An Electroneutrality Equation

NC

(2)

NA

| Zi | mi = | Zi | mi

i=1

i=1

where:

Zi =

species charge

NC, NA =

(liquid-liquid equilibrium)

A

(3)

ai = ai

i = 1,NM

ai =

A, O =

NM =

where:

Note: The required number of material balances, i.e. NB, completes the model

and assures that the number of equations and the number of unknowns are

equal. Normally these balances include an overall, a vapor phase, an organic

phase, and several component balances.

Thus, assuming NK equilibrium equations, the model has NK + NB + NM + 1

equations. The customary unknowns are:

The moles of H2O in the aqueous liquid phase plus all ionic and 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.

I-132

May 1994

Section 1.2

Thermodynamic Methods

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:

H2Ovap H2O

(4)

CO2vap CO2aq

(5)

+1

(6)

H2Oaq H + OH

+1

+1

HCO3 H + CO3

+1

NACLppt NA

(7)

(8)

(9)

+ CL

Based upon the general model described earlier, this leads to:

Equilibrium Expressions

KH2Ovap =

KCO2vap =

KH2Oaq =

KCO2aq =

(10)

aH2O

H2Ovap yH2Ovap P

CO2aq mCO2aq

(11)

CO2vap yCO2vap P

(12)

aH2O

H+1 mH+1 HCO31 mHCO31

KHCO3ion =

KNACLppt=

(13)

H+1 mH+1 CO32 mCO32

(14)

HCO31 mHCO31

NA+1 mNA+1 CL1 mCL2

(15)

aNACLppt

Electroneutrality Equation

mH+1 + mNA+1 = mHCO31 + 2mCO32 + mOH1 + mCL1

(16)

There are none in this example.

Volume I: Component and Thermophysical Properties

I-133

Thermodynamic Methods

Section 1.2

Overall material balance:

3H2Oin + 3CO2in + 2NACLin = 2NACLppt + 3H2O + (H2O / 55.51)

(3mCO2aq + 5mHCO31 + 4mCO32 + mH+1 + 2mOH1 +

mCL1 + mNA+1) + V(3yH2Ovap + 3yCO2vap)

(17)

where:

in = inflow or feed component in units of moles

V = overall vapor fraction on a mole basis

In equation (17), the products H2O and NACLppt are in units of moles.

Vapor balance

yH2Ovap + yCO2vap = 1

(18)

where:

y = mole fraction for vapor species

Sodium balance

NACLin = (H2O / 55.51)(mNA+1) + NACLppt

(19)

Chlorine balance

NACLin = (H2O / 55.51)(mCL1) + NACLppt

(20)

Carbon balance

CO2in = (H2O / 55.51)(mCO32 + mHCO31 + mCO2aq) + V (yCO2vap)

(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 constants, activity coefficients,

fugacity coefficients, and the activity of water, then the corresponding 12 unknowns (calculated variables) are:

V, yH2Ovap, yCO2vap, mH+1 mOH1, mCO32,

mHCO31, mNA+1, mCL1, mCO2aq, moles NACLppt,

and moles water.

164

I-134

PRO/II is given in Section 164, Electrolyte Models, of the PRO/II Keyword Input Manual. Additional models may be generated by the user with the PRO/II

Electrolyte Utility Package (EUP).

May 1994

Section 1.2

1.2.10

Thermodynamic Methods

Thermodynamic

Framework

thermodynamic quantities. Specifically these are:

Equilibrium constants -- normally strong functions of temperature and

weaker functions of pressure.

Aqueous-phase activity coefficients -- normally strong functions of temperature and composition and weaker functions of pressure.

Vapor-phase fugacity coefficients -- normally significant functions 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.

163

Equilibrium

Constants

in PRO/II, see Section 163, Electrolyte Thermodynamic Data, of the PRO/II

Keyword Input Manual.

By considering basic thermodynamic relationships and assuming a constant heat

capacity of reaction, the following general equation can be derived:

ln K (T) =

G H 1 1 Cp Tr Tr

ln + 1

R T Tr

RTr

R T T

(1)

where:

T=

temperature in Kelvins

Tr =

G = free energy of the reaction in the standard state at the reference temperature (and pressure, 1 bar). This is derived

from the standard-state Gibbs free energies of formation,

Gf , by first, summing the product of the reaction 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 .

Volume I: Component and Thermophysical Properties

I-135

Thermodynamic Methods

Section 1.2

conditions. Obtained from the standard-state enthalpy of formation, 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 Thermodynamics1. Values of Gf , Hf ,

and Cp for reaction species are usually available in the critically evaluated

data compilations of the National Bureau of Standards2 or the Russian Academy of Sciences3.

The chosen standard states for the thermodynamic framework are as follows:

Aqueous solutes - hypothetical, infinitely dilute solution at unit molality;

Solvent - pure fluid; Gaseous species - hypothetical 1 bar ideal gas; Solid

species - pure solid. These are the same standard states as used by the NBS2.

For some reactions, where sufficient measurements are available for K as a

function of temperature, fitted functions of temperature are used instead of

equation (1).

Aqueous Phase

Activities

reaction equilibria described in the previous section. Greater precision is added

by a good description of the following correction factors:

Activity coefficients of ions in solution.

Activity coefficients of molecules in solution.

Activity of water.

In PRO/II Electrolytes, these quantities can be represented in terms of a 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.

I-136

May1994

Section 1.2

Thermodynamic Methods

Ions

For ions the formulation used is:

ln i = DHi + BZi + Pi

(2)

defined as:

(3)

2 1 2

A Zi I /

DHi =

1 2

1+I /

where:

A=

and solvent density.1

NI

I=

ionic strength = 1 / 2

i=1

Zi =

charge on ion i

dilute solutions of ionic strength less than 0.1, this is the only term needed.

BZi =

interactions, defined as:

(4)

NO

Zi + Zj

BZi =

ij mj

2

j=1

where:

ij =

NO =

(1 + 1.5 / Zi Zj I)

(5)

number of ions with charge opposite to that of the ion being represented.

