PRO/II Process Engineering

TM

Electrolyte User Guide

© 2018 AVEVA Group plc and its subsidiaries. All rights reserved.
No part of this documentation shall be reproduced, stored in a ret rieval system, or transmitted by any
means, electronic, mechanical, photocopying, rec ording, or otherwise, without the prior written
permission of AVEVA. No liability is assumed with respect to the use of the information contained herein.
Although precaution has been taken in the preparation of this documentation, A VEVA assumes no
responsibility for errors or omissions. The information in this documentation is subject to change without
notice and does not represent a commitment on the part of AVEVA. The soft ware described in this
documentation is furnished under a license agreement. This soft ware may be used or copied only in
accordance with the terms of such license agreement.
ArchestrA, Aquis, Avantis, DYNS IM, eDNA, EYESIM, InBatch, InduSoft, InStep, IntelaTrac, InTouch,
PIPEPHASE, PRiSM, PRO/II, PROV IS ION, ROMeo, SIM4ME, SimCentral, SimSci, Skelta,
SmartGlance, Spiral Software, Termis, WindowMaker, WindowViewer, and Wonderware are trademarks
of AVEVA and/or its subsidiaries. An extensive listing of AVEVA trademarks can be found at:
https://sw.aveva.com/legal. All other brands may be trademarks of their respective owners.
Publication date: 9/7/2018
Contact Information
AVEVA Group plc
High Cross
Madingley Road
Cambridge
CB3 OHB. UK
https://sw.aveva.com/
For information on how to cont act sales, customer training, and technical support, see
https://sw.aveva.com/contact.
 Contents

Contents 1

Chapter E1
Electrolyte Module
Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E1-1
How to Use the Electrolyte Module in PRO/II . . . . . . . . . . . . . E1-5
GUI Access to Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . E1-7
Keyword Access to Electrolytes . . . . . . . . . . . . . . . . . . . . . . . E1-12
Application Guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E1-19
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E1-23
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E1-24

Chapter E2
Electrolyte Models
Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E2-1
Pregenerated Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E2-1
User-Added Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E2-8
Electrolyte Model Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E2-9
Summary of Electrolyte Models . . . . . . . . . . . . . . . . . . . . . . . E2-12
Alphabetical Component Index of Electrolyte Models . . . . . . E2-40

Chapter E3
Creating a User-Added Electrolyte Model
Available Tools for Creating Electrolyte Models . . . . . . . . . . . E3-1
Compatibility with Previous Versions of PRO/II . . . . . . . . . . . E3-2

Chapter E4
Electrolyte Effects In Simulations
Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E4-1
General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E4-1
Basic Unit Operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E4-3
Considerations Regarding Transport Properties . . . . . . . . . . . E4-10
Output Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E4-11
Speed Considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E4-11
Index 1

PRO/II Electrolytes User Guide Contents-1

Contents -2
 Chapter E1
Electrolyte Module

ELECTROLYTES
Overview
This chapter describes the Electrolyte add-on module available for
use in PRO/II. It describes electrolyte-related data entry using PRO-
VISION, the Graphical User Interface (GUI). It also describes key-
word entries in the General, Component, and Thermodynamic

ELECTROLYTES
sections of input data.

Contents of the Electrolyte Module

The Electrolyte Module provides a set of programs, data libraries,
and other files, including the following:
 The Lite Public Electrolyte Library provides aqueous data for
over 2300 electrolyte components. This library is available
only with the Electrolyte Module. It also includes the GeoChem
bank provides aqueous data for over 140 additional mineral and
metallic components frequently of interest.
 Version 7.0 of the Electrolyte Calculation engine from OLI
System, Inc.
 Chemistry Wizard from OLI Systems, Inc., for creating user-
added electrolyte models, private databanks, and executing
standalone flash drum calculations and sensitivity analyses.
 40 different aqueous electrolyte models arranged in 8 groups.
Three versions of each model are provided.
 The first version was created using Chemistry Wizard 3.1
for use in version 7.0 of the OLI calculation engine.
 The second version was created using Chemistry Wizard
version 1.0 for use in version 6.6 of the OLI calculation
engine.
 The third version was created by the (now obsolete) Elec-
trolyte Utility Package (EUP) for use in version 5.6 of the
OLI calculation engine.
The OLILIB data bank is part of the standard PROII component
library, and not actually part of the Electrolyte module. It contains
all necessary data for almost 800 electrolyte species.

PRO/II Electrolytes User Guide E1-1

 Capabilities of the Electrolyte Module
The Electrolyte Module supports only aqueous electrolyte models.
BATCH

These systems typically contain water with up to about 30 percent

solutes.
The Electrolyte Module includes only the Lite Public Electrolyte
ELECTROLYTES
BATCH

Library that provides aqueous data for about 2300 components and
for about 140 GeoChem components.

Compatibility of PRO/II With Older Electrolyte Versions

PRO/II, the Electrolyte Module, and the OLI Calculation Engine
installed for the Electrolyte Module are compatible with all earlier
versions of electrolyte models previously supported by PRO/II.
Earlier versions of pre-generated aqueous models are based on
older data file formats. These are exemplified by the older versions
of the electrolyte models (described above) included in the Electro-
lyte Module. While PRO/II still is able to support them, continuing
evolution of the format may prevent continued support in the future.
For this reason, customers should consider upgrading to the newest
version of the data files at their earliest convenience.
Although older versions of aqueous electrolyte models are included
and function properly, the programs that created them no longer are
available. When creating new models, users should use the current
Chemistry Wizard version 3.1.

Alternatives to the Electrolyte Module

OLI Systems, Inc. recently introduced their Mixed Solvent Electro-
lytes package (MSE) that handles stronger concentrations of sol-
utes. They also offer an expanded component library, currently
containing data for over 5100 components.
PRO/II is fully capable of utilizing all the features of the MSE pack-
age and the expanded libraries from OLI. This still includes support
for all existing aqueous models. Separate licensing is required.
Contact your PRO/II representative for licensing information and
further technical details.

Included Pre-Built Electrolyte Thermodynamic Models

Eight groups of electrolyte models are available after installing the
Electrolyte Module. When none of the pre-built models are satisfac-

E1-2 - July 2016 Electrolyte Module

 tory for your needs, use the Chemistry Wizard to create custom
models.
PRO/II simulates aqueous systems in a wide range of industrial
applications. The models apply to fixed component lists with a pre-

ELECTROLYTES
defined set of thermodynamic methods for K-values, enthalpies,
and densities. Table E2-2 on page E2-3 lists all 40 electrolyte mod-
els available for the following eight electrolyte groups in this
release:

Amine Systems Caustic Systems

ELECTROLYTES
Acid Systems Benfield Systems

Mixed Salt Systems Scrubber Systems

Sour Water Systems LLE and Hydrate Systems

The Graphical User Interface uses these groups to organize the 40

pre-generated electrolyte models for convenient selection.

Guidelines For Using Electrolyte Thermodynamics

Electrolyte models include calculation methods for all essential
properties. Proper usage requires observing these restrictions:
 Always declare an electrolyte model as a system (e.g.,
METHOD SYSTEM=DIPA70).
 It is not possible to define individual methods for K-value,
enthalpy, or density when using electrolyte thermodynamic
models.
 Electrolyte models cannot be used to calculate the following:
Non-aqueous systems.
Free water decant (i.e., non-rigorous LLE)
Water dew points
Hydrocarbon dew points
Entropy and heat capacity

 Aqueous Electrolyte models cannot be used to calculate non-

aqueous system. All the pre-generated models in the Electro-
lytes Module are aqueous electrolyte systems.

PRO/II Electrolytes User Guide E1-3

  Be careful when using both non-electrolyte and electrolyte
thermodynamic methods in the same simulation.
BATCH

The PRO/II electrolytic models use a different enthalpy basis

from that used for other thermodynamic systems. When
both are used, PRO/II automatically takes care of this dif-
ELECTROLYTES
BATCH

ference, but it may appear to be confusing.

To avoid this, select the electrolyte enthalpy method for all
non-electrolyte thermodynamic systems in a mixed applica-
tion. All systems then use the electrolyte model basis.

Unit Operations that support the Electrolyte Module

When electrolyte components are present in a simulation, PRO/II
calls the OLI calculation engine to calculate all their thermody-
namic properties. This is essentially a flash calculation algorithm
the behaves somewhat differently than the internal PRO/II flash.
Because of the differences, and due to the data requirements of
some unit operations, full support for electrolytes is inappropriate
or partially restricted in some unit operations.
The following is a partial listing of unit operations that support the
Electrolyte add-on:

Flash drum Mixer Calculator

Column ELDIST Pipe Heating/Cooling
algorithm curves
Controller Pump Stream Calculator
Optimizer Splitter Valve
Heat exchangers Reactors
Simple HX,  Conversion,
Rigorous HX, Equilibrium,
LNG Batch

Refer to Chapter E4, Electrolyte Effects In Simulations, for a dis-

cussion of the limitations of using electrolytes in PRO/II. The sub-
section “Basic Unit Operations” on page E4-3 specifically
addresses concerns for individual unit operations, including
descriptions of electrolyte-specific features and PRO/II features not
available for units using electrolyte thermodynamic methods. Sum-
maries of keyword input files for the Flash Drum (as an example of
a standard PRO/II unit with a few changes in functionality) and for
the ELDIST Distillation unit (which is specially designed for PRO/II

E1-4 - July 2016 Electrolyte Module

 Electrolytes (2)). Examples of keyword input files for units using
Electrolyte thermodynamic methods also are provided.

How to Use the Electrolyte Module in PRO/II

ELECTROLYTES
Preliminaries
The following activities must be completed before attempting to
model electrolyte components in a simulation.
1. Install the Electrolyte Add-on Module and the optional Chem-
istry Wizard program. Installation details are provided when

ELECTROLYTES
the licenses are acquired. More general information about
installing optional modules is available in the Getting Started
Guide.
2. Install at least one electrolyte thermodynamic model in the
form of a data base (.dbs) file. There are three options for
accomplishing this:
Use a pre-generated model
The Electrolyte module installed with PRO/II includes 40 pre-
generated data base files. Three versions of each data base file
are provided. Refer to “Pregenerated Models” in Chapter E2,
Electrolyte Models.
Use an older existing user-defined model
Early versions of PRO/II allowed user-defined electrolyte mod-
els having a pre-defined name M41.dbs through M60.dbs. If
you still have some of these files from previous versions, PRO/
II still can use them.
Create and use a new user-defined model
Use the Chemistry Wizard program to create a new user-
defined electrolyte model. Complete information is available in
the OLI Chemistry Wizard User Guide, located in the \Manu-
als\OLI\ directory installed with PRO/II. Also refer to “User-
Added Models” on page E2-8 to learn about some advantages
gained by using this tool.

Overview of Using Electrolytes In A Simulation

Once at least one electrolyte data base file is available, it is quite
straightforward to use it in a simulation. The following actions usu-
ally are involved.

PRO/II Electrolytes User Guide E1-5

 1. Declare an Electrolyte thermodynamic method in an existing or
new simulation.
2. Generate the electrolyte components from the electrolyte
BATCH

model. This is automatic in keywords and Run Batch. A dialog

provides this in the GUI.
ELECTROLYTES

3. Add generated electrolyte components to at least one stream.

BATCH

4. Configure at least one stream containing electolytes as a feed to

at least one unit operation that supports electrolytes.
5. Assign electrolyte thermodynamic methods to appropriate unit
operations.
The following sections describe each of these steps.

E1-6 - July 2016 Electrolyte Module

GUI Access to Electrolytes
Set Data Bank Search Hierarchy
When using Electrolyte thermodynamic methods with library com-
ponents, the OLILIB component databank must be searched first and

ELECTROLYTES
the SIMSCI databank second. To set this hierarchy,
Click the Hierarchy button highlighted in the Component
Selection dialog shown in Figure E1-1.
Figure E1-1: Changing the Data Bank Hierarchy

ELECTROLYTES

As shown in Figure E1-2, Highlight the PROII_10.1:OLILIB

entry in the Available Databanks: field; then click Insert
Before to move the OLILIB data bank to the top of the Cur-
rent Search Order.

PRO/II Electrolytes User Guide E1-7

 Figure E1-2: Adding Available Data Banks
BATCH
ELECTROLYTES
BATCH

See the online help for more information on setting the databank
search order hierarchy.
Notice in Figure E1-2 that an additional user-added library, MyElec1,
containing data bank NEWELEC1, is highlighted in the Available list.
custom libraries such as this also may be added to the search order.
Refer to the TDM User Guide to learn about creating custom com-
ponent data libraries.

Select An Electrolyte Model

The next essential step is to add an electrolyte model as a PRO/II
thermodynamic METHOD set. If it is the only METHOD set in the
simulation, or if it is designated the default METHOD set, all unit
operations use it by default.
Click the Thermodynamics Data button on the tool bar to dis-
play the Thermodynamics Data dialog box (Figure E1-3).

E1-8 - July 2016 Electrolyte Module

 Figure E1-3: Thermodynamic Data Dialog Box

ELECTROLYTES
ELECTROLYTES
Select Electrolyte in the Category list.
Select a group from the Electrolyte System: drop down list
box
Choose an electrolyte model from the Electrolyte Model: drop
down list box
Click the Add button to add the model to the simulation.
Click OK to save the model as part of the simulation, and to
generate the electrolyte components.

Generate Electrolyte Components

Generating electrolyte components means extracting electrolyte
data from the thermodynamic METHOD set and configuring it in a
form that is usable by PRO/II. In Run Batch and Keyword opera-
tion, generation always is automatic.
In the GUI, a dialog provides the option to generate the elec-
trolyte components automatically when clicking the OK
button (Figure E1-3) after an electrolyte model is selected.
Figure E1-4 illustrates the dialog.

PRO/II Electrolytes User Guide E1-9

 Figure E1-4: Generating Components From Electrolyte
BATCH
ELECTROLYTES
BATCH

Thermodynamics
To defer generation, select “NO” in response to this query.
This allows on-demand generation at a later time.
To generate the electrolyte components on demand:
Select Generate Electrolyte Components from the Input
menu.
All electrolyte components for the flow sheet (including com-
pounds and solid precipitates) are generated. There are no other
options. Also, if this step is omitted, PRO/II always generates elec-
trolyte components automatically before the simulation run.
Once the components are generated, no changes are allowed in the
component slate. Deleting an electrolyte model from the active
thermodynamic sets invalidates all electrolyte components and dis-
plays an information dialog.

Adding Electrolyte Data Base Files To A Simulation

To add your own models, specifically suited to your application, use
Chemistry Wizard 3.1 from OLI Systems, Inc. This generates data
base (.dbs) files suitable for use by PRO/II. To use the data base file
in a simulation:
Click the Modify... button shown at lower-left in Figure E1-3 to
open the Thermodynamic Data -Modification data entry win-
dow.
As shown in Figure E1-5, the DBS File Name: field allows add-
ing a data base file created with the Chemistry Wizard. The

E1-10 - July 2016 Electrolyte Module

 associated Browse... button provides a convenient means of
navigating to the data base file.
Figure E1-5: Adding an Electrolyte file to a Thermodynamic
Method

ELECTROLYTES
ELECTROLYTES

Click OK to save the selection and close the window.

Electrolyte Print Options Via the GUI

Calculated quantities unique to electrolyte applications can be
printed in the output report of a simulation. From the GUI,
 Navigate to Output menu -> Report Format -> Miscella-
neous data

PRO/II Electrolytes User Guide E1-11

 Figure E1-6: Electrolyte PRINT ION Options
BATCH
ELECTROLYTES
BATCH

Place a check mark in the check box to activate or change the

ION report option. (The figure is a partial representation of
Miscellaneous Report Options dialog.)

Keyword Access to Electrolytes

This section discusses the electrolytes-specific keywords in the
order in which data sections appear in a keyword input file. All
these options are analogous to the options described above for the
Graphical User Interface.

Electrolyte Print Options Via Key Words

TITLE ...
PRINT ION= PARTIAL or NONE or ALL
In a keyword input file, use the ION keyword on the PRINT state-
ment in the General Data category of input data. No other entries
on the PRINT statement are unique to electrolytes.
The ION entry has three options: ION=NONE or PART or ALL. The
default is PART.

NONE No electrolyte-specific output is printed.

PART Adds Liquid Rates table(s) to the Stream Component

Rates section(s) of the output. This table gives the flow
rates for ionic and/or other true species in the aqueous
solution. For ELDIST columns only, this adds tables Tray
Compositions for True Solution Species, Tray Liquid pH
and Ionic Strength, and Tray Component Scaling Indices.

E1-12 - July 2016 Electrolyte Module

 ALL Gives all output given by PART option. Adds Electrolyte
Thermo Summary section of the output. This section
gives the equilibrium phases and phase compositions
obtained from electrolyte flash calculations. Aqueous

ELECTROLYTES
solution compositions are reported as molalities for the
true chemical species. Also given are values for activity
and fugacity coefficients as well as equilibrium con-
stants. Adds Thermo Notes section to output. This section
gives explanatory notes useful for the interpretation of
the quantities given in the Electrolyte Thermo Summary.

ELECTROLYTES
Electrolyte Component Data
COMPONENT DATA ...
LIBID i, compID {, libno, name / ...} &
BANK=LibName:BankName {,...}

i A unique, contiguous component order number.

This applies to electrolyte components exactly
the same as other library components. Refer to
the Component Data Keyword Manual, Chapter
2, for a complete description.
compid A unique text-string identifier associated with
each component. Refer to the Component Data
Keyword Manual, Chapter 2, for a complete
description.
libno Identical usage as with other library components.
Refer to the Component Data Keyword Manual,
Chapter 2, for a complete description.
name Descriptive name. When supplied, this serves as
an alias for the component ID in the output
report. See example D below.
LibName Name of a component library (discussed below).
BankName Name of a data bank in the library (see below).
Components in OLI’s databanks that are not included in the SIMSCI
banks are available in the OLILIB bank. For electrolyte applications,
the recommended bank search order is OLILIB first and SIMSCI sec-
ond. This search order is used as the default whenever an electrolyte
thermodynamic method is used.
 Use the BANK entry on the LIBID statement of Component Data
to declare the component library search order. When using only

PRO/II Electrolytes User Guide E1-13

 banks form the default library, only the bank names are required
on the BANK entry:
BATCH

Example A: Minimum declaration of PROII Data banks only

LIBID 1, H2O / 2, NACL, BANK=OLILIB,SIMSCI {,...}
ELECTROLYTES
BATCH

 The full form of Bank= LibraryName:bankName must be used

to access banks from other libraries.

Example B: Full declaration of PROII data banks only

LIBID 1, H2O / 2, NACL, &
BANK=PROII_10.1:OLILIB, PROII_10.1:SIMSCI {,...}

Adding user-added data banks to the search order requires using the full
form. This form includes the library name and data bank name. The follow-
ing example adds bank NEWELEC1 from library MYELEC as the first data
bank in the search order, and with the PROII OLILIB as the second bank.

Example C: Declaration of user-added library and data bank

LIBID 1, H2O / 2, NACL, &
BANK=MYELEC:NEWELEC1, PROII_10.1:OLILIB, ...

Component names for the electrolyte models are listed in the “Sum-
mary of Electrolyte Models” on page E2-12. The names in these
lists are printed as they should be entered in the Component Data
section on the LIBID statement. However, a Pure Component
Library name, as given in the SIMSCI Component and Thermody-
namic Data Reference Manual, Chapter 1.4, Pure Component
Library–Alpha Sort, and Chapter 1.5, Pure Component Library–
Formula Sort, can be used instead of a corresponding electrolyte
model component name. For example, you could enter CAHYDROX
on the LIBID statement in place of the name CAOH2 when using the
electrolyte model SCRU.

Note: In contrast to conventional PRO/II, the Electrolytes version

does not allow two or more different names for the same compo-
nent to be used at the same time in the Component Data input.
Components can be renamed for printing purposes using the PRO/II
alias approach.

Example D: Assigning an alias for output reporting

LIBID 1,NACL,, HALITE

E1-14 - July 2016 Electrolyte Module

 causes the alias, HALITE, to be printed in the output in place of
NACL, the OLI library name

Electrolyte Thermodynamic Data

THERMODYNAMIC DATA ...

ELECTROLYTES
METHOD SYSTEM = elecid, {SETID = setid}
or
METHOD SYSTEM=DBSFIL, {SETID = setid}
and DBSFIL FILE= drive:\path\filename.dbs

SYSTEM Required entry to identify the electrolyte model

ELECTROLYTES
to use for the thermodynamic METHOD.
elecid A unique pre-defined identifier of a pregenerated
electrolyte model. Also may be a predefined
name of a version 6.6 user-added electrolyte
model (i.e, a model with an assigned invariant
name). Cannot be a user-generated name, as used
for version 7.0 user-added models.
SETID An optional identifier assigned to the METHOD
set. Often convenient for referencing the set.
setid .Text assigned as the identifier of the METHOD
set. Required when the SETID keyword is pres-
ent.
SYSTEM=DBSFIL Required when using a DBSFIL statement.
This replaces the actual identifier of an electro-
lyte model that has a user-assigned name.
DBSFIL This statement is required when using the SYS-
TEM=DBSFIL entry on the METHOD statement.
FILE= Required entry that locates and identifies the file
that defines the electrolyte model to use.
drive: Optional drive letter of the disk drive containing
the electrolyte file.
\path\ Optional path indicating the directory containing
the electrolyte model. If omitted, PRO/II expects
the model file to reside in the same directory as
the input file or the simulation data base.
filename.dbs Required. This identifies the file containing the
electrolyte model.
Each electrolyte model in PRO/II is characterized by a fixed list of
components, a fixed set of chemical equilibria, and a fixed set of
thermodynamic methods for K-values, enthalpy, and density. The
components and equilibria considered in the 40 pre-generated elec-

PRO/II Electrolytes User Guide E1-15

 trolyte models in PRO/II are summarized in Chapter E2, Electrolyte
Models.
BATCH

This section provides a summary of the THERMODYNAMIC DATA

keyword input, and a set of application guidelines.
ELECTROLYTES

Note: See Thermodynamic Framework in PRO/II in the PRO/II

BATCH

Reference Manual, Vol. 1, Chapter 3 for a summary of changes to

the thermodynamic framework and the mathematical model used
by PRO/II Electrolytes for the calculation of thermodynamic
quantities and chemical equilibrium, respectively.
The name of each pre-generated electrolyte model is treated in the
input as a keyword by the SYSTEM entry on a thermodynamic
METHOD statement.a system of thermodynamic methods. Refer to
Table E2-2, “Electrolyte Model Keywords and Data Files,” on
page E2-3 for a listing of all key words for all pre-generated elec-
trolyte models.

Example:
METHOD SYSTEM=SW01
where SW01 represents the name of an electrolyte model.
When multiple thermodynamic methods are needed for an applica-
tion, each of the selected methods should be assigned a method SET
identifier.

Example:
METHOD SYSTEM=SW01, SET=SET1
where SET1 is the SET identifier that may be used to assign the ther-
modynamic METHOD set to individual unit operations and streams.

Using User-added Electrolyte Methods

To use a user-added model that does not have a pre-assigned

name, the METHOD statement in the Thermodynamic section of
keyword input must use the alternative syntax that requires a
DBSFIL statement. For example, the following accesses a user-
generated model named MyElec1.dbs in directory
d:\MyStuff\ElecFiles\:
THERMODYNAMIC DATA
METHOD SYSTEM=DBSFIL, SETID=MySet
DBSFIL FILE= D:\MyStuff\ElecFiles\MyElec1.dbs

E1-16 - July 2016 Electrolyte Module

 This syntax also works for any pre-generated model installed in the
\System\ directory of the PRO/II installation. For example, the
mixed salt model named GENX70 resides in file M139.dbs.
Assuming the installed directory is C:\SIMSCI\PROII82\SYSTEM\,
the following keyword input accesses the model:

ELECTROLYTES
THERMODYNAMIC DATA
METHOD SYSTEM=DBSFIL, SETID=GENX70
DBSFIL FILE= C:\Program Files\SIMSCI\PROII82\SYS-
TEM\M139.DBS
For more information, see “Assigning Names to User-Added Mod-

ELECTROLYTES
els” on page E2-8.

Vapor-Phase Fugacity Coefficients

Four options are available for calculating vapor-phase fugacities
with PRO/II Electrolytes. These options, with their keywords, are:
 Ideal-Gas (IDEAL): all fugacity coefficients are assumed to be
1.0.
 Nothnagel method (NOTH): generally valid up to 20 atmo-
spheres, but not available for some vapor-phase components.
 Nakamura method (NAKA): generally valid at higher pres-
sures up to 200 atmospheres, but not available for some vapor-
phase components.
 Soave-Redlich Kwong (SRK) method: valid over a wide range
of conditions and generally recommended when vapor-phase
non-ideality is important. Also valid for any vapor-phase chem-
ical species given in OLI’s component databanks.
These options are specified on the METHOD statement with the PHI
entry. If no vapor fugacity option is specified, the calculations
default to ideal-gas.

PRO/II Electrolytes User Guide E1-17

 Examples:
METHOD
BATCH

SYSTEM=GENX, PHI=SRKMETHOD
SYSTEM=SW01, PHI=NOTH

Note: Only SYSTEM, SET, PHI, TRANSPORT, VISCOSITY, CONDUC-

TIVITY, SURFACE, and DIFFUSIVITY statements (see PRO/II Key-
ELECTROLYTES
BATCH

word Manual, Sec. 20, Thermodynamic Data) are available for

use with electrolyte thermodynamic methods. However, the
PETRO transport property option cannot be used with electrolyte
models, nor can the SIMSCI or API liquid-viscosity options. The
KVALUE, ENTHALPY, and DENSITY methods for electrolytes are auto-
matically set to the method declared by the SYSTEM entry and can-
not be modified individually on the METHOD statement.
Use of ENTHALPY = ELEC for Mixed Thermodynamic Applications
The thermodynamic framework for PRO/II Electrolytes uses a dif-
ferent basis, or zero-point, for enthalpies from regular PRO/II.
When both electrolyte and non-electrolyte thermodynamic methods
are used in a flowsheet, PRO/II takes care of this basis change auto-
matically if a stream is changed from one method to another.
However, to avoid the potentially confusing appearance of disconti-
nuities in output values of enthalpy, it is recommended that the
ENTH=ELEC option be used for all non-electrolyte thermodynamic
methods in mixed electrolyte/non-electrolyte thermodynamic appli-
cations. ENTH= ELEC is PRO/II’s IDEAL enthalpy method translated
by a constant to give numbers consistent with the enthalpy basis for
PRO/II Electrolytes.

Example:
METHOD SYSTEM=SALT, DEFAULT
METHOD SYSTEM=IDEAL, ENTHALPY=ELEC, SET=SET2
METHOD SYSTEM=SRK, ENTHALPY=ELEC, SET=SET3
Note that ENTH=ELEC is used with both non-electrolyte thermody-
namic methods, IDEAL and SRK. For these two methods, the
calculated enthalpy values will be obtained using the IDEAL
enthalpy method followed by a conversion to put these values on
the electrolyte basis.
An example in which this method is useful is when steam is flashed
off from an electrolyte unit (a stage in a multi-effect evaporator, for
example) and then condensed to provide duty for a heat exchanger
(the adjacent stage in the evaporator, for example). OLI’s flash cal-
culation has difficulty with adiabatic (fixed-duty) calculations for

E1-18 - July 2016 Electrolyte Module

 pure water in the two-phase region, with the result that the steam
side of the heat exchanger might fail to solve with electrolyte ther-
modynamic methods. Instead, the user could specify the IDEAL
thermodynamic method with ENTH=ELEC for the steam side of the
exchanger to produce a converged solution with consistent enthal-

ELECTROLYTES
pies for all streams.

Note: Whenever multiple enthalpy methods are used in a flow-

sheet, the safest (and recommended) practice for resetting the
enthalpy basis is to take the stream that is changing methods
through the reset unit that converts to the new enthalpy method.

ELECTROLYTES
See the discussion in the PRO/II Keyword Manual, Section 20.5,
Multiple Thermodynamic Sets.

Application Guidelines
General Information
PRO/II Electrolytes is composed of an integrated set of programs
developed by SIMSCI and OLI Systems, Inc. that allows you to
model and simulate aqueous electrolyte solutions. This includes,
under the PRO/II flow sheeting environment, algorithms for the
simulation of single-stage and multistage steady-state processes
involving aqueous electrolytes. These programs calculate both het-
erogeneous, multi-phase equilibria as well as homogeneous liquid-
phase reaction equilibria. The allowed phases at equilibrium
include vapor, aqueous liquid, organic liquid, and solid phases.
With respect to liquid-solid equilibria, saturation of multiple solid
phases can be calculated rigorously.
PRO/II Electrolytes simulates aqueous systems by solving mathe-
matical models that accurately represent these systems. These mod-
els are sets of nonlinear algebraic equations containing appropriate
thermodynamic parameters. Two thermodynamic methods are
available for electrolyte modeling, the OLI method and the NRTL
(Chen) method. The Electrolyte NRTL method can be used for
modeling very concentrated electrolyte solutions with very low
water content (as low as 0.3 wt%) as well as solutions with mixed
solvents ranging in composition from completely aqueous to almost
completely non-aqueous (again, with water content as low as
0.3 wt%).
PRO/II Electrolytes is built upon a rigorous thermodynamic frame-
work for aqueous electrolyte systems. This framework is an amal-

PRO/II Electrolytes User Guide E1-19

 gam based upon work by Bromley (3), Meissner (4,5), Pitzer (6,7),
Zemaitis (8,9), Nothnagel (10), Nakamura (11), and Tanger (12).
BATCH

The PRO/II Electrolytes module incorporates electrolyte models

created using standalone software from OLI Systems, Inc. The
PRO/II Electrolytes module has 40 built-in electrolyte models that
ELECTROLYTES
BATCH

can be applied to a wide range of problems of industrial interest,

including, but not limited to the following:
 Gas scrubbers/purification using carbonate, amine, or caustic
solutions
 Sour water strippers
 Amine towers
 Benfield processes
 Acid waste stream-neutralization drums
 Scale formation prediction for wells and pipes (oilfields, geo-
thermal fields)
 Underground injection well studies
 Solid salts manufacturing (potash, caustic, carbonates, etc.)
 Chlor-alkali plant processes.
The integration of electrolytes into PRO/II is, from the user’s point
of view, seamless. In many cases, a keyword input file for an elec-
trolytes problem could be identical (apart from entering the name of
the electrolyte model in the Thermodynamic Data section) to a non-
electrolyte PRO/II input file. The four most important things that
PRO/II Electrolyte users must remember are:
 PRO/II Electrolytes is designed for use in aqueous electrolyte
systems within the application guidelines given in Electrolyte
Thermodynamic Data. PRO/II Electrolytes cannot currently be
used for mixed-solvent or non-aqueous electrolyte systems,
with the exception of the user-generated models created in the
Electrolyte NRTL framework.
 The model chosen in the THERMODYNAMIC DATA keyword input
(Chapter E2, Electrolyte Models) must contain all of the com-
ponents appearing in any stream that is to be treated with that
thermodynamic method.
 PRO/II Electrolytes activates one new unit operation: the distil-
lation column algorithm ELDIST. See “Electrolyte Distillation
Column Algorithm (ELDIST)” on page E4-5.

E1-20 - July 2016 Electrolyte Module

  A few units are not available, and some other units have
reduced functionality when used with an electrolyte thermody-
namic method. These differences are discussed fully in Chapter
E4, Electrolyte Effects In Simulations.

ELECTROLYTES
 The Chemistry Wizard from OLI Systems, Inc. is installed with
PRO/II Electrolytes. It allows users to generate their own new
electrolyte models. See the discussion in Chapter E3, Creating
a User-Added Electrolyte Model.
If these few differences are kept in mind, users familiar with stan-
dard PRO/II keyword input can quickly make effective use of the

ELECTROLYTES
capabilities of the PRO/II Electrolytes module.

Thermodynamic Data Considerations

A first step in selecting an electrolyte model as a thermodynamic
method is to determine whether the application of interest falls
within the application guidelines for PRO/II Electrolytes. For
example, the expected pressures, temperatures, phases, and phase
compositions for the application should fall within the stated valid-
ity ranges for PRO/II Electrolytes. Next, the user needs to identify
one of the PRO/II Electrolyte models that contains all of the compo-
nents of interest in its component list (see Table E2-3, “Electrolyte
Model Components,” on page E2-9). However, for applications
using electrolyte models together with non-electrolyte thermody-
namic methods, the components to be treated by the non-electrolyte
methods do not need to be in the model’s component list if they will
not enter any unit using the electrolyte model.

Pressure, Temperature, and Composition Validity Ranges

The suggested application range for electrolyte thermodynamic
methods is summarized below.

General Ranges of Applicability

Temperature 32-572°F (0-300°C)
Pressure 0-1500 atm
Dissolved gases 0-30 mole%
Ionic solutes 0-30 ionic strength

Amine systems
Pressure 0-30 atm

PRO/II Electrolytes User Guide E1-21

 LLE systems
Organic solutes 10 weight%
BATCH

where the ionic strength (I) is defined as:

1 2

ELECTROLYTES

I = --- Z ions m ions

BATCH

(0-7)
2
ions
and Z denotes the ionic charge and m represents the molality of
the aqueous ion. Molality is defined as the moles of solute per
gram moles of Total Aqueous solvent.

Invalid Calculations for Electrolyte Models

 Non-aqueous electrolyte systems. See the Chemistry Wizard
User Guide for newer capabilities.
 Free water decant.
 Dew water calculations.
 Dew hydrocarbon calculations.
 Entropy and heat capacity calculations.

Special Case STREAM DATA Input

Due to the nature of the aqueous electrolyte flash algorithm, elec-
trolyte feed streams with little or no water require special handling
during input; you must specify the phase of the stream in the Stream
Data section. Note that water-free liquid feed streams are not per-
mitted. The algorithm also occasionally has difficulty converging
for vapors or liquids at conditions very near the vapor-liquid phase
boundary. Here again, if the user knows the phase of the stream, it
can be entered on the PROPERTY statement; this will assure conver-
gence but should be used with caution because the feed flash will
not be able to correct an incorrect phase designation.
1)Feeds with little or no H2O
Vapor feed Enter PHASE=V on PROPERTY statement
Solid feed Use SOLID card together with PROPERTY
statement
Liquid feed Not allowed. H2O must be the predominant
component in the liquid phase.

E1-22 - July 2016 Electrolyte Module

 2)Feeds near saturation
At pressures and temperatures close to vapor+ liquid saturation
conditions, it is recommended to enter the appropriate PHASE
(V or L) on the PROPERTY statement.

ELECTROLYTES
True Aqueous Solution Species and Reconstituted Components
The true chemical species in the aqueous solution are those aqueous
species that are included in the model’s ionic equilibria and VLE
expressions. Mass and charge balance constraints for the aqueous
phase, together with the model’s aqueous ionic equilibria expres-
sions, are used by PRO/II Electrolytes to calculate apparent concen-

ELECTROLYTES
trations of the model’s neutral components in the aqueous phase
automatically from the corresponding concentrations of the true
solution species (ionic and neutral). This calculation is referred to
as the reconstitution of model components. Concentrations and
rates are reported in the output for reconstituted components and, if
ION=PART or ALL is specified on the PRINT statement, they are also
reported for true solution species.