Bij,Cij,Dij =

Pi =

three interaction coefficients for each cation-anion interaction. These are each made 3-parameter functions of temperature. Thus, for each cation-anion interaction, there

are 9 coefficients that must be established.

defined as:

NM

2

Z1

Pi = BPij + 2 BPSjmj

4I

j=1

(6)

(0)

(1)

1 2

1 2

BPij = ij + ij 1 + 2I / 1 exp 2I / / 2I

(7)

where:

and

Volume I: Component and Thermophysical Properties

I-137

Thermodynamic Methods

Section 1.2

(8)

NS

k=1

and

(1)

1 2

1 2

BPPjk = jk 1 1 + 2I / + 2I exp 2I /

(9)

where:

NM =

NS =

(1)

(0)

ij , ij

molecule-molecule interaction.

temperature. Thus, for each interaction, there are 6 coefficients that must be

established.

Molecules Other Than Water

For molecules other than water, the Setschenow equation is used. Where

ij(0) and ij(1) parameters are available, the preferred formulation is from

Pitzer6,7. The Setschenow and Pitzer relations are:

NI

ln i = bi I + bj mj

(10)

j=1

where:

bi =

bj =

NI =

and

NS

ln i = 2 BPij mi

(11)

j=1

Water Activity

The water activity for multicomponent systems is obtained from an integrated form of the Gibbs-Duhem equation, together with a mixing rule suggested by Meissner and Kusik8. The formulation can be represented as:

I-138

May1994

Section 1.2

Thermodynamic Methods

(12)

NC NA

ln a

H2O

1

AZ

Zi Zj ij mi mj

i=1 j=1

NM

0.01801

i=1

NS

m + 2

BPW

m

m

i

ij

i

j

j=1

where:

NC

2

AZ = Zi mi

i=1

NA

Z2 m

i

i

i=1

(13)

(0)

(1)

1 2

BPWij = ij + ij exp 2I /

(14)

NC =

NA =

The above formulations are, in cases where the necessary interaction coefficients

have been fit to cover the conditions being simulated, quite adequate for predicting systems in which water is the principal solvent.

Vapor Phase

Fugacities

Ideal, all fugacity coefficients are assumed to be 1.0.

Nothnagel method, generally valid up to 20 atmospheres.

Nakamura method, generally valid up to 200 atmospheres.

Soave-Redlich-Kwong (SRK) method, valid over a wide range of conditions

and generally recommended when vapor-phase non-ideality is important.

Nothnagel Method

Nothnagel et al.9 developed a method for calculating fugacity coefficients in

mixtures at moderate pressures. The main feature of the method is the inclusion of dimerization effects on the second virial coefficient.

The equation of state is written as:

P=

(15)

nT R T

V nT bm

where:

bm =

nT =

P=

pressure, atmospheres

R=

T=

temperature, Kelvins

V=

Volume I: Component and Thermophysical Properties

I-139

Thermodynamic Methods

Section 1.2

nT is obtained from the solution of the dimerization equilibria described below. bm is given by a sum over all true species:

n bm = ni bi

(16)

where:

bi =

ni =

(17)

1 1 3

1 3

bi = b / + b /

B

8 A

For component j, the fugacity coefficient is given by:

zj

j = exp bj P / RT

y

(18)

where:

bj =

yj =

zj =

The true mole fractions zj are computed from the dimerization equilibria.

Each dimerization is described by an equilibrium constant Kij:

Kij =

zij ij

P

zi zj i j

(19)

1 3 1 3

ij = exp bi / + bj / P / 8RT

The dimerization equilibrium constants are related to the enthalpy and entropy of dimerization:

lnRTKij = Hij / RT Sij / R

(20)

(21)

where:

Hij = enthalpy of dimerization, cal/mole

Sij = entropy of dimerization, cal/mole

R=

(21)), 1.987 cal/mole K (right side of equation (21))

The correlations for Hij and Sij, along with the necessary parameters for

178 components, may be found in the original paper9.

I-140

May1994

Section 1.2

Thermodynamic Methods

Nakamura Method

Nakamura et al.10 proposed the following perturbed-hard-sphere equation of

state for gas mixtures:

P=

2

3

RT 1 + +

a

3

v

v

(v

+ c)

(1

(22)

where:

P=

pressure, atmospheres

R=

T=

temperature, Kelvins

v=

b=

a=

c=

In addition to equations for the reduced enthalpy difference and entropy difference, the following equation was presented for calculating the fugacity coefficient of a species k in the gas mixture:

n

5 ( 1) m c

4 32 b k 4 2 2

M

2

ln k =

+

yj akj

2 b

3

RT

v

(

m

+

1)

M (1 )

j=1

m=1

(1 )

4

a ck (1)m (m + 1) c

M

M

RTv

v

m=1 (m + 2)

1

+ ln z

2

+ 1 +

(23)

With the P, R, T, v, and terms defined earlier, the following definitions and

calculations apply:

n=

number of species

(24)

where:

=

pure-component parameter

pure-component parameter

(25)

b = yi bi

M

i=1

where:

yi =

ck =

pure-component parameter

Volume I: Component and Thermophysical Properties

I-141

Thermodynamic Methods

Section 1.2

(26)

c = yi ci

M

i=1

z=

compressibility factor =

n

Pv

RT

a = yi yj aij

(27)

(28)

i=1 j=1

aij = ij +

ij

T

pure-component parameter

ij =

interaction parameter

(29)

where:

ij = ij + ij

(30)

ij = ij + ij

(31)

ij =

i j

(32)

ij =

i j

(33)

ij =

0

1 0

0

+ j

2 i

(34)

where:

i =

ij =

interaction parameter

(21) through (34) are given in the original paper by Nakamura et al. for the

following components: Ar, CH4, C2H4, C2H6, C3H6, C3H8, CO, CO2, H2,

H2O, H2S, N2, NH3, and SO2.

SRK Method

Calculation of fugacity coefficients from the Soave-Redlich-Kwong equation of

state is described in Section 1.2.4, Equations of State, of this manual.

Note: For both the Nothnagel and Nakamura options, if an electrolyte model

contains a volatile species not covered in the original paper by Nakamura et

al. for the method (MEA and HClO are examples of such species) the fugacity

coefficients all default to 1.0 (ideal gas). The SRK option does not suffer from

this limitation.

I-142

May1994

Section 1.2

Thermodynamic Methods

Organic Phase

Activities

Activities of components in an organic liquid phase (if one exists) are obtained

from the Kabadi-Danner modification to the SRK equation of state. This method

is described in Section 1.2.4, Equations of State, of this manual.

Enthalpy

The pressure dependence of the enthalpy for vapor, liquid, and solid phases

is neglected in this thermodynamic framework. However, this does not introduce significant uncertainties in enthalpy calculations over the stated model

validity ranges for temperature (0 to 200 C) and pressure (up to 200 bars).

Because enthalpy is treated as pressure-independent, PRO/II Electrolytes 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:

NC

(35)

Hvap or Hsol = yi Hi

i=1

where:

Hi, yi = the standard state molar enthalpy and the mole fraction, respectively, of the ith vapor or solid component

NC =

solid phase.

Hi = Hfi,T +

r

T

Tr

(36)

Cp dT

i

where:

Cpi, H fi,Tr = the standard state, isobaric, molar heat capacity, and the

standard state molar enthalpy of formation for the ith

vapor or solid component

Tr =

Values of Cpi for vapor and solid species are obtained from empirical functions of temperature, which are given by:

Cp = Ai + BiT + CiT

(37)

(for vapor)

(38)

i

where:

Ai , Bi , C i =

Volume I: Component and Thermophysical Properties

constants characteristic of the ith vapor or solid

components.

I-143

Thermodynamic Methods

Aqueous Liquid

Phase

Section 1.2

The enthalpy of the aqueous solution, Haq, at the temperature and solution

composition of interest is evaluated using:

(39)

NI

NM

i=1

i=1

where:

Hw =

the molar enthalpy of pure water at the temperature of interest and at the vapor/liquid saturation pressure of H2O

xi =

NM, NI =

respectively

The enthalpy of pure water is obtained from the equation of state for H2O

given by Haar, Gallagher, and Kell11. At the temperature and solution composition of interest, Hi is evaluated using:

2 lni

Hi = Hi RT

(40)

where:

i =

R =

Values of i and (lni / T) are obtained from equations (2) through (9) for

ionic species and from equations (10) and (11) for molecular solutes. Values

of Hi are obtained from equation (36), using values of Cpi and H fi,Tr for

aqueous species and using the following relations to represent Cpi for ionic

and molecular solutes:

i

(41)

(42)

where:

Ai, Bi, and Ci =

Density

characteristic of the ith molecular solute

Vapor Phase

The density of the vapor phase is evaluated using the equation of state which

corresponds to the chosen vapor fugacity method.

I-144

May1994

Section 1.2

Thermodynamic Methods

The molar volume of the aqueous solution, vaq, at the temperature, pressure,

and solution composition of interest is evaluated using:

NM

NI

i=1

(43)

i=1

where:

vw =

the molar volume of pure water at the temperature and pressure of interest, as given by the HGK11 equation of state

vi,Tr =

ionic aqueous solute species, at the reference temperature

The density of an organic liquid phase is calculated using the Rackett

method for liquid density. This method is described in Section 1.2.3, Generalized Correlations, of this manual.

Solid Phase

The molar volume of the solid phase, vsol, at the temperature of interest is

evaluated using:

NC

(44)

vsol = xi vi,T

i=1

where:

vi,Tr = the standard state molar volume of the ith pure solid component at the reference temperature

Volume I: Component and Thermophysical Properties

I-145

Thermodynamic Methods

Section 1.2

References

1. Zemaitis, J.F. Jr., Clark, D.M., Rafal, M., and Scrivner, N.C., 1986, Handbook of Aqueous Electrolyte Thermodynamics, AIChE.

2a. Wagman, D.D., et al., 1968-1973, Selected Values of Chemical

Thermodynamic Properties, NBS Tech Note, 270-3 to 8.

2b. Chase, M.W. Jr., Davies, C.A., Downey, J.R. Jr., Frurip, D.J., McDonald,

R.A., and Syverud, A.N., 1985, JANAF Thermochemical Tables, 3rd edn.,

J. Phys. Chem. Ref. Data, 14, Supplement no. 1, 1856 pp.

2c. Wagman. D. D., et al., 1982, The NBS Tables of Chemical Thermodynamic

Properties, J. Phys. Chem. Ref. Data, 11, Supplement no. 2, 392 pp.

3. Glushko, V.P., editor, 1965-1981, Thermal Constants of Compounds, Russian Academy of Sciences, Vols. I-X.

4. Zemaitis, J.F., Jr., 1980, Predicting Vapor-Liquid-Solid Equilibria in Multicomponent Aqueous Solutions of Electrolytes, Thermodynamics of Aqueous Systems with Industrial Applications, S.A. Newman, ed., ACS

Symposium Series, 133, 227-246.

5. Bromley, L.A., 1973, Thermodynamic Properties of Strong Electrolytes in

Aqueous Solutions, AIChE J., 19, 313-320.

6. Pitzer, K.S., 1979, Theory: Ion Interaction Approach, Activity Coefficients

in Electrolyte Solutions, 1, 157-208, R.M. Pytkowicz, ed., CRC Press,

Boca Raton, FL.

7. Pitzer, K.S., 1980, Thermodynamics of Aqueous Electrolytes at Various

Temperatures, Pressures and Compositions, Thermodynamics of Aqueous

Systems with Industrial Applications, S.A. Newman, ed., ACS Symposium

Series, 133, 451-466.

8. Meissner, H.P., and Kusik, C.L., 1973, Aqueous Solutions of Two or More

Strong Electrolytes - Vapor Pressures and Solubilities, Ind. Eng. Chem.

Proc. Des. Dev., 12, 205-208.

9. Nothnagel, K.H., Abrams, D.S., and Prausnitz, J.M., 1973, Generalized Correlation of Fugacity Coefficients in Mixtures at Moderate Pressures, Ind.

Eng. Chem. Proc. Des. Dev., 12, 25-35.

10. Nakamura, R., Breedveld, G.J.F., and Prausnitz, J.M., 1976, Thermodynamic Properties of Gas Mixtures Containing Polar and Nonpolar Components, Ind. Eng. Chem. Proc. Des. Dev., 15, 557-564.

11. Haar, L., Gallagher, J.S., and Kell, G.S., 1984, NBS/NRC Steam Tables,

Hemisphere Press, Washington D.C., 320 pp.

I-146

May1994

Section 1.2

1.2.11

Thermodynamic Methods

Solid-Liquid Equilibria

General

Information

The solubility of solids in liquids can be described by the vant Hoff (idealsolubility) equation. This is sufficient for many systems where non-idealities

are small. Alternatively, solubility data, correlated as a function of temperature, may be entered directly. Precipitation of solid salts and minerals from

aqueous solutions may be calculated rigorously using PRO/II Electrolytes.