Example:
Calculate the results of an isothermal flash of the feed given below
at 1 bar and 25°C, where the numbers before denote moles.
Model components:
H2O, NaOH, HCl, NaCl
Feed components:
55.51 H2O + 1 NaOH + 1 HCl
Product in terms of True Chemical Species:

56.51 H2O + 1 NA+1 + 1 Cl-1 + 1.0E-7 OH-1 + 1.0E-7 H+1

Product in terms of Reconstituted Components:

56.51 H2O + 1 NaCl

Examples
Example E1-1: Solid Component Declaration
Set up a pure HCl vapor feed and a pure NaOH solid feed at 25°C
and 1 atm, together with a liquid H2O feed at vapor-liquid satura-
tion conditions of 100°C and 1 atm.

PRO/II Electrolytes User Guide E1-23

 ...
COMPONENT DATA
BATCH

LIBID
1, H2O/2, NAOH/3, HCL
THERMODYNAMIC DATA
ELECTROLYTES

METHOD
BATCH

SYSTEM=GENE
STREAM DATA
PROPERTY STRM=HCLV, TEMP=25, PRES=1, &
COMP=3, 0.5, PHASE=V
PROPERTY STRM=SOLD, TEMP=25, PRES=1
SOLID STRM=SOLD, COMP=2,0.5
PROPERTY STRM=WATR, TEMP=100, PRES=1, &
COMP=1, 100, PHASE=L

References
1. OLI Systems, Inc., 1995, Prochem User’s Manuals, Version 12,
Morris Plains, NJ.
2. V.B. Shah, and R.W. Bondy, 1991, “A New Approach to Solv-
ing Electrolyte Distillation Problems”, a paper presented at the
AIChE Annual Meeting in Los Angeles.
3. L. A. Bromley, 1973, “Thermodynamic Properties of Strong
Electrolytes in Aqueous Solutions”, AIChE J, 19:313-320.
4. H. P. Meissner, and C. L. Kusik, 1973, “Aqueous Solutions of
Two or More Strong Electrolytes - Vapor Pressures and Solu-
bilities”, IEC Proc. Des. Dev., 12:205-208.
5. H. P. Meissner, and N. A. Peppas,1973, “Activity Coefficients -
Aqueous Solutions of Polybasic Acids and their Salts”, AIChE
J., 19:806-809.
6. K. S. Pitzer, 1979, “Theory: Ion Interaction Approach”, Activity
Coefficients in Electrolyte Solutions, 1:157-208, R. M. Pytkow-
icz, ed., CRC Press, Boca Raton, FL.
7. K. S. Pitzer, 1980, “Thermodynamics of Aqueous Electrolytes
at Various Temperatures, Pressures and Compositions”, Ther-
modynamics of Aqueous Systems with Industrial Applications,
451-466, S. A. Newman, ed., ACS Symposium Series 133.
8. J. F. Zemaitis, Jr., 1980, “Predicting Vapor-Liquid-Solid Equi-
libria in Multicomponent Aqueous Solutions of Electrolytes”,
Thermodynamics of Aqueous Systems with Industrial Applica-

E1-24 - July 2016 Electrolyte Module

 tions, 227-246, S. A. Newman, ed., ACS Symposium
Series 133.
9. J. F. Zemaitis, Jr., D. M. Clark, M. Rafal, and N. C. Scrivner,
1986, Handbook of Aqueous Electrolyte Thermodynamics,

ELECTROLYTES
AIChE Press.
10. K. H. Nothnagel, D. S. Abrams, and J. M. Prausnitz, 1973,
“Generalized Correlation of Fugacity Coefficients in Mixtures
at Moderate Pressures”, IEC Process Des. Dev., 12:25-35.
11. R. Nakamura, G. J. F. Breedveld, and J. M. Prausnitz, 1976,
“Thermodynamic Properties of Gas Mixtures Containing

ELECTROLYTES
Polar and Nonpolar Components”, IEC Process Des. Dev.,
15:557-564.
12. J.C. Tanger, IV, and H.C. Helgeson, 1988, “Calculation of the
Thermodynamic and Transport Properties of Aqueous Species
at High Pressures and Temperatures: Revised Equations of
State for the Standard State Partial Molal Properties of Ions and
Electrolytes”, Am. J. Sci, 288:19-98.

PRO/II Electrolytes User Guide E1-25

BATCH
ELECTROLYTES
BATCH

E1-26 - July 2016 Electrolyte Module

 Chapter E2
Electrolyte Models
Overview

ELECTROLYTES
This chapter summarizes the forty pregenerated Electrolyte models
included with the PRO/II Electrolyte Module. To facilitate applica-
tion of these built-in models, the following tables are provided
 “Pre-generated Electrolyte Model Naming Conventions”
on page E2-2 explains the data base file naming scheme.
 “Electrolyte Model Keywords and Data Files” on page E2-
3 relates the electrolyte model name (used in the GUI) to
comparable keywords for each pregenerated model.
 “Electrolyte Model Components” on page E2-9 exhaus-
tively lists all the components available in each model.
 “Summary of Electrolyte Models” on page E2-12 lists all
components, all ionic species, and all electrolyte equations
in each model.
 “Alphabetical Component Index of Electrolyte Models” on
page E2-40 shows every pregenerated model in which each
component appears.

Pregenerated Models
Over the years, PRO/II has undergone many changes and has used
several versions of the OLI Electrolyte Calculation Engine. Differ-
ent versions of the OLI engine use different formats for the data
base files. For this reason, the Electrolyte Module provides three
versions of each of the 40 pregenerated electrolyte models. Naming
conventions were chosen to help identify the original version used

PRO/II Electrolytes User Guide E2-1

 to create each data base file. The naming conventions are listed in
Table E2-1.
BATCH

Table E2-1: Pre-generated Electrolyte Model

Naming Conventions

File Names in numeric order PRO/II OLI Engine Creation

ELECTROLYTES

Keyword Suffix Version Version Program

M01.dbs to M40.dbs 7.0 - 8.1 6.3-6.6 Chemistry

no keyword suffix Wizard 1.0
example: 
data file M06.dbs
keywords: DIPA alias M06

M41.dbs to M60.dbs 7.0 - 8.1 6.3-6.6 Chemistry

(user-defined models) Wizard 1.0
keywords M41 to M60
no keyword suffix and no alias
example: data file: M44.dbs 
keyword: M44 (no alias)

M61.dbs to M100.dbs prior to 7.0 5.6 Electrolyte

example: data file M66 (Obsolete in (Obsolete in Utility Package
keywords DIPA56 alias M66
PRO/II 8.0) PRO/II 8.0) (EUP)

M101.dbs to M140.dbs 8.2 7.0 Chemistry

example: data file M06.dbs Wizard 2.0
no keyword suffix
keywords: DIPA70 alias M106

With the naming conventions disclosed, Table E2-2 lists all the key-
words for all three versions of each of the 40 pregenerated models.
The table also lists the keywords for the older user-added models
that required pre-assigned file names.

E2-2 - July 2016 Electrolyte Models

 Table E2-2: Electrolyte Model Keywords and Data Files

Electrolyte Electrolyte
System Model Keywords Data File

ELECTROLYTES
Amines DEA56 DEA56, M62 M62.DBS
DEA66 DEA, M02 M02.DBS
DEA70 DEA70, M102 M102.DBS
DGA56 DGA56, M64 M64.DBS
DGA66 DGA, M04 M04.DBS
DGA70 DGA70, M104 M104.DBS

DIPA56 DIPA56, M66 M66.DBS

DIPA66 DIPA, M06 M06.DBS
DIPA70 DIPA70, M106 M106.DBS
MEA56 MEA56, M61 M61.DBS
MEA66 MEA, M01 M01.DBS
MEA70 MEA70, M101 M101.DBS

MDEA56 MDEA56, M65 M65.DBS

MDEA66 MDEA, M05 M05.DBS
MDEA70 MDEA70, M105 M105.DBS
TEA56 TEA56, M63 M63.DBS
TEA66 TEA, M03 M03.DBS
TEA70 TEA70, M103 M103.DBS

Acids ACIF56 ACIF56, M82 M82.DBS

ACID66 ACID, M22 M22.DBS
ACID70 ACID70, M122 M122.DBS
CL256 CL256, M71 M71.DBS
CL266 CL2, M11 M11.DBS
CL270 CL270, M111 M111.DBS

CLSF56 CLSF56, M81 M81.DBS

CLSF66 CLSF, M21 M21.DBS
CLSF70 CLSF70, M121 M121.DBS
HCL56 HCL56, M67 M67.DBS
HCL66 HCL, M07 M07.DBS
HCL70 HCL70, M107 M107.DBS

PRO/II Electrolytes User Guide E2-3

 Table E2-2: Electrolyte Model Keywords and Data Files
BATCH

Electrolyte Electrolyte
System Model Keywords Data File

PHOS56 PHOS56, M69 M69.DBS

PHOS66 PHOS, M09 M09.DBS
ELECTROLYTES

PHOS70 PHOS70, M109 M109.DBS

SULF56 SULF56, M68 M68.DBS
SULF66 SULF, M08 M08.DBS
SULF70 SULF70, M108 M108.DBS

Mixed Salts CANA56 CANA56, M72 M72.DBS

CANA66 CANA, M12 M12.DBS
CANA70 CANA70, M112 M112.DBS
CANX56 CANX56, M90 M90.DBS
CANX66 CANX, M30 M30.DBS
CANX70 CANX70, M130 M130.DBS

GENE56 GENE56, M86 M86.DBS

GENE66 GENE, M26 M26.DBS
GENE70 GENE70, M126 M126.DBS
GENX56 GENX56, M99 M99.DBS
GENX66 GENX, M39 M39.DBS
GENX70 GENX70, M139 M139.DBS

GEOT56 GEOT56, M79 M79.DBS

GEOT66 GEOT, M19 M19.DBS
GEOT70 GEOT70, M119 M119.DBS

HOTC56 HOTC56, M85 M85.DBS

HOTC66 HOTC, M25 M25.DBS
HOTC70 HOTC70, M125 M125.DBS
HOTX56 HOTX56, M98 M98.DBS
HOTX66 HOTX, M38 M38.DBS
HOTX70 HOTX70, M138 M138.DBS

OILF56 OIL56, M80 M80.DBS

OILF66 OILF, M20 M20.DBS
OILF70 OILF70, M120 M120.DBS
SALT56 SALT56, M70 M70.DBS
SALT66 SALT, M10 M10.DBS
SALT70 SALT70, M110 M110.DBS

E2-4 - July 2016 Electrolyte Models

 Table E2-2: Electrolyte Model Keywords and Data Files

Electrolyte Electrolyte
System Model Keywords Data File

Sour Water SW0156 SW0156, M74 M74.DBS

ELECTROLYTES
SW0166 SW01, M14 M14.DBS
SW0170 SW0170, M114 M114.DBS
SW1X56 SW1X56, M92 M92.DBS
SW1X66 SW1X, M32 M32.DBS
SW1X70 SW1X70, M132 M132.DBS

SW0256 SW0256, M75 M75.DBS

SWO266 SW02, M15 M15.DBS
SW0270 SW0270, M115 M115.DBS
SW2X56 SW2X56, M93 M93.DBS
SW2X66 SW2X, M33 M33.DBS
SW2X70 SW2X70, M133 M133.DBS

SW0356 SW0356, M76 M76.DBS

SW0366 SW03, M16 M16.DBS
SW0370 SW0370, M116 M116.DBS
SW3X56 SW3X56, M94 M94.DBS
SW3X66 SW3X, M34 M34.DBS
SW3X70 SW3X70, M134 M134.DBS

SW0456 SW0456, M77 M77.DBS

SW0466 SW04, M17 M17,DBS
SW0470 SW0470, M117 M117.DBS
SW4X56 SW4X56, M95 M95.DBS
SW4X66 SW4X, M35 M35.DBS
SW4X70 SW4X70, M135 M135.DBS

SW0556 SW0556, M78 M78.DBS

SW0566 SW05, M18 M18.DBS
SW0570 SW0570, M118 M118.DBS

Caustic CAUS56 CAUS56, M83 M83.DBS

Systems CAUS66 CAUS, M23 M23.DBS
CAUS70 CAUS70, M123 M123.DBS
CAUX56 CAUX56, M96 M96.DBS
CAUX66 CAUX, M36 M36.DBS
CAUX70 CAUX70, M136 M136.DBS

PRO/II Electrolytes User Guide E2-5

 Table E2-2: Electrolyte Model Keywords and Data Files
BATCH

Electrolyte Electrolyte
System Model Keywords Data File

CAU256 CAU256, M87 M87.DBS

CAU266 CAU2, M27 M27.DBS
ELECTROLYTES

CAU270 CAU270, M127 M127.DBS

CA2X56 CA2X56, M100 M100.DBS
CA2X66 CA2X, M40 M40.DBS
CA2X70 CA2X70, M140 M140.DBS

Benfield  BENF56 BENF56, M84 M84.DBS

Systems BENF66 BENF, M24 M24.DBS
BENF70 BENF70, M124 M124.DBS
BENX56 BENX56, M97 M97.DBS
BENX66 BENX, M37 M37.DBS
BENX70 BENX70, M137 M137.DBS

Scrubber  SCRU56 SCRU56, M73 M73.DBS

Systems SCRU66 SCRU, M13 M13.DBS
SCRU70 SCRU70, M113 M113.DBS
SCRX56 SCRX56, M91 M91.DBS
SCRX66 SCRX, M31 M31.DBS
SCRX70 SCRX70, M131 M131.DBS

LLE & TWL156 TWL156, M88 M88.DBS

Hydrate  TWL166 TWL1, M28 M28.DBS
Systems TWL170 TWL170, M128 M128.DBS
TWL256 TWL256, M89 M89.DBS
TWL266 TWL2, M29 M29.DBS
TWL270 TWL270, M129 M129.DBS

User-Added M41 M41 M41.DBS

OLI 6.6 M42 M42 M42.DBS
from  M43 M43 M43.DBS
Chemistry  M44 M44 M44.DBS
Wizard 1.0 M45 M45 M45.DBS
M46 M46 M46.DBS
M47 M47 M47.DBS
M48 M48 M48.DBS
M49 M49 M49.DBS

E2-6 - July 2016 Electrolyte Models

 Table E2-2: Electrolyte Model Keywords and Data Files

Electrolyte Electrolyte
System Model Keywords Data File

M50 M50 M50.DBS

ELECTROLYTES
M51 M51 M51.DBS
M52 M52 M52.DBS
M53 M53 M53.DBS
M54 M54 M54.DBS
M55 M55 M55.DBS
M56 M56 M56.DBS
M57 M57 M57.DBS
M58 M58 M58.DBS
M59 M59 M59.DBS
M60 M60 M60.DBS

User-Added Names are assigned as users create the .DBS files.

from OLI 7.0 Usage is :
from METHOD SYSTEM=DBSFILE
Chemistry  DBSFILE FILE= {Drive:\path\}filename.dbs
Wizard 2.0

Choosing An Appropriate Electrolyte Model

The electrolyte model chosen must contain all components appear-
ing in any stream or unit using that method. To reduce CPU time
and eliminate extraneous components from the printout, it is gener-
ally best to use the smallest model encompassing the flowsheet’s
components. Similarly, a model without solids will run faster than a
model with the same components that does allow solid precipita-
tion. Non-solids-forming models should be used only for flow
sheets where the user is certain precipitation will not occur. Models
with solids suppressed are designated by names ending in X; for
example, CAUX is the CAUS model without solid precipitation.
While all the pregenerated models perform properly, it is recom-
mended that users migrate to the newer “7.0” versions of the data
files (data base files M101 through M140) at their earliest conve-
nience.

PRO/II Electrolytes User Guide E2-7

 User-Added Models
If none of the 40 pregenerated models is suitable for an application,
BATCH

user-added, electrolyte models should be investigated. OLI Sys-

tems, Inc. provides the OLI Chemistry Wizard version 3.1 that
allows generation of user-added models that can be used in the
PRO/II Electrolytes program.
ELECTROLYTES

 Complete documentation of the new tool set is provided in the

OLI Chemistry Wizard User Guide.
 The basic electrolyte components in each model are listed in
Table E2-3 on page E2-9. A complete list of all species in each
model is available in the separate document PRO/II-OLI
6.6_Components.xls, a Microsoft Excel spreadsheet.
Both documents are included on the PRO/II installation disk. Dur-
ing installation, they may be copied to the \Manual\OLI subdirec-
tory of the PRO/II installation directory.

Assigning Names to User-Added Models

Note that the Chemistry Wizard does not use any assigned or
reserved names for the data base files it creates. This is in contrast
to earlier methods that required data base files to use one of the
reserved names (M41 through M60).
The naming rules are as follows:
 Names must conform to the DOS 8.3 model.
 The first character of the name should be a letter (A-Z)
 Names are NOT case sensitive; e.g., “A” and “a” alias each
other.
 Names may include embedded blanks, but their use is dis-
couraged.
Additionally, alternative keyword syntax allows electrolyte model
files to reside in any directory accessible by PRO/II. In the past,
files normally were required to reside in the same directory as the
.INP or .PRZ file, or in the PRO/II \System\ directory. The newer
DBSFIL statement allows entering the path along with the file
name. As with the file name, the path may contain embedded
spaces, and is not case sensitive.

E2-8 - July 2016 Electrolyte Models

 To use a user-added model that does not have a pre-assigned name,
the METHOD statement in the Thermodynamic section of keyword
input must use the alternative syntax that requires a DBSFIL state-
ment. For example, the following accesses a user-generated model
named MyElec1.dbs in directory d:\MyStuff\ElecFiles\:
THERMODYNAMIC DATA

ELECTROLYTES
METHOD SYSTEM=DBSFIL, SETID=MySet
DBSFIL FILE= D:\MyStuff\ElecFiles\MyElec1.dbs
This syntax also works for any pregenerated model installed in the
\System\ directory. For example, the mixed salt model named
GENX70 resides in file M139.dbs. Assuming the installed directory
is C:\Program Files\SIMSCI\PROII82\SYSTEM\, the following
keyword input accesses the model:
THERMODYNAMIC DATA
METHOD SYSTEM=DBSFIL, SETID=GENX70
DBSFIL FILE= C:\Program Files\SIM-
SCI\PROII82\SYSTEM\M139.DBS

Electrolyte Model Index

Model names (MEA, DEA, etc.) are grouped by systems of general
chemical or application interest.