This capability is described separately in Sections 1.2.9, Electrolyte Mathematical Model, and 1.2.10, Electrolyte Thermodynamic Equations, of this manual.

vant Hoff

Equation

by assuming that the activity coefficient of the solute in the liquid phase is one.

The solubility is then entirely determined by the ratio of the pure solids fugacity

to its standard-state fugacity in the liquid phase, which is that of a pure subcooled liquid. This ratio is one at the solutes triple point where the solubility

also becomes one. At lower temperatures, it can be calculated with fair accuracy

using the heat of melting; a more accurate estimate results if the heat capacity

change of melting is known. A full derivation of the ideal solubility (or vant

Hoff, after the Dutch chemist who first proposed it) equation is given by Prausnitz et al. The result is:

ln xi =

Hm T

Cp Tt

Cp Tt

1 +

ln

1

RT Tt

R T

R

T

(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 usually 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 solvent are of a similar chemical nature and form

a nearly ideal solution. For example, the solubility of aromatic hydrocarbons

in benzene is well described by equation (1).

Volume I: Component and Thermophysical Properties

Solid-Liquid Equilibria

I-147

Thermodynamic Methods

Section 1.2

Table 1.2.11-1 vant Hoff

Required pure component properties

Triple-point

temperature (Tt)

(or melting

temperature if Tt

is not available)

Application Guidelines

Components

be of a similar chemical

nature (i.e. form a nearideal solution).

Enthalpy of melting

Solubility Data

For systems where sufficient data exist, solid solubilities may be entered by

the user in the form of a correlation of solubility versus temperature. This

correlation has the same functional form as the vant Hoff equation:

ln xij = Aij + Bij T + Cij ln(T)

(2)

where:

xij =

temperature

For solubility of a solid solute i in a mixed solvent, theory dictates that the

mixing rule should have the following form:

ln xi = Zj ln xij

(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:

Zj =

Solubility Data

zj

(4)

1 zi

In a multicomponent mixture, data may be missing for one or more of the i,j

pairs appearing in the sum in equation (3). Three options are provided for

filling in missing values of xij. The default option is to fill in missing values

with xij as calculated by equation (1), the vant Hoff equation.

Note: When the vant Hoff equation is used as a FILL option, the Cp terms

are ignored.

The FILL = ONE option uses values of one (complete miscibility) for the solutes solubility in the missing solvents. The FILL = FREE option causes the

missing solvent or solvents to be ignored in the solubility calculation. In other

words, if a solvent k is missing solubility data for the solute, the sum in equation

(3) is only taken over those solvents for which data exist, and the mole fractions

in that sum are renormalized to a k-free (as well as solute-free) basis:

I-148

Solid-Liquid Equilibria

May 1994

Section 1.2

Thermodynamic Methods

Zj =

(5)

zj

1 zi zk

k

In equation (5) the sum is over all solvents k for which there are no solubility

data. Note that equation (5) is meaningless if no solvent in the mixture has

solubility data. If FILL = FREE is specified in such a case, the calculations

are defaulted to the vant Hoff equation.

Reference

Prausnitz, J.M., Lichtenthaler, R.N., and Gomes de Azevedo, E., 1986,

Molecular Thermodynamics of Fluid-Phase Equilibria, 2nd edition, PrenticeHall, Englewood Cliffs, NJ, Chapter 9.

Volume I: Component and Thermophysical Properties

Solid-Liquid Equilibria

I-149

Thermodynamic Methods

1.2.12

Section 1.2

Transport Properties

General

Information

Liquids

Vapors

Viscosity

Viscosity

Thermal Conductivity

Thermal Conductivity

Diffusivity

stream. Most library components include saturated vapor and liquid values

for viscosity, thermal conductivity, and surface tension as part of the stored

physical property data. Several correlations have also been included in

PRO/II which predict the above properties for hydrocarbon mixtures. Liquid

diffusivity is used by some of the unit operations but is not stored in the

component library. The transport methods are described in the sections that

follow.

With the exception of the PURE and TRAPP methods, there are no special

provisions to characterize the hydrocarbon type (paraffinic, olefinic, etc.).

While these non-characterizing methods may be used for all hydrocarbon

types, or petroleum fractions, the best accuracy is to be expected for paraffins, with a degradation in accuracy for olefins or aromatics. Non-hydrocarbon transport properties are best represented by the properties from structure

methods discussed in Section 1.1, Component Data.

27

PURE Methods

I-150

Transport Properties

PRO/II Note: For more information on specifying PURE methods, see Section

27, Transport and Special Properties, of the PRO/II Keyword Input Manual.

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:

May 1994

Section 1.2

Thermodynamic Methods

Table 1.2.12-2: Stream Average Properties

Stream Property

Additive Basis

2

2

m = wi 1

wi = Weight fraction

(1)

yi = Mole fraction

(2)

xi = Mole fraction

(3)

yi = Mole fraction

(4)

xi = Mole fraction

(5)

yi i (MWi)

13

m =

yi (MWi)1 3

i

Liquid Viscosity

m = xi 1i 3

i

Vapor Viscosity

yii (MWi)

12

m =

yi (MWi)1 2

i

Surface Tension

m = xi i

i

The user may also provide individual component values as a function of temperature either in tabular or equation forms.

PETRO Methods

27

PRO/II Note: For more information on specifying the PETRO methods, see Section 27 of the PRO/II Keyword Input Manual, Transport and Special Properties.

Liquid Viscosity

The method selected for liquid viscosity is dependent on the reduced temperature, which is in turn calculated by Kays rule. When the system is near

the critical point (0.98<Tr<1.0), the method developed by Letsou and Steil is

used. For the range 0.76<Tr<0.98, equations relating viscosity to reduced

temperature and acentric factors developed by Letsou and Steil (as cited in

section 9-12 in Reid, Prausnitz and Poling) are used. These methods were 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.

Volume I: Component and Thermophysical Properties

Transport Properties

I-151

Thermodynamic Methods

Section 1.2

For intermediate ranges (Tb<T<0.76Tc), 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 reference values are computed by the

methods described above.

After the mixture viscosity has been estimated using one of the above methods,

it is corrected for the effects of pressure using the method of Kouzel (also given

in the API Technical Data Book, pp. 11-47, 2nd edition). The vapor pressure,

needed for this method, is estimated with the Reidel equation.

If water decant is active for the thermodynamic method, water viscosities are

taken from the component data library. A wet viscosity is then calculated

for water/hydrocarbon streams by combining the hydrocarbon and water viscosities with the following mixing rule:

(6)

1 3

13

wet = xaq aq + xhc hc

where:

=

viscosity

x=

mole fraction

of the stream

References

I-152

Transport Properties

1.

2.

Saturated Liquid Volume, AIChE J., 17, 1341-1345.

3.

Kendall, J., and Monroe, K. P., 1917, The Viscosity of Liquids, II, The

Viscosity - Composition Curve for Ideal Liquid Mixtures, J. Amer. Chem.

Soc., 39, 1787-1802.

4.

5.

Elevated Pressures, AIChE J., 19, 409-411.

6.

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.

Temperature and a Relation Between Viscosity, Density, and Chemical

Constitution, J. Chem. Soc., Part II, 573-579.

May 1994

Section 1.2

Thermodynamic Methods

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 thermal 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:

wet =

(7)

1

w 2 + w 2

hc hc

aq aq

12

where:

=

thermal conductivity

w=

portions of the stream

References

1.

2.

Reidel, L., 1950, The Determination of the Thermal Conductivity and the

Specific Heat of Various Mineral Oils, Chem. Ing. Tech., 21, 349.

Surface Tension

The surface tension for hydrocarbon liquids is estimated with procedure 10A3.1

(Page 10-17) in the API Technical Data Book (3rd edition). Surface tension for

water is extracted from the component data library. Wet surface tension values for decant hydrocarbon systems are computed with the formula:

wet = xaq aq + xhc hc

(8)

where:

=

surface tension

x=

of the stream

Volume I: Component and Thermophysical Properties

Transport Properties

I-153

Thermodynamic Methods

Section 1.2

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:

12

wet =

1 2

(9)

1 2

1 2

where:

=

MW = molecular weight

subscripts aq and hc refer to the aqueous and hydrocarbon portions

of the stream

References

1.

at Normal Pressures, AIChE J., 16, 300-304.

2.

Dean, D.G., and Stiel, L.S., 1965, The Viscosity of Nonpolar Gas Mixtures at

Moderate and High Pressures, AIChE J., 11, 526-532.

3.

Herning, F., and Zipperer, L., 1936, Calculation of the Viscosity of Technical

Gas Mixtures from the Viscosities of the Individual Gases, Gas-U. Wasserfach., 79, 69.

The Roy-Thodos method is used to determine vapor thermal conductivities.

The function of temperature used is the one that is presented by the authors

for saturated hydrocarbons. This method is corrected for pressure effects using the equations of Stiel and Thodos.

Data for water are retrieved from the component data library. Wet conductivities are predicted for water/hydrocarbon systems as follows:

13

wet =

1 3

1 3

(10)

1 3

where:

y=

MW = molecular weight

subscripts aq and hc refer to the aqueous and hydrocarbon

portions of the stream.

I-154

Transport Properties

May 1994

Section 1.2

Thermodynamic Methods

References

TRAPP

Correlation

1.

Perry, R.H., and Green, D., 1984, Perrys Chemical Engineers Handbook,

6th edition, McGraw-Hill, New York.

2.

Roy, D., and Thodos, G., 1979, Thermal Conductivity of Gases, Ind.

Eng.Chem.Fundam., 9, 71-79.

3.

Stiel, L.I., and Thodos, G., 1964, The Thermal Conductivity of Nonpolar Substances in the Dense Gaseous and Liquid Regions., AIChE J., 10, 26.

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 earlier in this section.

A brief description of the method is presented here. For additional details,

see the Ely and Hanley reference paper.

The TRAPP method uses a one-fluid conformal model coupled with the

extended corresponding-states approach developed by Leland and his co-workers. Mathematically, the viscosity of a fluid mixture or component is given by:

x (, T ) = o (o, T o)F

(11)

(, T) = o (o, To)F (i, T)

(12)

where:

=

viscosity

thermal conductivity

F=

a dimensional factor

superscript refers to the potential or translational contribution

superscript refers to the contribution due to internal degrees

of freedom

This method is applicable to the full range of densities and temperatures, from

the dilute gas to the dense liquid. The required constants for each component

are the critical constants (Tc, Pc and Vc) and the acentric factor. The method is

currently restricted to the list of components given in Table 1.2.12-3.

Note: The authors of the TRAPP method recommend it not be used when water

is present. It should also be used with care at reduced temperatures above 0.925.

Volume I: Component and Thermophysical Properties

Transport Properties

I-155

Thermodynamic Methods

Section 1.2

Table 1.2.12-3: 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-BUTENE

2BT1

3-METHYLPENTANE

3MP

3-METHYL-1-BUTENE

3BT1

2,2-DIMETHYLBUTANE

22MB

2-METHYL-2-BUTENE

2BT2

2,3-DIMETHYLBUTANE

23MB

1-HEXENE

HXE1

n-HEPTANE

HEPTANE

1-HEPTENE

HPT1

n-OCTANE

OCTANE

PROPADIENE

ALEN

n-NONANE

NONANE

1,2-BUTADIENE

12BD

n-DECANE

DECA

BENZENE

BNZN

n-UNDECANE

UNDC

TOLUENE

TOLU

n-DODECANE

DDEC

m-XYLENE

MXYL

n-TRIDECANE

TRDC

o-XYLENE

OXYL

n-TETRADECANE

TDCN

p-XYLENE

PXYL

n-PENTADECANE

PNDC

ETHYLBENZENE

EBZN

n-HEXADECANE

HXDC

CARBON DIOXIDE

CO2

n-HEPTADECANE

HPDC

CARBON MONOXIDE

CO

CYCLOPENTANE

CP

HYDROGEN

H2

METHYLCYCLOPENTANE

MCP

HYDROGEN SULFIDE

H2S

CYCLOHEXANE

CH

OXYGEN

O2

METHYLCYCLOHEXANE

MCH

NITROGEN

N2

ETHYLCYCLOPENTANE

ECP

SULFUR DIOXIDE

SO2

ETHYLCYCLOHEXANE

ECH

WATER

H2O

ETHYLENE

ETLN

References

I-156

Transport Properties

1.

Thermodynamics of Mixtures of Molecules of Different Sizes, Trans.