Table E2-3: Electrolyte Model Components

Model Components Page
Amine Systems E2-12
MEA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / E2-12
C3H8 / MEAH
DEA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / E2-13
C3H8 / DEAH
TEA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / E2-13
C3H8 / TEAH
DGA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / E2-13
C3H8 / DGAH
MDEA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / E2-13
C3H8 / MDEAH

PRO/II Electrolytes User Guide E2-9

 Table E2-3: Electrolyte Model Components
Model Components Page
BATCH

DIPA H2O / CO2 / C2H6 / CH4 / H2S / N2 / C4H10 / E2-13

C3H8 / DIPAx (x = 1, 2, 3, 4, 5, 6, 7, CO2 or H2)
Acid Systems E2-13
ACID H2O / CO / CO2 / H2 / HCN / HCOOH / N2 / E2-13
ELECTROLYTES

NH3 / H3PO4
HCL H2O / HCl E2-14
CL2 H2O / HCl / Cl2 / HClO / N2 E2-14
CLSF H2O / HCl / Cl2 / HClO / N2 / O2 / SO2 / H2SO3 / E2-15
H2SO4
SULF H2O / SO2 / H2SO3 / H2SO4 E2-15
PHOS H2O / H3PO4 E2-16
Mixed Salt Systems E2-17
SALT H2O / NaCl / KCl E2-17
CANA, H2O / HCl / MgSO4 / Na2SO4 / NaCl / H2SO4 / E2-17
CANX CaSO4 / NaOH / CaCl2 / MgCl2 / Ca(OH)2 /
Mg(OH)2
HOTC, H2O / CO2 / CO / C2H6 / CH4 / H2S / H2 / N2 / E2-18
HOTX C3H8 / NaHCO3 / Na2CO3 / NaOH
GENE, H2O / CO2 / Cl2 / HClO / HCl / N2 / O2 / SO2 / E2-19
GENX NaOH / NaCl / NaHCO3 / Na2CO3
GEOT H2O / CO2 / NH3 / H2S / HCl / BaCl2 / CaCl2 / E2-20
CuCl2 / FeIICl2 / FeIIICl3 / KCl /LiCl / MgCl2 /
MnCl2 / NaCl / Na2S / Na2SO3 / Na2SO4 / PbCl2
/ SrCl2 / ZnCl2 / Na4EDTA / Ca2EDTA / B(OH)3
/ BaCO3 / BaSO4 / CaCO3 / CaSO4 / Fe3O4 /
MgCO3 / (NH4)2SO4 / SrCO3 / SrSO4
OILF H2O / CO2 / HCl / Na2SO4 / NaHCO3 / Na2CO3 / E2-23
MgCl2 / BaCl2 / CaCl2 / NaCl / NaOH / KCl / 
BaSO4 / CaCO3 / CaSO4 / BaCO3 / Ca(OH)2 /
K2CO3 / K2SO4 / KHCO3 / MgCO3 / Mg(OH)2 /
BaOH2 / KOH / MgSO4 / H2SO4
Sour Water Systems E2-25

E2-10 - July 2016 Electrolyte Models

 Table E2-3: Electrolyte Model Components
Model Components Page
SW01, H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH E2-25
SW1X / NaHCO3 / Na2CO3 / C2H6 / C3H8 / N2 / HCl /
HCN / H3PO4 / NaCl / NaHS / HCOOH

ELECTROLYTES
SW02, H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH E2-27
SW2X / NaHCO3 / Na2CO3 / HCl / NaCl / NaHS / HCN
/ ACETACID
SW03, H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH E2-28
SW3X / NaHCO3 / Na2CO3 / C2H6 / C3H8 / N2 / HCl /
HCN / C4H10 / NaCl / NaHS / H2 / O2 / CO
SW04, H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH E2-29
SW4X / NaHCO3 / Na2CO3 / C2H6 / C3H8 / N2 / C4H10
SW05 H2O / CO2 / H2S / NH3 E2-30
Caustic Systems E2-31
CAUS, H2O / Cl2 / HClO / HCl / SO2 / NaCl / Na2SO3 / E2-31
CAUX Na2SO4 / NaOH / H2SO4
CAU2, H2O / NaOH / KOH E2-32
CA2X
Benfield Systems E2-33
BENF, H2O / CO2 / CO / C2H6 / C2H4 / CH4 / H2S / H2 / E2-33
BENX N2 / NH3 / C3H8 / K2CO3 / KHCO3 / KHS /
H3PO4 / B(OH)3 / KOH
Scrubber Systems E2-34
SCRU, H2O / CO2 / HCl / HCN / HCOOH / N2 / O2 / E2-34
SCRX SO2 / NaOH / CaCO3 / CaCl2 / NaCl / Na2CO3 /
NaHCO3 / NaCOOH / Ca(OH)2
LLE and Hydrate Systems E2-36
TWL1 H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / E2-36
Toluene / NaOH / NaOH.H2O / Na2CO3 /
Na2CO3·10H2O / Na2CO3·H2O/ Na2CO3·7H2O /
NaHCO3 / NaCl / NaHS / HCl / CaCl2 /
CaCl2·H2O / CaCl2·2H2O / CaCl2·4H2O /
CaCl2·6H2O / Ca(HCO3)2 / CaCO3 / Ca(OH)2 /
NH4Cl / NH4HCO3 / NH4HS

PRO/II Electrolytes User Guide E2-11

 Table E2-3: Electrolyte Model Components
Model Components Page
BATCH

TWL2 H2O / NaCl / NaHSO4 / Na2SO4 / E2-38

Na2SO4·10H2O / NaOH / NaOH·H2O /
Ca(HSO4)2 / CaSO4 / CaSO4·2H2O / Ca(OH)2 /
HCl / N2 / CH4 / Methanol / Ethanol / M-Xylene
ELECTROLYTES

/ Benzene / Toluene / CaCl2 / CaCl2·H2O /

CaCl2·2H2O / CaCl2·4H2O / CaCl2·6H2O / HF /
H2SO4 / CaF2 / NaF

Summary of Electrolyte Models

All ionic equilibria given in the model summaries below take place
in aqueous solution. The ".ppt" suffix on a chemical species name
denotes a solid precipitate, and the "aq" suffix stands for a dis-
solved gas or an electrically neutral ion pair. The general form of a
vapor-liquid equilibrium expression is Cvap = Caq, where C
denotes a model component.

Amine Systems
MEA Model

Components:
H2O / CO2 / C2H6 / CH4 / H2S / N2 / C3H8 / C4H10 / MEAH

Ions:
OH-1 / HCO3-1 / H+1 / HS-1 / MEA-1 / MEAH2+1 / CO3-2 / S-
2

Ionic Equilibria:
CO2aq + H2O = H+1 + HCO3-1

H2O = H+1 + OH-1

H2Saq = H+1 + HS-1

HCO3-1 = H+1 + CO3-2

HS-1 = H+1 + S-2

MEACO2-1 + H2O = MEAHaq + HCO3-1

E2-12 - July 2016 Electrolyte Models

 MEAHaq + H2O = MEAH2+1 + OH-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for all components.

DEA, TEA, DGA, MDEA, and DIPA Models

ELECTROLYTES
Component lists for the other amine models differ from the MEA
model only with respect to their amine components; that is, DEAH,
TEAH, DGAH, MDEAH, or DIPAx replaces MEAH. In addition,
these other amine models do not consider vapor-liquid equilibrium
for their amine component. Finally, there is no MDEACO2-1 ion in
the MDEA model.

Acid Systems
ACID Model

Components:
H2O / CO / CO2 / H2 / HCN / HCOOH / N2 / NH3 / H3PO4

Ions:
OH-1 / CO3-2 / COOH-1 / H2P2O7-2 / H2PO4-1 / H3P2O7-1 /
HCO3-1 /

H+1 / HP2O7-3 / HPO4-2 / NH2CO2-1 / NH4+1 / CN-1 / P2O7-4 /

PO4-3

Ionic Equilibria:
CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

H2P2O7-2 = H+1 + HP2O7-3

H2PO4-1 = H+1 + HPO4-2

H3P2O7-1 = H+1 + H2P2O7-2

HCNaq = H+1 + CN-1

HCO3-1 = H+1 + CO3-2

HCOOHaq = H+1 + COOH-1

PRO/II Electrolytes User Guide E2-13

 HP2O7-3 = H+1 + P2O7-4

HPO4-2 = H+1 + PO4-3

BATCH

NH2CO2-1 + H2O = NH3aq + HCO3-1

NH3aq + H2O = NH4+1 + OH-1

ELECTROLYTES

P2O7-4 + H2O = 2PO4-3 + 2H+1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for H3PO4.

HCL Model

Components:
H2O / HCl

Ions:
OH-1 / H+1 / Cl-1

Ionic Equilibria:
H2O = H+1 + OH-1

HClaq = H+1 + Cl-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for all components.

CL2 Model

Components:
H2O / Cl2 / HClO / HCl / N2

Ions:
OH-1 / ClO-1 / H+1 / Cl-1

Ionic Equilibria:
Cl2aq + H2O = H+1 + Cl-1 + HClOaq

H2O = H+1 + OH-1

HClaq = H+1 + Cl-1

E2-14 - July 2016 Electrolyte Models

 HClOaq = H+1 + ClO-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for all components.

CLSF Model

ELECTROLYTES
Components:
H2O / Cl2 / HClO / HCl / N2 / O2 / SO2 / H2SO3 / H2SO4

Ions:
OH-1 / ClO-1 / H+1 / HSO3-1 / HSO4-1 / Cl-1 / S2O5-2 / SO3-
2
/ SO4-2

Ionic Equilibria:
Cl2aq + H2O = H+1 + Cl-1 + HClOaq

H2O = H+1 + OH-1

HClaq = H+1 + Cl-1

HClOaq = H+1 + ClO-1

HSO3-1 = H+1 + SO3-2

HSO4-1 = H+1 + SO4-2

S2O5-2 + H2O = 2SO3-2 + 2H+1

SO2aq + H2O = HSO3-1 + H+1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for H2SO3 / H2SO4.

SULF Model

Components:
H2O / SO2 / H2SO3 / H2SO4

Ions:
OH-1 / HSO3-1 / HSO4-1 / H+1 / S2O5-2 /

SO3-2 / SO4-2

PRO/II Electrolytes User Guide E2-15

 Ionic Equilibria:
H2O = H+1 + OH-1
BATCH

HSO3-1 = H+1 + SO3-2

HSO4-1 = H+1 + SO4-2

S2O5-2 + H2O = 2SO3-2 + 2H+1

ELECTROLYTES

SO2aq + H2O = HSO3-1 + H+1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O / SO2.

PHOS Model

Components:
H2O / H3PO4 / PO4

Ions:
OH-1 / H2PO4-1 / H3P2O7-1 / H+1 / HP2O7-3 / HPO4-2 / H2P2O7-
2
/

P2O7-4 / PO4-3

Ionic Equilibria:
H2O = H+1 + OH-1

H2P2O7-2 = H+1 + HP2O7-3

H2PO4-1 = H+1 + HPO4-2

H3P2O7-1 = H+1 + H2P2O7-2

HP2O7-3 = H+1 + P2O7-4

HPO4-2 = H+1 + PO4-3

P2O7-4 + H2O = 2PO4-3 + 2H+1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O only.

E2-16 - July 2016 Electrolyte Models

 Mixed Salt Systems
SALT Model

Components:
H2O / NaCl / KCl

ELECTROLYTES
Ions:
OH-1 / H+1 / K+1 / Na+1 / Cl-1

Precipitates and hydrates:

NaCl / KCl

Ionic Equilibria:
H2O = H+1 + OH-1

KClppt = K+1 + Cl-1

NaClppt = Na+1 + Cl-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O only.

CANA Model

Components:
H2O / HCl / MgSO4 / Na2SO4 / NaCl / H2SO4 / CaSO4 /
NaOH /

CaCl2 / MgCl2 / Ca(OH)2 / Mg(OH)2

Ions:
OH-1 / CaOH+1 / Cl-1 / H+1 / HSO4-1 / MgCl+1 / Mg+2 /
Na+1 /

NaSO4-1 / Ca+2 / SO4-2

Precipitates and hydrates:

MgSO4 / Na2SO4 / NaCl / CaSO4 / NaOH / CaCl2 / MgCl2 /

Ca(OH)2 / Mg(OH)2

Ionic Equilibria:
CaCl2ppt = Ca+2 + 2Cl-1

PRO/II Electrolytes User Guide E2-17

 Ca(OH)2ppt = Ca+2 + 2OH-1

CaOH+1 = Ca+2 +OH-1

BATCH

CaSO4aq = Ca+2 + SO4-2

CaSO4ppt = Ca+2 + SO4-2

ELECTROLYTES

H2O = H+1 + OH-1

HClaq = H+1 + Cl-1

HSO4-1 = H+1 + SO4-2

MgCl2ppt = Mg+2 + 2Cl-1

MgCl+1 = Mg+2 + Cl-1

Mg(OH)2ppt = Mg+2 + 2OH-1

MgSO4ppt = Mg+2 + SO4-2

Na2SO4ppt = 2Na+1 + SO4-2

NaClppt = Na+1 + Cl-1

NaOHppt = Na+1 + OH-1

NaSO4-1 = Na+1 + SO4-2

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O / HCl.

CANX Model
Identical to CANA model except that solid precipitation equilibria
are not considered.

HOTC Model

Components:
H2O / CO2 / CO / C2H6 / CH4 / H2S / H2 / N2 / C3H8 /
NaHCO3 /

Na2CO3 / NaOH

E2-18 - July 2016 Electrolyte Models

 Ions:
OH-1 / HCO3-1 / H+1 / HS-1 / Na+1 / CO3-2 / S-2

Precipitates and Hydrates:

NaHCO3 / Na2CO3 / NaOH

ELECTROLYTES
Ionic Equilibria:
CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

H2Saq = H+1 + HS-1

HCO3-1 = H+1 + CO3-2

HS-1 = H+1 + S-2

Na2CO3ppt = 2Na+1 + CO3-2

NaHCO3ppt = Na+1 + HCO3-1

NaOHppt = Na+1 + OH-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for NaHCO3 / Na2CO3 /
NaOH.

HOTX Model
Identical to HOTC model except that solid precipitation equilibria
are not considered.

GENE Model

Components:
H2O / CO2 / Cl2 / HClO / HCl / N2 / O2 / SO2 / NaOH /
NaCl /

NaHCO3 / Na2CO3

Ions:
OH-1 / ClO-1 / CO3-2 / HCO3-1 / H+1 / HSO3-1 / Na+1 / Cl-1
/

S2O5-2 / SO3-2

PRO/II Electrolytes User Guide E2-19

 Precipitates and Hydrates:
NaOH / NaCl / NaHCO3 / Na2CO3
BATCH

Ionic Equilibria:
Cl2aq + H2O = H+1 + Cl-1 + HClOaq

CO2aq + H2O = HCO3-1 + H+1

ELECTROLYTES

H2O = H+1 + OH-1

HClaq = H+1 + Cl-1

HClOaq = H+1 + ClO-1

HCO3-1 = H+1 + CO3-2

HSO3-1 = H+1 + SO3-2

Na2CO3ppt = 2Na+1 + CO3-2

NaClppt = Na+1 + Cl-1

NaHCO3ppt = Na+1 + HCO3-1

NaOHppt = Na+1 + OH-1

S2O5-2 + H2O = 2SO3-2 + 2H+1

SO2aq + H2O = HSO3-1 + H+1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for NaOH / NaCl /
NaHCO3 / Na2CO3.

GENX Model
Identical to GENE model except that solid precipitation equilibria
are not considered.