Farad. Soc., 64, 1447-1460.

2.

Ely, J. F., and Hanley, H. J. M., 1981, Prediction of Viscosity and Thermal

Conductivity in Hydrocarbon Mixtures-Computer Program TRAPP, Proceedings of 60th Annual Convention, Gas Processors Association.

May 1994

Section 1.2

Special Methods

for Liquid

Viscosity

Thermodynamic Methods

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 purposes and cannot be extrapolated.

Abbott et. al., (1970, 1971) give a correlation which agrees with the API

data quite well but breaks down when extrapolated.

The SimSci or Twu correlation is based on a perturbation expansion method.

Here, the properties of a real system (petroleum fractions, in this case) are expanded about the values of a reference system (chosen to be n-alkanes). The

kinematic viscosity of a petroleum fraction at 210 F is expressed in the following manner:

450

o 450

= ln 2 +

ln2 +

Tb

Tb

f2 = xSG 21.1141

x = 1.99873

(SG)

(14)

12

Tb

56.7394

12

(13)

1 + 2f2

1 2f2

(15)

Tb

SG = SG SG

(16)

450

o 450 1 + 2f1

= ln 1 +

ln 1 +

Tb

Tb 1 2f1

(17)

(18)

(SG)

12

Tb

You can then determine the relationship between viscosities at any two temperatures, given the kinematic viscosity at the 2 temperatures from equations

(13-18) above and using the generalized relationship developed by Wright

(and modified by Twu), given in equations (19-22) below.

lnln(Z) = A + Bln (T)

Z = + 0.7 + e

B=

(19)

2

(20)

(lnlnZ1 lnlnZ2)

(21)

(lnT1 lnT2)

(22)

where:

=

kinematic viscosity

Volume I: Component and Thermophysical Properties

Transport Properties

I-157

Thermodynamic Methods

Section 1.2

References

1.

Abbott, M.M., Kaufman, T.G., and Domash, L., 1971, A Correlation for

Predicting Liquid Viscosities of Petroleum Fractions, Can. J. Chem. Eng.,

49, 379.

2.

Twu, C.H., 1985, Internally Consistent Correlation for Predicting Liquid Viscosities of Petroleum Fractions, Ind. Eng. Chem. Proc. Des. Dev., 24, 1287.

3.

Hydrocarbons, J. of Materials, 4, 19.

API Method

The API method used in PRO/II is very similar to the SIMSCI correlation 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 linear function of API gravity. Hence,

this relationship is extended as follows:

r1

r1

ln() = ln( ) +

API API

ln(r1) ln(r2)

r2

r1

API API

(23)

where:

=

API =

API gravity

Since all the calculations are made at the same boiling point, equation (23)

can be simplified based on the definition of Watson characterization factor

and of API gravity as:

r2

= r1

(1 2)(K10)

(24)

r1

where:

K=

The viscosity of the reference fluid (either fluid 1 or fluid 2) can be expressed as:

ln( ) = C1 +

r

C2

3

6

+ C3ln(Tb) + C4Tb + C5T6 + C6Tb

T6

(25)

where:

C1, C2, C3, C4, C5, C6 = empirical constants.

I-158

Transport Properties

May 1994

Section 1.2

27

Thermodynamic Methods

PRO/II Note: For more information on specifying the SIMSCI (TWU) or API

liquid viscosity methods, see Section 27, Transport and Special Properties, of

the PRO/II Keyword Input Manual.

Reference

Twu, C. H., 1986, A Generalized Method for Predicting Viscosities of

Petroleum Fractions, AIChE J., 32, 2091-2094.

Liquid Diffusivity

PRO/IIs Dissolver unit requires the diffusivity of the solute in the solvent

liquid if the user does not supply mass transfer data. PRO/II can calculate

these diffusivities based on user-input data or can estimate them from the

Wilke-Chang correlation.

User-supplied Diffusivity Data

When the user supplies diffusivity data, the user must specify which component (or components) is to be considered the solute. Diffusivity data can then

be supplied for each solute in each solvent in the following form:

lnDij = c1 + c2 T + c3lnT

(26)

where:

Dij =

T=

temperature in Kelvins

c1, c2, c3 =

constants

rule is used:

lnDi,m = Xj ln Dij

(27)

where:

Di,m = diffusivity (in m2/sec) of solute i in solvent mixture

Xj

Volume I: Component and Thermophysical Properties

Transport Properties

I-159

Wilke-Chang Correlation

Wilke and Chang (1955) developed a method for estimating the diffusivity of

a solute at infinite dilution in a binary mixture. SimSci has adapted this

method slightly and put it in multicomponent form. The Wilke-Chang correlation is of limited accuracy, but it will generally provide a diffusivity that is

good to within 50%. The correlation should not be used in cases where the

solute is water or where the solute is electrolytic. The equation is as follows:

12

Di,m =

7.4x10

12

j Xj (jMj)

0.6

m Vi

(28)

where:

Di,m = diffusivity (in m2/sec) of solute i in solvent mixture

Xj

Mj =

molecular weight of solvent component j

temperature in Kelvins

Vi =

cm3/mole

The sum in equation (28) is taken over all solvents j. The factor accounts

for association of the solvent. It is taken as 2.6 for water, 1.9 for methanol,

1.5 for ethanol, 1.20 for propyl alcohols and n-butanol, and 1.0 for all other

solvents.

Reference

Wilke, C.R., and Chang, P., 1955, Correlation of Diffusion Coefficients

in Dilute Solutions, AIChE J., 1, 264-270.