GEOT Model

Components:
H2O / CO2 / NH3 / H2S / HCl / BaCl2 / CaCl2 / CuCl2 /
FeIICl2 /

E2-20 - July 2016 Electrolyte Models

 FeIIICl3 / KCl / LiCl / MgCl2 / MnCl2 / NaCl / Na2S /
Na2SO3 /

Na2SO4 / PbCl2 / SrCl2 / ZnCl2 / Na4EDTA / Ca2EDTA /

B(OH)3 /

BaCO3 / BaSO4 / CaCO3 / CaSO4 / Fe3O4 / MgCO3 /

ELECTROLYTES
(NH4)2SO4 /

SrCO3 / SrSO4

Ions:
OH-1 / NH4+1 / Ba+2 / BaOH+1 / Ca+2 / CaHCO3+1 / CaOH+1
/

Cu+2/FeII+2 / FeIIHCO3+1 / FeIIOH+1 / FeIII+3 / K+1 /

LI+1 / Mg+2 /

MgCl+1 / MgHCO3+1 / Mn+2 / MnHCO3+1 / MnOH+1 / Na+1 /

Pb+2 /

Sr+2 / Zn+2 / ZnHCO3+1 / H+1 / HCO3-1 / CO3-2 / NH2CO2-1 /

HS-1 /

S-2 / Cl-1 / NaSO4-1 / HSO3-1 / SO3-2 / HSO4-1 / SO4-2 /

EDTA-4 /

B(OH)3OH-1

Precipitates and Hydrates:

BaCO3 / BaSO4 / CaCO3 / Fe3O4 / MgCO3 / (NH4)2SO4 /

SrCO3 / SrSO4

Ionic Equilibria:
H2O = H+1 + OH-1

CO2aq + H2O = H+1 + HCO3-1

NH3aq + H2O = NH4+1 + OH-1

H2Saq = H+1 + HS-1

CaSO4aq = Ca+2 + SO4-2

PRO/II Electrolytes User Guide E2-21

 Na4EDTAaq = 4Na+1 + EDTA-4

Ca2EDTAaq = 2Ca+2 + EDTA-4

BATCH

B(OH)3aq + H2O = B(OH)3OH-1 + H+1

HCO3-1 = H+1 + CO3-2

ELECTROLYTES

NH2CO2-1 + H2O = NH3aq + HCO3-1

HS-1 = H+1 + S-2

BaOH+1 = Ba+2 + OH-1

CaHCO3+1 = Ca+2 + HCO3-1

CaOH+1 = Ca+2 + OH-1

FeIIHCO3+1 = FeII+2 + HCO3-1

FeIIOH+1 = FeII+2 + OH-1

HSO3-1 = H+1 + SO3-2

HSO4-1 = H+1 + SO4-2

MgCl+1 = Mg+2 + Cl-1

MgHCO3+1 = Mg+2 + HCO3-1

MnHCO3+1 = Mn+2 + HCO3-1

MnOH+1 = Mn+2 + OH-1

NaSO4-1 = Na+1 + SO4-2

ZnHCO3+1 = Zn+2 + HCO3-1

BaCO3ppt = Ba+2 + CO3-2

BaSO4ppt = Ba+2 + SO4-2

CaCO3ppt = Ca+2 + CO3-2

Fe3O4ppt + 8H+1 = FeII+2 + 2FeIII+3 + 4H2O

E2-22 - July 2016 Electrolyte Models

 MgCO3ppt = Mg+2 + CO3-2

(NH4)2SO4ppt = 2NH4+1 + SO4-2

SrCO3ppt = Sr+2 + CO3-2

ELECTROLYTES
SrSO4ppt = Sr+2 + SO4-2

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O / CO2 / NH3 / H2S.

OILF Model

Components:
H2O / CO2 / HCl / Na2SO4 / NaHCO3 / Na2CO3 / MgCl2 /
BaCl2 /

CaCl2 / NaCl / NaOH / KCl / BaSO4 / CaCO3 / CaSO4 /

BaCO3 /

Ca(OH)2 / K2CO3 / K2SO4 / KHCO3 / MgCO3 / Mg(OH)2 /

BaOH2 /

KOH / MgSO4 / H2SO4

Ions:
OH-1 / BaOH+1 / CaHCO3+1 / Ca+2 / CaOH+1 / Cl-1 / CO3-2 /

HCO3-1 / H+1 / HSO4-1 / K+1 / MgCl+1 / MgHCO3+1 / Mg+2 /

Na+1 / NaSO4-1 / Ba+2 / SO4-2

Precipitates and Hydrates:

Na2SO4 / NaHCO3 / Na2CO3 / MgCl2 / BaCl2 / CaCl2 /
NaOH /

KCl / BaSO4 / CaCO3 / CaSO4 / BaCO3 / Ca(OH)2 / K2CO3

/

K2SO4 / KHCO3 / MgCO3 / Mg(OH)2 / BaOH2 / KOH / MgSO4

Ionic Equilibria:
BaCl2ppt = Ba+2 + 2Cl-1

BaCO3ppt = Ba+2 + CO3-2

PRO/II Electrolytes User Guide E2-23

 BaOH2ppt = Ba+2 + 2OH-1

BaOH+1 = Ba+2 + OH-1

BATCH

BaSO4ppt = Ba+2 + SO4-2

CaCl2ppt = Ca+2 + 2Cl-1

ELECTROLYTES

CaCO3ppt = Ca+2 + CO3-2

CaHCO3+1 = Ca+2 + HCO3-1

Ca(OH)2ppt = Ca+2 + 2OH-1

CaOH+1 = Ca+2 + OH-1

CaSO4aq = Ca+2 + SO4-2

CaSO4ppt = Ca+2 + SO4-2

CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

HClaq = H+1 + Cl-1

HCO3-1 = H+1 + CO3-2

HSO4-1 = H+1 + SO4-2

K2CO3ppt = 2K+1 + CO3-2

K2SO4ppt = 2K+1 + SO4-2

KClppt = K+1 + Cl-1

KHCO3ppt = K+1 + HCO3-1

KOHppt = K+1 + OH-1

MgCl2ppt = Mg+2 + 2Cl-1

MgCl+1 = Mg+2 + Cl-1

MgCO3ppt = Mg+2 + CO3-2

E2-24 - July 2016 Electrolyte Models

 MgHCO3+1 = Mg+2 + HCO3-1

Mg(OH)2ppt = Mg+2 + 2OH-1

MgSO4ppt = Mg+2 + SO4-2

ELECTROLYTES
Na2CO3ppt = 2Na+1 + CO3-2

Na2SO4ppt = 2Na+1 + SO4-2

NaHCO3ppt = Na+1 + HCO3-1

NaOHppt = Na+1 + OH-1

NaSO4-1 = Na+1 + SO4-2

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O / CO2 / HCl.

Sour Water Systems

SW01 Model

Components:
H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH / NaHCO3
/ Na2CO3 /

C2H6 / C3H8 / N2 / HCl / HCN / H3PO4 / NaCl / NaHS /

HCOOH

Ions:
OH-1 / Cl-1 / CN-1 / CO3-2 / COOH-1 / H2P2O7-2 / H2PO4-1 /
H3P2O7-1 /

HCO3-1 / H+1 / HP2O7-3 / HPO4-2 / HS-1 / Na+1 / NH2CO2-1 /

NH4+1 /

C6H5O-1 / P2O7-4 / PO4-3 / S-2

Precipitates and Hydrates:

NaHCO3 / Na2CO3 / NaOH / NaCl

PRO/II Electrolytes User Guide E2-25

 Ionic Equilibria:
C6H5OHaq = H+1 + C6H5O-1
BATCH

CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

H2P2O7-2 = H+1 + HP2O7-3

ELECTROLYTES

H2PO4-1 = H+1 + HPO4-2

H2Saq = H+1 + HS-1

H3P2O7-1 = H+1 + H2P2O7-2

HClaq = H+1 + Cl-1

HCNaq = H+1 + CN-1

HCO3-1 = H+1 + CO3-2

HCOOHaq = H+1 + COOH-1

HP2O7-3 = H+1 + P2O7-4

HPO4-2 = H+1 + PO4-3

HS-1 = H+1 + S-2

Na2CO3ppt = 2Na+1 + CO3-2

NaClppt = Na+1 + Cl-1

NaHCO3ppt = Na+1 + HCO3-1

NaOHppt = Na+1 + OH-1

NH2CO2-1 + H2O = NH3aq + HCO3-1

NH3aq + H2O = NH4+1 + OH-1

P2O7-4 + H2O = 2PO4-3 + 2H+1

E2-26 - July 2016 Electrolyte Models

 Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for H3PO4 / NaHCO3 /
Na2CO3 / NaOH / NaCl / NaHS.

SW1X Model
Identical to SW01 model except that solid precipitation equilibria

ELECTROLYTES
are not considered.

SW02 Model

Components:
H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH / NaHCO3 /

Na2CO3 / HCl / NaCl / NaHS / HCN / ACETACID

Ions:
OH-1 / C6H5O-1 / Cl-1 / CN-1 / CO3-2 / HCO3-1 / H+1 / HS-1 /

Na2CO3 / NH2CO2-1 / NH4+1 / Acetate-1 / S-2

Precipitates and Hydrates:

NaHCO3 / NaOH / Na2CO3 / NaCl

Ionic Equilibria:
C6H5OHaq = H+1 + C6H5O-1

CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

H2Saq = H+1 + HS-1

ACETACIDaq = H+1 + Acetate-1

HClaq = H+1 + Cl-1

HCNaq = H+1 + CN-1

HCO3-1 = H+1 + CO3-2

HS-1 = H+1 + S-2

Na2CO3ppt = 2Na+1 + CO3-2

PRO/II Electrolytes User Guide E2-27

 NaClppt = Na+1 + Cl-1

NaHCO3ppt = Na+1 + HCO3-1

BATCH

NaOHppt = Na+1 + OH-1

NH2CO2-1 + H2O = NH3aq + HCO3-1

ELECTROLYTES

NH3aq + H2O = NH4+1 + OH-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for Acetic Acid /
NaHCO3 / NaOH / Na2CO3 / NaHS / NaCl.

SW2X Model
Identical to SW02 model except that solid precipitation equilibria
are not considered.

SW03 Model

Components:
H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH / NaHCO3 /

Na2CO3 /C2H6 /C3H8 / N2 / HCl / HCN / C4H10 / NaCl /

NaHS /

H2 / O2 / CO

Ions:
OH-1 / Cl-1 / CN-1 / CO3-2 / HCO3-1 / H+1 / HS-1 / Na+1 /
NH4+1 /

NH2CO2-1 / C6H5O-1 / S-2

Precipitates and Hydrates:

Na2CO3 / NaOH / NaHCO3 / NaCl

Ionic Equilibria:
C6H5OHaq = H+1 + C6H5O-1

CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

E2-28 - July 2016 Electrolyte Models

 H2Saq = H+1 + HS-1

HClaq = H+1 + Cl-1

HCNaq = H+1 + CN-1

HCO3-1 = H+1 + CO3-2

ELECTROLYTES
HS-1 = H+1 + S-2

Na2CO3ppt = 2Na+1 + CO3-2

NaClppt = Na+1 + Cl-1

NaHCO3ppt = Na+1 + HCO3-1

NaOHppt = Na+1 + OH-1

NH2CO2-1 + H2O = NH3aq + HCO3-1

NH3aq + H2O = NH4+1 + OH-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for Na2CO3 / NaOH /
NaHCO3 / NaHS / NaCl.

SW3X Model
Identical to SW03 model except that solid precipitation equilibria
are not considered.

SW04 Model

Components:
H2O / CO2 / H2S / NH3 / CH4 / C6H5OH / NaOH / NaHCO3 /

Na2CO3 / C2H6 / C3H8 / N2 / C4H10

Ions:
OH-1 / CO3-2 / HCO3-1 / H+1 / HS-1 / Na+1 / NH2CO2-1 /
NH4+1 /

C6H5O-1 / S-2

Precipitates and Hydrates:

NaOH / NaHCO3 / Na2CO3

PRO/II Electrolytes User Guide E2-29

 Ionic Equilibria:

 C6H5OHaq = H+1 + C6H5O-1

BATCH

 CO2aq + H2O = HCO3-1 + H+1

 H2O = H+1 + OH-1

ELECTROLYTES

 H2Saq = H+1 + HS-1

 HCO3-1 = H+1 + CO3-2

 HS-1 = H+1 + S-2

 Na2CO3ppt = 2Na+1 + CO3-2

 NaHCO3ppt = Na+1 + HCO3-1

 NaOHppt = Na+1 + OH-1

 NH2CO2-1 + H2O = NH3aq + HCO3-1

 NH3aq + H2O = NH4+1 + OH-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for NaOH / NaHCO3 /
Na2CO3.

SW4X Model
Identical to SW04 model except that solid precipitation equilibria
are not considered.

SW05 Model

Components:
H2O / CO2 / H2S / NH3

Ions:
OH-1 / HCO3-1 / H+1 / HS-1 / NH2CO2-1 / NH4+1 / CO3-2 / S-2

Ionic Equilibria:
CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

E2-30 - July 2016 Electrolyte Models

 H2Saq = H+1 + HS-1

HCO3-1 = H+1 + CO3-2

HS-1 = H+1 + S-2

NH2CO2-1 + H2O = NH3aq + HCO3-1

ELECTROLYTES
NH3aq + H2O = NH4+1 + OH-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for all components.

Caustic Systems
CAUS Model

Components:
H2O / Cl2 / HClO / HCl / SO2 / NaCl / Na2SO3 / Na2SO4
/

NaOH / H2SO4

Ions:
OH-1 / ClO-1 / H+1 / HSO3-1 / HSO4-1 / Na+1 / NaSO4-1 / Cl-
1
/

S2O5-2 / SO3-2 / SO4-2

Precipitates and Hydrates:

NaCl / Na2SO3 / Na2SO4 / NaOH

Ionic Equilibria:
Cl2aq + H2O = H+1 + Cl-1 + HClOaq

H2O = H+1 + OH-1

HClaq = H+1 + Cl-1

HClOaq = H+1 + ClO-1

HSO3-1 = H+1 + SO3-2

HSO4-1 = H+1 + SO4-2

PRO/II Electrolytes User Guide E2-31

 Na2SO3ppt = 2Na+1 + SO3-2

Na2SO4ppt = 2Na+1 + SO4-2

BATCH

NaClppt = Na+1 + Cl-1

NaOHppt = Na+1 + OH-1

ELECTROLYTES

NaSO4-1 = Na+1 + SO4-2

S2O5-2 + H2O = 2SO3-2 + 2H+1

SO2aq + H2O = HSO3-1 + H+1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O / Cl2 / HClO / HCl /
SO2.

CAUX Model
Identical to CAUS model except that solid precipitation equilibria
are not considered.

CAU2 Model

Components:
H2O / NaOH / KOH

Ions:
OH-1 / K+1 / Na+1 / H+1

Precipitates and Hydrates:

NaOH / KOH

Ionic Equilibria:
H2O = H+1 + OH-1

KOHppt = K+1 + OH-1

NaOHppt = Na+1 + OH-1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O only.

E2-32 - July 2016 Electrolyte Models

 CA2X Model
Identical to CAU2 model except that solid precipitation equilibria
are not considered.

Benfield Systems

ELECTROLYTES
BENF Model

Components:
H2O / CO2 / CO / C2H6 / C2H4 / CH4 / H2S / H2 / N2 / NH3
/ C3H8 /

K2CO3 / KHCO3 / KHS / H3PO4 / B(OH)3 / KOH

Ions:
OH-1 / CO3-2 / H2P2O7-2 / H2PO4-1 / H3P2O7-1 / HCO3-1 / H+1
/

HP2O7-3 / HPO4-2 / HS-1 / K+1 / NH2CO2-1 / NH4+1 / BO2-1 /

P2O7-4 / PO4-3 / S-2

Precipitates and Hydrates:

K2CO3 / KHCO3 / KOH

Ionic Equilibria:
CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

H2P2O7-2 = H+1 + HP2O7-3

H2PO4-1 = H+1 + HPO4-2

H2Saq = H+1 + HS-1

H3P2O7-1 = H+1 + H2P2O7-2

HCO3-1 = H+1 + CO3-2

P2O7-3 = H+1 + P2O7-4

HPO4-2 = H+1 + PO4-3

PRO/II Electrolytes User Guide E2-33

 HS-1 = H+1 + S-2

K2CO3ppt = 2K+1 + CO3-2

BATCH

KHCO3ppt = K+1 + HCO3-1

KOHppt = K+1 + OH-1

ELECTROLYTES

NH2CO2-1 + H2O = NH3aq + HCO3-1

NH3aq + H2O = NH4+1 + OH-1

P2O7-4 + H2O = 2PO4-3 + 2H+1

B(OH)3aq = BO2-1 + H2O + H+1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is not considered for K2CO3 / KHCO3 /
KHS / H3PO4 / B(OH)3 / KOH.

BENX Model
Identical to BENF model except that solid precipitation equilibria
are not considered.

Scrubber Systems
SCRU Model

Components:
H2O / CO2 / HCl / HCN / HCOOH / N2 / O2 / SO2 / NaOH
/ CaCO3 /

CaCl2 / NaCl / Na2CO3 / NaHCO3 / NaCOOH / Ca(OH)2

Ions:
OH-1 / CaHCO3+1 / Ca+2 / CaOH+1 / Cl-1 / CN-1 / CO3-2 /

COOH-1 / HCO3-1 / H+1 / HSO3-1 / Na+1 / CaCOOH+1 / S2O5-2

/ SO3-2

Precipitates and Hydrates:

NaOH / CaCO3 / CaCl2 / NaCl / Na2CO3 / NaHCO3 /

NaCOOH / Ca(OH)2

E2-34 - July 2016 Electrolyte Models

 Ionic Equilibria:
CaCl2ppt = Ca+2 + 2Cl-1

CaCO3ppt = Ca+2 + CO3-2

CaCOOH+1 = Ca+2 + COOH-1

ELECTROLYTES
CaHCO3+1 = Ca+2 + HCO3-1

Ca(OH)2ppt = Ca+2 + 2OH-1

CaOH+1 = Ca+2 + OH-1

CO2aq + H2O = HCO3-1 + H+1

H2O = H+1 + OH-1

HClaq = H+1 + Cl-1

HCNaq = H+1 + CN-1

HCO3-1 = H+1 + CO3-2

HCOOHaq = H+1 + COOH-1

HSO3-1 = H+1 + SO3-2

Na2CO3ppt = 2Na+1 + CO3-2

NaClppt = Na+1 + Cl-1

NaCOOHppt = Na+1 + COOH-1

NaHCO3ppt = Na+1 + HCO3-1

NaOHppt = Na+1 + OH-1

S2O5-2 + H2O = 2SO3-2 + 2H+1

SO2aq + H2O = HSO3-1 + H+1

Vapor-Liquid Equilibria:
Vapor-liquid equilibrium is considered for H2O / CO2 / HCl / HCN /
HCOOH / N2 / O2 / SO2.

PRO/II Electrolytes User Guide E2-35

 LLE and Hydrate Systems
TWL1 Model
BATCH

Components:
H2O / CO2 / H2S / NH3 / CH4 / C6H5OH /Toluene / NaOH /

NaOH·H2O / Na2CO3 / Na2CO3·10H2O / Na2CO3·H2O /

ELECTROLYTES

Na2CO3·7H2O / NaHCO3 / NaCl /NaHS / HCl / CaCl2 /

CaCl2·H2O /

CaCl2·2H2O / CaCl2·4H2O / CaCl2·6H2O /Ca(HCO3)2 / CaCO3

/

Ca(OH)2 / NH4Cl / NH4HCO3 / NH4HS

Ions:
OH-1 / HCO3-1 / NaCO3-1 / NH2CO2-1 / Cl-1 /HS-1 / C6H5O-1 /

CO3-2 / S-2 / CaCl+1 / CaHCO3+1 / CaOH+1 / H+1 /

Na+1 / NH4+1 / Ca+2

Precipitates and Hydrates:

CaCl2 / CaCO3 / Ca(OH)2 / Na2CO3 /NaCl / NaHCO3 / NaOH
/ NH4Cl /

NH4HCO3 / NH4HS / CaCl2·H2O / CaCl2·2H2O / CaCl2·4H2O /

CaCl2·6H2O / Na2CO3·10H2O / Na2CO3·H2O / Na2CO3·7H2O /

NaOH·H2O

Ionic Equilibria:
C6H5OHaq = H+1 + C6H5O-1

CaCl2·H2O = Ca+2 + 2Cl-1 + H2O

CaCl2·2H2O = Ca+2 + 2Cl-1 + 2H2O

CaCl2·4H2O = Ca+2 + 2Cl-1 + 4H2O

CaCl2·6H2O = Ca+2 + 2Cl-1 + 6H2O

E2-36 - July 2016 Electrolyte Models

 CaCl2aq = CaCl+1 + Cl-1

CaCl2ppt = Ca+2 + 2Cl-1

CaCl+1 = Ca+2 + Cl-1

CaCO3aq = Ca+2 + CO3-2

ELECTROLYTES
CaCO3ppt = Ca+2 + CO3-2

CaHCO3+1 = Ca+2 + HCO3-1

Ca(OH)2ppt = Ca+2 + 2OH-

CaOH+1 = Ca+2 + OH-1

CO2aq + H2O = H+1 + HCO3-1

H2O = H+1 + OH-1

H2Saq = H+1 + HS-1

HClaq = H+1 + Cl-1

HCO3-1 = H+1 + CO3-2

HS-1 = H+1 + S-2

Na2CO3·10H2O = 2Na+1 + CO3-2 + 10H2O

Na2CO3·H2O = 2Na+1 + CO3-2 + H2O

Na2CO3·7H2O = 2Na+1 + CO3-2 + 7H2O

Na2CO3ppt = 2Na+1 + CO3-2

NaClppt = Na+1 + Cl-1

NaCO3-1 = Na+1 + CO3-2

NaHCO3aq = Na+1 + HCO3-1

NaHCO3ppt = Na+1 + HCO3-1

NaOH·H2O = Na+1 + OH-1 + 1H2O

PRO/II Electrolytes User Guide E2-37

 NaOHppt = Na+1 + OH-1

NH2CO2-1 + H2O = NH3aq + HCO3-1

BATCH

NH3aq + H2O = NH4+1 + OH-1

NH4Clppt = NH4+1 + Cl-1

ELECTROLYTES

NH4HCO3ppt = NH4+1 + HCO3-1

NH4HSppt = NH4+1 + HS-1

Vapor-Liquid and Liquid-Liquid Equilibria:

Vapor-liquid equilibrium is considered for H2O / C6H5OH / CH4 /
CO2 / H2S / HCl / NH3 / Toluene.

TWL2 Model

Components:
H2O / NaCl / NaHSO4 / Na2SO4 / Na2SO4·10H2O /NaOH /

NaOH·H2O / Ca(HSO4)2 / CaSO4 / CaSO4·2H2O / Ca(OH)2 /

HCl / N2 / CH4 / Methanol / Ethanol / M-Xylene / Ben-

zene /

Toluene / CaCl2 / CaCl2·H2O / CaCl2·2H2O / CaCl2·4H2O /

CaCl2·6H2O / HF / H2SO4 / CaF2 / NaF

Ions:
OH-1 / Cl-1 / HF2-1 / HSO4-1 / NaSO4-1 / F-1 / SO4-2 / H+1 /

CaCl+1 / CaF+1 / CaOH+1 / Na+1 / Ca+2

Precipitates and Hydrates:

CaCl2 / CaF2 / Ca(OH)2 / CaSO4 / Na2SO4 / NaCl / NaF /
NaHSO4/

NaOH / CaCl2·H2O / CaCl2·2H2O / CaCl2·4H2O / CaCl2·6H2O

/

CaSO4·2H2O / Na2SO4·10H2O / NaOH·H2O

E2-38 - July 2016 Electrolyte Models

 Ionic Equilibria:
CaCl2·H2O = Ca+2 + 2Cl-1 + H2O

CaCl2·2H2O = Ca+2 + 2Cl-1 + 2H2O

CaCl2·4H2O = Ca+2 + 2Cl-1 + 4H2O

ELECTROLYTES
CaCl2·6H2O = Ca+2 + 2Cl-1 + 6H2O

CaCl2aq = CaCl+1 + Cl-1

CaCl2ppt = Ca+2 + 2Cl-1

CaCl+1 = Ca+2 + Cl-1

CaF2ppt = Ca+2 + 2F-1

CaF+1 = Ca+2 + F-1

Ca(OH)2ppt = Ca+2 + 2OH-1

CaOH+1 = Ca+2 + OH-1

CaSO4·2H2O = Ca+2 + SO4-2 + 2H2O

CaSO4aq = Ca+2 + SO4-2

CaSO4ppt = Ca+2 + SO4-2

H2O = H+ + OH-1

HClaq = H+ + Cl-1

HF2-1 = F-1 + HFaq

HFaq = H+1 + F-1

HSO4-1 = H+1 + SO4-2

Na2SO4·10H2O = 2Na+1 + SO4-2 + 10H2O

Na2SO4ppt = 2Na+1 + SO4-2

NaClppt = Na+1 + Cl-1

NaFaq = Na+1 + F-1

PRO/II Electrolytes User Guide E2-39

 NaFppt = Na+1 + F-1

NaHSO4ppt = Na+1 + HSO4-1

BATCH

NaOH·H2Oppt = Na+1 + OH-1 + H2O

NaOHppt = Na+1 + OH-1

ELECTROLYTES

NaSO4-1 = Na+1 + SO4-2

Vapor-Liquid and Liquid-Liquid Equilibria:

Vapor-liquid equilibrium is considered for H2O / Benzene / CH4 /
Ethanol / HCl / HF / Methanol / M-Xylene / N2 / Toluene.

Alphabetical Component Index of Electrolyte Models

The Electrolyte models that contain a given component (or ionic
species) are listed directly underneath the component names in this
index. The phases allowed for the components are given in paren-
theses following the component names, where:
AQ = aqueous phase (ion, ion pair, or dissolved neutral mole-
cule)
CI = completely ionized aqueous electrolyte
V= vapor phase
S = solid phase
HC = hydrocarbon or non-aqueous liquid phase.
For example, it can be deduced from the index that aqueous calcium
ion, Ca+2(AQ), hydroxide ion, OH-1(AQ), calcium mono-hydroxide
ion pair, CaOH+1(AQ), and solid calcium hydroxide, Ca(OH)2(S)
are included in the CANA model. The CANX model has the same
components as CANA; however, solid phases of the components
are not allowed. Consequently, Ca(OH)2 in the CANX model is
treated as an aqueous electrolyte that is completely ionized (CI).

E2-40 - July 2016 Electrolyte Models

A TEA2 CaCl+1 (AQ) Ca(OH)2 (CI)
C3H8 (V,AQ) TWL1 CANX1
Acetacid (AQ)
BENF6 TWL2 SCRX1
SW023
SW2X3 BENX6 CaCl2 (CI) Ca(OH)2 (S)
DEA7 CANX1 CANA1
Acetate-1 (AQ)
DGA7 GEOT1 OILF1
SW021 DIPA7 SCRX1 SCRU1
SW2X1 HOTC7 CaCl2 (S) TWL1
HOTX7

ELECTROLYTES
B CANA1 TWL2
MDEA7 OILF1 CaSO4 (AQ)
Ba+2 (AQ) MEA7 SCRU1 CANX1
GEOT1 SW017 TWL1 GEOT1
OILF1 SW037 TWL2 CaSO4 (S,AQ)
BaCl2 (CI) SW047 CaCl2·H2O (S) CANA1
GEOT1 SW1X7
TWL1 OILF1
BaCl2 (S) SW3X7
TWL2 TWL2
OILF1 SW4X7
TEA7 CaCl2·2H2O (S) CaSO4·2H2O (S)
BaCO3 (S) TWL1 TWL2
GEOT1 C4H10 (V,AQ)
TWL2 CH4 (V,AQ)
OILF1 DEA6
DGA6 CaCl2·4H2O (S) BENF1
BaOH+1 (AQ) TWL1 BENX1
DIPA6
GEOT1 TWL2 DEA1
MDEA6
OILF1 CaCl2·6H2O (S) DGA1
MEA6
Ba(OH)2 (S) SW036 TWL1 DIPA1
OILF1 SW046 TWL2 HOTC1
BaSO4 (S) SW3X6 CaCO3 (CI) HOTX1
GEOT1 SW4X6 SCRX1 MDEA1
OILF1 TEA6 MEA1
CaCO3 (S)
Benzene (V,AQ,HC) C6H5O-1 (AQ) SW011
GEOT1 SW021
TWL2 SW011 OILF1
BO2-1 (AQ) SW031
SW021 SCRU1
BENF1 SW041
SW031 TWL1
BENX1 SW1X1
SW041 CaCOOH+1 (AQ) SW2X1
B(OH)3 (AQ) SW1X1 SCRU1 SW3X1
BENF1 SW2X1 SCRX1 SW4X1
BENX1 SW3X1
CaF+1 (AQ) TEA1
GEOT1 SW4X1
TWL1 TWL2 CH4 (V,AQ,HC)
B(OH)3OH-1 (AQ) CaF2 (S)
C6H5OH (V,AQ) TWL1
GEOT1 TWL2 TWL2
SW011
C SW021 CaHCO3+1 (AQ) Cl-1 (AQ)
C2H4 (V,AQ) SW031 GEOT1 CANA1
SW041 OILF1 CANX1
BENF2
SW1X1 SCRU1 CAUS1
BENX2C2H6(V,AQ)
SW2X1 SCRX1 CAUX1
BENF2
BENX2 SW3X1 TWL1 Cl21
DEA2 SW4X1 Ca(HCO3)2 (CI) CLSF1
DGA2 C6H5OH (V,AQ,HC) TWL1 GENE1
DIPA2 TWL1 CaHSO4 (CI) GENX1
HOTC2 Ca+2 (AQ) TWL2 GEOT1
HOTX2 CaOH+1 (AQ) HCL1
CANA1
MDEA2 OILF1
CANX1 CANA1
MEA2 SALT1
GEOT1 CANX1
SW012 SCRU1
OILF1 GEOT1
SW032 SCRX1
SCRU1 OILF1
SW042 SW011
SCRX1 SCRU1
SW1X2 SW021
TWL2 SCRX1
SW3X2 SW031
Ca2EDTA (AQ) TWL1
SW4X2 SW1X1
GEOT1 TWL2

PRO/II Electrolytes User Guide E2a-1

 SW2X1 SW3X2 DIPAx (AQ) BENF3
SW3X1 SW4X2 DIPA2 BENX3
TWL1 TEA2 DIPAH2+1 (AQ) DEA3
TWL2 CO2 (V,AQ,HC) DIPA DGA3
Cl2 (V,AQ) TWL1 DIPA3
CAUS1 CO3-2 (AQ) E GEOT3
CAUX1 ACID2 EDTA-4 (AQ) HOTC3
CL21 BENF2 HOTX3
GEOT2
CLSF1 BENX2 MDEA3
Ethanol (V,AQ,HC)
ELECTROLYTES

GENE1 DEA2 MEA3

TWL2
GENX1 DGA2 SW013
ClO-1 (AQ) DIPA2 F SW023
CAUS1 GENE2 SW033
F-1 (AQ) SW043
CAUX1 GENX2 TWL2
CL21 GEOT2 SW053
Fe3O4 (S) SW1X3
CLSF1 HOTC2
GENE1 HOTX2 GEOT2 SW2X3
GENX1 MDEA2 FeII+2 (AQ) SW3X3
GEOT2 SW4X3
CN-1 (AQ) MEA2
OILF2 FeIICl2 (CI) TEA3
ACID1
SCRU2 GEOT2 H2S (V,AQ,HC)
SCRU1
SCRX1 SCRX2 FeIIHCO3+1 (AQ) TWL1
SW011 SW012 GEOT2 H2SO3 (CI)
SW021 SW022 FeIII+3 (AQ) CLSF3
SW031 SW032 SULF3
GEOT2
SW1X1 SW042 H2SO4 (CI)
SW052 FeIIICl3 (CI)
SW2X1 CANA3
SW1X2 GEOT2
SW3X1 CANX3
CO (V,AQ) SW2X2 FeIIOH+1 (AQ) CAUS3
ACID2 SW3X2 GEOT2 CAUX3
BENF2 SW4X2 CLSF3
TEA2 H
BENX2 OILF3
HOTC2 TWL1 H+1 (AQ) SULF3
HOTX2 COOH-1 (AQ) (all models) TWL2
SW032 ACID2 H2 (V,AQ) H3P2O7-1 (AQ)
SW3X2 SCRU2 ACID3 ACID3
CO2 (V,AQ) SCRX2 BENF3 BENF3
ACID2 SW012 BENX3 BENX3
BENF2 SW1X2 HOTC3 PHOS3
BENX2 Cu+2 (AQ) HOTX3 SW013
DEA2 GEOT SW033 SW1X3
DGA2 CuCl2 (CI) SW3X3 H3PO4 (CI)
DIPA2 GEOT2 H2O (V,AQ) ACID3
GENE2 (all models) BENF3
GENX2 D H2P2O7-2 (AQ) BENX3
GEOT2 DEACO2-1 (AQ) ACID3 PHOS3
HOTC2 BENF3 SW013
DEA2
HOTX2 BENX3 SW1X3
DEAH (AQ)
MDEA2 PHOS3 HCl (CI)
DEA2
MEA2 SW013 GEOT3
OILF2 DEAH2+1 (AQ)
DEA2 SW1X3 HCl (V,AQ)
SCRU2
DGACO2-1 (AQ) H2PO4-1 (AQ) CANA3
SCRX2
SW012 DGA2 ACID3 CANX3
SW022 DGAH (AQ) BENF3 CAUS3
SW032 DGA2 BENX3 CAUX3
SW042 DGAH2+1 (AQ) PHOS3 CL23
SW052 SW013 CLSF3
DGA2
SW1X2 SW1X3 GENE3
DIPACO2-1 (AQ) GENX3
SW2X2 H2S (V,AQ)
DIPA2

E2a-2 - July 2016 Electrolyte Models

 HCL3 SW014 TWL2 TWL2
OILF3 SW1X4 Mg+2 (AQ)
SCRU3 HF2-1 (AQ) K CANA4
SCRX3 TWL2 K+1 (AQ) CANX4
SW013 HF (V,AQ,HC) BENF4 GEOT4
SW023 TWL2 BENX4 OILF4
SW033 HP2O7-3 (AQ) CA2X4 MgCl+1 (AQ)
SW1X3 ACID4 CAU24 CANA4
SW2X3

ELECTROLYTES
BENF4 GEOT4 CANX4
SW3X3 BENX4 OILF4 GEOT4
TWL1 PHOS4 SALT4 OILF4
TWL2 SW014 K2CO3 (CI) MgCl2 (CI)
HClO (V,AQ) SW1X4 BENX4 CANX4
CAUS3
HPO4-2 (AQ) K2CO3 (S) GEOT4
CAUX3
CL23 ACID4 BENF4 MgCl2 (S)
CLSF3 BENF4 OILF4 CANA4
GENE3 BENX4 K2SO4 (S) OILF4
GENX3 PHOS4 OILF4 MgCO3 (S)
HCN (V,AQ) SW014 KCl (CI) GEOT5
ACID4 SW1X4 GEOT4 OILF5
SCRU4 HS-1 (AQ) KCl (S) MgHCO3+1 (AQ)
SCRX4 BENF4 OILF4 GEOT5
SW014 BENX4 SALT4 OILF5
SW024 DEA4 KHCO3 (CI) Mg(OH)2 (CI)
SW034 DGA4 BENX4
DIPA4 CANX5
SW1X4 KHCO3 (S)
SW2X4 GEOT4 Mg(OH)2 (S)
BENF4 CANA5
SW3X4 HOTC4
OILF4 OILF5
HCO3-1 (AQ) HOTX4
KHS (CI) MgSO4 (CI)
ACID4 MDEA4
BENF4
BENF4 MEA4 CANX5
BENX4
BENX4 SW014 MgSO4 (S)
KOH (CI)
DEA4 SW024 CANA5
BENX4
DGA4 SW034 OILF5
CA2X4
DIPA4 SW044 Mn+2 (AQ)
KOH (S)
GENE4 SW054
BENF4 GEOT5
GENX4 SW1X4
CAU24 MnCl2 (CI)
GEOT4 SW2X4
OILF4 GEOT5
HOTC4 SW3X4
SW4X4 MnHCO3+1 (AQ)
HOTX4 L
TEA4 GEOT5
MDEA4 Li+1 (AQ)
MEA4 HSO3-1 (AQ) MnOH+1 (AQ)
CAUS4 GEOT4 GEOT5
OILF4
CAUX4 LiCl (CI) M-Xylene (V,AQ,HC)
SCRU4
CLSF4 GEOT4 TWL2
SCRX4
SW014 GENE4 M
GENX4 N
SW024
SW034 GEOT4 MDEAH (AQ) N2 (V,AQ)
SW044 SCRU4 MDEA4 ACID5
SW054 SCRX4 MDEAH2+1 (AQ) BENF5
SW1X4 SULF4 MDEA4 BENX5
SW2X4 HSO4-1 (AQ) MEACO2-1 (AQ) CL25
SW3X CANA4 MEA4 CLSF5
SW4X4 CANX4 DEA5
TEA4 CAUS4 MEAH (V,AQ) DGA5
TWL1 CAUX4 MEA4 DIPA5
HCOOH (V,AQ) CLSF4 MEAH2+1 (AQ) GENE5
ACID4 GEOT4 MEA4 GENX5
SCRU4 OILF4 Methanol (V,AQ,HC) HOTC5
SCRX4 SULF4 HOTX5