I-160

Transport Properties

May 1994

Index

A

Acentric factor

I-5, I-11, I-16

Activity coefficient

I-39

Alcohol data package

I-117

application guidelines

I-54

binary interaction databank table

I-119

See also NRTL

recommended ranges

I-117

Alpha formulation

I-71

equation forms

I-72

function requirements

I-71

Amine data package

I-127

application guidelines

I-51

equilibrium reactions

I-127

heat of reaction correction

I-129

recommended ranges

I-129

required components

I-128

API Data Book

I-62, I-64 - I-65

API gravity

I-27

API liquid density

I-41, I-87

recommended ranges

I-65

Application guidelines

I-45

high pressure crude units

I-47

hydrofiners

I-48

low pressure crude units

I-46

lube oil units

I-48

reformers

I-48

solids

I-57

solvent de-asphalting units

I-48

Assay streams

I-19, I-136

Associating equation of state

I-80

equilibrium constant for HF association

I-82

extent of association

I-81

hexamerization equilibrium reaction

I-82

mixture properties

I-83

Redlich-Kwong cubic equations of state

I-81

ASTM distillation data

See Distillation data, ASTM D1160

See Distillation data, ASTM D2887

See Distillation data, ASTM D86

B

Benedict-Webb-Rubin-Starling

application guidelines

recommended ranges

Binary interaction parameters

I-84

I-50, I-52

I-85

I-73, I-86

Reference Manual

Blends

See Cutpoints, multiple sets

Braun K10

Bromley-Zemaitis term

I-47, I-63

I-137

C

Carbon Number

I-5

Chao-Seader

I-60

recommended ranges

I-60

Characterization

CAVETT

I-13

Lee-Kesler

I-16

SIMSCI

I-9

Chemical potential

I-38

Component data

library components

I-4

non-library components

I-3

petroleum components

I-9

Component properties

extrapolation conventions

I-7

fixed properties

I-6

properties from structure

I-8

temperature correlation equations

I-7

temperature-dependent properties

I-6

COSTALD liquid density

I-66

application guidelines

I-52 - I-53

characteristic volume

I-66

Critical compressibility factor

I-5

Critical pressure

I-5, I-16

Critical temperature

I-5, I-9 - I-10, I-16

Critical volume

I-5, I-10, I-16

Cubic equations of state

See Equation-of-state methods

Curl-Pitzer

I-62

application guidelines

I-46

Cutpoints

application guidelines

I-21

multiple sets

I-19, I-21

secondary set

I-19

D

DATAPREP

Debye-Hckel constant

Decanting free water

See Free water decanting

Density

definition

ideal

I-6

I-137

I-5

I-44

I-44

Index

Idx-1

Diffusivity

See Transport properties

Dimerization

Dimers

See Dimerization

Dipole moment

DIPPR library

Distillation data

API 1963 method

API 1987 method

ASTM D1160

ASTM D2887

ASTM D86

Edmister-Okamoto method

Dortmund modified UNIFAC, UFT2

I-56, I-116

I-5

I-4

I-25

I-24

I-22

I-23

I-24

I-25

I-104

E

Edmister-Okamoto

See Distillation data

Electrolyte mathematical model

Electrolyte thermodynamics

aqueous phase activities

density

enthalpy

equilibrium constants

molar volume

Nakamura method

Nothnagel method

organic phase activities

SRK method

vapor-phase fugacities

Electrolytes

application guidelines

mathematical model

thermodynamics

Enthalpy

basis

definition

heat of mixing

ideal

ideal-gas

liquid vapor

solid

Entropy

definition

ideal

Equation-of-state methods

alpha formulations

Benedict-Webb-Rubin-Starling

general cubic equation of state

Lee-Kesler-Plcker

mixing rules

Peng-Robinson

Peng-Robinson Huron-Vidal

Idx-2

Index

I-131

I-135

I-136

I-144

I-143

I-135

I-144

I-141

I-139

I-143

I-142

I-139

I-56 - I-57

I-131

I-135

I-5

I-43

I-41

I-111

I-41

I-16, I-143

I-144

I-143

I-41

I-43

I-44

I-69

I-71

I-84

I-69

I-85

I-73, I-78

I-74

I-79

Redlich-Kwong

I-69

Soave-Redlich-Kwong

I-74

Soave-Redlich-Kwong Huron-Vidal

I-79

Soave-Redlich-Kwong Kabadi-Danner

I-75

Soave-Redlich-Kwong modified

I-77

Soave-Redlich-Kwong PanagiotoupolosReid

I-76

Soave-Redlich-Kwong SimSci

I-77

UNIWAALS

I-83

van der Waals

I-69

Equilibrium

liquid-liquid

I-39 - I-40

solid-liquid

I-147

vapor-liquid

I-40

vapor-liquid electrolyte

I-39

Erbar-modified Chao-Seader

I-61

Erbar-modified Grayson-Streed

I-61

Estimating binary interaction parameters

I-107

azeotropic data

I-107

ideal data

I-107

infinite dilution data

I-107

mutual solubility data

I-107

F

FILL methods

See Filling in missing interaction data

See also Filling in missing solubility data

Filling in missing interaction data

I-107, I-109

databank search order

I-107

Filling in missing solubility data

I-148

Flash point

I-5

Flory-Huggins

I-96

See also Liquid activity methods

Free volume modification to UNIFAC,

UNFV

I-106 - I-107

Free water decanting

I-88

calculation methods

I-88

equation of state water solubility method I-89

kerosene water solubility method

I-89

SimSci water solubility method

I-89

Fugacity

I-38

coefficient

I-39

G

Gamma method

See Enthalpy, heat of mixing

Generalized correlation methods

API liquid density

Braun K10

Chao-Seader

COSTALD liquid density

Curl-Pitzer

Erbar modification to Chao-Seader

I-111

I-58

I-87

I-63

I-60

I-66

I-62

I-61

May 1994

I-61

Grayson-Streed

I-61

IDEAL

I-58

Improved Grayson-Streed

I-62

Johnson-Grayson

I-64

Lee-Kesler

I-64

Rackett liquid density

I-65

Glycol data package

I-120

binary interaction databank

I-121

GPA sour water data package

See GPSWATER data package

GPSWATER data package

I-125

equilibrium reactions

I-125

recommended ranges

I-126

required components

I-126

Gravity data

I-27

Grayson-Streed

application guidelines

I-47 - I-48, I-53, I-61

Gross heating value

I-5

Group interaction data

I-101

Dortmund modified UNIFAC, UFT2

I-104

free volume modified UNIFAC,

UNFV

I-105 - I-107

Lyngby modified UNIFAC, UFT1

I-104

H