PRO/II Electrolytes User Guide E2a-3

 MDEA5 Na2CO3.10H2O (S) GENE5 SW016
MEA5 TWL1 HOTC5 SW026
SCRU5 Na2S (CI) OILF5 SW036
SCRX5 GEOT5 SCRU5 SW046
SW015 Na2SO3 (CI) SW015 SW056
SW035 SW025 SW1X6
CAUX5
SW045 SW035 SW2X6
GEOT5
SW1X5 SW045 SW3X6
SW3X5 Na2SO3 (S) TWL1 SW4X6
ELECTROLYTES

SW4X5 CAUS5 NaHS (CI) TWL1

TEA5 Na2SO4 (CI) SW015 NH3 (V,AQ)
N2 (V,AQ,HC) CANX5 SW025 ACID6
TWL2 CAUX5 SW035 BENF6
Na+1 (AQ) GEOT5 SW1X5 BENX6
CA2X5 Na2SO4 (S) SW2X5 GEOT6
CANA5 CANA5 SW3X5 SW016
CANX5 CAUS5 TWL1 SW026
CAU25 OILF5 NaHSO4 (S) SW036
CAUS5 TWL2 TWL2 SW046
CAUX5 Na2SO4.10H2O NaOH (CI) SW056
GENE5 TWL2 CA2X5 SW1X6
GENX5 Na4EDTA (AQ) CANX5 SW2X6
GEOT5 GEOT5 CAUX5 SW3X6
HOTC5 GENX5 SW4X6
NaCl (CI)
HOTX5 HOTX5 NH3 (V,AQ,HC)
CANX5 SCRX5
OILF5 CAUX5 TWL1
SALT5 SW1X6 NH4+1 (AQ)
GENX5 SW2X6
SCRU5 GEOT5 ACID6
SCRX5 SW3X6 BENF6
OILF5 SW4X6
SW015 SCRX5 BENX6
SW025 NaOH (S) GEOT6
SW1X5 CANA6
SW035 SW2X5 SW016
SW045 CAU26 SW026
SW3X5 CAUS6
SW1X5 SW036
NaCl (S) GENE6
SW2X5 SW046
SW3X5 CANA5 HOTC6
CAUS5 SW056
SW4X5 OILF6 SW1X6
TWL2 GENE5 SCRU6
SALT5 SW2X6
Na2CO3 (CI) SW016 SW3X6
SCRU5 SW026
GENX5 SW015 SW4X6
HOTX5 SW036 TWL1
SW025 SW046
SCRX5 SW035 NH4Cl (S)
SW1X5 TWL1
TWL1 TWL2 TWL1
SW2X5 TWL2 NH4HCO3 (S)
SW3X5 NaOH·H2O (S)
NaCOOH (CI) TWL1 TWL1
SW4X5 SCRX5 TWL2 NH4HS (S)
Na2CO3 (S) NaCOOH (S)
NaSO4-1 (AQ) TWL1
GENE5 SCRU5
CANA6 (NH4)2SO4 (S)
HOTC5 NaF (S)
OILF5 CANX6 GEOT6
TWL2
SCRU5 CAUS6
NaHCO3 (CI)
CAUX6 O
SW015 GENX5
SW025 GEOT6 O2 (V,AQ)
HOTX5 OILF6
SW035 SCRX5 CLSF6
SW045 TWL2 GENE6
SW1X5
TWL1 NH2CO2-1 (AQ) GENX6
SW2X5
Na2CO3·H2O (S) SW3X5 ACID6 SCRU6
TWL1 SW4X5 BENF6 SCRX6
Na2CO3·7H2O (S) BENX6 SW036
NaHCO3 (S)
GEOT6 SW3X6
TWL1

E2a-4 - July 2016 Electrolyte Models

OH-1 (AQ) GENE7
(all models)6 GENX7
SCRU7
P SCRX7
P2O7-4 (AQ) SULF7
ACID6 SO3-2 (AQ)
BENF6 CAUS7
BENX6 CAUX7
CLSF7

ELECTROLYTES
PHOS6
SW016 GENE7
SW1X6 GENX7
Pb+2 (AQ) GEOT7
GEOT6 SCRU7
SCRX7
PbCl2 (CI)
SULF7
GEOT6
SO4-2 (AQ)
PO4-3 (AQ)
CANA7
ACID6 CANX7
BENF6 CAUS7
BENX6 CAUX7
PHOS6 CLSF7
SW016 GEOT7
SW1X6 OILF7
S SULF7
TWL2
S-2 (AQ) Sr+2 (AQ)
BENF7 GEOT7
BENX7 SrCl2 (CI)
DEA7
GEOT7
DGA7
DIPA7 SrCO3 (S)
GEOT7 GEOT7
HOTC7 SrSO4 (S)
HOTX7 GEOT7
MDEA7
MEA7
SW017 T
SW027 TEACO2-1 (AQ)
SW037 TEA7
SW047 TEAH (AQ)
SW057 TEA7
SW1X7 TEAH2+1 (AQ)
SW2X7 TEA7
SW3X7 Toluene (V,AQ,HC)
SW4X7 TWL1
TEA7 TWL2
TWL1
S2O5-2 (AQ) Z
CAUS7 Zn+2 (AQ)
CAUX7
GEOT7
CLSF7
GENE7 ZnCl2 (CI)
GENX7 GEOT7
SCRU7 ZnHCO3+1 (AQ)
SCRX7 GEOT7
SULF7
SO2 (V,AQ)
CAUS7
CAUX7
CLSF7

PRO/II Electrolytes User Guide E2a-5

ELECTROLYTES

E2a-6 - July 2016 Electrolyte Models

 Chapter E3
Creating a User-Added Electrolyte
Model
Available Tools for Creating Electrolyte Models

ELECTROLYTES
Users can develop their own user-added aqueous electrolyte
models for use in Electrolytes versions of PRO/II by using
Chemistry Wizard. PRO/II Electrolyte Chemistry Wizard can be
accessed from shortcut ‘PROII Electrolyte Chemistry’.

In addition, user can create their own user-added electrolyte

models using Chemistry Wizard from OLI Systems, Inc. This
upgrade includes OLI’s new state-of-the-art Mixed Solvent
Electrolyte (MSE) chemistry model that enables chemical process
simulations that heretofore were not possible to accomplish.
Documentation for MSE version of Chemistry Wizard is also
available from OLI Systems, Inc.

Other Documentation
The PRO/II installation package includes the following
documentation to instruct users in generating their own electrolyte
models. During installation, these files may be copied to the
\Manual\OLI subdirectory of the PRO/II installation directory.

 OLI Chemistry Wizard User Guide provides complete

documentation to use PRO/II Electrolyte Chemistry Wizard
installed with PRO/II.
 PRO/II-OLI 6.6_Components.xls, a Microsoft Excel spread-
sheet, provides an expanded list of electrolyte components as
included in the 40 pre-defined systems installed with PRO/II.
The 5.6, 6.6, and 7.0 versions of the predefined electrolyte data
base files all contain the same slate of electrolyte species and
components.

Both documents are included on the PRO/II installation disk.

PRO/II Electrolytes User Guide E3-1

 Compatibility with Previous Versions of PRO/II
Formerly, PRO/II incorporated version 5.6, and then version 6.3 of
BATCH

the OLI electrolytes calculation engine. These versions used the

Electrolyte Utility Package (EUP) provided by OLI Systems, Inc.,
to generate electrolyte models. This program now is obsolete.
ELECTROLYTES

Beginning with PRO/II version 7.1, PRO/II upgraded to OLI engine

version 6.6. Also, the EUP was replaced by the newer OLI Chemis-
try Wizard version 1.0. Concurrently, OLI Systems assumed
responsibility for support and documentation of the newer tools.
This program also is obsolete.
Beginning with version 9.1, PRO/II upgraded to version 8.2.4 of the
OLI engine and the accompanying Chemistry Wizard version 3.1.
These versions of the tools currently are used by PRO/II.
Note: All of the older tools mentioned in this section now are obso-
lete and no longer are available. When creating new electrolyte
models, be sure to use the current version of the Chemistry Wizard.
Note: While the older tools no longer are available, older electro-
lyte models created by using them still function properly in PRO/II.
Specifically, PRO/II still is able to translate and use electrolyte
models created for earlier OLI engine versions 5.6 and 6.6. How-
ever, we urge all electrolyte users to upgrade to the latest version at
their earliest convenience.

E3-2 - July 2016 Creating a User-Added Electrolyte Model

 Chapter E4
Electrolyte Effects In Simulations
Overview
Throughout the development of PRO/II Electrolytes, a major goal
has been to integrate the Electrolyte thermodynamic methods seam-

ELECTROLYTES
lessly into PRO/II’s graphical user interface (GUI). In other words,
as far as the unit operations are concerned, PRO/II Electrolytes
should operate as “just another thermodynamic method.” There are
several units still unavailable for use with Electrolytes, while others
have partial functionality or other special considerations. This doc-
ument discusses work-arounds, where possible, for these limita-
tions.

General Considerations
The most fundamental consideration that can make PRO/II Electro-
lytes different from other thermodynamic methods is that it is com-
pletely tied to the flash algorithm, K-value, enthalpy, and density
methods as developed by OLI Systems Inc. (Morris Plains, N.J.).
OLI’s flash algorithm does not work exactly the same as the “nor-
mal” flash in PRO/II. In some ways that is beneficial, but it can cre-
ate problems for a few PRO/II unit operations. The following are
important differences between the two, along with statements
regarding the consequences of those differences:
 There are conditions (most commonly where there is no aque-
ous liquid phase) in which OLI’s thermodynamic method is
simply not applicable. In such conditions, the flash will usually
fail to converge. This is in contrast to most non-electrolyte
PRO/II thermodynamic methods, in which the flash will usu-
ally return some sort of an answer even if you have chosen an
inappropriate method for the conditions.
 There are occasionally valid conditions for which OLI’s flash
fails to converge. The most common of these failures occurs in
adiabatic flashes with nearly pure fluids that cross a phase
boundary; this case will be discussed below in Simple HX. The
only other known significant problem is that OLI can have
problems converging a flash in which a large amount of a spar-
ingly soluble solid will precipitate out. This problem is allevi-
ated somewhat for internal flowsheet streams by implementing

PRO/II Electrolytes User Guide E4-1

 an initial guess for solids based on the solids in the feed. This
can be done for external feed streams by putting an estimate of
the solid that will precipitate on the SOLID statement for the
BATCH

stream.
 There are some thermodynamic quantities that OLI does not
calculate. In particular, OLI does not return values for the
entropy or heat capacity of electrolyte streams. This means that
ELECTROLYTES

electrolyte thermodynamic methods cannot be used for units

that require entropy, such as the Gibbs reactor. Some units also
use heat capacity internally; in some cases special adjustments
have been made to the code for electrolyte thermodynamic
methods.
 The list of specifications recognized by OLI’s flash is different
from that recognized by PRO/II’s flash. Many of the specifica-
tions can be translated, but some (such as isentropic flashes)
cannot.
 OLI, under the current release of PRO/II Electrolytes, will now
do liquid/liquid equilibrium (LLE); that is, it can handle a sec-
ond (organic) liquid phase. However, this capability is limited
to non-column unit operations such as the flash drum and the
splitter.

SPEC, DEFINE, VARY

In general, all of the flowsheet parameters as listed in Section 43 of
the PRO/II Keyword Manual are available for cross-referencing,
and anything that can be varied with other thermodynamic methods
can be varied with electrolytes. There are some stream properties
(for example, D86 and WFRAC) that do not make sense for aque-
ous electrolyte streams.
In addition, the electrolyte-specific stream property pH is available
for cross-referencing.

E4-2 - July 2016 Electrolyte Effects In Simulations

Basic Unit Operations
The following table indicates which unit operations support the use
of the Electrolyte module.
Table E4-1: Unit Operations That Support Electrolytes

Support Electrolytes NO Electrolyte Support

Flash Compressor

ELECTROLYTES
Pump, Valve, Mixer, Splitter Expander

Column ELDIST  Column (All algorithms

(Electrolyte Algorithm) except ELDIST)

Heat Exchangers Heat Exchangers 

Simple, Rigorous, LNG, Furnace (Fired Heater)
ACE

Reactors Reactors
Batch,  Gibbs, 
Conversion,  CSTR, 
Equilibrium Plug Flow

Solids Handling Solids Handling

Counter-Current Decanter Dryer
Crystallizer Freezer
Dissolver Melter
Filtering Centrifuge
Rotary Filter

Utilities Utilities
BVLE HEXTABLES
HCURVE Hydrates
Phase Envelope

Calculator (see DEFINE)

Controller, Optimizer

Pipe

Flash Drum
As with all flash-type units, the most important caution is not to use
electrolyte thermodynamic methods at conditions where it is not

PRO/II Electrolytes User Guide E4-3

 valid. Apart from that, most of the functionality of the unit is avail-
able for electrolytes. The flash drum is able to handle a second
(organic) liquid phase, as well as a vapor and/or precipitated solid
BATCH

phase. As mentioned before, the ISENTROPIC flash is not available.

The DEWHC and DEWWATER options are not available (or meaningful)
because electrolyte methods do not decant water.
The TPSPEC construct is currently limited with electrolytes. The one
ELECTROLYTES

added feature is the ability to SPEC the pH of an outlet liquid

stream. The only other internal flash spec allowed is a vapor or liq-
uid flowrate as a fraction of the molar flowrate of a stream that is
the only feed to the unit:
SPEC STRM=L1, RATE, RATIO, STRM=F1, RATE, VALUE=0.8

The REFFEED construct may also be used to reference a combined

unit feed. One can simulate any other TPSPEC by putting the flash
drum inside a controller loop.
For example, to specify a liquid weight fraction:
CONTROLLER UID=C1
SPEC STRM=L1, COMP=2, FRACTION(W), VALUE=0.3
VARY FLASH=FL1, TEMP

Pump, Valve, Mixer, Splitter

These units all work normally with electrolytes. There is a potential
problem in the Valve, in which the adiabatic flash may fail to con-
verge for a nearly pure fluid if the user is crossing a phase boundary.
Frequently, this may be alleviated simply by taking the valve in two
(or more) steps; a stream that will not converge when being throt-
tled from 50 to 15 psi may converge if it is taken to 20 psi in one
valve and then down to 15 in a second valve (in the second case it
gets a better initial guess). Alternatively, the valve can be simulated
by putting an ISOT flash (or a vapor-fraction-specified flash) inside
a controller with a controller specification of zero duty on the flash.

Compressor or Expander
Both of these units require entropy and are consequently not avail-
able with PRO/II Electrolytes. There are, however, still cases where
they may be used in electrolyte flow sheets. For example, if the
units operate only on a vapor phase (steam, for example), there is no
reason not to use a non-electrolyte thermodynamic method. Also, if
the stream in question is nearly pure water, the units may be

E4-4 - July 2016 Electrolyte Effects In Simulations

 replaced by a flash drum to give the DP in the flowsheet, and then
they may be modeled separately using a pure water stream to design
the unit and feed back the correct temperature for the flash drum.

Pipe
This unit is functional with PRO/II Electrolytes. The Pipe might
have problems doing two-phase flow with nearly pure water
streams because it does adiabatic/fixed-duty flashes on which OLI
may fail. Of course, the Pipe requires viscosities and sometimes

ELECTROLYTES
surface tensions. See the comments on Transport Properties below
for availability in regards to electrolytes.

Heat Exchangers
Simple HX
The full functionality of this unit, including all the Spec types, is
available to PRO/II Electrolytes.
There is, however, one commonly encountered condition that can
cause a problem: when the hot side of an exchanger is condensing
steam (in the case of a multi-effect evaporator, the steam may come
as the vapor from the cold side of another HX). The HX does a
fixed-duty flash on this stream. Unfortunately, OLI has great diffi-
culty converging for pure steam crossing the two-phase region. The
remedy for this situation is to use non-electrolyte thermodynamic
methods for the side of the HX that uses condensing steam; because
it is a pure water stream, there is no need to use electrolyte thermo-
dynamic methods anyway.

Rigorous HX
This unit is fully functional with PRO/II Electrolytes.

LNGHX
This unit is fully functional with PRO/II Electrolytes. The com-
ments regarding the use of condensing steam (see the HX discus-
sion above) apply here as well.

Electrolyte Distillation Column Algorithm (ELDIST)

This column algorithm was designed to solve non-ideal aqueous
electrolytic distillation columns involving ionic species. It uses a
Newton-Raphson method to solve the mass balance, vapor-liquid
equilibrium, and specification equations simultaneously. The

PRO/II Electrolytes User Guide E4-5

 K-values and enthalpies are supplied by the electrolyte thermody-
namic model.
BATCH

The Electrolytic Column Algorithm is selected from the Column

Algorithm drop-down list in the Column dialog box.

Note: Electrolytic thermodynamic models support only VLE, and

so total phase draws are not permitted.
ELECTROLYTES

Advantages and disadvantages of the Electrolytic Column Algo-

rithm follow:
 Advantages —
 Rigorously models ionic equilibrium systems.
 Solves highly non-ideal distillation columns.
 Disadvantages —
 Side columns are not supported.
 Pumparounds and tray hydraulics are not available
 Certain column specifications and variables are not 
permitted.
For the most part, the functionality of ELDIST is the same as that of
Chemdist. That means, for example, that pumparounds are not
allowed, and the range of Specs available is limited. In contrast to
Chemdist, ELDIST does not allow the specification of component
flows or mole fractions in liquid product streams. This is because
the presence of ionic reactions sometimes makes it ambiguous as to
the “correct” way to report the composition of a liquid (this is the
problem known as “reconstitution”). It should be noted that, as with
other units, non-allowed Specs may be met by putting the column
inside a controller or optimizer. Another limitation of ELDIST is
neither VLLE distillation nor liquid-liquid extraction is available.
Column hydraulics also are unavailable at present, but may be
enabled in the future.
Because electrolyte systems often are very non-ideal, ELDIST
sometimes has difficulty converging. Supplying initial estimates for
column tray temperatures and/or vapor-liquid flows (perhaps
obtained by solving a simplification of the problem) will often aid
convergence. Complete initial estimates (including compositions)
can be saved from one run with the PRINT PROFILE option. These
estimates not only help similar columns converge, but they also

E4-6 - July 2016 Electrolyte Effects In Simulations

 save calculation time because the ELDIST initial estimate generator
is somewhat time consuming.

Reactors
Equilibrium and Conversion Reactors
It should be remembered that, in PRO/II Electrolytes, you do not
necessarily need a Reactor to get a reaction. For example, water,
NaOH and HC1 will yield NaCl and H2O in a flash drum or any

ELECTROLYTES
other unit that does a flash. For reactions in aqueous solution that
involve only a “rearrangement” of ions, the Reactor is not neces-
sary.
If it is desired to use a reactor with Electrolyte thermodynamic
methods, the user is currently limited to isothermal mode with the
NOHBAL option turned on. These limitations will probably be
lifted in later releases of PRO/II Electrolytes. Of course, fixed-duty
mode can be simulated by putting an isothermal reactor in a control-
ler loop.

Gibbs Reactor
This unit requires entropy, and therefore cannot be used with elec-
trolyte thermodynamic methods. Again, since PRO/II Electrolytes
performs a simultaneous phase and chemical equilibration, the
functionality of a Gibbs reactor would be redundant if the only reac-
tions were ionic rearrangements.

Plug Flow and Continuously Stirred Tank Reactors

These units are not currently available with Electrolyte thermody-
namic methods. The primary reason for this is that neither unit is
able to handle components with phase type LS. Almost all reason-
able electrolyte models would contain such components.

Solids Handling Utilities

Dryer
This unit is not available with Electrolyte thermodynamic methods.
The main reason for this is that OLI has difficulty converging
flashes with lots of solid and little water. These would be conditions
likely to arise in the dryer. It might be possible to work around this
last problem by stringing multiple dryers in series to model one
unit.

PRO/II Electrolytes User Guide E4-7

 RFilter, FCentrifuge, CCDecanter
These units have their full functionality with Electrolyte thermody-
BATCH

namic methods. There is, however, one thing to watch out for.
These units are not designed to do phase equilibrium calculations,
so if the conditions are such that more solids will precipitate (or dis-
solve) in the unit, solids may appear (or disappear) in the filtrate
stream following solution of the unit.
ELECTROLYTES

Dissolver and Crystallizer

These two units may be used successfully with PRO/II Electrolytes
if care is taken in setting up the problem. If the only purpose is to
produce solid precipitate (or dissolve solids) to the equilibrium con-
centration, a flash drum should be used instead. The ability of OLI’s
flash to do SLE is a big advantage over PRO/II’s non-electrolyte
thermodynamic methods in this case. The crystallizer and dissolver
should be used with electrolytes in only two cases:
 When the process does not reach equilibrium.
 When it is important to know the particle size distribution
(PSD) of the product.
Both of these units are unable to go all the way to equilibrium (of
course, this is not an issue unless the kinetics are zero-order). In
such cases, the warning message will often say something similar to
“supersaturation limit reached.” The dissolver unit will also fail at
conditions such that all of the solid will dissolve. A flash drum
should be used in such cases.
As for the kinetics in these units, the parameters must be adjusted to
match experimental data. While the dissolver has a correlation to
predict mass transfer, that correlation is completely inappropriate
for electrolyte solutes. When testing different parameters to match
data, it is best (because of the problems getting to complete equilib-
rium) to start with “slow” kinetics and work your way up.
For electrolytes, both of these units operate only in isothermal
mode. Fixed-duty conditions may be simulated by putting the unit
in a controller loop.

Melter/Freezer
This unit exists only to circumvent non-electrolyte PRO/II’s inabil-
ity to do SLE, so it has no useful purpose for electrolytes and is
therefore disallowed.

E4-8 - July 2016 Electrolyte Effects In Simulations

 Calculator
See comments above regarding what may be accessed with the
DEFINE statement.

Stream Calculator
This unit is fully functional with PRO/II Electrolytes.

Flowsheet Control

ELECTROLYTES
You are likely to get warnings in electrolyte problems about compo-
nents with undefined separation factors. This is because a PRO/II
Electrolytes model will add any components it has to what is on the
LIBID statement, so there will be more components in the simula-
tion than the user might have thought. As long as none of these
added components are produced in the simulation, these warnings
may be safely ignored.

Miscellaneous
It is also possible to encounter a flash failure in this unit when doing
feed blending, such as is commonly done to figure the rate of a
makeup stream. This is because the unit first does an adiabatic flash
on the entire blended feed, even if only one or two components are
going to be picked out with an FPROD statement. In some cases,
even though you may just be figuring the makeup rate of a pure
water stream, the blended feed may put you in a composition region
that OLI cannot solve (for example, 1 mole of H2O with 100 moles
CaCO3). The workaround for this case, if all you want is water in
the makeup stream, is to make a dummy stream of pure solid
CaCO3 and put it into the blend with a factor of whatever is neces-
sary (-100, for example) to get rid of that component.

HCURVE
This unit works normally with Electrolytes. However, since electro-
lyte thermodynamic methods do not give you heat capacity or
entropy, those properties will be missing in the reports. The pseudo-
critical and petro reports are available, but are unlikely to give
meaningful quantities for electrolyte streams.

Phase Envelope
The Phase Envelope is available only with SRK and PR thermody-
namic methods and is therefore disallowed with Electrolytes.

PRO/II Electrolytes User Guide E4-9

 Hydrates
The Hydrates unit does not have a method set associated with it;
BATCH

therefore, it may be used with a stream exiting an electrolyte unit.

BVLE
The BVLE unit may be used with Electrolyte thermodynamic meth-
ELECTROLYTES

ods, provided water is one of the two components chosen for the
unit’s calculations. You must be careful not to specify the BVLE
unit such that it goes into a composition region where the flash will
not solve because there is too little water. It is probably preferable
to do BVLE-type analysis using the electrolyte flash capabilities in
the Chemistry Wizard software available from OLI, Inc.

Hextables
The Hextables utility is not yet available with Electrolyte thermody-
namic methods. The controllers, the optimizer, and recycle data all
work normally with electrolytes. See above, however, for com-
ments on what parameters can be used in SPEC and DEFINE state-
ments. With controllers and the optimizer, one must be careful not
to allow a VARY statement to create a condition where OLI cannot
solve a flash.

Case Study, Restart, Interactive

These options work exactly the same for Electrolyte problems as for
other problems.

Depressuring Unit
This unit is currently disallowed with Electrolytes.

Considerations Regarding Transport Properties

Currently, all transport property methods are allowed through key-
words with PRO/II Electrolytes (though most electrolyte models
will have at least one component for which TRAPP is not valid).
Vapor-phase transport methods should be chosen without regard to
the electrolyte nature of the problem; PETRO would typically be
the best option. For aqueous electrolyte streams, the recommended
method for the liquid phase is PURE, since the other methods in
PRO/II are primarily intended for hydrocarbon streams. The result-
ing transport properties will, for most liquid streams, be very close
to the values for pure water.

E4-10 - July 2016 Electrolyte Effects In Simulations

Output Considerations
To see what is going on in Electrolyte flowsheets, the user should
always use at least the PART setting (which is now the default) on
the PRINT ION flag. The user stream report writer works normally
with Electrolytes. There are, of course, several quantities, such as
heat capacities and entropies, which are not available. Several oth-
ers, such as RVP and GHV, will not be meaningful for electrolyte
streams. In addition, quantities such as NBP and TR, which depend

ELECTROLYTES
on averages of pure-component numbers, may not be meaningful
because some of the components in an electrolyte problem are
likely to be salts, for which (for example) there is no NBP or TC in
the library. For some of these numbers, dummy numbers (usually
water values) are “filled in” in the library to satisfy PRO/II input
checking; averages using these numbers will not be very meaning-
ful.

Speed Considerations
Compared to most other standard PRO/II thermodynamic methods,
Electrolytes is slow. This is unavoidable because it has to solve
chemical equilibria simultaneously with phase equilibria. For a
problem with the same number of components, Electrolytes will
typically be slower than a method like SRKM or NRTL by one or
two orders of magnitude.
One way to help the speed factor is to use the smallest model possi-
ble that includes all the components in the problem. It would proba-
bly be a good investment (especially if the model is going to be
used many times) to generate in a small model (for example, four
components) if the alternative were to use a much larger pre-gener-
ated model. Problems also run faster in “no-solids” models, and so
these versions should be used if it is known that there is no chance
of solid precipitation.
Because of the time that may be required for solution, it becomes
more worthwhile to provide good initial guesses. Results from ear-
lier runs may be saved and used in subsequent problems; the PRINT
PROFILE option on the Column is particularly useful for this pur-
pose. While saving profiles may not be worth the trouble for normal
columns, it can be quite worthwhile for an electrolyte column.

PRO/II Electrolytes User Guide E4-11

BATCH
ELECTROLYTES

E4-12 - July 2016 Electrolyte Effects In Simulations

 Index

A Composition range , E1-21

Compressor , E4-4
Acid systems , E2-13 Continuously stirred tank
Acid waste stream- reactor , E4-7
neutralization drums , E1-20 Controller
Amine systems , E2-12 loop, E4-4
validity ranges, E1-21 putting a column inside a, E4-6
Amine towers , E1-20 putting an isothermal reactor
inside a, E4-7
Application guidelines , E1-19 specification, E4-4
Convergence
B difficulty, E4-5, E4-6
failure, E4-1
Balance constraints, mass and Crystallizer , E4-8
charge , E1-23
Benfield systems , E1-20, E2-33
D
Blended feed , E4-9
BVLE unit , E4-10 DEFINE statement , E4-2, E4-9, E4-
10
Depressuring unit , E4-10
C Dew water calculations , E1-22
Calculations Dissolver , E4-8
invalid, E1-22 Distillation column , E4-5
Calculator Dryer , E4-7
description, E4-9 Duty , E4-4
stream, E4-9 fixed, E4-8
Case study , E4-10
Caustic systems , E2-31
CCDecanter , E4-8
E
Chemdist , E4-6 Electrolyte methods
Chemical equilibria , E4-11 acid stream neutralization, E1-
20
Chlor-alkali plant processes , E1-
20
amine towers, E1-20
Benfield processes, E1-20
Column , E4-5 chlor-alkali plant processes, E1-
Column hydraulics , E4-6 20
Component data gas scrubbers/purification, E1-
20
example, E1-14
important points, E1-20
fixed list, E1-15
in conjuction with non-
generating, E1-9 electrolyte methods, E1-4
overview, E1-13 mixed thermodynamic
reconstituted, E1-23 applications, E1-18

PRO/II Electrolytes User Guide Index-1

 scale formation prediction, E1- conditions, E4-1
20 duty, E4-4
solid salts manufacturing, E1-20 functionality, E4-3
BATCH

sour water strippers, E1-20 isentropic, E4-2, E4-4

underground injection well ISOT, E4-4
studies, E1-20 pressure drop, E4-5
Electrolyte models temperature, E4-5
acid systems, E2-13 TPSPEC, E4-4
amine systems, E2-12 Flowsheet control , E4-9
Benfield systems, E2-33
FPROD statement , E4-9
caustic systems, E2-31
component index, E2-40 Free water decant , E1-22
hydrate systems, E2-36 Freezer , E4-8
index, E2-9 Fugacity
invalid calculations, E1-22 calculating coefficients, E1-17
list of built-in, E2-1 vapor phase, E1-17
LLE systems, E2-36
mixed salt systems, E2-17
pregenerated, E2-1
scrubber systems, E2-34
G
selecting, E1-8
Gas scrubbers/purification , E1-20
sour water systems, E2-25
summary, E2-12 General data
supported, E1-3 overview, E1-11, E1-12
Electrolytic column algorithm General reactor , E4-7
(ELDIST) Gibbs reactor , E4-2, E4-7
advantages, E4-6
disadvantages, E4-6
uses, E4-5 H
ENTHALPY = ELEC
example , E1-18 HCURVE , E4-9
Entropy , E4-2, E4-9 Heat capacity , E4-2, E4-9
Entropy and heat capacity Heat exchanger
calculations , E1-22 LNGHX, E4-5
rigorous, E4-5
Equilibrium
simple, E4-5
calculations, E4-8
not reached, E4-8 Hextables utility , E4-10
Expander , E4-4 Hydrate systems , E2-36
Hydrates unit , E4-10

F
I
Fail to converge , E4-1
FCentrifuge , E4-8 Index
component, E2-40
Feed, blended , E4-9
electrolyte models, E2-9
Feeds
Initial estimate generator , E4-7
near saturation, E1-23
with little or no H2O, E1-22 Interactive option , E4-10
Flash Ionic species , E4-5
alternative to dissolver, E4-8 Ionic strength , E1-22

Index-2
 Isentropic flash , E4-2 P
Isothermal flash example , E1-23
Particle size distribution
(PSD) , E4-8
K PETRO transport properties , E4-
10
Kinetics , E4-8 pH , E4-4
Phase
envelope, E4-9
L equilibria, E4-8, E4-11
type LS, E4-7
LIBID statement , E4-9
Phase boundary , E4-4
Liquid phase, pure , E4-10
Pipe , E4-5
Liquid/liquid equilibrum
(LLE) , E4-2 Plug flow reactor , E4-7
Lists Pregenerated models , E2-1
components, E1-15 Pressure
thermodynamic methods, E1-15 drop, E4-5
LLE systems , E2-36 range, E1-21
valiidy ranges, E1-21 Print profile option , E4-6
LNGHX heat exchanger , E4-5 PRO/II’s graphical user
interface (GUI)
capability, E4-1
M limitations, E4-1
Pump , E4-4
Melter , E4-8
Mixed salt systems , E2-17
Mixer , E4-4 R
Reactor
N continuously stirred tank
reactor, E4-7
general, E4-7
Newton-Raphson method , E4-5
Gibbs, E4-7
Nonaqueous electrolyte isothermal, E4-7
systems , E1-22 plug flow, E4-7
Non-ideal aqueous electrolytic Reconstituted components , E1-23
distillation , E4-5
References , E1-24
NRTL (Chen’s) method , E1-19
Restart option , E4-10
RFilter , E4-8
O Rigorous heat exchanger , E4-5

OLI method , E1-19

Output S
limitations, E4-11
Scale formation prediction , E1-
20
Scrubber systems , E2-34
Simple heat exchanger , E4-5

PRO/II Electrolytes User Guide Index-3

 Solid salts manufacturing , E1-20 special case, E1-22
Solid species , E4-2 transport properties, E1-18
Transport properties , E1-18
BATCH

Solids
drying, E4-7 limitations, E4-10
filtering, E4-8 True aqueous solution
no-solids models, E4-11 species , E1-23
producing precipitate, E4-8
Solids handling utilities
ccdecanter, E4-8 U
crystallizer, E4-8
dissolver, E4-8 Underground injection well
dryer, E4-7 studies , E1-20
fcentrifuge, E4-8 Unit operations
freezer, E4-8 BVLE, E4-10
melter, E4-8 calculator, E4-9
rfilter, E4-8 calculator, stream, E4-9
Sour water systems , E1-20, E2-25 ccdecanter, E4-8
compressor, E4-4
SPEC statement , E4-2
controller loop, E4-4
SPEC statements , E4-10 crystallizer, E4-8
Speed , E4-11 dissolver, E4-8
Splitter , E4-4 distillation column, E4-5
dryer, E4-7
Stream calculator , E4-9 expander, E4-4
Stream data input , E1-22 fcentrifuge, E4-8
Supersaturation limit , E4-8 flash, E4-3
flowsheet control, E4-9
Surface tension , E4-5
freezer, E4-8
HCURVE, E4-9
heat exchanger, LNGHX, E4-5
T heat exchanger, rigorous, E4-5
heat exchanger, simple, E4-5
Temperature range , E1-21
hextables utility, E4-10
Thermodynamic data hydrates, E4-10
composition range, E1-21 melter, E4-8
fugacity, E1-17 mixer, E4-4
pressure range, E1-21 phase envelope, E4-9
temperature range, E1-21 pipe, E4-5
Thermodynamic methods pump, E4-4
application guidelines, E1-19 reactor, continuously stirred
available, E1-19 tank reactor, E4-7
built-in, E1-2 reactor, general, E4-7
choosing multiple, E1-16 reactor, Gibbs, E4-7
fixed list, E1-15 reactor, isothermal, E4-7
limitations, E4-1 reactor, Plug flow, E4-7
mixed, E1-18 rfilter, E4-8
non-electrolyte, E4-4 SPEC, DEFINE, VARY, E4-2
NRTL (Chen’s), E1-19 splitter, E4-4
OLI, E1-19 supported, E1-4, E4-3
valve, E4-4

Index-4
 V methods for determining
coefficients, E1-17
Validity ranges VARY statement , E4-2, E4-10
Amine systems, E1-21 Viscosity , E4-5
general, E1-21
LLE sytstems, E1-21
Valve , E4-4 W
Vapor-phase fugacity
calculating, E1-17 Water, removing , E4-7

PRO/II Electrolytes User Guide Index-5

BATCH

Index-6