Hayden-OConnell fugacity

application guidelines

dimerization equilibrium reactions

Heat capacity

See Specific heat capacity

Heat of combustion

Heat of formation

Heat of fusion

Heat of mixing

See Enthalpy, heat of mixing

See also Gamma method

See Redlich-Kister expansion

Heat of vaporization

See Latent heat of vaporization

Henrys law gas solubility

application guidelines

application ranges

Henrys constants

solute components

HEXAMER

See Associating equation of state

Hexamer equation of state

Hexamerization

See also Hexamer equation of state

Huron-Vidal SRK and PR

Hydrogen deficiency number

I-116

I-56

I-116

I-5

I-16

I-5

I-111

I-110

I-57

I-110

I-110

I-110

I-80

I-56, I-80

I-79

I-5

Reference Manual

I

IDEAL and LIBRARY

application guidelines

densities

enthalpies

entropies

K-values

Improved Grayson-Streed

application guidelines

Ionic solutions

Ionic systems

See Ionic solutions

I-58

I-53

I-59

I-59

I-59

I-59

I-62

I-47 - I-48

I-56, I-137

J

Johnson-Grayson

I-64

K

K-values

Kabadi-Danner SRK

application guidelines

mixing rule

I-39

I-75

I-50, I-52

I-75

L

Latent heat of vaporization

I-5, I-15

Lee-Kesler

application guidelines

I-47, I-64

Lightends data

I-29

matching

I-29, I-86

Liquid activity methods

I-90

Dortmund modified UNIFAC, UFT2

I-104

Flory-Huggins

I-96

free volume modified UNIFAC,

UNFV

I-106 - I-107

Lyngby modified UNIFAC, UFT1

I-104

Margules

I-93

modified UNIFAC, UFT3

I-105

NRTL

I-98

regular solution

I-95

UNIFAC

I-101

UNIQUAC

I-99

van Laar

I-94

Wilson

I-97

Liquid molar volume

I-5, I-145

Liquid-liquid equilibria

See Equilibrium, liquid-liquid

LLE

See Equilibrium, liquid-liquid

Local composition

I-97

Lower heating value

I-5

Lyngby modified UNIFAC, UFT1

I-104

Index

Idx-3

RK1

M

Margules

application guidelines

See also Liquid activity methods

Melting temperature

Molar volume of liquid

See Liquid molar volume

Molecular weight

Molecular weight data

API method

extended API (EXTAPI)

SimSci method

I-93

I-93

I-148

I-5

I-28

I-29

I-29

I-29

N

Normal boiling point

Normal melting point

NRTL I-98

application guidelines

I-5

I-5

I-54, I-56, I-98

P

Panagiotopoulos-Reid SRK and PR

mixing rule

Peng-Robinson

application guidelines

Petroleum components

acentric factor

CAVETT method

critical properties

Lee-Kesler method

SIMSCI method

Pitzer term

Pollutants

Poynting correction

PROCESS library

Pseudocomponents

I-76

I-76

I-74

I-47 - I-48, I-50

I-9, I-13, I-16

I-13

I-9, I-13, I-16

I-16

I-9

I-137

I-56

I-40, I-91

I-4

I-26

R

Rackett liquid density

one-fluid version

Rackett parameter

Radius of gyration

Raoults law

Redlich-Kister expansion

See Enthalpy, heat of mixing

Redlich-Kwong equation

Regular solution

application guidelines

Reid vapor pressure (RVP)

APICRIDE method

APINAPHTHA method

ASTM D323-73 method

ASTM D323-82 method

ASTM D4953-91 method

ASTM D5191-91 method

Idx-4

Index

I-65

I-66

I-5

I-5

I-59

I-112

I-71

I-95

I-95

I-31

I-31

I-31 - I-32

I-31

I-31

I-32

I-32

RK2

See Enthalpy, heat of mixing

S

SIMSCI library

I-4

SimSci modified SRK and PR

I-77

application guidelines

I-48, I-50, I-54, I-56

mixing rule

I-76

Soave-Redlich-Kwong

I-74

alpha formulation

I-72, I-74

Huron-Vidal modification

I-79

Kabadi-Danner modifications

I-75

Panagiotopoulos-Reid modification

I-76

SimSci modification

I-77

Soave-Redlich-Kwong SimSci

I-77

Solid molar volume

I-145

Solid-liquid equilibrium (SLE)

I-147 - I-148

FILL options

I-148

vant Hoff solubility

I-147

Solubility parameter

(Hildebrand)

I-5, I-12, I-16, I-95 - I-96

Sour water data package

I-122

application guidelines

I-50

Henrys Law constants

I-122

recommended ranges

I-124

Specific gravity

I-5, I-27

Specific heat capacity

I-5, I-16

Surface tension

See Transport properties

SWEQ

See Sour water data package

T

Thermal conductivity

See Transport properties

Thermodynamic Expert System (TES)

I-45

Transport properties

I-150

API method

I-158

diffusivity

I-159

PETRO methods

I-151

PURE methods

I-150

surface tension

I-5

thermal conductivity

I-5, I-153 - I-155

TRAPP methods

I-155

TWU method

I-157

viscosity

I-5, I-151, I-154, I-157

Wilke-Chang method

I-160

Triple-point pressure

I-5

Triple-point temperature

I-5, I-148

True boiling point (TBP) data

cubic spline

I-25

cutting into pseudocomponents

I-26

probability density function (PDF)

I-26

May 1994

quadratic fit

True vapor pressure (TVP)

application guidelines

Truncated virial fugacity

virial coefficients

I-26

I-31

I-32

I-114

I-114

U

UNIFAC

I-101

application guidelines

I-55

data estimation, FILL

I-107

Dortmund modified UNIFAC, UFT2

I-104

free volume modified UNIFAC,

UNFV

I-106 - I-107

Lyngby modified UNIFAC, UFT1

I-104

modified UNIFAC, UFT3

I-105

UNIQUAC

I-99

application guidelines

I-54, I-56

UNIWAALS

application guidelines

I-55 - I-56, I-83

User-supplied solid solubility

I-148

W

Water decant

See Free water decanting

Water handling methods

See Free water decanting

Watson K-factor

Wilke-Chang method

Wilson

application guidelines

I-27

I-160

I-56, I-97

V

van der Waals area and volume

van der Waals equation

van Laar

application guidelines

vant Hoff solid solubility

application guidelines

Vapor phase fugacity

equations of state

Hayden-OConnell

Nakamura

Nothnagel

truncated virial

Vapor pressure

Antoine equation

Vapor-liquid equilibria

See Equilibrium, vapor-liquid

Viscosity

See Transport properties

VLE

See Equilibrium, vapor-liquid

I-5

I-69

I-94

I-94

I-147

I-57

I-113

I-114, I-142

I-116

I-141

I-139

I-114

I-5

I-15

Reference Manual

Index

Idx-5

Idx-6

Index

May 1994

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